DESIGN OF A PLANT FOR PRODUCTION OF 36,000kg/day OF METHYL ETHYL

KETONE BY VAPOUR PHASE CATALYTIC DEHYDROGENATION OF 2-BUTANOL

DESIGN PROJECT

Presented to

The Department of Chemical Engineering

Covenant University, Canaan Land, Ota, Ogun State, Nigeria

BY

OKOYE CHIOMA CHIDIMMA

(11CF011991)
MEMBER OF TEAM COVENANT

In Partial Fulfilment of the requirements for the Degree

Bachelor of Engineering (Honours) in Chemical Engineering
Covenant University, Canaan Land, Ota, Ogun State, Nigeria

MARCH 2016

CERTIFICATION
This is to certify that the design project entitled DESIGN OF A PLANT FOR PRODUCTION
OF 36,000kg/day OF METHYL ETHYL KETONE BY VAPOUR PHASE CATALYTIC
DEHYDROGEN

OF

2-BUTANOLsubmitted

to

the

Department

of

Chemical

Engineering,Covenant University,Canaaland,Ota ,Ogun State,Nigeria,is a record of the original

design carried out by GroupCovenant Members in the Department of Chemical Engineering.

ii

DEDICATION
First of all, I dedicate this report to the Almighty God who kept and sustained me throughout this
period of this project. I would also like to dedicate this report to the staff of Chemical
Engineering Department for their guidance and support throughout this project. Lastly, this
report is also dedicated to my family, Mr. Sunday Okoye ,Mrs.Chioma Okoye,Onyinye Okoye
and Chinonye Okoye, my friends and loved ones who provided me with support throughout this
experience.

iii

Department of Chemical Engineering,

Covenant University,
Canaan Land, Ota,
Ogun State,
Nigeria.
November 10, 2015.
The Head,
Department of Chemical Engineering,
Covenant University,
Canaan Land, Ota,
Ogun State,
Nigeria.
Dear Sir,

LETTER OF TRANSMITTAL
In accordance with the regulations of the Department of Chemical Engineering, School of chemical &
Petroleum Engineering, College of Engineering and Covenant University, Canaan Land, Ota, Ogun State,
Nigeria, we the members of group COVEANANT, do hereby submit a Design Project entitled DESIGN
OF A PLANT FOR THE PRODUCTION OF 36,000KG/DAY OF METHYL ETHYL KETONE BY VAPOUR PHASE
CATALYTIC DEHYDROGENATION OF 2-BUTANOLin partial fulfilment of the requirements for the award
of the Bachelor of Engineering (Honours) Degree in Chemical Engineering at Covenant University,
Canaan Land, ota, Ogun State, Nigeria.
Yours faithfully,

iv

ACKNOWLEDGEMENT
The Design project on the preparation of MEK from DEHYDROGENATION of 2-Butanol was
a great chance for learning and professional development. I consider myself as a very lucky
individual as I was provided with an opportunity to be part of a team that designs a plant for the
preparation of MEK from Dehydrogenation of 2-Butanol.
I want to use this opportunity to express my deepest gratitude and special thanks to my
Supervisor Engr.Ojewumi,Miss Babatunde and the Covenant Team whose support, guidance
and encouragement was a source of inspiration throughout the execution of this project.
I give absolute thanks to God Almighty, whose glory and honor, brought me to the successful
conclusion of this project and for keeping me safe through all the difficult times, for granting me
wisdom and for always being faithful in my times of need, I give Him all the glory

TABLE OF CONTENTS
CONTENTS

PAGE

TITLE PAGE

CERTIFICATION

ii

DEDICATION

iii

LETTER OF TRANSMITTAL

iv

ACKNOWLEDGEMENT

TABLE OF CONTENTS

vi

LIST OF TABLES

vii

LIST OF FIGURES

viii

LIST OF SYMBOLS

ix

LIST OF APPENDICES

ABSTRACT

xi

CHAPTER ONE

13

1.0 INTRODUCTION

13

1.1 BACKGROUND OF STUDY

13

1.1.1

PHYSICAL AND CHEMICAL PROPERTIES OF 2-BUTANOL 16

1.1.2

PHYSICAL AND CHEMICAL PROPERTIES OF MEK

18

1.1.3

INDUSTRIAL APPLICATION OF MEK

21

1.2 AIM AND OBJECTIVE OF WORK

22

1.3 SIGNIFICANCE OF WORK

23

1.4 SCOPE OF WORK

23

1.5 LIMITATION OF WORK

24

CHAPTER TWO

25

2.0 THEORETICAL PRINCIPLES AND LITERATURE REVIEW

25

2.1 THEORETICAL PRINCIPLES

25

2.1.1

PRINCIPLE OF DISTILLATION

25

2.1.2

COMPRESSORS

27
vi

2.1.3

LIQUID LIQUID EXTRACTION

29

2.1.4

SEPARATOR

31

2.1.5

VAPOUR PRESSURE

32

2.1.6

PRINCIPLE OF ABSORPTION

33

2.1.7

PRINCIPLE OF VAPOURISATION

34

2.1.8

CATALYSIS

36

2.1.9

HEAT TRANSFER

36

2.1.10 CONDENSATION

38

2.2 LITERATURE REVIEW

2.2.1
2.2.2

39

SELECTION OF PROCESS ROUTE

39

REVIEW OF PAST WORKS ON MEK PRODUCTION FROM

DEHYDROGENATION OF 2-BUTANOL.

42

CHAPTER THREE

43

3.0 MATERIAL BALANCES FOR THE PLANT

43

3.1 INTRODUCTION

43

3.2 DESCRIPTION OF THE PROCESS

43

3.3 ASSUMPTION MADE

47

3.4 MATERIAL BALANCE

48

CHAPTER FOUR

54

4.0 ENERGY BALANCE FOR THE PLANT

54

4.1 INTRODUCTION

54

4.2 ENERGY BALANCE

56

REFERENCES

62

APPENDICES

64

A: MATERIAL BALANCES

64

B: ENERGY BALANCE

73

vii

LIST OF TABLES
Table

Name

Page

Table 1.1-

Physical Properties of MEK

19

Table 1.2

Industrial application of MEK

22

Table 3.1

Material Balance across Reactor

48

Table 3.2

Material Balance across Partial Condenser

49

Table 3.3

Material Balance across Absorption Column

50

Table 3.4

Material Balance across Extraction Column

52

Table 3.5

Material Balance across Solvent Recovery Unit

52

Table 3.6

Material Balance across Distillation Column

53

Table 4.1

Energy Balance across Preheater

56

Table 4.2

Energy Balance across Vaporizer

57

Table 4.3

Energy Balance across Superheater 1

57

Table 4.4

Energy Balance across Compressor

57

Table 4.5

Energy Balance across Superheater 2

58

Table 4.6

Energy Balance across Reactor

58

Table 4.7

Energy Balance across Condenser

59

Table 4.8

Energy Balance across Absorber

60

Table 4.9

Energy Balance across Solvent Recovery Unit

60

Table 4.10

Energy Balance across Distillation Column

61

Table 4.11

Energy Balance across Cooler system

61

viii

LIST OF FIGURES
Figure 1.1: Molecular Structure of MEK

15

Figure 1.2: Structure of 2-butanol

16

Figure 1.3: Chemical reaction of 2-butanol to give butane.

17

Figure 1.4: oxidation reaction of 2-butanol using KMnO4 as oxidizing agent.

17

Figure 1.5: Chemical reaction of MEK

19

Figure 1.6: Reaction of MEK with ammonia and hydrogen

20

Figure 1.7: Reaction of MEK with acetylene.

20

Figure 1.8: Halo form

20

Figure 1.9: Chemical reaction of MEK with hydrogen peroxide

21

Figure 2.1: Diagram of a Distillation Column

26

Figure 2.2: liquid liquid extraction column

29

Figure 2.3: A vapour liquid separator

32

Figure 2.4: A boiling point diagram shows how the equilibrium compositions of the components
in a liquid mixture vary with temperature at a fixed pressure.

33

Figure 2.5: Heat exchanger

38

Figure 2.6: Dehydrogenation of 2-Butanol

40

Figure 3.1: Block flow Diagram of MEK production

40

Figure 3.2: Process Flow Diagram for production of MEK

46

ix

Symbols

LIST OF SYMBOLS
Meaning

Heat of Vaporization

Relative Volatility

Reflux Ratio

Enthalpy

Cp

Heat Capacity

Distillate rate

Bottoms rate

Feed rate

Mass flow

Temperature

Qc

Condenser heat

QR

Reboiler heat

Heat

LIST OF APPENDICES

APPENDIX A: MATERIAL BALANCES CALCULATIONS

64

APPENDIX B: ENERGY BALANCES CALCULATIONS

73

xi

ABSTRACT
This project was performed in order to design a plant required for the production of Methyl
Ethyl Ketone of 99.9% purity at a continuous rate of 36,000 kg/day. The design shows all the
processes involved and the unit operations required to achieve the product by converting the raw
material 2-Butanol to Methyl Ethyl Ketone. Both material and energy balances was carried out
across the various unit operations for the process.
A detailed work on the material and energy balance calculations is contained in this report

xii

CHAPTER ONE
1. INTRODUCTION
Process design can be the design of new facilities or it can be the modification or
expansion of existing facilities. The design starts at a conceptual level and ultimately ends in
the form of fabrication and construction plans. It is an innovation activity gaps in the
industrial world and provide lasting and innovative solutions to the gaps. The activity aimed
at providing the most economically feasible and effective procedure to either manufacture a
new or an existing product.in this case MEK (methyl Ethyl ketone),which is an important
industrial solvent. Chemical engineering has consistently been one of the highest paid
engineering professions. There is a demand for chemical engineers in many sectors of
industry, including the traditional processing industries: chemicals, polymers, fuels, foods,
pharmaceuticals, and paper, as well as other sectors such as electronic materials and devices,
consumer products, mining and metals extraction, biomedical implants, and power
generation. The reason that companies in such a diverse range of industries value chemical
engineers so highly is the following:
I.

The creation of plans and specications and the prediction of the nancial outcome if
the plans were implemented is the activity of chemical engineering design. Design is
a creative activity, and as such can be one of the most rewarding and satisfying
activities undertaken by an engineer. The design does not exist at the start of the
project. The designer begins with a specic objective or customer need in mind and,
by developing and evaluating possible designs, arrives at the best way of achieving
that objectivebe it a better chair, a new bridge, or for the chemical engineer, a new
chemical product or production process. When considering possible ways of
achieving the objective, the designer will be constrained by many factors, which will
narrow down the number of possible designs

II.

Starting from a vaguely dened problem statement such as a customer need or a set
of experimental results, chemical engineers can develop an understanding of the
important underlying physical science relevant to the problem and use this
understanding to create a plan of action and set of detailed specications which, if
implemented, will lead to a predicted nancial outcome.
13

III.

