ChEg 3141 Process Industries I

Chapter -1
FUNDAMENTALS OF CHEMICAL MANUFACTURE

Chapter -2
NITROGEN INDUSTRIES

By
Yonas D. (MSc.)
Department of Chemical Engineereing
KiOT, Wollo University, Ethiopia
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 Chapter 1. Fundamentals of Chemical Manufacture
Batch Process

 Batch Process is a technique used in industries in which the

product is produced stage by stage over a series of workstations
and different batches of products are made.

 In the manufacture of various chemical products in chemical

process Industries batch process is used.

 Specialty chemicals such as medicines and pharmaceutical drugs

are often manufactured in much smaller quantities.

 They are usually made one batch at a time.

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 Examples of Batch Processes

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 Advantages of Batch Processes

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 Disadvantages of Batch Processing

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 Continuous Process

 Continuous process is a process in which the raw materials progress

through a unit operations in a continuous manner to produce an end
product.

 Product quality is achieved highly in continuous flow.

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 FLOW CHARTS

Definition: 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 arrows.
This diagrammatic representation illustrates a solution model to a
given problem.
Flowcharts are used in analyzing, designing, documenting or
managing a process or program in various fields.

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 Beer Process Flow Diagram

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 Types of Flowchart
 Basic Flowchart eg. Computer algorisims
 Audit Flow Diagram: is a diagram used in evaluation of a company's
financial reports and reporting processes
 Process Flowchart: a diagram of the steps in a process and their sequence
 Cross Functional Flowchart eg. business process mapping tool used to
articulate the steps and stakeholders of a given process
 Value-Added Flow Chart: mechanism to improve cycle times and
productivity by visually separating value-adding from non-value-adding
activities.
 Workflow Diagram: is an excellent visual aid for understanding how work
gets done within an organization

 Flowcharts are used in many industries including entertainment, engineering,

physical sciences and computer programming.
The purpose of all flowcharts is to communicate how a process works or
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should work without any technical or group-specific jargon.
 Advantages of using a flowchart

 Communication: Flowcharts are better way of communicating the

logic of a system to all concerned or involved.
 Proper documentation: Program flowcharts serve as a good
program documentation, which is needed for various purposes,
making things more efficient.

 Each flow chart is concerned with one particular process or system.

 Flow charts are an important tool for the improvement of
processes.
 By providing a graphical representation, they help project teams to
identify the different elements of a process and understand the
interrelationships among the various steps.
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 Raw materials for Chemical Industries
 It is a basic material that is used to produce goods, finished products,
energy, or intermediate materials which are feedstock for future
finished products
Primary Raw Materials:
Gaseous: Natural gas, refinery gases, coal Bed.
Liquids : Naphtha, kerosene, gas oil, middle distillates.
Solids : Coal, coke, wax, residues.
Oils and fats: Tallow and coconut oil, palm oil and other oil.
Biomass: Alcohol, paper, energy,
Salt: caustic soda, soda ash.
Sulphur
Lime stone
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 Basic Intermediates
Paraffins: Methane, Propane, Butane and higher hydrocarbons

 Olefins and Derivatives: Ethylene,Propylene,Butadiene,Alcohol,

vinyl chloride

 Aromatics: Benzene,Toluene,EthylBenzene,Xylene,Naphthalene

Secondary Intermediates are obtained from natural gas and crude

oils through different processing schemes

Monomer: Caprolactum, Adipic acid, Hexamethylene diamine,

Terephthalic acid and Acrylonitrile for synthetic
fibres,intermediates for dyestuff industry and pesticides.

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 Energy and Fuels
Energy
 Energy plays an important role for the development of any country and to
meet the challenges due to increasing population it has become one of the
very important to optimize its use and look for alternative energy resources.

 Coal remains the dominant source of energy meeting 52.4% of Ethiopia’s

prime energy needs in 2019-2020 while oil and natural gas met 41.6% of
energy requirement in 2015-2016.

 Biomass resources like crop residues, forage, grass, crops, wood residues,
forest residues, short rotation energy crops and cellulosic components.

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 Biomass Energy

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Fuels

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 Industrial Gases

 Industrial gases are gaseous materials that are manufactured for use in industry.

