US20100168492A1 - Alkaline earth metal compound-containing zeolite catalyst, preparation method and regeneration method thereof, and method for producing lower hydrocarbon - Google Patents

Alkaline earth metal compound-containing zeolite catalyst, preparation method and regeneration method thereof, and method for producing lower hydrocarbon Download PDF

Info

Publication number
US20100168492A1
US20100168492A1 US12/377,036 US37703607A US2010168492A1 US 20100168492 A1 US20100168492 A1 US 20100168492A1 US 37703607 A US37703607 A US 37703607A US 2010168492 A1 US2010168492 A1 US 2010168492A1
Authority
US
United States
Prior art keywords
component
alkaline
earth metal
catalyst
metal compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/377,036
Other languages
English (en)
Inventor
Chizu Inaki
Hirofumi Ito
Kazunori Honda
Koji Oyama
Atsushi Okita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JGC Corp
JCC Corp
Original Assignee
JCC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006262554A external-priority patent/JP2008080238A/ja
Priority claimed from JP2006266044A external-priority patent/JP2008080301A/ja
Application filed by JCC Corp filed Critical JCC Corp
Assigned to JGC CORPORATION reassignment JGC CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HONDA, KAZUNORI, INAKI, CHIZU, ITO, HIROFUMI, OKITA, ATSUSHI, OYAMA, KOJI
Publication of US20100168492A1 publication Critical patent/US20100168492A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/16—Oxidation gas comprising essentially steam and oxygen
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to an alkaline-earth metal compound-containing zeolite catalyst (zeolite-based catalyst that contains alkaline-earth metal compound) which is used in the synthetic process of lower hydrocarbons by dehydration condensation reaction from dimethyl ether and/or methanol, and also relates to a method for preparing the zeolite catalyst.
  • the present invention relates to an alkaline-earth metal compound-containing zeolite catalyst in which elimination of tetrahedral aluminum from zeolite framework is not likely to occur and exhibits slow formation rate of carbonaceous deposits during reaction, and relates to a method for producing the zeolite catalyst.
  • the present invention also relates to a method for producing a lower hydrocarbons utilizing the alkaline-earth metal compound-containing zeolite catalyst.
  • the present invention also relates to a method for regenerating the alkaline-earth metal compound-containing zeolite catalyst that is used in the synthetic process of lower hydrocarbons by dehydration condensation reaction from dimethyl ether and/or methanol.
  • Zeolite catalysts are used in various processes such as DTO reaction/MTO reaction for synthesizing lower hydrocarbons from dimethyl ether (hereafter referred to as DME) and/or methanol, MTG reaction for synthesizing gasoline from methanol, fluid catalytic cracking (FCC) or the like.
  • DME dimethyl ether
  • MTG reaction for synthesizing gasoline from methanol
  • FCC fluid catalytic cracking
  • deactivation of zeolite catalysts may occur.
  • the following is the main reason for deactivating zeolite catalysts.
  • elimination of aluminum from the zeolite framework may occur.
  • carbonaceous deposits are formed on the zeolite catalysts during the reaction.
  • Reduction of catalytic activity caused by the formation of carbonaceous deposits on the catalyst may be solved by providing a flow containing oxygen to the catalyst and burning the carbonaceous deposits on the catalyst.
  • a method is proposed for inserting aluminum into the framework by treating the dealuminated zeolite in particular conditions.
  • Patent Reference 1 Japanese Unexamined Patent Application, First Publication No. S59-136138
  • Patent Reference 2 Japanese Unexamined Patent Application, First Publication No. S60-257838
  • Patent Reference 3 Japanese Examined Patent Application, Second Publication No. H3-63430
  • Patent Reference 4 U.S. Pat. No. 4,559,314
  • Patent Reference 5 U.S. Pat. No. 4,784,747
  • Patent Reference 6 Japanese Patent, No. 2908959
  • Non Patent Reference 1 J. Catal., 93, 471 (1985)
  • Non Patent Reference 2 J. Chem. Soc. Faraday Trans. 1, 81, 2215 (1985)
  • the method for regenerating the dealuminated zeolite included a disadvantage in the applicability to industrial processes because of requirements for specific reagents or gas for the regeneration.
  • Patent Reference 11 Japanese Unexamined Patent Application, First Publication, No. S60-126233.
  • Patent Reference 11 Japanese Unexamined Patent Application, First Publication, No. S60-126233.
  • Patent Reference 11 it was not examined if lifetime of the zeolite catalyst modified with alkaline-earth metal compound was changed (or is not changed) by repeating regeneration of the catalyst after performing DTO reaction/MTO reaction.
  • steam resistance of the catalyst is not described in Patent Reference 11.
  • MFI-structure zeolite catalysts and SAPO-34 catalysts may be used.
  • the combustion reaction to burn the carbonaceous deposits on the catalyst is an exothermal reaction. So as to prevent changing the catalyst such as collapse of crystal structure, and for a stable operation of apparatus used in the process, it is preferable to inhibit large increase of temperature. Therefore, in the above-described combustion reaction, so as to depress oxygen concentration to a lower level, the air introduced to the catalyst must be diluted by inert gas such as steam and nitrogen.
  • the method includes a problem that an extra step is needed for inserting aluminum into the dealuminated zeolite. Therefore, in order to improve the lifetime of zeolite catalyst, it is necessary to produce a zeolite catalyst in which the framework aluminum is not likely to be eliminated.
  • an object of the present invention is to provide an alkaline-earth metal compound-containing zeolite catalyst, in which the elimination of tetrahedral aluminum from the zeolite framework is not likely to occur, and a simple inexpensive method for preparing the above-described zeolite catalyst.
  • Another object of the present invention is to provide a method for regenerating alkaline-earth metal compound-containing zeolite catalyst, by which method, catalytic activity of the alkaline-earth metal compound-containing zeolite catalyst is regenerated through a simple process, and lifetime of the catalyst is improved.
  • An alkaline-earth metal compound-containing zeolite catalyst according to the present invention is composed of a composite material comprising at least a first component, a second component, and a third component, wherein the first component is composed of at least one of zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites, the second component is composed of at least one of alkaline-earth metal compounds, and the third component is composed of at least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals.
  • the first component has a molar ratio of Si/Al of 10 or more and 300 or less. Content of the second component relative to the first component is 0.3 mass % or more and less than 10 mass % as alkaline-earth metal. Content of the third component relative to the first component is 15 mass % or more and 200 mass % or less.
  • the alkaline-earth metal compound-containing zeolite catalyst according to the present invention comprises the above-described first component composed of at least one of MFI-structure zeolites.
  • the second component of the alkaline-earth metal compound-containing zeolite catalyst according to the present invention is composed at least one of calcium compounds.
  • An alkaline-earth metal compound-containing zeolite catalyst according to the present invention may has a characteristic such that where an alkaline-earth metal compound-containing zeolite catalyst according to the present invention is exposed for 48 hours to an atmosphere having steam partial pressure of 0.35 MPa and nitrogen partial pressure of 0.15 MPa at 530° C., and the residual amount of tetrahedral aluminum in zeolite framework per unit mass of zeolite is measured, the residual amount of tetrahedral aluminum in the zeolite catalyst of the present invention is not smaller than five times of the residual amount of tetrahedral aluminum in the proton-type zeolite consisting of the first component which has been exposed for 48 hours to the above described atmosphere.
  • An alkaline-earth metal compound-containing zeolite catalyst according to the present invention may be used for synthesizing lower hydrocarbons from DME and/or methanol.
  • a method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to the present invention comprises: a mixing-kneading step of adding polar solvent to a composition composed at least of a first component, a second component, and a third component, and kneading to form a mixture; and a drying-calcination step of drying and calcining the mixture, where the first component is composed of at least one of zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites, the second component is composed of at least one of alkaline-earth metal compounds, and the third component is composed of at least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals.
