PROCESS FOR PRODUCTION OF HEXAMETHYLENEDIAMINE FROM CARBOHYDRATE-CONTAINING MATERIALS AND INTERMEDIATES THEREFOR
Processes are disclosed for the conversion of a carbohydrate source to hexamethylenediamine (HMDA) and to intermediates useful for the production of hexamethylenediamine and other industrial chemicals. HMDA is produced by direct reduction of a furfural substrate to 1,6-hexanediol in the presence of hydrogen and a heterogeneous reduction catalyst comprising Pt or by indirect reduction of a furfural substrate to 1,6-hexanediol wherein 1,2,6-hexanetriol is produced by reduction of the furfural substrate in the presence of hydrogen and a catalyst comprising Pt and 1,2,6-hexanediol is then converted by hydrogenation in the presence of a catalyst comprising Pt to 1,6 hexanediol, each process then proceeding to the production of HMDA by known routes, such as amination of the 1,6 hexanediol. Catalysts useful for the direct and indirect production of 1,6-hexanediol are also disclosed.
1 . A process for preparing hexamethylenediamine from a carbohydrate source, the process comprising: converting a carbohydrate source to a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6-hexanediol; and, converting at least a portion of the 1,6-hexanediol to hexamethylenediamine.
2 . The process of claim 1 , wherein the heterogeneous reduction catalyst comprises Pt.
3 . The process of claim 2 , wherein the heterogeneous reduction catalyst further comprises a support selected from the group consisting of zirconias, silicas, and zeolites.
4 . The process of claim 2 , wherein the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re.
5 . The process of claim 1 , wherein the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of about 60° C. and about 200° C. and a pressure of hydrogen in the range of about 200 psig to about 2000 psig.
6 . The process of claim 1 , wherein the carbohydrate source is glucose, fructose, or a mixture comprising glucose and fructose.
7 . A process for preparing hexamethylenediamine from a carbohydrate source, the process comprising: converting a carbohydrate source to a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce a reaction product comprising 1,2,6-hexanetriol; converting at least a portion of the 1,2,6-hexanetriol to 1,6-hexanediol; and converting at least a portion of the 1,6-hexanediol to hexamethylenediamine.
8 . The process of claim 7 , wherein the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re.
9 . The process of claim 7 , wherein the step of converting at least a portion of the 1,2,6-hexanetriol to 1,6-hexanediol is conducted in the presence of hydrogen and a hydrogenation catalyst comprising Pt.
10 . The process of claim 7 , wherein the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of about 60° C. and about 200° C. and a pressure of hydrogen in the range of about 200 psig to about 2000 psig.
11 . The process of claim 7 , wherein the reduction catalyst further comprises a support selected from the group consisting of zirconias, silicas, and zeolites.
12 . The process of claim 7 , wherein the reaction of the furfural substrate with hydrogen to produce 1,2,6-hexanetriol is carried out at a temperature in the range of about 100° C. and about 140° C. and a pressure of hydrogen in the range of about 200 psig to about 1000 psig.
13 . The process of claim 7 , wherein the catalyst comprises Pt and W supported on zirconia.
14 . A process for preparing 1,6-hexanediol from a carbohydrate source, the process comprising: converting the carbohydrate source to a furfural substrate; and, reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol.
15 . The process of claim 14 , wherein the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re.
16 . The process of claim 14 , wherein the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of about 60° C. and about 200° C. and a pressure of hydrogen in the range of about 200 psig to about 2000 psig.
17 . The process of claim 14 , wherein the reduction catalyst further comprises a support selected from the group consisting of zirconias, silicas, and zeolites.
18 . The process of claim 14 , wherein the carbohydrate source is glucose, fructose, or a mixture comprising glucose and fructose.
19 - 36 . (canceled)