CN104540926A - Integrated process for deasphalting and desulfurizing whole crude oil - Google Patents

Integrated process for deasphalting and desulfurizing whole crude oil Download PDF

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Publication number
CN104540926A
CN104540926A CN201380029767.0A CN201380029767A CN104540926A CN 104540926 A CN104540926 A CN 104540926A CN 201380029767 A CN201380029767 A CN 201380029767A CN 104540926 A CN104540926 A CN 104540926A
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China
Prior art keywords
dao
methods according
solvent
hydrocracking
reaction chamber
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CN201380029767.0A
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Chinese (zh)
Inventor
O·R·寇修格鲁
牛尾贤
中野宏二
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GC CATALYSTS AND CHEMICALS LT
Saudi Arabian Oil Co
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GC CATALYSTS AND CHEMICALS LT
Saudi Arabian Oil Co
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Publication of CN104540926A publication Critical patent/CN104540926A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454—Solvent desasphalting
    • C10G67/0463—The hydrotreatment being a hydrorefining
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454—Solvent desasphalting
    • C10G67/049—The hydrotreatment being a hydrocracking
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to processes for removing impurities, such as asphalt, from whole crude oil. The invention is accomplished by first deasphalting a feedstock, followed by processing resulting DAO and asphalt fractions. The DAO fraction is hydrocracked, resulting in removal of sulfur and hydrocarbons which boil at temperatures over 370 DEG C, and gasifying the asphalt portion.

Description

For the integrated form technique of whole crude diasphaltene and desulfurization
related application
This application claims the U.S. Provisional Patent Application the 61/655th submitted on June 5th, 2012, the right of priority of No. 732, it is incorporated to herein by reference of text.
Technical field
The present invention relates to a kind of for the treatment of whole crude therefrom to remove the integrated form technique of pitch and other impurity.Specifically, described integrated form technique comprises from this whole crude separate bitumen, then uses catalyzer via the step of hydrotreatment/this deasphalting oil of hydrocracking process, to remove material such as sulphur and nitrogen.Meanwhile, for the hydrogen of described hydrocracking step after the bituminous part reclaimed can be vaporized to produce.
Background technology
Common process for the treatment of crude oil comprises distillation, and various cracking afterwards, solvent refined and hydroconversion process, so that the series product needed for producing, and such as fuel, lube product, petroleum compound, chemical feedstocks and analogue.Illustrative processes is included in suitable air distillation post and distills the crude oil, and generates gas oil, petroleum naphtha, other gases and long residuum.This final section is further fractionation in vacuum distillation column, to generate so-called vacuum gas oil and vacuum residuum.This vacuum gas oil transfers to carry out cracking by fluid catalytic cracking or hydrocracking usually, and to produce more valuable light-duty transport fuel product, and this residual oil can be processed further, to generate extra useful product.Method involved in these techniques can comprise, such as, and the hydrotreatment of described residual oil or fluid catalytic cracking, coking, solvent deasphalting.Any materials reclaimed from crude distillation at fuel boiling point is directly used as fuel usually.
For describing above-mentioned technique in detail, solvent deasphalting is a kind of physical sepn technique, and wherein reclaim feed component with its virgin state, that is, they do not carry out chemical reaction.The paraffinic base solvent that usual use contains 3-8 carbon atom carrys out the component of separation of heavy crude oil fractions.It is a kind of flexible craft, usually normal pressure and decompression heavy oil residue is separated into two kinds of products substantially: (i) pitch, and (ii) deasphalting or demetallated residual oil, be hereinafter called " DAO " or " DMO ".The selection of solvent is determined by technician, and according to considered desired product, yield and amount, and other processing parameters such as service temperature and molten catalystoil ratio rate are selected.As general rule, along with described solvent molecule amount rises, the solubleness of described oil in described solvent also rises.Such as, propane or propane/Trimethylmethane mixture is usually used to manufacture lubricating oil bright stock.On the other hand, if DAO as described in use in as fluid catalytic cracking will be carried out in conversion, then the solvent (such as butane or pentane, or its mixture) with more high molecular will be used.The product of DAO solvation comprises above-mentioned those and lube oil hydrogenation cracking feed, fuel, the charging of hydrocracking device, fluid catalytic cracking charging or fuel oil blend.Can using described asphaltic products. as each grade bitumen blend components, use as fuel oil blend components or as the raw material of crude conversion units (such as coker).
