HADHRAMOUT UNIVERSITY

COLLAGE OF PETROLEUM & ENGINEERING

CHEMICAL ENGINEERING DEPARTMENT

PLANT DESIGN FOR METHANOL

DISTILLATION UNIT
PROJECT SUBMITTED IN FULFILLMENT
OF REQUIREMENTS FOR THE DEGREE OF BACHELOR OF SCINCE IN
CHEMICAL ENGINEERING

BY
AHMED SALEM MUHIMOOD AL-GARZI
SALEM ABED MUBARAK BIN SAAD
ABDULLAH OMER SALAH BABAKER
ADNAN MARAI SALEH BASLOOM
MAGED THABET SALEH AL-DALAH

SUPERVISOR
Dr. ABDULLAH SALEM MOHAMMED BAFAQEER

ALMUKALLA
FEBRUARY 2021
 TABLE OF CONTENTS
page
TITLE PAGE i

TABLE OF CONTENTS ii
LIST OF TABLES iv
LIST OF FIGURES v
LIST OF ABBREVIATIONS vi
CHAPTER I: INTRODUCTION 1
1.1 General introduction 2
1.2 Problem statement 5
1.3 Objective of project 5
1.4 Scope of project 6
1.5 Importance of project 6
CHAPTER II: THEORETICAL BACKGROUND 7
2.1 Background 8
2.2 History 8
2.3 Methanol formulas and structures 9
2.4 Identity 10
2.5 Methanol physical and chemical properties 11
2.6 Methanol demand 14
2.7 Uses of methanol 14
2.8 Applications of methanol 15
2.9 Production methanol methods 16
2.9.1 The production of methanol from natural gas 16
2.9.2 The production of methanol from biomass 17
2.9.3 Methanol production by gasification of heavy residues 18
2.10 Production methanol by formating natural gas 19
2.10.1 Reforming 19
2.10.2 Compression and Synthesis 20

ii
 2.10.3 Distillation 22

2.11 Methanol purification methods 22

2.11.1 Liquid liquid extraction 22
2.11.2 Membrane method 24
2.11.3 Distillation method 25
2.12 Selective method 26
2.13 Description of distillation method 27
CHAPTER III: MATERIAL BALANCE 30
3.1 Overall material balance 32
3.2 Material balance around expansion gas vessel 34
3.3 Material balance around first distillation column 36
3.4 Material balance around second distillation column 38
3.5 Material balance around third distillation column 40

REFERENCES

iii
 LIST OF TABLES

Table No. Page

2.1 Methanol formula and structures 9

2.2 Physical and chemical properties of methanol 11

2.3 Physical properties and chemical of methanol 12

2.4 Content pressure heat capacity of liquid methanol 13

2.5 Equipment summary table for the methanol distillation process 29

3.1 Compositions of crude methanol 31

3.2 Overall material balance 33

3.3 Material balance around expansion gas vessel 35

3.4 Material balance around first distillation column 37

3.5 Material balance around second distillation column 39

3.6 Material balance around third distillation column 41

3.7 Summary of all units streams by mass flow rate 42

3.8 Summary of all units streams by weight fractions 43

iv
 LIST OF FIGURES

Figure No page

2.1 Production of methanol from natural gas 16

2.2 Production of methanol from biomass 17

2.3 Block Diagram, SGP-based Methanol Plant 18

2.4 Process flaw diagram for crude methanol distillation unit 28
3.1 Block diagram of overall material balance 32
3.2 Block diagram of expansion gas vessel 34

3.3 Block diagram of first distillation column 36

3.4 Block diagram of second distillation column 38

3.5 Block diagram of third distillation column 40

v
 LIST OF ABBREVIATIONS

CH3OH Methanol

H2O Water

MTBE Methyl tertiary butyl ether

MTO Methanol- to- olefins

DME Dimethyl ether

LPG Liquefied petroleum gas

FAME Fatty acid methyl ester

MTG Methanol-to-Gasoline

Cu O copper oxide

Zn O zinc oxide

CH4 methane

C carbon

H2 hydrogen

OH Hydroxyl group

O Oxygen

RTECS Registry of Toxic Effects of chemical substance

EC Enzyme Commission number.

PAGE Polyacrylamide gel electrophoresis.

LLE Liquid -liquid extraction.

LMs Liquid membranes.

mn Mass flow rate in stream n

LEs Light ends

vi
 Chapter I
Introduction

1
 Chapter I

Introduction

1.1 General Introduction:

Methanol (CH3OH), also called methyl alcohol, wood alcohol, or wood spirit, the
simplest of a long series of organic compounds called alcohols, consisting of a methyl
group (CH3) linked with a hydroxy group (OH). Methanol was formerly produced by
the destructive distillation of wood. The modern method of preparing methanol is based
on the direct combination of carbon monoxide gas and hydrogen in the presence of
a catalyst. Increasingly, syngas, a mixture of hydrogen and carbon monoxide derived
from biomass, is used for methanol production.

Pure methanol is an important material in chemical synthesis. Its derivatives are used in
great quantities for building up a vast number of compounds, among them many
important synthetic dyestuffs, resins, pharmaceuticals, and perfumes. Large quantities are
converted to dimethylaniline for dyestuffs and to formaldehyde for synthetic resins. It is
also used in automotive antifreezes, in rocket fuels, and as a general solvent. The
methanol derived from wood is used chiefly for rendering industrial ethyl alcohol unfit
to drink . Methanol is a colorless liquid that boils at 64.96 °C (148.93 °F) and solidifies
at −93.9 °C (−137 °F). It forms explosive mixtures with air and burns with a nonluminous
flame. It is completely miscible in water. Methanol has an odour that is similar to ethyl
alcohol, the intoxicant of alcoholic beverages, but is a dangerous poison; many cases of
blindness or death have been caused by drinking mixtures containing it [1].

