Process Synthesis Learning Outcomes
Define process synthesis & explain its significance
Identify, compare, & evaluate design/process alternatives Make & justify design decisions State & rationalize heuristic rules for process synthesis
Develop a chemical process for a desired objective
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What is Process Synthesis?
Developing a chemical process
Structure, unit operations, flows, operating conditions
Scientific art that relies heavily on experience, heuristics, rules of thumbs,
Few exact mathematical models or automated procedures Heat exchanger & separation networks are exceptions
Why is it critical? Preliminary design costs 15-20% of the entire project cost, but fixes about 80% of subsequent costs
Eastman Chemical received Kirkpatrick award in 1985 for a new
process for Methyl Acetate, which replaced a reactor plus several separation units by one reactive distillation column Huge reduction in cost made conventional processes non-competitive
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Cyclohexane (Naphthene) Manufacture - I
How to develop this process structure? Is it good?
Is this the only way?
Raw materials? Units? Operating conditions?
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Cyclohexane Manufacture - II
Purge Product Cooler Flash Recycle Compressor Reactor Steam Light Ends
Boiler Feed Water (335 psia, 570 F) Make-Up Hydrogen Feed Preheater Benzene Feed Pump Pump
Stabilizer 15 psia
Cyclohexane Product
What is the major difference from the previous process? How to select?
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PFD vs. BFD
Alternate schematic representations of a chemical process
Material/energy streams, their states, flow directions, and unit
operating conditions
PFD (Process Flow Diagram) shows real processing equipment (physical units)
Heat exchanger, pump, distillation unit, reactor, etc. Often called process flowsheet
BFD (Block Flow Diagram) shows process operations
Heating, pumping, separation, reaction, etc.
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PFD for Cyclohexane
Purge Product Cooler Flash Recycle Compressor Reactor Steam Light Ends
Boiler Feed Water (335 psia, 570 F) Make-Up Hydrogen Feed Preheater Benzene Feed Pump Pump
Stabilizer 15 psia
Cyclohexane Product
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BFD for Cyclohexane
Compress 340 psia Heat 335 psia 570 F
N2 + H2 + CH4 Heat
Purge 320 psia Condense 320 psia DPT-120 F Flash Expand 320 psia 15 psia 120 F Split 320 psia
Light Ends Purge
H2 340 psia 120 F
V-Mix 340 psia
React 335-320 psia 570-430 F
Cool 320 psia DPT Pump 340 psia
Vaporize 340 psia
L-Mix 340 psia
C6H12+C6H6 15 psia 100 F
C6H6 15 psia 100 F
Pump 340 psia
Cool 100 F
Distil 20 psia
Expand 20 psia
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Process Synthesis Problem
Fully specified Raw Materials
PFD?
Each stream (material/energy) has a state
(P, T, F, x, y, f, etc.)
Fully specified Products
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Can a Stream Change its State by Magic?
Point A
Point B
P = 1 atm T = 30 C x, y, f
P = 1 atm T = 90 C x, y, f'
One single stream at two points in a process What must happen between A & B?
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Unit Operations Change Stream States in PFD
Changes in Stream States Rise in T
Unit Operations Heating
Plant Device/ Equipment Heat Exchanger
A physical unit must exist for each unit operation
If we know state changes, we can know the operations If we know the operations, we can know the units Once we know the units, we can know the PFD!
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Our Approach to Synthesis
State 1 Define States for Start Materials
(Raw Materials)
State 4
State 2 State 3
State 5
State 6
Define States for End Materials
(Final Products)
Identify plausible alternative paths via well-defined intermediate states
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Algorithm for Flowsheet Development
Define start & end states
c-changes?
x-changes?
Identify best intermediate states Recycle/purge materials, as & when needed Select & add operation to effect each state change
f-changes? P-changes?
T-changes? F-changes?
