Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol

Abstract

The invention relates to a process for producing a product gas comprising acetonitrile and/or hydrogen cyanide from a feed stream comprising ammonia and methanol over a solid catalyst comprising a support, a first metal and a second metal on the support, wherein the first metal and the second metal are in the form of a chemical compound, wherein the first metal is Fe, Ru or Co and the second metal is Sn, Zn, or Ge. The pressure is ambient pressure or higher and the temperature lies in a range from about 400° C. to about 700° C. Thus, the process for producing acetonitrile and/or hydrogen cyanide from ammonia and methanol may be catalyzed by a single catalyst and may be carried out in a single reactor. The invention also relates to a catalyst, a method for activating a catalyst and use of a catalyst for catalysing production of acetonitrile and/or hydrogen cyanide from ammonia and methanol.

Claims

1. A process comprising: producing a product gas comprising acetonitrile and/or hydrogen cyanide from a feed stream comprising ammonia and methanol over a solid catalyst at a pressure and a temperature, wherein the catalyst comprises a support, a first metal and a second metal on said support, wherein said first metal and said second metal are in the form of a chemical compound selected from the group consisting of an alloy consisting of the first metal and the second metal, a ternary carbide comprising the first metal and the second metal, and a mixture thereof, wherein said first metal is Fe, Ru, Ni or Co and said second metal is Sn, Zn, or Ge, wherein the catalyst comprises alloys between the first and second metals and/or ternary carbides comprising the first and the second metals, wherein the pressure is atmospheric pressure or higher and the temperature lies in a range from about 400° C. to about 700° C., and wherein the catalyst is capable of catalyzing the following reactions: 1a) formation of formamide from methanol and ammonia; 1b) decomposition of formamide to hydrogen cyanide; and 2) cyanation of methanol to acetonitrile.

2. A process according to claim 1, where the temperature lies in a range from about 500° C. to about 600° C.

3. A process according to claim 1, wherein the support is chosen between the following: alumina, a spinel of alumina, and a high temperature stable catalyst carrier in the form of an oxide, a carbide, or a nitride.

4. A process according to claim 1, wherein further comprising controlling the ratio between acetonitrile and hydrogen cyanide in the product gas by controlling the ratio of ammonia and methanol in the feed stream and/or the process temperature.

5. A process according to claim 1, wherein said first metal and said second metal are in the form of an alloy of the first metal and the second metal.

6. A process according to claim 1, wherein said first metal and said second metal are in the form of an alloy consisting of the first metal and the second metal.

7. A process according to claim 1, wherein said first metal and said second metal are in the form of a ternary carbide comprising the first metal and the second metal.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 is an XRD plot of activated catalyst according to the invention.

EXPERIMENT 1

(2) Table 1 below show data of experimental data. Table 1 shows a product gas composition at four different reaction temperatures.

(3) TABLE-US-00001 TABLE 1 10% Co-24% Sn/Al.sub.2O.sub.3 Outlet Inlet Dimethyl- Time Temp. Total flow MeOH NH3 MeOH HCN Acetonitrile ether # [h] [° C.] [Nml/min] [vol %] [vol %] [vol %] [vol %] [vol %] [vol %] 1 0.4 400.2 100.3 9.93 9.01 1.70 0.15 0.23 2.31 2 0.8 400.0 100.3 9.93 9.01 1.69 0.16 0.21 2.38 3 1.3 400.3 100.3 9.93 9.01 1.86 0.16 0.20 2.61 4 1.7 400.3 100.4 9.92 9.01 1.87 0.16 0.19 2.74 5 2.2 400.0 100.3 9.93 9.01 1.91 0.16 0.18 2.79 6 3.0 450.6 100.3 9.93 9.01 1.08 0.78 1.14 1.00 7 3.4 450.1 100.3 9.93 9.01 0.78 0.81 1.05 0.83 8 3.9 450.2 100.3 9.93 9.01 0.82 0.81 0.97 1.10 9 4.3 450.0 100.3 9.93 9.01 0.83 0.81 0.94 1.03 10 4.8 450.1 100.3 9.93 9.01 0.82 0.81 0.89 1.07 11 5.4 500.2 100.3 9.93 9.01 0.06 1.11 2.76 0.03 12 5.9 500.3 100.3 9.93 9.01 0.08 1.19 2.77 0.05 13 6.3 499.9 100.4 9.92 9.01 0.11 1.27 2.70 0.08 14 14.2 550.3 100.3 9.93 9.01 0 0.74 3.34 0 15 14.7 549.8 100.3 9.93 9.01 0 0.78 3.43 0 16 15.1 549.9 100.4 9.92 9.01 0 0.79 3.43 0

