CN102216429B - Integrated slurry hydrocracking and coking process - Google Patents
Integrated slurry hydrocracking and coking process Download PDFInfo
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- CN102216429B CN102216429B CN200980145006.5A CN200980145006A CN102216429B CN 102216429 B CN102216429 B CN 102216429B CN 200980145006 A CN200980145006 A CN 200980145006A CN 102216429 B CN102216429 B CN 102216429B
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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
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- Engineering & Computer Science (AREA)
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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 by refinery operation, the gas oil that particularly delayed coking obtains and prepare the method for overhead product hydrocarbon.SHC and coking and optional additive method comprehensively can be used for obtaining high quality (being high api gravity and/or low-sulfur) overhead product as crude oil fractionation and/or hydrotreatment.
Description of Related Art
Gas oil, particularly vacuum gas oil (VGO) produce in a large amount of refinery operation for the treatment of 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 compared with 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 material stream especially.But, the gas oil being produced by coking operation, for example delayed coking VGO is considered to low-quality product, need to further promote with fluid catalytic cracking (FCC), hydrocracking and/or hydrotreatment.Unfortunately, for example, due to the pollutent (metal and sulphur compound) of the deactivation metal supported catalyst of conspicuous level, and coke precursors in these material streams, coker gas oil is not easy according to this class ordinary method processing.Coker gas oil is changed into for more situation of selling well overhead product and the petroleum naphtha blend components of transport fuel and therefore follows a large amount of shortcomings.
The other method of known generation gas oil is slurry hydrocracking, and it refers to heavy hydrocarbon feedstocks in slurry phase or optionally in homogeneous catalyst system, uses oil soluble metal catalyzer under the existence of hydrogen and solid catalyst particle (for example, as metal nano aggregate), to transform as metal sulphide compound.Typical slurry method for hydrogen cracking is for example described in US 5,755,955 and US 5,474,977 in.Except the VGO being conventionally present in reactor effluent, slurry hydrocracking produces the refractory asphalt material stream of low value, due to its high viscosity and solids content, described material stream can not promote or even sneak into other products conventionally economically as in oil fuel or synthetic crude.
The concrete source of more and more concerned synthetic crude is pitch earth, seeks blend components to improve its flow performance.This inferior quality hydrocarbon-containing feedstock, by oil sands deposit, for example, reclaims in those of the large Athabasca district discovery of Alberta, Canada and Venezuela and the U.S..Pitch earth is considered to valuable " semisolid ", and oil is originated, and can be refined into many valuable the finished product, comprises transport fuel, for example gasoline or even petroleum chemicals.
In this area, still need to transform or promote to improve efficiency the method for heavy hydrocarbon (for example atmospheric tower and vacuum column Residual oil and gas oil).Also need low value the finished product, comprise the minimized this method of net production of gas oil and pitch.Also need total crude oil refining method, it comprises the former oil residue of lifting, those that are particularly obtained by 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, for example coking, hydrotreatment and/or crude oil fractionation comprehensively distillate streams with production high value, make undesired gas oil recirculation, preferably to disappearing simultaneously.The ability that about it, vacuum column residue is changed into lighter product, SHC is generally known in the art.But, surprisingly, disclose now except changing into more valuable petroleum naphtha and overhead product product and provide other important interests relevant to gained SHC/ coking integrated approach in SHC reactor, coker gas oil (for example delayed coking VGO) feeds in SHC and can suppress coke formation as heavy hydrocarbon feedstocks component or increment.