Add equipment for each operation
BFD
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PFD
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Example: Process for Naphthene
Product specs: 99 wt% Cyclohexane, 15 psia, 100 F
Defines the state of the final product stream
Understand product (physicochemical properties)
hydrocarbon, immiscible with water, flammable
MSDS maintained by OSHA (Occupational Safety & Health Agency) Cyclohexane: MW = 84.16, Density@20 C = 0.779, BP = 81 C,
Search literature & gather information
We must decide/fix many details at various levels
units, unit capacities, PFD, plant location, etc. Vinyl Acetate example in your text book.
Raw materials, reaction pathways, operating conditions, processing
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Naphthene via Benzene Hydrogenation
C6H6 (Benzene) + 3H2 C6H12
Highly exothermic, equilibrium-controlled, near 100% conversion
below 230 C How do T & P affect equilibrium conversion? Rate of reaction?
H = 266 kJ/mol
Catalysts: Ni/Alumina or Ni/Pd or Ni/Pt
Liquid phase: Catalyst suspended in liquid cyclohexane, 99.85%
conversion, 20-30 bar, 160-220 C Gas phase: Multi-stage, fixed bed, tubular reactors with inter-stage cooling, initial T < 370 C, exit T = 220-300 C
Cyclohexane is recycled to the reactor for heat removal What should be the limiting reactant?
or hazardous reactant
Heuristic: Use excess of other reactants to consume a valuable, toxic,
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Cyclohexane PFD - Start & End States
Hydrogen Feed (340 psia, 120 F) (97.5% H2, 2% CH4, 0.5% N2) PFD? Cyclohexane Product (15 psia, 100 F, 99 wt%)
Benzene Feed (100% pure, 15 psia, 100 F)
Any c-change?
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Cyclohexane PFD
Heat
H2 (340 psia, 120 F) N2 H2 CH4 C6H12 C6H6
PFD1?
C6H6 (15 psia, 100 F)
React 335-320 psia 570-430 F
PFD2?
C6H12 15 psia 100 F
Any more c-change? Any x-change? How to separate the reactor product to get C6H12 from PFD2?
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How to Separate Reactor Product?
What is the state of mixture?
V, L, S, VL, LS, VS, VLL, VLS?
Heuristic: For vapor mixtures, use partial condensation, absorption, adsorption, membrane separation, cryogenic distillation, and/or desublimation. Heuristic: For liquid mixtures, use distillation, stripping, enhanced distillation (extractive, azeotropic, reactive), liquidliquid extraction, crystallization, and/or adsorption. Heuristic: Condense or partially condense vapor mixtures using cooling water or refrigerant (i.e. condense & flash)
Does the mixture have condensable components? Are they desirable?
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Add Flash for First-cut Separation
H2 340 psia 120 F Heat N2 H2 CH4 C6H12 C6H6
PFD1?
C6H6 15 psia 100 F
React 335-320 psia 570-430 F
PFD3?
Flash ?
PFD4?
Can flash give high-purity products?
What should be in flash gas? liquid? What should be pressure and temperature?
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C6H12 15 psia 100 F
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Primary Purpose of Flash?
Liquefy completely? Two ways of condensing C6H6 and C6H12? Heuristic: Avoid compression.
Fact: Cooling or heating is cheaper than compression
Heuristic: Once attained, avoid losing pressure as long as possible.
Is higher pressure better for separating C6H6 and C6H12?
How low should flash temperature be?
BPT? DPT? < 0 C? 5 C? 20 C? 30 C? 50 C?
Heuristic: Avoid refrigeration.
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What Should be Flash T?
Which cooling agent? What is its temperature? Heuristic: For closed-circuit cooling system, use 90 F (30 C) for cooling water (CW) inlet and 120 F (45 C) for CW outlet.
Why restrict to 45 C?
Heuristic: For open-circuit system, use 45 C for CW outlet.
Inlet depends on source and discharge governed by environmental
regulations
Theoretical minimum temperature attainable in Singapore?
How much heat transfer area for that?
How closely should fluid temperatures approach each other?
What is the optimal approach?
