EP3004291B1 - Naphtha cracking - Google Patents

Naphtha cracking Download PDF

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Publication number
EP3004291B1
EP3004291B1 EP14807164.0A EP14807164A EP3004291B1 EP 3004291 B1 EP3004291 B1 EP 3004291B1 EP 14807164 A EP14807164 A EP 14807164A EP 3004291 B1 EP3004291 B1 EP 3004291B1
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Prior art keywords
stream
unit
light
cracking
heavy
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German (de)
English (en)
French (fr)
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EP3004291A1 (en
EP3004291A4 (en
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Gregory A. Funk
Mary Jo Wier
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Honeywell UOP LLC
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UOP LLC
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Priority claimed from US14/271,392 external-priority patent/US9328298B2/en
Priority claimed from US14/271,399 external-priority patent/US9328299B2/en
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Priority to PL14807164T priority Critical patent/PL3004291T3/pl
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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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a process for the production of light olefins from a naphtha feed stream. This invention also relates to an improved process for increasing the yields of light olefins.
  • Ethylene and propylene, light olefin hydrocarbons with two or three atoms per molecule, respectively, are important chemicals for use in the production of other useful materials, such as polyethylene and polypropylene.
  • Polyethylene and polypropylene are two of the most common plastics found in use today and have a wide variety of uses for both as a material fabrication and as a material for packaging.
  • Other uses for ethylene and propylene include the production of vinyl chloride, ethylene oxide, ethylbenzene and alcohol.
  • Steam cracking or pyrolysis of hydrocarbons produces essentially all of the ethylene and propylene.
  • Hydrocarbons used as feedstock for light olefin production include natural gas, petroleum liquids, and carbonaceous materials including coal, recycled plastics or any organic material.
  • An ethylene plant is a very complex combination of reaction and gas recovery systems.
  • the feedstock is charged to a cracking zone in the presence of steam at effective thermal conditions to produce a pyrolysis reactor effluent gas mixture.
  • the pyrolysis reactor effluent gas mixture is stabilized and separated into purified components through a sequence of cryogenic and conventional fractionation steps.
  • a typical ethylene separation section of an ethylene plant containing both cryogenic and conventional fractionation steps to recover an ethylene product with a purity exceeding 99.5% ethylene is described in an article by V. Kaiser and M. Picciotti, entitled, "Better Ethylene Separation Unit.” The article appeared in HYDROCARBON PROCESSING MAGAZINE, November 1988, pages 57-61 .
  • the hydrocarbon feedstream to the zeolitic catalyst typically contains a mixture of 40 to 95 wt-% paraffins having 4 or more carbon atoms per molecule and 5 to 60 wt-% olefins having 4 or more carbon atoms per molecule.
  • the preferred catalyst for such a zeolitic cracking process is an acid zeolite, examples includes several of the ZSM-type zeolites or the borosilicates. Of the ZSM-type zeolites, ZSM-5 was preferred.
  • zeolites containing materials which could be used in the cracking process to produce ethylene and propylene included zeolite A, zeolite X, zeolite Y, zeolite ZK-5, zeolite ZK-4, synthetic mordenite, dealuminized mordenite, as well as naturally occurring zeolites including chabazite, faujasite, mordenite, and the like. Zeolites which were ion-exchanged to replace alkali metal present in the zeolite were preferred. Preferred cation exchange cations were hydrogen, ammonium, rare earth metals and mixtures thereof.
  • European Patent No. 109,059B1 discloses a process for the conversion of a feedstream containing olefins having 4 to 12 carbon atoms per molecule into propylene by contacting the feedstream with a ZSM-5 or a ZSM-11 zeolite having a silica to alumina atomic ratio less than or equal to 300 at a temperature from 400 to 600°C.
  • the ZSM-5 or ZSM-11 zeolite is exchanged with a hydrogen or an ammonium cation.
  • the reference also discloses that, although the conversion to propylene is enhanced by the recycle of any olefins with less than 4 carbon atoms per molecule, paraffins which do not react tend to build up in the recycle stream.
  • the reference provides an additional oligomerization step wherein the olefins having 4 carbon atoms are oligomerized to facilitate the removal of paraffins such as butane and particularly isobutane which are difficult to separate from C 4 olefins by conventional fractionation.
  • a process is disclosed for the conversion of butenes to propylene. The process comprises contacting butenes with a zeolitic compound selected from the group consisting of silicalites, boralites, chromosilicates and those zeolites ZSM-5 and ZSM-11 in which the mole ratio of silica to alumina is greater than or equal to 350.
  • the conversion is carried out at a temperature from 500 to 600°C. and at a space velocity of from 5 to 200 kg/hr of butenes per kg of pure zeolitic compound.
  • the European Patent 109060B1 discloses the use of silicalite-1 in an ion-exchanged, impregnated, or co-precipitated form with a modifying element selected from the group consisting of chromium, magnesium, calcium, strontium and barium.
