Inorganic Industries Engineering

‫هندسة الصناعات غريالعضويه‬

Lecture 3
Dr.: Sameh Araby El-Mekawy
Outlines

Industrial Gases
Manufacture of Ammonia
 Industrial Gases
 The term “industrial gases” is “a collective term for combustible
and non-combustible gases generated on an industrial scale,
such as several (acetylene, hydrogen, carbon dioxide, nitrogen,
oxygen and argon)
 Their production is a part of the wider chemical Industry (where
industrial gases are often seen as "specialty chemicals").
 There are seven major companies whose combined gas-related
revenue accounted for over 75% of the global market at the end
of 2005:
AL: Air Liquide (French gas company)
BOC: BOC Gases (UK gas company)
AP: Air Products and Chemicals, Inc. (US gas company)
Praxair: Praxair, Inc. (US gas company)
Linde: Linde Gas (German gas company)
TNS: Taiyo Nippon Sanso Co. (Japanese gas company)
Airgas: Airgas, Inc. (major US distributor)
Uses of industrial gases
Hydrogen
1) As fuel for automobiles: Hydrogen fuel is a zero-emission fuel which
burns on reaction with oxygen. It is an exciting concept which aims to
power the automobiles by use of hydrogen instead of petroleum fuels.
2) Deuterium for electricity generation: the isotope of hydrogen is used
to make heavy water (D2O). This heavy water is used in nuclear reactors
as a coolant.
3) Large quantities of hydrogen are used to hydrogenate oils to form fats,
for example to make margarine.
4) It is also used to remove sulfur from fuels during the oil-refining process.
5) In the chemical industry it is used to make ammonia for agricultural
fertilizer (the Haber process) and cyclohexane and methanol, which are
intermediates in the production of plastics and pharmaceuticals.
 Carbon dioxide
 Widely used in the food industry for
applications such as removing the caffeine
from coffee beans to make decaffeinated
coffee.
 Carbon dioxide can be obtained as a solid in
the form of dry ice by allowing the liquified
CO2 to expand rapidly.
 It is used primarily as a cooling agent. Its
advantages include lower temperature than
that of water ice and not leaving any residue
(other than incidental frost from moisture in
the atmosphere).
 Dry ice is used as a refrigerant for ice-cream
and frozen food. Gaseous CO2 is extensively
used to carbonate soft drinks.
 Being heavy and non-supporter of
combustion it is used as fire extinguisher.
 Oxygen
1) The greatest commercial use of oxygen gas is in the steel industry.
2) Large quantities are also used in the manufacture of a wide range of
chemicals including HNO3and H2O2.
3) It is also used to make epoxyethane (ethylene oxide), used as antifreeze
and to make polyester, and chloroethene, the precursor to PVC.
4) Oxygen gas is used for oxy-acetylene welding and cutting of metals.
5) A growing use is in the treatment of sewage and of effluent from
industry.
 Nitrogen
1) It is used to make fertilizers, nitric acid, nylon, dyes and explosives. To
make these products, nitrogen must first be reacted with hydrogen to
produce ammonia. This is done by the Haber process. 150 million
tonnes of ammonia are produced in this way every year.

2) Nitrogen gas is also used to provide an unreactive (inert) atmosphere. It

is used in this way to preserve foods, and in the electronics industry
during the production of transistors and diodes. Large quantities of
nitrogen are used in annealing stainless steel and other steel mill
products. Annealing is a heat treatment that makes steel easier to work.

3) Liquid nitrogen is often used as a refrigerant. It is used for storing

sperm, eggs and other cells for medical research and reproductive
technology. It is also used to rapidly freeze foods, helping them to
maintain moisture, colour, flavour and texture.
 Cryogenics: The branches of physics and engineering that
study very low temperatures, how to produce them, and how
materials behave at those temperatures.

