XYLENE POWER LTD.

ELECTROLYTIC HYDROGEN

By Charles Rhodes, P. Eng., Ph.D.

HYDROGEN HYPE VERSUS REALITY:
Paul Martin discusses "Hydrogen Hype Versus Reality", with emphasis that hydrogen is primarily a useful chemical rather than a fuel.
 

ELECTROLYSIS OF WATER:
Reference: Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments

Reference: Major Reference
 

EXTRACTION OF DEUTERIUM AND PRODUCTION OF HEAVY WATER:
Heavy water (D2O) is needed as both a moderator and a coolant in CANDU reactors. CANDU reactors are needed for efficient production of start fuel for Fast Neutron Reactors.

Electrolysis of natural water forms a mixture of H2, HD and D2 gas molecules. H2 is naturally 6420X as abundant as HD. These molecule types can be separated either by gaseous diffusion or by liquification followed by evaporation. The H2 can be used to make ammonia. The D2 can be combined with O2 to make heavy water. The HD can be combined with F to make HF and DF. These two molecular types can again be separated by gaseous diffusion or by evaportion. The DF can be reformed to give D2. Combining the D2 with O2 again yields D2O.

The economics of this heavy water production process are driven by the markets for green H2 gas and HF gas. If there is no demand for green H2 gas a different heavy water production technique will likely be more economic.
 

TRANSPORT OF HYDROGEN:
By repurposing the existing natural gas distribution piping network electrolytic hydrogen gas can be efficiently stored and redistributed. During the winter the waste heat from the electrolysis process can be used for comfort heating. Hydrogen will be required for meeting peak winter heating loads, for powering heavy duty vehicles and for converting biomass into high energy density aircraft fuel.

Hydrogen can be stored and transported for meeting the peak winter heating load in rural areas by chemically combining compressed hydrogen gas with liquid toluene to form liquid methyl cyclohexane, which is a stable transportable and storable liquid at normal temperatures and atmospheric pressure. At the thermal load the hydrogen can be extracted from the methyl cyclohexane, allowing recycling of the toluene.

An update on Chiyoda Corp's proprietary system using CMH (methyl cyclohexane) as an H2 carrier. At the point of use, the MCH is dehydrogenated to form toluene and 3 molecules of H2. The toluene is shipped back to the site where H2 is produced from water electrolysis using renewable electricity or similar.

Part of the secret sauce is the catalysts that operate under mild conditions without forming excessive amounts of coke or other byproducts. The MCH carries 6% removable H2. So 94% of the MCH mass returns as toluene to the hydrogenation site. This seems like a large amount of material to move around that is simply a convenient though flammable carrier. Never the less, the Chiyoda folks are pressing on. The news article says little of use about the catalysts except that getting the Pt particles on the catalyst support to sub nanometer size improved is function greatly. That is expected. The problem historically is keeping the Pt particles from skating around and agglomerating into larger particles with less surface and less activity.

Chiyoda FP Hydrogen Energy

Demo plant promo page. Where does the missing product go in each conversion cycle? There will be emissions.

Chiyoda Corp

For marine fuel applications anhydrous ammonia (NH3) is a practical energy dense means of storing hydrogen as a liquid. However, anhydrous ammonia is too dangerous for general consumer use and needs the immediate proximity of large amounts of water to safely absorb even small leaks.
 

APPLICATION OF ELECTROLYTIC HYDROGEN:
Use of off-peak or otherwise constrained non-fossil fuel electricity for production of electrolytic hydrogen is critical for reduction of overall CO2 emissions to the atmosphere and for electricity system power and voltage stabilization in the absence of fossil fuel generation. A primary application for electrolytic hydrogen is for conversion of biomass into methanol and then upgrading methanol into synthetic gasoline. A seconday application for electrolytic hydrogen is for production of ammonia and ammonia based fertilizers. In certain situations it makes engineering sense to use electrolytic hydrogen as a wind power energy transport medium or as a vehicle fuel. In order to financially enable use of electrolytic hydrogen the purchase price of an off-peak electrcal kWh must be small compared to the purchase price of an on-peak electrical kWh. As of November 2016 stupid Ontario government policy is preventing constructive use of surplus non-fossil electrical kWh for production of electrolytic hydrogen in Ontario. Any fix to this governmental problem involves apportioning the Global Adjustment over kW instead of over kWh.

