Ammonia and Nitric

Process industries I
Introduction
Ethiopia has the potential to accelerates its industrial development particularly in
area of : Sugar, food, beverage, leather , textile, cement, building materials and
chemical processing industries.
Ethiopia has high potential for development of processing industries.
Current contribution of the manufacturing industries to Gross Domestic

Production(GDP) has been around 6% for many years.
Small scale and cottage industries contribution to GDP is about 2%.
Many industrial goods are still scarce and in short supply in Ethiopia.
The per capita consumption of industrial goods in Ethiopia is low.
Example: Sugar is about 4kg, soap and edible oil is less than1kg.
Proactive industrial investment required to satisfy the growing demands of

industrial goods.
Department of chemical
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Proactive investment measures and subsequent growth of industrial sector in Ethiopia
have to be accompanied by development of qualified and productive skilled man power.
Therefore, students of chemical engineering and science as well as for those engineers
and technologists should engaged in development taking place in the area of process
industries and technology.
It is identified that 10 primary raw materials produce 20 basic chemicals. The origins of
primary raw materials are fossil, biomass, minerals, hydrosphere and atmospheric natural
resources.
10 primary raw materials are:

Hydrocarbons: crude oil, natural gas and coal
Biomass: plant and animal
Minerals: rocket, salt and sulphur
Water and air
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Chemical and allied industries : by the diversity of raw materials it uses, by

the variety of goods it produce and by the broadness of the market, chemical
industry is one o the difficult industrial braches to define it precisely.
In the context of a broader approach , the chemical industries are defined as

process industries that involve chemical and/or physical transformation of raw
materials to produce chemical and chemical related allied products.
This broad definition will help to include soap, detergent, silicates, plastics,
synthetic fibers, fertilizers, pesticide, cement, glass, ceramics and other process
industries.
The global chemical industry is still concentrated in 16 countries that account

for about 80% of global chemical production. These are US, Japan, Germany,
China, France, UK, Italy, Republic of Korea,
Department Brazil, etc.
of chemical
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The top ten transnational companies of the world having sales of chemical
products are listed in table below.
Company headquarters 2007 Rank
chemical
sales in
billion
BASF SE, Ludwigshafen Germany $65.3 1
DOW Chemical, Midland, Michigan, USA $53,5 2
INEOS, Lyndhurst, UK $43.6 3
Lyondell Bassel, Houston, Texas, USA $42.8 4
Formosa Plastics, Taiwan $31.9 5
DuPoint, Wilmington, Delaware, USA $28.5 6
Saudi Basic Industries Corp, Saudi $26.4 7
Arabia
Bayer, AG, Leverkusen, Germany $24.2 8
Mitsubishi chemical, Tokyo, Japan $22.2 9
Akzo Noble/Imperial Chemical
Department of chemical $19.9 10
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Industries(ICI) engineering
Process Industries I
Chemical and allied industries in Africa:
Africa is currently neither a major consumer nor producer of chemicals in
global terms.
The developed of chemical industries in Africa is very much observed in
Northern, western and Southern Africa. The establishment has been
facilitated by access to larger markets and by presence of petroleum.
Northern region: Algeria, Egypt, Libya, Morocco and Tunisia.
Western region: Nigeria
Southern: South Africa
The chemical market in Africa is primarily targeted at meeting local needs
rather than being export-oriented. China and India are major exporters of
chemicals to Africa.
Chemical and allied industries in Ethiopia:
About 200 chemical and allied industries in Ethiopia, most of them are tiny
and small private with low production volume. Few basic chemical
industries such as Aluminum Sulphate and sulphuric acid , Caustic soda,
Soda ash, Plastics, Rubber, soap and detergents, pesticides, silicate
industries: cement, glass and Department
ceramics,ofpredominantly
chemical
owned by the state.
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Majority of Ethiopian chemical and allied industries depend heavily on imported raw
materials(plastics, rubber, pesticides, soap and detergents).
The manufacturing /industrial sector of Ethiopia economy is undeveloped and its

contribution to GDP has been 6% and the economic sector of chemical industries is little
developed.
There is no as such a well established institutional frame work specifically responsible for
the development of chemical industries in Ethiopia.
No chemical R & D centers or institute to support the sub-sector.
The Chemical Institute or Corporation currently formulated will responsible for the
expansion and development of the sector.
Almost all Ethiopian chemical industries produce easily formulated consumer products.
The chemicals produced locally lack competitiveness capacity both in quality and price.
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Classification of chemical industries of Ethiopia based on their raw

