CN1238473C - Two-stage hydrocracking process - Google Patents

Two-stage hydrocracking process Download PDF

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CN1238473C
CN1238473C CNB018230563A CN01823056A CN1238473C CN 1238473 C CN1238473 C CN 1238473C CN B018230563 A CNB018230563 A CN B018230563A CN 01823056 A CN01823056 A CN 01823056A CN 1238473 C CN1238473 C CN 1238473C
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hydrocracking
zone
hydrogen
product
hydrocracking zone
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CN1492918A (en
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V·P·塔卡尔
D·L·埃利格
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention relates to a two-stage hydrocracking method which is characterized in that a second hydrocracking zone is operated at low pressure beneficial to the cracking of a high paraffin hydrocarbon effluent of a first hydrocracking zone, a hydrogen supplemented gas material flow partially compressed is conveyed into the second hydrocracking zone, and subsequently, gas recovered from an effluent of the second hydrocracking zone is compressed to form supplemented gas conveyed to the hydrocracking zone in the first stage. The second hydrocracking zone does not contain a recycle gas material flow.

Description

Two-stage hydrocracking process
Invention field
The present invention relates to be called in this area the hydroconversion process of hydrocracking.This method commercialization is used in the refinery with the last running of reduction crude oil or the molecular-weight average of middle runnings.The present invention more directly relates to the comprehensive hydrotreatment/method for hydrogen cracking with specific hydrogen make-up flow path.
Background of invention
Bulk petroleum deutero-hydrocarbon is converted into value hydrocarbons cut as motor spirit by the method for refining that is called as hydrocracking.In this method, heavy feedstocks is contacted with the fixed bed of solid catalyst under the condition at high temperature and high pressure in the presence of the hydrogen, make most of charging molecule be cracked into less and have more volatile molecule.Oil-fired high economic worth has promoted the extensive progress of hydrocracking catalyst and relevant processing technology.
Crude petroleum fractions contains a large amount of organosulfurs and nitrogen.Sulphur and nitrogen must be removed to satisfy the specification requirement of modern fuels.The running of removing or reducing for hydrocracking reactor of sulphur and nitrogen also is useful.Sulphur and nitrogen are to be removed by the process that is called as hydrotreatment, and in this process, organosulfur and nitrogen are converted into hydrogen/sulfide and ammonia.Because the similarity of hydrotreatment and the employed treatment condition of hydrocracking, often two processes are combined into one and have the single Integrated Processing Unit of reactor and common product recovery part independently continuously that is specifically designed to two reactions.
Correlation technique
Hydrotreatment and hydrocracking all are the commercial methods of widespread use.The economic and practical of the highly significant of method for hydrogen cracking makes people pour into great effort in this method of improvement and the better convenient catalyst that exploitation is used for this method.The 174-183 page or leaf that is entitled as " hydrocracking science and technology " (Hydrocracking Science and Technology) book that Julius Scherzer and A.J.Gruia work, Marcel Dekker Inc.1996 publish provides the summary of different hydrocracking process flow scheme and classification thereof and to the description of hydrocracking catalyst.Figure 10 .2,10.3 and 10.4 shows the hydrotreating reactor that is positioned at the hydrocracking reactor upstream.As pointing out in this place, hydrotreating reactor reduces the sulphur that is combined in the target oil molecule and the content of nitrogen is a kind of way that has gained public acceptance thereby at first the feed stream of hydroeracking unit is sent into.Can use two placed in-line hydrocracking reaction districts, thereby have the intermediate product of certain form to separate the amount that reduction is brought the hydrogen sulfide and the product hydrocarbon of second hydrocracking zone into by hydrocarbon phase between the hydrocracking zone.Shown in Figure 10 .4 and 10.5, such device is commonly called the two-stage hydrocracking device.
Employed high pressure makes and must to make great efforts to keep all with the pressure of the hydrocracking ejecta that is recycled and must make great efforts product recovery zone employing in treating processes to reduce pressure as separation mechanism in the hydrocracking.Thus, typically, the ejecta of high-pressure reactor (for example hydrocracking reactor) is flowed in the container of operating under the pressure near the reaction zone top hole pressure that is called as high-pressure separator (HPS).The steam logistics that reclaims from HPS normally is circulated to the recycle gas of reactor or the precursor of hydrogen-rich gas stream.
Common way is to use a multi-stage compressor or a series of compressor with hydrogen make-up logistics pressurization and use another compressor that recycle gas stream is pressurizeed in the method for hydrogen cracking.The use of two different compressors is shown in for example US-A-4,197,184.
