1

Production of 120 Kiloton per year of

High Density Polyethylene
GROUP MEMBERS
• FAISAL NADEEM UW-14-Ch.E-BSC-040
• JAWWAD ZAIB KHAN UW-14-Ch.E-BSC-049
• SAMI-UL-HASSAN UW-14-Ch.E-BSC-043
• ARIF-ULLAH KHAN UW-14-Ch.E-BSC-045

PROJECT SUPERVISORS
Ms. RABIA SABIR
Ms. AASIA FARUKH

2
 Production of 120 Kiloton per year of HDPE
Exhaust Gases
Exhaust Gases

93.5°C
1 2 3 4 5 30.5 bar
Feed 8
400°C 292°C
25.7°C 400°C 199.6°C 41.62 bar 40.32 bar
25 °C F-101 43.35 bar F-102 R-102
P-101 43.35 bar R-101 41.62 bar
1.01 bar K-201 Coolant in 100°C Freon Coolant in
44.3 bar K-202
6
Air, Natural Gas Air, Natural Gas
301°C 7 FL-201 10

45 bar E-201
105°C
Coolant out 98°C Waste Water E-202
9 35 bar
37.42 bar
18°C Freon Coolant out
34.3 bar
11
Ethylene Gas
Recycle n-hexane Condenser
12 28
25°C n-hexane
15°C 25°C Vapors
20 8.08 bar Cooler E-104
34.31 bar 25°C 25°C 1.01 bar 110°C
8.08 bar 8.08 bar 18 E-104 27 1.01 bar
19
n-hexane 24 85°C
E-101 CW in CW out 25°C 1.01 bar
FL-
14 8.08 bar CW in CW out
202 25°C
13 25
1.01 bar R-103 22 85°C
Aqueous Waste n-hexane R-104 To Recovery N2 Gas
15°C 7.4 bar
34.31 bar 16 DC-1 Section
17 15 85°C
TiCl4 +(C2H5)3Al 25°C 85°C 8.4 bar 23
21 26 29
1.01 bar 8.08 bar Pure HDPE
H2 Gas 85°C 85°C Powder
E-103
P-103 1.01 bar FD-1
MX-1
P-102 N2 Gas
Energy Balance:

Heat of reaction Method:

1 2 1 2
∑outlet(Hi+gZi+ Vi )Fi-∑inlet(Hj+gZj+ Vj )Fj= Q-W
2 2
• Potential and kinetic energy are relatively small in chemical
process application.
• Expect Pump, turbine and compressor most chemical process
do not involve work.
• Energy balance equation reduce to
∑ outlet(Hi Fi)- ∑ inlet(Hj Fj)=Q
• Specific enthalpy is calculate by the by equation
𝑇
Hi= ‫ 𝑓𝑒𝑟𝑇׬‬Cpidt
• The heat capacity is usually calculate by that
equation as a function of Temperature is
Cpi= a+b.T+c.T2+d.T3
• The final form of equation to calculate Specific
enthalpy is:
𝑇
𝑏 𝑐 𝑑
Hi = a. T + . T2 + . T3 + . T4
2 3 4 𝑇𝑟𝑒𝑓
𝑏 2 2 𝑐 3 3 𝑑 4 4
Hi=a(T-Tref)+ (T -𝑇𝑟𝑒𝑓 )+ (T -𝑇𝑟𝑒𝑓 )+ (T -𝑇𝑟𝑒𝑓 )
2 3 4
Reactor (R-101):
Heat of formation for components:
Δ Hf° for C2H5OH = -234.96 KJ/mols
Δ Hf° for H2O = -242 KJ/mols
Δ Hf° for C2H4 = 52.33 KJ/mols

CH3CH2OH → CH2=CH2 +H2O

° σ °
∆𝐻𝑓𝑖 = (𝜎𝑖𝐻𝑓𝑖 )
Δ Hf° = (+1) (-242) +(+1) (52.33) +(-1) (-234.96)
= 45.29 KJ/mols ( at 1atm and at 25°C)
 C2 H5OH → C2 H 4 + H 2 O
Required ∆Hr
Temperature
UNKNOWN

298 𝑇𝑥𝑟𝑛
σ(‫ 𝐶 𝑛𝑥𝑟𝑇׬‬pidT) σ(‫׬‬298 𝐶 pidT)

