WO2007079324A2 - Melanges methanol-eau dans la fabrication d’olefines par conversion d’oxygenates - Google Patents

Melanges methanol-eau dans la fabrication d’olefines par conversion d’oxygenates Download PDF

Info

Publication number
WO2007079324A2
WO2007079324A2 PCT/US2006/061877 US2006061877W WO2007079324A2 WO 2007079324 A2 WO2007079324 A2 WO 2007079324A2 US 2006061877 W US2006061877 W US 2006061877W WO 2007079324 A2 WO2007079324 A2 WO 2007079324A2
Authority
WO
WIPO (PCT)
Prior art keywords
oxygenate
methanol
oxygenate conversion
stream
oxygenates
Prior art date
Application number
PCT/US2006/061877
Other languages
English (en)
Other versions
WO2007079324A3 (fr
Inventor
Lawrence W. Miller
Sterling T. Miller
Andrea G. Bozzano
Original Assignee
Uop Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/322,412 external-priority patent/US20070155999A1/en
Priority claimed from US11/463,757 external-priority patent/US20080039670A1/en
Application filed by Uop Llc filed Critical Uop Llc
Publication of WO2007079324A2 publication Critical patent/WO2007079324A2/fr
Publication of WO2007079324A3 publication Critical patent/WO2007079324A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • This invention relates generally to the conversion of oxygenates to olefins and, more particularly, to light olefins using methanol-water mixtures.
  • Light olefin materials generally include ethylene, propylene and mixtures thereof. These light olefins are essential building blocks used in the modern petrochemical and chemical industries.
  • a major source for light olefins in present day refining is the steam cracking of petroleum feeds.
  • Molecular sieves such as microporous crystalline zeolite and non-zeolitic catalysts, particularly silicoaluminophosphates (SAPO), are known to promote the conversion of oxygenates to hydrocarbon mixtures, particularly hydrocarbon mixtures composed largely of light olefins.
  • SAPO silicoaluminophosphates
  • Such processing wherein an oxygenate-containing feed is primarily methanol or a methanol-water combination (including crude methanol), typically results in the conversion of methanol to light olefins (mostly ethylene and propylene) is commonly referred to as Methanol-to-Olefin (MTO) processing.
  • MTO Methanol-to-Olefin
  • DME dimethyl ether
  • DME is a typical byproduct or intermediate of such reaction processing.
  • DME and other oxygenate byproducts can desirably be recycled to the oxygenate conversion reactor for conversion to valuable olefin products, preferably, light olefins.
  • Such recovery and subsequent processing have conventionally been subject to various limitations and restrictions.
  • the separation and recovery of DME from a propylene-containing stream can be problematic for conventional techniques such as conventional fractionation.
  • DME desirably is removed from the propylene feedstock to a polypropylene unit.
  • DME can be scrubbed from the oxygenate conversion reactor effluent vapors using methanol. Methanol, however, also commonly absorbs significant and undesirable quantities of olefins, particularly propylene. Recycle of such absorbed olefins will undesirably and unnecessarily increase the capital cost of upstream equipment and also increase the utilities required for proper operation of the system.
  • MTO processing converts methanol to ethylene and propylene as its primary products
  • the process also has some selectivity to heavy olefins, i.e., C 4 + olefins, which are commonly of relatively low commercial value.
  • the amounts of light olefins resulting from MTO processing can be further increased by reacting, i.e., cracking, heavier hydrocarbon products, particularly heavier olefins such as C 4 and C 5 olefins, to light olefins.
  • This combination of light olefin product and propylene and butylene cracking in a riser cracking zone or a separate cracking zone provides flexibility to the process which overcomes the equilibrium limitations of the aluminophosphate catalyst.
  • the invention provides the advantage of extended catalyst life and greater catalyst stability in the oxygenate conversion zone.
  • a general object of the invention is to provide or result in improved processing of an oxygenate-containing feedstock to light olefins.
  • a more specific objective of the invention is to overcome one or more of the problems described above.
  • the general object of the invention can be attained, at least in part, through a process for producing light olefins from a methanol-containing feedstock.
  • a process for producing light olefins from a methanol-containing feedstock involves contacting the methanol-containing feedstock in an oxygenate conversion reactor with an oxygenate conversion catalyst and at reaction conditions effective to convert the methanol-containing feedstock to an oxygenate conversion product stream comprising light olefins, C 4 + hydrocarbons and oxygenates.
  • At least a liquid portion of the oxygenate conversion product stream is contacted in an absorber with a solvent mixture comprising at least methanol and water.
  • the solvent mixture is effective to absorb a significant portion of the oxygenates from the contacted portion of the oxygenate conversion product stream.
  • the oxygenate conversion product stream comprises the oxygenate dimethyl ether.