  • the first component has a molar ratio of Si/Al of 10 or more and 300 or less.
  • Content of the second component relative to the first component is 0.3 mass % or more and less than 10 mass % as alkaline-earth metal.
  • Content of the third component relative to the first component is 15 mass % or more and 200 mass % or less.
  • a method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to the present invention further comprises a steam treatment step where the composite material obtained by the above-described drying-calcination step is made contact to steam or reaction atmosphere that generates steam.
  • the above-described first component is preferably composed of at least one of MFI-structure zeolites.
  • the second component is composed of at least one of calcium compounds.
  • a method of producing lower hydrocarbons according to the present invention is a method for synthesizing lower hydrocarbons from DME and/or methanol, where the alkaline-earth metal compound-containing zeolite catalyst is used in the synthesis, and yield of propylene is 40 mass % or more, yield of methane is less than 1.0 mass %, and yield of carbon monoxide is 0.5 mass % or less.
  • a method for regenerating alkaline-earth metal compound-containing zeolite catalyst according to the invention is a method for regenerating alkaline-earth metal compound-containing zeolite catalyst used for synthesizing lower hydrocarbons from DME and/or methanol.
  • the method includes a step of calcining an alkaline-earth metal compound-containing zeolite catalyst of the present invention in a flow containing oxygen and steam.
  • the above-described calcination of the alkaline-earth metal compound-containing zeolite catalyst is performed at 400° C. or more and 700° C. or less.
  • An alkaline-earth metal compound-containing zeolite catalyst according to the present invention is composed of a composite material comprising at least a first component, a second component, and a third component, wherein the first component is composed of at least one of zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites, the second component is composed of at least one of alkaline-earth metal compounds, and the third component is composed of at least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals.
  • the first component has a molar ratio of Si/Al of 10 or more and 300 or less, content of the second component relative to the first component is 0.3 mass % or more and less than 10 mass % as alkaline-earth metal, and content of the third component relative to the first component is 15 mass % or more and 200 mass % or less.
  • the catalyst of this constitution has a long catalytic lifetime since the elimination of aluminum from the zeolite framework is inhibited by the presence of the second component and the third component. Therefore, by the improvement of overall catalytic lifetime, loading weight of catalyst and frequency of recharging the catalyst are reduced, and it is possible to reduce the equipment cost and the operation cost.
  • a method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to the present invention comprises: a mixing-kneading step of adding polar solvent to a composition composed at least of a first component, a second component, and a third component, and kneading to form a mixture; and a drying-calcination step of drying and calcining the mixture, where the first component is composed of at least one of zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites, the second component is composed of at least one of alkaline-earth metal compounds, and the third component is composed of at least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals, the first component has a molar ratio of Si/Al of 10 or more and 300 or less, content of the second component relative to the first component is 0.3 mass % or more and less than 10 mass % as alkaline
  • an alkaline-earth metal compound-containing zeolite catalyst can be obtained easily and at low cost by using generally available and inexpensive proton-type MFI-structure zeolite or ammonium type MFI-structure zeolite, mixing with the second component and the third component, kneading, drying, and calcining the mixture of the zeolite.
  • This catalyst is not likely to occur elimination of tetrahedral aluminum from the zeolite framework, and has excellent steam resistance and a long catalytic lifetime.
  • the alkaline-earth metal compound-containing zeolite catalyst is used in the method of producing lower hydrocarbons according to the present invention, lower hydrocarbons can be obtained at a high yield.
  • the improvement of the catalytic lifetime frequency of regeneration is decreased. Therefore, productivity of lower hydrocarbons is increased and production cost can be reduced.
  • a method for regenerating alkaline-earth metal compound-containing zeolite catalyst according to the present invention is a method for regenerating alkaline-earth metal compound-containing zeolite catalyst used for synthesizing lower hydrocarbons from DME and/or methanol.
  • the alkaline-earth metal compound-containing zeolite catalyst of the present invention is calcined in a flow containing oxygen and steam, thereby improving the catalytic lifetime. Therefore, frequency of regeneration of catalyst is decreased. As a result, it is possible to reduce the cost for synthesizing lower hydrocarbons from DME and/or methanol.
  • steam can be used as a dilution gas in the time of regenerating the catalyst, it is not necessary to provide extra facilities such as a cryogenic air separator or the like.
  • FIG. 1 is a graph showing relative catalytic lifetime of catalysts A to F prepared in Experimental Examples 1-7 versus extent of steam treatment.
  • An alkaline-earth metal compound-containing zeolite catalyst according to the present invention is composed of a composite material comprising at least a first component, a second component, and a third component, wherein the first component is composed of at least one of zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites, the second component is composed of at least one of alkaline-earth metal compounds, and the third component is composed of at least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals.
  • the first component has a molar ratio of Si/Al of 10 or more and 300 or less. Content of the second component relative to the first component is 0.3 mass % or more and less than 10 mass % as alkaline-earth metal. Content of the third component relative to the first component is 15 mass % or more and 200 mass % or less.
  • the alkaline-earth metal compound-containing zeolite catalyst according to the present invention comprises the above-described first component composed of at least one of MFI-structure zeolites, where “MFI-structure” is a name of a framework structure defined in the International Zeolite Association.
  • the proton-type zeolite or ammonium-type zeolite that constitutes the first component has a molar ratio of Si/Al of 10 or more and 300 or less.
  • the content of the second component as alkaline-earth metal relative to the first component be 0.3 mass % or more and less than 10 mass %.
  • the content of the second component as alkaline-earth metal relative to the first component is less than 0.3 mass %, acidic properties of the catalyst and dealumination cannot be controlled sufficiently.
  • the content of the second component as alkaline-earth metal relative to the first component is more than 10 mass %, it is not preferable because side reactions are caused by excessive amount of the alkaline-earth metal compound (mainly composed of oxide and carbonate).
  • the content of the third component relative to the content of the first component is preferably 15 mass % or more and 200 mass % or less.
  • the content of the third component relative to the first component is less than 15 mass %, there occurs problems such as decrease in physical strength of the obtained catalyst resulting in powderization of the catalyst during using the catalyst.
  • the content of the third component relative to the first component exceeds 200 mass %, proportion of the first component active to the reaction is decreased, and catalytic performance is deteriorated.
  • the first component constituting the composite material is composed of at least one of zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites that have a MFI-structure.
  • zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites that have a MFI-structure.
  • the alkaline-earth metal compound of the second component may be selected from magnesium carbonate (MgCO 3 ), magnesium hydroxide (Mg(OH) 2 ), magnesium oxide (MgO), magnesium acetate ((CH 3 COO) 2 Mg), magnesium nitrate (Mg(NO 3 ) 2 ), magnesium aluminate (MgAl 2 O 4 ), magnesium orthosilicate (Mg 2 SiO 4 ), calcium carbonate (CaCO 3 ), calcium hydroxide (Ca(OH) 2 ), calcium oxide (CaO), calcium acetate ((CH 3 COO) 2 Ca), calcium nitrate (Ca(NO 3 ) 2 ), calcium aluminate (CaAl 2 O 4 ), calcium orthosilicate (Ca 2 SiO 4 ), strontium carbonate (SrCO 3 ), strontium hydroxide (Sr(OH) 2 ), strontium oxide (SrO), strontium acetate ((CH 3 COO) 2 Sr), strontium
