CN102216429A - Integrated slurry hydrocracking and coking process - Google Patents
Integrated slurry hydrocracking and coking process Download PDFInfo
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- CN102216429A CN102216429A CN2009801450065A CN200980145006A CN102216429A CN 102216429 A CN102216429 A CN 102216429A CN 2009801450065 A CN2009801450065 A CN 2009801450065A CN 200980145006 A CN200980145006 A CN 200980145006A CN 102216429 A CN102216429 A CN 102216429A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/06—Gasoil
Abstract
Integrated slurry hydrocracking (SHC) and coking methods for making slurry hydrocracking (SHC) distillates are disclosed. Representative methods involve passing a slurry comprising a recycle SHC gas oil, a coker gas oil, a vacuum column resid, and a solid particulate through an SHC reaction zone in the presence of hydrogen to obtain the SHC distillate. Recovery of an SHC pitch from fractionation of the SHC reaction zone effluent provides an additional possibility for integration with the coker, and particularly via the upgrading of the SHC pitch in the coker to provide coke and lighter hydrocarbons such as SHC vacuum gas oil (VGO).
Description
Invention field
The present invention relates to use slurry hydrocracking (SHC) to promote, particularly the gas oil that obtains of delayed coking and prepare the method for overhead product hydrocarbon by refinery operation.SHC and coking and optional additive method such as crude oil fractionation and/or hydrotreatment comprehensively can be used for obtaining high quality (being high api gravity and/or low-sulfur) overhead product.
Description of Related Art
Gas oil, particularly vacuum gas oil (VGO) produce in a large amount of refinery operation of treatment of heavy hydrocarbon raw material.This generic operation comprises coking, crude oil fractionation and viscosity breaking.Coking method (for example delayed coking or fluid coking) comprises normal pressure and vacuum column residue heat (being on-catalytic) cracking to produce than lighter hydrocarbons and solid coke.For example referring to Meyers, R.A., Handbook of Petroleum RefiningProcesses, the 3rd edition, the 12nd chapter, McGraw-Hill (2004).Delayed coking has become the main method of lifting " the bucket end " refinery process materials flow especially.Yet by the gas oil that coking operation produces, for example delayed coking VGO is considered to low-quality product, needs further to promote with fluid catalytic cracking (FCC), hydrocracking and/or hydrotreatment.Unfortunately, because the pollutent (for example metal and sulphur compound) of the deactivation metal supported catalyst of conspicuous level, and the coke precursors in these materials flows, coker gas oil is not easy to handle according to this class ordinary method.Coker gas oil is changed into the more situation of selling well overhead product and the petroleum naphtha blend components that are used for transport fuel therefore follow a large amount of shortcomings.
The other method of known generation gas oil is the slurry hydrocracking, and it refers to heavy hydrocarbon feedstocks at slurry mutually or choose wantonly and use oil soluble metal catalyzer such as metal sulphide compound to transform in the presence of hydrogen and solid catalyst particle (for example as the metal nano aggregate) in homogeneous catalyst system.Typical slurry method for hydrogen cracking for example is described in US 5,755,955 and US 5,474,977 in.Except that the VGO that is present in usually in the reactor effluent, the slurry hydrocracking produces the refractory pitch materials flow of low value, because its high viscosity and solids content, described materials flow can not promote economically usually or even sneak in other products such as oil fuel or the synthetic crude.
The concrete source of the synthetic crude of more and more being paid close attention to is pitch earth, seeks blend components to improve its flow performance.This inferior quality hydrocarbon-containing feedstock is for example reclaimed in those of the big Athabasca district of Alberta, Canada and Venezuela and U.S. discovery by oil sands deposit.Pitch earth is considered to valuable " semisolid ", and oil is originated, and it can be refined into many valuable the finished product, comprises transport fuel, for example gasoline or even petroleum chemicals.
Still need be in this area to improve the method that efficient transformed or promoted heavy hydrocarbon (for example atmospheric tower and vacuum column Residual oil and gas oil).Also need the low value the finished product, comprise the minimized this method of gas oil and bituminous net production.Also need total crude oil refining method, it comprises and promotes former oil residue, particularly those that are obtained by the heavy crude raw material with remarkable ratio.
Summary of the invention
Aspect of the present invention relates to and finds the slurry hydrocracking (SHC) can be effectively and other method of refining, and for example coking, hydrotreatment and/or crude oil fractionation comprehensively with the materials flow of production high value overhead product, make undesired gas oil recirculation simultaneously, preferably to disappearing.About it vacuum column residue is changed into the gently ability of product, SHC is generally known in the art.Yet, surprisingly, disclose now except that changing into more valuable petroleum naphtha and overhead product product and provide other important interests relevant with gained SHC/ coking integrated approach in the SHC reactor, coker gas oil (for example delayed coking VGO) infeeds as heavy hydrocarbon feedstocks component or increment can suppress coke formation among the SHC.
