WO2015063255A1 - Procédé de conversion de composés oxygénés en oléfines - Google Patents

Procédé de conversion de composés oxygénés en oléfines Download PDF

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Publication number
WO2015063255A1
WO2015063255A1 PCT/EP2014/073426 EP2014073426W WO2015063255A1 WO 2015063255 A1 WO2015063255 A1 WO 2015063255A1 EP 2014073426 W EP2014073426 W EP 2014073426W WO 2015063255 A1 WO2015063255 A1 WO 2015063255A1
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Prior art keywords
catalyst
reactor
regenerator
olefins
entrained gases
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PCT/EP2014/073426
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English (en)
Inventor
Richard Addison Sanborn
Jeroen Gerard MARSMAN
Leslie Andrew Chewter
Ye Mon Chen
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Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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Publication of WO2015063255A1 publication Critical patent/WO2015063255A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts
    • 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

  • the invention provides a process for converting oxygenates to olefins.
  • the process includes regenerating the catalyst and then passing the regenerated catalyst along with any entrained gases from the regenerator to the reactor.
  • Oxygenate-to -olefin (“OTO") processes are well described in the art. Typically, oxygenate-to -olefin processes are used to produce predominantly ethylene and propylene. An example of such an oxygenate-to -olefin process is described in US Patent Application Publication No. 2011/112344, which is herein incorporated by reference.
  • the publication describes a process for the preparation of an olefin product comprising ethylene and/or propylene, comprising a step of converting an oxygenate feedstock in an oxygenate-to- olefins conversion system, comprising a reaction zone in which an oxygenate feedstock is contacted with an oxygenate conversion catalyst under oxygenate conversion conditions, to obtain a conversion effluent comprising ethylene and/or propylene.
  • U.S. Patent 6965057 describes a process for converting an oxygenate feedstock into an olefin product comprising reacting the oxygenate with a catalyst to form olefins and coked catalyst.
  • the coked catalyst is contacted with an oxygen containing gas to regenerate the catalyst. At least 60% of the entrained oxygen is removed from the regenerated catalyst and the catalyst is returned to the reactor.
  • the patent describes stripping the catalyst with an inert gas or steam in a separate vessel in fluid communication with the regenerator.
  • U.S. Patent 7423191 describes a similar process comprising regenerating the spent catalyst by combustion gases and stripping the regenerated catalyst of gases entrained in the regenerating step.
  • the stripping step is accomplished using nitrogen gas.
  • the regenerated catalyst is passed through a regenerated catalyst stripper before it is returned to the reactor.
  • the invention provides a process for providing a regenerated catalyst stream to an oxygenate to olefins conversion reactor comprising: a) regenerating an at least partially deactivated molecular sieve catalyst by contacting the catalyst with a regeneration medium in a catalyst regenerator; b) passing a flue gas stream from the regenerator to a gas/solid separation device and returning any solids to the regenerator; and c) passing the
  • the invention further provides a process for converting oxygenates to olefins comprising: a) contacting an oxygenate containing stream with a molecular sieve catalyst in an oxygenate to olefins conversion reactor under oxygenate to olefins conversion conditions to form olefins and an at least partially deactivated catalyst; b) regenerating the at least partially deactivated molecular sieve catalyst by contacting the catalyst with a regeneration medium in a catalyst regenerator; c) passing a flue gas stream from the regenerator to a gas/solid separation device and returning any solids to the regenerator; and d) passing the regenerated catalyst and any entrained gases to the reactor without stripping the entrained gases from the catalyst.
  • the invention provides an improved process for converting oxygenates to olefins, and it specifically provides an improved method of regenerating and reusing the
  • the process uses any entrained gases that are carried out of the regenerator with the catalyst as a hot, low steam content dilution gas to the reactor. This prevents additional catalyst deactivation that occurs on contact with steam at high temperatures.
  • the prior art teaches the stripping of the regenerated catalyst to remove entrained gases, but an improved process is obtained by keeping the entrained gases with the regenerated catalyst.
