WO2004037753A1 - Method and system for reducing decomposition byproducts in a methanol to olefin reactor system - Google Patents
Method and system for reducing decomposition byproducts in a methanol to olefin reactor system Download PDFInfo
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- WO2004037753A1 WO2004037753A1 PCT/US2003/027794 US0327794W WO2004037753A1 WO 2004037753 A1 WO2004037753 A1 WO 2004037753A1 US 0327794 W US0327794 W US 0327794W WO 2004037753 A1 WO2004037753 A1 WO 2004037753A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00119—Heat exchange inside a feeding nozzle or nozzle reactor
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/0015—Controlling the temperature by thermal insulation means
- B01J2219/00155—Controlling the temperature by thermal insulation means using insulating materials or refractories
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
- B01J2219/00252—Formation of deposits other than coke
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
- B01J2219/0218—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components of ceramic
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
- B01J2219/0236—Metal based
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- 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
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- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/919—Apparatus considerations
- Y10S585/92—Apparatus considerations using apparatus of recited composition
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/919—Apparatus considerations
- Y10S585/921—Apparatus considerations using recited apparatus structure
- Y10S585/922—Reactor fluid manipulating device
- Y10S585/923—At reactor inlet
Definitions
- This invention is to a system and method for reducing methanol decomposition byproducts in a methanol to olefm reactor system. More particularly, the invention concerns reducing the formation of metal catalyzed side reaction byproducts by forming and/or coating at least a portion of the feed vaporization and introduction system, e.g., the feed introduction nozzle, with a material that reduces the formation of metal-catalyzed side reaction byproducts.
- Light olefins defined herein as ethylene and propylene, serve as feeds for the production of numerous important chemicals and polymers.
- Light olefins traditionally are produced by cracking petroleum feeds. Because of the limited supply and escalating cost of petroleum feeds, the cost of producing olefins from petroleum sources has increased steadily. Efforts to develop and improve olefin production technologies, particularly light olefins production technologies, have increased.
- a feedstock containing an oxygenate is vaporized and introduced into a reactor.
- oxygenates include alcohols such as methanol and ethanol, dimethyl ether, methyl ethyl ether, methyl formate, and dimethyl carbonate.
- MTO methanol to olefin
- the oxygenate-containing feedstock includes methanol.
- the methanol contacts a catalyst under conditions effective to create desirable light olefins.
- molecular sieve catalysts have been used to convert oxygenate compounds to olefins.
- Silicoaluminophosphate (SAPO) molecular sieve catalysts are particularly desirable in such conversion processes because they are highly selective in the formation of ethylene and propylene.
- undesirable byproducts may be formed through side reactions.
- the metals in conventional reactor walls may act as catalysts in one or more side reactions. If the methanol contacts the metal reactor wall at sufficient temperature and pressure, the methanol may be converted to undesirable methane and/or other byproducts.
- Byproduct formation in an MTO reactor is undesirable for several reasons. First, increased investment is required to separate and recover the byproducts from the desired light olefins. Additionally, as more byproducts are formed, less light olefins are synthesized.
- Japanese Laid Open Patent Application JP 01090136 to Yoshinari et al. is directed to a method for preventing decomposition of methanol or dimethyl ether and coking by sulfiding the metal surface of a reactor. More particularly, the method includes reacting methanol and/or dimethyl ether in the presence of a catalyst at above 450° C in a tubular reactor made of Iron and/or Nickel or stainless steel.
- the inside wall of the reactor is sulfided with a compound such as carbon disulfide, hydrogen disulfide or dimethyl sulfide. Additionally, a sulphur compound may be added to the feed.
- a compound such as carbon disulfide, hydrogen disulfide or dimethyl sulfide.
- a sulphur compound may be added to the feed.
- the present invention provides the ability to produce light olefins while reducing or eliminating the formation of metal catalyzed side reaction byproducts in a feed vaporization and introduction (“FVI") system.
- An FVI system is the region of the reactor system beginning at the point that at least a portion of the feedstock is in a vaporized state and extending to the point that the feedstock exits the feed introduction nozzle and enters the MTO reactor.
- olefin separation and purification costs can be reduced.
- the resulting purified olefin stream is particularly suitable for use as a feed in the manufacture of polyolefins.
- One embodiment of the present invention provides a method for forming light-olefins from an oxygenate-containing feedstock, including directing the feedstock through a feed introduction nozzle attached to an MTO reactor and having an inner surface, at least a portion of which is formed of a first material resistant to the formation of metal catalyzed side reaction byproducts.
- a material that is "resistant to the formation of metal catalyzed side reaction byproducts" is less catalytically active to the formation of metal catalyzed side reaction byproducts than carbon steel.
- the present invention also provides a feed vaporization and introduction system for an MTO reactor, comprising a feed introduction nozzle including a first generally tubular member having a first end for receiving a feedstock from a heating unit, a second end adjacent a reactor unit, and an inner surface forming a conduit for delivering the feedstock from the first end to the second end. At least a portion of the inner surface is formed of a first material that is resistant to the formation of metal catalyzed side reaction byproducts.
- the temperature of the feedstock and/or at least a portion of the FVI system is controlled with a thermally insulating material or a cooling system to further reduce the amount of metal catalyzed side reaction byproducts that is produced.
- FIG. 1 illustrates a flow diagram of a methanol to olefin reactor system including the FVI system and the MTO reactor;
- Fig. 2 illustrates a nozzle jacketing configuration in accordance with one embodiment of the present invention
- Fig. 3 illustrates a nozzle jacketing and cooling system in accordance with another embodiment of the present invention.
- the present invention is directed to reducing or eliminating the formation of metal catalyzed side reaction byproducts in reactor systems, and in particular, in methanol to olefin (MTO) reactor systems.
- MTO methanol to olefin
- metal catalyzed side reactions may occur before the feedstock enters the reactor.
- the feedstock Before entering the reactor, the feedstock passes through a feed vaporization and introduction (“FVI") system wherein the feedstock is at least partially vaporized by one or more heating devices, is passed through feed lines to a feed introduction nozzle or nozzles, and is introduced into the reactor.
