Fundamentals of Chemical

Manufacture
 Chemical Process
 A industrial chemical process is a process to
produce economically a desired product from a
variety of starting materials through a
succession of treatment steps.

Raw Physical Chemical Physical

treatment treatment treatment Products
materials stepsi stepsi stepsi

Recycle
 Chemical Process
Reactor

Raw Physical Chemical Physical

treatment treatment treatment Products
materials stepsi stepsi stepsi

Recycle

 The raw materials undergo a number of

physical treatment steps to put them in the form
in which they can be reacted chemically.
 The treated raw materials pass through the
reactor
 The products then undergo further physical
treatment-separations, purifications, etc- for the
final desired product to be obtained.
 Raw Materials (1)
 Raw materials, also known as a feedstock,
are basic materials that are used to produce
goods, finished products, energy, or
intermediate materials which are feedstock for
other products.
 Raw materials are materials that have been
unprocessed (or minimally processed). So
they are in the form in which they are found in
nature without any thing done to them.
 Raw materials usually come from a plant or
tree, an animal and a mine.
 Raw Materials (2)
 Raw materials are sold in what is called the
factor market. This is because raw materials
are factors of production along with labor and
capital.

 Raw materials are so important to the

production process that the success of a
country’s economy can be determined by the
amount of natural resources the country has
within its own border
 Raw Materials (3)

 Examples of raw materials

 Grains such as wheat and rice
 Vegetables such as carrots and onions
 Meat such as beef and chicken
 Wood from a tree
 Honey from a bee’s nest
 Minerals or metal from a mine
 Crude oil (chemicals, fuels, plastics, etc.)
 Raw ratex
 Coal
 Raw Materials (4)

Latex being collected from a rubber tree

Raw Materials (5)

Crude oil
 Raw Materials (6)

Raw materials
in Africa
 Basic Feedstock Demands in
Chemical Industry
 Raw materials for the Chemical Industry must
be available in a stable and good quality.

 Security of supply must be guaranteed.

 Raw Materials must be available at world

market prices.

 Oil and gas meet the demands since a long

time ago.
 Feedstock in Chemical Industry
(organic chemicals)

 Carbon containing raw materials are the basis

for production of organic chemicals:
 Mineral oil and its derivatives
 Natural gas
 Coal
 Renewable raw materials

 Biomass is the only renewable carbon based

feedstock for the chemical industry.
 Biomass
 Biomass is materials generated by living
organism, typically cellular structure of a plant
or animal or chemical products generated by
the organism.
 Wood, Crops, Gabage, Landfill gas, etc.

 Nature produces the vast amount of 170 billion

tons of biomass per year by photosynthesis,
75% of which is carbohydrates. Only 3~4% of
these compounds are used for food and non
food purposes.
 Biomass carbohydrates are the most abundant
renewable resources. – Feedstock for the
Green Chemistry of the future.
 Chemical Processes

Chemical Processes can be classified into

two processes;

 Batch Process
Continuous Process
 Batch Process
 In batch processes, reactants are charged
at the beginning of the reaction and
products are removed at the end of
reaction.

 Reactants are usually added manually to

an agitated vessel and the temperature is
raised to the required level by heating the
reactor jacket or coils in the reactor.
 Batch
Reactor
 Batch
Reactor
Batch Reactor

Colorants being
produced in a batch
reactor. The top of
the reactor is at floor
level and the rest of
the reactor is
suspended below it.
 Batch Reactor
producing formic
acid
 Continuous Process
 In continuous processes, reactants are
charged continuously and products are
also removed continuously while reactions
are going on in reactors.

 A steady state must be reached where the

flow rate of reactant solutions into the
reactor equals the flow rate of product
solution out of the reactor. Otherwise the
tank would be empty or overflow.
Continuous
Stirred-Tank
Reactor
(CSTR)
Continuous Fermenter
 Continuous
Stirred-Tank
Reactor (CSTR)
for poly(ethene)
production
Continuous Stirred-Tank Reactor (CSTR)
 Continuous Process
 In a continuous stirred-tank reactor
(CSTR), an agitator is deliberately
introduced to disperse the reactants
thoroughly into the reaction mixture
immediately after they entered the tank.