Close to half of the world's methanol is used in energy-related applications. Methanol

can be used on its own as a vehicle fuel or blended directly into gasoline to produce a
high-octane, efficient fuel with lower emissions than conventional gasoline. Methanol

2
vehicle fuels have widespread use in China and have been introduced in several countries
outside of China. Methanol is also used as a cooking fuel and in thermal applications
(industrial boilers, furnaces, and kilns), primarily in China. Methanol is also emerging as
a clean-burning marine fuel that can cost-effectively meet the shipping industry’s
increasingly stringent emissions regulations. In recent years, the use of methanol in the
production of olefins or methanol-to-olefins (MTO) has grown rapidly.Methanol is used
to produce methyl tertiary butyl ether (MTBE), a gasoline component that improves air
quality, and dimethyl ether (DME), a clean-burning fuel with similar properties to
propane.Methanol is also a key component in biodiesel, a renewable fuel that can be used
in place of, or blended with conventional diesel fuel. The renewable sources are presented
with their yearly quantity while the finite resources are shown with their total quantity. It
shows that for the renewable resources solar has by far the largest supply quantity and
both solar and wind energy could cover the world’s total energy demand by themselves
.However, both wind and solar energy are highly variable and depend on the season, the
time of the day and the weather. This non-controllable variance in the available energy
can be combated on twofronts. On one side, storage technologies can work as a bridge to
overlap the production and demand curve. On the other side, other energy resources,
which are more constant and dispatchable, can be added to the energy mix to cover the
gap between production and demand. The major methanol end-uses in fuels applications
include: 1) Gasoline Blend stock: In some countries, methanol is blended directly with
gasoline. Methanol has attractive properties as a fuel blending component; it has a high
octane number, combusts efficiently, emits fewer harmful by- products than gasoline, and
is relatively low-cost . 2) Dimethyl Ether (DME): DME can be used to blend into LPG,
as a replacement for LPG fuel in heating and cooking applications, as a transportation
fuel in modified diesel engines, and for power generation . 3) Methyl Tert-Butyl Ether
(MTBE): MTBE (an oxygenate) is added to gasoline to increase its octane number. Use
of MTBE in a gasoline blend also allows for a cleaner combustion process, emitting less
pollution . 4) Biodiesel: Biodiesel is the product obtained when vegetable oil or animal
fat is chemically reacted with an alcohol - methanol, for example - to produce a compound
known as a fatty acid alkyl ester. When methanol is used, the product is fatty acid methyl
ester (FAME) . 5) Methanol-to-Gasoline (MTG): MTG refers to the process of making
gasoline via a methanol route. In some ways, MTG is a misnomer, because methanol is
often an intermediate in the process, and units are back-integrated to coal or natural gas.

3
Some MTG units in China may run on merchant methanol . 6) Others: Methanol can also
be used as a fuel in power generation plants and in methanol fuel cells. [2]

The main reactions for methanol production are:

CO + 2 H2 → CH3OH -91 kJ/mol (1)

CO2 + 3 H2 → CH3OH + H2O -49 kJ/mol (2)

The synthesis of carbon oxides to methanol is based on a Cu O/Zn O based catalysts,

e.g. Synetix catalysts. This catalyst type has proved its performance in adiabatic as
well as in isothermal reactors. The conversion of carbon oxides to methanol is an
exothermic process which takes place at high pressures and low temperatures. The
synthesis unit operates at 40 - 110 bar and around 200 to 300 °C. The aim is to achieve
a relatively high carbon efficiency so as to minimize the amount of synthesis gas to be
processed.[3].

Although some is still produced from old and inefficient coal gasification plants,
Methanol is mainly produced in areas of the world where a large supply of Natural Gas
is available at an economical supply cost. By creating the necessary chemical reactions
within the process, natural gas is converted into a valuable liquid product that is easily
transported to markets in Europe, Asia and America by ship. The two main essential
ingredients, (feedstock) to produce Methanol here at ‘Ampco’ are basically Natural Gas
and Water. However it is simply not enough to mix gas and water, (as steam) together. A
lot of other conditions are also necessary. These extra conditions include a lot of heat and
pressure, in addition to another necessary material. This other material is called a Catalyst.
This is something that promotes, (encourages) the ingredients in this particular process to
‘crack’ and ‘reform’ into something entirely different from the original feedstock. This is
the first major step in the production of Methanol, and the process is given the general
name of ‘Steam Reforming . In order to understand the Steam Reforming process, First,
most people will know what H2O is. It is of course water, but it is still H2O even if it is
in solid form, (ice), or as a vapor (steam). crack H2O into its basic elements of H2 and
O to get two types of gas :Hydrogen and Oxygen. This is what is done in a Steam
Reformer, some of that H2O, (as steam) cracks to go back to the elements that originally
formed it . However, not only is H2O cracked, something similar happens to the Natural
gas. Natural gas is composed of Hydrocarbons and the major part of this gas that feeds

4
Ampco is the simplest type of Hydrocarbon, Methane, (CH4) . The formula CH4 shows
that there is one piece (atom) of Carbon (C), and four pieces, (atoms), of Hydrogen, (H)
in this molecule. When this Methane molecule also cracks into its basic parts, so these
elements can be reformed into something else. And if controlled correctly, the result is
exactly the correct mixture of gases to make Methanol[4].

1.2 Problem statement

The world methanol consumption has surpassed 25 million tons per annum and is still
growing steadily ,indicating an increasing importance of methanol in the bulk chemicals
market. The most valued property is its ability to transport energy efficiently . Methanol
is produce as crude that contain many different impurities from natural gas after that it
sold in the local and international markets with less purity and lower prices .Therefore
,some companies resorted to increasing its purity after production by the equivalent of
100% and increasing its marketing value ,as well as for its unlimited uses that require
high purity of methanol . This project was done depending on design a methanol
distillation unit to purification crude methanol to cover increasing of local and
international market request.

1.3 Objectives

The main objective of this project is to design a methanol distillation unite to

purification the crude methanol, the detailed objectives of this study include:

1 ) To carry out the calculations of material balance of the process.

2 ) To perform the calculations of energy balance of the process.

3 ) To design the equipment's of the process (condenser, distillation column,

reboiler).

4 ) To study control systems and safety of the process.

5 ) To estimate the costs of the plant

5
 1.4 Scope of Project:

• Providing the industrial processing by enough quantity of pure methanol.