Standard C2 H5OH → C 2 H4 + H 2 O KNOWN

temperature ∆𝐻𝑟°

298 𝑇𝑥𝑟𝑛
∆Hr=∑react (‫ 𝐶 𝑛𝑥𝑟𝑇׬‬pidT) + ∆𝐻𝑟° + ∑prod(‫׬‬298 𝐶 pidT)
Δ Hr at reaction temperature:
𝑟𝑒𝑓 𝑇𝑥𝑛
Δ Hr = σ𝑟𝑒𝑎𝑐𝑡(‫ )𝑡𝑑 𝑖𝑝𝐶 𝑛𝑥𝑇׬‬+ Δ Hr° σ𝑝𝑟𝑜𝑑𝑢𝑐𝑡(‫)𝑡𝑑 𝑖𝑝𝐶 𝑓𝑒𝑟𝑇׬‬
𝐽 𝐽 𝐽
= −3.46 × 104 + 4.52 × 104 + 1.15 × 104
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
4 𝐽 𝑘𝑗
= 2.58 × 10 or 25.8
𝑚𝑜𝑙 𝑚𝑜𝑙

∑ outlet(Hi Fi)- ∑ inlet(Hj Fj)=Q- rΔ Hr

10 𝐽
∑ inlet(Hj Fj) = 1.97 × 10
ℎ𝑟
𝐽
∑ outlet(Hi Fi) = 8.35 × 109
ℎ𝑟
rΔ Hr 9.21 × 10 9 𝐽
= ℎ𝑟
 9 𝐽 10 𝐽 9 𝐽
Q= 8.35 × 10 − 1.97 × 10 +9.21 × 10
ℎ𝑟 ℎ𝑟 ℎ𝑟
𝐽 𝑘𝐽
Q= 4.35 × 109 or 4.35 × 106
ℎ𝑟 ℎ𝑟

Input Output
Temperature = 400 °C Temperature = 200 °C
Pressure = 4335Kpa Pressure = 4162Kpa
Components kmol/hr Enthalpy(kj/hr) Components kmol/hr Enthalpy(kj/hr)

Ethanol 541.28 3.40E+04 Ethanol 193.72 13794.98404

Water 72.80 1.34E+04 Water 422.26 6051.392815
Ethylene 0.00 0 Ethylene 346.33 9017.716995
Hin 1.97E+07 Hout 8.35E+06
Reactor (R102):
𝑟𝑒𝑓 𝑇𝑥𝑛
Δ Hr = σ𝑟𝑒𝑎𝑐𝑡(‫ )𝑡𝑑 𝑖𝑝𝐶 𝑛𝑥𝑇׬‬+ Δ Hr° σ𝑝𝑟𝑜𝑑𝑢𝑐𝑡(‫)𝑡𝑑 𝑖𝑝𝐶 𝑓𝑒𝑟𝑇׬‬
𝐽 𝐽 𝐽
= −3.46 × 104 + 3.49 × 104 + 2.4 × 104
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
4 𝐽 𝑘𝑗
= 2.58 × 10 25.8
𝑚𝑜𝑙 𝑚𝑜𝑙

∑ outlet(Hi Fi)- ∑ inlet(Hj Fj)=Q- rΔ Hr

10 𝐽
∑ inlet(Hj Fj) = 2.00 × 10
ℎ𝑟
𝐽
∑ outlet(Hi Fi) = 1.42 × 1010
ℎ𝑟
r ΔHr 4.91 × 10 9 𝐽
= ℎ𝑟
 ∑ outlet(Hi Fi)- ∑ inlet(Hj Fj)=Q- rΔ Hr
𝐽 𝐽 𝐽
Q =1.42 × 1010 − 2.00 × 1010 +9.21 × 109
ℎ𝑟 ℎ𝑟 ℎ𝑟
9 𝐽 6 𝑘𝐽
Q =3.86 × 10 or 3.86 × 10
ℎ𝑟 ℎ𝑟

Input Output
Temperature = 400 °C Temperature = 292 °C
Pressure = 4462Kpa Pressure = 4032Kpa
Components kmol/hr Enthalpy(kj/hr) Components kmol/hr Enthalpy(kj/hr)
Ethanol 193.72 6.69E+06 Ethanol 193.72 1.04E+06
Water 422.26 5.70E+06 Water 422.26 5.32E+06
Ethylene 346.33 7.68E+06 Ethylene 346.33 7.32E+06
Hin 2.00E+07 Hout 1.42E+07
Fired Heater(F-101)

