CN110003945A - Improved residue method for transformation including carrying bed depth hydroconversion stage and depitching stage secretly - Google Patents

Abstract

The present invention relates to the method for conversion of heavy hydrocar-bonaccous feedstock, at least 50 weight % of the hydrocarbon raw material at least 300 DEG C at a temperature of boil, especially decompression residuum.Raw material is set to be subjected to first entrainment bed (slurry) deep hydrogenation transformation stage a), it is optionally followed by the stage b) of separation light fraction, and the heavy residual fraction generated by stage b) is obtained, at least 80 weight % of the heavy residual fraction have at least 250 DEG C of boiling point.Then the effluent that the fraction or stage a) obtained to stage b) obtains carries out the second entrainment bed depth hydroconversion stage c).Air speed is less than 0.1h when stage a) is to c) total^‑1.The effluent that stage c) is generated is fractionated to separate light fraction.By obtained heavy distillat (its 80 weight % at least 300 DEG C at a temperature of boil) be sent into depitching stage e).Then it preferably converted selected from boiling bed hydrogenation, converting de-asphalted fraction DAO in the stage f) of fluid catalystic cracking and fixed bed hydrogenation cracking.

Description

Improved residue including carrying bed depth hydroconversion stage and depitching stage secretly Method for transformation

Technical field

The present invention relates to the conversion of heavy hydrocarbon feedstocks, the heavy hydrocarbon feedstocks include that the boiling point of at least 50 weight % is at least 300 DEG C of fraction.It is crude oil material or the original that is generated directly or after the treatment by the normal pressure of crude oil and/or vacuum distillation Material, such as normal pressure or decompression residuum.

From the point of view of technical standpoint and economic angle, increase the value relative difficulty of these Residual oils.This is because new supervision Limitation greatly reduces the maximum allowable content of sulphur in bunker fuel oil (from 3 weight % to the sulphur of 0.5 weight %).In addition, market It is especially required under atmospheric pressure in the fuel lower than 380 DEG C, distilled at a temperature of being practically even lower than 320 DEG C.

Background technique

The patent FR 2 906 814 of applicant company describes a kind of method, and this method includes (producing the depitching stage Raw deasphalted oil), the hydroconversion stage (generate effluent) of the deasphalted oil and the distillation stage of the effluent (generate the residue for returning to the depitching stage together with raw material) is continuously connected together.That patent describes a series of Method, wherein hydroconversion stage is in 0.1h^-1To 5h^-1Conventional air speed (HSV) under carry out, the SDA stage is in hydroconversion stage Upstream carry out.The a large amount of pitches generated limit the maximum horizontal of the total conversion of this method.

The patent FR-2 964 386 of applicant company describes processing and is produced by the normal pressure or vacuum distillation of crude oil or crude oil The sequence of the method for raw raw material.This method includes boiling bed hydrogenation transformation stage (referred to as H-Oil or LC-Fining work Skill), followed by the separation phase of light fraction (boiling point be lower than 300 DEG C, preferably shorter than 375 DEG C), and by gained heavy distillat directly into The row depitching stage, to generate deasphalted oil (DAO).DAO can be hydrocracked or hydrotreating or fractionation.

The boiling bed hydrogenation transformation stage is in 0.1h^-1To 10h^-1Air speed (HSV) under carry out.The embodiment of the patent is in HSV = 0.3h^-1With the conversion ratio about about 60 weight % of ebullated bed part (relative to 540 DEG C+residue, i.e., at 540 DEG C or higher At a temperature of the residue that boils) under carry out.

This simple and economy method can be realized in the same reaction zone to be thermally integrated, and can obtain high-quality DAO；However, bituminous production is high, which has limited the achievable maximum total conversions of this method.

(patent US 7 938 952) be it is known that have two boiling bed hydrogenation transformation stages of intermediate separation at least 0.1h^-1Total air speed under operate (referred to as H-Oil technique), to separate light fraction and gained double distilled to be distributed into second plus hydrogen Then transformation stage directly distills the effluent generated by the second hydro-conversion." total air speed " is understood to refer in standard temperature Spend the total volume with the flow of the hydrocarbon raw material obtained under pressure condition divided by the reactor for constituting hydroconversion stage.

The patent FR 3 033 797 of applicant company describes a kind of handle by crude oil or normal pressure or decompression by crude oil The method of the raw material generated is distilled, at least 80 weight % of the raw material have at least 300 DEG C of boiling point.This method includes adding hydrogen Transformation stage (the first hydro-conversion) then separates light fraction (boiling point be lower than 350 DEG C), and obtained heavy distillat is carried out and the The hydro-conversion (the second hydro-conversion) of one hydro-conversion separation；Resulting effluent is then fractionated by distillation.Hydrogen should be added to turn Change method is in low total HSV, preferably 0.05h^-1To 0.09h^-1Lower operation.

The advantages of low total HSV is High Purity, this allow to obtain for high-caliber residue conversion ratio (> 75%), with the residue of low content asphalitine and conradson carbon residue.The stability of liquid efflunent is improved.Hydrogen is added to turn The deposit content for changing exit reduces, this makes this method have better operability.The total conversion of this method by The limitation of unconverted heavy effluent.

Summary of the invention

Have already sought a kind of method now, have improved properties quality, especially have fuel (naphtha, kerosene, Diesel oil) high conversion, to adapt to market.

The method of the nearest prior art (FR 3 033 797) can be modified to improve turning for deep hydrogenation transformation stage Rate, while further decreasing total HSV.

Applicant company is it has been proved that preferably solution is to increase depitching in the method for the nearest prior art In the stage, this allows to obtain the yield and quality of high-caliber DAO, and can handle at least one transformation stage DAO, at least one described transformation stage preferably carries out at high HSV, and therefore improves conversion ratio, while significantly improving and can operate Property and in terms of capital invested save substantial contribution and investment repayment it is more preferable.Compared with the method with higher total HSV, The present invention can also be further reduced the yield of pitch.

More particularly it relates to the method for transformation of hydrocarbon raw material, at least 50 weight % of the hydrocarbon raw material, preferably at least 80 weight % at least 300 DEG C at a temperature of boil, the method includes following successive phases:

In stage a), in presence of hydrogen, at least one first phase reactor as entrainment bed operation, Under the absolute pressure of 2MPa to 35MPa, 300 DEG C to 550 DEG C at a temperature of, with 50 Sm³/m³To 5000 Sm³/m³Hydrogen Amount is converted using the first deep hydrogenation that the first slurry catalyst carries out the hydrocarbon raw material,

Optionally, the stage b) of light fraction is separated from by some or all of first hydro-conversion generation effluent, And at least one heavy distillat is obtained, at least 80 weight % of the heavy distillat have at least 250 DEG C of boiling point,

In stage c), by the second of the heavy distillat that some or all of stage a) generation liquid efflunent or stage b) generate Deep hydrogenation conversion in presence of hydrogen as entrainment bed operation at least one second phase reactor in, 2MPa extremely Under the absolute pressure of 35MPa, 300 DEG C to 550 DEG C at a temperature of, with 50 Sm³/m³To 5000 Sm³/m³Amounts of hydrogen, use Second slurry catalyst carries out,

And air speed is less than 0.1h when stage a) is to c) total^-1, air speed is to obtain in standard temperature and pressure conditions when total Reactor total volume relative to stage a) and c) hydroconversion stage a) liquid charging stock flow,

At least one light fraction and at least one will be separated by some or all of second hydro-conversion generation effluent The stage d) of a heavy distillat, at least 80 weight % of the heavy distillat have at least 300 DEG C of boiling point,

At a temperature of deasphalting stage e) by the heavy distillat generated by stage d) at 60 DEG C to 250 DEG C, use to A kind of hydrocarbon solvent with 3 to 7 carbon atoms and solvent/raw material ratio (volume/volume) are 4/1 to 9/1 less, obtain depitching Fraction DAO and pitch.

Advantageously, this method includes the stage f) of transform portion or whole de-asphalted fraction DAO optionally distilled.

Preferably, DAO is distilled before transformation stage f), to separate heavy distillat, at least 80 weight % have at least 375 DEG C, or at least 400 DEG C, or at least 450 DEG C, or at least 500 DEG C, preferably at least 540 DEG C of boiling point, and by the double distilled branch Divide or be all sent into transformation stage f).

Preferably, part or all by DAO fraction is preferably sent directly into the transformation stage, which is selected from The method operation of fixed bed hydrogenation cracking, fluid catalystic cracking or boiling bed hydrogenation conversion, these methods may include preparatory Hydrotreating.

According to a preferred embodiment, part or all of de-asphalted fraction DAO in presence of hydrogen, 5MPa extremely Under the absolute pressure of 35MPa, be advantageously 300 DEG C to 500 DEG C at a temperature of, in 0.1h^-1To 5h^-1HSV under, 100 Sm³/m³To 1000 Sm³/m³(standard cubic meter (Sm³) every cubic metre of (m³) liquid charging stock) and amounts of hydrogen under, and containing extremely A kind of few group VIII non-noble metal j element and at least one Section VI b race's element simultaneously contain the carrier comprising at least one zeolite Bed hydroprocessing cracking is fixed in the presence of catalyst.

According to another preferred form, part or all of de-asphalted fraction DAO carries out fluidized bed in the presence of a catalyst and urges Change cracking FCC, the catalyst is preferably free of metal, includes aluminium oxide, silica, silica/alumina, and preferred Include at least one zeolite.

According to another preferred form, part or all of de-asphalted fraction DAO carries out boiling bed hydrogenation conversion, in hydrogen In the presence of, under the absolute pressure of 2MPa to 35MPa, 300 DEG C to 550 DEG C at a temperature of, in 50 Sm³/m³To 5000 Sm³/ m³Under the amounts of hydrogen of liquid charging stock, in 0.1 h^-1To 10 h^-1HSV, and containing carrier and at least one be selected from nickel and cobalt Group VIII metal and at least one Section VI b race metal selected from molybdenum and tungsten catalyst in the presence of carry out.

At least part of the de-asphalted fraction DAO can be recycled to stage a) and/or stage c).

Advantageously, in separation phase d), the effluent generated by second hydro-conversion is separated at least one Light fraction and at least one heavy distillat, at least 80 weight % of the heavy distillat have at least 375 DEG C, or at least 400 DEG C, or extremely It is 450 DEG C few, or at least 500 DEG C, preferably at least 540 DEG C of boiling point.

