Method for increasing yields of light oil and total liquid products, promoting the combustion of CO and reducing NOx emission in flue gas in the petroleum refining FCC process and the improved FCC catalyst

Abstract

The present invention relates to non-noble metal catalyst comprising Cu—Al/Ce—Al complex oxides and aluminum oxide support. The catalysts comprise Ce—Al complex oxide and Cu—Al complex oxide successively loaded on the aluminum oxide support, wherein the loading weight ratio is 0.02-0.10 for Ce—Al—O/Al 2 O 3 and 0.05-0.15 for Cu—Al—O/Al 2 O 3 , and the Cu—Al complex oxide is dispersed in cluster form on the surface of the aluminum oxide support pre-covered with high dispersed nanoparticles of the Ce—Al complex oxide. Furthermore, the present invention relates to a process for preparing the catalysts, their use as FCC process additive with high catalytic activity, high hydrothermal stability and ability of promoting CO combustion and reducing NOx exhaust and increasing yields of light oil and total liquid products in the improved FCC process of petroleum refining and the improved FCC catalyst which is obtained after treatment in the presence of said FCC process additive.

1 . A method of increasing the yields of light oil and total liquid products, promoting the combustion of CO and/or reducing the emission of NOx in petroleum refining FCC process, comprising the step of using a non-noble metal complex oxide catalyst as FCC additive which comprises Ce—Al complex oxide and Cu—Al complex oxide successively loaded on an aluminum oxide support, and the ratio of the loading weight is 0.02-0.10 for Ce—Al—O/Al 2 O 3  and 0.05-0.15 for Cu—Al—O/Al 2 O 3 , respectively.  
     
     
         2 . A method according to  claim 1  characterized in that the loading weight ratio is 0.04-0.06 for Ce—Al—O/Al 2 O 3  and 0.08-0.11 for Cu—Al—O/Al 2 O 3 , respectively.  
     
     
         3 . A method according to  claim 1  characterized in that said Ce—Al complex oxide covers a surface of the aluminum oxide support in the form of nanoparticles.  
     
     
         4 . A method according to  claim 1  characterized in that a structure of said Ce—Al complex oxide can be presented by the general formula [I]:  
       [Ce 1−y Al y][O   2−y/2 □ y-2 ]  [I] 
       wherein y=0.05-0.30, □ represents the vacancy in the structure.  
     
     
         5 . A method according to  claim 1  characterized in that said Cu—Al complex oxide is dispersed in cluster form on the aluminum oxide support, wherein the support is pre-covered with the particles of Ce—Al complex oxide.  
     
     
         6 . A method according to  claim 1  characterized in that a structure of said Cu—Al complex oxide can be presented by the general formula [II]:  
       [Cu 1-3x/2 Al x □ x/2 ]O   [II] 
       wherein x=0.05-0.23, and □ represents the vacancy in the structure.  
     
     
         7 . A method according to  claim 1  characterized in that said aluminum oxide support has a particle size of 10-100 μm.  
     
     
         8 . A method according to  claim 1  characterized in that said aluminum oxide support is γ-Al 2 O 3 .  
     
     
         9 . An improved FCC catalyst which is obtained after treatment in the presence of a non-noble metal complex oxide catalyst as a FCC process additive which comprises Ce—Al complex oxide and Cu—Al complex oxide successively loaded on an aluminum oxide support, and the ratio of the loading weight is 0.02-0.10 for Ce—Al—O/Al 2 O 3  and 0.05-0.15 for Cu—Al—O/Al 2 O 3 , respectively.  
     
     
         10 . A FCC catalyst according to  claim 9  characterized in that said ratio of the loading weight is 0.04-0.06 for Ce—AlO/Al 2 O 3  and 0.08-0.11 for Cu—Al—O/Al 2 O 3 , respectively.  
     
     
         11 . A FCC catalyst according to  claim 9  characterized in that said Ce—Al complex oxide covers the surface of the aluminum oxide support in the form of nanoparticles.  
     
     
         12 . A FCC catalyst according to  claim 9  characterized in that a structure of said Ce—Al complex oxide can be represented by the general formula [I]:  
       [Ce 1−y Al y ][O 2−y/2 □ y/2 ]  [I] 
       Wherein y=0.05-0.30, □ represents the vacancy in the structure.  
     
     
         13 . A FCC catalyst according to  claim 9  characterized in that said Cu—Al complex oxide is dispersed in cluster form on the aluminum oxide support, wherein the support is pre-covered with the particles of Ce—Al complex oxide.  
     
     
         14 . A FCC catalyst according to  claim 9  characterized in that said Cu—Al complex oxide can be represented by the general formula [II]:  
       [Cu 1-3x/2 Al x □ x/2 ]O   [II] 
       Wherein x=0.05-0.23, □ represents the vacancy in the structure.  
     
     
         15 . A FCC catalyst according to  claim 9  characterized in that said aluminum oxide support has a particle size of 10-100 μm.  
     
     
         16 . A FCC catalyst according to any one of  claims 9  to  15  characterized in that said aluminum oxide support is γ-Al 2 O 3 .