Input Output

Temperature = 25.7 °C Temperature = 400 °C

Pressure = 4335Kpa Pressure = 4305Kpa

Components kmol/hr Enthalpy(kj/hr) Components kmol/hr Enthalpy(kj/hr)

Ethanol 541.28 2.09E+03 Ethanol 193.72 1.87E+07

Water 72.80 1.70E+03 Water 422.26 9.77E+05

Ethylene 0.00 0 Ethylene 346.33 0

Hin 3.79E+3 Hout 1.97E+07

 𝐻𝑂𝑢𝑡 − 𝐻𝐼𝑛 = 𝑄
3 𝑘𝐽
∑ inlet(H.F) = 3.79 × 10
ℎ𝑟
7 𝑘𝐽
∑ outlet(H.F) = 1.97 × 10
ℎ𝑟

7 𝑘𝐽 3 𝑘𝐽
Q = 1.97 × 10 - 3.79 × 10
ℎ𝑟 ℎ𝑟
7 𝑘𝐽
= 1.97251 × 10
ℎ𝑟
7 𝑘𝐽
So 1.97 × 10 of heat is required to heat the feed in the
ℎ𝑟
first Fired heater.
Fired Heater(F-102)

Input Output
Temperature = 200 °C Temperature = 400 °C
Pressure = 4193Kpa Pressure = 4162Kpa
Components kmol/hr Enthalpy(kj/hr) Components kmol/hr Enthalpy(kj/hr)
Ethanol 193.72 2.70E+06 Ethanol 193.72 6.69E+06
Water 422.26 2.56E+06 Water 422.26 5.70E+06
Ethylene 346.33 3.12E+06 Ethylene 346.33 7.68E+06
Hin 8.40E+06 Hout 2.00E+07
 𝐻𝑂𝑢𝑡 − 𝐻𝐼𝑛 = 𝑄
6 𝑘𝐽
∑ inlet(H.F) = 8.04 × 10
ℎ𝑟
7 𝑘𝐽
∑ outlet(H.F) = 2.00 × 10
ℎ𝑟

7 𝑘𝐽 6 𝑘𝐽
Q = 2.00 × 10 - 2.00 × 10
ℎ𝑟 ℎ𝑟
7 𝑘𝐽
= 1.16 × 10
ℎ𝑟
7 𝑘𝐽
So 1.16 × 10 of heat is required to heat the feed in the
ℎ𝑟
first Fired heater.
Compressor (K-201)
𝑝𝑣 = 𝑛𝑅𝑇

𝑚
𝑝𝑣 = 𝑅𝑇
𝑀

𝑷𝑴
𝓹=
𝑹𝑻

4500 × 46 𝑘𝑔
𝓅𝐶2𝐻5𝑂𝐻 = 𝓅𝐶2𝐻5𝑂𝐻 = 48.712
8.314 × 515 𝑚3
Components Mass Flow Rate Mole Fraction Density kg/m3
(kg/hr)
Ethanol 2096.3 0.08 48.713
Water 10221.5 0.39 27.21
Ethylene 13890.8 0.53 17.5

Average density of gases = (Mole fraction × 𝓅 ) 𝔦

= 0.08 × 48.17 + 0.39 × 27.21 + 0.53 × 17.5

𝑘𝑔
𝓅𝐴𝑣𝑎 = 23.46 𝑚3
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒
𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝐹𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 =
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
26209
= 23.46
𝑚3
= 1117.18 ℎ𝑟
We know that,
Work done by compressor = 𝑣. ΔP
= 𝑣 × (𝑃2 − 𝑃1 )
= 1117.18 × 4500 − 4162
= 377606.8 kj/hr

377606.8 × 1ℎ𝑟
=
3600 𝑠

= 104.89 𝐾𝑊
Now,
𝐻𝑂𝑢𝑡 − 𝐻𝐼𝑛 = 𝑄 − 𝑊
𝐾𝐽
Hin= 4.56*109
ℎ𝑟
Hout= 9
4.82*10 kj/hr
So.
Q = 4.82*109 - 4.56*109 + 3.77*105
Q = 2.60*108 kj/hr
Compressor(K-202)