 Cryogens, like liquid nitrogen, are further used for specialty

chilling and freezing applications. Some chemical reactions,
like those used to produce the active ingredients for the
popular statin drugs, must occur at low temperatures of
approximately -100 °C. Special cryogenic chemical reactors
are used to remove reaction heat and provide a low
temperature environment. The freezing of foods and
biotechnology products, like vaccines, requires nitrogen in
blast freezing or immersion freezing systems.
Manufacture of Industrial Gases
Raw Materials AIR
Composition of dry atmospheric air
 Nitrogen, oxygen and argon are almost exclusively recovered from
atmospheric air.
 Atmospheric Air is comprised of a mixture of invisible permanent
and variable gases as well as suspended microscopic particles (both liquid
and solid)
1) Permanent Gases – Form a constant proportion of the total atmospheric
mass
 78.08% Nitrogen (N2)
 20.95% Oxygen (O2)
 <1% Argon (Ar)
2) Variable Gases – Distribution and concentration varies in space and
time
 Water vapor (H2O) 0 to 4%
 Carbon Dioxide (CO2) 0.038%
 Methane(CH4) 0.00017%
 Ozone(O3) 0.000004%
3) Aerosols – An aerosol is a suspension of fine solid particles or liquid
droplets, in air typically ranging in size from 0.001 to 100 μm. (e.g. dust)
 Intake Air purification
 The first step in processing air is removing contaminants from the air stream. Before
distillation the air should be purified from different impurities and components. Failure
to do this results in the buildup of these contaminants in the liquid air distillation
column inside the cold box. The worst of these is acetylene, which can decompose
explosively.
 Acetylene is a very hazardous reactive contaminant. Because acetylene has a low
solubility in LOX, if it enters the cold box it concentrates in LOX and precipitates out
as a solid at concentrations as low as 4 ppm to 6 ppm (depending on the LOX
pressure). The solid is relatively unstable and requires little energy to ignite.
 However, any hydrocarbon is hazardous because it can be exposed to pure oxygen in
parts of the system. Mixing any hydrocarbon with pure oxygen creates a combustion
explosion hazard.
 Trace contaminants can be put into three main categories based on the potential
problems they cause in the ASU (plugging, reactive, or corrosive) as shown in Table 2.
 Plugging contaminants concentrate, precipitate out as a solid, or both in the ASU
process. While plugging is an operating problem, it can also lead to dry boiling or pool
boiling, which can in turn concentrate the reactive contaminants to form flammable
mixtures. The plugging contaminants of most concern are water, carbon dioxide, and
nitrous oxide.
 Corrosive contaminants (acid gases and ammonia) can react with equipment and
piping causing operating problems and impacting equipment life.
 Air purification technologies
1. Removal of acidic compounds like H2S, Carbon dioxide and oxides of
nitrogen can be carried out by using Caustic scrubbers (air is washed by
solution of the sodium hydroxide or potassium hydroxide).
2. Clearing air from acetylene:
Air clearing from acetylene because it’s very dangerous for the air separation
plant so it’s important to clear air from it because if acetylene aggregation it
will be explosion. Acetylene has low part pressure in the air so it can’t distant
in heat exchanger and in regenerator and it’s aggregation in liquid. Acetylene
has low solubility in air, oxygen and nitrogen so it can be very easy clean in
SiO2.H2O filters.
3. An electrostatic precipitator (ESP) is a filtration device that removes fine
particles, like dust and smoke, from a flowing gas using the force of an
induced electrostatic charge minimally impeding the flow of gases
through the unit.
4. Spraying air with water cleans the air of water-soluble substances, dusts
and vaporized air compressor lubricants.
 Air separation technologies
Air separation technology is based on the fact that the fundamental
components of air all have different physical properties and air separation
is therefore realized through, for example, distinguishing between
molecule sizes, distinguishing between difference in diffusion rates
through certain materials, adsorption preference special materials have
towards certain gasses of the atmosphere and difference in boiling
temperatures.

The most common methods to perform gas separation are:

1) Pressure swing adsorption (PSA)
2) Membrane separation
3) Cryogenic separation (has a share of far more than 90% on the
worldwide production)
Air separation technologies
 These methods have common characteristics such as
1) they use air as a feedstock;
2) they are physical processes - no chemical reactions are involved;
3) the products are consistently high quality and contain no unwanted
contaminants
 Cryogenic separation is applied whenever high purity, large quantities, liquid
products or argon is required.
 Membrane and adsorption plants have a high load range and can be started and
powered up to full production within a few minutes.
 A cryogenic plant needs about 2 hours for the start from cold condition until the
beginning of production of oxygen and nitrogen.
1)Pressure swing adsorption (PSA)

Schematic representation of Pressure Swing Adsorption method (PSA).

 PSA provides separation of oxygen or nitrogen from air without liquefaction.
The process operates around ambient temperature; a zeolite (adsorbent bed)
(molecular sponge) is exposed to high pressure air, As soon as the pressure is
reduced again, the gas is desorbed (released). This additionally frees up the
adsorbent, ready for the next cycle.
 The basis of PSA is that when gases are put under high pressure, the gases are
attracted to solid surfaces and hence are adsorbed. This is a proportional
relationship, in that the higher the pressure, the more gas is adsorbed.
 These systems rely on the zeolites to trap nitrogen and hence produce oxygen
with high purity
 Different gases can be adsorbed by using different solid particles, based on what
the gases are more easily attracted to, so this method typically has relatively
high product purity
2) Membrane separation