Prior art is also included within the method for hydrogen cracking carries out adsorption treatment to remove polynuclear aromatic (PNA) compound to the hydrocarbon liquid phase recycle stream, as US-A-4, and 447,315 and US-A-5, shown in 190,633.
Summary of the invention
The present invention is a kind of two-stage hydrocracking process, and its Partial Feature is to be to have new hydrogen flow path.All hydrogen make-up stream enters in the treating processes by the subordinate phase hydrocracking reactor, and the working pressure of this subordinate phase hydrocracking reactor is low, is enough to adopt three grades of partial gases of make-up gas compressor.The steam that will reclaim from the subordinate phase reactor is sent in the third stage of compression zone.The low pressure that has been found that subordinate phase hydrocracking reaction district helps uncracked alkane in the cracking fs hydrocracking reactor.Therefore, preferred operational condition of subordinate phase and technical process produce and have synergitic influencing each other.
The feature of the embodiment of wide region of the present invention is a kind of two-stage hydrocracking process, this method comprise hydrogen and comprise feed stream that boiling point is higher than 371 ℃ hydrocarbon be fed in comprise first pressure hydrocracking condition down and contain the first hydrocracking reaction district of hydrocracking catalyst, and produce the first hydrocracking reaction district ejecta that comprises hydrogen, hydrogen sulfide, unconverted feed component and product hydrocarbon; The first hydrocracking zone ejecta is separated to produce the recycle gas stream and first liquid process streams, first liquid process streams is sent into the bottoms that the product fractionation zone produces overhead product product logistics and comprises unconverted feed component; The second hydrocracking reaction district under the alkane selective hydrogenation cracking conditions that comprises the second lower pressure is sent in bottoms and the logistics of hydrogen make-up gas, produce the second hydrocracking zone ejecta logistics; The second hydrocracking zone ejecta logistics is separated into vapor phase stream and liquid phase stream and liquid phase stream is sent into the product fractionation zone; With vapor phase stream compression and with vapor phase stream as a supplement gas stream send into the hydrotreatment reaction zone.In this embodiment, first hydrocracking zone can comprise with the independent bed or the hydrotreating catalyst of reactor types, and is preferably operating under the pressure than the high 2068kPa of pressure in second hydrocracking zone at least.
Brief description of the drawings
Accompanying drawing is a process flow sheet of having simplified, and show among the figure that hydrogen make-up enters subordinate phase hydrocracking reactor 27, and the steam flow of this reactor ejecta is sent into the third stage 31 of the make-up gas compressor that uses in the flow process.
Detailed Description Of The Invention and embodiment preferred
The crude oil major part of producing can not directly be used as modern fuels or petrochemical material.If above-mentioned crude refining will must be increased air-polluting sulphur and nitrogen to slough to be present in the fuel.Another purpose that crude oil must be refined is to reduce the molecular-weight average of crude oil heavy component, thereby satisfies the volatility of fuel or the requirement on the flowability.At last, refining is to satisfy concrete hydrocarbon product quality standard to require necessary.
Required refining can realize with several method.One of method of generally acknowledging is to carry out continuous catalytic hydrogenation to handle and catalytic hydrocracking.This is a kind of perfect method of using in many petroleum refineries.The present invention relates to the improvement of two-stage hydrocracking flow process, be intended to reduce the cost of device and improve it potentially distillating product.
Multiple petroleum derived feed can be added in the treating processes.Typical raw material comprises that almost any boiling point is higher than about 204 ℃ heavy mineral oil or synthetic oil cut.Therefore, the raw material that can expect is for example straight run gas oil, vacuum gas oil, metal removal oil, coker overhead product, catalytic cracking unit overhead product and analogue.Preferred raw material should not contain the bituminous matter that can predict.Hydrocracking raw material can contain the nitrogen of 1ppm to 1.0 weight %, exists with the organic nitrogen compound form usually.The sulfocompound that is enough to provide greater than the sulphur content of 0.15 weight % also is provided raw material usually.Above-mentioned raw materials can also contain list or polynuclear aromatic compound with 35 volume % or higher amount.The boiling point that enters the compound in the charging in the hydrotreatment district can be in the wide region between about 204 ℃ to about 593 ℃, and in the preferred scope between about 316 ℃ to about 550 ℃.