In typical integrated approach, low-quality coker gas oil combines the total heavy hydrocarbon feedstocks for SHC with the recirculation SHC gas oil of the downstream fractionation/Separation and Recovery by SHC effluent.As mentioned above, although this raw material of part also comprises conventional component conventionally, for example vacuum column Residual oil, the existence of coker gas oil improves SHC reactor effluent quality, particularly at the coking yield about reducing and petroleum naphtha and the overhead product yield of raising.In addition, coker gas oil (1) easily obtains conventionally in a large number, the in the situation that of particularly processing heavy crude in refinery, (2) due to the pollutent of used catalyst in these methods of high-caliber being harmful to (deactivation), be difficult to use FCC, hydrocracking or hydrotreatment further to promote.But, determined now that coker gas oil is attractive increment raw material (for example with vacuum column residue combination), is used SHC effectively cracking to obtain compared with hydrogen and more valuable clean overhead product and optional naphtha products.In addition, according to some embodiments, SHC for example, enters coker entrance with the pitch by product that additional advantage: SHC is comprehensively provided of coking (delayed coking or fluid coking) together with the common atmospheric tower of processing in coking operation or vacuum column Residual oil.In coker, therefore the processing of SHC pitch is allowed this by product is transformed/promote into more hydrocarbon and the solid coke of high value.No matter whether treatment S HC pitch in coker, the gas oil final product that reduces in comprehensive SHC/ coking method, for example yield of the hydrocarbon of boiling point within the scope of VGO 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) is as the clean yield of VGO, because these heavy boiling point fraction recirculation are back to SHC reaction zone, the overhead product of hydrotreatment has sufficiently high api gravity (for example at least 20 °), makes it attractive for sneaking in the synthetic crude of carrying via pipeline.Therefore, the overhead product of hydrotreatment, or even there is no the SHC overhead product of hydrotreatment can be used as only to have minor amount or substantially do not have boiling point be that the high quality transport fuel blend components of the hydrocarbon of the representative temperature (being for example greater than 343 DEG C (650 °F)) of gas oil obtains.
SHC method also can be by the SHC overhead product product of recovery is distillated to streams hydrotreatment together with the straight run distillate being obtained by crude oil fractionation and/or other refineries and is 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 improving processing efficiency and product yield, reduction or eliminate aspect low value refractory by product and/or relevant fund cost reduction.According to specific embodiments of the present invention, crude oil vacuum column bottoms material stream provides a part of heavy hydrocarbon feedstocks of SHC reactor, and for example, in SHC reactor exit and coker gas oil (coking VGO) combination.Another part vacuum column residue or also can be processed in coker from other cuts itself of this tower.In another embodiment, the heavy hydrocarbon feedstocks that coker gas oil or this refinery's gas oil component of a part optionally for example, provide a part to use SHC to process together with straight run gas oil (straight run VGO), the SHC pitch separating with SHC effluent by fractionation for example can enter again, in coker (delayed coking unit or fluid coker) to promote.
Understood these and other aspects and the embodiment that the present invention relates to by following detailed description.
Accompanying drawing summary
Fig. 1 has described a kind of typical method, wherein slurry hydrocracking is incorporated to the clean product with the overhead product by crude production hydrotreatment and coke in the typical flow process figure of refinery with existing coker, wherein has seldom or there is no refractory gas oil as total production of VGO.
Fig. 2 has described second typical integrated approach.
Describe in detail
Embodiment of the present invention relates to slurry hydrocracking (SHC) and combines with coking the purposes that promotes heavy hydrocarbon feedstocks.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 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 interests described above.Except 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 to reduce the total molecular weight of heavy hydrocarbon feedstocks, and/or removes organosulfur and nitrogen compound and metal.According to each embodiment, for example, when in typical gas oil scope (343 DEG C (650 °F)-566 DEG C (1050 °F)) and only 80 % by weight at the most of the boiling point of the heavy hydrocarbon feedstocks of signal portion, conventionally when 60 % by weight heavy hydrocarbon feedstocks are the compound of boiling point more than 566 DEG C (1050 °F) at the most, SHC be improved (for example forming by suppressing coke).
Except 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 DEG C (650 °F) above crude oil atmospheric distillation tower residue, boiling point is 566 DEG C (1050 °F) above crude oil vacuum distillation tower residue, tar, pitch earth, coal oil and shale oil.The raw material of other asphaltenes, for example, comprise that the full cut of heavy crude or tops petroleum crude oil also can be used as the component that SHC processes.Except bituminous matter, these of heavy hydrocarbon feedstocks other may components and other conventionally also contain significant metal pollutant (for example nickel, iron and vanadium), high-content organosulfur and nitrogen compound and Gao Kanglaxun carbon residue.The metal content of this class component can be for example 100-1,000 ppm by weight, and total sulfur content can be 1-7 % by weight, api gravity can be-5 ° to 35 °.The Kang Laxun carbon residue of this class component is generally at least 5%, conventionally 10-30 % by weight.In a word, many heavy hydrocarbon feedstocks components of SHC method, comprise coker gas oil, have make they to the catalysis conversion method of other types as hydrocracking and the harmful performance of fluid catalytic cracking.