 The principal Fuel gases provided are as follows:

i) Producer gas (CO, N2,H2 with steam added to reduce ΔH to Zero.)

ii) Water gas (CO, H2): made by passing steam over incandescent coke.

iii) Coke oven gas (H2,CH4,CO)

iv) Carburetted or oil gas (Water gas and pyrolyzed oil)

v) Natural gas and LPG(Liquefied Petroleum gas)

 Other Industrial gases are as follows:

a) Nitrogen b)Oxygen c)Carbon dioxide d) Argon e) Hydrogen f) Helium g)Acetylene.

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 Industrial gases are used in a wide range of industries, which include

i)Oil and gas ii)Petrochemicals iii)Chemicals iv)Power v)Mining

vi)steelmaking vii)metals viii)Environmental protection
ix)Medicine x)Pharmacueticals xii)Biotechnology xiii)Food and
Fertilizers xiv)Nuclear power xv)Electronics and Aerospace.

Fuel Gases
Type Kcal/m Principal use
Producer gas (CO, N2, H2) 1200-1600 Steel Industry heating
Water gas (CO, H2) 2500-2700 Heating, Chemical
synthesis
Coke oven gas (H2,CH4,CO) 4500-8000 Heating, Chemical
synthesis
Carburetted or oil gas(Water gas 4000-9000 Heating,
and pyrolyzed oil)

Natural gas and LPG(Liquefied

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6000-14000 Heating, Chemical 20
Petroleum gas) synthesis
 Manufacture of producer gas

Quantitative requirements:
Basis:100 NM3 of Producer gas
Raw Materials:
Coke:20-25 kg
Coal or blast furnace coke Or Coal:25-30 kg
Air Air:60-80 NM3
steam Steam:8-10 kg
Plant capacity:25000-250000 m3/day

Process Description:
Steam and air mixture injected in bottom of a water- cooled jacket
steel furnace.
It is equipped with rotating grate to remove fusible ash.

Solid fuel is added from hopper valve on top of the furnace.

Producer
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gas is cooled by passing through a waste heat boiler 21
 Producer gas flow sheet

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 Manufacture of Water gas by Continuous process
Raw Materials: Quantitative Requirements:
Bituminous Basis: 100 m3 of water gas from C
 coal C as coke: 55kg
steam (or) C as coal: 58kg
Air: 220Nm3
Steam:80 kg
Plant capacity: 250000-1,500,000 m3/day

Process Description

 Newer process invented in 1940’s by Germans.

 Low purity grade oxygen made by air separation procedure

 The correct ratio of steam, oxygen and coal is added to the reactor.

 It yields a self-sustaining reaction of Zero heat release

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 Water gas flow sheet

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 Chapter 2 Nitrogen Industries
Ammonia Synthesis

 Ammonia is produced basically from Hydrocarbon, water, air

and energy.

 The hydrogen and energy source is usually hydrocarbon.

 The primary raw material or resources of hydrogen and energy

are hydrogen containing materials such as Natural Gas (NG) or
petroleum or coal, water and biomass.

 Air provides Nitrogen and Oxygen

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World production of Ammonia
In 2003, the world production capacity was 109 million
tones ammonia.
Most of the production capacity was located in the following
regions [ IFA, 2005]:
 • Asia (46 % of world capacity)

 • East Europe and central Asia (14 %)

 • North America (11 %)

 • West Europe (9 %), with this share falling from a level of

13 % in 1988
 • Middle East (7 %)

 • Latin America (6 %)

 • Central Europe (4 %)

 • Africa (1 %) Ethiopia (0%)

 Methods of Production: Haber process
Chemical reaction:
N2 +3 H2 Fe
2NH3
ΔH= -22Kcal
Process Description:
i) Ammonia synthesis gas (3 moles pure H2 :1 mole pure N2 is compressed to
the operating pressure 100-1000 atm.
ii) It is sent through a filter to remove compression oil and additionally through
a high temperature guard converter.
iii) It converts CO and CO2 to CH4 and removes traces of H2O,H2S,P and As.
iv) The cool gas is added along the outside of the converter tube walls to provide
cooling.
v) carbon steel can be used for the thick wall pressure vessel and internal tubes.
vi) The preheated gas flows next through the inside of the tube .
vii) It contains promoted porous iron catalyst at 500-550 oC.
viii)The NH3 product with an 8-30% conversion depending on process
conditions.
ix) It is removed by condensation first with water cooling and then NH3
refrigeration.
x) The unconverted N2 and H2 mixture is recirculated to allow an 85-90% yield
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 Ammonia Synthesis(Haber process) flow sheet

