A.

Energy Balance around Reactor

^ ^
∆𝐻 = ∑ 𝜉𝑗∆𝐻°𝑟𝑗 + ∑ 𝑛𝑜𝑢𝑡 𝐻𝑜𝑢𝑡 − ∑ 𝑛𝑖𝑛 𝐻𝑖𝑛
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠

144.4 300
𝐻1^ =∫ 𝐶𝑝 𝑜𝑥𝑦(𝑙𝑖𝑞)𝑑𝑇 + ∆𝐻𝑣 + ∫ 𝐶𝑝 𝑜𝑥𝑦(𝑣𝑎𝑝)𝑑𝑇
25 144.4

= 5763.88 + 8800 + 10700.65 = 25264.53 cal/mol = 105709.33 kj/kmol

300
𝐻2^ = ∫ 𝐶𝑝 𝑂2 (𝑔)𝑑𝑇 = 8470 𝑘𝑗/𝑘𝑚𝑜𝑙
25

300
𝐻3^ = ∫ 𝐶𝑝 𝑁2 (𝑔)𝑑𝑇 = 8120 𝑘𝑗/𝑘𝑚𝑜𝑙
25

144.4 380
𝐻4^ =∫ 𝐶𝑝 𝑜𝑥𝑦(𝑙𝑖𝑞)𝑑𝑇 + ∆𝐻𝑣 + ∫ 𝐶𝑝 𝑜𝑥𝑦(𝑣𝑎𝑝)𝑑𝑇
25 144.4

= 5763.88 + 8800 + 18232.71 = 32796.59 cal/mol = 137224.23 kj/kmol

380
𝐻5^ = ∫ 𝐶𝑝 𝑂2 (𝑔)𝑑𝑇 = 11060 𝑘𝑗/𝑘𝑚𝑜𝑙
25

380
𝐻6^ = ∫ 𝐶𝑝 𝑁2 (𝑔)𝑑𝑇 = 10544 𝑘𝑗/𝑘𝑚𝑜𝑙
25

284 380
𝐻7^ =∫ 𝐶𝑝 𝑃𝐴(𝑙𝑖𝑞)𝑑𝑇 + ∆𝐻𝑣 + ∫ 𝐶𝑝 𝑃𝐴(𝑣𝑎𝑝)𝑑𝑇
25 284

= 13908.11 + 11850 + 13767.48 = 39525.59 cal/mol = 165379.04 kj/kmol

100 380
𝐻8^ = ∫ 𝐶𝑝 𝐻2 𝑂(𝑙𝑖𝑞)𝑑𝑇 + ∆𝐻𝑣 + ∫ 𝐶𝑝 𝐻2 𝑂(𝑣𝑎𝑝)𝑑𝑇
25 100

=5.655 + 40.656 + 9.494 = 56.260 kj/mol = 56260 kj/kmol

380
𝐻9^ = ∫25 𝐶𝑝 𝐶𝑂2 (𝑔)𝑑𝑇 = 15373 𝑘𝑗/𝑘𝑚𝑜𝑙

202 380
^
𝐻10 =∫ 𝐶𝑝 𝑀𝐴(𝑙𝑖𝑞)𝑑𝑇 + ∆𝐻𝑣 + ∫ 𝐶𝑝 𝑀𝐴(𝑣𝑎𝑝)𝑑𝑇
25 202

= 8940.69 + 5850 + 8604.82 = 23395.51 cal/mol = 97889.16 kj/kmol

∆°𝐻 = −34318.92 + 14162.66 − 7677.76 = −27834.02 𝑘𝑗

 0 ^
∑ 𝑛𝑖𝑛 𝐻𝑖𝑛 = 7677.76 𝑘𝑗/𝑠

0 ^
∑ 𝑛𝑜𝑢𝑡 𝐻𝑜𝑢𝑡 = 14162.66 𝑘𝑗/𝑠

° 𝑚𝑜𝑙 𝑘𝑗 𝑚𝑜𝑙 𝑘𝑗
∑ 𝜉𝑗 ∆𝐻𝑟𝑗 = (63000 ∗ −1234.31 ) + (5000 ∗ −3030.72 )
ℎ𝑟 𝑚𝑜𝑙 ℎ𝑟 𝑚𝑜𝑙
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠
𝑚𝑜𝑙 𝑘𝑗
+ (7000 ∗ −4376.14 )
ℎ𝑟 𝑚𝑜𝑙

