CN105264050A - Naphtha cracking - Google Patents
Naphtha cracking Download PDFInfo
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- CN105264050A CN105264050A CN201480031738.2A CN201480031738A CN105264050A CN 105264050 A CN105264050 A CN 105264050A CN 201480031738 A CN201480031738 A CN 201480031738A CN 105264050 A CN105264050 A CN 105264050A
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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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
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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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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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
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
- C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
- C10G59/04—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only including at least one catalytic and at least one non-catalytic reforming step
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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
- C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
- C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
- C10G61/04—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only the refining step being an extraction
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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
- C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
- C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
- C10G61/06—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only the refining step being a sorption process
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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
- C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
- C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
- C10G63/04—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only including at least one cracking step
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—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
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for increasing the yields of light olefins and the yields of aromatics from a hydrocarbon stream is presented. The process includes a first separation to direct the light components that are not reformable to a cracking unit, with the remainder passed to a second separation unit. The second separation unit extracts normal components from the hydrocarbon stream to pass to the cracking unit. The resulting hydrocarbon stream with reduced light ends and reduced normals is passed to a reforming unit.
Description
The statement of right of priority
The application advocates the U.S. Provisional Application the 61/830th all applying on June 4th, 2013, No. 964 and the 61/830th, No. 981 and all apply for the U. S. application the 14/271st on May 6th, 2014, No. 392 and the 14/271st, the rights and interests of No. 399.
Technical field
The present invention relates to a kind of method of producing light olefin from naphtha feed stream.The invention still further relates to the method for the improvement improving selectivity of light olefin hydrocarbon.
Background technology
The light olefin that ethene and propylene, per molecule have two or three atoms is respectively the important chemical substance for the production of other suitable material (such as polyethylene and polypropylene).Polyethylene and polypropylene are two kinds of modal plastics used now and as manufactured materials and of many uses as wrapping material.The purposes of other ethene and propylene comprises produces vinylchlorid, oxyethane, ethylbenzene and ethanol.Substantially all ethene and propylene are produced in steam cracking or hydrocarbon pyrolysis.The hydrocarbon being used as charging for the production of light olefin comprises Sweet natural gas, petroleum liquid and carbonaceous material (comprising coal, recycled plastic or any organic materials).
Ethylene plant is the extremely complicated combination of reaction and gas recovery system.Under the existence of steam, charging is fed in cracking region to produce the gaseous mixture of pyrolysis reactor effluent under effective heat condition.Stablize the gaseous mixture of pyrolysis reactor effluent and be isolated into the component of purifying via a succession of low temperature and known fractionating step.The typical ethylene separate part of ethylene plant is (containing low temperature and known fractionating step with recovered ethylene product, ethylene product has the purity more than 99.5% ethene) be described in the article shown by V.Kaiser and M.Picciotti, the name of article is called " good ethylene separation device." article to be published in the HYDROCARBONPROCESSINGMAGAZINE the 57 to 61 page in November, 1988 and to be incorporated herein by reference.
Currently known methods for improving the transformation efficiency of the ethylene product part of self-boiled stony fracture solution explained hereafter, with by disproportionation or the more ethene of metathesis olefin production and propylene.Described technique is disclosed in United States Patent (USP) the 5th, and 026,935 and 5,026, in No. 936, wherein combination adopts replacement(metathesis)reaction step and catalytic pyrolysis step with by metathesis C4 and compared with the more ethene of molecule manufacture of heavy and propylene.Catalytic pyrolysis step adopts zeolite catalyst to transform the hydrocarbon flow that per molecule has 4 or more carbon atoms, thus production per molecule has the alkene of less carbon atom.The mixture of the alkene of the hydrocarbon incoming flow of the zeolite catalyst alkane typically containing 40wt% to 95wt% (per molecule have 4 or more a carbon atom) and 5wt% to 60wt% (per molecule have 4 or more a carbon atom).At United States Patent (USP) the 5th, in 043, No. 522, disclosing the catalyzer being preferred for this type of zeolite cracking technology is sour zeolite, and example comprises several ZSM type zeolite or borosilicate.In ZSM type zeolite, ZSM-5 is preferred.This U.S. Patent Publication other can be used for cracking technology and comprise Wessalith CS, X zeolite, zeolite Y, zeolite ZK-5, zeolite ZK-4, synthesizing flokite with the material containing zeolite producing ethene and propylene, remove aluminize mordenite and naturally occurring zeolite (comprising chabazite, faujusite, mordenite and fellow thereof).Be preferred through ion-exchange to replace the alkali-metal zeolite be present in zeolite.Positively charged ion preferably for cationic exchange is hydrogen, ammonium, rare earth metal and composition thereof.