- FVI feed vaporization and introduction
- the inner surface of at least a portion of the FVI system may be formed of metal which absorbs heat from the reactor volume thereby creating conditions in the FVI system that are conducive to the formation of metal catalyzed side reaction byproducts.
- the present invention provides a method for making an olefin product from an oxygenate-containing feedstock while reducing the amount of reaction byproducts formed in the FVI system.
- the method includes forming at least a portion of the FVI system, e.g., at least a portion of the feed introduction nozzle, particularly the inner surface of at least a portion of the FVI system, of one or more materials which is resistant to the formation of metal catalyzed side reaction byproducts.
- a material that is "resistant to the formation of metal catalyzed side reaction byproducts" is less catalytic to the formation of metal catalyzed side reaction byproducts than carbon steel.
- the inner surface of the nozzle is coated with the material.
- the entire feed introduction nozzle is be formed of a material resistant to the formation of metal catalyzed side reaction byproducts.
- the material is a metal alloy, an elemental metal, a non-metal, or a combination of the three.
- the method and system also includes, in one embodiment, maintaining at least a portion of the FVI system, e.g., the inner surface of at least a portion of the feed introduction nozzle, and/or the feedstock contained therein at a temperature effective to reduce or eliminate the formation of metal catalyzed side reaction byproducts in the FVI system.
- the temperature of at least a portion of the inner walls of the FVI system will be less than the temperature of the MTO reactor.
- the temperature of the inner walls of at least a portion of the FVI system, and/or the feedstock ⁇ contained therein is maintained below about 400° C, 350° C, 300° C, 250° C, 200° C or below about 150° C.
- the present invention is also directed to a method and system including maintaining at least a portion of the FVI system, e.g., the inner surface of at least a portion of the feed introduction nozzle, and/or the feedstock contained therein at an elevated temperature.
- the elevated temperature can be effective to superheat the feedstock.
- the temperature of the inner walls of at least a portion of the FVI system, and/or the feedstock contained therein is maintained above 400° C, 450° C, 500° C, 550° C, 600° C, or above 650° C.
- the inventors have discovered that as the feedstock passes through the FVI system, the oxygenate contacts the inner metal surface of one or more of the heating devices, the feed introduction nozzle or nozzles, and/or the lines connecting the heat exchangers to the feed introduction nozzles.
- the metal surface of the heat exchangers, the lines and/or the feed introduction nozzles acts as a catalyst at high temperatures and converts some of the methanol in the feedstock to hydrogen, carbon monoxide, carbon dioxide, methane and/or graphite.
- This side reaction may be illustrated as follows:
- the tendency of the FVI system to form undesirable metal catalyzed side-reaction byproducts is especially favorable because the ratio of metal surface area to quantity of feedstock is much higher in the FVI system than in the MTO reactor itself.
- the ratio of metal surface area to quantity of feedstock is particularly high in sparger nozzle and grid-type nozzle assemblies.
- a grid type nozzle assembly the feedstock is fed into an area beneath a grid which may be a flat or conical and which preferably includes a plurality of openings through which the feedstock passes as it enters the reactor volume.
- the temperature in the FVI system is conducive to the formation of metal catalyzed side-reaction byproducts because heat is transferred from hot material in the MTO reactor to the FVI system.
- the increased surface area of sparger and grid-type nozzle assemblies facilitates heat transfer from the reactor to the FVI system.
- a portion of the feed introduction nozzle may extend into the reactor volume of the reactor further increasing the formation of metal catalyzed side reaction byproducts.
- the temperature within the reactor volume is generally much higher than the minimum temperatures that are conducive to the formation of metal catalyzed side reaction byproducts.
- Heat from the MTO reactor is transferred to the nozzle which may extend into the reactor volume. This heat transfer may be significantly increased if the nozzle protrudes into a dense phase zone of the reactor wherein heated solid particles continuously collide with the exterior surface of the nozzle. Accordingly, with conventional nozzle designs, the temperature of the metal-containing nozzle will increase to temperatures conducive to promote undesirable side reactions which are catalyzed by the heated inner metal surface of the nozzle.
- metal catalyzed side reaction byproducts is particularly a problem in feed introduction nozzles.
- a portion of the inner surface of the FVI system can sheer or break away from the FVI system. This wastage facilitates the decomposition of the methanol-containing feedstock to side reaction byproducts.
- This concept often referred to as "metal dusting,” can be described as a catastrophic form of carburization. The phenomenon can produce rapid metal wastage, producing pits and grooves as the affected metal disintegrates into a mixture of powdery carbon and metal particles. Metal dusting corrosion has negatively impacted the efficiency and productivity of processes within numerous industries.
- metal dusting facilitates the formation of metal catalyzed side reaction byproducts because the ratio of metal surface area to volume of feedstock increases as metal dusting occurs.
- the occurrence of metal dusting can be reduced or eliminated by coating or forming at least a portion of the FVI system, particularly the inner surface of at least a portion of the FVI system, of a material that is resistant to the formation of metal catalyzed side reaction byproduct.
- Fig. 1 illustrates an MTO reactor system in accordance with one embodiment of the present invention.
- the MTO reactor system includes a feedstock vaporization and introduction system, or FVI system, which is generally designated by numeral 102, and an MTO reactor, which is generally designated by numeral 104.
- the FVI system 102 is a region of the reactor system beginning at the point that at least a portion of the feedstock is in a vaporized state and extending to the point that the feedstock exits the feed introduction nozzle and enters the MTO reactor, as illustrated in Fig.l .
- At least a portion of the FVI system may be formed of one or more metals, or an alloy of metals to accommodate the temperature and pressure of the feedstock as it is transported to the reactor.
- a liquid oxygenate feedstock or feed stream 108 containing an oxygenate such as methanol is shown being directed to heating device 106 which heats the feedstock to a temperature just below, at or above the feedstock bubble point.
- heating device 106 which heats the feedstock to a temperature just below, at or above the feedstock bubble point.