  • the third component is composed of at least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals.
  • ⁇ -alumina Al 2 O 3
  • Al 2 O 3 ⁇ -alumina
  • boehmite AlO(OH)
  • aluminum hydroxide Al(OH) 3
  • alumina sol alumina sol or the like
  • Silicon dioxide (SiO 2 ) may be used as the silicon oxides.
  • Silicon hydroxides may have a form of orthosilicate (H 4 SiO 4 ), metasilicate (H 2 SiO 3 ) or the like.
  • Kaolin, bentonite or the like may be used as the clay minerals.
  • additives composed of graphite, cellulose or the like may be added to the alkaline-earth metal compound-containing zeolite catalyst of the present invention.
  • the residual amount of tetrahedral aluminum in the zeolite framework per unit mass of zeolite in the alkaline-earth metal compound-containing catalyst is preferably not smaller than 5 times, more preferably not smaller than 10 times, of the residual amount of tetrahedral aluminum in the zeolite framework per unit mass of zeolite in the proton-type zeolite consisting of the first component.
  • the residual amount of tetrahedral aluminum in the zeolite framework per unit mass of zeolite in the alkaline-earth metal compound-containing catalyst after exposure to the above-described conditions is not smaller than 5 times of the residual amount of tetrahedral aluminum in the zeolite framework per unit mass of zeolite in the proton-type zeolite consisting of the first component treated with steam under the same condition, it is possible to reduce the degree of deterioration of catalytic activity caused by exposure to steam in the reaction atmosphere or in the regeneration atmosphere. Therefore, it is possible to increase the number of times of regeneration of the catalyst, and decrease the frequency for recharging the catalyst.
  • An alkaline-earth metal compound-containing zeolite catalyst according to the present invention is composed of a composite material comprising at least a first component, a second component, and a third component, wherein the first component is composed of at least one of zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites, the second component is composed of at least one of alkaline-earth metal compounds, and the third component is composed of at least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals, where the first component has a molar ratio of Si/Al of 10 or more and 300 or less, content of the second component relative to the first component is 0.3 mass % or more and less than 10 mass % as alkaline-earth metal, and content of the third component relative to the first component is 15 mass % or more and 200 mass % or less.
  • the zeolite catalyst of the above-described constitution has a long catalytic lifetime. Therefore, by the improvement of the overall catalytic lifetime, loading weight of catalyst and frequency of recharging the catalyst are reduced, and it is possible to reduce the equipment cost and the operation cost of the reaction system.
  • a composition at least containing a first component, a second component, and a third component is mixed with a polar solution and kneaded, to prepare a mixture composed of at least the first component, the second component, the third component, and polar solution.
  • At least one of zeolites having a Si/Al molar ratio of 10 or more and 300 or less, selected from a group consisting of proton-type zeolites and ammonium type zeolites is used as the first component.
  • At least one of alkaline-earth metal compounds is used as the second component.
  • At least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals is used.
  • content of the second component relative to the first component is controlled to be 0.3 mass % or more and less than 10 mass %.
  • Content of the third component relative to the first component is controlled to be 15 mass % or more and 200 mass % or less.
  • added amount of polar solution is controlled to be 10 mass % or more and 150 mass % or less.
  • polar solution water is most preferably used.
  • organic polar solution including alcohol group solution such as ethanol and propanol, ether group solution such as diethyl ether and tetrahydrofuran, ester group solution, amid group solution, sulfoxide group solution.
  • Such material may include organic acid such as acetic acid, aqueous ammonia, graphite, cellulose group or the like.
  • the mixture obtained in the mixing-kneading step is formed into a shaped catalyst, for example, by extrusion molding using an extruder, or by spheronization molding using a spheronizer (marumerizer).
  • the shaped catalyst obtained in the molding step is dried by a drying machine, and is subjected to calcination using a furnace such as muffle furnace, tunnel furnace or the like, thereby preparing a composite material.
  • a furnace such as muffle furnace, tunnel furnace or the like
  • drying-calcination step it is preferable to perform the drying of the shaped catalyst under conditions at 80° C. or more and 150° C. or less for a duration of 0.5 hours or more and 30 hours or less.
  • the shaped catalyst after drying is subjected to calcination at 350° C. or more and 750° C. or less for a duration of not shorter than 1 hour and not longer than 50 hours.
  • a method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to the present invention comprises: mixing-kneading step of adding polar solvent to a composition composed at least of a first component, a second component, and a third component, and kneading to form a mixture; and drying-calcination step of drying and calcining the mixture to prepare a composite material, where the first component is composed of at least one of zeolites selected from a group consisting of proton-type zeolites and ammonium type zeolites, the second component is composed of at least one of alkaline-earth metal compounds, and the third component is composed of at least one selected from a group consisting of aluminum oxides, aluminum hydroxides, silicon oxides, silicon hydroxides, and clay minerals.
  • the first component has a molar ratio of Si/Al of 10 or more and 300 or less, content of the second component relative to the first component defined is 0.3 mass % or more and less than 10 mass % as alkaline-earth metal, and content of the third component relative to the first component is 15 mass % or more and 200 mass % or less.
  • this preparation method by constituting the first component using generally available proton-type zeolite and/or ammonium-type zeolite, and by mixing and kneading the first component with the second component and the third component to form a mixture, and drying and calcining the mixture, it is possible to produce simply and inexpensively an alkaline-earth metal compound-containing zeolite catalyst having excellent steam resistance, and long catalytic lifetime.
  • the alkaline-earth metal compound-containing zeolite catalyst consisting of the composite material obtained in the above-described drying-calcination step may be subjected to a steam treatment step where the catalyst is made contact to steam; or air and/or inert gas (e.g., nitrogen and carbon dioxide) that contains steam in an amount of not less than 10 vol %.
  • the catalyst may be made contact to reaction atmosphere that generates steam.
  • the steam treatment it is allowable to use conditions in which steam partially exist as liquid water.
  • the above described reaction that generates steam refers to the reaction in which dehydration of reactants occurs on the catalyst surface, thereby generating steam.
  • DTO reaction/MTO reaction and dehydration of alcohol are examples of the reaction.
  • the duration for making the composite material contact to steam or the reaction atmosphere generating steam is not shorter than 1 hour and not longer than 50 hours.
  • DME and/or methanol is supplied as a gas, and the gas is made contact with the alkaline-earth metal compound-containing zeolite catalyst.
  • the method for making the catalyst to contact with the gas fixed bed reactor or fluid bed reactor may be applied.
  • the synthetic reaction of lower hydrocarbons from DME and/or methanol may be performed using a wide range of temperature/pressure conditions.
  • the reaction temperature is not lower than 300° C. and not higher than 750° C., more preferably not lower than 400° C. and not higher than 650° C. Where the reaction temperature is lower than 300° C., activity of the catalyst is not sufficient. Where the reaction temperature exceeds 750° C., formation rate of the carbonaceous deposits is fast, catalytic activity is reduced rapidly, and change of the catalyst such as collapse of the zeolite structure occurs.
  • DME and/or methanol as a raw material may be diluted with steam, inert gas, carbon dioxide or the like and is supplied to the alkaline-earth metal compound-containing zeolite catalyst.
  • the weight hourly space velocity (WHSV) which is the ratio of the supplied quantity of DME as a raw material to the quantity of the catalyst, is preferably not less than 0.025 g-DME/(g-catalyst ⁇ hour) and not more than 50 g-DME/(g-catalyst ⁇ hour).
  • WHSV is less than 0.025 g-DME/(g-catalyst ⁇ hour), it is not cost effective since space time yield is reduced. On the other hand, where the WHSV is higher than 50 g-DME/(g-catalyst ⁇ hour), catalytic lifetime and catalytic activity are not sufficient.