(4) The catalyst used in EXPERIMENT 1 of Table 1 was 600 mg of a catalyst which prior to activation comprised 10 wt % Co, 24 wt % Sn on a Al.sub.2O.sub.3 carrier. In all experiments, the feed stream comprised 9.9 vol % CH.sub.3OH (MeOH) and 9.0 vol % NH.sub.3 (ammonia) in N.sub.2. From Table 1 it is seen that acetonitrile is present in the outlet gas or product gas at temperatures of 400° C. and 450° C., however only at a comparatively low percentage of the product gas, but that at process temperatures of 500° C. and 550° C. the percentage of acetonitrile in the outlet gas is increased considerably. It is also seen that at 550° C., there is no methanol or dimethyl ether in the product gas, and that the amount of methanol and dimethyl ether at 550° C. is rather low. At 500° C. and 550° C., the main product is acetonitrile, and the methanol conversion is complete. Thus, the process and catalyst of the invention operates to form a C.sub.2 species from a C.sub.1 species.

EXPERIMENT 2

(5) Table 2 shows data of further experiments. Table 2 shows data of product gas composition for different ratios between methanol and ammonia, and for different flow rates.

(6) TABLE-US-00002 TABLE 2 10% Co-24% Sn/Al.sub.2O.sub.3 Outlet Inlet Dimethyl- Time Temp. Total flow MeOH NH3 MeOH HCN Acetonitrile ether # [h] [° C.] [Nml/min] [vol %] [vol %] [vol %] [vol %] [vol %] [vol %] 1 5.4 500.2 100.3 9.93 9.01 0.06 1.11 2.76 0.03 2 5.9 500.3 100.3 9.93 9.01 0.08 1.19 2.77 0.05 3 6.3 499.9 100.4 9.92 9.01 0.11 1.27 2.70 0.08 4 6.8 499.9 100.5 16.52 8.35 0.70 1.50 2.73 1.02 5 7.2 500.0 100.5 16.52 8.35 0.81 1.48 2.51 1.31 6 7.7 500.2 100.4 16.53 8.35 0.70 1.50 2.55 0.80 7 8.1 500.0 50.5 16.43 8.36 0.40 1.24 3.15 0.38 8 8.6 499.7 50.5 16.43 8.36 0.28 1.09 3.25 0.21 9 9.0 500.2 50.5 16.43 8.36 0.29 1.10 3.24 0.22 10 9.8 550.8 50.5 16.43 8.36 0 0.20 4.39 0 11 10.3 550.2 50.5 16.43 8.36 0 0.20 4.36 0 12 10.7 550.2 50.5 16.43 8.36 0 0.22 4.39 0

(7) The catalyst used in the Experiment 2 shown in Table 2 was 600 mg of a catalyst which prior to activation comprised 10 wt % Co, 24 wt % Sn on a Al.sub.2O.sub.3 carrier. In the first three tests of Experiment 2, the feed stream comprised 9.9 vol % CH.sub.3OH (MeOH) and 9.0 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1.1:1; in the subsequent nine tests of Experiment 2, the feed stream comprised 16.5 vol % CH.sub.3OH (MeOH) and 8.4 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 2.0:1.

(8) From Table 2 it is seen that acetonitrile is the main constituents out of methanol (MeOH, CH.sub.3OH), hydrogen cyanide (HCN), acetonitrile (CH.sub.3CH) and dimethyl ether in the outlet gas or product gas.