Before the commencement of work, the designer is supposed to provide as complete,

and as simple, a statement of the necessities as possible. If in any case the
requirement (need) arises from outside the design group, from a customer or from
another department, then the designer will have to elucidate the real requirements
through discussion. When writing specifications for others, such as for the
mechanical design or purchase of a piece of equipment, the design engineer should be
aware of the restrictions (constraints) that are being placed on other designers. A
well-thought-out, comprehensive specification of the requirements for a piece of
equipment defines the external constraints within which the other designers must
work.

1.1 BACKGROUND OF STUDY

Methyl ethyl ketone (MEK), also known as 2-butanone, is a colorless organic liquid with an
acetone-like odor and has a low boiling point. It is miscible partially with water and many
conventional organic solvents and also forms azeotropes with a number of organic liquids. MEK
can be produced using dehydrogenation of secondary butyl alcohol and as a byproduct of butane
oxidation. For the purpose of this study, the dehydrogenation of secondary butyl alcohol will be
considered. (Arora & Sharma, November 2015)
MEK may be irriating to eyes,mucos membrances,and in high concentrations,narcotic .MEK is
similar to but more irritating than acetone.the vapor is irritating to mucos membrances and
conjunctiva.no serious poisonings were reported in man except for dermatitis.dermatitis can
result if excessive repeated prolonged skin contact occurs.Minor skin contacts have been shown
to cause no evidence of irritation .MEK can recognized at 25ppm by its odor,which is similar to
acetone but more irritating.the warning properties prevent inadvertent exposure to toxic levels.
MEK is used industrially as a solvent in the manufacture of adhesives, protective coatings,
inks and magnetic tapes. It is also the preferred extraction solvent for dewaxing lube oil. In
addition to industrial uses, methyl ethyl ketone is also used in various household products,
including paints, paint removers, varnishes and glues. Methyl ethyl ketone may enter the
environment during its production, transport and use. It may also be released from vehicle
exhausts, natural sources and during the breakdown of other chemicals. MEK is distinguished by
its exceptional solvency, which enables it to formulate higher-solids protective coatings. The
14

molecular formula of methyl ethyl ketone is CH3COCH2CH3; its molecular structure is given
as:

Figure 1.1: Molecular Structure of MEK (wikipedia, wikipedia/MEK-molecularstructure, 2015)

Because of MEKs high reactivity, it is estimated to have a short atmospheric lifetime of
approximately eleven hours.
For the general population, exposure to methyl ethyl ketone can occur from cigarette
smoking. People may also breathe in small amounts when using household products that contain
methyl ethyl ketone. If exposed to methyl ethyl ketone, the potential adverse health effects that
may occur depend on the way people are exposed and the amount to which they are exposed.
Breathing in high levels of methyl ethyl ketone vapour can cause irritation of the nose, throat and
lungs and chest tightness. Ingestion may cause inflammation of the mouth and stomach upsets.
Methyl ethyl ketone can be absorbed into the body following through inhalation, ingestion or
prolonged skin exposure causing headache, dizziness, tiredness, slurred speech, low temperature,
fitting and coma. Heart problems and high levels of blood sugar can also occur. (Arora &
Sharma, November 2015)

15

1.1.1 PHYSICAL AND CHEMICAL PROPERTIES OF 2-BUTANOL

1.1.1.1

PHYSICAL PROPERTIES:

2-Butanol is a secondary alcohol with formula C4H7OH which is produced in a two (2)-step
process from hydration of butanes. It can also be manufactured industrially by the hydration of 1butene in the presence of sulphuric acid.
It is used as solvent for paints and resins, manufacture of industrial cleaners, perfumes; it
serves as a flavoring agent.
Physical properties are:

Colorless liquid

Strong alcoholic odour

Flash point below 26oC

Boiling point at 99.5oC

Melting point: 115 C

Density: 0.808 g/mL at 25 C

Vapor density : 2.6 (vs air)

Vapor pressure : 12.5 mm Hg ( 20 C)

Refractive index: n20/D 1.397(lit.)

Water Solubility : 12.5 g/100 mL (20 c) (wikipedia, 2-Butanol, 2015)

Figure 1.2: Structure of 2-butanol

16

1.1.1.2

CHEMICAL PROPERTIES

2-butanol which is a secondary alcohol has molecular formula of C4H10O and molecular mass
74.12 gmol-1. It can be easily oxidized as well as undergo elimination (dehydration) and
substitution reactions. 2-butanol is dehydrated (removal of H2O) on heating with concentrated
sulphuric acid to give butane.

Figure 1.3: Chemical reaction of 2-butanol to give butane.

2-butanol are oxidized, by dehydrogenation, to form butanal and butanone respectively. The
oxidation can be achieved using oxidizing agents such as KMnO4 or K2Cr207.The reactions
involve the loss of the -OH hydrogen together with a hydrogen atom from the adjacent alkyl
group.

Figure 1.4: oxidation reaction of 2-butanol using KMnO4 as oxidizing agent.

2-butanol undergoes substitution reaction when reacted with sodium. The acidic part of the OH group shows up in their reaction with reactive metals (such as sodium) to liberate hydrogen
gas.
Specifically, in relation to our study, and the production of Methyl Ethyl Ketone. A notable
reaction undergone is the dehydration reaction which when carried out on the 2-butanol, an
elimination reaction in regards to the molecules present in the compound is observed. (wikipedia,
2-Butanol, 2015)

17

1.1.2 PHYSICAL AND CHEMICAL PROPERTIES OF MEK

1.1.2.1

PHYSICAL PROPERTIES

MEK is a low boiling solvent with an atmospheric boiling point of 175.3 0F (79.60C).
Methyl Ethyl Ketone (MEK) is a chemically stable compound also known as 2-butanone. MEK
is a flammable, colorless liquid possessing a typical ketonic odor. It has very good solvent
properties, a fast evaporation rate, and is miscible with organic solvents. Some of the physical
properties are listed below.

Boiling point at 1 atm, 0C

Azeotrope with water, bp, 0C
Wt.% ketone in vapor
Auto ignition temperature, 0C
Coefficient of cubic expansion, per 0C
Critical pressure, atm
Critical temperature , 0C
Density, g/mL at 200C
Dielectric constant
Dipole moment, debye units
Electrical conductivity, mho
Boiling point at 1 atm, 0C
Azeotrope with water , bp, 0C
Wt.% ketone in vapor
Auto ignition temperature, 0C
Coefficient of cubic expansion, per 0C
Critical pressure, atm
Critical temperature , 0C
Density, g/mL at 200C
Dielectric constant
Dipole moment, debye units
Electrical conductivity, mho
conductivity, mho
Freezing point, 0C
Heat of combustion, cal/g
Heat of fusion, cal/g
Heat of vaporization, cal/g

79.6
73.4
88.7
515.6
0.00119
43
260
0.8037
18.51
2.74
5.0 x 10-8
79.6
73.4
88.7
515.6
0.00119
43
260
0.8037
18.51
2.74
5.0 x 10-8
5.0 x 10-8
-86.3
8084
24.7
106
18

Molecular weight
Refractive index nD
Ketone in water
Water in ketone
Solubility parameter
Specific heat, cal/g 0C
Surface tension, dyn/cm

72.104
1.3791
26.3
11.8
9.3
0.549
24.6

Table 1.1: Physical properties of MEK (Arora & Sharma, November 2015)

1.1.2.2

CHEMICAL PROPERTIES

Methyl Ethyl ketone can be widely utilized in chemical synthesis. Its reactivity centers
around the carbonyl group and its adjacent hydrogen atoms. Condensation, ammonolysis,
halogenations, and oxidation can be carried out under the proper conditions. Some typical
reactions are described below.

Figure 2.5: Chemical reaction of MEK

Self-Condensation:
Aldol condensation of 2 moles of MEK yields a hydroxy ketone, which readily dehydrates to
an unsaturated ketone:
Condensation with other Compounds:
Reaction with aldehydes gives higher ketones, as well as ketals and cyclic compounds,
depending on reaction conditions. - ii ketones are produced by the condensation of MEK with
aliphatic esters. MEK condenses with glycols and organic oxides to give derivatives of
dioxolane. Sec-Butyl amine is formed by reacting MEK with aqueous ammonia and hydrogen:
19

Figure 1.6: Reaction of MEK with ammonia and hydrogen.

An excess of MEK in this reaction will produce di-sec-butyl amine. Reacting MEK with
acetylene gives methyl pentynol, a hypnotic compound:

Figure 1.7: Reaction of MEK with acetylene. (Arora & Sharma, November 2015)

Halo form reaction:

This is a chemical reaction where a halo form (CHX3, where X is a halogen) is produced by
the exhaustive halogenation of a methyl ketone (a molecule containing the RCOCH3 group) in
the presence of a base. R may be alkyl or aryl. The reaction can be used to produce chloroform
(CHCl3), bromoform (CHBr3), or iodoform (CHI3).
This reaction was traditionally used as a chemical test for qualitative organic analysis to
determine the presence of a methyl ketone, or a secondary alcohol oxidizable to a methyl ketone
through the iodoform test. In organic chemistry, this reaction may be used to convert a terminal
methyl ketone into the analogous carboxylic acid. (L. Cao, 2015)

Figure 1.8: Halo form reaction

20

Miscellaneous Reactions
Oxidation of MEK with oxygen produces diacetyl, a flavoring material. Chlorination yields
mixtures of several monochloro and dichloride derivatives in various percentages depending on
reaction conditions. The reaction of MEK with hydrogen peroxide gives a mixture of peroxides
and hydro peroxides which is used to cure polyester resins at room temperature:

Figure 1.9: Chemical reaction of MEK with hydrogen peroxide

MEK peroxides are widely used as catalysts for the polymerization of polyester resins at
room temperature. The condensation product of MEK and m-phenyl diamine is an efficient
curing agent for epoxy resins. MEK and cobalt acetate function together as a specific catalyst for
single-stage oxidation of p-xylene to terephthalic acid. Aliphatic monoketones, such as MEK
also function as catalysts in the polymerization of polyethylene terephthalate where, it is
claimed, they speed condensation times and cause less yellowing of the polymer than antimony
trioxide. MEK is also used in the preparation of complex catalysts used in the syndiotacic
polymerization of - olefins such as propylene. Phenol, glyoxal, formaldehyde, acetaldehyde,
furfuraldehyde, and other chemicals can be reacted with MEK to form resins useful for
adhesives, coatings, molded products, and electrical insulation. MEK reacts with acrylonitrile to
produce a dinitrile, which upon hydrogenation produces amines. (Perona, 2004)

1.1.3 INDUSTRIAL APPLICATION OF METHYL ETHYL KETONE (MEK)

1.1.3.1 as a solvent:
Butanone is an effective and common solvent and is used in processes involving gums,
resins, and cellulose acetate and nitrocellulose coatings and in vinyl films. For this reason it finds
use in the manufacture of plastics, textiles, in the production of paraffin wax, and in household
products such as lacquer, varnishes, paint remover, a denaturing agent for denatured alcohol,
21

glues, and as a cleaning agent. It has similar solvent properties to acetone but has a significantly
slower evaporation rate. Butanone is also used in dry erase markers as the solvent of the erasable
dye. (wikipedia, industrial application of MEK, 2015)
1.1.3.2 as a welding agent:
As butanone dissolves polystyrene, it is sold as "polystyrene cement" for use in connecting
together parts of scale model kits. Though often considered an adhesive, it is actually functioning
as a welding agent in this context. (wikipedia, industrial application of MEK, 2015)