  • the lower hydrocarbons generated on the alkaline-earth metal compound-containing zeolite catalyst flow out from the reactor, and can be separated to objective products in accordance with generally-known separation-purification method.
  • a method of regenerating alkaline-earth metal compound containing zeolite catalyst according to the present invention is a method for regenerating alkaline-earth metal compound containing zeolite catalyst used for synthesizing lower hydrocarbons from DME and/or methanol.
  • the method includes a step of calcining an alkaline-earth metal compound-containing zeolite catalyst of the present invention in a flow containing oxygen and steam.
  • the alkaline-earth metal compound-containing zeolite catalyst is calcined in a flow that contains oxygen and steam, thereby regenerating catalytic activity.
  • proportion of the flow rate of steam relative to the flow rate of oxygen in the flow containing oxygen and steam is preferably not less than 5 and not more than 2000, more preferably, not less than 15 and not more than 1000.
  • the flow containing oxygen and steam may contain a recycled exhaust gas from the reactor being used for regenerating the catalyst, and inert gas such as carbon dioxide and argon gas.
  • a temperature for calcining the alkaline-earth metal compound-containing zeolite catalyst is preferably not lower than 400° C. and not higher than 700° C., more preferably, not lower than 450° C. and not higher than 650° C.
  • the temperature for calcining the alkaline-earth metal compound-containing zeolite catalyst is less than 400° C., carbonaceous deposits on the catalysts cannot be burned, and catalytic activity cannot be recovered sufficiently.
  • the temperature for calcining the alkaline-earth metal compound-containing zeolite catalyst exceeds 700° C., change of the catalyst such as collapse of zeolite structure may occur.
  • the period for calcining the alkaline-earth metal compound-containing zeolite catalyst at the above-described temperature range is preferably not shorter than 3 hours and not longer than 300 hours, more preferably, not shorter than 5 hours and not longer than 150 hours.
  • a method of regenerating alkaline-earth metal compound containing zeolite catalyst according to the invention is a method for regenerating alkaline-earth metal compound containing zeolite catalyst used for synthesizing lower hydrocarbons from DME and/or methanol.
  • this method by calcining the alkaline-earth metal compound-containing zeolite catalyst in a flow that contains oxygen and steam, it is possible to improve the lifetime of the catalyst. Therefore, frequency of regenerating the catalyst is reduced, resulting in reduction of cost for synthesizing lower hydrocarbons from DME and/or methanol.
  • steam may be used as a dilution gas. Therefore, requirement for extra facilities such as a cryogenic air separator for nitrogen production can be avoided.
  • catalyst A 100 g of an ammonium type MFI-structure zeolite (CBV15014G provided by Zeolyst International) having a molar ratio of Si/Al of 75 was calcined at 550° C. and proton-type MFI-structure zeolite was obtained.
  • this catalyst is referred to as catalyst A.
  • the catalyst A in an amount of 100 g was mixed with 5.0 g of calcium carbonate (CaCO 3 ) under solid state and a mixture of both materials was prepared. The mixture was calcined at 550° C. for 6 hours in air. The thus obtained catalyst is hereafter referred to as catalyst B.
  • catalyst C 100 g of the above-described ammonium type MFI structure zeloite was mixed with 5.0 g of calcium carbonate. After adding an appropriate amount of ion-exchanged water, the mixture was kneaded and a mixed body was prepared. After drying the mixed body at 120° C., the mixed body was calcined at 550° C. for 12 hours in air.
  • catalyst C 100 g of the above-described ammonium type MFI structure zeloite was mixed with 5.0 g of calcium carbonate. After adding an appropriate amount of ion-exchanged water, the mixture was kneaded and a mixed body was prepared. After drying the mixed body at 120° C., the mixed body was calcined at 550° C. for 12 hours in air.
  • catalyst C 100 g of the above-described ammonium type MFI structure zeloite was mixed with 5.0 g of calcium carbonate. After adding an appropriate amount of ion-exchanged water, the mixture was kn
  • catalyst D 100 g of the above-described ammonium type MFI structure zeloite was mixed with 28 g of boehmite (containing 70% of Al 2 O 3 ). After adding an appropriate amount of ion-exchanged water, the mixture was kneaded and a mixed body was prepared. The mixed body was extruded using an extruder. A shaped catalyst obtained by the extrusion molding was dried at 120° C., and was calcined at 550° C. for 12 hours in the air. The thus obtained catalyst is hereafter referred to as catalyst D.
  • catalyst E 100 g of the above-described ammonium type MFI structure zeolite was mixed with 28 g of the above-described boehmite and 5.0 g of calcium carbonate. After adding an appropriate amount of ion-exchanged water, the mixture was kneaded and a mixed body was prepared. The mixed body was extruded using an extruder. A shaped catalyst obtained by the extrusion molding was dried at 120° C., and was calcined at 550° C. for 12 hours in the air. The thus obtained catalyst is hereafter referred to as catalyst E.
  • catalyst F 100 g of the above-described ammonium type MFI structure zeloite was mixed with 28 g of the above-described boehmite and 25 g of calcium carbonate. After adding an appropriate amount of ion-exchanged water, the mixture was kneaded and a mixed body was prepared. The mixed body was extruded using an extruder. A shaped catalyst obtained by the extrusion molding was dried at 120° C., and was calcined at 550° C. for 12 hours in the air. Thus obtained catalyst is hereafter referred to as catalyst F.
  • catalyst G 100 g of the above-described ammonium type MFI structure zeloite was mixed with 262 g of the above-described boehmite and 5.0 g of calcium carbonate. After adding an appropriate amount of ion-exchanged water, the mixture was kneaded and a mixed body was prepared. The mixed body was extruded using an extruder. A shaped catalyst obtained by the extrusion molding was dried at 120° C., and was calcined at 550° C. for 12 hours in the air. Thus obtained catalyst is hereafter referred to as catalyst G.
  • the catalyst A obtained by the Experimental Example 1 was subjected to the following treatment.
  • the catalyst A was evacuated at 400° C. for 3 hours. After that, 27 Al-MAS-NMR spectrum of the catalyst A was measured using a NMR spectrometer (Bruker DRX-400), thereby performing quantitative analysis of the amount of tetrahedral aluminum in zeolite framework per unit mass of zeolite. The measured amount of tetrahedral aluminum in zeolite framework in Comparative Example A1 was defined as 100.
  • the catalyst A was subjected to a steam treatment by exposing the catalyst to an atmosphere having steam partial pressure of 0.35 MPa, nitrogen partial pressure of 0.15 MPa, at 530° C., for 48 hours.
  • the catalyst A treated with steam was evacuated at 400° C. for 3 hours. After that, 27 Al-MAS-NMR spectrum of the catalyst A treated with steam was measured using an NMR spectrometer (Bruker DRX-400), thereby performing quantitative analysis of the amount of tetrahedral aluminum in zeolite framework per unit mass of zeolite.
  • the relative amount of the tetrahedral aluminum in the Comparative Example A2 compared to the amount of tetrahedral aluminum in the Comparative Example A1 is shown in Table 1.
  • the catalyst B obtained by the Experimental Example 2 was subjected to the same treatments as the Comparative Example A1, and in the same manner as described-above, relative amount of the tetrahedral aluminum in the Comparative Example A3 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst B was subjected to the same treatments as the Comparative Example A2, and in the same manner as described-above, the relative amount of the tetrahedral aluminum in the Comparative Example A4 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst C obtained by the Experimental Example 3 was subjected to the same treatments as the Comparative Example A1, and in the same manner as described-above, the relative amount of the tetrahedral aluminum in the Comparative Example A5 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst C was subjected to the same treatments as the Comparative Example A2, and in the same manner as described-above, the relative amount of the tetrahedral aluminum in the Comparative Example A6 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst D obtained by the Experimental Example 4 was subjected to the same treatments as the Comparative Example A1, and in the same manner as described-above, the relative amount of the tetrahedral aluminum in the Comparative Example A7 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst D was subjected to the same treatments as the Comparative Example A2, and in the same manner as described-above, the relative amount of the tetrahedral aluminum in the Comparative Example A8 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst F obtained by the Experimental Example 6 was subjected to the same treatments as the Comparative Example A1, and in the same manner as described-above, the relative amount of the tetrahedral aluminum in the Comparative Example A9 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst F was subjected to the same treatments as the Comparative Example A2, and in the same manner as described-above, the relative amount of the tetrahedral aluminum in the Comparative Example A10 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst E obtained by the Experimental Example 5 was subjected to the same treatments as the Comparative Example A1, and in the same manner as described-above, the relative amount of the tetrahedral aluminum in the Example A1 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • the catalyst E was subjected to the same treatments as the Comparative Example A2, and in the same manner as described-above, relative amount of the tetrahedral aluminum in the Example A2 compared to the amount of tetrahedral aluminum in the Comparative Example A1 was determined. The result is shown in Table 1.
