UNIVERSITI TEKNOLOGI MARA CAWANGAN TERENGGANU, KAMPUS BUKIT BESI

FACULTY OF CHEMICAL ENGINEERING

CHE231: INTRODUCTION TO CHEMICAL ENGINEERING PLANT DESIGN

PROJECT TITLE: PRODUCTION OF ACRYLIC ACID VIA CATALYTIC

OXIDATION OF PROPYLENE
COMPANY’S NAME: DOW CHEMICAL COMPANY
LECTURER’S NAME: MADAM NURUL ‘UYUN BINTI AHMAD

NOORUL SA’ADAH QURAISYAH BT GENERAL MANAGER

MOHD ALI
(2015858416)

NADHRAH MUNIRAH BT ZAINI PROCESS ENGINEER

(2015857686)

MUHAMMAD AIZAT BIN AZHARI SAFETY OFFICER

(2015868348)
 ABSTRACT

Acrylic acid is a commonly used, yet extremely valuable, chemical intermediate used to
produce polymers, textiles, and numerous other industrial and consumer products. Because of the
lucrative market for this product, this design project focuses on the optimization of an acrylic acid
plant. Due to the simplicity of the initial design of the plant, this optimization involved more
investigation of native reaction kinetic characteristics rather than extra pieces of equipment. By
using 300oC-350oC temperature for reaction to occur, it allows the desired product to have its
highest conversion (95%-99.5%), thereby generating much higher process revenue. In order to
maintain this conversion of acrylic acid, the specific liquid-liquid extraction equipment was
designed which is, Rotating Disc Contactor. The material used to build this equipment depends on
the solution that enter the column which is acrylic acid that

I
 ACKNOWLEDGEMENT

This project consumed huge amount of work, research and dedication. Still,
implementation would not have been possible if we did not have a support of many individuals
and organizations. Therefore we would like to extend our sincere gratitude to all of them.

First of all we are thankful to our lecturer, Madam Nurul ‘Uyun bt Ahmad for giving
logistical support and for providing necessary guidance concerning projects implementation.

We are also grateful to the Dow Chemicals Company for provision of expertise, and
technical support in the implementation. Without their superior knowledge and experience, the
Project would like in quality of outcomes, and thus their support has been essential.

Nevertheless, we express our gratitude toward our project members for their kind co-
operation and encouragement which help us in completion of this project.

II
 TABLE OF CONTENTS
ABSTRACT I
ACKNOWLEDGEMENT II
TABLE OF CONTENTS III-IV

CHAPTER ONE : INTRODUCTION

1.1 Background of the Study 1
1.2 Problem Statement 2
1.3 Objective of the Study 2

CHAPTER TWO: PROCESS DESCRIPTION

2.1 Introduction 3
2.2 Process Alternatives 4
2.3 Process Background 5
2.4 Catalysts choice 6
2.5 Block Flow Diagram 7
2.6 Process Flow Diagram 8
2.7 Piping and Instrumentation Diagram 9
2.8 Process Description 10
2.8.1 Reaction And Quench 10
2.8.2 Product Recovery 10
2.8.3 Purification 10

CHAPTER THREE: SITE LOCATION

3.1 Introduction 11
3.2 Location 11
3.3 Site Layout 12
3.4 Plant Layout 13

CHAPTER FOUR: LIQUID-LIQUID EXTRACTION UNIT

4.1 Definition 14
4.2 Liquid-Liquid Extraction Process 15
4.2.1 General 15-16
4.3 Choices Of Solvent 17
4.4 Solvent Chosen 18
4.5 Principles Of Liquid-Liquid Extraction 18
4.6 Rotating Disc Contactor 19
4.6.1 General Description 20
4.6.2 Operation Principle 20
4.6.3 Materials Of Construction 21
4.6.4 Process Control (Cascade Control) 21

III
CHAPTER FIVE: MASS BALANCE CALCULATION
5.1 Liquid-Liquid Extraction Unit Mass Balance 22-23
5.2 Theoretical Stages Graph 24
5.3 Actual Stages Calculation 25
5.4 Column Sizing 25

CHAPTER SIX: SAFETY ASSESSMENT

6.1 Safety Issues 26
6.2 Medical Management 27
6.3 First Aid 27
6.3.1 General 27
6.3.2 Contact With Eyes 28
6.3.3 Contact With Skin 28
6.3.4 Inhalation 28
6.4 Bulk Storage Facilities And Accessories
6.4.1 General Consideration 29-30
6.4.2 Design Consideration 30
6.4.3 Temperature Control Of Storage Tank And Accessories 31-32
6.5 HAZOP Study 33
6.6 Personal Protective Equipment 34

CONCLUSION 35
REFERENCES 36
APPENDIX 37-48

IV
CHAPTER ONE
INTRODUCTION
1.1 BACKGROUND OF THE STUDY

Acrylic acid is a commonly used chemical intermediate, which because of its widespread
uses, is a valuable chemical commodity. Because of this fact, this design project invests
the optimization of an acrylic acid plant, to see if such a plant could be a profitable
undertaking. The most widely accepted process for making acrylic acid is the vapor phase
oxidation of propylene. This is normally done as a standard process involving two reactors
in series, utilizing two separate catalysts. In this arrangement, the first reactor converts the
propylene to acrolein while the second reactor completes the conversion from acrolein to
acrylic acid. Then, the aqueous solution of acrylic acid enter quench tower and then liquid-
liquid extraction column for further separation process. In this report, the main objective is
to produce the most suitable liquid-liquid extraction column to achieve highest conversion
rate. The conversion of acrylic acid is approximately 99.5%.