The integrated approach of preparing the method for SHC overhead product generally include the heavy hydrocarbon feedstocks that makes to comprise coker gas oil under hydrogen exists by SHC reaction zone so that SHC effluent to be provided.Heavy hydrocarbon feedstocks can, but be not necessarily present in the heterogeneous slurry catalyst system in SHC reactor, wherein catalyzer is solid particulate form.But, with regard to present disclosure, wherein catalytically-active metals is present in liquid phase and the homogeneous catalyst system that is dissolved in heavy hydrocarbon feedstocks (for example as oil soluble metal compound as metallic sulfide) 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.
SHC reaction is conventionally under the recycle gas of the combination of hydrogen exists and be enough at least a portion heavy hydrocarbon feedstocks to be cracked under the condition of lighter boiling point SHC overhead product cut and carry out, and described SHC overhead product cut is reclaimed from the effluent of SHC reactor.The recycle gas of combination for the hydrogen rich stream that for example, reclaimed by the SHC effluent overhead gas stream of high-pressure separator (as) and for replace that SHC reactor or reaction zone consume 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 (thering is " one way " hydrogen) to represent alternative operator scheme, wherein can use and there is a large amount of possible hydrogen source that changes purity.
The recovery of SHC overhead product generally includes and uses SHC effluent, or for example, compared with flash separation and/or the distillation of low boiler cut or its cut (thering is the cut of lower distillation end point), using SHC overhead product as separating with the SHC gas oil of supervening (or unconverted) in SHC effluent compared with low boiling component.Therefore can use single hop flash separation SHC effluent in SHC high-pressure separator, or as selecting, use in as atmospheric fractional tower or SHC atmospheric distillation tower multiple segregation section to reclaim SHC overhead products at SHC separation column.Typical especially embodiment comprises makes SHC effluent enter normal pressure or vapor rectification process tower and for example, using SHC overhead product as overhead product or the (C that have some lighting ends, removes that sides stream
4 -hydrocarbon product) reclaim.Other products reclaim then can by make bottom product or residue thus first (for example normal pressure) SHC separation column enter the second (for example vacuum) SHC separation column and reclaim SHC gas oil (for example heavy VGO) and carry out.Then make at least a portion SHC gas oil be recycled to SHC reactor described above or reaction zone.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 optionally make it stand hydrotreatment as described in more detail below.
If form slurry with heavy hydrocarbon feedstocks, upwards by SHC reaction zone, slurry has the solid content of 0.01-10 % by weight conventionally conventionally.Solid particulate is generally the compound of catalytically-active metals, or the metal of element form, separately or for example load on refractory material, as on inorganic, metal oxide (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.
Comprise 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 for the catalytically-active metals of hydrotreatment, its amount with the required hydrotreatment of effective catalysis and/or hydrocracking reaction mix in heavy hydrocarbon feedstocks using for example provide can solid particulate substantially not in the presence of as petroleum naphtha and/or overhead product product by hydrotreatment what slurry effluent in fractionation compared with low boiling hydrocarbon.Typical metal comprises iron, nickel, molybdenum, vanadium, tungsten, cobalt, ruthenium and composition thereof.Catalytically-active metals can be used as solid particulate and for example, exists as sulfide (iron sulphide) or other ionic compounds using element form or as organic compound or mineral compound.Metal or metallic compound nano aggregate also can be used for forming described solid particulate.