• Execute this project at nearest time as possible.

• Get more pure methanol by physical processes to use in local market.

1.5 Importance of Project:

The goal of the project is to increase the purity of methanol produced by other
companies that sell it at low prices. Through purification, we obtain the highest market
value of methanol by removing impurities that reduce the price of methanol during the
methanol distillation unit. It is also considered an important investment through the
positive use of methanol in full compliance with all applicable local and international
environmental requirements.

6
 Chapter II
Literature Review

7
 Chapter II

2.1 Background

Methanol, also known as methyl alcohol amongst other names, is a chemical with
the formula CH3OH (a methyl group linked to a hydroxyl group,
often abbreviated MeOH). It is a light, volatile, colorless, flammable liquid with a
distinctive alcoholic od our similar to that of ethanol. Methanol, known as methyl alcohol,
is a transparent liquid with chemical formula CH3 OH. It is volatile, flammable, and toxic
for human consumption Methanol is a polar substance, soluble in water. The -OH group
is responsible for its polarity. The electronegativity difference between atoms in the -OH
group generates a negative region. This region influences the carbon and hydrogens
region making it positive [ 5 ].

2.2 History

Methanol has been produced and used for millennia, with the ancient Egyptians using it
in the embalming process – it was part of the mixture of substances produced in the
destructive distillation (pyrolysis) of wood. However, it was not until 1661 that Robert
Boyle produced pure methanol through further distillation, and only in 1834 was the
elemental composition determined by Jean-Baptiste Dumas and Eugene Peligot. At a
similar time, commercial operations using destructive distillation were beginning to
operate .There are many parallels between the industrial production of methanol and
ammonia and it was the early development of the high pressure catalytic process for the
production of ammonia that triggered investigations into organic compounds:

8
hydrocarbons, alcohols and so on. At high pressure and temperature, hydrogen and
nitrogen will only form ammonia, however the story is very different when combining
hydrogen and carbon oxides at high pressure and temperature, where the list of potential
products is lengthy and almost all processes result in a mixture of products. Through
variations in the process, the catalyst, the conditions, the equipment or the feedstock, a
massive slate of industrial ingredients suddenly became available and a race to develop
commercial processes ensued [ 6 ] .

2.3 Methanol Formulas and Structures [ 7 ]

Table(2.1): Methanol formula and structures

Type Formula or Structure
Methanol Moleculal CH4O or CH3OH
Formulas
Methanol Ball and
Sticks Structural
Model

Methanol Sticks
Structural Model

Methanol Wire-Frame
Structural Model

Methanol Space-Filling
Structural Model

9
2.4 Identity [ 8 ]

Common name: methanol

Chemical formula: CH3OH

Chemical structure:

Relative molecular mass: 32.04

Common synonyms: methyl alcohol; methyl carbinol;

wood alcohol; wood spirits Spirits ;
wood
naphtha; Columbian spirits;
Manhattan

Abbreviations: None

CAS registry number: 67-56-1

RTECS number: PC 1400000

United Nations number: 1230

EC number: 603-001-00-X

Conversion factors 1 ppm= 1.31 mg/m3

1 mg/m3 = 0.763 ppm at 25 oc and
101.4 kPa (760 mmHg)

10
2.5 Methanol Physical and chemical properties

Table (2.2): Physical and chemical properties of methanol[ 7 ]

Property Value

Chemical formula CH3OH or CH4O

Molecular Weight 32.04

Molar Mass 32.042 g/mol

Density 0.791 g/mL at 25 ºC

Boiling Point 64.7 ºC

Melting Point -98ºC

Odor Sweet and pungent

Appearance Colourless liquid

Flash Point 11.1ºC

Viscosity (cP) 0.544 at 25ºC

Dielectric Constant 33.00 at 20ºC

Dipole Moment 1.7

UV cutoff 210 nm

Refractive Index 1.329 at 20ºC

Vapor Density 1.11 (vs. air)

Exact Mass 32.026215 g/mol

Monoisotopic Mass 32.026215 g/mol

11
Table (2.3) : Physical and chemical properties of methanol [ 7 ] :

Property Value

Solubility in water miscible

Vapor pressure 13.02 kPa (at 20 °C)

Odor Sweet and pungent

log P −0.69

Acidity (pKa) 15.5

Conjugate acid Methyloxonium

Magnetic susceptibility (χ) −21.40·10−6 cm3/mol

Refractive index (nD) 1.33141

UV cutoff 210 nm

Refractive Index 1.329 at 20ºC

Vapor Density 1.11 (vs. air)

Exact Mass 32.026215 g/mol

Monoisotopic Mass 32.026215 g/mol

12
 Table (2.4): Constant pressure heat capacity of liquid methanol [ 7 ]
Temperature Ideal Gas Heat Temperature Ideal Gas Heat
[K] Capacity [K] Capacity
[J/(mol*K)] [J/(mol*K)]

298.15 79.5 81.13 298.15

298.15 81.11 83.7 298.

298.15 80.24 85.8 313.2

298.15 80.35 85.8 298.2

298.15 81.0 80.8 311.

298. 81.32 86.2 323.

298.15 80.28 75.77 270.

298.15 81.56 86.6 300.8

298.15 80.22 83.56 313.15

298.15 81.47 79.9 292.0

288.15 78.90 78.2 270.

298.15 81.92 79.9 290.1

293.15 80.8 83.3 298.

13
2.6 Methanol demand [ 10 ]

'There are over 90 methanol plants worldwide with a combined production capacity of
about 110 million metric tons (almost 36.6 billion gallons or 138 billion liters), According
to the consulting firm IHS, global methanol demand reached 70 million metric tons in
2015, driven in large part by emerging energy applications for methanol which now
account for over 40% of methanol consumption, Demand growth for methanol is being
driven by its energy use applications. In 2017, 57% of global demand for methanol came
from China, with other parts of the Asia, Pacific accounting for 16%, Europe 150/0, North
America 9% and Latin America 3%. The primary buyers of methanol are large chemical
companies who process methanol for other applications. These buyers include Celanese,
BP, Momentive, Sanjiang, Sailboat, Sabiq and BASF.