  • US 2011/0245556 describes ethylene production by steam cracking of normal paraffins.
  • US 2012/0273392 describes a process for increasing benzene and toluene production.
  • US 2010/0300932 describes a process for a hydrocarbon fraction with a high octane number and a low sulfur content.
  • the heavier olefins having six or more carbon atoms per molecule which are produced in commercial ethylene plants are useful for the production of aromatic hydrocarbons.
  • Portions of the olefin product include olefins with four carbon atoms per molecule. This portion includes both mono-olefins and di-olefins and some paraffins, including butane and iso-butane. Because the portion with four carbon atoms per molecule is generally less valuable and requires significant processing to separate di-olefins from the mono-olefins, processes are sought to improve the utilization of this portion of the ethylene plant product and enhancing the overall yield of ethylene and propylene.
  • the present invention provides for a process according to claim 1 to optimize and improve the yields of light olefins and aromatics.
  • the process includes passing a hydrocarbon stream to a first separation unit to generate a first light stream and a first heavy stream.
  • the first light stream is made up of hydrocarbon components that are light ends, and are not readily reformable, but that can readily be cracked in a cracking reactor to generate light olefins.
  • the first heavy stream is passed to a hydrotreating unit to remove residual sulfur compounds and nitrogen compounds, and generates a treated heavy stream.
  • the heavy stream is passed to a second separation unit to produce an extract stream comprising the normal hydrocarbons from the heavy hydrocarbon stream.
  • the separation unit also generates a raffinate stream comprising the non-normal components of the heavy hydrocarbon stream.
  • the process further includes passing the first light stream and the extract stream to a cracking unit to generate a light olefin product stream.
  • the process includes passing the raffinate stream to a reforming unit to generate a reformate process stream comprising aromatics.
  • the cracking unit can be a steam cracker, or a catalytic naphtha cracker, with the hydrocarbon stream comprising a straight run naphtha.
  • the first light stream includes C5- hydrocarbons, and some C6 hydrocarbons.
  • the cut for the first separation column includes sending hexanes, methyl cyclopentane, methylpentanes and dimethylbutanes in the first light stream.
  • the Figure is a process flow for increasing yields of light olefins from a naphtha cracker.
  • the production of light olefins is generated from the cracking of heavier hydrocarbons using cracking units.
  • the cracking units are designed for targeted flow rates to convert a hydrocarbon feedstream.
  • the yields can be changed, or increased, by controlling the feedstream makeup, or its content. By manipulating the feedstream content, the yields from a cracking unit can be increased.
  • the production of aromatics for feed to an aromatics complex can also be increased by controlling the feedstream makeup to reforming units in the conversion of non-aromatic constituents to aromatic constituents.
  • the process of the present invention concerns the optimization of operating a cracking unit and a reforming unit, where the feed to each unit is held substantially constant.
  • the process utilizes a straight run naphtha feedstream to be split and passed to the two units.
  • a straight run naphtha feedstream is meant to include a full boiling range naphtha feedstream.
  • the process provides for the conversion of a relatively low value naphtha feedstream into higher value products such as light olefins and aromatic compounds.
  • While to present invention is aimed at optimizing the yields of the two process units, a cracking unit and a catalytic reforming unit, the process can also be used to improve the yields of each individual unit.
  • Hydrocarbon streams comprise a complex mixture.
  • the first separation process is typically around boiling points, where cuts are made on boiling point ranges. Other means of separation are also employed downstream to pull out specific classes of hydrocarbons.
  • a typical feedstream to a cracking unit, and a reforming unit is a straight run naphtha feedstream. But it is intended that other feedstreams can be used for this process, and as used hereinafter, the term naphtha feedstream is meant to encompass other potential hydrocarbon feedstreams that can be used in cracking and reforming.
  • a naphtha feedstream is passed to a cracking unit to generate light olefins.
  • the process for producing light olefins includes passing a hydrocarbon feedstream 8 to a first separation column 10.
  • the column 10 generates a first light stream 12 and a first heavy stream 14.
  • the first heavy stream 14 is passed to a hydrotreating unit 20 to generate a treated heavy stream 22.
  • the treated heavy stream 22 is passed to a second separation unit 30 to generate a first extract stream 32 and a raffinate stream 34.
  • the first extract stream 32 comprises normal hydrocarbons
  • the raffinate stream 34 comprises non-normal hydrocarbons.
  • the first extracts stream 32 and the first light stream 12 are passed to a cracking unit 40 to generate light olefins.
  • the cracking unit 40 can be a stream cracker, or a catalytic naphtha cracking unit.
