Supported catalyst for producing h2 and/or co from low molecular weight hydrocarbons

Abstract

Chemical combination (C) between an active solid phase which is covalently bound to the surface of an inert solid phase, caracterized in that said solid active phase essentially consists in a solid solution of a mixture of at least a magnesium oxide type phase compound and at least a magnesium silicate type phase compound in which Al, and Rh and/or Ni cations are soluted and caracterized in that said inert solid phase is either a compound represented by the general formula (I): Al a Ni b Rh c Mg d Si e O f   (I) wherein a, b, c, d, and e are integers which are greater than or equal to 0, f is an integer greater than 0, the sum a+b+c+d≠0, and wherein (3a+2b+3c+2d+4e)/2=f, or a mixture of compounds represented by the said general formula (I), provided that at least one of the Si, Al, Mg, Rh or Ni elements, which is present in the solid active phase, is also present in the solid inert phase. Use of a catalyst in chemical reactions involving the conversion hydrocarbonaceous feedstocks.

1 - 18 . (canceled)  
   
   
       19 . A chemical combination (C) between an active solid phase which is covalently bound to the surface of an inert solid phase, characterized in that said solid active phase essentially consists in a solid solution of a mixture of at least a magnesium oxide type phase compound and at least a magnesium silicate type phase compound in which Al, and Rh and/or Ni cations are soluted and characterized in that said inert solid phase is either a compound represented by the general formula (I):  
       Al a Ni b Rh c Mg d Si e O f   (I)  wherein a, b, c, d, and e are integers which are greater than or equal to 0, f is an integer greater than 0, the sum a+b+c+d≠0, and    wherein (3a+2b+3c+2d+4e)/2=f, or a mixture of compounds represented by the said general formula (I),    provided that at least one of the Si, Al, Mg, Rh or Ni elements, which is present in the solid active phase, is also present in the solid inert phase.    
   
   
       20 . The chemical combination according to  claim 19 , wherein the amount of active phase on the inert support is in the range from 1% to 90% weight by weight and preferably between 5% and 60% weight by weight of the total combination.  
   
   
       21 . The chemical combination according to  claim 19 , wherein the inert phase is in a form of beads, pellets, disks or monoliths.  
   
   
       22 . The chemical combination according to  claim 19 , wherein the inert phase is chosen among the compounds represented by the general formula (I) as defined above, wherein: 
 either a=2, b=c=d=e=0 and f=3,    either a=2,b=c=0, d=1, e=3 and f=10,    either e=1 and a=b=c=d=0, f=2    either a=b=c=0, d=2, e=1 and f=4,    or a=2, b=c=d=0, e=2 and f=7,    and a mixture thereof.    
   
   
       23 . Process for the preparation of the chemical combination (C) according to  claim 19 , characterized in that it comprises the successive following steps: 
 Step (a): An hydrotalcite-type precursor of the formula (II):      [[Mg 1-a Al a (OH) 2 ] z+ (CO 3   2−   z/2 ), m H 2 O]  (II),    wherein 0<a<1 and z is the total electrical charge of the cationic element, is calcined to form a mixed oxyde of the formula (III):      [(2−2 a )MgO, a Al 2 O 3 ]  (III);    Step (b): The mixed oxyde of the formula (III), is mixed with water and put to react at alkaline pH, with SiO 2 .NaOH solution, together with a Rh +++  salt, a Ni ++  salt or a mixture of both salts, to form a chemical combination (C′), between an active solid phase which is covalently bound to the surface of an inert solid phase, characterized in that said solid active phase essentially consists an hydrotalcite active solid phase of the formula (IV):      [Rh x Ni y Mg p Al m (OH) 2 ] 2+ (A n−   z/n ) k H 2 O,  (IV)    wherein A n−  is mainly a silicate or a polysilicate anion;    0≦x≦0.3, preferably 0≦x≦0.1;    0≦y≦0.9, preferably 0≦y≦0.3;    0≦p≦0.9, preferably 0.3≦p≦0.8;    0≦m≦0.5, preferably 0.1≦m≦0.4;    0≦k≦10, preferably 0≦k≦5;    x+y>0;    0.5≦y+p≦0.9, preferably 0.6≦y+p≦0.8;    x+y+p+m=1; and    z is the total electrical charge of the cationic element, and characterized in that said inert solid phase is an hydrotalcite inert solid phase of the formula (V):      [[Mg 2-2a-p Al 2a-m (OH) 2 ] z′+ (A n′−   z′/n′ ), k′ H 2 O]  (V),    wherein A n′−  is mainly a silicate or a polysilicate anion;    0≦2−2a−p≦0.9, preferably 0.3≦2−2a−p≦0.8;    0≦2a−m≦0.5, preferably 0.1≦2a−m≦0.4;    0≦k′≦10, preferably 0≦k'≦5;    p+m=1; and    z′ is the total electrical charge of the cationic element;    Step (c): The chemical combination (C′), is calcined to form the chemical combination (C).    
   
