Techno-Economic Feasibility Report on Production of Methyl Ester Sulfonate From Palm Oil

Techno-Economic Feasibility Report on Production of Methyl

Ester Sulfonate From Palm Oil

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CERTIFICATE

This is to certify that the project entitled Techno-Economic Feasibility Report

on the production of Methyl Ester Sulfonate from Palm Oil which is hereby

presented by Mr. Ronak Jain in partial fulfillment of the requirements of the

award of the degree of Bachelor of Technology at the Indian Institute of

Technology, Roorkee, is a genuine account of his work carried out during the

period from August 2013 to April 2014 under our supervision and guidance.

Date: 30-04-2014

(Dr. R. Bhargava) (Dr. V. K. Agrawal)

Department of Chemical Engineering Department of Chemical Engineering

Indian Institute of Technology, Roorkee Indian Institute of Technology, Roorkee

Roorkee 247 667 Roorkee 247 667



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ACKNOWLEDGEMENT

It is with a deep sense of gratitude and indebtedness that I express my sincere gratefulness to my

project guide Dr. Vijay Kumar Agarwal, Head of Department, Department of Chemical

Engineering, Indian Institute of Technology, Roorkee, under whose able guidance, constant

supervision and encouragement, this work has been accomplished. I thank him for taking time

out of his busy schedule and aiding us with his priceless suggestions, encouragement and

cooperation, which in turn helped us, enhance the scientific merit of the present project work.

Without his guidance and mentorship, this work would never have reached its completion. The

constant motivation and support from him made us understand the depths of various techniques

and processes being used in the current scenario.

I would also like to convey my heartfelt gratitude to Dr. Ravindra Bhargava, Assistant

Professor, Department of Chemical Engineering, Indian Institute of Technology, Roorkee, for

his never ending support and help throughout the course of the project. I thank him for helping us

overcome many difficulties and perfect several processes.

I would also thank my Institution and entire staff of Central Library, IIT Roorkee who provided

me with facilities for various books, research papers and internet.

( Ronak Jain)



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LETTER OF TRANSMITTAL

Ref. No. ACME Synthetics Ltd./Plant/Design/2013-14

Date: 30/04/2014

The General Manager

M/S ACME Synthetics Ltd.

Re: Techno-economic feasibility report on the Palm oil Based Methyl Ester Sulfonate

Production.

Dear Sir,

I thankfully acknowledge the receipt of your letter ref. no. ACME Synthetics.

Ltd./Plant/Design/2014 dated August 2013. I am sending you the techno-economic feasibility

report on the manufacture of 95 TPD Methyl Ester Sulfonate for your kind perusal.

After making a detailed survey and study of various processes available, it has been concluded

that the production of Methyl Ester Sulfonate using Imported Palm oil as raw material is best

suited for your case. Exhaustive study of the process design and economics has been done and

the results say that the project is both technically and economically viable.

The total capital investment required is Rs 948,495,274 and the reference payback period is

3.611 years.

Any query regarding the report or elaboration of any point is always welcome.

Assuring you of our reliable and best services.

Yours truly,

Ronak Jain



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Table of Contents II. Summary .................................................................................................................................................. 6

III. Project Details ................................................................................................................................... 8

1.Introduction ............................................................................................................................................ 8

1.1 Problem statement and description ................................................................................................. 8

1.2 Introduction to the format of the Report ......................................................................................... 9

2. Project Description .............................................................................................................................. 10

2.1 Uses and present status of the product ......................................................................................... 10

2.2 Available Processes, Technologies and Selection ........................................................................ 12

2.3 Raw materials ................................................................................................................................ 46

3. Material and Energy Flow Information........................................................................................... 66

3.1 Trans-esterification ....................................................................................................................... 67

3.2 Sulfonation .................................................................................................................................... 86

4.Detailed Design of Equipment ............................................................................................................. 89

4.1 Process design ............................................................................................................................... 89

4.2 Mechanical Design ...................................................................................................................... 185

4.3 BIS standard Drawing of Equipments......................................................................................... 204

4.4 Specification of Major Equipments ............................................................................................ 205

4.5 Major Engineering Problems of Plant ......................................................................................... 214

5. Material Storage and Handling Facilities .......................................................................................... 232

6. Process Instrumentation and Controls ........................................................................................... 247

6.1 Types of Control System ............................................................................................................. 249

6.2 Design and Operation of typical Control Systems ...................................................................... 252

IV. Environmental Protection and Energy Conservation .................................................................... 263

1. Environmental Aspects ..................................................................................................................... 263

1.1 Air Pollution ................................................................................................................................ 263

1.2 Liquid effluents ........................................................................................................................... 272

1.3 Solid Waste Disposal .................................................................................................................. 280

1.4 Noise Pollution ............................................................................................................................ 280



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2. Energy Conservation ......................................................................................................................... 283

V. Plant Utilities .................................................................................................................................... 294

1. Process and Instrumentation Air: ...................................................................................................... 295

2. Heat Transfer Media ......................................................................................................................... 298

3. Water ................................................................................................................................................ 299

4. Refrigeration ..................................................................................................................................... 307

5. Electricity and Power Requirements: ................................................................................................ 308

VI. Organizational Structure and Manpower Requirement ................................................................. 310

1. Organizational structure ................................................................................................................ 310

2. Manpower requirement ................................................................................................................. 313

3. Organizational Chart ......................................................................................................................... 319

VII. Market Prospects ........................................................................................................................... 320

VIII. Site Selection and Project Layout ................................................................................................. 325

IX. Economic Evaluation and Profitability of the Project ................................................................... 340

1. Estimation of Capital Investment ...................................................................................................... 340

2. Manufacturing Costs ......................................................................................................................... 344

3. Profitability Analysis .................................................................................................................... 347

4. Breakeven Point ............................................................................................................................ 348

X. References ......................................................................................................................................... 351



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II. Summary

This project report is an attempt towards making a techno-economic evaluation of installing

a plant for production of Methyl Ester Sulfonate with an installed capacity of 95 Tons/day.

Starting from vegetable oil, the technology to produce Methyl Ester Sulfonate involves

converting the oil to methyl ester followed by hydrogenation to reduce the degree of

unsaturation and then sulfonating the ester to produce MES.

Refined, bleached and deodorized palm oil is used as the feedstock as the price of palm oil is

less as compared to others. Also, its availability is not an issue since it can be easily imported.

Moreover, the reaction yield with palm oil is excellent. Other major raw materials used are

Methanol and Sulfur. For production of Methyl Ester, Lurgi Transesterification is used since the

process is well known and is widely used for methyl ester production. Sulfonation is done by

burning sulphur in air. The technology used is of Chemithon since this technology is widely

known and has many advantages over Ballestra technology.

SO3 is produced by sulfur burning in the air/SO3 sulfonation plant. There are significant safety

advantages to a sulfur burning system. With sulfur burning air/SO3 sulfonation processes, the

only SO3 on site is the small quantity of dilute gaseous material in the process piping between

the converter (SO2 to SO3) and the sulfonation reactor. Even in the world's largest sulfonation

plant (20,000 kg/hr active production) this amounts to only about 100 kg of dilute SO3 gas. The

sulfur burning process is much safer than transporting, storing and handling tank truck (18,000

kg) or rail car (72,000 kg) quantities of oleum or liquid SO3.

Considering many factors the site selected for our plant is the Navi Mumbai Special Economic

Zone (NMSEZ). It is located in the satellite township near Mumbai known as Navi Mumbai in

the state of Maharashtra. Navi Mumbai Special Economic Zone (NMSEZ) is situated in the most

industrialized part of India. NMSEZ is regarded to be the best SEZ in India as sea, rail, air and

road and a state of the art trans-shipment hub connect it.



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Cost, Profitability and employment

Plant capacity: 95TPD

Total Capital Investment Rs - 948,495,274

Net Profit: Rs - 211853137.7

Payback Period: years - 3.611 Years

MES selling Price: Rs. 133.66

Return on investment: - 25.68 %

Break Even Capacity: - 14013445.34 kg/year



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III. Project Details

1.Introduction

1.1 Problem statement and description

A Techno-economic feasibility report is to be prepared for production of Methyl Ester

Sulphonate with an installed capacity of 95 Tons/day.

