Process Industries

A Teaching Material Prepared For 4th Year Chemical Engineering

Students By:
Dr. Yalew W/Amanuel
(Department of Chemical Engineering)
Structure of the chemical industry
Mode of operations in the chemical industry

 Batch process - A process that is not in continuous or

mass production; operations are carried out with discrete
quantities of material or a limited number of items (1T of
X and 2T of Y)
Pharmacuticals
Agrochemicals
Dyestuffs
Food additives
Perfumes
Vitamins
Pigments
Mode of operations in the chemical industry

Advantages of batch processes

 Good for small amounts of speciality chemicals
 Make a range of products using same equipment
 Good for developing new products
 Easier to scale up from lab scale
 Generally cheaper set up costs

Disadvantages of batch processing

 Frequent start up and shutdown of equipment
 Cleaning time between batches
 May be batch to batch variability
 Not good for bulk chemical production
Mode of operations in the chemical industry

 Continuous process - Industrial process that

continuously receives raw materials and processes them
through to completed units (1T/h of X and 2T/h of Y).

 Sulphuric acid production

 Sodium hydroxide production

 Ammonia production

 Petrol production

 Chlorine production

 Methanol production
Mode of operations in the chemical industry

Advantages of Continuous Processing

 Good for large volumes (bulk chemicals)
 Fewer start up and shutdowns

 Potentially greater yields

 Potentially
easier to maintain quality or spot out of specification
product sooner

Disadvantages of Continuous Processing

 Requires
periodic shutdown of whole plant for inspection
and maintenance
 Mayrely on critical pieces of equipment which have the
potential to stop production on whole plant
 Higher initial costs
 Flowsheets
 Flow sheets are used to describe the operating details of
chemical processes. There are a number of basic types:
 Flowcharts (or block diagrams),
 Process flow sheets (or Process Flow Diagrams),
 Piping and Instrumentation Diagrams (PID).

Levels of Flow Diagrams

 Block Flow Diagram (BFD)
 Process Flow Diagram (PFD)
 Piping and Instrumentation Diagram (P&ID) – often
referred to as Mechanical Flow Diagram

BFD Level of
Level of Conceptual
Complexity Understanding
PFD Increases
Increases
P&ID
Important components of a Flowsheet

 Schematic representations

 Arrangement of equipment

 Interconnections

 Movement of material

 Stream connections

 Stream flows/quantities

 Stream compositions

 Operating conditions

 etc
Block Flow Diagram (BFD)
BFD shows overall processing picture of a chemical complex
 Flow of raw materials and products may be included on a
BFD
 BFD is a superficial view of facility
Process Flow Diagram (PFD)
 It Conveys the major processing steps represented
by the equipment
 Useful for conveying the heat and material balances
 Useful for conveying major pieces of equipment
 Useful for conveying processing conditions
 Useful for conveying utilities
 A typical commercial PFD will contain the following
information:
 All major pieces of equipments in the process will be
represented along with a descriptive name and number.
 All process flow streams will be shown and identified with a
number. A description of the process conditions and chemical
composition of each stream will be included.
 All utility streams supplied to major equipment that provides
a process function will be shown.
 Basic control loops will be shown.
Process Flow Diagram (PFD)

 Essential Information  Optional Information

 Stream Number  Component Mole Fractions
 Temperature (°C)  Component Mass Fractions
 Pressure (bar)  Individual Component Flow
 Vapor Fraction Rates (kg/h)
 Total Mass Flow Rate  Volumetric Flow Rates (m3/h)
(kg/h)  Significant Physical Properties
 Total Mole Flow Rate  Density
(kmol/h)  Viscosity
 Individual Component  Other
Flow Rates (kmol/h)  Thermodynamic Data
 Heat Capacity
 Stream Enthalpy
 K-values
 Stream Name
Process Flow Diagram (PFD)
Piping and Instrumentation Diagram (P&ID)
 Equipment details and arrangement (item no., name,
dimensions, materials of construction, rate or capacity,
occupation time, T, P, materials handled, heat duty, power)
 Pipe details
 Valves
 Ancillary fittings
 Pumps
 Instrumentation and
control loops
 Services (utilities)
 Symbols
 Layout
BFD include the material balance calculations.
PFD complete mass and energy balance and preliminary
equipment specs.
P&ID includes the mechanical and instrumentation details.
Chapter 1: Nitrogen Industries
Chapter 1: Nitrogen Industries

Nitrogen Industries

Ammonia Sodium Ammonium Potassium

Nitrate Sulphate Nitrate

Ammonium Nitric Ammonium Cyanide

Nitrate Acid Phosphate
Production process of Nitrogen
 The production of nitrogen from the air is the predominant
method of manufacture.
 The first rectification of N2 and O2 using Joule Thomson effect
was carried out by Linde in 1906.
 After six year Claude rectified them by combined effect of
external work and internal work in cooling the air to liquefaction
point.

