WO2001064340A1 - Tamis moleculaire de silico-aluminophosphates contenant du thorium destine a la production d'olefines - Google Patents

Tamis moleculaire de silico-aluminophosphates contenant du thorium destine a la production d'olefines Download PDF

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Publication number
WO2001064340A1
WO2001064340A1 PCT/US2001/004667 US0104667W WO0164340A1 WO 2001064340 A1 WO2001064340 A1 WO 2001064340A1 US 0104667 W US0104667 W US 0104667W WO 0164340 A1 WO0164340 A1 WO 0164340A1
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sapo
molecular sieve
catalyst
silicoaluminophosphate
thorium
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PCT/US2001/004667
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English (en)
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Krishna K. Rao
Ronald G. Searle
Xiaobing Feng
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Exxonmobil Chemical Patents Inc.
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Priority to AU2001236984A priority Critical patent/AU2001236984A1/en
Publication of WO2001064340A1 publication Critical patent/WO2001064340A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • This invention relates to a silicoaluminophosphate molecular sieve containing thorium and to a method for converting an oxygenate feedstock to a product including an olefin.
  • this invention is directed to a method for converting an oxygenate feedstock to a product including an olefm by contacting the feedstock with a silicoaluminophosphate molecular sieve containing thorium.
  • Olefins have traditionally been produced through the process of petroleum cracking. Because of the limited availability and high cost of petroleum sources, the cost of producing olefins from such petroleum sources has the potential to steadily increase. Light olefins such as ethylene and propylene serve as feeds for the production of numerous chemicals and polymers.
  • Alcohols may be produced by fermentation or from synthesis gas.
  • Synthesis gas can be produced from natural gas, petroleum liquids, carbonaceous materials including coal, recycled plastics, municipal wastes, or any organic material.
  • alcohols and alcohol derivatives may provide non-petroleum based routes for hydrocarbon production.
  • SAPOs Silicoaluminophosphates
  • olefins particularly ethylene and propylene
  • molecular sieves can also be zeolitic (zeolites). Such catalysts are also used for catalyzing the oxygenate-to-olefm conversion reaction.
  • Zeolitic molecular sieves include, but are not limited to, mordenite, chabazite, erionite, ZSM-5, ZSM-34, ZSM-48 and mixtures thereof. Methods of making these molecular sieves are known in the art. ZSM-5 was the first and most extensively studied catalyst for the conversion of methanol to olefins.
  • regenerator This process is typically referred to as regeneration, and typically talces place in a vessel called a regenerator.
  • U.S. Patent No. 4,025,576 to Chang et al. teaches a multistage process for converting light alcohols to olefins using certain crystalline zeolites having a high silica: alumina ratio and a constrained access to the crystalline space, for example HSZM-5.
  • Cheng et al. indicate that a critical feature of the invention, namely conducting the conversion from alcohol to olefin at subatmospheric partial pressure of the reactant feed and using certain crystalline zeolites, enhances selectivity for olefin production and permits complete conversion of the alcohol.
  • U.S. Patent No. 4,752,651 to Kaiser et al. discloses a process for converting methanol to olefin (MTO) using non-zeolitic molecular sieves, such as S APO-34, that contain an element selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc.
  • the catalyst is a crystalline silicoaluminophosphate molecular sieve comprising a silicoaluminophosphate framework and thorium.
  • the atomic ratio of silicon in the silicoaluminophosphate framework to thorium is from about 0.01 :1 to about 1000:1, more preferably from about 0.1 :1 to about 500:1, and most preferably from about 0.5:1 to about 50:1.
  • the invention is directed to a catalyst for converting an oxygenate feedstock to a product including an olefin, comprising the crystalline silicoaluminophosphate molecular sieve and a binder.
  • the thorium-containing S APO catalyst is of great benefit in large scale commercial processes of making olefin product from oxygenate feedstock, particularly making olefins containing ethylene or propylene from feedstock comprising methanol or dimethyl ether.
  • the method of making a product including an olefin from an oxygenate feedstock comprises contacting a silicoaluminophosphate molecular sieve having a silicoaluminophosphate framework and thorium with an oxygenate feedstock under conditions effective to convert the feedstock to the product including an olefin.
  • the invention provides a product including an olefin made according to this method.
