Distillation Analysis: Ethylbenzene/Styrene Separation

System Specifications
- Feed: 20,000 kg/h at 25°C, 100 kPa
- Feed Composition: 54% Ethylbenzene, 46% Styrene (mass basis)
- Operating Pressure: 100 kPa
- Specified Reflux Ratio: 7.4148
- Key Component Specifications: 3% impurity in both streams

1. Suitable Thermodynamic Property Package

For the Ethylbenzene/Styrene system, Peng–Robinson (PR) or SRK are suitable cubic EOS
models because:
• Both components are aromatic hydrocarbons with similar structure
• Similar molecular weights (106.2 vs 104.2)
• Close normal boiling points (136.2°C vs 145.2°C)
• Near-ideal behavior in the liquid phase at ~1 bar
• Cubic EOS handle hydrocarbon VLE well

Recommendation: PR for improved liquid density and vapor pressure predictions.

2. Flowsheet diagram (with stream names & conditions).

BK10 Chao-Seader

Grayson-Streed Peng-Robinson
 SRK UNIQUAC

Wilson

3. Number of Theoretical Trays

Estimated using the Fenske equation (minimum stages at total reflux) and applying
efficiency/correlation for actual stages. Average relative volatility α ≈ 1.28; minimum stages
are roughly 25–30 for the specified split.

Fenske (minimum stages):

𝐿𝐾 𝐻𝐾
𝑁ₘᵢₙ = ln '(𝑥! , 𝑥 , 𝐻𝐾. · (𝑥" , 𝑥 , 𝐿𝐾.0
! "
ln(𝛼)

4. Feed Tray Location – Kirkbride Equation

Kirkbride:
,
𝑁% 𝐵 𝑥'(,* 𝑥+(,!
log#$ 6 7 = 0.206 ⋅ log#$ = ⋅ @ A ⋅ B
𝑁& 𝐷 𝑥+(,* 𝑥'(,"

𝑁% 𝑁%
log#$ 6 7 = 0.206 log#$ (0.860 ⋅ (0.869), ⋅ 1.0) = −0.038617 ⇒ = 10-$.$/01#2
𝑁& 𝑁&
≈ 0.9149

For N = 30: N_s ≈ 16 (below feed), N_r ≈ 14 (above feed). Feed tray ≈ Tray 16 from bottom.
5. Minimum & Actual Reflux (Underwood)
Underwood (for saturated liquid feed, q = 1):
3
!
Solve θ from (∑6 4 -5 = 0 with α'( > θ > α+( )
!

𝑥!,6 α6
(𝑅768 = U − 1)
α6 − θ
6

R = 1.2·R_min and R = 7.4148 ⇒ R_min ≈ 6.18.

6. Actual Stages (Gilliland Correlation)

Definitions:

X = (R − R_min)/(R + 1)

Y = (N − N_min)/(N + 1)

Using R = 7.41 and R_min ≈ 6.15–6.18 ⇒ X ≈ 0.15. From Gilliland’s chart (e.g., Eduljee fit), Y
≈ 0.32 ⇒ N ≈ 42.

7. Condenser and Reboiler Duties

Energy balance (total condenser):

𝑄9 = (𝑅 + 1) 𝐷 λ!

𝑄: = 𝑄9 + 𝐹 ℎ; − 𝐷 ℎ! − 𝐵 ℎ"

Property Package Condenser Duty (MJ/h) Reboiler Duty (MJ/h)

Peng-Robinson 4.90 10.91
SRK 4.73 10.87
Chao-Seader 4.95 10.94
Grayson-Streed 4.94 10.94
Wilson 5.03 10.91
UNIQUAC 5.03 10.91
BK10 4.73 10.86

8. Recovery of Styrene
From simulation data:
 𝑭Styrene→Bottoms 𝟖𝟖𝟖𝟏
RecoveryStyrene = × 𝟏𝟎𝟎% = × 𝟏𝟎𝟎% = 𝟗𝟔. 𝟓𝟑%
𝑭Styrene→Feed 𝟗𝟐𝟎𝟎

9. Property Package Comparison (Simulation)

Property Overhead Bottoms Min Min Actual Optimal Condenser Reboiler
Package Temp Temp Reflux Trays Trays Feed Duty Duty
(°C) (°C) (Rmin) (Nmin) (N) (MJ/h) (MJ/h)
Peng- 135.7 144.8 6.179 28.2 58.29 28.17 3.068 3.49
Robinson
SRK 135.9 145.0 6.052 28.5 55.66 27.66 3.114 3.547
Chao- 136.4 146.2 6.25 29.1 52.65 25.53 3.053 3.505
Seader
Grayson- 136.3 146.2 6.24 29.0 52.53 27.01 3.053 3.505
Streed
Wilson 135.9 144.4 5.898 27.8 52.70 27.05 3.066 3.503
UNIQUAC 135.8 144.3 6.10 27.6 51.62 26.81 3.066 3.503

BK10 133.6 142.3 6.163 26.8 57.95 28.10 3.065 3.503

10. Hand Calculation Details

Component data (used across packages):

Component MW (g/mol) Normal Boiling Point (°C)