 The process for the liquefaction is:

1. Filtration of air: to remove particulates and then
compressed to 531Kpa.
2. Oxidation: An oxidation chamber converts traces of
hydrocarbons into carbon dioxide and water.
Production process of Nitrogen
3. Water separation: The air is then passed through a water
separator that removes some of the water.
4. Cooling: A heat exchanger cools the sample down to very low
temperatures.
5. Fractionation: Most of the nitrogen-oxygen mixture, now at –
168 0C and 496Kpa enters the bottom of a fractionating
column. The more volatile nitrogen rises to the top of the
column as a gas.
6. After being cooled in the heat exchanger, a small amount of
nitrogen-oxygen mixture is fed to the main expander valve and
the extremely cold gas is recycled into the heat exchanger to
keep the system cold.
Production process of Nitrogen
Production process of Ammonia
 Ammonia is an important nitrogenous material used:-
• As fertilizer, In heat treatment, Paper pulping, Nitric
acid and nitrate manufacturing, Nitric acid esters and
nitro compound manufacture, Explosive of various types,
and as a refrigerant.
 It contains the highest amount of nitrogen (82%).
 It has a melting point of –77.7°C.
 Boiling point –33.4°C, and density 0.817 at –79°C and 0.617
at 15°C and also it is colorless gas.
 Has a pungent smell and is irritating to eyes and lungs
 Is non flammable, toxic and corrosive
Ammonia
Industry Use
Fertilizer Production of: ammonium sulfate, (NH4)2SO4; ammonium phosphate,
(NH4)3PO4; ammonium nitrate, NH4NO3; urea, (NH2)2CO.

Chemicals Synthesis of: nitric acid, nitroglycerine; sodium hydrogen carbonate

(sodium bicarbonate), NaHCO3; sodium carbonate,Na2CO3; hydrogen
cyanide (hydrocyanic acid), HCN; hydrazine, N2H4 (used in rocket
propulsion systems).

Explosives Ammonium nitrate, NH4NO3

Fibres & Nylon, -[(CH2)4-CO-NH-(CH2)6-NH-CO]-, and other polyamides
plastics
Refrigeration Used for making ice, large-scale refrigeration plants, air-conditioning
units in buildings and plants.

Pharmaceutic Used in the manufacture of drugs

als
Pulp & paper Ammonium hydrogen sulfite, NH4HSO3, enables some hardwoods to be
used

Mining & Used in nitriding (bright annealing) steel; used in zinc and nickel
metallurgy extraction
Ammonia
At present, over 95% of all commercial fertilizer nitrogen is
supplied by or derived from synthetic NH3

Ammonia fertilisers are:

• Ammonium nitrate fertilizer

NH3(aq) + HNO3(aq)  NH4NO3(aq)
• Ammonium phosphate fertilizer
3NH3(aq) + H3PO4(aq)  (NH4)3PO4(aq)
• Ammonium sulfate fertilizer
2NH3(aq) + H2SO4(aq)  (NH4)2SO4(aq)
• Urea fertilizer
2NH3(aq) + CO2(g)  (NH2)2CO(aq) + H2O(l)
Ammonia
 Feedstock for Ammonia Production with Suitable Processing Methods
Feedstock Methods
Natural gas Steam Reforming
Liquefied petroleum gas Steam Reforming
Naphtha Steam Reforming
Refinery gases Steam Reforming
Heavy oil Partial oxidation
Coal Gasification
 Natural gas (CH4) is the raw material widely used in the steam reforming
process as it posses the highest hydrogen to carbon ratio. 75-85% of the
cost of anhydrous ammonia is Natural Gas

Natural gas Heavy oil coal

Energy consumption 1 1.3 1.7
Investment cost 1 1.4 2.4
Production cost 1 1.2 1.7
Ammonia
 Nitrogen and hydrogen are chemically combined in 1:3
proportions to produce ammonia.
 For this purpose, large quantities of nitrogen and hydrogen
must be produced.
 Fortunately, large quantity of nitrogen is available in
atmospheric air while hydrogen is extracted from NG.
 Thus purification and extraction procedure are needed to be
carried out on atmospheric air and NG during ammonia
production process.
Ammonia
 The following is an example of production:

STEP 1: CH4(g) + H2O(l) CO(g) + 3H2(g)

STEP 2: CO(g) + H2O(l) CO2(g) + H2(g)

 Carbon dioxide is then removed so the H2 can react with nitrogen.

