Sustainable Energy

Linfeng Zhang
 Chapter 10 Hydrogen production

• Hydrogen is an energy carrier and not a source of energy.

• It holds great promise as fuel for land and sea vehicles,
especially when used in high efficiency fuel cells.
• Fuel for large air- and spacecraft owing to its high
energy-to-weight ratio when in cryogenic form.
• Industrial and domestic fuel for generation of heat and
electricity.
• A means for transporting large quantities of energy over
long distances.
 The advantages of hydrogen
1. Low pollution
Hydrogen burns cleanly, producing only water. Pollution
may be associated with some hydrogen production
processes.
2. Controllability
At ambient temperatures, hydrogen reacts extremely
slowly with oxygen. Catalysts permit adjusting the
reaction speed over a large range from very low-
temperature flames to intense ones.
3. Safety
o Being the lightest of all gases, it quickly rises and disperses,
while liquid fuels form pools that spread the fire.
o The smallness of the hydrogen molecule causes this gas to
leak easily through tiny cracks and holes, making it difficult
to accumulate in explosive concentrations.
o At 1 atmosphere, the auto-ignition temperature for
hydrogen is about 580 C, whereas that for gasoline is as low
as 260 C.
o Hydrogen/air mixtures with less than 4.1% fuel (in volume)
will not catch fire.
o Hydrogen is totally nontoxic and can be inhaled in high
concentration.
 Processes for the production of
hydrogen
1. chemical
2. electrolytic
3. thermolytic
4. Photolytic
5. biological
 10.2 Chemical Production of Hydrogen

• Hydrogen was produced by passing steam

over red-hot iron filings. The iron combines
with oxygen in the water, liberating hydrogen:

ferrous ferric oxide

 10.2.2 Metal–Water Hydrogen Production

• Small amounts of hydrogen are produced even now by

making aluminum chips react with potassium hydroxide(KOH).
 10.2.3 Large-scale Hydrogen Production

• The bulk of the hydrogen produced in the world is

made from fossil fuels.
• Hydrocarbons and alcohols, among other substances,
can yield hydrogen when submitted to partial
oxidation, steam reforming, or thermal
decomposition.
 Viscosity and density

o Partial oxidation is preferred for a heavy

hydrocarbon.
o Steam reforming is more convenient for
natural gas and light hydrocarbon.
o Thermal decomposition is limited for co-
product of carbon black.
 a. Partial Oxidation

• Partial oxidation is accomplished by reacting a

fuel with a restricted amount of oxygen

• for the case of methane,

 b. Steam Reforming

• carbon-steam reaction

• methane
 c. Thermal Decomposition

Methanol

Ethanol

Methane
CH4 → 2H2 + C
Hydrogen Production Plants (steam reforming)
 Desulfurization
• Sulfur tends to poison the catalysts required in some of the
subsequent steps
• If the feedstock is in gaseous form, sulfur can be removed by
spraying it with a calcium-based slurry.

CaCO3(s) + SO2(g) → CaSO3(s) + CO2(g)

 Shift Reaction

• The shift reaction promotes the combination of carbon

monoxide with water.

• For fuel cells, the shift reaction is used to (nearly) eliminate all
the CO.
 Steam reforming for natural gas

+)

Why endothermic reaction?

• Methane burns into liquid water with 890 MJ/kmole heat.

• The combustion heat of 4 kmoles of hydrogen, into liquid
water, is 4 × 286 = 1144 MJ.

• The products have more energy than the reactants—the

reaction is endothermic.
• In fixed installations, this heat usually comes from the
combustion of hydrocarbons:

• In the more compact automotive and residential uses, the

heat may conveniently come from the combustion of part of
the hydrogen in the reformate.
 Methanation
• The transformation of syngas into methane, part of the
process of transforming any fossil fuel into the more valuable
“natural gas,” is called methanation.
• eliminating most of the CO impurity

• This is the reverse of steam reforming of methane

• Carbon dioxide can also be transformed into methane

 Endothermic or exothermic?

Thermodynamic data
Example: exothermic or endothermic?
Methanol-to-hydrogen converter
Step 1
(1)If the methanol were evaporated and burned
heat to be generated: 676.34MJ per kmole of water vapor.

(2) If the alcohol is first decomposed and then burned

2 kilomoles of hydrogen, 2 × 241.82 = 483.64 MJ

1kilomole of carbon monoxide, 282.99 MJ

total: 766.63 MJ.

(3) This is an endothermic decomposition

heat input: 766.63 − 676.34 = 90.29MJ per kmole of methanol
 To get rid of CO
Step 2

• CO releases 282.99 MJ/kmol

• Hydrogen releases 241.8.
• The reaction is exothermic
282.99− 241.8 = 41.19MJ of heat per kmole of
CO.
 The overall reaction
Step 3

• Endothermic reaction
90.29 − 41.19 = 49.00MJ /kmole of methanol
 Step 4 Energy budget
• For each kmole of methanol, 1 kmole of water
is required.
• The system works by taking in the correct
alcohol/water mixture, evaporating it, and
heating it to the reaction temperature,
between 200 and 600 oC.
• ΔHVAP is the amount of energy required to
vaporize the fuel/water mixture.
• ΔHCP is the energy required to raise the
temperature of the vaporized fuel/water to
the operating temperature.
• ΔHREACT is 49MJ per kmole of methanol.