(9) It is also seen that at increasing the ratio CH.sub.3OH:NH.sub.3 from about 1:1 to 2:1 provides a higher amount of hydrogen cyanide, dimethyl ether and methanol in the product gas, when the flow is unchanged. However, when the flow is reduced by half, the amounts of hydrogen cyanide, dimethyl ether and methanol in the product gas is reduced.

(10) Again, Experiment 2 shows that the process and catalyst of the invention operates to form a C.sub.2 species from a C.sub.1 species.

EXPERIMENT 3

(11) Table 3 shows data of further experiments. Table 3 shows data of product gas composition for different ratios between methanol and ammonia, and for different flow rates.

(12) TABLE-US-00003 TABLE 3 10% Fe-24% Sn/Al.sub.2O.sub.3 Outlet Inlet Dimethyl- Time Temp. Total flow MeOH NH3 MeOH HCN Acetonitrile ether # [h] [° C.] [Nml/min] [vol %] [vol %] [vol %] [vol %] [vol %] [vol %] 1 0.4 399.6 100.4 9.97 9.00 8.39 0.46 0.00 0.21 2 0.9 399.7 100.4 9.97 9.00 8.14 0.47 0.00 0.22 3 1.3 400.4 100.4 9.97 9.00 8.09 0.50 0.00 0.21 4 1.8 400.3 100.3 9.97 9.00 7.92 0.50 0.00 0.21 5 2.2 453.7 100.4 9.97 9.00 1.24 1.74 0.26 0.42 6 2.7 450.6 100.4 9.97 9.00 1.80 1.78 0.23 0.44 7 3.1 449.4 100.4 9.97 9.00 1.89 1.77 0.23 0.45 8 3.5 449.8 100.4 9.97 9.00 1.92 1.75 0.22 0.45 9 4.0 504.0 100.4 9.97 9.00 0.00 1.59 0.38 0.42 10 4.4 500.8 100.4 9.97 9.00 0.00 1.89 0.35 0.46 11 4.9 500.6 100.4 9.97 9.00 0.00 2.02 0.34 0.47 12 5.3 499.7 100.4 9.97 9.00 0.00 2.08 0.33 0.47 13 5.8 499.6 100.3 4.98 9.50 0.00 1.69 0.00 0.22 14 6.2 499.9 100.3 4.98 9.50 0.00 1.68 0.00 0.22 15 6.7 499.8 100.3 4.98 9.50 0.00 1.67 0.00 0.22 16 7.1 499.6 150.2 5.00 9.50 0.00 1.81 0.00 0.21 17 7.6 499.5 150.2 5.00 9.50 0.00 1.81 0.00 0.21 18 8.0 500.4 150.2 5.00 9.50 0.00 1.81 0.00 0.20 19 8.4 400.5 100.4 9.97 9.00 8.21 0.30 0.00 0.21 20 8.9 399.6 100.4 9.97 9.00 8.14 0.28 0.00 0.21 21 9.3 400.2 100.4 9.97 9.00 8.30 0.28 0.00 0.23 22 9.8 452.1 100.4 9.97 9.00 2.35 1.56 0.24 0.44 23 10.2 450.6 100.4 9.97 9.00 2.98 1.54 0.22 0.44 24 10.7 450.4 100.4 9.97 9.00 2.93 1.53 0.21 0.44 25 11.1 450.1 100.4 9.97 9.00 3.03 1.52 0.21 0.44

(13) The catalyst used in the Experiment 3 shown in Table 3 was 600 mg of a catalyst which prior to activation comprised 10 wt % Fe, 24 wt % Sn on a Al.sub.2O.sub.3 carrier.

(14) In the tests numbered 1-12 and the tests numbered 19-25 of Experiment 3, the feed stream comprised 10.0 vol % CH.sub.3OH (MeOH) and 9.0 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1.1:1; in the tests 14-18 of Experiment 3, the feed stream comprised 5.0 vol % CH.sub.3OH (MeOH) and 9.54 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1:1.9.

(15) From Table 3 it is seen that hydrogen cyanide is the main product out of hydrogen cyanide (HCN), acetonitrile (CH3CH) and dimethyl ether (DME) at 450° C. and above.