 The residence time is calculated by

dividing the volume of the tank by the
average volumetric flow rate of reactants
(or products).
 Continuous Process
 The product stream drawn off continuously,
in the ideal state of perfect mixing, will
have the same composition as the
contents of the tank.

 As soon as the reactants enter the tank

they are mixed but a portion of reactants
leaves in the product stream flowing out.
To reduce this effect, a number of stirred
tanks connected in series can be used.
 CSTRs connected in series

Reactants

Products
 Batch vs Continuous Process (1)

 Advantages of Batch Process

 A variety of different products can be produced using
the same reactor.
 Slow reaction can be carried out.
 Reactants in any state including solids can be used.
 Lower investment costs.
 Scale-up (expansion) is rather easy.
 Cleaning is easily implemented.
 Batch vs Continuous Process (2)

 Disadvantages of Batch Process

 Risk of contamination increases if more than one
product are produced in the reaction vessel.
 Expensive down time while the reactor is being filled
and emptied.
 Larger workforce are required.
 It can be difficult to control highly exothermic reactions.
 No constant quality of products. (The product quality of
each batch would be slightly different.)
 Batch vs Continuous Process (3)
 Advantages of Continuous Process
 The most cost effective if large quantities of the
products are being made.
 No expensive down time.
 Automated process requires less labour.
 Continuous processes are easier to control and
facilitate the manufacture of uniform products (equal
quality of products).

 Disadvantages of Continuous Process

 High capital cost of setting up the plant are required.
 Costs rise if the plant is not operated continuously.
 Flowcharts
 A flowchart is a type of diagram that represents
an algorithm, workflow or process showing the
steps as boxes of various kinds, and their order
by connecting them with arrow.

 Flowcharts are used in designing and

documenting simple processes or programs.

 Flowcharts visualize what is going on and

thereby help understand a process, and perhaps
also find a flaw, bottlenecks, etc.
 Start

Greet Customer

Scan Items
Tell customer
the total

Credit card Credit

card
or cash?
Scan card
Cash
Pass? No
Start/End
Take cash
payment Action/Task

Give receipt Decision

Thank customer

End
Flowcharts for Chemical Processes (1)
 Flowcharts for chemical processes come in
many types and are used for many purposes.

 Simple blocks often show only material and

energy flows and operating conditions.

 More detailed ones show everything in a

process and become extremely complicated.

 Specialized flowcharts show such details as

fire lines, instruments and control systems, air
lines, drains, etc.
Flowcharts for Chemical Processes (2)
 Flowcharts coordinate the sequence of unit
operations and unit processes. They indicate;
 The points of entrance for raw materials and
necessary energy.
 The points of removal of the product and the by-
products.

 The most concise flowchart would be the one

drawn skillfully including data covering not
only materials, but labor and utilities as well.
 Typical flowchart for a sulfur-burning
double-absorption contact sulfuric acid plant
Flowchart for sulfuric acid concentration process
Flowchart for manufacture of superphosphate
 Energy and Fuel
 Energy is an indirectly observed quantity
often understood as the ability of a physical
system to do work on other physical systems.

 Forms of Energy
 Potential energy
 Kinetic energy
 Thermal energy
 Electric energy
 Chemical energy
 Nuclear energy
 Energy in Chemical Industry
 Chemical process industries consume more
than one-third of energy used by all the
manufacturing industries. (in 1984)

 In chemical process industries, large amount

of energy is needed for the production of
steam for evaporation, heating, and drying.

 Energy is also needed for pumping reactants

and product, mixing reactants, and
controlling the processes.
 Energy in Chemical Industry
 Chemical engineers should be familiar with
the broad technical aspects of energy
production and use.

 Chemical engineers work with power,

refrigeration, and air-conditioning engineers
for proper coordination of the production of
energies and their use in chemical
processes in order to obtain the cheapest
manufacturing cost.
 Primary Energy
 Primary energy is an energy form found in
nature that has not been subjected to any
conversion or transformation process.

 It is energy contained in raw fuels, and other

forms of energy received as input to a system.
Primary energy can be non-renewable or
renewable.