Due to increasing demand for surfactants and growing concern for environment, research for

new chemicals that are biodegradable and can be used as surfactants has been going on for the

past few years.MES derived from palm oil and coconut oil derivatives has been in the limelight

with the increase in crude oil prices and the resultant increase in price of petrochemicals.It offers

an environment friendly and viable alternative to the currently used linear alkyl Benzene

Sulphonate.

Methyl ester sulphonate(MES) is a sulphonated anionic surfactant derived from oleochemical

Methyl esters.An MES molecule basically consists of a lipophilic and a hydrophilic part.The

lipophilic part(oleochemical) is fat/oil friendly and hydrophilic part (sulphonate) is water

friendly.When MES is placed in oil-water mixture,it arranges itself such that hydrophilic part

remains towards water and lipophilic part towards oil.Thus,it is a surfactant.

The typical cut of Fatty acid methyl ester sulphonate (FAMES (C16-C18)) shows interesting

surface activity (about 90% compared toLABS), high detergent, dispersing and emulsifying

power in hard water, high lime soap dispersion and moderate foam levels. FAMES show high

stability to pH and temperature hydrolysis. Therefore, they can be incorporated in detergent bars.

Methyl ester sulfonates have a wide range of application and important biological properties. As

aggregated value the FAMES can be used in cosmetics, as auxiliary agents inthe production of

fibers, plastics, and rubber, and in leather manufacture.



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1.2 Introduction to the format of the Report

In this report,available processes for the production of MES have been compared and based on

economic and environmental factors,a suitable method has been chosen.Also,the detailed

specifications,testing procedures and government policies of raw materials used have been

given.Appropriate assumptions were made and material and energy balances were made based

on the allotted capacity. Environmental protection and Energy conservation has also been

discussed.Environmental aspects like Air pollution,Liquid effluents,Solids disposal have been

discussed in detail. Organizational Structure and Manpower requirement, Market prospects of

the Product have been discussed in detail too. Besides, Site Selection and Project Lay Out have

been done while considering their critical points.



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2. Project Description

2.1 Uses and present status of the product

Laundry detergent plays a major role in removing soils and stains from fabrics in household uses.

These detergents are inthe form of powder, liquid, or paste and normally comprise asurface-

active agent or surfactant as the main cleaning ingredient. Manufacturers in the detergent

industry have become extremely competitive over the performance, cost-effectiveness and

environmental attributes of detergents. Linear alkyl benzene (LAS) which is currently major

surfactant is a petroleum product and environmental polluting. Due to depletion of petroleum

resources and environmental concerns it has become important to find its alternative. In the

search of alternate substitute Methyl Ester Sulphonate(MES) is the most important product. It

may be produced from renewable resources such as palm oil or coconut oil and also

environmental friendly. The Malaysian Palm Oil Board (MPOB) studies revealed that SME

(sulfonated methyl ester) has the potential to biodegrade faster than LAS.

SME has been produced and applied in detergents and cleaning products widely by large

companies such as Lion Corporation and Stepan. Huish has a plant in Houston that produces

82,000 tons of sulfonates per year; Huish is producing SME from palm oil and using it in

commercial laundry detergents such as Costco Kirkland Brand Select Ultra and Safeway Select

Ultra. The Safeway Select Ultra II has the highest level of SME, containing approximately

23.5% SME, and it has a very low cost per load (US $0.125 per wash).

The methyl ester sulphonate (MES) market is currently in its growth phase, and participants are

engaged inbuilding product awareness to ratchet up market prospects. A prominent aspect set to

drive growth is thatMES can be used as biodegradable surfactants in detergents, notes the

analyst of this research service.

Usage of MES in this manner is nearly untapped but current vibration in the surfactants market

for greenand biodegradable raw materials to be used may lead to potential high demand for MES

surfactants. Highscheme pricing is expected to recover development cost, though some large

suppliers may absorb costthrough captive usage. In the current scenario, product distribution and



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promotions are carried out targeting selected customers at least until customers at large are ready

to accept MES. Emphasizing the green advantage can deliver considerable marketing mileage.

Competition in this space is becoming more intense and marketing strategies at this stage will

enable better product outreach and visibility, effectively communicating attributes and benefits

of MES, which scores better than other anionic surfactants, particularly linear alkyl benzene

sulphonate (LAS), on multiple counts. MES has excellent characteristics such as high purity and

active level, and is devoid of any volatile organic compound (VOC). It is also gentle on the skin,

has low percent of di-salt (around 5.0 to 10.0 percent), is white/near white in color,and is suitable

for both liquid and powder detergents. Feedstock availability issues cloud market prospects.

The production of MES is an expensive procedure entailing heavy investment and prior technical

expertise. Feedstock for methyl esters is obtained from plant and tallow resources, and producers

are dogged by feedstock availability concerns. MES supplied for the detergent market is usually

a blend of C-16 methylester (greater than 95 percent) and C-18 (less than 5 percent). However,

other cuts such as C-12 and C-14also find their way into these markets. Palm-based feedstock is

claimed to be a better source for C-16 and C-18 cuts compared to other resources. The onus is on

MES producers to acquire the appropriate cuts of methyl ester. Careful selection of feedstock

needs to be undertaken and the incoming raw materials must undergo testing to ensure a

competitive source.

With a host of potential applications besides detergent and personal care formulations, raising

consumer awareness seems to be the crucial effort required for market expansion. For instance,

MES can be used as floatation agents in mining.It can be used as de-fattening agents for leather

application because it helps dissolve fat and dirt on leather surfaces. Regulatory and

environmental bodies are advocating the use of green surfactants such as MES as the next

generation of surfactants.



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Applications of MES

1) Detergents

Powdered detergent

Liquid detergent

2) Dishwash and Handwash

Liquid dishwash

Gel dishwash

Paste dishwash

3) Cosmetic

4) Agrochemical

5) Hard surface cleaner

6) Pesticide composition

7) Emulsifier in personal care product

8) Technical Applications

2.2 Available Processes, Technologies and Selection

Starting from vegetable oil/animal fats, the technology to produce MethylEster Sulfonate

involves converting the oil/fats to methyl ester followed by hydrogenation to reduce the

degree of unsaturation andthen sulphonating the ester to produce MES.



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2.2.1 Steps for Production of Methyl Ester Sulfonate:

Splitting of Fat:

Esterification: Esters are organic compounds in which an organic group (represented by R)

replaces an acidic hydrogen atom in a hydroxyl group.

The most common esters are carboxylic esters, where the acid in question is a carboxylic acid.

Fatty acids are carboxylic acids and form carboxylic esters with alcohols and with methanol,

they form methyl esters.

Trans-esterification: Trans-esterification is the chemical reaction between triacyl glycerides and

alcohol in the presence of a catalyst to produce mono-esters. Both the straight and branched

chain triacyl glyceride molecules are transformed in this process to mono-esters and glycerol.

The trans-esterification process actually consists of a sequence of three consecutive reversible

reactions. That is, conversion of triacyl glycerides to diacyl glycerides, then the conversion of the

diacyl glycerides to monoacyl glycerides. The monoacyl glycerides are finally converted into

glycerol. Each step yields one molecule of the ester and its reaction is reversible.



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Hydrogenation of methyl ester :

Sulfonation:

Aging (Digestion):



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Re-esterification:

Neutralising:

Di-salt formation:

Hydrolysis:

Acid digestion leads to colour development with Klett values ranging from 1000-12000 on

acid.So,bleaching is imperative.

Colour varies with J2V number of the feedstock.Products with low J2V acceptable.Thus,the

feedstock is limited to palm stearin /coconut.



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2.2.2 Process available for producing methyl ester from fatty acids:

The two most important criteria to be met for an oil to be suitable for detergent grade Methyl

ester are:

Chain Length distribution

Saturation of fatty acid Carbon chain

Based on these parameters,oils like palm oil,Coconut oil, Palm stearin, Palm kernel, tallow are

suitable for making detergent grade Methyl ester.

