A Process to Produce Hydrogen from Air and Water that also Produces Fertilizer as byproduct

A Process to Produce Hydrogen from Air and Water that also Produces Fertilizer as byproduct

Inventor & Author: Diji N J

Abstract

Hydrogen and ammonium nitrate are produced from water and air using concentrated solar energy or nuclear thermal waste energy in presence of catalyst. The only reactants required are cheap air (nitrogen) and water and some catalysts to improve the efficiency of the reaction. By-products (ammonium nitrate) of the said reaction are used in the production of fertilizers. The whole reaction system forms a complete environment friendly cycles or cycle that naturally exists; from water (H20) to H2 and O2 to again water by engine or fuel cell; Nitrogen to ammonium nitrate, that can be used in fertilizer production to plants to animals to then again to nitrogen to atmosphere by denitrifying bacteria. So the new concept is the most reliable and appropriate replacement of fossil fuel or any other system of fuel (from well to wheel). This process of making hydrogen would be more efficient than existing two step cycles since second step of recycling nitrogen will be done by nature itself. This process is not only environment friendly but also enhances environment by producing fertilizer for plant growth.

Introduction

I have developed a new concept to produce hydrogen using only air and water. This done by producing hydrogen and ammonium nitrate from water using some energy and catalyst; the concept is so unique and marvelous that it will change the way automobiles are driven. The only reactants required are cheap air (nitrogen) and water and some catalysts to improve the efficiency of the reaction. Byproducts (ammonium nitrate) of the said reaction are used in the production of fertilizers. These fertilizers are then used by plants and converted back into basic components like nitrogen to the air. And the hydrogen and oxygen from splitting water is used to power the prime mover of the automobile and converted back to water. So the whole process forms a complete cycle. So the new concept is the most reliable and appropriate replacement of fossil fuel or any other system of fuel (from well to wheel).

Electric Vehicle Disadvantages

Electric supply depends on Thermal power Stations. Losses in distribution of electricity and Charge / discharge cycle of battery. Houses use 5-30 hp per day; Vehicle needs 10-200 hp per hour; so more power stations are required. Electric cars shift harmful emission from cars to PowerStation. There is no reduction in actual effective Emissions. Electric vehicle is suitable for developed countries having surplus electricity. Not suitable for countries where power cuts are common.

Advantages of Hydrogen

Zero Emission, Safer>Hydrogen disperse into upper air quickly due to low density. More manufactures are developing hydrogen vehicles. Renewable

New Concept

Use air and water to produce hydrogen and ammonium nitrate using solar energy or nuclear/thermal PowerStation's waste energy. The reaction is as follows:

N2 + 3 H2O → NH4NO3 + H2

This would be a more sustainable way to produce hydrogen and ammonium nitrate. Ammonium nitrate is widely used in fertilizers and in explosives. The above reaction uses widely available and cheap; air (nitrogen) and water as reactants. Since ammonium nitrate is solid and hydrogen is gas separation of products will be very easy

Barriers

Major Barriers of project are Concentrated Solar Energy Nuclear / Thermal waste energy Capital Cost, Coupling Concentrated Solar Energy and Thermochemical cycles. Finding favorable conditions for Ammonium nitrate production. Partners of new project can be Fertilizer manufacturers, Ammonia manufacturers, Nitric acid manufacturers.

Existing Hydrogen Production methods

Direct Thermal Splitting of water; efficiency very low (1-3%)

Electrolysis; efficiency is less than 10%

High-temperature electrolysis; efficiency less than 40%

Thermal decomposition of water; efficiency is less than 50%

Photochemical splitting of water requires ultraviolet rays to work; doesn’t work on direct sunlight

Photo-biological water splitting efficiency is 7-10%

Following are the reasons why direct Thermal decomposition of water is not favored

Operation of the reactor for over 50 hours "on-sun" at 2600-2900 K nozzle surface temperature without failure of materials.

Dissociation of water and separation of hydrogen at 1 to 2 % overall efficiency (solar to hydrogen.

Cannot use nuclear PowerStation waste thermal energy since temperature required are very high.

New Concept Basic Process

N2 + 3 H2O → NH4NO3 + H2( ΔH = +360.3 kJ/mol)

Split di-nitrogen to nitrogen atoms using iron catalyst and then react nitrogen atom with water. Certain groups of iron atoms on surface of catalyst dissociate di-nitrogen into monatomic nitrogen. Ammonia can be used as a water splitting catalyst. Combine nitrogen and hydrogen to produce ammonia, part of which can be oxidized to nitric acid and combined with the remaining ammonia to produce the Ammonium nitrate. Some ammonia and nitric acid can be removed to sell separately.

