CN105264050B - Naphtha pyrolysis - Google Patents
Naphtha pyrolysis Download PDFInfo
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- CN105264050B CN105264050B CN201480031738.2A CN201480031738A CN105264050B CN 105264050 B CN105264050 B CN 105264050B CN 201480031738 A CN201480031738 A CN 201480031738A CN 105264050 B CN105264050 B CN 105264050B
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The present invention provides a kind of improve from the method for the yield of light olefin and the yield of aromatics obtained by hydrocarbon flow.Method includes the first separation so that non-reformable light components are introduced into cracker, while residue is sent in the second separator.Second separator extracts linear component to be sent in cracker from hydrocarbon flow.Light fraction with reduction and the gained hydrocarbon flow of the straight chain of reduction are sent in reformer.
Description
The statement of priority
The application advocates to apply for the U.S. Provisional Application No. 61/830,964 and the 61/830th on June 4th, 2013,
No. 981 and apply for the U. S. application the 14/271,392nd on May 6th, 2014 and the rights and interests of No. 14/271,399.
Technical field
The present invention relates to a kind of method from naphtha feedstream production light olefin.The invention further relates to improve lightweight alkene
The improved method of hydrocarbon yield.
Background technology
Ethene is respectively to be used to produce other applicable materials with the light olefin that propylene, per molecule have two or three atoms
Expect the important chemical substance of (such as polyethylene and polypropylene).Polyethylene and polypropylene are two kinds of most common modelings used now
Material and it is used as manufacture material and widely used as packaging material.The purposes of other ethene and propylene includes production vinyl chloride, ring
Oxidative ethane, ethylbenzene and ethanol.Steam cracking or hydrocarbon pyrolysis produce essentially all of ethene and propylene.For producing light olefin
Be used as charging hydrocarbon include natural gas, petroleum liquid and carbonaceous material (including coal, recycled plastic or any organic material).
Ethylene plant is reaction and the extremely complicated combination of gas recovery system.In steam under effective heat condition
In the presence of charging is fed in cracking region to produce the admixture of gas of pyrolysis reactor effluent.Stable pyrolysis reactor stream
Go out the admixture of gas of thing and the component of purifying is separated into via a succession of low temperature and known fractionating step.Ethylene plant
(containing low temperature and known fractionating step to reclaim ethylene product, ethylene product has more than 99.5% typical ethylene separate section
The purity of ethene) it is described in by V.Kaiser and the written articles of M.Picciotti, entitled " the preferable ethene of article
Separator." article be published in the HYDROCARBON PROCESSING MAGAZINE pages 57 to 61 in November, 1988 and
It is incorporated herein by reference.
Known method be used for improve self-boiled stony fracture solution technique productions ethylene product part conversion ratio, with by disproportionation or
Double decomposition alkene produces more ethene and propylene.The technique is disclosed in U.S. Patent No. 5,026,935 and No. 5,026,936
In, wherein combination uses metathesis reaction step with catalytic pyrolysis step to be manufactured more by double decomposition C4 and heavier molecule
More ethene and propylene.Catalytic pyrolysis step uses zeolite catalyst to convert hydrocarbon of the per molecule with 4 or more carbon atoms
Stream, there is the alkene of less carbon atom so as to produce per molecule.The hydrocarbon charging stream of zeolite catalyst typically contains 40wt%
To 95wt% alkane (per molecule with 4 or more carbon atoms) and 5wt% to 60wt% alkene, (per molecule is with 4
Individual or more carbon atom) mixture.In U.S. Patent No. 5,043,522, disclose and be preferred for such zeolite and split
The catalyst for solving technique is sour zeolite, and example includes several ZSM types zeolites or borosilicate.In ZSM type zeolites, ZSM-5 is
Preferably.The U.S. Patent Publication other can be used for cracking technology with produce the material containing zeolite of ethene and propylene include boiling
Stone A, X zeolite, zeolite Y, zeolite ZK-5, zeolite ZK-4, synthesizing flokite, go aluminize modenite and naturally occurring boiling
Stone (including chabasie, faujasite, modenite and its fellow).The alkali gold being present in through ion exchange with replacing in zeolite
The zeolite of category is preferable.The cation for being preferably used in cation exchange is hydrogen, ammonium, rare earth metal and its mixture.