  • At least a portion of the oxygenate conversion product stream is contacted in an absorber with a solvent mixture comprising at least methanol and water effective to absorb and recover a significant portion of the dimethyl ether from the oxygenate conversion product stream. At least a portion of the dimethyl ether absorbed from the conversion product stream is subsequently introduced into the oxygenate conversion reactor and reacted to form additional oxygenate conversion products.
  • the process involves treating the oxygenate conversion product stream in a gas concentration system to recover light olefins and to form a C 4 + hydrocarbon stream also containing oxygenates.
  • the C 4 + hydrocarbon stream also containing oxygenates may desirably comprise the portion of the oxygenate conversion product stream contacting with the solvent mixture in the absorber and wherein as a result of said contacting a C 4 + hydrocarbon stream having a reduced oxygenate content is formed.
  • At least a portion of the C 4 + hydrocarbon stream having a reduced oxygenate content contacts with an olefin cracking catalyst in an olefin cracking reactor at reaction conditions effective to convert C 4 and C 5 olefins therein contained to a cracked olefins effluent stream comprising light olefins.
  • a system for converting methanol to light olefins includes a reactor for contacting a methanol- containing feedstream with catalyst and converting the methanol-containing feedstream to an oxygenate conversion product stream comprising light olefins, C 4 + hydrocarbons and oxygenates.
  • the system also includes an absorber wherein at least a portion of the oxygenate conversion product stream contacts a solvent mixture comprising at least methanol and water. The solvent mixture is effective to absorb a significant portion of the oxygenates from the contacted portion of the oxygenate conversion product stream.
  • a first return line is provided wherein at least a portion of the oxygenates absorbed from the contacted portion of the oxygenate conversion product stream is introduced to the oxygenate conversion reactor for contact with the oxygenate conversion catalyst and at reaction conditions effective to convert at least a portion of the oxygenates to oxygenate conversion products.
  • light olefins are to be understood to generally refer to C 2 and C 3 olefins, i.e., ethylene and propylene.
  • Oxygenates are hydrocarbons that contain one or more oxygen atoms. Typical oxygenates include alcohols and ethers, for example.
  • References to "C x hydrocarbon” are to be understood to refer to hydrocarbon molecules having the number of carbon atoms represented by the subscript "x".
  • C x -containing stream refers to a stream that contains C x hydrocarbon.
  • C x + hydrocarbons refers to hydrocarbon molecules having the number of carbon atoms represented by the subscript "x” or greater.
  • C 4 + hydrocarbons include C 4 , C 5 and higher carbon number hydrocarbons.
  • FIG. 1 is a simplified schematic diagram of a process for the production of olefins and, more specifically, a process for the production of olefins, particularly light olefins; via oxygenate conversion processing in accordance with one embodiment.
  • FIG. 2 is a simplified schematic diagram of a section of a treatment and hydrocarbon recovery zone in accordance with one embodiment.
  • FIG. 3 a simplified schematic diagram of a pre-olefin cracking C 4 + hydrocarbon stream treatment zone in accordance with one embodiment.
  • FIG. 4 a simplified schematic diagram of a pre-olefin cracking C 4 + hydrocarbon stream treatment zone in accordance with another embodiment.
  • FIG. 5 a simplified schematic diagram of a processing scheme in accordance with another embodiment.
  • an oxygenate-containing feedstock can be converted to olefins and, more particularly, to light olefins via a catalytic reaction such as in an oxygenate conversion reactor.
  • Heavier hydrocarbons e.g., C 4 + hydrocarbons
  • the light olefins e.g., C 2 and C 3 olefins
  • the process stream can desirably be processed by contacting at least a portion of the oxygenate conversion product stream in an absorber with a solvent mixture including at least methanol and water, as such a solvent mixture has been found to be particularly effective in the liquid-liquid absorption or liquid-liquid contact and removal of a significant portion of the oxygenates from the contacted portion of the oxygenate conversion product stream without detrimentally also absorbing significant quantities of olefins also present in the product stream.
  • a solvent mixture including at least methanol and water
  • the solvent mixture employed in such absorption or removal may desirably consist essentially of methanol and water.
  • references to a "significant portion" as used herein in reference to oxygenates absorbed or removed from the contacted portion of the oxygenate conversion product stream are to be understood to generally constitute at least 70% of the oxygenates present therein.
  • references to a "significant portion" as used herein in reference to oxygenates absorbed or removed from the contacted portion of the oxygenate conversion product stream are to be understood to generally constitute at least 80% of the oxygenates present therein. In accordance with other certain preferred embodiments, references to a "significant portion” as used herein in reference to oxygenates absorbed or removed from the contacted portion of the oxygenate conversion product stream are to be understood to generally constitute at least 95% of the oxygenates present therein.