materials sources:
Local raw materials:
Abijata Soda Ash Enterprise
Ethiopian Spice Extraction
Balezaf Alcohol Industries
Fincha and Metehara Ethanol Plants
Tabor Ceramics Industries
Glass Industries
Zeway Caustic Soda
Muger Cement industries
Messobe Cement Indusries
Derba Cement Industries
National Cement Industries
Foreign and local raw materials:
Alkyd resin Factory/Linseed oil
Repppi and other Detergent plants/caustic soda
East African Soap and Detergent plants
Awash Melkassan Sulpheric acid Factory/water and Air
Industrial gases(Carbon dioxide) of chemical
Department
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Foreign base raw material :
Horizon Addis Tyre and other Rubber Processing Industries
Plastic and Foam Processing Industries
Ethiopian pulp and Paper Industries
Adami Tulu Pesticides Formulation Plant
Pharmaceutical Industries
Paint Industries
Chora Gas and Chemical products
Bekas Chemicals
East Africa Soap and Detergent Industries
Gulelie Soap factory
Nazreth Soap factory
Cosmetics/hair & skin care products
The current Ethiopian market is quite small for many chemicals.
It is impossible to satisfy the growing demand of industrial goods of the
Ethiopian population with the existing factories unless proactive industrial
investment measures are taken.
Departiment of chemical
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Unit operation/process flow chart of industries:
Unit operations generally used to represent the physical operation taking place in a particular
processing step of industrial plant.
Sustainable operation of any chemical and allied process industries generally depend on
efficient operation of a unit or component called unit operation.
In practice, unit operation is expanded to cover processing steps that also involve both chemical
and physical changes.
Any process industry can be defined and represented by logically or rationally interconnected
unit operations.
Unit operations, individually as well as collectively are capable of transforming raw materials
into useful and marketable products and can be represented as a group or specific unit
operation at level of single equipment.
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Raw Raw Material

Input material materials transformat
storages preparation ion U.Os
U.Os U.Os
Product
Product purification
separation &
Waste U.Os Packing
treatment U.Os
Plant U.Os
Byproduct Product storage

Storage U.Os
U.Os
Fig. 1 Flow Chart of the unit operation group of a typical processing industry
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The purpose and function of the specific unit operation contained in each
group as represented in Fig. 1 will depend on the nature of the process .
Through succession of operational steps integrated in a rational or logical
manner, every industrial process is designed to produce a desired products.
Almost all industrial process consists of a combination of:
1.Physical process(size reduction, adsorption, absorption, stripping, evaporation,
condensation, crystallization, extraction, filtration, pumping, compressing etc. )
2. Chemical process (involving reaction such as alkylation, calcinations,
polymerization etc.
Exercises:
1. Assess the resource potential of Ethiopia that can be used for the development
of chemical and allied industries.
2. Discuss the importance of industries in the economy of the country (How they support
the GDP and GTP of the country?)
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Process Industries
Bach versus Continuous Processing:

Batch processing/one-off production: is a technique used in
manufacturing , in which the object in question(product) is created stage by
stage over a series of workstations/unit operation, and different batches of
product are made.
Example: water purification, manufacturing of ink, paints and adhesives etc.
Advantages:
1. reduce initial capital (cost of setting up the machines)
2. can be useful for small businesses who cannot afford to run continuous
production lines.
3. Useful for a factory that makes seasonal items(product for which it is
difficult to forecast demand)
4. A trial run for production, or product that have a high profit margin.
Drawbacks: inefficiencies, idle time/downtime, cycle time etc.
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Continuous Processing: is a flow production method used to manufacture,
produce, or process materials without interruption. The materials, either dry bulk
or fluids that are being processed are continuously in motion, undergoing
chemical reactions or subject to mechanical or heat treatment.
Continuous usually means operating 24 hours per day, seven days per week with
infrequent maintenance shutdowns, such as semi-annual or annual.
Some chemical plants can operate for more than one or two years without a
shutdown. Blast furnaces can run four to ten years without stopping.
Examples: oil refining, blast furnace(iron), power station, natural gas processing,
sanitary waste water treatment, rotary kilns for calcining lime or cement etc.
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Most of the industries are very capital intensive and the management is
therefore very concerned about lost operating time.
Shutting down and starting up many continuous processes typically results

in off quality product that must be reprocessed or disposed of.
Many tanks, vessel and pipes cannot be left full of materials because of
unwanted chemical rxn, settling of suspended materials or crystallization or
hardening of materials.
Continuous processes use process control to automate and control

operational variables such as flow rates, tank levels, pressures,
temperatures and machine speeds.
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Industrial Gases:
Industrial gases perform varied and essential functions in economy. Some
are raw materials for the manufacture of other chemicals.
Examples: oxygen, carbon dioxide, nitrogen, hydrogen
Carbon dioxide: noncorrosive in nature, light in weight, easily shipped in
solid form, relatively high specific gravity, excellent refrigerating effect, its
low temperature.
In liquid and solid form has been known for over a century. Solid form is
for refrigerating ad freezing ice cream, meat, and other foods. Also
important as source of carbon dioxide for inert atmosphere and
occasionally for carbonated beverages, liquid form as a fire-extinguishing
materials, and gaseous state has many application in chemical industries .
Manufacturing of CO2:
Most important for commercial production:
1. recovery from synthesis gas in ammonia production
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2. Recovery from the production of ethanol by fermentation
3. Recovery from natural wells
Hydrogen: has long been an important gaseous raw material for the
chemical and petroleum industries. Hydrogen is sold as gas and liquid.
Hydrogen is derived almost exclusively from carbonuous materials ,
primarily hydrocarbons, and/or water.. Example: electrolysis of water,
steam reforming of HC, and thermal dissociation of natural gas, partial
oxidation process.
Oxygen:
Chemical industry is a large consumer of oxygen, using in such application
as acetylene and ethylene oxide production and in ammonia and methanol
production via partial oxidation of hydrocarbons.
Potentially used for synthetic fuels production: coal gasification and coal
liquefaction.
Oxygen is produced by the liquefaction and rectification of air .
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Processes Industries I
Energy and Fuels:
Energy: most energy generation involves the conversion of some type of
fuel usually by combustion. Temperature is the driving force for energy
conversion, so it is n important variable.
Energy plays a key role for the rapid development of industrial sector.
Fossil fuels and geothermal, wind, solar, tidal, human, animal, and nuclear
energies are all competitive energy sources.
Fossil fuels are solids, liquids and gases.
Solid fuels: peat, lignite, coal
Peat: partially decomposed organic matter.
Lignite: is a fuel intermediate in composition between peat and coal
Coal: the most important of the solid fuels. Coal can be treated before,
during, or after to reduce sulfur emissions.
Pulverized coal has been increasingly used during recent years in suspension
firing for power plant installations b/c of high thermal efficiency with w/c it
can be burned, low cost operation and maintenance, and its great flexibility.
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Liquid fuels: fuel oils, tar, tar oil, kerosene and alcohol.
Fuel oils: the only important liquid fuel used for power generation. It is the
fraction of petroleum crude oil that cannot be converted economically by the
refiner into higher-priced products. It consists of a mixture of the liquid
residues from the cracking processes and fractions.
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Mining and Manufacture of Sulfur:

Sulphur :
a multivalent non-metal, abundant, tasteless, and odorless.
yellow crystalline structure/amorphous
Naturally occurs near volcanoes and with fossil fuel or HC as
impurities(pyrites, gypsum).
Elemental sulphur mined by Frasch Process or recovered as H2S as a
byproduct from natural gas, petroleum.
H2S S by Claus process (desulphurization of petroleum,
petrochemicals)
95% world production is produced as by-product from processing of natural
gas and crude oil
By-product sulphur is known as recovered sulphur and naturally
occurring-mined sulphur.
Upon melting converted to thick viscous liquid at about 190oc.
At 300oc flowing liquid.
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Processes Industries I
Chemical properties of sulfur:
SO2 dissolved in H2O to form sulfurous acid(oxidation)
SO3dissolved in H2O to form sulfuric acid(oxidation)
Upon heating react with almost all the elements.
Technology of sulphur production: heated air
Frasch process sulphur plus air
Claus process
Gypsum process
water(160-180oc)
Barren
Fig. 2 Frach Process Molten cap
sulphur rock
by heat
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Claus Process: HC gases with H2S content of 25% suitable for the
recovery of sulfur
H2S scrubbed from natural gases or other gaseous by absorption in
aqueous monoethanolamine or diethanolamine. The aqueous base is then
stripped of recover H2S .
H2S burnt partially to SO2 in air.
2H2S + 3O2 2SO2 + 2H2O 90 % yield
2H2S + 2SO2 3S + 2H2O
CaSO4 + CH4 CaS + CO2 + 2H2O: gypsum reduction process
CaS + CO2 + H2O H2S + CaCO3
Technology of Sulphuric Acid Industries:
H2SO4 is a strong , heavy acid and has tendency to absorb moisture from
air, generating much heat.
Mixture of H2SO4 and free SO3 is equivalent to sulfuric acid
concentration of over 100% and called fuming sulfuric acid or oleum.
More sulphuric acid is produced than any other chemicals in the world.
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Sulphur and sulphur compounds are the only raw materials for production of H2SO4.
0.33 to 0.34kg of sulphur consumed per kg of 100% H2SO4 produced.
Global production of H2SO4 is 300 million tons per year.
Highly reactive and dissolves most metals, releasing hydrogen
Freezes at 10.37oc, boils at 340oc and soluble in all proportions in water.
Baume scale is suitable to measure H2SO4 concentration in the range of 0 to 93%.
Use of Sulphuric Acid:
used in wide range of concentrations from very dilute for pH control to the strong fuming acid
used in organic synthesis.
Fertilizers production, dyes, explosive, textile and fibers processing, leather tanning, water
treatment, digesting agent, drying agent, acidifying agent, hydrolyzing agent, neutralizing agent,
dehydrating agent, oxidizing agent, absorbing agent, purifying agent, as catalyst, etc.
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Sulphuric acid process:
Sulphuric acid is commercially produced by one of the following processes:
Contact process
Lead chamber process
Both process uses sulphur/sulphur compounds, air and water as raw materialsc.
Core technologies of both processes are oxidation and absorption.
Contact Process: (double absorption and single absorption process)
currently dominant and the technology is very much matured
Accompanied by high conversion and absorption efficiencies, w/c also
result in reduction of emission.
Three basic reaction stapes of the process:
Step 1: production of SO2:-
S + O2 SO2 (exothermic rxn.)
Step 2: SO2 conversion to SO3:-
SO2 + 1/2O2 V2O5 SO3 (exothermic rxn.)
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Step 3: absorption of SO3 to form sulfuric acid:
SO3 is absorbed into counter-current flow of water contained in strong acid
to give highly concentrated H2SO4.
SO3 + H2O H2SO4
Each steps are elaborated by thermodynamic conditions, stoichiometric
consideration, setting optimum temperature, pressure, concentration of
reactant.
Many process have been developed according to large number of source of
raw materials.
Raw material sources:
1. Elemental sulphur(75%): desulphurization of HC & natural solid sulphur
2. Pyrites/ferrous sulphide ores: FeS & FeS2 10%
3. Non-freeous sulphide ores: metal sulphide
4. Spent acids regeneration(5%): organic and in organic spent acids:-alkylation process,
sulphonation process generates large amount of spent acid.
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Unit operation of Contact Process:
1. Sulphur melter and fliter: 140-165oc, moisture, acidity, dust, etc removed and
molten sulphur filtered. Lime added to reduce acidity.
2. Air blower and filter: air filtered and compressed and pass through drying tower to
remove moisture.
3. Drying tower: H2SO4 used as drying agent
4. Sulphur burner: total oxidation/combustion of sulphur to SO2 &temp. raises 1050oc
5. Feed water tank
6. Waste heat boiler: SO2 at 1050oc cooled to 430-470oc
7. Intermediate absorber
8. Final absorber
9. Converter with heat exchanger: SO2 converted to SO3, reversible and
exothermic rxn. K with T to favor formation of SO3. but in T slows
down reaction rate. U.Op system must be designed to handle these two
conflicting situations. multi bed converter solve the problem. Number of
catalyst bed vary from 3 to 5.
yield of SO3 generally depends on: increased O2 concentration, SO3
removal, increased pressure, catalyst effectiveness and reaction time.
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Dryin
Air Stea
g
m
tower
Sulph SO2
ur Waste
SO2,1050oc heat
burne
r boiler
Oxidation
H2O chamber
Sulph
S ur
Melter H2O Fin
&filter Int. a
abs abs
orb r
er
H2SO4 H2SO4
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Conversion of SO2 can further increased by removing and absorbing SO3
using intermediate absorber /double absorption process.
Rate of reaction plays an important part in determining inlet temperature and
amount of catalyst used. If inlet T is low, rate of reaction low so more catalyst
required .
Optimum rxn. Rate is determined by amount of catalyst used operating T
required for maximum yield of SO3.
Conversion with double absorption process: SO2 conversion of 85-95%
achieved in first and second catalyst stage/bed before sending to intermediate
absorber.
SO3 gas already formed is absorbed by 98-99%H2SO4 in the intermediate
absorber.
Absorption of SO3 in intermediate absorber shifts reaction equilibrium
towards to formation of more SO3 in the converter.
The SO3 formed in the last one or two converter absorbed in the final
absorber.
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Absorption: the converter exit gases containing SO3 is cooled in an