Conventional solvent deasphalting method is carried out when not having catalyzer or sorbent material.United States Patent (USP) the 7th, 566, No. 394 (its disclosure is incorporated to herein by reference), teaches the method for the solvent deasphalting of the improvement adopting solid adsorbent.Improvement in the party's science of law causes nitrogen to be separated with DAO with polynuclear aromatic hydrocarbons.Then described sorbent material is removed together with described asphaltic products., and be transported to pitch bay, or gasify in the membranous wall gasifier needing solid.
Well-known hydrocracking technique is commercially in many refineries.The classical application of hydrocracking technique one is included in standard element the incoming flow of processing 370 DEG C to 520 DEG C boilings, and in so-called " residual oil unit " processing at those of 520 DEG C and above boiling.Briefly, hydrocracking is that macromolecular C-C key in feedstream forms more micromolecular a kind of technique with more high volatile volatile and economic worth by its fracture.In addition, increase H/C ratio by the hydrogenation via aromatics, and by removing organosulfur and organic nitrogen compound, hydrocracking technique typically improves the quality of hydrocarbon raw material.
Consider and result from the distinct economic of hydrocracking, existing in a large number to improving the exploitation of hydrocracking technique and to have more the exploitation of active catalyst not unexpected.
In implementation, hydrocracking unit generally includes two main region: reaction zone and disengaging zone.Also have three kinds of standard configurations: there is or do not have the single-stage of recirculation, crossfire (" one way "), and there is the two-stage process of recirculation.Various parameter is depended on to the selection of conversion zone configuration, the selection of the quality of such as raw material, product specification and editing objective and catalyzer.
The hydrocracking technique of single-stage, one way is harsher than typical hydroprocessing technique, but carry out under being not so good as the operational condition of conventional total head hydrocracking technique harshness.Gentle hydrocracking has more cost benefit than harsher technique, but in general, it causes the desired middle distillate product producing small amount, the quality that its tool is low compared with the product of conventional hydro cracking.
Single or multiple catalysts system can be used according to such as processed raw material and product specification.Single-stage hydrocracking unit is generally the most easy configuration on list or dual catalyst system, is intended to maximize middle distillate yield.Dual catalyst system is used in stacking bed configuration or two different reactors.
In the first catalysis region in single reactor or in the first reactor of two-reactor system, refinery feedstock on the hydrotreating catalyst of one or more amorphous bases usually.Then the effluent of the described first step is passed to described second catalyst system, it has catalyzer or the zeolite catalyst composition of the amorphous base of hydrogenation and/or hydrocracking function, is located at the second reactor bottom single reactor or in dual reactor systems.
] two stage arrangement (its can also " recirculation-to-consume light " operational mode run) in, carry out raw material described in refining by the hydrotreating catalyst bed passed in described first reactor.Described effluent is passed to fractional column with the H seethed with excitement in the temperature range being separated in 36-370 DEG C together with second stage effluent 2s, NH 3, lighter-than-air gas (C 1-C 4), petroleum naphtha and diesel product.There is no H 2s, NH 3deng unconverted bottom material be transported to the described second stage to transform completely.Then the hydrocarbon of the boiling higher than 370 DEG C is recycled to described first step reactor or described second stage reactor.
The effluent of hydrocracking unit is transported to distillation column in order to fractionation respectively at 36-180 DEG C, 180-240 DEG C, 240-370 DEG C and higher than the petroleum naphtha seethed with excitement in the nominal range of 370 DEG C, rocket engine fuel/kerosene, diesel oil, and unconverted product.Described had high-quality by the rocket engine fuel/kerosene fuel product of hydrocracking (i.e. smoke point >25 millimeter) and diesel product (that is, cetane value >52) and far above global transport fuel specification.While the effluent of hydrocracking unit has low aromaticity usually, any remaining aromatics all will reduce main indicative character, smoke point and the cetane value of these products.