  • FIG. 1 illustrates a simplified schematic process flow diagram for a process scheme, generally designated by the reference numeral 10, for the production of olefins, particularly light olefins, via oxygenate (e.g., methanol) conversion processing.
  • oxygenate e.g., methanol
  • An oxygenate-containing feedstock shown as a line 12 and such as generally composed of methanol and, if desired, one or more additional light oxygenates such as one or more of ethanol, dimethyl ether (“DME”), diethyl ether, or mixtures thereof, is introduced into an oxygenate conversion reactor section 14 wherein the oxygenate-containing feedstock contacts with an oxygenate conversion catalyst at reaction conditions effective to convert the oxygenate-containing feedstock to an oxygenate conversion product stream, shown as a line 16, such as comprising light olefins and C 4 + hydrocarbons, in a manner as is known in the art, such as, for example, utilizing a fluidized bed reactor.
  • a line 16 such as comprising light olefins and C 4 + hydrocarbons
  • an oxygenate conversion product stream may also typically include or contain additional components or materials such as either or both fuel gas hydrocarbons and oxygenate species including unreacted feed oxygenates, e.g., methanol, as well as oxygenate byproduct species such as dimethyl ether and such as formed in situ as a byproduct or intermediate of the desired methanol-to-oxygenate conversion process as well varying or trace quantities of other oxygenate byproducts.
  • fuel gas hydrocarbons and oxygenate species including unreacted feed oxygenates, e.g., methanol, as well as oxygenate byproduct species such as dimethyl ether and such as formed in situ as a byproduct or intermediate of the desired methanol-to-oxygenate conversion process as well varying or trace quantities of other oxygenate byproducts.
  • oxygenate byproducts are typically in the nature of light alcohols, aldehydes and ketones.
  • suitable such oxygenate-containing feedstock may constitute commercial grade methanol, crude methanol or various combinations thereof. Crude methanol may be an unrefined product from a methanol synthesis unit. Moreover, in the interest of factors such as improved catalyst stability, embodiments utilizing higher purity methanol feeds may be preferred.
  • suitable feeds may comprise methanol or a methanol and water blend, with possible such feeds having a methanol content of between 65% and 100% by weight, preferably a methanol content of between 80% and 100% by weight and, in accordance one preferred embodiment, a methanol content of between 95% and 100% by weight.
  • the oxygenate conversion product stream of the line 16 is appropriately processed through a compressor section 24, such as may be desirably composed of a plurality of compression stages. Additional processing steps may intervene between the reactor section 14 and the compressor section 24 to cool and/or reduce the volume or concentration of byproduct in the product stream in line 16.
  • the resulting compressed oxygenate conversion product stream, shown as a line 26, such as after appropriate cooling (not shown) is introduced into an appropriate treatment and hydrocarbon recovery zone 30. As described in greater detail below and in accordance with one preferred embodiment (see FIG.
  • such a treatment and hydrocarbon recovery zone may desirably include one or more unit operations whereby the oxygenate conversion product stream can be treated, such as via a liquid-liquid absorption, extraction or contact and removal with a methanol and water solvent mixture to remove and desirably recover selected species, such as oxygenates, such as DME.
  • the oxygenate conversion product stream can be processed through a conventional oxygenate recovery scheme such as involving separate contacting such as in a wash column with first either a methanol or low purity water (e.g., recycle water) wash stream followed with a subsequent water wash stream such as in a water wash column such as to recover remaining methanol or with a high purity water to recover remaining oxygenate materials.
  • the treatment and hydrocarbon recovery zone 30 may desirably include a hydrocarbon recovery section such as generally composed of a gas concentration system.
  • a hydrocarbon recovery section such as generally composed of a gas concentration system.
  • the oxygenate conversion product stream materials can be processed to at least separately concentrate and recover a fuel gas stream 34, an ethylene stream 36, a propylene stream 40 and a mixed C 4 + hydrocarbon stream 42, such as generally composed of butylenes and heavier hydrocarbons.
  • a mixed C 4 + hydrocarbon stream may result through processing involving washing a corresponding precursor stream with a solvent mixture of methanol and water to recover oxygenates therefrom.
  • the mixed C 4 + hydrocarbon stream 42 can be introduced into an olefin cracking reactor section 44 wherein at least a portion of the C 4 and C 5 olefin hydrocarbon products are cracked to form a cracked olefin effluent, shown as the line 46, comprising C 2 and C 3 olefins.
  • the cracked olefin effluent from the line 46 if desired but not shown, can be appropriately introduced into the treatment and hydrocarbon recovery zone 30 wherein selected cracked olefin effluent species can be appropriately separated, such as in a manner known in the art.