  • the invention provides a method of making a polyolefin from an oxygenate feedstock, comprising contacting a silicoaluminophosphate molecular sieve described above with an oxygenate feedstock under conditions effective to convert the feedstock to an olefin product, and contacting the olefin product with a polyolefin-forming catalyst under conditions effective to form the polyolefin.
  • Another embodiment of the invention is directed to a polyolefin made by this process.
  • the polyolefin comprises polyethylene or polypropylene.
  • the silicoaluminophosphate molecular sieve is preferably selected from the group consisting of S APO-5, S APO-8, S APO- 11 ,
  • the silicoaluminophosphate is selected from the group including SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34 and
  • the oxygenate feedstock is preferably selected from the group consisting of methanol; ethanol; n-propanol; isopropanol; C 4 -C 20 alcohols; methyl ethyl ether; dimethyl ether; diethyl ether; di-isopropyl ether; formaldehyde; dimethyl carbonate; dimethyl ketone; acetic acid; and mixtures thereof. More preferably, the oxygenate feedstock is methanol, dimethyl ether, or a mixture thereof. In order to convert the oxygenate to olefin product, the process is preferably performed at a temperature between 200°C and 600°C.
  • the silicoaluminophosphate molecular sieves of this invention comprise a three-dimensional microporous crystal framework structure of [Si0 2 ], [A10 ] and [PO 2 ] corner sharing tetrahedral units.
  • the way Si is incorporated into the structure can be determined by 29 Si MAS NMR. See Blackwell and Patton, J Phys. Chem., 92, 3965 (1988).
  • the desired SAPO molecular sieves will exhibit one or more peaks in the 29 Si MAS NMR, with a chemical shift ⁇ (Si) in the range of -88 to -94 ppm and with a combined peak area in that range of at least 20% of the total peak area of all peaks with a chemical shift ⁇ (Si) in the range of -88 ppm to -115 ppm, where the ⁇ (Si) chemical shifts refer to external tetramethylsilane (TMS).
  • Silicoaluminophosphate molecular sieves are generally classified as being microporous materials having 8, 10, or 12 membered ring structures. These ring structures can have an average pore size ranging from about 3.5-15 angstroms.
  • silicoaluminophosphate molecular sieves comprise a molecular framework of corner-sharing [SiO 2 ], [A10 2 ], and [P0 2 ] tetrahedral units. This type of framework is effective in converting various oxygenates into olefin products.
  • the [PO 2 ] tetrahedral units within the framework structure of the molecular sieve of this invention can be provided by a variety of compositions.
  • these phosphorus-containing compositions include phosphoric acid, organic phosphates such as triethyl phosphate, and aluminophosphates.
  • the phosphorous-containing compositions are mixed with reactive silicon and aluminum-containing compositions under the appropriate conditions to form the molecular sieve.
  • the [AlO 2 ] tetrahedral units within the framework structure can be provided by a variety of compositions.
  • aluminum-containing compositions examples include aluminum alkoxides such as aluminum isopropoxide, aluminum phosphates, aluminum hydroxide, sodium aluminate, and pseudoboehmite.
  • the aluminum-containing compositions are mixed with reactive silicon and phosphorus-containing compositions under the appropriate conditions to form the molecular sieve.
  • the [SiO ] tetrahedral units within the framework structure can be provided by a variety of compositions.
  • these silicon-containing compositions include silica sols and silicium alkoxides such as tetra ethyl orthosilicate.
  • the silicon-containing compositions are mixed with reactive aluminum and phosphorus-containing compositions under the appropriate conditions to form the molecular sieve.
  • Suitable silicoaluminophosphate molecular sieves include SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31,
  • the silicoaluminophosphate is selected from the group including SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-44 and mixtures thereof.
  • the preferred silicoaluminophosphate is selected from the group consisting of SAPO-18, SAPO-34 and mixtures thereof.
  • the term mixture is synonymous with combination and is considered a composition of matter having two or more components in varying proportions, regardless of their physical state.
  • the silicoaluminophosphate molecular sieves are synthesized by hydrothermal crystallization methods generally known in the art. See, for example, U.S. Pat. Nos. 4,440,871; 4,861,743; 5,096,684; and 5,126,308, the methods of making of which are fully incorporated herein by reference.
  • a reaction mixture is formed by mixing together reactive silicon, aluminum and phosphorus components, along with at least one template. Generally the mixture is sealed and heated, preferably under autogenous pressure, to a temperature of at least 100°C, preferably from 100-250°C, until a crystalline product is formed. Formation of the crystalline product can take anywhere from around 2 hours to as much as 2 weeks. In some cases, stirring or seeding with crystalline material will facilitate the formation of the product.