Components Mass Flow Rate Mole Fraction Density kg/m3

(kg/hr)
Ethanol 2096.3 0.08 37.60
Water 10221.5 0.39 22.88
Ethylene 13890.8 0.53 14.71
• Work done by compressor = 𝑣. ΔP
= 𝑣 × (𝑃2 − 𝑃1 )
= 797.37 × 3500 − 3050
= 358817.1 kj/hr
358817.1 ×1ℎ𝑟
=
3600 𝑠
= 99.67 𝐾𝑊
• Now,
𝐻𝑂𝑢𝑡 − 𝐻𝐼𝑛 = 𝑄 − 𝑊
Hin= 6.74*108 kj/hr
Hout= 8.16*108 kj/hr
• So.
Q= 8.16*108 - 6.74*108 + 3.5*105
Q= 1.42*108 kj/hr
 Heat Exchanger (E201)

Input Output
Temperature = 301 °C Temperature = 100 °C
Pressure = 4500Kpa Pressure = 4430Kpa
Components kmol/hr Enthalpy(kj/hr) Components kmol/hr Enthalpy(kj/hr)
Ethanol 45.58 1.08E+06 Ethanol 45.58 1.38E+04
Water 567.86 5.51E+06 Water 567.86 6.05E+03
Ethylene 496.1 7620698 Ethylene 496.1 9.02E+03
Hin 1.42E+07 Hout 3.44E+06
 𝐻𝑂𝑢𝑡 − 𝐻𝐼𝑛 = 𝑄

𝑘𝐽
∑ inlet(Hj Fj) = 1.42 × 107
ℎ𝑟
6 𝑘𝐽
∑ outlet(Hi Fi) = 3.44 × 10
ℎ𝑟

7 𝑘𝐽
Q = −1.08 × 10
ℎ𝑟
Q= m Cp ΔT
1.08 × 107 = m ( 4.18× 25 )
m = 105719 kg/hr
Heat Exchanger (E201)

Input Output
Temperature = 105°C Temperature = 30 °C
Pressure = 3500Kpa Pressure = 3430Kpa
Components kmol/hr Enthalpy(kj/hr) Components kmol/hr Enthalpy(kj/hr)
Ethanol 7.9 4.53E+04 Ethanol 7.9 2.60E+03
Water 20.3 5.54E+04 Water 20.3 3.43E+03
Ethylene 496.1 1.87E+06 Ethylene 496.1 1.07E+05
Hin 1.97E+06 Hout 1.13E+05
 𝐻𝑂𝑢𝑡 − 𝐻𝐼𝑛 = 𝑄
𝑘𝐽
∑ inlet(Hj Fj) = 1.97 × 106
ℎ𝑟
5 𝑘𝐽
∑ outlet(Hi Fi) = 1.13 × 10
ℎ𝑟

6 𝑘𝐽
Q = −1.86 × 10
ℎ𝑟
Q= m Cp ΔT
1.86 × 106 = m ( 4.18× 25 )
m = 14815 kg/hr
ENERGY BALANCE ON POLYMERIZATION
SECTION
• REACTOR (R-103):
• Exothermic reaction
• 𝐶2 𝐻4 → (𝐶2 𝐻4 )35

Component Ethylene Polyethylene

(j/mole) (j/mole)
Heat of 52330 93600
formation

• ℎ𝑒𝑎𝑡 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 25°𝐶 = ‫ט‬. 𝐻𝑒𝑎𝑡 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

− ‫ט‬. ℎ𝑒𝑎𝑡𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑠
𝑗
= 3223670( )
𝑚𝑜𝑙𝑒
Component ‫ט‬ A(j/mole) B((j/mole) C(j/mole) D(j/mole)