economizer before it enters into absorption tower.
SO3 + (98%H2SO4 + 2%H2O) 2H2SO4
Water cannot absorb SO3 gases. The direct absorption of SO3 by water is too
exothermic and forms a fine mist of acid w/c totally prevents formation of
liquid acid. That is why all sulphuric acid plant uses concentrated acid for
absorption
Oleum absorption system: H2SO4 with additional SO3 is called oleum.
Oleum is a fuming sulphuric acid that contains free SO3 dissolved in H2SO4.
Lower concentration of H2SO4 obtained by diluting oleum with water.
A significant amount of heat of solution is generated during dilution of oleum.
Hence cooling is required.
Reading assignment: Lead chamber process and Recovery
of Used Sulfuric cid
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Process Industries I:- Ammonia
Out line
What is ammonia?
Ammonia production Industry
Steam/air reforming industry
Overall reaction
Desulphurization
Primary and Secondary Reformer
Shift Conversion(effects of catalysts on reaction rate)
Methanation
Haber-Bosch Process(Le Chateliers principle)
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Ammonia industries:
What is Ammonia?
Consists of Nitrogen and Hydrogen
Ammonia(NH3) is the most important man made synthetic chemical critically needed for
existence of human kind.
Ammonia is the second massively produced inorganic chemicals in the world next to
sulphuric acid.
plant require nitrogen for growth and to produce protein, but cannot take nitrogen found
in air directly. So it should soluble in water in compound form.
Natural gas or methane currently contributes 77% of raw materials of ammonia industries.
Steam reforming is the most economical route for production of ammonia.
Gaseous/liquid HC reforming process contributes 10%
Coal/coke gasification technology contributes 13%
Typical plant capacity in large scale: 1,000 2000 ton/day
Standard capacity in terms of profitable 1500ton/day.
Limits of plant capacity depend on: feedstock and fuel supply system, compression
pressure, water and air pollution; and liquid ammonia product ammonia storage conditions.
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Ammonia plant may stand alone or integrated with other plants(urea, DAP,
nitric acid, ammonium nitrate and other NPK fertilizers) and easily integrated
on the basis of single HC or other single hydrogen source raw material.
physical and chemical properties of ammonia:
Combines with acids to form salts, excellent solvents for salts, has an
exceptional capacity to ionize electrolytes. Nitrates and urea soluble in
aqueous ammonia, alkali metals and alkaline earth metals readily soluble,
sulfur and phosphorus dissolve in ammonia.
Oxides, fluorides, hydroxides, sulfates, sulfites, and carbonates are insoluble
in ammonia
Ammonia is superior to water in solvating organic compounds such as
benzene, CCl4, and hexane.
Ammonia is stable at ordinary temperatures, but decomposes(450-500oc)
into hydrogen and nitrogen at elevated temperatures.
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Application of ammonia:
Ammonia is the single most widely used compound in fertilizer industry(urea , NH4NO3, DAP,
NH4SO4, NH4CL, NP etc.).
80-85% of ammonia is currently used as raw materials in manufacture of nitrogenous fertilizers.
15-20% of ammonia used in several industrial application: manufacture of plastics, fibers, explosive,
amines and other organic compounds.
Ammonia needed in food and beverage industry as source of nitrogen nutrient for growth of yeast
and micro-organisms.
Used as a facilitator in Solvay process for producing soda ash.
Used in pulp and paper, and in rubber production for stabilization of latex to prevent coagulation.
Used as corrosion inhibitor in petroleum refineries and curing agent in tanning industries
Used for removal of Nox from flue-gases.
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Global production: second massively produced inorganic chemicals next to
H2SO4
The bulk growth will be in China, Middle East, Latin America and Africa
Ammonia production:
Produced from HC, water and air using energy
Hydrogen and energy sources are usually HC
Basic raw materials : Natural gas
Steam reforming process(most efficient route), partial oxidation and gasification
Alternative feed stocks: crude oil, fuel oil, refinery gases, coal and other HC
Raw material selection:
Economy of production require careful selection of raw materials, process
choice and energy management.
Investment cost of heavy oil(40%) and coal (140%) higher than natural gas
Energy perspective, heavy oil 40% and coal 80% energy intensive than natural
gas.
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Fig.2: investment cost, production cost and energy consumption
Comparing Natural gas Heavy oil Coal

