NATIONAL DIPLOMA IN CHEMICAL ENGINEERING
HEXCO
LEARNING OUTCOME 02
Produce Basic Process Flow Diagrams
Comprehensive Study Notes
Topics Covered
2.1 Specify Product and Raw Materials
2.2 Select Processes — Classification & States
2.3 Define Unit Operations — Deep Analysis
2.4 Develop Logical Sequencing of Unit Operations
Mass Balance & Energy Balance Worked Examples
Standard PFD Symbols & Stream Tables
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2.1 Specify Product and Raw Materials
Before designing any process, a chemical engineer must clearly define the inputs and outputs of the
entire system. This step forms the foundation upon which all subsequent process decisions — reactor
selection, separation method, diagram type — are based.
What Must Be Specified
• Desired product — identity, phase (solid/liquid/gas), and required purity grade
• Raw materials (feedstocks) — chemical identity, source, and purity of inputs
• Quantities — production rate (e.g. tonnes/day) and corresponding feed rates
• By-products and waste streams — must be identified even if not the main goal
• Operating constraints — temperature limits, pressure limits, safety restrictions
Example — Ammonia Production (Haber Process):
• Product: NH₃ (ammonia) — anhydrous liquid, 99.9% purity
• Raw materials: N₂ (from air separation) and H₂ (from steam reforming of natural gas)
• Stoichiometric ratio: N₂ : H₂ = 1 : 3 (molar)
• Production rate: e.g. 1000 tonnes/day
Without this step, it is impossible to perform meaningful mass or energy balances, or to select
appropriate equipment.
2.2 Select Process
Process Classification
Processes are classified by how materials enter and leave the system over time.
Type Description Characteristics Example
All materials charged at
Unsteady state; flexible; Pharmaceuticals,
Batch once; reaction proceeds;
high labour cost brewing
product removed at end
Feed and withdrawal occur Steady state; high
Oil refining, ammonia
Continuous simultaneously without throughput; lower unit
synthesis
interruption cost
One reactant charged at
Used for controlled Polymerisation,
Semi-Batch start; another fed gradually
exothermic reactions chlorination
during reaction
Semi-Continuous Mostly continuous with Hybrid of batch and Some fermentation
periodic interruptions for continuous processes
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Type Description Characteristics Example
regeneration
Steady State vs Transient State
The General Balance Equation governs all processes:
IN − OUT + GENERATION − CONSUMPTION = ACCUMULATION
State Accumulation Simplified Equation Typical Process
IN − OUT + GEN − Continuous plants at
Steady State =0
CON = 0 normal operation
Startup, shutdown,
Transient (Unsteady) ≠0 Full equation applies
batch processes
Batch processes are inherently transient because concentrations and temperature change continuously
with time. The design equation for a batch reactor with first-order reaction A → B is:
dCₐ/dt = −k·Cₐ → ln(Cₐ₀/Cₐ) = k·t
Where Cₐ₀ = initial concentration, Cₐ = concentration at time t, k = rate constant (s ⁻¹)
2.3 Define Unit Operations
A unit operation is a fundamental physical or chemical step within a larger process. Every industrial
process is a logical sequence of unit operations. They are grouped into four main categories:
A. Separation Processes
1. Distillation
Separates liquid mixtures based on differences in volatility (vapour pressure). The more volatile
component concentrates in the vapour phase and is removed at the top of the column.
Key parameter — Relative Volatility (α):
αₐᵦ = (yₐ/xₐ) ÷ (yᵦ/xᵦ) = Pₐ* / Pᵦ*
If α = 1, separation by distillation is impossible. The larger α, the easier the separation.
Reflux Ratio (R):
R = L / D
• L = liquid returned to column top (reflux)
• D = distillate product withdrawn
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• Higher R → better separation but much higher energy cost
• Minimum reflux ratio (Rmin) → requires infinite number of theoretical trays
Overall Material Balance on a Distillation Column:
F = D + B (total flow)
F·z_F = D·y_D + B·x_B (component balance)
Where F = feed, D = distillate, B = bottoms; z, y, x = compositions
2. Gravitational Separation
Exploits density differences between phases to achieve separation. No chemical change occurs —
purely physical.
• Settling tanks — allow heavy particles/liquid to sink by gravity
• Centrifuges — use centrifugal force to enhance gravitational separation (g-forces up to
10,000×g)
• Cyclones — use rotational flow to separate solids from gases
3. Liquid-Liquid Extraction
A selective solvent is used to preferentially dissolve one component from a mixture. The solvent must
be immiscible with the original mixture.
• Solute transfers from the feed phase (raffinate) into the solvent (extract)
• Solvent is then recovered by distillation and recycled
• Industrial examples: metal extraction from ores, recovery of antibiotics
4. Membrane Filtration
A semi-permeable membrane separates components based on size, charge, or molecular weight
differences.