Ethylbenzene 106.2 136.2
Styrene 104.2 145.2
K-values and relative volatility (α) by package:

Property Package K-value EB K-value Styrene α = K_EB/K_St

Peng-Robinson 1.006 0.791 1.272
SRK 1.007 0.788 1.278
Chao-Seader 1.007 0.788 1.278
Grayson-Streed 1.007 0.787 1.280
Wilson 1.004 0.864 1.162
UNIQUAC 1.004 0.876 1.146
BK10 1.007 0.783 1.286
Worked example (PR):

Given: 𝑥!,I" = 0.97, 𝑥!,JK = 0.03, 𝑥",I" = 0.03, 𝑥",JK = 0.97, o

α = 1.272

0.97 0.97
ln '(0.03. ⋅ (0.03.0 ln(1044.4)
𝑁768 = = ≈ 28.8
ln(1.272) 0.241

𝑅 − 𝑅768 7.41 − 6.15

𝑋= = ≈ 0.150
𝑅+1 7.41 + 1
𝑁 − 28.8
From Gilliland: 𝑌 ≈ 0.32 ⇒ = 0.32 ⇒ 𝑁 ≈ 42
𝑁+1
11. Results Summary by Property Package (Hand Calcs)
Property α R_min N_min N (actual) Feed Tray
Package
Peng- 1.272 6.15 28.8 42 16
Robinson
SRK 1.278 6.18 28.5 43 16
Wilson 1.162 6.12 37.2 48 17
UNIQUAC 1.146 6.10 39.1 50 17
BK10 1.286 6.05 27.8 40 15

Conclusions
• Best Property Package: Peng–Robinson (overall balance for hydrocarbon VLE).
• Design Parameters: Theoretical trays ≈ 30; feed tray ≈ 15–18 from bottom; actual reflux
ratio 7.41; styrene recovery 96.5%.
• Energy Requirements: Condenser ≈ 8.7 MJ/h, Reboiler ≈ 9.7 MJ/h (design summary), with
package-wise duties listed above.

12. Sensitivity Studies

To evaluate the effect of condenser pressure on distillation performance, a sensitivity study
was carried out by varying the condenser pressure in the range 0.2 – 1.0 bar. Key
performance indicators such as condenser and reboiler duties, reflux ratio, tray
requirements, and product temperatures were analyzed.

12.1 Sensitivity Table

12.2 Sensitivity Plots

Condenser Pressure vs Condenser Duty
• As condenser pressure increases (0.2 → 1 bar), condenser duty becomes less negative (i.e.,
the cooling requirement decreases).

• Physically, this happens because higher condenser pressure raises condensation temperature,
reducing the temperature difference with the coolant and hence lowering heat removal.

• Trade-off: less cooling duty is beneficial for utilities, but may compromise separation
efficiency

Condenser Pressure vs Reboiler Duty

• Reboiler duty shows a decreasing trend with increasing condenser pressure.

• At lower condenser pressures, higher relative volatility improves separation, requiring slightly
more reboiler energy.

• At higher pressures, the duty drops but separation efficiency decreases, often requiring more
trays/reflux to compensate.

Condenser Pressure vs Column Temperatures

• Condenser temperature increases strongly with condenser pressure (approx. 84 °C → 135 °C).

• Reboiler temperature stays nearly constant (~145 °C).

• This indicates that condenser temperature is the main variable affected by column pressure,
which has direct implications for the choice of cooling utility (e.g., refrigeration at low pressure vs
cooling water at higher pressure).

Condenser Pressure vs Reflux/Trays

• Both minimum reflux ratio and actual number of trays increase with pressure.

• At low pressures, separation is easier (lower reflux, fewer trays).

• At high pressures, separation is harder, so more reflux and trays are needed to achieve the same
product purity.

• This highlights the classic trade-off between energy duties and equipment size/complexity.

13. Discussion of Trade-Offs (heating vs pressure), product purity versus heat

duties
Pressure vs Energy Trade-offs

• Lower Pressure (0.2–0.5 bar): Easier separation (fewer trays, lower reflux), but condenser
runs at very low temperatures (84–105 °C), requiring costly refrigeration and higher cooling duty.

• Higher Pressure (0.8–1.0 bar): Condenser runs at 130–135 °C (cooling water feasible), but
separation is harder, needing more trays and higher reflux.

Product Purity vs Heat Duty

• High Purity (97%): High reflux (~7.4) and large condenser/reboiler duties.

• Relaxed Purity (95%): Cuts reflux and trays, reducing both duties by ~15–25%, but at the
cost of product quality.

Property Package Impact

• Energy predictions vary by ~6% across models (BK10 lowest, UNIQUAC/Wilson highest).
• These differences have major economic impact over plant life.

Optimal Strategy

Best operating window: 0.6–0.8 bar.

• Condenser temp (~115–125 °C) allows cooling water.

• Separation remains feasible without excessive trays.
• Balances hot and cold utility costs.

Economic Considerations

• Choice depends on relative cost of steam vs refrigeration.

• Moderate pressures avoid refrigeration and still achieve high purity, but ~10–15%
energy savings are possible if refrigeration is affordable.