(16) It is also seen that increasing the ratio CH3OH:NH3 from about 1:1 to 1:1.9 results in a decrease in the HCN production and a halving of the DME production. The product gas contains no acetonitrile at this ratio.

(17) Increasing the flow rate from 100 to 150 Nml/min results in an increase of HCN in the product gas.

EXPERIMENT 4

(18) Table 4 shows data of further experiments. Table 4 shows data of product gas composition for different ratios between methanol and ammonia, and for different flow rates.

(19) TABLE-US-00004 TABLE 4 10% Fe-12% Zn/Al.sub.2O.sub.3 Outlet Inlet Dimethyl- Time Temp. Total flow MeOH NH3 MeOH HCN Acetonitrile ether # [h] [° C.] [Nml/min] [vol %] [vol %] [vol %] [vol %] [vol %] [vol %] 1 0.4 400.0 100.3 9.97 9.00 0.00 0.11 1.14 0.28 2 0.8 400.3 100.3 9.97 9.00 0.00 0.11 1.09 0.36 3 1.3 400.2 100.4 9.97 9.00 0.00 0.11 1.10 0.36 4 1.7 400.3 150.2 9.99 9.00 0.00 0.09 0.81 0.92 5 2.1 400.1 150.2 9.99 9.00 0.00 0.09 0.85 0.89 6 2.6 400.4 150.2 9.99 9.00 0.00 0.09 0.85 0.85 7 2.9 400.2 100.4 16.54 8.35 1.26 0.00 0.51 2.95 8 3.3 400.8 100.4 16.54 8.35 1.16 0.00 0.51 2.91 9 3.8 400.4 100.4 16.54 8.35 1.14 0.00 0.50 2.95 10 4.2 454.2 100.4 16.54 8.35 0.00 0.57 2.44 0.00 11 4.6 450.6 100.4 16.54 8.35 0.00 0.48 2.36 0.00 12 5.1 450.3 100.5 16.53 8.35 0.00 0.44 2.32 0.03 13 5.5 450.5 100.4 16.54 8.35 0.00 0.39 2.31 0.04 14 6.0 450.1 100.3 9.97 9.00 0.00 0.41 1.70 0.00 15 6.4 450.2 100.4 9.97 9.00 0.00 0.42 1.71 0.00 16 6.8 449.9 100.3 9.97 9.00 0.00 0.43 1.69 0.00 17 7.3 450.0 100.3 4.98 9.50 0.00 0.18 1.11 0.00 18 7.7 450.1 100.3 4.98 9.50 0.00 0.20 1.15 0.00 19 8.2 450.3 100.3 4.98 9.50 0.00 0.20 1.14 0.00

(20) The catalyst used in the Experiment 4 shown in Table 4 was 600 mg of a catalyst which prior to activation comprised 10 wt % Fe, 12 wt % Zn on a Al.sub.2O.sub.3 carrier.

(21) In the tests 1-6 of Experiment 4, the feed stream comprised 10.0 vol % CH.sub.3OH (MeOH) and 9.0 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1.1:1; in the tests 7-13 of Experiment 4, the feed stream comprised 16.54 vol % CH.sub.3OH (MeOH) and 8.35 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1:2.0. The subsequent three test were with a feed stream comprising 10.0 vol % CH.sub.3OH (MeOH) and 9.0 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1.1:1, and the last three tests of Experiment 4 were with a feed stream comprising 5.0 vol % CH.sub.3OH (MeOH) and 9.5 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1:1.9.

(22) From Table 4 it is seen that acetonitrile and hydrogen cyanide are present in the product gas in all tests, except from the three tests where the temperature is 400° C. and the ratio between methanol and ammonia in the feed stream is 1:2.0. In those three test, no HCN is present in the product gas.

EXPERIMENT 5

(23) Table 5 shows data of further experiments, with a catalyst comprising Ni and Sn on a Al.sub.2O.sub.3. Table 5 shows data of product gas composition for different ratios between methanol and ammonia, and for different flow rates.