Type Pore Size Separates Application
Microfiltration 0.1–10 μm Bacteria, particles Sterile filtration
Ultrafiltration 0.001–0.1 μm Proteins, viruses Dairy, pharma
Nanofiltration ~0.001 μm Divalent ions Water softening
Reverse Osmosis < 0.001 μm All solutes, salts Desalination
B. Purification Methods
5. Adsorption
A substance (adsorbate) adheres to the surface of a solid adsorbent material via physical or chemical
forces.
• Common adsorbents: activated carbon, silica gel, zeolites, alumina
• Activated carbon has an enormous surface area: up to 3000 m²/g
• Used to remove colours, odours, impurities from gases or liquids
• Adsorbents can be regenerated by heating or pressure reduction
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Industrial uses: removal of VOCs from waste gases, drying of solvents, purification of hydrogen.
6. Recrystallization
The solid product is dissolved in a hot solvent. As the solution cools, pure crystals nucleate and grow
while impurities remain dissolved in the mother liquor.
• Relies on the fact that solubility increases with temperature for most solids
• Slow cooling → large, pure crystals; fast cooling → many small crystals
• Very common in pharmaceutical and fine chemical manufacturing
• Impure solids with similar chemical properties can be separated this way
C. Reaction Processes — Reactor Types
7. Continuous Stirred Tank Reactor (CSTR)
A well-mixed vessel where reactants are continuously fed in and products continuously removed. The
concentration inside the tank is uniform and equal to the exit concentration.
Design equation (first-order reaction, A → B):
τ = Xₐ / [k(1 − Xₐ)]
Rearranged for conversion:
Xₐ = kτ / (1 + kτ)
Where τ = V/Fₐ₀ = space time, Xₐ = conversion, k = rate constant
• Reaction occurs at the lowest concentration (exit concentration) → slowest rate
• Requires larger volume than PFR for the same conversion
• Excellent temperature control due to perfect mixing
• Best for: liquid-phase reactions, highly exothermic reactions, reactions needing isothermal
conditions
8. Plug Flow Reactor (PFR)
A tubular reactor where fluid flows through without axial mixing. Concentration varies continuously
along the reactor length from inlet to outlet.
Design equation (first-order reaction):
τ = (1/k) × ln[1/(1 − Xₐ)]
• Operates at the highest rate at the inlet (high concentration) → more efficient use of volume
• Requires smaller volume than CSTR for the same conversion
• Harder to control temperature — risk of hotspots in exothermic reactions
• Best for: gas-phase reactions, fast reactions, high conversion requirements
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CSTR vs PFR — Direct Comparison
Feature CSTR PFR
Mixing Perfect (uniform conc.) No axial mixing
Concentration profile Uniform = exit conc. Decreases along length
Volume needed Larger (for same conversion) Smaller (more efficient)
Temperature control Easy Difficult
Best application Liquid-phase, exothermic Gas-phase, high conversion
Reaction rate Always at lowest (exit) rate Starts high, decreases to exit
9. Packed Bed Reactor (PBR)
A tube filled with solid catalyst particles. Reactants flow through the bed and react on the catalyst
surface. Design uses catalyst weight (W) rather than volume:
dFₐ/dW = r'ₐ
Where r'ₐ = rate per unit mass of catalyst (mol/kg·s)
Pressure drop — Ergun Equation:
ΔP/ΔZ = −[G(1−φ)/(ρ_g · D_p · φ³)] × [150(1−φ)μ/D_p + 1.75G]
Where: G = superficial mass velocity, φ = void fraction, D_p = particle diameter, μ = viscosity
• Used in: Haber process (NH₃), Contact process (SO₃), catalytic reforming
• Catalyst can deactivate — periodic regeneration required
10. Fluidized Bed Reactor
Solid catalyst particles are suspended (fluidized) by an upward-flowing gas stream. The bed behaves
like a boiling liquid.
Minimum Fluidization Velocity (u_mf) — when drag = gravity:
u_mf = D_p²(ρ_p − ρ_f)g·φ_mf³ / [150μ(1 − φ_mf)]
Fluidization regimes with increasing gas velocity:
Fixed bed → Minimum fluidization → Bubbling bed → Turbulent → Fast fluidization → Pneumatic
transport
Advantages Disadvantages
Excellent heat transfer — uniform temperature Catalyst attrition (particle breakage)
Continuous catalyst regeneration possible Gas bypassing in bubbles reduces efficiency
Good gas-solid contact Complex hydrodynamics — difficult to model
Expensive cyclone systems needed to retain
Large-scale operation possible
catalyst
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D. Heat Exchangers
Heat exchangers transfer thermal energy between two fluid streams without mixing them. They are
found throughout every chemical process — heating reactants, cooling products, and recovering waste
heat.