MEK is consumed in large quantities in a variety of industries. Some industries and their
various application of MEK is listed below.
INDUSTRY
Adhesive manufacture
Electroplating
Electroplating
Laboratory chemicals
Machinery manufacture and repair
Metal degreasing
Paint manufacture
Paint stripping
Paper coating
Pesticide manufacturing (insecticides)
Printing

APPLICATION
Carpet adhesive solvents
Cold-cleaning solvents
Vapor degreasing solvents
Solvents-extraction
Solvents
Solvents
Solvents
Solvents
Solvents
Solvents
Solvents for flexography and gravure printing

Table 1.2: industrial application of MEK (Arora & Sharma, November 2015)

1.2 AIM AND OBJECTIVES OF THE DESIGN PROJECT

The aim of this design is to design a plant with a capacity of 36,000kg/day that produces
Methyl Ethyl Ketone (MEK) of 99.9% purity by vapour phase catalytic dehydrogenation of 2butanol.
The objectives of the design project are to:

Design a plant for the continuous production process of MEK;

22

1.3

Use cost efficient and optimal energy methods for production;

Obtain a high percentage purity of the product;

Incorporate zinc-oxide brass as the reaction catalyst;

Calculate the material and energy balances of the plant;

Obtain mechanical and chemical design of the plant; and

Perform HAZOP analysis of process equipments

SIGNIFICANCE OF WORK
Methyl Ethyl Ketone (MEK) is a highly useful and sought after solvent whose application

cut across so many industries such as paints,coating, printing and machinery industries. The
design project would to a large extent bring clearer insight on the use of vapour phase
dehydrogenation of 2-butanol to maximise the production of MEK.

1.4

SCOPE OF WORK
This Report tries to show how economics, safety, environmental considerations and

operability influence the choices taken in conveyig the task to fulfilment and also the various
contributions made by the various areas of study which includes;

Process Design- this area involves a well detailed Process flow Diagrams (PFD), Detailed

Equipment lists, An estimated cost list for the equipment, a detailed material balance and an
overall Energy balance for all the plant items.

Mechanical Design- Provision of recommendations on the mechanical design of the

secondary alcohol vaporizer, absorber, distillation column etc and preparation of mechanical
design specifications for key processes

Chemical Engineering Design- Preparation of a detailed chemical Engineering design of

all items of equipment and a design specification sheet for all the items.

23

1.5

LIMITATIONS OF WORK

The limitation of this design project is that one is limited to only use one process of
producing methyl ethyl ketone which is the vapor phase catalytic dehydrogenation of 2Butanol

MEK has come under fire due to some of its properties. It has been touted of being toxic
to the ozone layer thereby leading to global warming; it has also been linked to being
carcinogenic even though this has not been proved. Some countries have placed MEK on
their Hazard control lists.

24

CHAPTER TWO
2. THEORETICAL PRINCIPLES AND LITERATURE REVIEW
2.1 THEORETICAL PRINCIPLES
2.1.1PRINCIPLES OF DISTILLATION:
Distillation is separation process based on a strategy of isolating the constituents of mixture
(either a fluid or gaseous). It is a physical process and not a chemical process utilizing the
difference in the boiling temperatures of the constituents to separate them from the each other. In
this project, we are dealing with alcoholic distillation, a way of separating secondary alcohol, 2buatanol can be separated from Methyl ethyl ketone (MEK) based on the boiling points (79.64
C (175.35 F; 352.79 K) for MEK and 98 to 100 C; 208 to 212 F; 371 to 373 K for 2-butanol).
(wikipedia, 2-Butanol, 2015)
Distillation can take place either in pure components also known as a complete separation or in a
partial separation. Distillation in the production of methyl ethyl ketone for dehydrogenation of 2butanol as a separation process is inevitable. Also, distillation separation of components from a
liquid mixture depends on certain characteristics of the components such as differences in
boiling points of the individual components, concentrations of the components present, depends
on the vapour pressure characteristics of liquid mixtures, difference in volatility between the
components. (Tham, 2009)

3 Relative Volatility
Relative volatility is a measure comparing the vapor pressures of the components in a
liquid mixture of chemicals. (https://en.wikipedia.org/wiki/Relative_volatility, Retrieved October
2015). For a liquid mixture of two components (called a binary mixture) at a
given temperature and pressure, the relative volatility is defined as:
( )

= ( ) =

Where,
= the relative volatility of the more volatile component to the less volatile
component

25

= the vaporliquid equilibrium concentration of component in the vapor phase

= the vaporliquid equilibrium concentration of component in the liquid phase
= the vaporliquid equilibrium concentration of component

in the vapor phase

= the vaporliquid equilibrium concentration of component

in the liquid phase

= Henry's law constant (also called the K value or vapor-liquid distribution ratio)
of a component

Figure 2.1: Diagram of a Distillation Column

26

2.1.2 COMPRESSORS
Compressors are similar to pumps: both increase the pressure on a fluid and both can transport
the fluid through a pipe. As gases are compressible, the compressor also reduces the volume of a
gas. Liquids are relatively incompressible; while some can be compressed, the main action of a
pump is to pressurize and transport liquids. (Perry et al, 2007)
2.1.2.2TYPES OF COMPRESSORS
2.1.2.3 CENRTIFUGAL COMPRESSORS
Centrifugal compressors use a rotating disk or impeller in a shaped housing to force the gas to
the rim of the impeller, increasing the velocity of the gas. A diffuser (divergent duct) section
converts the velocity energy to pressure energy. They are primarily used for continuous,
stationary service in industries such as oil refineries, chemical and petrochemical plants and
natural gas processing plants. (Dixon, 1978) Their application can be from 100 horsepower (75
kW) to thousands of horsepower. With multiple staging, they can achieve high output pressures
greater than 10,000 psi (69 MPa).
Many large snowmaking operations (like ski resorts) use this type of compressor. They are also
used in internal combustion engines as superchargers and turbochargers. Centrifugal
compressors are used in small gas turbine engines or as the final compression stage of mediumsized gas turbines. (Aungier,2000)
2.1.2.4 DIAGONAL COMPRESSORS
Diagonal or mixed-flow compressors are similar to centrifugal compressors, but have a radial
and axial velocity component at the exit from the rotor. The diffuser is often used to turn
diagonal flow to an axial rather than radial direction.
2.1.2.5 RECIPROCATING COMPRESSORS
Reciprocating compressors use pistons driven by a crankshaft. They can be either stationary or
portable, can be single or multi-staged, and can be driven by electric motors or internal
combustion engines. Small reciprocating compressors from 5 to 30 horsepower (hp) are
commonly seen in automotive applications and are typically for intermittent duty. Larger
reciprocating compressors well over 1,000 hp (750 kW) are commonly found in large industrial
27

and petroleum applications. Household, home workshop, and smaller job site compressors are
typically reciprocating compressors 1 hp or less with an attached receiver tank. (Bloch et al,
1996)
Other types of compressors include:

IONIC LIQUID PISTION COMPRESSORS

ROTARY SCREW COMPRESSORS

ROTARY VANE COMPRESSORS

SCROLL COMPRESSORS

DIAPHGRAM COMPRESSORS

AIR BUBBLE COMPRESSOR

28

2.1.3 LIQUID LIQUID EXTRACTION:

Liquidliquid extraction (LLE) consists in transferring one (or more) solute(s) contained in a
feed solution to another immiscible liquid (solvent). The solvent that is enriched in solute(s) is
called extract. The feed solution that is depleted in solute(s) is called raffinate.

Figure 2.2: liquid liquid extraction column (wikipedia/liquid liquid extraction column, 2015)
Liquidliquid extraction is a basic technique in chemical laboratories, where it is performed
using a variety of apparatus, from separatory funnels to countercurrent distribution
equipment.This type of process is commonly performed after a chemical reaction as part of the
work-up.
The term partitioning is commonly used to refer to the underlying chemical and physical
processes involved in liquidliquid extraction, but on another reading may be fully synonymous
with it. The term solvent extraction can also refer to the separation of a substance from a mixture
by preferentially dissolving that substance in a suitable solvent. In that case, a soluble compound
is separated from an insoluble compound or a complex matrix. (chemwiki, 2015)

29

Solvent extraction is used in nuclear reprocessing, ore processing, the production of fine
organic compounds, the processing of perfumes, the production of vegetable oils and biodiesel,
and other industries.
Liquidliquid extraction is possible in non-aqueous systems: In a system consisting of a
molten metal in contact with molten salts, metals can be extracted from one phase to the other.
This is related to a mercury electrode where a metal can be reduced, the metal will often then
dissolve in the mercury to form an amalgam that modifies its electrochemistry greatly. For
example, it is possible for sodium cations to be reduced at a mercury cathode to form sodium
amalgam, while at an inert electrode (such as platinum) the sodium cations are not reduced.
Instead, water is reduced to hydrogen. A detergent or fine solid can be used to stabilize an
emulsion, or third phase In solvent extraction, a distribution ratio is often quoted as a measure of
how well-extracted a species is. The distribution ratio (D) is equal to the concentration of a
solute in the organic phase divided by its concentration in the aqueous phase. Depending on the
system, the distribution ratio can be a function of temperature, the concentration of chemical
species in the system, and a large number of other parameters. Note that D is related to the G of
the extraction process.
In solvent extraction, two immiscible liquids are shaken together. The more polar solutes
dissolve preferentially in the more polar solvent, and the less polar solutes in the less polar
solvent.
After performing liquid-liquid extraction, a quantitative measure must be taken to determine
the ratio of the solutions total concentration in each phase of the extraction. This quantitative
measure is known as the distribution ratio or distribution coefficient. (chemwiki, 2015)
Separation factors:
The separation factor is one distribution ratio divided by another; it is a measure of the
ability of the system to separate two solutes. For instance, if the distribution ratio for nickel (DNi)
is 10 and the distribution ratio for silver (DAg) is 100, then the silver/nickel separation factor
(SFAg/Ni) is equal to DAg/DNi = SFAg/Ni = 10. (chemwiki, 2015)

30

Decontamination factor:
This is used to express the ability of a process to remove a contaminant from a product. For
instance, if a process is fed with a mixture of 1:9 cadmium to indium, and the product is a 1:99
mixture of cadmium and indium, then the decontamination factor (for the removal of cadmium)
of the process is 0.11 / 0.01 = 11 (chemwiki, 2015)
2.1.4 PRINCIPLES OF SEPARATION:
In chemistry and chemical engineering, a separation process, or a separation technique, or
simply a separation, is a method to achieve any mass transfer phenomenon that converts a
mixture of substances into two or more distinct product mixtures (which may be referred to as
fractions) at least one of which is enriched in one or more of the mixture's constituents. In some
cases, a separation may fully divide the mixture into its pure constituents. Separations are carried
out based on differences in chemical properties or physical properties such as size, shape, mass,
density, or chemical affinity, between the constituents of a mixture. They are often classified
according to the particular differences they use to achieve separation. (wikipedia, 2015)
SEPARATOR:
A vaporliquid separator is a device used in several industrial applications to separate a
vaporliquid mixture. A vaporliquid separator may also be referred to as a flash drum, knockout drum, knock-out pot, compressor suction drum or compressor inlet drum. When used to
remove suspended water droplets from streams of air, it is often called a demister.
Method of operation:
For the common variety, gravity is utilized in a vertical vessel to cause the liquid to settle to
the bottom of the vessel, where it is withdrawn.
In low gravity environments such as a space station, a common liquid separator will not
function because gravity is not usable as a separation mechanism. In this case, centrifugal force
needs to be utilized in a spinning centrifugal separator to drive liquid towards the outer edge of
the chamber for removal. Gaseous components migrate towards the center.