Methyl esters of fatty acids can be made either by esterification of the fatty acids or trans-

esterification of the triglycerides usingmethanol.

Esterification Processes:

There are two general methods used for esterification: the Batch process and the Continuous

process.

Esterification can be done batch wise under pressure at a temperature of 200250 C. As it is an

equilibrium reaction, the water is removed continuously to obtain a high-ester yield

Henkel has developed a continuous countercurrent esterification using a doubleplate reaction

column. The technology is based on the principle of an esterification reaction with the

simultaneous absorption of the superheated methanol vapor and desorption ofthe methanolwater

mixture.The reaction is carried out at a pressure ofapproximately 1000 kPa and a temperature of

240 C. One advantage of this process is the excess methanol can be kept significantly lower at

1.5:1 molar ratio of methanol: fatty acid versus the batch process at34:1 molar ratio. The methyl

ester, having undergone distillation, does not require further refining. The excess methanol is

rectified and reused.



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The continuous esterification process is superior to the batch process, in that the same high yield

can be obtained in a much shorter dwell time and with substantially less excess methanol. The

esterification process is a preferred method for the production of esters from specific fatty acids.

Trans-esterification Processes:

Trans-esterification of fats and oils is the most commonly used process for the manufacture of

methyl esters, except in cases where methyl esters of specific fatty acids are needed.

Triglycerides can readily be trans-esterified batchwise at atmospheric pressure and at a slightly

elevated temperature of approximately 6070oC with an excess of methanol and in the presence

of an alkaline catalyst. The mild reaction conditions, however, requires the removal of free fatty

acids from the oil by refining or pre-esterification before trans-esterification. This pretreatment is

not required if the reaction is carried out under high pressure (9000 kPa) and high temperature

(240oC). Under these conditions, simultaneous esterification and trans-esterification take place.

The mixture at the end of the reaction is allowed tosettle. The lower glycerine is drawn off

whereas the upper methyl ester layer is washed to remove entrained glycerine and is then

processed further. The excess methanol is recovered in the condenser, sent to rectifying column

for purification, and recycled.

Continuous trans-esterification is well suited for large capacity requirements. Depending on the

quality of the feedstock, the unit can be designed to operate at high pressure and high

temperature or at atmospheric pressure and slightly elevated temperature.

Figure 2.2(i) shows a Henkel process flow diagram operated at 9000 kPa pressure and 240oC

using unrefined oil as feedstock. Unrefined oil, methanol in excess, and catalyst are metered and

heated to 240oC before feeding into the reactor. The bulk of the excess methanol is flashed off as

it leaves the reactor and is fed to a bubble tray column for purification. The recovered methanol

is recycled into the system. The mixture from the reactor enters a separator where the glycerine



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in excess of 90% concentration is removed. The methyl ester is subsequently fed to a distillation

column for purification. Further fractionation into special cuts may follow if desired.

Fig 2.2(i) : Continuous Transesterification by Henkel process

Figure 2.2(ii) shows a Lurgi process flow diagram operating at normal pressure. The process

requires the use of a degummed and de-acidified feedstock. The refined vegetable oil and

methanol are reacted in a two-stage mixersettler arrangement in the presence of a catalyst. The

glycerine produced in the reaction, dissolved in the surplus methanol, is recovered in the

rectification column. Most of the entrained methanol and glycerine are recovered from the

methyl ester in the countercurrent scrubber. The methyl ester can be further purified by

distillation.



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Fig 2.2(ii): Continuous Transesterification by Lurgi process

2.2.3 Air/SO3 Sulfonation Equipment

Four possible sources of SO3 gas used for an air/SO3 sulfonation system are:

Sulfuric acid plant converter gas

SO3 from boiling concentrated oleum

Liquid SO3

Sulfur burning in equipment specifically designed to produce SO3 gasfor sulfonation

Converter gas from a sulfuric acid plant contains 1012% SO3 and appears to be apotential SO3

source for sulfonation. There are several problems with using a sulfuricacid plant as an SO3

source for sulfonation. Nevertheless, such an arrangement has beencommercially installed and at

first glance appears to be an attractive, low cost method ofsupplying SO3 gas to a sulfonation

plant. Physical location is a limiting factor; as thesulfonation plant must be installed as closely as



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possible to the sulfuric acid plant converter. In addition, the sulfonation plant can run only when

the sulfuric acid plant is running.

There are three other more subtle difficulties when using a sulfuric acid plant as an SO3source

for sulfonation. First, the SO3 gas at approximately 18% concentration must be diluted to the

normal range for sulfonation (typically 47%). An auxiliary air supply must be installed, which

adds expense and complexity. Second, because sulfuric acid absorption towers are used for air

drying, the air/SO3 from a sulfuric acid plant has a higher dew point (typically 35C) than that

required in a sulfonation plant (typically 60C to 80C). The high dew point causes product

quality problems in the sulfonation process and accelerates corrosion of the process equipment.

Third, the pressure of the air/SO3 from the sulfuric acid plant is usually not sufficient to

overcome the pressure drop of the sulfonation system. Compressing the air/SO3 from the

converter is not trivial as it requires a high alloy compressor to withstand the corrosive

environment created by the wet air/SO3 stream. This problem can be overcome, but the solution

is not inexpensive. Considering all the problems inherent in utilizing the converter gas stream

from a sulfuric acid plant, the conclusion is that it is technically feasible. However this choice

adds significant operational difficulties and does not result in a major cost saving sover installing

a complete sulfur burning sulfonation plant.

Another possible source of SO3 for sulfonation is produced by boiling oleum to produce gaseous

SO3 which is then blended with dry air. It is practically limited to locations where fresh oleum

can be received, and depleted oleum returned by pipeline. Compared to sulfur burning, this

process somewhat reduces the equipment requirement. However,it still requires an air supply

system, an oleum boiler and an SO3 metering system. Unlike a sulfur burning plant which

generates its own heat for air dryer regeneration, this air supply system requires an external

source of heat which adds extra utility expenses. Also, significant safety hazards are associated

with handling concentrated oleum. Suchan installation may be economical for a few site

locations.



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Some of the first air/SO3 sulfonation plants installed were based on use of liquid SO3.These

plants require an air supply system identical to the system described below for a sulfur burning

plant except that it also requires an external heat source for air dryer regeneration. In addition, a

liquid SO3 plant requires an SO3 storage system. This storage system is usually a large 20,000 to

80,000 kg storage tank located in a heated room and maintained at a temperature of about 40

43C. Heating the SO3 storage room can be a significant cost in colder climates. In case of SO3

leaks, the room must be sealed and should have provision for scrubbing any SO3 that escapes

into the rooms atmosphere. In the sulfonation process, the liquid SO3 is metered from the

storage tank into a steam heated vaporizer where it is evaporated and mixed into the dried air

stream from the air supply system. From this point on, the process is identical to a sulfur burning

air/SO3 sulfonation plant, described below. A liquid SO3 storage and metering system is shown

in Fig. 2.2(iii). Because of the rigorous storage requirements imposed by the hazardous nature of

liquid SO3, the installed cost for a liquid SO3 sulfonation facility is close to that for a sulfur

burning installation

Fig 2.2(iii):Sulphonation by liquid SO3



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Sulfonation equipment based on liquid SO3 has become increasingly undesirable for the

following reasons:

Safety concerns

Liquid SO3 is unavailable in many parts of the world

Sulfur is readily available worldwide

Sulfur is relatively inexpensive.

Therefore, SO3 is produced by sulfur burning, air/SO3 sulfonation plant.

There are significant safety advantages to a sulfur burning system. With sulfur burning air/SO3

sulfonation processes, the only SO3 on site is the small quantity of dilute gaseous material in the

process piping between the converter (SO2 to SO3) and the sulfonationreactor. Even in the

world's largest sulfonation plant (20,000 kg/hr active production) this amounts to only about 100

kg of dilute SO3 gas. The sulfur burning process is much safer than transporting, storing and

handling tank truck (18,000 kg) or rail car (72,000 kg) quantities of oleum or liquid SO3.