The open one kind of European Patent No. 109,059B1 is by making (have 4 to 12 carbon atoms containing per molecule into stream
Alkene) with ZSM-5 or ZSM-11 zeolites (have less than or equal to 300 silica：Alumina atom ratio) at 400 DEG C
To the method contacted at a temperature of 600 DEG C so that the chemical conversion propylene that circulates will be fed.By ZSM-5 or ZSM-11 zeolites and hydrogen or ammonium sun from
Son exchanges.Reference paper is also disclosed, although being improved by circulating alkene of any per molecule having less than 4 carbon atoms to propylene
Conversion, unreacted alkane tends to accumulate in recycle stream.Reference paper provides extra oligomerization step, wherein making tool
Have the olefin oligomerizations of 4 carbon atoms and alkane from C4 separation of olefins be difficult to by conventional fractionation to help to remove, for example, butane and
Especially iso-butane.In related European patent 109060B1, a kind of method by butenc into propylene is disclosed.Method includes
Butylene is set to be contacted with zeolite compound, the zeolite compound is selected from by silicalite, boron matter rock, colored silicalite and these zeolites
ZSM-5 and ZSM-11 (wherein silica：The mol ratio of aluminum oxide is more than or equal to the group of 350) composition.At 500 DEG C to 600
Converted at a temperature of DEG C and under space velocities of the pure zeolite compound 5kg/h of every kg to 200kg/h butylene.European patent
109060B1 discloses the purposes existing in the form of ion exchange, dipping or co-precipitation of silicalite -1, silicalite -1 have be selected from by
The modifying element for the group that chromium, magnesium, calcium, strontium and barium form.
In general, the heavier alkene that per molecule has six or more carbon atoms (is produced in commercially available ethylene plant
In) it is applied to production aromatic hydrocarbon.The part of olefin product includes the alkene that per molecule has four carbon atom.This part includes single
Alkene and alkadienes and some alkane, including butane and iso-butane.Because per molecule has the general valency in the part of four carbon atom
Value is smaller and needs sizable processing with dines separation and monoolefine, so seeking method to improve ethylene plant product
The utilization rate of this part and the total recovery for improving ethene and propylene.
It is difficult to keep high conversion while the high selectivity of acquisition ethene and propylene in naphtha pyrolysis.Therefore need
It is improved in terms of Catalyst and process to realize this target.
The content of the invention
The present invention provides a kind of method for making the yield optimization of light olefin and aromatics and improving yield.Method includes will
Hydrocarbon flow is sent in the first separator to generate the first lightweight stream and the first heavy stream.First lightweight stream is by hydrocarbon group
Divide and formed, the hydrocarbon component is light fraction and is to be not easy what is reformed, but can easily be cracked in cracking reactor
To generate light olefin.First heavy stream is sent in hydrotreater to remove remaining sulphur compound and nitrification
Thing, and generate the heavy stream of processing.Heavy stream is sent in the second separator and extracts stream, the extraction to produce
Stream includes the straight-chain hydrocarbons from heavy hydrocarbons stream.Separator also generates the raffinate of the non-linear component comprising heavy hydrocarbons stream
Material flow.Method further comprises the first lightweight stream being sent in cracker to generate light olefin production with extraction stream
Logistics.Method includes raffinate material flow being sent in reformer to generate the reformate processing stream for including aromatics.
Cracker can be steam crackers, or catalytic naphtha cracker, wherein hydrocarbon flow include straight-run naphtha.
In one embodiment, the first lightweight stream includes C5 hydrocarbon and some C6 hydrocarbon.The cut of first knockout tower is included in the first light material
Hexane, methyl cyclopentane, methylpentane and dimethylbutane are transmitted in stream.
By implementation below and schema, other targets of the invention, advantage and application are for those skilled in the art
For will become aobvious and be apparent from.
Brief description
Fig. 1 is the method flow diagram for improving the yield from the light olefin obtained by naphtha pyrolysis device.
Embodiment
The production of light olefin is generated by the hydrocarbon using cracker cracking heavier.In order to which target flow rate design is split
Device is solved to convert hydrocarbon charging stream.Can be by controlling into stream supply or the change of its content or improving yield.Fed by manipulating
Content is flowed, the yield of cracker can be improved.In addition, being changed into by nonaromatic components in aromatic component, it can also pass through control
The yield entered stream supply and improve the aromatics for being used for aromatic complexes charging of reformer.The method of the present invention is related to optimization
Ground operates cracker and reformer, wherein the charging of each device is held substantially constant.In one embodiment, method
Using waiting to divide and the straight-run naphtha to be passed delivered in two devices enters stream.As used below, straight-run naphtha is fed
Stream is intended to include full boiling range naphtha to enter stream.Method is used to the naphtha feedstream of relative low value changing into more high price
The product (such as light olefin and aromatic compounds) of value.