European patent the 109th, No. 059B1 open a kind of by making incoming flow (having the alkene of 4 to 12 carbon atoms containing per molecule) contact the method incoming flow to be changed into propylene with ZSM-5 or ZSM-11 zeolite (having the silicon-dioxide being less than or equal to 300: alumina atom ratio) at the temperature of 400 DEG C to 600 DEG C.ZSM-5 or ZSM-11 zeolite and hydrogen or ammonium cation are exchanged.Reference paper is also open, although have by any per molecule of circulation the conversion that the alkene being less than 4 carbon atoms is increased to propylene, unreacted alkane tends to accumulate in recycle stream.Reference paper provides extra oligomerization step, the olefin oligomerization wherein making to have 4 carbon atoms to help to remove the alkane being difficult to from C4 separation of olefins by conventional fractionation, such as butane and Trimethylmethane especially.In related European patent 109060B1, a kind of method butenc being become propylene is disclosed.Method comprises makes butylene contact with zeolite compound, and described zeolite compound is selected from the group be made up of silicite, boron matter rock, colored silicite and these zeolites ZSM-5 and ZSM-11 (wherein silicon-dioxide: the mol ratio of aluminum oxide is more than or equal to 350).Transform at the temperature of 500 DEG C to 600 DEG C and under the space velocity of every kg pure zeolite compound 5kg/h to 200kg/h butylene.The purposes that the open silicite-1 of European patent 109060B1 exist with ion-exchange, dipping or co-precipitation form, silicite-1 have the modifying element being selected from the group be made up of chromium, magnesium, calcium, strontium and barium.
Generally speaking, the comparatively heavy olefins (being produced in commercially available ethylene plant) that per molecule has six or more carbon atoms is applicable to production aromatic hydrocarbon.The part of olefin product comprises the alkene that per molecule has four carbon atom.This part comprises monoolefine and diolefine and some alkane, comprises butane and Trimethylmethane.Because it is less and need sizable processing with dines separation and monoolefine that per molecule has the part general value of four carbon atom, so method of seeking is to improve the utilization ratio of this part of ethylene plant product and to improve the total recovery of ethene and propylene.
High conversion is kept while being difficult to obtain the highly selective of ethene and propylene in naphtha cracking.Therefore need to carry out improving to realize this target in Catalyst and process.
Summary of the invention
The invention provides a kind of yield optimization of light olefin and aromatics and improve the method for yield of making.Method comprises and is sent in the first tripping device hydrocarbon flow to generate the first lightweight stream and the first heavy stream.First lightweight stream is made up of hydrocarbon component, and described hydrocarbon component is lighting end and for what be not easy to reform, but can easily carries out cracking to generate light olefin in cracking reactor.First heavy stream is sent to remove remaining sulphur compound and nitrogen compound in hydrotreater, and the heavy stream of generating process.Be sent to by heavy stream to produce extraction stream in the second tripping device, described extraction stream comprises the straight chain hydrocarbon from heavy hydrocarbons stream.Tripping device also generates the extract remainder stream of the non-linear component comprising heavy hydrocarbons stream.Method comprise further by the first lightweight stream with extraction stream be sent in cracker to generate light olefin product stream.Method comprises the reformate process stream being sent to by extract remainder stream and comprising aromatics in reformer with generation.