In the representative example of a conventional method for hydrogen cracking, heavy gas oil added in the treating processes and with the hydrocarbon recycle stream mix.The mixture of resulting these two kinds of liquid phase streams is heated in indirect heat exchange equipment and mix with hydrogen-rich gas stream subsequently.The mixture of reinforced hydrocarbon, recycle hydrocarbons and hydrogen heat in process furnace also be warming up to desirable hydrocracking reaction district temperature in thus.In reaction zone, the mixture of hydrocarbon and hydrogen contacts with one or more solid hydrocracking catalyst beds that maintain under the hydrocracking condition.The hydrocarbon that this contact causes entering in a large number reactor is to lower molecular weight thereby also be the conversion of lower boiling molecule.
Produced the reaction zone ejecta logistics of the mixture that comprises in the reaction residual hydrogen that do not consume, light hydrocarbon (for example methane, ethane, propane, butane and pentane) that hydrocarbon charging cracking forms and other byproduct of reaction (for example hydrogen sulfide and the ammonia of hydrogenating desulfurization and hydrodenitrification reaction formation) thus.The reactor ejecta also contains desirable product hydrocarbon and the unconverted hydrocarbon charging that is higher than desired product boiling range of some boiling points in gasoline, diesel oil fuel, kerosene and/or oil fuel boiling range.Thus, hydrocracking reaction district ejecta comprises the wide region of all cpds and the mixture of multiple class.
Typically, hydrocracking reaction district ejecta and catalyst bed are disengaged, realize heat recuperation, deliver to then in the steam-liquid displacement zone that generally includes at least one high-pressure separator thereby carry out heat exchange with the charging of delivering to reaction zone.Before separating, this can carry out extra cooling.In some cases, can use heat-lightening to steam separator in the upstream of high-pressure separator.Another selection is to use " cold " separator that is intended to remove condensation product from the steam that comes from heat separator.To send into the product recovery zone that comprises one or more separation columns from the liquid that these steams-liquid displacement zone reclaims.The isocrackate recovery method is on record, the method for routine can be used for the present invention.
In many cases, total conversion obtained in the hydrocracking reactor is incomplete, and some heavy hydrocarbon is removed from the product recovery zone as " drag stream " of discharging from the product fractionation plant.From hydrocracking process, discharge drag stream and can allow in reaction zone, to adopt not too exacting terms.The amount of drag stream can wide region for the 1-20 volume % of process feeds logistics in, but preferred in the scope of 2-10 volume %.Unconverted hydrocarbon can be circulated to fs or subordinate phase, preferred cycle is to subordinate phase.If the comprehensive treating process process comprises hydrotreating reactor, recycle stream can be admitted in the fs hydrotreating reactor.Also it directly can be sent in the fs hydrocracking reactor.
On hydrotreatment and hydrocracking catalyst and Technology, obtained remarkable progress in recent years.But, the commercialization method for hydrogen cracking is being that the selectivity that has aspect the hydrocarbon of the boiling point in the selected boiling range is far from perfection with feedstock conversion.Compromise between operational variable is that optimization method compares need, and optionally improves the target that is still whole industry.The purpose of present method is to provide a kind of processing only to need the selective hydrogenation cracking method of limited cracking with the relative lightweight charging that is converted into desired product.Specific purposes of the present invention provide a kind of its boiling point that is used to contain significant quantity selective hydrogenation cracking method of the feed stream of the hydrocarbon in desired product boiling range.
In the method, preferably at first make feed stream through hydrotreating step.Traditionally, this implements as the means of removing desulfuration and nitrogen from raw material, and its purpose is to prepare raw material is used for the downstream hydrocracking reactor.One of reason of doing like this is that lower sulphur and nitrogen content can increase the hydrocracking catalyst activity that has observed.But hydrotreatment is dispensable.For example, that hydrotreatment is become is unnecessary in the use of amorphous in the fs (nonzeolite) hydrocracking catalyst.Shown in reference, usually hydrotreatment is combined with first hydrocracking stage.This can realize by the party upstream that independent hydrotreating reactor is directly placed the front of first hydrocracking reactor or actually hydrotreating catalyst is loaded in hydrocracking catalyst.
Hydrotreatment is to improve charging quality step rather than conversion or cracking step.The hydrotreating reactor ejecta preferably comprises the hydrocarbon mixture that has with the identical boiling range of charging that enters the hydrotreatment district.The conversion that a small amount of (preferably being less than 10%) undertaken by cracking only takes place in the hydrotreatment process.Most preferably in the hydrotreatment district, only be less than 5% conversion.The conversion that is taken place will produce some low boiling hydrocarbons, change but most of charging by the hydrotreatment district small boiling point only takes place preferably.Thus, carry out fractionation is the ejecta of downstream hydrocracking zone with what produce the logistics of final product overhead product.Conversion in hydrotreating step is normally undesirable, because it has reduced the productive rate of desirable middle runnings product.The term of Shi Yonging " conversion " refers to the feed stream molecule is transformed into the required chemical transformation of product hydrocarbon of the part of the overhead product that reclaims from reaction zone separately herein.Thus, conversion relates to the variation of boiling point rather than relates generally to hydrogenation and the chemical transformation of desulfurization.