  • the molecular sieve product will be formed in solution. It can be recovered by standard means, however, such as by centrifugation or filtration. The product can also be washed, recovered by the same means and dried. As a result of the crystallization process, the recovered sieve contains within its pores at least a portion of the template used in making the initial reaction mixture. The crystalline structure essentially wraps around the template, and the template must be removed to obtain catalytic activity. Once the template is removed, the crystalline structure that remains has what is typically called an intracrystalline pore system.
  • the SAPO molecular sieve can contain one or more templates. Templates are structure directing or affecting agents, and typically contain nitrogen, phosphorus, oxygen, carbon, hydrogen or a combination thereof, and can also contain at least one alkyl or aryl group, with 1 to 8 carbons being present in the alkyl or aryl group. Mixtures of two or more templates can produce mixtures of different sieves or predominantly one sieve where one template is more strongly directing than another.
  • Representative templates include tetraethyl ammonium salts, cyclopentylamine, aminomethyl cyclohexane, piperidine, triethylamine, cyclohexylamine, tri-ethyl hydroxyethylamine, morpholine, dipropylamine
  • DP A pyridine
  • Preferred templates are triethylamine, cyclohexylamine, piperidine, pyridine, isopropylamine, tetraethyl ammonium salts, and mixtures thereof.
  • the tetraethylammonium salts include tetraethyl ammonium hydroxide (TEAOH), tetraethyl ammonium phosphate, tetraethyl ammonium fluoride, tetraethyl ammonium bromide, tetraethyl ammonium chloride, tetraethyl ammonium acetate.
  • Preferred tetraethyl ammonium salts are tetraethyl ammonium hydroxide and tetraethyl ammonium phosphate.
  • molecular sieve or catalyst containing the molecular sieve must be activated prior to use in a catalytic process. Activation is performed in such a manner that template is removed from the molecular sieve, leaving active catalytic sites with the microporous channels of the molecular sieve open for contact with feed.
  • the activation process is typically accomplished by calcining, or essentially heating the template at a temperature of from 200 to 800°C in the presence of an oxygen-containing gas. In some cases, it may be desirable to heat in an environment having a low oxygen concentration. This type of process can be used for partial or complete removal of the template from the intracrystalline pore system.
  • silicoaluminophosphate molecular sieves may be admixed (blended) with other materials. When blended, the resulting composition is typically referred to as a silicoaluminophosphate (SAPO) catalyst, with the catalyst comprising the SAPO molecular sieve.
  • SAPO silicoaluminophosphate
  • Materials which can be blended with the molecular sieve can be various inert or catalytically active materials, or various binder materials. These materials include compositions such as kaolin and other clays, various forms of rare earth metals, other non-zeolite catalyst components, zeolite catalyst components, alumina or alumina sol, titania, zirconia, quartz, silica or silica or silica sol, and mixtures thereof. These components are also effective in reducing overall catalyst cost, acting as a thermal sink to assist in heat shielding the catalyst during regeneration, densifying the catalyst and increasing catalyst strength.
  • the amount of molecular sieve which is contained in the final catalyst product ranges from 10 to 90 weight percent of the total catalyst, preferably 30 to 70 weight percent of the total catalyst.
  • Additional olefin-forming molecular sieve materials can be mixed with the silicoaluminophosphate catalyst if desired.
  • molecular sieves Several types exist, each of which exhibit different properties. Structural types of small pore molecular sieves that are suitable for use in this invention include AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, DDR, EDI, ERI, GOO, KFI, LEV, LTA, MON, PAU, PHI, RHO, THO, and substituted forms thereof.
  • Structural types of medium pore molecular sieves that are suitable for use in this invention include MFI, MEL, MTW, EUO, MTT, HEU, FER, AFO, AEL, TON, and substituted forms thereof. These small and medium pore molecular sieves are described in greater detail in the Atlas of Zeolite Structural Types, W.M. Meier and D.H. Olsen, Butterworth Heineman, 3rd ed., 1997, the detailed description of which is explicitly incorporated herein by reference.
  • Preferred molecular sieves which can be combined with a silicoaluminophosphate catalyst include ZSM-5, ZSM-34, erionite, and chabazite.