31

For both varieties of separator, the gas outlet may itself be surrounded by a spinning mesh
screen or grating, so that any liquid that does approach the outlet strikes the grating, is
accelerated, and thrown away from the outlet.
The vapor travels through the gas outlet at a design velocity which minimizes the
entrainment of any liquid droplets in the vapor as it exits the vessel. The feed to a vaporliquid
separator may also be a liquid that is being partially or totally flashed into a vapor and liquid as it
enters the separator. (MIT, 2015)

Figure 2.3: A vapour liquid separator (wikipedia, 2015)

2.1.5 Vapor Pressure

The vapor pressure of a liquid at a particular temperature is the equilibrium pressure
exerted by molecules leaving and entering the liquid surface. (Tham, 2009) Special points
regarding vapor pressure are as follows:

Energy input raises vapor pressure

Vapor pressure is related to boiling

The ease with which a liquid boils depends on its volatility

32

The vapor pressure and hence the boiling point of a liquid mixture depends on the relative
amounts of the components in the mixture.

Distillation occurs because of the differences in the volatility of the components in the
liquid mixture.

Boiling Point Diagram

Boiling point diagram shows how the equilibrium compositions of the components in a
liquid mixture vary with temperature at a fixed pressure.

Figure 2.4: A boiling point diagram shows how the equilibrium compositions of the components
in a liquid mixture vary with temperature at a fixed pressure. (Tham, 2009)

The boiling point of A is that at which the mole fraction of A is 1. The boiling point of B is
that at which the mole fraction of A is 0. In this example, A is the more volatile component and
therefore has a lower boiling point than B. The upper curve in the diagram is called the dew-point
curve while the lower one is called the bubble-point curve. The dew-point is the temperature at
which the saturated vapour starts to condense. The bubble-point is the temperature at which the
liquid starts to boil. The region above the dew-point curve shows the equilibrium composition of
the superheated vapour while the region below the bubble-point curve shows the equilibrium
composition of the sub-cooled liquid. (Tham, 2009)
The difference between liquid and vapour compositions is the basis for distillation operations.
2.1.6 PRINCIPLES OF ABSORPTION:
Absorption, or gas absorption, is a unit operation used in the chemical industry to separate
gases by washing or scrubbing a gas mixture with a suitable liquid. The absorbent used for this
project is water.
33

The fundamental physical principles underlying the process of gas absorption are the
solubility of the absorbed gas and the rate of mass transfer. One or more of the constituents of
the gas mixture dissolves or is absorbed in the liquid and can thus be removed from the mixture.
In some systems, this gaseous constituent forms a physical solution with the liquid or the solvent,
and in other cases, it reacts with the liquid chemically. (wikipedia, absorption_chemistry, 2015)
The purpose of such scrubbing operations may be any of the following: gas purification
(e.g., removal of air pollutants from exhausts gases or contaminants from gases that will be
further processed), product recovery, or production of solutions of gases for various purposes.
Gas absorption is usually carried out in vertical counter current columns. The solvent is fed
at the top of the absorber, whereas the gas mixture enters from the bottom .The absorbed
substance is washed out by the solvent and leaves the absorber at the bottom as a liquid solution .
The solvent is often recovered in a subsequent stripping or desorption operation. This second
step is essentially the reverse of absorption and involves counter current contacting of the liquid
loaded with solute using and inert gas or water vapor. (Terry, 2015)
The absorber may be a packed column, plate column, spray column , venturi scrubbers ,
bubble column , falling films , wet scrubbers ,stirred tanks. Tray absorbers are used in
applications where tall columns are required, because tall, random-type packed towers are
subject to channeling and maldistribution of the liquid streams. Plate towers can be more easily
cleaned. Plates are also preferred in applications having large heat effects since cooling coils are
more easily installed in plate towers and liquid can be withdrawn more easily from plates than
from packings for external cooling. Tray columns have got some disadvantage. These are slow
reaction rate processes, higher pressure drops than packed beds and plugging and fouling may be
occur. (Terry, 2015)
2.1.7 PRINCIPLES OF VAPOURIZATION:
A phase transition is the transformation of a thermodynamic system from one phase or state
of matter to another one by heat transfer. The term is most commonly used to describe transitions
between solid, liquid and gaseous states of matter, and, in rare cases, plasma. A phase of a

34

thermodynamic system and the states of matter have uniform physical properties. The change
from liquid to gas is vapourization.
Vaporization happens at any boiling point. It occurs in two forms; Evaporation and Boiling.
It is a phase transition from the liquid phase to vapor (a state of substance below critical
temperature and critical pressure) that occurs at temperatures below the boiling temperature at a
given pressure. Evaporation usually occurs on the surface.
Evaporation may occur when the partial pressure of vapor of a substance is less than the
equilibrium vapour pressure.
We define the evaporation process as one that starts with a liquid product and ends up with a
more concentrated, but still liquid and still pumpable concentrate as the main product from the
process. It occurs at the liquids surface. (Adams, 1926)
The major requirement in the field of evaporation technology is to maintain the quality of
the liquid during evaporation and to avoid damage to the product. This may require the liquid to
be exposed to the lowest possible boiling temperature for the shortest period of time. The most
common types of evaporators are:
1.

Falling Film Evaporators

2.

Rising Film Evaporators

3.

Forced Circulation Evaporators

4.

Plate Evaporators
Boiling is a phase transition from the liquid phase to gas phase that occurs at or above the

boiling temperature. Boiling, as opposed to evaporation, occurs below the surface.

Boiling is a

rapid vaporization that occurs at or above the boiling temperature and at or below the liquid's
surface.

35

The boiling point corresponds to the temperature at which the vapour pressure of the liquid
equals the atmospheric pressure. If the liquid is open to the atmosphere (that is, not in a sealed
vessel), it is not possible to sustain a pressure greater than the atmospheric pressure, because the
vapour will simply expand until its pressure equals that of the atmosphere. For this reason,
boiling point varies with the pressure of the environment. Evaporation is a surface phenomenon
whereas boiling is a bulk phenomenon. (wikipedia, vapourization, 2015)
2.1.8 CATALYSIS:
Catalysts are substances that speed up a reaction but which are not consumed by it and do
not appear in the net reaction equation. In addition, catalysts affect the forward and reverse rates
equally; this means that catalysts have no effect on the equilibrium constant and thus on the
composition of the equilibrium state. (sciencezen, 2015)
Catalysts function by allowing the reaction to take place through an alternative mechanism
that requires a smaller activation energy. This change is brought about by a specific interaction
between the catalyst and the reaction components. Recall that the rate constacnt of a reaction is
an exponential function of the activation energy, so even a modest reduction of E a can yield an
impressive increase in the rate.
Catalysts are conventionally divided into two categories: homogeneous and heterogeneous.
Enzymes, natural biological catalysts, are often included in the former group, but because they
share some properties of both but exhibit some very special properties of their own they are
treated here as a third category. (chemwiki/catalysis, 2015)

2.1.9 HEAT TRANSFER

Basics of Heat Transfer
In the simplest of terms, the discipline of heat transfer is concerned with only two things:
temperature, and the flow of heat. Temperature represents the amount of thermal energy
available, whereas heat flow represents the movement of thermal energy from place to place.
(Efunda, 2015)

36

On a microscopic scale, thermal energy is related to the kinetic energy of molecules. The
greater a material's temperature, the greater the thermal agitation of its constituent molecules
(manifested both in linear motion and vibrational modes). It is natural for regions containing
greater molecular kinetic energy to pass this energy to regions with less kinetic energy.
Several material properties serve to modulate the heat transferred between two regions at
differing temperatures. Examples include thermal conductivities, specific heats, material
densities, fluid velocities, fluid viscosities, surface emissivity, and more. Taken together, these
properties serve to make the solution of many heat transfer problems an involved process.
(Efunda, 2015)
Heat Transfer Mechanisms
Heat transfer mechanisms can be grouped into 3 broad categories namely:
1. Conduction
2. Convection
3. Radiation.
Conduction:
Regions with greater molecular kinetic energy will pass their thermal energy to regions
with less molecular energy through direct molecular collisions, a process known as conduction.
In metals, a significant portion of the transported thermal energy is also carried by conductionband electrons. (wikipedia, conduction, 2015)
Convection:
When heat conducts into a static fluid it leads to a local volumetric expansion. As a result
of gravity-induced pressure gradients, the expanded fluid parcel becomes buoyant and displaces,
thereby transporting heat by fluid motion (i.e. convection) in addition to conduction. Such heatinduced fluid motion in initially static fluids is known as free convection. (wikipedia,
wikipedia/convection, 2015)
Radiation:
All materials radiate thermal energy in amounts determined by their temperature, where the
energy is carried by photons of light in the infrared and visible portions of the electromagnetic
spectrum. When temperatures are uniform, the radiative flux between objects is in equilibrium

37

and no net thermal energy is exchanged. The balance is upset when temperatures are not
uniform, and thermal energy is transported from surfaces of higher to surfaces of lower
temperature. (wikipedia, wikipedia/radiation, 2015)
Heat exchanger is a device built for heat transfer from one medium to another. Diagram of
a Heat exchanger is shown below.

Figure 2.5: Heat exchanger Heat exchanger (Alaqua, 2015)

2.1.9 CONDENSATION:
Condensation is the change of the physical state of matter from gas phase into liquid phase. It
can also be defined as the change in the state of water vapor to liquid water when in contact with
a liquid or solid surface or cloud condensation nuclei within the atmosphere. When the transition
happens from the gaseous phase into the solid phase directly, the change is called deposition.
Condensation is deposition of a liquid or a solid from its vapour, generally upon a surface that is
cooler than the adjacent gas. A substance condenses when the pressure exerted by its vapour
exceeds the vapour pressure of the liquid or solid phase of the substance at the temperature of the
surface where condensation occurs. Heat is released when a vapour condenses. Unless this heat
is removed, the surface temperature will increase until it is equal to that of the surrounding
vapour.