 Total Primary Energy Supply (TPES) is a

term used to indicate the sum of production
and imports subtracting exports and storage
changes.
Primary Energy Sources (Fuels)

 Fossil fuels

 Nuclear fuel

 Renewable resources
Fossil Fuels
Nuclear Fuel
Renewable Resources
World Total Primary Energy Supply
by Fuels in 2012
Primary Energy Supply (%)
Oil 31.4
Coal/Peat/Shale 29.0
Natural Gas 21.3
Biofuels and waste 10.0
Nuclear 4.8
Hydro 2.4
Others(Renewable) 1.1

 TPES in 2012 : 155,505 TWh (or 13,371 Mtoe)

 TWh: Trillion watt hours
 Mtoe: Million tonne of oil equivalent
TPES by
resources
World Total Primary Energy Supply
by Region in 2012
Region Supply (%)
OECD 39.2
Middle East 5.1
Non-OECD Europe/Eurasia 8.9
China 21.8
Asia (w/o China) 12.3
Africa 5.5
Bunkers 2.6

 TPES in 2012 : 155,505 TWh (or 13,371 Mtoe)

 TWh: Trillion watt hours
 Mtoe: Million tonne of oil equivalent
Primary Energy Use (world market)
Energy Key Indicators (1993, 2011, 2020)
 Coal
 Despite its poor environmental credentials,
coal remains a crucial contributor to energy
supply in many countries.
 Coal is the most wide-spread fossil fuel
around the world, and more than 75 countries
have coal deposits.
 The current share of coal in global power
generation is over 40%, but it is expected to
decrease in the coming years, while the
actual coal consumption in absolute terms
will grow.
 Coal
 While the global reserves of coal have
decreased by 14% between 1993 and 2011,
the production has gone up by 68% over the
same time period.
 Compared to the 2010 survey, the most
recent data shows that the proved coal
reserves have increased by 1% and
production by 16%.
 The future of coal depends primarily on the
advance of clean coal technologies to
mitigate environmental risk factors, CO2
emissions, in particular.
 Coal
 Coal is playing an important role in delivering
energy access, because it is widely available,
safe, reliable and relatively low cost.

 One of the major challenges facing the world

at present is that approximately 1.2 billion
people live without any access to modern
energy services.

 Access to energy is a fundamental pre-

requisite for modern life and a key tool in
eradicating extreme poverty across the globe.
 Coal
 Many countries with electricity challenges,
particularly those in Asia and southern Africa,
are able to access coal resources in an
affordable and secure way to fuel the growth
in their electricity supply.
 Coal will therefore play a major role in
supporting the development of base-load
electricity where it is most needed.
 Coal-fired electricity will be fed into national
grids and it will bring energy access to
millions, thus facilitating economic growth in
the developing world.
Coal Reserves : Top 5 Countries
Coal Production/Consumption
 Oil

 Oil has been the premier energy resource

with a wide range of possible applications.
Its main use however, will be shifting
towards transport and the petrochemical
sector.

 In future oil’s position at the top of the

energy ladder will face a strong challenge
from other fuels such as natural gas.
 Oil
 The oil resource assessments have
increased steadily between 2000 and 2009,
and about a half of this increase is due to the
reclassification of the Canadian oil sands and
the revisions undertaken in major OPEC
countries: Iran, Venezuela and Qatar.

 Compared to the 2010 survey, the proved oil

reserves increased by 37% and production
by 1% in the 2013 survey.
Crude Oil Reserves: Top 5 Countries
Oil Production/Consumption
 Natural Gas
 Natural gas is yet another fossil fuel resource
that will continue making significant
contribution to the world energy economy.

 The cleanest of all fossil-based fuels, natural

gas is plentiful and flexible.

 It is increasingly used in the most efficient

power generation technologies, such as,
Combined Cycle Gas Turbine (CCGT) with
conversion efficiencies of about 60%.
 Natural Gas
 The reserves of conventional natural gas
have grown by 36% over the past two
decades and its production by 61%.

 Compared to the 2010 survey, the proved

natural gas reserves have grown by 3% and
production by 15% in the 2013 survey.

 In its search for secure, sustainable and

affordable supplies of energy, the world is
turning its attention to unconventional energy
resources. Shale gas is one of them.
Natural Gas Reserves : Top 5 Countries
Natural Gas Production/Consumption
 Uranium and Nuclear
 The nuclear industry has a relatively short
history: the first nuclear reactor was
commissioned in 1954.

 Uranium is the main source of fuel for

nuclear reactors.