  • the regenerator vessel is a simpler vessel as it does not have a stripping section, and an optional separate stripping vessel is not needed. Further, this provides a faster startup time because the catalyst temperature is not lowered by contact with a stripping gas. This process also reduces the gas loading in the gas/solid separation of the regenerator and in downstream equipment.
  • This process also removes any need for the import of an external stripping gas or for producing additional steam to be used as a stripping gas.
  • the oxygenate to olefins process receives as a feedstock a stream comprising one or more oxygenates.
  • An oxygenate is an organic compound that contains at least one oxygen atom.
  • the oxygenate is preferably one or more alcohols, preferably aliphatic alcohols where the aliphatic moiety has from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms and most preferably from 1 to 4 carbon atoms.
  • the alcohols that can be used as a feed to this process include lower straight and branched chain aliphatic alcohols.
  • ethers and other oxygen containing organic molecules can be used.
  • oxygenates include methanol, ethanol, n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethyl ether, di- isopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid and mixtures thereof.
  • the feedstock comprises one or more of methanol, ethanol, dimethyl ether, diethyl ether or a combination thereof, more preferably methanol or dimethyl ether and most preferably methanol.
  • the oxygenate is obtained as a reaction product of synthesis gas.
  • Synthesis gas can, for example, be generated from fossil fuels, such as from natural gas or oil, or from the gasification of coal.
  • the oxygenate is obtained from biomaterials, such as through fermentation.
  • the oxygenate feedstock can be obtained from a pre-reactor, which converts methanol at least partially into dimethylether and water. Water may be removed, by e.g., distillation. In this way, less water is present in the process of converting oxygenates to olefins, which has advantages for the process design and lowers the severity of
  • the oxygenate to olefins process may in certain embodiments, also receive an olefin co-feed.
  • This co-feed may comprise olefins having carbon numbers of from 1 to 8, preferably from 3 to 6 and more preferably 4 or 5.
  • suitable olefin co-feeds include butene, pentene and hexene.
  • the oxygenate feed comprises one or more oxygenates and olefins, more preferably oxygenates and olefins in an oxygenate:olefm molar ratio in the range of from 1000: 1 to 1 : 1, preferably 100: 1 to 1 : 1. More preferably, in a oxygenate:olefm molar ratio in the range of from 20 : 1 to 1 : 1, more preferably in the range of l8:l to 1 : 1, still more preferably in the range of l5:l to 1 : 1, even still more preferably in the range of l4: l to 1 : 1.
  • the olefin co-feed may also comprise paraffins. These paraffins may serve as diluents or in some cases they may participate in one or more of the reactions taking place in the presence of the catalyst.
  • the paraffins may include alkanes having carbon numbers from 1 to 10, preferably from 3 to 6 and more preferably 4 or 5.
  • the paraffins may be recycled from separation steps occurring downstream of the oxygenate to olefins conversion step.
  • the oxygenate to olefins process may in certain embodiments, also receive a diluent co-feed to reduce the concentration of the oxygenates in the feed and suppress side reactions that lead primarily to high molecular weight products.
  • the diluent should generally be non-reactive to the oxygenate feedstock or to the catalyst. Possible diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, methane, water and mixtures thereof. The more preferred diluents are water and nitrogen with the most preferred being water.
  • the diluent may be used in either liquid or vapor form.
  • the diluent may be added to the feedstock before or at the time of entering the reactor or added separately to the reactor or added with the catalyst.
  • the diluents is added in an amount in the range of from 1 to 90 mole percent, more preferably from 1 to 80 mole percent, more preferably from 5 to 50 mole percent, most preferably from 5 to 40 mole percent.
  • steam is produced as a by-product, which serves as an in-situ produced diluent.
  • additional steam is added as diluent.
  • the amount of additional diluent that needs to be added depends on the in-situ water make, which in turn depends on the composition of the oxygenate feed. Where the diluent provided to the reactor is water or steam, the molar ratio of oxygenate to diluent is between 10: 1 and 1 :20.
  • the oxygenate feed is contacted with the catalyst at a temperature in the range of from 200 to 1000 °C, preferably of from 300 to 800 °C, more preferably of from 350 to 700 °C, even more preferably of from 450 to 650°C.
