ChEg 3141 Process Industries I

Chapter I
FUNDAMENTALS OF CHEMICAL MANUFACTURE
&
NITROGEN INDUSTRIES

By
Dr.Murugesan A.
Associate Professor,
Department of Chemical Engg.,
KiOT,Wollo University,
Ethiopia
 Chapter 1.1 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.
Examples of Batch Processes
Advantages of Batch Processes
Disadvantages of Batch Processing
 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.
 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.
 Different symbols used in Flowcharts

Flowcharts use special shapes to represent

different types of actions or steps in a process.
 Lines and arrows show the sequence of the
steps and the relationships among them.
 These are known as flowchart symbols.
The type of diagram dictates the flowchart
symbols that are used.

Line
Arrow
Circle Square
 Types of Flowchart

• Basic Flowchart
• Audit Flow Diagram
• Process Flowchart
• Cross Functional Flowchart
• Value-Added Flow Chart
• Data Flow Diagram
• Workflow Diagram
Flowchart needs:
A flowchart is a pictorial or graphical representation of a process.

 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

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.

Importance of a flow chart

 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.
 Concept of a flowchart
A flow chart is a graphical or symbolic representation of a
process.
Each step in the process is represented by a different symbol and
contains a short description of the process step.
The flow chart symbols are linked together with arrows showing
the process flow direction.
Linear flow chart
This type of flowchart is a diagram that displays the sequence of
work steps that make up a process.
This tool can help identify rework and redundant or unnecessary
steps within a process.
 Raw materials for Chemical Industries
Primary Raw Materials:
Gaseous: Natural gas, condensate, 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: Chlorine, caustic soda, soda ash.
Sulphur
Lime stone
 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
Monomer: Caprolactum, Adipic acid, Hexamethylene
diamine,Terephthalic acid and Acrylonitrile for
synthetic fibres,intermediates for dyestuff industry
and pesticides.
 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 while oil and natural gas met
41.6% of energy requirement in 2019-2020.

 Biomass resources like crop residues, forage, grass, crops, wood

residues, forest residues, short rotation energy crops and cellulosic
components.
Biomass Energy
Fuels
 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)
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.
 Although a huge variety of gases and mixtures are available in gas cylinders.
 The industry producing these gases is known as the industrial gases. These Industrial
gases are often seen as “Specialty chemicals”.

 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/m3 Principal use

Producer gas (CO, N2, H2) 1200-1600 Steel Industry heating
Water gas (CO, H2) 2500-2700 Heating, Chemical
synthesis
Coke oven gas 4500-8000 Heating, Chemical
(H2,CH4,CO) synthesis
Carburetted or oil 4000-9000 Heating,
gas(Water gas and
pyrolyzed oil)
Natural gas and 6000-14000 Heating, Chemical
LPG(Liquefied Petroleum synthesis
gas)
 Manufacture of producer gas

Quantitative requirements:
Raw Materials:
Basis:100 NM3 of Producer gas
Coal or blast furnace coke Coke:20-25 kg
Air Or Coal:25-30 kg
Air:60-80 NM3
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 gas is cooled by passing through a waste heat boiler

Producer gas flow sheet
 Manufacture of Water gas by Continuous process

Raw Materials: Quantitative Requirements:

Basis: 100 m3 of water gas from C
Bituminous C as coke: 55kg
Anthracite or coal (or) C as coal: 58kg
Air: 220Nm3
Steam:80 kg
Plant capacity: 250000-1,500,000 Nm3/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.
Indian coal can be used to increase the ash
content >30%
 Chapter1.2 Nitrogen Industries
Ammonia Synthesis(Haber process)
Pertinent Properties of Ammonia
i) Molecular weight:17.03
ii) Melting point: -77.7oC
iii) Boiling point: -33.4oC
iv) Solubility: very soluble in water
v) Grades: Anhydrous or Liquefied NH3 stored at 80oF with a pressure 175 psi.
Raw materials:
Hydrogen from synthesis gas
N2 from air in synthesis gas process
Quantitative requirements:

Basis:1 ton NH3-85% yield

H2 : 0.21 ton or 2000Nm3
N2 : 0.96 ton or 1400 Nm3
Synthesis catalyst: 0.2 kg
Power: 850 KWH
Fuel gas for compressors: 3800 Kcal
Cooling water: 12.5 tons
Plant capacity: 100-1500 tons/day of NH3
 Methods of Production: Haber process
Chemical reaction:
Fe
N2 +3 H2 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) Therefore 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
End use applications of Ammonia:
i)Direct application as fertilizer : 25% ii)Urea : 21%
iii)Ammonium phosphate: 16% iv)Nitric acid :12% v)Miscellaneous: 12%
vi)Ammonium nitrate : 8% vii)Ammonium sulfate: 3% viii)Acrylonitrile : 3%

Manufacture of Ammonia by Haber Process

 Ammonium Nitrate(NH4NO3)
Pertinent Properties:
i)Molecular weight: 80.05 ; ii)Melting point :170oC ; iii)Boiling point :Decomposes at 200oC
iv)Solubility : Soluble in water (900gm/litre at 20oC),alcohol and Ammonia
v)Grades: White hygroscopic crystals or granules, Fertiliser (93-95% containing 33%N)
vi)It is exlosive when mixed with combustible materials or exposed to high temperatures
Raw Materials:
57-60% HNO3 from oxidation absorption tower
Liquid NH3
Clay such as diatomaceous earth, Keiselguhr for coating to avoid explosions.
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:
i) Fertilizer in USA 85% and in India above 90% ; ii) Explosives in USA is 12%
 Manufacture of Nitric acid(HNO3)
( Ammonia Oxidation Process)
Pertinent Properties:
i)Molecular weight: 63.03 ; ii)Melting point : -42oC ; iii)Boiling point :86oC with
decomposition ; iv)Solubility : completely miscible with water ; v)Grades: Concentrated
(95%) ; commercial : 52-68% ; Fuming : >86%
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 credit : 1 ton ii) 3 NO2 + H2O ----- 2 HNO3 + NO
Power : 10-30 KWH

End Uses:
i)80 % Nitric acid is used as fertilisers
ii) 19 % is used as explosives
iii) 1% miscellaneous
Process flowchart of HNO3
Manufacture
Process Description:
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.
 Ammonium sulphate(NH4)2SO4)
Pertinent Properties:
i)Molecular weight: 132.14 ; ii)Melting point :235-280oC and decomposes ; 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
 Ammonium phosphate(NH4H2PO4)
Pertinent Properties:
i)Molecular weight: 115 ; ii)Melting point :Decomposes ; 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 nitrate 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 Fertilizer ii) Fire retardants iii)nutrient yiest culture iv)ammoniated dentrifices
 Sodium Nitrate(NaNO3)
Pertinent 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)It is also used in waste water Industry.
 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

Raw Materials: End Uses:

Ammonium nitrate
Potassium chloride
Potassium hydroxide
Nitric acid
Chemical Reactions:
i) NH4NO3 + KCl
i) Potassium nitrate is used as Food preservative of salted
meat ; ii) It is used as thickening agent in soups (okra
soup) in west African cuisine.
iii)It is used as fertilizers.
iv) It is used as toothpaste for sensitive teeth.
v)It is also used as kidney tablets in Thailand.
KNO3 + NH4Cl

ii) KOH + NH4NO3--------- KNO3 + NH4OH

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

 Cyanide ( Andrussow process)

Pertinent properties:
 Formula: CN-
 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:
2 CH4 + 2 NH3 + 3 O2 2HCN + 6 H2O

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 such as sepia toning.
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