(24) TABLE-US-00005 TABLE 5 10% Ni-24% Sn/Al.sub.2O.sub.3 Outlet Inlet Dimethyl- Time Temp. Total flow MeOH NH3 MeOH HCN Acetonitrile ether # [h] [° C.] [Nml/min] [vol %] [vol %] [vol %] [vol %] [vol %] [vol %] 1 0.3 400.3 100.4 9.97 9.00 1.88 0.14 0.37 2.54 2 0.8 400.3 100.4 9.97 9.00 1.90 0.13 0.31 2.65 3 1.2 399.9 100.4 9.97 9.00 1.89 0.12 0.28 2.65 4 1.7 453.4 100.4 9.97 9.00 0.95 0.23 1.44 0.65 5 2.1 450.0 100.4 9.97 9.00 1.13 0.19 1.22 0.87 6 2.6 450.1 100.4 9.97 9.00 1.19 0.17 1.14 0.94 7 3.0 450.1 100.4 9.97 9.00 1.23 0.17 1.07 1.00 8 3.5 450.1 100.4 9.97 9.00 1.29 0.15 1.01 1.04 9 3.9 503.2 100.4 9.97 9.00 0.00 0.56 2.27 0.00 10 4.4 500.4 100.4 9.97 9.00 0.00 0.59 2.17 0.00 11 4.8 499.9 100.4 9.97 9.00 0.00 0.60 2.11 0.00 12 5.2 499.9 100.4 9.97 9.00 0.00 0.62 2.05 0.01 13 5.7 553.4 100.4 9.97 9.00 0.00 0.38 2.84 0.00 14 6.1 550.3 100.4 9.97 9.00 0.00 0.48 2.71 0.00 15 6.6 549.9 100.4 9.97 9.00 0.00 0.54 2.68 0.00 16 7.0 550.0 100.4 9.97 9.00 0.00 0.55 2.66 0.00 17 8.1 550.1 100.3 4.98 9.50 0.00 0.24 1.53 0.00 18 8.5 549.9 100.3 4.98 9.50 0.00 0.24 1.63 0.00 19 8.9 549.9 100.3 4.98 9.50 0.00 0.24 1.69 0.00 20 9.4 550.0 100.5 16.53 8.35 0.00 0.35 3.79 0.00 21 9.8 550.0 100.5 16.53 8.35 0.00 0.47 3.83 0.00 22 10.3 550.1 100.5 16.53 8.35 0.00 0.52 3.93 0.00 23 10.7 600.2 100.4 9.97 9.00 0.00 0.40 1.65 0.00 24 11.2 600.1 100.4 9.97 9.00 0.00 0.40 1.69 0.00 25 11.6 600.2 100.4 9.97 9.00 0.00 0.41 1.64 0.00

(25) In tests 1-16 and 23-25 of Experiment 5, the feed stream comprised 10.0 vol % CH.sub.3OH (MeOH) and 9.0 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1.1:1; in the tests 17-19 of Experiment 5, the feed stream comprised 5.0 vol % CH.sub.3OH (MeOH) and 9.5 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1:1.9. In the tests 20-22 the feed stream comprised 16.54 vol % CH.sub.3OH (MeOH) and 8.35 vol % NH.sub.3 (ammonia) in N.sub.2, i.e. a ratio CH.sub.3OH:NH.sub.3 ratio of 1:2.0.

(26) It is seen from Table 5, that also a Ni—Sn catalyst on a Al.sub.2O.sub.3 carrier is effective in catalyzing the conversion of ammonia and methanol to hydrogen cyanide and acetonitrile. At temperatures of 500° C. and above, the conversion of methanol is complete.

EXPERIMENT 6

(27) Table 6 shows data on further experiments with a catalyst comprising Fe and Sn on a Al.sub.2O.sub.3 support. Table 6 shows data of product gas composition for different ratios between methanol and ammonia, and for different flow rates.