 Total identified uranium resources in 2013

have grown by 12.5% since 2008 and they
are sufficient for over 100 years of supply
based on current requirements.
 Uranium and Nuclear
 Total nuclear electricity production has been
growing during the past two decades and
reached an annual output of about 2600TWh
by the mid-2000s, although the three major
nuclear accidents have slowed down or even
reversed its growth in some countries.

 The nuclear share of total global electricity

production reached its peak of 17% by the
late 1980s, but since then it has been falling
and dropped to 13.5% in 2012.
Chernobyl, Ukraine, in 1983
Fukushima, Japan, in 2011
Kyshtym, Russia, in 1957
Plutonium production plant and
reprocessing facility
 Uranium and Nuclear
 Japan used to be one of the countries with a
high share of nuclear (30%) in its electricity
mix and high production volumes. In 2013,
Japan had only two of its 54 reactors in
operation.

 The rising costs of nuclear installations and

lengthy approval times required for new
construction have had an impact on the
nuclear industry.
 Uranium and Nuclear

 The slowdown has not been global, as

new countries, primarily in the rapidly
developing economies in the Middle East
and Asia, are going ahead with their
plans to establish a nuclear industry.
Nuclear Power : Top 5 Countries
 Hydro Power
 Hydro power provides a significant amount of
energy throughout the world and is present in
more than 100 countries, contributing
approximately 15% of the global electricity
production.

 The top 5 largest markets for hydro power in

terms of capacity are Brazil, Canada, China,
Russia and the United States of America.

 China significantly exceeds the others,

representing 24% of global installed capacity.
 Hydro Power
 In several other countries, hydro power
accounts for over 50% of all electricity
generation, including Iceland, Nepal and
Mozambique for example.

 In many cases, the growth in hydro power

was facilitated by the lavish renewable
energy support policies and CO2 penalties.

 Over the past two decades the total global

installed hydro power capacity has increased
by 55%
Hydro Power : Top 5 Countries
 Wind
 Wind is available virtually everywhere on earth,
although there are wide variations in wind
strengths.
 The total resource is vast; estimated to be
around a million GW ‘for total land coverage’.
 World wind energy capacity has been doubling
about every three and a half years since 1990.
 Total capacity at the end of 2011 was over
238GW and annual electricity generation
around 377TWh, roughly equal to Australia’s
annual electricity consumption.
 Wind
 China, with about 62GW, has the highest
installed capacity.
 Denmark, with over 3GW, has the highest level
per capita. Wind accounts for about 20% of
Denmark’s electricity production.
 As governments begin to cut their subsidies to
renewable energy, the business environment
becomes less attractive to potential investors.
 Lower subsidies and growing costs of material
input will have a negative impact on the wind
industry in recent years.
Wind Power : Top 5 Countries
 Solar PV
 Solar energy is the most abundant energy
resource and it is available for use in its direct
(solar radiation) and indirect (wind, biomass,
hydro, ocean etc.) forms.
 About 60% of the total energy emitted by the
sun reaches the Earth’s surface.
 Even if only 0.1% of this energy could be
converted at an efficiency of 10%, it would be
four times larger than the total world’s
electricity generating capacity of about
5000GW.
 Solar PV
 The use of solar energy is growing strongly
around the world, in part due to the rapidly
declining solar panel manufacturing costs.
 For instance, between 2008–2011 PV
capacity has increased in the USA from
1168MW to 5171MW, and in Germany from
5877MW to 25039MW.
 The anticipated changes in national and
regional legislation regarding support for
renewables is likely to moderate this growth.
League Tables Reserves : Top 5 Countries
 Bioenergy and Waste
 Bioenergy is a broad category of energy
fuels manufactured from a variety of
feedstocks of biological origin and by
numerous conversion technologies to
generate heat, power, liquid biofuels and
gaseous biofuels.

 The term “traditional biomass” mainly refers

to fuelwood, charcoal, and agricultural
residues used for household cooking,
lighting and space-heating in developing
countries.
 Bioenergy and Waste
 The industrial use of raw materials for
production of pulp, paper, tobacco, pig iron
so on, generates byproducts such as bark,
wood chips, black liquor, agricultural
residues, which can be converted to
bioenergy.