- a series of heating devices may be implemented in the present invention to gradually heat the feedstock in steps as described in U.S. Patent No. 6,121,504 to Kuechler et al., the entirety of which is incorporated herein by reference.
- a series of lines will transfer the feedstock between the heating devices to the feed introduction nozzle.
- the lines may be formed of a metal or alloy such as steel to accommodate the temperature and pressure of the feedstock.
- These metal lines or pipes in addition to the lines or pipes in the individual heating units may catalyze the formation of metal catalyzed side reaction byproducts. As a result, separation costs are increased and reaction efficiency is decreased.
- the heating device is a shell and tube heat exchanger wherein the heating medium may be product effluent 118, as shown in Fig. 1, a heat integration stream, e.g., from a water stripper or quench tower, or any other material having a higher temperature than the feedstock.
- the heating device 106 will cause at least a portion of the feedstock stream to vaporize.
- the point at which at least a portion of the feedstock vaporizes is defined herein as the FVI system inlet 114.
- the FVI inlet may be within the heating device 106, the feed introduction nozzle 112 or anywhere therebetween.
- the heated feedstock is directed through line or lines 110 to a feed introduction nozzle 112.
- Conventional feed introduction nozzles are formed of a metal or alloy such as carbon steel.
- the metal or alloy may act as a catalyst in side reactions at high temperatures to form undesirable byproducts.
- the nozzle may be formed, at least in part, of a material which is resistant to the formation of metal catalyzed side reaction byproducts.
- the nozzle may be formed, at least in part, of a material that does not significantly promote the formation of metal catalyzed side reaction byproducts.
- the nozzle may protrude into the MTO reactor volume, as illustrated in Figs. 1-3. Alternatively, the portion of the nozzle adjacent the reactor may be oriented flush with the interior surface of the reactor wall.
- the heated feedstock passes through the feed introduction nozzle 112 and enters the MTO reactor 104.
- the pressure in the MTO reactor may be less than the pressure of the feedstock within the FVI system, and the temperature within the MTO reactor may be much higher than the temperature in the FVI system. Accordingly, a portion or the entirety of the heated feedstock may vaporize as it exits the feed introduction nozzle and enters the MTO reactor.
- the point that the feedstock exits the feed introduction nozzle 112 and enters the MTO reactor 104 is defined herein as the FVI system outlet 116.
- the methanol in the feed stream contacts a molecular sieve catalyst under conditions effective to form an olefin product which exits the reactor in product effluent 118.
- the product effluent 118 from the MTO reactor 104 may be directed to the heat exchanger 106 in order to heat the feed stream 108.
- the product effluent 118 after the product effluent 118 has heated the feed stream 108, it may be directed in line 120 to a product separation and purification system (not shown).
- the product effluent is directed to the product separation and purification system without first being directed to a heat exchanger.
- At least a portion of the one or more heating devices, feed lines and/or feed introduction nozzles is formed, at least in part, of a material which does not substantially promote, e.g., is resistant to, the formation of metal catalyzed side reaction byproducts, as described above.
- the material can be an elemental metal, an alloy, or a nonmetal.
- At least a portion of the FVI system is formed of an alloy containing at least 10 weight percent nickel, preferably at least 30 weight percent nickel, more preferably at least 50 weight percent nickel and most preferably at least 60 weight percent nickel.
- conventional feed introduction nozzles e.g., formed of carbon steel, typically contain less than 10 weight percent nickel.
- Nickel-containing alloys are desirable because nickel oxide forms at the inner surface of the at least a portion of the FVI system.
- the nickel oxide coating layer on the inner surface of at least a portion of the FVI system is particularly resistant to the formation of metal catalyzed side reaction byproducts from a methanol- containing feedstock.
- Exemplary non-limiting alloys that contain at least 10 weight percent nickel include 263, 276, 302, 304, 305, 308, 309, 310, 314, 316, 317, 321, 330, 347, 409, 600, 601, 602CA, 617, 625LCF, 671, 690, 693, 754, 758, 800, 803, 825, 864, 904, CF-3, CF-8M, CH-20, CK-20, DS, HH, and HK.
- Exemplary non-limiting alloys that contain at least 30 weight percent nickel include 263, 276, 330, 400, 409, 600, 601, 602CA, 617, 625LCF, 671, 690, 693, 754, 758, 800, 803, 825, 864, DS, and TD.
- Exemplary non-limiting alloys that contain at least 50 weight percent nickel include 263, 276, 400, 600, 601, 602CA, 617, 625LCF, 671, 690, 693, 754, 758, and TD.
- Exemplary non-limiting alloys that contain at least 60 weight percent nickel include 400, 600, 601, 602CA, 625LCF, 693, 754, 758, and TD.
- the alloy contains at least 20 weight percent chromium, preferably at least 25 weight percent chromium, more preferably at least 30 weight percent chromium and most preferably at least 40 weight percent chromium.
- conventional feed introduction nozzles formed of carbon steel typically contain less than 20 weight percent chromium.
- Chromium-containing alloys are desirable because chromium oxide forms at the inner surface of the at least a portion of the FVI system.
- the chromium oxide coating layer on the im er surface of the at least a portion of the FVI system is particularly resistant to the formation of metal catalyzed side reaction byproducts from a methanol-containing feedstock.
- Exemplary non-limiting alloys that contain at least 20 weight percent chromium include 309, 310, 329, 442, 446, 904L, 754, TD, 758, 693, 602CA, 625 LCF, 601, 690, 671, 617, 263, 825, 803, 800, 864, 956 and 2205.
- Exemplary non-limiting alloys that contain at least 25 weight percent chromium include 310, 329, 758, 693, 602CA, 690, 671, and 803.
- Exemplary non-limiting alloys that contain at least 30 weight percent chromium include 758 and 671.
- Exemplary non-limiting alloys that contain at least 40 weight percent chromium include 671.
- the alloy contains at least 2 weight percent aluminum, preferably at least 4 weight percent aluminum.
- conventional feed introduction nozzles formed of carbon steel contain less than 2 weight percent aluminum.
- elemental aluminum or similar metal e.g., palladium
- Aluminum is particularly effective in reducing the formation of metal catalyzed side reaction byproducts from a methanol-containing feedstock.