  • the feed may be contacted with the catalyst at a temperature in the range of from 530 to 620 °C, or preferably of from 580 to 610 °C.
  • the feed may be contacted with the catalyst at a pressure in the range of from 0.1 kPa (1 mbar) to 5 MPa (50 bar), preferably of from 100 kPa (1 bar) to 1.5 MPa (15 bar), more preferably of from 100 kPa (1 bar) to 300 kPa (3 bar).
  • Reference herein to pressures is to absolute pressures.
  • WHSV is defined as the mass of the feed (excluding diluents) per hour per mass of catalyst.
  • the WHSV should preferably be in the range of from 1 hr -1 to 5000 hr 1 .
  • the process takes place in a reactor and the catalyst may be present in the form of a fixed bed, a moving bed, a fiuidized bed, a dense fiuidized bed, a fast or turbulent fiuidized bed, a circulating fiuidized bed.
  • riser reactors, hybrid reactors or other reactor types known to those skilled in the art may be used.
  • more than one of these reactor types may be used in series.
  • the reactor is a riser reactor.
  • the advantage of a riser reactor is that it allows for very accurate control of the contact time of the feed with the catalyst, as riser reactors exhibit a flow of catalyst and reactants through the reactor that approaches plug flow.
  • the feedstocks described above are converted primarily into olefins.
  • the olefins produced from the feedstock typically have from 2 to 30 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, most preferably ethylene and/or propylene.
  • diolefins having from 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins may be produced in the reaction.
  • the feedstock preferably one or more oxygenates
  • the oxygenate is methanol
  • the olefins are ethylene and/or propylene.
  • the products from the reactor are typically separated and/or purified to prepare separate product streams in a recovery system.
  • Such systems typically comprise one or more separation, fractionation or distillation towers, columns, and splitters and other associated equipment, for example, various condensers, heat exchangers, refrigeration systems or chill trains, compressors, knock-out drums or pots, pumps and the like.
  • the recovery system may include a demethanizer, a deethanizer, a depropanizer, a wash tower often referred to as a caustic wash tower and/or quench tower, absorbers, adsorbers, membranes, an ethylene-ethane splitter, a propylene-propane splitter, a butene- butane splitter and the like.
  • additional products, by-products and/or contaminants may be formed along with the preferred olefin products.
  • the preferred products, ethylene and propylene are preferably separated and purified for use in derivative processes such as polymerization processes.
  • the products may comprise C4+ olefins, paraffins and aromatics that may be further reacted, recycled or otherwise further treated to increase the yield of the desired products and/or other valuable products.
  • C4+ olefins may be recycled to the oxygenate to olefins conversion reaction or fed to a separate reactor for cracking.
  • the paraffins may also be cracked in a separate reactor, and/or removed from the system to be used elsewhere or possibly as fuel.
  • the product will typically comprise some aromatic compounds such as benzene, toluene and xylenes.
  • xylenes can be seen as a valuable product.
  • Xylenes may be formed in the OTO process by the alkylation of benzene and, in particular, toluene with oxygenates such as methanol. Therefore, in a preferred embodiment, a separate fraction comprising aromatics, in particular benzene, toluene and xylenes is separated from the gaseous product and at least in part recycled to the oxygenate to olefins conversion reactor as part of the oxygenate feed.
  • part or all of the xylenes in the fraction comprising aromatics are withdrawn from the process as a product prior to recycling the fraction comprising aromatics to the oxygenate to olefins conversion reactor.
  • the C4+ olefins and paraffins formed in the oxygenate to olefins conversion reactor may be further reacted in an additional reactor containing the same or a different molecular sieve catalyst.
  • the C4+ feed is converted over the molecular sieve catalyst at a temperature in the range of from 500 to 700 °C.
  • the additional reactor is also referred to as an OCP reactor and the process that takes place in this reactor is referred to as an olefin cracking process.
  • a product which includes at least ethylene and/or propylene and preferably both.
  • the gaseous product may comprise higher olefins, i.e. C4+ olefins, and paraffins.
  • the gaseous product is retrieved from the second reactor as part of a second reactor effluent stream.