A major application of hydrogen is for reducing iron oxide to iron without releasing CO2. This process is described at:
Reduction of Iron Oxides With Hydrogen - A Review
and at
Assesment of Hydrogen Direct Reduction for Fossil-Free Steelmaking

This web page examines the production of hydrogen gas by electrolysis of water, with no emission of CO2 to the atmosphere and use of electrolytic hydrogen for limited period energy storage. A technology limiting issue with electrolysis equipment is use of platinum at the positive electrode.
 

2018 HYDROGEN CONFERENCE PRESENTATIONS:
Mississauga 2018 Hydrogen Conference Presentations
 

ELECTROLYSIS OF WATER:
Electrolysis of water yields three products, hydrogen gas, oxygen gas and heat. This web page relies on data published by Hydrogenics with respect to the practically realizable electrolysis efficiency.

The company Hydrogenics manufactures a product known as HySTAT type V which electrolyzes water to form hydrogen gas. Hydrogenics claims that when its equipment is operated at full design capacity the practical conversion ratio is in the range 4.9 kWh / Nm^3 to 5.2 kWh / Nm^3 of hydrogen at a pressure of 10 barg. For unit comparison, according to Hydrogenics:
1 Nm^3 = 38 SCF.
Volumetrically:
1 m^3 = [(1 m / (.0254 m / inch)) X (1 foot / 12 inch)]^3
= 35.315 feet^3,
so the absolute temperatures at which a Nm^3 and a SCF are defined are different. It appears that hydrogenics is defining a Nm^3 at 0 degrees C and a standard cubic foot (SCF) at 21 degrees C.

Thus the hydrogen production rate is in the range:
(1 Nm^3 / 5.2 kWh) X (1000 Nlit / Nm^3) X (1 mole / 22.4 lit) X (2 gm / mole) X (1 kg / 1000 gm)
= 0.01717 kg / kWh
to
(1 Nm^3 / 4.9 kWh) X (1000 Nlit / Nm^3) X (1 mole / 22.4 lit) X (2 gm / mole) X (1 kg / 1000 gm)
= .01822 kg / kWh

The required input electrical energy per hydrogen molecule formed is:
(1 Wh / 0.01717 g ) X (3600 s / h) X (2 g / 6.023 X 10^23 molecules) X (1 j / w-s) X (1 eV / 1.602 X 10^-19 j) = 4.34597 eV / hydrogen (H2) molecule

One way of producing liquid methanol (CH3OH) is via the chemical reaction:
CO + 2 H2 = CH3OH

One litre of methanol at room temperature has a mass of about 0.7866 kg. The mass of contained hydrogen is:
(4 / 32) X 0.7866 kg = 0.098325 kg

The electical energy required to separate that hydrogen from water using a Hydrogenics electrolyzer is:
0.098325 kg X 1 kWh / 0.01717 kg = 5.726558 kWh

If the required electrical energy can be purchased at $0.055 / kWh the electricity cost of the hydrogen in the litre of methanol is:
5.726558 kWh X $0.055 / kWh = $.31496

Clearly the electrical energy cost per kWh must be very low and/or the waste heat from the electrolysis process must have value for displacing purchased heating fuel in order for production of methanol from electrolytic hydrogen to make economic sense.
 

HYDROGEN GAS ENERGY STORAGE:
Hydrogen can potentially be stored in deep underground salt caves. When the walls of these caves are sprayed with water they form a seal that is sufficient for storage of natural gas and will likely also be acceptable for storing hydrogen gas.