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Minimum Temperature Approach
t1
T2 TL = T2 t1
Heat Exchanger
t2
T1
TR = T1 t2
Minimum Temperature Approach = Tmin = min(TL, TR)
Heuristic: Near-optimal min T-approaches are 10 F for below ambient, 20 F for up to 300 F (150 C), and 50 F for higher Heuristic: Near-optimal min T-approaches are 10 C for liquids (high heat transfer coefficient systems), 20 C for gases, and 5 C for refrigeration What should be flash temperature?
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Fix Flash Conditions
H2 340 psia 120 F
Heat H2+N2+CH4+vapors
PFD1?
C6H6 15 psia 100 F
React 335-320 psia 570-430 F
PFD3?
N2+H2+CH4 C6H6+C6H12
Flash 320 psia 120 F PFD4?
C6H12 15 psia 100 F
C6H12+C6H6+gases
Any x-change? How to purify C6H12 in PFD4? State of the mixture? Recall heuristic. Is distillation easy for C6H6 & C6H12? Recall: Used excess H2 to consume most of C6H6!
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Add Distillation
H2 340 psia 120 F Heat N2 H2 CH4 C6H12 C6H6 H2+N2+CH4
PFD1?
C6H6 15 psia 100 F
React 335-320 psia 570-430 F
PFD3?
Flash 320 psia 120 F
C6H12+C6H6
PFD5? Distil P?
Top Product? C6H12+C6H6 15 psia 100 F
How to determine P & T?
PFD6?
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Operating P & T for Distillation
Heuristic: Distillation becomes easier at lower pressure, but avoid vacuum
How do VLE characteristics change with P? Why avoid vacuum?
Heuristic: Prefer atmospheric distillation (1-5 atm) Heuristic: Prefer CW in condenser, if possible Heuristic: If CW condenser not possible, then consider higher pressure What is the top product? What is its state?
What type of condenser?
What to do with top product? What to do with flash gas?
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Fix Distillation P & Recycle Flash Gas
Heat H2+N2+CH4
H2 340 psia 120 F
PFD1?
React 335-320 psia 570-430 F
PFD3?
Flash 320 psia 120 F PFD5?
C6H6 15 psia 100 F
From where to recycle C6H12? What are the two possible places? Does it need to be pure?
Distil 20 psia
PFD6?
Light Ends C6H12+C6H6 15 psia 100 F
Which is the best? Why? (P? benzene? Distil capacity?)
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Recycle Cyclohexane
Heat H2 340 psia 120 F
PFD1?
React 335-320 psia 570-430 F
PFD3?
Flash 320 psia 120 F PFD5?
C6H6 15 psia 100 F
C6H12+C6H6+gases
Distil 20 psia PFD6?
Light Ends
C6H12+C6H6 15 psia 100 F
Any x-change? What does PFD1 do?
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Mixing in PFD1
Fact: Mixing streams with very different viscosities is difficult
Dissolving sugar in water/tea Dissolving a polymer in a solvent
Fact: Mixing liquid and gas is difficult
Fuel injection in car engine Hydrogen & benzene in the liquid-phase reactor for cyclohexane
Heuristic: Avoid mixing a gas with liquid
Mix liquids or gases
What are the states of streams into PFD1?
Liquid, gas, solid?
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Expand PFD1 - Mix Liquid Streams
H2 340 psia 120 F
PFD9?
React 335-320 psia 570-430 F
PFD3?
Flash 320 psia 120 F
PFD5? Distil 20 psia
Light Ends C6H12+C6H6 15 psia 100 F
C6H6 15 psia 100 F
PFD7?
L-Mix P?
PFD8?
What should be P & T of L-Mix? 15 psia? 320 psia? Intermediate? Which heuristic rule can you invoke?
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PFD6?
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Fix L-Mix Pressure
H2 340 psia 120 F
PFD9?
React 335-320 psia 570-430 F
PFD3?