It is contemplated that the yield optimization of two processing units (cracker and catalytic reforming unit), while method is also
Available for the yield for improving each isolated system.Hydrocarbon flow includes complex mixture.First separating technology typically enters around boiling point
OK, wherein cut is made in boiling range.Downstream also uses other separation methods to extract the hydrocarbon of particular category.
The yield of downstream processing units can be improved by having found the more complicated separation of hydrocarbon flow, while keep downstream processes to fill
The virtually constant flow rate put.The typical feed stream of cracker and reformer is that straight-run naphtha enters stream.So
And wish that other enter stream and can be used for this technique, and as used below, it is available that term naphtha feedstream is intended to cover other
In the potential hydrocarbon charging stream of cracking and reformation.
In an embodiment of this method, naphtha feed is streamed in cracker to generate lightweight alkene
Hydrocarbon.As shown in fig. 1, producing the method for light olefin includes hydrocarbon charging stream 8 being sent in the first knockout tower 10.Knockout tower 10
Generate the first lightweight stream 12 and the first heavy stream 14.First heavy stream 14 is sent in hydrotreater 20 with life
Into the heavy stream 22 of processing.The heavy stream 22 of processing is sent in the second separator 30 to generate the first extraction stream
32 with raffinate material flow 34.First extraction stream 32 includes straight-chain hydrocarbons, and raffinate material flow 34 includes non-straight chain hydrocarbon.By the first extraction
The lightweight stream 12 of feeding stream 32 and first is sent in cracker 40 to generate light olefin.Cracker 40 can split for steam
Solve device or catalytic naphtha cracker.
First lightweight stream 12 can include C5 hydrocarbon and be isolate of the light hydrocarbon from straight-run naphtha stream.It is found for example that methyl
The C6 compounds of pentamethylene are more difficult to reform, and consequently found that the first knockout tower of transfer operation 10 (includes sending out some C6
Compound (including methyl cyclopentane) and top stream 12) it is favourable.Heavy stream 14 can include C7 and heavier component, and certain
A little C6 components easily reformed, such as hexamethylene.
Second separator 30 is preferably adsorption separation device, and separates and controlled by selected adsorbent with desorption agent
System.As far as the process be concerned, design the second separator 30 for by the straight-chain hydrocarbons in the range of C5 to C11 with processing heavy material
The separation of stream 22.Separate straight-chain hydrocarbons and itself and the raffinate material flow 34 comprising non-straight chain hydrocarbon are transmitted in extraction stream 32.For
The desorption agent of method for optimizing is the alkane of straight chain C 12.
Raffinate material flow 34 can be sent in reformer 50 to generate the processing stream 52 for including aromatics.It will can handle
Stream 52 is sent in aromatic complexes, so as to change into the product of higher value.
In one embodiment, method includes the yield of the aromatics obtained by improving self-catalysis reformer 50.Side
Method may include the heavy stream for being delivered from the generation of other processing units, such as heavy cracking stream, and wherein heavy cracking stream includes C7
It is streamed to the hydrocarbon of heavier and by heavy cracking in reformer 50.Reformer is preferably to continue catalytic reforming unit,
Wherein catalyst makes catalyst be circulated by reactor to regenerator in moving bed, so as to regenerated catalyst.This side
Method provides continuous processing.
In the method for the yield of aromatics of the gained of reformer unit 50 is improved, method includes keeping virtually constant
Flow, while change feed composition to improve aromatics yield.Method is sent to stone brain including straight-run naphtha is entered into stream 8
In oily splitter 10 logistics 14 is remained to generate heavy bottoms.Heavy bottoms residual logistics 14 is sent to hydrotreater 20
In with generation processing heavy stream 22.The heavy stream 22 of processing is sent to the weight in adsorption separation device 30 to handle certainly
Material stream 22 isolates straight-chain hydrocarbons.Straight-chain hydrocarbons is transmitted in extraction stream 32, and the generation of adsorption separation device 30 includes non-linear
The raffinate material flow 34 of hydrocarbon.Raffinate material flow 34 is sent in catalytic reforming unit 50.Non-straight chain hydrocarbon is easier than straight-chain hydrocarbons
Aromatic compounds is reformatted into, and the feed composition for changing reformer 50 can improve aromatics yield without improving feed flow
Speed.