   
       24 . Process for the preparation of the chemical combination (C) according to  claim 19 , characterized in that it comprises the successive following steps: 
 Step (a): An hydrotalcite-type precursor of the formula (VI):      [[Mg 1-a Al a (OH) 2 ] z+ (A n″−   z′/n″ ), k ″H 2 O]  (VI),    wherein 0<a<1, A n″−  is mainly a silicate or a polysilicate anion; and z is the total electrical charge of the cationic element, is calcined to form a mixed oxyde/silicate of the formula (VII):      [(2−2 a )MgO, a Al 2 O 3   ,a ′Al 2 Si 2 O 7   ,b ′MgSiO 4   ,d ′SiO 2 ]  (VII);    Step (b): The mixed oxyde/silicate of the formula (VII), is put to react with a Rh +++  salt, a Ni ++  salt or a mixture of both salts, to form a chemical combination (C′) as defined above;    Step (c): The chemical combination (C′), is calcined to form the chemical combination (C).    
   
   
       25 . Process for the preparation of the chemical combination (C) according to  claim 19 , characterized in that it comprises the successive following steps: 
 Step (a): A powder mixture of boehmite (Al 2 O 3 , w H 2 O) and α-alumina, is added to an alkaline aqueous silicate solution, to form a dispersion which is supplemented with at least one inorganic hydrosoluble salt chosen from hydrosoluble inorganic salts of Al +++ , Rh +++ , Mg ++  and Ni ++ , to form a chemical combination (C″) between an active solid phase which is covalently bound to the surface of an inert solid phase, characterized in that said solid active phase essentially consists an hydrotalcite active solid phase of the formula (IV) as defined above, and characterized in that said inert solid phase is a α-alumina.    Step (b): The chemical combination (C″) obtained in of step (a), is calcined to form the chemical combination (C).    
   
   
       26 . Chemical combination (C′), between an active solid phase which is covalently bound to the surface of an inert solid phase, characterized in that said solid active phase essentially consists an hydrotalcite active solid phase of the formula (IV):  
       [Rh x Ni y Mg p Al m (OH) 2 ] z+ (A n−   z/n ) k H 2 O,  (IV)  
     wherein A n−  is mainly a silicate or a polysilicate anion; 
 0≦x≦0.3, preferably 0≦x≦0.1;  
 0≦y≦0.9, preferably 0≦y≦0.3;  
 0≦p≦0.9, preferably 0.3≦p≦0.8;  
 0≦m≦0.5, preferably 0.1≦m≦0.4;  
 0≦k≦10, preferably 0≦k≦5;  
 x+y>0;  
 0.5≦y+p≦0.9, preferably 0.6≦y+p≦0.8;  
 x+y+p+m=1; and  
 z is the total electrical charge of the cationic element,  
 and characterized in that said inert solid phase is an hydrotalcite inert solid phase of the formula (V):  
   [[Mg 2-2a-p Al 2a-m (OH) 2 ] z′+ (A n′−   z′/n′ ), k ′H 2 O]  (V),  
 wherein A n′−  is mainly a silicate or a polysilicate anion;  
 0≦2−2a−p≦0.9, preferably 0.3≦2−2a−p≦0.8;  
 0≦2a−m≦0.5, preferably 0.1≦2a−m≦0.4;  
 0≦k′≦10, preferably 0≦k′≦5;  
 p+m=1; and  
 z′ is the total electrical charge of the cationic element;  
 