  • the olefin feed is contacted with the catalyst at a temperature in the range of from 500 to 700 °C, preferably of from 550 to 650°C, more preferably of from 550 to 620°C, even more preferably of from 580 to 610°C; and a pressure in the range of from 0.1 kPa (1 mbara) to 5 MPa (50 bara), preferably of from 100 kPa (1 bara) to 1.5 MPa (15 bara), more preferably of from 100 kPa ( 1 bara) to 300 kPa (3 bara).
  • Reference herein to pressures is to absolute pressures.
  • the C4+ olefins are separated into at least two fractions: a C4 olefin fraction and a C5+ olefin fraction.
  • the C4 olefins are recycled to the oxygenate to olefins conversion reactor and the C5+ olefins are fed to the OCP reactor.
  • the cracking behavior of C4 olefins and C5 olefins is believed to be different when contacted with a molecular sieve catalyst, in particular above 500 °C.
  • the cracking of C4 olefins is an indirect process which involves a primary oligomerisation process to a C8, C12 or higher olefin followed by cracking of the oligomers to lower molecular weight hydrocarbons including ethylene and propylene, but also, amongst other things, to C5 to C7 olefins, and by-products such as C2 to C6 paraffins, cyclic hydrocarbons and aromatics.
  • the cracking of C4 olefins is prone to coke formation, which places a restriction on the obtainable conversion of the C4 olefins.
  • paraffins, cyclics and aromatics are not formed by cracking.
  • the conversion of the C4 olefins is typically a function of the temperature and space time (often expressed as the weight hourly space velocity).
  • WHSV weight hourly space velocity
  • C5 olefin cracking is ideally a relatively straight forward- process whereby the C5 olefin cracks into a C2 and a C3 olefin, in particular above 500°C.
  • This cracking reaction can be run at high conversions, up to 100%, while maintaining, at least compared to C4 olefins, high ethylene and propylene yields with a significantly lower by-product and coke make.
  • C5+ olefins can also oligomerise, this process competes with the more beneficial cracking to ethylene and propylene.
  • the C4 olefins are recycled to the oxygenate to olefins conversion reactor.
  • the C4 olefins are alkylated with, for instance, methanol to C5 and/or C6 olefins.
  • These C5 and/or C6 olefins may subsequently be converted into at least ethylene and/or propylene.
  • the main by-products from this oxygenate to olefins conversion reaction are again C4 and C5 olefins, which can be recycled to the oxygenate to olefins conversion reactor and olefin cracking reactor, respectively.
  • the gaseous products further include C4 olefins
  • at least part of the C4 olefins are provided to (i) the oxygenate to olefins conversion reactor together with or as part of the oxygenate feed, and/or (ii) the olefin cracking reactor as part of the olefin feed, more preferably at least part of the C4 olefins is provided to the oxygenate to olefins conversion reactor together with or as part of the oxygenate feed.
  • the gaseous products further include C5 olefins
  • at least part of the C5 olefins are provided to the olefin cracking reactor as part of the olefin feed.
  • the olefin feed to the olefin cracking reactor comprises C4+ olefins, preferably C5+ olefins, more preferably C5 olefins.
  • the oxygenate to olefins conversion reactor and the optional OCP reactor are operated as riser reactors where the catalyst and feedstock are fed at the base of the riser and an effluent stream with entrained catalyst exits the top of the riser.
  • gas/solid separators are necessary to separate the entrained catalyst from the reactor effluent.
  • the gas/solid separator may be any separator suitable for separating gases from solids.
  • the gas/solid separator comprises one or more centrifugal separation units, preferably cyclone units, optionally combined with a stripper section.
  • the reactor effluent is preferably cooled in or immediately after the gas/solid separator to terminate the conversion process and prevent the formation of by-products outside the reactors.
  • the cooling may be achieved by use of a water quench.
  • the catalyst may be returned to the reaction zone from which it came, another reaction zone, a stripping zone or a regeneration zone. Further, the catalyst that has been separated in the gas/solid separator may be combined with catalyst from other gas/solid separators before it is sent to a reaction zone, a stripping zone or the regeneration zone.
  • a portion of the coked molecular sieve catalyst is withdrawn from the reactor and introduced into a regeneration system.
