CATALYST COMPOSITIONS AND METHODS FOR ALCOHOL PRODUCTION FROM SYNTHESIS GAS
In one aspect of this invention, catalytic compositions produced by calcining intermediates of the formula [NR 4 ] x [M 1 2 M 2 S 8 ] are provided, wherein M 1 is Mo or W; M 2 is Co, Ni, or Pd; x is 2 or 3; and R is a C 3 -C 8 alkyl group. Another aspect provides catalytic compositions produced by calcining intermediates of the formula A x [M 1 2 M 2 S 8 ], wherein A is selected from K, Rb, Cs, Sr, and Ba. Also provided are methods for making the compositions, and methods of using the compositions for the catalytic conversion of syngas into C 1 -C 4 alcohols such as ethanol.
1 . A compound of the formula [NR 4 ] x [M 1 2 M 2 S 8 ], wherein:
M 1 is Mo or W;
M 2 is Co, Ni, or Pd;
x is 2 or 3;
x is 2 when M 2 is Ni or Pd;
x is 3 when M 1 is Mo and M 2 is Co; and
R is a C 3 -C 8 linear or branched alkyl group,
wherein the X-ray diffraction intensity of the most-intense reflection of a disulfide phase of M 2 is less than 50% of the most-intense reflection of M 1 S 2 .
2 . The compound of claim 1 , wherein said X-ray diffraction intensity of the most-intense reflection of a disulfide phase of M 2 is less than 25% of the most-intense reflection of M 1 S 2 .
3 . The compound of claim 1 , wherein said compound does not include any crystalline disulfide phase of M 2 .
4 . The compound of claim 1 , wherein M 2 is Co.
5 . The compound of claim 1 , wherein M 2 is Ni.
6 . The compound of claim 1 , wherein M 2 is Pd.
7 . The compound of claim 1 , wherein R is an n-alkyl group.
8 . The compound of claim 7 , wherein said n-alkyl group is n-butyl.
9 . The compound of claim 7 , wherein said n-alkyl group is n-pentyl.
10 . The compound of claim 7 , wherein said n-alkyl group is n-hexyl.
11 . The compound of claim 1 , wherein said compound has the formula [NR 4 ] 3 [Mo 2 CoS 8 ].
12 . The compound of claim 1 , wherein said compound has the formula [NR 4 ] 2 [Mo 2 NiS 8 ].
13 . The compound of claim 1 , wherein said compound has the formula [NR 4 ] 3 [W 2 CoS 8 ].
14 . The compound of claim 1 , wherein said compound has the formula [NR 4 ] 2 [W 2 CoS 8 ].
15 . The compound of claim 1 , wherein said compound has the formula [NR 4 ] 2 [W 2 NiS 8 ].
16 . A composition comprising a compound according to claim 1 , and further comprising a polar solvent.
17 . A composition comprising at least two compounds, wherein each of said two compounds is independently selected from the formula [NR 4 ] X [M 1 2 M 2 S 8 ], wherein:
M 1 is Mo or W;
M 2 is Co, Ni, or Pd;
x is 2 or 3;
x is 2 when M 2 is Ni or Pd;
x is 3 when M 1 is Mo and M 2 is Co; and
R is a C 3 -C 8 linear or branched alkyl group,
wherein the X-ray diffraction intensity of the most-intense reflection of a disulfide phase of M 2 is less than 50% of the most-intense reflection of M 1 S 2 .
18 . The composition of claim 17 , said composition comprising [NR 4 ] 2 [Mo 2 NiS 8 ] and [NR 4 ] 2 [Mo 2 CoS 8 ].
19 . The composition of claim 17 , said composition comprising [NR 4 ] 2 [W 2 NiS 8 ] and [NR 4 ] 2 [W 2 CoS 8 ].
20 . The composition of claim 17 , wherein M 2 is Pd for at least one of said two compounds.