One that proposes in hydrotreatment and/or hydrocracking heavy oil fraction or whole crude main technological challenge is that the pollutent of lower concentration is such as containing organic nickel or the compound of vanadium and the impact of polynuclear aromatic compound.These organometallic compounds and other pollutents, reduce activity or the life-span of hydrotreating catalyst.Described pollutent and polynuclear aromatic hydrocarbons cause the processing performance reduced, to the needs of running cost increasing capital and refinery's machining cell.Metal in the residue cut of described crude oil is deposited on the hole of hydrotreating catalyst, and causes catalyst deactivation.In following disclosure, these problems are processed and are solved.
The technique of prior art conventional in field of the present invention comprises and distilling the crude oil, with remaining lighting end (petroleum naphtha and diesel oil fuel) after aftertreatment distillation.These lighting ends are desulfurized and/or process () when petroleum naphtha i.e. " restructuring ", to improve its quality, are then transported to fuel tank for further use.Vacuum residuum as mentioned above, processes through solvent deasphalting, in order to fixing deasphalted oil and pitch.Then by being vaporized, pitch is further processed or it is transported to " pitch bay ".
Prior art processes demonstrates the process to former oil fraction or overhead product, instead of the process to crude oil itself, and this is consistent with the present invention.See such as PCT/EP2008/005210, wherein by overhead product for the production of bituminous matter and DAO; United States Patent (USP) the 3rd, wherein carries out solvent extraction to vacuum residuum by 902, No. 991, carries out hydrocracking and the gasification of DAO and pitch subsequently; Disclosed U.S. Patent application 2011/0198266, its display process to vacuum residuum; Disclosed U.S. Patent application 2008/0223754, wherein by the residual oil from distil process for the manufacture of bituminous matter and DAO; And EP683218, it also teach that and processes residual hydrocarbon product.Also see such as United States Patent (USP) the 8th, 110,090; 7,347,051; 6,357,526; 6,241,874; 5,958,365; 5,384,297; 4,938,682; 4,039,429; With 2,940, No. 920; And disclosed U.S. Patent application 2006/0272983; PCT/KR2010/007651; European patent application 99141; And disclosed Japanese patent application 8-231965.All documents discussed in this article are incorporated to herein all by reference of text.
By eliminating to distillation and to the needs processing described petroleum naphtha and diesel oil distillate, the present invention simplifies and improves prior art processes.Or rather, as by finding, the present invention is entirely flowed by hydrocracking and eliminates above-mentioned step and simplifies whole crude processing.
The present invention can be seen in disclosure below how to realize.
accompanying drawing is sketched
Fig. 1 shows the schematic diagram of the technique of the present invention of the embodiment using single reactor.
Summary of the invention
Can understand the present invention best by referring to Fig. 1, described Fig. 1 illustrates universal method of the present invention, and system used in its practice.
With reference to Fig. 1, the feedstream of crude oil " 10 " is added to reaction chamber " 11 ", to carry out solvent deasphalting to it, produces pitch fractions " 12 " thus, and deasphalted oil fraction or " DAO 13 " as mentioned above.The foregoing describe the mode that can realize this fractionating process, that is, use the paraffinic base solvent containing one or more carbon atom (containing 3-8 carbon).Catalyzer or sorbent material are unnecessary; But, see No. the 7th, 566,394, United States Patent (USP) above (it is incorporated to herein by reference), teach the de-asphalting processes of the improvement using sorbent material.Do not use distillation, be not also separated light constituent.
Described " DAO " " 13 " are transferred to hydrocracking/hydrotreating zone " 14 ".It is to be understood that although Fig. 1 describes single reactor, " reaction, can be used for the various methods of hydrocracking, to comprise " one way, crossfire " with " two-stage.Described reactor contains one or more catalyzer, and it removes heteroatoms such as sulphur and nitrogen from described DAO.Such catalyzer is well known in the art, need not repeat at this.Exemplary catalyzer is such as submit on August 2nd, 2011 and be incorporated to the catalyzer described in PCT/US11/46272 herein by reference.Described scission reaction occurs in the presence of hydrogen gas, and described hydrogen is supplied as explained below.