In typical integrated approach, low-quality coker gas oil and the total heavy hydrocarbon feed that is used for SHC by the recirculation SHC gas oil combination of the downstream fractionation/Separation and Recovery of SHC effluent.As mentioned above, although this raw material of part also comprises conventional component usually, vacuum column Residual oil for example, the existence of coker gas oil improves SHC reactor effluent quality, particularly about the coking yield that reduces and the petroleum naphtha and the overhead product yield of raising.In addition, coker gas oil (1) obtains usually easily in a large number, particularly refinery handle under the situation of heavy crude and (2) because the pollutent of catalyst system therefor in these methods of high-caliber being harmful to (deactivation) is difficult to use FCC, hydrocracking or hydrotreatment further to promote.Yet, determined that now coker gas oil is attractive increment raw material (for example with the combination of vacuum column residue), with its use SHC effectively cracking to obtain than hydrogen and more valuable clean overhead product and optional naphtha products.In addition, according to some embodiments, SHC enters the coker inlet with the pitch by product that additional advantage: SHC comprehensively is provided of coking (for example delayed coking or fluid coking) with atmospheric tower of handling usually or vacuum column Residual oil in coking operation.In the coker SHC bituminous handle therefore allow this by product is transformed/promote the more hydrocarbon and the solid coke of high value.Treatment S HC pitch in coker no matter whether, the gas oil final product that reduces in the comprehensive SHC/ coking method, for example the yield of the hydrocarbon of boiling point in the VGO scope has reduced the demand of hydrotreatment respectively and/or this class product of hydrocracking.
According to a typical embodiments, the hydrotreatment combination of comprehensive SHC/ coking method and SHC overhead product.Because the gas oil product of low (or not existing) such as the clean yield of VGO, because these heavy boiling point fraction recirculation are back to the SHC reaction zone, the overhead product of hydrotreatment has sufficiently high api gravity (for example at least 20 °), makes it for attractive in the synthetic crude of sneaking into via pipe-line transportation.Therefore, the overhead product of hydrotreatment, or even not have the SHC overhead product of hydrotreatment can be used as only to have minor amount or do not have substantially boiling point be that the high quality transport fuel blend components of hydrocarbon of the representative temperature (for example greater than 343 ℃ (650)) of gas oil obtains.
The SHC method also can be by the SHC overhead product product that will reclaim together with the straight run distillate that is obtained by the crude oil fractionation and/or other refinery's overhead product materials flow hydrotreatments and comprehensive with the existing refinery processing and treating method that is generally used for removing sulfur-bearing and nitrogenous compound from overhead product.This comprehensively can advantageously reduce the total fund cost of a complete set of equipment.As mentioned above, SHC and existing coking, optional hydrotreatment and optional other conventional refinery operation comprehensively can provide remarkable interests aspect processing efficiency and product yield, reduction or elimination low value refractory by product and/or the relevant fund cost reduction improving.According to specific embodiments of the present invention, the materials flow of crude vacuum column bottoms provides a part of heavy hydrocarbon feedstocks of SHC reactor, and combines with coker gas oil (for example coking VGO) at the SHC reactor exit.Another part vacuum column residue or also can be processed in coker from other cuts itself of this tower.In another embodiment, coker gas oil or the optional heavy hydrocarbon feedstocks that provides a part to use SHC to handle with straight run gas oil (for example straight run VGO) of this refinery's gas oil component of a part can enter again in the coker (for example delayed coking unit or fluid coker) to promote by fractionation and the isolating SHC pitch of SHC effluent.
Understand these and other aspects and the embodiment that the present invention relates to by following detailed description.
The accompanying drawing summary
Fig. 1 has described a kind of typical method, wherein the slurry hydrocracking is incorporated among the typical flow process figure of refinery with existing coker with by the overhead product of crude production hydrotreatment and the clean product of coke, wherein has seldom or do not have total production of refractory gas oil such as VGO.
Fig. 2 has described second typical integrated approach.
Describe in detail
Embodiment of the present invention relates to slurry hydrocracking (SHC) and makes up the purposes that promotes heavy hydrocarbon feedstocks with coking.The typical heavy hydrocarbonaceous feedstock of SHC is for to be recovered and recycled to the SHC gas oil of SHC reactor (or reaction zone) and the mixture of refinery's coker gas oil by the SHC effluent.According to an embodiment, for example heavy hydrocarbon feedstocks comprises vacuum column residue and coker gas oil (for example being obtained by delayed coking unit or fluid coker).Refinery's coker operations and SHC comprehensively provide important as mentioned above interests.Except that the SHC gas oil and coker gas oil of recirculation, heavy hydrocarbon feedstocks also can contain other components that can have benefited from SHC operation reducing the total molecular weight of heavy hydrocarbon feedstocks, and/or removes organosulfur and nitrogen compound and metal.According to each embodiment, as the boiling point of the heavy hydrocarbon feedstocks of signal portion 80 weight % at the most in typical gas oil scope (for example 343 ℃ (650)-566 ℃ (1050)) and only, when 60 weight % heavy hydrocarbon feedstocks are the compound of boiling point more than 566 ℃ (1050) at the most usually, SHC be improved (for example forming) by suppressing coke.