In general, stage a) and c) at 5MPa to 25MPa, the absolute pressure of preferably 6MPa to 20MPa, at 350 DEG C to 500 DEG C, at a temperature of preferably 370 DEG C to 480 DEG C, more preferable 380 DEG C to 430 DEG C, with 100Sm³/m³To 2000 Sm³/m³, very excellent Select 200 Sm³/m³To 1500 Sm³/m³Amounts of hydrogen, to be at least 0.05h^-1, preferably 0.05h^-1To 0.09h^-1When air speed (HSV) it carries out.

In general, stage e) uses the solvent selected from butane, pentane and hexane and its mixture to carry out.

An embodiment according to the present invention, the first slurry catalyst and/or second of the first deep hydrogenation conversion a) Deep hydrogenation conversion the second slurry catalyst c) includes carrier and active phase, the activity mutually containing at least one selected from molybdenum and The Section VI b race metal of tungsten, Section VI b race metal are preferably molybdenum, Section VI b race metal preferably at least one selected from nickel, The group VIII base metal of cobalt, ruthenium and iron combines, and the group VIII base metal is preferably nickel.

An embodiment according to the present invention, the first slurry catalyst and/or second of the first deep hydrogenation conversion a) Deep hydrogenation conversion the second slurry catalyst c) is obtained by the precursor for dissolving in organic phase, the precursor be preferably selected from by Mo, The organo-metallic compound of more carbonyls composition of the naphthenate and Mo, Co, Fe and Ni of Co, Fe and Ni, the precursor Preferably molybdenum naphthenate.

Summary of the invention

Raw material

The raw material handled in the context of the present invention is its at least 50 weight %, and preferably at least 80 weight % have at least 300 DEG C (T20=300 DEG C), preferably at least 350 DEG C or at least 375 DEG C of those of boiling point.

These be crude oil or by crude oil normal pressure and/or vacuum distillation generate heavy hydrocarbon fractions.These are also possible to often Press residual oil and/or decompression residuum, especially by hydrotreating, be hydrocracked and/or normal pressure that hydro-conversion generates and/or decompression Residual oil.These be also possible to depressurize distillate, come from catalytic cracking unit such as FCC(fluid catalystic cracking), come from coking list Member or the fraction from visbreaking unit.

Preferably, these are decompression residuum.In general, these residual oil are its at least 80 weight % at least 450 DEG C or higher, And the fraction to boil under typically at least 500 DEG C or 540 DEG C of boiling point.

From for producing lubricant, deasphalted oil (raffinate generated by deasphalting units) or pitch (by deasphalting units The residue of generation) unit in the aromatic fraction that extracts can also be suitable as raw material.

Raw material is also possible to residual fraction (such as the normal pressure generated by H-Coal technique generated by the direct liquefaction of coal Residual oil and/or decompression residuum), the decompression distillate generated by the direct liquefaction (such as H-Coal technique) of coal, from coal or The residue of the pyrolysis of shale oil, or by lignocellulose biomass direct liquefaction generate residual fraction, individually or As the mixture with coal and/or petroleum distillate.

All these raw materials can be used alone or use as mixture.

Above-mentioned raw materials contain impurity, such as metal, sulphur, nitrogen, conradson carbon residue and heptane insolubles, also referred to as C₇Pitch Matter.Tenor is typically larger than 20 weight ppm, most often greater than 100 weight ppm.Sulfur content is greater than 0.1 weight %, typically larger than 1 weight % is greater than 2 weight %.C₇The content of asphalitine (according to the heptane insoluble asphalitine of standard NFT60-115) is minimum 0.1 weight % and typically larger than 3 weight %.The content of conradson carbon residue is at least 1 weight %, typically at least 3 weight % or at least 5 Weight %.The content of conradson carbon residue is defined by standard ASTM D 482, and to those skilled in the art, is represented The well known evaluation of the amount of the carbon residue generated after being pyrolyzed in standard temperature and pressure conditions.

The first stage (stage a)) of deep hydrogenation conversion

Raw material is handled in hydroconversion stage a), which includes at least one phase reactor as entrainment bed operation. One or more phase reactor series connection and/or placement in parallel.These hydroconversion reactions devices are entrainment bed (referred to as " slurry Bed ") reactor of type.The method of known many operation entrainment beds, the catalyst and operating condition of these methods are substantially different. For example, in patent US 4 299 685 or US 6 660 158 or US 7 001 502 or US 7 223 713 or US 7 585 406 or US 7 651 604 or US 7 691 256 or US 7 892 416 or US 8 017 000 or US 8 105 482 or US The paper of 8 110 090 or Casta eda et al., " Current situation of emerging technologies For upgrading of heavy oils ", 2014, Catalysis Today, the 220-222 volumes, the 248-273 pages, Or works " the 18th chapter of Heavy Crude Oils:From Geology to Upgrading, An Overview " “Catalytic Hydrotreatment and Hydroconversion: Fixed Bed, Moving Bed, Entrainment is described in Ebullated Bed and Entrained Bed " (being published by é ditions Technip in 2011) Bed process.According to the present invention, each phase reactor has entrainment bed operation.According to the present invention, each phase reactor With entrainment bed operation.The bed includes at least one slurry hyd reforming catalyst, that is to say, that it enters instead together with raw material It answers device and is entrained with reactor together with effluent.It particularly, can by the suitable density of catalyst and suitable granularity To realize this entrainment.

At this stage a) in, the raw material entrainment bed hydroprocessing conversion specified conditions under convert.Stage a) 2MPa extremely 35MPa, preferably 5MPa are to 25MPa, and under the absolute pressure of preferably 6MPa to 20MPa, at 300 DEG C to 550 DEG C, preferably 350 DEG C extremely 500 DEG C, preferably 370 DEG C to 480 DEG C carry out at a temperature of more preferable 380 DEG C to 430 DEG C.The hydrogen advantageously mixed with raw material 50 Sm that preferably obtain in standard temperature and pressure conditions of amount³/m³To 5000 Sm³/m³Liquid charging stock, preferably 100 Sm³/m³To 2000 Sm³/m³, highly preferred 200 Sm³/m³To 1500 Sm³/m³。

Slurry hyd reforming catalyst has the granularity and density for being suitable for its entrainment.The entrainment of catalyst is interpreted as anticipating Refer to its in one or more phase reactors by the circulation of liquid stream, the slurry catalyst is together with raw material described It is recycled in one or more phase reactors, and from one or more of phase reactors together with the liquid efflunent of generation Middle discharge.Since its size is small, (it can become between several nanometers to about 100 microns (usual 0.001 microns to 100 microns) Change), therefore slurry catalyst is very well dispersed in raw material to be transformed, therefore substantially improves the hydrogen in entire reactor Change and hydroconversion reactions, significantly reduce the formation of coke and significantly improve the conversion ratio of the heavy distillat of raw material.These slurries Material catalyst is well known to those skilled in the art.

Slurry catalyst can be suitable for activation under conditions of outside reactor ex situ formed and activation, then with Raw material injects together.Slurry catalyst can also be formed in situ and activate under the reaction condition of a hydroconversion stage.

Slurry catalyst or its precursor are injected together with the inlet of reactor with raw material to be transformed.Catalyst and original Material and the product of this method of conversion pass through reactor together, and then they are entrained with reactor together with reaction product.These The case where catalyst has (patent US 4 303 634) in powder form, this is following slurry supported catalysts, either " can There is (patent US 5 288 681) in the form of dissolubility " catalyst.In the reactor, according to the property of catalyst, slurry catalysis Agent is the form of the solid particle of dispersion, the molecular entity of colloid or dissolution in the feed.It can be according to the method for the present invention Used in such precursor and catalyst be widely described in document.

Slurry catalyst used can be the powder of heterogeneous solid (such as natural crystal, ferric sulfate etc.), by water-soluble Property the dispersed catalyst that generates of precursor, such as the mixture of phosphomolybdic acid, ammonium molybdate or molybdenum oxide or nickel oxide and ammonium hydroxide, or by can The precursor for being dissolved in organic phase generates.Preferably, used catalyst is generated by the precursor for dissolving in organic phase.Dissolve in organic phase Precursor is preferably selected from the organometallic being made of more carbonyls of the naphthenate of Mo, Co, Fe and Ni and these metals Close object, such as 2 ethyl hexanoic acid molybdenum or 2 ethyl hexanoic acid nickel, acetyl acetone or nickel acetylacetonate, C₇-C₁₂The molybdenum of fatty acid or Tungsten salt etc..Preferably, precursor is molybdenum naphthenate.Slurry catalyst can use in the presence of surfactants, to improve metal Dispersion, especially when catalyst is bimetallic catalyst.

According to a preferred embodiment, " oil-soluble " catalyst is used, and (it can be with carbon raw material by precursor A part of raw material to be processed, external feed etc.) mixing, which is optionally at least partially dried, then or is simultaneously led to Addition sulphur compound is crossed to vulcanize and heat.The preparation of these catalyst is described in the prior art.

Additive can be added during preparing catalyst, or can be incited somebody to action before slurry catalyst is injected reactor Additive is added to the slurry catalyst.These are such as diesel oil, aromatics additive, solid particle, and size is preferably smaller than 1mm etc..Preferred additive is inorganic oxide, such as aluminium oxide, silica or mixed alumina/silica, is born The dead catalyst (such as being supported on aluminium oxide and/or silica) of load, the element (example containing at least one group VIII Such as Ni or Co) and/or at least one group VIB element (such as Mo or W).For example, referring to patent US 2008/177124 Described in catalyst.Also optional pretreated coke can be used.These additives describe extensively in the literature.

Slurry catalyst can be near advantageous by before introducing the raw material in one or more hydroconversion stages A kind of few active phase precursor is directly injected into one or more hydroconversion reactions devices and/or raw material and obtains.The addition of precursor It can introduce continuously or in batches and (depend on operation, the type of feed of processing, required product specification and operability).According to one One or more slurry catalyst precursors and hydrocarbon ils are pre-mixed to form dilution precursor pre-composition by a or multiple embodiments, The hydrocarbon ils is for example made of hydrocarbon, and at least 50 weight % of the total weight relative to hydrocarbon ils have 180 DEG C to 540 DEG C of boiling point. According to one or more embodiments, precursor or dilution precursor pre-composition are dispersed in heavy hydrocarbon feedstocks, such as pass through dynamic Mix (such as using rotor, blender etc.) or by static mixing (such as using syringe, by positive feed, by quiet State mixer etc.), or be only added only in raw material to obtain mixture.It can be used well known by persons skilled in the art any mixed It closes and precursor or diluted precursor mixture is dispersed in the raw material of one or more hydroconversion stages by stirring technique.