Conventionally, need this metallic compound for example, to be formed as metal sulfate (ferric sulfate monohydrate) original position by catalyst precursor as solid particulate, described precursor, in the environment of hydrotreatment reaction zone, or decomposes or reaction forms the solid particulate (for example, as iron sulphide) of required good distribution and catalytic activity in pre-treatment step.Precursor also comprises the oil soluble organometallic compound containing significant catalytically-active metals, and its thermolysis forms the solid particulate (for example iron sulphide) with catalytic activity.This compound conventionally can high dispersing in heavy hydrocarbon feedstocks, and conventionally under pre-treatment or hydrotreatment reaction zone conditions, change into the solid particulate being included in slurry effluent.The preparation of typical case's original position solid particulate, comprises the precursor pre-treatment of heavy hydrocarbon feedstocks and final required metallic compound is for example described in to US5, in 474,977.
Other suitable precursors comprise that the compound that can change into catalytic activity (or having more catalytic activity) is as the metal oxide of metallic sulfide.In specific embodiments, the mineral of containing metal oxide can be used as the precursor of solid particulate, and it is included in for example, catalytically-active metals (for example iron sulphide) on inorganic refractory metal oxide carrier (aluminum oxide).Bauxite represents special precursor, and the conversion that is wherein contained in the ferric oxide crystal in these mineral is provided as the iron sulphide catalyzer of solid particulate, and therefore, after transforming, iron sulphide loads on the aluminum oxide being mainly present in bauxite precursor.
Condition in SHC reactor or reaction zone generally include the pressure of temperature, 3.5MPa (500psig)-21MPa (3000psig) of 343 DEG C of (650 °F)-538 DEG C (1000 °F) and 1-30 volume heavy hydrocarbon feedstocks/hour/volume described in the air speed in SHC district.In SHC reaction zone, used catalyst and condition are suitable for promoting heavy hydrocarbon feedstocks to provide compared with low boiling component in the SHC effluent that leaves SHC reaction zone, i.e. SHC overhead product cut.SHC overhead product usually used as the distillation end point having conventionally the cut more than petroleum naphtha from total SHC effluent (as mentioned above, optionally remove hydrogen rich stream be recycled to SHC reactor in after) in be recovered.SHC overhead product for example can be used as the distillation end point temperature having and is generally 204 DEG C (400 °F)-399 DEG C (750 °F), the cut that is generally 260 DEG C of (500 °F)-343 DEG C (650 °F) is recovered, and wherein heavier boiling-point compound is recovered with the recirculation of SHC gas oil or in the SHC asphalt material stream that optionally enters coker.
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 feeds SHC effluent (optionally after removing hydrogen rich stream) respectively.Then fractionation (for example, in vacuum tower) higher SHC cut can provide SHC gas oil (for example heavy VGO) and SHC pitch.The replacement scheme separating as single hop in high-pressure separator, SHC overhead product can, by SHC effluent for example, be recovered as sideing stream of SHC atmospheric fractional tower or distillation tower compared with low boiling component by fractionation (using multistage vapour-liquid equilibrium to separate) conduct.Then can be in the future since then the residue of a SHC separation column or bottoms feed the 2nd SHC separation column, for example in vacuum tower for example, so that SHC gas oil, SHC pitch and optionally other cuts, SHC lightweight VGO to be provided.With the comprehensive SHC/ coking method of the hydrotreatment combination of SHC overhead product in, this SHC lightweight of all or part VGO can as described belowly (mix or combination) charging as hydrotreatment district together with SHC overhead product.
The typical embodiments according to the present invention, the yield of SHC overhead product (distillation end point is within the scope of these) is generally at least 30 % by weight (for example 30-65 % by weight) of the SHC effluent weight (combination weight of for example SHC overhead product and SHC gas oil) of combination, conventionally at least 35 % by weight (for example 35-55 % by weight), conventionally at least 40 % by weight (for example 40-50 % by weight).Depend on required final product, SHC overhead product fractionation own for example can be had to the petroleum naphtha and the diesel oil fuel that change distillation end point temperature to obtain.For example, relative light naphthar can be separated with SHC overhead product, it has the distillation end point temperature of 175 DEG C of (347 °F)-193 DEG C (380 °F).According to other embodiments, separable relative heavy naphtha, it has the distillation end point temperature of 193 DEG C of (380 °F)-204 DEG C (400 °F).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 DEG C (280 °F)-160 DEG C (320 °F), 168 DEG C (335 °F)-191 DEG C (375 °F) and 193 DEG C (380 °F)-216 DEG C (420 °F).