  • a stream (shown as the line 52), such as generally composed of methanol, water and recovered oxygenates ami such as may contain some residual olefins, exits from the treatment and hydrocarbon recovery zone 30.
  • the line 52 may desirably be introduced into a processing section 54, such as in ihe form of a fmctionator, for example, wherein at least a portion of the water (signified by the line 56) can be separated therefrom and at least a portion of the previously absorbed oxygenates and methanol as well as residual olefins (signified by the line 60) can be returned or introduced to the oxygenate conversion reactor section 14 for contact with the oxygenate conversion catalyst and at reaction conditions effective to convert at least a portion of the oxygenates to oxygenate conversion products.
  • a processing section 54 such as in ihe form of a fmctionator, for example, wherein at least a portion of the water (signified by the line 56) can be separated therefrom and at least a portion of the previously absorbed oxygenates and methanol as well as residual olefins (signified by the line 60) can be returned or introduced to the oxygenate conversion reactor section 14 for contact with the oxygenate conversion catalyst and at reaction conditions effective to convert at least a portion
  • Such pre-coking has been found to increase the selectivity of oxygenate conversion catalysts for light olefins. Such pre-coking can be accomplished by contacting freshly regenerated oxygenate conversion catalyst with the returned or recycled oxygenate stream 60.
  • a treatment and hydrocarbon recovery zone generally designated by the reference numeral 70, and such as for use in or as part of an olefin production scheme, such as the olefin production scheme 10 described above.
  • the treatment and hydrocarbon recovery zone 70 desirably includes one or more unit operations whereby an oxygenate conversion product stream can be treated with a methanol and water solvent mixture to desirably remove and preferably recover selected species, such as oxygenates, such as DME.
  • a compressed oxygenate conversion effluent stream or, in accordance with a preferred embodiment, at least a liquid portion thereof, here designated by the reference numeral 72 is introduced into an oxygenate recovery section 74, such as may include at least one absorber column and one or more appropriately selected washer columns.
  • an oxygenate recovery section 74 a stream 76 of an appropriate solvent mixture of methanol and water, such as described above, is desirably introduced and oxygenates such as methanol, dimethyl ether (DME) and other trace oxygenates including carbonyls such as acetaldehyde are absorbed therein or otherwise separated from the hydrocarbon product materials.
  • oxygenates such as methanol, dimethyl ether (DME) and other trace oxygenates including carbonyls such as acetaldehyde are absorbed therein or otherwise separated from the hydrocarbon product materials.
  • the oxygenate recovery section 74 forms or results in an oxygenate-rich methanol/water stream, shown as a line 80, such as comprises such oxygenate materials in methanol/water and such as may contain some residual olefins, and a stream such as comprises such hydrocarbon product materials, shown as a line 82.
  • the oxygenate-rich methanol/water stream of line 80 can, if desired, be treated in a manner such as known in the art such as described above relative to the stream shown as the line 52 in FIG. 1, for example.
  • the hydrocarbon product material stream of line 82 can be further processed such as by being introduced into an caustic wash section 84 wherein such hydrocarbon product material can be processed such as by being conventionally washed with a caustic solution (not shown) to neutralize any acid gases and dried prior to passage of a resulting treated stream 86 onto a desired gas concentration and product recovery system 90.
  • Gas concentration and product recovery systems such as used for the processing of the effluent resulting from such oxygenate conversion processing are well known to those skilled in the art and do not generally form limitations on the broader practice of the invention as those skilled in the art and guided by the teachings herein provided will appreciate.
  • the remaining hydrocarbon product material can be processed such as to form desired hydrocarbon fraction streams.
  • the gas concentration and product recovery system 90 may desirably form a fuel gas stream 92, an ethylene stream 94, a propylene stream 96 and a mixed C 4 + hydrocarbon stream 100, such as generally composed of butylene and heavier hydrocarbons.
  • FIG. 3 there is more specifically illustrated a processing scheme in accordance with one embodiment and here generally designated by the reference numeral 1 10.
  • a mixed C 4 + hydrocarbon stream such as described above and here shown as the line 112 results through processing involving washing a corresponding oxygenate-rich C 4 + hydrocarbon stream, shown as the line 114, with a solvent mixture of methanol and water to recover oxygenates therefrom.
  • the oxygenate-rich C 4 + hydrocarbon stream from the line 114 is introduced into a lower portion of a first wash column 116.
  • a solvent mixture shown as the line 120 and comprising at least methanol and water, is introduced into an upper portion of the wash column 1 16.
  • a first wash column is sometimes hereinafter referred to as a methanol/water wash column.