parameters
Investment cost 1.0 1.4 2.4
Production Cost 1.0 1.2 1.7
Energy consumption 1.0 1.4 1.8
When natural gas not available, heavy oil may be attractive under special
environmental consideration.
Partial oxidation process targeted to utilize heavy residues, plastics recycle
and other wastes, thereby solving pollution problems.
Country may have large deposit of coal but not of natural gas , has a
competitive utilizing of coal as a raw materials
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Block diagram of steam/air reforming process:

Natural gas
ZnO desulphurization ZnS
H2O/fuel Primary reformer Fuel gases/ H2, CO, CO2
Air Heat
Secondary reformer
Power
Shift conversion Heat
Heat condensate CO2

CO2 removal
Power
Methanation
Power
Compression
Power Heat
Ammonia synthesis
purge/flash gas
NH3
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Process Industries I: ammonia
Desulphurization: hydrogenation process
CS2 + 4H2 2H2S + CH4
ZnO + H2S ZnS +H2O
ZnS + H2O ZnO + H2S (regeneration of ZnO)
Interchangeability use of two absorption bed.
Primary reforming:
Steam/gas mixtures heated to 500-600oc before entering to primary reformer
Steam to methane ration= 3-5
Optimum amount of process steam determined by steam to carbon molar
ratio(S/C-ratio)<3 for reforming process.
Nickel catalyst used
General steam reforming reaction: CH2n+1 + nH2O (2n+1)H2 +nCO
CH4 + H2O 3H2 + CO
CO + H2O H2 + CO2
CH4 + 2H2O 4H2 + CO2 (endothermic reaction)
30-40% incoming natural gas burnt for endothermic rxn.
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Process Industries I: Ammonia
Side Rxn. CH4 +CO2 2CO + 2H2
CO + H2O CO2 + H2
CH4 C + 2H2
CO C + CO2
Carbon(C):- deactivate catalyst, damage compressors and blowers.
Counteracted by using high steam-natural gas ratio(3-5)
Only 30-40% of natural gas feed reformed in primary unit.
Secondary reforming:-
Gaseous/un reacted natural gas + controlled air combustion/oxidation rxn
Gases from primary reformer
Filtered air SPR steam for turbines
Seconda H2,N2,
ry CO,H2O,CO2
reformer WHB Minor: CH4
BFW
Departiment of chemical 37
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Partial oxidation and reforming , both takes place in SR.
T=1270-1290oc
endth. rxn
exth. 980oc
950oc
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Process Industries I:ammonia
Shift reaction/conversion unit operation:
To convert CO to CO2 for easy removal of carbon
Raw process from coming SR contains 12-15%CO
CO + H2O CO2 + H2: In different shift rxn.
Exothermic and reversible reaction.
Low T operation and acceptable fast reaction consider optimal conversion yield
Different section of shift conversion:
1. HTS bed of Fe2O3 catalyst to promote reaction
2. Guard bed of ZnO to capture H2S may released from iron oxide
3. Cooling section to realize required low T
4. LTS bed of Cu/ZnO/Al2O3 to maintain low temperature(H2, N2, CO2, CH4, gas cooled
and excess heat is condensed. Heat released during condensation used for generation of
CO2 scrubbing solution