Fundamental design equation:
Q = U × A × ΔT_lm
Where: Q = heat duty (W or kW), U = overall heat transfer coefficient (W/m²·K), A = heat transfer area
(m²), ΔT_lm = Log Mean Temperature Difference (°C or K)
Log Mean Temperature Difference (counter-current flow):
ΔT_lm = (ΔT₁ − ΔT₂) / ln(ΔT₁/ΔT₂)
ΔT₁ = T_hot,in − T_cold,out ΔT₂ = T_hot,out − T_cold,in
Energy balance (adiabatic assumption — no heat lost to surroundings):
Q = ṁₕ·Cpₕ·(Tₕ,in − Tₕ,out) = ṁ_c·Cp_c·(T_c,out − T_c,in)
Counter-current flow is always more efficient than co-current (parallel) flow because it maintains a
larger temperature driving force throughout the exchanger.
2.4 Develop Logical Sequencing of Unit Operations
Unit operations must be arranged in a logical order that maximises efficiency, safety, and yield while
minimising cost and waste. The sequence is documented using three types of diagrams.
2.4.1 Types of Chemical Process Diagrams
Block Flow Diagram (BFD)
The simplest representation. Each rectangular block represents an entire process section. Arrows show
flow direction. No equipment detail or instrumentation is shown.
• Used in the early conceptual design stage
• Communicates the overall process logic to non-engineers
• Example — Contact Process for H₂SO₄:
[S Combustion] → [Catalytic Oxidation SO₂→SO₃] → [Absorption] →
[H₂SO₄ Product]
Process Flow Diagram (PFD)
The intermediate-level engineering document. Shows all major equipment with standard symbols,
numbered streams, and key process data.
• Shows: reactors, distillation columns, heat exchangers, pumps, compressors, vessels
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• Annotated with: temperature, pressure, flow rate, and composition for each stream
• Shows major control loops and utility connections
• Used for detailed process design and performing mass/energy balances
Piping and Instrumentation Diagram (P&ID)
The most detailed engineering diagram. Used by engineers during construction, operation,
maintenance, and safety reviews (HAZOP).
• Every pipe labelled with: diameter, material (e.g. CS = carbon steel), insulation
• All valves shown: gate, globe, check, ball, butterfly, control valves
• All instruments tagged: thermocouples (TE), pressure transmitters (PT), flow meters (FT/FE)
• All control loops shown with feedback/feedforward logic
• Safety devices: Pressure Relief Valves (PRV), rupture disks, emergency isolation valves
Instrument Tag Format (ISA standard): FIC-101
F = Flow (measured variable) | I = Indicating | C = Controller | 101 = loop number
2.4.2 Scale of Process View — Comparison
Diagram Level of Detail Primary Users Stage of Project
BFD Overview / conceptual Management, clients Feasibility / concept
PFD Process level detail Process engineers FEED / detailed design
Full equipment & All engineering
P&ID Construction, operation
instruments disciplines
2.4.3 Method for Drawing a PFD — Step by Step
Step 1 — Define the Process
• List all unit operations in logical sequence (reaction before separation, separation before
purification, etc.)
• Identify all recycle streams and purge streams
Step 2 — Draw Equipment Using Standard Symbols
Equipment Standard Symbol Description Notes
Circle divided by two lines (shell
Heat Exchanger Show hot/cold sides
& tube)
Vertical cylinder with internal
Distillation Column Lines = trays
horizontal lines
Circle with solid triangle
Pump Triangle tip = outlet
(pointing flow direction)
Compressor Circle with curved aerofoil blade For gases only
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Equipment Standard Symbol Description Notes
Circle with stirrer/agitator
CSTR Jacket shown outside
symbol inside
Rectangle or cylinder
PFR / PBR Hatching = catalyst packing
(horizontal)
Storage Tank Flat-bottomed vertical cylinder Domed or cone roof
Valve Bowtie shape on pipe line X through = control valve
Step 3 — Number and Label All Streams
• Assign a unique stream number to every process line (e.g., stream 1, 2, 3...)