- Aluminum-containing alloys are desirable because aluminum oxide forms at the inner surface of the at least a portion of the FVI system.
- the aluminum oxide coating layer on the inner surface of the at least a portion of the FVI system is particularly resistant to the formation of metal catalyzed side reaction byproducts from a methanol-containing feedstock.
- Exemplary non-limiting alloys that contain at least 2 weight percent aluminum include 602CA, 693 and 956.
- Exemplary non-limiting alloys that contain at least 4 weight percent aluminum include 956.
- Iron is one non-limiting example of a metal which is particularly undesirable because of its effectiveness in forming metal catalyzed side reaction byproducts at high temperatures.
- the alloy additionally or alternatively contains less than 70 weight percent iron, preferably less than 50 weight percent iron, more preferably less than 30 weight percent iron, more preferably less than 10 weight percent iron, and most preferably less than 5 weight percent iron.
- conventional feed introduction nozzles formed of carbon steel contain more than 70 weight percent iron.
- Iron is a particularly undesirable material in the FVI system because iron catalyzes the formation of side reaction byproducts from a methanol-containing feedstock.
- Exemplary non-limiting alloys that contain less than 70 weight percent iron include 263, 276, 330, 400, 600, 601, 602CA, 617, 625LCF, 671, 690, 693, 754, 758, 800, 803, 825, 864, DS, and TD.
- Exemplary non-limiting alloys that contain less than 50 weight percent iron include 263, 276, 330, 400, 600, 601, 602CA, 617, 625LCF, 671, 690, 693, 754, 758, 800, 803, 825, 864, DS, and TD.
- Exemplary non-limiting alloys that contain less than 30 weight percent iron include 276, 400, 600, 601, 602CA, 617, 625LCF, 671, 690, 693, 754, 758, 825, and TD.
- Exemplary non-limiting alloys that contain less than 10 weight percent iron include 276, 400, 600, 602CA, 617, 625LCF, 671, 690, 693, 754, 758, 825, and TD.
- Exemplary non-limiting alloys that contain less than 5 weight percent iron include 400, 617, 625LCF, 671, 693, 754, 758, 825, and TD.
- the alloy contains at least 2 weight percent copper, preferably at least 15 weight percent copper, and more preferably at least 35 weight percent copper.
- conventional feed introduction nozzles formed of carbon steel contain undetectable amounts of copper.
- elemental copper can also be implemented in the at least a portion of the FVI system if the temperature and reactor conditions are maintained below a level that would melt or rupture the at least a portion of the FVI system. Copper is particularly effective in reducing the formation of metal catalyzed side reaction byproducts from a methanol-containing feedstock.
- Exemplary non-limiting alloys that contain at least 2 weight percent copper include 825 and 400.
- An exemplary non-limiting alloy that contains at least 35 weight percent copper includes 400.
- At least a portion of the FVI system is formed of an alloy selected from the group consisting of 410, 304, 316, 400, 330, 800, 600, 825, 601, 625, 617, 956, 693 and 671.
- at least a portion of the FVI system is formed of an alloy selected from the group consisting of TD, 758, 625, 601 and 276.
- at least a portion of the FVI system is formed of an alloy selected from the group consisting of 693, 602, 690, 671, 617, 263 and 956.
- at least a portion of the FVI system, preferably the feed introduction nozzle is formed of a material other than carbon steel.
- the material is an alloy resistant to the formation of metal catalyzed side reaction byproducts. Additionally or alternatively, the alloy is resistant to carburization and metal dusting. See, e.g., Paper No. 02394 entitled Nickel-Base Material Solutions to Metal Dusting Problems from the Corrosion 2002 Conference, which is incorporated herein by reference. Table 1, below, provides a composition comparison of various commercial alloys that may be implemented in accordance with the present invention. Commercial variations are known to occur within the industry for each alloy provided below, and the compositional weight percentages provided herein are non-limiting.
- the material that is resistant to the formation of metal catalyzed side reaction byproducts may be a non-metal.
- Insulating materials that are capable of withstanding relatively high pressures and temperatures, e.g., those temperatures and pressures typical in the FVI system of an MTO reactor, are particularly effective at reducing the formation of metal catalyzed side reaction byproducts.
- Exemplary non-metals that may form at least a part of the FVI system include insulating materials such as ceramics, fire brick, high temperature calcium silicate, alumina and silica-alumina ceramics, diatomaceous silica brick and cements and fillers.
- the inner surface of at least a portion of the FVI system e.g., the feed introduction nozzle
- the insulating material is formed of the insulating material.
- additional insulating materials which may be incorporated in the present invention, see Petroleum Processing Handbook, W.F. Bland and R.L. Davidson eds., McGraw Hill Publishers, pages 4-137 to 4-147 (1967), the entirety of which is incorporated herein by reference.
- the specific characteristics of the insulation, e.g., density, material and thickness, implemented in accordance with the present invention may be selected based on the specific reaction conditions inside the reactor, the composition and physical properties of the feedstock, and the composition and physical properties of the heating devices, lines, and/or feed introduction nozzles.
- FVI system is formed of an outer metal-containing tube or conduit mechanically or adhesively associated with an inner tube or conduit formed from one or more non-metal materials.
- the inner tube may be an insert within the outer metal- containing tube.
- the insert is held in place against the outer conduit by mechanical interactions or with an adhesive.
- the feed introduction nozzle may be formed of an outer metal nozzle having an inner insert formed of the insulating material.
- the insert includes a conduit through which the feedstock may pass as it is directed to the reactor unit. As the feedstock flows through the two-piece feed introduction nozzle, the feedstock contacts the insulating material which does not catalyzed the formation of side reaction byproducts.
- the metal portion of the feed introduction nozzle optionally is formed of an elemental or alloy material that is resistant to the formation of metal catalyzed side reaction byproducts, as described above.
- the outer material is formed of a non-metal material that does not catalyze the formation of side reaction byproducts from methanol.
- the feed introduction nozzle is formed of two different non- metal materials that are resistant to the formation of metal catalyzed side reaction byproducts.
