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

Abstract

An alkaline-earth metal compound-containing zeolite catalyst 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 defined 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.

1 . An alkaline-earth metal compound-containing zeolite catalyst 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,   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.   
   
   
       2 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 1 , wherein the first component is composed of at least one of MFI-structure zeolites. 
   
   
       3 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 1 , wherein the second component is composed of at least one of calcium compounds. 
   
   
       4 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 2 , wherein the second component is composed of at least one of calcium compounds. 
   
   
       5 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 1 , having a characteristic such that
 where the alkaline-earth metal compound-containing zeolite catalyst 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.,   the residual amount of tetrahedral aluminum in the alkaline-earth metal compound-containing zeolite catalyst 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 same atmosphere.   
   
   
       6 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 1 , which is used in a time of synthesizing lower hydrocarbons from dimethyl ether and/or methanol. 
   
   
       7 . A method for preparing an alkaline-earth metal compound-containing zeolite catalyst, comprising:
 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,   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,   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.   
   
   
       8 . A method for preparing an alkaline-earth metal compound-containing zeolite catalyst, further comprising a steam treatment step where a composite material obtained by the drying-calcination step is made contact to steam or reaction atmosphere that generates steam. 
   
   
       9 . A method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to  claim 7 , wherein the first component is composed of at least one of MFI-structure zeolites. 
   
   
       10 . A method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to  claim 7 , wherein the second component is composed of at least one of calcium compounds. 
   
   
       11 . A method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to  claim 9 , wherein the second component is composed of at least one of calcium compounds. 
   
   
       12 . A method of producing lower hydrocarbons by synthesizing lower hydrocarbons from dimethyl ether and/or methanol, using the alkaline-earth metal compound-containing zeolite catalyst according to  claim 6 , wherein 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. 
   
   
       13 . A method for regenerating an alkaline-earth metal compound-containing zeolite catalyst used for synthesizing lower hydrocarbons from dimethyl ether and/or methanol, comprising a step of calcining the alkaline-earth metal compound-containing zeolite catalyst according to  claim 6  in a flow containing oxygen and steam. 
   
   
       14 . A method for regenerating an alkaline-earth metal compound-containing zeolite catalyst according to  claim 13 , wherein a temperature for calcining the alkaline-earth metal compound-containing zeolite catalyst is controlled in the range from 400° C. to 700° C. 
   
   
       15 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 2 , having a characteristic such that
 where the alkaline-earth metal compound-containing zeolite catalyst 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.,   the residual amount of tetrahedral aluminum in the alkaline-earth metal compound-containing zeolite catalyst 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 same atmosphere.   
   
   
       16 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 3 , having a characteristic such that
 where the alkaline-earth metal compound-containing zeolite catalyst 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.,   the residual amount of tetrahedral aluminum in the alkaline-earth metal compound-containing zeolite catalyst 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 same atmosphere.   
   
   
       17 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 4 , having a characteristic such that
 where the alkaline-earth metal compound-containing zeolite catalyst 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.,   the residual amount of tetrahedral aluminum in the alkaline-earth metal compound-containing zeolite catalyst 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 same atmosphere.   
   
   
       18 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 2 , which is used in a time of synthesizing lower hydrocarbons from dimethyl ether and/or methanol. 
   
   
       19 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 3 , which is used in a time of synthesizing lower hydrocarbons from dimethyl ether and/or methanol. 
   
   
       20 . An alkaline-earth metal compound-containing zeolite catalyst according to  claim 4 , which is used in a time of synthesizing lower hydrocarbons from dimethyl ether and/or methanol. 
   
   
       21 . A method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to  claim 8 , wherein the first component is composed of at least one of MFI-structure zeolites. 
   
   
       22 . A method for preparing an alkaline-earth metal compound-containing zeolite catalyst according to  claim 8 , wherein the second component is composed of at least one of calcium compounds.