2.7 Uses of Methanol [ 11 ]

• Methanol is widely used in the production of acetic acid and formaldehyde.

• In order to discourage the recreational consumption of ethanol, methanol is often

added to it as a denaturant.

• This compound is also used as an antifreeze (an additive that is used to lower the
freezing point of a liquid) in many pipelines.

• It is also used in sewage treatment plants since it serves as a carbon-based food

source for denitrifying bacteria.

• The polyacrylamide gel electrophoresis (PAGE) technique involves the use of

methanol as a detaining agent.

• A mixture of water and methanol is used in high-performance engines in order

to increase power.

• Methanol is used in the production of hydrocarbons, olefins, and some aromatic

compounds.

• It is also used in the production of methyl esters and methylamines.

14
2.8 Applications of methanol [ 10 ]:

The main application for methanol is formaldehyde. Formaldehyde is used in a

vast range of end-products including:

a. Consumer products: Photographic film, paper towels, cosmetics,

carpeting, fumiture , cabinets, solvents, and paint;

b. Automotive industry: Under the bonnet components ,antifreeze, fuel

system components, brake pads;

c. Health care applications: Vaccine manufacturing, hard gel capsule

manufacturing, pharmaceutical research;

d. Construction industry: Carpet underlays structural wood panels.

Methanol can be arine i i ta that have been specially designed for this purpose. Methanol
ignificantly re issions of sulphur oxides (SOX), nitrogen oxides (NOx) a p rt!fya e matter.
mbared) to conventional bunker fuel or marine diesel. Methalfbl al sed in smaller
volumes to produce fuel cells, for power generation (notably f eking rposes), and for
industrial boilers (notably in China).

15
2.9 Production methanol methods

2.9.1 The production of methanol from natural gas [ 12 ]:

Natural gas

Desulfurization

Pre – reforming Air

Autothermal reforming Air sepration

Methanol synthesis Hydrogen Feul gas

Methanol distillation

Pure methanol

Figure (2.1) : The production of methanol from natural gas

16
2.9.2 The production of methanol from biomass [ 13 ] :

Particulate matter
Wood
gaseous emission
Pressurized
Heat charach, liquid
waste

Heat Gas condition Tar, methane

,gases emission

Catalytic reaction Liquid wastes

Gaseous emission ,
Steam Distillation Partriculate matter,
Liquied waste

Figure (2.2) : The production of methanol from biomass.

17
2.9.3 Methanol Production by Gasification of Heavy Residues [14]

Approximately 2.5 million metric tons per year or about 10% of the estimated 1994 world
methanol production capacity is based on the gasification of coal or heavy residues. 87%
of this gasification- based capacity is located in onIy two countries, namely the United
States of America and Germany. Over 90% of gasification-based methanol production
operates with LURGI isothermal reactors. This includes all the large capacity ones.
Against this background of current experience it is clear that there is a case to be made
for the statement that, given the right circumstances, gasification can be an alternative to
natural gas. The kind of synthesis gas produced by a gasification plant has, however,
certain implications for the synthesis technology. The purpose of this paper is to review
the technological aspects of methanol production from residual oil gasification using the
SHELL Gasification Process ("SGP") as a typical proven oil gasification process for this
application and to review the economic circumstances in which such a technology is a
real alternative to natural gas.

Waste Water Vanadium Cake

Figure (2.3) : Block Diagram, SGP-based Methanol Plant

18
2.10 Production methanol by formation of natural gas [15 , 16]

The main process area of the plant can be divided into three sections as shown in Figure
2.1 :

• Reforming
• Compression and Synthesis
• Distillation

In addition, a number of support utilities are required, including a conventional water

treatment plant, an ion-exchange demineralizer to produce higher quality water for
boilers, a package boiler, a cooling water system, an inert gas system, an instrument air
system and an electricity generator.

2.10.1 Reforming

The term "steam-hydrocarbon reforming" refers to the endothermic reaction between

steam and methane (or any other alkane) which produces carbon monoxide, carbon
dioxide and hydrogen. The reaction is carried out in a furnace at high temperatures over
a nickel catalyst inside tubes. Fired burners supply heat for the endothermic reaction:

Ni/8000C
CH4 + H2O CO + 3H2 ∆H = +206 kJ mol-1

Under these conditions, the water gas shift reaction also occurs to a small extent:

Ni/8000C
CO + H2O CO2 + H2 ∆H = +206 kJ mol-1

Thus the products of the reforming reaction ("synthesis gas") include carbon oxides and
hydrogen as well as unreacted methane, nitrogen, and steam. They leave the furnace at
over 800oC. Heat is recovered from this stream as it is cooled to 32 oC.

The recovered heat is used to generate high-pressure steam; heat boiler feed water, and
to supply heat to the distillation section. Some heat, which cannot be recovered, is

19
4y45rejected to the atmosphere (air coolers) and the cooling water system. After
cooling, steam in the reformed gas is condensed and recycled to water treatment. Waste
flue gases leave the furnace at over 1000°C. In order to increase plant efficiency and
decrease thermal pollution, the flue gas is used to generate and superheat high pressure
steam, preheat the reactants (steam and hydrocarbons), and heat the combustion air to
the furnace. The flue gas leaves the stack at 150oC. Maui gas is considered almost
sulphur-free but, as sulphur in only trace amounts is a poison to the reformer catalyst, a
sulphur removal system is included in the process as a precautionary measure.
Desulphurization of the hydrocarbon feedstock is carried out at 400 oC. It is mixed with
a small amount of hydrogen-rich purge gas from the converter and passed over a cobalt-
molybdenum catalyst that converts any thiols, sulphides and carbonyl sulphides to
hydrogen sulphide H2S. It then passes through a zinc-oxide bed where the H2S is
absorbed by the zinc oxide.

2.10.2 Compression and Synthesis

The "synthesis gas" from the reformer is then compressed in a centrifugal compressor.
A turbine which draws its power from the high pressure steam system drives this
compressor. Extraction steam from the turbine is used in the reforming reaction and
drives other turbines in the process. The compressed synthesis gas enters the converter
reactor containing copper zinc and catalyst and the synthesis reaction occurs, according
to the equation:

2H2 + CO CH3OH ∆H = -92 kJ mol-1

This reaction is highly exothermic and this excess heat is used to heat boiler feed water
and to pre-heat reactant gas.