The HPS container can contain some limited separation subsidiaries or for example tower tray or structure weighting material, thereby promotes to separate the better separation that can provide than simple single stage flash.But, thick wall of container of the high pressure requirement in this container and pipeline, this greatly increases equipment cost, has reached because of the too expensive degree that can not use bigger high-pressure separation apparatus (for example tower).Do not have the backflow of HPS or boil again.Therefore, the separation in the high-pressure separator will be coarse, and the cut of discharging from HPS has suitable overlapping at composition.
In the common usage of hydrocracking technology, high-pressure separator is to operate under the pressure near upstream reactor.Some pressure can take place descend, for example fluid shifts time institute's inherent pressure by pipeline and control valve and descends, but HPS is that 1034kPa operates under with interior pressure in the pressure difference with upstream reactor usually.This cost to the highly significant that preferably compresses again for the hydrogen-rich gas of avoiding being circulated in the reaction zone that do not reduce pressure among the HPS increases.
Typically, hydrocracking process is the highest processing method of pressure in the petroleum refinery.Therefore, the pressure that does not have to supply with near hydrocracking reactor in the reaction process anaplerotic reaction, consume with ejecta in the hydrogen make-up of the hydrogen that loses.Therefore, need to increase the pressure of charging or hydrogen make-up.Typically, this is to realize by the dedicated compressor that is called as make up compressor.Use independent recycle compressor to make the gas stream circulation of process.Using stage compression in comprising the equipment of make up compressor is a kind of basic way.This is because realize the compression of this type in a step, and for example from 689kPa to 17,237kPa needs much bigger energy input.
Accompanying drawing is a process flow sheet of having simplified, and wherein shows the needed common equipment of this method of enforcement, for example valve, pump and Controlling System.Referring to accompanying drawing, feed stream enters technological process by pipeline 1 and mixes with the rich hydrogen makeup gas stream by pipeline 2.The term of Shi Yonging " richness " refers to that the volumetric molar concentration of the chemical substance of indication or a compounds is higher than 50% and preferably be higher than 70% herein.Mixture with hydrogen make-up and feed stream mixes with the recycle gas stream of pipeline 12 subsequently.If necessary, use the equipment that does not have to show that feed stream is heated.The hydrotreatment reaction zone of representing with reactor 5 is sent in charging and hydrogen by pipeline 4.The reaction that occurs in this district produces the light hydrocarbon that hydrogen sulfide and ammonia and some are produced by undesirable side reaction, but micro-cracking only takes place the heavier hydrocarbon that enters reactor.Form the logistics of mixed phase hydrotreatment reaction zone ejecta thus and send into the first hydrocracking reaction district of reactor 7 representatives by pipeline 6.Reactor 7 is converted in the major part of the feed compound that is enough to enter under the condition of compound of lower molecular weight and moves.These conditions generally include be higher than about 12, the pressure of 409kPa, but pressure can be low to moderate 10,342kPa.Usually use 13,788 to 17, the pressure of 237kPa.Produced for example mixed phase first hydrocracking zone ejecta logistics of hydrogen and hydrogen sulfide, reaction product and the unconverted feed hydrocarbon of liquid phase of contained gas thus.
The ejecta logistics of the first hydrocracking reaction district is sent into high-pressure separator (HPS) 9 by pipeline 8.The design of this container and operation are the liquid phase streams of removing in the vapor phase stream of removing to the pipeline 10 for the mixed phase mixture separation that will enter and the pipeline 13.Subsequently vapor phase stream is sent into pipeline 10 as recycle gas stream.Because recycle gas stream is with the pressure recovery that reduced, must use the recycle compressor 34 with the desirable inlet pressure of its compression and back because of the pressure drop in two reactors and the pipeline.Liquid phase stream contains the hydrocarbon and the unconverted feed hydrocarbon of most product cut boiling range.The product that these materials are only sent into by separation column 14 representatives by pipeline 13 reclaims and the disengaging zone.Thereby between HPS9 and tower 14, carry out the additional vapor liquid of one or many usually and tell most of light hydrocarbon (for example methane and propane) that produces as by product.