38

Partial condensation is a separation operation used when the feed mixture consists of different
chemical species that have different tendencies to condensate/evaporate (different boiling point).
By removing heat from a gas feed mixture, part of components will condensate, thus the partial
condensation. The liquid has the tendency to go on the bottom of the fraction column and the
vapors will have the tendency to separate from the liquid and move to the top of the column.
The property that makes this separation possible is the volatility of the components. A
component with a higher volatility will evaporate faster, and thus has the tendency to move up to
the top of the column. The components with a lower volatility will remain on the bottom of the
column, as a liquid phase.
The main problem with this kind of separation is that usually, the components have a low
volatility range which means it is quite difficult to perform the operation of separation through
only one partial condensation/vaporization process. (WW2010, 2015)
2.2 LITERATURE REVIEW
2.2.1 SELECTION OF PROCESS ROUTE:
There are various ways in which MEK can be produced some of the methods are listed below
and emphasis made on the preferred one.
1. Vapor phase catalytic dehydrogenation of 2- Butanol.
2. Liquid phase oxidation of n-Butane.
3. Direct oxidation of n-Butanes, Hoechst-Wacker process.
4. Direct oxidation of n-Butanes, Maruzen process
Commercially, MEK is predominantly produced by the catalytic dehydrogenatio of SBA in
vapor phase over ZnO or Brass catalyst. It can, however be produced by the selective direct
oxidation of the olefin in a variety of processes, including the HoechstWacker-type process
employing a palladium(II) catalyst .
Most MEK (88%) is produced today by dehydrogenation of 2-butanol. 2-butanol can be easily
produced by the hydration of n-butenes(from petrochemically produced C4 raffinates). The
39

remaining MEK is produced by process in which liquid butane is catalytically cracked giving
both acetic acid and MEK.
The vapor phase dehydrogenation process gives high conversion of 2-butanol and high
selectivity of MEK of about 95 mole%. Other advantages of this process include better yield,
longer catalyst life, simple production separation and lower energy consumption.
Of all the processes, it has been found that dehydrogenation of 2-butabol has more advantages
and is more economical compared to other processes, so this process has been selected for
design. The process is further explained below.
VAPOR PHASE DEHYDROGENTAION OF 2-BUTANOL:
MEK is prepared by vapor phase dehydrogenation of 2-butanol. A 2 step process from butanes ,
which are first hydrated to give 2-butanol, is used. The dehydrogenation of 2-butanol is an
exothermic reaction (51 KJ/Kgmol). The reaction is as follows.

Figure2.6: Dehydrogenation of 2-butanol.

The equilibrium constant for 2-butanol can be calculated as follows:
log Kp = -2790/T + 1.51*log T + 1.856
Where T = reaction temperature, K

Kp= equilibrium constant, bar.

The MEK concentration in the reaction mixture increases and reaches its maximum at
approximately 3500C. Copper, Zinc or Bronze are used as catalysts in gas phase
dehydrogenation. Commercially used catalysts are reactivated by oxidation, after 3 to 6 months
use. They have a life expectance of several years.

40

Sec-butyl alcohol is dehydrogenated in a multiple tube reactor, the reaction heat being supplied
by heat transfer oil. The reaction products leave the reactor as gas and are split into crude MEK
and hydrogen on cooling. The hydrogen is purified by further cooling. The crude MEK is
separated from uncreated reactants and by-products by distillation.
LIQUID PHASE OXIDATION OF n-BUTANE
MEK is produced as a by-product in the liquid phase oxidation of n-butane to acetic acid. Autoxidation
of n-butane takes place in the liquid phase according to the radical mechanism yielding MEK as an
intermediate and acetic acid as end-product with mass ratio 0.2:1.0 by non-catalyzed liquid phase
oxidation at 180oC and 53 bars with remixing. Continuous oxidation under plug flow conditions at
150oC, 65 bars and a residence time of 2-7 minutes forms MEK and acetic acid at a mass ratio of 3:1.
DIRECT OXIDATION OF n-BUTENES (HOECHST-WACKER PROCESS)

In direct oxidation of n-butanes by Hoechst-Wacker process, oxygen is transferred in a

homogenous phase on to n-butenes using redox salt pair, PdCl2 / CuCl2. 95 per cent conversion of nbutanes can be obtained with MEK selectivity of about 86 percent.
Disadvantages of the process are:

Formation of chlorinated butanone and n-butryaldehyde; and

Causes corrosion due to free acids.

DIRECT OXIDATION OF n-BUTANES, MARUZEN PROCESS

The Maruzen process is similar to the Hoechst-Wacker process except that oxygen is transferred by an
aqueous solution of palladium sulphate and ferric sulphate. The process is commercially good to get
MEK via direct oxidation of n-butenes, but is generally not accepted due to formation of undesirable by
products. The process is patented and not much information is available.

41

2.2.2 REVIEW OF PAST WORKS ON MEK PRODUCTION FROM

DEHYDROGENATION OF 2-BUTANOL.
1. Dehydrogenation of Sec-Butanol to Methyl Ethyl Ketone over Cu-ZnO Catalysts
Prepared by Different Methods: Co-precipitation and Physical Mixing
Cu-ZnO catalysts prepared by co-precipitation and physical mixing methods were
characterized to investigate the roles of ZnO by X-ray diffraction (XRD), N2O chemisorption
decomposition and evaluated for the vapour-phase dehydrogenation of sec-butanol (SBA) to
methyl ethyl ketone (MEK). ZnO not only could disperse Cu species, but also prevent Cu0
from sintering. Cu-ZnO catalyst by co-precipitation method exhibited excellent reactivity.
(Yun Feng Hu, 2013)
2. The production of methyl ethyl ketone from n-butene
In this preliminary design the production of methyl ethyl ketone (MEK) from normal butene,
with secondary butyl alcohol (SBA) as intermediate, is described. This design is split into
two parts. In the first part SBA is obtained from n-butene by absorption in sulphuric acid,
followed by hydrolysis with water. Sulphuric acid and SBA are separated in a stripper. The
sulphuric acid is reconcentrated and recycled to the absorber. The SBA is purified in an
azeotropic distillation unit, using di-isobutylene as entrained. In the second part of the design,
SBA is vaporized and fed to a multitubular, isothermal reactor, filled with a Cu/Ni on SiO2
catalyst. The SBA is dehydrogenized; forming MEK and hydrogen. The hydrogen is purified
and sold as a valuable by-product. The MEK is purified in two fractionation columns and
obtained with a purity of 99.1 wt."-%. The capacity of the plant is 33,731 tons of MEK per
year. An economic evaluation shows that this plant can pay itself back within approximately
1.5 to 2 years. (A.H. Amer, 1988)

42

CHAPTER 3
3.0 MATERIAL BALANCES FOR THE PROCESS
3.1 INTRODUCTION:
Material balances are the basis of process design. A material balance taken over the
complete process will determine the quantities of raw materials required and products produced.
Balances over individual process units set the process stream flows and compositions. Material
balances are also useful tools for the study of plant operation and trouble shooting. They can be
used to check performance against design; to extend the often limited data available from the
plant instrumentation; to check instrument calibrations; and to locate sources of material loss.
All mass/material balances are based on the principle of conservation of mass that is massr
can neither be created nor destroyed with an exception of nuclear processes according to
Einsteins equation; E=mc2.
The general conservation equation for any process system can be written as:
Material out Material in + Generation Consumption = Accumlation
For a steady state process the accumulation term is zero and thus for a continuous steady
state process, the general balance equation for any substance involved in the process can be
written as:
Material in + Generation = Material out + Consumption
If no chemical reaction takes place, material balance is computed on the basis of chemical
compounds mass basis that are used whereas if a chemical reaction occurs molar units are used.
Also it is worthwhile to note that when a reaction occurs an overall balance is not
appropriate but a reactant balance (a compound balance) is.
a.

PROCESS DESCRIPTON

Pre-Heater

In the dehydrogenation of 2-butanol, the cold feed of 2-Butanol is mixed with recycle stream and
then pumped from the feed tank to a steam heater and heated up to 373K (stream1), the heating
medium being used is dry saturated steam at 140C.
43

Vaporizer

This Stream 1 is further fed to thermo-syphon vaporizer which is heated by the reactor vapor.
The heating medium in vaporizer is heated reaction products discharged from the reactor at
673K i.e. (Stream 5) and itself gets cooled down to 425K.

Knock-Out Drum

Stream 2 is further fed to knockout drum to remove entrained liquid which is recycled back to
the vaporizer. Knockout drum consists of a hollow vertical drum having inclined sieve plates
known as demister for the passage of clean gas. Separation in knock-out drum is based on the
principle of density difference of the liquid and the clean gas.

Super-Heater 1

The dry alcohol vapours are fed to the super-heater 1 where they are heated to increase the
temperature of the vapours to 573K. The vapours are heated with the help of flue gases at high
temperature of 813K.

Compressor

The superheated vapours are then compressed with the help of a compressor to increase the
pressure as well as increasing the temperature of the vapours.

Super-Heater 2

The compressed vapours are then fed to the super-heater 2 to increase the vapours temperature of
773K with the help of flue gases at 813K high temperature.

Reactor

The superheated vapours are fed to the reactor in which the butanol is dehydrated to produce
MEK and hydrogen, according to the reaction:
CH3CH2CH3CHOH

CH3CH2CH3CO + H2

The conversion of alcohol to MEK is 90 per cent and the yield is taken as 100 per cent. Initially,
preheated vapours of secondary-butyl alcohol are passed through a reactor (Step 1) containing a
catalytic bed of zinc oxide or brass (zinc-copper alloy) which is maintained between 400C and
44

500C. A mean residence time of two to eight seconds at normal atmospheric pressures is
required for conversion from secondary-butyl alcohol to MEK.

Partial Condenser

The reaction product from the reactor are cooled to a suitable temperature in the vaporizer and
the cooled products are then fed to the condenser where almost 80% of the MEK and unreacted
2-butanol are condensed and sent to the distillation column while the non-condensable hydrogen
with the un-condensed MEK and unreacted 2-butanol are sent to the absorber.

Absorption Column

In the absorption column the uncondensed MEK and alcohol are absorbed in water. Around 98
per cent of the MEK and alcohol can be considered to be absorbed in this unit, giving a 10 per
cent w/w solution of MEK. The water feed to the absorber is recycled from the next unit, the
extractor. The vent stream from the absorber, containing mainly hydrogen, are dried and used as
a furnace fuel.

Extraction Column

In the extraction column the MEK and alcohol in the solution from the absorber are extracted
into tri-chloro-ethylane (TCE). The raffinate, water containing around 0.5 per cent w/w MEK, is
recycled to the absorption column. The extract, which contains around 20 per cent w/w MEK,
and a small amount of butanol and water, is fed to the solvent recovery.

Solvent Recovery

In the solvent recovery, the unit separates the MEK and alcohol from the solvent TCE. The
solvent containing a trace of MEK and water is recycled to the extraction column. The bottom
product is solvent, i.e. 1, 1, 2-trichloroethane and the distillate from this column (Stream 15) is
MEK and alcohol. The recovery of solvent is 99.9%. The solvent is first cooled down to room
temperature and then fed to the extraction column.

Distillation Column

The distillate from the solvent recovery column is fed to this distillation column along with the
condensate from partial condenser containing MEK and 2-Butanol, which is mixed first and then
45

fed into the column. The distillate is MEK and the bottom product is 2-Butanol. The 2-Butanol
discharged from the bottom of the column will be sent back to the feed tank.