Except that SHC gas oil and coker gas oil, other components of typical heavy hydrocarbon feedstocks comprise Residual oil, and for example boiling point is that 343 ℃ (650) above crude oil atmospheric distillation tower residue, boiling point is 566 ℃ (1050) above crude oil vacuum tower residue, tar, pitch earth, coal oil and shale oil.The raw material of other asphaltenes for example comprises that the full cut of heavy crude or tops petroleum crude oil also can be used as the component that SHC handles.Except that bituminous matter, other possibility components of these of heavy hydrocarbon feedstocks and other also contain significant metal pollutant (for example nickel, iron and vanadium), high-content organosulfur and nitrogen compound and Gao Kanglaxun carbon residue usually.The metal content of this class component can for example be 100-1,000 ppm by weight, and total sulfur content can be 1-7 weight %, api gravity can be-5 ° to 35 °.The Kang Laxun carbon residue of this class component is generally at least 5%, usually 10-30 weight %.In a word, many heavy hydrocarbon feedstocks components of SHC method comprise coker gas oil, have to make their catalysis conversion method such as hydrocracking and deleterious performances of fluid catalytic cracking to other types.
The integrated approach for preparing the method for SHC overhead product generally include make comprise coker gas oil heavy hydrocarbon feedstocks in the presence of hydrogen by the SHC reaction zone so that SHC to be provided effluent.Heavy hydrocarbon feedstocks can, but not necessarily be present in the heterogeneous slurry catalyst system in the SHC reactor, wherein catalyzer is a solid particulate form.Yet, with regard to present disclosure, wherein catalytically-active metals is present in the liquid phase and the homogeneous catalyst system that is dissolved in (for example as oil soluble metal compound such as metallic sulfide) in the heavy hydrocarbon feedstocks is also included within the definition of SHC method, this is because homogeneous process is suitable for promoting similar heavy hydrocarbon feedstocks equally, has the same advantageous results relevant with embodiment discussed herein.
In the presence of the recycle gas of the combination of hydrogen and be enough at least a portion heavy hydrocarbon feedstocks is cracked under the condition of light boiling point SHC overhead product cut and carry out, described SHC overhead product cut is reclaimed from the effluent of SHC reactor usually for SHC reaction.The recycle gas of combination for the hydrogen rich stream that reclaims by the SHC effluent overhead gas stream of high-pressure separator (for example as) and be used for replacing the SHC reactor or reaction zone consumes and purge or exhaust stream in or the mixture of the fresh supplemented hydrogen of hydrogen by solution loss.Do not have the operation of hydrogen recycle (promptly having " one way " hydrogen) to represent the alternate operator scheme, wherein can use to have a large amount of possible hydrogen source that changes purity.
The recovery of SHC overhead product generally includes uses the SHC effluent, or than the flash separation and/or the distillation of low boiler cut or its cut (cut that for example has low distillation end point), with the SHC overhead product as separating than the SHC gas oil of supervening (or unconverted) in low boiling component and the SHC effluent.Therefore can use single hop flash separation SHC effluent in the SHC high-pressure separator, or, in SHC separation column pressure fractionating tower as usual or SHC atmospheric distillation tower, use a plurality of segregation sections to reclaim the SHC overhead product as selecting.Typical especially embodiment comprise make the SHC effluent enter normal pressure or vapor rectification process tower and with the SHC overhead product as overhead product or the (C that for example have some lighting ends, removes that sides stream
4 -Hydrocarbon product) reclaims.Other products reclaim then can by make bottom product or residue thus first (for example normal pressure) SHC separation column enter second (for example vacuum) the SHC separation column and reclaim SHC gas oil (for example heavy VGO) and carry out.Make at least a portion SHC gas oil be recycled to SHC reactor or reaction zone as mentioned above then.SHC vacuum fractionation tower not only can be used for separating SHC gas oil, for example conduct is sideed stream, and can be used for separating SHC pitch, for example as vacuum column bottom product or residue, and SHC lightweight VGO, can choose wantonly and make it stand hydrotreatment as described in more detail below.
If form slurry with heavy hydrocarbon feedstocks, upwards by the SHC reaction zone, then slurry has the solid content of 0.01-10 weight % usually usually.Solid particulate is generally the compound of catalytically-active metals, or the metal of element form, separately or load on refractory material such as the inorganic, metal oxide (for example aluminum oxide, silica, titanium dioxide, zirconium white and composition thereof).Other suitable refractory materials comprise carbon, coal and clay.Zeolite and non-zeolitic molecular sieves are also as solid carrier.Using an advantage of carrier is the ability that it serves as the sorbent material of " coke getter " or bituminous matter precursor, and described bituminous matter precursor can cause processing unit incrustation in addition.