= -34318.92 kj/s

∆𝐻° = 𝑄 = −34318.92 + 14162.66 − 7677.76 = −27834.02 𝑘𝑗

𝐿0
1. Reflux ratio 𝐷
= 1.3
2. Raoult’s law P=𝑋𝑖 ∗ 𝑃𝑖𝑠𝑎𝑡 is applied

Equation used :

 Antonie equation :

𝐵
𝑃𝑖𝑠𝑎𝑡 = 𝑒 (𝐴−𝑇−𝐶) T in (K) P in (mm Hg)

 Heat capacity for liquid :

Cp(cal/mol*C) = 41.69 + 7.773*10−2 𝑇 T in (°𝐶)

 Heat capacity for vapour (range 150°𝐶 − 450°𝐶)

Cp(cal/mol*K)= a + b*T + c∗ 𝑇 2 + d∗ 𝑇 3

The inlet temperature of first distillation :

P = 𝑃 𝑠𝑎𝑡 ∗ 𝑋𝑃𝐻 + 𝑃 𝑠𝑎𝑡 ∗ 𝑋𝑀𝐴 + 𝑃 𝑠𝑎𝑡 ∗ 𝑋𝑜𝑥𝑦

𝐵 𝐵 𝐵
P=[(0.677) ∗(𝑒 (𝐴−𝑇−𝐶) + (0.0538) ∗ 𝑒 (𝐴−𝑇−𝐶) + (0.269) ∗ 𝑒 (𝐴−𝑇−𝐶)
 For PH
A = 15.9984
B = 4467.01
C = 83.15

 For MA
A = 16.2747
B = 3765.65
C = 82.15

 For O-xylene
A = 16.1156
B = 3396.57
C = 59.46

Solving for T = 195.2°𝐶

The top temperature of first distillation :

𝐵
1
P= 𝑦𝑖 , 𝑃𝑖𝑠𝑎𝑡 = 𝑒 (𝐴−𝑇−𝐶)
∑𝑛
𝑖 𝑃𝑠𝑎𝑡
𝑖

1
608 mm Hg = 0.0207 0.161 0.817
+ 𝑠𝑎𝑡 + 𝑠𝑎𝑡
𝑃𝑠𝑎𝑡
𝑃𝐴 𝑃𝑀𝐴 𝑃𝑜𝑥𝑦

Solving for 𝑇 = 169.7°𝐶

Top temperature after condensation :

𝑃𝑑𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒 = 𝑋𝑃𝐻 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑀𝐴 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑜𝑥𝑦 ∗ 𝑃 𝑠𝑎𝑡

𝐵 𝐵 𝐵
𝑃𝑑𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒 =[(0.0207) ∗(𝑒 (𝐴−𝑇−𝐶) + (0.161) ∗ 𝑒 (𝐴−𝑇−𝐶) + (0.817) ∗ 𝑒 (𝐴−𝑇−𝐶)

 For PH
A = 15.9984
B = 4467.01
C = 83.15

 For MA
A = 16.2747
B = 3765.65
C = 82.15
  For O-xylene
A = 16.1156
B = 3396.57
C = 59.46

Solving for 𝑇 = 141.9°𝐶

For bottom temperature of the distillation :

