UNIT OPERATION

BKF 3463
SEM I 2016/2017

INTEGRATED PROJECT
PRODUCTION OF 70000 MTA ETHYLENE FROM METHANE

Name of Lecturer : Dr. NOOR SABRINA BINTI AHMAD MUTAMIM

Section : 01
Date of Submission : 9th Disember 2016
Group Members :

No Name ID

MOHAMAD ABDUL FATTAH BIN

1 KA14139
AHMAD
MUHAMMAD SYARIF WIRAI BIN ABD
2 KA1427
RAZAK

3 NUR AIN BINTI ZAKARIA KA14144

4 NOR NADIRA BT ABDUL RAHMAN KA14132

5 FARES AHMED QAID ALAW KA14003

TABLE OF CONTENTS

CHAPTER TITLE PAGE

1 Project Discription

2 Process Synthesis And Flow Sheeting

3 Material Balance

4 Energy Balance

5 Process Equipment Sizing

6 Economic Analysis

7 References
1.0. PROJECT DISCRIPTION
1.1 Introduction

Figure 1.1: Molecular structure of Ethylene.

Ethylene is classified as alkene in a chemical family. It is the first member of the alkenes.
The chemical formula for Ethylene is C2H4. Ethylene is a volatile, colourless gas with a sweet
odour. (Milne G. W. A., 2004). The physical and chemical properties of Ethylene as in Table 1.1
below.

Table 1.1: Physical and chemical properties of Ethylene.

Ethylene is regulated under the Clean Air Act (CAA) as a Volatile Organic Compound
(VOC). Hence, the flammability aspect is the primary hazard associated with ethylene. Workers
that handling Ethylene must wear personal protective equipment (PPE), which goggle and mask.
It is because having eye contact with rapidly expanding ethylene gas may cause severe irritation
and burns. (American Chemistry Council, 2004)
1.2 Applications Of Ethylene
Ethylene is the raw material used in the manufacture of polymers such as polyethylene (PE),
polyethylene terephthalate (PET), polyvinyl chloride (PVC) and polystyrene (PS) as well as
fibres and other organic chemicals. These products are used in a wide variety of industrial and
consumer markets such as the packaging, transportation, electrical/electronic, textile and
construction industries as well as consumer chemicals, coatings and adhesives. Ethylene is used
to make PVC products (source: Hydro Polymers)
Besides, Ethylene also used in agriculture sector. First of all, it is used to boost up plant.
It promotes the growth of plant by diffusing the Ethylene gas to the plant cell. By doing this, it
prevents roots from curving geotropically, so that the plant will continue life vertically. (Stanley,
1973) Second of all, it enhance ripening of fruits, as the Ethylene gas known as the fruit ripening
hormone. For instance, by exposing mature honeydew melons to 1000 ml l_1 C 2H4 for 24 h
subsequently induced ripening and eliminated chilling injury in fruit stored at 2.5C for 2 weeks.
(Mikal, 1998)

Figure 1.3: Application of Ethylene used globally.

The largest outlet, accounting for 60% of ethylene demand globally, is polyethylene. Low
density polyethylene (LDPE) and linear low density polyethylene (LLDPE) mainly go into film
applications such as food and non-food packaging, shrink and stretch film, and non-packaging
uses. High density polyethylene (HDPE) is used primarily in blow moulding and injection
moulding applications such as containers, drums, household goods, caps and pallets. HDPE can
also be extruded into pipes for water, gas and irrigation, and film for refuse sacks, carrier bags
and industrial lining.
The next largest consumer of ethylene is ethylene oxide (EO) which is primarily used to
make ethylene glycol. Most monoethylene glycol (MEG) is used to make polyester fibres for
textile applications, PET resins for bottles and polyester film. MEG is also used in antifreeze
applications. Other EO derivatives include ethyoxylates (for use in shampoo, kitchen cleaners,
etc), glycol ethers (solvents, fuels, etc) and ethanolamines (surfactants, personal care products,
etc).
 Ethylene dichloride (EDC) is made by the chlorination of ethylene and can then be
cracked to make vinyl chloride monomer (VCM). Nearly all VCM is used to make polyvinyl
chloride which has its main applications in the construction industry.
Ethylene can be reacted with benzene to make ethylbenzene which is further processed
into styrene. The main outlets for styrene are polymers and synthetic rubbers such as
polystyrene, acrylonitrile-butadiene-styrene (ABS) and styrene butadiene rubber (SBR).
1.3 Market Survey And Analysis

During 20092014, world ethylene consumption grew at an average rate of almost 4.5% per
year, while capacity increased at a slower rate of about 3.5%.

GLOBAL DEMAND

Polyethylene, the largest ethylene derivative market that contribute over 60% of global ethylene
consumption in 2014. Where the Markets include film packaging, making containers and articles
for home and light industrial use. During 20142019, polyethylene will continue to be the largest
consumer of ethylene, growing at an average rate of 4.5% per year to account for nearly 62% of
the ethylene market in 2019.

The next-largest derivative market is ethylene oxide for ethylene glycol used primarily to
produce PET where it is to make polyethylene terephthalate fibers, bottles and other goods. In
2014, ethylene oxide contribute 15% of total world consumption. Ethylene oxide use to make
ethylene glycol is expected to grow at about 4% per year for the next five years. China is
expected to account for about 42% of the increased ethylene consumption in ethylene oxide in
the next five years, illustrating the continued rapid share gain for bottle and especially traditional
polyester fiber use (Markit, 2014).

Figure 1.4: World consumption of ethylene in 2014 (Markit, 2014)

Ethylene dichloride accounts for 10% of the world ethylene market in 2014. Taiwan (20%),
Japan (18%), Central Europe (17%), the United States (16%) and Western Europe (13%) have
the highest regional share for ethylene dichloride, while the Middle East, Southeast Asia and
China are among the lowest at 38%. Ethylene consumption for ethylene dichloride (primarily
for vinyl chloride and polyvinyl chloride resin) will grow at an average annual rate of about 3%,
with the United States, the Middle East and China accounting for nearly 72% of the increased
ethylene consumption.
Growth in world ethylene consumption will be driven by growth in the usage of polyethylene to
make the people daily use product. For instance ethylene oxide derive to ethylene glycol is use to
make polyethylene terephthalate (PET) resins that going to be used to make PET fiber, bottles
and other packaging. Meanwhile ethylene dichloride is use for making PVC plastic that are very
necessary to construction and making a pipe. Together these end uses represent about 86% of
world ethylene consumption.

Global demand for ethylene is forecast to grow faster over the next five years. The most
important regions in terms of growth are the CIS/Baltic states (about 10% average annual
growth), India (about 9.5% average annual growth), China (about 8% average annual growth),
the United States (about 5% average annual growth), and the Middle East (about 4.5% average
annual growth). These five regions account for 91% of the volume growth between 2014 and
2019. Western Europe is the only region expected to consume substantially less ethylene in the
next five years.

Ethylene consumption is expected to grow at about 4% per year over the next five years.
Capacity additions will match this growth (Markit, 2014).

PRICE OF RAW MATERIAL

Figure 1.5: World Ethylene Cash Costs (Eramo, 2013)

In spite of its higher demand in the world market the raw material and method to produce
ethylene varies from one country to other country. From the figure its show that naphtha cracking
use higher cost to produce ethylene compare to ethane cracking. Ethane cracking use the lowest
cost to produce ethylene and ensure a higher profit. However method and raw material use
depend on the availability of the raw material in the country. For instance in Malaysia naphtha
cracking was used to produce ethylene. The highest producer of ethylene using this method and
raw material is lotte chemical which located at johor.
TRENDS

Figure 1.6 : Total Capacity Growth Of Ethylene (Eramo, 2013)

From the figure it show the total capacity growth based on region in certain period of time. From
1980 through 1990 the trend was relatively evenly spread. Forward to 2010 until 2020 the Asia
Pacific dominate the trend with a steady growth. They continue to increase at a pretty rapid rate.

Major Companies Involved in the Global Ethylene Market (research, 2012)

BASF
ExxonMobil Chemical
INEOS, Formosa Plastics Corporation
DuPont
Dow Chemical
Lyondell Basell Industries
Saudi Basic Industries Corporation
Sumitomo Chemical
Chevron Phillips
2.0 PROCESS SYNTHESIS AND FLOW SHEETING

2.1 Process Flow Diagram

Figure 2.1 : Process Flow Diagram (PFD) for Production of Ethylene from Methane
2.2 Desription of The Overall Process

In this process, the main objective is to cope the production of ethylene by 70000 MTA. The
reactant use in this process is methane and oxygen. Methane is one of the component in natural
gas while oxygen from air. As we can see from figure 2.1, the process started at the OCM
Reactor (R-101). As the methane and oxygen react, it will form ethylene and also ethane, the
product of the reactor is ethylene, water, and ethane, as the unreacted feed to the reactor,
methane, oxygen, nitrogen and also unreacted ethane is shown as product of the reactor.

The product from the reactor is feed to the Carbon Dioxide And Hydrogen Absorber(V-101), we
assume that all the water and carbon monoxide will be treated by monoethanolamine(MEA) and
the product from the absorber is methane, ethylene, oxygen, nitrogen and also ethane. The
carbon monoxide and water is flow into the Desorber (V-102) before being release to the
environment.

The product of the Absorber is feed into the Demethanizer (T-101) for separate the methane,
ethylene, ethane from oxygen and nitrogren. As we can see in the chapter 3, not all the methane
and is recover at the distillate and some are going to the bottom as well. The distillate containt of
methane, oxygen, nitrogen and also ethylene, while the bottom containt methane, ethane and
ethylene. The distillate product is feed into Disstillation Column (T-102) and separate againt to
remove the oxygen and nitrogen. The distillate containt oxygen, methane, nitrogen and ethylene,
while the bottom is containt methane and ethylene. The bottom product is recycle back to the
process to reduce the amount of reactant use.

As we can see from paragraph 3, the bottom product of T-101 contain methane, ethane, and
ethylene. This product feed into Dethanizer (T-103) to separate the methane from ethane and
ethylene. The distillate product contains methane, ethylene and ethane, while the bottom product
contain ethane and ethyle. The bottom product is being store in the tank label as T-101, as
byproduct, ethane. The distillate product is feed into Demethanizer (T-104).

In this Demethanizer, the main function is to separate the ethylene and ethane from methane,the
distillate product containt small amount of ethylene and also ethane, while the product of bottom
containt methan, ethylene and ethane. The desired product of ethylene is store in tank label (T-
102)

2.3 Desription of Unit Operation

3.0 MATERIAL BALANCE

3.1. OCM Reactor (R-101)

ninletCH4 noutletCH4
ninletC2H6 noutletC2H6
ninletO2 noutletO2
ninletN2 noutletN2
noutletC2H4
noutletH2O
noutletCO2

Figure 3.1 : OCM Reactor (R-101)

Information taken from the Fini et. al, 2014

1. Ratio of CH4 to O2 is 3:1
2. CH4 conversion is 13.3%
3. O2 conversion is 94.8%
4. C2 selectivity is 49%
5. Ratio of C2H6 to C2H4 is 0.52

Assumption :
1. Molar flowrate C2H4 is same as production which is 70000 MTA or equivalent to
315.0939 kmol/hr.
2. The calculation method use extend of reaction method to calculate the mole reaction
balance (Felder et. al, 2005)
3. The calculation is involve the molar flowrate of recyle CH4.

The reaction involve in the reactor is also taken from Tyler Fini et. al, 2014. The author state that,

CH4 +1/2O2 C2H4 +H2O (Reaction 3.1)

CH4 + 1/4O2 C2H6 + 1/2H2O (Reaction 3.2)
CH4 + 2O2 CO2 + 2H2O (Reaction 3.3)

Table 3.1 : Composition of Component by Stream

 COMPONENT STREAM 6 (KMOL/HR) STREAM 7 (KMOL/HR)
CH4 7661.7887 6642.7708
O2 2553.9296 132.8043
C2H4 315.0939
C2H6 163.8488
H2O 916.3016
CO2 61.1325
N2 9607.6399 9607.6399
Unreacted C2H6 403.2520 403.2520

MOLAR FLOWRATE C2H4 OUTLET

MT 1 year 1 day 1000 kg Kmol

n outlet C2 H 4 (
= 70000 )(
(
year 330 day 24 hr
)()MT
)(
28.05 kg
)
n outle t C 2 H4
=315.0939 kmol /hr

MOLAR FLOWRATE C2H6 OUTLET

n outlet C 2 H6
=0.52 (3.1)
n
outlet C 2 H4

n outlet C2 H 6
=0.52( n outlet )
C 2 H4

n outlet C2 H 6
=0.52(315.0939 kmol /hr)
n outlet C2 H 6
=163.8488 kmol /hr

MATERIAL BALANCE BY EXTEND OF REACTION FOR REACTIVE SPECIES

n outlet =ninlet 1 2 3
CH 4 CH 4
(3.2)
1 1
n outlet =ninlet 2 3 (3.3)
O2
2 1 4 2
O2

1
n outlet = (3.4)
2 1
C2 H 4

1
n outlet = (3.5)
2 2
C2 H 6

1
n outlet = 1 + 2 +2 3 (3.6)
H2O
2
n outlet = 3
CO2
(3.7)
From the 3.4,
1
n outlet =
2 1
C2 H 4

kmol
1=2(315.0939 )
hr
kmol
1=630.1878
hr

From 3.5,
1
n outlet
=
2 2
C2 H 6

2 =2(163.8488 kmol/hr )
2 =327.6976 kmol/h r

From the information number 4,

noutlet + noutlet
C 2 H4
=0.52
C 2 H6

n outlet + n outlet
H2 O CO 2

kmol kmol
315.0939 +163.8488
hr hr
=0.52
1
1+ 2 + 2 3 + 3
2
kmol kmol
315.0939 +163.8488
hr hr
=0.52
kmol 1 kmol
630.1878 + (327.6976 )+3 3
hr 2 hr
kmol
3 =61.1325
hr

Calculate the the molar flowrate oulet for H2O, taken from 3.6
1
n outlet = 1 + 2 +2 3
H2O
2
kmol 1 kmol kmol
n outlet =630.1878
H2O
hr 2
+ 327.6976( hr )
+2(61.1325
hr
)
kmol
n outlet =916.3016
H2O
hr

Calculate the the molar flowrate oulet for CO2, taken from 3.7

n outlet = 3
CO2

kmol
n outlet =61.1325
CO2
hr
Calculate the the molar flowrate inlet and outlet for CH4, taken from 3.1 and information number
2
ninlet n outlet
CH 4
=0.133
CH 4

n inlet CH 4

n
( inlet ) CH 4

n outlet =0.867
CH 4

n outlet =ninlet 1 2 3
CH 4 CH 4

n

( inlet )=n inlet 1 2 3
CH 4
CH 4

0.867
n
( inlet ) CH 4

1 + 2+ 3= ninlet 0.867 CH 4

n inlet =7661.7887 kmol/h r

CH 4

7661.7887 kmol /hr n outlet

=0.133 CH 4

7661.7887 kmol /hr

n outlet =6642.7708 kmol/hr
CH 4

Calculate the the molar flowrate inlet and outlet for O2, taken from 3.2, information number 1,
and information number 3,
ninlet 3
CH 4
=
n inlet
O2
1
n inlet
n inlet = CH 4

O2
3
kmol
n inlet =2553.9296
O2
hr
ninlet noutlet
O2
=0.133
O2

ninletO2

kmol
2553.9296 noutlet
hr O2

=0.133
kmol
2553.9296
hr
n outlet =132.8043 kmol /hr
O2

Calculate the the molar flowrate inlet and outlet for N2,
 n inlet 0.21
O2
=
ninlet
N2
0.79
n inlet (0.79)
n inlet = O2

N2
0.21
n inlet =noutlet =9607.6399 kmol /h r
N2 N2

Calculate unreacted feed C2H6

ninlet
CH 4
=0.95
ninlet + n inlet
CH 4 C2 H 6

7661.7887 kmol /hr

=0.95
kmol
7661.7887 + n inlet
hr C 2H6

n inlet =n outlet =403.2520 kmol/hr

C 2H 6 C 2 H6

3.2 A/B/C CO2 AND H2O ABSORBER (V-101)

ninlet MEA 8

7 10
niuletCH4 noutletCH4
ninletC2H6 noutletC2H6
ninletO2 noutletO2
ninletN2 noutletN2
ninletC2H4 noutletC2H4
ninletH2O 9
ninletCO2 noutletMEA
noutletCO2
noutletH2O

Figure 3.2 : A/B/C Absorber (V-101)

Assumption :
1. All H2O and CO2 is 100% absorb by the V-101 absorber
 Table 3.2 : Composition of Component by Stream

COMPONENT STREAM 7 STREAM 8 STREAM 9 STREAM 11

(KMOL/HR) (KMOL/HR) (KMOL/HR) (KMOL/HR)
CH4 6642.7708 6642.7708
O2 132.8043 132.8043
C2H4 315.0939 315.0939
C2H6 567.1088 567.1008
H2O 916.3016 916.3016
CO2 61.1325 61.1325
N2 9607.6399 9607.6399
MEA

3.3. Desorber (V-102)

noutletCO2

12

ninletCO2
ninletH2O
9

11
noutletH2O

Figure 3.3 : Desorber (V-102)

Assumption :
1. CO2 is 100% absorb by the desorber

Table 3.3 : Composition of Component by Stream

COMPONENT STREAM 9 STREAM 12 STREAM 11

 (KMOL/HR) (KMOL/HR) (KMOL/HR)
H2O 916.3016 916.3016
CO2 61.1325 61.1325

3.4 A/B/C/D Demethanizer (T-101)

14
noutletCH4
noutletO2
noutletN2
noutletC2H4

13
ninletCH4
ninletC2H6
ninletO2
ninletN2
ninletC2H4

ninletCH4
ninletC2H6
19
ninletC2H4

Figure 3.4 : A/B/C/D Demethanizer (T-101)

Assumption :
 1. Methane is light key, while ethylene is heeavy key
2. No ethane at the distillate,
3. No oxygen and nitrogen at the Bottom
4. 2 % of methane is recover at the bottom
5. 2 % of ethylene is recover at the disttilate

Table 3.4 : Composition of Component by Stream

COMPONENT STREAM 13 STREAM 14 STREAM 19

(KMOL/HR) (KMOL/HR) (KMOL/HR)
CH4 6642.7708 6509.9154 114.8554
O2 132.8043 132.8043
C2H4 315.0939 6.3019 308.792
C2H6 567.1008 567.1008
N2 9607.6399 9607.6399

3.5. A/B/C Distillation Column (T-102)

15
noutletO2
noutletCH4
noutletN2
noutletC2H4

14
6
ninletCH4
ninletO2
nintletN2
ninletC2H4

16
noutletCH4
noutletC2H4

Figure 3.5 : A/B/C Distillation (T-102)

Assumption :
1. All the oxygen at the distillate
2. Ethylene is light key and methane is heavy key
3. All oxygen and nitrogen is at top
4. 2% of methane is recover at the bottom
5. 2% of ethane is recover at the top

Table 3.5 : Composition of Component by Stream

COMPONENT STREAM 14 STREAM 15 STREAM 16

(KMOL/HR) (KMOL/HR) (KMOL/HR)
CH4 6509.9154 6379.7171 130.1983
O2 132.8043 132.8043
C2H4 6.3019 0.1260 6.1759
N2 9607.6399 9607.6399

3.6. Deethanizer (T-103)

22
noutletCH4
noutletC2H6
noutletC2H4

20
ninletCH4
ninletC2H6
ninletC2H4

21
noutletC2H6
noutletC2H4

Figure 3.6 : Deethanizer (T-103)

Assumption and calculation:

1. Ethylene as Light Key
2. Ethane as Heavy Key
3. Assume no methane at the bottom
 4. Assume 2% of ethylene at the bottom
5. Assume 2% of ethane at top

Table 3.6 : Composition of Component by Stream

COMPONENT STREAM 20 STREAM 22 STREAM 21

(KMOL/HR) (KMOL/HR) (KMOL/HR)
CH4 114.8554 114.8554
C2H4 308.792 302.6162 6.1768
C2H6 567.1008 11.3420 555.7588

3.7 Ethane Tank (TK-101)

21
ninletC2H6
ninletC2H4

Figure 3.7 : Ethane Tank (TK-101)

Table 3.7 : Composition of Component by Stream

COMPONENT STREAM 21
(KMOL/HR)
C2H4 6.1768
C2H6 555.7588
Therefore, the purity of ethane can be define as

ninletC 2 H 6
Purity= 100
ninletC 2 H 6 +ninletC 2 H 4
555.7588
Purity= 100
555.7588+6.1768

Purity=98.9

3.8. Demethanizer (T-104)

23
noutletC2H6
noutletC2H4

22
ninletCH4
ninletC2H6
ninletC2H4

24
noutletCH4
noutletC2H6
noutletC2H4
Figure 3.8 : Ethane Tank (TK-101)

Assumption and calculation:

 1. Ethane as Light Key
2. Ethylene as Heavy Key
3. Assume no methane at the bottom
4. Assume 2% of ethane at bottom
5. Assume 2% of ethylene at top

Table 3.8 : Composition of Component by Stream

COMPONENT STREAM 22 STREAM 23 STREAM 24

(KMOL/HR) (KMOL/HR) (KMOL/HR)
CH4 114.8554 112.558292 2.29711
C2H4 302.6162 6.052324 296.564
C2H6 11.3420 11.342

3.9 Ethylene Tank (TK-102)

24
ninletC2H6
ninletC2H4

Figure 3.9 : Ethylene Tank (TK-102)

Table 3.9 : Composition of Component by Stream

COMPONENT STREAM 24
(KMOL/HR)
CH4 2.29711
C2H4 296.564
 C2H6 11.342

Therefore, the purity of ethane can be define as

ninletC 2 H 4
Purity= 100
ninletC 2 H 4 +ninletC 2 H 6+ nCH 4
296.564
Purity= 100
296.564 +2.29711+11.342

Purity=95.6087

3.10 Summary From The Material Balances.

From the calculation in part 3.1 until 3.9, the production of ethylene is 296.5639 kmol/hr, while
the required production is 315.0939 kmol/hr. Therfore, we need to recalculate all the material
balance all of the equipment by taking ratio of required production over calculated
production.The ratio is shown below.

Required Production 315.0939 kmol/hr

=
Calculated production 296.5639 kmol/hr
Required Production
=1.0625
Calculated production

For the natural feed inlet, the molar flowrate can be defined as

Natural feed=Stream 6+ Molar flowrate unreacted C 2 H 6Stream16

Natural feed =8140.6505+428.4553138.3357
Natural feed=8430.7701 kmol/hr

For the air feed inlet, the molar flowrate can be defined as,

Air feed=Molar flow rateO2 + Molar Flowrate N 2

Air feed=2713.5502+ 10208.1174
Air feed=12921.6682kmol /hr
 Table 3.10: Summary of number of mole of each component in each pipeline
Equipment Stream Component Calculated Required
Production Production
(kmol/hr) (kmol/hr)
OCM Reactor Stream 6 CH4 7661.7887 8140.6505
(R-101) O2 2553.9296 2713.5502
N2 9607.6399 10208.1174
Unreacted C2H6 403.252 428.4553
Stream 7 CH4 6642.7708 7057.9440
O2 132.8043 141.1046
C2H4 315.0939 334.7873
C2H6 163.8488 174.0894
H2O 916.3016 973.5705
CO2 61.1325 64.9533
N2 9607.6399 10208.1174
Unreacted C2H6 403.252 428.4553
A/B/C CO2 Stream 7 CH4 6642.7708 7057.9440
AND H2O O2 132.8043 141.1046
ABSORBER (V-
101 C2H4 315.0939 334.7873
C2H6 567.1088 602.5531
 H2O 916.3016 973.5705
CO2 61.1325 64.9533
N2 9607.6399 10208.1174
Stream 9 H2O 916.3016 973.5705
CO2 61.1325 64.9533
Stream 11 CH4 6642.7708 7057.9440
O2 132.8043 141.1046
C2H4 315.0939 334.7873
C2H6 567.1008 602.5446
N2 9607.6399 10208.1174

Calculated Required
Equipment Stream Component Production Production
(kmol/hr) (kmol/hr)
H2O 916.3016 973.5705
Stream 9
Desorber (V- CO2 61.1325 64.9533
102) Stream 12 CO2 61.1325 64.9533
Stream 11 H2O 916.3016 973.5705
CH4 6642.7708 7057.9440
O2 132.8043 141.1046
Stream 13 C2H4 315.0939 334.7873
C2H6 567.1008 602.5446
N2 9607.6399 10208.1174
A/B/C/D CH4 6509.9154 6916.7851
Demethanizer
(T-101) O2 132.8043 141.1046
Stream 14
C2H4 6.3019 6.6958
N2 9607.6399 10208.1174
CH4 114.8554 122.0339
Stream 19 C2H4 308.792 328.0915
C2H6 567.1008 602.5446
A/B/C Stream 14 CH4 6509.9154 6916.7851
Distillation
O2 132.8043 141.1046
Column (T-102)
C2H4 6.3019 6.6958
 N2 9607.6399 10208.1174
CH4 6379.7171 6778.4494
O2 132.8043 141.1046
Stream 15
C2H4 0.126 0.1339
N2 9607.6399 10208.1174
CH4 130.1983 138.3357
Stream 16
C2H4 6.1759 6.5619

Calculated Required
Equipment Stream Component Production Production
(kmol/hr) (kmol/hr)
CH4 114.8554 122.034
Stream 20 C2H4 308.792 328.092
C2H6 567.1008 602.545
Deethanizer CH4 114.8554 122.034
(T-103) Stream 22 C2H4 302.6162 321.53
C2H6 11.342 12.0509
C2H4 6.1768 6.5629
Stream 21
C2H6 555.7588 590.494
CH4 114.8554 122.034
Stream 22 C2H4 302.6162 321.53
C2H6 11.342 12.0509
Demethanizer CH4 112.55829 119.593
Stream 23
(T-104) C2H4 6.052324 6.43059
CH4 2.29711 2.44068
C2H4 296.5639 315.099
Stream 24
C2H6 11.342 12.0509
4.0 ENERGY BALANCE

Table 4.1 : Melting point and boiling point of the components with their latent heats.
Substance Latent Heat of Boiling Latent Heat of Vaporization, Hv
Fusion, Hf (kJ/mol) Point, Tb () (kJ/mol)
Methane -74.85 -161.5 8.179
Oxygen 0 -182.97 6.82
Water -285.84(l) 100 40.656
-241.83(g)
Ethylene 52.28 -103.7 13.54
Ethane -84.67 -88.6 14.72
Carbon -393.5 -78 _
dioxide
Nitrogen 0 -195.8 5.577

Table 4.2 : Heat capacity constant of each component.

Substance A x103 Bx105 Cx108 Dx1012
Methane 34.31 5.469 0.3661 -11.00
Oxygen 29.10 1.158 -0.6076 1.311
Water (l)75.4 - - -
(g)33.46 0.6880 0.7604 -3.593
Ethylene 40.75 11.47 -6.891 17.66
Ethane 49.37 13.92 -5.816 7.280
Carbon dioxide 36.11 4.233 -2.887 7.464
Nitrogen 29 0.2199 0.5723 -2.871

Equation (4.1) is used to calculate the enthalpy change for each of the component.
T2
H= A +B T +C T 2+ D T 3 dT (4.1)
T1

Equation 4.2 is used to calculate the energy balance for the reaction.
= n n (4.2)

Where for each component

T2

H= A + B T +C T 2 + DT 3 dT + Hf
T1

Equation 4.3 is used when the process involve change of phase.

=+ (4.3)
4.1 OCM Reactor (R-101)

Table 4.3 : Heat Balance in OCM Reactor

The inlet at 700C and the outlet at 300C0
0

Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
Methane 7661788.7 -38.5505 6642770.8 -62.9602
Oxygen 2553929.6 21.86 132804.3 8.47
Water - 0 916301.6 9.57
Ethylene - 0 315093.9 68.0278
Ethane - 0 163848.8 -65.3812
Carbone dioxide - 0 61132.5 11.58
Nitrogen 9607639.9 20.59 9607639.9 8.12
Unreacted C2H6 403252.0 -23.4970 403252.0 -65.3812
o
Reference (25C ,1atm)
= n n
Q = H = -345256955.1 - (-51190790.93) = -294066164.1 kJ/hr
4.2 Cooler E-103

Table 4.4: Heat Balance in Cooler

The inlet at 300C0 and the outlet at -83C0

Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
Methane 6642770.8 11.8898 6642770.8 -3.5341
Oxygen 132804.3 8.47 132804.3 -3.1065
Ethylene 315093.9 15.7478 315093.9 -4.0417
Ethane 567100.8 19.2888 567100.8 -4.8959
Nitrogen 9607639.9 8.12 9607639.9 -3.1251
Reference at 25C0
= n n
Q = H = -57963592.12 174020834.3 = -231984426.4 kJ/hr

4.3 Heater E-101

Table 4.5: Heat Balance in Heater

The inlet at 25C0 and the outlet at 700C0

Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
Methane 7531590.4 0 7531590.4 36.5412
Reference at 25C0
= n n
Q = H = 275213421.7 0 = 275213421.7 kJ/hr

4.4 Compressor C-101

The inlet at 1 atm and the outlet at 5 atm

Q = 1/ x P
8.314 J
1 1000 L 12161569.5mol 28.97 Kg mol . k
Q= (51 ) atm
1.1839 Kg hr 1000 mol atm
0.08206 L .
mol . k
Q = 1.20603968 * 1011 J/hr = 1.20603968*108 kJ/hr
4.5 Heater E-104

Table 4.6: Heat Balance in Heater

The inlet at 7C0 and the outlet at 700C0

Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
Methane 130198.3 -0.6333 130198.3 36.5412
Ethylene 6175.9 -0.7665 6175.9 55.5719
0
Reference at 25C
= n n
Q = H = 5100808.61 (-87188.41) = 5187997.02 kJ/hr

4.6 Heater E-102

Table 4.7: Heat Balance in Heater

The inlet at 25C0 and the outlet 700C0

Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
Oxygen 2553929.6 - 2553929.6 21.86
Nitrogen 9607639.9 - 9607639.9 20.59
Reference at 25C0
= n n
Q = H = 253650206.6 0 = 253650206.6 kJ/hr
4.7 Demethanizer T-101 A/B/C/D

Table 4.8: Heat Balance in Demethanizer T-101 A/B/C/D

The inlet at -83C0, the top is at -110C0, and the bottom at -7C0
Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
6642770.8 6509915.4 -4.3180
Methane -3.5341 114855.4 -1.1136
132804.3 132804.3 -3.8620
Oxygen -3.1065 0
0
6301.9 -4.8431
Ethylene 315093.9 -4.0417
308792.0 -1.3370
0 0
Ethane 567100.8 -4.8959
567100.8 -1.6199
9607639.9 -3.9023
Nitrogen 9607639.9 -3.1251
0 0
Reference at 25C0
= n n
Q = H = -66776754.38 (-57963589.29) = -8813165.091 kJ/hr

4.8 Cooler E-105

Table 4.9: Heat Balance in Cooler E-105

The inlet at -7C0 and the outlet at -17C0

Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
Methane 114855.4 -1.1136 114855.4 -1.4502
Ethane 567100.8 -1.6199 567100.8 -2.0969
Ethylene 308792.0 -1.3370 308792.0 -1.7307
0
Reference at 25C
= n n
Q = H = -1890143.28 (-1459404.46) = -430738.816 kJ/hr
4.9 Deethanizer T-103

Table 4.10: Heat Balance in Deethanizer T-103

The inlet at -17C0, the top at -81C0, and the bottom at -2C0
Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
114855.4 114855.4 -3.4745
Methane -1.4502 0 0
11342.0 -4.2858
Ethane 567100.8 -2.0969
555758.8 -1.4320
302616.2 -3.9790
Ethylene 308792.0 -1.7307
6176.8 -1.1358
0
Reference at 25C
= n n
Q = H = -2454646.7 (-1890143.28) = -564503.41 kJ/hr

4.10 Demethanizer T-104

Table 4.11: Heat Balance in Demethanizer T-104

The inlet at -81C0, the top at -108C0, and the bottom -9C0

Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
114855.4 114855.4 -4.2613
Methane -3.4745 0 0
11115.2 -5.6798
Ethane 11342.0 -4.2858
226.8 -1.7164
6052.3 -4.7866
Ethylene 302616.2 -3.9790
296563.9 -1.4166
0
Reference at 25C
= n n
Q = H = -1002037.06 (-1651784.49) = 649747.43 kJ/hr
4.11 Distillation E-102

Table 4.12: Heat Balance in Distillation E-102

The inlet at -110C0, the top at -101C0, and the bottom at 7C0
Inlet Outlet
Species ^ n out (mol/hr) ^
n (mol/hr) H (kJ/mol) H out (kJ/mol)
6509915.4 6379717.1 -4.0612
Methane -4.3180 130198.3 -0.6333
132804.3 132804.3 -3.6111
Oxygen -3.8620 0
0
126.0 -4.5853
Ethylene 6301.9 -4.8431
6175.9 -0.7665
9607639.9 -3.6434
Nitrogen 9607639.9 -3.9023
0 0
0
Reference at 25C
= n n
Q = H = -61481118.06 (-66145118.8) = 4664000.76 kJ/hr
5.0 PROCESS EQUIPMENT SIZING
5.1
5.2
5.3 A/B/C/D Demethanizer (T-101)

14
noutletCH4
noutletO2
noutletN2
noutletC2H4

13
ninletCH4
ninletC2H6
ninletO2
ninletN2
ninletC2H4

ninletCH4
ninletC2H6
19
ninletC2H4

Figure 5.1 : A/B/C/D Demethanizer (T-101)

Assumption :
1. Methane is light key, while ethylene is heeavy key
2. No ethane at the distillate,
3. No oxygen and nitrogen at the Bottom
4. 2 % of methane is recover at the bottom
5. 2 % of ethylene is recover at the disttilate
6. Assume feed inlet is at boiling point (q=1)
7. Assume R=1.3Rmin

Table 5.2 : The Sizing of T-101

Design Value
Minumum Theoretical Stages (Nm) 1.4819
Minimum Reflux Ratio (Rmin) 0.02702
Reflux ratio (R) 0.04
Theoretical Stages (N) 29.64
5.4. Deethanizer (T-103)

noutletCH4
noutletC2H6
noutletC2H4

20
ninletCH4
ninletC2H6
ninletC2H4

21
noutletC2H6
noutletC2H4

Figure 5.4 : Deethanizer (T-103)

Assume
1. Ethylene as Light Key
2. Ethane as Heavy Key
3. Assume no methane at the bottom
4. Assume 2% of ethylene at the bottom
5. Assume 2% of ethane at top
6. Assume feed inlet is at boiling point (q=1)
7. Assume R=1.3Rmin

Table 5.4 : The Sizing of T-103

Design Value
Minumum Theoretical Stages (Nm) 12.6257
Minimum Reflux Ratio (Rmin) 3.14522
Reflux ratio (R) 4.0888
Theoretical Stages (N) 22.9558

5.5 Demethanizer (T-104)

 noutletCH4
noutletC2H6
noutletC2H4

22
ninletCH4
ninletC2H6
ninletC2H4

24
noutletC2H6
noutletC2H4

Figure 5.5 : Ethane Tank (TK-101)

Assume
1. Ethylene as Light Key
2. Ethane as Heavy Key
3. Assume no methane at the bottom
4. 2 % of methane is recover at the bottom
5. 2 % of ethylene is recover at the disttilate
6. Assume feed inlet is at boiling point (q=1)
7. Assume R=1.3Rmin

Table 5.5 : The Sizing of T-104

Design Value
Minumum Theoretical Stages (Nm) 9.5604
Minimum Reflux Ratio (Rmin) 1.07073
Reflux ratio (R) 1.3920
Theoretical Stages (N) 31.8679
6.0 ECONOMIC ANALYSIS
7.0 REFERENCES

American Chemistry Council.2004. Ethylene: Product Stewardship Guidance Manual

Eramo, M. (2013). Ethylene Industry Worldwide. united states: Technip.

G. W. A. Milne (2004). Gardners Commercially Important Chemicals: Synonyms, Tradenames,

and Properties. John Wiley & Sons, Inc Publishing.

Markit, I. (2014, October). IHS Markit. Retrieved from IHS Markit:

https://www.ihs.com/products/ethylene-chemical-economics-handbook.html

Mikal E.S. (1998). Postharvest Biology and Technology: Effect of ethylene on quality of fresh
fruits and vegetables, 279292.

Stanley P.B. (1973). Ethylene in Plant Growth, 70(2), 591-597.

Research, t. m. (2012). transparency market research. Retrieved from transparency market

research: http://www.transparencymarketresearch.com/ethylene-and-propylene.html

Richard M. Felder, R. W. (2005). Elemetary Principles of Chemical Process. United States of

America: John Wiley & Sons, Inc.

Tyler Fini, C. P. (2014). Oxidative Coupling of Methane to Ethylene. University of Pennsylvania.