 Ammonia is manufacture using the Haber process, which employs

an iron/iron oxide catalyst. The reaction is exothermic.

STEP 3: N2(g) + 3H2(g) 2NH3(g); ΔH = -91kJ mol-1

 By using Le Chatelier’s principle you can predict the way in

which temperature and pressure will alter the equilibrium yield of
ammonia.
Production process of Ammonia
Production process of Ammonia
 Ammonia manufacturing based on hydrocarbon steam
reforming consists of the following steps:

1. Desulphurization
2. Steam treatment (Primary reforming)
3. Conversion of residual methane by air, which
contributes the nitrogen required (secondary
reforming or post composition)
4. Catalytic conversion of CO by steam (shift conversion)
5. CO2 removal
6. CO removal by treatment with cuprous derivatives or
with methanol: methanation can also be resorted.
7. Ammonia synthesis
Desulphurization
 The first step in the process is to remove sulfur compounds
from the feedstock because sulfur deactivates the catalysts
used in subsequent steps. Sulfur removal requires catalytic
hydrogenation to convert sulfur compounds in the feedstocks
to gaseous hydrogen sulfide using a cobalt molybdenum
catalyst:
H2 + RSH → RH + H2S (gas)
 The gaseous hydrogen sulfide is then adsorbed and removed by
passing it through beds of zinc oxide where it is converted to
solid zinc sulfide:
H2S + ZnO → ZnS + H2O
 The gas from the desulphuriser is mixed with process steam,
usually coming from an extraction turbine.
 The steam/gas mixture is then heated further to 500-600°C
in the convection section before entering the primary reformer.
Desulphurization
 Primary Reforming (PR)
 Gas from the desulphuriser is compressed, mixed with excess
steam and the preheated mixture enters the primary reformer at a
temperature in the range of 400 – 600 ºC.
 The heated desulphurized natural gas and the steam then
reacted in the presence of a nickel or nickel-chromium catalyst to
form hydrogen and carbon monoxide:
CH4 + H2O → CO + 3H2

 The reaction in the primary reformer takes place in the catalytic

tube packed with nickel catalyst operated at elevated temperature
of about 800 - 813 ºC and pressure of 40 bar.

 The overall reaction is highly endothermic and additional heat

is required to raise the temperature to 780-830ºC at the reformer
outlet, which is supplied using flue gas generated by the
combustion of externally supplied fuel (again NG) in the PR.
 Primary Reforming
 The hydrocarbon conversion rate in the primary reformer in
the conventional steam reforming plant is about 60-70 %.
 The primary reformer consists of a large number of
catalyst filled tubes.
 The applied steam to carbon molar ratio (S/C ratio) is
typically around 3.0; although the actual optimum ratio
depends on several factors, such as the feedstock quality,
purge gas recovery, primary reformer capacity, shift
operation, and the plant steam balance. In new plants, the
optimum S/C ratio may be lower than 3.0.
 Upon leaving the primary reformer, the gas is a mixture of
CO2, CO, H2O, CH4 and H2 at a temperature of
approximately 800ºC.
Primary Reforming
The Secondary Reformer
 The main objective of secondary reforming is to add the nitrogen
required for the synthesis and to complete the conversion of the
hydrocarbon feed.

 This is done in secondary reformer where process gas is mixed

with preheated compressed air and then passed over
nickel catalyst. The reformer outlet temperature is about 1000°C,
and up to 99 per cent of the hydrocarbon feed to primary reformer is
converted.

 The further combustion of the un-reacted methane hydrocarbons raises

the temperature to over 1000oC, allowing the remaining methane to be
converted to H2 and CO. The outlet gas from the secondary reformer
consists primarily of CO2, CO,H2, and N2 and it is cooled immediately to
350oC and 450oC downstream of the reformer in Waste Heat
Boiler installed after secondary reformer.
The Secondary Reformer

The process gas is

mixed with the air in a
burner and then passed
over a nickel-
containing secondary
reformer catalyst.
H2 + air → N2 + H2O
Shift conversionr
 The process gas from the secondary reformer contains 12 – 15 % CO
(dry gas base). Most of this CO will be converted in the shift section to
CO2 and H2., according to the reaction:

CO + H2O CO2 + H2 (- 41 kJ/mol)

 This reaction is carried out in two steps with intermediate heat removal,
a) a high temperature shift (HTS) and b) a low temperature shift (LTS).