- the outer material is a non-porous non-metal material in order to prevent leakage of the feedstock to the external environment.
- the inner surface of the one or more of the heating devices, feed lines and/or feed introduction nozzles is coated with a material that is resistant to the formation of metal catalyzed side reaction byproducts.
- the feed introduction nozzle need not be formed of a material resistant to the formation of metal catalyzed side reaction byproducts.
- one or more of the heating devices, feed lines and/or feed introduction nozzles optionally are formed of a material that is resistant to the formation of metal catalyzed side reaction byproducts.
- the present invention may include maintaining the temperature of at least a portion of the FVI system and/or feedstock contained therein at a temperature effective to reduce or eliminate the formation of metal catalyzed side reaction byproducts.
- maintaining the temperature of the FVI system and/or feedstock contained therein is not necessary for the present invention because the FVI system is formed at least in part of a material which does not significantly promote the formation of metal catalyzed side reaction byproducts. Accordingly, the amount of side reaction byproducts produced by the FVI system in accordance with the present invention may be low or undetectable even at high temperatures.
- FVI system and/or of the feedstock contained therein at a temperature effective to reduce or eliminate the formation of metal catalyzed side reaction byproducts is to thermally insulate at least a portion of the FVI system, e.g., a portion or all of the feed introduction nozzle, with an insulating material.
- insulating materials include: ceramics, fire brick, high temperature calcium silicate, alumina and silica-alumina ceramics, diatomaceous silica brick and cements and fillers.
- the specific characteristics of the insulation e.g., density, material and thickness, implemented in accordance with the present invention may be selected based on the specific reaction conditions inside the reactor, the composition and physical properties of the feedstock, and the composition and physical properties of the heating device, lines, and/or feed introduction nozzle.
- the temperature of the feed introduction nozzle, and/or of the inner metal-containing nozzle surface thereof and/or the feedstock itself may be controlled with a cooling system.
- a cooling system may include a cooling tube helically wrapped around the feed introduction nozzle. As cooling medium flows through the tube and around the feed introduction nozzle, the metal in the feed introduction nozzle as well as the feedstock flowing therethrough can be maintained at a temperature effective to minimize or eliminate the formation of metal catalyzed side-reaction byproducts.
- the feedstock is maintained at a temperature effective to reduce, minimize or eliminate the formation of metal catalyzed side reaction byproducts.
- the feedstock may act as a cooling agent for cooling the inner metal surface of one or more of the following portions of the FVI system: at least a portion of the heating device, at least a portion of the line, and/or at least a portion of the feed introduction nozzle.
- the desired temperature of the feedstock throughout the FVI system is preferably below about 400°C, 350°C, 300°C, 250°C, 200°C or below about 150°C.
- These relatively low temperatures may be maintained by controlling the heating characteristics and number of the feedstock heating devices, and/or by insulating and/or cooling one or more of the following portions of the FVI system: at least a portion of the heating devices, at least a portion of the lines, and/or at least a portion of the feed introduction nozzles, as discussed in more detail below.
- the inventors have found that the introduction of a low temperature feedstock into a hot MTO reactor does not substantially affect the formation of light olefins in the MTO reactor.
- the inventive method and system includes maintaining at least a portion of the inner surfaces of the feed vaporization and introduction system, e.g., the inner surface of the feed introduction nozzle, at a temperature effective to reduce or eliminate the formation of metal catalyzed side reaction byproducts.
- the temperature of the metal-containing inner surfaces of the FVI system may be maintained at the desired temperature in a variety of ways.
- one or more of the heating devices, the lines between the feed heating devices and the feed introduction nozzle or nozzles, and/or the feed introduction nozzle itself may be jacketed with a thermally insulating material.
- one or more of the heating devices, the lines between the feed heating devices and the feed introduction nozzle, and/or the feed introduction nozzle itself may include a cooling device for controlling the temperature of all or a portion of the FVI system.
- the invention is also directed to an FVI system having a temperature monitoring and controlling feature, and to feed introduction nozzles incorporating a jacket formed of a thermally insulating material and/or incorporating a cooling system.
- Fig. 2 illustrates one embodiment of the present invention which reduces or eliminates metal catalyzed side reaction byproduct formation caused by heat transfer from the MTO reactor to the inner surface of the feed introduction nozzle.
- a feed introduction nozzle 112 is shown in Fig. 2 penetrating the reactor wall 204.
- the portion of the feed introduction nozzle which is inside the reactor volume 208 is identified as the internal nozzle section 210.
- Methanol stream 206 from the heating device (not shown) travels through a line or pipe (not shown) and enters the feed introduction nozzle 112.
- the methanol stream 206 passes through the feed introduction nozzle 112 and enters the inner reactor volume 208 wherein the methanol contacts a catalyst under conditions effective to convert the methanol to light olefins.
- An insulating material 212 covers at least a portion of the outer nozzle surface 218 of the internal nozzle section 210 of the feed introduction nozzle 112. The insulating material reduces the quantity of heat that is transferred from the reactor volume 208 to the internal nozzle section 210 of the feed introduction nozzle 112. As a result, the metal on the inner nozzle surface 216 of the feed introduction nozzle can be maintained at a temperature effective to reduce, minimize or eliminate the formation of metal-catalyzed side reaction byproducts.
- FVI system outlet 116 may be exposed to the reactor volume 208, the amount of heat transferred from the reactor volume to the portion of the inner nozzle surface 216 of the feed introduction nozzle that is adjacent the FVI system outlet 116 is minimal because the feedstock may tend to cool the inner nozzle surface 216 adjacent the FVI system outlet.
- a relatively small amount of hot material in the reactor will contact the FVI system outlet 116 because the flow characteristics of the feedstock as it enters the reactor volume 208 will tend to direct the hot material away from the FVI system outlet 116. Accordingly, even the portion of the inner nozzle surface 216 that is adjacent the FVI system outlet 116 can be maintained at temperatures effective to reduce, minimize or eliminate the formation of metal catalyzed side reaction byproducts.