46

FLOW SHEET FOR THE PRODUCTION OF

METHYL ETHYL KETONE
Make up water

6
169KPa
642 K
2
142KPa
373 K

11
150KPa
300 K

13'
13
121KPa
300 K

18
101KPa
303 K

16

14
300 K

2-butanol feed

17
141
KPa
308
K

P-78

Pre-heater
Storage

1
145KPa
298 K

1'
144KPa
373 K

MEK Storage
Separator

Vaporizer

Reactor
Absorber

3
133KPa
373 K

Pump
3'
131KPa
573 K

5
353KPa
773 K

Cooler

12
101KPa
310 K

15

Distillation Column

Superheater 1
4
355KPa
583 K

Compressor

10
156KPa
335 K

Superheater 2

7
163KPa
398 K

9
299 K

Partial Condenser

Solvent Recovery Column

E-34

Liq-Liq Extraction Column

Separator
19

Figure 3.2 Process flow diagram for production of MEK

3.3 ASSUMPTIONS MADE

1. Material loss between the steam heater and the second super-heater is negligible.
2. Only 98% of the MEK and 2-butanol entering the absorption column is absorbed.
3. MEK is 10% of the absorption product.
4. The raffinate from the extraction column contains 99.5% water, 0.5% MEK and no 2butanol.
5. The extract contains 20% MEK.
6. No spillage across any unit operation.
7. Perfect separation in the absorption column
8. Perfect separation of TCE in the extraction column

47

3.4 MATERIAL BALANCE ACROSS ALL UNIT OPERATIONS

Choosing a Basis:
The correct choice of the basis for a calculation will often determine whether the calculation
proves to be simple or complex.
A time basis was chosen in which the results will be presented. The basis for calculations was
chosen as 1 hour and thus results will be presented in kg/h.
Reactor

2-butanol XF

X (kg)

MEK

Reactor

2-butanol
H2

XR

MATERIAL BALANCE ACROSS REACTOR

IN
Components

Mass Flow

OUT
%

Components

(kg/hr)
MEK
2 Butanol
H2
TOTAL

Mass Flow

(kg/hr)

1720.2

100

1720.2

100

MEK

1506.34

87.567

2 Butanol

172.02

10

H2

41.84

2.432

TOTAL

1720.2

100

TABLE 3.1: MATERIAL BALANCE ACROSS REACTOR

Partial Condenser

MATERIAL BALANCE ACROSS PARTIAL CONDENSER

IN
Components

Mass Flow

OUT
%

Components
48

Mass Flow

(kg/hr)

(kg/hr)
MEK

MEK

1506.33

87.567 condensable

1205.07

70.054

301.27

17.514

137.62

8.000

34.4

1.999

41.84

2.432

1720.2

100

MEK noncondensable
2 Butanol
2 Butanol

172.02

10 condensable
2 Butanol
noncondensable

H2

41.84

TOTAL

2.432 H2

1720.2

100 TOTAL

TABLE 3.2: MATERIAL BALANCE ACROSS PARTIAL CONDENSER

Absorption Column:
MEK= 0.00803

H2O= 1.597

MEK= 0.17513
2-Butanol = 0.02x

Absorption
column 2

MEK= 0.02(0.17513)
Butanol= 0.0004

H2=0.024324

H2= 0.024324

MEK=0.0035

MEK= 0.1716 + 0.00803 = 0.1796

H2O= 1.597 and 2 = 0.0196

MATERIAL BALANCE ACROSS ABSORPTION COLUMN

IN
Components

Mass Flow

OUT
%

Components

49

Mass Flow

(kg/hr)

(kg/hr)
MEK to

MEK noncondensable

extraction
301.27

9.599 column

308.95

9.844

6.02

0.192

MEK
raffinate
stream

13.81

0.440 MEK to drier

2 Butanol

2 Butanol to

non-

extraction

condensable

34.4

1.096 column

33.716

1.074

2 Butanol to
drier
H2

41.84 1.333

H2 to drier

0.6881

0.022

41.84

1.333

H2O to
H2O raffinate
stream

extraction
2747.16

87.532 column

2747.16

87.532

0.1059

0.003

3138.48

100

Negligible
losses
TOTAL

3138.48

100

TABLE 3.3: MATERIAL BALANCE ACROSS ABSORPTION COLUMN

50

Extraction column:
: MEK = 0.00803

Raffinate H2O= 1.597

B
MEK= 0.1796

Extractor

2-butanol= 0.0196x

MEK= 0.17157

2-butanol= 0.0196

H2O= 1.597

TCE= 0.667

R = TC
R- Recycle from next operation (TCE)

MATERIAL BALANCE ACROSS EXTRACTION COLUMN

IN
Components

Mass Flow

OUT
%

Components

(kg/hr)

Mass Flow

(kg/hr)
MEK to
solvent

MEK

308.95

7.291 recovery

295.135

6.965

13.81

0.326

MEK to
absorption
column
2 Butanol to
solvent
2 Butanol
H2O

33.716
2747.16

0.7957 recovery
64.834 H2O

TCE from

TCE to

recycle

solvent

stream

1147.4

27.079 recovery

33.716

0.7957

2747.16

64.834

1147.4

27.079

Negligible
losses
51

0.005

0.0001

TOTAL

4237.226

100

4237.226

100

TABLE 3.4: MATERIAL BALANCE ACROSS EXTRACTION COLUMN

Solvent Recovery Unit:

TCE= 0.667

MEK= 0.17157

2-Butanol = 0.0196x

Solvent
Recovery
Unit

MEK= 0.17157
2-Butanol= 0.0196

TCE= 0.667

MATERIAL BALANCE ACROSS SOLVENT RECOVERY UNIT (DISTILLATION

COLUMN 1)
IN
Components

Mass Flow

OUT
%

Components

(kg/hr)

Mass Flow

(kg/hr)

MEK

295.135

19.992

MEK

295.135

19.992

2 Butanol

33.716

2.284

2 Butanol

33.716

2.284

TCE

1147.4

77.724

TCE

1147.4

77.724

1476.251

100

TOTAL

TOTAL

1476.251

100

TABLE 3.5: MATERIAL BALANCE ACROSS SOLVENT RECOVERY UNIT

(DISTILLATION COLUMN 1)

52

Distillation Column:
MEK= (0.17157 + 0.70054)

Distillation
Column

= 0.872

1500kg/hr. (flow rate as given)

2-Butanol= 0.0196 + 0.08

= 0.0996
2-Butanol (recycled back to the reactor)

MATERIAL BALANCE ACROSS DISTILLATION COLUMN

IN
Components

Mass Flow

OUT
%

Components

(kg/hr)

(kg/hr)

MEK
condensable

Mass Flow

99.9% pure
1205.07

72.093 MEK

1500.2

89.749

MEK from
solvent
recovery unit

295.135

17.656
2 Butanol

2 Butanol
condensable

back to
137.62

8.233 storage tank

171.33

10.249

2 Butanol
from solvent
recovery unit

33.716

2.017
Negligible
losses

TOTAL

1671.541

100 TOTAL

0.011
1671.541

TABLE 3.6: MATERIAL BALANCE ACROSS DISTILLATION COLUMN

Detailed calculations are shown in Appendix B.

53

0.00066
100

CHAPTER 4
a. ENERGY BALANCE FOR THE PLANT
4.1 INTRODUCTION
ENERGY BALANCES
As with mass, energy can be considered to be separately conserved in all but nuclear processes.
The conservation of energy, however, differs from that of mass in that energy can be generated
(or consumed) in a chemical process. Material can change form, new molecular species can be
formed by chemical reaction, but the total mass flow into a process unit must be equal to the
flow out at the steady state. The same is not true of energy. The total enthalpy of the outlet
streams will not equal that of the inlet streams if energy is generated or consumed in the
processes; such as that due to heat of reaction.
Energy can exist in several forms: heat, mechanical energy, electrical energy, and are the total
energy that is conserved.
In process design, energy balances are made to determine the energy requirements of the
process: the heating, cooling and power required. In plant operation, an energy balance (energy
audit) on the plant will show the pattern of energy usage, and suggest areas for conservation and
savings.
A general equation can be written for the conservation of energy:
Accumulation = Energy In + Generation Consumption Energy out
This is a statement of the first law of thermodynamics. An energy balance can be written for any
process step. Chemical reaction will evolve energy (exothermic) or consume energy
(endothermic). For steady-state processes the accumulation of both mass and energy will be zero.
The energy balance was carried out around cooler condenser and the second distillation column.
In chemical processes the kinetic and potential energy terms are usually small compared with
heat and work terms, and can normally be neglected.
If the kinetic and potential energy terms are neglected the energy equation reduces to
54

H2 H1 = Q W
For many processes the work term will be zero, or negligibly small, and equation above reduces
to the simple heat balance equation:
Q = H2 H1
Where heat is generated in the system; for example in a chemical reactor:
Q = QP + QS
QS = Heat generated in the system. If heat is evolved (exothermic processes) QS is taken as
positive, and if heat is absorbed (endothermic processes) it is taken as negative.
QP = Process heat added to the system to maintain required system temperature.
Hence:
QP = H2 H1 QS
H1 = enthalpy of the exit stream
H2 = enthalpy of the outlet stream.
For a practical reactor, the heat added (or removed) Qp to maintain the design reactor
temperature will be given by:
QP= Hproducts Hreactants Qr
Where
Hproducts is the total enthalpy of the product streams, including unreacted materials and byproducts, evaluated from a datum temperature of 25C;
Hreactants is the is the total enthalpy of the feed streams, including excess reagent and inerts,
evaluated from a datum of 25C;

55

Qr is the total heat generated by the reactions taking place, evaluated from the standard heats of
reaction at 25C (298 K).
This equation can be written in the form:
Tout

QP =

Tout

ni cpi dT

Tref

ni cpi dT [H rxn ] mol of product formed

Tref

Cp = A + BT + CT 2 + DT 3
4.2 ENERGY BALANCE ACROSS ALL UNIT OPERATIONS:
ENERGY BALANCE ACROSS COLD FEED PREHEATER
Components