The catalytically-active metals that is used for hydrotreatment comprises from those of the IVB of periodictable family, the VB of family, the VIB of family, the VIIB of family or the VIII of family, and its amount with required hydrotreatment of effective catalysis and/or hydrocracking reaction is mixed in the heavy hydrocarbon feedstocks can be fractionated than low boiling hydrocarbon in by hydrotreatment what slurry effluent as petroleum naphtha and/or overhead product product in the presence of not substantially at solid particulate for example to provide.Typical metal comprises iron, nickel, molybdenum, vanadium, tungsten, cobalt, ruthenium and composition thereof.Catalytically-active metals can be used as solid particulate with element form or as organic compound or mineral compound such as sulfide (for example iron sulphide) or the existence of other ionic compounds.Metal or metallic compound nano aggregate also can be used for forming described solid particulate.
Usually, need this metallic compound to form by catalyst precursor such as metal sulfate (for example ferric sulfate monohydrate) original position as solid particulate, described precursor or decomposes in pre-treatment step or reaction forms the solid particulate (for example as iron sulphide) of required good distribution and catalytic activity in hydrotreatment reaction zone environment.Precursor also comprises the oil soluble organometallic compound that contains meaningful catalytically-active metals, and its thermolysis forms the solid particulate (for example iron sulphide) with catalytic activity.But this compound usually high dispersing and changes into the solid particulate that is included in the slurry effluent usually under pre-treatment or hydrotreatment reaction zone conditions in heavy hydrocarbon feedstocks.The preparation of typical case's original position solid particulate comprises that the precursor pre-treatment with heavy hydrocarbon feedstocks and final required metallic compound for example is described in US5, in 474,977.
Other suitable precursor comprise the compound that can change into catalytic activity (or having more catalytic activity) such as the metal oxide of metallic sulfide.In specific embodiments, the mineral of containing metal oxide compound can be used as the precursor of solid particulate, and it is included in the catalytically-active metals (for example iron sulphide) on the inorganic refractory metal oxide carrier (for example aluminum oxide).The precursor that the bauxite representative is special, the iron sulphide catalyzer that provides as solid particulate is provided the ferric oxide crystalline that wherein is contained in these mineral, and therefore, after transforming, iron sulphide loads on the aluminum oxide that mainly is present in the bauxite precursor.
Condition in SHC reactor or the reaction zone generally include the pressure of temperature, 3.5MPa (500psig)-21MPa (3000psig) of 343 ℃ of (650)-538 ℃ (1000) and 1-30 volume heavy hydrocarbon feedstocks/hour/air speed in the described SHC of volume district.Catalyst system therefor and condition are suitable for promoting heavy hydrocarbon feedstocks to provide than low boiling component in the SHC reaction zone in leaving the SHC effluent of SHC reaction zone, i.e. SHC overhead product cut.The SHC overhead product usually as the distillation end point that has usually the cut more than petroleum naphtha from total SHC effluent (choosing wantonly after removing hydrogen rich stream and being recycled in the SHC reactor as mentioned above), be recovered.The SHC overhead product for example can be used as the distillation end point temperature that has and is generally 204 ℃ (400 °F)-399 ℃ (750 °F), the cut that is generally 260 ℃ of (500)-343 ℃ (650) is recovered, and wherein heavier boiling-point compound is recovered with the recirculation of SHC gas oil or in choosing the SHC pitch materials flow that enters coker wantonly.
According to specific embodiments, SHC overhead product and higher SHC cut can be recovered as overhead product and the tower bottoms stream of leaving the high pressure hot separator that infeeds SHC effluent (choosing wantonly after removing hydrogen rich stream) respectively.Fractionation (for example in vacuum tower) higher SHC cut can provide SHC gas oil (for example heavy VGO) and SHC pitch then.As the isolating replacement scheme of single hop in high-pressure separator, the SHC overhead product can, for example be recovered as sideing stream of SHC atmospheric fractional tower or distillation tower by in the SHC effluent than low boiling component by fractionation (promptly using the multistage vapour-liquid equilibrium to separate) conduct.Then can be in the future since then the residue or the bottoms of a SHC separation column infeed the 2nd SHC separation column, for example in the vacuum tower so that SHC gas oil, SHC pitch and optional other cuts, for example SHC lightweight VGO to be provided.With the comprehensive SHC/ coking method of the hydrotreatment of SHC overhead product combination in, this SHC lightweight of all or part VGO can be as described below with the charging of SHC overhead product (mixing or combination) as the hydrotreatment district.