  • the regeneration system comprises a regenerator where the coked catalyst is contacted with a regeneration medium, preferably an oxygen-containing gas, under regeneration temperature, pressure and residence time conditions.
  • Suitable regeneration media include oxygen, 0 3 , SO 3 , N 2 0, NO, N0 2 , N 2 C"5, air, air enriched with oxygen, air diluted with nitrogen or carbon dioxide, oxygen and water, carbon monoxide and/or hydrogen.
  • the regeneration conditions are those capable of burning at least a portion of the coke from the coked catalyst, preferably to a coke level of less than 75% of the coke level on the catalyst entering the regenerator. More preferably the coke level is reduced to less than 50% of the coke level on the catalyst entering the regenerator and most preferably the coke level is reduced to less than 30% of the coke level on the catalyst entering the regenerator. Complete removal of the coke is not necessary as this may result in degradation of the catalyst.
  • the regeneration temperature is in the range of from 200 °C to 1500 °C, preferably from 300 °C to 1000 °C, more preferably from 450 °C to 700 °C and most preferably from 500 °C to 700 °C.
  • the catalyst is regenerated at a temperature in the range of from 550 to 650 °C.
  • the preferred residence time of the coked molecular sieve catalyst in the regenerator is in the range of from 1 minute to several hours, most preferably 1 minute to 100 minutes.
  • the preferred volume of oxygen in the regeneration medium is from 0.01 mole percent to 10 mole percent based on the total volume of the regeneration medium.
  • regeneration promoters typically metal containing compounds such as platinum and palladium are added to the regenerator directly or indirectly, for example with the coked catalyst composition.
  • a fresh molecular sieve catalyst is added to the regenerator.
  • a portion of the regenerated molecular sieve catalyst from the regenerator is returned to the reactor, directly to the reaction zone or indirectly by pre- contacting with the feedstock.
  • the burning of coke is an exothermic reaction and in certain embodiments, the temperature in the regeneration system is controlled to prevent it from rising too high.
  • Various known techniques for cooling the system and/or the regenerated catalyst may be employed including feeding a cooled gas to the regenerator, or passing the regenerated catalyst through a catalyst cooler. A portion of the cooled regenerated catalyst may be returned to the regenerator while another portion is returned to the reactor. In certain embodiments, there is not sufficient coke on the catalyst to raise the temperature of the catalyst to desired levels.
  • a liquid or gaseous fuel may be fed to the regenerator where it will combust and provide additional heat to the catalyst.
  • Catalysts suitable for use in the conversion of oxygenates to olefins may be made from practically any small or medium pore molecular sieve.
  • a suitable type of molecular sieve is a zeolite.
  • Suitable zeolites include, but are not limited to AEI, AEL, AFT, AFO, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, EUO, FER, GOO, HEU, KFI, LEV, LOV, LTA, MFI, MEL, MON, MTT, MTW, PAU, PHI, RHO, ROG, THO, TON and substituted forms of these types.
  • Suitable catalysts include those containing a zeolite of the ZSM group, in particular of the MFI type, such as ZSM-5, the MTT type, such as ZSM-23, the TON type, such as ZSM-22, the MEL type, such as ZSM-11, and the FER type.
  • Other suitable zeolites are for example zeolites of the STF-type, such as SSZ-35, the SFF type, such as SSZ-44 and the EU-2 type, such as ZSM-48.
  • Preferred zeolites for this process include ZSM-5, ZSM-22 and ZSM-23.
  • a suitable molecular sieve catalyst may have a silica-to-alumina ratio (SAR) of less than 280, preferably less than 200 and more preferably less than 100.
  • the SAR may be in the range of from 10 to 280, preferably from 15 to 200 and more preferably from 20 to 100.
  • a preferred MFI-type zeolite for the oxygenate to olefins conversion catalyst has a silica-to-alumina ratio, SAR, of at least 60, preferably at least 80. More preferred MFI- type zeolite has a silica-to-alumina ratio, SAR, in the range of 60 to 150, preferably in the range of 80 to 100.
  • the zeolite-comprising catalyst may comprise more than one zeolite.