  • Thorium can be incorporated into the SAPO catalyst through any one of the standard methods well known to whose skilled in the art.
  • thorium can be incorporated by ion-exchange, impregnation, or direct synthesis methods.
  • thorium is incorporated by ion exchange.
  • a solution of thorium is first made by dissolving the desired amount of a thorium-containing compound in water under mild conditions. Preferably, the water is de-ionized. The temperature of mixing is dependent upon the thorium-containing compound's solubility in water, or whatever other medium is selected. The process may be conducted under pressure or at atmospheric pressure. After adequate mixing, the solution is then added to the selected amount of the molecular sieve. The resulting mixture is stirred as required. In some cases, stirring is not required and the mixture may be left undisturbed for a time adequate to permit the desired level of incorporation. The catalyst product is then filtered, optionally washed, dried, and calcined by methods well known to those skilled in the art.
  • thorium is impregnated into the SAPO molecular sieve.
  • a limited amount of water solution of the thorium-containing compound is dripped into the molecular sieve such that all the solution is totally absorbed and there is no excess solution, i.e., all the thorium in the solution ends up in the molecular sieve.
  • the molecular sieve is vigorously tumbled while adding the loading solution to uniformly distribute the metal.
  • thorium containing catalysts can be synthesized by hydrothermal crystallization for an effective time at an effective pressure and temperatures from a reaction mixture containing active resources of thorium, silicon, aluminum and phosphorous, and preferably organic templating.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferable lined with an inert plastic material such as polytetrafluoroethylene (PTFE) and heated, preferably under autogenous pressure at a temperature between 50 °C and 250 °C, and preferably between 100-200 °C, until crystals of the ThSAPO product are obtained, usually about a period of from hours to several weeks.
  • the crystallization time is from about 2 hours to about 30 days and typically from about 4 hours to about 20 days.
  • the product is then recovered by any suitable method such as centrifugation or filtration.
  • the amount of thorium which is incorporated into the molecular sieve may vary over a wide range depending, at least in part, on the selected molecular sieve catalyst and the incorporation method.
  • the amount of thorium incorporated is measured on an atomic thorium basis in terms of silicon to thorium ratio.
  • the silicon to thorium atomic ratios are in the range from about 0.01 : 1 to about 1000: 1 , preferably from about 0.1 : 1 to about 500:1, and most preferably from about 0.5:1 to about 50:1.
  • thorium to a SAPO molecular sieve enhances the selectivity of ethylene and propylene, especially ethylene produced from the conversion of oxygenate-containing feedstock such as methanol, to olefins. Further, the presence of thorium reduces the amount of undesirable by-products such as Ci-C 4 paraffin and reduces the amount of coke the reaction deposits on the catalyst.
  • a feed containing an oxygenate is contacted in a reaction zone of a reactor apparatus with an activated molecular sieve catalyst at process conditions effective to produce light olefins, i.e., an effective temperature, pressure, WHS V (weight hour space velocity) and, optionally, an effective amount of diluent, correlated to produce light olefins.
  • process conditions effective to produce light olefins i.e., an effective temperature, pressure, WHS V (weight hour space velocity) and, optionally, an effective amount of diluent, correlated to produce light olefins.
  • the oxygenate feed is contacted with the catalyst when the oxygenate is in a vapor phase.
  • the process may be carried out in a liquid or a mixed vapor/liquid phase.
  • different conversions and selectivities of feed-to-product may result depending upon the catalyst and reaction conditions.
  • Olefins can generally be produced at a wide range of temperatures.
  • An effective operating temperature range can be from about 200°C to 700°C.
  • the formation of the desired olefin products may become markedly slow.
  • the process may not form an optimum amount of product.
  • An operating temperature of at least 300°C, and up to 600°C is preferred.
  • the conversion of oxygenates to produce light olefins may be carried out in a variety of large scale catalytic reactors, including, but not limited to, fluid bed reactors and concurrent riser reactors as described in "Free Fall Reactor," Fluidization Engineering, D. Kunii and O. Levenspiel, Robert E. Krieger
  • WHSV weight hourly space velocity
  • WHSV is defined as the weight of hydrocarbon in the feed per hour per weight of silicoaluminophosphate molecular sieve content of the catalyst.
  • the hydrocarbon content will be oxygenate and any hydrocarbon which may optionally be combined with the oxygenate.