Or monatomic nitrogen reacts with water to form NH3 and NOx, N2O and H2O can be reacted to form ammonium nitrate. Reactors may be free-boiling vessels, circulating systems, or pipe reactors. Nitric acid can be made by mixing nitrogen dioxide (NO2) with water, or Nitric acid can also be synthesized by oxidizing ammonia – nitric acid (HNO3). The acid-base reaction of ammonia with nitric acid gives a solution of ammonium nitrate:

HNO3(aq) + NH3(g) -> NH4NO3(aq)

A more direct process should be investigated like:

2N+H2O > N2O +H2 and then N2O + H2O > NH4NO3 (ammonium nitrate)

Essence of the new concept

The concept is simple; we use air and water to produce hydrogen and ammonium nitrate, the reaction is as follows:

N2 + 3 H2O → NH4NO3 + H2

This would be a more sustainable way to produce hydrogen and ammonium nitrate. Ammonium nitrate is widely used in fertilizers and in explosives. The above reaction uses widely available and cheap air (nitrogen) and water as reactants. Since ammonium nitrate is solid and hydrogen is gas separation of products will be very easy. The enthalpy of reaction would be:

N2 (0) + 3 H2O [(-241.8 )*3] → NH4NO3 (-365.1) + H2 (0)

Values in brackets ( H_f ) are enthalpy of formation. so enthalpy of above reaction will be

-365.1 - (-241.8 *3)= +360.3. This is more than what requires to produce hydrogen directly from water, that is around +241.8. but in the above reaction we get ammonium nitrate as byproduct which can be used in fertilizer and explosives. This ammonium nitrate will be converted back to nitrogen by plants>animals>secretion/death>denitrification bacteria. So there would be a complete nitrogen cycle. Water to hydrogen again to water by engine or fuel cell, so there will be a complete hydrogen cycle too. So the above reaction is worth trying as an alternative since we get ammonium nitrate as byproduct. Ammonium nitrate is normally produced using the acid-base reaction of ammonia with nitric acid; both these reactants are very costlier than nitrogen and water which is used in reaction proposed by me. So overall cost of producing both hydrogen and ammonium nitrate by the above reaction using air and water will be very low and will be sustainable due to the cycles (hydrogen and nitrogen cycles) described above.

Note: Covalent triple bond of N2is unstable than ionic bonds or even double or single bonds. Since unstable molecule has more internal energy than stable one it will release energy while changed to stable one. So the above concept is really feasible.

Advantage of concept

This concept is the most environmentally friendly renewable energy concept ever. Byproducts (ammonium nitrate) of this process used to produce hydrogen, is used to produce fertilizers. So this is the only H2 production technology that also helps grow plants.

Since this concept uses Only Air and water; it is renewable. User can get the profit of selling the by-products which can be used for production of fertilizers.

Since this reaction can be operated by the waste heat energy in nuclear and thermal reactors or concentrated solar energy. Thus it is renewable

This not only environment friendly but also enhances environment by producing fertilizer for plant growth

Benefits Of Concept

Since this concept uses Only Air and water; it is renewable. User can get the profit of selling the byproducts which can be used for production of fertilizers.

Benefit of concept to the environment

There are absolutely no harmful emissions from this process.

Byproduct of this reaction can be used in fertilizer production and these fertilizers can be used to cultivate crops or even forest.

The whole reaction system forms a complete environment friendly cycles or cycle that naturally exists ; from water (H20) to H2 and O2 to again water by engine or fuel cell. N2 to ammonium nitrate that can be used in fertilizer production to plants to animals to then again to N2 to atmosphere

Benefits to manufacturers

Since the process of making hydrogen is of zero emission and also produce byproducts that can be used to produce fertilizers. The Government and Public will appraise the manufactures or even promote or will subsidize the process.

Since the process is not only environmentally safe but also enhances plant growth, the environmental protection agencies and celebrities will promote the concept. This will increase brand equity of manufacturers.

Since the cost of H2 will be neutralized by fertilizer production the whole cost of running vehicle will be very low so costumers will be more satisfied. actual prices of ammonium nitrate are somewhere in between $800/ton and $46,000/ton depending on factors like subsidy to farmers and developed status of country.

Objective of project

Find a sustainable solution for today’s fuel crisis

Identify a cost competitive solar, nuclear/thermal waste energy-powered water splitting process for hydrogen production

Design and construct lab scale experiments for the major reaction sections of the cycle

Chemical reaction engineering for producing hydrogen and ammonium nitrate from nitrogen and water

Investigate process alternatives, materials, catalysts, diagnostics and favorable conditions

Approach

Approach is to do Experimental work (kinetics, thermodynamics, favorable conditions for ammonium nitrate & Hydrogen), Simulate process configuration and conditions, Process design and evaluation. Characterize process energy and stream flows, Calculation of energy/heat requirements, efficiency, Evaluation of process alternatives, uncertainties, System optimization, parameter studies, Define component sizes and quantities –costs. Thermodynamically make this reaction more favorable and side reactions less favorable. Increase pressure since ammonium nitrate is solid

Losses in existing water splitting cycle

Existing water splitting cycle produces useless by products. Recycling them requires lot of energy. For E.g.: in zinc oxide cycle

Water splitting

Zn + H2O -> ZnO+ H2 (ΔH = -62 kJ/mol@700 K)

Recycling zinc

ZnO->Zn + ½ O2 (ΔH = 557 kJ/mol@2300 K)

Huge amount of energy is required to recycle zinc. Most of energy is used to recycle zinc

In general two step cycle efficiency is very low since second step requires additional energy to recycle the reactants like iron oxide back to iron.