Cracker can be steam crackers, or catalytic naphtha cracker, and wherein hydrocarbon flow comprises virgin naphtha.In one embodiment, the first lightweight stream comprises C5 hydrocarbon and some C6 hydrocarbon.The cut of the first knockout tower is included in the first lightweight stream and transmits hexane, methylcyclopentane, methylpentane and dimethylbutane.
By following embodiment and graphic, other targets of the present invention, advantage and application will become aobvious to those skilled in the art and easily know.
Accompanying drawing is sketched
Fig. 1 improves the method flow diagram from the yield of the light olefin of naphtha cracking device gained.
Embodiment
The production of light olefin is generated by the hydrocarbon using cracker cracking compared with heavy.In order to target flow rate design cracker is with convert hydrocarbons incoming flow.By controlling incoming flow supply or the change of its content or improving yield.By manipulation incoming flow content, the yield of cracker can be improved.In addition, changing in aromatic component by nonaromatic components, the incoming flow supply also by controlling reformer improves the output of the aromatics being used for aromatic complexes charging.Method of the present invention relates to optimally operation cracker and reformer, and wherein the charging of each device keeps in fact constant.In one embodiment, method utilizes and waits to divide and wait the virgin naphtha incoming flow that is sent in two devices.As hereafter use, virgin naphtha incoming flow is intended to the naphtha feed stream comprising full boiling range.Method is used for the product (such as light olefin and the aromatic substance) circulation of the naphtha feed of relative low value being changed into more high value.
The present invention is intended to the yield optimization making two treatment unit (cracker and catalytic reforming unit), and while method also can be used for the yield improving each isolated system.Hydrocarbon flow comprises complex mixture.First separating technology typically carries out around boiling point, wherein obtained cut in boiling range.Downstream also adopts other separation methods to extract the hydrocarbon of particular category.
Find that the more complicated separation of hydrocarbon flow can improve the yield of downstream processing units, kept the flow rate constant in fact of downstream processing units simultaneously.The typical feed stream of cracker and reformer is virgin naphtha incoming flow.But wish that other incoming flows can be used for this technique, and as hereafter use, term naphtha feed stream is intended to contain other potential hydrocarbon incoming flows that can be used for cracking and reformation.
In an embodiment of present method, naphtha feed is spread and delivers in cracker to generate light olefin.As shown in fig. 1, produce the method for light olefin to comprise hydrocarbon incoming flow 8 is sent in the first knockout tower 10.Knockout tower 10 generates the first lightweight stream 12 and the first heavy stream 14.First heavy stream 14 is sent in hydrotreater 20 with the heavy stream 22 of generating process.The heavy stream 22 of process is sent in the second tripping device 30 to generate the first extraction stream 32 and extract remainder stream 34.First extraction stream 32 comprises straight chain hydrocarbon, and extract remainder stream 34 comprises non-straight chain hydrocarbon.First extraction stream 32 and the first lightweight stream 12 are sent in cracker 40 to generate light olefin.Cracker 40 can be steam crackers or catalytic naphtha cracker.
First lightweight stream 12 can comprise C5 hydrocarbon and be the isolate of light hydrocarbon from virgin naphtha stream.Find that the C6 compound of such as methylcyclopentane is more difficult to reform, and therefore find that transfer operation first knockout tower 10 (namely comprise and send out some C6 compound (comprising methylcyclopentane) and overhead stream 12) is for favourable.Heavy stream 14 can comprise C7 and comparatively heavy component, and some C6 component of easily reforming, such as hexanaphthene.
Second tripping device 30 is preferably adsorption separation device, and separation is controlled by selected adsorbent and desorption agent.With regard to present method, design the second tripping device 30 and be separated with the heavy stream 22 of process for by the straight chain hydrocarbon in C5 to C11 scope.Be separated straight chain hydrocarbon and it is transmitted in the extract remainder stream 34 comprising non-straight chain hydrocarbon and extract in stream 32.Desorption agent for preferred method is straight chain C 12 alkane.