Fig 2.2(iv):Sulphonation by sulphur burning

The basic plant package for a sulfur burning, air/SO3 sulfonation installation includes a sulfur

supply system, air supply system, SO3 gas plant system, SO3 absorber system, sulfonator,



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neutralizer, effluent gas clean-up system, control system and motor control center as shown in

Fig. 2.2 (iv).

Capacities for commercial sulfur burning air/SO3sulfonation units range from 250 to 20,000

kg/hr of 100% detergent active. Typically, an air/SO3 sulfonation plant is designed to sulfonate

with approximately 47% (volume) SO3.

As Figure 2.2(v) illustrates, the process air is first compressed to a pressure of approximately1

kg/cm2 (15 psig) using either a rotary compressor or a high efficiency centrifugal compressor. In

larger sulfonation plants capacities greater than 4000 kg/hr the process air capacity should be

adjustable without venting between approximately 60 to100percent of full capacity (while

maintaining efficiency). This ability conserves electric power if the plant is operated at partial

capacity. A direct expansion air chiller vessel cools the compressed air to a temperature of 7C

(45F). The chilled air is then dried in dual, automatic pulse-less desiccant-type air dryers to a

dew point of 80C (112F). The lack of a pulse in the air stream is vital to product quality.



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Fig 2.2(v): Air Supply system

If the air pulses, there will be a momentary interruption in mole ratiowhich results in a loss of

product quality. The result is product with high free oil, dark color and possibly other

undesirable by-products. The dual air dryers are equipped with 11 individual bubble tight control

valves. The control valves ensure absolutely no interruption of process air when changing dryers

and a smooth pressure transition when the dryers switch to regeneration cycle. A cooling air



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blower supplies cool air to the regenerated (off-line) air dryer to reduce the bed temperature to an

acceptable level prior to bringing the regenerated air dryer back on-line. This is important if the

dryer bed is too hot, the process air dew point will be higher than desirable due to the increased

equilibrium concentration of water in the hot air exiting the dryer. A regeneration/utility air

blower supplies cooling air to the double pipe gas coolers used in the gas plant. Hot air (200C)

leaving the low maintenance double pipe coolers regenerates the off-line air dryer. During the air

dryer cooling cycle in smaller plants, there generation/utility air vents to the atmosphere or is

sent to other processes where the heat in the air can be used. In larger plants (greater than 4000

kg/hr) the heat may be recovered as steam. In this case, the gas plant is modified so that it

produces steam instead of hot air and a portion of this steam heats the regeneration air.

Fig 2.2(vi): Sulphur supply system

In the sulfur supply system shown in Figure 2.2(vi), bright Frasch or by-product sulfur flows by

gravity to one of two gear pumps. Typically dual strainers, pumps, and flow meters are provided

minimize down time during maintenance. The sulfur passes through a highly accurate mass flow

meter prior to delivery to the sulfur burner. Because the mole ratio is the most important process

variable, control of the sulfur flow to the sulfur burning air/SO3 gas plant is one of the two most



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important process control functions in the plant. The entire sulfur supply system is steam

jacketed because the sulfur has freezing point of 112.8C.

Sulfur is normally handled at its viscosity minimum, which is 136C. A steam and condensate

system supplies the necessary tracing circuits for the sulfur supply piping.

Fig 2.2(vii):SO3 generator



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In the SO3 gas generator, illustrated in Figure 2.2(vii), the metered sulfur is delivered to the

refractory-lined atomizing sulfur burner where combustion with the dry process air generates

sulfur dioxide (SO2). The atomizing burner ensures instant, constant sulfur burning. The sulfur

dioxide gas leaving the burner is cooled to 420C and delivered to three-stage vanadium pent-

oxide (V2O5) catalytic converter, where the gas is filtered and converted to sulfur trioxide (SO3).

The conversion efficiency of the converter is between99.0 and 99.5%. Prior to entering the inlet

mist eliminator, the sulfur trioxide gas leaving the converter is cooled to nearly ambient

temperature in an SO3 double pipe cooler followed by an SO3 water cooled heat exchanger. The

inlet mist eliminator removes traces of sulfuric acid or oleum from the cooled SO3 gas stream.

Heat recovered from the second to third pass converter interstage cooler and SO3 cooler

regenerates the air dryers, eliminating the need for an external heat source. Heat recovered from

the SO2 and first to second pass interstage cooler can be used to generate steam in the optional

heat recovery system. In state of the art sulfonation plants, computer aided hot gas piping design

eliminates troublesome hot gas expansion joints in the gas plant. The enhanced piping design

improves significantly plant reliability and eliminates a possible source of inadvertent SO2 or

SO3 discharge to the environment.

An inline double pipe ignition air heater warms the combustion air stream for sulfur burner

preheating and ignition. A gas-fired duct type start-up heater in there generation/utility airline

preheats the SO3 and first to second pass interstage cooler.

The start-up heater, used during a cold plant start-up, reduces to less than two hours the time

required to achieve stable conversion of SO2 to SO3 so thatsulfonation can begin. These features

significantly reduce the time required for gas plant start-up and eliminate the use of sulfur as a

fuel to heat the gas plant during start-ups.

Production of SO2, which must be scrubbed from the exhaust gas prior to discharge to the

atmosphere, is minimized, therefore reducing plant operating costs



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Fig 2.2(viii):SO3 absorber unit

The SO3 absorber unit, shown in Figure 2.2(viii), is capable of treating the total output from the

SO3 generation system to form 98% sulfuric acid. It is a convenience in plant startup, shutdown

and product changeover. It is also recommended in situations where frequent power failures can

interrupt production. With this equipment, the plant can be restarted without forming off-

specification product. If this unit is not used, thesulfonation reactor itself must be used to scrub

SO3 from the process gas during gas plant start-ups. This is an undesirable procedure, however,

as the gas plant has not stabilized during the start-up process and the mole ratio of SO3 to

feedstock is unknown. The practical solution to this problem is to purposely under-sulfonate

alkylbenzene during the start-up. The off-specification material made in this start-up procedure

can be stored and later blended back into the product. The SO3 absorber system is almost a

necessity if only alcohol feedstocks are run in the plant, because alcohol sulfuric acids cannot

bestored and reused.



2014

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SO3 mixed in air enters the absorber column where it contacts 98% sulfuric acid. TheSO3 is

absorbed into the acid, which separates from the remaining air in the scrubber body. A mesh pad

mist eliminator removes entrained acid mist from the air as it exits the vessel. Water is added to

control the concentration of the sulfuric acid as it flows through the acid circulation system. An

instrument system with dual conductivity sensors holds the acid concentration at 98% by

controlling water addition. A heat exchanger in the absorber circulation loop removes heat of

dilution.

The sulfonator is the heart of a sulfonation plant. Sulfonic acid forms in the sulfonatorwhen an

SO3-in-air mixture is injected into the reactor simultaneously with the desired organic feed under

carefully controlled conditions of mole ratio, SO3 gas concentration and temperature. Potential

organic feedstocks include alkylates, alcohols, ethoxylatedalcohols, methyl esters and alpha

olefins.

Several types of commercial sulfonators are available. In broad classifications they are film

reactors, including the Chemithon Annular Falling Film Reactor, theBallestra, IIT and Siprec

multitube film reactors; the Chemithon dispersed phase or jet reactors; and stirred tank or

cascade type reactors. Film reactors are the most common in detergent processing for consumer

products, especially to produce cosmetic quality materials from oleo chemical feedstocks. In a

film reactor, the organic feedstock is extruded onto the wall of the reactor (reaction surface) as a

continuous film. Organic feed rate to the reactor vessel is measured by a highly accurate mass

flow meter and controlled by a variable speed driven gear pump. The proper organic feed rate is

based on the preset sulfur-to-organic mole ratio. The SO3, diluted with very dry air, flows over

the film of organic material. The SO3 diffuses into the organic film and reacts to form sulfonic

acid. In almost all commercial reactors both the organic and SO3flow concurrently from the top

of the reactor to the bottom. The heat of reaction is removed by cooling water which flows

through cooling jackets underneath the reaction surface of the reactor.



