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 method for generating a catalyst derived from [R 4 N] x [M 1 2 M 2 S 8 ], said catalyst capable of converting syngas into one or more reaction products comprising at least one C 1 -C 4 alcohol when in the presence of a catalytic promoter, said method comprising:
(a) preparing a solution A of a compound of the formula [NH 4 ] 2 [M 1 S 4 ] in a first polar solvent, wherein M 1 is Mo or W;
(b) preparing a solution B of a salt or compound of a Group VIII element M 2 in a second polar solvent, wherein M 2 is Co, Ni, or Pd, wherein x is 2 when M 2 is Ni or Pd, and wherein x is 3 when M 1 is Mo and M 2 is Co;
(c) when x is 3, preparing a solution C containing a reducing agent dissolved in a third polar solvent miscible in the first or second polar solvents;
(d) preparing a solution D of a compound of the formula R 4 NZ in a fourth polar solvent, wherein R is a C 3 -C 8 alkyl group, and wherein Z is a monovalent anion;
(e) combining solutions A, B, C (if any), and D, to form a precipitate comprising a compound of the formula [R 4 N] x [M 1 2 M 2 S 8 ];
(f) removing the first, second, third (if any), and fourth solvents from the precipitate; and
(g) calcining the precipitate under inert atmosphere to form the catalyst.
2 . The method of claim 1 , wherein solution A and solution B are mixed to form a solution comprising a compound of the formula [NH 4 ] x [M 1 2 M 2 S 8 ], prior to mixing with solution C and/or solution D.
3 . The method of claim 1 , wherein solution B and solution D are mixed prior to mixing with solution A.
4 . The method of claim 1 , wherein step (f) is performed under inert atmosphere.
5 . The method of claim 1 , wherein step (g) is performed under inert atmosphere.
6 . The method of claim 1 , wherein steps (f) and (g) are performed without exposing said precipitate to oxygen between said steps.
7 . The method of claim 6 , wherein step (g) is performed in an alcohol-synthesis reactor.
8 . The method of claim 6 , wherein said catalytic promoter is combined with said compound [R 4 N] x [M 1 2 M 2 S 8 ] prior to step (g).
9 . The method of claim 1 , wherein solution D further comprises a base.
10 . The method of claim 1 , wherein Z is selected from the group consisting of hydroxide, acetate, formate, and bicarbonate.
11 . The method of claim 1 , wherein said salt of a Group VIII element M 2 is selected from the group consisting of acetate salt, chloride salt, bromide salt, and nitrate salt.
12 . A method for generating a catalyst derived from E y [M 1 2 M 2 S 8 ], said catalyst capable of converting syngas into one or more reaction products comprising at least one C 1 -C 4 alcohol when in the presence of a catalytic promoter, wherein:
E is selected from the group consisting of K, Cs, Rb, Sr, and Ba;
M 1 is Mo or W;
M 2 is a Group VIII element Co, Ni, or Pd;
x is 2 when M 2 is Ni or Pd;
x is 3 when M 1 is Mo and M 2 is Co;
y is x when E is K, Cs, or Rb; and
y is x/2 when E is Sr or Ba;
said method comprising:
(a) preparing a solution A of a compound of the formula [NH 4 ] 2 [M 1 S 4 ] in a first polar solvent;
(b) preparing a solution B of a salt or compound of M 2 in a second polar solvent,
(c) when x is 3, preparing a solution C containing a reducing agent dissolved in a third polar solvent miscible in said first or second polar solvents;
(d) preparing a solution D of a compound of the formula selected from the group consisting of KOH, CsOH, RbOH, Sr(OH) 2 , and Ba(OH) 2 in a fourth polar solvent;
(e) combining said solutions A, B, C (if any), and D, to form a precipitate comprising a compound of the formula E y [M 1 2 M 2 S 8 ];
(f) removing said first, second, third (if any), and fourth solvents from said precipitate; and
(g) calcining said precipitate under inert atmosphere to form said catalyst.
13 . The method of claim 12 , wherein said step (d) is conducted in the presence of a complexing agent suitable to promote solubilization of said compound provided in step (d).
14 . The method of claim 13 , wherein said complexing agent is a crown ether.
15 . The method of claim 12 , wherein step (f) is performed under inert atmosphere.
16 . The method of claim 12 , wherein step (g) is performed under inert atmosphere.
17 . The method of claim 12 , wherein steps (f) and (g) are performed without exposing said precipitate to oxygen between said steps.
18 . The method of claim 17 , wherein step (g) is performed in an alcohol-synthesis reactor.
19 . The method of claim 17 , wherein said catalytic promoter is combined with said compound E y [M 1 2 M 2 S 8 ] prior to step (g).
20 . The method of either of claims 1 or 12 , wherein said first polar solvent is selected from the group consisting of acetonitrile, dimethylformamide, tetrahydrofuran, C 1 -C 4 alcohols, and mixtures thereof.
21 . The method of either of claims 1 or 12 , wherein said second polar solvent is selected from the group consisting of acetonitrile, dimethylformamide, tetrahydrofuran, C 1 -C 4 alcohols, and mixtures thereof.
22 . The method of either of claims 1 or 12 , wherein said third polar solvent, when present, is selected from the group consisting of acetonitrile, dimethylformamide, tetrahydrofuran, C 1 -C 4 alcohols, and mixtures thereof.
23 . The method of either of claims 1 or 12 , wherein said fourth polar solvent is selected from the group consisting of acetonitrile, dimethylformamide, tetrahydrofuran, C 1 -C 4 alcohols, and mixtures thereof.
24 . The method of either of claims 1 or 12 , wherein said first, second, third (if present), and fourth polar solvents are the same.
25 . The method of either of claims 1 or 12 , comprising removal of solvent by filtration.
26 . The method of either of claims 1 or 12 , comprising removal of solvent by heating.
27 . The method of either of claims 1 or 12 , wherein step (g) is performed at a temperature selected from about 350-500° C. for a time selected from about 1-10 hours.
28 . The method of either of claims 1 or 12 , wherein the molar ratio of sulfur to the combined total of molybdenum, if present, tungsten, if present, and said Group VIII element(s) in the catalyst is at least about 1.5:1.
29 . The method of claim 28 , wherein said molar ratio is at least about 1.9:1.
30 . The method of claim 29 , wherein said molar ratio is at least about 2.0:1.
31 . The method of claim 30 , wherein said molar ratio is at least about 2.1:1.
32 . A method of producing at least one C 1 -C 4 alcohol from syngas, said method comprising contacting hydrogen and carbon monoxide with a catalyst produced according to the method of either of claims 1 or 12 and combined with a suitable catalytic promoter.
33 . The method of claim 32 , wherein said catalyst is exposed to O 2 for less than six hours prior to contacting said catalyst with hydrogen and carbon monoxide.
34 . The method of claim 32 , wherein said catalyst is exposed to O 2 for less than one hour prior to contacting said catalyst with hydrogen and carbon monoxide.
35 . The method of claim 32 , wherein said catalyst is not substantially exposed to O 2 prior to contacting said catalyst with hydrogen and carbon monoxide.
36 . The method of claim 32 , wherein at least 25% of the total C 1 -C 4 alcohols produced is ethanol.
37 . The method of claim 36 , wherein at least 50% of the total C 1 -C 4 alcohols produced is ethanol.