  • Tetrahedral aluminum in the zeolite framework cause acid sites, that is catalytic active sites.
  • the tetrahedral aluminum are eliminated from the framework to lead a decrease of acid sites and the catalytic activity. Therefore, the catalyst having a large amount of residual tetrahedral aluminum after the exposure to steam atmosphere can be regarded as a catalyst having high steam resistance, and not likely to subject the elimination of tetrahedral aluminum from the zeolite framework.
  • the catalyst C was prepared by kneading MFI zeolite and calcium carbonate in the presence of water, and calcining the mixture. Therefore, compared to catalyst B in which raw materials were mixed in a solid state, it is considered that calcium carbonate were highly dispersed into the micropore of the zeolite and it would be more effective to prevent the elimination of tetrahedral aluminum from the zeolite framework.
  • catalyst D showed the relative amount of tetrahedral aluminum of 115%, which was increased compared to that in the catalyst A. It is considered that because of the addition of boehmite, aluminum atoms are inserted into the zeolite framework during the calcination.
  • catalyst F showed a relative amount of tetrahedral aluminum of 155%, which was more than the catalyst A.
  • boehmite may cause the insertion of aluminum into the zeolite framework during calcination.
  • Comparative Example A10 it was confirmed that the amount of tetrahedral aluminum in the catalyst F decreased to 63% after exposing the catalyst to an atmosphere having steam partial pressure of 0.35 MPa, nitrogen partial pressure of 0.15 MPa, at 530° C., for 48 hours. In Comparative A10, it was confirmed that by adding boehmite and calcium carbonate to the zeolite, it was possible to obtain a catalyst which was not likely to subject elimination of tetrahedral aluminum and had high steam resistance.
  • Example A1 catalyst E showed a relative amount of tetrahedral aluminum of 142%. It was confirmed that the residual amount of tetrahedral aluminum in the catalyst E was increased compared to the catalyst A. It is considered that because of the addition of boehmite, aluminum are inserted into the zeolite framework during the calcination.
  • Example A2 it was confirmed that the amount of tetrahedral aluminum in the zeolite framework decreased to 86% after exposing the catalyst to an atmosphere having steam partial pressure of 0.35 MPa, nitrogen partial pressure of 0.15 MPa, at 530° C., for 48 hours.
  • composing the MFI zeolite with the appropriate amount of aluminum oxide and/or aluminum hydroxide and calcium carbonate can yield the most steam rersistant catalyst which has the least possibility of the elimination of tetrahedral aluminum from the zeolite framework among all catalysts in Table 1.
  • Performance of the catalyst A was tested with an isothermal reactor. DME and nitrogen were mixed together at flow rates of 1,272 Ncm 3 /hour and 1,272 Ncm 3 /hour, respectively. Then, the resulting mixture was transferred to an isothermal reactor, and reacted with the catalyst A at 530° C. under atmospheric pressure.
  • the weight hourly space velocity (WHSV) which is the ratio of the supplied quantity of DME as a raw material to the quantity of the catalyst, was set to be 9.6 g-DME/(g-catalyst ⁇ hour).
  • Relative catalytic lifetime, and yields (in mass %) of propylene, methane and carbon monoxide are shown in Table 2.
  • the relative catalytic lifetime denotes a lifetime compared to the catalytic lifetime in Comparative Example A11 which was defined as 100.
  • Catalyst A was treated with steam for 24 hours by exposing the catalyst to an atmosphere having steam partial pressure of 0.08 MPa, nitrogen partial pressure of 0.02 MPa, at 530° C.
  • Performance of the steam-treated catalyst A was tested with an isothermal reactor. DME and nitrogen were mixed together at flow rates of 1,272 Ncm 3 /hour and 1,272 Ncm 3 /hour, respectively. Then, the resulting mixture was transferred to an isothermal reactor, and reacted with the steam-treated catalyst A at 530° C. under atmospheric pressure.
  • the weight hourly space velocity (WHSV) which is the ratio of the supplied quantity of DME as a raw material to the quantity of the catalyst, was set to be 9.6 g-DME/(g-catalyst ⁇ hour). Relative catalytic lifetime, and yields (in mass %) of propylene, methane and carbon monoxide are shown in Table 2.
  • Catalyst A was treated with steam for 48 hours by exposing the catalyst to an atmosphere having steam partial pressure of 0.35 MPa, nitrogen partial pressure of 0.15 MPa, at 530° C.
  • Performance of the steam-treated catalyst A was tested with an isothermal reactor. DME and nitrogen were mixed together at flow rates of 1,272 Ncm 3 /hour and 1,272 Ncm 3 /hour, respectively. Then, the resulting mixture was transferred to an isothermal reactor, and reacted with the steam-treated catalyst A at 530° C. under atmospheric pressure.
  • the weight hourly space velocity (WHSV) which is the ratio of the supplied quantity of DME as a raw material to the quantity of the catalyst, was set to be 9.6 g-DME/(g-catalyst ⁇ hour). Relative catalytic lifetime, and yields (in mass %) of propylene, methane and carbon monoxide are shown in Table 2.
  • Catalyst A was treated with steam for 96 hours by exposing the catalyst to an atmosphere having steam partial pressure of 0.35 MPa, nitrogen partial pressure of 0.15 MPa, at 530° C.
  • Performance of the steam-treated catalyst A was tested with an isothermal reactor. DME and nitrogen were mixed together at flow rates of 1,272 Ncm 3 /hour and 1,272 Ncm 3 /hour, respectively. Then, the resulting mixture was transferred to an isothermal reactor, and reacted with the steam-treated catalyst A at 530° C. under atmospheric pressure.
  • the weight hourly space velocity (WHSV) which is the ratio of the supplied quantity of DME as a raw material to the quantity of the catalyst, was set to be 9.6 g-DME/(g-catalyst ⁇ hour).
  • the relative catalytic lifetime, and yields (in mass %) of propylene, methane and carbon monoxide are shown in Table 2.
  • FIG. 1 shows the relative lifetime of catalysts versus the extent of steam treatments.
  • the horizontal axis denotes the extent of steam treatment which was defined by the product of steam partial pressure and the duration of the steam treatment.
  • the vertical axis of FIG. 1 denotes the relative catalytic lifetime of catalysts A-G in Comparative Examples A11-A27 and Examples A3-A7 compared to the lifetime of catalyst A in Comparative Example A11 which was defined as 100.
  • steam resistance of catalysts A to E can be expressed as catalyst E>catalyst C>catalyst D>catalyst B>catalyst A.
  • This order approximately corresponds with the order of residual proportion of tetrahedral aluminum obtained by 27 Al-MAS-NMR spectra (Table 1).
  • Catalyst F had long catalytic lifetime even when the steam treatment was not performed (Comparative Example A26). It is considered that a large content of calcium carbonate contribute the improvement of the catalytic lifetime.
  • catalyst F When catalyst F was used without the steam treatment, yield of methane was 1.8 mass %, and yield of carbon monoxide was 3.10 mass % which was higher than the case of using the other catalysts (Comparative Example A26). It was considered that high calcium content in catalyst F resulted in the decomposition of DME on the basic sites.
  • the catalyst E which was obtained by mixing ammonium type MFI structure zeolite with boehmite and appropriate amount of calcium carbonate, kneading the mixture with appropriate amount of ion-exchanged water, drying and calcining the mixture, had the highest steam resistance.
  • catalytic lifetime was largely enhanced and side reactions such as generation of methane and generation of carbon monoxide could be effectively inhibited.