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Figure 2.2(ix) shows a Chemithon Annular Film Reactor. This patented reactor is unique in

many ways. It employs interchangeable, factory calibrated organic metering flanges. These

flanges ensure that the flow of organic to any two points on the reaction surface is equal, within

1%. When combined with the geometric design of the reactor that similarly controls the flow of

SO3 to the reaction surfaces, these features ensure that mole ratio control is maintained on a

micro scale throughout the sulfonator. Cooling jackets on the reactor remove most of the heat of

reaction. Additionally, the patented recycle system allows the reactor to overcome the increase in

viscosity of the sulfonic acid as its level of sulfonation increases. The product exiting the reactor

is instantly quench cooled by removing the acid, pumping it through a heat exchanger to cool,

and then returning it to the bottom of the reactor. This cooling process reduces the time that the

sulfonic acid is held at an elevated temperature and results in better product quality. Aside

benefit is that the reactor is more compact less than two meters in height and therefore

considerably less expensive to install.

Figure 2.2(ix): Chemithon Annular Film Reactor



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Figure 2.2(x): Chemithon Annular Film Reactor (installed)

Figure 2.2(x) shows this reactor installed in a typical sulfonator. Upon exiting the reactor, the

spent gas is separated from the sulfonic acid recycle stream in the liquid separator and cyclone

vessels. Sulfonic acid product discharges from the recycle stream at a controlled rate,

maintaining continuity of the quantity of material in the reactor system. The acid product from

the reactor can then be fed directly to the digestion and hydration system (or optional degasser

system) where reaction with absorbed SO3 is completed. Hydration water is injected and mixed

with the sulfonic acid, leaving the digesters to remove anhydrides.



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Figure 2.2(xi): Multi-tube Reactor (Ballestra)

Figure 2.2(xi) shows a typical multi-tube sulfonation reactor. The multi-tube reactor is the other

commonly employed film sulfonator design. In this reactor the organic feed is distributed among

a number of parallel reaction tubes, 25 mm in diameter, 7 meters long.The tubes are arranged

like the tube bundle in a vertical shell and tube heat exchanger. The organic and SO3 gas flow

concurrently down the reactor tube, react and exit the bottom of the reactor into a separator

vessel. The heat of reaction is removed by cooling water which flows through the reactor jackets.

The approximate residence time of the acid from the top of the reactor through the separator and

cyclone and to the neutralizer is two to three minutes.



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*

Figure 2.2(xii): Neutralization

A continuous neutralizer system is illustrated in Figure 2.2(xii). The neutralizer combines

sulfonic acid or organo-sulfuric acid with a neutralizing agent, additives, and diluent (water), in a

dominant bath neutralization. The result is a solution of neutral active matter (slurry or paste) of

the desired composition and pH. Caustic soda, usually 50 wt%NaOH, is the most common

neutralizing agent. However, caustic potash, aqueous ammonia, tri-ethanolamine, and other

agents are compatible with the neutralizer. A recycle loop circulates neutral slurry through a heat

exchanger to remove heat of neutralization, mixing and pumping. Individual metering and/or

gear pumps feed sulfonic acid, neutralizing agent, dilution water, buffer solution and any

additives into the loop to mix through a high shear mixer. A positive displacement pump

circulates paste through the process heat exchanger and a large portion of this stream recycles

back to the mixer. A pressure control valve allows product to leave the recycle system as feed

enters. A pH sensor is placed in the recycle line near the inlet to the mixer. The in-linepH sensor



2014

34

measures an accurate pH on dilute slurries, and produces a single-valued output signal that is

proportional to pH on concentrated pastes. The signal from the sensor feeds to the pH control

system in either case, and controls the flow of the neutralizing agent into the process. Use of a

buffer promotes stability in the pH control loop. Cooling water is also recirculated and

automatically adjusted to maintain a desired temperature at the process heat exchanger inlet.

Therefore, higher melting point products can be processed without plugging the heat exchanger

during start-up.

Figure 2.2(xiii): Effluent gas treatment

Effluent process gases leaving the sulfonation system or SO3 absorber are virtually free of

residual SO3, but contain any unconverted SO2 gas and entrained particulate anionic materials

(acidic mists of sulfonic and sulfuric acids). This gas stream is not suitable for direct discharge to

atmosphere. The recommended clean-up system, shown in Figure 2.2(xiii), employs an

electrostatic precipitator designed to collect particulate mists and a packed tower scrubber to

absorb SO2 gas in a dilute caustic. Final effluent gases cleaned to contain less than 5 ppm SO2



2014

35

and less than 10 mg/m3 combined sulfate mist and neutralized organic mist are suitable for

discharge to the atmosphere.

2.2.4 Bleaching

Acid Bleaching (Chemithon)

The aging process in the digester completes the sulfonation reaction but causes a four-fold

increase in the color of the MESA. The digested MESA, methanol and dilute hydrogen peroxide

are combined in a loop and the reaction mixture is passed through a methanol refluxing vessel

where the bleaching of the MESA is completed. The process temperature in the bleaching vessel

is controlled by heat transfer surfaces submerged in the reactants. The process pressure is

independently controlled. The non-condensable vapors discharged from the bleaching vessel are

processed in an effluent gas treatment system. The bleached MESA is continuously neutralized

with 50% sodium hydroxide to a pH of 5.5 to 7.5. Any residual peroxide can be decomposed by

the addition of a molar equivalent of sodium sulfite. The neutral paste is transferred to a

concentrating and / or methanol removal system. MES based on a methyl ester below a

molecular weight of 245 is stripped rather than dried to remove the methanol making the

concentrated product. Higher molecular weight MES is dried, removing both methanol and

water, making the ultra-concentrated solid product forms. The recovered methanol is distilled

and recycled back to the bleaching process.



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Fig. 2.2(xiv): Acid Bleaching



2014

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Fig. 2.2(xv): Neutral Bleaching (Ballestra)



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Fig. 2.2(xvi): Acid Vs Neutral Bleaching

2.2.5 Drying

Methyl ester Sulfonate is hydrolytically unstable.It will rapidly hydrolyse if fromulation is

aqeuous and basic.So,drying is necessary.It cane be done either by spray drying or by Turbo tube

drying.

The stripper / dryer consists of a supply system, a preheater, a proprietary dryer, a separation

vessel, a product discharge device (typically a plodder), a vacuum system and an overhead

condenser, Figure 2.2 (xvii) The MES product is powdered or diluted as appropriate for

application in liquid, bar, granular, and tablet detergent products.



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Fig. 2.2(xvii): Drying

2.2.6. Technologies available and their source

Lion, Desmet Ballestra and Chemithon have been developing their MES sodium salt dried

powders technology for over 20 years. The sulphonation companies, Desmet Ballestra and

Chemithon have been involved in the plant investments in Huish, Texas, US (Sun Products Corp

since its 2008 merger with Unilever North America). Since then they have both been competing



2014

40

to deliver a high quality, chemically stable MES sodium salt in solid forms. In addition, Henkel,

Lion and Stepan were also early MES process and product developers.

Lion Eco recently installed its own MES process technology in Malaysia. The company

developed a continuous trans-esterification process using unrefined feedstock known as the ES

process.The free fatty acid in the oil is pre-esterified by passing the feedstock and methanol

through a packed column of a specialcatalyst resin, after which trans-esterification is conducted

through a two-stage reactor. A high conversion rate of more than 99% is claimed.

MES has been manufactured in Japan by Lion Corporation and in USA by

Stepan and Huish Detergents. Huish produces commercial quantities of MES in a free flowing

powder form while both Lion and Stepan have their products in liquid forms.