Extract remainder stream 34 can be sent in reformer 50 to generate the process stream 52 comprising aromatics.Process stream 52 can be sent in aromatic complexes, thus change into the product of more high value.
In one embodiment, method comprises the yield improving the aromatics that autocatalysis reformer 50 obtains.Method can comprise and transmits the heavy stream that generates from other treatment unit, such as heavy cracking stream, and wherein heavy cracking stream comprises C7 and delivers in reformer 50 with the hydrocarbon and heavy cracking being spread compared with heavy.Reformer is preferably and continues catalytic reforming unit, and wherein catalyzer is in moving-bed, and catalyzer is circulated to revivifier by reactor, thus regenerated catalyst.This method provides continuous processing.
In the method for the yield of the aromatics of raising reformer unit 50 gained, method comprises maintenance flow constant in fact, changes feed composition to improve aromatics yield simultaneously.Method comprises virgin naphtha incoming flow 8 to be sent in petroleum naphtha splitter 10 and remains logistics 14 to generate heavy bottoms.Heavy bottoms is remained logistics 14 to be sent in hydrotreater 20 with the heavy stream 22 of generating process.The heavy stream 22 of process is sent in adsorption separation device 30 to isolate straight chain hydrocarbon from the heavy stream 22 of process.Straight chain hydrocarbon is transmitted in extraction stream 32, and adsorption separation device 30 generates the extract remainder stream 34 comprising non-straight chain hydrocarbon.Extract remainder stream 34 is sent in catalytic reforming unit 50.Non-straight chain hydrocarbon is easier than straight chain hydrocarbon is reformatted into aromatic substance, and the feed composition changing reformer 50 can improve aromatics yield and not improve feed flow rate.
Method utilizes adsorption separating method with separate hydrocarbons incoming flow, and hydrocarbon incoming flow is through division and through being sent in cracker and reformer.Typical incoming flow is naphtha feed stream, and the usefulness of cracker and catalytic reforming unit is all improved.Adsorption separation device is by straight-chain paraffin and non-linear alkane separation.Non-linear component comprises branched alkanes, cycloalkanes and aromatics.Method preferably utilizes petroleum naphtha splitter to isolate the light component of the C5-component comprised in petroleum naphtha.C5-component was removed, because C5-component can not change into aromatics before being sent in reformer by petroleum naphtha.
By virgin naphtha and can deliver in petroleum naphtha stripper compared with the hydrocarbon of light component to help the petroleum naphtha of stripping C5-component.Hydrotreatment virgin naphtha and can be sent in reformer subsequently.Hydrotreatment removes sulphur and other impurity, and sulphur and other impurity can serve as the catalyzer poison in downstream processing units.
An aspect of this method is for a change fed to the distribution of the hydrocarbon in cracker and reformer.Change the usefulness that charging distribution can strengthen cracker and reformer.Do not carry out standard operation petroleum naphtha being split into C5-, but carry out one improvement, be improved to adjustment splitter is difficult to reformation additional component to make the overhead stream of petroleum naphtha splitter 10 comprise.Additional component in overhead stream comprises dimethylbutane, methylpentane, straight chain hexane and methylcyclopentane (MCP).These additional component are sent in cracker 40.Remove by these components being drifted from heavy bottoms, the subsequent flows be sent in reformer improves aromatics yield.
The another aspect of this method is that additional separation heavy bottoms remains logistics.Also more be difficult to reform but the additional component being more easily cracked into light olefin comprises heavier straight-chain paraffin.Adsorption separation system allows to be separated the straight-chain paraffin be not easy by fractionation separates.Subsequently linear component to be sent in cracker and non-linear component is sent in reformer.
An aspect of present method is the yield optimization making cracker and reformer.Can to design cracker and reformer and size sets naphtha feed stream for predetermined amount of flow.Interpolation petroleum naphtha splitter and adsorption separation device allow feed composition to be transferred in cracker and reformer, keep the flow constant being in fact sent to two devices simultaneously.