  • the silicoaluminophosphate molecular sieve content is intended to mean only the silicoaluminophosphate molecular sieve portion that is contained within the catalyst. This excludes components such as binders, diluents, inerts, rare earth components, etc.
  • the reaction conditions for making olefin from oxygenate comprise a WHSV of at least about 20 hr "1 producing olefins and a TCNMS of less than about 0.016.
  • TCNMS is defined as the Normalized Methane Selectivity (NMS) when the temperature is less than 400°C.
  • NMS Normalized Methane Selectivity
  • the NMS is defined as the methane product yield divided by the ethylene product yield wherein each yield is measured on, or is converted to, a weight % basis.
  • T is the average temperature within the reactor in °C:
  • NMS TCNMS l+(((T-400)/400) x 14.84)
  • the pressure also may vary over a wide range, including autogenous pressures.
  • Effective pressures may be in, but are not necessarily limited to, pressures of from about 0.1 kPa to about 10 MPa.
  • Preferred pressures are in the range of about 5 kPa to about 5 MPa, with the most preferred range being of from about 50 kPa to about 0.5 MPa.
  • the foregoing pressures are exclusive of any oxygen depleted diluent, and thus, refer to the partial pressure of the oxygenate compounds and/or mixtures thereof with feedstock. At the lower and upper end of the foregoing pressure ranges, the rate of selectivity, conversion and/or reaction may not be optimum.
  • One or more inert diluents may be present in the feedstock, for example, in an amount of from 1 to 99 molar percent, based on the total number of moles of all feed and diluent components fed to the reaction zone (or catalyst).
  • diluents are compositions which are essentially non-reactive across a molecular sieve catalyst, and primarily function to make the oxygenates in the feedstock less concentrated.
  • Typical diluents include, but are not necessarily limited to helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, paraffins, alkanes (especially methane, ethane, and propane), alkylenes, aromatic compounds, and mixtures thereof.
  • the preferred diluents are water and nitrogen. Water can be injected in either liquid or vapor form.
  • the process may be carried out in a batch, semi-continuous or continuous fashion. The process can be conducted in a single reaction zone or a number of reaction zones arranged in series or in parallel.
  • the level of conversion of the oxygenates can be maintained to reduce the level of unwanted by-products. Conversion can also be maintained sufficiently high to avoid the need for commercially undesirable levels of recycling of unreacted feeds. A reduction in unwanted by-products is seen when conversion moves from 100 mol % to about 98 mol % or less. Recycling up to as much as about 50 mol % of the feed is commercially acceptable. Therefore, conversions levels which achieve both goals are from about 50 mol % to about 98 mol % and, desirably, from about 85 mol % to about 98 mol %. However, it is also acceptable to achieve conversion between 98 mol % and 100 mol % in order to simplify the recycling process.
  • Oxygenate conversion may be maintained at this level using a number of methods familiar to persons of ordinary skill in the art. Examples include, but are not necessarily limited to, adjusting one or more of the following: the reaction temperature; pressure; flow rate (i.e., WHSV); level and degree of catalyst regeneration; amount of catalyst re-circulation; the specific reactor configuration; the feed composition; and other parameters which affect the conversion.
  • the molecular sieve catalyst can be continuously introduced as a moving bed to a regeneration zone where it can be regenerated, such as for example by removing carbonaceous materials or by oxidation in an oxygen-containing atmosphere.
  • the catalyst is subject to a regeneration step by burning off carbonaceous deposits accumulated during the conversion reactions.
  • the oxygenate feedstock comprises at least one organic compound which contains at least one oxygen atom, such as aliphatic alcohols, ethers, carbonyl compounds (aldehydes, ketones, carboxylic acids, carbonates, esters and the like).
  • the alcohol can include an aliphatic moiety having from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms.
  • the method of making the preferred olefin product in this invention can include the additional step of making these compositions from hydrocarbons such as oil, coal, tar sand, shale, biomass and natural gas.
  • Methods for making the compositions are known in the art. These methods include fermentation to alcohol or ether, making synthesis gas, then converting the synthesis gas to alcohol or ether.
  • Synthesis gas can be produced by known processes such as steam reforming, autothermal reforming and partial oxidization.
  • Ethylene and propylene are selectively produced from an oxygenate using the catalyst according to the invention.
  • selectivity of ethylene plus propylene is from 50%-95% of the feeds' hydrocarbon content.
  • selectivity of ethylene and propylene is 70-95%, and more preferably 80-95%.