Several technologies for manufacturing MES have been patented. Huish, which has a plant

capacity of 80,000 TPA, uses the Chemithon technology for the MES and the Lurgi technology

for the methyl esters (ME). RBD (refined bleached deodorized) palm stearin (RBDPS) is

used as a raw material by Huish Detergents. The challenges for MES in detergent use include the

low foam characteristics and the formulation constraints when using MES in a liquid form in a

high pH environment. The availability of MES in a dry free flowing powder or flaked form in

recent years has overcome part of the manufacturing issues as the product can be directly added

to the detergent formulation in a post addition step. Chemithon Turbo Tube Drier (TTD) is a key

process unit producing an off white flake, which is then milled (pin milled) to give a fine white

powder, which is free flowing without the use of flow aids, such as 4A zeolite powder, as used

by Lion and KLK to obtain free flowing MES powders.

Since Ballestra and Chemithon technologies are fully known(by the companies websites and

available literature),one of them is chosen by making a comparison between both.



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2.2.7 Ballestra technology

DesmetBallestra started the R&D on the MES in the mid-seventies with extensive pilot-plant

activities leading to industrial plants in 1979. In 1985 the first Falling Film Reactors were

installed and a technical cooperation implemented with Henkel Co. Since 1994, it continued

R&D focusing on the ME characteristics, bleaching techniques, drying and physical shape

modification.

Processing steps:

Last Generation MTFR

(Multitube Film Sulphonation

Reactor)

Advantages

Use of consolidated and well

proven sulphonation process

Possibility to retrofit existing

plant

Maximised conversion

ME->MES

Minimized reaction by-products

Fig. 2.2(xviii): Ballestra Technology



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42

Double Step Loop-Neutralization

Advantages

Use of well proven process

No solvents

No need for costly corrosion-proof equipment

Minimized Di-Salt content

High active MES paste

Neutral Bleaching

Advantages

No solvent

No viscosity aid

No hazardous by-products (as in case of acidic-bleaching)

No risk of explosivity

Low MES paste colour

Vacuum Drying by Wiped Film Evaporator

Advantages

Short and narrowly-distributed

drying time

Bone-dry MES production



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preserving product quality

High reliability

Obtainable MES Product Specifications

MES in paste form:

Total active matter: 30-70%

Composition:

Ester Sulfonates: 97% min

NEA: 3% max

UnSulfonated matter: 1.8-2.5%

Na2SO4: 2-3%

pH: 6-8%

Colour (Klett): 50-70 typical

MES in dry-powder form:

Total active matter: 85-90%

Dry content: 97-98%

Water: 2-3%

Na2SO4: 2-3%

Colour (Klett): 100 max

2.2.8 Chemithon technology

The Chemithon plant represents the very latest sulfonation technology, based on more than 54

years' experience and continuous improvement as the industry's foremost innovator of

sulfonation processes and equipment. Chemithon proven technology results in durable, highly

reliable processes and equipment to sulfonate/sulfate the broadest range of feedstocks and



2014

44

produce the highest quality surfactant products on the market. Flexibility, ease of operation,

precision control and high equipment quality are hallmarks of Chemithon design.

1 Process Air and Sulfur Supply

System

4 Sulfonator System 7 Exhaust Gas Clean-up

System

2 Feedstock 5 SO3 Absorber

System 8 Final Product

3 SO3 Gas Generator System 6 Neutralizer System

Fig 2.2(xix): Automated Sulfonation Plant Flow Diagram (Chemithon)

There are currently more than 450 Chemithon plants operating or under construction in almost

every part of the world. Today, Chemithon supplies processes and equipment for complete plant

systems, all aspects of sulfonation, light and dense powder production, liquid products, as well as

final product handling, offsite support systems and complete technical services.

Impact

Jet SO3 Reactor Annular Falling Film Reactor



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Precise gas and liquid

distribution results in 1, 4-diaxane

levels less than 20 ppm for ethoxy

sulfates.

Three meter height makes it easy

to install, adjust and service.

Patented recycle system ensures

complete reaction and absolute

temperature control and

flexibility.

Innovative design results in

maximum conversion rates on all

feedstocks.

Advanced cyclone / separator

minimizes cyclone waste to



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2.2.9 Selection of Technology/process

Refined, Bleached and deodorized palm oil is used as the feedstock as the price of palm oil is

less as compared to others.Also,its availability is not an issue since it can be easily

imported.Moreover,the reaction yield with palm oil is excellent. For production of Methyl Ester,

Lurgi Transesterification is used since the process is well known and is widely used for methyl

ester production. Sulphonation is done by burning sulphur in air. The technology is used is of

Chemithon since the technology is widely known and has many advantages over Ballestra

technology. All the details of the selected Chemithon technology have been provided in earlier

sections.

2.3 Raw materials

Following are the basic raw materials for production of MES:-

Refined, Bleached and deodorized Palm oil

Methanol (CH3OH)

Sulphur

MES can be produced from different ME feedstocks which, in turn, can be derived from

vegetable oils such as soybean, rapeseed, canola, coconut oil, palm/palm derivatives, and animal

fats such as tallow and lard. The choice of feedstock is cost dependent. Lauric oils (C12 and

C14) normally have a higher cost as compared to the palmitics (C16 and C18), which have a

lower and relatively stable price. From an economic standpoint, the preferred feed is palm oil.

Palm oil is a type of vegetable oil that is used all over the world as a cooking oil and in

processed foods like chocolate bars, ice cream, instant noodles, and margarine. Derivatives of

palm oil are also used in cosmetics, soaps, shampoos and detergent. Crude palm oil is normally

processed by a physical refining process in which the oil is turned into a golden yellow refined

oil for further end use applications.



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2.3.1 Detailed Specifications

Palm oil has a balanced fatty acid composition in which the level of saturated fatty acids is

almost equal to that of the unsaturated fatty acids. Palmitic acid (44%-45%) and oleic acid (39%-

40%) are the major component acids, with linoleic acid (10%-11%) and only a trace amount of

linolenic acid. The low level of linoleic acid and virtual absence of linolenic acid make the oil

relatively stable to oxidative deterioration. Several surveys conducted by MPOB have showed

that the Malaysian palm oil has a narrow compositional range. The specifications for the palm oil

are given in Malaysian Standard MS814:2007 (Table 2.3.1)

Fig. 2.3.1



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Palm oil is unique among vegetable oils because it has a significant amount of saturated acids

(10%-15%) at the two-position of its triglycerides. The appreciable amounts of disaturated (POP

and PPO) and mono-saturated (POO, OPO and PLO) allow it to be easily separated into two

products; palm olein and palm stearin. A wide range of fractions with different properties to suit

requiremets of the food industry is made available through dry fractionation.

Table 2.3.1



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PARAMETER

ERERERER

S

UNIT

COCONUT

GROUNDNUT

SUNFLOWER

RICEBRA

N

PALM

CASTOR

PALMKERNEL

SOYABEAN

Ester

Content

% 96.5Min 96.5Min 96.5Min 96.5Min 96.5Min 96.5Min 96.5Min 96.5Min

AcidValue

mg

KOH/g

m

0.5max.

0.5max.

0.5max.

0.5max.

0.5max.

0.5max.

0.5max.

0.5max.

IodineValue(Wij

s)

-

9-11 85-95 120-144 92-100 46-55 82-88 1218 120-141

Flashpoint C 134140 134140 134140 134140 134140 134140 134140 134140

Table 2.3.3 Specifications of Methyl Esters of Vegetable Oils



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HydroxylValue - - - - - - 160170 - -

Viscosity g/sec.

@ 25 C

4.55.5

4.56.0

45.5

4.55.5

4.55.5

3.54.5

4.55.5

4.55.5

Moisture - 0.2max 0.2max 0.2max 0.2max 0.2max 0.2max 0.2max 0.2max

Density g/sec.