In one embodiment, production light olefin and aromatics in make the method for the yield optimization of downstream process comprise by from hydrocarbon flow optionally separate hydrocarbons component make the method for the yield optimization of aromatics and light olefin.Method comprises and is sent in the first knockout tower 10 first hydrocarbon flow 8 to generate the first lightweight stream 12 and the first heavy stream 14.First heavy stream 14 is sent in hydrotreater 20 with the heavy stream 22 of generating process.The heavy stream 22 of process is sent in the second tripping device 30 to generate extraction stream 32 and extract remainder stream 34.Extraction stream 32 and the first lightweight stream 12 are sent in cracker 40.In order to keep the constant flow being sent to cracker 40, extraction stream 32 and the first lightweight stream 12 are supplemented by the second hydrocarbon flow 6 be sent in cracker 40.Extract remainder stream 34 is sent in catalytic reforming unit 50 to generate the process stream 52 that aromatic content improves.
Hydrocarbon flow typically for cracking is naphtha stream, and the first hydrocarbon flow and the second hydrocarbon flow can be virgin naphtha, and stream generates by division virgin naphtha.In one embodiment, the second hydrocarbon flow can be light naphtha stream, and it can generate during production naphtha stream.Adjusting process and flow rate are to keep the flow rate constant being in fact sent to cracker and catalytic reforming unit.Helping this to control by dividing the first and second hydrocarbon flows, wherein can reduce or improve the second hydrocarbon flow 6 according to the content of the first lightweight stream 12 generated by the first knockout tower 10 and the content of the extraction stream 32 generated by the second tripping device 30.
Method can comprise upstream tripping device further to obtain virgin naphtha and to carry out dividing the process of light naphtha stream and remaining naphtha stream.
Be sent in catalytic reforming unit by extract remainder stream, the straight-chain paraffin wherein in extract remainder stream is removed.Extract remainder stream can be used as the downstream fusion stream of gasoline or other products.Preferably, extract remainder stream to be sent in catalytic reforming unit to improve the yield of aromatics, reformer product stream to be sent in aromatic complexes simultaneously.
Optimization method generates the first lightweight stream from the first knockout tower 10.First lightweight stream comprises the C5-component from naphtha stream, because described C5-component is not easy to be reformatted into aromatics.It has also been found that operation first knockout tower 10 is to send out some C6 component and lightweight overhead stream 12.These components comprise methylcyclopentane (MCP), straight chain hexane, methylpentane and dimethylbutane.Cracking is generated to the technique of heavy cracking stream (wherein component has a large amount of C7 hydrocarbon), heavy cracking can be spread and deliver in reformer.
An example is for illustration of passing through the attainable improvement of this method.
Table-analog result
Simulation is based on the information operated from device.Scheme adopts constant straight run (SR) naphtha feed of the 1370KMTA of cracker.Division SR petroleum naphtha and keep the constant rate of cracker, reduces the SR petroleum naphtha content being sent to cracker simultaneously, and improves from the lighting end of the first knockout tower and extract from the second tripping device improves.Residuum is introduced in catalytic reforming unit.
As can be seen from the results, relative to basic condition, selectivity of light olefin hydrocarbon significantly improves, and even larger by rising to of the second tripping device.Equally, as can be seen from aromatics yield, add the content that the second tripping device can improve the hydrocarbon changing into aromatics.In addition, result shows the constant RONC (research octane number (RON)) of aromatics generated to be maintained by reformer, can reduce the content of catalyzer, thus can saving resource and running cost in a large number.
Although with thinking that preferred embodiment describes the present invention at present, it should be understood that the present invention is not limited to disclosed embodiment, but be intended to contain and be included in various amendment in the category of appended claims and equivalent.
Specific embodiments
Although following content is described in conjunction with particular, this specification sheets should be understood and be intended to illustrate and the category not limiting aforementioned embodiments and appended claims.