Method using adsorption separating method to separate hydrocarbon charging stream, hydrocarbon charging flow through division and it is communicated to cracker with
In reformer.It is naphtha feedstream typically to enter stream, and the efficiency of cracker and catalytic reforming unit is changed
Enter.Adsorption separation device is by linear paraffin and non-linear alkane separation.Non-linear component includes branched alkanes, cycloalkanes and aromatics
Thing.Method includes the light components of the C5- components in naphtha preferably by naphtha splitter to isolate.By naphtha
C5- components are removed before being sent in reformer, because C5- components can not change into aromatics.
The hydrocarbon of straight-run naphtha and relatively lightweight component can be delivered to in naphtha stripper the stone that C5- components are stripped with help
Cerebrol.Hydrotreating straight-run naphtha and then it can be sent in reformer.It is miscellaneous with other that hydrotreating removes sulphur
Matter, sulphur may act as the catalyst poison in downstream processing units with other impurities.
The one side of the method is fed to the distribution of the hydrocarbon in cracker and reformer to change.Change charging point
Cloth can strengthen the efficiency of cracker and reformer.Do not enter to be about to the standard operation that naphtha splits into C5-, but carry out one
Kind is improved, and is improved to adjust splitter with so that the top stream of naphtha splitter 10 includes being difficult to the additional component reformed.
Additional component in the stream of top includes dimethylbutane, methylpentane, straight chain hexane and methyl cyclopentane (MCP).By these volumes
Outer component is sent in cracker 40.By the way that these components are removed from heavy bottoms stream, reformer is sent to
In rear afterflow improve aromatics yield.
The another aspect of the method is that additional separation heavy bottoms remain logistics.It is also more difficult to be cracked into reform but be easier
The additional component of light olefin includes heavier linear paraffin.Adsorption separation system allows separation to be easily detected by fractionation separation
Linear paraffin.Then linear component is sent in cracker and non-linear component is sent in reformer.
The one side of this method is to make the yield optimization of cracker and reformer.Cracker can be filled with reforming
Put the naphtha feedstream for being designed and being set with size for predetermined amount of flow.Add naphtha splitter and adsorbing separation dress
Putting allows feed composition being transferred in cracker and reformer, while keeps being sent to the substantial perseverance of two devices
Fixed flow.
In one embodiment, in the method bag of production light olefin and the yield optimization for making downstream process in aromatics
The method for including the yield optimization by making aromatics and light olefin from the separation hydrocarbon component of hydrocarbon flow selectivity.Method includes will
First hydrocarbon flow 8 is sent in the first knockout tower 10 to generate the first lightweight stream 12 and the first heavy stream 14.By the first weight
Material stream 14 is sent in hydrotreater 20 with the heavy stream 22 of generation processing.The heavy stream 22 of processing is sent to
With generation extraction stream 32 and raffinate material flow 34 in second separator 30.Extraction stream 32 is passed with the first lightweight stream 12
Deliver in cracker 40.In order to keep being sent to the constant flow of cracker 40, the light material of stream 32 and first is extracted
Stream 12 is supplemented by the second hydrocarbon flow 6 being sent in cracker 40.Raffinate material flow 34 is sent to catalytic reforming dress
Put in 50 to generate the processing stream 52 of aromatic content raising.
The hydrocarbon flow for being typically used for cracking is naphtha stream, and the first hydrocarbon flow and the second hydrocarbon flow can be straight run stone brain
Oil, and stream can be generated by dividing straight-run naphtha.In one embodiment, the second hydrocarbon flow can be light naphtha
Stream, it can be generated during naphtha stream is produced.Regulation technique is heavy with catalysis to keep being sent to cracker with flow rate
The virtually constant flow rate of engagement positions.This control is helped by dividing the first and second hydrocarbon flows, wherein can be according to logical
Cross the content of the first lightweight stream 12 of the first knockout tower 10 generation and the extraction stream 32 generated by the second separator 30
Content reduce or improve the second hydrocarbon flow 6.
Method can further comprise upstream separator with obtain straight-run naphtha and enter line splitting light naphtha stream with
The process of remaining naphtha stream.
Raffinate material flow is sent in catalytic reforming unit, wherein the linear paraffin in raffinate material flow has been removed.
Raffinate material flow can be used as gasoline or the downstream of other products blends stream.Preferably, raffinate material flow is sent to catalysis weight
To improve the yield of aromatics in engagement positions, while reformer product is streamed in aromatic complexes.
