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process selection MEK
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CHAPTER 1
PROCESS SELECTSION
1.1.0 Introduction
Methyl ethyl ketone is an organic compound with the formula CH3C(O)CH2CH3.In nature
Methyl ethyl ketone can found at tree and also found in small amounts in some fruits and
vegetables. By human made methyl ethyl ketone can found in air from car and truck
exhausts. Methyl ethyl ketone is flammable, colourless liquid with a sharp, sweet
butterscotch odour reminiscent of acetone. It is soluble in water and commonly used as an
industrial solvent. It is lighter than water .in IUPC name its call as 2-Butanone and the other
name the 2-Butanone are Methyl-acetone . The most important thing methyl ethyl ketone is
group as carbonyl group methyl ethyl ketone is produced by 5 technic. However,only 2
technic is always use which are liquid phase oxidation of n-butane and dehydrogenation. All
of this process has their advantage and disadvantage.
The task is to design equipment and processes for the large-scale chemical industry to
produce Methylethyl ketone. It is aimed to obtain high-productivity process in safe and
economic ways with minimum production rate of 50 matrix tonne per year. The amount
production of methyl ethyl ketone is based on the market demand and process selection.
1.1.1 Properties Methyl ethyl ketone
Physical properties
Methyl ethyl ketone is colourless and the odour likes acetone. Methyl ethyl ketone is
completely mix together with water to form homogenous solution and readily soluble in
various solvents such as ethers and alcohols. Table 1.1.1 shows the list of physical properties
for methyl ethyl ketone such as boiling and melting point, critical temperature and pressure,
liquid density and viscosity, as well as values of various heat types and acidity.
Table 1 Physical properties
Name 2-butanone
Chemical formula CH3C(O)CH2CH3
Formula weight 72.12
Synonyms Methyl ethyl ketone, meetco
Appearance Colorless
Behaviour Flammable liquid
Boiling point 79.6 C0
Melting point -86.5 C0
Vapour pressure 70mmgH
Specific garavity(water=1) 0.806
Water solubility Completely soluble
Form Colourless liquid
Stability Stable, but highly flammable
(M.Sharma, Jaypee Institute of Engineering , April, 2010)
Chemical properties
Methyl Ethyl ketone can be utilized in chemical synthesis. Most of the reactivity happens at
carbonyl group and its adjacent hydrogen atoms. From the proper condition, condensation,
ammonolysis, halogenations, and oxidation can be carried out. Some reaction shown below
Self- condensation
Condensation of 2 moles of MEK yields a hydroxy ketone, which readily dehydrates to an
unsaturated ketone:
Condensation with other compound
Compounds Reaction with aldehydes gives higher ketones, as well as metals and cyclic
compounds, depending on reaction conditions. β- ii ketones are produced by the condensation
of MEK with aliphatic esters. MEK condenses with glycols and organic oxides to
givederivatives of dioxolane.Sec-Butyl amine is formed by reacting MEK with aqueous
ammonia and hydrogen:
The excess MEK will produced di-sec butylamine and the reaction of MEK with ecetylne
give methyl phenol.
Other reaction
Oxidation of MEK with oxygen produces acetyl, a flavouring material. Chlorination yields
mixtures of several monochloro and dichloro 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.
Source:http://www.sbioinformatics.com/
1.1.3 Use and Application
Its one of the many solvents used as a raw material in the manufacture plastics, textiles, in the
production of paraffin wax, and in household products such as lacquer, varnishes, and
production of paint and ink. It is efficient and versatile solvent for surface coatings. MEK is
especially valuable in formulating high solids coatings, which help to reduce emissions from
coating process it done.MEK is also used in dry erase marker as the solvent of the erasable
dye and in synthesis of MEK peroxide, a catalyst for some polymerization reactions.
Other than that,Methyl ethyl ketone is use as welding agent for example when MEK
dissolves polystyrene, it is sold as “polystyrene cement” use as connecter between the part of
body kit.Other usage methyl ethyl ketone can use as extraction solvent in the processing of
foodstuffs and food ingredients for example in fractionation of fats and oils, decaffeination of
tea and coffee, and extraction of flavourings.
1.1.4 Types of process to produce MEK
There are a few processes for the production of MEK, which is vapor phase dehydrogenation
of 2- Butanol, liquid phase oxidation of n-Butane, direct oxidation of n-Butanes, Hoechst-
Wacker process and direct oxidation of n-Butanes, Maruzen process.