Since the reaction is exothermic, low temperatures favor conversion to methanol. On

the other hand, the rate of reaction increases with increasing temperature. Pressure will
also affect the position of the equilibrium, with increasing pressure favoring methanol
formation. The final conditions used involve a copper oxide based catalyst at about 5
MPa (50 atmospheres) pressure and about 270oC. As carbon monoxide is used up in the
methanol synthesis reaction the water gas shift reaction reverses producing more
carbon monoxide:
H2 + CO2 CO + H2O ∆H = +41 kJ mol-1

20
These reactions combine to produce approximately 40% conversion of carbon oxides to
methanol each pass through the reactor. On leaving the reactor the gas mixture is
cooled and methanol and water condense out. The remaining gas is returned to the
circulator, mixed with incoming compressed synthesis gas and recycled through the
methanol converter.

Hence, the overall reactions by which methanol is produced from synthesis gas may be
summarized into the following equation:

Cu-Zn
CO2 + CO + 5H2 2CH3OH + H2O + heat

A feature of the steam reforming reaction and the methanol synthesis reaction is that for
every three moles of hydrogen gas produced in the steam reformer, only two moles are
used in the recycled gas being returned to the methanol converter and the mixture must
be purged to remove this excess. At present this purge is used as fuel in the reformer,
but the potential for using hydrogen as a feedstock for other reactions (e.g. production
of ammonia, reduction of iron sands) should be noted.

It should also be noted that although the converter catalyst is highly specific in
producing methanol, some side reactions occur which produce higher alcohols (ethanol,
propanol, butanol) and alkanes. These may be summarized:

n CO + 2(n-‰)H2 CnH2nOH + (n-1)H2O

n CO + CH3OH + 2nH2 CnH2n+3OH + nH2O

The crude methanol and water produced in the converter are reduced in pressure in a
letdown "flash" vessel. Gas from this vessel is recycled to the furnace as fuel. The
crude is then sent to "in process storage". This crude methanol contains a large range
of impurities which have to be removed to produce methanol of chemical grade quality.
The technique used for purification is distillation.

21
2.103 Distillation methanol :

The raw methanol produced in the methanol synthesis unit contains dissolved gase s and
a quantity of undesired but unavoidable by-products that have either lower or higher
boiling point than methanol the purpose of the distillation unit is to remove those
impurities in order to achieve the desired methanol purity specification three -column
methanol distillation This is accomplished in the following process step Degas sing
Removal of low-boiling by-products Removal of high-boiling by-products Dissolved
gases are driven out of the raw methanol simply by flashing it at a low pressure into t he
expansion -gas vessel of light and remaining dissolved gases is carried out in a light ends
column finally the methanol is separated from the heavy ends in a pure methanol
distillation section consisting of one or two columns the split of steam and inves tment
cost depend on the distillation concept The first pure methanol column operat es at
elevated pressure and the second column at atmospheric pressure the overhead vapors of
the pressurized column heat the sump of the atmospheric column thus about 40 per cent
of the heating steam and in turn about 40 percent of the cooling capacity are saved the
split of the refining column into tow allows for very high single -train capacities [14 ].

2.11 Methanol purification methods :

2.11.1 Liquid -liquid extraction :

Liquid -liquid extraction (LLE) is the process of separation of a liquid mixture of

components where liquid solvents are used followed by dilution of one or more
components of the initial mixture. This downstream process is significantly useful in
Bioprocess technology. This is aunit process which requires the knowledge of phase
behavior and physicochemical characterization of different compounds. This review
summarizes the theory of LLE, advantages and shortcomings of the process and its
applications in different fields of Bioprocess Technology. Liquid-liquid extraction (LLE)
is an important method to separate constituents(solutes) of homogeneous liquid solutions.
In this separation process, second liquid solvent is added which is immiscible or partially

22
miscible with the feed and the solutes of the mixture are distributed between the two
phases. A quantitative measure of the how a component will distribute between the two
phases is called the distribution or partition coefficient. Distribution coefficient is the ratio
of the concentrations of the solute in the two different solvents when the system reaches
equilibrium. LLE as a method of separation is used if the distillation process is not
feasible, requires more energy or is too complex. LLE is also used if the material is heat
sensitive and non-volatile [ 17 ]. Liquid-liquid extraction is an efficient way of removing
pollutants or products from an aqueous mixture. It can be applied widely in different
fields, for example in the separation of hydrocarbons in petroleum industry, aromatics
removal from fuel oils to improve their burning qualities or in the extraction of phenol
from coal tar liquor .LLE is also applicable to many separation processes in the bioprocess
technology field. These include for example high boiling organics from wastewater,
essential oil extractions and protein purifications [18]. The advantages of this process
include its effectiveness towards compounds with high boiling points even in low
concentrations, azeotropic mixtures (mixtures with points that when boiled, have the
same composition in vapor than initially, thus cannot be altered by simple distillation)
and with heat sensitive compounds like large organic molecules. Disadvantages are the
large consumption of possibly toxic solvent, which also when recycled in the system
requires costly equipment. Thus, right selection of the solvent in achieving a sustainable
process is required and creates challenges to the large-scale industry implementation of
the process. If the aim of the process is to achieve a pure extract, the LLE as a downstream
process is most often only the initial step. Further purification, such as distillation,
crystallization or second extraction might be needed. This can heavily influence the cost
and complicity of the process design and has to be taken into consideration when planning
an overall efficient process [19] .