Flash 320 psia 120 F
PFD5? Distil 20 psia
Light Ends C6H12+C6H6 15 psia 100 F
C6H6 15 psia 100 F
PFD7?
L-Mix 320 psia
PFD8?
What about gas streams?
PFD6?
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Expand Purge for Disposal
Compress 340 psia Heat 335 psia 570 F
N2 + H2 + CH4 Heat
Purge 320 psia Condense 320 psia DPT-120 F Flash Expand 320 psia 15 psia 120 F Split 320 psia
Light Ends Purge
H2 340 psia 120 F
G-Mix 340 psia
React 335-320 psia 570-430 F
Cool 320 psia DPT Pump 340 psia
Vaporize 340 psia
L-Mix 340 psia
C6H12+C6H6 15 psia 100 F
C6H6 15 psia 100 F
Pump 340 psia
Cool 100 F
Distil 20 psia
Expand 20 psia
Any change by magic? What about heat from the reactor?
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Assign Units to Operations
React: Multi-stage, gas-phase, catalytic, fixed bed tubular reactors with inter-stage coolers that produce steam
Boiler feed water (BFW) on shell sides of coolers & reactors
Mix: Pipeline joints Expand: Expansion valves (Any other option? Why not?) Heat, cool, vaporize: Appropriate shell & tube exchangers with cooling water or steam Flash: Vertical flash drum Distillation: Column with a partial condenser & reboiler Purge / Split: Pipe splits Pump / Compress: Centrifugal pump or compressor
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Cyclohexane PFD
Purge Product Cooler Flash Recycle Compressor Reactor Steam Light Ends
Boiler Feed Water (335 psia, 570 F) Make-Up Hydrogen Feed Preheater Benzene Feed Pump Pump
Stabilizer 15 psia
Cyclohexane Product
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Reading
Tutorial exercises involve synthesis + simulation
Do not rush to simulate without developing a PFD on paper
Read SSL Chapters 1, 3, & 5
Basics of PFD development - Vinyl Chloride (Ch 1) Heuristic rules for design & synthesis (Ch 5) References on synthesis (Ch 1, SSL) Handbooks, encyclopedias, Hydrocarbon Processing, etc.
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Practice Exercise
Formaldehyde (HCHO) is fully soluble in water, alcohols and other
polar solvents. However, aqueous formaldehyde is not a simple physical solution of formaldehyde in water, but a complex mixture of various hydrated chemical species. Develop a process to produce 40 wt% aqueous formaldehyde (1 atm, 40 C) using methanol (CH3OH, 2 atm, 40 C) and ambient air as raw materials via the following gas-phase, catalytic reactions at 1.5 atm and 600-650 C:
The conversion of methanol in the reactor is almost 100%. 50-60%
of the formaldehyde is produced via reaction (1), making the overall reaction highly exothermic. Boiling points of methanol and aqueous formaldehyde are 65 C and 98.9 C respectively. High-pressure (HP) steam is available at 400 C in the plant. Assume other utilities, as you need and justify your steps.
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CH3OH + 0.5O2 HCHO + H2O DH = -156 kJ CH3OH HCHO + H2 DH = +85 kJ
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Improving a PFD
Energy integration leads to alternate PFDs
Match hot streams with cold streams, under what conditions? Where can you conserve energy in this process?
Alternate reaction pathways, separation methods, etc.
Simulators, heuristic rules, simple costing, experience, etc. useful in
selecting the best
Optimize operating conditions via process simulators
Unit/stream conditions may change, but PFD largely unchanged Simulators handy in estimating properties and conditions (e.g. Flash,
BPs of Benzene and C6H12) On-line optimization using simulators
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Other Heuristics
Estimated Ps for heat exchangers are
1 psi for boiling & condensing 3 psi for a gas 5 psi for a low-viscosity liquid 7-9 psi for a high-viscosity liquid 20 psi for a fluid through furnace
Other units (reactors, columns, etc.) Flow velocities (gas & liquid)
Determine pipe sizes
Standard pipe and tube dimensions
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