MEK is prepared by secondary-butyl alcohol dehydrogenation. Consist of two step
which are first hydrated to give to produce secondary-butyl alcohol from butenes. Then
followed by dehydrogenation of secondary-butyl alcohol is an exothermic reaction to form
MEK and hydrogen gas. The reaction is as follows.
.
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. 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.
In the process of liquid phase oxidation of butane MEK is produced as a by-product
and acetic acid is the main product for this process. MEK has occasionally been
commercially available in significant quantities from the liquid-phase oxidation of butane to
acetic acid. Depending on the demand for acetic acid, this by-product methyl ethyl ketone can
be marketed or recycled.
Initially, n-butane and compressed air or oxygen are fed into a reactor along with a catalyst,
typically cobalt, manganese or chromium acetate to produce acetic acid, MEK and other by-
products such as ethanol, ethyl acetate, formic acid, and propionic acid, like shown bellow
Air is bubbled through the reactant solution at specified temperature and pressure this
conditions must be carefully controlled to facilitate MEK production and prevent competing
reactions that form acetic acid and other by-products. Process conditions can be varied
producing different ratios of product components through the choice of raw material, reaction
conditions, and recovery methods. The purification section of the plant is complex and highly
specialized utilizing three- phase distillation in conjunction with straight extraction. The low-
boiling organics such as MEK are separated from the crude acetic acid by conventional
distillation. Azeotropic distillation is used to dry and purify the crude acetic acid. Recovery
and purification of the various by- products require several distillation columns and involve
extractive distillation or azeotrope breakers or both.
In direct oxidation of n-butanes by Hoechst-wacker process, oxygen is transferred in
a homogenous phase on to n-butanes using redox salt pair, PdCl2 / CuCl2. 95% conversion
of n-butanes can be obtained with the MEK selectivity of about 86%. The main disadvantage
of this product is the formation of chlorinated butanones and b- butryaldehyde and corrosion
caused due to free acids.
The Maruzen process is similar to the Hoechst-Wacker process except that oxygen is
transferred by an aqueous solution of palladium sulfate and ferric sulfate. This method is
attractive commercial route to get MEK via direct oxidation of n-butenes, but it is patented
and very less information is available about this process. This process is generally not
accepted due to formation of undesirable by products.
Table 2 comparison of the process
Process Dehydrogenation Liquid phase oxidation Direct oxidation
Hoechst-Wacker process
Direct oxidation
Maruzen process
Raw material Sec-Butyl alcohol Butane Butenes Butenes
Main product MEK Acetic acid MEK MEK
By product - MEK Chlorinated butanone and
n- butryaldehyde
Chlorinated butanone and
n- butryaldehyde
Catalyst Copper, zinc or bronze Non- catalysed PdCl2/CuCl2 Palladium sulphate/ ferric
sulphate
Catalyst life Long - Short Short
Conversion Higher conversion rate; 80-
95%
Low coversion 95% 95%
Yield Very high Very low High High
Selectivity 95% 86% 90%
Energy consumption Very low Very low - -
Economical feasi- bility Less than liquid phase
oxidation
Very high - Not known
Separation process Very simple - Not known as process is
patented
Not known as pro- cess is
patented.
Sources : Divyesh Arora & Mohit sharma Jaypee Institute of Engineering & Technology
1.1. 5 Process selection
There are four type of process can be used in production of MEK, So the scoring method was
used to identify which of the process is the best to produce MEK. The evaluation was done
by set the critical factor for the reference standard and the score of zero was given, mean
“same as”, the sign of + given mean as “ better than” and the last sign – is mean worse than.
Lastly it will total up and the ranking was given. From the table bellow we can see that the
rank of each process.
Table 3 Scoring method
Critical success
factor
Scoring method
Dehydrogenation Liquid phase
oxidation
Direct oxidation
Hoechst-Wacker
process
Direct oxidation
Maruzen process
Main product 0 - 0 0
By product + 0 - -
Catalyst 0 + 0 0
Catalyst life + + - -
conversion 0 - 0 0
Yield + - 0 0
Selectivity + + +
Energy
consumption
+ + - -
Economical
feasibility
- + -
Separation
process
+ - -
Total 5 2 -3 -4
Rank 1 2 3 4
From this scoring method, all the processes, it has been found that dehydrogenation has more
advantages and is more economical compared to other processes, so this process has been
selected for designing. Commercially, MEK was produced by the catalytic dehydrogenation
of secondary-butyl alcohol in vapor phase over ZnO or Brass act as catalyst. Nowadays
around 88% MEK was produced by dehydrogenation of secondary-butyl alcohol, which can
be easily produced by the hydration of n-butenes.