First embodiment of the present invention is a kind ofly producing the method making the Optimizing manufacture of downstream process in light olefin and aromatics, and method comprises and is sent in the first knockout tower the first hydrocarbon flow to generate the first lightweight stream and the first heavy stream; First heavy stream is sent in hydrotreater with the heavy stream of generating process; The heavy stream of process is sent in the second tripping device to generate extraction stream and extract remainder stream; Extraction stream, the first lightweight stream and the second hydrocarbon flow are sent in cracker; Be sent in catalytic reforming unit with by extract remainder stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in first embodiment of this section, wherein the first hydrocarbon flow is virgin naphtha stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in first embodiment of this section, wherein the second hydrocarbon flow is light naphtha or straight run stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in first embodiment of this section, the total flux wherein making to be sent to cracker keeps constant.One embodiment of the invention be the previous example of this section to, any or all embodiment in first embodiment of this section, it comprises further virgin naphtha flow point is cleaved into the first hydrocarbon flow and the second hydrocarbon flow.
Second embodiment of the invention be a kind of hydrocarbon flow composition of optimizing to improve the method for the usefulness of downstream process, method comprises and is sent in the first knockout tower hydrocarbon flow to generate the first lightweight stream and the first heavy stream; First heavy stream is sent in hydrotreater with the heavy stream of generating process; The heavy stream of process is sent in the second tripping device to generate the first extraction stream and the extract remainder stream comprising non-straight chain hydrocarbon that comprise straight chain hydrocarbon; With the first lightweight stream and first are extracted stream and are sent in cracker to generate light olefin.One embodiment of the invention be the previous example of this section in second embodiment of this section, any or all embodiment, it comprises further and being sent in catalytic reforming unit by extract remainder stream.One embodiment of the invention be the previous example of this section in second embodiment of this section, any or all embodiment, wherein the first lightweight stream comprises C5 hydrocarbon.One embodiment of the invention be the previous example of this section in second embodiment of this section, any or all embodiment, wherein the first lightweight stream comprise methylcyclopentane with compared with the hydrocarbon of lightweight.One embodiment of the invention be the previous example of this section in second embodiment of this section, any or all embodiment, wherein the first lightweight stream comprise hexanaphthene with compared with the product of lightweight.One embodiment of the invention are that the previous example of this section is in second embodiment of this section, any or all embodiment, wherein cracker generates the remaining stream of cracker, and comprises cracker heals to spread further and deliver in reformer.One embodiment of the invention be the previous example of this section in second embodiment of this section, any or all embodiment, wherein hydrocarbon flow is cracking naphtha stream.One embodiment of the invention be the previous example of this section in second embodiment of this section, any or all embodiment, wherein the second tripping device is adsorption separation device.
Third embodiment of the invention is a kind of method improving the aromatic content of reformation logistics, and method comprises to be sent to by hydrocarbon flow in splitter tower and comprises the overhead stream of light hydrocarbon to generate and comprise the bottoms stream of heavy hydrocarbon; Bottoms are spread and delivers in hydrotreater with the heavy stream of generating process; The heavy stream of process is sent in tripping device and comprises the extraction stream of straight chain hydrocarbon to generate and comprise the extract remainder stream of non-straight chain hydrocarbon; With extract remainder stream is sent in catalytic reforming unit with generate aromatic content improve process stream.One embodiment of the invention are that the previous example of this section is to, any or all embodiment in the 3rd embodiment of this section, wherein splitter tower is petroleum naphtha splitter tower, and overhead stream comprises C6 and the hydrocarbon compared with lightweight, and bottoms stream comprises C7 and the hydrocarbon compared with heavy.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 3rd embodiment of this section, it comprises further and overhead stream being sent in cracker.One embodiment of the invention are that the previous example of this section is to, any or all embodiment in the 3rd embodiment of this section, it comprises further naphtha feed flow point is cleaved into first part and second section, and first part is sent in cracker, and second section is sent in splitter tower.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 3rd embodiment of this section, its comprise further operation splitter tower and tripping device to keep being sent to the constant mass rate of catalytic reforming unit.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 3rd embodiment of this section, wherein cracker is catalytic naphtha cracker or naphtha steam cracking device.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 3rd embodiment of this section, wherein hydrocarbon flow is virgin naphtha stream.