1
1.2 PROBLEM STATEMENT

Nowadays, the amount of acrylic acid production is become more from year to year due to
its variety applications in order to fulfil human basic needs. Hence, due to this reason, the
production of acrylic acid in acrylic plant must be increased in order to meet the required
demand. When the amount or capacity of production is increase in the acrylic plant, all the
operating conditions of reactor and separation sections must be adjusted to another new
optimum condition in order to maintain the desired purity products. Therefore, the acrylic
acid plant has to precede optimization in order to overcome a large amount of acrylic acid
production. Moreover, liquid-liquid extraction column play an important role in producing
the high purity of acrylic acid. Hence, the safety issues must be taken into consideration to
as it is very important in every plant. According to the Acrylic Acid MSDS (2005), acrylic
acid is potentially hazardous material which will bring effect on living things’ respiratory
system, eyes, skin, or ingestion. Apart from that, loss of materials can cause the economic
loss of that company and accidents incident may occurs because propylene is a flammable
gas. Hence, optimization on this two recovery system can prevent the loss of hazardous
materials to the environment, economic loss and improve safety in the acrylic acid plant.

1.3 OBJECTIVE OF THE STUDY

The objectives of this study are:

 To simulate a production of acrylic acid process.

 To optimize the operating conditions in liquid-liquid extraction column which is
separation sections of acrylic acid plant.

2
 CHAPTER TWO
PROCESS DESCRIPTION
2.1 INTRODUCTION

This chapter describes the process used in the production of acrylic acid. There are many
processes that can produced acrylic acid but in this report, oxidation via propylene was
used in order to produce high quality of acrylic acid. The first section provides detailed
process description from raw materials to acrylic acid as final product. This chapter
provides the details diagram of block flow diagram and process flow diagram. The second
section discusses in details about the catalysts used for high conversion rate of acrylic acid.

3
2.2 PROCESS ALTERNATIVES

There are a few methods available for producing acrylic acid. List below shows the popular
method in producing acrylic acid.

1) Production of Acrylic Acid via Catalytic Oxidation of Propylene.

This process is a two stages vapor phase oxidation of propylene. It is consists of

two reactors in series and utilizing two separate catalysts which is molybdedum-
bismuth and molybdenum-vanadium.

2) Reppe Process

The production process is divided in two parts. First, the reaction of formaldehyde
and acetylene to form butynediol and second is hydrogenation to form butanediol.
These reactions take place in a trickle column reactor containing copper acetylide
catalyst with bismuth as promoter on magnesium silicate.

3) Ketene process

This process start with reaction of acetylene with water and carbon monoxide,
or an alcohol and carbon monoxide to give acrylic acid.

4
2.3 PROCESS BACKGROUND

From the list above, to establish a safe and economical industrial process for producing
acrylic acid is by catalytic oxidation of propylene, we have investigated the fundamentals
relating to the oxidation process including elucidation of properties of oxidation catalysts,
precise measurement of explosion limits and the like, and found several important facts.
The present invention has been achieved on the basis of these new findings and provides a
process for producing acrylic acid in a high space-time-yield as a condensate of a high
concentration by oxidation of propylene at a high concentration under specific restricted
conditions and also for prolonging catalytic activity. The present invention is characterized
by the conditions for oxidation reactions in acrylic acid production process by two step
vapour phase catalytic oxidation, which comprises converting propylene mainly into
acrolein by subjecting a gas mixture containing propylene, molecular oxygen and an inert
gas to the first catalytic oxidation and then subjecting the product gas from the first reaction
to the second catalytic oxidation reaction optionally together with steam added, and the
oxidation conditions used in accordance with the present invention are as follows:

 The catalyst for the first catalytic oxidation reaction is a Mo-Bi based composite
oxide catalyst and that for the second catalytic oxidation reaction is a Mo-V based
composite oxide catalyst. (The inventors used (Mo-Bi) catalysts comprising Mo-
Bi-Fe-Co-Ni-B-Na-K-Si-O as the first step catalyst and (Mo-V) catalysts
comprising Mo-V-Sb-Ni-Nb-Cu-Si-O as the second step catalyst).
 The product gas resulting from the second catalytic oxidation reaction is subjected
to an acrylic acid recovery step where the acrylic acid is recovered as an aqueous
solution, and all of the remaining waste gas obtained from the acrylic acid recovery
step is subjected to catalytic oxidation combustion; and a part of combusted waste
gas is recycled to the first reactor.

5
 The molar ratio of molecular oxygen to propylene is 1.17 to 2.50, the concentration of the
propylene is 5 to 14%; and the concentration of the combusted waste gas is 5 to 95%. In
one embodiment of the present invention, the gas to be subjected to the second catalytic
oxidation reaction resulting from the first oxidation reaction and an optional gas mixture
added comprising molecular oxygen and steam has the following composition, the
composition being indicated as the sum of the gas to be fed to the first oxidation reaction
and the optional gas mixture added: the molar ratio of the molecular oxygen to the
propylene being 1.75 to 2.50, and the molar ratio of the steam to the propylene being 0.5
to 5.0. According to the present invention, it is possible without complicated control to
utilize waste gas from the second reactor outlet as dilution gas at the first reactor inlet and
to obtain acrylic acid of a high concentration in a high space time yield and a condensate
of high acrylic acid concentration and to prevent the first step catalyst from deterioration.
Further disposal of the waste gas can be carried out simultaneously. The reaction
stoichiometry is given below:

C3H6 + O2 C3H4O + H2O

1
C3H4O + 2O2 C3H4O2

2.4 CATALYSTS CHOICE

Table below shows reasonable conversion and acrylic acid selectivity of the catalyst used.