One or more active phase precursors of unsupported catalyst can be liquid form, such as dissolve in organic The metal precursor of medium, such as molybdenum caprylate and/or molybdenum naphthenate or water soluble compound, such as phosphomolybdic acid and/or seven molybdic acids Ammonium.

According to an embodiment, the slurry catalyst, the i.e. carrier comprising active phase can be loaded.In such case Under, loaded catalyst can be advantageously obtained by following:

By grinding fresh or used load hydrogenation reforming catalyst or the fresh mixing with used catalyst of grinding Object, or

By impregnating at least one active phase precursor on carrier, the carrier shows the granularity for being suitable for its entrainment, and Preferably 0.001 μm to 100 μm of size.

The slurry supported catalyst preferably comprises carrier, such as silica, aluminium oxide, silica/alumina, two The combination of titanium oxide, clay, carbon, coal, coke, carbon black, lignite or these structures, and highly preferred aluminium oxide.

One or more elements of the activity phase containing periodic table of elements 4-12 race of the slurry supported catalyst, can With or can not be deposited on carrier.The activity of the slurry catalyst mutually advantageously containing at least one selected from molybdenum and tungsten the The metal of VIb race metal, Section VI b race is preferably molybdenum.Section VI b race metal can be selected from nickel, cobalt, iron, ruthenium at least one It is combined with the group VIII base metal of preferred nickel.

In the present specification, the race of chemical element is according to CAS classification (CRC Handbook of Chemistry and Physics, CRC Press publish, edit D.R. Lide, the 81st edition, 2000-2001) provide.For example, according to CAS classification Group VIII metal corresponds to the metal according to the new IUPAC column of the 8th, 9 and 10 classified.

In the case where slurry supported catalyst, the content of the base metal of group VIII, especially nickel is advantageously 0.5% to 10%, it is indicated with the weight of metal oxide (especially NiO), and preferably 1 weight % to 6 weight %.Section VI b race Metal, the content of especially molybdenum is advantageously 1% to 30%, with metal oxide (especially molybdenum trioxide MoO₃) weight It indicates, and preferably 4 weight % to 20 weight %.Tenor is expressed as metal oxide relative to slurry supported catalyst Weight weight percent.

Advantageously, slurry supported catalyst can additionally comprise at least one dopant (element week selected from phosphorus, boron and halogen The Section VII a race or the 17th race of the new representation of phase table), preferred phosphorus.

According to one or more embodiments, relative to the heavy hydrocarbon feedstocks at reactor inlet, slurry catalyst it is dense Degree is the active metal of 10 weight ppm to 10000 weight ppm, preferably 50 weight ppm to 6000 weight ppm, preferably 100 weights Measure ppm to 1000 weight ppm, particularly preferred 100 weight ppm to 800 weight ppm.

In an embodiment according to the method for the present invention, urged in each reactor using the slurry of several types Agent.

In an embodiment according to the method for the present invention, each reactor, which contains, one or more to be suitable as pressing from both sides Slurry catalyst with bed operation.

In an embodiment according to the method for the present invention, one or more slurry catalysts are partly or entirely again Recycling catalyst.This is because used slurry can be recycled in distillation stage in order to limit the consumption of fresh slurry catalyst Catalyst and one or more entrainment bed hydroprocessing conversion zones can be reinjected.In general, not being in entrainment bed reactor Direct catalyst recycle, but one or more separation and optional one or more processing are carried out, such as burning, solvent are washed It washs, gasify or the combination in any other isolation technics or these stages, to recycle the particle containing slurry catalyst.Then may be used They are at least partly recycled directly to hydroconversion stage, or partly or entirely it is being recycled to catalyst preparation It reprocesses before.

Separation phase b)-is optional

This method preferably carries out stage b).

By at least part of the hydroconversion stage a) effluent generated, one or more points preferably can be all undergone From the stage.

The purpose for carrying out the separation phase be at least one light fraction (" the first light fraction ") is separated from effluent, thus At least one heavy liquid fraction is obtained, at least 80 weight % have at least 250 DEG C, preferably at least 300 DEG C of boiling point.

Then light fraction can at least partly be sent to distillation stage, in distillation stage, light fraction is then advantageously and gently Matter gas (H₂And C₁-C₄) separation, such as by passing through flash tank.Hydrogen is recycled, then advantageously in the deep hydrogenation transformation stage A) inlet is recycled or is passed to other units of deep hydrogenation transformation stage c) and/or oil plant.Then The lighter liquid fraction separated with light gas advantageously can be sent into fractionation stage d).The lighter liquid fraction separated in this way Light gas containing dissolution, naphtha (boiling temperature is lower than 150 DEG C of fraction), (boiling point is 150 DEG C to 250 DEG C to kerosene Fraction) and at least part boiling point be 250 DEG C to 375 DEG C of diesel oil.

Containing boiling point by the heavy liquid fraction that stage b) generates is 250 DEG C, preferably 300 DEG C or higher compound, spy Be not boiling point be 375 DEG C to lower than those of 540 DEG C (decompressions distillates) and boiling temperature be 540 DEG C or it is higher those, Corresponding to decompression residuum (it is unconverted fraction).Therefore it can contain part of fraction of fuel-oil, i.e., boiling point be 250 DEG C extremely 375 DEG C of compound.

The heavy liquid fraction is entirely or partly sent to hydroconversion stage c).

Separation phase can be carried out by any separator well known by persons skilled in the art.Preferably, separation phase B) it is carried out by one or more concatenated flash tanks, is preferably only carried out by a flash tank.Preferably, flash tank is close It is operated under the pressure and temperature of the operating condition of the last one reactor of hydroconversion stage a).

In another embodiment, separation phase is carried out by a series of several flash tanks, and the flash tank is in difference It is operated under the operating condition of the last one reactor of hydroconversion stage a), and several light liquids can be obtained and evaporated Point.Then the latter can entirely or partly be sent to distillation stage.

In another embodiment, separation phase passes through one or more steam strippings (entrainment) and/or hydrogen stripped (entrainment) tower carries out.In this way, light fraction and heavy will be separated by the effluent that hydroconversion stage a) is generated Liquid distillate.

In another embodiment, separation phase by atmospheric distillation tower individually carry out or be followed by vacuum distillation tower into Row.

Separation phase is also possible to the combination of these different embodiments.

Optionally, it is sending to before hydroconversion stage c) according to the present invention, the experience boiling of heavy liquid fraction can be made Point is 540 DEG C or the separation phase of lower compound.At least 80 weight % of gained heavy distillat have the boiling for being at least 540 DEG C Point.The separation can be used one or more strippers and be carried out by steam stripping and/or hydrogen stripped.

Second deep hydrogenation converts (stage c))

The heavy distillat that the liquid efflunent or separation phase b) that stage a) is obtained obtain is in stage c) as entrainment bed operation At least one phase reactor in carry out deep hydrogenation conversion.It may or may not the effluent or the fraction It is recycled to stage a).Stage a) and c) be the different phase carried out in the different areas.

Operating condition interval used, catalyst are to those of described in stage a).

The operating condition of stage c) and the operating condition of stage a) are identical or different.

According to the present invention, the total volume of the reactor relative to stage a) and c), takes in standard temperature and pressure conditions It is total when air speed (HSV), i.e., the flow of the liquid charging stock of hydroconversion stage a) be less than 0.1h^-1, typically at least 0.05h^-1, preferably 0.05h^-1To 0.09h^-1。

Fractionation stage d)

The effluent that then hydroconversion stage c) is generated completely or partially carries out fractionation stage d).The fractionation can pass through one A or multiple concatenated flash tanks carry out, and are preferably carried out by the sequence of at least two continuous flash drums, preferably by one or Multiple steam strippings and/or hydrogen stripped tower carry out, and are more preferably carried out by atmospheric distillation tower, for reduced crude, more preferably By atmospheric distillation tower and vacuum tower, for reduced crude, even more preferably from by one or more flash tanks, atmospheric distillation tower and Vacuum tower.This fractionation can also be carried out by the combination of above-mentioned different separators.

The purpose for carrying out fractionation stage is the distillate (gasoline, diesel oil) that separates light gas and economically can be improved, with Just at least one heavy liquid fraction is obtained, at least 80 weight % are at least 300 DEG C, or at least 350 DEG C, advantageously at least 375 DEG C, or boil at least 400 DEG C, or at least 450 DEG C, or at least 500 DEG C, and preferably obtain residual fraction, 80 weight % exist It boils at least 540 DEG C or higher temperature.Preferably, separation decompression residuum (by air-distillation, is then evaporated under reduced pressure normal pressure Residual oil), the initial boiling point of the residual oil is 540 DEG C.

Depitching stage e)

Then, according to the method for the present invention, by the heavy liquid fraction obtained in stage d) and its residual fraction into Row depitching stage e), to obtain depitching hydrocarbon-fraction (referred to as DAO) and pitch.

Depitching usually 60 DEG C to 250 DEG C at a temperature of, using at least one hydrocarbon solvent with 3 to 7 carbon atoms It carries out；Preferably, solvent is butane, pentane or hexane and their mixture, is optionally added at least one additive. Solvent/raw material ratio (volume/volume) in depitching is usually 4/1 to 9/1, usual 4/1 to 8/1.

The solvent and additive that can be used are widely described.The recycling of solvent is carried out according to opticritical method Be possible with it is advantageous, i.e., by supercritical conditions in segregation section use solvent.This method can especially significantly improve The overall economics of technique.The depitching can in one or more mixer-settlers or in one or more extraction columns into Row.

It can be used using the technology of at least one extraction column and preferred only one extraction column (for example, Solvahl^TMWork Skill).

Deasphalting units generate depitching hydrocarbon-fraction DAO(and are also referred to as deasphalted oil or depitching raffinate) (it is practically free of C₇Asphalitine) and residual bitumen, wherein most of impurity of residue is concentrated and is discharged.