Also depend on the concrete separation/fractionation conditions for reclaiming SHC overhead product, this material stream is conventionally containing a large amount of organic nitrogen compounds and organosulfur compound.For example, in this material stream, be substantially generally 0.1-4%, 0.2-2.5% conventionally, conventionally 0.5-2% with organosulfur compound as the total sulfur that the form of alkylbenzene thiophthene exists.In SHC overhead product substantially with organic nitrogen compound as non-alkaline aromatic substance, comprise that the total nitrogen that carbazole (cabazole) form exists will be generally 100ppm-2%, conventionally 100-750ppm.SHC overhead product also contains the polycyclic aromatic hydrocarbons (polyaromatics) of signal portion conventionally, 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 % by weight of SHC overhead product, and the amount of monocyclic aromatics (for example benzene and benzene derivative are as Alkylaromatics) only accounts for 20 % by weight at the most conventionally.
For example, except SHC gas oil (heavy SHC VGO), the heavy hydrocarbon feedstocks of SHC reactor or reaction zone for example comprises, by the coker gas oil (heavy coker gas oil) postponing or fluid coking is produced as mentioned above, and common vacuum column Residual oil.Except SHC and coker gas oil, other typical gas oil components that can be included in heavy hydrocarbon feedstocks comprise that the straight run gas oil being reclaimed by crude oil fractionation is as vacuum gas oil.Other gas oils of producing in refinery comprise diasphaltene gas oil and viscosity breaker gas oil.The combination heavy hydrocarbon feedstocks of gas oil and the SHC reaction zone that comprises these gas oils therefore can be for boiling point is 343 DEG C (650 °F) mixture to the hydrocarbon of 593 DEG C of (1100 °F) distillation end points, and wherein other typical distillation end points are 566 DEG C (1050 °F), 538 DEG C (1000 °F) and 482 DEG C (900 °F).Typical SHC gas oil has the distillation end point temperature of 427 DEG C of (800 °F)-538 DEG C (1000 °F).Under straight run vacuum gas oil condition, distillation end point depends on the cut point cutout (cutoff) between crude oil vacuum separation column, particularly vacuum gas oil and 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 conventionally, and other gas oil component obtain after one or more hydrocarbon conversion reactions.
SHC can be advantageously and hydrotreatment combination, make by the SHC overhead product reclaiming or its cut (for example naphtha fraction or diesel fuel fractions) in hydrotreatment district catalytic hydroprocessing to reduce total sulfur and/or total nitrogen content.According to specific embodiments, for example, can obtain sulphur content for being less than 30 ppm by weight, be conventionally less than 10 ppm by weight, be even less than the naphtha fraction of the hydrotreatment of 5 ppm by weight.Can obtain sulphur content for being less than 50 ppm by weight, conventionally be less than 20 ppm by weight, even be less than the diesel oil fuel of the hydrotreatment of 10 ppm by weight.Hydrotreatment SHC overhead product to be so that the overhead product of hydrotreatment to be provided, or therefore the cut of hydrotreatment SHC overhead product can provide to follow and be suitable for the low-sulfur product of tolerance limit and even super low sulfur petroleum naphtha and diesel oil distillate.According to preferred embodiment, SHC overhead product has the api gravity that is enough to mix in crude oil or the synthetic crude for example being obtained by oil-sand.Typical case's api gravity value is for example, for being greater than 20 ° (25 °-40 °), and is greater than 35 ° (for example 40 °-55 °).