Usually do not wish a large amount of these type of light compounds are sent into the tower that produces overhead product.Therefore, the liquid of discharging from HPS 9 flows into the tower after can steaming separator or cold high pressure separator or both by the conventional heat-lightening that does not show in the accompanying drawings.These be in usually separator before the product recovery tower and extraction column and product recovery tower itself all with volatile matter for example hydrogen sulfide drive in the vapor phase of discharge.Not the overhead product product and the unconverted compound of the recovery of sulfide hydrogen and (validity that depends on the upstream hydrotreatment) organosulfur have been stayed substantially thus.Low-sulfur and nitrogen content help the activity of the hydrocracking catalyst in the subordinate phase usually.
Depend on that a plurality of specific refineries factor will send into the compound separation of product fractionation zone and become one or more overhead product product logistics.Can use two towers to implement this separation, wherein the lighting end extraction column often is positioned at before the principal product separation column.The overhead product product can comprise the petroleum naphtha boiling range product of pipeline 15, the kerosene boiling range product of pipeline 16 and the diesel boiling range product of pipeline 17.Hydrocracking zone seldom can carry out 100% conversion that is fed to product, but is that part charging between about 5 to 40 volume % is discharged from process as " unconverted " or " viscosity " material with ratio.Although it is unconverted that this material is classified as, this material has experienced considerable hydrogenation and desulfurization is handled, and therefore, compares with corresponding feed compound, and this material has higher quality usually.The cracking that takes place in the technological process also can change the relative composition of these heavy material, thereby makes more difficult cracked or more resistant to elevated temperatures compound concentrations than its concentration height in charging.The term of Shi Yonging " unconverted " refers in the logistics of spawn overhead product to be higher than the compound that the part of the logistics of desired value is discharged as boiling point from the product fractionation zone herein.
The logistics that will comprise unconverted hydrocarbon materials is discharged from tower 14 by pipeline 18.This material contains the paraffins of greater concn usually than feed stream.If wish, can randomly the part of unconverted material be extracted out as drag stream from process.Preferably the unconverted material of pipeline 18 is sent into adsorption zone 19, the design of this adsorption zone and operation are in order optionally to adsorb polynuclear aromatic compound (PNAs).The technology of cycle of treatment logistics has obtained commercialization and has used and be described in for example US-A-4 in the method for hydrogen cracking, and 447,315, US-A-4,618,412, US-A-4,954,242 and US-A-5, in 190,633 reference such as grade.PNA removes and helps avoiding deposition and reduction effectiveness of heat exchanger in its cold part in process (for example heat exchanger).PNA these positions deposition can cause in pipeline and the interchanger over-drastic pressure drop and reduce heat exchanger effectiveness.The main purpose of removing PNAs in present method is the steady running that promotes the downstream hydrocracking zone.Owing to preferably depress operation at low hydrogen, the deposition of PNA can make in this district activity of such catalysts and work-ing life with greater than normal degree reduction.This PNA removes the district and can operate under the condition of the bottom of tower 14 discharge logistics.Multiple sorbent material (comprising aluminum oxide) is known, preferably uses gac.To produce the processing logistics that records the lower no conversion hydrocarbon of PNA content by the listed method of reference after the contact.
Treated hydrocarbon stream is mixed from 19 discharges of PNA adsorption zone and with the hydrogen-rich gas stream that pipeline 25 is carried by pipeline 20.In the method, this gas stream is the makeup gas stream of whole process and preferably extracts from the second stage 24 of three grades of compressed sequences.The flow velocity of makeup gas stream should satisfy desirable hydrogen concentration in second hydrocracking zone in downstream usually.If feed stream only need seldom hydrotreatment or owing to the hydrogen demand in certain other the reason treating processes is low, then use the makeup gas stream of recycle gas filling pipeline 25.But, preferably do not have recycle gas to enter second zone of cracking.Preferably will compress and feed first hydrocracking zone from all gas that the second hydrocracking zone ejecta reclaims again.Further preferably only use a HPS to implement gas delivery as shown in the figure.
If necessary, with the heating of the mixed phase stream of unconverted hydrocarbon and hydrogen, and only feed in the second hydrocracking reaction district by reactor 27 representatives by pipeline 26.This reactor contains the bed of hydrocracking catalyst and operates under alkane selective cracking condition, and the key distinction of the condition in this condition and fs is its relative low hydrocracking pressure.The preferred working pressure in this district is about 8270 to 12,400kPa.Have been found that with traditional elevated pressures of use in first hydrocracking zone 7 and compare that so low pressure promotes the cracking of paraffins.