Optimization method generates the first lightweight stream from the first knockout tower 10.First lightweight stream is included from naphtha stream
C5- components, because the C5- components are not easy to be reformatted into aromatics.It has also been found that the first knockout tower 10 is operated to send out certain
A little C6 components and stream 12 at the top of lightweight.These components include methyl cyclopentane (MCP), straight chain hexane, methylpentane and dimethyl
Butane.Technique for being cracked to form heavy cracking stream (wherein component has substantial amounts of C7 hydrocarbon), can crack streaming by heavy
Into reformer.
One example is used to illustrate to pass through the achievable improvement of the method.
Table-analog result
Simulation is based on the information operated from device.Scheme uses 1370 KMTA of cracker constant straight run (SR)
Naphtha feed.Divide SR naphthas and keep the constant flow rate of cracker, while reduce the SR stones for being sent to cracker
Cerebrol content, and the light fraction from the first knockout tower improves and the extract from the second separator improves.By residue
It is introduced into catalytic reforming unit.
From the results, it was seen that relative to basic condition, selectivity of light olefin hydrocarbon significantly improves, and passes through the second separator
Rise to it is even more big.Equally, can be seen that the second separator of addition from aromatics yield can improve and change into aromatics
The content of the hydrocarbon of thing.In addition, (organon is pungent by the constant RONC of aromatics for as a result indicating that to keep by reformer generation
Alkane value), the content of catalyst can be reduced, thus can largely save resource and running cost.
Although with it is now recognized that preferred embodiment describes the present invention, it should be understood that the present invention is not limited to institute
Disclosed embodiment, but it is intended to cover be included in various modifications and equivalent in the category of appended claims.
Specific embodiment
Although illustrate herein below with reference to particular, it should be understood that this specification is intended to illustrate and is not intended to limit foregoing
The category of embodiment and appended claims.
First embodiment of the present invention is a kind of production for making downstream process in production light olefin and aromatics
The method of optimization, method, which includes, to be sent to the first hydrocarbon flow 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 generation processing；By the heavy stream of processing
It is sent in the second separator to generate extraction stream and raffinate material flow；Will extraction stream, the first lightweight stream and second
Hydrocarbon flow is sent in cracker；It is sent to by raffinate material flow in catalytic reforming unit.One embodiment of the present invention
Case is one, any or all embodiment in previous example to first embodiment of this section of this section, wherein
First hydrocarbon flow is straight-run naphtha stream.One embodiment of the invention for this section previous example to the first of this section
One, any or all embodiment in individual embodiment, wherein the second hydrocarbon flow is light naphtha or straight run stream.This hair
A bright embodiment is one in previous example to first embodiment of this section of this section, any or all
Embodiment, wherein making the total flow for being sent to cracker keep constant.One embodiment of the invention is the elder generation of this section
One, any or all embodiment in preceding embodiment to first embodiment of this section, it further comprises will be straight
Evaporate naphtha stream and split into the first hydrocarbon flow and the second hydrocarbon flow.
Second embodiment of the invention for it is a kind of optimization hydrocarbon flow composition to improve the method for the efficiency of downstream process,
Method, which includes, to be sent to hydrocarbon flow in the first knockout tower to generate the first lightweight stream and the first heavy stream；By the first heavy
Stream is sent in hydrotreater with the heavy stream of generation processing；The heavy stream of processing is sent to the second separation dress
With first extraction stream of the generation comprising straight-chain hydrocarbons and the raffinate material flow comprising non-straight chain hydrocarbon in putting；With by the first lightweight stream
It is sent to the first extraction stream in cracker to generate light olefin.One embodiment of the invention is previous for this section
One, any or all embodiment in embodiment to second embodiment of this section, it further comprises extract remainder
Stream is sent in catalytic reforming unit.One embodiment of the invention for this section previous example to the second of this section
One, any or all embodiment in embodiment, wherein the first lightweight stream includes C5 hydrocarbon.The implementation of the present invention
Scheme is one, any or all embodiment in previous example to second embodiment of this section of this section, wherein
First lightweight stream includes methyl cyclopentane and the hydrocarbon of relatively lightweight.One embodiment of the invention is the previous embodiment party of this section
One, any or all embodiment in case to second embodiment of this section, wherein the first lightweight stream includes hexamethylene
With the product of relatively lightweight.One embodiment of the invention is the previous example of this section into second embodiment of this section
One, any or all embodiment, wherein cracker generation cracker remnants streams and further comprise cracker
Heels is streamed in reformer.One embodiment of the invention for this section previous example to the second of this section
One, any or all embodiment in embodiment, wherein hydrocarbon flow are cracking naphtha stream.The implementation of the present invention
Scheme is one, any or all embodiment in previous example to second embodiment of this section of this section, wherein
Second separator is adsorption separation device.