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 End use applications of Ammonia:
 used in the manufacture of nitric acid; certain alkalies such as soda
ash; dyes; pharmaceuticals such as sulfa drugs, vitamins and
cosmetics; synthetic textile fibers such as nylon, rayon and acrylics;

 In petroleum industry to neutralize the acid constituents of crude oil

and for protection of equipment from corrosion.

 used in the mining industry for extraction of metals such as copper,

nickel and molybdenum from their ores.

 In areas of water and wastewater treatment, such as pH control, in

solution form to regenerate weak anion exchange resins scavenger in
boiler water treatment.

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 Cont…d

 It is used as the developing agent in photochemical processes such

as white printing, blue printing and in the diazo duplication
process.

 It is a widely used refrigerant in industrial refrigeration systems

found in the food, beverage, petro-chemical and cold storage
industries.

 it is used in the rubber industry for the stabilization of natural

and synthetic latex to prevent premature coagulation.

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 Manufacture of Nitric acid(HNO3)
( Ammonia Oxidation Process)
Properties:
i)Molecular weight: 63.03 ; ii)Melting point : -42oC ; iii)Boiling point :86oC with
decomposition ; iv)Solubility : completely miscible with water

Raw Materials:
 NH3
Filtered air Classification of Processes:
Platinum-rhodium make-up catalyst i) Oxidation of NH3 to NO
ii) Oxidation of NO to NO2
Quantitative Requirements:
iii) Absorption of NO2 in water
Basis: 1 ton Nitric acid(100%)
iv) Concentration of HNO3
 Anhydrous Ammonia : 0.287-0.290 ton
Air : 3000 Nm3
Platinum(2-10% Rh promoted) : 0.1 gm Overall Chemical reactions:
Process water : 120 tons i) 2 NO + O2 -------- 2NO2
 steam :1 ton ii) 3 NO2 + H2O ----- 2 HNO3 + NO
Power : 10-30 KWH

End Uses:
i)80 % Nitric acid is used as fertilisers, eg. ammonium nitrate , calcium nitrate.
ii)4/7/2022
19 % is used as explosives 32
 Production Process
i) Compressed air is mixed with anhydrous
ammonia and fed into the shell and tube
converter.
ii) The converter section consists of Pt-Rh
alloy in the form of 60-80 mesh wire gage
packed in layers.
iii) Gas is passed downward for the contact
time about 2.5X10-4 sec in the catalyst zone
at 800oC
iv) Product gases containing 10-12% NO is
passed through heat recovery units.
v) Air is added to convert NO to NO2 at a
temperature 40-50oC in the system.
vi) Finally it reacts with water to give 57-60%
Nitric acid.
vii) Then it is concentrated to 95% Nitric acid
by using 93% Sulphuric acid.
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 Process flowchart of HNO3 Manufacture

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 Ammonium Nitrate (NH4NO3)
Properties:
i)Molecular weight: 80.05 ; ii)Melting point :170oC ; iii)Decomposes at 200oC
iv)Solubility : Soluble in water (900gm/litre at 20oC),alcohol and Ammonia
v)Grades: White crystals or granules, Fertiliser -93-95% containing 33%N
vi)It is explosive when mixed with combustible materials or exposed to high temperatures
Raw Materials:
57-60% HNO3 from oxidation absorption tower
Liquid NH3

Quantitative Requirements:
Basis: 1 ton of ammonium nitrate(98%yield) Methods of Production: Ammonium
Ammonia : 0.22 ton nitrate is produced by Prilling Process
60% HNO3 : 1.38
Plant capacity : 100-500 tons/day
Chemical Reaction:

NH3 + HNO3 NH4NO3 ΔH= -20.6Kcal

End Uses:
4/7/2022 i) Fertilizer in USA 85% and in India above 90% ; ii) Explosives in USA is 12%
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Flow diagram for Ammonium Nitrate production

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 Ammonium sulphate(NH4)2SO4)
Properties:
i)Molecular weight: 132.14 ; ii)Melting point :235-280oC ; iii)It contains 21% N2&
24% Sulphur
iv)Solubility : Soluble in water (70.6gm/100 gm water at 0oC),Insoluble in acteone,
alcohol and ether.