Catalyst Temperature, oC Product Conversion, %

Mo-Bi-Fe-Co-Ni-B-Na-K- 350 65
Si-O (known as
molybdenum-bismuth)
Mo-V-Sb-Ni-Nb-Cu-Si-O 325 73
(known as molybdenum-
vanadium)

6
2.5 BLOCK FLOW DIAGRAM

7
2.6 PROCESS FLOW DIAGRAM

8
2.7 PIPING AND INSTRUMENTATION DIAGRAM

9
2.8 PROCESS DESCRIPTION

2.8.1 REACTION AND QUENCH

Chemical-grade (CG) propylene is mixed with steam and air and fed to a two-step
oxidation reaction system. In the first step, the propylene is oxidized to acrolein
and, in the second step, the acrolein is oxidized to acrylic acid. Both steps are
carried out in tubular, fixed-bed reactors. The heat generated by the exothermic
reactions is used to generate steam. The effluent from the reaction system is sent to
a quench tower, where the acrylic acid formed is absorbed in water. Part of the
residual gas obtained by the top of the quench tower is incinerated, with the balance
being recycled to the first-step reactor. The aqueous solution is sent to downstream
units for product recovery.

2.8.2 PRODUCT RECOVERY

The aqueous solution from the quench step is fed to an extractor, where the acrylic
acid is separated by liquid-liquid extraction with a solvent. The top portion of the
extractor, containing the acrylic acid, is sent to a solvent-recovery column to
recover a two-phase overheads stream. This two-phase stream is separated and the
organic phase, containing the solvent, is recycled to the extractor. The aqueous
phase is mixed with the raffinate from the extraction step and sent to a raffinate
stripper to minimize the solvent losses. The bottom stream from the solvent-
recovery column is then fed to the crude acrylic-acid column, where a concentrated
acrylic acid stream is obtained as the bottom product. The column overhead stream,
mainly comprised of acetic acid and light impurities, is sent to a recovery column.
The bottom stream from the recovery column is sent to the crude acrylic acid
column and the overhead stream is recycled to the solvent recovery column.

2.8.3 PURIFICATION

In the purification area, the concentrated acrylic acid stream from the crude acrylic
acid column is fed to the product column. In this column, ester-grade acrylic acid
is obtained as the overhead product. The column bottoms are sent to a dedimerizer
to convert the dimer impurity, formed in the process, back to acrylic acid. Finally,
the product from the dedimerizer is sent to the bottoms stripper column, where the
heavy ends are separated and sent to waste.

10
CHAPTER THREE

SITE LOCATION
 3.1 INTRODUCTION

This chapter includes the details of site location for the production of acrylic acid plant. It
includes the reasons for the chosen location. There are so many factors for the acrylic acid
plant location which include the safety of surrounding as well.

3.2 LOCATION

Gebeng Factor Pengerang

Propylene will be supply by
Petronas MTBE Sdn Bhd.
Port and highway will be use
as transportation.
Water is supply by Semambu
water treatment plant.
Pahang Fire and Rescue
Department and Petronas
Centralised Emergency
Facility
Energy will be supplied by
Tenaga National Berhad
(TNB)
Raw Material availability
Transportation Facility
Water Supply
Flood and Fire Protection
Energy Availability
Lotter Chemical Titan
Holding will supply us
propylene.
Port and highway will be
used as transportation.
A desalination will be
supplying water for us.
Central Emergency and Fire
service Pengerang Integrated
Complex.
Energy will be supplied by
Tenaga National Berhad
(TNB)

We have made the decision to choose Gebeng as our plant location. It is because of
the water supply. The Semambu Water Treatment Plant currently can supply about 2MG/D
of water. It is absolutely enough water supply for our plant for the cooling and other
processes. It is also because of there is Petronas Centralised Emergency Facility nearby.
They are specialized in chemicals so if any incident happen in the plant they can solved it
quickly. They are also equipped with HAZMAT that is specialized for hazardous and
dangerous chemical.

11
 3.3 SITE LAYOUT

PARKING AREA
3.4

HEADQUARTERS

ASSEMBLY

POINT 1

ASSEMBLY CAFETERIA
POINT 2

RECEIVING

PLANT

(REFER PLANT PRODUCT STORAGE SHIPPING

LAYOUT)
UTILITIES

FUTURE
 3.4 PLANT LAYOUT

W AREA 2
A T
SOLVENT
SEPARATION AREA E
S R
L L X RECOVERY
T E
E A I I T R
COLUMN
T Q Q R E C
W M U U A C O
A E RAFFINATE I I C O L
T N
D D T V U
E T STRIPPER O CRUDE
E M
R R
ACRYLIC R N
Y
ACID

COLUMN
W

AREA 3
AREA 1 PRODUCTION AREA
REACTION AREA

PRODUCT
REACTOR
COLUMN
2 Q T
U O
E W
N E
C R
DEDIMERIZER
H

REACTOR

1
BOTTOM

STRIPPER

PROPY-
AIR STEAM
LENE

FUTURE
 CHAPTER FOUR
LIQUID-LIQUID EXTRACTION UNIT
4.1 DEFINITION

Terms in the liquid-liquid extraction unit:

 Extract

This is the exit stream from the process being substantially Solvent material into
which the Solute has transferred.

 Feed

This is the inlet stream to the unit in which the substance to be extracted is originally
dissolved.

 Liquid-Liquid Extraction

This is the unit operation by which a substance or substances may be substantially

passed from solution in one liquid to solution in another by the contacting of the
liquids. This process is also known as Solvent Extraction.

 Raffinate

This is the exit stream from the process being substantially Feed material from
which the Solute has been transferred.