The dehydrogenation process gives high conversion of secondary-butyl alcohol and
high selectivity of MEK which is about 95mole%. This process also give a better yield,
longer catalyst life, simple production separation and lower energy consumption. From this
benefits we can reduce the cost of the production.
This dehydrogenation processes initially, preheated vapors of secondary-butyl alcohol
are passed through a reactor, which contain a catalytic bed of zinc oxide or brass as catalyst
which are the temperature should be maintained between 400° and 550°C, at normal
atmospheric pressures is required to convert it to MEK. Product gases from the reaction
vessel are then condensed and sent to a distillation column for fractioning. The main fraction
MEK is typically obtained at an 85 to 90% yield. The uncondensed gas may be scrubbed with
water or a nonaqueous solvent to remove any entrained ketone or alcohol from the hydrogen-
containing gas. The hydrogen may then be re-used or recycle back or burned in a furnace, or
flared.
CHAPTER 2
Market Analysis
2.1 INTRODUCTION
Methyl ethyl ketone or butanone normally use as a solvent in many applications due to its
outstanding chemical properties like acetone but some off the properties may vary with
acetone and that make MEK more widely as solvent. MEK had low boiling point but not to
low compare to acetone. This make the evaporation rate of MEK is slower then acetone so
that is easy to use and store. Other chemical properties is MEK is highly dissolve chemical
that partially dissolve in water and fully dissolve in other organic chemical. Because of this
properties MEK is widely use in processes involving gums, resins, cellulose acetate and
nitrocellulose in coatings and vinyl films processing. It also been use in paint, lacquer,
varnishes and also use as paint remover. Other important use of MEK is act as dissolving
agent in glues and adhesive industry.
Methyl ethyl Ketone is one of demanding chemical and the demand of MEK increase
every year. Even the middle east the supplied of raw material to produce MEK but North
America becomes the largest producer of MEK follow by western euro, and Japan. This there
is the largest production of MEK base on article by Chemical Weekly on April 2007. China
had been the most country the import the MEK for their industry. However nowadays the
table had change because China try to become one of main producer of MEK for its own
industrial use. This shown China start to monopoly the MEK market. If China can
monopolize MEK production and uses the price of MEK will depends solely to China. This
will may affect all the industry that uses MEK as raw material in other country. To overcome
this problem, other country that use MEK in industry shouldn’t depends on other country to
supply then with this chemical. Lastly the factor that make the market demand going wild
because one of the main country that produce MEK which Japan was effected by the
earthquake. The earthquake that happen on 2011 cause the largest production of MEK in
Japan to shutdown
2.2 MARKET DEMAND FOR GLOBAL
Base on the study that had been conducted by Grand View Research in September 2014 the
value of global market for MEK may be reach to USD 3.26 billion by 2020 or higher base on
demand and the widely field use MEK as their raw material. The main driving force or key
that cause this demand for global MEK market to growing faster was for paints and coatings
in infrastructure, automotive and home. Growing demand from key end-use industries such as
construction and automotive, particularly from high growth market such as Asia Pacific and
Latin America, is expected to further fuel its demand. MEK also used as synthetic rubber in
domestic products and act as a liquid solvent in chemical manufacturing, especially for drugs
and cosmetics. Increasing market penetration of MEK in pharmaceutical applications is also
expected to have a positive influence on market growth. However, the main challenges to
participate in this market are the unstable price of raw material and environmental hazards.
Even do some company may shift to some material produce by bio-fuel solvent base to
replace the MEK but this bio-fuel solvent base is too costly to produce compare to MEK.
This make sure the market and demand of MEK remain strong for the future unless a new
breakthrough found to replace the MEK.
Base on this study, there are some kind finding that suggest that market of MEK remain
strong:
Global MEK market was 1,319.2 kilotons in 2013 and is expected to reach 1,754 kilo
tons by 2020, growing at a CAGR of 4.2% from 2014 to 2020.