According to the quality, operating condition and solvent for use of the heavy liquid fraction conveyed, DAO yield is usually 40 weights Measure % to 90 weight %.

It is given in the table below according to the deasphalting typical operation conditions range of solvent:

Solvent	Propane	Butane	Pentane	Hexane	Heptane
						Pressure, MPa	3 - 4	3 - 4	2 - 4	2 - 4	2 - 4
Temperature, DEG C	45 - 90	80 - 130	140 - 210	150 - 230	160 - 250
						Solvent/raw material ratio, V/V	6 - 10	5 - 8	3 - 6	3 - 6	3 - 5

Deasphalting condition is suitable for the quality of the DAO obtained and enters deasphalting raw material.

These conditions make the content and C of conradson carbon residue₇The content of asphalitine significantly reduces.Depitching hydrocarbon obtained Fraction DAO advantageously shows more preferably less than 0.08 weight % or to be less than less than 0.5 weight %, preferably smaller than 0.1 weight % The C of 0.07 weight %₇Asphalt content.

In one embodiment, the whole of the de-asphalted fraction DAO or preferred a part are recycled to stage a) And/or stage c).

The conversion (stage f)) of DAO fraction

DAO fraction can entirely or partly be sent to additional transformation stage f).Preferably, DAO is sent directly to conversion rank Section.Preferably, all DAO fractions are fed directly to the transformation stage, that is to say, that in addition to optional one or more fractionation stages Except, without any processing.

The stage allows to for the conversion ratio of this method being increased to very high horizontal (relative to 540 DEG C+fraction) simultaneously And it generally reaches greater than 90%.Targeted transformation method in this stage is fixed bed hydrogenation cracking, fluid catalystic cracking FCC Or boiling bed hydrogenation conversion is (for example, in patent US 4 521 295 or US 4 495 060 or US 4 457 831 or 1995 On March 19, to 23 days in, the paper of Aiche, Texas Houston, paper number 46d, " Second generation H-Oil DC method described in ebullated bed technology ")；It can carry out adding hydrogen before these method for transformation Processing.

If desired, air-distillation can be carried out to the depitching hydrocarbon-fraction DAO, optionally then it is evaporated under reduced pressure, Especially when stage c) does not include distillation.

The fraction of the product that economically can be improved obtained is gasoline fraction (150 DEG C -), one or more middle distillates Fraction (150-375 DEG C) and one or more boiling points are 375 DEG C or higher heavier fraction.

It is somebody's turn to do (these) heavier fraction and is preferably fed to transformation stage f).

The fraction is generally characterized by (low conradson carbon residue, low C₇Asphalt content, low-sulfur, tenor).

In one embodiment, depitching hydrocarbon-fraction DAO advantageously acts as evaporating with the light liquids generated by stage b) At least part divided and the distillation of preferably all of mixture.

In another embodiment, the mixture transformation stage f) can be sent into (to steam without being fractionated in advance It evaporates).

For distillation, DAO can also be with the raw material outside this method, for example, by (crude oil) primary fractionation of oil plant Decompression distillate, reduced crude or the vacuum residue fraction mixing of generation.

This method is preferably without distillation.Then DAO fraction (part or all of) is sent as it is to stage f).

Transformation stage can be fixed bed hydrogenation cracking.It can be advantageously in one comprising one or more catalytic beds Or it is carried out in multiple reactors or in only one reactor.

Fixed bed hydrogenation cracking uses acid catalyst in presence of hydrogen.The presence of nitrogen and other impurity in the mixture It needs to be pre-processed in advance to prevent catalyst inactivation.Thus it is common to use the fixation of at least one hydrotreating catalyst Then bed uses the fixed bed of at least one hydrocracking catalyst.These catalyst are well known to those skilled in the art.It is excellent One of applicant company's catalyst described in patent EP B 113 297 and EP B 113 284 can be used in choosing.

Catalyst contains at least one group VIII non-noble metal j element (Ni and/or Co) and at least one Section VI b race member Plain (Mo and/or W).The content of group VIII element is advantageously the 1 weight % to 10 weight % of the total weight relative to catalyst Oxide, preferably 1.5 weight % to 9 weight %, very preferably 2 weight % to 8 weight %.The content of Section VI b race element has It is sharply the oxide of the 5 weight % to 40 weight % of the total weight relative to catalyst, preferably 8 weight % are non-to 37 weight % Often preferably 10 weight % to 35 weight %.

The carrier of hydrotreating catalyst is usually aluminium oxide；The carrier of hydrocracking catalyst contains one or more boilings Stone (most commonly zeolite Y or zeolite beta), usually as the mixture with aluminium oxide and/or silica/alumina.Zeolite Weight content be usually less than 80 weight %.

Hydrotreating and hydrocracking catalyst can also contain at least one organic additive.

The operation is being advantageously 300 DEG C preferably at 5MPa to 35MPa, the absolute pressure of preferably 10MPa to 20MPa To 500 DEG C, carried out at a temperature of preferably 350 DEG C to 450 DEG C.HSV is selected according to the characteristic of raw material to be processed and required conversion ratio And hydrogen partial pressure.Preferably, HSV is 0.1 h^-1To 5 h^-1, and preferably 0.15 h^-1To 2 h^-1.The hydrogen advantageously mixed with raw material Tolerance is preferably 100 Sm³/m³To 1000 Sm³/m³Liquid charging stock, and preferably 500 Sm³/m³To 3000 Sm³/m³。

The boiling bed hydrogenation transformation stage (H-Oil DC) for handling DAO fraction can be advantageously in 2MPa to 35MPa, preferably Under the absolute pressure of 5MPa to 25MPa, preferably 6MPa to 20MPa, at 300 DEG C to 550 DEG C, preferably 350 DEG C to 500 DEG C, preferably It is carried out at a temperature of 380 DEG C to 470 DEG C, more preferable 400 DEG C to 450 DEG C.The amounts of hydrogen advantageously mixed with raw material is preferably 50 Sm³/m³To 5000 Sm³/m³Liquid charging stock (obtains) in standard temperature and pressure conditions, preferably 100 Sm³/m³To 2000 Sm³/m³, highly preferred 200 Sm³/m³To 1000 Sm³/m³.Preferably, the HSV in the stage is 0.1h^-1To 10h^-1, preferably 0.15h^-1To 5h^-1。

Hydrogenation conversion catalyst for ebullated bed contains the element of one or more periodic table of elements 4-12 races, sinks Product is on carrier.It can be advantageously used comprising carrier, preferably amorphous carrier, such as silica, aluminium oxide, titanium dioxide The combination of silicon/aluminium oxide, titanium dioxide or these structures, the catalyst of highly preferred aluminium oxide.The catalyst contains at least one Kind is selected from nickel and cobalt, preferably the group VIII metal of nickel and at least one Section VI b race metal selected from molybdenum and tungsten, Section VI b race Metal is preferably molybdenum.

Advantageously, hydrogenation conversion catalyst is preferred the of nickel comprising alumina support and at least one selected from nickel and cobalt The catalyst of group VIII metal and at least one Section VI b race metal selected from molybdenum and tungsten；Preferably, the metal of Section VI b race is molybdenum. Preferably, hydrogenation conversion catalyst includes nickel and molybdenum.

Nickel content is advantageously 0.5 weight % to 10 weight %(and is indicated with the weight of nickel oxide (NiO)), and preferably 1 Weight % to 6 weight %, and molybdenum content is advantageously 1 weight % to 30 weight %(with molybdenum trioxide (MoO₃) weight indicate), Preferably 4 weight % to 20 weight %.

This catalyst uses advantageously in the form of extrudate or bead.The diameter of extrudate be, for example, 0.5mm extremely 2.0mm, length are 1mm to 5mm.These catalyst are well known to those skilled in the art.

It (is described in the prior art, such as FR 3 033 797) according to routine techniques, used hydrogenation conversion catalyst It can be substituted partially by taking out by fresh catalyst, preferably take out used hydrogenation conversion catalyst in reactor bottom It is introduced into reactor with by fresh catalyst.The catalyst and/or regeneration (nothing that fresh catalyst can be entirely or partly previously used Coke) catalyst and/or more raw catelyst (having been added the regenerated catalyst for increasing the compound of catalyst activity) and/or again The catalyst of activation is (by extracting poisonous substance and inhibitor (such as the deposited metal generated by hydrodemetallization reaction) and removing shape At coke and be re-activated) substitution.

The effluent generated by transformation stage f) is usually then distilled, is evaporated with recycling the gasoline that economically can be improved and diesel oil Point.Remaining unconverted fraction can be recycled to one of stage of this method.

In another embodiment, transformation stage f) can be carried out by fluid catalytic cracking unit.DAO can be with The heavy charge coprocessing of one or more VGO, HDT VGO or residue type, or individually processing.

Fluid catalytic cracking unit can only include a reactor, handle heavy charge and DAO or only handle DAO, Or two different reactors, a processing heavy charge and another processing DAO.In addition, each reactor can be upstream Formula reactor or downflow reactor.In general, the two reactors can have identical flow pattern.

When catalytic cracking is with the progress of the coprocessing of one or more heavy charges and DAO:

1) in single up-flow reactor, reactor outlet temperature (ROT) is 450 DEG C to 650 DEG C, preferably 470 DEG C to 620 DEG C, and C/O ratio is 2 to 20, preferably 4 to 15.

2) in single downflow reactor, reactor outlet temperature (ROT) is 480 DEG C to 650 DEG C, and C/O ratio is 10 to 50.

3) in two different up-flow reactors, the first reactor for carrying out the cracking of one or more heavy charges exists 450 DEG C to 650 DEG C, preferably 470 DEG C to 620 DEG C of reactor outlet temperature (ROT1) and 2 to 20, under preferably 4 to 15 C/O ratio Operation.The second reactor of the cracking of DAO is carried out at 500 DEG C to 600 DEG C, preferably 520 DEG C to 580 DEG C of reactor outlet temperature (ROT2) it under, is operated with 2 to 20 C/O ratio.

4) in two different downflow system FCC reactors, the first FCC reaction of the cracking of one or more heavy charges is carried out Device is operated at 480 DEG C to 650 DEG C of reactor outlet temperature (ROT1) with 10 to 50 C/O ratio.Carry out the cracking of DAO 2nd FCC reactor is operated at 570 DEG C to 600 DEG C of reactor outlet temperature (ROT2) with 10 to 50 C/O ratio.