 Solute

This is the substance or substances which are to be transferred from the Feed.

 Solvent

This is the second liquid phase fed to the process into which the Solute is
transferred. The Solvent should be substantially immiscible with the Feed.

14
4.2 LIQUID-LIQUID EXTRACTION PROCESS

4.2.1 GENERAL

Liquid-Liquid Extraction is the process of extracting a Solute from a Feed by use of a

Solvent to produce an Extract and a Raffinate. In its simplest form, it may take the guise
of a single stage mixing and separation unit analogous to a single stage flash in distillation.
The choice of Solvent is critical in effecting a Liquid-Liquid Extraction. Factors affecting
the choice are summarized later; it is usually necessary to compromise in one area or
another. As in distillation it is frequently impossible to achieve the separation required by
use of a single stage unit, and a multistage unit is required. These units are summarized
later and modes of operation further considered. A number of pitfalls in operation and
design of Liquid-Liquid Extraction units are briefly mentioned.

4.3 CHOICE OF SOLVENT

The choice of solvent is influenced by many factors some of which are listed below:

 High Selectivity
The ability of a solvent to extract a component or class of components in preference
to others. This factor will determine the number of extraction stages required.

 Distribution or Partition Coefficient

The ratio of the solubility of the solute in the Solvent compared to the feed. This
factor will affect the selectivity and the amount of Solvent phase required.

 Density
The greater the density difference between the feed and the solvent the easier it will
be to obtain phase separation.

 Viscosity
A high viscosity will inhibit both mass transfer and separation of the phases. A low
viscosity (say less than 10 cP) is desirable.

 Interfacial Tension
This affects the settling, coalescence and mass transfer coefficient of a system.
Coalescence and settling are generally aided by high interfacial tension whilst mass
transfer is hindered.

15
  Volatility
The solvent is likely to need to be separated from the solute and/or the Feed. If this
is to be done by distillation the volatility should, where possible, be chosen to allow
this separation to be easily effected.

 Stability
The solvent should be stable at process conditions in order to minimize losses by
degradation and generation of further impurities.

 Corrosiveness
If possible, there is a strong incentive to use a component that is already in the
process, such as a reactant feed stream, as the solvent. This may avoid additional
materials handling, environmental and corrosion penalties later in the process.

 Toxicity
The advantages of a non-toxic solvent are self-evident in considering inherent
process safety and capital cost. Some solvents now appear on the "Environmental
Red List" and should be avoided.

 Cost
The extraction process may only be a small part in the overall process and solvent
losses should not greatly affect process economics.

No solvent is likely to meet all the above criteria and the list is not claimed to be
exhaustive. A compromise will be necessary based on overall process economics. A
common approach to solvent selection is to carry out a literature survey of solvents used in
similar processes. It may be necessary to consult with Physical Property specialists or with
a Liquid-Liquid Extraction expert.

16
4.4 SOLVENT CHOSEN

The first improvement made is in choosing a new solvent for the liquid-liquid
extraction process. The new compound, isopropyl acetate, replaces di-isopropyl ether and
is advantageous in several aspects, the most important being the ability to remove the need
for refrigerated water in the solvent recovery tower's condenser. This change is facilitated
due to isopropyl acetate's higher boiling point, 90oC, which allows for a higher temperature
in the condenser (Smallwood 195-200). In the evacuated conditions, this higher
temperature falls at approximately 37oC as compared to the 13oC dictated in the base case
thus allowing for 30oC cooling water to be used to condense the distillate. By freeing
ourselves of the refrigerated water, we are able to save over $11,000,000 per year in utility
costs. This solvent exhibits a solubility of 1.8g of water/100ml of solvent (Scheflan 472-
473). This is slightly less than that of di-isopropyl ether. Thus less water is taken into the
product stream exiting the extraction tower. This ultimately reduces the loads on some of
the heat exchangers present.

Isopropyl acetate is also advantageous in that its usage allows for an approximate
one-third reduction in the solvent flowrate. For, due to a greater affinity for acrylic acid,
less solvent is needed. This, in turn, reduces the number of stages needed in the solvent
recovery tower (McCabe 295-300). These changes are seen in economic savings for both
equipment cost and bulk solvent cost.

Another aspect introduced with the solvent involves the addition of inhibitors to the
system. These compounds reduce the formation of the acrylic acid dimer and allow
operating temperatures to slightly exceed the previously described cutoff of 90 oC. In fact,
by using these inhibitors we are able to raise the temperature in our reboiler to 95oC without
the fear for dimerization (Armeniades). The dilute aqueous stream, stream 16, from the
refluxed gas absorber, T-101, enters the top of the acid extraction unit, T-102. The acid
fraction of the stream is removed by an organic solvent.

The solvent must have a high solubility for acrylic acid and a low solubility for
water. One solvent with these characteristics is n-pentane, which has a high affinity for
both acetic and acrylic acid and a boiling point of 36oC.