The typical embodiments according to the present invention, the yield of SHC overhead product (distillation end point is in these scopes) is generally at least 30 weight % (for example 30-65 weight %) of the SHC effluent weight (for example combination weight of SHC overhead product and SHC gas oil) of combination, usually at least 35 weight % (for example 35-55 weight %), at least 40 weight % (for example 40-50 weight %) usually.Depend on required final product, can be with the fractionation of SHC overhead product own to obtain for example have petroleum naphtha and the diesel oil fuel that changes the distillation end point temperature.For example, relative light naphthar can be separated with the SHC overhead product, it has the distillation end point temperature of 175 ℃ of (347)-193 ℃ (380).According to other embodiments, separable relative heavy naphtha, it has the distillation end point temperature of 193 ℃ of (380)-204 ℃ (400).Petroleum naphtha can be fractionated into one or more naphtha fractions, for example light naphthar, gasoline and heavy naphtha, its typical distillation end point is respectively 138 ℃ (280)-160 ℃ (320), 168 ℃ (335)-191 ℃ (375) and 193 ℃ (380)-216 ℃ (420).
Also depend on the concrete separation/fractionation conditions that is used to reclaim the SHC overhead product, this materials flow contains a large amount of organic nitrogen compounds and organosulfur compound usually.For example, the basic total sulfur that exists with the form of organosulfur compound such as alkylbenzene thiophthene is generally 0.1-4% in this materials flow, usually 0.2-2.5%, 0.5-2% usually.Substantially with organic nitrogen compound such as non-alkaline aromatic substance, comprise that the total nitrogen that carbazole (cabazole) form exists will be generally 100ppm-2%, usually 100-750ppm in the SHC overhead product.The SHC overhead product also contains the polycyclic aromatic hydrocarbons (polyaromatics) of signal portion usually, for example 2 cyclophane compounds of group (for example fused aromatic ring, for example naphthalene and naphthalene derivatives) and polynuclear aromatic compound.According to some typical embodiments, the combined amount of 2 cyclophane compounds of group and polynuclear aromatic compound is at least 50 weight % of SHC overhead product, and the amount of monocyclic aromatics (for example benzene and benzene derivative such as Alkylaromatics) only accounts for 20 weight % at the most usually.
Except that SHC gas oil (for example heavy SHC VGO), the heavy hydrocarbon feedstocks of SHC reactor or reaction zone comprises by the coker gas oil (for example heavy coker gas oil) and the common vacuum column Residual oil that postpone or fluid coking is produced as mentioned above.Except that SHC and coker gas oil, other typical gas oil components that can be included in the heavy hydrocarbon feedstocks comprise straight run gas oil such as the vacuum gas oil that is reclaimed by the crude oil fractionation.Other gas oils of producing in the refinery comprise diasphaltene gas oil and viscosity breaker gas oil.Gas oil and comprise the combination heavy hydrocarbon feedstocks of the SHC reaction zone of these gas oils therefore can be for boiling point be 343 ℃ (650) mixture to the hydrocarbon of 593 ℃ of (1100) distillation end points, wherein other typical distillation end points are 566 ℃ (1050), 538 ℃ (1000) and 482 ℃ (900).Typical SHC gas oil has the distillation end point temperature of 427 ℃ of (800)-538 ℃ (1000).Under straight run vacuum gas oil condition, distillation end point depends on the cut point cutout (cutoff) between crude oil vacuum fractionation tower, particularly vacuum gas oil and the vacuum column tower bottom distillate.Therefore, be suitable for the refinery's gas oil component in the heavy hydrocarbon of SHC reactor, for example straight run is produced by crude oil fractionation or distillation procedure usually, and other gas oil component obtain later at one or more hydrocarbon conversion reactions.
SHC can be advantageously and the hydrotreatment combination, make the SHC overhead product that will reclaim or its cut (for example naphtha fraction or diesel fuel fractions) in the hydrotreatment district catalytic hydroprocessing to reduce total sulfur and/or total nitrogen content.According to specific embodiments, for example, can obtain sulphur content for less than 30 ppm by weight, usually less than 10 ppm by weight, even less than the naphtha fraction of the hydrotreatment of 5 ppm by weight.Can obtain sulphur content for less than 50 ppm by weight, usually less than 20 ppm by weight, even less than the diesel oil fuel of the hydrotreatment of 10 ppm by weight.Hydrotreatment SHC overhead product to be providing the overhead product of hydrotreatment, or therefore the cut of hydrotreatment SHC overhead product can provide and follow low-sulfur product and even super low sulfur petroleum naphtha and the diesel oil distillate that is suitable for tolerance limit.According to embodiment preferred, the SHC overhead product has for example is enough to mix the crude oil that obtained by oil-sand or the api gravity in the synthetic crude.Typical case's api gravity value is greater than 20 ° (for example 25 °-40 °) with greater than 35 ° (for example 40 °-55 °).
In other embodiments, comprehensively can comprising of SHC method and hydrotreatment for example makes other refinery's overhead product materials flows, and for example straight run distillate is by hydrotreatment district or reactor.Whether no matter one or more other materials flows and SHC overhead product combined hydrogenation are handled, hydrotreatment is all carried out in the presence of the hydrogeneous materials flow of recirculation of hydrotreating catalyst fixed bed and combination.Typical hydroprocessing condition comprises the temperature of 260 ℃ of (500)-426 ℃ (800), pressure and the 0.1-10hr of 7.0MPa (1000psig)-21MPa (3000psig)
-1Liquid hourly space velocity (LHSV).Understand as this area, (LHSV is with the hr of unit for liquid hourly space velocity
-1Expression) be volume of liquid flow rate on the catalyst bed divided by bed volume, expression is the liquid of the equivalent catalyst bed volume of processing per hour.LHSV and reactor residence time reciprocal closely related.Suitable hydrotreating catalyst is included on the refractory inorganic oxide carrier material of either, is selected from the metal of nickel, cobalt, tungsten, molybdenum and composition thereof.