   
   
       27 . Chemical combination (C″) between an active solid phase which is covalently bound to the surface of an inert solid phase, characterized in that said solid active phase essentially consists an hydrotalcite active solid phase of the formula (IV):  
       [Rh x Ni y Mg p Al m (OH) 2 ] z+ (A n−   z/n ) k H 2 O,  (IV)  
     wherein A n−  is mainly a silicate or a polysilicate anion; 
 0≦x≦0.3, preferably 0≦x≦0.1;  
 0≦y≦≦0.9, preferably 0≦y≦0.3;  
 0≦p≦0.9, preferably 0.3≦p≦0.8;  
 0≦m≦0.5, preferably 0.1≦m≦0.4;  
 0≦k≦10, preferably 0≦k≦5;  
 x+y>0;  
 0.5≦y+p≦0.9, preferably 0.6≦y+p≦0.8;  
 x+y+p+m=1; and  
 z is the total electrical charge of the cationic element,  
 and characterized in that said inert solid phase is a α-alumina.  
 
   
   
       28 . Chemical combination according to  claim 26 , wherein the active phase is selected from:  
       [Ni 0.08 Mg 0.60 Al 0.32 (OH) 2 ] 0.32+ (SiO 3   2− ) 0.16   k H 2 O,  [Ni 0.08 Rh 0.0015 Mg 0.60 Al 0.3185 (OH) 2 ] 0.32+ (SiO 3   2− ) 0.16   k H 2 0,  [Rh 0.005 Mg 0.71 Al 0.285 (OH) 2 ] 0.32+ (SiO 3   2− ) 0.16   k H 2 0,  [Ni 0.01 Rh 0.0002 Mg 0.67 Al 0.3198 (OH) 2]   0.32+ (SiO 3   2− ) 0.16   k H 2 0,  [Ni 0.02 Mg 0.63 Al 0.35 (OH) 2 ] 0.35+ (SiO 3   2− ) 0.175   k H 2 0,  [Rh 0.0004 Mg 0.65 Al 0.3496 (OH) 2 ] 0.35+ (SiO 3   2− ) 0.175   k H 2 0,  [Ni 0.02 Mg 0.78 Al 0.20 (OH) 2 ] 0.35+ (SiO 3   2− ) 0.175   k H 2 0,  [Rh 0.0004 Mg 0.80 Al 0.1996 (OH) 2 ] 0.20+ (SiO 3 ) 0.10   k H 2 0, and  [Ni 0.027 Rh 0.00085 Mg 0.6477 Al 0.32445 (OH) 2 ] 0.3253+ (SiO 3   2− ) 0.16265   k H 2 0.  
   
   
       29 . Chemical combination (C) characterized in that it is obtained by calcination of the combination (C′) or of the combination (C″) as defined in  claim 27 .  
   
   
       30 . Use of the chemical combination (C) as defined in  claim 27 , a catalyst in chemical reactions involving the conversion hydrocarbonaceous feedstocks.  
   
   
       31 . Production of Synthesis gas, by catalytic partial oxidation of methane or of low-boiling liquid hydrocarbons characterized in that the worked catalyst is the chemical combination as defined in  claim 27 .  
   
   
       32 . Production of Synthesis gas, by steam reforming of methane or of low-boiling liquid hydrocarbons, characterized in that the worked catalyst is the chemical combination as defined in  claim 27 .  
   
   
       33 . Production of Synthesis gas, by dry reforming (CO 2 ) of methane or of low-boiling liquid hydrocarbons, characterized in that the worked catalyst is the chemical combination as defined in  claim 27 .  
   
   
       34 . The said inert solid phase can be others classical catalytic supports such as zirconia or magnesium oxide or silicon or silicon carbide, molybdenum carbide, refractory alloys available in several forms (beads, pellets, monoliths, disks, . . . ).  
   
   
       35 . Use of a composition according to  claim 19  which the operating catalyst conditions one in the range of 500 to 1300° C. and preferably between 600 to 1100° C.  
   
   
       36 . Use of a composition according to  claim 19  which the operating catalyst conditions one in the range of 10 5  Pa to 5·10 6  Pa and preferably between 10 5  Pa to 3·10 6  Pa.