𝑃𝑏𝑜𝑡𝑡𝑜𝑚 = 𝑋𝑃𝐻 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑀𝐴 ∗ 𝑃 𝑠𝑎𝑡

𝐵 𝐵
𝑃𝑏𝑜𝑡𝑡𝑜𝑚 =[(0.999) ∗(𝑒 (𝐴−𝑇−𝐶) + (0.001) ∗ 𝑒 (𝐴−𝑇−𝐶) ] = 456 mm Hg

 For PH
A = 15.9984
B = 4467.01
C = 83.15

 For MA
A = 16.2747
B = 3765.65
C = 82.15

Solving for 𝑇 = 260.9°𝐶

Overall Energy Balance :

Fhf + Q c + Q R = DhD + BhB

1) Condenser energy balance :

VHV + Q C = DhD + LhL

𝑄𝐶 = 𝑉(ℎ𝐷 − 𝐻𝑉 )

Where (ℎ𝐷 − 𝐻𝑉 ) = 𝜆 = latent heat of vaporization

2) Reboiler energy balance :

Q R = DhD + BhB − Fhf − Q c
 144.4 260.9
hv = [∫25 𝐶𝑝𝑜𝑥𝑦 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑜𝑥𝑦 + ∫144.4 𝐶𝑝𝑜𝑥𝑦 (𝑣𝑎𝑝)𝑑𝑇] ∗ (0.817) +
202 260.9 260.9
[ ∫25 𝐶𝑝𝑀𝐴 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑀𝐴 + ∫202 𝐶𝑝𝑀𝐴 (𝑣𝑎𝑝) 𝑑𝑇] ∗ (0.161) + [∫25 𝐶𝑝𝑃𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗
(0.0207) = 88.27 kj/mol

hD =
141.9 141.9
[∫25 𝐶𝑝𝑜𝑥𝑦 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑜𝑥𝑦 ] ∗ (0.817) + [ ∫25 𝐶𝑝𝑀𝐴 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑀𝐴 ] ∗ (0.161) +
141.9
[∫25 𝐶𝑝𝑃𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗ (0.0207) = 23.53 kj/mol

hB =
144.4 169.7 169.7
[∫25 𝐶𝑝𝑜𝑥𝑦 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑜𝑥𝑦 + ∫144.4 𝐶𝑝𝑜𝑥𝑦 (𝑣𝑎𝑝)𝑑𝑇] ∗ (0) + [ ∫25 𝐶𝑝𝑀𝐴 (𝑙𝑖𝑞)𝑑𝑇 +
161.7
𝜆𝑀𝐴 ] ∗ (0.999) + [∫25 𝐶𝑝𝑃𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗ (0.001) = 29.82 kj/mol

hF =
144.4 195.2 195.2
[∫25 𝐶𝑝𝑜𝑥𝑦 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑜𝑥𝑦 + ∫144.4 𝐶𝑝𝑜𝑥𝑦 (𝑣𝑎𝑝)𝑑𝑇] ∗ (0.269) + [ ∫25 𝐶𝑝𝑀𝐴 (𝑙𝑖𝑞)𝑑𝑇 +
150.3
𝜆𝑀𝐴 ] ∗ (0.677) + [∫25 𝐶𝑝𝑃𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗ (0.0538)] = 47.78 kj/mol

Calculating heat of condenser Qc and heat of reboiler Qr :

λoxy = 8800 cal/mol

λPA = 11850 cal/mol
λMA = 5850 cal/mol

𝜆𝑚𝑖𝑥 = 𝑋𝑃𝐴 𝜆𝑃𝐴 + 𝑋𝑀𝐴 𝜆𝑀𝐴 + 𝑋𝑜𝑥𝑦 𝜆𝑜𝑥𝑦 = 35.0491 kj/mol

Qc = -3050396.95 kj/hr

Qr = ℎ𝐷 𝐷 + ℎ𝐵 𝐵 − 𝐹ℎ𝐹 − 𝑄𝑐 = 747044.35 kj/hr

The inlet temperature of second distillation :