- Fig. 2 illustrates the insulating material 212 covering the entire internal nozzle section 210 of the feed introduction nozzle 112.
- the insulating material 212 may cover a portion of the internal nozzle section 210 of the feed introduction nozzle 112.
- the insulating material may cover a portion of the FVI outlet 116.
- the insulating material may additionally or alternatively provide increased thermal protection for the metal contained in the feed introduction nozzle and the feedstock contained in the FVI system by extending the insulating material into and/or through the reactor wall 204.
- the opening in the reactor wall through which the feed introduction nozzle extends must be increased in size in order to allow the insulating material to traverse the reactor wall.
- the insulating material 212 may also extend to cover all or a portion of the external nozzle section 214 of the feed introduction nozzle 112.
- the insulating material may extend to cover additional areas of the FVI system.
- the insulating material may cover all or a portion of the heating devices and/or the lines directing the feedstock from the heating devices to the feed introduction nozzle.
- Fig. 3 illustrates an embodiment of the present invention wherein the feed introduction nozzle 112 includes a cooling system generally designated by numeral 302.
- the feed introduction nozzle 112 is a generally cylindrical tube defining a feedstock pathway 308.
- a second larger diameter cylindrical tube is oriented coaxially to the feed introduction nozzle 112 thereby forming an outer cooling pathway 306 around the feedstock pathway 308.
- a cooling medium 304 such as water or a cooling steam, e.g., from a water stripper or quench tower, or any other material having a lower temperature than the feedstock in the feed introduction nozzle, is introduced into cooling pathway 306 at cooling inlet 310 and is circulated in the cooling pathway 306 around the feedstock in the feedstock pathway 308.
- exterior nozzle end 314 of the cooling pathway 306 is closed-off so that the cooling medium flows toward the reactor.
- the cooling medium 304 is passed through the cooling pathway 306 and withdraws heat from the feed introduction nozzle and/or the feedstock.
- the feed introduction nozzle 112 and/or the feedstock can be maintained at a temperature effective to minimize or eliminate the formation of metal catalyzed side reaction byproducts.
- This embodiment of the present invention has the additional advantage of providing the ability to control and vary the temperature of the feedstock and of the feed introduction nozzle.
- the temperature of the feedstock/feed introduction nozzle can be modified by varying the flow rate and/or temperature of the cooling medium which passes over the nozzle and feedstock pathway.
- the cooling medium 304 may exit the feed introduction nozzle within the reactor through diluent outlet 312, as shown in Fig. 3, or outside of the reactor through a cooling medium outlet (not shown). If the cooling medium 304 exits the feed introduction nozzle within the reactor through diluent outlet 312, the cooling medium will mix with the oxygenate feedstock inside the reactor. In this manner, the invention provides an additional advantage in that the partial pressure of the oxygenate introduced into the MTO reactor may be carefully controlled in order to obtain a desired product selectivity and/or oxygenate conversion as discussed, for example, in U.S. Patent Application Serial No. 09/506,843 to Fung et al., the entirety of which is incorporated herein by reference. Thus, the cooling medium may be selected from one or more of the diluents more fully discussed below.
- Fig. 3 illustrates the cooling system 302 traversing the reactor wall
- the cooling system 302 may provide thermal protection for a portion of the feed introduction nozzle rather than the entire feed introduction nozzle.
- the cooling system 302 may cover the entirety or only a portion of the internal nozzle section 210 of the feed introduction nozzle 112.
- the cooling system may, or may not, extend partially or entirely through the reactor wall 204.
- the cooling system 302 may cover all or a portion of the external nozzle section 214.
- the cooling system may extend to cover additional areas of the FVI system.
- the cooling system may cover all or a portion of the heating device(s) and/or the line(s) directing the feedstock from the heating device(s) to the feed introduction nozzle.
- the jacketing and cooling embodiments may be combined.
- the nozzle may include a feedstock pathway, a cooling system and a jacket formed of one or more of the thermally insulating materials discussed above.
- Either the jacket or the cooling system may be the outermost layer depending on the MTO reactor conditions, the cooling medium used, the physical properties of the nozzle, the physical properties of the heating devices and the physical properties of the lines connecting the heating devices to the feed introduction nozzle.
- a plurality of the same or different jacketing layers and/or the same or different cooling systems may be implemented in the present invention.
- the jacketing and/or cooling embodiments may be combined with the low temperature feedstock embodiment.
- the temperature of the metal- containing inner surface of at least a portion of the FVI system can be maintained at a temperature effective to reduce or eliminate the formation of metal catalyzed side reaction byproducts, e.g., below about 400°C, 350°C, 300°C, 250°C, 200°C, or below about 150°C.
- the FVI system may be maintained at a temperature effective to maintain the feedstock at liquid-vapor equilibrium throughout the FVI system. Because the feedstock is maintained at a temperature effective to maintain the feedstock in a liquid- vapor equilibrium throughout the FVI system, superheating of the vapor is minimized or eliminated thereby reducing the formation of reaction byproducts through metal-catalyzed side reactions.
- the feedstock may be entirely vaporized prior to entering the reactor.
- the feedstock may pass through a valve 122 in line 110, as shown in Fig. 1 , wherein the feed is , subjected to a pressure drop and the feedstock is further vaporized.
- the feedstock may be superheated so long as the temperature of the superheated feedstock is maintained below temperatures conducive to the formation of metal catalyzed side reaction byproducts.
- the invention also provides for the ability to monitor the temperature of any point along the FVI system including one or more of the heating devices, the lines, and/or the feed introduction nozzle.
- a thermocouple may be implemented on the inner and/or outer surface of the feed introduction nozzle and/or on the inner and/or outer surface of the cooling system or insulating material.
- the temperature of the feedstock and/or of the metal in the feed introduction nozzle may be monitored to determine whether conditions are conducive to the formation of metal catalyzed side-reaction byproducts.
- the characteristics of the cooling medium may be modified responsive to variations in temperature of any inner or outer nozzle surfaces.
- the characteristics of the cooling medium e.g., flow rate and/or temperature, may be modified to lower the temperature of the inner nozzle surface to non-reactive temperatures.