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CO2 removal:
Removal of bulk CO2 by action of solvents using chemical and physical
absorption-stripping.
solvent used for chemical absorption: hot potassium carbonate solution,
aqueous amine solution, activated methyl diethanolamine(MEA).
Physical absorption: glycol dimethylethers(selexol), propylene carbonate, etc
Hot potassium carbonate solution
Absorption reaction: (K2CO3 + H2O) + CO2 2KHO3
Striping /desorption process: 2KHO3 (K2CO3 + H2O) + CO2
MEA
Absorption reaction:
(2RNH2 + H2O) + CO2 (RNH3)2CO3
[(RNH3)2CO3 + H2O] + CO2 2RNH3HCO3
Striping /desorption process:
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Methanation:
The reverse process or reaction of steam reforming of methane.
CO and CO2 remaining in synthesis gas , poisonous ammonia synthesis
catalyst and must be removed by conversion to CH4.
Cox (2+x)H2 CH4 + xH2O
CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 + 2H2O
Rxn. at 300oc in reactor filled with nickel catalyst.
Excess of H2 gas and relatively low T make complete conversion of Cox to
methane and water.
H2, N2,CO,CO2, H2O, CH4
Methnator
H2,N2,H2O,CH4
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Synthesis gas drying: water, CO, CO2 must be removed(cooling and condensation or by
adsorption) before entering the converter.
Synthesis gas compression:
Gas entering compressor virtually has no oxide of carbon.
Ammonia synthesis is favored by high pressure process(mole of NH3< mole of
3H2 and N2).
Le Chaliers principle , volume contraction, a pressure increase give high yield
of ammonia.
Pressure increased by use of compressor(100-250 bar, 350-550oc)
Molecular sieve used to remove H2O, CO, CO2
H2, N2, CH4, Air
Molecular sieve
H2, N2,CH4,Ar
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Depending on the pressure, ammonia production classified into three:
1.Low pressure ammonia process: 100-300atm
2. Medium pressure ammonia process: 300-600atm
3. High pressure ammonia process: 600-1000atm
High pressure equipment are expensive, sensitive, and prone to explosion.
Increase in pressure brings high yield of ammonia.
The main limit is the high cost of high pressure equipment.
Ammonia synthesis:
Mixture of gas cooled, compressed, & fed into ammonia synthesis loop
Iron used as a catalyst
N2(g) + 3H2(g) 2NH3(g) (exothermic reaction)
Pressure increase causes equilibrium to shift to the right, higher yield of NH3
Ammonia mole fraction decrease as the temperature increase
Only 20-30% is reacted per pass in converter due to unfavorable equilibrium
Purge gas is scrubbed with water using absorber-stripper system
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H2, N2 un reacted gases/H2,N2 purge gases
Compressor
Ammonia Separator
converter
Separator
Liquid NH3
Fig. Ammonia synthesis by steam reforming
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Ammonia production by partial oxidation:
Steam reforming process is restricted to light HC ranging from natural
gas(methane) to light naphtha. Not applicable for higher HC, such as fuel oil,
coal, etc.
Impurities(sulfur, heavy metals) from such HC, poison sensitive nickel
catalyst.
Cracking reaction depositing carbon w/c might block catalysts pores and
restrict gas flows
Partial oxidation/gasification process offers alternative for future utilization
of heavy fuels, coal and polymer wastes.
Ammonia production by partial oxidation of coal:
main unit operation:
1. air separation unit 6. Methanation and drying
2. Coal preparation 7. Liquid N2 wash and N2 supply
3. Coal gasification 8. Compressor
4. Shift reactor 9. Ammonia synthesis plant
5. CO2/H2S removal
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Air separation unit:
Required to produce relatively pure stream O2 for gasification and NH3
ammonia synthesis
N2 in excess of stiochiomietric requirement of ammonia synthesis used to push
dried milled coal into gasifies.
Coal preparation:
Coal milled and dried to reduce moisture content to appr.5%
Dried coal pressurized with nitrogen to meet Gasifier injection pressure
requirement
Gasification:
Partial oxidation of coal and other carbonaceous feedstock in presence of
oxygen and/or steam, to produce synthesis gas (gsyngas: CO &H2).
High temperature, non-catalytic process (>99%cabon conversion achieved)
Raw syngas is quenched with water and gas mixture cooled, solidifying ash as
slag and absorbing process heat in gaseous mixtures
Raw gas scrubbed in water to remove traces of carry over ash before it enters
shift converter.
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Process industries I: ammonia
Carbon monoxide shift unit:
Convert CO to CO2 and maximize total hydrogen production.
CO + H2O H2 + CO2 (exothermic)
COS + H2O CO2 + H2S
HCN + H2O CO + NH3
CO2/H2S removal:
Remove CO2 and H2S from syngas
Counter current flowing alkaline used as a solvent in main absorber.
Lean solvent supplied to absorber with flow and temperature control.
CO2 and H2S separated by heating the solvent in stripping column.
A little over 30% of CO2 removed from ammonia production used for
urea synthesis.
Methanation:
Small amount of CO and CO2 must be removed
Cox + (2+x)H2 CH4 + xH2O
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Ammonia synthesis:
Cleaned synthesis gas(mainly H2) blended with N2
N2 + 3H2 2NH3
Heat released recovered as steam
Reaction takes place at high pressure and relatively high temperature
Ammonia produced is condensed and separated.
Application:
Ammonia production and urea production using coal of Yayu, Ilababure Zone,
Oromia Region, Western Ethiopia:
Chinese company named COMPLANT conducted Feasibility Study Report to establish
combined complex plant to produce 300,000tons of urea and 30,000tons of methanol annually
based on ammonia produced by gasification of coal.
Coal mine at Yayu can support synthesis of ammonia up to 282,000 tons/year.
Gasification process of ammonia plant utilizes 72 tones/hour of pulverized and dried coal,
26,000Nm3/h enriched oxygen and 28tons of steam.
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Process Industries I: Nitric acid industries
Out line:
Introduction
Properties of nitric acid
Uses of nitric acid
Global production and consumption
Process technology
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Process Industries I: Nitric acid industries
Nitric acid is strong acid and power full oxidizing agent.
Important in the production of chemicals such as fertilizers, synthetic fibers, dyes,