• Create a Stream Table below the diagram
Example Stream Table:
Stream No. 1 2 3 4 5
Temperature
25 450 450 50 20
(°C)
Pressure (bar) 200 200 198 197 197
Flow (mol/h) 400 400 350 350 50
N₂ (mol%) 25 25 21.4 21.4 0
H₂ (mol%) 75 75 64.3 64.3 0
NH₃ (mol%) 0 0 14.3 14.3 100
Mass Balance — Fully Worked Example
Process: Ammonia synthesis N₂ + 3H₂ → 2NH₃
Given Data:
• Feed: 100 mol/h N₂ and 300 mol/h H₂ (stoichiometric 1:3 ratio)
• Single-pass conversion of N₂: 25%
Step 1 — Choose a Basis
Basis = 100 mol/h of N₂ fed to reactor
Step 2 — Apply Stoichiometry
N₂ reacted = 100 × 0.25 = 25 mol/h
H₂ reacted = 25 × 3 = 75 mol/h
NH₃ produced = 25 × 2 = 50 mol/h
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Step 3 — Construct Material Balance Table
Component Feed In (mol/h) Reacted (mol/h) Out (mol/h) Mole %
N₂ 100 −25 75 21.4%
H₂ 300 −75 225 64.3%
NH₃ 0 +50 50 14.3%
TOTAL 400 −50 net 350 100%
Step 4 — Atom Balance Verification
• N atoms IN: 100 × 2 = 200 | N atoms OUT: 75×2 + 50×1 = 200 ✓
• H atoms IN: 300 × 2 = 600 | H atoms OUT: 225×2 + 50×3 = 600 ✓
Both atom balances close → mass balance is correct.
Energy Balance — Fully Worked Example
Process: Cooling toluene product stream using a shell-and-tube heat exchanger
Given Data:
• Hot stream: 500 kg/h of toluene, enters at 150°C, must leave at 50°C
• Cp of toluene = 1.69 kJ/kg·K
• Cooling water enters at 20°C, exits at 40°C
• Cp of water = 4.18 kJ/kg·K
• Overall heat transfer coefficient U = 500 W/m²·K
• Counter-current flow arrangement
Step 1 — Calculate Heat Removed from Toluene
Q = ṁ × Cp × ΔT = 500 × 1.69 × (150 − 50)
Q = 500 × 1.69 × 100 = 84,500 kJ/h = 23.47 kW
Step 2 — Calculate Required Cooling Water Flow Rate
ṁ_w = Q / (Cp_w × ΔT_w) = 84,500 / (4.18 × 20)
ṁ_w = 84,500 / 83.6 = 1,010.8 kg/h
Step 3 — Calculate Log Mean Temperature Difference
Counter-current arrangement:
ΔT₁ = T_hot,in − T_cold,out = 150 − 40 = 110°C
ΔT₂ = T_hot,out − T_cold,in = 50 − 20 = 30°C
ΔT_lm = (110 − 30) / ln(110/30) = 80 / 1.299 = 61.6°C
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Step 4 — Calculate Required Heat Transfer Area
A = Q / (U × ΔT_lm) = 23,470 / (500 × 61.6)
A = 23,470 / 30,800 = 0.762 m²
Therefore, the heat exchanger requires approximately 0.76 m² of heat transfer area.
Step 5 — Overall Energy Balance Check
Heat given by toluene = Heat gained by water:
Q_toluene = 84,500 kJ/h
Q_water = 1010.8 × 4.18 × (40 − 20) = 84,503 kJ/h ≈ 84,500 kJ/h ✓
The energy balance closes — the calculation is correct.
Exam Tips & Summary
Topic What Examiners Expect
Define all 4 types with industrial examples and compare steady vs
Process types
transient state
Write full equation: IN − OUT + GEN − CON = ACCUM; show how
General balance
it simplifies at steady state
Name, state the principle, give one industrial example, and sketch if
Unit operations
possible
CSTR vs PFR: explain why PFR needs less volume (concentration
Reactor comparison
profile argument)
Reactor design eqs. Know CSTR: Xₐ = kτ/(1+kτ) PFR: τ = (1/k)ln[1/(1−Xₐ)]
Mass balance Show all 4 steps: basis → stoichiometry → table → atom check
Energy balance Q = mCpΔT; then LMTD; then A = Q/(UΔT_lm); show check at end
BFD (simplest) → PFD (intermediate) → P&ID (most detailed);
Diagram types
know what each contains
Numbered streams, stream table with T/P/flow/composition,
Drawing a PFD
standard symbols, mass & energy balance data
KEY FORMULAS TO MEMORISE:
General Balance: IN − OUT + GEN − CON = ACCUMULATION
Distillation: F = D + B | F·z_F = D·y_D + B·x_B
CSTR: Xₐ = kτ / (1 + kτ)
PFR: τ = (1/k) · ln[1/(1 − Xₐ)]
Heat Exchanger: Q = U·A·ΔT_lm | Q = ṁ·Cp·ΔT
LMTD: ΔT_lm = (ΔT₁ − ΔT₂) / ln(ΔT₁/ΔT₂)
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Good luck, Jack! Study smart, not just hard.
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