Along certain geographically favorable corridors it may make sense to use large diameter high pressure steel pipelines filled with hydrogen to both store and transport energy. The issue is that locations favorable for wind energy generation tend to be along sea coasts. Canada has one of the longest sea coasts in the world. However, much of the Canadian population does not live near the sea coast. Hence moving wind energy from locations where it is economic to generate to major population centers requires long energy transmission corridors. If the energy is transmitted via a high voltage electric transmission line the energy losses are low but the transmission line provides almost no energy storage. If the energy is transmitted via hydrogen gas in a pipeline the energy losses at each end of the circuit are relatively high but the pipe itself provides energy storage that is essential to give value to wind generated energy. A further advantage of this strategy is that part of the hydrogen can be directly used to displace natural gas in residential heating.

The success of the hydrogen gas energy transmission scheme rests on the existence of sufficient seasonal hydraulic energy storage elsewhere in the electricity system to balance out seasonality in the wind generation. In British Columbia and Washington State there are immense amounts of seasonal hydraulic energy storage on the Columbia and Peace Rivers. There is favorable wind generation along the south and west coasts of Alaska. There are existing energy transmission corridors to Prince Rupert and to Kitimat. Thus if the governments of Alaska, British Columbia and Washington State act together and resolve the necessary treaty issues there is potential for wind generation to play a major role in the Pacific North West.

The situation for wind generation in Ontario is not nearly so rosy. In Northern Ontario close to Hudson's Bay and James Bay there is good natural wind generation. A hydrogen pipeline could be built from northern Ontario to southern Ontario. However, Ontario is missing a critical ingrediant which is seasonal hydraulic energy storage to balance seasonality in wind generation. While access to some of Quebec's hydraulic energy storage might be achieved via a transmission intertie, the costs of that intertie are very high and the amount of seasonal hydraulic energy storage that Quebec might provide is not sufficient to meet Ontario's projected requirements as existing nuclear reactors reach the ends of their working lives.

To understand the importance of seasonal hydraulic energy storage in this matter it is illuminating to consider the amount of energy that can be stored in a practical large diameter high pressure steel pipeline. The technology of such pipelines is highly developed because large diameter high pressure steel pipelines are currently used for interprovincial and interstate transmission of oil and natural gas.
 

SPERA HYDROGEN:
The Chiyoda Chemical Corporation of Japan has a new process called Spera Hydrogen that may revolutionize the use of hydrogen storage and marine and railway transport.

The process is basically:
3 H2(gas) + C7 H8 + 205 kJ / mole = C7 H14

This is a reversible chemical reaction where C7 H8 (toluene) and
C7 H14 (methyl cyclohexane)
are both easily manageable liquids at room temperature and pressure.

By comparison the enthalpy of formation of water is -285.8 kJ / mole. Hence formation of 3 H2O molecules after storage in the above reaction releases:
3 X -285.8 kJ / mole = 857.4 kJ / mole methyl cyclohexane.
Producing the hydrogen using electrolysis operating at 60% efficiency requires:
(3 X 285.8 KJ) / 0.6 = 1429 kJ / mole of methyl cyclohexane. Joining the toluene and the hydrogen requires at least an additional 205 kJ / mole of methyl cyclohexane. Thus from an electricity to hydrogen thermal energy storage perspective the overall process efficiency is at best about:
(857.4 kJ) / (1429 kJ + 205 kJ) = 0.5247 = 52.47%.

However, if the electrolysis and the hydrogen binding to the toluene can be performed on the same site so that the waste heat from the electrolysis is used to supply the 205 kJ / mole required to bind the hydrogen to the toluene then the process efficiency rises to about 60%.

The overall process efficiency further improves if the heat liberated during the process of extracting hydrogen from methyl cyclohexane can be usefully used to displace other purchased fuel.

Chiyoda is currently attempting to protect its intellectual property relating to this process. I suspect that the Japanese Fuel Cell Vehicle (FCV) manufacturers have been aware that this process was under development and have made long term market plans accordingly.

Chiyoda is currently attempting to build equipment based on this process to displace liquified natural gas in international shipping. However, this Spera Hydrogen process also has major potential implications to the Integrated Zero Emission (INZEM) energy plan. The Spera Hydrogen process might be less expensive to implement than compressed hydrogen gas storage for urban customers and almost certainly will be less expensive than compressed hydrogen storage as a means of providing peak winter heating to rural customers who have no access to piped natural gas.