  • the catalyst comprises at least a more-dimensional zeolite, in particular of the MFI type, more in particular ZSM-5, or of the MEL type, such as zeolite ZSM-11, and a one-dimensional zeolite having 10-membered ring channels, such as of the MTT and/or TON type.
  • zeolites in the hydrogen form are used in the zeolite-comprising catalyst, e.g., HZSM-5, HZSM-11, and HZSM-22, HZSM-23.
  • the zeolite-comprising catalyst e.g., HZSM-5, HZSM-11, and HZSM-22, HZSM-23.
  • at least 50wt%, more preferably at least 90wt%, still more preferably at least 95wt% and most preferably 100wt% of the total amount of zeolite used is in the hydrogen form.
  • suitable molecular sieves are siliocoaluminophosphates (SAPOs). SAPOs have a three dimensional microporous crystal framework of P02+, A102-, and Si02 tetrahedral units.
  • Suitable SAPOs include SAPO-17, -18, 34, -35, -44, but also SAPO-5, -8, -11, -20, -31, -36, 37, -40, -41, -42, -47 and -56; aluminophosphates (A1PO) and metal substituted (silico)aluminophosphates (MeAlPO), wherein the Me in MeAlPO refers to a substituted metal atom, including metal selected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIB and lanthanides of the Periodic Table of Elements.
  • Preferred SAPOs for this process include SAPO-34, SAPO-17 and SAPO-18.
  • Preferred substituent metals for the MeAlPO include Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr.
  • the molecular sieves described above are formulated into molecular sieve catalyst compositions for use in the oxygenates to olefins conversion reaction and the olefin cracking step.
  • the molecular sieves are formulated into catalysts by combining the molecular sieve with a binder and/or matrix material and/or filler and forming the composition into particles by techniques such as spray-drying, pelletizing, or extrusion.
  • the molecular sieve may be further processed before being combined with the binder and/or matrix. For example, the molecular sieve may be milled and/or calcined.
  • Suitable binders for use in these molecular sieve catalyst compositions include various types of aluminas, aluminophosphates, silicas and/or other inorganic oxide sol.
  • the binder acts like glue binding the molecular sieves and other materials together, particularly after thermal treatment.
  • Various compounds may be added to stabilize the binder to allow processing.
  • Matrix materials are usually effective at among other benefits, increasing the density of the catalyst composition and increasing catalyst strength (crush strength and/or attrition resistance).
  • Suitable matrix materials include one or more of the following: rare earth metals, metal oxides including titania, zirconia, magnesia, thoria, beryllia, quartz, silica or sols, and mixtures thereof, for example, silica-magnesia, silica-zirconia, silica- titania, and silica-alumina.
  • matrix materials are natural clays, for example, kaolin.
  • a preferred matrix material is kaolin.
  • the molecular sieve, binder and matrix material are combined in the presence of a liquid to form a molecular sieve catalyst slurry.
  • the amount of binder is in the range of from 2 to 40 wt%, preferably in the range of from 10 to 35 wt%, more preferably in the range of from 15 to 30 wt%, based on the total weight of the molecular sieve, binder and matrix material, excluding liquid (after calcination).
  • the slurry may be mixed, preferably with rigorous mixing to form a substantially homogeneous mixture.
  • suitable liquids include one or more of water, alcohols, ketones, aldehydes and/or esters. Water is the preferred liquid.
  • the mixture is colloid-milled for a period of time sufficient to produce the desired texture, particle size or particle size distribution.
  • the molecular sieve, matrix and optional binder can be in the same or different liquids and are combined in any order together, simultaneously, sequentially or a combination thereof.
  • water is the only liquid used.
  • the slurry is mixed or milled to achieve a uniform slurry of sub-particles that is then fed to a forming unit.
  • a slurry of the zeolite may be prepared and then milled before combining with the binder and/or matrix.
  • the forming unit is a spray dryer.
  • the forming unit is typically operated at a temperature high enough to remove most of the liquid from the slurry and from the resulting molecular sieve catalyst composition.
  • the particles are then exposed to ion-exchange using an ammonium nitrate or other appropriate solution.
  • the ion exchange is carried out before the phosphorous impregnation.