As mentioned above, the SHC method is advantageously comprehensive with refinery's coking operation such as delayed coking unit or fluid coker, wherein from the coker gas oil of delayed coking or fluid coking, for example heavy coker gas oil or coking VGO enter the SHC reaction zone to promote, and therefore advantageously are suppressed in the SHC reactor and form coke.Another comprehensive possibility of other SHC/ coking comprises that other use is by downstream separation and/or fractionation SHC effluent and the SHC pitch that reclaims or the higher cut or the cut (cut that for example has higher initial boiling point) of this effluent.Typical SHC pitch materials flow can for example be reclaimed in the bottoms by the SHC vacuum column.The specific embodiments that is recovered as the tower bottoms stream of leaving high pressure hot separator or SHC atmospheric fractional tower according to higher SHC effluent fraction wherein, the vacuum fractionation that can carry out this tower bottoms stream is to obtain to be recycled to the SHC gas oil and the materials flow of heavier SHC pitch of SHC reactor.SHC pitch can enter in the coker (for example delayed coking unit or fluid coker) so that SHC and coking are further comprehensive, make coker not only be used for residue at the bottom of the transformed eukaryotic void tower tower, and be used to transform SHC pitch, obtain other more products of high value by this SHC product thus.Typical case's SHC pitch comprise or substantially by boiling point greater than 482 ℃ (900 °F), usually greater than 538 ℃ (1000 °F), form greater than the hydrocarbon of the temperature of 593 ℃ (1100) usually.
Therefore, the present invention relates to promote in the above described manner the total flow process figure of refinery or the method for crude oil, especially wherein coker gas oil is total method of the heavy hydrocarbon feedstocks part of SHC method.Because SHC gas oil and the internal recycle of SHC pitch in this general flow chart or method, all clean products are overhead product or coke substantially, wherein seldom or not produce low value SHC gas oil and SHC pitch.According to typical embodiments of the present invention, the yield of overhead product product (for example the overhead product of hydrotreatment) as mentioned above and coke accounts at least 80% (for example 80-99%) of overall process yield, accounts at least 85% (for example 85-95%) of this yield usually.
Other aspects of the present invention relate to uses as mentioned above that the SHC method prepares synthetic crude or synthetic crude blend components.This method comprises that the gas oil that makes derived from delayed coking unit or fluid coker enters the SHC method, and wherein this method is with hydrotreater is optional comprehensive as mentioned above.Depend on the fractionation conditions that is used for downstream processing SHC effluent, can obtain having basic all boiling points in the overhead product scope or the SHC overhead product of lower hydrocarbon.In typical embodiments,, be boiling point greater than the hydrocarbon under the temperature of 343 ℃ (650) less than 10 weight %SHC overhead products usually less than 20 weight %.This SHC method can be in addition and crude fractionating column comprehensive, making will be from the straight run distillate of crude oil atmospheric distillation tower with the hydrotreatment of SHC overhead product.VGO and/or can enter SHC reactor or reaction zone (making that promptly VGO is with the SHC gas oil of recirculation and the coker gas oil part for heavy hydrocarbon feedstocks) from the vacuum residue (or Residual oil) of vacuum tower.
The typical process flow figure that the specific embodiments of aforesaid method is carried out in elaboration is depicted among Fig. 1.Be to be understood that the rationale that Fig. 1 represents the present invention and/or relates to.As the those skilled in the art with present disclosure knowledge understand easily, and the method for each other embodiments has configuration, component and the operating parameters by concrete raw material, product and the decision of product quality specification part according to the present invention.
According to the embodiment that Fig. 1 sets forth, slurry hydrocracking (SHC) reactor or reaction zone 20 are merged among the flow process figure of refinery.The heavy hydrocarbon feedstocks 1 of this reaction zone 20 is the combination from coking vacuum gas oil (VGO) materials flow 2 of delayed coking method 30 and SHC VGO (for example SHC heavy VGO) recycle stream 3.Another component of the heavy hydrocarbon feedstocks 1 of SHC method 20 is to contain the vacuum column residue materials flow (or Residual oil) 4 from crude vacuum column or tower 40 that boiling point is the hydrocarbon of 566 ℃ (1050) above (promptly having the cut point temperature) usually.As shown in Figure 1, atmospheric tower 80 is created in atmospheric residue or the reduced oil materials flow 13 that fractionated common cut point temperature is 343 ℃ (650) in the vacuum column 40.