The distinctive feature of another of this method is to use second stage hydrogen make-up as unique hydrogen logistics of sending into the subordinate phase hydrocracking zone.It is relevant with " lower pressure helps the hydrocracking conversion of paraffins in subordinate phase " this counterintuitive understanding being done like this.This comes from relevant alkane hydrocracking research, and is considered to derive from the dehydrogenation step of cracking mechanism.Depend on its source, typical fresh feed can contain the aromatic hydrocarbon of 35 to the 50 volume % that have an appointment.The liquid circulation logistics of hydrocracking process will have much lower aromatic content, and its representative total aromatics substrate concentration is less than 10%.
The hydrogen make-up of being sent into process by pipeline 21 is compressed in first step compressor 22 and is sent into the second stage or second compressor 24 by pipeline 23.Depend on the compressor section design that comprises these three compressor stages, pipeline 23 can be in compressor section inside.Preferably will come from partial all gas logistics subsequently and send into second hydrocracking reactor by pipeline 25.This layout makes the hydrogen make-up of pipeline 21 use the mode of the pressure of three grades of compressions to be admitted to technological process with domination.And only need the one-level compression need send into hydrogen make-up with higher pressure in the front that make-up gas feeds second hydrocracking zone time.
Because the benefit of this point and new hydrogen flow path, the capital and the running cost that relate to gas compression are reduced.But lower working pressure has lowered the cost of process vessel and pipeline in the subordinate phase, thereby has brought the bigger reduction of construction investment.Second hydrocracking zone preferably be lower than about 12,409kPa and operating under the inlet pressure than the low 2068kPa of the inlet pressure of leading to first hydrocracking zone (comprising any hydrotreatment the preceding district) at least.Depend on Several Factors, second hydrocracking zone can be than operating under the inlet pressure more than the low 3450kPa of first hydrocracking zone.Employed lower pressure has brought another advantage of this method in the subordinate phase.Oneself is through finding that this lower pressure increases the conversion of alkane, and this conversion has improved product quality by the pour point that reduces the diesel boiling range hydrocarbon that is reclaimed usually.
The hydrocarbon that reclaims as drag stream at the bottom of the tower of product recovery tower can be the product of high value, but can not be considered to purpose overhead product or converted product for this transformation definition.Usually the side line of desirable hydrocracking " overhead product " product as the product separation column reclaimed, comprise petroleum naphtha, kerosene and diesel oil distillate in the product.The products distribution of present method by feed composition and under the conversion rate at reaction zone under the selected operational condition selectivity of catalyst determined.Therefore, it has considerable variation range.It is the production of about 127-371 ℃ middle runnings that present method is specially adapted to as, boiling spread that the ASTM test procedure is determined by being correlated with.
Term " middle runnings " comprises diesel oil, aviation kerosene and kerosene boiling range cut.Term " kerosene " and " aviation kerosene " refer to about 127-288 ℃, and diesel boiling range refers to the hydrocarbon boiling point of 127-371.It has been generally acknowledged that gasoline and naphtha fraction are C5 to 204 ℃ of whole cuts of available hydrocarbon.The boiling range of the various product cuts that reclaim in any specific refinery will be along with factors such as character, local market, refinery and the product prices of for example crude petroleum sources and is changed.Further about kerosene and diesel fuel properties details referring to ASTM standard D-975 and D-3699, about the character details of aero-turbine charging referring to ASTM standard D-1655.These definition regulations be present in inherent variation range in charging between the different refineries and the desirable product.Typically, this definition requires the production boiling point to be lower than about 371 ℃ overhead product hydrocarbon.