Raw Materials:
 NH3
Sulphuric acid
Chemical Reaction:

i) 2NH3 + H2SO4 (NH4)2SO4

ii) (NH4)2CO3 + CaSO4 (NH4)2SO4+ CaCO3

End Uses:
i) Ammonium sulphate is used as Soil Fertilizers
ii) It is used as Food additive
iii) It is used to prepare persulfate salts.
iv)It is used as Flame retardant
v)It is also used in aerial firefighting
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 Ammonium phosphate(NH4H2PO4)

Pertinent Properties:
i)Molecular weight: 115 ; ii) Density : 1.80 gm/cc
iv)Solubility : Soluble in water (32gm/ 100 cc at 15oC)
Diammoniam phosphate:
i)Molecular weight: 132 ; ii)Melting point :Decomposes ;iii) Density : 1.62 gm/cc
iv)Solubility : 131gm/100 cc at 15oC)

Raw Materials: Methods of Production: Ammonium

Phosphoric acid & Sulphuric acid phosphate is produced by Neutralization
Anhydrous Liquid NH3 and granulation Process .
KCl
Chemical Reaction:
NH3 + H3PO4 NH4H2HPO4 ΔH= -ve

Monoammonium phosphate
NH3 + NH4H2HPO4 (NH4 )2HPO4
Diammonium phosphate

End Uses:
i) Chemical
4/7/2022 Fertilizer ii) Fire retardants iii)nutrient yiest culture iv)ammoniated dentrifices
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 Sodium Nitrate(NaNO3)
Properties: (Chile saltpeter)
i)Molecular weight: 84.99 ; ii) Boiling point :380oC and decomposes ; iii)Melting point :
308oC ; Density :2.257 g/cm3 ; odour :sweet ;
iv)Solubility : Soluble in water (73 gm/100 mL water at 0oC), soluble in ammonia, alcohol

Raw Materials:
 Nitric acid
Sodium bicarbonate
Sodium carbonate
Sodium hydroxide
Chemical Reactions:

i) 2HNO3 + Na2CO3 2NaNO3 + H2O + CO2

ii) HNO3 + NaHCO3 NaNO3 + H2O + CO2

iii) 2HNO3 +NaOH NaNO3 + H2O

End Uses:
i) Sodium nitrate is used to prepare aqua regia
ii) It is used as Food additive
iii) It is used as oxidizer in fireworks.
iv)It is used in Heat storage & solar power plants
v)It4/7/2022
is also used in waste water Industry. 39
 Potassium Nitrate(KNO3)
(Saltpeter)
Pertinent Properties:
i)Molecular weight: 101.1 ; ii)Melting point :334oC ; iii)Boiling point :Decomposes at 400oC
iv)Solubility : Soluble in water , glycerol and Ammonia
v)Grades: White solid ; vi)Density : 2.109 gm/cm3

End Uses:
Raw Materials:
i) Potassium nitrate is used as Food preservative of salted
Ammonium nitrate
meat ; ii) It is used as thickening agent in soups okra soup)
Potassium chloride
iii)It is used as fertilizers
Potassium hydroxide
iv) It is used as toothpaste for sensitive teeth
Nitric acid
v)It is also used as kidney tablets in Thailand.
Chemical Reactions:

i) NH4NO3 + KCl KNO3 + NH4Cl

ii) KOH + NH4NO3--------- KNO3 + NH4Cl

iii)HNO3 + KCl ------------- KNO3 + HCl

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 Cyanide ( Andrussow process)

properties:
 Formula: HCN
 Molecular weight : 26.02 g/mol
 A cyanide is a chemical compound that contains the group C≡N
 This group is known as cyano group.
Raw Materials:
i) CH4 ; ii) Ammonia; iii) Air
Chemical Reaction:
2HCN + 6 H2O
2 CH4 + 2 NH3 + 3 O2

End Uses:
i) The cyanide compound Sodium nitroprusside is used in clinincal chemistry.
ii) Cyanide is also used in jewelry making.
iii) It is also used in certain kinds of photography

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