 The share of bioenergy in TPES has been

estimated at about 10% in 1990. Between
1990 and 2010 bioenergy supply has
increased from 38 to 52EJ as a result of
growing energy demand.
 Bioenergy and Waste

 New policies to increase the share of

renewable energy and indigenous energy
resources are also driving demand.

 However, it is difficult to make accurate

comparisons with earlier figures because of
poor availability and low level of
standardization of data.
Energy Resources in Ethiopia
 Overview
Energy in Ethiopia
Prim. Electricit CO2-emi
Capita Production Import
energy y ssion
Million TWh TWh TWh TWh Mt
2004 69.96 246 225 16.3 2.29 5.07
2007 79.09 265 243 23.0 3.17 5.96
2008 80.71 369 344 24.7 3.42 6.83
2009 82.80 380 353 26.7 3.72 7.42
2012 84.73 4.65 5.86
Change
18.4 % 54 % 57 % 64 % 62 % 46 %
2004-09
Mtoe = 11.63 TWh . Prim. energy includes energy losses
 Hydro Power in Ethiopia
 Hydropower accounts for the bulk of
Ethiopia's electric power generating capacity
and output. In 2002, the country's generating
capacity stood at 501 MW, with hydropower
accounting for 451 MW, and conventional
thermal at 50 MW.

 Electricity production for that same year was

2.024 TWh, of which 2.003 TWh and 20 GWh
came from hydroelectric and conventional
thermal plants, respectively.
 Hydro Power in Ethiopia

 Electric power consumption in 2002 totaled

1.882 TWh. In 2008 electricity production
was 3.715 TWh.

 The Gilgel Gibe III Dam, which is expected

to be completed in 2016, will add 1870 MW
capacity to the country's power production,
more than doubling the country's
production.
Gilgel Gibe III Dam
 Hydro Power in Ethiopia

 The Grand Ethiopian Renaissance Dam is

currently under construction on the Blue Nile
River in Ethiopia.

 According to the Ethiopian government, as

of October 2014, the dam is 40% complete.

 The dam with 6,000 MW capacity will be

the largest hydroelectric power plant in
Africa when completed, as well as the 11th
largest in the world.
Grand Ethiopian Renaissance Dam
 Oil and Natural Gas in Ethiopia

 Ethiopia has small reserves of oil and natural

gas.

 As of January 2003, the country's crude oil

and natural gas reserves were placed at
428,000 barrels (68,000 m3) and 880 billion
cubic feet (2.5×1010 m3), respectively.

 Ethiopia has no crude oil refining capacity

and must import all refined petroleum
products.
 Oil and Natural Gas in Ethiopia
 Due to high maintenance and operating
costs, Eritrea and Ethiopia agreed to shut
down their joint operations at the petroleum
refinery at Assab and import refined petroleum
products.

 Total imports of refined petroleum products

was 24,910 barrels per day (3,960 m3/d) and
total consumption was an estimated 23,000
barrels per day (3,700 m3/d) in 2001.
 Wind Farm in Ethiopia
 The 153 MW Adama wind farm had been
built in May 2015. It is the largest wind farm
in sub-Saharan Africa.

 Hydro power which is subject to rainfall is

less reliable than wind turbines specially
during dry season or when droughts happen.

 The wind in Ethiopia is specially strong during

dry season so that it can complement hydro
dams.
Adama Wind Farm
Adama Wind Farm
Industrial Gases
 Carbon Dioxide,
 Chemical formula : CO2
 Molecular weight : 44.01 g/mol
 Appearance : colorless gas
 Odor : Odorless
 Density
 Solid : 1562 kg/m3 (at 1 atm and -78.5 ℃)
 Liquid : 770 kg/m3 (at 56 atm and 20 ℃)
 Gas : 1.977 kg/m3 (at 1 atm and 0 ℃)
 Melting point : - 56.6 ℃ (at 5.1 atm)
 Sublimation conditions : - 78.5 ℃ (at 1 atm)
 Carbon Dioxide, CO2
 Solid carbon dioxide (dry ice) was produced
from liquid material by Thilorier, French
inventor, for the first time in 1835.

 In 1924, the solid product gained industrial

importance through its first and still most
important use for refrigeration.

 Dry ice is used primarily as a cooling agent.