Although the hydrotreatment district is maintained at and it is characterized in that under the hydroprocessing condition and hydrocracking zone is maintained under the hydrocracking condition, these conditions can be similar to a certain extent.The pressure of being kept in hydrotreatment and the hydrocracking reaction district all should be at about 6895-17, in the wide region of 237kPa.Preferably in first hydrocracking zone, use and be higher than 10, the pressure of 342kPa.Reaction zone is with every meter 3843 to 3033 standard rices 3The hydrogen of (every barrel of raw material 5,000 to 18,000 standard cubic foot hydrogen) moves with the ratio of hydrocarbon.Be higher than every meter in preferred this ratio of each hydrocracking zone 31100 standard rices 3Thus, although second hydrocracking zone is operated under lower pressure, this district is under the gentle hydrocracking condition.The hydrotreatment district can operate under about 232-354 ℃ temperature in.Hydrocracking zone can be operated under 338-427 ℃ temperature in.In the method, the operational condition of reaction zone comprises that liquid hourly space velocity is about 0.2 to 10hr -1, and be preferably about 1.0 to about 2.5hr -1
The preferred embodiments of the invention be characterized as a kind of two-stage hydrocracking process, comprising at least first step of first hydrogen fill-in stream by the make-up gas compressor train is compressed to first intermediate pressure; To comprise boiling point is higher than about 371 ℃ hydrocarbon feed stream, recycle hydrogen logistics and the second hydrogen make-up logistics and is fed in the hydrotreatment district under the hydroprocessing condition and produces and comprise the hydrotreatment district ejecta logistics that hydrogen, hydrogen sulfide and boiling point are higher than about 371 ℃ unconverted feed component; The ejecta logistics of hydrotreatment district is fed in the hydrocracking condition that comprises first pressure descends and contain first hydrocracking zone of hydrocracking catalyst, and produce the first hydrocracking zone ejecta logistics; The first hydrocracking zone ejecta logistics is separated, produce the recycle gas stream and first liquid process streams, this first liquid process streams is sent into the product fractionation zone, produce overhead product product logistics and contain the bottoms of unconverted feed component; Bottoms by the PNA adsorption zone, is sent into second hydrocracking zone under the alkane selective cracking condition that comprises the second lower pressure with the first hydrogen make-up gas logistics then together, produce the second hydrocracking zone ejecta logistics; The second hydrocracking zone ejecta logistics is separated into vapor phase stream and liquid phase stream, and liquid phase stream is sent into the product fractionation zone; Vapor phase stream in the end is compressed to the second higher pressure in the one-level make-up gas compressor train, and subsequently vapor phase stream is replenished logistics as second hydrogen and send into the hydrotreatment reaction zone.
Present method can be used two kinds of dissimilar catalyzer, hydrotreating catalyst and hydrocracking catalysts.This catalyzer of two types has a lot of similarities usually.For example, they can have more similar particle shape and granularity.Common two kinds of catalyzer all comprise inorganic carrier material and at least a metal hydride.But all the process adjustment is to realize different functions owing to each class catalyzer, and two class catalyzer also make a marked difference.One of the most tangible difference is that hydrocracking catalyst also comprises one or more acid cracking components (for example silica-alumina and/or Y-zeolite).Hydrotreating catalyst does not generally contain zeolitic materials or molecular screen material, only comprises one or more metals that are positioned on the amorphous alumina usually.In others, for example at aspects such as the metal that uses as hydrogenation component, the distribution of particle pore volume and density, two class catalyzer also have difference.The catalyzer that is applicable to the reaction zone of present method can be available from several retailer.
Typically, hydrocracking and hydrotreating catalyst all contain the base metal hydrogenation component that is selected from nickel, cobalt, molybdenum and tungsten and may contain promotor, for example are stated from the phosphorus compound on the inorganic oxide catalyst.Metal hydride often is group vib and/or VIII family metal component, and is about 2 to about 18 weight % (in common metal oxide) based on the concentration of final each underlying metal of catalyzer.The platinum metals preferably exists with the low concentration of about 0.1 to 1.5 weight %.The preferred form of catalyzer is the extrudate with symmetric shape of cross section (preferred cylindric or multi-blade).The particulate cross-sectional diameter is .635mm to 3.175mm (1/40 to 1/8 inch) normally, and preferred .794mm to 2.116mm (1/32 to 1/12 inch).US-A-4 has shown four lobate cross section shapes of the clover shape of similar four leaves in 028,227.This patent and US-A-4,510,261 have also described other shape that can be used for catalyzer.
Preferred high-activity hydrogenation catalyst comprises hydrogenation component, and they are included in aluminum oxide porous nickel and the molybdenum of extruding on the carrier that contains phosphorus compound.US-A-4,738,944, US-A-4,818,743 and US-A-5,389,595 provide the production details of the hydrotreating catalyst that contains these four kinds of components, and above-mentioned patent is incorporated herein this paper.
That hydrotreatment and hydrocracking catalyst all preferably comprise is highly porous, form evenly and with respect to infusible solid support material under the employed condition in the hydrocarbon conversion process.Catalyzer can comprise the various solid support materials that are used for hydrocarbon conversion catalyst traditionally, for example comprises the refractory inorganic oxide of aluminum oxide, titanium dioxide, zirconium dioxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide or silica gel, clay etc.The solid support material of preferred hydrotreating catalyst is an aluminum oxide.