insecticides, fungicides, and explosive.
Raw materials occur in the form of nitrate salts
Before 20th century, HNO3 prepared commercially by reacting sulphuric acid with
either sodium nitrate/potassium nitrate
In1903 electric-furnace superseded the nitrate-sulphuric acid technology.
Depleting natural nitrate as well as energy intensive and costly arc process led to
development of ammonia oxidation synthesis technology
Oxidation of NH3 to give nitric oxide followed by oxidation of nitric oxide to
nitrogen dioxide solution.
Nitrogen oxide absorbed in water to give nitric acid
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Process industries I:Nitric acid production
Nitric acid industries:
Nitric acid is a color less liquid at room temperature and atmospheric pressure.
Soluble in water in all proportions and there by release heat of solution.
Strong acid and power full oxidizing agent
Azeotropic point w/c influence techniques associated with strong acid
production.
80% of nitric acid produced is used in manufacturing of ammonium nitrate,
nitro phosphate, and NPK fertilizers.
Explosive manufacturing utilizes nitric acid for organic nitration.
nitric acid mainly used in the form of weak nitric acid.
Concentrated acid accounting for only 10% of total production
Roughly 90% of nitric acid is manufactured for on site consumption within the
facility.
Demand is largely related to the demand for the end products for w/c it serves
as input.
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Process industries I: Nitric acid Industries
Process technology of nitric acid industries:
sodium nitrate-sulphuric acid process
Nitric acid production by ammonia oxidation
Nitric acid production by ammonia oxidation:

NH3 vaporized and filtered
Air purified using two or three stage filtration and pressurized
Oxidation and absorption are the central processing
Three main processing steps:

Ammonia oxidation to nitrogen monoxide(NO)
Nitrogen monoxide oxidation to nitrogen dioxide(NO2)
Nitrogen dioxide absorption by water.
NO to NO2 in the cooler-reactor
Efficiency of ammonia oxidation favored by low pressure.
Absorption process favored by high pressure

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Process industries I: nitric acid industries
Based on pressure used, oxidation and absorption process can be classified into
three:
Low pressure (pressure below 1.7 bar)
Medium pressure (1.7-6.5 bar)
High pressure(6.5-13bar)
Nitric plant can be operate either as single-pressure or dual-pressure pocess

system
Mono pressure process: all unit operation operates at either moderate(0.3-
0.6MPa) or high pressure(0.7-1.2MPa)
Dual-pressure process: oxidation of ammonia at atmospheric or moderate
pressure(0.3-0.6 MPa) and absorption of nitrogen oxides at high pressure(1.1-
1.3 MPa)
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Major unit operation:
Air filtration and compression(air heated by hot process gas from ammonia oxidizer)
Air pre heater, waste heat boiler
Ammonia vaporizer(vaporized, superheated, pressure maintained)
Air/ammonia mixer
Ammonia oxidizer
Tail gas pre-heater
Absorption
Tail gas heating
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Air-ammonia mixture and filtration:
Ammonia mixed with water at ratio of 1:10
Poor ammonia air mixing and poor gas distribution across catalyst reduce
yield to 10%
Ensure that lower explosive limit for ammonia is not exceeded(12% for
atmospheric oxidation or 10% for case of pressure)
Ammonia oxidation/converter:
Pre-heated ammonia-air introduced to converter.
4NH3 + 5O2 44NO + 6H2O + Q T=800-900oc
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Ammonia 4NH3 + 5O2 44NO + 6H2O + Q T=800-900oc
Air
NH3-Air
Mixer
Ammonia
Oxidizer
NO, H2O,O2,N2
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Yield of ammonia oxidation depends on:
Catalyst(platinum and rhodium) temperature and pressure
Operating temperature very important for optimal yield of NO
Above 900oc NO decompose to N2 &O2
Below 800oc NO2 will be formed (slow reaction) which does not
produce HNO3 when dissolved in water.
4NH3 + 3O2 N2 + 6H2O, when T>900oc
4NH3 + 4O2 N2O + 6H2O, when T<800oc
NH3,
efficiency 1bar
%NO 4bar
Toc
Fig. relation of ammonia oxidation and temperature
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Cooler-reactor:
Highly exothermic reactions recovered by waste heat boiler(WHB)
fitted in ammonia converter.
NO will not oxidized when temperature is above 150oc
2NO + O2 2NO2 + Q T<150oc

Excess air is added to ammonia converter (gas mixture from ammonia
oxidation get enough oxygen)
Heat recovery from tail gas in WHB
NO2 gets dissolved in water condensate to form diluted nitric acid
Collected diluted acid drawn by pump and discharged to bottom of the

absorption tower.
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Absorption:
The absorber is operated with counter current flow of water
Tail/waste gas
water
Absorber
NO2, H2O, N2, NO,O2
Secondary air line
50-60%HNO3
Fig. absorption system in nitric acid production.
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Gas enters at bottom, dilute nitric acid
Cold water entering at top reacts with NO2 to produce nitric acid
Absorption columns are equipped with sieve plates
High reaction yield and good absorption efficiency are essential
parameters for HNO3 production
Bleaching: HNO3 sent bleaching tower to eliminate its color
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Process Industries I:Ammonium Nitrate Production
Ammonium nitrate production:
An important nitrogenous fertilizer with a 34% nitrogen content
Representing about 12% of total nitrogen consumption worldwide.
More readily available to crops in balanced and timely manner than
urea
80-85% of globally produced
Ammonium nitrate is produced by neutralizing nitric acid with
ammonia
Marketed in solid or liquid form.
Formation of Prills, crystals or granules closely related to usage of
different unit operation and to degree of nitric acid acid concentration.