23
2.11.2 Membrane Method [ 20 ] :

A membrane is a semipermeable barrier between two phases. If one component of a

mixture moves through the membrane faster than another mixture component, a
separation can be accomplished. The basic properties of membrane operations make them
ideal for industrial production: they are simple in concept and operation; they are modular
and easy to scale-up; and they are low in energy consumption with a remarkable potential
for an environmental impact, and energetic aspects.
Polymeric and inorganic membranes are used commercially for many applications
including gas separations, water purification, particle filtration, and macromolecule
separations . If membranes are viewed as semipermeable phase separators, then the
traditional concept of membranes as polymer films can be extended to include liquids.
They are defined as liquid membranes (LMs). Liquid membrane system involves a liquid
which is an immiscible with the source (feed) and receiving (product) solutions that serves
as a semipermeable barrier between these two liquid and gas phases .liquid membrane
systems are being studied extensively by researchers in such fields as analytical,
inorganic, and organic chemistry; chemical engineering, biotechnology, and biomedical
engineering; and wastewater treatment .Research and development activities within these
disciplines involve diverse applications of liquid membrane technology, such as gas
separations, recovery of valued or toxic metals, removal of organic compounds,
development of sensing devices, and recovery of fermentation products and some other
biological systems. The term liquid membrane transport includes processes incorporating
liquid-liquid extraction (LLE) and membrane separation in one continuously operating
device. It utilizes an extracting reagent solution, immiscible with water, stagnant or
flowing between two aqueous solutions (or gases), the source or feed and receiving or
strip phases. In most cases, the source and receiving phases are aqueous and the
membrane organic, but the reverse configuration can also be used. A polymeric or
inorganic microporous support (membrane) may be used as bearer (as in SLM) or barrier
(as in many BLM technologies) or not used, as in ELM and layered BLM .The commonly
accepted mechanism for the transport of a solute in LM is solution diffusion. The solute
species dissolve in the liquid membrane and diffuse across the membrane due to an
imposed concentration gradient. Different solutes have different solubilities and diffusion

24
coefficients in a LM. The efficiency and selectivity of transport across the LM may be
markedly enhanced by the presence of a mobile complexation agent (carrier) in the liquid
membrane. Carrier in the membrane phase reacts rapidly and reversibly with the desired
solute to form a complex. This process is known as facilitated or carrier-mediated liquid
membrane separation. In many cases of LM transport, the facilitated transport is
combined with coupling counter- or cotransport of different ions through LM. The
coupling effect supplies the energy for uphill transport of the solute.The general
properties of liquid membrane systems have been a subject of extensive theoretical and
experimental studies. Some general characteristics
of LM processes are :
(1) Liquid membrane separation is a rate process and the separation occurs due to a
chemical potential gradient, not by equilibrium between phases.
(2) LMis defined based on its function, not thematerial used in fabrication

2.11.3 Distillation method :

Distillation is one of the oldest and most common methods for the purification
of liquids. It has been used for centuries to concentrate dilute alcoholic beverages and to
obtain perfumes from fruits and flowers. In this paper various methods of distillation,
operating principles ,equipment for distillation are discussed in detail. Various design
and operating policies for binary distillation columns are discussed with objective
of maximizing production rate .Significant increasing in capacity can be realized
by optimum design of column-i.e. number of trays, trays hold up ,reflux drum hold up
etc and optimum operation -i.e .reflux ratio and start up procedure .Equipment and
column size issues discussed here may be useful to practicing engineers in early
stage of distillation design .Some issues in the design and operation of a batch and
continuous distillation column are addressed [ 21 ].

Distillation is the process of heating a liquid solution, or a liquid-vapor mixture, to derive

a vapor and then collecting and condensing this vapor. In the simplest case, the products
of a distillation process are limited to an overhead distillate and a bottoms, whose
compositions di reforms that of the feed. Distillation is one of the oldest and most

25
common method for chemical separation. Historically one of the most known application
is the production of spirits from wine. Today many industries use distillation for
separation within many categories of products:
petroleum refining, petrochemicals, natural gas processing and, of course, beverages are
just some examples. The purpose is typically the removal of a light component from a
mixture of heavy components, or the other way around, the separation of a heavy product
from a mixture of light components.
The aim of this practicum is to refresh your theoretical knowledge on distillation and to
show you working distillation column in real life. One of the goals of this practicum is
also to write a good report which contains physically correct explanations for the
phenomena you observed. In the following sections a description of the distillation
column is given, your theoretical knowledge is refreshed and the practical tasks are
discussed. The nal section is about the report you are expected to hand in to pass the
practicum. The report is an important part of the practicum as it trains your ability to
present results in a sciatic way [ 22 ].

2.12 Selective method:

The liquid – liquid extraction is not appropriate method to use because it need chemicals
solvent and need several columns to extraction and recovery solvents .also, membrane
method cannot be used due to the purification rate in this method is low and membrane
cost is high. However, the use of distillation is the best method compare with liquid –
liquid extraction and membrane methods because it has less cost.

26
2.13 Description of methanol distillation process:

Materials come from one of the method of productio n (crude methanol) contains
substances which boils in temperature less than boiling point of methanol and other
substances which boil in temperature more than boiling point of methanol, so we can
get pure methanol of 100% by distillation. The feed enters to the distillation unit in the
weight percentages of composition are: 83% methanol, 16% water, 0.8%light end (which
are acetone and methyl format) & 0.2% fu el gas (02+CO2+CO) [ 23 ]. First stage the feed
enters to the expansion gas vessel where the full gas is completely separated under
conditions of 1 bar and 30°C .Second stage the liquid stream from the vessel enter to the
first distillation tower in composition Of 83.166% methanol,16.0 32% water and
0.802 % light ends. the temperature of the bottom of the tower is 68 C° & at the top
is79 C° and the pressure at the top is 1.4 bar and at the bottom is 1.6 bar. The heating
at the bottom of the tower by reboiler From the highest point of the tower we get light
materials where cooled & pu mped part of these materials return through the top part of
the to the tower in order to achieve the principle of distillation .Third stage from the
bottom of the first tower feed come out through the pump which raise the pressure to the
second tower and enter the second tower in composition of 83.8 38% methanol and
16.162% water . That works under conditions of 118 C° in the top of the tower and
130.8 C in the bottom and 6 bar pressure in the top and 7 bar pressure in the bottom.