  • the first light stream 12 can comprise C5- hydrocarbons, and is a separation of the light hydrocarbons from the straight run naphtha stream. It was found that C6 compounds, such as methyl cyclopentane are more difficult to reform, and therefore it was found to be advantageous to pass operate the first separation column 10 to include sending some C6 compounds, including methyl cyclopentane, out with the overhead stream 12.
  • the heavy stream 14 can comprise C7 and heavier components, and some C6 components that are readily reformed, such as cyclohexane.
  • the second separation unit 30 is preferably an adsorption-separation unit, and the separation is controlled by the choice of adsorbent and desorbent.
  • the second separation unit 30 is designed for separating normal hydrocarbons in the C5 to C11 range from the treated heavy stream 22.
  • the normal hydrocarbons are separated and sent out in the extract stream 32, with a raffinate stream 34 comprising non-normal hydrocarbons.
  • the desorbent for the preferred process is a normal C12 paraffin.
  • the raffinate stream 34 is passed to a reforming unit 50 to generate a process stream 52 comprising aromatics.
  • the process stream 52 can be passed to an aromatics complex for conversion to higher value products.
  • the process includes increasing the yields of aromatics from the catalytic reforming unit 50.
  • the process can include passing a heavy stream generated from other process units, such as a heavy cracker stream, wherein the heavy cracker stream comprises C7 and heavier hydrocarbons and is passed to the reforming unit 50.
  • the reforming unit is preferably a continuous catalytic reforming unit wherein the catalyst is in a moving bed, and the catalyst is cycled through the reactor to a regenerator for regenerating the catalyst. This provides for a continuous process.
  • the process includes maintaining a substantially constant flow, while changing the feed composition to increase the aromatics yields.
  • the process includes passing a straight run naphtha feed stream 8 to a naphtha splitter 10 to generate a heavy bottoms stream 14.
  • the heavy bottoms stream 14 is passed to a hydrotreating unit 20 to generate a treated heavy stream 22.
  • the treated heavy stream 22 is passed to an adsorption separation unit 30 to separate out normal hydrocarbons from the treated heavy stream 22.
  • the normal hydrocarbons are passed out in an extract stream 32, and the adsorption separation unit 30 generates a raffinate stream 34 comprising non-normal hydrocarbons.
  • the raffinate stream 34 is passed to the catalytic reforming unit 50.
  • the non-normal hydrocarbons more readily reform to aromatics compounds over the normal hydrocarbons, and the change in feed composition to the reforming unit 50 increases the aromatics yields without increasing the feed flowrate.
  • the process utilizes an adsorption separation process for separating the hydrocarbon feedstream that is split and passed to a cracking unit and a reforming unit.
  • the typical feedstream is a naphtha feedstream, and the performance of both the cracking unit and the catalytic reforming unit are improved.
  • the adsorption separation unit separates normal paraffins from the non-normal paraffins.
  • the non-normal components include branched paraffins, naphthenes and aromatics.
  • the process preferably utilizes a naphtha splitter to separate out the light components that include C5- components in the naphtha.
  • the C5-components are removed from the naphtha prior to passing the naphtha to the reformer, since the C5- components are not capable of being converted into aromatics.
  • the straight run naphtha can be fed to the naphtha stripper with a lighter component hydrocarbon to facilitate the stripping of the naphtha of the C5- components.
  • the straight run naphtha has been hydrotreated, and can then be passed to the reforming unit.
  • the hydrotreatment removes sulfur and other impurities that can act as poisons to catalysts in downstream processing units.
  • One aspect of this process is to change the distribution of hydrocarbons that are fed to the cracking unit and the reforming unit.
  • the change in feed distribution enhances the performance of both the cracking unit and the reforming unit.
  • one improvement is to adjust the splitter to include in the overhead stream of the naphtha splitter 10, additional components that are difficult to reform. Additional components in the overhead include dimethylbutanes, methylpentanes, normal hexanes and methyl cyclopentane (MCP). These additional components are passed to the cracking unit 40. By removing these components from the heavy bottoms stream, the subsequent stream passed to the reforming unit enhances aromatics yields.
  • a further aspect of this process is an additional separation of the heavy bottoms stream. Additional components that are also more difficult to reform, but are more readily cracked to light olefins include heavier normal paraffins.
  • the adsorption separation system allows for the separation of normal paraffins that not readily separated by fractionation. The normal components are then passed to the cracking unit, and the non-normal components are passed to the reforming unit.
  • One aspect of the present process is the optimization of yields for a cracking unit and a reforming unit.
  • the cracking unit and reforming unit can have been designed and sized for a predetermined flow of a naphtha feedstream.
  • the addition of the naphtha splitter and the adsorption separation unit allows for shifting the compositions of the feeds to the cracking unit and the reforming unit, while maintaining substantially constant flows to the two units.
  • the process for optimizing the production of downstream operations in the production of light olefins and aromatics includes a process for optimization of the production of aromatics and light olefins through the selective separation of hydrocarbon components from a hydrocarbon stream.