17
4.5 PRINCIPLES OF LIQUID-LIQUID EXTRACTION

Solvent extraction depends on a favorable distribution of the solute between the

solvent and feed streams. The two important parameters which fix the number of extraction
stages and the solvent usage are the distribution coefficient and the selectivity factor. The
distribution or partition coefficient, K, is defined as:-

CR
K=
CE

Where C refers to the composition of a component in any consistent convenient units and
the subscripts E and R refer to the extract and raffinate phase respectively. A high value of
K is required for the component to be extracted, this determines the quantity of solvent
required to affect the recovery. Ideally K is independent of the concentration of the solute
and the ratio of extract to raffinate phase. The separation or selectivity factor, S, is defined
as:-

K1
S=
K2

Where the subscript 1 refers to the component to be preferentially extracted and subscript
2 refers to the component to be preferentially retained. The separability of component 1
from component 2 increases with increasing separation factor. A high value of s indicates
the potential for a high degree of separation in a small number of extraction stages. A paper
by Souders and Mott indicated the relative uses of fractional distillation, extractive
distillation and liquid-liquid extraction. The design of a separations facility to carry out a
particular separation was said to be the same in a case when fractional distillation was used
with a relative volatility of 1.5, extractive distillation with a relative volatility of 2.0 and
liquid-liquid extraction with a selectivity factor of 6.0. It is possible sometimes to tailor a
particular solvent to give the desired combination of selectivity and partition coefficient.
In a mixed hydrocarbon solvent this might be achieved by varying the proportion of
aromatic to paraffinic material for example or in a chemical solvent pH might be varied to
influence solvent activity. A solvent may be tailored to "pick up" a given solute from a
particular feed then "drop it" into a further solvent by addition of acid or alkali to alter the
pH or some chemical equilibrium constant. Choice as to whether to make the raffinate or
the extract phase continuous will be based on a number of considerations. These include
the stability of the mixture interface which may improve mass transfer but inhibit settling,
the relative mass transfer coefficients which may be influenced by surface tension and more
mundane considerations such as inventory of flammable or toxic materials.

18
4.6 ROTATING DISC CONTACTOR

4.5m

H-4.5m

0.58m

19
4.6.1 GENERAL DESCRIPTION

A rotating disc contactor (RDC) consists of a vertical cylindrical container

that is evenly subdivided into a number of compartments by a series of rings. In the
middle of each compartment, there is a disc supported by an axle. The discs are
designed for easy disassembly for maintenance. The highest-density liquid enters
the RDC at the top. The liquid with the lowest density enters at the bottom and
flows upwards in the opposite direction to the liquid with the higher density that
flows downwards. Rotation dispenses one of the liquids in the other one. Varying
the rotational speed allows simple adjustment of droplet size of the dispensed phase
and thus the efficiency of the RDC. The rotor axle is fastened to a ball-shaped
swinging roller bearing at the top and is centered (and supported) by a slide bearing
at the bottom. There are one or more intermediate slide bearings depending on the
size of the RDC. This set-up makes it possible for the RDC to continue working
when the rotor is in a stationary position. Repairs can then be carried out on the
mechanical seal while the RDC remains in operation. Obviously, appropriate
precautions have to be taken when doing this

4.6.2 OPERATION PRINCIPLE

A Rotating Disc Contactor (RDC) is a type of process column used in the

chemical industry to remove impurities from liquids. The apparatus consists of a
vertical cylindrical vessel, divided lengthwise into a number of equally spaced
compartments by a series of stator rings. A rotor disc supported by a shaft is
centered in each compartment. A rotating disc contactor can remove impurities
from water and other fluids using a liquid solvent (in a process called solvent
extraction).

The separation process is based on the counter-current principle: the liquid

with the higher density enters the vessel at the top, and the liquid with the lower
density enters at the bottom. Due to the difference in relative density, the two
liquids pass each other as they move through the compartments. The process of
mixing and separating the two liquids is reinforced by the rotation of the rotor discs.
Varying the column diameter, column length, compartment height, flow speed and
rotational speed allows for adjustment of the droplet size in the dispersed phase.

20
4.6.3 MATERIALS OF CONSTRUCTION

The corrosion problem affects many industries. In chemical industries it is one of

the most serious, and perhaps the most costly, of the problems confronting the
chemical engineer, not only because of the added cost to production due to
replacement of apparatus, shutdowns for repair, etc., but also because of possibility
of contamination of the product through catalytic action or otherwise. Therefore
losses due to corrosion can run into hundreds of millions of ringgits. Hence, any
development that will have to be made to control or reduce this problem must be
welcomed by the chemist and the engineer. Due to the large corrosive effects of
acrylic acid and acetic acid, stainless steel must be used in constructing all towers.
This choice reduces the occurrence of rust and erosion on the equipment thus
lowering replacement costs and repair (Kroschwitz 287-309). Tower internals
should be fabricated out of glass, polyethylene, or polypropylene. These materials
are relatively resistant to corrosive effects of the acids. This is apparent in the base
case's choice of a polyethylene packing for the quench tower. In the solvent
recovery tower, stainless steel packing is used. Stainless steel trays are found on
the other towers in order to prolong the structures' lives and withstand column
conditions.

4.6.4 PROCESS CONTROL (CASCADE CONTROL

21
 CHAPTER FIVE
MASS BALANCE CALCULATIONS
5.1 LIQUID-LIQUID EXTRACTION UNIT MASS BALANCE

 Assumptions:
1. Feed is given: 2000kmol/hr
2. Solvent is given: 3000kmol/hr
3. Efficiency of liquid-liquid extraction is 90%

Extract Solvent
V1 = 3750 kmol/hr VN+1 = 3000 kmol/hr
YA1 = 0.2 VA1 = 750 kmol/hr
YC(N+1) = 1
YB1 = 0.2 VB1 = 750 kmol/hr

YC1 = 0.6 VC1 = 2250 kmol/hr LLE

Raffinate
Feed
LN = 1250 kmol/hr
LO = 2000 kmol/hr
XAO = 0.4 LAO = 800 kmol/hr XAN = 0.04 LAN = 50 kmol/hr
XBO = 0.6 LBO = 1200 kmol/hr XBN = 0.94 LBN = 1175 kmol/hr

