ETHYLENE FROM ETHANOL MANUFACTURING PLANT

In Partial Fulfillment

of the Requirements for

Chemical Engineering Calculations

JUAN A. DE LA CRUZ

JOSE A. DE LA CRUZ

MAY 2020
 EXECUTIVE SUMMARY

One of the most vital polymer precursors in the world is ethylene. It serves as a main feedstock
to produce plastics, anti-freeze and others. One of the traditional techniques of producing
ethylene is via steam cracking of naphtha or lighter hydrocarbons such as ethane. Such process
utilizes fossil fuels as its primary feedstock. But fossil fuels reserves can eventually run low. The
world’s current consumption of this non-renewable reserve is at a rate of 4 billion tonnes a year.
Continuous extraction at this rate will cause the deposits to be gone by 2052 [ CITATION Our12 \l
1033 ]. In order to sustain the need for such product, an increasing interest in utilizing
biologically-derived feedstocks, such as corn or cellulosic ethanol is being exploited. Up to date,
the biologically-derived feedstock plants all over the world have increased by 2.7% year over
year concentrating in the countries of US and Europe [ CITATION Cro17 \l 1033 ]. This project aims
to provide an alternative way of producing high-quality ethylene from that available bioethanol
in the Philippines using ethanol dehydration reactions to mass-produce ethylene. Around 6850
MT/day of 96% v/v ethanol will be used as a feedstock to produce around 4000 MT/day of
99.92% mol gaseous ethylene using a reactor operating at the reaction temperature of 400 deg
Celsius and pressures of 4,136 kPa. The reaction needs to be catalyzed using 1 cm pelletized
gamma-alumina catalysts. After the dehydration reaction, the reaction products enter a separation
train consisting of flash separation section, atmospheric distillation section and an adsorption
section to achieve the target product purity. The proposed plant location will be in the Phase II of
Phoenix Petroterminal and Industrial Park having a total land area of 12 hectares. The plant will
operate only 333 days per year including maintenance during shut downs. The entire project
targets to penetrate 2% of the total ethylene import of the Philippines which is currently at 10%
[ CITATION Dubai \l 1033 ]. Based from the financial analysis, the project is estimated to have a
payback period of 4.92 years with a return of investment of 509.72%. Furthermore, in
comparison with the CO2 emission of the proposed plant of 0.082 t CO2/t ethylene, it is
imperative that it is more eco-friendly due to the lowered emission of 95% against the naphtha
fed or ethane fed ethylene plant which is at 1.57t CO 2/t ethylene. The prospect of the product
made from the plant is a head-turner for consumers that patronize eco-friendly products which is
at par with the current ethylene prices and more environmentally friendly in terms of its CO 2
emissions.
 PROCESS DESCRIPTION AND BASIS

1.1 PROJECT DEFINITION

1.1.1 Customer

The main customers for this are plastic companies that require ethylene for
polymerization into products such as high-density polyethylene (HDPE), low-density
polyethylene (LDPE), polystyrene, ethylene glycol or polyvinyl chloride (PVC). Ethylene
demand is generally classified as fitness-to standard, based upon the existing characteristics of
ethylene produced by cracking of fossil fuels. Most customers require ethylene to be polymer
grade or 99.92 % pure based from the data acquired from Chevron Phillips [ CITATION Che10 \l
1033 ]. In most industrializing countries, the growing demand for plastics and other products that
uses ethylene increases and resultantly, a yearly increase in demand of 5.4% for ethylene is
projected. Transparency Market Research (TMR) indicated that the rising demand for
downstream products from India, China, and the Middle East, will propel growth of the overall
ethylene and propylene market in the next years to come. In any case, under the more
conservative and stringent scenarios, the world ethylene demand could certainly triple to 360 MT
by 2050 [ CITATION Mar13 \l 1033 ].

The project specifically aims to sell the said product to Citipoly Industries Incorporated
in Valenzuela City. Citipoly Industries uses gaseous ethylene to manufacture pelletized HDPE
and LDPE as their main products [ CITATION Cit10 \l 1033 ]. The feedstock requires high-quality
ethylene (99.92 % purity) to meet their product specification.

1.1.2 Location

One of the major factors that will affect the profitability of the project to be established is
the site of the plant. The production of ethylene requires ethanol as the feedstock for the reaction.
Based on the ethanol supply available and demand for ethylene, it was decided to build the plant
in the Philippines specifically in Phoenix Petroterminal & Industrial Park (PPIP) situated in
Calaca, Batangas. Different site locations could affect the overall economics of the plant due to
some factors that need to be accounted such as the supply of ethanol, price of ethanol, price of
ethylene, cost of transportation of product to the consumer, environmental regulations and many
more. Considerations and explanation of the site location will be discussed here.

[ CITATION Pho16 \l 1033 ]

[ CITATION Pho16 \l 1033 ]

1.2 PROCESS DESCRIPTION

1.2.1 Brief Description of Process Flowsheet

The dehydration process begins with pumping 6850 MT/day of feedstock ethanol to a
high pressure to meet the desired reaction pressure, enters a heat exchanger to achieve a feed
temperature of 400 deg Celsius and is directed in a reactor. The resulting products are sent
through an intricately designed separation trains to purify the ethylene product and obtain the
product specification of 99.92% mol at a rate of 4000 MT/day. The final product is then
transported directly into the customer’s barge, or into on-site spherical storage tanks. The
separation train produces a waste stream of mostly water, which is sent directly to an off-site or
on-site waste treatment facility and is processed for discharge.

1.2.2 Chemistry

The target dehydration reaction of ethanol to obtain ethylene is shown below:

C2H5OH H2O + C2H4

The reaction follows a zero-order having a standard heat of reaction approximately

932.71 kJ/kg. The reaction does not occur under ambient temperature and pressure and exhibits
an equilibrium that favors ethanol formation. A reactor that operates at high temperature
specifically at 400 deg C is needed to achieve the desired reaction and shift the equilibrium
toward product formation. Side reactions that might be produced from this reaction are listed in
approximate order of decreasing frequency [ CITATION Val83 \l 1033 ].

2C2H5OH H2O + (C2H5)2O

C2H5OH H2 + CH3COH
C2H5OH + 2H2 H2O + 2CH4
C2H5OH + H2O 2H2 + CH3COOH
C2H5OH + H2 H2O + C2H6

Since the target product should have a purity of at most 99.92 %, nearly all of the
byproducts should be removed from the final stream. These two main factors form the basis of
this plant design: a high temperature reactor to achieve the desired reaction and an intricately
planned separation trains to achieve desired product specification.
 PROCESS FLOW DIAGRAM

2.1 OVERALL PROCESS FLOW DIAGRAM

Ethanol
Ethylene

167.54 kPa

400°C
Feed: 167.54 kPa
Total: 33.25 MT/day
96% EtOH

Reactor Unit
Heat Exchanger

Ethanol Storage E-2

Furnace

167.54 kPa

Compressor

99.92% mol Ethylene

Separation Unit
Purge Water

On-site or Third
Party
Wastewater
Treater
2.1.1 Equipment 1 – Distillation Section
2.1.2. Equipment 2 – Flash Separation Section
2.1.3. Equipment 3 – Adsorption Section
 MATERIAL BALANCE

3.1 OVERALL MATERIAL BALANCES

Influent Effluent
STREAM WWTREAT (121,180 kg/h)
(Mass flowrate) FEED (285,388 kg/h) PURGE (34 kg/h)
PRODUCT (164,174 kg/h)
TOTAL 285,388 kg/h 285,388 kg/h
3.1.1 Equipment 1 – Distillation Section

Stream Table (Material Balance)

Stream ID DISTIL S302 S308 S311 RECYC WWTREAT

Ethylene 440.5 440.5 422.2 18.3 422.2 18.3
Water 1.19E5 1.19E5 1555.6 1.17E5 1555.6 1.17E5
Ethanol 8717.22 8717.22 4929.7 3787.52 4929.7 3787.52
Diethyl-Ether 568.53 568.53 216.7 351.83 216.7 351.83
Methane 5.03 5.03 0.04 4.99 0.04 4.99
Acetaldehyde 601.75 601.75 576.4 25.35 576.4 25.35
Ethane 35.53 35.53 28.2 7.33 28.2 7.33
Acetic Acid 37.51 37.51 0.03 37.48 0.03 37.48
Hydrogen 0.01 0.01 0.01 0 0.01 0
Total Mass Flow 7728. 7728.8
1.29E5 1.29E5 1.21E5 1.21E5
(kg/h) 88 8

Utilities Stream Table (Material Balance)

FROM COOL TO COOL STEAM
Stream ID STEAM (IN)
TOW TOW (OUT)
Low
Low Pressure
Type Cooling Water Cooling Water Pressur
Steam
e Steam
Pressure (kPa) 101.30 101.30 350 350
Temperature (°C) 20 85 150 150
Total Mass Flow
3.15E5 3.15E5 3.15E5 3.15E5
(kg/h)
3.1.2. Equipment 2 – Flash Separation Section

Stream Table (Material Balance)

FLASH TO
Stream ID S202 S203 S204 DISTIL PRODUCT
SEP HEAT
Ethylene 1.64E5 1.64E5 1.64E5 410.40 440.5 1.64E5 1.64E5

Water 1.19E5 1.19E5 1.19E5 1.18E5 1.19E5 0.00 0.00

Ethanol 8730.12 8730.12 8730.12 8221.45 8717.22 0.00 0.00

Diethyl-
681.13 681.13 681.13 70.03 568.53 112.60 112.60
Ether
Methane 8.02 8.02 8.02 0.01 5.03 3.00 3.00
Acetaldehy
664.30 664.30 664.30 419.20 601.75 62.55 62.55
de
Ethane 35.69 35.69 35.69 18.21 35.53 0.16 0.16

Acetic Acid 37.51 37.51 37.51 37.35 37.51 0.00 0.00

Hydrogen 5.01 5.01 5.01 0.00 0.01 0.00 0.00

Total
Mass Flow 2.93E5 2.93E5 2.93E5 1.27E5 1.29E5 1.64E5 1.64E5
(kg/h)

Utilities Stream Table (Material Balance)

TO FROM
Stream ID S209 S210 CW (IN) COOL COOL
TOW TOW
Cooling Cooling Cooling Cooling Cooling
Type
Water Water Water Water Water
Pressure (kPa) 101.30 101.30 101.30 101.30 101.30
Temperature (°C) 70 85 20 85 20
Total Mass Flow 3.15E5 3.15E5 3.15E5 3.15E5 3.15E5
 (kg/h)

Utilities Stream Table (Material Balance)

Stream ID ADSORB S405 TO HEAT PURGE

Ethylene 1.64E5 1.64E5 1.64E5 0.0

Water 16.29 16.29 0.00 16.29

Ethanol 12.90 12.90 0.00 12.90

Diethyl-Ether 112.60 112.60 112.60 0.00

Methane 3.00 3.00 3.00 0.00

Acetaldehyde 62.55 62.55 62.55 0.00

Ethane 0.16 0.16 0.16 0.00

Acetic Acid 0.00 0.00 0.00 0.00

Hydrogen 4.99 4.99 0.00 4.99

Total Mass Flow (kg/h) 1.64E5 1.64E5 1.64E5 34.18

3.1.3. Equipment 3 – Adsorption Section

 CONCLUSION

The design objectives of this plant design were to produce 99.92% mol ethylene that is cheaper
than the local market price and to provide lower carbon emission in comparison with naphtha fed
or ethane fed ethylene plants. The produced 99.92% mol ethylene was sold at $2.08/kg and
comparing to the market price of which taxed and tariffed is at $2.20/kg. Hence, meeting the
design objective of providing a cheaper cost at the same industrial grade. The carbon emission of
the designed ethylene plant was computed at 0.082 t CO2/t ethylene and in comparison, with
naphtha fed plant 1.57±0.56 t CO2/t ethylene and the ethane fed 1.28±0.92 t CO2/t ethylene, the
plant has a 95% reduction in carbon emission. Hence, also meeting the lowered carbon emission
in the current plant design. The financial feasibility of the plant is acceptable in consideration of
the return of investment at 509.72% with a capital at $300M and a payback period of 4.92 years.
The local ethylene market is currently at $16M and constantly grows at 11.6% per year and a
proposed market penetration of 3.9% for the span of 30 operational years provide a cumulative
net income before tax of $1.83B. Therefore, the plant design cover both technical and financial
viability of constructing the proposed plant.
REFERENCES

Ag Marketing Resource Center. (2016). Overview of Current Ethanol Market: Prices,

Production, Profitability, and Co-Products. Retrieved from Ag Marketing Resource Center:
http://www.agmrc.org/renewable-energy/renewable-energy-climate-change-report/renewable-
energy-climate-change-report/april-2016-report/overview-of-current-ethanol-market-prices-
production-profitability-and-co-products/

Anchor Ethanol Limited. (2007). Ethanol Product Specifications. Auckland, New Zealand.

Chevron Phillips Chemical Company LP. (2010). Ethylene. The Woodlands, TX: Chevron
Phillips Chemical Company LP.

Citipoly Industries Inc. (2010). Citipoly Industries Inc. Retrieved from

http://www.citipoly.com/about.php

CropEnergies AG. (2016, May 3). Retrieved February 22, 2017, from
http://www.cropenergies.com/Pdf/en/Bioethanol/Markt/Dynamisches_Wachstum.pdf

Department of Agriculture. (2016). Directory of Bioethanol Producers. Retrieved from Sugar

Regulatory Administration: http://www.sra.gov.ph/wp-
content/uploads/downloads/2016/03/DIRECTORY-OF-BIOETHANOL-PRODUCERS-2015-
20161.pdf

Department of Economic Development. (2016, May 16). Philippines-Economic Overview, Trade

Analysis and Technical Requirements for Export. Retrieved February 28, 2017, from Dubai
Exports:
http://www.dedc.gov.ae/StudiesAndResearchDocument/MTR016052016PHILIPPINES.pdf
APPENDIX

Calculation Sheets

I. Distillation Section

The Fenske-Underwood-Gilliland Method (FUG) Shortcut was used to determine the flow
stream concentration of the components in the distillation section. Coupled with this approach is
the use of COCO Software to facilitate simulations of the distillation process.
The following equations were used to calculate preliminary assumptions:
N −Nmin 1+54.4 γ γ −1
=1−exp ⁡( x )
N +1 11 +117.2 γ γ 0.5
xi xi
( )
xf
d=( αi )Nmin ( )b
xr
Dxd Bxb
Nmin=
( )( )
log
Bxb Dxd
log αi
Ki yi ( xr)
αi= =
Kr yi (xi)
α =( αtop x αbottom )0.5
❑
αi ( xiD ) min
∑ αi−∅ =Rmin+1
i
❑
αi( ziF)
∑ αi−∅ =1−q
i
 II. Flash Separation Section

Entering Flash Drum 1 (FD201)

Molecular Molar Flow Mole

Stream ID S203
Weight (kmol/h) Fraction
Ethylene (1) 1.64E5 28.00 5872.70 0.46
Water (2) 1.19E5 18.00 6584.42 0.52
Ethanol (3) 8730.12 46.00 189.78 0.01
Diethyl-Ether (4) 681.13 74.00 9.20 0.00
Methane (5) 8.02 16.00 0.50 0.00
Acetaldehyde (6) 664.30 44.00 15.10 0.00
Ethane (7) 35.69 30.00 1.19 0.00
Acetic Acid (8) 37.51 60.00 0.63 0.00
Hydrogen (9) 5.01 2.00 2.51 0.00
Total Mass Flow
2.93E5 - 1.3E4 -
(kg/h)

A Multi-Component Flash Distillation calculation was carried out at the flash temperature of
4000 kPa and a temperature of 50 deg C (FD201). The table for K Values of the components
involved is given below.

Component K Value
Ethylene 458
Water 0.00459
Ethanol 0.0709
Diethyl-ether 10
Methane 1240
Acetaldehyde 0.67
Ethane 1.10
Acetic Acid 0.00485
Hydrogen 1310
K values at 4000 kPa and 50 deg C
The formulas used in the calculation are as follows:

V ∑ ( K i −1 ) z i
g ( )
F
=
1+ ( K i −1 ) (
V
)
F
 dgk −∑ ( K i−1 ) 2 z i
=
V 2
d ( ) 1+ ( K i−1 ) V
F ( F ( ))
V V gk
( ) =( ) −
F k+1 F k dg k
( )
V
d( )F
Example:
Assuming V/F = 0.20 (20% vaporized)
V ( 458−1 ) (0.46) ( 0.00459−1 ) (0.52) ( 0.0709−1 ) (0.01497) ( 10−1 ) (7.257 x 10−4 ) ( 1240−
g ( )= + +
F 1+ ( 458−1 ) (0.20) 1+ ( 0.00459−1 ) (0.20) 1+ ( 0.0709−1 ) (0.20)
+
1+ (10−1 ) (0.20)
+
1+ ( 1

g ( VF )=1.63177684
dgk ( 458−1 )2 (0.46) ( 0.00459−1 )2 (0.52) ( 0.0709−1 )2 (0.01497) ( 10−1 )2 (7.257 x 10−4)
= + + + +
V ( 1+ ( 458−1 ) ( 0.20 ) )2
( 1+ ( 0.00459−1 ) ( 0.20 ) )2
( 1+ ( 0.0709−1 )❑
( 0.20 ) )
2
( 1+ ( 10−1 ) ( 0.20 ) ) 2
d( )
F
dgk
=−12.168437
V
d( )
F
V 1.63177684
( ) =0.2−
F k+1 −12.168437
V
( ) =0.33409913
F k+1
V V
This resulting value of ( ) is once again used to calculate g
F k+1 F ( )
. Iterations was done in excel

and the resulting value of g ( VF ) in this case is 0.466 (46.6% vaporize).

To calculate the mole fraction of each component in the liquid and vapor form, the following
equations were used:
z1
x 1=
V
1+ ( K 1−1 ) ( )
F
y 1=K 1 x 1
To calculate the stream of the top and bottom, the following equations were used:

Vapor Stream=x ( VF ) ( Total Molar Feed Flow ) (Molar Mass)

V
Liquid Stream= y ( 1− ) ( Total Molar Feed Flow ) ( Molar Mass)
F

Performing the calculations for all the species;

Stream ID x y S205 S204
Ethylene 0.00 0.99 1.64E5 410.40
Water 0.97 0.00 472.84 1.18E5
Ethanol 0.03 0.00 508.67 8221.45
Diethyl-Ether 0.00 0.00 611.10 70.03
Methane 0.00 0.00 8.02 0.01
Acetaldehyde 0.00 0.00 245.10 419.20
Ethane 0.00 0.00 17.48 18.21
Acetic Acid 0.00 0.00 0.16 37.35
Hydrogen 0.00 0.00 5.00 0.00
Total Mass Flow
- - 1.66E5 1.27E5
(kg/h)
 Values of x and y were rounded to the nearest hundredths.

*Same process of calculations was done for entering gaseous stream in Flash Drum 2 (FD202)
but at a temperature of 4deg C and a pressure of 3000kPa. The values of K used are given below.

Component K Value
Ethylene 45.60
Water 0.00029856
Ethanol 0.00021777
Diethyl-ether 0.0018905
Methane 0.005
Acetaldehyde 0.0028678
Ethane 0.000077554
Acetic Acid 0.000012148
Hydrogen 5
K values at 3000kPa and 4deg C
The second set of calculations resulted to a value of 0.9917 (99.17% vaporized).
 III. Adsorption Section

The adsorber’s efficiency to

remove water, ethanol and
hydrogen has been based on the
removal performance of
the Zeolite 13X adsorbents
(Grace Davison, 2016).
 Source: Isotherms for Adsorption Capacity of Zeolite (SYLOBEAD) 13X, Grace Davison Corp.

Partial pressure of water;

P A = y A ( P o)
Vapor pressure of pure of water at 4 deg Celsius is 6.1 torr [ CITATION Cla16 \l 1033 ].
Partial pressure of water in S405;

P A =0.00154 ( 6.1 torr ) ( 101325 Pa 1 hPa

760torr ) 100 Pa
( )

P A =0.0125 hPa

Reading from the graph (at 4 deg Celsius),

14 kg water
Capacity=
100 kg adsorbent
Therefore, the researchers assumed that all the water and other components have been removed
completely since the mass of water to be removed is around 16.29 kg (highest among the three)
and maybe achieved by increasing the mass of the adsorbents.