𝑃𝑑𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒 = 𝑋𝑃𝐻 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑀𝐴 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑜𝑥𝑦 ∗ 𝑃 𝑠𝑎𝑡

𝐵 𝐵
760 𝑚𝑚 𝐻𝑔 = [(0.0207) ∗(𝑒 (𝐴−𝑇−𝐶) + (0.161) ∗ 𝑒 (𝐴−𝑇−𝐶) + (0.817) ∗
𝐵
𝑒 (𝐴−𝑇−𝐶) ]

Solving for 𝑇 = 150.3°𝐶

The bottom temperatur of the distillation :

𝑃𝑏𝑜𝑡𝑡𝑜𝑚 = 𝑋𝑃𝐻 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑀𝐴 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑜𝑥𝑦 ∗ 𝑃 𝑠𝑎𝑡

 𝐵 𝐵 𝐵
456 𝑚𝑚 𝐻𝑔 = [(0.114) ∗(𝑒 (𝐴−𝑇−𝐶) + (0.886) ∗ 𝑒 (𝐴−𝑇−𝐶) + (0) ∗ 𝑒 (𝐴−𝑇−𝐶) ]

Solving for 𝑇 = 186.5°𝐶

The top temperature of distillation :

𝑃𝑡𝑜𝑝 = 𝑋𝑃𝐻 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑀𝐴 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑜𝑥𝑦 ∗ 𝑃 𝑠𝑎𝑡

𝐵 𝐵
649.66 𝑚𝑚 𝐻𝑔 = [(5.15 ∗ 10−6 ) ∗(𝑒 (𝐴−𝑇−𝐶) + (1.879 ∗ 10−4 ) ∗ 𝑒 (𝐴−𝑇−𝐶) + (0.998) ∗
𝐵
𝑒 (𝐴−𝑇−𝐶) ]

Solving for 𝑇 = 135.9°𝐶

Top temperature after condensation :

𝑃𝑡𝑜𝑝 = 𝑋𝑃𝐻 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑀𝐴 ∗ 𝑃 𝑠𝑎𝑡 + 𝑋𝑜𝑥𝑦 ∗ 𝑃 𝑠𝑎𝑡

𝐵 𝐵
649.66 𝑚𝑚 𝐻𝑔 = [(5.1 ∗ 10−6 ) ∗(𝑒 (𝐴−𝑇−𝐶) + (1.878 ∗ 10−4 ) ∗ 𝑒 (𝐴−𝑇−𝐶) + (0.998) ∗
𝐵
𝑒 (𝐴−𝑇−𝐶) ]

Solving for 𝑇 = 135.8°𝐶

hV =
135.9 135.9 135.9
[∫25 𝐶𝑝𝑜𝑥𝑦 (𝑙𝑖𝑞)𝑑𝑇] ∗ (0.998) + [ ∫25 𝐶𝑝𝑀𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗ (5.15 ∗ 10−6 ) + [∫25 𝐶𝑝𝑃𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗
(5.15 ∗ 10−6 ) = 21.97 kj/mol

hD =
135.8 135.8 135.8
[∫25 𝐶𝑝𝑜𝑥𝑦 (𝑙𝑖𝑞)𝑑𝑇] ∗ (0.998) + [ ∫25 𝐶𝑝𝑀𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗ (5.15 ∗ 10−6 ) + [∫25 𝐶𝑝𝑃𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗
(5.15 ∗ 10−6 ) = 21.96 kj/mol

hB =
144.4 186.5 186.5
[∫25 𝐶𝑝𝑜𝑥𝑦 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑜𝑥𝑦 + ∫144.4 𝐶𝑝𝑜𝑥𝑦 (𝑣𝑎𝑝)𝑑𝑇] ∗ (0) + [ ∫25 𝐶𝑝𝑀𝐴 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑀𝐴 ] ∗
186.5
(0.886) + [∫25 𝐶𝑝𝑃𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗ (0.114) = 33.724 kj/mol