Optional, heavy hydrocarbon feedstocks 1 for example also comprises from vacuum column 40 and for example contains the VGO cut 5a that boiling point is the hydrocarbon of 343 ℃ of (650)-566 ℃ (1050).Can choose wantonly with the part of this VGO cut 5a or from the different VGO cut 5b of vacuum column 40 and directly infeed in the overhead product hydroprocessing process 50.Optional other materials flows that are used as the increment raw material of hydroprocessing process 50 are the fractionated straight run 11 that partly obtains as the overhead product of crude oil stream 12 in crude oil atmospheric tower or tower 80.But other materials flows of hydrotreatment are from a part of SHC VGO recycle stream 3 of SHC separation column 70 or different SHC VGO cut 3a, for example are in a ratio of light VGO than low boiler cut with SHC VGO recycle stream 3.Therefore, SHC overhead product 7, any combination or all one are used from the product that obtains as total method, have the overhead product 14 of the hydrotreatment of the nitrogen compound that reduces as mentioned above and oxidation of sulfur compound impurities and/or api gravity among optional and materials flow 11,5b and/or the 3a, and it can be used as the blend components of synthetic crude.
The SHC method comprises that therefore SHC reaction zone 20 is used to promote VGO materials flow 2 from delayed coking method 30 with comprehensive method, and as mentioned above, it advantageously is suppressed in SHC reactor or the reaction zone and forms coke.Make then total SHC effluent materials flow 6 stand downstream separation/fractionation operation with the product that reclaim to promote, remove deasphalting and make intermediate recirculation.According to the described embodiment of Fig. 1, use high pressure hot separator (HHPS) 60 to separate total SHC effluent to reclaim the SHC overhead product 7 of common boiling point more than petroleum naphtha.Then will be by the SHC effluent, the particularly higher cut 8 that reclaims in the bottoms of HHPS 60 fractionation in usually as the SHC separation column 70 of vacuum column operation.The SHC separation column separates SHC VGO recycle stream 3 with SHC pitch materials flow 9, as mentioned above, it is advantageously used for the raw material of delayed coking unit 30.Delayed coking unit 30 produces coke 10 and as the coking VGO materials flow 2 of recycle stream (in total method), it is refinery's gas oil component of the heavy hydrocarbon feedstocks 1 of SHC method 20.
Fig. 2 describes alternative flow, and it is the variation scheme of embodiment that Fig. 1 paints, and wherein the reference number of Fig. 1 is used to represent similar process stream shown in Figure 2 and equipment.According to this embodiment, use first (for example normal pressure) SHC separation column 60-A to replace HHPS (reference number 60 among Fig. 1) to reclaim SHC overhead product 7-A, it is sideing stream of taking out from a SHC separation column 60-A, and (the C for example that for example has lighting end in total SHC effluent materials flow 6 of removing
4 -Hydrocarbon product).Higher cut 8-A takes out from a SHC separation column 60-A as bottom product, fractionation in second of separation column 70 (for example vacuum) SHC separation column 70 in corresponding to Fig. 1 then.Then can be in the second vacuum fractionation tower 70 the separation column bottom product to obtain SHC VGO recycle stream 3, SHC pitch materials flow 9 and SHC VGO cut 3a, the latter can be compare with SHC VGO recycle stream 3 light boiling point fraction, for example lightweight VGO.
As shown in Figure 2, SHC pitch materials flow 9 is as delayed coking unit, the particularly raw material of coking fractional distillation column 30-A.Use T type valve or switching valve 30-C that coking fractional distillation column bottom product 16 is entered among one of two coke drums 30-B.Take out coke 10 then and with the coker liquids 15 that reclaims for example as the heavy coker gas oil, with choose any one kind of them or multiple light coker hydrocarbon product 17 is sent the coking fractional distillation column 30-A that is used for fractionation coking VGO 2 back to together as coker overhead product and/or coking naphtha, can with its in hydroprocessing process 50 with SHC overhead product 7-A and optional other materials flow combined hydrogenations processing as mentioned above.
In total method described in Fig. 1 and Fig. 2, wherein that SHC method and delayed coking unit is comprehensive, mainly produce the clean product of the overhead product 14 of coke 10 and hydrotreatment thus.As understanding from this specification sheets, whole aspects of the present invention relate to slurry hydrocracking (SHC) and pyrogenic comprehensive so that the refinery operation optimizing.In view of present disclosure, can realize several advantages as can be seen and can obtain other favourable results.Those skilled in the art will recognize that the suitability of method disclosed herein to any a large amount of comprehensive SHC methods.The scope that in above method, to make various variations and not depart from present disclosure that it will be appreciated by those skilled in the art that with knowledge of obtaining by present disclosure.
Claims (10)
1. integrated approach for preparing slurry hydrocracking (SHC) overhead product, described method comprises:
A) make comprise coker gas oil heavy hydrocarbon feedstocks in the presence of hydrogen by the SHC reaction zone so that SHC to be provided effluent; With
B) from described SHC effluent, reclaim described SHC overhead product.
