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).