Catalyst compositions and process for direct production of hydrogen cyanide in an acrylonitrile reactor feed stream

Abstract

The present invention relates to catalyst compositions containing a mixed oxide catalyst of formula (I) or formula (II) as described herein, their preparation, and their use in a process for ammoxidation of various organic compounds to their corresponding nitriles and to the selective catalytic oxidation of excess NH 3 present in effluent gas streams to N 2 and/or NO x .

1 . A catalyst composition comprising a mixed oxide catalyst of formula (I) or (II):
   Mo 12 X 1   a X 2   b X 3   c X 4   d X 5   e X 6   f O h   (I)
     FeMo i Cr j Bi k M m N n Q q X x Y y O r   (II)
   wherein in the formula (I):
 X 1  is Cr and/or W; 
 X 2  is Bi, Sb, As, P, and/or a rare earth metal; 
 X 3  is Fe, Ru, and/or Os; 
 X 4  is Ti, Zr, Hf, B, Al, Ga, In, TI, Si, Ge, Sn, and/or Pb; 
 X 5  is Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mn, Re, V, Nb, Ta, Se, and/or Te; 
 X 6  is an alkaline earth metal and/or an alkali metal; 
 0≤a≤5; 
 0.03≤b≤25; 
 0≤c≤20; 
 0≤d≤200; 
 0≤e≤8; 
 0≤f≤3; and 
 h is the number of oxygen atoms required to satisfy the valence requirements of the component elements other than oxygen present in formula (I), where 
 1≤c+d+e+f≤200; 
 0≤e+f≤8; and 
   wherein in the formula (II):
 M is Ce and/or Sb; 
 N is La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, B, Al, Ga, In, TI, Si, Ge, Sn, Pb, P, and/or As; 
 Q is W, Ru, and/or Os; 
 X is Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mn, Re, V, Nb, Ta, Se, and/or Te; 
 Y is an alkaline earth metal and/or an alkali metal; 
 0.2≤i≤100; 
 0≤j≤2; 
 0≤k≤2; 
 0.05≤m≤10; 
 0≤n≤200; 
 0≤q≤8; 
 0≤x≤30; 
 0≤y≤8; 
 j and k<i; 
 m>j; and 
 r is the number of oxygen atoms required to satisfy the valence requirements of the component elements other than oxygen present in formula (II), 
   wherein:
 4≤m+n+q+x+y≤200; 
 0≤q+x+y≤30; and 
   wherein the catalyst composition has a surface area of from 2 to 500 m 2 /g as determined by the Brunauer-Emmett-Teller (BET) method.   
     
     
         2 . The catalyst composition according to  claim 1 ,
 wherein in the formula (I):
 0≤a≤3; 
 0.04≤b≤20; 
 0≤c≤15; 
 0≤d≤175; 
 0≤e≤5; 
 0≤f≤2; 
 3≤c+d+e+f≤175; and 
 0≤e+f≤5, and 
   wherein in the formula (II):
 0.3≤i≤50; 
 0≤j≤1.5; 
 0≤k≤1.5; 
 0.1 m≤8; 
 0≤n≤100; 
 0≤q≤3; 
 0≤x≤10; 
 0≤y≤3; 
 j and k<i; 
 m>j; 
 4.5≤m+n+q+x+y≤100; 
 0≤q+x+y≤10. 
   
     
     
         3 . The catalyst composition according to  claim 2 ,
 wherein in the formula (I):
 0≤a≤1; 
 0.05≤b≤15; 
 0.1≤c≤9; 
 0≤d≤150; 
 0≤e≤2; 
 0≤f≤1, 
 5≤c+d+e+f≤150; and 
 0≤e+f≤2, and 
   wherein in the formula (II):
 0.5≤i≤50; 
 0≤j≤0.5; 
 0≤k≤0.75; 
 0.2≤m≤5; 
 0≤n≤60; 
 0≤q≤1.5; 
 0≤x≤5; 
 0≤y≤2; 
 j and k<i; 
 m>j; 
 5≤m+n+q+x+y≤60; and 
 0≤q+x+y≤7.5. 
   
     
     
         4 . The catalyst composition according to  claim 1 , wherein the catalyst composition consists of a mixed oxide catalyst of the formula (I) or (II). 
     
     
         5 . The catalyst composition according to  claim 1 , wherein the catalyst composition further comprises a support selected from the group consisting of silica, zirconia, titania, alumina and mixtures thereof. 
     