• ΔHLOSS can be minimized by good insulation. It

is negligible in this example.
 Where is this 150MJ from?
1. This energy can be obtained by burning 150/242 = 0.62
kmole of hydrogen.

2. 3 kmoles of hydrogen are produced, about 20% must be

burned in the burner.

The fuel processor converts 676MJ of methanol into 575MJ

of hydrogen, a ratio of 85%.
 Compact Fuel Processors

Fuel
water

Input: fuels (methanol, methane, etc.), water, air

Output: H2, CO2
No external heat source needed
FuelCell Energy
10.3 Electrolytic Hydrogen

• A method of using a direct electric

current (DC) to drive an chemical
reaction.
• Reduction at cathode:
2 H+(aq) + 2e− → H2(g)
• Oxidation at anode:
2 H2O(l) → O2(g) + 4 H+(aq) + 4e−
 Liquid Electrolyte Electrolyzers
• pure water cannot be used as an electrolyte due to its low
conductivity,.

• Add a substance that increases the conductivity.

– Acids satisfy this requirement (and are used in some

electrolyzers), but they are frequently avoided because of
corrosion problems.

– Alkaline electrolytes are better; they almost invariably use

potassium hydroxide in concentrations of 25% to 30% (about 6
M).

Potassium is preferred to sodium owing to its higher conductivity.

 Solid-Polymer Electrolyte Electrolyzers
• Solid-polymer electrolyzers are dramatically more compact
than KOH electrolyzers and do not require electrolyte controls.
They can operate at much higher current densities than liquid
electrolyte devices.

• RFC: reversible fuel cell in our lab

 Efficiency of an ideal fuel cell
∆G
η=
∆H

• ΔG the Gibbs free energy change

• ΔH the enthalpy change.
• ΔH−ΔG is the released heat.
 Efficiency of an ideal electrolyzer

• when ΔG units of energy are supplied, gases capable of

releasing ΔH units of energy on recombining are formed and a
quantity of heat ΔH−ΔG is absorbed by the electrolyzer from
the environment.

• The efficiency of an ideal electrolyzer is

• Efficiency is larger than unity.

• ΔH is nearly independent of temperature

• ΔG falls rapidly as temperature rises.

• Efficiency increases with temperature.

• At RTP (298K and 1atm)
the ΔH for the reaction is 285.9 MJ/kmole
the ΔG is 237.2 MJ/kmole (all per kilomole of water). The
ideal efficiency of a water electrolyzer,

• divide top and bottom of the equation by qneN0

 The efficiency of any electrolyzer at RTP

• V is the required operating voltage

• If the operating voltage is less than 1.484 V, the electrolyzer

absorbs heat and tends to work below ambient temperature.

• If the operating voltage is higher than 1.484 V, the electrolyzer

must releases heat and tends to operate at above ambient
temperature.
• The amount of heat exchanged with the environment is
𝑄𝑄̇ = (1.484 − 𝑉𝑉)𝐼𝐼

• The operating voltage of an electrolyzer depends on the

current forced through the device.
• If V is less than 1.484v, the electrolyzer absorbs heat.
• If V is higher than 1.484v, it releases heat.
Voltage, efficiency, and heat rejection as a
function of current in a typical electrolyzer
10.5 Photolytic Hydrogen
• Although there is only a 2.51 eV energy
difference between a molecule of water and
its elements, to dissociate it directly, it is
necessary to overcome a 5.15 eV barrier.

• Thus, photons or phonons with less than 5.15

eV cannot initiate the direct water dissociation
reaction.
• For direct photolysis the input energy must be 5.15 + 4.40 =
9.55 eV per molecule of water.

• The result is a hydrogen/oxygen mixture with 2.51 eV more

energy than the initial water.

• The efficiency of this “fuel” production is 2.51/9.55 = 0.263.

 Solar Photolysis

1.366 kilowatts per square metre

The cumulative energy distribution in the solar spectrum

• about 22% of the energy is associated with
photons having more than 2.51 eV, the energy
necessary to dissociate water.
• However, without catalysts, photons with
more than 5.15 eV are necessary to initiate
the reaction.
Dissociation of water
• A catalyst, X, may, for instance, be oxidized in the presence of
water under the influence of light:
Hydroxide ion

• The threshold energy for this reaction is 3.8 eV, somewhat

less than the 5.15 eV necessary in the absence of catalysts.
• The reaction would use only 3% of the solar energy
 Homework 5 (Due 4/13/2020)
(1)
(2)