Process for the production of hydrogen

• US 7,022,306 B1
• Filed: 03/21/2003
• Issued: 04/04/2006
• Est. Priority Date: 03/21/2003
• Status: Active Grant

• Current Assignee: UOP Llc (Honeywell International Inc.)
• Original Assignee: UOP Llc (Honeywell International Inc.)
• Inventors: Vanden Bussche, Kurt M., Nemeth, Laszlo T., Oroskar, Anil R., Rayner, Christine M.
• Primary Examiner(s): DUNN, COLLEEN P
• Application Number:
  US10/395,319
• Time in Patent Office: 1,110 Days
• Field of Search: 252/373, 423/648.1, 423/658.2
• US Class Current: 423/648.1
• CPC Class Codes: C01B 13/0214 Hydrogen peroxide
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0244 the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/044 Selective oxidation of carbon monoxide
• CPC Class Codes: C01B 2203/0838 by heat exchange with exothermic reactions, other than by combustion of fuel
• CPC Class Codes: C01B 2203/0844 the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
• CPC Class Codes: C01B 2203/0866 by combination of different heating methods
• CPC Class Codes: C01B 2203/1229 Ethanol
• CPC Class Codes: C01B 2203/1288 Evaporation of one or more of the different feed components
• CPC Class Codes: C01B 3/323 Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents

Abstract

A process and apparatus are disclosed for the generation of hydrogen from hydrogen rich compounds. The process uses hydrogen peroxide as an oxidizer with a hydrogen rich compound forming a mixture such that when the mixture is exposed to a catalyst forming a hydrogen rich gas.

Claims

1. A process for the generation of an H₂ containing gas comprising contacting a liquid organic compound and a liquid oxidizer in the presence of an initiator at ambient pressure to produce the H₂ containing gas.

2. The process of claim 1 wherein the initiator is selected from the group consisting of catalysts, chemical initiators and heat.

3. The process of claim 1 wherein the organic compound is an oxygenate.

4. The process of claim 1 wherein the oxidizer is selected from the group consisting of hydrogen peroxide, organic peroxides, hydroperoxides, and mixtures thereof.

5. The process of claim 4 wherein the oxidizer is hydrogen peroxide.

6. The process of claim 3 wherein the oxygenate is selected from the group consisting of alcohols, diols, triols, ethers, ketones, diketones, esters, sugars, and mixtures thereof.

7. The process of claim 6 wherein the oxygenate is selected from the group consisting of alcohols having 12 or fewer carbons, ketones having 12 or fewer carbons, esters having 12 or fewer carbons, diols having 12 or fewer carbons, triols having 12 or fewer carbons, ethers having 12 or fewer carbons, organic acids having 12 or fewer carbons, sugars having 12 carbons or less, and mixtures thereof.

8. The process of claim 7 wherein the oxygenate is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, dimethylether, diethylether, isopropylether, methyl tert-butyl ether, methyl tert-amyl ether, glucose, sorbitol, and mixtures thereof.

9. The process of claim 8 wherein the oxygenate is methanol.

10. The process of claim 8 wherein the oxygenate is ethanol.

11. The process of claim 2 wherein the catalyst comprises a metal selected from the group consisting of Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and mixtures thereof.

12. The process of claim 11 wherein the metal is dispersed on a support.

13. The process of claim 12 wherein the support is an inorganic oxide selected from the group consisting of silicas, aluminas, titania, zirconia, yttria, carbon, silicon carbide, diatomaceous earth, clay, molecular sieves, and mixtures thereof.

14. The process of claim 11 wherein the catalyst comprises a metal selected from the group consisting of Mn, Fe, V, Pt, Pd, Rh, Re, Os, Ru, Ir, Co, Cu, Ni, Mo, Au, Ag and mixtures thereof.

15. The process of claim 1 wherein the oxidizer is an aqueous solution comprising hydrogen peroxide concentration between about 10 weight percent and about 90 weight percent.

16. The process of claim 1 wherein the oxygenate and oxidizer are mixed in a mass ratio between about 0.25 and about 9.75.

17. The process of claim 16 wherein the oxygenate and hydrogen peroxide are mixed in a mass ratio between about 0.7 and about 3.

18. The process of claim 1 wherein the gas having a hydrogen content greater than 5 weight percent.

19. The process of claim 1 where the oxidizer further comprises a diluent.

20. The process of claim 2 wherein the catalyst comprises a decomposition catalyst for oxidizer decomposition and a reforming catalyst for reforming of the oxygenate.

21. The process of claim 20 wherein the decomposition and reforming catalysts are in separate catalyst beds.

22. The process of claim 20 wherein the decomposition and reforming catalysts comprise a mixture in a catalyst bed.

23. The process of claim 20 further comprising a watergas shift catalyst.

24. The process of claim 23 further comprising an oxidation catalyst for the conversion of CO to CO₂.

25. The process of claim 20 wherein the decomposition catalyst comprises a transition metal selected from the group consisting of V, Fe, Co, Ru, Cu, Ni, Mn, Mo, Pt, Au, Ag, Pd, Rh, Re, Os, Ir, and mixtures thereof.

26. The process of claim 25 wherein the decomposition catalyst comprises MnO₂.

27. The process of claim 20 wherein the reforming catalyst comprises a transition metal selected from the group consisting of Cr, Au, Zn, Cu, Pt, Ag, Pd, Rh, Re, Os, Ru, Ir, and mixtures thereof.

28. The process of claim 27 wherein the catalyst comprises ZnO.

29. The process of claim 20 wherein the catalyst mixture comprises a ratio of the decomposition catalyst to the reforming catalyst in the range from about 0.1 to about 10.0.

30. The process of claim 23 wherein the watergas shift catalyst comprises at least one metal selected from the group consisting of Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and mixtures thereof.

31. The process of claim 30 wherein the watergas shift catalyst comprises Cu and ZnO.

32. The process of claim 24 wherein the oxidation catalyst comprises a metal selected from the group consisting of Ru, Pt, Au, and mixtures thereof.

33. The process of claim 1 further comprising the step of purifying the hydrogen containing gas.

34. The process of claim 1 further comprising mixing the oxygenate and oxidizer prior to the step of mixing the mixture of oxygenate and oxidizer with an initiator.

35. A process for the production of hydrogen comprising the steps of:

mixing an alcohol and hydrogen peroxide in the presence of a decomposition catalyst at ambient pressure, wherein a gaseous product comprising hydrogen and carbon monoxide is produced and the decomposition catalyst is at least one metal selected from the group consisting of Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Sn, and mixtures thereof; and

passing the product gas over a reforming catalyst, wherein a product comprising hydrogen and carbon dioxide is produced and the reforming catalyst is at least one metal selected from the group consisting of Cr, Au, Zn, Cu, Pt, Ag, Pd, Rh, Re, Os, Ru, Ir, and mixtures thereof.

36. The process of claim 35 wherein the alcohol is selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, butanol, and mixtures thereof.

37. The process of claim 35 further comprising mixing oxygen with the product in the presence of a an oxidizing catalyst for selective oxidation of the carbon monoxide, wherein the catalyst is selected from the group consisting of Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Ru, Au, Hg, and mixtures thereof.

38. The process of claim 35 further comprising the step of premixing the alcohol and hydrogen peroxide prior to mixing with the first catalyst.