Paints and coating dominated the global MEK application market and accounted for
56.3% of the total volume in the year 2013. Increasing construction spending in Asia
Pacific is expected to drive the demand for MEK in paints and coatings. Printing inks
is expected to be the fastest growing application segment for MEK at an estimated
CAGR of 4.9% from 2012 to 2020. Increasing demand from food and packaging
industry is expected to drive the demand for MEK in printing inks over the next
several years.
Asia Pacific emerged as the leading regional market for MEK and accounted for
55.8% of total market volume in 2013. Asia Pacific is also expected to be the fastest
growing market for MEK, at an estimated CAGR of 5.0% from 2012 to 2020.
Increasing infrastructure spending coupled with a positive outlook on the regional
automotive industry, particularly in China and India is expected to drive the regional
demand for MEK over the next six years.
North America and Europe are mature markets for MEK are expected to grow at a
relatively sluggish rate over the forecast period. These developed markets are
characterized particularly by increasing adoption of bio-based alternatives to MEK.
The global market for MEK is moderately concentrated with top four companies,
namely ExxonMobil Chemical, Maruzen Petrochemical, Zibo Qixiang and Sasol
Solvents accounting for over 55% of the total market share. Other major market
players include Tasco Chemical, Shell Chemicals, Tonen Chemical, PetroChina
Lanzhou, Fushun Petrochemical, SK Energy and Idemistu Kosan.
2.3 Market Demand in India
India is one of the country has large industry that using MEK as solvent. The current demand
of MEK in India is estimated around 30,000 tons per year. India still cannot satisfy the demand of
MEK as CETEX Petrochemical LTD. is the only producer of MEK in India. So, it imports MEK from
various countries to satisfy those demands (Table 1).
Country Imports(tons)
Taiwan 672
Japan 2,036
China 1,467
South Africa 3,286
Singapore 39
UK 1,085
Netherlands 45
Table 1: Imports of MEK into India (2007-2008)
The major uses of MEK in India are for printing then followed by adhesives and
painting industries. The imports data of MEK in Table 2 shows that the imports have
increased from 13,544 tons in 2005-06 to about 31,500 tons in the year 2010-11. About 17.3
per cent compounded growth rate had been registered during that period.
Years Quantity(Tons)
2005-06 13,544
2006-07 17,758
2007-08 22,091
2008-09 20,668
2009-10 24,556
2010-11 32,626
Table 2: Imports of MEK into India
CHAPTER 3
SITE LOCATION
3.1 INTRODUCTION
The location of the site is an important part in the process of setting up a chemical
plant. Proposed site location will have a significant effect on the profitability of a project and
the availability of space for future expansions of plant. The optimization of production of the
plant is greatly depends on the suitability of the proposed location. Careful consideration
must be made in selecting the most suitable site because of its long-term consequences. A
different factors that will affect the selection of site also need to be considered properly. It is
also preferable to consider the suitable site location on a local basis. However, if there are no
suitable areas for the construction of chemical plant and no local markets exists for the
chemical products, it is necessary and preferably to consider industrial regions elsewhere.
According to Sampat, 2011, India was one of the countries that is demanding for more
production of methyl ethyl ketone. India was importing methyl ethyl ketone from a few
countries such as United Kingdom, South Africa and Taiwan to meet their demands. Other
than that, Japan producers now have started to cutting of their exports to meet their domestic
shortage. This is because one of the factories producing methyl ethyl ketone in Japan was
closed due to damage from the earthquake. Based on Global and China Methyl Ethyl Ketone
Industry Report (2010-2012), 2011, the demands for methyl ethyl ketone increase, especially
from the largest consumer which is China. Export of methyl ethyl ketone from Chinese
manufacturers also rises because of the capacity reduction caused by Japanese earthquake.
3.2 GENERAL CONSIDERATION IN SELECTING SITE LOCATION
According to Sinnot and Towler, 2013, there are ten important factors that need to be
considered when selecting a suitable site location for the production of methyl ethyl ketone.
Methyl ethyl ketone is categorized in the petrochemical industry and it is crucial to select site
location properly. The important factors are all listed as below:
1. Supply of raw materials.
2. Availability of suitable land.
3. Transport facilities.
4. Availability of utilities: Water, Electricity.
5. Market location.
6. Local community consideration.
7. Availability of labour.
8. Climate.
9. Environmental impact including effluent proposal.
10. Political and strategic consideration.
Above all the factors, the major factors that first need to be considered are proximity to major
transport networks, raw materials supply and the market for the product chemical (Ray and
Sneesby, 1998).