XCN = 0.02 LCN = 25 kmol/hr

22
 𝐿𝑜 + 𝑉𝑁+1 = 𝑀
2000 + 3000 = 5000
𝑀 = 5000
𝐿𝑜 𝑋𝐴𝑜 + 𝑉𝑁+1 𝑌𝐴𝑁+1 = 𝑀𝑋𝐴𝑀
2000(0.4) + 3000(0) = 5000(𝑋𝐴𝑀 )
𝑋𝐴𝑀 = 0.16
𝐿𝑜 𝑋𝐶𝑜 + 𝑉𝑁+1 𝑌𝐶𝑁+1 = 𝑀𝑋𝐶𝑀
2000(0) + 3000(1) = 5000(𝑋𝐶𝑀 )
𝑋𝐶𝑀 = 0.6

The following are then plotted onto the ternary diagram graph to find the compositions for 𝐿𝑁 and
V1

23
5.2 THEORETICAL STAGES GRAPH

24
5.3 ACTUAL STAGES CALCULATION

𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒕𝒉𝒆𝒐𝒓𝒆𝒕𝒊𝒄𝒂𝒍 𝒔𝒕𝒂𝒈𝒆𝒔

𝑬𝒐 = 𝒙 𝟏𝟎𝟎%
𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒂𝒄𝒕𝒖𝒂𝒍 𝒔𝒕𝒂𝒈𝒆𝒔

7
90 = 𝑥 100%
𝑎𝑐𝑡𝑢𝑎𝑙

Actual = 7.78 stages

5.4 COLUMN SIZING

 450 cm diameter
 4.50 m high
 Tower internals fabricated out of glass, polyethylene, or polypropylene
 Tower constructed out of stainless steel

25
 CHAPTER SIX
SAFETY ASSESSMENT
6.1 SAFETY ISSUES

It is recommended that the steam-to-propylene ratio at the reactor inlet never be set less
than 4:1 on a mole basis. This steam is used to inhibit the formation of coke on the catalyst
below temperatures of 330ºC. As with any reaction involving the partial oxidation of a
fuel-like feed material (propylene) considerable attention must be paid to the composition
of hydrocarbons and oxygen in the feed stream. This stream is a potential explosion hazard.
Operation outside of the explosion limits (LEL and UEL) is strongly recommended for a
packed bed reactor. The explosion limits for propylene in air at 25ºC are LEL = 2.0 mol%
propylene and UEL = 11.1 mol% propylene. At elevated temperatures and using a 4:1
steam-to-propylene ratio (see above) in the feed, the lower explosion limit (LEL) is
changed significantly. In this case it is easier to define a minimum oxygen concentration
(MOC) for the stream. Below the MOC, flame propagation and hence explosions are not
possible. For the packed bed reactor you can assume an average value of MOC = 5.6 mol
% oxygen. The UEL at typical temperatures used for this reaction is 15.3 mol % propylene.
The second safety concern is that associated with the highly exothermic polymerization of
AA which occurs in two ways. First, if this material is stored without appropriate additives,
then free radical initiation of the polymerization can occur. This potentially disastrous
situation is discussed by Kurland and Bryant [1]. Secondly, AA dimerizes when in high
concentrations at temperatures greater than 90°C. Therefore, process conditions in the
separation section (X-301 and T-302) should never exceed this temperature.

26
6.2 MEDICAL MANAGEMENT

Medical management should determine an employee’s fitness to work with or around

acrylic acid and establish procedures to be followed if an exposure incident occurs. Two
issues to be considered in the overall fitness to work with acrylic acid are vision and
respiratory system capability. Employees with severely restricted, or faulty vision, should
be carefully examined prior to work assignment. Contact lenses are not recommended for
use in areas where there is a potential for exposure to acrylic acid.

6.3 FIRST AID

6.3.1 GENERAL

Every employee working in a potentially dangerous environment (with chemicals,

machinery, etc.) should know a few basic first aid steps to follow in case of emergency.
In the event of an emergency, it is important that the scene be surveyed to determine
what occurred, and to ensure that there is no danger to self while assistance is provided.
The location of all emergency eyewash stations and showers should be known so that
in the event of an exposure they are immediately accessible. The phone number(s) to
call for emergency medical services and all workplace specific emergency procedures
should be readily accessible. When providing first aid to a person who has been
exposed to acrylic acid, the person should be removed from the area to prevent further
exposure. If the person can walk they should walk out of the immediate area. Liquid
acrylic acid is extremely slippery so care is necessary to prevent a fall that would
increase exposure. The type of exposure the person has experienced should be
determined - eye or skin contact, inhalation or ingestion. If possible, do not leave an
injured person alone. Any available person should be instructed to call for help while
assistance is being provided to the affected individual. Any person assisting the
exposed person must take care not to also become injured. Clothing or skin
contaminated with liquid acrylic acid may secondarily contaminate rescue and medical
personnel by direct contact. In the event of an accidental exposure to acrylic acid while
working alone, the worker should leave the area. After finding a co-worker and
instructing him/her to call for help, the exposed worker should follow procedures to
remove or dilute the contamination. Two way communication such as hand held radios
are a best practice when personnel are working with hazardous chemicals.

27
6.3.2 CONTACT WITH EYES

In case of eye exposure to acrylic acid at any concentration, the person should
immediately go to the nearest eyewash station and flush his/her eyes with water for at
least 20 minutes while holding eyelids open and away from the eyes. A physician
should be contacted immediately for further medical attention. If a physician is not
immediately available, the process of flushing the eyes with water should be continued
for a second 20 minute period. Do not put any ointments or medications on a person’s
eyes unless specifically instructed by a physician.

