Metal-supported crystalline silica aluminophosphate catalyst and process for producing the same

Abstract

Disclosed is a metal-supported catalyst produced by (a) preparing a dispersion of crystalline silicoaluminophosphate particles; (b) mixing an aqueous active ingredient metal compound solution into the dispersion; (c) spray-drying the mixture; (d) washing the spray-dried product and (e) heat-treating (calcining) the washed product at 400 to 900° C. Also disclosed is an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst having a content of aluminum phosphate in the catalyst of 0.1 to 40% by weight in terms of Al 2 O 3 +P 2 O 5 based on the metal-supported crystalline silicoaluminophosphate particles.

1 . A process for producing a metal-supported crystalline silicoaluminophosphate catalyst, the process comprising the following steps (a) to (c) and (e):
 (a) preparing a dispersion of crystalline silicoaluminophosphate particles;   (b) mixing an aqueous active ingredient metal compound solution into the dispersion;   (c) spray-drying the mixture; and   (e) heat-treating (calcining) the spray-dried product at 400 to 900° C.   
     
     
         2 . The process for producing a metal-supported crystalline silicoaluminophosphate catalyst according to  claim 1 , wherein the step (c) is followed by the following step (d).
 (d) washing the spray-dried product.   
     
     
         3 . The process for producing a metal-supported crystalline silicoaluminophosphate catalyst according to  claim 1 , wherein the crystalline silicoaluminophosphate particles have been washed and/or calcined after the synthesis thereof. 
     
     
         4 . The process for producing a metal-supported crystalline silicoaluminophosphate catalyst according to  claim 1 , wherein the crystalline silicoaluminophosphate is at least one member selected from the group consisting of SAPO-5, SAPO-11, SAPO-34, and SAPO-37. 
     
     
         5 . The process for producing a metal-supported crystalline silicoaluminophosphate catalyst according to  claim 1 , wherein the crystalline silicoaluminophosphate is SAPO-34. 
     
     
         6 . The process for producing a metal-supported crystalline silicoaluminophosphate catalyst according to  claim 1 , wherein the active ingredient metal compound is a compound of an element selected from the group 8, 9, 10, 11, and 12 elements of the periodic table or a mixture thereof (including an alloy). 
     
     
         7 . The process for producing a metal-supported crystalline silicoaluminophosphate catalyst according to  claim 1 , wherein the amount of the active ingredient metal supported is in a range of 0.1 to 10% by weight in terms of metal. 
     
     
         8 . A metal-supported crystalline silicoaluminophosphate catalyst comprising a crystalline silicoaluminophosphate with an active metal ingredient supported thereon, the metal-supported crystalline silicoaluminophosphate catalyst meeting the requirements that the retention of specific surface area as measured by BET and the retention of crystallinity after hydrothermal treatment under conditions of (1) an air atmosphere having a moisture content of 10% by volume, (2) a temperature of 700° C., and (3) a treatment time of 20 hours are not less than 80% and not less than 80%, respectively. 
     
     
         9 . The metal-supported crystalline silicoaluminophosphate catalyst according to  claim 8 , wherein the crystalline silicoaluminophosphate is at least one member selected from the group consisting of SAPO-5, SAPO-11, SAPO-34, and SAPO-37. 
     
     
         10 . The metal-supported crystalline silicoaluminophosphate catalyst according to  claim 8 , wherein the crystalline silicoaluminophosphate is SAPO-34. 
     
     
         11 . The metal-supported crystalline silicoaluminophosphate catalyst according to  claim 8 , wherein the active metal ingredient is a metal of an element selected from the group 8, 9, 10, 11, and 12 elements of the periodic table or a mixture thereof (including an alloy). 
     
     
         12 . The metal-supported crystalline silicoaluminophosphate catalyst according to  claim 8 , wherein the amount of the active metal ingredient supported is in a range of 0.1 to 10% by weight in terms of metal. 
     
     
         13 . The metal-supported crystalline silicoaluminophosphate catalyst according to  claim 8 , which has been obtained by the process for producing a metal-supported crystalline silicoaluminophosphate catalyst according to  claim 1 . 
     
     
         14 . An aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst comprising: metal-supported crystalline silicoaluminophosphate particles having a surface modified with aluminum phosphate, the content of aluminum phosphate in the catalyst being 0.1 to 40% by weight in terms of Al 2 O 3 +P 2 O 5  based on the metal-supported crystalline silicoaluminophosphate particles. 
     
     
         15 . The aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 14 , wherein the value of x in (Al 2 ) x .(PO 4 ) 3  representing the aluminum phosphate is 0.1 to 3. 
     
     
         16 . The aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 14 , wherein the crystalline silicoaluminophosphate particles are at least one member selected from the group consisting of SAPO-5, SAPO-11, SAPO-34, and SAPO-37. 
     
     
         17 . The aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 14 , wherein the crystalline silicoaluminophosphate is SAPO-34. 
     
     
         18 . The aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 14 , wherein the supported metal is a metal of an element selected from the group 8, 9, 10, 11, and 12 elements of the periodic table or a mixture thereof (including an alloy). 
     
     
         19 . The aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 14 , wherein the amount of the metal supported is in a range of 0.1 to 10% by weight in terms of metal. 
     
     
         20 . A process for producing an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst, the process comprising the following steps (f) to (i):
 (f) preparing a dispersion of a metal-supported crystalline silicoaluminophosphate particles;   (g) mixing an aqueous aluminum phosphate solution into the dispersion;   (h) spray-drying the mixture; and   (i) heat-treating (calcining) the spray-dried product at 400 to 700° C.   
     
     
         21 . The process for producing an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 20 , wherein the metal-supported crystalline silicoaluminophosphate particles have been obtained by the following steps (a) to (c) and (e):
 (a) preparing a dispersion of crystalline silicoaluminophosphate particles;   (b) mixing an aqueous active ingredient metal compound solution into the dispersion;   (c) spray-drying the mixture; and   (e) heat-treating (calcining) the spray-dried product at 400 to 900° C.   
     
     
         22 . The process for producing an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 21 , wherein the step (c) is followed by the following step (d):
 (d) washing the spray-dried product.   
     
     
         23 . The process for producing an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 21 , wherein the crystalline silicoaluminophosphate particles have been washed and/or calcined after the synthesis thereof. 
     
     
         24 . The process for producing an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 21 , wherein the crystalline silicoaluminophosphate particles are at least one member selected from the group consisting of SAPO-5, SAPO-11, SAPO-34, and SAPO-37. 
     
     
         25 . The process for producing an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 21 , wherein the crystalline silicoaluminophosphate particles are SAPO-34. 
     
     
         26 . The process for producing an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 21 , wherein the active ingredient metal compound is a compound of an element selected from the group 8, 9, 10, 11, and 12 elements of the periodic table or a mixture thereof (including an alloy). 
     
     
         27 . The process for producing an aluminum phosphate-modified metal-supported crystalline silicoaluminophosphate catalyst according to  claim 21 , wherein the amount of the active ingredient metal supported is in a range of 0.1 to 10% by weight in terms of metal based on the crystalline silicoaluminophosphate particles. 
     
     
         28 . A NOx reducing catalyst for exhaust gas treatment according to  claim 8 . 
     
     
         29 . A NOx reducing catalyst for exhaust gas treatment according to  claim 14 .