hF =
 144.4 195.2 195.2
[∫25 𝐶𝑝𝑜𝑥𝑦 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑜𝑥𝑦 + ∫144.4 𝐶𝑝𝑜𝑥𝑦 (𝑣𝑎𝑝)𝑑𝑇] ∗ (0.817) + [ ∫25 𝐶𝑝𝑀𝐴 (𝑙𝑖𝑞)𝑑𝑇 + 𝜆𝑀𝐴 ] ∗
150.3
(0.161) + [∫25 𝐶𝑝𝑃𝐴 (𝑙𝑖𝑞)𝑑𝑇] ∗ (0.0207)] = 55.486 kj/mol

Calculating heat of condenser Qc and heat of reboiler Qr :

λoxy = 8800 cal/mol

λPA = 11850 cal/mol
λMA = 5850 cal/mol

𝜆𝑚𝑖𝑥 = 𝑋𝑃𝐴 𝜆𝑃𝐴 + 𝑋𝑀𝐴 𝜆𝑀𝐴 + 𝑋𝑜𝑥𝑦 𝜆𝑜𝑥𝑦 = 36.75 kj/mol

Qc = -2617831.642 kj/hr

Qr = ℎ𝐷 𝐷 + ℎ𝐵 𝐵 − 𝐹ℎ𝐹 − 𝑄𝑐 = 1585005.14 kj/hr

Stream 1 2 3 4 5 6 7 8 9
number
Temperature 25 84.74 25 84.74 32.5 240 80 300 380
( oC )
Pressure 1 1 1 2 2 2 2 2 1.8
(bar)

Stream 10 11 12 13 14 15 16 17 18
number
Temperature 170 195.2 56.25 105 25 169.7 260.9 150.3 135.9
( oC )
Pressure 1.8 1 1 1 2 2 0.8 0.6 1
(bar)

Stream number 19 20 21
Temperature ( oC ) 135.9 180 135.8
Pressure (bar) 0.85 0.6 1

sub 𝒏𝟎𝒊𝒏 (kmol/hr) 𝑯^𝒊𝒏 (kj/kmol) 𝒏𝟎𝒐𝒖𝒕 (kmol/hr) 𝑯^𝒐𝒖𝒕 (kj/kmol)

𝑪𝟖 𝑯𝟏𝟎 123.63 𝑯^𝟏 30.91 𝑯^𝟒
𝑶𝟐 373.46 𝑯^𝟐 2.57 𝑯^𝟓
𝑵𝟐 1404.91 𝑯^𝟑 1404.91 𝑯^𝟔
𝑪𝟖 𝑯𝟒 𝑶𝟑 ---- ---- 77.89 𝑯^𝟕
𝑯𝟐 𝑶 ---- ---- 301.66 𝑯^𝟖
𝑪𝑶𝟐 ---- ---- 93.96 𝑯^𝟗
 𝑪𝟒 𝑯𝟐 𝑶𝟑 ---- ----- 6.18 𝑯^𝟏𝟎

sub 𝒏𝟎𝒊𝒏 (kmol/hr) 𝑯^𝒊𝒏 (kj/kmol) 𝒏𝟎𝒐𝒖𝒕 (kmol/hr) 𝑯^𝒐𝒖𝒕 (kj/kmol)

𝑪𝟖 𝑯𝟏𝟎 123.63 105709.33 30.91 137224.23
𝑶𝟐 373.46 8470 2.57 11060
𝑵𝟐 1404.91 8120 1404.91 10544
𝑪𝟖 𝑯𝟒 𝑶𝟑 ---- ---- 77.89 165379.04
𝑯𝟐 𝑶 ---- ---- 301.66 56260
𝑪𝑶𝟐 ---- ---- 93.96 15373
𝑪𝟒 𝑯𝟐 𝑶𝟑 ---- ----- 6.18 97889.16