Fourth embodiment of the invention is a kind of method of producing light olefin, and method comprises and is sent in the first knockout tower hydrocarbon flow to generate the first lightweight stream and the first heavy stream; First heavy stream is sent in hydrotreater with the heavy stream of generating process; The heavy stream of process is sent in the second tripping device to generate the first extraction stream and the extract remainder stream comprising non-straight chain hydrocarbon that comprise straight chain hydrocarbon; With the first lightweight stream and first are extracted stream and are sent in cracker to generate light olefin.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 4th embodiment of this section, it comprises further and being sent in reformer by extract remainder stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 4th embodiment of this section, wherein the first lightweight stream comprises C5 hydrocarbon.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 4th embodiment of this section, wherein the first lightweight stream comprise methylcyclopentane with compared with the hydrocarbon of lightweight.One embodiment of the invention are that the previous example of this section is to, any or all embodiment in the 4th embodiment of this section, wherein cracker generates cracker heavy stream, and comprises further and being sent in reformer by cracker heavy stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 4th embodiment of this section, wherein cracker is cat-cracker.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 4th embodiment of this section, wherein cracker is steam cracking device.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 4th embodiment of this section, wherein hydrocarbon flow is virgin naphtha stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 4th embodiment of this section, wherein the second tripping device is adsorption separation device.
Fifth embodiment of the invention is a kind of method of producing light olefin, and method comprises and is sent in cracker by cracker incoming flow, comprises and hydrocarbon incoming flow is split into first part and second section; First part is sent in the first tripping device and comprises the extraction stream of straight-chain paraffin to generate and comprise the extract remainder stream of non-linear alkane; Be sent in cracker with by extraction stream and second section.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 5th embodiment of this section, wherein method comprises further and first part to be sent in the second tripping device to generate lightweight overhead stream and heavy bottoms remains logistics; Being spread by heavy bottoms residue delivers in the first tripping device; Deliver in cracker with lightweight top is spread.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 5th embodiment of this section, it comprises further and heavy bottoms residue is spread the heavy bottoms delivered to generating process in hydrotreater and remain logistics; Deliver in the first tripping device with the bottoms of process are spread.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 5th embodiment of this section, wherein the first tripping device is adsorption separation device and the second tripping device is separation column.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 5th embodiment of this section, wherein hydrocarbon incoming flow is virgin naphtha stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 5th embodiment of this section, it comprises further and being sent in reformer by extract remainder stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 5th embodiment of this section, wherein reformer for continue catalyst regeneration process.One embodiment of the invention are that the previous example of this section is to, any or all embodiment in the 5th embodiment of this section, wherein cracker generates heavy byproduct stream, and process comprises further and being sent in reformer by heavy byproduct.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 5th embodiment of this section, the division of wherein hydrocarbon incoming flow through setting size to keep the constant feed rate of cracker.
Sixth embodiment of the invention is a kind ofly produce the method for light olefin from virgin naphtha incoming flow, and method comprises naphtha feed flow point is cleaved into first part and second section; First part is sent in petroleum naphtha splitter separation column to generate lightweight overhead stream and heavy bottoms remains logistics; Heavy bottoms residue is spread and delivers in naphtha hydrotreater to generate the naphtha stream of hydrotreatment; The naphtha stream of hydrotreatment is sent in adsorption separation device and generates extraction stream and extract remainder stream; Extraction stream, lightweight overhead stream and second section are sent in naphtha cracker complex; Be sent in reformer with by extract remainder stream.One embodiment of the invention be the previous example of this section to, any or all embodiment in the 6th embodiment of this section, it comprises further and controls the division of naphtha feed stream and the operation of petroleum naphtha splitter separation column to generate the constant total flow rate being sent to naphtha cracker complex.