@ 25 C

0.880.89

0.870.88

0.880.89

0.880.89

0.870.89

0.92-0.94

0.870.89

0.880.89

CetaneNumb

er

- >_51 >_51 >_51 >_51 >_51 >_51 >_51 >_51

SulphurCont

ent

% 0.035 max 0.035 max 0.035 max 0.035 max 0.035 max 0.035 max 0.035 max 0.035 max

Caprylic % 815 - - - - - 2.05.0 -

Capric % 69 - - - - - 25 -

Lauric % 3842 - - - - - 4045 -

Myristic % 1517 0.030.06 0.050.10 0.040.09 0.20.5 - 1015 0.030.06

Palmitic % 810 1315 47 2729 4044 - 1012 911

Stearic %

25

2-5

25

24

25

1-2

13

25

Oleic % 510 5560 2327 3538 4244 3-4 2225 2327

Ricinoleic % - - - - - 8991 - -

Linoleic % 13 2327 6267 3032 1013 3-4 25 5357

Linolenic % 0.03 - 0.010.05 - - 1-2 - 712

Arachidic % - 0.01 - 0.030.07 0.020.05 - - 0.010.05

USES In

Surfactants,

Resin,

as Biodiesel

In

Surfactants

and

Emulsifiers,

asBiodiesel

In Resin

manufacturing

, as Biodiesel

In

Lubricants,

Resin,

surfactants,

as Biodiesel

In

Emulsifiers,

Surfactants

, as

Biodiesel

In

Lubricants,

Surfactants,

Anti-

oxidants, as

Biodiesel

In

Surfactants,

as Biodiesel

In Resin

manufacturing,

as Biodiesel

Table 2.3.4: Specifications of Methanol



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2.3.2 Requirement of Raw materials

By simulation,for producing 3985.3365 kg of Methyl ester Sulphonate, 5164.0575 kg Palmoil

and 576.4847 kg Methanol are required as raw materials (per hour basis).

Table 2.3.5: Specifications of Sulphur



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2.3.3 Availability of Raw materials

In many respects, oil palms are a wonder crop in the countries where they grow predominantly

in Malaysia and Indonesia, but also in Papua New Guinea, and increasingly in Africa and Latin

America. Oil palms have a lifespan of 25 -28 years and yield more oil per hectare of land than

any other crop in the world. They are also relatively less reliant on fertilizers, pesticides and

water compared to other monoculture crops.Indonesia and Malaysia are the worlds largest

producers of palm oil, supplying not only foreign markets but also substantial domestic demand

for this vegetable oil. For these reasons, palm oil makes up more or less a third of the 151 million

tonnes of vegetable oil produced worldwide. And it is here to stay. From approximately 50

million tonnes of palm oil produced in 2010, demand is expected to reach 77 million tonnes in

2050 to help feed the worlds growing population and the increased affluence of emerging

economies like India and China, which consume ~16 percent and 12 percent of global palm oil,

respectively. About 60 percent of palm oil consumption is concentrated in China, Europe, India,

Indonesia and Malaysia.

India is basically a net importer of the palm oil. India produces around 70000 tons of palm oil

annually which stands at approximately 0.2% share in the worlds total production. Kerala is the

largest palm producing state in India.

India, which is one of the largest importer and consumer of edible oils in the World, imports

nearly 3 million tons of palm oil annually (mainly from Malaysia and Indonesia). This implies

that the country is dependent on palm oil imports for over 25% of its annual edible requirement.



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Fig. 2.3.2: Palm oil production and consumption

The domestic production is very meager at 0.5 lakh tons. Palm oil production in India has grown

at 22.7% CAGR over the past five years to reach 105,513 MMT in 2011. However, India would

continue to be a net importer of palm oil, with most of its demand expected to be met through

imports.

Andhra Pradesh is the leading palm oil producing state in India contributing approximately 86

%of countrys production, followed by Kerala (10%) and Karnataka (2%). Other palm oil

producing states include Orissa, Tamil Nadu, Goa and Gujarat. Andhra Pradesh has been the

largest palm oil producing state in India, having shown more than100% achievability of the

targeted acreage from2004-05 to 2009-10 under the Oil Palm Development Programme. Other

states like Karnataka have achieved~85% and Tamil Nadu has achieved ~60% of the targeted

acreage over the same period.

India imports CPO mainly from Indonesia while from Malaysia it imports mostly refined,

bleached and deodorized (RBD) palm olein. India imports about 65,000 tonnes of palm oil from

Malaysia every month.



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Palm oil imported into India is used in various forms- consumed directly as 'palm oil' after

refining, used in the manufacture of Vanaspati, for blending with other vegetable oil, crude oil

and kernel oil for industrial purposes, etc.

Despite being the worlds fourth largest oilseed producing country, Indias share of palm oil

production is small, accounting for 0.2% share in the total world produce. Of the 15 MHa under

oil palm fruit production globally, acreage under oil palm in India stands at ~155,202 Ha, which

contributes to 1% of the global acreage. However, the acreage has been growing at a significant

rate of 21% CAGR during the last five years. Implementation of the Oil Palm Development

Programme (OPDP) is being carried out by Horticulture Departments and Agriculture

Departments of the concerned State Governments. Financial assistance, cultivation subsidies, etc.

are provided to farmers for encouraging the oil palm cultivation in India under the OPDP

programme.

Import of Palm Oil in India

Palm oil has dominated Indian

imports since the mid-1990s, for its

logistical advantages, contractual

flexibility, and consumer acceptance,

as the lowest priced oil. Indias palm

oil imports have grown at a CAGR of

~17.09% to reach~7.4 MMT in 2011-

2012.

Palm oil contributes to around 77%

(as on 2011) of the total edible oils

that are imported in the country.



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The other two raw materials can easily be obtained indigenously as there are easily available.

2.3.4 Government policies for import of palm oil

Export - Import policies are one the major factors which influence the market for palm oil in

India. From the 1970s to 1994 the State Trading Corporation controlled edible oil imports. The

quantity to be imported was decided by a center based ministerial committee depending on the

domestic supply and demand conditions, as also the balance-ofpaymentsituation prevailing in the

country. The government undertook an initiative, known as the Technology Mission on Oilseeds,

wherein imports were restricted during1994-1998 to help foster self-sufficiency. After signing on

with WTO, oil imports were placed under the Open General License (OGL), allowing unlimited

imports by private traders in India.

Since 2000, there have been constant revisions in the import duty structure

of crude and refined palm oil, wherein the import duty from 75% in 2001 was curtailed to 65%in

2003 and was raised back to 66.3% in 2004. The duty was again slashed in 2007 to 51.5% and



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then finally to 20.6% in March, 2008.In response to growing domestic food inflation, in April

2008, most duties on crude edible oil were abolished.

Note: CVD: Countervailing duties, SAD: Special Additional Duty Source: Solvent Extractors Association (SEA)

In 2000, the Government introduced a system of tariff rate values, which meant that import

prices were calculated based on the tariff revenue per ton imported and adjusted according to

current world prices at the time. This was done primarily to avoid under-invoicing by importers.

Indian consumers, being extremely price sensitive, also had a good measure of influence on the

composition of oil imported. The table below indicates the prevailing tariff values for palm oil

imports into India. These values indicate the floor price in CIF US$/MT, below which the

respective oils cannot be imported. However, on the back of increasing international prices,

Indian average import prices stood at $830/MT in 2010 up from $440/MT in 2006. Hence, the

tariff values today are much lower than the actual import prices, as they havent been revised

since March 2007.



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Source: Solvent Extractors Association

2.3.5 Prevailing prices

India imported crude palm oil (CPO) at an average price of $0.83/kg (in 2010) and crude palm

kernel oil (CPKO) at $1.02/kg (in 2010) mainly from Indonesia and refined palm oil, also called

refined, bleached and deodorized (RBD) palm olein from Malaysia.

The current price of RBD palm oil is approximately US $760-800/metric ton

The current price of sulphur is approximately US $200-500/metric ton

The current price of methanol is approximately US $500-600/metric ton

Factors influencing Palm Oil Prices

Oilseeds production at domestic and global level

The supply-demand and price scenario of competitive oils, viz., soy oil.

The Government export-import policy

The supply-demand scenario of all oils and oilseeds in the consuming centres, viz., India,

China and EU. This in turn is manifested as imports from these countries.

The palm oil production cycle: April - December is peak production period.

Import regulations imposed in the importing countries.