When only carrying out catalytic cracking to DAO:

1) in up-flow reactor, reactor is at 500 DEG C to 600 DEG C, preferably 520 DEG C to 580 DEG C of reactor outlet temperature (ROT) it under, is operated with 2 to 20 C/O ratio.

2) in downflow reactor, reactor is at 570 DEG C to 600 DEG C of reactor outlet temperature (ROT2), with 10 to 50 C/O ratio operation.

By two FCC reactors generate used catalyst logistics by any gas well known by persons skilled in the art/ Solid separation system is separated with cracking effluent, and is regenerated in common renewing zone.

Effluent (or two effluents, if there is two reactors) from catalyst cracker is admitted to Fractionation zone.The unit for separation generally includes the primary separation of effluent, so that especially can be can be improved on production economy Fraction, such as gasoline, middle distillate and heavy distillate fraction.Remaining unconverted fraction can be recycled to this method One of stage.

The catalyst in fluid catalystic cracking stage is usually usually 40 microns to 140 microns and most commonly by average diameter It is formed for 50 microns to 120 microns of particles.

Catalytic cracking catalyst includes at least one suitable matrix, such as aluminium oxide, silica or silica/oxygen Change aluminium, presence or absence of the y-type zeolite being dispersed in the matrix.

Catalyst can additionally comprise at least one zeolite, show the shape selective of one of following structure type: MEL (such as ZSM-11), MFI (such as ZSM-5), NES, EUO, FER, CHA (such as SAPO-34), MFS or MWW.It can also be with Include one of following zeolite: NU-85, NU-86, NU-88 and IM-5 also have shape selective.

It is that better propylene/isobutyl is obtained in cracking effluent that these, which show the advantages of zeolite of shape selective, Alkene selectivity, i.e., higher propylene/isobutene ratio.

Relative to the total amount of zeolite, the ratio for showing the zeolite of shape selective can be according to raw materials used and required production The structure of object and change.In general, using 0.1 weight % to 60 weight %, preferably 0.1 weight % to 40 weight %, especially 0.1 weight Measure the zeolite with shape selective of % to 30 weight %.

One or more zeolites can be dispersed in the matrix based on silica, aluminium oxide or silica/alumina, Relative to the weight of catalyst, the ratio of zeolite (all zeolites of combination) is usually 0.7 weight % to 80 weight %, preferably 1 weight Measure % to 50 weight %, more preferable 5 weight % to 40 weight %.

Using several zeolites, they can be incorporated in a kind of only matrix or several different matrix.Performance The zeolite total content of shape selective is less than 30 weight % out.

The catalyst used in catalyst cracker, which may include, is dispersed in aluminium oxide, silica or titanium dioxide Y type ultra stable zeolite in silicon/alumina host, wherein adding the additive based on zeolite ZSM5, the total amount of ZSM5 crystal is low In 30 weight %.

Detailed description of the invention

Fig. 1 illustrates the present invention.

It includes deep hydrogenation conversion zone A, wherein carrying out deep hydrogenation transformation stage a).Raw material 1 turns in the presence of hydrogen 2 Change, gained effluent 3 separate in segregation section B (stage b), optionally then progress stage b ')).Obtain light fraction 4 and double distilled Divide 5.The latter is sent into deep hydrogenation conversion zone C, it carries out deep hydrogenation transformation stage c) in the presence of hydrogen 6.From gained stream Light fraction 8 and heavy distillat 9 are separated in object 7 out, and heavy distillat 9 is imported into depitching section E, wherein carrying out depitching using solvent 12 Stage e).Deasphalted oil DAO 10 is sent to conversion zone F, transformation stage f) is carried out in conversion zone F and recycles pitch 11.Then Transformation stage f) the effluent 13 generated is typically sent to separation phase, to recycle the fraction that economically can be improved, such as gasoline And diesel oil.

Specific embodiment

Following embodiment illustrates exemplary implementation scheme according to the method for the present invention and does not limit its scope, He Yugen Some performance qualities are compared according to the method for the prior art.

Embodiment 1,2,4 and 5 is not according to the present invention.Embodiment 3 and 6 is according to the present invention.

Raw material

Heavy charge is derived from the decompression residuum (VR) of Ural crude oil, and main feature is listed in the table below in 1.For different realities Example is applied, which is identical fresh feed.

Table 1: the composition of the raw material of this method

The raw material in stage		A
			Raw material		Ural VR
Density		1.000
			540 DEG C+content	Weight %	77.9
Viscosity at 100 DEG C	cSt	880
			Conradson carbon residue	Weight %	17.0
C7Asphalitine	Weight %	6.8
			Nickel+vanadium	Weight ppm	233
Nitrogen	Weight %	6010
			Sulphur	Weight %	2.715

Embodiment 1 (not according to the present invention): air speed and moderate temperature (total HSV=0.30h when having high^-1 + 420℃/ 420 DEG C) scheme in+depitching stage (SDA)

In this embodiment, two entrainment bed reactors (the first and second deep hydrogenation conversion zones) are placed in series, in high space-time It is operated under fast (HSV) and moderate temperature, with segregation section between step and downstream de-asphalting processes.

Hydro-conversion section A

The fresh feed of table 1 is all sent into the first entrainment bed hydroprocessing conversion zone A comprising there are hydrogen and be based on molybdenum naphthenate The three-phase of slurry catalyst carry bed reactor secretly, the catalyst concn in raw material is the molybdenum of 250 weight ppm.The section is as tool There is the entrainment bed of the upper up-flow of liquids and gases to operate.

The condition applied in hydro-conversion section A is shown in table 2.

Table 2: the operating condition of hydro-conversion section A

Section		A
			Total P	MPa	16
Temperature	℃	420
			Amounts of hydrogen	Sm3/m3	900

These operating conditions can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Segregation section B

The liquid efflunent generated by A sections is then sent into segregation section B, segregation section B is by the reaction in the first hydro-conversion section A The single gas/liquid separation composition operated under the pressure and temperature of device.Thus separation " light " fraction and " weight " fraction." light " fraction 350 DEG C of molecular composition is mainly lower than by boiling point, " weight " fraction is mainly by least 350 DEG C of the at a temperature of hydrocarbon molecule group boiled At.

Hydro-conversion section C

The heavy distillat that is generated by segregation section B individually and is all sent into there are hydrogen and the slurry catalyst based on molybdenum naphthenate In second hydro-conversion section C, catalyst concn in raw material is the molybdenum of 250 weight ppm.Described section includes having liquids and gases Upper up-flow three-phase carry secretly bed reactor.

The condition applied in hydro-conversion section C is shown in table 3.

Table 3: the operating condition of hydro-conversion section C

Section		C
			Total P	MPa	15.6
Temperature	℃	420
			Amounts of hydrogen	Sm3/m3	750

These operating conditions can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Distillation stage D

It will be sent into distillation stage D from the effluent of hydro-conversion section C, by flash tank, air-distillation followed by vacuum distillation group At at a temperature of unconverted decompression residuum (VR) heavy distillat for boiling from its recycling at least 540 DEG C, relative to fresh feed Yield and its quality be given in Table 4 below.

Table 4: by the yield and quality of the distillation stage D VR generated

Fraction		Unconverted decompression residuum
			Yield (A) relative to fresh feed	Weight %	37.0
540 DEG C+content	Weight %	100
			Gravity	g/cm3	1.061
Conradson carbon residue	Weight %	14.2
			Nickel+vanadium	Weight ppm	22
Nitrogen	Weight %	0.49
			Sulphur	Weight %	0.444
Saturate	Weight %	20.2
			Aromatic hydrocarbons	Weight %	41.3
Resin	Weight %	33.4
			C7Asphalitine	Weight %	5.1

Depitching section E

The decompression residuum generated by D sections is sent into depitching section E.The condition description applied in deasphalting units is in table 5.

Operating condition in table 5:SDA unit E

Raw material		The decompression residuum of D sections of generations
			Solvent		Butane
Extractor pressure	MPa	3.0
			T It is averageExtractor	℃	95
Solvent/raw material ratio	V/V	8

At the end of E sections, DAO fraction is obtained, it can (fixed bed hydrogenation cracking, FCC or recycling in the conversion process To the hydroconversion process in ebullated bed in a mild condition) economically improve, and " pitch " fraction, it is difficult in economy Upper raising.

Table 6 gives the yield and quality of both products.

Table 6: by the yield and quality of the depitching section E effluent generated

Fraction		DAO	Pitch
				Yield (D) relative to unconverted VR	Weight %	57.2	42.8
Yield (A) relative to fresh feed	Weight %	22.2	15.8
				Density	g/cm3	0.9725	1.208
Conradson carbon residue	Weight %	4.6	27.0
				C7Asphalitine	Weight %	0.11	11.8
Nickel+vanadium	Weight ppm	<4	50
				Nitrogen	Weight %	0.36	0.66
Sulphur	Weight %	0.336	0.588

Overall performance quality

Using the program not according to the present invention, for 0.30h^-1It is total when air speed (HSV) and moderate temperature (420/420 DEG C), After DAO is fully converted to 540 DEG C-fraction in Hydrocracking unit, the conversion ratio of 540 DEG C+fraction of heavy is 80 weight %. In addition, unconverted VR contains the conradson carbon residue and C of high-content₇Asphalitine (respectively 14.2 weight % and 5.1 weight %).Cause This, relative to fresh starting material, the conventional scheme is along with the significant pitch for generating 15.8 weight %.

Embodiment 2 (not according to the present invention): air speed and the high temperature (h of total HSV=0.30 when having high^-1 + 450℃/ 450 DEG C) scheme in+depitching stage (SDA)

In this embodiment, two entrainment bed reactors (the first and second deep hydrogenation conversion zones) are placed in series, in high space-time It is operated under fast (HSV) and high temperature, to realize the high conversion of residue, with segregation section between step and downstream depitching work Skill.

Hydro-conversion section A

The fresh feed of table 1 is all sent into the first entrainment bed hydroprocessing conversion zone A comprising there are hydrogen and be based on molybdenum naphthenate The three-phase of slurry catalyst carry bed reactor secretly, the catalyst concn in raw material is the molybdenum of 250 weight ppm.The section is as tool There is the entrainment bed of the upper up-flow of liquids and gases to operate.