  • the olefins produced by the oxygenate-to-olef ⁇ n conversion reaction of the present invention can be polymerized to form poly olefins, particularly polyethylene and polypropylene. Processes for forming polyolefins from olefins are known in the art. Catalytic processes are preferred. Particularly preferred are metallocene, Ziegler/Natta and acid catalytic systems.
  • a preferred pblyolefin-forming catalyst is a metallocene catalyst.
  • the preferred temperature range of operation is between 50 and 240°C and the reaction can be carried out at low, medium or high pressure, being anywhere within the range of about 1 to 200 bars.
  • an inert diluent can be used, and the preferred operating pressure range is between 10 and 150 bars, with a preferred temperature range of between 120 and 230°C.
  • the temperature generally be within a range of 60 to 160°C, and that the operating pressure be between 5 and 50 bars.
  • numerous other olefin derivatives may be formed from the olefins recovered therefrom.
  • aldehydes include, but are not limited to, aldehydes, alcohols, acetic acid, linear alpha olefins, vinyl acetate, ethylene dichloride and vinyl chloride, ethylbenzene, ethylene oxide, cumene, isopropyl alcohol, acrolein, allyl chloride, propylene oxide, acrylic acid, ethylene-propylene rubbers, and acrylonitrile, and trimers and dimers of ethylene, propylene or butylenes.
  • aldehydes include, but are not limited to, aldehydes, alcohols, acetic acid, linear alpha olefins, vinyl acetate, ethylene dichloride and vinyl chloride, ethylbenzene, ethylene oxide, cumene, isopropyl alcohol, acrolein, allyl chloride, propylene oxide, acrylic acid, ethylene-propylene rubbers, and acrylonitrile, and trimers and dimers of ethylene

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  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne un tamis moléculaire de silico-aluminophosphates, qui contient du thorium et que l'on utilise dans un procédé de fabrication d'un produit comprenant une oléfine à partir d'une charge d'alimentation à base d'oxygénats. Ledit procédé consiste à utiliser le catalyseur à base de silico-aluminophosphates qui contient du thorium ; et à mettre ledit catalyseur, dans son état activé, au contact d'une charge d'oxygénats, dans des conditions permettant la production d'un produit oléfinique.
PCT/US2001/004667 2000-03-01 2001-02-13 Tamis moleculaire de silico-aluminophosphates contenant du thorium destine a la production d'olefines WO2001064340A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001236984A AU2001236984A1 (en) 2000-03-01 2001-02-13 Thorium-containing sapo molecular sieve for producing olefins

Applications Claiming Priority (2)

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US51668400A 2000-03-01 2000-03-01
US09/516,684 2000-03-01

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003074177A2 (fr) * 2002-02-28 2003-09-12 Exxonmobil Chemical Patents Inc. Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion
US6783659B2 (en) * 2001-11-16 2004-08-31 Chevron Phillips Chemical Company, L.P. Process to produce a dilute ethylene stream and a dilute propylene stream
WO2005046867A1 (fr) 2003-11-10 2005-05-26 Exxonmobil Chemical Patents Inc. Protection de sites catalytiques de tamis moleculaires metalloaluminophosphate
US6906232B2 (en) 2002-08-09 2005-06-14 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
US6995111B2 (en) 2002-02-28 2006-02-07 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
US7074739B2 (en) * 2002-11-19 2006-07-11 Exxonmobil Chemical Patents Inc. Multi-component molecular sieve catalyst compositions and their use in aromatics reactions
US7166757B2 (en) * 2004-07-30 2007-01-23 Exxonmobil Chemical Patents Inc. Conversion of oxygenates to olefins
US7186875B2 (en) * 2004-07-30 2007-03-06 Exxon Mobil Chemical Patents Inc. Conversion of oxygenates to olefins
US7199278B2 (en) * 2004-07-30 2007-04-03 Exxonmobil Chemical Patents Inc. Conversion of oxygenates to olefins
US7199277B2 (en) * 2004-07-01 2007-04-03 Exxonmobil Chemical Patents Inc. Pretreating a catalyst containing molecular sieve and active metal oxide
US7208442B2 (en) 2002-02-28 2007-04-24 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