  • the ammonium nitrate is used to ion exchange the zeolite to remove alkali ions.
  • the zeolite can be impregnated with phosphorous using phosphoric acid followed by a thermal treatment to H+ form.
  • the ion exchange is carried out after the phosphorous impregnation.
  • alkali phosphates or phosphoric acid may be used to impregnate the zeolite with phosphorous, and then the ammonium nitrate and heat treatment are used to ion exchange and convert the zeolite to the H+ form.
  • the catalyst may be formed into spheres, tablets, rings, extrudates or any other shape known to one of ordinary skill in the art.
  • the catalyst may be extruded into various shapes, including cylinders and trilobes.
  • the average particle size is in the range of from 1-200 ⁇ , preferably from 50-100 ⁇ . If extrudates are formed, then the average size is in the range of from 1 mm to 10 mm, preferably from 2 mm to 7 mm.
  • the catalyst may further comprise phosphorus as such or in a compound, i.e.
  • a MEL or MFI-type zeolite comprising catalyst additionally comprises phosphorus.
  • the molecular sieve catalyst is prepared by first forming a molecular sieve catalyst precursor as described above, optionally impregnating the catalyst with a phosphorous containing compound and then calcining the catalyst precursor to form the catalyst.
  • the phosphorous impregnation may be carried out by any method known to one of skill in the art.
  • the phosphorus-containing compound preferably comprises a phosphorus species such as PO 4 3" , P-(OCH 3 ) 3 , or P 2 O 5 , especially P0 4 3 ⁇ .
  • the phosphorus-containing compound comprises a compound selected from the group consisting of ammonium phosphate, ammonium dihydrogen phosphate, dimethylphosphate, metaphosphoric acid and trimethyl phosphite and phosphoric acid, especially phosphoric acid.
  • the phosphorus containing compound is preferably not a Group II metal phosphate.
  • Group II metal species include magnesium, calcium, strontium and barium; especially calcium.
  • phosphorus can be deposited on the catalyst by impregnation using acidic solutions containing phosphoric acid (H 3 P0 4 ). The concentration of the solution can be adjusted to impregnate the desired amount of phosphorus on the precursor. The catalyst precursor may then be dried.
  • the catalyst precursor containing phosphorous (either in the framework or impregnated) is calcined to form the catalyst.
  • the calcination of the catalyst is important to determining the performance of the catalyst in the oxygenate to olefins process.
  • the calcination may be carried out in any type of calciner known to one of ordinary skill in the art.
  • the calcination may be carried out in a tray calciner, a rotary calciner, or a batch oven optionally in the presence of an inert gas and/or oxygen and/or steam
  • the calcination may be carried out at a temperature in the range of from 400 °C to
  • Calcination time is typically dependent on the degree of hardening of the molecular sieve catalyst composition and the temperature and ranges from about 15 minutes to about 2 hours.
  • the calcination temperatures described above are temperatures that are reached for at least a portion of the calcination time.
  • a rotary calciner there may be separate temperature zones that the catalyst passes through.
  • the first zone may be at a temperature in the range of from 100 to 300 °C. At least one of the zones is at the temperatures specified above.
  • the temperature is increased from ambient to the calcination temperatures above and so the temperature is not at the calcination temperature for the entire time.
  • the calcination is carried out in air at a temperature of from 500 °C to 600 °C.
  • the calcination is carried out for a period of time from 30 minutes to 15 hours, preferably from 1 hour to 10 hours, more preferably from 1 hour to 5 hours.
  • the calcination is carried out on a bed of catalyst.
  • a bed of catalyst For example, if the calcination is carried out in a tray calciner, then the catalyst precursor added to the tray forms a bed which is typically kept stationary during the calcination. If the calcination is carried out in a rotary calciner, then the catalyst added to the rotary drum forms a bed that although not stationary does maintain some form and shape as it passes through the calciner.
  • the process of the invention provides for regenerating at least partly deactivated catalyst from the oxygenate to olefins conversion reactor.
  • the regenerated catalyst is regenerated as described previously and then the catalyst along with any entrained gases from the regenerator as passed to the reactor without stripping to remove the entrained gases.