Should remember, except DAO, the solvent deasphalting of described crude oil produces pitch fractions " 12 ".By this pitch fractions together with oxygen " 16 " and steam " 17 ", transfer to vaporizer " 15 ".These components, that is, described oxygen and steam, can with pure form, or via, such as atmospheric air provides.By blended to described pitch, oxygen and steam under the temperature and pressure that hydrogen can be made to produce.In described embodiment, this hydrogen " 18 " is directed to DAO hydrocracking unit " 14 ", in order to supply for required hydrogen hydrocracking technique occurs.(it should be noted that the gasification of pitch is optional step, and can replace via the hydrogen such as supplying separate source).Various product, such as gas 19 and upgrading crude oil 20, gains and gasification product 21 are used to electrical production or for other purposes.
By being separated with described DAO by the asphalt component of described crude oil, eliminate the problem of the catalyst failure such as caused because of the metal existed in described pitch fractions.The life cycle of catalyzer adds, and to off-response device and more conversion materials need decline.
In technique described herein, described hydrocracking technique occurs under the condition of standard hydrogenation cracking, that is, from about 100 to the pressure within the scope of about 200bar, from about 350 DEG C to the temperature within the scope of about 450 DEG C, 0.1 and 4.0h -1lHSV, and from about 500 to about 2500SLt/Lt hydrogen-oil ratio rate.
Embodiment
Present embodiment describes embodiment of the present invention, wherein by the gasification of " SDA " cut for the production of hydrogen, then described hydrogen is used for the hydrocracking of DAO cut.It should be understood that and can supply H through other modes 2.
In the reaction chamber described by " 11 " in such as Fig. 1, with butane solvent and sorbent material, use field known technology, solvent deasphalting is carried out to the crude oil sample of 1000Kg.Analyzed described crude oil before diasphaltene, this result analyzed is presented in following table, the 1st row.
After diasphaltene, also analyze described pitch fractions and deasphalting oil or " DAO ", these results are presented in described form the 2nd and 3 and arrange.
By described pitch fractions is gasified by oxygen and steam and blended the entering in membranous wall reactor or vaporizer (in Fig. 1, " 14 " described) of described pitch fractions.Described mixture is heated to 1045 DEG C, there is the steam/hydrocarbons ratio rate (by weight) of 0.6 and the oxygen of 1.0: pitch ratio.
After completing gasification, by this crude syngas product and steam blended, described steam produces by boiler or by the process of heat exchanger to water-gas shift (" WGS ") reactor, its 318 DEG C, the pressure of a bar and 3 water hydrogen ratios under run.Which increase hydrogen yield.
All analyses and result are all presented in following, in the table be described in more detail below.
Form: component is summarized
When occurring when gasifying, described DAO part is introduced in the hydrocracking unit of the standard shown in " 14 ", and 360 DEG C, under the hydrogen partial pressure of 115bar, with 0.3h -1total liquid hourly space velocity, use that nickel-molybdenum promotes, the unbodied VGO hydrocracking catalyst of the loading ratio of 3:1 and VGO zeolite catalyst carry out hydrocracking.See PCT/US11/46272, it is merged in above in order to catalyzer used herein.
Analyze the low molecular weight hydrocarbons (C leaving the product of described hydrocracking room 1-C 4), the content of upgrading crude oil, oxygen, steam and hydrogen.These values are presented in 4-5 row in described form.Also analyze various minor component and the boiling fraction of upgrading crude oil, and analyze described crude oil and DAO in a like fashion.For describing this form in detail, the 1st row present the analysis of crude oil used in described reaction (" CO ").2nd is classified as the analysis of obtained DAO and the 3rd analysis being classified as pitch fractions.4th row are presented on the information of the gas produced in described hydrocracking step, and the information that the 5th is classified as described upgrading crude oil.Finally, the 6th, 7 and 8 row refer to the reactant being added to described reactor as discussed above.