Third embodiment of the invention is a kind of method for the aromatic content for improving flow of reformate, and method is included hydrocarbon
Stream is sent in splitter tower to generate the top stream comprising light hydrocarbon and the bottoms stream comprising heavy hydrocarbon；By bottom
Residue is streamed in hydrotreater with the heavy stream of generation processing；The heavy stream of processing is sent to separation dress
In putting the extraction stream of straight-chain hydrocarbons and the raffinate material flow comprising non-straight chain hydrocarbon are included to generate；It is sent to by raffinate material flow
In catalytic reforming unit with generate aromatic content raising processing stream.One embodiment of the invention is the previous reality of this section
One, any or all embodiment in scheme to the 3rd embodiment of this section are applied, wherein splitter tower is naphtha point
Device tower, and hydrocarbon of the top stream comprising C6 and relatively lightweight are split, and bottoms stream includes the hydrocarbon of C7 and heavier.The one of the present invention
Individual embodiment is one, any or all embodiment party in previous example to the 3rd embodiment of this section of this section
Case, it further comprises top being streamed in cracker.One embodiment of the invention is the previous implementation of this section
One, any or all embodiment in scheme to the 3rd embodiment of this section, it further comprises naphtha feed
Flow point is cleaved into Part I and Part II, and Part I is sent in cracker, and Part II is sent to point
Split in device tower.One embodiment of the invention is one in previous example to the 3rd embodiment of this section of this section
Individual, any or all embodiment, it further comprises operating splitter tower and separator to keep being sent to catalytic reforming
The constant mass flow of device.One embodiment of the invention for this section previous example to this section the 3rd implement
One, any or all embodiment in scheme, wherein cracker are that catalytic naphtha cracker or naphtha steam split
Solve device.One embodiment of the invention is, times in previous example to the 3rd embodiment of this section of this section
What or all embodiments, wherein hydrocarbon flow is straight-run naphtha stream.
Fourth embodiment of the invention is a kind of method for producing light olefin, and method includes is sent to the by hydrocarbon flow
With the first lightweight stream of generation and the first heavy stream in one knockout tower；First heavy stream is sent in hydrotreater
With the heavy stream of generation processing；The heavy stream of processing is sent in the second separator to generate the comprising straight-chain hydrocarbons
One extraction stream and the raffinate material flow comprising non-straight chain hydrocarbon；Cracking is sent to by the first lightweight stream and the first extraction stream
To generate light olefin in device.One embodiment of the invention for this section previous example to this section the 4th implement
One, any or all embodiment in scheme, it further comprises raffinate material flow being sent in reformer.This hair
A bright embodiment is one, any or all reality in previous example to the 4th embodiment of this section of this section
Scheme is applied, wherein the first lightweight stream includes C5 hydrocarbon.One embodiment of the invention is the previous example of this section to originally
Section the 4th embodiment in one, any or all embodiment, wherein the first lightweight stream include methyl cyclopentane with
The hydrocarbon of relatively lightweight.One embodiment of the invention is one in previous example to the 4th embodiment of this section of this section
Individual, any or all embodiment, wherein cracker generate cracker heavy stream, and further comprise cracker heavy
Stream is sent in reformer.One embodiment of the invention for this section previous example to this section the 4th implement
One, any or all embodiment in scheme, wherein cracker are cat-cracker.One embodiment of the present invention
Case is one, any or all embodiment in previous example to the 4th embodiment of this section of this section, wherein splitting
Solution device is steam cracking device.One embodiment of the invention for this section previous example to this section the 4th implement
One, any or all embodiment in scheme, wherein hydrocarbon flow are straight-run naphtha stream.One embodiment of the invention
For one, any or all embodiment in previous example to the 4th embodiment of this section of this section, wherein second
Separator is adsorption separation device.