Losses in new water splitting cycle

In the new proposed water splitting cycle by-product is useful in fertilizer production

Water splitting

N2 + 3 H2O → NH4NO3 + H2( ΔH = +360.3 kJ/mol)

Recycling of nitrogen will be done by nature. Ammonium nitrate will be converted back to nitrogen by Plants>animals>secretion/death>denitrification bacteria. So new concept water splitting would be more efficient

Summary of new hydrogen production

Nitrogen is heated to 723K and passed over iron catalyst to form monatomic nitrogen. Monatomic nitrogen is used to split water in presence of ammonia or other catalyst. Nitrogen and hydrogen are combined to produce ammonia, part of which can be oxidized to nitric acid and combined with the remaining ammonia to produce the ammonium nitrate. The products are cooled below 430K to form solid ammonium nitrate and gaseous hydrogen. Or nitrogen and steam are heated to 723K and passed over iron catalyst to form ammonia and nitric acid

Following is the reaction where ammonia is used in water splitting mechanism

FSEC's metal sulfate – ammonia (MSO4-NH3) hybrid photo/thermochemical water splitting cycles are represented by the following reactions:

Where, M = Zn, Mg, Ca, Ba, Fe, Co, Ni, Mn, Cu.

About Ammonium Nitrate

Ammonium nitrate is commonly used in agriculture as a high-nitrogen fertilizer, and it has also been used as an oxidizing agent in explosives, including improvised explosive devices. It is the main component of ANFO, a very popular explosive. 9 million tons of ammonium nitrate is produced in US. Approximately 15 to 20 % of this amount was used for explosives and the balance for fertilizer. Ammonium nitrate decomposes into gases including oxygen when heated (non-explosive reaction).Ammonium nitrate decomposes in temperatures normally well above 200°C. actual prices of ammonium nitrate are somewhere in between $800/ton and $46,000/ton depending on factors like subsidy to farmers and developed status of country.

Challenges

Pure solid ammonium nitrate melts at 169°C. On further heating it decomposes by way of a complex set of reactions. Up to about 250°C it decomposes primarily into N2O and H2O. Above 300°C reactions producing N2, NO, NO2 etc., become significant. These reactions are exothermic and irreversible. Once the Ammonium nitrate has started to decompose, then a runaway reaction will normally occur as the heat of decomposition is very large. Ammonium nitrate evolves so much heat that this runaway reaction is normally impossible to stop.

Nitrogen Cycle

Plants cannot use nitrogen from air they obtain it from nitrates and ammonium salts in the soil. These nitrates taken up by plants are converted into amino acids which are building blocks of protein. These proteins are used by animal who feeds on plants. Nitrogen returns to soil by excretion or death or subsequent decay. This nitrogen are returned to air by denitrifying bacteria or again used by plants.

References:

Ammonium nitrate:

Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0070494398

Nitric Acid:

Paul, May (November 2007). "Nitric Acid". Retrieved 2009-05-28.

Ammonia:

Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.),

Watersplitting:

http://www.hydrogen.energy.gov/pdfs/review06/pd_10_weimer.pdf

http://www.hydrogen.energy.gov/pdfs/review05/pd28_weimer.pdf

http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&u=%2Fnetahtml%2FPTO%2Fsearch-adv.htm&r=0&p=1&f=S&l=50&Query=ttl%2F%22water+splitting%22%0D%0A&d=PTXT

Ammonia production:

Twygg, Martyn V. (1989). Catalyst Handbook (2nd Edition ed.). Oxford University Press. ISBN 1-874545-36-7.

Max Appl (2006). Ammonia, in Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a02_143.pub2.

Enriching the Earth: Fritz Haber, Carl Bosch, and the Transformation of World Food Production by Vaclav Smil (2001) ISBN 0-262-19449-X

Iron as catalyst to split Nitrogen to monatomic Nitrogen:

G. Ertl, S. B. Lee and M. Weiss (1982). "Kinetics of nitrogen adsorption on Fe(111)". Surface Science 114 (2-3): 515–526. doi:10.1016/0039-6028(82)90702-6.

Fundamentals of Chemical Reaction Engineering Mark E. Davis, Robert J. Davis

Nitrogen Cycle:

Steven B. Carroll; Steven D. Salt (2004). Ecology for gardeners. Timber Press.. ISBN 9780881926118.

Chapin, S.F. III, Matson, P.A., Mooney H.A. 2002. Principles of Terrestrial Ecosystem Ecology. Springer, New York 2002 ISBN 0387954430

Inventor : Diji N J

Address: Nedunghayil house

Vennala P.O.

Ernakulam

Kerala

India

Phone: +91-04843929730

Mobile: +91-7736419388

Email: delvezone@hotmail.com

© Diji N J and https://sites.google.com/site/h2fromairandwater/, 2009-2017. Unauthorized use and/or duplication of this material without express and written permission from this site’s author and/or owner is strictly prohibited. Excerpts and links may be used, provided that full and clear credit is given to Diji N J and https://sites.google.com/site/h2fromairandwater/ with appropriate and specific direction to the original content.