Foregoing disclosure proposes feature of the present invention, and it is the simplified method for reducing impurity such as sulphur and nitrogen in raw material such as crude oil, and it does not comprise distillation.In brief, described crude oil, through solvent deasphalting, generates DAO and pitch.Then DAO described in hydrocracking in the presence of a catalyst, to carry out desulfurization and denitrogenation to it, and becomes overhead product by any hydrocarbon conversion had more than 370 DEG C of boiling points.Meanwhile, described pitch fractions is gasified to produce hydrogen.In one embodiment, described hydrogen is led back to described hydrocracking reactor, and for this technique.The character of described raw material will change and can comprise the ash content of the amount in about 2% to about 10% scope of total raw material.Described raw material can be liquid or solid.Preferably there is the liquid starting material of the component from the boiling point of about 36 DEG C to about 2000 DEG C.Described raw material can be such as bitumeniferous oil (bituminous, oil), sand, shale oil, coal or biological liquid, and preferably containing the sulphur lower than 20ppmw.
In implementation, it is desirable to make described crude oil stand paraffinic base solvent to be separated DAO and pitch.Described solvent comprises one or more C 3-C 7alkane, it can be straight or branched.Preferably, described solvent comprise one or, most preferred, the mixture of butane.Solvation occurs under the temperature and pressure of the threshold value lower than these temperature and pressure.
Carry out diasphaltene step particularly preferably under the existence of solid adsorbent by discussed, solid adsorbent is preferably enough to provide 20:0.1 to the 10:1 hydrocarbon of (expressing by W/W): the amount of sorbent material ratio is added into.
After separation, DAO is delivered to hydrocracking unit, wherein under transformable condition, carries out hydrocracking, but be preferably from about 100 to about 200bar pressure, from the temperature of about 350 DEG C to about 500 DEG C, about 0.1 to about 4.0h -1lHSV and from about 500 to about 2500SLt/Lt hydrogen: oil ratio rate.The hydrocracking system of any standard can be used, comprise single reactor, multiple reactors of series operation, fixed-bed reactor, ebullated bed reactor, etc.
In described hydrocracking technique, using catalyzer, being preferably incorporated to catalyzer herein above by quoting.Preferably, catalyzer contains the active metal of about 2% to about 40% by weight, from the total pore volume of about 0.3 to about 1.5cc/g, from about 200 to about 450m 2the total surface area of/g, and the average pore diameter of at least 50 dusts.
For described active metal as mentioned above, preferably from the metal of VI, VII or group VIIIB, and one or more that can comprise in Co, Ni, W and Mo.Although do not require so to do, usually described catalyzer is incorporated in carrier such as aluminum oxide, silicon-dioxide, zeolite or by such as steam, ammonia, acid elution and/or transition metal is inserted its structure and come on the zeolite of modification.
While the hydrocracking of described DAO, preferably the temperature of about 900 DEG C to about 1700 DEG C, and under from about 20bar to the pressure of about 100bar, the pitch part of described crude oil is gasified in vaporizer such as membranous wall formula reactor, gasify containing O 2gas existence under carry out, it can be, such as, purity oxygen or more preferably, atmospheric gas.Can control to enter the amount of pitch in described gasifying reactor and oxygen by setting tool.This instrument is known by the technical staff, does not need to repeat at this.Preferably control pitch and O 2amount allow partially combusted stoichiometric balance to make to produce immediately.This by determining that the hydrocarbon content of described crude oil is determined, such as can complete in foregoing embodiments.Preferably, selection is carried out to this amount and make described oxygen by weight: carbon ratio is in from about 0.2:1.0 to the scope of about 5:0.1.
Optionally, steam can be added to described vaporizer.When so incorporated, it also adds with the amount of the carbon content based on described crude oil, and preferably by weight to present from about 0.1:1.0 to the ratio of about 100:1.0.Gasification generates the product sometimes referred to as " synthetic gas ", and it is made up of hydrogen and carbon monoxide substantially.In one embodiment of the invention, the synthetic gas produced by gasification is transported to water-gas shift reaction room, and processed to produce H 2and CO 2, afterwards, by H 2be separated.Can by the pure H of gained 2guide to described hydrocracking reaction.
The technique processed described synthetic gas can be included in the temperature from about 150 DEG C to about 400 DEG C, and from about 1 to the process of the pressure of about 60bar.