  • the catalyst F which was obtained by mixing ammonium type MFI structure zeolite with boehmite and a large amount of calcium carbonate, kneading the mixture with appropriate amount of ion-exchanged water, drying and calcining the mixture, had relatively high steam resistance. However, even after the steam treatment, side reactions such as generation of methane and generation of carbon monoxide could not be inhibited by the use of the catalyst F. Even though recycled in a reactor, methane and carbon monoxide have poor reactivity and are not converted to olefin. Therefore decomposition reaction for generating methane and carbon monoxide is not desirable. It is understood that the catalyst F is not appropriately used for a reaction for generating lower hydrocarbons from DME and/or methanol.
  • catalyst C which was obtained by mixing ammonium type MFI-structure zeolite with appropriate amount of calcium carbonate, kneading the mixture with ion-exchanged water, drying and calcining the mixture, elimination of tetrahedral aluminum from the zeolite framework was inhibited by the calcium compound, resulting in higher steam resistance than that of catalyst A consisting of proton type MFI-structure zeolite.
  • catalyst D which was obtained by mixing ammonium type MFI-structure zeolite with boehmite, kneading the mixture with ion-exchanged water, drying and calcining the mixture, elimination of aluminum from the zeolite framework was inhibited by the effect of aluminum oxide and/or aluminum hydroxide, resulting in higher steam resistance than that of catalyst A consisting of proton type MFI-structure zeolite.
  • the catalyst E which was obtained by mixing ammonium type MFI structure zeolite with boehmite and appropriate amount of calcium carbonate, kneading the mixture with ion-exchanged water, drying and calcining the mixture, had the highest steam resistance by the effects of calcium compound and aluminum oxide and/or aluminum hydroxide.
  • the catalyst F which was obtained by mixing ammonium type MFI structure zeolite with boehmite and a large amount of calcium carbonate, kneading the mixture with ion-exchanged water, drying and calcining the mixture, had lower steam resistance than that of catalyst E (Table 1).
  • methane and carbon monoxide showed high yields.
  • methane and carbon monoxide showed high yields in the reaction using catalyst F.
  • Zeolite catalysts D and E were prepared in the same manners as above-described Experimental Examples 4 and 5, respectively.
  • catalyst H In accordance with the method of preparing a zeolite catalyst disclosed in a Patent Reference (Japanese Unexamined Patent Application, First Publication No. 2005-138000), Ca-containing MFI-structure zeolite catalyst was obtained. This catalyst is hereafter referred to as catalyst H.
  • catalytic lifetime was defined as an elapsed time from the time the reaction started to the time the conversion of DME became less than 99.0%.
  • Catalyst D was treated with steam for 24 hours by exposing the catalyst to an atmosphere having a steam partial pressure of 0.08 MPa, nitrogen partial pressure of 0.02 MPa, at 530° C.
  • Performance of the steam-treated catalyst D was tested with an isothermal reactor. DME and nitrogen were mixed together at flow rates of 1,272 Ncm 3 /hour and 1,272 Ncm 3 /hour, respectively. Then, the resulting mixture was transferred to an isothermal reactor, and reacted with the steam-treated catalyst D at 530° C. under atmospheric pressure.
  • the weight hourly space velocity (WHSV) which is the ratio of the supplied quantity of DME as a raw material to the quantity of the catalyst, was set to be 9.6 g-DME/(g-catalyst ⁇ hour). DME and nitrogen were supplied to the reactor until the DME conversion was decreased to 5% or less.
  • Catalyst D was treated with steam for 24 hours by exposing the catalyst to an atmosphere having a steam partial pressure of 0.08 MPa, nitrogen partial pressure of 0.02 MPa, at 530° C.
  • Example B2 Air and steam were mixed together at flow rates of 143 Ncm 3 /hour and 1,272 Ncm 3 /hour, respectively. Then, the resulting mixture was transferred to the isothermal reactor, thereby burning carbonaceous deposits on the catalyst D used in Example B1 at 550° C. under atmospheric pressure. After that, catalytic performance was tested in the same manner as in Comparative Example B1. Relative catalytic lifetime of Example B2 compared to the catalytic lifetime of Example B1 defined as 100 was shown in Table 3.
  • Catalyst E was treated with steam for 24 hours by exposing the catalyst to an atmosphere having a steam partial pressure of 0.08 MPa, nitrogen partial pressure of 0.02 MPa, at 530° C.
  • Catalyst E was treated with steam for 24 hours by exposing the catalyst to an atmosphere having a steam partial pressure of 0.08 MPa, nitrogen partial pressure of 0.02 MPa, at 530° C.
  • Example B4 Air and steam were mixed together at flow rates of 143 Ncm 3 /hour and 1,272 Ncm 3 /hour, respectively. Then, the resulting mixture was transferred to the isothermal reactor, thereby burning carbonaceous deposits on the catalyst E used in Example B3 at 550° C. under atmospheric pressure. After that, in the same manner as in Comparative Example B1, test of catalytic performance was performed in an isothermal reactor. Relative catalytic lifetime of Example B4 compared to the catalytic lifetime of Example B3 defined as 100 was shown in Table 3.
  • Catalyst H was treated with steam for 24 hours by exposing the catalyst to an atmosphere having a steam partial pressure of 0.08 MPa, nitrogen partial pressure of 0.02 MPa, at 530° C.
  • Catalyst H was treated with steam for 24 hours by exposing the catalyst to an atmosphere having a steam partial pressure of 0.08 MPa, nitrogen partial pressure of 0.02 MPa, at 530° C.
  • catalyst D was treated with steam and was used in a synthetic reaction of lower hydrocarbons from DME, and was subsequently regenerated in a flow of air and nitrogen. In this case, catalytic lifetime was decreased after the regeneration.
  • catalyst D was treated with steam and was used in a synthetic reaction of lower hydrocarbons from DME, and was subsequently regenerated in a flow of air and steam. In this case, catalytic lifetime was improved by the regeneration.
  • catalyst E was treated with steam and was used in a synthetic reaction of lower hydrocarbons from DME, and was subsequently s regenerated in a flow of air and nitrogen. In this case, catalytic lifetime was decreased after the regeneration.
  • catalyst E was treated with steam and was used in a synthetic reaction of lower hydrocarbons from DME, and was subsequently regenerated in a flow of air and steam. In this case, catalytic lifetime was improved by the regeneration.
  • catalyst H was treated with steam and was used in a synthetic reaction of lower hydrocarbons from DME, and was subsequently regenerated in a flow of air and steam. In this case, catalytic lifetime was almost unchanged by the regeneration.
  • Catalyst D which is composed of MFI-structure zeolite and aluminum oxide and/or aluminum hydroxide
  • Catalyst E which is composed of MFI-structure zeolite, calcium carbonate, and aluminum oxide and/or aluminum hydroxide
  • Catalyst H which is composed of Ca-containing MFI-structure zeolite without aluminum oxide nor aluminum hydroxide, catalytic lifetime did not largely change before and after the regeneration, whether steam was supplied or not during the regeneration.
  • the catalyst D which is composed of MFI-structure zeolite and aluminum oxide and/or aluminum hydroxide
  • the catalyst E which is composed of MFI-structure zeolite, aluminum oxide and/or aluminum hydroxide, and calcium carbonate. It is considered that the steam may operate the nature of aluminum oxide and/or aluminum hydroxide to improve the catalytic lifetime.
  • An alkaline-earth metal compound-containing zeolite catalyst and method for preparing the same according to the present invention may be applied to various processes such as synthetic reaction of gasoline using methanol as the raw material (MTG reaction), olefin cracking, fluid catalytic cracking (FCC), hydrogen dewaxing, isomerization of paraffin, production of aromatic hydrocarbon, alkylation of aromatic compound, oxidation reaction using hydrogen peroxide, and production of ethanolamine group.
  • a method of regenerating an alkaline-earth metal compound containing zeolite catalyst according to the present invention may be applied to regeneration step of catalyst in various processes such as synthetic reaction of gasoline using methanol as the raw material (MTG reaction), cracking or the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US12/377,036 2006-08-30 2007-08-29 Alkaline earth metal compound-containing zeolite catalyst, preparation method and regeneration method thereof, and method for producing lower hydrocarbon Abandoned US20100168492A1 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2006234518 2006-08-30
JP2006-234518 2006-08-30
JP2006262554A JP2008080238A (ja) 2006-09-27 2006-09-27 Ｍｆｉ構造ゼオライト触媒の再生方法
JP2006-262554 2006-09-27
JP2006266044A JP2008080301A (ja) 2006-08-30 2006-09-28 アルカリ土類金属化合物含有ゼオライト触媒およびその調製方法、並びに、低級炭化水素の製造方法
JP2006-266044 2006-09-28
PCT/JP2007/066766 WO2008026638A1 (en) 2006-08-30 2007-08-29 Alkaline earth metal compound-containing zeolite catalyst, preparation method and regeneration method thereof, and method for producing lower hydrocarbon

