Sulfur-containing palladium-carbon catalyst and method for preparing and using the same

1. A sulfur-containing palladium-carbon catalyst, comprising

active carbon,

palladium loaded on the active carbon at a loading amount of about 0.5 to 10 wt % of the total weight of the catalyst,

sulfidized palladium compounds prepared by partially passivating the palladium loaded on the active carbon by a sulfur-containing compound at a molar ratio of the sulfur-containing compound to the palladium of about 0.1:1 to 10:1, and

the sulfur-containing compound selectively adsorbed on the surface of the catalyst,

wherein the sulfur-containing compound is selected from the group consisting of a thiol, a thioether, an alkyl disulfide, thiofuran, ammonium hydrosulfide, a hydrosulfide of an alkaline metal, and a mixture thereof.

2. The sulfur-containing palladium-carbon catalyst of claim 1 , wherein the active carbon has a granularity of about 50 to 1000 mesh.

3. The sulfur-containing palladium-carbon catalyst of claim 1 , wherein the active carbon has a special surface area of about 600 to 1800 m 2 /g.

4. A sulfur-containing palladium-carbon catalyst as described in claim 1 , wherein the catalyst is prepared by

loading palladium on an active carbon to obtain a palladium-carbon catalyst,

mixing the palladium-carbon catalyst with a solvent to obtain a slurry,

adding a sulfur-containing compound to the slurry and treating the palladium-carbon catalyst at a predetermined temperature, and

removing liquid from the treated palladium carbon catalyst and drying to obtain the sulfur-containing palladium-carbon catalyst.

5. The sulfur-containing palladium-carbon catalyst as described in claim 4 , wherein the solvent is methanol, ethanol, acetone, methyl isobutyl ketone, isopropanol, tert-butanol, isoamyl ketone, octanone, water, or a mixture thereof.

6. The sulfur-containing palladium-carbon catalyst as described in claim 1 , wherein the sulfur-containing compound is methyl mercaptan, ethyl thiol, methyl thioether, ethyl thioether, diphenyl thioether, dimethyl disulfide, thiofuran, ammonium hydrosulfide, potassium hydrosulfide, or a mixture thereof.

7. A method for preparing a sulfur-containing palladium-carbon catalyst as described in claim 1 , comprising

loading palladium on an active carbon to obtain a palladium-carbon catalyst,

mixing the palladium-carbon catalyst with a solvent to obtain a slurry,

adding a sulfide to the slurry and treating the palladium-carbon catalyst at a predetermined temperature, and

removing liquid from the treated palladium carbon catalyst and drying to obtain the sulfur-containing palladium-carbon catalyst.

8. The method of claim 7 , wherein molar ratio of the sulfide added to the slurry to the palladium loaded on the catalyst is about 0.1:1 to 10:1.

9. The method of claim 8 , wherein the molar ratio of the sulfide added to the slurry to the palladium loaded on the catalyst is about 0.1:1 to 1:1.

10. The method of claim 7 , wherein the solvent is an alcohol, a ketone, water, or a mixture thereof.

11. The method of claim 10 , wherein the solvent is methanol, ethanol, acetone, methyl isobutyl ketone, isopropanol, tert-butanol, isoamyl ketone, octanone, water, or a mixture thereof.

12. The method of claim 7 , wherein a volume ratio of the palladium-carbon catalyst to the solvent to form the slurry is about 1:5 to 1:1000.

13. The method of claim 7 , wherein the active carbon has a granularity of about 50 to 1000 mesh.

14. The method of claim 13 , wherein the active carbon has a granularity of about 80 to 500 mesh.

15. The method of claim 7 , wherein the active carbon has a special surface area of about 600 to 1800 m 2 /g.

16. The method of claim 15 , wherein the active carbon has the special surface area of about 1000 to 1500 m 2 /g.

17. The method of claim 7 , wherein an amount of palladium that is loaded on the active carbon is about 0.5 to 10 wt % of the total weight of the catalyst.

18. The method of claim 17 , wherein the amount of loaded palladium is about 1 to 5 wt % of the total weight of the catalyst.

19. The method of claim 7 , wherein the predetermined temperature is about 20° C. to 100° C.

20. The method of claim 7 , wherein the palladium loaded on the catalyst is treated with the sulfide for more than 10 minutes.

21. The method of claim 7 , wherein the palladium is loaded on the active carbon by

dissolving the active carbon in a first solvent to form a first slurry,

adding a solution containing palladium ions to the first slurry and mixing thoroughly to form a mixture,

adjusting pH of the mixture to about 7.1 to 9 and filtering and washing to obtain a filter cake,

dissolving the filter cake in a second solvent to form a second slurry,

adding a reductive reagent to the second slurry to reduce the palladium ions, and

removing liquid from the reduced second slurry to obtain the palladium-loaded active carbon catalyst.

22. The method of claim 21 , wherein the reduction reagent is formaldehyde, methanol, formic acid, or an alkali metal salt of formic acid or hydrazine hydrate.

23. The method of claim 21 , wherein a molar ratio of the reduction reagent to the loaded palladium is about 2:1 to 200:1.

24. A method for making para-phenyl diamines comprising

reacting 4-ADPA and an aliphatic ketone in liquid phase hydrogenation in presence of the sulfur-containing palladium-carbon catalyst of claim 1 .

25. The method of claim 24 , wherein an amount of the loaded palladium on the sulfur-containing palladium-carbon catalyst is about 0.01 to 1 wt % of the 4-ADPA.

26. The method of claim 24 , wherein the 4-ADPA and the aliphatic ketone are reacted in a one-step procedure.

27. The method of claim 26 , wherein the reaction is conducted at about 90° C. to 240° C. and hydrogen gas pressure of about 1 to 5 MPa.

28. The method of claim 24 , wherein the 4-ADPA and the aliphatic ketone are reacted in a two-step procedure.

29. The method of claim 28 , wherein the 4-ADPA and the aliphatic ketone are reacted to form an intermediate at about 120° C. to 150° C., and the intermediate is reacted with hydrogen gas in a solvent in the presence of the sulfur-containing palladium-carbon catalyst.

30. The method of claim 29 , wherein the intermediate is hydrogenated at about 90° C. to 220° C. and hydrogen gas pressure of about 1 to 5 MPa.

31. The method of claim 24 , wherein a molar ratio of the 4-ADPA to the aliphatic ketone is about 1:2 to 1:10.