Classifications

• • 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
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
• • 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
• • 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
  • C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/82—Phosphates
  • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
  • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/40—Ethylene production

Definitions

• MTO methanol to olefin
• SAPOs silico aluminophosphates
• US-A-4,499,327 discloses that many of the SAPO family of molecular sieves can be used to convert methanol to olefins.
• preferred SAPOs are those that have pores large enough to adsorb xenon (kinetic diameter of 4.0 ⁇ ) but small enough to exclude isobutane (kinetic diameter of 5.0 A).
• a particularly preferred SAPO is SAPO-34.
• US-A-4,752,651 discloses the use of nonzeolitic molecular sieves (NZMS) including ELAPOs and MeAPO molecular sieves to catalyze the methanol to olefin reaction.
• NZMS nonzeolitic molecular sieves
• molecular sieves having the empirical formula (EL x Al y P z )0 2 (hereinafter ELAPO) where EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof and x, y and z are the mole fractions of EL, Al and P respectively and having a predominantly plate crystal morphology wherein the average smallest crystal dimension is at least 0.1 micron and has an aspect ratio of less than or equal to 5.
• ELAPO empirical formula
• EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof
• x, y and z are the mole fractions of EL, Al and P respectively and having a predominantly plate crystal morphology wherein the average smallest crystal dimension is at least 0.1 micron and has an aspect ratio of less than or equal to 5.
• this invention relates to an ELAPO containing catalyst and a process for converting methanol to light olefins using the catalyst.
• one embodiment of the invention is a process for converting methanol to light olefins comprising contacting the methanol with a catalyst at conversion conditions, the catalyst comprising a crystalline metal aluminophosphate molecular sieve having a chemical composition on an anhydrous basis expressed by an empirical formula of:
• EL x Al y P z
• EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof
• x is the mole fraction of EL and has a value of at least 0.005
• y is the mole fraction of Al and has a value of at least 0.01
• z is the mole fraction of P and has a value of at least 0.01
• x + y + z 1
• the molecular sieve characterized in that it has predominantly a plate crystal morphology, wherein the average smallest crystal dimension is at least 0.1 micron and has an aspect of less than or equal to 5.
• Another embodiment of the invention is a catalyst for converting methanol to light olefins comprising a crystalline metallo aluminophosphate molecular sieve having an empirical chemical composition on an anhydrous basis expressed by the formula: (EL ⁇ Al y P z )0 2
• EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof
• x is the mole fraction of EL and has a value of at least 0.005
• "y” is the mole fraction of Al and has a value of at least 0.01
• "z” is the mole fraction of P and has a value of at least 0.01
• x + y + z 1, the molecular sieve characterized in that it has a crystal morphology wherein the average smallest crystal dimension is at least 0.1 micron.
• ELAPO electroactive polymer
• ELAPOs are molecular sieves which have a three-dimensional microporous framework structure of AIO 2 , P0 2 and EL0 2 tetrahedral units.
• the ELAPOs have the empirical formula
• EL x Al y P z
• EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof
• x is the mole fraction of EL and has a value of at least 0.005
• y is the mole fraction of Al and has a value of at least 0.01
• z is the mole fraction of P and has a value of at least 0.01
• x + y + z 1.
• Preferred metals (EL) are silicon, magnesium and cobalt with silicon being especially preferred.
• ELAPO The preparation of various ELAPOs are well known in the art and may be found in US-A-: 4,554,143 (FeAPO); 4,440,871 (SAPO); 4,853,197 (MAPO, MnAPO, ZnAPO, CoAPO); 4,793,984 (CAPO), 4,752,651 and 4,310,440.
• the ELAPO molecular sieves are synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of EL, aluminum, phosphorus and a templating agent.
• Reactive sources of EL are the metal salts such as the chloride and nitrate salts. When EL is silicon a preferred source is fumed, colloidal or precipitated silica.
• Preferred reactive sources of aluminum and phosphorus are pseudo-boehmite alumina and phosphoric acid.
• Preferred templating agents are amines and quaternary ammonium compounds.
• An especially preferred templating agent is tetraethylammonium hydroxide (TEAOH).
• the reaction mixture is placed in a sealed pressure vessel, optionally lined with an inert plastic material such as polytetrafluoroethylene and heated preferably under autogenous pressure at a temperature between 50°C and 250°C and preferably between 100°C and 200°C for a time sufficient to produce crystals of the ELAPO molecular sieve. Typically the time varies from 1 hour to 120 hours and preferably from 24 hours to 48 hours.
• the desired product is recovered by any convenient method such as centrifugation or filtration.
• the ELAPO molecular sieves of this invention have predominantly a plate crystal morphology.
• predominantly greater than 50% of the crystals.
• Preferably at least 70% of the crystals have a plate morphology and most preferably at least 90% of the crystals have a plate morphology.
• plate morphology is meant that the crystals have the appearance of rectangular slabs.
• the aspect ratio is less than or equal to 5.
• the aspect ratio is defined as the ratio of the largest crystalline dimension divided by the smallest crystalline dimension.
• a preferred morphology which is encompassed within the definition of plate is cubic morphology.
• cubic is meant not only crystals in which all the dimensions are the same, but also those in which the aspect ratio is less than or equal to 2. It is also necessary that the average smallest crystal dimension be at least 0.1 microns and preferably at lest 0.2 microns. As is shown in the examples, the morphology of the crystals and the average smallest crystal dimension is determined by examining the ELAPO molecular sieve using Scanning Electron Microscopy (SEM) and measuring the crystals in order to obtain an average value for the smallest dimension.