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Major unit operation of ammonium nitrate plant:
Production line used in formation of pills(low/high density), crystals or
granules (high density, concentrated) vary in process detail and in
arrangement of unit operations.
Table : Major unit operation of ammonium nitrate plant
Prill production Crystal production Granule production line:

line: A line: B C
1. Neutralization 1. Neutralization 1. Neutralization
2. Evaporation 2. Evaporation 2. Separation
3. Prilling 3. Crystallization 3. Cooling System
4. Dryer 4. Centrifuge 4. Grinding & granulation
5. screening 5. Screening &Dryer 5. screening
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Neutralization:
NH3 + HNO3 NH4NO3 (exothermic rxn.)
Production line A & B utilizes relatively low HNO3 concentration and hence
require evaporator, prill tower drier & crystallizer.
Extent of heat generation depends on degree of nitric acid concentration.
preformed in a single stage or in two stages.
Normal neutralizers: @ atmospheric pressure followed by flash evaporation
Pressure neutralizers:@ elevated pressure
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Evaporation:
Multi-effective evaporation section running under vacuum for flash
evaporation
Solution is steam heated in multi effect evaporation
system(upto99%NH4NO3melt)
Ammonia must be recovered by entrainer
pH and temperature must both be strictly controlled to limit losses of
ammonia
Liquid product will significantly decreases cost of evaporation, prill
drying, crystallization, etc
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Prilling: ammonium nitrate melt is atomized into droplets to fall down along
prill tower where they cool and solidify
Crystallization: evaporation process proceeds in to higher degree of saturation
in crystallization.
Solution that contain ammonium crystals then separated by centrifuge.
Granulation: requires more equipment such as fluidized bed granulation, drum
granulation etc.
Advantageous over prilling is that quantity of exhaust air to be treated is
much smaller and pollution abatement equipment is cheaper.
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Mixing the filling material:
NH4NO3 is highly hygroscopic materials & easily caked when comes to
moist environment.
This makes necessary to dust prills, crystals or granules with an
inert/filling materials(clay, limestone, dolomite, etc) materials. This also
helps to avoid possibility of explosion.
Drying/Screening:
NH4NO3 is dried(usually in drum) using hot air & is screened to get
correct product size.
Over size and under size recycled either in mixing tank, to crystallizers,
or to granulator.
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Process Industries I:Ammonium sulfate Production
Ammonium sulfate production:
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Ammonia and Nitric

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Ammonia and Nitric

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Process industries I

Ethiopia has high potential for development of processing industries.

Current contribution of the manufacturing industries to Gross Domestic

Small scale and cottage industries contribution to GDP is about 2%.

The per capita consumption of industrial goods in Ethiopia is low.

Proactive industrial investment required to satisfy the growing demands of

10 primary raw materials are:

Biomass: plant and animal

Minerals: rocket, salt and sulphur

Water and air

Chemical and allied industries : by the diversity of raw materials it uses, by

In the context of a broader approach , the chemical industries are defined as

The global chemical industry is still concentrated in 16 countries that account

The manufacturing /industrial sector of Ethiopia economy is undeveloped and its

No chemical R & D centers or institute to support the sub-sector.

Classification of chemical industries of Ethiopia based on their raw

Raw Raw Material

Byproduct Product storage

Bach versus Continuous Processing:

Shutting down and starting up many continuous processes typically results

Continuous processes use process control to automate and control

Mining and Manufacture of Sulfur:

0.33 to 0.34kg of sulphur consumed per kg of 100% H2SO4 produced.

Global production of H2SO4 is 300 million tons per year.

Highly reactive and dissolves most metals, releasing hydrogen

Freezes at 10.37oc, boils at 340oc and soluble in all proportions in water.

Baume scale is suitable to measure H2SO4 concentration in the range of 0 to 93%.

Use of Sulphuric Acid:

Absorption: the converter exit gases containing SO3 is cooled in an

Ammonia production Industry

Steam/air reforming industry

Primary and Secondary Reformer

Shift Conversion(effects of catalysts on reaction rate)

Haber-Bosch Process(Le Chateliers principle)

NH4SO4, NH4CL, NP etc.).

80-85% of ammonia is currently used as raw materials in manufacture of nitrogenous fertilizers.

amines and other organic compounds.

Used as a facilitator in Solvay process for producing soda ash.

Used for removal of Nox from flue-gases.

Comparing Natural gas Heavy oil Coal

Block diagram of steam/air reforming process:

H2O/fuel Primary reformer Fuel gases/ H2, CO, CO2

Heat condensate CO2

To convert CO to CO2 for easy removal of carbon

Raw process from coming SR contains 12-15%CO

CO + H2O CO2 + H2: In different shift rxn.

Exothermic and reversible reaction.

Different section of shift conversion:

1. HTS bed of Fe2O3 catalyst to promote reaction

3. Cooling section to realize required low T

CO2 scrubbing solution

H2, N2,CO,CO2, H2O, CH4

Properties of nitric acid

Uses of nitric acid

Global production and consumption

Important in the production of chemicals such as fertilizers, synthetic fibers, dyes,

Nitric acid production by ammonia oxidation

Nitric acid production by ammonia oxidation:

Air purified using two or three stage filtration and pressurized

Oxidation and absorption are the central processing

Three main processing steps:

Nitrogen dioxide absorption by water.

NO to NO2 in the cooler-reactor

Efficiency of ammonia oxidation favored by low pressure.