Fifth embodiment of the invention is a kind of method for producing light olefin, and method, which includes, spreads cracker charging
Deliver in cracker, including hydrocarbon charging flow point is cleaved into Part I and Part II；Part I is sent to first point
From in device the extraction stream of linear paraffin and the raffinate material flow comprising non-straight alkane are included to generate；With will extract stream
It is sent to Part II in cracker.One embodiment of the invention for this section previous example to the of this section
One, any or all embodiment in five embodiments, wherein method further comprise Part I being sent to second
In separator logistics is remained to generate stream at the top of lightweight with heavy bottoms；Heavy bottoms residue is streamed to the first separation
In device；It is streamed to by lightweight top in cracker.One embodiment of the invention is the previous embodiment party of this section
One, any or all embodiment in case to the 5th embodiment of this section, it further comprises remaining heavy bottoms
Logistics is sent in hydrotreater and remains logistics with the heavy bottoms of generation processing；Spread with by the bottoms of processing
Deliver in the first separator.One embodiment of the invention for this section previous example to this section the 5th embodiment party
One, any or all embodiment in case, wherein the first separator is adsorption separation device and the second separator is
Fractionating column.One embodiment of the invention for this section previous example to the 5th embodiment of this section in one,
Any or all embodiment, wherein hydrocarbon charging stream are straight-run naphtha stream.One embodiment of the invention is the elder generation of this section
One, any or all embodiment in preceding embodiment to the 5th embodiment of this section, it further comprises raffinate
Material is streamed in reformer.One embodiment of the invention is the 5th real to this section for the previous example of this section
One, any or all embodiment in scheme are applied, wherein reformer is to continue catalyst regeneration process.The one of the present invention
Individual embodiment is one, any or all embodiment party in previous example to the 5th embodiment of this section of this section
Case, wherein cracker generate heavy byproduct stream, and processing further comprises heavy byproduct being sent in reformer.
One embodiment of the invention is one, any or institute in previous example to the 5th embodiment of this section of this section
There is an embodiment, the division of wherein hydrocarbon charging stream is sized to keep the constant feed rate of cracker.
Sixth embodiment of the invention for it is a kind of from straight-run naphtha enter stream produce light olefin method, method bag
Containing naphtha feedstream is split into Part I and Part II；Part I is sent in naphtha splitter fractionating column
To generate stream and heavy bottoms residual logistics at the top of lightweight；Heavy bottoms residue is streamed to naphtha hydrotreater
In to generate the naphtha stream of hydrotreating；The naphtha stream of hydrotreating is sent to generation extraction material in adsorption separation device
Stream and raffinate material flow；Stream at the top of extraction stream, lightweight and Part II are sent in naphtha cracker complex；With by raffinate
Material is streamed in reformer.One embodiment of the invention is the 6th real to this section for the previous example of this section
One, any or all embodiment in scheme are applied, it further comprises the division and the naphtha that control naphtha feedstream
The operation of splitter fractionating column is sent to the constant overall flow rate speed of naphtha cracker complex to generate.
It need not be described in further detail, it is believed that those skilled in the art, which can be used to be previously described, farthest utilizes this hair
It is bright, and the essential characteristic of the present invention is may easily be determined, can be to the present invention in the case of without departing from the spirit and category
Various changes and modifications can be made to make it suitable for various uses and condition.Therefore, foregoing preferably particular should be regarded only
To be exemplary, rather than remainder of this disclosure is limited in any way, and be intended to cover the category of appended claims
Interior included various change and equivalent.
Except as otherwise noted, otherwise above, all temperature are illustrated with degree Celsius (degrees Celsius), institute
There are part and percentage to be by weight.
Claims (7)
1. it is a kind of production light olefin and aromatics in make downstream process Optimizing manufacture method, it includes：
First hydrocarbon flow is sent in the first knockout tower includes methyl cyclopentane, straight chain hexane, methylpentane, diformazan to generate
First lightweight stream of base butane and C5- hydrocarbon and the first heavy stream including hexamethylene and C7+ heavier hydrocarbon；
First heavy stream is sent in hydrotreater with except desulfuration and other impurity for making catalyst poisoning, with generation
The heavy stream of processing；
By the heavy stream of processing be sent in the second separator with generation include heavier straight-chain hydrocarbons extraction stream and including
The raffinate material flow of branched paraffin, cycloalkanes and aromatics；
Extraction stream, the first lightweight stream and the second hydrocarbon flow are sent in cracker, wherein being sent to cracker
Total flow keeps constant；With
Raffinate material flow is sent in catalytic reforming unit to generate the product of aromatic content raising.
2. method according to claim 1, wherein cracker generate cracker remnants streams, and further comprise cracker
Heels is streamed in reformer.