From the top of the tower we get 100% pure methanol & it's cooled to 30°C & pumped
part of these materials return through the top part of the tower as reflex Fourth stage the
bottom liquid of the second tower we get 59% water 41% methanol which enter to
the Third tower which works under condition which in the top of the tower 64.5 C° &
in the bottom of the tower 74 C°and 1 bar pressure in the top and 1.2 bar pressure in the
bottom.so we can get from the top of th e tower 100% pure methanol &from the bottom
of the tower we get 100% water & by this unite we get 100% pure methanol ready for
using in several field .

27
Figure ( 2.4 ) : Process flaw diagram for crude methanol distillation unit [ 24 ]

28
 Table(2.5): Equipment summary table for the methanol distillation process.

Towers T-101 T-102 T-103 Vessels V-101

Top Temperature (°C) 68 118 64.5 Temperature (°C) 30

Bottom Temperature (°C) 79 130.8 74 Pressure (bar) 1

Top Pressure (bar) 1.4 6 1

Bottom Pressure (bar) 1.6 7 1.2

29
 Chapter III
Material Balance

30
 CHAPTER 3

MATERIAL BALANCE

It is will known that the material and energy balance calculations are one of the most
important steps in the design of chemical industry systems.In this chapter the mass
balance of various units in the methanol distillation plant is carried out.

It is required to produce 300000 ton of pure methanol per the year .

Assume the system is at steady state ( input = output , accumulation = 0).

The crude methanol feed contain the following compositions :

Table ( 3.1 ): compositions of crude methanol

Composition Weight fraction

Methanol 0.83
Water 0.16
Light ends 0.008
Fuel gas 0.002

31
3.1 Overall material balance :

Figure (3.1): Block diagram of overall material balance.

The basis of design ( production rate ) is 300000 ton per year of pure methanol
ton 1000 kg year day kg
m10 (CH3OH) =300000 × × × = 37878.79
year ton 330 day 24 hr hr

To calculate the amount of feed (m1 ) of the process make overall material balance of
methanol
❖ Overall material balance of methanol :
Input = Output
m1 (CH3OH) = m10 (CH3OH)

0.83 × m1 = 37878.79
kg
m1 = 45637.1 hr

32
 Amount of components in the feed :

❖ Amount of methanol :
kg
m 1(CH3OH) = 0.83 × 45637.1 = 37878.79 hr

❖ Amount of water :
kg
m 1 (H2O)= 0.16 × 45637.1 = 7301.94 hr

❖ Amount of light ends :

kg
m 1(light ends ) = 0.008 × 45637.1 = 365.1
hr

❖ Amount of fuel gas :

kg
m 1(fuel gas ) = 0.002 × 45637.1 = 91.27 hr

Table (3.2): overall material balance.

Stream No kg kg
Input ( ) Out put ( )
hr hr

Stream Stream Stream Stream Stream

Component 1 2 4 9 10
37878.79
Methanol ---- ---- ---- 37878.79

Water 7301.94 ---- ---- 7301.94 ----

Light end 365.1 ---- 365.1 ---- ----

Fuel gas 91.27 91.27 ---- ---- ----

Total 45637.1 45637.1

33
3.2 Material balance around Expansion Gas Vessel

Figure (3.2): Block diagram of expansion gas vessel.

❖ Material balance of fuel gas

Input = Output
m1(fuel gas) = m2(fuel gas) + m3(fuel gas)

91.27 = m2(fuel gas) + 0

kg
m2(fuel gas) = 91.27 hr

❖ Material balance of methanol :

Input = Output
m1 (CH3OH) = m2 (CH3OH) + m3 (CH3OH)

37878.79 =0 + m3(CH3OH)
kg
m3 (CH3OH) = 37878.79 hr

34
 ❖ Material balance of water :
Input = Output
m1 (H2O) = m2 (H2O) + m3 (H2O)

7301.94 = 0 + m3 (H2O)
kg
m3(H2O) = 7301.94 hr

❖ Material balance of light ends

Input = Output
m1 (light ends) = m2 (light ends) + m3 (light ends)

365.1 = 0 + m3 (light ends)

kg
m3 (light ends) = 365.1 hr

Table ( 3.3 ): Material balance around expansion gas vessel.

Stream No kg kg
Input (hr) Output ( hr )
Stream (1) Stream (2) Stream (3)
Component
Methanol 37878.79 ----- 37878.79

Water 7301.94 ----- 7301.94

Fuel Gas 91.27 91.27 -----

Light ends 365.1 ----- 365.1

Total 45637.1 45637.1

35
3.3 Material balance around first distillation column:

Figure (3.3): Block diagram of first distillation column.

❖ Material balance of light ends:
Input = output
m3 (light ends) = m4 (light ends) + m5 (light ends)
365.1 = m4 (light ends) + 0
kg
m4 (light ends) = 365.1 hr

❖ Material balance of methanol:

Input = output
m3 (CH3OH)= m4 (CH3OH) + m5 (CH3OH)
37878.79 =0 + m5 (CH3OH)
kg
m5 (CH3OH)= 37878.79 hr

❖ Material balance of water:

Input = output
m3 (H2O) = m4 (H2O) + m5 (H2O)
7301.94 = 0 + m5 (H2O)
kg
m5 (H2O) =7301.94 hr

36
 Table ( 3.4 ): Material balance around the first distillation column.
kg
Stream NO kg Output ( hr )
Input ( hr )

Stream (3)
Stream (5)
Component Stream (4)

Methanol 37878.79 ----- 37878.79

Water 7301.94 ----- 7301.94

Fuel Gas ----- ----- -----

Light ends 365.1 365.1 -----

45545.83 45545.83
Total

37
3.4 Material balance around second distillation column:

Figure (3.4) :Block diagram of second distillation column.

For 86.58% recovery of methanol [23]

m6 (CH3OH) = 0.8658 ∗ m5 (CH3OH)
kg 𝑘𝑔
m6 (CH3OH) = 0.8658 ∗ 37878.79 =32795.46 ℎ𝑟
hr

❖ Material balance of methanol (CH3OH) :

Input = Output
𝑚5 (CH3OH) = 𝑚6 (CH3OH) + 𝑚7 (CH3OH)

37878.79 = 32795.46 + m7 (CH3OH)

m7 (CH3OH) = 37878.79 − 32795.46

kg
m7 (CH3OH) = 5083.33 hr

38
 ❖ Material balance of water (H2O):
Input = Output
m5 (H2O) = m6 (H2O) + m7 (H2O)

7301.94 =0 + m7 (H2O)
kg
m7 (H2O) = 7301.94
hr

7301.94 =0 + m7 (H2O)
kg
m7 (H2O) = 7301.94 hr

Table ( 3.5 ): Material balance around the second distillation column.