- the conditions in the MTO reactor including the pressure, temperature, weight hourly space velocity (WHSV), etc., are conducive to converting the methanol to light olefins, as discussed in more detail below.
- At least a portion of the FVI system, especially the feed introduction nozzle, is monitored and/or maintained at conditions, e.g., temperatures, effective to reduce, minimize or substantially eliminate the formation of metal catalyzed side-reaction byproducts irrespective of the conditions within the MTO reactor. That is, the conditions within the MTO reactor may or may not be conducive to the formation of metal catalyzed side- reaction byproducts.
- the present invention may be implemented with a deactivated or passivated reactor.
- molecular sieve catalysts have been used to convert oxygenate compounds to light olefins.
- Silicoaluminophosphate (SAPO) molecular sieve catalysts are particularly desirable in such a conversion process, because they are highly selective in the formation of ethylene and propylene.
- SAPO siicoaluminophosphate
- the feedstock preferably contains one or more aliphatic-containing compounds that include alcohols, amines, carbonyl compounds for example aldehydes, ketones and carboxylic acids, ethers, halides, mercaptans, sulfides, and the like, and mixtures thereof.
- the aliphatic moiety of the aliphatic-containing compounds typically contains from 1 to about 50 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.
- Non-limiting examples of aliphatic-containing compounds include: alcohols such as methanol and ethanol, alkyl-mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl-sulfides such as methyl sulfide, alkyl- amines such as methyl amine, alkyl-ethers such as dimethyl ether, diethyl ether and methylethyl ether, alkyl-halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehydes, and various acids such as acetic acid.
- alcohols such as methanol and ethanol
- alkyl-mercaptans such as methyl mercaptan and ethyl mercaptan
- alkyl-sulfides such as methyl sulfide
- alkyl-amines such as methyl amine
- alkyl-ethers such as dimethyl ether
- the feedstock contains one or more oxygenates, more specifically, one or more organic compound(s) containing at least one oxygen atom.
- the oxygenate in the feedstock is one or more alcohol(s), preferably aliphatic alcohol(s) where the aliphatic moiety of the alcohol(s) has from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.
- the alcohols useful as feedstock in the process of the invention include lower straight and branched chain aliphatic alcohols and their unsaturated counterparts.
- Non-limiting examples of 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 is selected from one or more of methanol, ethanol, dimethyl ether, diethyl ether or a combination thereof, more preferably methanol and dimethyl ether, and most preferably methanol.
- the various feedstocks discussed above is converted primarily into one or more olefin(s).
- the olefin(s) or olefin monomer(s) produced from the feedstock typically have from 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and most preferably ethylene and/or propylene.
- Non-limiting examples of olefin monomer(s) include ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene- 1, hexene-1, octene-1 and decene-1, preferably ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene- 1, hexene-1, octene-1 and isomers thereof.
- Other olefin monomer(s) include unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
- the feedstock preferably of one or more oxygenates
- a molecular sieve catalyst composition into olefin(s) having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
- the olefin(s), alone or combination are converted from a feedstock containing an oxygenate, preferably an alcohol, most preferably methanol, to the preferred olefm(s) ethylene and/or propylene.
- the most preferred process is generally referred to as gas-to-olefins
- GTO methanol-to-olefms
- a methanol containing feedstock is converted in the presence of a molecular sieve catalyst composition into one or more olefins, preferably and predominantly, ethylene and/or propylene, often referred to as light olefins.
- the feedstock in one embodiment, contains one or more diluents, typically used to reduce the concentration of the feedstock.
- the diluents are generally non-reactive to the feedstock or molecular sieve catalyst composition.
- Non-limiting examples of diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, water, essentially non-reactive paraffins (especially alkanes such as methane, ethane, and propane), essentially non-reactive aromatic compounds, and mixtures thereof.
- the most preferred diluents are water and nitrogen, with water being particularly preferred.
- the feedstock does not contain any diluent.
- the diluent may be used either in a liquid or a vapor form, or a combination thereof.
- the diluent is either added directly to a feedstock entering into a reactor or added directly into a reactor, or added with a molecular sieve catalyst composition.
- the amount of diluent in the feedstock is in the range of from about 1 to about 99 mole percent based on the total number of moles of the feedstock and diluent, preferably from about 1 to 80 mole percent, more preferably from about 5 to about 50, most preferably from about 5 to about 25.
- other hydrocarbons are added to a feedstock either directly or indirectly, and include olefin(s), paraffin(s), aromatic(s) (see for example U.S. Patent No. 4,677,242, addition of aromatics) or mixtures thereof, preferably propylene, butylene, pentylene, and other hydrocarbons having 4 or more carbon atoms, or mixtures thereof.
- the process for converting a feedstock, especially a feedstock containing one or more oxygenates, in the presence of a molecular sieve catalyst composition of the invention is carried out in a reaction process in a reactor, where the process is a fixed bed process, a fluidized bed process (includes a turbulent bed process), preferably a continuous fluidized bed process, and most preferably a continuous high velocity fluidized bed process.
- a fluidized bed process includes a turbulent bed process
- the reaction processes can take place in a variety of catalytic reactors such as hybrid reactors that have a dense bed or fixed bed reaction zones and/or fast fluidized bed reaction zones coupled together, circulating fluidized bed reactors, riser reactors, and the like. Suitable conventional reactor types are described in for example U.S. Patent No.
- Dual riser reactors or other reactor designs optionally include a plurality of feed introduction nozzles, which may be formed and/or coated with a material resistant to the formation of metal catalyzed side reaction byproducts in accordance with the present invention.
- the preferred reactor types are riser reactors generally described in
- the amount of liquid feedstock fed separately or jointly with a vapor feedstock to a reactor system is in the range of from 0.1 weight percent to about 85 weight percent, preferably from about 1 weight percent to about 75 weight percent, more preferably from about 5 weight percent to about 65 weight percent based on the total weight of the feedstock including any diluent contained therein.
- the liquid and vapor feedstocks are preferably the same composition, or contain varying proportions of the same or different feedstock with the same or different diluent.