The composition of catalyzer and physical properties (for example shape and surface-area) are not considered to have determinate to use of the present invention.For example, catalyzer can exist with the form of ball, sheet, particle, fragment, ball or various special shape (for example tri-lobed extrudate), is positioned in the reaction zone as fixed bed.In addition, can be applicable to the moving bed reaction district (wherein reinforced the and catalyzer of hydrocarbon with adverse current or and the form of stream by) form prepare catalyzer.Another kind of select to be to use fluidized-bed or boiling bed hydrogenation cracking case (wherein charging is upward through the catalyst bed of turbulent segmentation cloth) or suspension type reaction zone (wherein catalyzer mixes and starches in charging, and the mixture that obtains is transported in the reaction zone.Charging can be passed through reactor in mobile mode up or down with liquid phase or mixed phase.Thus, reaction zone must not be a fixed bed system as shown in the figure.
Granules of catalyst can comprise oil droplet or the extrusion molding known with any method preparation well known in the prior art.The preferred catalyst mode that uses in present method is an extrudate.
Can be by using oil drop method, for example at US-A-2,620,314, US-A-3,096,295, US-A-3,496,115 and US-A-3, described in 943,070, above-mentioned patent is incorporated herein this paper.Be formed for the spherical catalyst of the hydrotreatment part or the hydrocracking part of present method.The mixture that this method preferably includes molecular sieve, alumina sol and jelling agent splashes into the oil bath of keeping at elevated temperatures.Mixture drips and is maintained in the oil bath up to being shaped as hydrogel sphere.Subsequently ball is taken out from initial oil bath continuously, and typically in oil and ammonia solution, it is carried out specific burin-in process with further its physical properties of improving.Other reference of describing the application of oil drop method in the catalyzer manufacturing comprises US-A-4,273,735, US-A-4,514,511 and US-A-4,542,113.US-A-4,514,511, US-A-4,599,321, US-A-4,628,040 and US-A-4,640,807 have described the spherical catalyst particulate production of using different methods.
Hydrocracking catalyst is advisable to comprise 1 weight % to 90 weight %Y-zeolite, preferably comprises 5 weight % to 80 weight %Y-zeolites.The zeolites catalyst composition also should comprise porous refractory inorganic oxide carrier (matrix), and this matrix can constitute about 10 to 99 weight % of final catalyst composition carrier, and preferred 20 to about 95 weight %.Most preferred matrix comprises the mixture of silica-alumina and aluminum oxide, and wherein silica-alumina is 15 to 85 weight % of described matrix.Preferred substrate comprises the aluminum oxide of about 5 weight % to about 45 weight % simultaneously.
The Y-zeolite has US-A-3, the basic X-ray diffraction pattern of illustrating in 130,007.About 24.20 to 24.40 dusts of Y-zeolite elementary cell gravel size decision, most preferably from about 24.30 to 24.38 dusts.The Y-zeolite is preferably through dealuminzation and have framework SiO greater than 6 2: Al 2O 3Ratio most preferably has the framework SiO between 6 to 25 2: Al 2O 3Ratio.Can expect that other zeolite (for example Beta-zeolite, Omega-zeolite or ZSM-5) can be used to replace preferred Y-zeolite or therewith as the zeolite component of hydrocracking catalyst.

Claims (4)

1. two-stage hydrocracking process, comprising:
(a) with hydrogen with comprise the feed stream that boiling point is higher than 371 ℃ hydrocarbon and send into the hydrocracking condition that comprises first pressure under and first hydrocracking zone that contain hydrocracking catalyst, generation comprises the first hydrocracking zone ejecta logistics of hydrogen, hydrogen sulfide, unconverted feed component and product hydrocarbon;
(b) the first hydrocracking zone ejecta is separated to produce the recycle gas stream and first liquid process streams, the aforesaid liquid process-stream is sent into the bottoms that the product fractionation zone produces overhead product product logistics and comprises unconverted feed component;
(c) bottoms and the logistics of hydrogen make-up gas are sent into second hydrocracking zone under the alkane selective hydrogenation cracking conditions that comprises the second lower pressure, produced the second hydrocracking zone ejecta logistics;
(d) the second hydrocracking zone ejecta logistics is separated into vapor phase stream and liquid phase stream, and liquid phase stream is sent into the product fractionation zone; With
(e) send the vapor phase stream compression and with resulting compressed vapor phase stream into the first hydrocracking reaction district, (a) provides at least a portion hydrogen to step.
2. according to the process of claim 1 wherein bottoms was passed through the polynuclear aromatic compound adsorption zone before sending into second hydrocracking zone.
3. according to the method for claim 1 or 2, wherein second hydrocracking zone is operated under the inlet pressure than the low 2068kPa at least of first hydrocracking zone.
4. according to the method for claim 1 or 2, wherein second hydrocracking zone is being lower than 12, operates under 409kPa and the inlet pressure than the low at least 2068kPa of first hydrocracking zone.
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