The condition applied in hydro-conversion section A is shown in table 7.

Table 7: the operating condition of hydro-conversion section A

Section		A
			Total P	MPa	16
Temperature	℃	450
			Amounts of hydrogen	Sm3/m3	900

These operating conditions can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Segregation section B

The liquid efflunent generated by A sections is then sent into segregation section B, segregation section B is by the reaction in the first hydro-conversion section A The single gas/liquid separation composition operated under the pressure and temperature of device.Thus separation " light " fraction and " weight " fraction." light " fraction 350 DEG C of molecular composition is mainly lower than by boiling point, " weight " fraction is mainly by least 350 DEG C of the at a temperature of hydrocarbon molecule group boiled At.

Hydro-conversion section C

The heavy distillat that is generated by segregation section B individually and is all sent into there are hydrogen and the slurry catalyst based on molybdenum naphthenate In second hydro-conversion section C, catalyst concn in raw material is the molybdenum of 250 weight ppm.Described section includes having liquids and gases Upper up-flow three-phase carry secretly bed reactor.

The condition applied in hydro-conversion section C is shown in table 8.

Table 8: the operating condition of hydro-conversion section C

Section		C
			Total P	MPa	15.6
Temperature	℃	450
			Amounts of hydrogen	Sm3/m3	750

These operating conditions can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Distillation stage D

It will be sent into distillation stage D from the effluent of hydro-conversion section C, by flash tank, air-distillation followed by vacuum distillation group At at a temperature of unconverted decompression residuum (VR) heavy distillat for boiling from its recycling at least 540 DEG C, relative to fresh feed Yield and its quality be given in Table 9 below.

Table 9: by the yield and quality of the distillation stage D VR generated

Fraction		Unconverted decompression residuum
			Yield (A) relative to fresh feed	Weight %	7.1
540 DEG C+content	Weight %	100
			Density	g/cm3	1.089
Conradson carbon residue	Weight %	16.8
			Nickel+vanadium	Weight ppm	20
Nitrogen	Weight %	0.43
			Sulphur	Weight %	0.258
Saturate	Weight %	18.7
			Aromatic hydrocarbons	Weight %	39.5
Resin	Weight %	35.2
			C7Asphalitine	Weight %	6.7

Depitching section E

The decompression residuum generated by D sections is sent into depitching section E.The condition applied in deasphalting units describes in table 10.

Operating condition in table 10:SDA unit E

Raw material		The decompression residuum of D sections of generations
			Solvent		Butane
Extractor pressure	MPa	3.0
			T It is averageExtractor	℃	95
Solvent/raw material ratio	V/V	8

At the end of E sections, DAO fraction is obtained, it can (fixed bed hydrogenation cracking, FCC or recycling in the conversion process To the hydroconversion process in ebullated bed in a mild condition) economically improve, and " pitch " fraction, it is difficult in economy Upper raising.

Table 11 lists the yield and quality of both products.

Table 11: by the yield and quality of the depitching section E effluent generated

Fraction		DAO	Pitch
				Yield (D) relative to unconverted VR	Weight %	44.2	55.8
Yield (A) relative to fresh feed	Weight %	3.1	4.0
				Density	g/cm3	0.9732	1.202
Conradson carbon residue	Weight %	6.9	24.6
				C7Asphalitine	Weight %	0.13	11.9
Nickel+vanadium	Weight ppm	<4	35
				Nitrogen	Weight %	0.39	0.46
Sulphur	Weight %	0.217	0.290

Overall performance quality

Using the program not according to the present invention, for 0.30h^-1It is total when air speed (HSV) and high temperature (450/450 DEG C), adding After DAO is fully converted to 540 DEG C-fraction in hydrogen Cracking Unit, the conversion ratio of 540 DEG C+fraction of heavy is 94.9 weight %.This Outside, unconverted VR contains the conradson carbon residue and C of high-content₇Asphalitine (respectively 16.8 weight % and 6.7 weight %), this meaning Taste the only unconverted VR of 44.2 weight % can be recycled in the form of DAO.Accordingly, with respect to fresh starting material, this is often Rule scheme is along with the significant pitch for generating 4.0 weight %.

Embodiment 3(is according to the present invention): according to the present invention with it is low when air speed and have moderate temperature (total HSV= 0.068h^-1+ 420 DEG C/420 DEG C) scheme of+SDA

In this embodiment, it is following process program that the present invention, which illustrates: the entrainment bed reactor that there are two tools is placed in series, Air speed (HSV=0.068h when low^-1) and moderate temperature (420 DEG C/420 DEG C) under operate, and have step between segregation section With downstream de-asphalting processes, as described in reference to fig. 1.

Hydro-conversion section A

The fresh feed of table 1 is all sent into the first entrainment bed hydroprocessing conversion zone A comprising there are hydrogen and be based on molybdenum naphthenate The three-phase of slurry catalyst carry bed reactor secretly, the catalyst concn in raw material is the molybdenum of 250 weight ppm.The section is as tool There is the entrainment bed of the upper up-flow of liquids and gases to operate.

The condition applied in hydro-conversion section A is shown in table 12.

Table 12: the operating condition of hydro-conversion section A

Section		A
			Total P	MPa	16
Temperature	℃	420
			Amounts of hydrogen	Sm3/m3	900

These operating conditions can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Segregation section B

The liquid efflunent generated by A sections is then sent into segregation section B, segregation section B is by the reaction in the first hydro-conversion section A The single gas/liquid separation composition operated under the pressure and temperature of device.Thus separation " light " fraction and " weight " fraction." light " fraction 350 DEG C of molecular composition is mainly lower than by boiling point, " weight " fraction is mainly by least 350 DEG C of the at a temperature of hydrocarbon molecule group boiled At.

Hydro-conversion section C

The heavy distillat that is generated by segregation section B individually and is all sent into there are hydrogen and the slurry catalyst based on molybdenum naphthenate In second boiling bed hydrogenation conversion zone C, catalyst concn in raw material is the molybdenum of 250 weight ppm.Described section includes having liquid Bed reactor is carried secretly with the three-phase of the upper up-flow of gas.

The condition applied in hydro-conversion section C is shown in table 13.

Table 13: the operating condition of hydro-conversion section C

Section		C
			Total P	MPa	15.6
Temperature	℃	420
			Amounts of hydrogen	Sm3/m3	750

These operating conditions can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Distillation stage D

It will be sent into distillation stage D from the effluent of hydro-conversion section C, by flash tank, air-distillation followed by vacuum distillation group At at a temperature of unconverted decompression residuum (VR) heavy distillat for boiling from its recycling at least 540 DEG C, relative to fresh feed Yield and its quality provided in the following table 14.

Table 14: by the yield and quality of the distillation stage D VR generated

Fraction		Unconverted decompression residuum
			Yield (A) relative to fresh feed	Weight %	6.1
540 DEG C+content	Weight %	100
			Density	g/cm3	1.054
Conradson carbon residue	Weight %	12.7
			Nickel+vanadium	Weight ppm	4
Nitrogen	Weight %	0.33
			Sulphur	Weight %	0.187
Saturate	Weight %	21.1
			Aromatic hydrocarbons	Weight %	44.1
Resin	Weight %	32.4
			C7Asphalitine	Weight %	2.5

Depitching section E

The decompression residuum generated by D sections is sent into depitching section E.The condition applied in deasphalting units describes in table 15.

Operating condition in table 15:SDA unit E

Raw material		The decompression residuum of D sections of generations
			Solvent		Butane
Extractor pressure	MPa	3.0
			T It is averageExtractor	℃	95
Solvent/raw material ratio	V/V	8

At the end of E sections, DAO fraction is obtained, it can (fixed bed hydrogenation cracking, FCC or recycling in the conversion process To the hydroconversion process in ebullated bed in a mild condition) economically improve, and " pitch " fraction, it is difficult in economy Upper raising.Table 16 lists the yield and quality of both products.

Table 16: by the yield and quality of the depitching section E effluent generated

Fraction		DAO	Pitch
				Yield (D) relative to unconverted VR	Weight %	60.2	39.8
Yield (A) relative to fresh feed	Weight %	3.8	2.4
				Density	g/cm3	0.9749	1.201
Conradson carbon residue	Weight %	3.9	26.0
				C7Asphalitine	Weight %	<0.05	6.3
Nickel+vanadium	Weight ppm	<4	10
				Nitrogen	Weight %	0.22	0.50
Sulphur	Weight %	0.153	0.238

Overall performance quality

There is total HSV=0.068h using according to the present invention^-1And the program with moderate temperature (420/420 DEG C), weight The yield of 540 DEG C+fraction of matter (referred to as unconverted decompression residuum) is only the 6.1 weight % relative to fresh feed, remote low In embodiment 1(under identical temperature levels) in unconverted 37.0 weight % of decompression residuum yield and embodiment 2(reactor exist Operated at very high temperature) in 7.1 weight %.However, with Examples 1 and 2 (conventional method not according to the present invention) phase Than unconverted VR contains the conradson carbon residue and C of lower content₇Asphalitine, this allows to recycle in unconverted VR 60.2 weight % can be recycled in a greater amount of DAO(in this embodiment, relative to the 57.2 weight % and embodiment 2 in embodiment 1 In 44.2 weight %).Therefore, the program according to the present invention is generated along with the lower pitch relative to starting fresh feed, 2.4 weight %(are equivalent to relative to 15.8 weight % in embodiment 1 and 4.0 weight % in embodiment 2).In addition, with implementation The DAO fraction generated in example 1 and 2 is compared, the DAO generated in the method according to the invention also contain less impurity (sulphur, Nitrogen, conradson carbon residue and C₇Asphalitine).Therefore, the not embodiment according to the present invention of this DAO ratio according to the method for the present invention The two kinds of DAO generated in 1 and 2 are easier to convert.If all DAO are converted in Hydrocracking unit, by means of root The very high conversion ratio of starting 540 DEG C+fraction of heavy can be therefore obtained according to the embodiment of the invention.This is because In this case (DAO is converted completely in Hydrocracking unit) has total HSV=0.068h using according to the present invention^-1And And the program with moderate temperature (420/420 DEG C), the conversion ratio of 540 DEG C+fraction of heavy is 96.9 weight %, i.e., than implementing Example 1(is under identical temperature levels) high 17 points and operated at very high temperatures than embodiment 2(reactor) it is 2 high Point.