3. method according to claim 1, it further comprises the first lightweight stream and extraction stream being sent to cracker
In to generate light olefin.
4. method according to claim 3, wherein cracker generate cracker heavy stream, and further comprise cracker
Heavy stream is sent in reformer.
5. method according to claim 3, wherein the second separator is adsorption separation device.
6. method according to claim 3, it further comprises operating the first knockout tower and operates the second knockout tower, wherein first
The generation of lightweight stream and the generation of the first extraction stream remain the constant feed rate into cracker.
7. method according to claim 1, wherein cycloalkanes are hexamethylene.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361830964P | 2013-06-04 | 2013-06-04 | |
| US201361830981P | 2013-06-04 | 2013-06-04 | |
| US61/830,981 | 2013-06-04 | ||
| US61/830,964 | 2013-06-04 | ||
| US14/271,399 | 2014-05-06 | ||
| US14/271,399 US9328299B2 (en) | 2013-06-04 | 2014-05-06 | Naphtha cracking |
| US14/271,392 | 2014-05-06 | ||
| US14/271,392 US9328298B2 (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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| CN105264050A CN105264050A (en) | 2016-01-20 |
| CN105264050B true CN105264050B (en) | 2017-12-08 |
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| EP (1) | EP3004291B1 (en) |
| KR (1) | KR102318318B1 (en) |
| CN (1) | CN105264050B (en) |
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| US20150045598A1 (en) * | 2013-08-07 | 2015-02-12 | Uop Llc | Flexible process for enhancing steam cracker and platforming feedstocks |
| EP3455336B1 (en) * | 2016-05-11 | 2020-12-23 | Uop Llc | Process for naphtha cracking and reforming |
| WO2020021356A1 (en) * | 2018-07-27 | 2020-01-30 | Sabic Global Technologies B.V. | Process of producing light olefins and aromatics from wide range boiling point naphtha |
| KR20220067522A (en) | 2020-11-17 | 2022-05-24 | 한국화학연구원 | Method of separating naphtha cracker generated from naphtha using adsorption bed |
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| CN101228104A (en) * | 2005-10-07 | 2008-07-23 | Sk能源株式会社 | Process for increasing production of light olefins from hydrocarbon feedstock in catalytic cracking |
| CN101368111A (en) * | 2007-08-16 | 2009-02-18 | 中国石油天然气集团公司 | Hydrogenation modification method for catalytically cracked gasoline |
| CN101899325A (en) * | 2009-05-26 | 2010-12-01 | Ifp公司 | The production method of the hydrocarbon fraction of high-octane rating and low sulfur content |
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| EP1365004A1 (en) * | 2002-05-23 | 2003-11-26 | ATOFINA Research | Production of olefins |
| US20050101814A1 (en) * | 2003-11-07 | 2005-05-12 | Foley Timothy D. | Ring opening for increased olefin production |
| US20100155300A1 (en) * | 2008-12-24 | 2010-06-24 | Sabottke Craig Y | Process for producing gasoline of increased octane and hydrogen-containing co-produced stream |
| US8283511B2 (en) * | 2010-03-30 | 2012-10-09 | Uop Llc | Ethylene production by steam cracking of normal paraffins |
| US8679320B2 (en) * | 2011-04-29 | 2014-03-25 | Uop Llc | Process for increasing benzene and toluene production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228104A (en) * | 2005-10-07 | 2008-07-23 | Sk能源株式会社 | Process for increasing production of light olefins from hydrocarbon feedstock in catalytic cracking |
| CN101368111A (en) * | 2007-08-16 | 2009-02-18 | 中国石油天然气集团公司 | Hydrogenation modification method for catalytically cracked gasoline |
| CN101899325A (en) * | 2009-05-26 | 2010-12-01 | Ifp公司 | The production method of the hydrocarbon fraction of high-octane rating and low sulfur content |
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| EP3004291A4 (en) | 2017-02-08 |
| PL3004291T3 (en) | 2019-09-30 |
| KR102318318B1 (en) | 2021-10-28 |
| TW201508057A (en) | 2015-03-01 |
| EP3004291A1 (en) | 2016-04-13 |
| WO2014197205A1 (en) | 2014-12-11 |
| TWI488955B (en) | 2015-06-21 |
| EP3004291B1 (en) | 2019-02-06 |
| KR20160015325A (en) | 2016-02-12 |
| CN105264050A (en) | 2016-01-20 |
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