(28) TABLE-US-00006 TABLE 6 10% Fe-24% Sn/Al.sub.2O.sub.3 Outlet Inlet Dimethyl- Time Temp. Total flow MeOH NH3 MeOH HCN Acetonitrile ether # [h] [° C.] [Nml/min] [vol %] [vol %] [vol %] [vol %] [vol %] [vol %] 1 0.4 450.1 100.3 5.0 9.5 0.00 1.60 0.00 0.48 2 0.9 449.9 100.3 5.0 9.5 0.00 1.62 0.30 0.49 3 1.3 450.2 100.3 5.0 9.5 0.00 1.62 0.30 0.52 4 1.8 499.7 100.3 5.0 9.5 0.00 1.28 0.55 0.16 5 2.2 500.9 100.3 5.0 9.5 0.00 1.44 0.57 0.21 6 2.7 500.2 100.3 5.0 9.5 0.00 1.44 0.55 0.23 7 3.1 499.9 100.3 5.0 9.5 0.00 1.47 0.56 0.25 8 3.7 539.1 100.3 5.0 9.5 0.00 0.67 0.63 0.01 9 4.1 550.9 100.3 5.0 9.5 0.00 0.82 0.69 0.01 10 4.6 549.9 100.3 5.0 9.5 0.00 0.90 0.65 0.01 11 5.0 550.1 100.3 5.0 9.5 0.00 0.94 0.63 0.01 12 5.4 449.9 150.3 5.0 9.5 0.00 1.45 0.00 0.44 13 5.8 450.1 150.3 5.0 9.5 0.00 1.46 0.21 0.45 14 6.3 450.2 150.3 5.0 9.5 0.00 1.43 0.20 0.45 15 7.4 450.1 50.5 4.9 9.5 0.00 1.10 0.00 0.35 16 7.8 449.9 50.5 5.0 9.5 0.00 1.30 0.36 0.52 17 8.3 450.1 50.5 5.0 9.5 0.00 1.32 0.37 0.55 18 8.7 503.7 150.3 5.0 9.5 0.00 1.70 0.00 0.25 19 9.1 500.4 150.3 5.0 9.5 0.00 1.78 0.00 0.28 20 9.6 500.2 150.3 5.0 9.5 0.00 1.74 0.00 0.27 21 10.0 500.0 150.3 5.0 9.5 0.00 1.84 0.00 0.25 22 10.5 500.2 50.5 4.9 9.5 0.00 1.45 0.65 0.13 23 10.9 499.8 50.5 4.9 9.5 0.00 1.28 0.55 0.07 24 11.4 500.0 50.5 5.0 9.5 0.00 1.26 0.51 0.06 25 11.5 449.4 100.3 13.1 8.7 3.87 1.85 0.38 0.84 26 11.9 450.3 100.3 13.1 8.7 3.56 1.75 0.37 0.91 27 12.4 450.3 100.3 13.1 8.7 3.64 1.68 0.36 0.92 28 12.8 495.8 100.3 13.1 8.7 0.00 2.45 0.63 0.51 29 13.3 500.4 100.3 13.1 8.7 0.00 2.53 0.60 0.55 30 13.7 500.2 100.3 13.1 8.7 0.00 2.55 0.59 0.57 31 14.2 500.1 100.3 13.1 8.7 0.00 2.53 0.57 0.54 32 15.1 450.1 50.6 13.0 8.7 1.48 1.83 0.51 1.01 33 15.5 449.9 50.6 13.0 8.7 1.63 1.78 0.51 1.08 34 16.0 449.9 50.6 13.0 8.7 1.57 1.78 0.51 1.08 35 16.4 450.0 150.3 13.1 8.7 7.35 1.48 0.29 0.49 36 16.8 449.9 150.3 13.1 8.7 7.15 1.24 0.29 0.63 37 17.3 450.0 150.3 13.1 8.7 7.19 1.20 0.28 0.65 38 17.7 449.9 150.3 13.1 8.7 7.19 1.19 0.29 0.65 39 19.2 500.1 150.3 13.1 8.7 0.00 2.93 0.47 0.53 40 19.7 500.1 150.3 13.1 8.7 0.00 2.98 0.46 0.57 41 20.1 499.8 150.3 13.1 8.7 0.00 2.96 0.46 0.56 42 20.6 500.2 50.6 13.0 8.7 0.00 2.10 0.59 0.32 43 21.0 500.1 50.6 13.0 8.7 0.00 2.06 0.59 0.27 44 21.5 499.9 50.6 13.0 8.7 0.00 2.15 0.56 0.30 45 21.9 499.8 100.3 5.0 9.5 0.00 1.91 0.26 0.14 46 22.3 500.0 100.3 5.0 9.5 0.00 1.90 0.26 0.13 47 22.8 500.0 100.3 5.0 9.5 0.00 1.89 0.24 0.13