• SEM Scanning Electron Microscopy
• the ELAPOs which are synthesized using the process described above will usually contain some of the organic templating agent in its pores.
• the templating agent in the pores must be removed by heating the ELAPO powder in an oxygen containing atmosphere at a temperature of about 200° to about 700°C until the template is removed, usually a few hours.
• a preferred embodiment of the invention is one in which the metal (EL) content varies from 0.005 to 0.05 mole fraction. If EL is more than one metal then the total concentration of all the metals is between 0.005 and 0.05 mole fraction.
• An especially preferred embodiment is one in which EL is silicon (usually referred to as SAPO).
• SAPO silicon
• the SAPOs which can be used in the instant invention are any of those described in U.S. Patent 4,440,871. Of the specific crystallographic structures described in the '871 patent, the SAPO-34, i.e., structure type 34, is preferred.
• the SAPO-34 structure is characterized in that it adsorbs zenon but does not adsorb isobutane, indicating that it has a pore opening of about 4.2 A.
• the ELAPO molecular sieve of this invention may be used alone or they may be mixed with a binder and formed into shapes such as extrudates, pills, spheres, etc. Any inorganic oxide well known in the art may be used as a binder. Examples of the binders which can be used include alumina, silica, aluminum-phosphate, silica-alumina, etc. When a binder is used, the amount of ELAPO which is contained in the final product ranges from 10 to 90 weight percent and preferably from 30 to 70 weight percent.
• the conversion of methanol to light olefins is effected by contacting the methanol with the ELAPO catalyst at conversion conditions, thereby forming the desired light olefins.
• the methanol can be in the liquid or vapor phase with the vapor phase being preferred.
• Contacting the methanol with the ELAPO catalyst can be done in a continuous mode or a batch mode with a continuous mode being preferred.
• the amount of time that the methanol is in contact with the ELAPO catalyst must be sufficient to convert the methanol to the desired light olefin products.
• the contact time varies from about 0.001 hr. to about 1 hr. and preferably from about 0.01 hr.
• the Weight Hourly Space Velocity (WHSV) based on methanol can vary from about 1 hr "1 to about 1000 hr "1 and preferably from about 1 hr "1 to about 100 hr '1 .
• the process must be carried out at elevated temperatures in order to form light olefins at a fast enough rate.
• the process should be carried out at a temperature of 300°C to 600°C, preferably from 400°C to 550°C and most preferably from 450°C to 525°C.
• the process may be carried out over a wide range of pressure including autogenous pressure.
• the pressure can vary from about 0 kPa to 1724 kPa and preferably from 34 kPa to 345 kPa.
• the methanol feedstock may be diluted with an inert diluent in order to more efficiently convert the methanol to olefins.
• diluents examples include helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, e.g., methane, aromatic hydrocarbons, e.g., benzene, toluene and mixtures thereof.
• the amount of diluent used can vary considerably and is usually from 5 to 90 mole percent of the feedstock and preferably from 25 to 75 mole percent.
• the actual configuration of the reaction zone may be any well known catalyst reaction apparatus known in the art. Thus, a single reaction zone or a number of zones arranged in series or parallel may be used. In such reaction zones the methanol feedstock is flowed through a bed containing the ELAPO catalyst. When multiple reaction zones are used, one or more ELAPO catalyst may be used in series to produce the desired product mixture. Instead of a fixed bed, a dynamic bed system, e.g., fluidized or moving, may be used. Such a dynamic system would facilitate any regeneration of the ELAPO catalyst that may be required. If regeneration is required, the ELAPO catalyst can be continuously introduced as a moving bed to a regeneration zone where it can be regenerated by means such as oxidation in an oxygen containing atmosphere to remove carbonaceous materials.
• SAPOs molecular sieves
• the mixture was now placed in a steel pressure reactor equipped with a turbine stirrer.
• the mixture was now stirred and heated to 100°C over a 6 hour period, held at 100°C for 6 hours, then heated to 175°C over a period of 3 hours and held there for the reaction time of 24, 36 or 48 hours.
• the reaction mixture was cooled to ambient temperature and the solid product recovered by centrifugation and washed with water. All the products were analyzed and found to be SAPO-34 molecular sieves.
• Example 1 The catalysts prepared in Example 1 were evaluated for the conversion of methanol to light olefins in a fixed bed pilot plant. A 4 gram sample in the form of 20-40 mesh agglomerates was used for the testing. Before testing, each sample was calcined in air in a muffle oven at 650°C for 2 hours and then pre-treated in situ by heating to
• the pretreated sample was now contacted with a feed consisting of methanol and H 2 0 in a 1/0.44 molar ratio at 435°C, 5 psig and 2.5 hr " 1 MeOH WHSV.
• the composition of the effluent was measured by an on-line GC after
• the average smallest crystallite dimension was determined by measuring 20 representative crystallites in one or more micrographs obtained using a Scanning Electron Microscope at 30,000x magnification. The data indicate that when the smallest crystal dimension is greater than 0.1 micron and the crystal morphology is plates, a greater amount of ethylene is produced. It is also observed that when the crystal morphology is cubic and the smallest dimension is greater than 0.2 microns, one obtains the highest production of ethylene. Note that when the smallest dimension is less than 0.1 , one obtains poor results (greater propylene production) even though the crystal morphology is plates.

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• 2001
  • 2001-03-22 KR KR1020037012305A patent/KR100793508B1/ko not_active IP Right Cessation
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