Schematic representation of Membranes for Air separation

 Separation of gases with membranes relies on the different affinities of one or more
gases towards the membrane material, causing one gas to be permeate faster (or slower)
than others. The membrane could be composed of Microporous Organic Polymers,
Zeolites or Ceramic.
 Air is directed into a vessel and put in contact to the membrane material which is at the
interface with another vessel. The mixture is allowed to diffuse into the second vessel
under a pressure gradient which promotes the mass transport through the membrane
separating the retentate (slower gas) from the permeate (faster gas).
 Advantages: the most valuable is the high cost-efficiency (both for the mechanical
simplicity of the system and for low-energy regeneration) in fact, they do not require
thermal regeneration in their operation.
 Disadvantages: Selectivity for a required gas component. This means that high
permeable membranes have low selectivity, requiring several run for a good separation,
and highly selective membranes have low permeability, meaning long operational
times.
3) Cryogenic distillation process

Schematic representation of Cryogenic distillation method

 Cryogenic air separation process is one of the most popular air separation
process, used frequently in medium to large scale plants.
 In the cryogenic gas processing, various equipment is used like the
distillation columns, heat exchangers, cold interconnecting piping etc.
which operate at very low temperatures and hence must be well insulated.
These items are located inside sealed "cold boxes". Cold boxes are tall
structures with either round or rectangular cross section. Depending on
plant type, size and capacity, cold boxes may have a height of 15 to 60
meters and 2 to 4 meters on a side.
 Cryogenic air separation is the most common and standard technology used
for the separation of air into its constituents.
 Pure gases can be separated from air by first cooling it until it liquefies, then
selectively distilling the components at their various boiling temperatures.
 The process can produce high purity gases but is energy-intensive.
 This process was pioneered by Carl von Linde in the early 20th century and
is still used today to produce high purity gases.

 Principle
Cryogenic air separation technology is based on the fact that the different
constitute gases of air all have different boiling points and by manipulating
immediate environment in terms of temperature and pressure the air can be
separated into its components
Several important principles are involved in the process and are summarized
below:
• When work is done on air, by compressing it, it becomes hotter.
• When compressed air is expanded through and opening or valve it becomes
cooler.
• When air is expanded in a turbine it does work on the rotors and cools by
approximately ten times as much as in simple expansion.
• When a mixture of liquids is in equilibrium with its vapour, the vapour above
the liquid is richer in the more volatile component (i.e. more of the lower
boiling liquid vapourises).
• The boiling point of a liquid is lower at lower pressure.
Process description
The cryogenic air separation flow diagram given below does not represent any
particular plant and shows in a general way many of the important steps involved
in producing oxygen, nitrogen, and argon as both gas and liquid products

Block diagram of cryogenic air separation plant

Process description
There are various thermodynamic processes needed in cryogenic air separation, of
which fundamental ones are: air compression, air purification, heat exchanging,
distillation and product compression.
Air compression
 Atmospheric air is pre-filtered (to remove dust), and compressed using a centrifugal
compressor to a pressure required.
 Since the compressor heats up the air, it is cooled in inter stage coolers and water-
cooled after cooler to condense any water vapors.

Air purification
 Air is then processed through a pre-purification unit. During this process, compressed
air is generally passed through a pre- purification unit which removes any remaining
water vapors, as well as carbon dioxide to avoid freeze of water vapors and carbon
dioxide in the cryogenic equipment.
 The air passes through a molecular sieve adsorber. The adsorber contains zeolite and
silica gel-type adsorbents, which trap the carbon dioxide, heavier hydrocarbons, and
any remaining traces of water vapor. Periodically the adsorber is cleaned to remove the
trapped impurities. This usually requires two absorbers operating in parallel, so that
one can continue to process the air-flow while the other one is flushed
Heat exchanging for cooling
 After purification, air passes through a plate- fin heat exchanger where it is cooled to
a temperature at which it is partially liquid. This cooling is done in brazed aluminum
heat exchangers which allow the exchange of heat between the incoming feed air and
cold products and waste gas streams exiting the separation process. The exiting gas
streams are warmed to close-to-ambient air temperature and incoming feed air
liquefied.
 The air is passed through heat exchangers for further cooling and for removal of water
vapor and carbon dioxide by freezing.