6.3.3 CONTACT WITH SKIN

If acrylic acid comes in contact with a person’s skin or clothing, the individual should
immediately go to the nearest safety shower and rinse off the acrylic acid. Once under
the shower, all contaminated clothing and shoes should be removed. The affected
area(s) of the person should be washed continuously with large quantities of water for
at least 15 minutes or longer if odor persists. A physician or emergency medical
services should be contacted for further assistance. No ointments or medications should
be applied to the skin without specific instruction from a physician. All contaminated
clothing must be appropriately de-contaminated prior to re-use. Do not take items
contaminated with acrylic acid home for laundering. If the facility is not equipped to
decontaminate clothing and other items, they should be properly disposed of and
replaced. Contaminated leather items cannot be adequately decontaminated and must
be discarded.

6.3.4 INHALATION

If acrylic acid vapors are inhaled, the affected person should immediately be removed
from the contaminated area to a well-ventilated area. Emergency medical assistance
should be requested. Acrylic acid exposure usually causes mucous membrane irritation,
sore throat, and coughing. Rapid development of respiratory distress with chest pain,
difficulty breathing, swelling of the throat and accumulation of fluid in the lungs
(shortness of breath, cyanosis, expectoration, cough) may occur. Lung injury may
progress over several hours. Medical professionals or those properly trained may
consider administration of oxygen.

28
6.4 BULK STORAGE FACITILIES AND ACCESSORIES

6.4.1 GENERAL CONSIDERATIONS

The recommended bulk storage temperature range is 15 to 25°c (59 to 77°f). This
temperature range avoids freezing and allows time to detect and react to a potential
inadvertent polymerization. A possible product quality consideration is the rate of
dimer formation, which depends on the storage temperature. Avoid methods of heating
that can generate high surface temperatures. Heat transfer fluids maintained at ≤ 35-
45°c (95-113°f) can be used to heat acrylic acid containing vessels and piping systems.
Under no circumstances should steam be used to heat or thaw acrylic acid. Localized
high temperatures can quickly initiate polymerization. Uncontrolled polymerization
can be violent and may result in serious injury and/or loss of property. Electrical heat
tracing should not be used on piping systems (including pumps, valves and filters) or
vessels in acrylic acid service unless it can be ensured that the resulting maximum
electrical tracing temperature cannot exceed 35-45°c (95-113°f) during heating or
thawing. Self-limiting or constant-wattage electrical heat tracing limited to
temperatures below 65°c (149°f) and instrumented to control at ≤ 35-45°c is acceptable
for this service because of their additional safety features. An independent high
temperature shutdown at ≤ 35-45°c (95-113°f) may also be included as an additional
safety feature to guard against failure of the tracing system.

Adequate inhibition is necessary to avoid polymerization in properly stored acrylic

acid. The standard level of inhibitor in commercially available acrylic acid is 180-220
ppm MEHQ. In addition to the MEHQ inhibitor, the presence of dissolved oxygen in
the acrylic acid liquid is essential for stabilization. Therefore, an atmosphere containing
5 to 21 vol. % of oxygen should be maintained above the acrylic acid. Never use an
inert atmosphere. Dissolved oxygen converts carbon centered radicals to oxygen
centered radicals, which the MEHQ can trap to stabilize the acrylic acid. Typically a
minimum 10% void volume in acrylic acid bulk storage vessels is used as a buffer
against tank overflow. This also provides adequate oxygen containing gas to activate
the MEHQ inhibitor. Avoid freezing when possible. Freezing causes all impurities to
concentrate in the liquid phase. Potentially leaving the crystalline phase severely
deficient in MEHQ inhibitor and dissolved oxygen. Never remove acrylic acid from a
partially thawed vessel or system. Such material may be uninhibited or contain most of
the inhibitor required for the entire contents of the vessel or system. Freezing can also
cause loss of circulation by plugging piping, valves and pumps which may lead to
safety hazards.

29
 Never try to start a pump which might contain frozen acrylic acid. Take every
precaution to keep acrylic acid free of contamination, for example, by using dedicated
equipment and lines. Never store or handle acrylic acid in a facility without first
carefully reviewing the design of all vessels and accessories for potential hazards.
Never store in a vessel where steam can accidentally heat the material directly through
a heat transfer surface or by direct addition to the vessel. Storage in process vessels or
in storage tanks designed for other chemicals can lead to unsafe conditions. All acrylic
acid storage vessels (including charge or weigh tanks) should have a high temperature
alarm. The purpose of this alarm is to detect an inadvertent polymerization or the
introduction of excessive heat from external sources. Properly located and maintained
redundant temperature probes (minimum 2) connected to a high temperature alarm can
provide early warning of potentially unsafe conditions and allow for corrective action.
All acrylic acid pumps should be protected from overheating. If deadheaded, many
types of pumps can quickly overheat and cause a violent polymerization, which could
result in serious injury and/or loss of property. Avoid condensation in vent lines and
nozzles. Condensed acrylic acid will be free of inhibitor and can quickly polymerize.
Polymerization can lead to dangerous plugging of the pressure relief or vacuum relief
vent system. Periodically inspect vent nozzles and lines for polymer. Promptly remove
any polymer found in the system. Polymer can cause plugging and may promote further
polymerization under some conditions. It is good practice not to leave stagnant lines or
nozzles liquid-full for over one week. Dissolved oxygen is slowly consumed and must
be replenished by occasional circulation or clearing the lines with a gas containing 5 to
21 vol. % of oxygen. Depletion of oxygen can cause polymer formation and plugging.
Indoor acrylic acid storage facilities must be well ventilated to prevent local
accumulation of vapors and their potential harmful effects on personnel.