Embodiment 4 (not according to the present invention): air speed and moderate temperature (total HSV=0.30h when having high^-1 + 420℃/ 420 DEG C) scheme of the transformation stage of DAO in+depitching stage (SDA)+FCC unit

In this embodiment, two entrainment bed reactors (the first and second deep hydrogenation conversion zones) are placed in series, in high space-time It is operated under fast (HSV) and moderate temperature, there are segregation section and downstream de-asphalting processes between step.

Hydro-conversion section A

The fresh feed of table 1 is all sent into the first entrainment bed hydroprocessing conversion zone A comprising there are hydrogen and be based on molybdenum naphthenate The three-phase of slurry catalyst carry bed reactor secretly, the catalyst concn in raw material is the molybdenum of 250 weight ppm.The section is as tool There is the entrainment bed of the upper up-flow of liquids and gases to operate.The condition applied in hydro-conversion section A is shown in table 2.These operations Condition can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Segregation section B

The liquid efflunent generated by A sections is then sent into segregation section B, segregation section B is by the reaction in the first hydro-conversion section A The single gas/liquid separation composition operated under the pressure and temperature of device.Thus separation " light " fraction and " weight " fraction." light " fraction 350 DEG C of molecular composition is mainly lower than by boiling point, " weight " fraction is mainly by least 350 DEG C of the at a temperature of hydrocarbon molecule group boiled At.

Hydro-conversion section C

The heavy distillat that is generated by segregation section B individually and is all sent into there are hydrogen and the slurry catalyst based on molybdenum naphthenate In second hydro-conversion section C, catalyst concn in raw material is the molybdenum of 250 weight ppm.Described section includes having liquids and gases Upper up-flow three-phase carry secretly bed reactor.The condition applied in hydro-conversion section C is shown in table 3.These operating condition energy It is enough to obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Distillation stage D

It will be sent into distillation stage D from the effluent of hydro-conversion section C, by flash tank, air-distillation followed by vacuum distillation group At at a temperature of unconverted decompression residuum (VR) heavy distillat for boiling from its recycling at least 540 DEG C, relative to fresh feed Yield and its quality be given in Table 4.

Depitching section E

The decompression residuum generated by D sections is sent into depitching section E.The condition description applied in deasphalting units is in table 5.? At the end of E sections, obtains DAO fraction and be difficult to " pitch " fraction economically improved.Table 6 gives the yield of both products And quality.

The conversion zone F of DAO

Fluid catalytic cracking unit, also referred to as FCC unit are subsequently sent to by the DAO fraction that depitching section E is generated.The conversion Unit allows to DAO fraction (it is 540 DEG C+fraction) being converted to lighter fraction.Therefore, this allows to improve starting The total conversion of raw material (decompression residuum (VR) generated by Ural crude oil, feature is listed in Table 1 below).On the other hand, such as table Shown in 17, unconverted 540 DEG C+fraction, original of the yield relative to FCC are still contained by the liquid distillate that FCC unit generates Material is 2.5 weight %.Compared with the embodiment 1 that wherein all DAO are converted in Hydrocracking unit, the conversion of DAO is this In the case of be not all of.

Table 17: by the yield and quality of the FCC unit F effluent generated

Unit		FCC
			Gasoline yield (C5- 220 DEG C)	Weight %	37.9
Diesel yield (220-360 DEG C)	Weight %	15.6
			It depressurizes distillate yield (360-540 DEG C)	Weight %	15.8
Decompression residuum yield (540 DEG C+)	Weight %	2.5

Overall performance quality

Using the program not according to the present invention, for 0.30h^-1It is total when air speed (HSV) and moderate temperature (420/420 DEG C), 540 DEG C+fraction of heavy (referred to as unconverted decompression residuum) is relative to the yield of fresh feed (as described in example 1 above) 37.0 weight %.Then the fraction is sent to deasphalting units mainly to recycle DAO fraction.It is former accordingly, with respect to fresh starting Material, this conventional scheme not according to the present invention is along with the significant pitch for generating 15.8 weight %.In this case, the DAO Fraction converts in FCC unit.Using the sequence scheme not according to the present invention, for 0.30h^-1It is total when air speed (HSV) and Moderate temperature (420/420 DEG C), the conversion ratio of 540 DEG C+fraction of heavy are 78 weight %.

Embodiment 5 (not according to the present invention): air speed and high temperature (total HSV=0.30h when having high^-1 + 450℃/ 450 DEG C) scheme of the transformation stage of DAO in+depitching stage (SDA)+in FCC unit

In this embodiment, two entrainment bed reactors (the first and second deep hydrogenation conversion zones) are placed in series, when high It is operated under air speed (HSV) and high temperature, to realize the high conversion of residue, there is segregation section and downstream depitching work between step Skill.

Hydro-conversion section A

The fresh feed of table 1 is all sent into the first entrainment bed hydroprocessing conversion zone A comprising there are hydrogen and be based on molybdenum naphthenate The three-phase of slurry catalyst carry bed reactor secretly, the catalyst concn in raw material is the molybdenum of 250 weight ppm.The section is as tool There is the entrainment bed of the upper up-flow of liquids and gases to operate.The condition applied in hydro-conversion section A is shown in table 7.These operations Condition can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Segregation section B

The liquid efflunent generated by A sections is then sent into segregation section B, segregation section B is by the reaction in the first hydro-conversion section A The single gas/liquid separation composition operated under the pressure and temperature of device.Thus separation " light " fraction and " weight " fraction." light " fraction 350 DEG C of molecular composition is mainly lower than by boiling point, " weight " fraction is mainly by least 350 DEG C of the at a temperature of hydrocarbon molecule group boiled At.

Hydro-conversion section C

The heavy distillat that is generated by segregation section B individually and is all sent into there are hydrogen and the slurry catalyst based on molybdenum naphthenate In second hydro-conversion section C, catalyst concn in raw material is the molybdenum of 250 weight ppm.Described section includes having liquids and gases Upper up-flow three-phase carry secretly bed reactor.The condition applied in hydro-conversion section C is shown in table 8.These operating condition energy It is enough to obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Distillation stage D

It will be sent into distillation stage D from the effluent of hydro-conversion section C, by flash tank, air-distillation followed by vacuum distillation group At at a temperature of unconverted decompression residuum (VR) heavy distillat for boiling from its recycling at least 540 DEG C, relative to fresh feed Yield and its quality be given in Table 9.

Depitching section E

The decompression residuum generated by D sections is sent into depitching section E.The condition applied in deasphalting units describes in table 10. At the end of E sections, DAO fraction is obtained, it can (fixed bed hydrogenation cracking, FCC or be recycled to boiling in the conversion process Hydroconversion process in bed in a mild condition) economically improve, and " pitch " fraction, it is difficult to economically improve. Table 11 lists the yield and quality of both products.

The conversion zone F of DAO

Fluid catalytic cracking unit, also referred to as FCC unit are subsequently sent to by the DAO fraction that depitching section E is generated.The conversion Unit allows to DAO fraction (it is 540 DEG C+fraction) being converted to lighter fraction.Therefore, this allows to improve starting The total conversion of raw material (decompression residuum (VR) generated by Ural crude oil, feature is listed in Table 1 below).On the other hand, such as table Shown in 18, unconverted 540 DEG C+fraction, original of the yield relative to FCC are still contained by the liquid distillate that FCC unit generates Material is 2.7 weight %.Compared with the embodiment 2 that wherein all DAO are converted in Hydrocracking unit, the conversion of DAO is this In the case of be not all of.

Table 18: by the yield and quality of the FCC unit F effluent generated

Unit		FCC
			Gasoline yield (C5- 220 DEG C)	Weight %	37.1
Diesel yield (220-360 DEG C)	Weight %	15.9
			It depressurizes distillate yield (360-540 DEG C)	Weight %	16.5
Decompression residuum yield (540 DEG C+)	Weight %	2.7

Overall performance quality

Using the program not according to the present invention, for 0.30h^-1It is total when air speed (HSV) and high temperature (450/450 DEG C), heavy 540 DEG C+fraction (the referred to as unconverted decompression residuum) yields relative to fresh feed (as described in example 2 above) are 7.1 weights Measure %.Then the fraction is sent to deasphalting units mainly to recycle DAO fraction.Accordingly, with respect to fresh starting material, this Kind conventional scheme not according to the present invention is along with the pitch for generating 4.0 weight %.In this case, DAO fraction is mono- in FCC It is converted in member.Using sequence scheme not according to the present invention, for 0.30h^-1It is total when air speed (HSV) and high temperature (450/450 DEG C), the conversion ratio of 540 DEG C+fraction of heavy is 94.6 weight %.

Embodiment 6(is according to the present invention): it is according to the present invention with it is low when air speed and have moderate temperature (total HSV= 0.068h^-1+ 420 DEG C/420 DEG C) scheme of the transformation stage of DAO in+depitching stage (SDA)+in FCC unit

In this embodiment, it is following process program that the present invention, which illustrates: the entrainment bed reactor that there are two tools is placed in series, Air speed (HSV=0.068h when low^-1) and moderate temperature (420 DEG C/420 DEG C) under operate, and have step between segregation section With downstream de-asphalting processes, as described in reference to fig. 1.

Hydro-conversion section A

The fresh feed of table 1 is all sent into the first entrainment bed hydroprocessing conversion zone A comprising there are hydrogen and be based on molybdenum naphthenate The three-phase of slurry catalyst carry bed reactor secretly, the catalyst concn in raw material is the molybdenum of 250 weight ppm.The section is as tool There is the entrainment bed of the upper up-flow of liquids and gases to operate.The condition applied in hydro-conversion section A is shown in table 12.These operations Condition can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Segregation section B

The liquid efflunent generated by A sections is then sent into segregation section B, segregation section B is by the reaction in the first hydro-conversion section A The single gas/liquid separation composition operated under the pressure and temperature of device.Thus separation " light " fraction and " weight " fraction." light " fraction 350 DEG C of molecular composition is mainly lower than by boiling point, " weight " fraction is mainly by least 350 DEG C of the at a temperature of hydrocarbon molecule group boiled At.