     
         6 .- 10 . (canceled) 
     
     
         11 . A process for preparing the catalyst composition of formula (I) according to  claim 1 , the process comprising:
 (i) preparing a first mixture comprising:
 source compounds of elements Cr and/or W in an aqueous solution; 
 full or partial amounts of elements Bi, Sb, As, P, and/or a rare earth metal; 
 full or partial amounts of elements Fe, Ru, and/or Os, an alkali metal element and/or an alkaline earth metal element; 
 full or partial amounts of elements Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mn, Re, V, Nb, Ta, Se, Te, Hf, B, Ga, In, TI, Ge, Sn, and/or Pb; 
   (ii) preparing a second mixture comprising source compounds of at least one or more of full or partial amounts of Mo, Si, Ti, Zr, and Al in an aqueous solution, and of remaining amounts of the step (i) elements required in the mixed oxide catalysts of formula (I) and formula (II);   (iii) adding the first mixture to the second mixture under conditions sufficient to react and form precipitate slurry, with optional use of a basic compound to adjust pH;   (iv) filtering the precipitate slurry;   (v) optionally mixing the precipitate slurry with the source compounds of any remaining amounts of the step (ii) Mo, Si, Ti, Zr and Al elements required in the mixed oxide catalysts of formula (I) and formula (II) to form a catalyst precursor; and   (vi) drying and calcining the catalyst precursor to form the catalyst composition.   
     
     
         12 . A process for preparing the catalyst composition of formula (II) according to  claim 1 , the process comprising:
 (i) preparing a first mixture comprising:
 source compounds of elements Fe, Cr, and Bi in an aqueous solution; 
 full or partial amounts of elements of at least t one or more of Ce and/or Sb; 
 full or partial amounts of elements La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, B, Al, Ga, In, TI, Si, Ge, Sn, Pb, P and/or As, W, Ru and/or Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mn, Re, V, Nb, Ta, Se and/or Te; and an alkaline earth metal and/or an alkali metal; 
   (ii) preparing a second mixture comprising source compounds of at least one or more of full or partial amounts of Mo, Si, Ti, Zr, and Al in an aqueous solution, and of remaining amounts of step (i) elements required in the mixed oxide catalysts of formula (I) and formula (II);   (iii) adding the first mixture to the second mixture under conditions sufficient to react and form a precipitate slurry, with optional use of a basic compound to adjust pH;   (iv) filtering the precipitate slurry;   (v) optionally mixing the precipitate slurry with the source compounds of any remaining amounts of the step (ii) Mo, Si, Ti, Zr and Al elements required in the mixed oxide catalysts of formula (I) and formula (II) to form a catalyst precursor; and   (vi) drying and calcining the catalyst precursor to form the catalyst composition.   
     
     
         13 .- 16 . (canceled) 
     
     
         17 . A process of preparing a catalyst composition coated onto a monolith support, comprising coating the monolith support with the catalyst composition according to  claim 1  by dip coating, wash coating, curtain coating, vacuum coating, chemical vapor deposition, sputter coating or mixtures thereof. 
     
     
         18 . The process according to  claim 11 , wherein the calcining step occurs at a temperature from about 300° C. to about 900° C. in the presence of air, an inert gas, carbon dioxide, steam or mixtures thereof. 
     
     
         19 . A process for ammoxidation of an alcohol or an alcohol-containing mixture, a nitrile or a nitrile-containing mixture, a ketone or a ketone-containing mixture, an aldehyde or an aldehyde-containing containing mixture, a carboxylic acid or a carboxylic acid-containing mixture, an ester or an ester-containing mixture, an ether or an ether-containing mixture, or mixtures thereof comprising reacting the alcohol or the alcohol-containing mixture, the nitrile or the nitrile-containing mixture, the ketone or the ketone-containing mixture, the aldehyde or the aldehyde-containing containing mixture, the carboxylic acid or the carboxylic acid-containing mixture, the ester or the ester-containing mixture, the ether or the ether-containing mixture, or mixtures thereof with NH 3  and O 2  in the presence of a catalyst composition to provide HCN and/or ACN and/or corresponding nitriles, wherein the catalyst composition comprises a mixed oxide catalyst of formula (I) or (II):
   Mo 12 X 1   a X 2   b X 3   c X 4   d X 5   e X 6   f O h   (I)
     FeMo i Cr j Bi k M m N n Q q X x Y y O r   (II)
   wherein in the formula (I):
 X 1  is Cr and/or W; 
 X 2  is Bi, Sb, As, P, and/or a rare earth metal; 
 X 3  is Fe, Ru, and/or Os; 
 X 4  is Ti, Zr, Hf, B, Al, Ga, In, TI, Si, Ge, Sn, and/or Pb; 
 X 5  is Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mn, Re, V, Nb, Ta, Se, and/or Te; 
 X 6  is an alkaline earth metal and/or an alkali metal; 
 0≤a≤5; 
 0.03≤b≤25; 
 0≤c≤20; 
 0≤d≤200; 
 0≤e≤8; 
 0≤f≤3; and 
 h is the number of oxygen atoms required to satisfy the valence requirements of the component elements other than oxygen present in formula (I), where 
 1≤c+d+e+f≤200; 
 0≤e+f≤8; and 
   wherein in the formula (II):
 M is Ce and/or Sb; 
 N is La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, B, Al, Ga, In, TI, Si, Ge, Sn, Pb, P, and/or As; 
 Q is W, Ru and/or Os; 
 X is Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mn, Re, V, Nb, Ta, Se and/or Te; 
 Y is an alkaline earth metal and/or an alkali metal; 
 0.2≤i≤100; 
 0≤j≤2; 
 0≤k≤2; 
 0.05≤m≤10; 
 0≤n≤200; 
 0≤q≤8; 
 0≤x≤30; 
 0≤y≤8; 
 j and k<i; 
 m>j; and 
 r is the number of oxygen atoms required to satisfy the valence requirements of the component elements other than oxygen present in formula (II), where 
 4≤m+n+q+x+y≤200; 
 0≤q+x+y≤30; and 
   wherein the catalyst composition has a surface area of from 2 to 500 m 2 /g as determined by the Brunauer-Emmett-Teller (BET) method.   
     