3.2.1 Supply of raw materials
Availability of raw materials need to be considered because it is the one that will affect the
desired product. Higher conversion of desired product with less by-product can be achieved
when suitable raw materials for the process are used. Other than that, the proposed plant must
be built near to the raw materials supplier, including the catalyst, in order to reduce the cost
of transportation and time. This is an advantage to the company as fewer budgets are needed
for transportation making the plant more profitable. Factors such as distance of plant from
source of supply, composition quality of raw materials, price of raw materials, transportation
expenses and storage requirement must also be considered to choose the suitable suppliers of
raw materials.
3.2.2 Availability of suitable land
The geographical factor of the proposed site must be evaluate properly. The land for site
location should be available and enough for the proposed plant and for the future expansion.
The land must ideally flat, well drained and have a suitable load-bearing characteristics.
Particular care must be taken in consideration also when building plants on reclaimed land
near the ocean in earthquake zone. The price of land also must be considered when selecting
the plant site. Price of land will depends on the location of property and may vary between a
highly industrial area and a rural district (Sinnot and Towler, 2013). Normally, the land price
will increase time by time.
3.2.3 Transport facilities
The more transport facilities available close to a proposed plant, the more preferable the site
location is. According to Sinnott and Towler, 2013, plant site should be located near to at
least two major types of transportation, such as roads, railway, waterway or a seaport. It can
be divided in three categories which are road, sea and air transportation. Suitable selection of
transport facilities not only ease the transfer of raw materials to the plant, it is also important
for export purposes and can ensure that the products is delivered accordingly.
3.2.4 Availability of utilities
Every plant requires utilities to run the plant. The plant will run smoothly with a good
provided utilities. Cheap sources of utilities such as water and electricity are also will be
considered in selecting site location. Electricity is used to power the plant, thus plant needs to
be located at near to a cheap source of power. Cheap rate of electricity and water are
preferable as it can lower the utilities costs and increasing the profit of the plant. The price for
utilities are differ for each country as each country will have their own demands for utilities
and have their own company that handles the utilities.
3.2.5 Market location
The marketing area have a significant role in selecting the plant site location. A good plant
location is a location that close to the target market, near to the raw material suppliers,
intermediate distribution centre and customers. This aspects important for the cost of
products distribution and time for delivering the products. It is an advantageous for buyers to
purchase from a nearby source. However, methyl ethyl ketone is a heavy chemical industry
and it need to be built at certain distance from residential and community area.
3.2.6 Local community consideration
At different locations, local community may have different characters and facilities which
give an effect on the proposed plant. Full consideration must be given to the safe location of
the plant so that it does not impose a significant additional risk to the community (Sinnot and
Towler, 2003).
3.2.7 Availability of labour
The availability of labor type and supply in the vicinity of a proposed plant site must be
analysed. Workers who have skilled construction usually will be brought in from outside the
site area. However, there should be an adequate pool of unskilled labor available locally and
labor suitable for training to operate the plant (Sinnot and Towler, 2003).
3.2.8 Climate
The climate, especially the extreme weathers can have an influence on the operation of the
plant. For instance, the protective shelters should be implemented around the process
equipments during cold climate whereas cooling and air conditioning equipments are
required during summer which both will increase the cost significantly (Sinnot and Towler,
2003). Therefore it is very important to analyse all the factors when selecting a plant site such
as rainfall, temperature and wind.
3.2.9 Environmental impact including effluent proposal
According to Sinnot and Towler, 2003, one of each industrial plant will produce waste
products especially chemical plants. The site selected should have satisfactory and efficient
disposal system for plant wastes or effluents such as the drainage systems and dumping sites.
The waste disposal must be treated according to standard and procedure of Department of
Environment (DOE). Water discharge has to be treated before channelled to open drains.
Therefore, before commencement of operation, each plant also has to obtain approval for site
suitability from Department Of Environment to make sure a site location chosen will secure a
smooth operation for the plant and gives low impact on the environment.
3.2.10 Political and strategic consideration
Governments have given the capital grants, tax concessions, and other inducements to direct
a new investment to preferred locations, such as areas of high unemployment. The
availability of such grants can be the overriding consideration in site selection (Sinnot and
Towler, 2003).
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