Distillation
 Partially liquefied air is sent to the double column distillation system integrated
with crude argon column, where it is separated into O2, N2 and crude argon
fractions.
 The distillation is the heart of the cryogenic air separation process.
 The air stream which is part liquid and part gas enters the base of the high-
pressure fractionating or distillation column. As the air moves up the column, it
loses additional heat. The oxygen continues to liquefy, leading to the formation
of oxygen-rich mixture in the bottom of the column, and other gases like
nitrogen and argon flow to the top as a vapor.
Product compression
 The gases are sometimes pressurized to meet user requirement and supplied
by pipeline to large industrial users adjacent to or nearby to the production
plant or stored as liquid.
Distillation of air
4. Nitrogen boils at
-196oC so it can be
1. Air has to be Colder at the top removed from the
condensed into a top of the column
liquid. This happens as a gas.
at -200oC.

2. This is done by
compressing the air

5. At -185oC
3. At-200oC carbon
oxygen is still a
dioxide and water
liquid so can be
are solids so can be
taken out the
easily taken out.
bottom of the
Warmer at the bottom column.
 Manufacture of Ammonia: NH3
 Nitrogen is the starting point for an important group of compounds.
First, nitrogen is combined with hydrogen to make ammonia (NH3).
The production of ammonia is sometimes called industrial nitrogen
fixation.
 The formation of ammonia from nitrogen and hydrogen is very
difficult to accomplish. The two elements do not easily combine.
 German chemist Fritz Haber in 1905 found that nitrogen and
hydrogen would combine if they were heated to a very high
temperature with a very high pressure. He also found that a catalyst
was needed to make the reaction occur. The catalyst he used
was iron metal, though other metals are sometimes used
 Reactivity of Nitrogen: The dissociation energy of the N≡N bond
is very large(946 kJ mol) and dissociation of nitrogen molecules
into atoms is not readily effected until very high temperatures,
being only slight even at 3000 K. It is this high bond energy
coupled with the absence of bond polarity that explains the low
reactivity of nitrogen, in sharp contrast to other triple bond
structures such as -C ≡ N,-C ≡ C-.
 Nitrogen is an inert molecule and will only react with other
elements, including oxygen, at very high temperature. Yet
nitrogen and oxygen form an array of oxides in which nitrogen
exhibits a whole range of oxidation state from +1 to +5: N2O,
NO, N2O3, NO2, N2O4, and N2O5. At high temperature, nitrogen
gas also reacts with H2, Li, the Group 2A elements, B, Al, C, Si,
Ge, and many transition elements.
PROPERTIES OF AMMONIA
A colourless liquefied gas
Has a pungent smell and is irritating to eyes and lungs
Is a gas at room temperature (b.p. -33.4°C)
Is non flammable
Is toxic
Is corrosive
Is considered dangerous for the environment
Ammonia is soluble in aqueous solutions
Ammonia is a gas at room temperature and pressure
Haber Process
Ammonia, NH3, is produced commercially by the Haber Process.
Fe
N2(g) + 3H2(g) 2NH3(g) DH = -92 KJmol-1
460 oC
200 atm
Raw Materials
 N2(g) is taken from the air via a process of Cryogenic separation.
 H2(g) is obtained from either the catalytic steam reforming of natural gas
(methane) or naphtha, or the electrolysis of brine at chlorine plants
 Modern ammonia-producing plant first converts natural gas (i.e., methane)
or LPG (liquefied petroleum gases such as propane and butane) or
petroleum naphtha into gaseous hydrogen. The method for producing
hydrogen from hydrocarbons is known as steam reforming.
CH4 + H2O ⇌ CO + 3 H2 ΔH = 206 kJ.mol-1
 Modern Method of Manufacturing Ammonia
While all ammonia plants use this basic process, details such as operating pressures,
temperatures, and quantities of feedstock vary from plant to plant.
The manufacturing process consists the following stages as shown from the block
diagram
Desulphurization
 Hydrocarbon feedstocks contain sulphur in the form of H2S andCS2
 The catalyst used in the reforming reaction is deactivated
(poisoned) by sulphur.
 The problem is solved by catalytic hydrogenation of the sulphur
compounds as shown in the following equation:
H2+RSHRH + H2S(g)
 The gaseous hydrogen sulphide is then removed by passing it
through a bed of zinc oxide where it is converted to solid zinc
sulphide:
H2S+ZnO  ZnS+H2O
Primary (Steam) Reforming.
 Reforming is the process of converting natural gas or
naptha (CnH2n+2) into hydrogen, carbon monoxide
and carbon dioxide.
 Steam and natural gas are combined at a 3:1 ratio.
This mixture is preheated and passed through
catalyst-filled tubes in the primary reformer.
 Catalytic steam reforming of the sulphur-free
feedstock produces synthesis gas (hydrogen and
carbon monoxide). Using methane as an example:

CH4 + H2O ↔ CO + 3H2 ∆H = 49.2 kcal/mol

Secondary reformer
 From the primary reformer, the mixture flows to the
secondary reformer.
 Air is fed into the reformer to completely convert
methane to CO in the following endothermic
reaction.
Ni/15-20atm/1000-1100oC
CH4 + Air CO + H2O + N2
Shift Conversion.
 The carbon monoxide is converted to carbon dioxide with the
assistance of catalyst beds at different temperatures.
CO+H2O → CO2+H2
 This water-gas shift reaction is favorable for producing carbon
dioxide which is used as a raw material for urea production. At
the same time more hydrogen is produced.
Purification (Methanation)
 CO is an irreversible poison for the catalyst used in the
synthesis reaction, hence the need for its removal
 The synthesis gas is passed over another catalyst bed in the
methanator, where remaining trace amounts of carbon
monoxide and dioxide are converted back to methane using
hydrogen.
CO+3H2CH4+H2O
CO2+4H2  CH4+2H2O
Note that the first equation is the opposite of the reformer reaction
 Methane is an inert gas with respect to ammonia catalyst, while
CO2 and CO can poison the catalyst.
 Ammonia Converter.
 After leaving the compressor, the gaseous mixture goes through
catalyst beds in the synthesis converter where ammonia is
produced with a three-to-one hydrogen-to-nitrogen stoichiometric
ratio.
 Not all the hydrogen and nitrogen are converted to ammonia. The
unconverted hydrogen and nitrogen are separated from the
ammonia in the separator and re-cycled back to the synthesis gas
compressor and to the converter with fresh feed.
Kinetics
A catalyst (iron) is used to speed up the rate of reaction
and to lower the high activation energy in breaking the
N2 triple bond. However, if the temperature is too
high, it begins to get destroyed and must be changed
more regularly.
The reaction mechanism, involving the heterogeneous
catalyst, is believed to be as follows:
1. N2 (g) → N2 (adsorbed)

2. N2 (adsorbed) → 2N (adsorbed)

3. H2 (g) → H2 (adsorbed)

4. H2 (adsorbed) → 2H (adsorbed)

5. N (adsorbed) + 3H (adsorbed)→ NH3 (adsorbed)

6. NH3 (adsorbed) → NH3 (g)

Ammonia Separation
The removal of product ammonia is accomplished via mechanical
refrigeration or absorption/distillation. The choice is made by
examining the fixed and operating costs. Typically, refrigeration is
more economical at synthesis pressures of 100 atm or greater. At lower
pressures, absorption/distillation is usually favored.
 Effect of temperature and pressure
on Haber Process
In the Haber Process for the production of ammonia,
based on the reversible reaction:
N2(g) + 3H2(g) 2NH3(g)
it is observed that:
• As the total pressure increases, the amount of ammonia
present at equilibrium increases.
• As the temperature decreases, the amount of ammonia at
equilibrium increases.
 Haber Process

N2(g) + 3H2(g) 2NH3(g)

USES OF AMMONIA
 Ammonia is also used for the production of plastics, explosives,
nitric acid HNO3(via the Ostwald process) and intermediates for
dyes and pharmaceuticals.
 Around 85% of the ammonia is used in fertilizer manufacture:
 Ammonium salts are used as fertilizers because they contain nitrogen
in a form that plants can use. The fertilizer Nitram is ammonium
nitrate and is made from a solution of ammonia in water and nitric
acid in an acid-base reaction:
NH3(aq) + HNO3(aq) NH4NO3(aq)

Similar neutralization reactions with phosphoric(V) and sulphuric acids:

2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)
 HEALTH AND SAFETY
 The occupational health and safety issues associated with ammonia production
and storage are: Fire/explosion injuries Poisoning Suffocation
 NH3 is a toxic gas that is highly irritating to eyes and lungs. Exposure to high
doses can be fatal. Plants must be well ventilated and contain readily available
breathing apparatus.
 NH3 reacts readily and explosively with a wide range of chemicals such as acids.
Fires and explosions may occur in the parts of the plant where hydrogen is
produced, requiring careful design and safety features.
 NH3 boils at –33°C and hence liquid ammonia can cause frost bite and severe
burning.
 As ammonia is highly soluble in water, it is extremely toxic to the environment,
both in its gaseous form and when dissolved in water.
 Workers involved in the handling of liquid ammonia storage and transport need
to wear impervious gloves, face shields, and rubber boots and aprons.
 CO gas produced during reforming is toxic and exposure to this gas must also be
carefully monitored.
 The site used for ammonia production is often connected directly to the sites of
plants synthesizing other chemicals, such as urea and nitric acid, thus minimising
the hazards and costs associated with transport of the chemical.