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/066766 A-371-Of-International WO2008026638A1 (en) 2006-08-30 2007-08-29 Alkaline earth metal compound-containing zeolite catalyst, preparation method and regeneration method thereof, and method for producing lower hydrocarbon

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/654,787 Division US8673803B2 (en) 2006-08-30 2012-10-18 Alkaline-earth metal compound-containing zeolite catalyst, method for preparing same, method for regenerating same, and method for producing lower hydrocarbons

Publications (1)

Publication Number Publication Date
US20100168492A1 true US20100168492A1 (en) 2010-07-01

Family

ID=39135920

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/377,036 Abandoned US20100168492A1 (en) 2006-08-30 2007-08-29 Alkaline earth metal compound-containing zeolite catalyst, preparation method and regeneration method thereof, and method for producing lower hydrocarbon
US13/654,787 Active US8673803B2 (en) 2006-08-30 2012-10-18 Alkaline-earth metal compound-containing zeolite catalyst, method for preparing same, method for regenerating same, and method for producing lower hydrocarbons

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/654,787 Active US8673803B2 (en) 2006-08-30 2012-10-18 Alkaline-earth metal compound-containing zeolite catalyst, method for preparing same, method for regenerating same, and method for producing lower hydrocarbons

Country Status (6)

Country Link
US (2) US20100168492A1 (ko)
EP (1) EP2072126A4 (ko)
KR (1) KR101354667B1 (ko)
CN (1) CN101505868B (ko)
TW (1) TWI406707B (ko)
WO (1) WO2008026638A1 (ko)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120130138A1 (en) * 2009-07-30 2012-05-24 Jgc Corporation Method for manufacturing propylene and catalyst for manufacturing propylene
US9382169B2 (en) 2009-06-22 2016-07-05 Jgc Corporation Lower olefins producing catalyst and method for producing lower olefins using same
US10213773B2 (en) * 2012-06-29 2019-02-26 Basf Se Process for the conversion of oxygenates to olefins

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110230333A1 (en) * 2010-03-16 2011-09-22 Uop Llc Olefin Cracking Catalyst and Manufacturing Process
AU2013283348B2 (en) * 2012-06-29 2017-03-02 Basf Se Method for the conversion of oxygenates to olefins
CN106833730B (zh) * 2017-01-20 2018-08-31 河北玺尧新能源科技有限公司 一种以石油醚和甲醇为原料制备汽油的方法
CN106669791B (zh) * 2017-01-20 2019-08-27 河北玺尧新能源科技有限公司 一种改性zsm-5分子筛催化剂及其制备方法和应用
CN109575978B (zh) * 2017-09-28 2021-01-08 中国石油化工股份有限公司 一种生物油脂的加工方法

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4375458A (en) * 1977-08-17 1983-03-01 Mobil Oil Corporation Synthesis of large crystallite zeolites
US4429176A (en) * 1982-02-08 1984-01-31 Mobil Oil Corporation Active zeolite catalysts of improved stability
US4456780A (en) * 1979-07-27 1984-06-26 Mobil Oil Corporation Extending zeolite catalyst life for disproportionation by treating with phosphorus and/or steam
US4461845A (en) * 1983-01-17 1984-07-24 Mobil Oil Corporation Reactivation of steam-deactivated catalysts
US4544793A (en) * 1982-11-24 1985-10-01 Director-General Of Agency Of Industrial Science And Technology Crystalline zeolite, method of preparing same and process for the production of olefins using same as catalyst
US4559314A (en) * 1982-03-22 1985-12-17 Mobil Oil Corporation Zeolite activation
US4579993A (en) * 1984-08-22 1986-04-01 Mobil Oil Corporation Catalyst for methanol conversion by a combination of steaming and acid-extraction
US4663492A (en) * 1982-02-08 1987-05-05 Mobil Oil Corporation Active zeolite catalysts of improved stability for producing gasoline from methanol
US4748747A (en) * 1986-09-26 1988-06-07 Hommelwerke Gmbh Dimension-measuring probe with a pivoted probing arm
US4784747A (en) * 1982-03-22 1988-11-15 Mobil Oil Corporation Catalysts over steam activated zeolite catalyst
US5506182A (en) * 1993-04-07 1996-04-09 Idemitsu Kosan Co., Ltd. Modified zeolite Y catalyst composition
US20050085375A1 (en) * 2001-12-14 2005-04-21 Hermann Bach Method for thermally decoking a zeolite catalyst
US20070032379A1 (en) * 2003-11-05 2007-02-08 Jgc Corporation Catalyst, process for preparing the catalyst and process for producing lower hydrocarbon with the catalyst