As finding above, can arbitrfary point measurement gas content in technique described herein.Therefore, measure in synthetic gas after CO content, can preferably with from about 3:1 to about 5:1 with the mol ratio of CO, water is joined in reaction chamber.
Other facts of the present invention will be clearly to technician, need not repeat at this.
The term adopted and to express be use as the term described and do not have restricted, and be not intended to get rid of shown and feature that is that describe or its part any equivalents in the use of these terms and expression.Various possible amendment is within the scope of the present invention all approved.

Claims (22)

1., for reducing a method for the impurity in hydrocarbon-containifirst raw material, described method comprises:
I () carries out solvent deasphalting to described raw material in the first reaction chamber, with production pitch fractions and deasphalted oil (DAO) cut;
(ii) in the second reaction chamber be separated and the 3rd reaction chamber, described DAO cut and pitch fractions is processed;
(iii) in described second reaction chamber DAO described in hydrocracking therefrom to remove sulphur and nitrogen, and in order to distill out any hydro carbons had more than 370 DEG C of boiling points contained in described DAO; And
(iv) in described 3rd reaction chamber by by described pitch fractions and oxygen with steam is blended makes described pitch fractions gasify, therefrom to produce hydrogen.
2. method according to claim 1, described method comprises introduces described second reaction chamber by the described hydrogen produced in described 3rd reaction chamber.
3. method according to claim 1, wherein said solvent deasphalting is included in lower than under the critical temperature of described solvent and the temperature and pressure of emergent pressure, by described crude oil and containing C 3-C 7the solvent of carbon atom.
4. method according to claim 3, wherein said solvent comprises normal butane and Trimethylmethane.
5. method according to claim 1, described method also comprises and is contacted with solid adsorbent by described crude oil.
6. method according to claim 3, described method be included in lower than under the critical temperature of described solvent and the temperature and pressure of emergent pressure by described crude oil and solvent.
7. method according to claim 3, wherein said crude oil and solvent blended with the weight ratio from 10:1 to 200:1w/w.
8. method according to claim 1, described method is included in the pressure from 100-200bar, from the temperature of 350 DEG C to 500 DEG C, from 0.1 to 4.0h -1lHSV, and from 500 to 2,500SLt/Lt hydrogen: DAO described in hydrocracking under DAO ratio.
9. method according to claim 1, described method is included in DAO described in hydrocracking in multiple rooms of series connection.
10. method according to claim 1, the room of wherein said hydrocracking is fixed bed, ebullated bed or suspension bed room.
11. methods according to claim 1, described method comprises DAO described in hydrocracking in the presence of a catalyst, and described catalyzer contains the active metal from 2-40wt%, from the hole solvent of 0.33 to 1.50cc/gm, 250-450m 2the surface-area of/g, and the mean pore size of at least 50 dusts.
12. methods according to claim 11, wherein said active metal is VI, VII or group VIIIB metal.
13. methods according to claim 11, wherein said active metal comprises Co, Ni, W or Mo.
14. methods according to claim 11, wherein said catalyzer is present on carrier.
15. methods according to claim 14, wherein said carrier comprises aluminum oxide, silicon-dioxide or zeolite.
16. methods according to claim 15, wherein said carrier is zeolite.
17. methods according to claim 16, wherein said zeolite by using the process of at least one in steam, ammonia or acid to carry out modification, and contains at least one transition metal.
18. methods according to claim 17, wherein said at least one transition metal is Zn or Ti.
19. methods according to claim 1, described method is included in and described pitch fractions is gasified from the temperature of 900 DEG C to 1700 DEG C and the pressure from 20bar to 100bar.
20. methods according to claim 1, described method also comprises the amount of at least one in the pitch and oxygen and steam adjusted in described 3rd reaction chamber, causes the partially combusted stoichiometric balance of described pitch to provide.
21. methods according to claim 19, wherein based on described oxygen: the described stoichiometric ratio of carbon ratio is that weighing scale is from 0.2:1:0 to 10:0.2.
22. methods according to claim 19, described method comprises based on the carbon weight in described crude oil, and pitch and steam are introduced described 3rd reaction chamber by the ratio with 0.1 to 1.0 to 10:0.1.
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