In other embodiments, comprehensively can comprising of SHC method and hydrotreatment for example makes other refineries distillate streams, and for example straight run distillate is by hydrotreatment district or reactor.No matter whether one or more other material are flowed and the processing of SHC overhead product combined hydrogenation, under the existence that hydrotreatment is all flowed at the hydrogeneous material of recirculation of hydrotreating catalyst fixed bed and combination, carry out.Typical hydroprocessing condition comprises the temperature of 260 DEG C of (500 °F)-426 DEG C (800 °F), pressure and the 0.1-10hr of 7.0MPa (1000psig)-21MPa (3000psig)
-1liquid hourly space velocity (LHSV).As understood in the art, (LHSV, with the hr of unit for liquid hourly space velocity
-1represent) be volume of liquid flow rate on catalyst bed divided by bed volume, represent the liquid of the equivalent catalyst bed volume of processing per hour.The inverse of LHSV and reactor residence time is closely related.Suitable hydrotreating catalyst is included in refractory inorganic oxide carrier material, is selected from the metal of nickel, cobalt, tungsten, molybdenum and composition thereof.
As mentioned above, SHC method advantageously with refinery coking operation as delayed coking unit or fluid coker comprehensive, wherein from the coker gas oil of delayed coking or fluid coking, for example heavy coker gas oil or coking VGO enter SHC reaction zone to promote, and are therefore advantageously suppressed in SHC reactor and form coke.Another comprehensive possibility of other SHC/ coking comprises other use by downstream separation and/or fractionation SHC effluent and the SHC pitch reclaiming or higher cut or the cut (for example having the cut of higher initial boiling point) of this effluent.Typical SHC asphalt material stream can for example reclaim in the bottoms by SHC vacuum column.According to the specific embodiments that wherein higher SHC effluent fraction is recovered as the tower bottoms stream of leaving high pressure hot separator or SHC atmospheric fractional tower, can carry out the vacuum fractionation of this tower bottoms stream to obtain the SHC gas oil that is recycled to SHC reactor, and heavier SHC asphalt material stream.SHC pitch for example can enter, in coker (delayed coking unit or fluid coker) so that SHC and coking are further comprehensive, make coker not only for residue at the bottom of transformed eukaryotic void tower tower, and for transforming SHC pitch, obtain other more products of high value by this SHC product thus.Typical case SHC pitch comprises or is substantially being greater than 482 DEG C (900 °F) by boiling point, is conventionally greater than 538 DEG C (1000 °F), is conventionally greater than the hydrocarbon composition of the temperature of 593 DEG C (1100 °F).
Therefore, the present invention relates to promote in the above described manner 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.The internal recycle in this general flow chart or method due to SHC gas oil and SHC pitch, substantially all clean products are overhead product or coke, 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 overhead product of hydrotreatment described above) and coke accounts at least 80% (for example 80-99%) of overall process yield, conventionally accounts at least 85% (for example 85-95%) of this yield.
Other aspects of the present invention relate to use SHC method described above and prepare synthetic crude or synthetic crude blend components.The method comprises to be made to enter SHC method derived from the gas oil of delayed coking unit or fluid coker, and wherein the method is with hydrotreater is optionally comprehensive as mentioned above.Depend on the fractionation conditions for downstream processing SHC effluent, can obtain having substantially all boiling points within the scope of overhead product or the SHC overhead product of lower hydrocarbon.In typical embodiments, be less than 20 % by weight, being conventionally less than 10 % by weight SHC overhead products is the hydrocarbon of boiling point at the temperature that is greater than 343 DEG C (650 °F).This SHC method can be in addition and crude fractionating column comprehensive, make the hydrotreatment together with SHC overhead product of the straight run distillate from crude oil atmospheric distillation tower.VGO and/or can enter SHC reactor or reaction zone (making VGO and the SHC of the recirculation gas oil part for heavy hydrocarbon feedstocks together with coker gas oil) 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 in Fig. 1.Be to be understood that Fig. 1 represents the present invention and/or the rationale relating to.What as having, those skilled in the art of present disclosure knowledge easily understood, according to the present invention, the method for each other embodiments has the configuration, component and the operating parameters that are partly determined by concrete raw material, product and product quality specification.
The embodiment of setting forth according to Fig. 1, slurry hydrocracking (SHC) reactor or reaction zone 20 are merged in the flow process figure of refinery.The heavy hydrocarbon feedstocks 1 of this reaction zone 20 is for example, from coking vacuum gas oil (VGO) the material stream 2 of delayed coking method 30 and the combination of SHC VGO (SHC heavy VGO) recycle stream 3.Another component of the heavy hydrocarbon feedstocks 1 of SHC method 20 is conventionally to contain the stream of the vacuum column residual material from crude vacuum column or tower 40 (or Residual oil) 4 that boiling point is the hydrocarbon of 566 DEG C (1050 °F) above (having cut point temperature).As shown in Figure 1, to be created in the common cut point temperature of fractionation in vacuum column 40 be atmospheric residue or the topping oil flow 13 of 343 DEG C (650 °F) to atmospheric tower 80.