  • oxygenates such as dimethyl ether (DME) and other trace oxygenates including carbonyls such as acetaldehyde are absorbed in or otherwise effectively removed via the methanol/water solvent mixture and thus are separated from the C 4 + hydrocarbon product materials.
  • a line 122 Exiting from a lower portion of the methanol/water wash column 116 is a line 122 generally composed of a stream of oxygenate-rich methanol/water and such as may contain some residual olefins.
  • Such an oxygenate-rich methanol/water stream can, if desired, be treated in a manner such as known in the art such as described above relative to the stream shown as the line 52 in FIG. 1, for example.
  • a sieve drier, a stripper column or some alternative device or apparatus can be employed, if desired, to effect desired removal of water therefrom prior to return or recycle thereof or component portions therefrom to an associate oxygenate conversion reactor.
  • a line 124 Exiting from an upper portion of the methanol/water wash column 116 is a line 124 generally composed of a stream containing the methanol/water washed C 4 + hydrocarbons.
  • the line 124 generally composed of the stream containing the washed C 4 + hydrocarbons may also contain some residual amount of oxygenates such as residual amounts of DME and the like.
  • such a line 124 may also contain methanol such as carried over with the C 4 + hydrocarbon.
  • the processing scheme 110 desirably also includes a second or follow-up wash column, designated by the reference numeral 130.
  • the line 124 generally composed of the stream containing the washed C 4 + hydrocarbons can desirably introduced into a lower portion of the second wash column 130.
  • a solvent comprising and, in accordance with at least certain preferred embodiments, consisting essentially of wash water is introduced via a line 132 into an upper portion of the second wash column 130.
  • a second wash column is sometimes hereinafter referred to as a water wash column.
  • residual oxygenates and carryover methanol are desirably washed or otherwise effectively removed from the processed material such as to form the line 112 composed of a C 4 + hydrocarbon stream having an appropriately reduced oxygenate content and a line 134 composed of a water stream containing removed oxygenates and carryover methanol.
  • such C 4 + hydrocarbon streams having a reduced oxygenate content generally desirably have an oxygenate content of less than 1500 ppmw equivalent water based on oxygen.
  • C 4 + hydrocarbon streams having a reduced oxygenate content have an oxygenate content of less than 1000 ppmw equivalent water based on oxygen and more preferably have an oxygenate content of less than 650 ppmw equivalent water based on oxygen.
  • C 4 + stream materials can, in specific embodiments, be appropriately processed through a drying or other water removal process such as via a stripper column or a dryer system, such as to appropriately reduce the water content thereof.
  • the C 4 + hydrocarbon stream having an appropriately reduced oxygenate content can be desirably processed, as described above, through an olefin cracking reactor section wherein at least a portion of the C 4 and C 5 olefin hydrocarbon products can desirably be cracked to form additional light olefins products.
  • olefin cracking processing can desirably be practiced after the C 4 + hydrocarbon stream has been appropriately processed through a drying or other water removal process, as described above.
  • the water stream containing removed oxygenates and carryover methanol of line 134 can be appropriately treated, such as in a manner known in the art, to permit appropriate recovery, recycle or disposal of the component portions thereof.
  • a sieve drier, a stripper column or some alternative device or apparatus can be employed, if desired, to effect desired removal of water therefrom prior to return or recycle of removed oxygenates and/or methanol therefrom to an associated oxygenate conversion reactor.
  • a second wash column such a processing may advantageously better ensure reduced or minimal methanol carryover with the C 4 + materials and thus reduce or minimize possible impact thereof on downstream processing.
  • such inclusion of such a second wash column can better ensure oxygenate removal by affording a further opportunity remove oxygenates such as may have remained in the process stream after treatment in the first wash column.
  • FIG. 4 there is more specifically illustrated a processing scheme, generally designated by the reference numeral 140, in accordance with another embodiment, wherein a mixed C 4 + hydrocarbon stream, such as described above and shown as the line 142, results through processing involving washing a corresponding oxygenate-rich C 4 + hydrocarbon stream with a solvent mixture of methanol and water to recover oxygenates therefrom.
  • the processing scheme 140 differs primarily from the processing scheme 110 described above in that the processing scheme 140 combines methano I/water washing and water washing in a single column.
  • an oxygenate-rich C 4 + hydrocarbon stream shown as a line 144, is introduced into a lower portion of a wash column 150.
  • a solvent mixture comprising at least methanol and water is introduced via a line 152 into an intermediate portion of the wash column 150.