(29) It is seen from Table 6, that also a Fe—Sn catalyst on a Al.sub.2O.sub.3 carrier is effective in catalyzing the conversion of ammonia and methanol to hydrogen cyanide and acetonitrile.

EXPERIMENT 7

(30) Table 7 shows data on further experiments with a catalyst comprising Co and Sn on a Al.sub.2O.sub.3 support. Table 7 shows data of product gas composition for different ratios between methanol and ammonia, and for different flow rates.

(31) TABLE-US-00007 TABLE 7 10% Co-24% Sn/Al.sub.2O.sub.3 Outlet Inlet Dimethyl- Time Temp. Total flow MeOH NH3 MeOH HCN Acetonitrile ether # [h] [° C.] [Nml/min] [vol %] [vol %] [vol %] [vol %] [vol %] [vol %] 1 0.4 450.1 100.3978 10.0 9.0 1.22 0.47 0.9 1.4 2 0.8 450.1 100.3978 10.0 9.0 1.32 0.44 0.8 1.6 3 1.3 450.1 100.3978 10.0 9.0 1.40 0.41 0.8 1.7 4 1.7 503.6 100.401 10.0 9.0 0.00 0.61 2.2 0.0 5 2.2 500.4 100.3849 10.0 9.0 0.00 0.70 2.1 0.0 6 2.6 499.9 100.3978 10.0 9.0 0.00 0.72 2.1 0.0 7 3.1 500.1 100.3978 10.0 9.0 0.00 0.77 2.1 0.0 8 3.5 499.8 100.3267 5.0 9.5 0.00 0.49 1.5 0.0 9 4.0 499.7 100.3363 5.0 9.5 0.00 0.51 1.5 0.0 10 4.4 500.0 100.3267 5.0 9.5 0.00 0.52 1.4 0.0 11 5.0 499.9 50.48469 5.0 9.5 0.00 0.17 1.7 0.0 12 5.5 499.8 50.49114 4.9 9.5 0.00 0.24 1.7 0.0 13 5.9 499.9 50.48469 5.0 9.5 0.00 0.25 1.6 0.0 14 6.6 500.1 50.48469 5.0 9.5 0.00 0.29 0.0 0.0 15 7.1 499.9 150.2778 5.0 9.5 0.00 0.92 1.3 0.0 16 7.5 499.9 150.2778 5.0 9.5 0.00 0.91 1.3 0.0 17 8.0 500.2 150.2778 5.0 9.5 0.00 0.86 1.2 0.0

(32) It is seen from Table 7, that also a Co—Sn catalyst on a Al.sub.2O.sub.3 carrier is effective in catalyzing the conversion of ammonia and methanol to hydrogen cyanide and acetonitrile. A total flow of 50-150 Nml/min containing either 10.0 vol % methanol and 9.0 vol % ammonia in nitrogen (corresponding to a CH.sub.3OH:NH.sub.3 ratio of 1.11:1) or 5.0 vol % methanol and 9.5 vol % ammonia in nitrogen (corresponding to a CH.sub.3OH:NH.sub.3 ratio of 0.53:1) was used. When the CH.sub.3OH:NH.sub.3 ratio is decreased to 0.53:1, both the hydrogen cyanide and the acetonitrile concentrations decrease; however, the selectivity towards the two increases. When the total inlet flow is lowered to 50 Nml/min, the production of acetonitrile increases while the hydrogen cyanide concentration decreases accordingly.

EXPERIMENT 8

(33) Table 8 shows data on further experiments with a catalyst comprising Co and Sn on Al.sub.2O.sub.3 support. Table 8 shows data of product gas composition for different ratios between methanol and ammonia, and for different flow rates.