Its advantages include lower temperature
than that of water ice and not leaving an
residue.
 Uses of Carbon Dioxide
 Dry ice sublimates at – 78.5℃ at 1 atm. This
extreme cold makes the solid dangerous to
handle without protection because it can
cause frostbite.
 The largest use of dry ice is for preserving
frozen foods, ice cream, meat, and other
foods where mechanical cooling is
unavailable.
 An added advantage is that a carbon dioxide
atmosphere reduces meat and food bacteria
spoilage by limiting the supply of oxygen to
the bacteria.
 Uses of Carbon Dioxide
 Dry ice is also important as a source of
carbon dioxide for inert atmospheres and
occasionally for carbonated beverages.
 Gaseous carbon dioxide has many
applications in chemical industry, such as in
the manufactures of fire-extinguishers and
salicylic acid.
 Carbon dioxide has advantages over ordinary
acids in neutralizing alkalies, because it is
easily shipped in solid form, is noncorrosive
in nature, and is light in weight.
 Manufacture of Carbon Dioxide

 Recovery from synthesis gas in ammonia

production

 Recovery as a by-product in the production

of substitute natural gas (SNG)

 Recovery from the production of ethanol by

fermentation

 Recovery from natural wells

Recovery of CO2 from NH3 Production
 Catalytic steam reforming of sulfur-free
feedstock is used to form hydrogen and
carbon monoxide.
CH4 + H2O → CO + 3H2
 Next step is to convert carbon monoxide to
carbon dioxide and more hydrogen
CO + H2O → CO2 + H2 (CO2 is recovered)
 To produce ammonia, the hydrogen is then
catalytically reacted with nitrogen.
3H2 + N2 → 2NH3
CO2 by-product from SNG Production

 A high-heat content gas similar to natural gas

can be produced from coal,
C + H2O (steam) → CO + H2 Gasification
CO + H2O → CO2 + H2 (CO2 is recovered)

 At sufficiently high pressure the hydrogen will

hydrogenate some of carbon to yield methane.
C + 2H2 → CH4
CO + 3H2 → CH4 + H2O Methanation
CO2 from Ethanol Production by Fermentation

 Carbon dioxide is a by-product of the

fermentation of sugar in the brewing of beer,
whisky and other alcoholic beverages and
in the production of bioethanol.

 Yeast metabolizes sugar to produce CO2

and ethanol as follows:

C6H12O6 → 2 CO2 + 2 C2H5OH

 CO2 from Natural Wells
 Acids liberate CO2 from most metal
carbonates. Consequently, it may be obtained
directly from natural carbon dioxide springs,
where it is produced by the action of acidified
water on limestone.
 The reaction between hydrochloric acid and
calcium carbonate (limestone) is shown below:
CaCO3 + 2 HCl → CaCl2 + 2 H2CO3
 Carbonic acid decomposes to water and CO2
H2CO3 → CO2 + H2O
Flowchart for CO2 from fuel oil or natural gas
 Manufacture of Dry Ice
 Carbon dioxide-rich gas is pressurized and
refrigerated until it liquifies.

 The pressure is reduced. When this occurs

some liquid carbon dioxide vaporizes, causing
a rapid lowering of temperature of the
remaining liquid.

 As a result, the extreme cold causes the liquid

to solidify into a snow-like solid. Finally, the
snow-like solid carbon dioxide is compressed
into either small pellets or larger blocks of dry
ice.
Manufacture of Dry Ice
 Hydrogen
 Chemical formula : H2

 Molecular weight : 2.02 g/mol

 Appearance : colorless gas

 Odor : Odorless

 Density : 0.08988 g/L (at 0 ℃ )

 Melting point : - 259.16 ℃

 Boiling point : - 252.88 ℃

 Hydrogen
 Hydrogen has long been an important raw
material for the chemical and petrochemical
industries.

 Hydrogen gas was first artificially produced in

the early 16th century, via the mixing of
metals with acids.