  • Oxygenates such as dimethyl ether (DME) and other trace oxygenates including carbonyls such as acetaldehyde are absorbed in the methano I/water solvent mixture and thus are separated from the C 4 + hydrocarbon product materials.
  • DME dimethyl ether
  • carbonyls such as acetaldehyde
  • the methano I/water washed C 4 + hydrocarbon product materials advance towards the upper portion of the wash column 150, whereat a solvent or wash fluid comprising and, in accordance with at least certain preferred embodiments, consisting essentially of wash water is introduced via a line 154.
  • wash water is desirably effective to wash or otherwise effectively remove residual oxygenates and carryover methanol from the processed material such as to form the line 142 composed of an oxygenate-free C 4 + hydrocarbon stream.
  • a line 156 Exiting from a lower portion of the wash column 150 is a line 156 generally composed of a stream of oxygenate-rich methanol/ water and such as may contain some residual olefins.
  • Such an oxygenate-rich methanol/water stream can, if desired, be treated in a manner such as known in the art such as described above relative to the stream shown as the line 52 in FIG. 1, for example.
  • Such a single wash column processing scheme can advantageously reduce equipment costs, as compared to the above-described multiple wash column processing scheme.
  • FIG. 5 A processing scheme in accordance with one such embodiment is illustrated in FIG. 5 and generally designated by the reference numeral 210.
  • an oxygenate-rich C 4 + hydrocarbon stream shown as the line 212, and such as resulting from an oxygenate conversion reactor section such as described above and not here shown, is introduced into an appropriate splitter processing device or apparatus 214 to effect such a process split.
  • suitable such processing devices to effect such a process split may include a fractionation column, a flash drum or the like.
  • the splitter device 214 desirably forms, produces or results in a stream, shown as the line 215, composed of lighter carbon-containing materials (e.g., C 4 materials) and in which lighter oxygenates such as DME and/or water concentrate and a stream, shown as the line 216, composed of heavier carbon-containing materials (e.g., C 5 + materials) and in which the heavier oxygenates concentrate.
  • the stream line 216 can be appropriately introduced into an oxygenate recovery section 220 such as comprising a methanol/water wash column.
  • a stream 222 of an appropriate solvent mixture of methanol and water, such as described above, is desirably introduced and heavier oxygenates are absorbed therein or otherwise separated from the C 5 + hydrocarbon product materials.
  • the oxygenate recovery section 220 forms or results in an oxygenate-rich methanol/water stream, shown as a line 224, such as comprises such oxygenate materials in methanol/water and such as may contain some residual olefins and a stream such as comprises such washed C 5 + hydrocarbon product materials, shown as line 226.
  • the light oxygenate and/or water removal section 230 produces or results in a mixed C 4 + hydrocarbon stream, shown as a 232, and a stream containing separated light oxygenates and/water, shown as a line 234.
  • the mixed C 4 + hydrocarbon stream line 232 can be introduced into an olefin cracking reactor section (not shown), as described above, wherein at least a portion of the C 4 and C 5 olefin hydrocarbon products are cracked to form a cracked olefin effluent.
  • the stream line 234 containing separated light oxygenates and/water can be appropriately treated, such as in a manner known in the art, to permit appropriate recovery, recycle or disposal of the component portions thereof.
  • the stream line 234 or selected portions thereof can desirably be recycled back to the oxygenate conversion reactor for desired processing.
  • desirable methanol and water combinations or mixtures for appropriately balancing maximizing oxygenate extraction while minimizing C 4 + hydrocarbon extraction generally include between 5 and 80 percent by weight methanol.
  • desirable methanol and water combinations or mixtures for appropriately balancing maximizing oxygenate extraction while minimizing C 4 + hydrocarbon extraction generally include between 20 and 95 percent by weight water.
  • such C 4 + hydrocarbon streams having a reduced oxygenate content generally desirably have an oxygenate content of less than 800 ppmw equivalent water based on oxygen.
  • C 4 + hydrocarbon streams having a reduced oxygenate content preferably have an oxygenate content of less than 650 ppmw equivalent water based on oxygen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L’invention concerne des schémas de traitement et des dispositifs pour la fabrication d’oléfines légères à partir d’une matière première contenant des oxygénates et utilisant des mélanges méthanol-eau pour récupérer les oxygénates, par exemple pour un traitement ultérieur pour former des oléfines légères supplémentaires.
PCT/US2006/061877 2005-12-30 2006-12-11 Melanges methanol-eau dans la fabrication d’olefines par conversion d’oxygenates WO2007079324A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11/322,412 2005-12-30
US11/322,412 US20070155999A1 (en) 2005-12-30 2005-12-30 Olefin production via oxygenate conversion
US11/463,757 US20080039670A1 (en) 2006-08-10 2006-08-10 Methanol-Water Mixtures in Olefin Production Via Oxygenate Conversion
US11/463,757 2006-08-10