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2.3.6 Testing procedures

Palm oil

PalmOilTester is a simple and accurate testing system that, within a few minutes, enables to

determine Free Fatty Acid (FFA), Peroxide Value (PV), DOBI& Carotene in raw and refined

palm oil.

The Plus Version can also test Iodine Value and Anisidine Value (AnV) in palm oil. Thanks to

its simplicity and reliability, PalmOilTester is used by palm oil producers in Malaysia, Thailand,

Indonesian, Nigeria etc. during all production stages: in the oil mills where the fruit is crushed, in

refineries, during acceptance, during storage and when the finished product is sold.

Fig. 2:PalmOilTester Equipment

Analysis

The analytical system includes:

A Spectrophotometric Analyser with

solid state emitters (LEDs) and reading

and incubation cells thermostated at 37

C.

A Kit of pre-vialed, disposable reagents

with a low toxicity developed by the

research laboratories of CDR and a 12-

month shelf-life.

Pipettes to simplify the collection of the

samples.

Print Manager: software that enables

the connection of the analyser to the PC

in order to store and print the results of

the tests.

Operators manual and functional illustrated sheets.



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PalmOilTester is able to test raw palm oil and Kernel Palm Oil and provides the following

information:

Free Fatty Acids 1 minute

Peroxide Value 4 minutes

DOBI & Carotene 6 minutes

Iodine Value 6 minutes

p-Anisidine Value 2 minutes

This system significantly reduces testing time because it enables to test up to 14 samples

simultaneously, which means that it is possible to perform 80 FFA tests, 70 Peroxide Value

tests, 40 Iodine Value tests and 40 p-Anisidine Value testsin an hour.

Simple Methods

Palm Oil Tester analytical methods are simpler and faster as compared to traditional ones. Tests

can be performed in a few simple steps:

1. Heat the palm oil, which is solid at room temperature.

2. Select the parameter to measure from the menu: the system automatically selects the

correct wavelength.

3. Use the supplied pipette to add the correct volume of reagent and sample, then mix.

4. Follow the displayed instructions.

5. The result is automatically calculated in a few minutes, displayed and printed by means

of the on-board printer.

No Technical Support and Maintenance Expenses

Unlike NIR systems or other photometric systems, this system does not require regular

calibrations: it is supplied pre-calibrated, although the calibration parameters can be

changed quickly and simply.



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The system does not require costly spare parts: the analyser uses LED luminous sources and

does not therefore require the maintenance that is usually needed for photometers with

tungsten luminous filaments. The absence of moving parts eliminates the risk of damages.

Table 2.3.6 PalmOil Tester Analytical Kits

Analysis N.Tests Code Range

Free Fatty Acids Low 100 *300120 Palm Oil: 0,01 - 0,54% Palmitic Acid

Palm Kernel Oil: 0,01 - 0,45% lauric acid

Free Fatty Acids High 100 *300129 1 - 12,57% Palmitic Acid

Palm Kernel Oil: 1 - 10,60% lauric acid

Peroxide Value 100 *300190 Refined Oil:0,1 - 25,4 meqO2/Kg

Raw Oil: 0,5 - 0,5 meqO2/Kg

DOBI & Carotene 100 *300195 DOBI 0,1 - 20

Carotene 0,1 - 862,26 ppm of -carotene

p-Anisidine Value 100 *300510 0,5 - 100 AnV

Iodine Value 100 *300555 2 - 100 I.V.



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Technical Specifications

System: 6-channel photometer with temperature controlled at 37 C

Measurement: solid state opto-electronic devices

Photometric range: 0.0-2.3 Abs; (0.0-4,0 Abs) ampl

Outputs: 1 connection for host PC, 1 connection for sw update

Overall weight: 2.5 Kg

Overall dimensions: 315 mm x 190 mm x 165 mm

Power supply: 12V dc

Absorption: 1.4A max

Environmental operating conditions: the system and its accessories can be used at

room temperatures ranging from 15 C to 35 C and with a relative humidity of 20% -

90% without condensation.

Reference Standards

EN 50081/1. Electromagnetic compatibility: emission residential environments light

industry.

EN 55022. A Measurement of radio disturbances on IT equipment.

ENV 50140 Electromagnetic compatibility: immunity test in presence of radiated

electromagnetic RM fields.



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Table 2.3.6: IMPCA* REFERENCE SPECIFICATIONS(Specification for Methanol)

Item Limit Method

Appearance Clear and free IMPCA 003-98

Purity (% WT on dry basis) IMPCA 001 Min 99.85 IMPCA001-02

Acetone (mg/kg) Max 30 IMPCA001-02

Colour Max. 5 ASTM D1209-05

PT-CO Max. 0.1 ASTM E1064-05

Water % W/W Max. 1 deg C ASTM D1078-05

Distillation Range

at 760 mm Hg

64.6 to 0.1 ASTM D4052-02

Specific Gravity 20/20 0.791-0.793 ASTM D1363-06

Potassium Permanganate Min 60 IMPCA001-02

Ethanol(mg/kg) Max. 50 IMPCA002-98

Chloride as Cl - (mg/kg)

Max. 0.5 ASTM D 3961-98

Sulphur(mg/kg) Max. 0.5 IMPCA001-02

Pt-Co Scale Max. 30

ASTM E 346-03

Acidity as Acetic acid (mg/kg) Max. 30 ASTM D 1613-06

Total Iron (mg/kg) max 0 Max. 0.1 ASTME 394-04

Non Volatile Matter

(mg/1000 ml)

Max 8 ASTM D 1353-03



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PURITY OF METHANOL METHOD (IMPCA 001-02)

Scope

This method describes a procedure for the determination of the purity and impurities (e.g.

Acetone, ethanol) of Methanol.

Method summary

Internal standard is added to the sample and subsequently the major impurities are identified and

quantified by GC/FID. The purity on dry basis is calculated.

Apparatus

1. Gaschromatograph with FID detector.

2. GLC column (DB 1 - 60 m x 0.32 mm ID and 5.0 m film thickness) or equivalent.

3. Volumetric flask 100 ml.

4. Micropipette of 10 l.

Chemicals

1. sec-Butanol (= 2-Butanol).

2. Ethanol.

3. iso-Propanol (= 2-Propanol).

4. iso-Butanol (= 2-Methyl-1-Propanol).

5. Acetone.

6. Methyl acetate.

7. Quality control sample.

Procedure

Prepare the gas chromatograph as described in the manual and use the correct settings



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Injection temperature: 275 C.

Detection temperature: 275 C.

Oven temperature: start 10 min. @ 30C; rise 7.5C/min; final 15 min @ 100C.

Carrier gas: Helium.

Split: 50 ml/min.

Column pressure: approx. 100 kPa.

Injection volume: 1 l.

When the method is newly set-up or not used for a long period, determine the response

factors for all relevant impurities for 2 concentration levels (e.g. 5 mg/kg and 100

mg/kg).

The difference between the response factors determined at both levels should not exceed

5%. The average response factors are used for the quantification of the individual

impurities.

Run a GLC scan of the Quality control sample.

When the quality of the determination is within the predetermined criteria, the

responsefactors are still valid. In all other cases new response factors may have to be

determinedprior to the reanalysis of the quality control sample. When the quality control

sample still isnot within the predetermined criteria, a new control sample will have to be

prepared andchecked

Run a GLC scan of the sample under the same GLC conditions.

Transfer approx. 80 ml of sample to a 100 ml volumetric flask.

Add 10 l of sec-Butanol (5.1) as internal standard and fill up to the mark with sample and

homogenize.

Run a GLC scan of this mixture under the same GLC conditions.

Calculation

Calculate the concentration of the impurities ethanol, iso-propanol, iso-butanol, acetone and



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Methylacetate in mg/kg by the internal standard method as follows:

where:

RF = response factor for the component relative to sec-Butanol

Conc. = concentration of sec-Butanol in mg/kg.

When already some sec-Butanol is present in the original sample, a correction in the internal

standard concentration has to be made.

Techno-Economic Feasibility Report on Production of Methyl Ester Sulfonate From Palm Oil

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