HEAT LOST

Component

HEAT
GAINED

ENERGY

Heat lost by

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

335400

100

dry saturated

Heat load on

335400

100

335400

100

pre heater

steam
TOTAL

335400

100

TABLE 4.1: ENERGY BALANCE ACROSS COLD FEED PREHEATER

ENERGY BALANCE ACROSS VAPORIZER

Components

HEAT LOST

Component

HEAT
GAINED

ENERGY

Heat lost by

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

958000

100

Heat gained

reaction

by 2-butanol

products

feed liquid
56

958000

100

TOTAL

958000

100

958000

100

TABLE 4.2: ENERGY BALANCE ACROSS VAPORIZER

ENERGY BALANCE ACROSS SUPER HEATER 1

Components

HEAT LOST

Component

HEAT
GAINED

ENERGY

Heat lost by

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

538000

100

flue gas

Heat gained

538000

100

538000

100

by 2-butanol
feed vapour

TOTAL

538000

100

TABLE 4.3: ENERGY BALANCE ACROSS SUPER HEATER 1

ENERGY BALANCE ACROSS COMPRESSOR

ENERGY

Heat lost by

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

168650

100

compression

Heat gained

168650

100

168650

100

by 2-butanol
feed vapour

TOTAL

168650

100

TABLE 4.4: ENERGY BALANCE ACROSS COMPRESSOR

ENERGY BALANCE ACROSS SUPER HEATER 2

Components

HEAT LOST

Component
57

HEAT

GAINED
ENERGY

Heat lost by

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

704000

100

flue gas

Heat gained

704000

100

704000

100

by 2-butanol
feed vapour

TOTAL

704000

100

TABLE 4.5: ENERGY BALANCE ACROSS SUPER HEATER 2

ENERGY BALANCE ACROSS REACTOR

Components

HEAT LOST

Component

HEAT
GAINED

ENERGY

Heat lost due

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

1160000

100

Heat gained

to reaction,

by reactor,

Qr

Qp

TOTAL

1160000

1160000

100

1160000

100

TABLE 4.6: ENERGY BALANCE ACROSS REACTOR

ENERGY BALANCE ACROSS CONDENSER

Components

HEAT LOST

Component

HEAT
GAINED

ENERGY

Heat lost due

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

304000

26.32946475

Heat gained
58

1154600

100

to reduction

by cooling

in vapor

water

temperature,
Q1
Heat lost due

742000

64.26468041

108600

9.405854842

1154600

100

to
condensation,
Q2
Heat loss due
to further
cooling of
vapor, Q3
TOTAL

1154600

100

TABLE 4.7: ENERGY BALANCE ACROSS CONDENSER

ENERGY BALANCE ACROSS ABSORBER

Components

HEAT LOST

Component

HEAT
GAINED

ENERGY

Heat of

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

137000

52.9120964

condensation

Heat gained

242299.512

93.58084041

13819.3335

5.337298586

1944.0519

0.750831106

857.1026

0.331029893

by water

of MEK
Heat of

22300

8.612698903

condensation

Heat gained
by MEK

of alcohol
Heat of

120

Heat gained

solution
Heat loss due

by alcohol
99500

38.42885833

negligible
59

to off gases
TOTAL

losses
258920

100

258920

100

TABLE 4.8: ENERGY BALANCE ACROSS ABSORBER

ENERGY BALANCE ACROSS SOLVENT RECOVERY UNIT

Components

HEAT LOST

Component

HEAT
GAINED

ENERGY

Heat Lost by

ENERGY

FLOW

FLOW

(kJ/hr)

(kJ/hr)

75000

15.46391753

feed

Heat gained

272000

56.08247423

52300

10.78350515

160350

33.06185567

350

0.072164948

485000

100

by
condensate

Heat lost by

410000

84.53608247

utility steam

Heat gained
by distillate
Heat gained
by bottom
product

negligible
losses

TOTAL

485000

100

TABLE 4.9: ENERGY BALANCE ACROSS SOLVENT RECOVERY UNIT

ENERGY BALANCE ACROSS DISTILLATION COLUMN

Components

HEAT LOST

Component

HEAT
GAINED

Heat Lost by
feed

161000

5.768541741

Heat gained
by
condensate
60

2415000

86.46443179

Heat lost by

2630000

94.23145826

utility steam

Heat gained

340300

12.18378722

37756

1.351780988

by distillate
Heat gained
by bottom
product

negligible

2056

0.073665353

2791000

100

losses
TOTAL

2793056

100

TABLE 4.10: ENERGY BALANCE ACROSS DISTILLATION COLUMN

ENERGY BALANCE ACROSS COOLER SYSTEM

Heat lost by

233100

90.13921114

distillate

Heat gained

258600

100

258600

100

by cooling
water

Heat lost by

25500

9.860788863

258600

100

bottoms
product
TOTAL

TABLE 4.11: ENERGY BALANCE ACROSS COOLER SYSTEM

Detailed calculations are shown in Appendix B

61

References
1. (2015, November 3). Retrieved from sciencezen: http://www.sciencezen.com/partialcondensation
2. Alaqua. (2015). Heat Exchanger. (Alaqua Inc) Retrieved November 7, 2015, from Alaqua
Inc: http://www.alaquainc/heat_exchanger.com
3. Arora, D., & Sharma, M. (November 2015). Methyl Ethyl Ketone: A TechnoCommercial Profile. Jaypee Institute of Engineering and Technology, Department of
chemical engineering.
4. britannica. (2015, November 5). Retrieved from condenser:
httption://www.britannica.com/condenser
5. catalysis. (2015, November 5). Retrieved from chemwiki:
http://www.chemwiki.ucdavis.edu/complex_reactions/catalysis
6. Davis, A. (2005). Reciprocating compressor basics. In A. Davis, Reciprocating
compressor basics. Noria corporation .
7. Efunda. (2015). Heat transfer:overview. Retrieved November 7, 2015, from Efunda:
http://www.efunda.com/formulae/heat_transfer/home/overview.cfm
8. https://en.wikipedia.org/wiki/2-Butanol. (October 2015). wikipedia/2-Butanol.
(wikipedia, Foundation Inc) Retrieved November 3, 2015, from wikipedia:
https://en.wikipedia.org/wiki/2-butanol
9. https://en.wikipedia.org/wiki/Relative_volatility. (Retrieved October 2015). Relative
Voaltility.
10. Perry, R.H & Green D.W. (2007). Perry chemical engineering handbook. Mc Graw Hill.
11. rhum-agricole. (Retrieved October,2015., October). Distillation.
12. S.L, D. (1978). compressors. In Fluid Mechanics, Thermodynamics of turbomachinery
(third ed). Pergamon Press.
13. Tham, M. T. (2009). Distillation. Distillation Principles.

62

14. Treybal, R. .. (1981). Mass transfer operations. In R. .. Treybal, Mass transfer

operations/absorption (pp. 275,281,282). McGraw hill .
15. wikipedia. (2015, november 5). Retrieved from liquid liquid extraction column:
http://en.wikipedia.org
16. wikipedia. (2015, November 3). Retrieved from separators: http://www.wikipedia.org
17. wikipedia. (2015). wikipedia/convection. (wikipedia, foundation inc) Retrieved
November 6, 2015, from wikipedia: https://en.wikipedia.org/wiki/Convection
18. wikipedia. (2015, Novenmber 4th). wikipedia/MEK-molecular-structure. Retrieved from
Wikipedia: www.wikipedia.com
19. wikipedia. (2015). wikipedia/radiation. (wikipedia, foundation) Retrieved November 6,
2015, from wikipedia: https://en.wikipedia.org/wiki/Radiation

63

APPENDICES
A.

MATERIAL BALANCE:

The material balance was done around the following units:

Reactor

2-butanol XF

MEK

Reactor

X (kg)

2-butanol
H2
XR

RMM of 2-butanol =74

Moles of 2-butanol =

X(kg)
74

= 0.01351x

Moles of the2-Butanol that reacted 0.90 0.01351x = 0.012162x

From the equation:
CH3CH2CH3CHOH

Yields

CH3CH2CH3CO + H2

Mole ratio for the reaction is 1:1

Hence moles of the MEK reacting is 1 (0.012162x) = 0.012162x
Mass of MEK then is 0.012162x 72=0.875676x
10

Mass of 2-butanol is 100 x = 0.10x

Mass of then H2 is 0.0121622=0.024324x
X (kg)

Reactor

MEK = 0.87567
2-Butanol=0.10
H2 =0.024324

64

All the components leaving the reactor are discharged directly into the cooler condenser for the
next operation.
Partial-condenser

Condensate (which is then directly sent to the final purification column) comprises:
80% MEK= 0.80.875676x = 0.70054x
80% 2-Butanol=0.80 0.10x = 0.08x
Incondensable stream comprises:
20% MEK=0.2 0.875676x = 0.175135x
20% 2-Butanol= 0.2 0.10x = 0.02x
100% H2=0.024324x

MEK =

0.875676x

Partialcondenser

(Non-condensable)

2-Butanol=012

MEK= 0.01369
2-Butanol= 0.02

H2=0.024324
H2=0.024324

(Condensate)
MEK= 0.70054x
2-butanol= 0.08x

65

MEK =0.175135

Absorption column:

MEK= 0.5% = 0.005

H2O= 99.5% = 0.995

(Non-condensable)
MEK= 0.175135
2-Butanol= 0.02

K
Absorption
MEK
column

= 0.02(0.175135)
2-Butanol= 0.02(0.02)
H2=0.024324
J

H2=0.024324

J
MEK = 0.98(0.175135) + 0.005 = 0.1
2-Butanol= 0.98(0.02)
H2O=?

75

MEK balance around the absorption column

0.175135x + 0.005K = 0.02(0.175135X) + 0.1J

0.175135x + 0.005K = 0.003503X + 0.1J
J = 1.716x + 0.05K

Overall balance
(0.024324x + 0.02x + 0.175135x) + K = 1.716x + 0.05k + (0.024324x + 0.0004x +
0.003503x)
k = 1.605x
Performing a new balance around the absorption column to express the k -value in terms of x in
the above equations gives the following values:

66

MEK= 0.00803

H2O= 1.597

MEK= 0.17513

Absorption
column 2

2-Butanol = 0.02x

MEK= 0.02(0.17513)
Butanol= 0.0004

H2=0.024324

H2= 0.024324

MEK= 0.1716 + 0.00803 = 0.1796

H2O= 1.597 and 2 = 0.0196

Raffinate: MEK= 0.005K = 0.005(1.605x) = 0.00803x

H2O= 0.995K = 0.995(1.605x) = 1.597x
Stream J: MEK= 0.1J = 0.1{1.716x + 0.05(1.605x)} = 0.1796x
H2O= 1.597x
2-butanol = 0.0196x

67

MEK=0.0035

Extraction column
: MEK = 0.00803

Raffinate H2O= 1.597

B
Extractor

MEK= 0.1796
2-butanol= 0.0196x
H2O= 1.597

MEK= 0.17157
2-butanol= 0.0196
TCE= 0.667

R = TC
R- Recycle from next operation (TCE)

MEK Balance around the extractor

0.1796x = 0.00803x + 0.2
= 0.858x
Overall balance
+= +
1.7962x + = 1.605x + 0.858x
= 0.667x
TCE = 0.858x (0.17157x + 0.0196x)
= 0.667x (Which is approximately = )

68

Solvent Recovery Unit

For this unit operation, the balances were obtained from the previous unit operation i.e. the
extraction column and are indicated in the block diagram below.

TCE= 0.667

MEK= 0.17157

2-Butanol = 0.0196x

Solvent
Recovery
Unit

MEK= 0.17157
2-Butanol= 0.0196

TCE= 0.667

Distillation Column
The material balance for the second distillation column is given as follows;

MEK= (0.17157 + 0.70054)

= 0.872

Distillation
Column

1500kg/hr (flow rate as given)

2-Butanol= 0.0196 + 0.08

= 0.0996
2-Butanol (recycled back to the reactor)

Balancing around this gives:

69

MEK:
0.872x = 1500
x=

1500
= .
0.872

2-Butanol:
0.0996x
x = 0.0996(1720.2)
= . (Returning to the reactor)

CALCULATION OF ACTUAL MASS OF THE COMPONENTS IN ALL THE

STREAMS

The streams are indicated in the diagrams above.