Hydro-conversion section C

The heavy distillat that is generated by segregation section B individually and is all sent into there are hydrogen and the slurry catalyst based on molybdenum naphthenate In second boiling bed hydrogenation conversion zone C, catalyst concn in raw material is the molybdenum of 250 weight ppm.Described section includes having liquid Bed reactor is carried secretly with the three-phase of the upper up-flow of gas.The condition applied in hydro-conversion section C is shown in table 13.These operations Condition can obtain the liquid efflunent with reduced conradson carbon residue, metal and sulfur content.

Distillation stage D

It will be sent into distillation stage D from the effluent of hydro-conversion section C, by flash tank, air-distillation followed by vacuum distillation group At at a temperature of unconverted decompression residuum (VR) heavy distillat for boiling from its recycling at least 540 DEG C, relative to fresh feed Yield and its quality provided in table 14.

Depitching section E

The decompression residuum generated by D sections is sent into depitching section E.The condition applied in deasphalting units describes in table 15. At the end of E sections, DAO fraction is obtained, it can (fixed bed hydrogenation cracking, FCC or be recycled to boiling in the conversion process Hydroconversion process in bed in a mild condition) economically improve, and " pitch " fraction, it is difficult to economically improve. Table 16 lists the yield and quality of both products.

The conversion zone F of DAO

Fluid catalytic cracking unit, also referred to as FCC unit are subsequently sent to by the DAO fraction that depitching section E is generated.The conversion Unit allows to DAO fraction (it is 540 DEG C+fraction) being converted to lighter fraction.Therefore, this allows to improve starting The total conversion of raw material (decompression residuum (VR) generated by Ural crude oil, feature is listed in Table 1 below).On the other hand, such as table Shown in 19, unconverted 540 DEG C+fraction, raw material of the yield relative to FCC are still contained by the liquid distillate that FCC unit generates For 2.4 weight %.Compared with the embodiment 3 that wherein all DAO are converted in Hydrocracking unit, the conversion of DAO is in this feelings It is not all of under condition.

Table 19: by the yield and quality of the FCC unit F effluent generated

Unit		FCC
			Gasoline yield (C5- 220 DEG C)	Weight %	39.4
Diesel yield (220-360 DEG C)	Weight %	15.4
			It depressurizes distillate yield (360-540 DEG C)	Weight %	15.5
Decompression residuum yield (540 DEG C+)	Weight %	2.4

Overall performance quality

Using the program according to the present invention, using 0.068h^-1Total HSV and moderate temperature (420/420 DEG C), 540 DEG C of heavy + fraction (referred to as unconverted decompression residuum) is 6.1 weight % relative to the yield of fresh feed (as described in example 3 above).With Embodiment 4 and 5(conventional method not according to the present invention) it compares, this unconverted VR contains the conradson carbon residue of lower content And C₇Asphalitine, this allows to recycle a greater amount of DAO(in unconverted VR can be recycled 60.2 weights in this embodiment % is measured, relative to 57.2 weight % in embodiment 4 and 44.2 weight % in embodiment 5).Therefore, the party according to the present invention Case is generated along with the lower pitch relative to starting fresh feed, is equivalent to 2.4 weight %(relative to 15.8 in embodiment 4 4.0 weight % in weight % and embodiment 5).In addition, compared with the DAO fraction generated in embodiment 4 and 5, according to this hair The DAO generated in bright method also contains less impurity (sulphur, nitrogen, conradson carbon residue and C₇Asphalitine).Therefore, according to this hair Two kind DAOs of this DAO of bright method in FCC unit than generating in not embodiment according to the present invention 4 and 5 are easier Conversion.After converting DAO in FCC unit, in the sequence scheme according to the present invention, for 0.068h^-1It is total when air speed (HSV) and moderate temperature (420/420 DEG C), the conversion ratio of 540 DEG C+fraction of heavy is 96.7 weight %, i.e., than embodiment 4(in phase It is synthermal it is horizontal under) high 18 points and operated at very high temperatures than embodiment 5(reactor) high 2 points.

Other solvents, such as pentane (C₅), it can be used for deasphalting process, rather than such as this 6 fourths as described in the examples Alkane (C₄).Use C₅Depitching allows to increase DAO yield and enhances advantages of the present invention.

Claims (12)

1. the method for transformation of hydrocarbon raw material, at least 50 weight % of the hydrocarbon raw material, temperature of the preferably at least 80 weight % at least 300 DEG C The lower boiling of degree, the method includes following successive phases:

In stage a), in presence of hydrogen, at least one first phase reactor as entrainment bed operation, 2 To the absolute pressure of 35MPa, 300 DEG C to 550 DEG C at a temperature of, with 50 to 5000Sm³/m³Amounts of hydrogen, use first slurry Material catalyst carries out the first deep hydrogenation conversion of the hydrocarbon raw material,

Optionally, the stage b) of light fraction is separated from by some or all of first hydro-conversion generation effluent, And at least one heavy distillat is obtained, at least 80 weight % have at least 250 DEG C of boiling point,

In stage c), some or all of generated liquid efflunent by stage a) or generated by stage b) the of heavy distillat Two deep hydrogenations convert in presence of hydrogen, as entrainment bed operation at least one second phase reactor in, 2 to Under the absolute pressure of 35MPa, 300 DEG C to 550 DEG C at a temperature of, with 50 to 5000Sm³/m³Amounts of hydrogen, use the second slurry Catalyst carries out,

Air speed is less than 0.1h when stage a) is to c) total^-1, when total air speed be obtain in standard temperature and pressure conditions it is opposite The flow of the liquid charging stock of the hydroconversion stage a) of reactor total volume in stage a) and c),

At least one light fraction and at least one will be separated by some or all of second hydro-conversion generation effluent The stage d) of a heavy distillat, at least 80 weight % of the heavy distillat have at least 300 DEG C of boiling point,

At a temperature of deasphalting stage e) by the heavy distillat generated by stage d) at 60 DEG C to 250 DEG C, using at least A kind of hydrocarbon solvent with 3 to 7 carbon atoms and 4/1 to 9/1 solvent/raw material ratio (volume/volume), obtain de-asphalted fraction DAO and pitch.

2. the method according to claim 1 comprising transform portion or all rank of the de-asphalted fraction DAO optionally distilled Section is f).

3. method according to claim 2, wherein distilling DAO, before transformation stage f) to separate heavy distillat, at least 80 Weight % has at least 375 DEG C, or at least 400 DEG C, or at least 450 DEG C, or at least 500 DEG C, preferably at least 540 DEG C of boiling point, and And transformation stage f) is partly or entirely sent into the heavy distillat.

4. according to the method for any one of preceding claims, wherein part or all of DAO fraction to be preferably sent directly into conversion rank Section, the transformation stage use the method selected from fixed bed hydrogenation cracking, fluid catalystic cracking or boiling bed hydrogenation conversion to grasp Make, these methods may include preparatory hydrotreating.

5. method according to claim 4, part of or whole de-asphalted fraction DAO in presence of hydrogen, 5MPa extremely Under the absolute pressure of 35MPa, be advantageously 300 DEG C to 500 DEG C at a temperature of, in 0.1h^-1To 5h^-1HSV under, 100 Sm³/m³To 1000 Sm³/m³Under the amounts of hydrogen of liquid charging stock, and containing at least one group VIII non-noble metal j element and Bed hydroprocessing is fixed in the presence of at least one Section VI b race's element and the catalyst for containing the carrier comprising at least one zeolite Cracking.

6. method according to claim 4, part of or whole de-asphalted fraction DAO carries out fluidized bed in the presence of a catalyst Catalytic cracking FCC, the catalyst are preferably free of metal, include aluminium oxide, silica, silica/alumina, and preferred Include at least one zeolite.

7. method according to claim 4, part of or whole de-asphalted fraction DAO carries out boiling bed hydrogenation conversion, In the presence of hydrogen, under the absolute pressure of 2MPa to 35MPa, 300 DEG C to 550 DEG C at a temperature of, in 50 Sm³/m³To 5000 Sm³/m³Under the amounts of hydrogen of liquid charging stock, in 0.1 h^-1To 10 h^-1HSV under, and be selected from containing carrier and at least one It is carried out in the presence of the catalyst of the group VIII metal and at least one Section VI b race metal selected from molybdenum and tungsten of nickel and cobalt.

8. according to the method for any one of preceding claims, wherein at least part of the de-asphalted fraction DAO is recycled To stage a) and/or stage c).

9. according to the method for any one of preceding claims, wherein will be produced by second hydro-conversion in separation phase d) Raw effluent is separated at least one light fraction and at least one heavy distillat, and at least 80 weight % of the heavy distillat have extremely It is 375 DEG C few, or at least 400 DEG C, or at least 450 DEG C, or at least 500 DEG C, preferably at least 540 DEG C of boiling point.

10. according to the method for any one of preceding claims, in which:

Stage a) and c) at 5MPa to 25MPa, the absolute pressure of preferably 6MPa to 20MPa, at 350 DEG C to 500 DEG C, preferably At a temperature of 370 DEG C to 480 DEG C, more preferable 380 DEG C to 430 DEG C, in 100 Sm³/m³To 2000 Sm³/m³, highly preferred 200 Sm³/m³To 1500 Sm³/m³Amounts of hydrogen under, at least 0.05 h^-1, preferably 0.05 h^-1To 0.09 h^-1When air speed (HSV) it is carried out under,

Stage e) uses the solvent selected from butane, pentane and hexane and its mixture to carry out.

11. according to the method for any one of preceding claims, wherein the first slurry catalysis of first deep hydrogenation conversion a) The second slurry catalyst of agent and/or second deep hydrogenation conversion c) includes carrier and active phase, and the activity mutually contains At least one Section VI b race metal selected from molybdenum and tungsten, Section VI b race metal are preferably molybdenum, Section VI b race metal preferably with At least one group VIII base metal combination selected from nickel, cobalt, ruthenium and iron, the group VIII base metal are preferably nickel.

12. according to claim 1 to the method for 11 any one, wherein the first slurry catalysis of first deep hydrogenation conversion a) The second slurry catalyst of agent and/or second deep hydrogenation conversion c) is obtained by the precursor for dissolving in organic phase, before described Body is preferably selected from the organic gold being made of the naphthenate of Mo, Co, Fe and Ni and more carbonyls of Mo, Co, Fe and Ni Belong to compound, and the precursor is preferably molybdenum naphthenate.