Optionally, 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 DEG C of (650 °F)-566 DEG C (1050 °F).Can optionally directly feed in overhead product hydroprocessing process 50 by a part of this VGO cut 5a or from the different VGO cut 5b of vacuum column 40.Other material streams of the optional increment raw material as hydroprocessing process 50 are the straight run 11 that the overhead product part as crude oil stream 12 of fractionation obtains in crude oil atmospheric tower or tower 80.Other material streams that can hydrotreatment for 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 the light VGO compared with low boiler cut with SHC VGO recycle stream 3.Therefore, SHC overhead product 7, in optional and material stream 11,5b and/or 3a, any combination or all is used from the overhead product 14 obtaining as the hydrotreatment of product, the nitrogen compound with reduction described above and oxidation of sulfur compound impurities and/or the api gravity of total method, and it can be used as the blend components of synthetic crude.
SHC method, comprise SHC reaction zone 20 therefore with comprehensive method for promoting the VGO material stream 2 from delayed coking method 30, as mentioned above, it is advantageously suppressed in SHC reactor or reaction zone and forms coke.Then making total SHC flow out streams 6 stands downstream separation/fractionation operation reclaiming the product that promotes, except deasphalting and makes intermediate recirculation.According to embodiment described in Fig. 1, use high pressure hot separator (HHPS) 60 to separate to reclaim the SHC overhead product 7 of common boiling point more than petroleum naphtha total SHC effluent.Then will be by SHC effluent, the higher cut 8 particularly reclaiming in the bottoms of HHPS 60 fractionation in the SHC separation column 70 usually used as vacuum column operation.SHC separation column flows 9 by SHC VGO recycle stream 3 with SHC asphalt material and separates, and as mentioned above, it is advantageously used for the raw material of delayed coking unit 30.Delayed coking unit 30 produces coke 10 and the coking VGO material stream 2 as recycle stream (in total method), and it is refinery's gas oil component of the heavy hydrocarbon feedstocks 1 of SHC method 20.
Fig. 2 describes alternative flow, its change programme that is embodiment that Fig. 1 paints, and wherein the reference number of Fig. 1 is for similar process stream and equipment shown in presentation graphs 2.According to this embodiment, use first (for example normal pressure) SHC separation column 60-A to replace HHPS (reference number 60 in Fig. 1) to reclaim SHC overhead product 7-A, it is sideing stream of taking out from a SHC separation column 60-A, and for example in the total SHC removing flows out streams 6, has lighting end (for example C
4 -hydrocarbon product).Higher cut 8-A takes out from a SHC separation column 60-A as bottom product, then for example, in second of separation column 70 (vacuum) SHC separation column 70 fractionation in corresponding to Fig. 1.Then can be in the second vacuum fractionation tower 70 Fractionator Bottom product to obtain SHC VGO recycle stream 3, SHC asphalt material stream 9 and SHC VGO cut 3a, the latter can for example, for comparing light boiling point fraction, lightweight VGO with SHC VGO recycle stream 3.
As shown in Figure 2, SHC asphalt material stream 9 is as delayed coking unit, the particularly raw material of coking fractional distillation column 30-A.Use T-shaped valve or switching valve 30-C that coking fractional distillation column bottom product 16 is entered in one of two coke drums 30-B.Then take out coke 10 and using reclaim coker liquids 15 for example as heavy coker gas oil, with choose any one kind of them or multiple lighter coker hydrocarbon product 17 is sent the coking fractional distillation column 30-A for fractionation coking VGO 2 back to together with coker overhead product and/or coking naphtha, can by its in hydroprocessing process 50 with SHC overhead product 7-A and optional other material stream combined hydrogenation processing as mentioned above.