6.4.2 DESIGN CONSIDERATION

It is recommended that fail-safe positioning of automated valves and emergency

backup power for critical instrumentation is included in the design. Follow all codes
and regulations applicable to the geographic location of the facility. Contact your
acrylic acid supplier for additional guidance. A floating roof tank is not recommended
for acrylic acid storage as it creates a seal or barrier between the acrylic acid and its
source of oxygen replenishment above the roof. Use of a floating roof tank for acrylic
acid storage dramatically increases the likelihood of a runaway polymerization.

30
6.4.3 TEMPERATURE CONTROL OF STORAGE TANK & ACCESSORIES

The installation of a reliable freeze protection system, which avoids accidental

overheating of the acrylic acid, is highly recommended for all climates where freezing
can occur. Thawing frozen acrylic acid can be extremely hazardous. Piping systems
located outdoors (including valves, pumps and filters) should be insulated and heat-
traced to avoid cold spots, which can result in plugging by frozen acrylic acid. Under
no circumstances should steam be used to heat or thaw acrylic acid. Electrical heat
tracing should not be used on piping systems (including pumps, valves and filters) or
vessels in acrylic acid service unless it can be ensured that the resulting maximum
electrical tracing temperature cannot exceed 35-45°c (95-113°f) during heating or
thawing. Self-limiting or constant-wattage electrical heat tracing limited to
temperatures below 65°c (149°f) and instrumented to control at ≤35- 45°c is acceptable
for this service because of their additional safety features. An independent high
temperature shutdown at ≤ 35-45°c (95-113°f) may also be included as an additional
safety feature to guard against failure of the tracing system.

Heat transfer fluid can be used if controlled to preclude dangerous overheating as

described below. All storage tanks located outdoors should be insulated for freeze
protection and controlled between 15 to 25°C (59 to 77°F) by a properly designed heat
transfer fluid system. This temperature range prevents freezing, reduces dimer
formation and provides additional time for potential emergency response.
Temperatures of 32°c (90°f) or higher can be hazardous and should be immediately
investigated. Exceeding 32°c (90°f), even for a short time, may reduce the shelf life of
the product. Investigation must include determining the cause for the abnormally high
temperature and correcting that cause. Failure to correct could jeopardize the stability
of the acrylic acid and necessitate emergency response. During colder months, the
system can be used to avoid freezing but the heat transfer fluid must be maintained at
≤ 35-45°c (95-113°f) to avoid dangerous overheating. The heat transfer fluid can also
be adjusted as needed to provide cooling during warmer weather and/or to remove heat
generated by pumps. When establishing the design criteria for the heat transfer fluid
system, the heat introduced during circulation by the pump should be considered as
well as the potential need to control dimer formation for quality reasons. Cooling
capacity over and above that needed to control temperature to prevent dimer formation
can delay detection of temperature increases indicative of polymerization during the
onset of an emergency.

31
Four commonly used temperature control systems for bulk acrylic acid tanks are given
below, in order of preference:

 External heat exchanger with acrylic acid tube side and heat transfer fluid on
the shell side. Tank insulated and piping containing liquid acrylic acid insulated
and heat-traced.
 Heat transfer fluid circulated through a heat transfer jacket on the outside tank
wall. Tank insulated and piping containing liquid acrylic acid insulated and
heat-traced.
 Heat transfer fluid circulated through a heat transfer coil inside the tank. Tank
insulated and piping containing liquid acrylic acid insulated and heat-traced.
 Tank located inside a building with a reliable heating system for freeze
protection. The design of indoor bulk storage facilities and accessories must
address the special fire, health and reactivity hazards inherent to indoor storage
facilities. All storage tanks located indoors must be vented to the outside.

32
6.5 HAZOP STUDY

HAZOP guide word and meaning

Word Meaning
No Negation of design intent
Less Quantitative decrease
More Quantitative increase
Part Of Qualitative decrease
As Well As Qualitative increase
Reverse Logical opposite intent
Other Than Complete substitution

33
6.6 PERSONAL PROTECTIVE EQUIPMENT

 Eye Protection
Use of a face shield, in conjunction with splash goggles, offers additional protection
of the face from splashing. Goggles should be non-vented, and designed
specifically to protect against chemical splash. If an employee wears corrective
lenses, chemical goggles should be worn over the lenses.

 Skin Protection
Skin protection may be found in many forms. Hand protection such as chemical
resistant gloves, protective arm sleeves, aprons, full body coveralls, boots, and head
coverings are among the types available. Skin protection must be made of a material
impervious to acrylic acid. Skin protection for the purpose of preventing chemical
exposure may be worn in conjunction with other types of PPE. Skin protection PPE
is available in a variety of sizes, and should be available in a size that fits the
employee.

 Head Protection
Hard hats are recommended for protection from falling objects, overhead liquid
leaks, and chemical splashes.

34
 CONCLUSION

In conclusion, rotating disc contactor is the main objective in this report as it is the main
separation process in the acrylic acid plant. The rotating disc contactor used cascade controller to
operate the liquid-liquid unit extraction. The sizing and the diameter is stated in the previous pages
and to summarize the height of the tower is 4.5meter and the spacing between the disc is 58cm.
Based on the calculation, the theoretical stages obtained is 7 meanwhile the actual stages is 7.78.
The purity of the acrylic acid depends on the stages obtained.

For the site location to build the acrylic acid plant is located in Pahang for its advantages
and its nearness to the raw material and it is far from the community as acrylic acid can be very
dangerous if inhaled in a huge amount.

Lastly, the safety hazard for this plant is discussed in details in the safety assessment
section. The material safety data sheet (MSDS) for both acrylic acid and isopropyl acetate are
stated in the appendices section.

35
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36