At this time I do not know the complexity and required operating temperatures of either the hydrogenation equipment or the hydrogen gas recovery equipment. The toluene is completely recycled.

Clearly this process increases the energy loss overhead in using hydrogen for energy storage. However, this process appears attractive as a heavy vehicle fuel and as a means of storing rural peak heating fuel instead of using 10,000 psi compressed hydrogen tanks.

The difference in chemical energy density between the methyl cyclohexane and the toluene is not sufficient to use this process for fueling long range aircraft.
 

HYDROGEN GAS SAFETY:
In a confined space hydrogen gas is quite dangerous because it will naturally rise in air and form an explosive air-hydrogen mixture at ceiling level. However, in outdoor locations hydrogen is much less dangerous because it will naturally rise in the atmosphere rather than pooling near ground level.

A major issue in using steel pipelines for containing hydrogen is that the range of air-hydrogen volumetric ratio mixtures over which explosive combustion occurs is much wider than for methane. The resulting safety issues require large pipeline design safety margins. A pipeline may have to be completely evacuated and/or filled with pure nitrogen prior to filling it with hydrogen. Thus the pipeline and its instrumentation, in addition to being rated for positive pressure must also be rated for a negative pressure. Also the hydrogen temperature everywhere in the system, particularly near pipeline compressor discharge ports, must be kept low to avoid hydrogen induced pipe cracking. The hydrogen (H2) molecule is small compared to pipeline metal molecules, so hydrogen will slowly diffuse into pipeline metals, particularly along grain boundaries. The rate of hydrogen diffusion into the metal increases as the temperature increases. The effect of the intersticial hydrogen is to increase the propensity for stress related cracking. It may be possible to minimize this hydrogen cracking through use of a suitable internal pipe coating.
 

HYDROGEN GAS CHEMICAL ENERGY STORAGE IN A PIPE:
Define:
Ec = hydrogen chemical energy stored in pipeline
Ee = electrical energy recoverable from pipeline
K = hydrogen chemical energy per mole
P = absolute pressure in pipeline
Po = atmospheric pressure
V = contained gas volume of pipeline
Vs = steel volume in pipeline
S = hoop stress in pipeline wall
W = pipeline wall thickness
R = pipe inside radius
L = length of pipeline
To = freezing point of water = 273.15 degrees K
T = operating gas temperature in pipeline in degrees K
Rho = density of pipe steel
Ms = mass of pipe steel

Ec = K (number of moles of H2 in pipeline)
= K (contained volume of pipeline) X (number of moles per unit volume)
= K (contained volume of pipeline) X (number of moles per unit volume at pressure Po, temperature To ) X (P / Po) X (To / T)

However:
V = Pi R^2 L

From ideal gas theory:
(number of moles per unit volume at pressure Po, temperature To ) = 1 mole / 22.4 lit
= 1 mole / (22.4 X 10^-3 m^3)
= 44.643 moles / m^3

Hence:
Ec = K (contained volume of pipeline) X (number of moles per unit volume at pressure Po, temperature To) X (P / Po) X (To / T)
= K (Pi R^2 L) X (44.643 moles / m^3) X (P / Po) X (To / T)

The pipeline operating pressure P expressed in terms of wall hoop stress S is given by:
P 2 R L = 2 W S L
or
P = (2 W S L) / (2 R L)
= W S / R

Thus:
Ec = K (Pi R^2 L) X (44.643 moles / m^3) X (P / Po) X (To / T)
= K (Pi R^2 L) X (44.643 moles / m^3) X (W S / R Po) X (To / T)
= K S (Pi R W L) X (44.643 moles / m^3) X (1 / Po) X (To / T)

The steel volume Vs in the pipeline is given by:
Vs = 2 Pi R W L

Hence:
Ec = K (S / Po) (Pi R W L) X (44.643 moles / m^3) X (To / T)
= K (S / Po) (Vs / 2) X (44.643 moles / m^3) X (To / T)

However:
Vs Rho = Ms
or
Vs = Ms / Rho

Thus:
Ec = K (S / Po) (Vs / 2) X (44.643 moles / m^3) X (To / T)
= K (S / Po) (Ms / 2 Rho) X (44.643 moles / m^3) X (To / T)

Note that the stored chemical energy is directly proportional to the volume of steel or mass of steel in the pipeline.
 