1) Reactor
From the balances carried out in the previous exercise the value of X was obtained as 1720.2kg
based on the 1 hour basis.
In = out
Entering stream:
XF + XR= X where: XF = feed and XR = feed as recycle
Leaving streams:
MEK = 0.87567x = 0.87567 1720.2 = .
70

2-butanol = 0.10x = 0.10 1720.2 = .

H2= 0.024324x = 0.024324 1720.2 = .
2) Cooler condenser
In = out
Entering Stream
MEK = 0.87567x = 0.87567 1720.2 = .
2-butanol = 0.10x = 0.10 1720.2 = .
H2= 0.024324x = 0.024324 1720.2 = .

Leaving Stream
MEK = 0.70054x = 0.70054 1720.2 = .
2-butanol= 0.08x = 0.08 1720.2 = .
Non-condensable
MEK= 0.175135x = 0.175135 1720.2 = .
2-Butanol = 0.02x = 0.02 1720.2 = .
H2= 0.024324x = 0.024324 1720.2 = .
3) Absorption column
Entering stream:
MEK= 0.175135x = 0.175135 1720.2 = .
2-Butanol = 0.02x = 0.02 1720.2 = .
71

H2= .
Raffinate stream:
MEK 0.00803x = 0.00803 1720.2 = .
H2O: 1.597x = 1.597 1720.2 = .
Leaving stream:
MEK 0.1796x = 0.1796 1720.2 = .
H2O 1.597x = 1.597 1720.2 = .
2-butanol = 0.0196x = 0.0196 1720.2 = .
H2= .
MEK 0.0035x = 0.0035 1720.2 = .
4) Extractor
Entering stream:
MEK 0.1796x = 0.1796 1720.2 = .
H2O 1.597x = 1.597 1720.2 = .
2-butanol = 0.0196x = 0.0196 1720.2 = .
Recycle stream = TCE (Trichloroethane)
TCE: 0.667x = 0.667 1720.2 = .
Leaving stream:
MEK:0.17157x = 0.17157 1720.2 = .
2-butanol 0.0196x = 0.0196 1720.2 = .
72

5) Solvent Recovery Unit

Entering stream:
MEK: 0.17157x = 0.17157 1720.2 = .
2-butanol 0.0196x = 0.0196 1720.2 = .
Leaving stream:
MEK: 0.17157x = 0.17157 1720.2 = .
2-butanol 0.0196x = 0.0196 1720.2 = .
TCE: 0.667x = 0.667 1720.2 = . (This is recycled back into the extractor)
6) Distillation column 2
In = out
Entering stream:
MEK: 0.17157x + 0.70054x = 0.872x
2-butanol: 0.0196x + 0.08x = 0.0996x (this is recycled back to the reactor)
Leaving stream
99.99% pure MEK at 1500kg/hr.
B. ENERGY BALANCE:
The energy balance was done around the following units

73

ENERGY BALANCE ACROSS THE CONDENSER:-

MEK=301.27

MEK= 1506.33 kg
MEK = 0.8554
2-butanol =172.02 kg
2-Butanol=012
H2 =41.84kg

(Non-condensable)
2-Butanol= 34.4

Coolercondenser

H2=0.02376

H2= 41.84

Condensate
MEK =1205.07
2-butanol= 137.62

The vapor enters condenser at 141.50C (414.5K) at 1 bar pressure.

Liquid and the vapor leaving the condenser are in equilibrium.
At the MEK mole fraction x = 0.88 of the condensate we get both liquid and vapor temperature
from the T- x- y diagram. 299.6K = liquid temperature, 335.7K = vapor temperature
We take cooling water enters at 250C and leaving at 280C

Cpmix = 2.24 KJ/kg.

Heat loss to reduction in vapor temperature from 459K to 335.7K

Q1= 1720.2 x 2.24 x (414.5 - 335.7)

= 3.04 x 105 KJ/ hr

Heat loss due to condensation

Total mass condensed= 1205.07 + 137.62 = 1342.7kg
74

Q2 = 1342.7 x 552.5 KJ/kg

= 7.42 x 105 KJ/hr

Heat loss due to further cooling of a part of vapor is

Q3 = 1342.7 x 2.24 x (335.7 299.6)
= 1.086 x 105 KJ/hr

Total heat lost = Q = Q1 + Q2 + Q3

= (4.75 + 7.42 + 1.086) x 105 KJ/hr
= 11.546 x 105 KJ/hr

Heat gained by cooling water = Heat lost by Vapor

11.546 105

Mass flow of cooling water = 4.2(2825)

= 9.16 x 104 kg / h

ENERGY BALANCE ACROSS THE ABSORBER:MEK= 13.8

MEK= 301.27
2-Butanol =34.4kg

H2O= 2747.16

Absorption
column

MEK= 0.02(0.17513)
Butanol=
6.88
MEK=6.02

H2= 41.8

H2=41.8
MEK= 308.95
H2O= 2747.16 and 2 = 33.7

75

H2O= 2747.16 and 2 = 33.7

Heat of condensation of MEK = 308.95 x 435.2

= 1.37 x 105 KJ/hr

Heat of condensation of alcohol is = 33.7 x 550.6

= 0.223 x 105 KJ/hr

Heat of solution = (308.95 + 33.7) x 0.35

= 0.00120 x 105 KJ/hr.
Heat gained by off gases from 320C to 62.4
Mean Cp = 1.89KJ/kg
= (41.8 + 6.88 + 6.02) x 1.89 x (62.4 32)
= 0.995 x 105 KJ/hr.
Total heat released = 2.59 x 105 KJ/hr.

Heat gained by irrigating liquor

a) Water: 2747.16 x 4.2 x (T 300)
b) MEK: 308.95 x 2.13 x ( T-300 )
c) Alcohol: 33.7 x 2.747 x (T- 300 )
Total heat gained = 0.123 x 105 (T-300) KJ/hr

Heat released = heat gained

= > 2.59 x 105 = 0.123 x 105 (T 300)
76

= > T = 321K

ENERGY BALANCE ACROSS THE EXTRACTION COLUMN:It is assume that the extraction process is isothermal. All that streams come at 500C and
leaves at 500C.

ENERGY BALANCE ACROSS THE SOLVENT RECOVERY UNIT:Entering stream:

MEK: 0.17157 = 0.17157 1720.2 = .
2-butanol 0.0196 = 0.0196 1720.2 = .
TCE: 0.667 = 0.667 1720.2 = .
Total Mass = 1476.25kg
Leaving stream:
MEK: 0.17157 = 0.17157 1720.2 = .
2-butanol 0.0196 = 0.0196 1720.2 = .
TCE: 0.667 = 0.667 1720.2 = . (This is recycled back into the extractor)
Stream Temperatures were obtained from HYSYS Simulation.
From x-y diagram we get Rm = 0.38.
R= 2Rm = 0.76

Feed:
2-butanol =

33.716
74

= 0.4556/

77

MEK =

TCE =

295.135
72

1147.4
133.5

= 4.1/

= 8.6/

Total = 13.1556 kmol /hr

Mole fraction of MEK

4.1

XMEK = 13.1556 = 0.312

Feed temperature = 500C
F . HF =
= 1476.25 x 1.018 x (50)
F . HF = 0.75 x 105 KJ/hr

Distillate:Alcohol =

MEK =

33.716
74

295.135
72

= 0.4556/

= 4.1/

Total = 4.556kmol/hr

D = 4.556 kmol/hr
4.1

Mole fraction of MEK, XMEK = 4.556 = 0.90

From the HYSYS Simulation, distillate temperature = 700C
78

Cp mix = 2.273 KJ/kg

D. HD =
= 328.851 x 2.273 x 70
= 0.523 x 105 KJ/hr

Bottoms:
TCE =

1147.4
133.5

= 8.6/

Total = 8.6 kmol/hr

From the HYSYS simulation, the temperature obtained, T = 1250C (bottoms)

Cp TCE = 1.118 KJ/kgK

B. HB =
= 1147.4 1.118 125
= 1.6035 x 105 KJ/hr

Condenser :Qc = V x (Hv - HL)

Qc =
V = (1 + R ) x D
D = 4.556 kmole/hr
V = ( 1 + 0.76 ) x 4.556 = 8.02 kmole/hr.

79

= 2.72 x105 KJ/hr

Qc = 2.72 x105 KJ/hr
2.72105

Cooling water requirement = 4.186(4224)

= 3.61x 103 kg/hr

Reboiler:Overall heat balance

F. HF + QB = Qc + D.HD + B. HB
QB = Qc + D . HD + B. HB - F. HF
QB = DHD + B. HB + Qc FHF
QB = 0.523 x 105 + 1.6035 x 105 + 2.72 x105 - 0.75 x 105
QB = 4.1 x 105 KJ/hr

Utility steam supplied at Medium pressure (MP) is available at 3.302 bar steam temperature =
410 K

Steam requirement is =

4.1 105
2152

= 190.5 kg/hr

80

ENERGY BALANCE ACROSS THE DISTILLATION COLUMN:-

QC

F=1671.33kg/h
XF=0.88

D=1500kg/h
XD=0.999

QR

B=171.33kg/h
XB=0.001

Taking reflux ratio (R.R) = 2.8 (obtained from HYSYS)

Total energy balance equation is:
HF+QR=QC+HD+HB
Condenser:
Qc = V x
81

V = (1 +R) x D
V = (1 + 2.8) x 1500
V= 5700kg/hr
Qc = 5700 x 423.7
= 2.415 x 106KJ/hr
2.415 106

So, mass flow rate of cooling water = 4.186 (4224)

= 3.205 x 104 kg/h
Reboiler:
QB = DHD + BHB + Qc - FHF
FHF =
= 1671.33 x 2.241 x (43)
F.HF = 1.61 x 105 KJ/hr
DHD =
= 1500 x 2.394 x 94.76
= 3.403 x 105 KJ/hr
BHB =
= 171.33 2.862 77
= 0.37756 x 105 KJ/hr
QB = 26.3 x 105 KJ/hr

Utility Steam supplied at medium pressure (MP) Steam available at = 3.302 bar. Steam
temperature = 410 k

Steam requirement =

26.3 105
2152

= 1222.12 kg/hr.
82

ENERGY BALANCE AROUND COOLER SYSTEM

Distillate & the residue both has to be cooled

Distillate
Heat load to cool the distillate from 94.76 to 29.850C =1500 2.394 (94.76 29.85)
= 2.331 x 105 KJ/hr.
2.331 105

So, cooling water requirement,= 4.187 (4224)

=3093 kg/hr

For 2-Butanol
Recycle 2-butanol is 77 to 250C
Heat load = 171.33 2.862 (77 25)
= 2.55 x 104 KJ/hr
2.55 104

Cooling water requirement = 4.187(4224)

= 338.3 kg/hr.

83