  • the process includes passing a first hydrocarbon stream 8 to a first separation column 10 to generate a first light stream 12 and a first heavy stream 14.
  • the first heavy stream 14 is passed to a hydrotreating unit 20 to generate a treated heavy stream 22.
  • the treated heavy stream 22 is passed to a second separation unit 30 to generate an extract stream 32 and a raffinate stream 34.
  • the extract stream 32 and the first light stream 12 are passed to a cracking unit 40.
  • the extract stream 32 and the first light stream 12 are supplemented with a second hydrocarbon stream 6 passed to the cracking unit 40.
  • the raffinate stream 34 is passed to a catalytic reforming unit 50 to generate a process stream 52 with increased aromatics content.
  • the typical hydrocarbon stream used for cracking is a naphtha stream
  • the first hydrocarbon stream and the second hydrocarbon stream can be a straight run naphtha, and the streams can be generated by a splitting of the straight run naphtha.
  • the second hydrocarbon stream can be a light naphtha stream, that can be generated during the production of the naphtha streams.
  • the process and flow rates are adjusted to maintain substantially constant flow rates to the cracking unit, and to the catalytic reforming unit. This control is facilitated by the split of the first and second hydrocarbon streams, wherein the second hydrocarbon stream 6 can be reduced or increased in response to the amount of the first light stream 12 generated by the first separation column 10 and the amount of the extract stream 32 generated by the second separation unit 30.
  • the process can further include an upstream separation unit to take the straight run naphtha and make a course splitting with a light naphtha stream and a remaining naphtha stream.
  • the raffinate stream is passed to a catalytic reforming unit, where the raffinate stream has had normal paraffins removed.
  • the raffinate stream can be used as a downstream blending stream for gasoline or other product. It is preferred that the raffinate stream is passed to the catalytic reforming unit to increase the yields of aromatics, with the reforming unit product stream passed to an aromatics complex.
  • the optimization process generates the first light stream from the first separation column 10.
  • the first light stream comprises C5- components from the naphtha stream as they are not readily reformable to aromatics. It has also been found that the first separation column 10 is operated to send some C6 components out with the light overhead stream 12. These components include methyl cyclopentane (MCP), normal hexane, methyl pentanes, and dimethylbutanes.
  • MCP methyl cyclopentane
  • normal hexane normal hexane
  • methyl pentanes methyl pentanes
  • dimethylbutanes dimethylbutanes
  • the simulations are based upon information from the unit operations.
  • the cases assume a constant straight run (SR) naphtha feed of 1370 KMTA to the cracking unit.
  • the SR naphtha was split and a constant flow to the cracking unit was maintained, with decreasing the amount of SR naphtha to the cracking unit as light ends from the first separation column were increased and the extract from the second separation unit was increased. The remainder is directed to the catalytic reforming unit.
  • the light olefin yields increase significantly over the base case, and the improvement with the second separation unit is even more substantial.
  • the addition of the second separation unit increases the amount of hydrocarbons converted to aromatics.
EP14807164.0A 2013-06-04 2014-05-21 Naphtha cracking Active EP3004291B1 (en)

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US201361830964P 2013-06-04 2013-06-04
US201361830981P 2013-06-04 2013-06-04
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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US20150045598A1 (en) * 2013-08-07 2015-02-12 Uop Llc Flexible process for enhancing steam cracker and platforming feedstocks
WO2017196619A1 (en) * 2016-05-11 2017-11-16 Uop Llc Use of platforming process to isomerize light paraffins
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 (ko) 2020-11-17 2022-05-24 한국화학연구원 흡착 베드를 이용하여 나프타로부터 생성된 나프타 분해물을 분리하는 방법

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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
KR100632571B1 (ko) * 2005-10-07 2006-10-09 에스케이 주식회사 탄화수소 원료 혼합물로부터 접촉분해공정을 통해서 경질올레핀계 탄화수소 화합물을 증산하는 방법
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US20100155300A1 (en) * 2008-12-24 2010-06-24 Sabottke Craig Y Process for producing gasoline of increased octane and hydrogen-containing co-produced stream
US8246811B2 (en) * 2009-05-26 2012-08-21 IFP Energies Nouvelles Process for the production of a hydrocarbon fraction with a high octane number and a low sulfur content
US8283511B2 (en) * 2010-03-30 2012-10-09 Uop Llc Ethylene production by steam cracking of normal paraffins
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TW201508057A (zh) 2015-03-01
TWI488955B (zh) 2015-06-21
WO2014197205A1 (en) 2014-12-11
KR20160015325A (ko) 2016-02-12
KR102318318B1 (ko) 2021-10-28
CN105264050A (zh) 2016-01-20
CN105264050B (zh) 2017-12-08
EP3004291A1 (en) 2016-04-13
EP3004291A4 (en) 2017-02-08

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