A B C
O-xylene 16.1156 3395.57 59.46
Phthalic anhydride 15.9984 4467.01 83.15
Maleic anhydride 16.2747 3765.65 82.15

Heat of vaporization (cal/mol)

O-xylene 8800
Phthalic anhydride 11850
Maleic anhydride 5850

a 10*b 10^5*c 10^10*d

O-xylene -3.786 1.424 -8.224 1.798
Phthalic anhydride -1.064 1.562 -1.023 2.411
Maleic anhydride -3.123 0.8323 -5.217 1.156

REACTOR DESIGN DATA :

The catalysis and reaction engineering group has obtained information regarding the o-xylene to
phthalic anhydride reaction. In addition , the complete combustion reaction for each organic
component occurs . The major advantage of our catalyst is that CO formation is eliminated and no
heavy impurity is made .

The catalyst must operate between 300oC and 400oC and pressure between 1 atm to 3 atm . In this
range , the kinetics are as follows : partial pressures in atm , 𝑟𝑖 in kmol/hr , 𝑘𝑜 =1 kmol/hr.kg
catalyst.atm2 , R=1.987 cal/K mole , T in k .
𝑘 27000
𝑟1 = 𝑘1 𝑝𝑜𝑥𝑦 𝑝𝑜2 𝑙𝑛 𝑘1 =- 𝑅𝑇
+ 19.837
0

𝑘 31000
𝑟2 = 𝑘2 𝑝𝑝𝑎 𝑝𝑜2 𝑙𝑛 𝑘2 =- 𝑅𝑇
+ 20.86
0
 𝑘3 28600
𝑟3 = 𝑘3 𝑝𝑜𝑥𝑦 𝑝𝑜2 𝑙𝑛 =- + 18.97
𝑘0 𝑅𝑇

𝑘 27900
𝑟4 = 𝑘4 𝑝𝑜𝑥𝑦 𝑝𝑜2 𝑙𝑛 𝑘4 =- 𝑅𝑇
+ 19.23
0

𝑘 30400
𝑟5 = 𝑘5 𝑝𝑚𝑎 𝑝𝑜2 𝑙𝑛 𝑘5 =- 𝑅𝑇
+ 20.47
0

The lower flammability limit of o-xylene in air is 1 mole % and the upper flammability limit is 6 mole
% . For safety reasons it is necessary that process conditions not be within these limits. It is also
necessary that o-xylene content fo the reactor never exceed 10 mole % , because if that limit is
exceeded the catalyst no longer operates at the desired selectivity , the reaction could become
oxygen starved , forming significant amounts of CO and other undesired byproducts .

At this time , we are unsure as to whether a packed bed reactor or a fluidised bed reactor is the
better choice . For shell and tube packed bed , the catalyst would be in tubes .

We assume data for fluidised bed as follows :

 Spherical catalyst particle , diameter dp = 300mm

 Catalyst particle density ρcat = 1600 kg/m3
 Void fraction at minimum fluidization Ɛmf = 0.5
 Heat transfer coefficient from bed to tube wall h = 300 W/m2 oC
 Reactor should operate between 2umf to 5umf

For umf , we use correlation of Wen and Yu :

𝑑𝑝 𝑢𝑚𝑓 𝑟𝑔
𝑅𝑒𝑚𝑓 = 𝑚
= (sqrt (33.72 + 0.0408 Ar)-33.7)

Where
𝑑𝑝 ^3(𝑟𝑠−𝑟𝑔) 𝑔
Ar =
𝑚^2

For shell and tube packed bed we assume data as follows :

 Catalyst particle diameter dp = 3mm
 Catalyst particle density ρcat = 1600 kg/m3
 Void fraction Ɛ = 0.5
 Heat transfer coefficient from packed bed to tube wall h = 60 W/m2oC

Shell diameter is a function of heat transfer characteristics and frictional

losses .