Without the need to describing in further detail, believe that those skilled in the art can use previous description farthest to utilize the present invention, and can be easy to determine essential characteristic of the present invention, when not being suitable for various uses and condition departing from variations and modifications can be made to the present invention when spirit of the present invention and category to make it.Therefore, aforementioned preferred particular should only be considered as exemplary, but not limits rest part of the present disclosure by any way, and the interior included various change of the category being intended to contain appended claims and equivalent.
Except as otherwise noted, otherwise in the preceding article, all temperature are all set forth with degree Celsius (degreesCelsius), and all parts and per-cent are all by weight.
Claims (10)
1. producing the method making the Optimizing manufacture of downstream process in light olefin and aromatics, it comprises:
First hydrocarbon flow is sent in the first knockout tower to generate the first lightweight stream and the first heavy stream;
First heavy stream is sent in hydrotreater with the heavy stream of generating process;
The heavy stream of process is sent in the second tripping device to generate the first extraction stream and extract remainder stream; With
First extraction stream, the first lightweight stream and the second hydrocarbon flow is sent in cracker.
2. method according to claim 1, the total flux being wherein sent to cracker keeps constant.
3. method according to claim 1, wherein the first lightweight stream comprises C5-hydrocarbon.
4. method according to claim 1, wherein the first lightweight stream comprises methylcyclopentane and the hydrocarbon compared with lightweight.
5. method according to claim 1, wherein cracker generates the remaining stream of cracker, and comprises cracker heals to spread further and deliver in reformer.
6. method according to claim 1, wherein the first extraction stream comprises straight chain hydrocarbon, and extract remainder stream comprises non-straight chain hydrocarbon; With
First lightweight stream and first are extracted stream to be sent in cracker to generate light olefin.
7. method according to claim 1, it comprises further and being sent in reformer by extract remainder stream.
8. method according to claim 6, wherein cracker generates cracker heavy stream, and comprises further and being sent in reformer by cracker heavy stream.
9. method according to claim 6, wherein the second tripping device is adsorption separation device.
10. method according to claim 6, it comprises operation first knockout tower and operation the second knockout tower further, and wherein the generation of the first lightweight stream and the first generation extracting stream remain the constant feed rate entering cracker.
Applications Claiming Priority (9)
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| US14/271,392 | 2014-05-06 | ||
| US14/271,392 US9328298B2 (en) | 2013-06-04 | 2014-05-06 | Naphtha cracking |
| US14/271,399 US9328299B2 (en) | 2013-06-04 | 2014-05-06 | Naphtha cracking |
| PCT/US2014/038870 WO2014197205A1 (en) | 2013-06-04 | 2014-05-21 | Naphtha cracking |
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| CN105264050B CN105264050B (en) | 2017-12-08 |
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| KR (1) | KR102318318B1 (en) |
| CN (1) | CN105264050B (en) |
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| CN112513229A (en) * | 2018-07-27 | 2021-03-16 | 沙特基础工业全球技术公司 | Process for producing light olefins and aromatics from wide boiling naphtha |
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| US20150045598A1 (en) * | 2013-08-07 | 2015-02-12 | Uop Llc | Flexible process for enhancing steam cracker and platforming feedstocks |
| CN108463539B (en) * | 2016-05-11 | 2020-07-24 | 环球油品公司 | Isomerization of light paraffins using a platinum reforming process |
| KR102671504B1 (en) | 2020-11-17 | 2024-06-03 | 한국화학연구원 | Method of separating naphtha cracker generated from naphtha using adsorption bed |
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| EP3004291B1 (en) | 2019-02-06 |
| WO2014197205A1 (en) | 2014-12-11 |
| TW201508057A (en) | 2015-03-01 |
| EP3004291A1 (en) | 2016-04-13 |
| PL3004291T3 (en) | 2019-09-30 |
| CN105264050B (en) | 2017-12-08 |
| KR20160015325A (en) | 2016-02-12 |
| TWI488955B (en) | 2015-06-21 |
| EP3004291A4 (en) | 2017-02-08 |
| KR102318318B1 (en) | 2021-10-28 |
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