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049573A (en) * 1976-02-05 1977-09-20 Mobil Oil Corporation Zeolite catalyst containing oxide of boron or magnesium
US4326994A (en) * 1980-02-14 1982-04-27 Mobil Oil Corporation Enhancement of zeolite catalytic activity
US4393265A (en) * 1981-07-24 1983-07-12 E. I. Du Pont De Nemours & Co. Light monoolefins from methanol and/or dimethyl ether
CA1216866A (en) * 1983-01-17 1987-01-20 Clarence D. Chang Conversion of alcohols and/or ethers to olefins
JPS6042224A (ja) 1983-08-15 1985-03-06 モビル　オイル　コ−ポレ−シヨン ゼオライト類の処理法
JPS60126233A (ja) * 1983-12-13 1985-07-05 Agency Of Ind Science & Technol 低級オレフインの製造方法
EP0163429A3 (en) 1984-05-21 1986-04-02 Mobil Oil Corporation Methanol conversion using reactivated zeolite catalyst materials
JPH0683590B2 (ja) 1984-07-04 1994-10-19 株式会社東芝 空気調和機
JPS6251630A (ja) * 1985-08-29 1987-03-06 Agency Of Ind Science & Technol 低級オレフインの製造方法
EP0229952A3 (en) * 1985-12-30 1988-05-11 Mobil Oil Corporation A process for making light olefins from alcohols and ethers
JP3063430B2 (ja) 1992-11-04 2000-07-12 松下電器産業株式会社 熱転写シート
US6048816A (en) * 1996-10-02 2000-04-11 Mobil Oil Corporation Catalyst and process for converting methanol to hydrocarbons
DE69832938T2 (de) * 1997-10-15 2006-08-10 China Petro-Chemical Corp. Krackkatalysator für die Produktion von leichten Olefinen und dessen Herstellung
KR100629939B1 (ko) 2004-10-15 2006-09-28 에스케이 주식회사 단열반응기에서 미정제 메탄올로부터 디메틸에테르의제조방법
JP4639840B2 (ja) 2005-02-23 2011-02-23 パナソニック電工株式会社 粒状物体の検査方法及びそれを用いる検査装置
JP4761023B2 (ja) 2005-03-15 2011-08-31 株式会社ジェイテクト ブラシレスモータの制御装置
JP4715265B2 (ja) 2005-03-25 2011-07-06 パナソニック電工株式会社 シングルレバー混合水栓

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4375458A (en) * 1977-08-17 1983-03-01 Mobil Oil Corporation Synthesis of large crystallite zeolites
US4456780A (en) * 1979-07-27 1984-06-26 Mobil Oil Corporation Extending zeolite catalyst life for disproportionation by treating with phosphorus and/or steam
US4663492A (en) * 1982-02-08 1987-05-05 Mobil Oil Corporation Active zeolite catalysts of improved stability for producing gasoline from methanol
US4429176A (en) * 1982-02-08 1984-01-31 Mobil Oil Corporation Active zeolite catalysts of improved stability
US4559314A (en) * 1982-03-22 1985-12-17 Mobil Oil Corporation Zeolite activation
US4784747A (en) * 1982-03-22 1988-11-15 Mobil Oil Corporation Catalysts over steam activated zeolite catalyst
US4544793A (en) * 1982-11-24 1985-10-01 Director-General Of Agency Of Industrial Science And Technology Crystalline zeolite, method of preparing same and process for the production of olefins using same as catalyst
US4461845A (en) * 1983-01-17 1984-07-24 Mobil Oil Corporation Reactivation of steam-deactivated catalysts
US4579993A (en) * 1984-08-22 1986-04-01 Mobil Oil Corporation Catalyst for methanol conversion by a combination of steaming and acid-extraction
US4748747A (en) * 1986-09-26 1988-06-07 Hommelwerke Gmbh Dimension-measuring probe with a pivoted probing arm
US5506182A (en) * 1993-04-07 1996-04-09 Idemitsu Kosan Co., Ltd. Modified zeolite Y catalyst composition
US20050085375A1 (en) * 2001-12-14 2005-04-21 Hermann Bach Method for thermally decoking a zeolite catalyst
US20070032379A1 (en) * 2003-11-05 2007-02-08 Jgc Corporation Catalyst, process for preparing the catalyst and process for producing lower hydrocarbon with the catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9382169B2 (en) 2009-06-22 2016-07-05 Jgc Corporation Lower olefins producing catalyst and method for producing lower olefins using same
US20120130138A1 (en) * 2009-07-30 2012-05-24 Jgc Corporation Method for manufacturing propylene and catalyst for manufacturing propylene
US10213773B2 (en) * 2012-06-29 2019-02-26 Basf Se Process for the conversion of oxygenates to olefins

Also Published As

Publication number Publication date
TW200817088A (en) 2008-04-16
CN101505868B (zh) 2012-05-23
KR101354667B1 (ko) 2014-02-04
CN101505868A (zh) 2009-08-12
EP2072126A4 (en) 2014-08-20
US20130045861A1 (en) 2013-02-21
EP2072126A1 (en) 2009-06-24
KR20090049585A (ko) 2009-05-18
WO2008026638A1 (en) 2008-03-06
US8673803B2 (en) 2014-03-18
TWI406707B (zh) 2013-09-01

Similar Documents

Publication Publication Date Title
US8673803B2 (en) Alkaline-earth metal compound-containing zeolite catalyst, method for preparing same, method for regenerating same, and method for producing lower hydrocarbons
EP2460784B1 (en) Method for producing propylene and catalyst for producing propylene
US9260356B2 (en) Method for making a catalyst comprising a phosphorus modified zeolite to be used in a MTO process
US10549267B2 (en) Zeolite catalysts, methods for producing zeolite catalysts, and methods for producing lower olefins
US10099209B2 (en) Alumina bound catalyst for selective conversion of oxygenates to aromatics
US20210213433A1 (en) Zeolite catalyst and method for producing lower olefin
JPS6245210B2 (ko)
US10556229B2 (en) Composite catalyst, method for producing composite catalyst, method for producing lower olefin and method for regenerating composite catalyst
JP5050466B2 (ja) プロピレンの製造方法
JP2008080301A (ja) アルカリ土類金属化合物含有ゼオライト触媒およびその調製方法、並びに、低級炭化水素の製造方法
JP3072348B2 (ja) 低級オレフィンの製造方法
JP6446033B2 (ja) 不飽和炭化水素の製造方法
US20180304240A1 (en) Bifunctional catalyst
JP4414169B2 (ja) オレフィンの製造方法
JP5632438B2 (ja) ジメチルエーテルまたはメタノールを原料とする低級炭化水素合成用カルシウム化合物含有ゼオライト触媒の調製方法
WO2012015060A1 (ja) プロピレンの製造方法
JP6228682B2 (ja) プロピレンの製造方法およびプロピレン製造用触媒
US20230405562A1 (en) Composit catalyst, method for producing composit catalyst, and method for producing lower olefins
JPH1033987A (ja) 芳香族炭化水素製造用触媒
CN115228506A (zh) 一种用于c4烯烃裂解制乙烯和丙烯的zsm-11催化剂及其制备方法
JPWO2018173269A1 (ja) ゼオライト含有触媒および低級オレフィンの製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: JGC CORPORATION,JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:INAKI, CHIZU;ITO, HIROFUMI;HONDA, KAZUNORI;AND OTHERS;REEL/FRAME:022234/0355

Effective date: 20090203

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION