CHE331: Chemical Reaction Engineering (Theory)

Batch: FA20-CHE Section:

Group #
Student Name Registration Number
Muhammad Usman FA20-CHE-024
Muhammad Danish FA20-CHE-038
Saeed Ahmed FA20-CHE-068
Waqar Ahmed FA20-CHE-078
Muhammad Anees FA20-CHE-105
Date Assigned: March 08, 2023 Due
Date: March 30, 2023

Instructor:
Dr. Muhammad Haris Hamayun

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Table of Contents
INTRODUCTION: ........................................................................................................................................ 2
Production process of ethylene glycol: ............................................................................................................ 3
Selection of a catalyst: ..................................................................................................................................... 3
The proposed plant design innovation ......................................................................................................... 4
Process description: ....................................................................................................................................... 4
Process flow diagram of Ethylene Glycol: ............................................................................................... 5
Reaction conditions: ........................................................................................................................................ 5
Recycling and reuse: ........................................................................................................................................ 6
Process optimization: ....................................................................................................................................... 6
Product purification: ........................................................................................................................................ 6
Reaction parameters: ....................................................................................................................................... 7
Stochiometric table for flow system: ............................................................................................................... 7
References ...................................................................................................... Error! Bookmark not defined.

INTRODUCTION:
Mono ethylene glycol is one of the important chemicals used in all over the world; it is 26 th most
produced material. Mono ethylene glycol is use in the cooling agent, lubricant as a raw material
for the production of polyester fiber.

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In Pakistan mono ethylene glycol is primary being consumed as a raw material for the
manufacturing of polyester fiber. The quantum of mono ethylene glycol is being consumed as anti-
freezing agent is very small. The subjected project is based on the production of Mono Ethylene
Glycol (MEG) by the hydrolysis of the Ethylene Oxide and is converted into products by using the
tabular reactor whereas Ethylene Oxide is manufactured by Oxidation of Ethylene Over Sliver
Catalytic bed in tubular reactor. The project involves the designing of the reactor, evaporator and
distillation column. [1]

Production process of ethylene glycol:

The production of ethylene glycol (EG) through the oxidation of ethylene involves two main
reactions: the oxidation of ethylene to ethylene oxide, and the conversion of ethylene oxide to
ethylene glycol. These reactions are described below:

Selection of a catalyst:
C2H4 + 0.5O2 → C2H4O ΔH = -1067 KJ/mol
C2H4 + 3O2 → 2CO2 + 2H2O
C2H4O + 2.5O2 →2CO2 + 2H2O
C2H4O + H2O → HOCH2CH2OH
The standard method of producing EO involves an epoxidation reaction by which ethylene is
epoxidized to EO using oxygen as an oxidant. The reaction is catalyzed by a silver-based catalyst
at a temperature of 200 ◦C to 260 ◦C and at 1 MPa to 3 MPa [2]Since the reaction occurs at high
temperatures and oxygen is present in the reactor, it is possible for ethylene and EO to react,
resulting in the formation of unwanted water and carbon dioxide. This undesirable reaction results
in an estimated yearly loss of as much as USD 1.2 billon . Furthermore, as ethylene and EO
reactions are naturally exothermic. This process also generates approximately 3.4 million tons of
carbon dioxide per year, which gives greenhouse gas emissions. Issues with EO handling can result
in minor purity and off-spec production of MEG in EO/EG integrated plants. These factors gives
the motivation to seek process improvement opportunities with respect to the production of MEG
from ethylene. [3]
In 2009, it was discovered that the oxidation reaction of ethylene to EO could be achieved in a gas-
expanded liquid phase using methyltrioxorhenium (MTO) as the homogenous catalyst, pyridine-
N-oxide as the catalyst promoter, hydrogen peroxide (H2O2) as the oxidant, and methanol as the
solvent. Under these circumstances, ethylene dissolves better in the solvent and reacts with H2O2

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at the surface sites of the MTO catalyst without producing any CO2. The application of MTO
catalyst in EO production has been studied recently in the literature In this improved scheme, the
excess ethylene left over after the oxidation reaction is recycled back to the main epoxidation
reactor. The excess H2O2 is decomposed to H2O and O2 in a separate unit, deriving in a safer
operation. [4]

The proposed plant design innovation

• the ethylene-to-EO plant is integrated with an EO-to-MEG plant to reduce utility costs and
recover high-value products.
• a multitube glycol reactor is used in conjunction with al MTO catalyst in the ethylene-to
EO reactor for the purpose of energy savings and cost reduction. Also the production of
CO2 is eliminated.

Process description:
The process to convert ethylene to EO consists of two reactors (REAC-1 and REAC-2), a flash
drum (V-1), and three distillation columns (C-1, C-2, and C-3).The feed is introduced to the first
reactor (REAC-1). Ethylene and hydrogen peroxide react in the presence of the MTO catalyst to
produce ethylene oxide and water in the reactor.
C2H4 + H202 → C2H40 + H20
The residence time of the reactor is assumed to be 0.25 h.The vapor outlet of the flash drum (V1),
which is mostly ethylene, is compressed and recycled back to the first reactor after cooling down
to the feed temperature. The liquid outlet stream of the flash drum (V-1) enters the second reactor
(REAC-2), and the remaining H2O2 is decomposed to water and oxygen before entering the
distillation columns. [2]
C2H40 + H20→ C2H6O2
A train of three distillation columns in series is used to separate the product and recycle the
unreacted reactant and solvent. The process to convert EO to MEG, DEG, and TEG consists of a
reactor (REAC-3), a triple-effect evaporator (EVA-1, EVA-2, EVA-3). This outlet stream is sent
to a triple-effects evaporator for purification and is modeled as a series of three flash unit blocks
with heat supplies Q1, Q2, and Q3. The glycols and water with impurities are transferred to a
dehydrator for further processing. The overhead vapor streams of the triple-effect evaporator are
collected and condensed as a recycle stream. The bottom liquid stream of the triple-effect
evaporator is transferred to the dehydrator (C-4) for removal of waste stream, which consists of

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water and aldehydes. The product stream from the dehydrator is sent to the MEG distillation
column (C-5). The column is operated in a vacuum to distilling high-grade pure polyester MEG of
99.99% purity. Other heavier glycols are transferred to a second column (C-6) for further
processing of DEGs and TEGs.

Process flow diagram of Ethylene Glycol:

Material and energy balance were applied across following unit

• Reactor 1
• Reactor 2
• Reactor 3
• Absorber
• Stripper
• Distillation Column (C1, C2, C3)
• Pumps
• Storage tank
• Evaporators ( EVA 1, EVA2, EVA3)

Reaction conditions:
• The use temperatures and pressures must be carefully balanced against the potential for side
reactions and catalyst deactivation. The reaction conditions can be optimized to achieve

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 high yields and minimize the formation of by-products. The optimized temperature and
pressure of this 5.02 MPa and 282K

Recycling and reuse:

• Unreacted ethylene and water can be recycled back into the oxidation reactor
Process optimization:
This can involve optimizing the reaction conditions and catalyst selection as well as improving the
separation and purification steps of the process. The use of high-efficiency distillation columns
can improve the separation of EG from water and other impurities.

Product purification:
The purification of EG can also be optimized to increase the purity of the final product and
minimize the formation of by-products. This can involve using advanced separation technologies.

Overall, the use of a combination of these strategies can help maximize the production yield and
minimize the by-products in the production of EG. These strategies should be tailored to the
specific catalyst system and reaction kinetics to achieve optimal results. Table 1 [2]
Parameters Feed stream

Pressure (MPa) 5
Temperature (K) 313
Flow rate (kg/h) 160,263
Composition ( mass %)

Hydrogen peroxide 12.21

Methanol 64.21
Ethylene 10.97
Ethylene oxide 0.40
Oxygen 0
Water 12.21
Total 100

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Reaction parameters:
Reaction Reaction Reaction Rate Constant Reference Activation
Type Rate Temp. Energy
1 LHHW −r = k CH2O2 CEL 6.2 × 10−6 s 293K 57 k J /mol
Ccat. −1

2 Power −r = k CH2O2 2 62.5m3/kmol.s 313K 57.7 k J mol

law

Table 2 [5]

Stochiometric table for flow system:

C2H4 + H202 → C2H4O + H20

A B C D
Symbol Feed Rate to the Change (mol) Remaining (mol)
reactor (mol/time)

C2H4 FAO - FAOX FA= FA0(1-X)

H202 FB0 = θBFA0 -- FAOX FB= FAO(θB-X)

C2H4O FC0 = 0 FAOX FC = FA0X

H2 0 FDO = 0 FAOX FD = FAOX

Total FTO FT= FT0 – FA0X

C2H40 + H20→ C2H6O2

A B C

Symbol Feed Rate to the Change (mol) Remaining (mol)

reactor (mol/time)

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 C2H40 FAO - FAOX FA= FA0(1-X)
H2 0 FB0 = θBFA0 -- FAOX FB= FAO(θB-X)

C2H6O2 FC0 = 0 FAOX FC = FA0X

Total FTO FT= FT0 – FA0X

Reaction rate:

-r A = KCC2H402

Muhammad Danish Selection of catalyst

Muhammad Usman Process description
Saeed Ahmed Processes for enhancing the product
yield
Waqar Ahmed
Product purification: Table
1 table 2
Muhammad Anees Stochiometric tables

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 Stage 3
Production of ethylene glycol in lotte chemicals in Pakistan is 700000 MT/annum
(CHEMANALYST, n.d.)
Which reactor is use for the production of ethylene glycol?
A PFR (Plug Flow Reactor) is commonly used in the production of ethylene glycol due to its
suitability for continuous flow reactions and its ability to provide good mixing and heat transfer
characteristics. Here are a few reasons why a PFR is preferred for ethylene glycol production:
• Continuous Operation:
• High Conversion Efficiency:
• Good Mixing:
• Heat Transfer:
• Scalability:
Design of reactor for our process
Assumption:
• we use water insulation jacket to convert this reactor into isothermal.
• Water is in excess form.
• Reaction proceed at high temperature(313k) and pressure(5Mpa).
Mole Balance
𝑥 𝑑𝑥
V=Fa0∫0 −𝑟𝐴

Rate law
-rA= kCA2
Stoichiometry equation
C2H40 + H20→ C2H6O2

A B C

Symbol Feed Rate to the Change (mol) Remaining (mol)

reactor (mol/time)

C2H40 FAO - FAOX FA= FA0(1-X)

H2 0 FB0 = θBFA0 -FAOX FB= FAO(θB-X)

C2H6O2 FC0 = 0 FAOX FC = FA0X

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 Total FTO FT= FT0 – FA0X

𝑭𝑨
CA= 𝑽
CA=CA0(1-X)
𝑉0 𝑋
V=𝐾𝐶𝐴0(1−𝑋)
Solution:
Polymath code

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So the volume of the reactor at 85% conversion is 8.016 m3.
Economic
Per Metric Ton of Ethylene glycol is 1150$
=700000×1150$
=805000000$
Conclusion
If we use MTO catalyst for the production of ethylene oxide. There is no carbon dioxide is
produced. Ethylene to ethylene oxide plant is integrated with an ethylene oxide to ethylene glycol
plant to reduce utility cost and recover high value product.
This method is efficient and profitable for ethylene glycol production and also maximize the yield
and minimize the by product

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References

[1] M. A. Fawad Ashraf, "production of MEG by hydrolysis of ethylene oxide," no. 2014, pp. 1-
2.

[2] M. Ghanta and Lee, "Highly Selective Homogeneous Ethylene Epoxidation in Gas (Ethylene)-
," pp. 59, 180–187, 2013.

[3] N. Tripathi, "Production of 1,3 Butadiene and Associated Co-Products Ethylene and Propylene
from Lignin," p. 58, 2019.

[4] K. Weissermel and Arpe, Industrial organic Chemistry, Washington, DC, 2003.

[5] W. Schumb and C. Satterfield, . Hydrogen Peroxide. In ACS Monograph Series; Reinhold
Publishing Corporation, New York,NY, USA,, 1955, pp. New York, NY, USA, 1955; p.
128

CHEMANALYST. (n.d.). Retrieved from Mono Ethylene Glycol price trend and fore cast:
https://www.chemanalyst.com/Pricing-data/mono-ethylene-glycol-4

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