 Initially, the process gas is passed through a bed of FeO/Cr catalyst at

350 – 380 °C and then over a CuO/ZnO catalyst at approximately 200 –
220 °C. The final residual CO content of the gas is 0.2 – 0.4 %.

 In the HTS, process gas mixes with high-pressure steam and passes over
a at a temperature of about 400oC. The process gas is then cooled to
around 200oC the HTS , where remaining CO is shifted to CO2 over a.

 The process gas is then condensed to remove excess steam (condensate)

before removal of CO2.
CO2 & CO removal
 After shift conversion and condensate removal, the process gas contains
mostly H2, N2, CO2.
 The CO2 (formerly CO) is also detrimental to the synthesis catalysts, so it
too must be removed.
 CO2 removal is by both chemical and physical processes,where the CO2
either reacts with or is adsorbed onto a circulating chemical solvent
solution.
 This CO2/solvent solution is then regenerated via a stripper, from which
the CO2 may be either vented to waste or collected for use elsewhere.
 The solvents used in chemical absorption processes are mainly aqueous
amine solutions, e.g. mono ethanolamine (MEA) activated
methyl diethanolamine (aMDEA) or hot potassium
carbonate solutions. Other typicalchemical solvents are glycol
dimethylethers (Selexol), potassium carbonate and others. The
regeneration of the solvents (in the stripper) occurs by steam stripping or
by flash tanks.
CO2 & CO removal
Methanation Process
 The final step in producing the hydrogen is to use catalytic
methanation to remove any small residual amounts of carbon monoxide
or carbon dioxide from the hydrogen, in the presence of nickel catalyst.
CO + 3H2 CH4 + H2O ∆H = -206 kJ/mol
CO2 + 4H2 CH4 +2H2O ∆H = -165 kJ/mol
 Any small amounts of CO and CO2 still remaining in the synthesis gas are
converted to inert methane by catalytic methanation (which is the reverse
of the reforming reactions/ hydrogenation).
 The small amounts of CO and CO2, remaining in the synthesis gas, can
poison the ammoniasynthesis catalyst and must be removed usually by
conversion to CH4 by hydrogenation in the methanator:

 These reactions take place at a temperature of around 300 °C in a

reactor filled with a nickel based catalyst. The residual concentration of
these carbon oxides is usually less than 10 ppmv.
Ammonia Synthesis
 The first breakthrough in the large-scale synthesis of ammonia resulted
from the development of the Haber process in 1913 in which ammonia
was produced by the direct combination of two elements, nitrogen and
hydrogen, in the presence of a catalyst (iron oxide with small
quantities of cerium and chromium) at a relatively high temperature
(350 and 550 °C) and under a pressure of 100 – 250 bar.

N2 + 3H2 → 2NH3 (-46 kJ/mol)

 Only 20 – 30 % of the synthesis gas is converted per pass to ammonia,

due to unfavourable equilibrium conditions. The unreacted gas is recycled
after removing the ammonia formed.Fresh synthesis gas is supplemented
in the loop.
Ammonia Synthesis
 As the exothermic synthesis reaction proceeds, there is a
reduction in volume and so a higher pressure and lower
temperature favors the reaction.
 The temperature of the catalyst needs to be controlled, as
the heat of reaction at the necessary equilibrium and reaction
rate produces a rise in temperature.
 Subdividing the catalyst into several is one
layers
technique which can achieve this temperature control. In this
technique, between the layers, the gases are cooled either
directly by adding cooled synthesis gas or indirectly by
generating steam. Various converter designs can be utilised
for this purpose
Ammonia Synthesis
 Le Chatelier’s Principle states that whatever is done to a reaction,
the reaction will act to oppose it.
 Increasing the pressure causes the equilibrium position to
move to the right resulting in a higher yield of ammonia
since there are more gas molecules on the left hand side of the equation
(4 in total) than there are on the right hand side of the equation (2).
Increasing the pressure means the system adjusts to reduce the effect of
the change, that is, to reduce the pressure by having fewer gas
molecules.
 Decreasing the temperature causes the equilibrium
position to move to the right resulting in a higher yield of
ammonia since the reaction is exothermic (releases heat). Reducing the
temperature means the system will adjust to minimise the effect of the
change, that is, it will produce more heat since energy is a product of the
reaction, and will therefore produce more ammonia gas as well
However, the rate of the reaction at lower temperatures is extremely
slow, so a higher temperature must be used to speed up the reaction
which results in a lower yield of ammonia.
Ammonia Synthesis
Ammonia Synthesis
Ammonia Synthesis
Ammonia Synthesis