 Hydrogen gas is highly flammable and will

burn in air at a very wide range of
concentrations between 4% and 75% by
volume.
Hydrogen Used for Typical Products
Raw materials to be
hydrogenated Product

Phenol Cyclohexanol
Nitrogen Ammonia
Naphthalene Tetralin
Olein Stearin
Diisobutylene Isooctane
Carbon monoxide Methanol
 Hydrogen Manufacture

 Electrolytic Method

 Steam-Hydrocarbon Reforming Process

 Partial Oxidation Process

H2 Production by Electrolytic Method
 The electrolytic process produces high-purity
hydrogen and consists of passing direct
current through an aqueous solution of alkali,
and decomposing the water as follow;
2 H2O(l) → 2H2(g)+ O2(g)
 The decomposition voltage for the
electrolysis is generally 2.0 to 2.25 V.
 A typical commercial cell electrolyzes a 15%
NaOH solution, uses an iron cathode and a
nickel-plated-iron anode, and operates at 60
to 70 ℃.
H2 Production by Electrolytic Method
 H2 Production by Steam-Hydrocarbon
Reforming Process
 Steam reforming is a method for producing
hydrogen, carbon monoxide, or other useful
products from hydrocarbon fuels such as natural
gas.
 This is achieved in a processing device called a
reformer which reacts steam at high temperature
with the fossil fuel.
 Light hydrocarbons (methane and propane) are
preferred for the process and natural gas is the
most common. The steam methane reformer is
widely used in industry to make hydrogen.
 H2 Production by Steam-Hydrocarbon
Reforming Process
 Steam reforming of natural gas - sometimes
referred to as steam methane reforming (SMR)
- is the most common method of producing
commercial bulk hydrogen.
 Hydrogen is used in the industrial synthesis of
ammonia and other chemicals. At high
temperatures (700 – 1100 °C) and in the
presence of a metal-based catalyst (nickel),
steam reacts with hydrocarbon to yield carbon
monoxide and hydrogen.
𝑚
C𝑛H𝑚 + 𝑛H2O ⇄ 𝑛CO + ( + 𝑛)H2
2
 H2 Production by Steam-Hydrocarbon
Reforming Process
𝑚
C𝑛H𝑚 + 𝑛H2O ⇄ 𝑛CO + ( + 𝑛)H2
2
 The above reaction is the reforming reaction
that is highly endothermic and the moles of
product exceed the moles of reactants.
 So, the reaction goes to completion at high
temperature and low pressure.
(Le Chatelier’s Principle)
 Additional hydrogen can be recovered by a
lower-temperature water-gas shift reaction with
the carbon monoxide produced.
CO + H2O ⇌ CO2 + H2
 Le Chatelier’s Principle
 When a system at equilibrium is subjected to
change in concentration, temperature,
volume, or pressure, then the system
readjusts itself to (partially) counteract the
effect of the applied change and a new
equilibrium is established.
 Or whenever a system in equilibrium is
disturbed the system will adjust itself in such
a way that the effect of the change will be
nullified.
 H2 Production by Steam-Hydrocarbon
Reforming Process

 The water-gas shift reaction is the reaction

of carbon monoxide and water vapor to form
carbon dioxide and hydrogen (the mixture is
water gas).

 The reaction (CO + H2O ⇌ CO2 + H2) that is

mildly exothermic is favored by low
temperature.
Simplified Hydrogen Production Process
H2 Production by Partial Oxidation Process

 Partial oxidation process ranks next to steam-

hydrocarbon processes in the amount of
hydrogen made.

 The process uses natural gas, refinery gas, or

other hydrocarbon gas mixtures as feedstocks.
Its chief advantage is that it can also accept
liquid hydrocarbon feedstocks such as gas oil,
diesel oil, and even heavy fuel oil.
H2 Production by Partial Oxidation Process

 This process employs noncatalytic partial

combustion of the hydrocarbon feed with
oxygen in the presence of steam in a
combustion chamber at flame temperature
between 1300 and 1500℃.

 When methane is the principal component of

the feedstock, the reaction involved are:
CH4 + 2O2 → CO2 + 2H2O ∆𝐻 = +802 kJ
CH4 + CO2 → 2CO + 2H2 ∆𝐻 = −206 kJ
CH4 + H2O → CO + 3H2 ∆𝐻 = −247 kJ
H2 Production by Partial Oxidation Process

 The first reaction is highly exothermic and

produces enough heat to sustain the other two
reactions, which are endothermic. The net
reaction is as follows:
1
CH4 + O → CO + 2H2
2 2

 The above reaction is exothermic and so the

overall process is a net producer of heat; for
efficient operation, heat recovery (using waste
heat boilers) is important.