Stream NO 𝑘𝑔
𝑘𝑔 Output (ℎ𝑟 )
Input( ℎ𝑟 )

Stream (5)
Stream (7)
Stream (6)
Component

Methanol 37878.79 32795.46 5083.33

Water 7301.94 ----- 7301.94

Fuel Gas ----- ----- -----

Light ends ----- ----- -----

45180.73 45180.73
Total

39
3.5 material balance around third distillation column

Figure (3.5): Block diagram of third distillation column.

❖ Material balance for methanol :

Input = Output
m7 (CH3OH) = m8 (CH3OH) + m9 (CH3OH)
5083.33 = m8 (CH3OH) + 0
kg
m8 (CH3OH) = 5083.33
hr

❖ Material balance for water :

Input = Output
m7 (H2O) = m8 (H2O) + m9 (H2O)
7301.94 = 0 + m9 (H2O)
kg
m9 (H2O) = 7301.94 hr

40
 Table ( 3.6 ): Material balance around the third distillation column .

Stream NO kg
kg Output( hr)
Input( hr)

Component Stream (7) Stream (8) Stream (9)

Methanol 5083.33 5083.33 -----

Water 7301.94 ----- 7301.94

Fuel Gas ----- ----- -----

Light ends ----- ----- -----

Total 12385.27 12385.27

41
 Table (3.7): Summary of all units streams by mass flow rate(kg/hr).

Stream NO.
1 2 3 4 5 6 7 8 9 10
Component

Methanol 37878.79 ---- 37878.79 ---- 37878.79 32795.46 5083.33 5083.33 ---- 37878.79

Water 7301.94 ---- 7301.94 ---- 7301.94 ---- 7301.94 ---- 7301.94 ----

Light Ends 365.1 ---- 365.1 365.1 ---- ---- ---- ---- ---- ----

Fuel Gas 91.27 91.27 ---- ---- ---- ---- ---- ---- ---- ----

Total 45637.1 91.27 45545.83 365.1 45180.73 32795.46 12385.27 5083.33 7301.94 37878.79

42
 Table (3.8): Summary of all units streams by weight fraction

Stream NO.
1 2 3 4 5 6 7 8 9 10
Component

100%
Methanol 83% ---- 83.166% ---- 83.838% 100% 41% 100% ----

16% 16.032%
Water ---- ---- 16.162% ---- 59% ---- 100% ----

Light Ends 0.8% ---- 0.802% 100% ---- ---- ---- ---- ---- ----

Fuel Gas 0.2% 100% ---- ---- ---- ---- ---- ---- ---- ----

Total 100% 100% 100% 100% 100% 100% 100% 100% 100% 100%

43
 REFERENCES

[1] https://en.wikipedia.org/wiki/Methanol.

[2] HIS Chemical Prospectus, Methanol into Fuels Applications, Special Report Prospectus,
2015.
[3] Company Browser, Methanol, Uhde GmbH, 2005.
[4]J.Jackson, March, 2006,” AMPCO Methanol process basic description” .
http://www.atlanticmethanol.com/public/downloads/UWQhC/ampcomethanolbasicprocess.pdf
[5] National Institute for Occupaional Safety and Health ,22 August 2008,”The Emergency
Response Safety and Health Database : Methanol “. Retrieved 17 March 2009.

https://www.technology.matthey.com/article/61/3/172-182/.

[6] https://www.sigmaaldrich.com/chemistry/solvents/methanol-center.html.

[7] Lide , D,R,ed. (2005) . CRC Handbook of Chemistry and physics(86th ed). BocaRaton
(FL):CRC Press. ISBN 0-8493-0486-5 https://en.wikipedia.org/wiki/Methanol

[8] World health organization,GENEVA 1997,”Mathan health safety gudie”.

[9] Encychlopedia of chemical Technology Volume 16.

[10] Ministry of Business, Lnnovation and employment ,2018 ,”Methanol applications”.

[11] https://byjus.com/chemistry/uses-of-methanol-and-ethanol/

[12] Company Browser, Methanol, Uhde GmbH, 2005.

[13] Lurgi Megamethanol www.lurgi.com.
[14] C. A. A. Higman, 22-23 November, 1995,” Methanol Production by
Gasification of Heavy Residues”, London.
[15] Www.methanex.com.
[16] Global Environmental Report ,2005. www.methanex.com.

44
[17] Kubek, D. J., “Liquid-liquid extraction”, in Protein Purification Process Engineering ,
Rogger Harrison (ed.) Marcel Dekker, Inc. New York (1994) pp 87- 91.
[18] Richardson J.F., Harker C.H., Backhurst J.R. Coulson and Richardson's Chemical
Engineering Volume 2 - Particle Technology and Separation Processes 2001. 5th Edition.
Elsevier Ltd.
[19] Engineering Thermodynamics, Separation Process part 1; Lecture Material 2016.
[20] Prof.Dr.Marco Mazzotti and Dr. Matteo Gazzani,Octoper 7,2016”Membrane Separations
Rate Controlled Separation Processes”.

[21] Bhatia,TA . Patil,KI .Choudhary, PA ,2009,”Distillation operations-methods,Operational

and Design Issues”.

[22] Batista,E.,Meirelles,A.,1997,”Simulation and thermal integration SRV in extractive

distillation column.J.Chem.Eng.Jpn.3,45-51.
[ 23 ] Bin Harharah.H.,2010”Plant design of methanol distillation unit “.

[24] Qingjuan Zheng1. Shiyu Li1, 10 April 2018,” Process Optimization of Coke Oven Gas to
Methanol Based on the Downgrade of By‑Product Steam”.

45