  • the prior art teaches the removal of the entrained gases, but it has now been discovered that the process can be improved by returning those gases to the reactor.
  • the entrained gases may comprise regeneration medium and or combustion products formed when the coke is combusted in the regenerator.
  • the entrained gases may therefore include oxygen, carbon monoxide and/or carbon dioxide.
  • Other gases such as nitrogen are also typically present depending on the regeneration medium used in the regenerator. For example, if air is used as a regeneration medium, then any of the components present in the air may also be found in the entrained gases that are passed to the reactor.
  • the prior art teaching of stripping may occur inside the regenerator vessel or in a separate vessel.
  • the process of this invention does not provide for feeding stripping gases to the regenerator or to a separate vessel to remove the entrained gases. Since this process uses fluidized catalyst, a fluidization gas may be added to the catalyst in the regenerator or between the regenerator and the reactor to improve and/or facilitate the flow of catalyst through the catalyst return line. This may result in the removal of a portion of the entrained gases, but it is preferred to retain as much of the entrained gas as possible with the catalyst. In one embodiment, at least 45% of the entrained gases that were removed with the catalyst from the regenerator are fed into the reactor with the catalyst.
  • At least 50% of the entrained gases that were removed with the catalyst from the regenerator are fed into the reactor with the catalyst.
  • at least 70% of the entrained gases that were removed with the catalyst from the regenerator are fed into the reactor with the catalyst.
  • at least 80% of the entrained gases that were removed with the catalyst from the regenerator are fed into the reactor with the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de conversion de composés oxygénés en oléfines comprenant : a) la mise en contact d'un courant contenant des composés oxygénés avec un catalyseur à base de tamis moléculaire dans un réacteur de conversion de composé oxygéné en oléfines dans des conditions de conversion de composé oxygéné en oléfines afin de former des oléfines et un catalyseur au moins partiellement désactivé ; b) la régénération du catalyseur à base de tamis moléculaire au moins partiellement désactivé en mettant le catalyseur en contact avec un milieu de régénération dans un régénérateur de catalyseur ; c) le passage d'un courant de gaz effluent issu du régénérateur sur un dispositif de séparation gaz/solide et le renvoi de tous les solides vers le régénérateur ; et d) le passage du catalyseur régénéré et de tous les gaz entraînés dans le réacteur sans épuration des gaz entraînés du catalyseur.
PCT/EP2014/073426 2013-10-31 2014-10-31 Procédé de conversion de composés oxygénés en oléfines WO2015063255A1 (fr)

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EP13191196.8 2013-10-31
EP13191196 2013-10-31

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030125598A1 (en) * 2001-12-31 2003-07-03 Chisholm Paul N. Converting oxygenates to olefins over a catalyst comprising acidic molecular sieve of controlled carbon atom to acid site ratio
US6965057B2 (en) 2004-03-24 2005-11-15 Exxonmobil Chemical Patents Inc. Oxygenate to olefin process
US20060149108A1 (en) * 2004-12-30 2006-07-06 Miller Lawrence W Oxygenate conversion reactor catalyst coolers
US7423191B2 (en) 2004-12-16 2008-09-09 Uop Llc Method and system for catalytically converting oxygenates and regenerating and stripping catalyst
US20110112344A1 (en) 2009-11-10 2011-05-12 Leslie Andrew Chewter Process and integrated system for the preparation of a lower olefin product

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030125598A1 (en) * 2001-12-31 2003-07-03 Chisholm Paul N. Converting oxygenates to olefins over a catalyst comprising acidic molecular sieve of controlled carbon atom to acid site ratio
US6965057B2 (en) 2004-03-24 2005-11-15 Exxonmobil Chemical Patents Inc. Oxygenate to olefin process
US7423191B2 (en) 2004-12-16 2008-09-09 Uop Llc Method and system for catalytically converting oxygenates and regenerating and stripping catalyst
US20060149108A1 (en) * 2004-12-30 2006-07-06 Miller Lawrence W Oxygenate conversion reactor catalyst coolers
US20110112344A1 (en) 2009-11-10 2011-05-12 Leslie Andrew Chewter Process and integrated system for the preparation of a lower olefin product

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