- the conversion temperature employed in the conversion process, specifically within the reactor system, is in the range of from about 200°C to about 1000°C, preferably from about 250°C to about 800°C, more preferably from about 250°C to about 750 °C, yet more preferably from about 300°C to about 650°C, yet even more preferably from about 350°C to about 600°C most preferably from about 350°C to about 550°C.
- the conversion pressure employed in the conversion process varies over a wide range including autogenous pressure.
- the conversion pressure is based on the partial pressure of the feedstock exclusive of any diluent therein.
- the conversion pressure employed in the process is in the range of from about 0.1 kPaa to about 5 MPaa, preferably from about 5 kPaa to about 1 MPaa , and most preferably from about 20 kPaa to about 500 kPaa.
- the weight hourly space velocity (WHSV), particularly in a process for converting a feedstock containing one or more oxygenates in the presence of a molecular sieve catalyst composition within a reaction zone, is defined as the total weight of the feedstock excluding any diluents to the reaction zone per hour per weight of molecular sieve in the molecular sieve catalyst composition in the reaction zone.
- the WHSV is maintained at a level sufficient to keep the catalyst composition in a fluidized state within a reactor.
- the WHSV ranges from about 1 hr -1 to about 5000 hr -
- the WHSV is greater than 20 hr-1 , preferably the WHSV for conversion of a feedstock containing methanol, dimethyl ether, or both, is in the range of from about 20 hr-1 to about 300 hr-1.
- the superficial gas velocity (SGV) of the feedstock including diluent and reaction products within the reactor system is preferably sufficient to fluidize the molecular sieve catalyst composition within a reaction zone in the reactor.
- the SGV in the process is at least 0.1 meter per second (m/sec), preferably greater than 0.5 m/sec, more preferably greater than 1 m/sec, even more preferably greater than 2 m/sec, yet even more preferably greater than 3 m/sec, and most preferably greater than 4 m/sec. See for example U.S. Patent Application Serial No. 09/708,753 filed November 8, 2000, which is herein incorporated by reference.
- the example compares the reactivity of a methanol feedstock in a stainless steel reactor at various temperatures with the reactivity of a passivated reactor.
- All data presented was obtained using a microflow reactor.
- the microflow reactor used was a No. 316 stainless steel reactor (1/4 inch outer diameter) located in a furnace to which vaporized methanol was fed.
- 316 stainless steel is less catalytically active to the formation of metal catalyzed side reaction byproducts than carbon steel, and is thus resistant to the formation of metal catalyzed side reaction byproducts in accordance with the present invention.
- the vaporized methanol was maintained at 120o C.
- the methanol conversion reactions were performed at 25 psig (172 kPag) methanol pressure and at a methanol feed rate of 80 ⁇ l/min.
- the control experiment was performed under identical reaction conditions except that a coated reactor was used.
- the coated reactor was 1/16 inch in diameter and was made of steel coated with a thin layer of fused silica.
- Valco valve The collected samples were analyzed by on-line gas chromatography (Hewlett Packard 6890) equipped with a flame ionization detector. CO, CO2 and H2 were not analyzed. The measured conversions of methanol, which were calculated on the carbon basis, would have been higher if CO, CO2 and H2 were included in the calculations.
- Table 2 summarizes the results of the conversions (Wt. %) of methanol reacting on the lab reactor.
- the percent conversion of oxygenate over the surface of a metal reactor is less than 1.0 percent, preferably less than 0.8 percent, more preferably less than 0.4 percent, and most preferably less than 0.05, e.g., below detection limits.
- the invention includes maintaining the feedstock while it is in the FVI system, especially the feed introduction nozzle, at conditions, e.g., temperature, effective to substantially eliminate the formation of metal catalyzed side reaction byproducts. "Substantially eliminate” is defined herein as less than 0.05 percent conversion to byproducts excluding CO, CO2 and H2.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EA200500597A EA008699B1 (en) | 2002-10-21 | 2003-09-05 | Method for the production of olefins |
DE60326873T DE60326873D1 (en) | 2002-10-21 | 2003-09-05 | PROCESS FOR INHIBITING DECOMPOSITION IN A METHANOL-TO-OLEFIN REACTOR SYSTEM |
AU2003265933A AU2003265933A1 (en) | 2002-10-21 | 2003-09-05 | Method and system for reducing decomposition byproducts in a methanol to olefin reactor system |
EP03809516A EP1562878B1 (en) | 2002-10-21 | 2003-09-05 | Method for reducing decomposition by-products in a methanol to olefin reactor system |
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US10/274,739 | 2002-10-21 | ||
US10/274,739 US6737556B2 (en) | 2002-10-21 | 2002-10-21 | Method and system for reducing decomposition byproducts in a methanol to olefin reactor system |
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US7034196B2 (en) * | 2002-06-19 | 2006-04-25 | Exxonmobil Chemical Patents Inc. | Method and apparatus for reducing decomposition byproducts in a methanol to olefin reactor system |
US7125821B2 (en) * | 2003-09-05 | 2006-10-24 | Exxonmobil Chemical Patents Inc. | Low metal content catalyst compositions and processes for making and using same |
US8029914B2 (en) * | 2005-05-10 | 2011-10-04 | Exxonmobile Research And Engineering Company | High performance coated material with improved metal dusting corrosion resistance |
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Also Published As
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US6737556B2 (en) | 2004-05-18 |
EP1562878A1 (en) | 2005-08-17 |
CN1688523A (en) | 2005-10-26 |
US20040152935A1 (en) | 2004-08-05 |
US20040077912A1 (en) | 2004-04-22 |
CN100334044C (en) | 2007-08-29 |
EA008699B1 (en) | 2007-06-29 |
DE60326873D1 (en) | 2009-05-07 |
ATE426582T1 (en) | 2009-04-15 |
AU2003265933A1 (en) | 2004-05-13 |
US7338645B2 (en) | 2008-03-04 |
EA200500597A1 (en) | 2005-12-29 |
ES2324033T3 (en) | 2009-07-29 |
EP1562878B1 (en) | 2009-03-25 |
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