(34) TABLE-US-00008 TABLE 8 10% Co-24% Sn/Al.sub.2O.sub.3 Outlet Inlet Dimethyl- Time Temp. Total flow MeOH NH3 MeOH HCN Acetonitrile ether # [h] [° C.] [Nml/min] [vol %] [vol %] [vol %] [vol %] [vol %] [vol %] 1 0.4 399.6 100.6 9.9 9.0 3.51 0.38 0.00 2.40 2 0.9 399.8 100.6 9.9 9.0 3.70 0.40 0.00 2.43 3 1.4 400.3 100.6 9.9 9.0 3.78 0.39 0.00 2.40 4 1.8 453.2 100.6 9.9 9.0 0.00 0.73 0.86 1.66 5 2.3 450.3 100.6 9.9 9.0 0.00 0.71 0.82 1.86 6 2.8 449.9 100.6 9.9 9.0 0.00 0.66 0.76 1.99 7 3.2 450.1 100.6 9.9 9.0 0.00 0.60 0.65 2.13 8 3.7 503.7 100.6 9.9 9.0 0.00 1.22 1.77 0.31 9 4.2 500.1 100.6 9.9 9.0 0.00 1.19 1.59 0.52 10 4.6 500.1 100.6 9.9 9.0 0.00 1.20 1.47 0.60 11 5.1 499.7 102.7 9.7 8.8 0.00 1.18 1.43 0.66 12 6.2 549.7 100.6 10.0 9.0 0.00 0.74 2.42 0.00 13 6.6 548.5 100.5 10.0 9.0 0.00 0.99 2.45 0.00 14 7.1 550.3 100.6 9.9 9.0 0.00 1.17 2.45 0.00

(35) It is again seen from Table 8, that a Co—Sn catalyst on a Al.sub.2O.sub.3 carrier is effective in catalyzing the conversion of ammonia and methanol to hydrogen cyanide and acetonitrile. In the experiment of Table 8, the carrier gas was argon. Therefore, it was possible to determine whether the direct decomposition of ammonia to nitrogen and hydrogen occurs over the catalyst. As no nitrogen was detected, this reaction does not appear to take place at the tested temperatures.

(36) It should be noted that even though the feed stream of Experiments 1 to 8 comprised about 75 vol % to 80 vol % carrier gas, such as N.sub.2 or argon, the invention is not limited to such a feed stream. It is conceivable that the feed stream comprises much more ammonia and methanol, e.g. that the feed stream essentially consists of ammonia and methanol.

(37) FIG. 1 is an XRD plot of an activated Co—Sn catalyst supported on Al.sub.2O.sub.3 according to the invention. In the XRD plot, intensity peaks corresponding to specific compounds have been identified, as indicated by the legend of FIG. 1 and in Table 9 below.

(38) TABLE-US-00009 TABLE 9 wt % D (A) a (A) c (A) Co.sub.3SnC 1.4 185 3.821 CoAl.sub.2O.sub.4 51 56 7.987 CoSn 4.5 502 5.276 4.26 CoSn.sub.2 1 809 6.354 5.45 gamma- 42 122 7.933 Al.sub.2O.sub.3 Sn 0.2 3837 5.825 3.18

(39) In FIG. 1, the main phase is gamma-Al.sub.2O.sub.3 giving a high background. It is seen from Table 9 that the spent or activated catalyst comprises alloys between the Co and Sn, e.g. CoSn and CoSn.sub.2, as well as a ternary carbide comprising the first and the second metals, in the form of Co.sub.3SnC.

(40) The term “ternary carbides” is meant to denote a carbide comprising the first and second metals; the plural form of the term is not meant to denote that different types of ternary carbides exist. Instead the plural form of the term “ternary carbides” indicate that more than one molecule of the carbide is comprised in the catalyst. Likewise, the term “alloys between the first and second metal” is not meant to indicate that more than one type of alloy is comprised in the catalyst, only that more than one alloy molecule is comprised within the catalyst.

(41) While the invention has been illustrated by a description of various embodiments and while these embodiments have been described in considerable detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of applicant's general inventive concept.