Publications (2)

Publication Number Publication Date
WO2007079324A2 true WO2007079324A2 (fr) 2007-07-12
WO2007079324A3 WO2007079324A3 (fr) 2007-12-13

Family

ID=38228919

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/061877 WO2007079324A2 (fr) 2005-12-30 2006-12-11 Melanges methanol-eau dans la fabrication d’olefines par conversion d’oxygenates

Country Status (1)

Country Link
WO (1) WO2007079324A2 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050124838A1 (en) * 2003-12-05 2005-06-09 Kuechler Keith H. Catalyst fluidization in oxygenate to olefin reaction systems

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050124838A1 (en) * 2003-12-05 2005-06-09 Kuechler Keith H. Catalyst fluidization in oxygenate to olefin reaction systems

Also Published As

Publication number Publication date
WO2007079324A3 (fr) 2007-12-13

Similar Documents

Publication Publication Date Title
US11255604B2 (en) Process for removing light components from an ethylene stream
AU2007300392B2 (en) Enhanced oxygenate conversion and product cracking integration
US8257661B2 (en) Integration of OTO process with direct DME synthesis
TWI392661B (zh) 用於甲醇製烯烴方法之吸收－脫甲烷塔
US20040039239A1 (en) Method and reactor system for converting oxygenate contaminants in an MTO reactor system product effluent to hydrocarbons
EP2338865A1 (fr) Procédé pour éliminer des polluants oxygénés d'un flux d'hydrocarbures
US20090005624A1 (en) Integrated Processing of Methanol to Olefins
US20140350319A1 (en) Process for removing oxygenated contaminants from an hydrocarbonstream
CN101333144B (zh) 从烯烃物流中脱除二甲醚的方法
US20080039670A1 (en) Methanol-Water Mixtures in Olefin Production Via Oxygenate Conversion
US9878962B2 (en) Process and plant for producing olefins from oxygenates
CA2646165C (fr) Traitement integre de methanol en olefines
WO2007079324A2 (fr) Melanges methanol-eau dans la fabrication d’olefines par conversion d’oxygenates
US11046627B2 (en) MTP/MTO technology process integrated for propylene production
CN214693946U (zh) 用于纯化1-戊烯的设备
CN112321380A (zh) 用于纯化1-戊烯的方法和设备

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06849117

Country of ref document: EP

Kind code of ref document: A2