PROCESS FOR GENERATION OF HYDROGEN AND SYNGAS

• US 20140295518A1
• Filed: 09/02/2012
• Published: 10/02/2014
• Est. Priority Date: 09/30/2011
• Status: Abandoned Application

• Current Assignee: Council of Scientific & Industrial Research
• Original Assignee: Council of Scientific & Industrial Research
• Inventors: Rayalu, Sadhana Suresh, Chakrabarti, Tapan, Joshi, Meenal Vivek, Mangrulkar, Priti Ashok, Labhsetwar, Nitin Kumar, Yadav, Renu Mahendra Singh, Prabhu, Chandan, Wate, Satish Ramchandra
• Application Number:
  US14/129,270
• Publication Number:
  US 20140295518A1
• Time in Patent Office: Days
• US Class Current: 435/168
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: C01B 3/06 by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by electrolysis of water C25B1/04
• CPC Class Codes: C01B 32/40 Carbon monoxide
• CPC Class Codes: C01B 32/60 Preparation of carbonates or bicarbonates in general of percarbonates C01B15/10; of specific carbonates or bicarbonates according to the cation C01B-C01G
• CPC Class Codes: C12P 3/00 Preparation of elements or inorganic compounds except carbon dioxide recovery of carbon dioxides as by-products C12F3/02
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The present invention is related to a process for generation of hydrogen and syngas based on biomimetic carbonation and photocatalysis. A path breaking way has been developed for generation of solar fuels in specific hydrogen by coupling biomimetic carbonation with photocatalysis. Efforts are being made worldwide to mimic the reaction for fixation of anthropogenic CO2 into calcium carbonate using carbonic anhydrase (CA) as a biocatalyst. CA is being employed to accelerate the rate of hydration of CO2 to form carbonate ions and proton. Presently carbonate is being precipitated from aqueous solution as calcium carbonate given a suitable saturation of calcium and carbonate ions by addition of appropriate buffer. A major breakthrough in the area of generation of solar fuels like hydrogen has been achieved by coupling biomimetic carbonation with photocatalysis. This approach may prove to be a revolutionary technical advancement required for hydrogen economy demanding carbon neutral hydrogen production. Also the production of hydrogen in addition to carbonates as end products during biomimetic carbonation may make the process commercially viable to be adopted by industries emitting carbon dioxide. The carbonate rich stream has been photocatalytically reduced to formaldehyde. This breakthrough thus opens new horizons in the area of carbon sequestration by virtue of the fact that end product of carbon sequestration is not only environmentally benign product of calcite but it would lead to the generation of clean energy including hydrogen, methane and methanol. Maximum hydrogen evolution has been observed up to 101.14 μmoles/mg of, free CA, 156.8 μmoles/mg of immobilised CA and 101.14 μmoles/mg of CA 6684.5 μmoles/mg of stabilised CA using TiO2/Zn/Pt as photocatalyst. The problem of using Zn as a metal donor has been overcome by illuminating the system. Hydrogen evolution to the tune of 84 μmoles/mg of CA has been observed for system with Zn as metal donor in the presence of Pt as co-catalyst with illumination.

Claims

1. A process for generation of hydrogen and syngas by biomimetic carbonation and photocatalysis wherein the said process comprising steps of;

a) accelerating hydration rate of CO₂ in the presence of an enzyme by bubbling CO₂ (g) in to the water under pressure in the range of 2 bar to 4 bar for 45 min to 60 min followed by closing the vessel and adding an enzyme dissolved in tris buffer to obtain bicarbonates and hydrogen ions;

b) reducing the hydrogen ions as obtained in step (a) in the presence of a photocatalyst and/or metal donor and sacrificial donor singly or in combination with a co-catalyst under illumination or without illumination to obtain hydrogen.

c) reducing the bicarbonates from step (a) of claim 1 to carbon monoxide in the presence of photocatalyst and optionally using metal donor and sacrificial donor singly or in combination;

d) admixing the carbon monoxide as obtained in step (c) with hydrogen as obtained in step (b) to form syngas.

2. A process as claimed in claim 1, wherein enzyme used in step (a) is selected from the group consisting of carbonic anydrase, carbonic anydrase immobilized on chitosan beads, SEN CA or an analogue thereof.

3. A process as claimed in claim 1, wherein the concentration of enzyme is ranging from 1 to 5 mg/I of CO₂ saturated water.

4. A process as claimed in claim 1, wherein the photocatalyst used in step (b) and (c) is selected from the group consisting of titania, zinc oxide, zinc in the presence of light, nanoferrite, n-doped mesotitania, perovskite, mixed oxides, supported TiO₂ and carbon nanoparticle.

5. A process as claimed in claim 4, wherein the concentration of titania was varied from 1 to 65 mg/I of CO2 saturated water,

6. A process as claimed in claim 4, wherein the quantity of TiO₂ used in the reaction is in the range of 0.01 to 10 mol % of active species with respect to the substrate.

7. A process as claimed in claim 4, wherein the concentration of zinc oxide/zinc was varied from 10 to 65 mg/l of CO₂ saturated water

8. A process as claimed in claim 4, wherein the quantity of zinc oxide used in the reaction is in the range of 0.01 to 10 mol % of active species with respect to the substrate.

9. A process as claimed in claim 1, wherein the sacrificial donor used in step (b) and (c) is selected from the group consisting of ethanol and methanol.

10. A process as claimed in claim 1, wherein metal donor used in step (b) and (c) is selected from the group consisting of zinc, magnesium, copper, aluminum.

11. A process as claimed in claim 1, wherein co catalyst used in step (b) is selected from the group consisting of platinum, zinc, nickel, copper, manganese, magnesium, iron and tin.

12. A process as claimed in claim 1, wherein the source of illumination is selected from tungsten filament lamp and solar light.

13. A process as claimed in claim 1, wherein the photocatalyst used is recovered by filtration and is reused for several cycles with consistent activity.

14. A process as claimed in claim 1, wherein yield of hydrogen is in the range of 0.015-6684.57 μ

moles/4 h.

15. A process as claimed in claim 1, further comprising formation of formaldehyde along with CO.

16. A process as claimed in claim 5, wherein yield of formaldehyde is in the range of 0.0004-0.345 ppm.

17. A process as claimed in claim 1, wherein yield of hydrogen in syngas is in the range of 0.049-17.03.03 μ

moles/4 h.

18. A process as claimed in claim 1, wherein yield of CO in syngas is in the range of 0.0042-19.84 μ

moles/4 h.