RECOVERABLE ELECTRICAL ENERGY:
If we assume that the chemical energy in hydrogen gas is to be converted into electrical energy via a combined cycle gas turbine (CCGT) or a fuel cell at about a 50% recovery efficiency, then:
Ee = Ec / 2
giving:
Ee = K (S / Po) (Ms / 4 Rho) X (44.643 moles / m^3) X (To / T)

The Gibbs free energy for converting H2 gas to H2O vapor is:
K = 228.61 kJ / mole

An important parameter for energy storage evaluation purposes is:
Ee / Ms = (S / Po)(K / 4 Rho) X (44.643 moles / m^3) X (To / T)
which gives the mass of pipe steel necessary to store a unit of recoverable electrical energy.

Such a pipeline would likely be made of high strength steel with a specified minimum yield stress (SMYS) of 52,000 psi and for safety reasons would likely be operated at a maximum wall hoop stress of:
S = 52,000 psi / 3
= 17,333 psi

Atmospheric pressure Po is:
Po = 14.7 pounds / inch^2
giving:
(S / Po) = 17,333 psi / 14.7 psi
= 1179.1

The density of iron is:
Rho = 7850 kg / m^3

The typical contained gas temperature is 15 degrees C = 288.15 degrees k, giving: (To / T) = (273.15 / 288.15)
= 0.9479

THUS: Ee / Ms = (S / Po) (K / 4 Rho) X (44.643 moles / m^3) X (To / T)
= (1179.1) [(228.61 kJ / mole) / (4 X 7850 kg / m^3)] X (44.643 moles / m^3) X (0.9479)
= (1179.1) [(228.61 kJ) / (4 X 7850 kg)] X (44.643) X (0.9479)
= 363.27 kJ / kg

In terms of kWh: 1 kWh = 1 kJ / s X 3600 s
or
1 kJ = 1 kWh / 3600

Hence: Ee / Ms = 363.27 kJ / kg X (1 kWh / 3600 kJ)
= 0.1009 kWh / kg

Thus one tonne of pipe steel can safely store:
1000 kg X 0.1001 kWh / kg = 100.1 kWh.

In Ontario the electricity requirement in the summer is about 2 kW / person. Hence if there was one tonne of hydrogen containing pipe steel for every one of the 13,500,000 men, woman and children in the province of Ontario the system could store sufficient electrical energy for about
(1 tonne / person X 100.1 kWh / tonne) / (2 kW / person) = 50 hours.
That is nowhere near the 250 hour length of the province wide low wind periods that occur during the summer in Ontario.

The fundamental problem that Ontario faces is seasonal wind energy and almost no seasonal hydraulic energy storage. That combination makes nuclear reactors and some hydraulic generation the only sources of firm non-fossil electrical energy.

Another issue that should be considered is the number of tonnes of CO2 which are emitted during production, transport, field welding and burial of large amounts of steel pipe.
 

LIQUID HYDROGEN:
An alternative means of storing energy with hydrogen is liquid hydrogen. In 1969 rocket engines powered by liquid hydrogen took men to the moon, so liquid hydrogen is a proven large scale energy technology. One of the issues with liquid hydrogen is that the storage tanks must be very large so that their surface area to volume ratio is small, to minimize storage losses via heat conduction through the tank walls which causes unintended evaporation of the liquid hydrogen. Due to the required storage tank sizes liquid hydrogen is not viable for propelling private cars but might be viable for propelling railway trains. The outstanding issue is whether liquified hydrogen can financially compete with the compressed hydrogen and Spera Hydrogen processes.
 

This web page last updated October 15, 2024.