In total method described in Fig. 1 and Fig. 2, wherein by comprehensive to SHC method and delayed coking unit, mainly produce thus the clean product of the overhead product 14 of coke 10 and hydrotreatment.As understood from this specification sheets, whole aspects of the present invention relate to the comprehensive so that refinery operation optimizing of slurry hydrocracking (SHC) and coking.In view of present disclosure, can find out and can realize several advantages 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.There is the scope that can make various variations in above method and do not depart from present disclosure that it will be appreciated by those skilled in the art that of the knowledge that obtained by present disclosure.
Claims (10)
1. an integrated approach of preparing slurry hydrocracking (SHC) overhead product, described method comprises:
A) heavy hydrocarbon feedstocks that makes to comprise coker gas oil, SHC gas oil and at least one crude oil atmospheric distillation tower residue, crude oil vacuum distillation tower residue, tar, pitch earth, coal oil or shale oil under hydrogen exists by SHC reaction zone so that SHC effluent to be provided;
B) by the SHC separated from bitumen existing in SHC gas oil and SHC effluent;
C) make described SHC gas oil be recycled to described SHC reaction zone; With
D) 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 described SHC effluent, and makes described SHC gas oil be recycled to described SHC district, and described heavy hydrocarbon feedstocks comprises described SHC gas oil and described coker gas oil thus.
4. according to the method for claim 3, wherein by SHC effluent described in flash separation or fractionation using described SHC overhead product as separating with described SHC gas oil compared with low boiling component.
5. according to the method for claim 1, its also comprise by the overhead product raw material that comprises described SHC overhead product in hydrotreatment district hydrotreatment to obtain the overhead product of hydrotreatment.
6. according to the method for claim 5, wherein, except described SHC overhead product, described overhead product raw material also comprises straight run.
7. according to the method for claim 5, the overhead product of wherein said hydrotreatment has the api gravity of at least 20 °.
8. according to the method for claim 1, it also comprises by SHC effluent described in flash separation or fractionation and reclaiming SHC pitch as 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. by slurry hydrocracking (SHC), coking and hydrotreatment comprehensively being prepared to a method for overhead product hydrocarbon component, described method comprises:
A) coker gas oil that make to comprise SHC gas oil, is obtained by delayed coking unit or fluid coker and the slurry of solid particulate hydrogen exist under by SHC reaction zone so that SHC effluent to be provided;
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) by the hydrotreatment of described SHC overhead product to obtain as the synthetic crude of 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 | 2008-11-15 | ||
| US12/271,851 US20100122932A1 (en) | 2008-11-15 | 2008-11-15 | Integrated Slurry Hydrocracking and Coking Process |
| PCT/US2009/059644 WO2010056437A2 (en) | 2008-11-15 | 2009-10-06 | Integrated slurry hydrocracking and coking process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102216429A CN102216429A (en) | 2011-10-12 |
| CN102216429B true 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 |
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| Country | Link |
|---|---|
| US (1) | US20100122932A1 (en) |
| CN (1) | CN102216429B (en) |
| CA (1) | CA2742016A1 (en) |
| WO (1) | WO2010056437A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| TR201906967T4 (en) * | 2013-03-15 | 2019-06-21 | Bechtel Hydrocarbon Technology Solutions Inc | Systems and methods for external processing of flash field gas oil from a delayed coking 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 |
| WO2016096982A1 (en) | 2014-12-17 | 2016-06-23 | Haldor Topsøe A/S | Process for conversion of a 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 |
| KR102474323B1 (en) * | 2017-07-17 | 2022-12-08 | 사우디 아라비안 오일 컴퍼니 | Systems and methods for processing heavy oil |
| 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 |
| US11566190B2 (en) * | 2020-07-24 | 2023-01-31 | Lummus Technology Llc | Integrating ebullated bed hydrocracking and coking units |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20100122932A1 (en) | 2010-05-20 |
| WO2010056437A3 (en) | 2010-07-01 |
| CA2742016A1 (en) | 2010-05-20 |
| WO2010056437A2 (en) | 2010-05-20 |
| CN102216429A (en) | 2011-10-12 |
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