𝑪𝟐 𝑯𝟒 1 1.424 0.014394 -49.92 -

(𝑪𝟐 𝑯𝟒 )𝟓𝟎 50 1.424 0.014394 -49.92 -

N-Hexane 1 -4.413 0.58197 -0.0003119 0.0006494

∆𝐻
𝑇𝑅𝐸𝐹𝐸𝑅𝐸𝑁𝐶𝐸
=න 𝐶𝑃 . 𝑑𝑡
𝑇
∆𝑯𝑹𝑬𝑨𝑪𝑻𝑨𝑵𝑻𝑺
𝑩 2
𝑪 3
= 𝑨 𝑻𝑹𝑬𝑭𝑬𝑹𝑬𝑵𝑪𝑬 − 𝑻 + 𝑻 −𝑻 + 𝑻𝑹𝑬𝑭𝑬𝑹𝑬𝑵𝑪𝑬 − 𝑻
2 𝑹𝑬𝑭𝑬𝑹𝑬𝑵𝑪𝑬 3
𝑫
+ 𝑻𝑹𝑬𝑭𝑬𝑹𝑬𝑵𝑪𝑬 − 𝑻 4
4
 Reactor (R-104)
∆𝑯85°𝑪 = ∆𝑯𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔 + ∆𝑯𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔 + ∆𝑯𝑹𝒆𝒇𝒆𝒓𝒏𝒄𝒆

∆𝑯𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − ∆𝑯𝑹𝑬𝑨𝑪𝑻𝑨𝑵𝑻𝑺 + 𝒓 × ∆𝑯𝒓 = 𝑸

Input Output
Temperature = 85 °C Temperature = 85 °C
Pressure = 808Kpa Pressure = 808Kpa
Components kmol/hr Enthalpy(kj/hr) Components kmol/hr Enthalpy(kj/hr)
Ethylene 489.14 1.60E+14 Ethylene 78.26 2.50E+13
n-Hexane 2.39 0.00E+00 n-Hexane 2.39 3.20E+09
Polyethylene 0.00 0.00E+00 Polyethylene 821[B] 4.75E+15
Hin 1.60E+14 Hout 4.78E+15
• Heat removed through N-Hexane:
joule
= −2.66471E + 12 × 0.60
seconds
= 1.59846𝐸 + 12
= 2.66471𝐸 + 12 − (1.59846𝐸 + 12)
=1.065274𝐸 + 12

• HEAT REMOVED THROUGH WATER:-

𝑄 = 𝑚. λ
𝜆 = 3683960( 8.08 𝑏𝑎𝑟𝑟)
𝑄
𝑚=
λ
1.065274𝐸 + 12
𝑚=
3683960
𝐾𝑔
𝑚 = 289165.4633
ℎ𝑜𝑢𝑟
 ∆𝑯85°𝑪 = ∆𝑯𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔 + ∆𝑯𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔 + ∆𝑯𝑹𝒆𝒇𝒆𝒓𝒏𝒄𝒆
∆𝑯𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − ∆𝑯𝑹𝑬𝑨𝑪𝑻𝑨𝑵𝑻𝑺 + 𝒓 × ∆𝑯𝒓 = 𝑸
• Heat removed through N-hexane:
𝑗𝑜𝑢𝑙𝑒
= −2.93302𝐸11 × 0.60
𝑠𝑒𝑐𝑜𝑛𝑑𝑠
= 1.759812𝐸 + 11
= −2.93302𝐸 + 11 + (1.759812𝐸 + 12)
=1.173208𝐸 + 11
• Heat removed through water:-

Q=
𝑄 = 𝑚. 𝜆
• Heat Requirements:
Two types of heat requirements:
I. Heat required to raise the product temperature at discharge
temperature
II. Heat required to remove the n-hexane contents from HDPE
powder
Component Inlet Temperature(K) Outlet Temperature (K)

HDPE 358 383

Nitrogen 398 388

Heat required to raise the product temperature at discharge temperature:

𝑸𝟏 = 𝒎𝒔𝑪𝒑𝒔𝑻 + 𝒎𝒉, 𝒐𝒖𝒕𝑪𝒑𝒉𝑻

Q1= 13696×1.9986× (383-358) + 1.848×2.43055× (383-358)

Q1= 687257.7166 W
• Heat required to remove the n-hexane contents from HDPE
powder:

𝑸𝟐 = 𝒎𝒉 [𝑪𝒑𝒍𝑻 +  + 𝑪𝒑𝒗𝑻]
Q2=35 ×[2.430555 ×(383-358) + 0.25578 + 1.96759 ×(388-383)]
Q2=2480.016175 W
• Total heat required: 𝑸𝒕 = 𝑸𝟏 + 𝑸𝟐
= 687257.7166 + 2480.016175
=689737.7328 W

• Amount of Nitrogen required:

𝒎 = 𝑸𝒕/(𝑪𝒑𝑻)

689737.7326
𝑚= ×(398 − 388)]
1.0491

m=32872.83065 kg/hr