US7319178B2 (en) 2002-02-28 2008-01-15 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
US7358410B2 (en) 2004-12-30 2008-04-15 Exxonmobil Chemical Patents Inc. Processes for forming polypropylene from an oxygenate-contaminated monomer feedstock
EP2098287A1 (fr) 2008-03-03 2009-09-09 ExxonMobil Chemical Patents Inc. Procédé de formulation de composition de catalyseur de tamis moléculaire en contrôlant un ajout de composant
WO2024124153A1 (fr) * 2022-12-08 2024-06-13 California Institute Of Technology Tamis moléculaire cit-16 p, sa synthèse, sa transformation et son utilisation

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WO1986000297A1 (fr) * 1984-06-27 1986-01-16 Union Carbide Corporation Conversion amelioree de gaz de synthese en carburants liquides pour moteurs
WO1998029370A1 (fr) * 1996-12-31 1998-07-09 Exxon Chemical Patents Inc. Conversions de composes oxygenes au moyen de catalyseurs a tamis moleculaires non zeolitiques a mailles fines

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
WO1986000297A1 (fr) * 1984-06-27 1986-01-16 Union Carbide Corporation Conversion amelioree de gaz de synthese en carburants liquides pour moteurs
WO1998029370A1 (fr) * 1996-12-31 1998-07-09 Exxon Chemical Patents Inc. Conversions de composes oxygenes au moyen de catalyseurs a tamis moleculaires non zeolitiques a mailles fines

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6783659B2 (en) * 2001-11-16 2004-08-31 Chevron Phillips Chemical Company, L.P. Process to produce a dilute ethylene stream and a dilute propylene stream
US6790342B1 (en) 2001-11-16 2004-09-14 Chevron Phillips Chemical Company Lp Process to produce a dilute ethylene stream and a dilute propylene stream
US7208442B2 (en) 2002-02-28 2007-04-24 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
WO2003074177A3 (fr) * 2002-02-28 2003-12-31 Exxonmobil Chem Patents Inc Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion
US6995111B2 (en) 2002-02-28 2006-02-07 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
US7319178B2 (en) 2002-02-28 2008-01-15 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
WO2003074177A2 (fr) * 2002-02-28 2003-09-12 Exxonmobil Chemical Patents Inc. Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion
EA007871B1 (ru) * 2002-02-28 2007-02-27 Эксонмобил Кемикэл Пейтентс Инк. Каталитические композиции, включающие молекулярные сита, их приготовление и применение в процессах превращения
CN1327964C (zh) * 2002-02-28 2007-07-25 埃克森美孚化学专利公司 包括分子筛的催化剂组合物、其制备及在转化方法中的应用
US7378563B2 (en) 2002-08-09 2008-05-27 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
US6906232B2 (en) 2002-08-09 2005-06-14 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
US7276638B2 (en) 2002-11-19 2007-10-02 Exxonmobil Chemical Patents Inc. Multi-component molecular sieve catalyst compositions and their use in aromatics reactions
US7074739B2 (en) * 2002-11-19 2006-07-11 Exxonmobil Chemical Patents Inc. Multi-component molecular sieve catalyst compositions and their use in aromatics reactions
WO2005046867A1 (fr) 2003-11-10 2005-05-26 Exxonmobil Chemical Patents Inc. Protection de sites catalytiques de tamis moleculaires metalloaluminophosphate
US7199277B2 (en) * 2004-07-01 2007-04-03 Exxonmobil Chemical Patents Inc. Pretreating a catalyst containing molecular sieve and active metal oxide
US7199278B2 (en) * 2004-07-30 2007-04-03 Exxonmobil Chemical Patents Inc. Conversion of oxygenates to olefins
US7186875B2 (en) * 2004-07-30 2007-03-06 Exxon Mobil Chemical Patents Inc. Conversion of oxygenates to olefins
US7166757B2 (en) * 2004-07-30 2007-01-23 Exxonmobil Chemical Patents Inc. Conversion of oxygenates to olefins
US7358410B2 (en) 2004-12-30 2008-04-15 Exxonmobil Chemical Patents Inc. Processes for forming polypropylene from an oxygenate-contaminated monomer feedstock
EP2098287A1 (fr) 2008-03-03 2009-09-09 ExxonMobil Chemical Patents Inc. Procédé de formulation de composition de catalyseur de tamis moléculaire en contrôlant un ajout de composant
WO2024124153A1 (fr) * 2022-12-08 2024-06-13 California Institute Of Technology Tamis moléculaire cit-16 p, sa synthèse, sa transformation et son utilisation

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