     
         20 . The process according to  claim 19 ,
 wherein in the formula (I):
 0≤a≤3; 
 0.04≤b≤20; 
 0≤c≤15; 
 0≤d≤175; 
 0≤e≤5; 
 0≤f≤2; 
 3≤c+d+e+f≤175; and 
 0≤e+f≤5, and 
   wherein in the formula (II):
 0.3≤i≤50; 
 0≤j≤1.5; 
 0≤k≤1.5; 
 0.1≤m≤8; 
 0≤n≤100; 
 0≤q≤3; 
 0≤x≤10; 
 0≤y≤3; 
 j and k<i; 
 m>j; 
 4.5≤m+n+q+x+y≤100; 
 0≤q+x+y≤10. 
   
     
     
         21 . The process according to  claim 19 ,
 wherein in the formula (I):
 0≤a≤1; 
 0.05≤b≤15; 
 0.1≤c≤9; 
 0≤d≤150; 
 0≤e≤2; 
 0≤f≤1, 
 5≤c+d+e+f≤150; and 
 0≤e+f≤2, and 
   wherein in the formula (II):
 0.5≤i≤50; 
 0≤j≤0.5; 
 0≤k≤0.75; 
 0.2≤m≤5; 
 0≤n≤60; 
 0≤q≤1.5; 
 0≤x≤5; 
 0≤y≤2; 
 j and k<i; 
 m>j; 
 5≤m+n+q+x+y≤60; and 
 0≤q+x+y≤7.5. 
   
     
     
         22 . The process according to  claim 19 , wherein the catalyst composition consists of a mixed oxide catalyst of the formula (I) or (II). 
     
     
         23 .- 37 . (canceled) 
     
     
         38 . The process according to  claim 19 , wherein the ammoxidation is of CH 3 OH, EtOH, propanol or mixtures thereof. 
     
     
         39 . The process according to  claim 19 , wherein the ammoxidation is of propionitrile, acetonitrile, methacrylonitrile or mixtures thereof. 
     
     
         40 . The process according to  claim 19 , wherein the ammoxidation is of acetone; methyl ethyl ketone; methyl esters of acetic, formic, and propionic acid; dimethyl esters of oxalic acid; acetals of formaldehyde and acetaldehyde; acrolein; methyl, ethyl, and propyl ethanoates; dimethyl ether, diethyl ether, methyl ethyl ether, MTBE; or mixtures thereof. 
     
     
         41 .- 49 . (canceled) 
     
     
         50 . A process for selective catalytic oxidation (SCO) of NH 3  to N 2  and/or NO x  in the presence of O 2  comprising reacting the NH 3  with the O 2  in the presence of the catalyst composition according to  claim 1 . 
     
     
         51 . The process according to  claim 50 , wherein the NH 3  and O 2  are present in an effluent stream of a primary AN reactor or an ammoxidation reactor. 
     
     
         52 .- 53 . (canceled) 
     
     
         54 . The process according to  claim 50 , wherein the catalyst composition comprises the mixed oxide catalyst of formula (I). 
     
     
         55 . The process according to  claim 50 , wherein the catalyst composition comprises the mixed oxide catalyst of formula (II). 
     
     
         56 . (canceled)