2. according to the process of claim 1 wherein that described coker gas oil is obtained by delayed coking unit or fluid coker.
3. according to the method for claim 1 or 2, it also comprises by reclaiming SHC gas oil in the described SHC effluent, and makes described SHC gas oil be recycled to described SHC district, and described thus heavy hydrocarbon feedstocks comprises described SHC gas oil and described coker gas oil.
4. according to the method for claim 3, wherein by flash separation or the described SHC effluent of fractionation and with described SHC overhead product as separating with described SHC gas oil than low boiling component.
5. according to each method among the claim 1-4, its also comprise will comprise described SHC overhead product the overhead product raw material in the hydrotreatment district hydrotreatment to obtain the overhead product of hydrotreatment.
6. according to the method for claim 5, wherein except that described SHC overhead product, described overhead product raw material also comprises straight run.
7. according to the method for claim 5 or 6, the overhead product of wherein said hydrotreatment has at least 20 ° api gravity.
8. according to each method among the claim 1-7, it also comprises by flash separation or the described SHC effluent of fractionation and SHC pitch is reclaimed as the higher component.
9. method according to Claim 8, it also comprises makes described SHC pitch enter the coker of producing described coker gas oil.
10. one kind by comprehensively preparing the method for overhead product hydrocarbon component with slurry hydrocracking (SHC), coking and hydrotreatment, and described method comprises:
A) slurry that makes the coker gas oil that comprises SHC gas oil, obtain by delayed coking unit or fluid coker and solid particulate in the presence of hydrogen by the SHC reaction zone so that SHC to be provided effluent;
B) from described SHC effluent, reclaim described SHC gas oil, SHC overhead product and SHC pitch;
C) make described SHC gas oil be recycled to described SHC reaction zone;
D) with the hydrotreatment of described SHC overhead product to obtain described synthetic crude as the overhead product of hydrotreatment; With
E) make described SHC pitch be recycled to described delayed coking unit or described fluid coker to obtain coke produced.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/271,851 US20100122932A1 (en) | 2008-11-15 | 2008-11-15 | Integrated Slurry Hydrocracking and Coking Process |
| US12/271,851 | 2008-11-15 | ||
| PCT/US2009/059644 WO2010056437A2 (en) | 2008-11-15 | 2009-10-06 | Integrated slurry hydrocracking and coking process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102216429A true CN102216429A (en) | 2011-10-12 |
| CN102216429B CN102216429B (en) | 2014-08-06 |
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| CN200980145006.5A Expired - Fee Related CN102216429B (en) | 2008-11-15 | 2009-10-06 | Integrated slurry hydrocracking and coking process |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20100122932A1 (en) |
| CN (1) | CN102216429B (en) |
| CA (1) | CA2742016A1 (en) |
| WO (1) | WO2010056437A2 (en) |
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| CN110408426A (en) * | 2018-04-28 | 2019-11-05 | 何巨堂 | The delayed coking method of heavy oil straight run residue and heavy-oil hydrogenation hot cracked product residual oil |
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| US8231775B2 (en) * | 2009-06-25 | 2012-07-31 | Uop Llc | Pitch composition |
| US8877039B2 (en) | 2012-03-28 | 2014-11-04 | Uop Llc | Hydrocarbon conversion process |
| FR3023298B1 (en) | 2014-07-01 | 2017-12-29 | Total Marketing Services | PROCESS FOR DESAROMATISATION OF PETROLEUM CUTTERS |
| US9777226B2 (en) | 2014-09-08 | 2017-10-03 | Uop Llc | Methods and systems for slurry hydrocracking with reduced feed bypass |
| US10041011B2 (en) * | 2014-11-06 | 2018-08-07 | Uop Llc | Processes for recovering hydrocarbons from a drag stream from a slurry hydrocracker |
| US20160137930A1 (en) * | 2014-11-18 | 2016-05-19 | Uop Llc | Slurry hydrocracking process using spent hydroprocessing catalyst |
| RU2698807C2 (en) | 2014-12-17 | 2019-08-30 | Хальдор Топсеэ А/С | Method of converting hydrocarbon stream |
| US10603657B2 (en) | 2016-04-11 | 2020-03-31 | Saudi Arabian Oil Company | Nano-sized zeolite supported catalysts and methods for their production |
| US11084992B2 (en) | 2016-06-02 | 2021-08-10 | Saudi Arabian Oil Company | Systems and methods for upgrading heavy oils |
| CN110892043A (en) * | 2017-07-17 | 2020-03-17 | 沙特阿拉伯石油公司 | System and method for processing heavy oil by refining after oil upgrading |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20100122932A1 (en) | 2010-05-20 |
| CN102216429B (en) | 2014-08-06 |
| WO2010056437A3 (en) | 2010-07-01 |
| CA2742016A1 (en) | 2010-05-20 |
| WO2010056437A2 (en) | 2010-05-20 |
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