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An Industrial Training Report

Of

India Glycols Limited


(Kashipur, distt. U.S.Nagar, Uttarakhand)

Guided By: Submitted To:


Mr. Arpit Shah Mr. S. Devarajan

Submitted By:
Ankit Shah
N. Satlianjoy
Shashwat Lal Das
1

Acknowledgements
I am greatly thankful to Mr. S. Devarajan (AGM, P&A), Mr. A.K. Yadav
(DGM-MEG), Mr. J.D. Kumar (HOD-Technical Services), Mr. Alok Singhal
(DGM-Technical Services), Mr. S. K. Saxena (AGM-MEG), Mr. Naveen Kohli
(DM-MEG), Mr. Ashutosh Yadav (DM-MEG), Mr. Arpit Shah (Sr. Engineer-
Technical Services), Mr. Mohit Mittal (Sr. Engineer-Technical Services), Mr.
Siddharth Gupta (Jr. Engineer-Technical Services), without whose cooperation
this work could not have taken the present form.

Also I am thankful to all the employees and the workers of IGL whose kind
and keen support in helping us understanding the working of refinery can hardly
be overlooked.

Further I extend our cordial thanks to Dr. Shishir Sinha (IIT Roorkee),
whose support and guidance will always form an unformidable base of this
current work.
Contents

I Manufacturing Processes at India Glycols Limited 3


1.1 About India Glycols Limited . . . . . . . . . . . . . . . . . . . . 4
1.2 Plant Information . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 Distillery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 Conversion Process . . . . . . . . . . . . . . . . . . . . . . 7
1.3.2 Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.4 Bio-Gas Plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.5 Industrial Gases Unit/Air Separation Unit . . . . . . . . . . . . 10
1.6 Mono-Ethylene Glycol Plant (MEG) . . . . . . . . . . . . . . . . 11
1.6.1 Conversion Process . . . . . . . . . . . . . . . . . . . . . . 11
1.7 Ethoxylate Plant . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.8 Specialty Chemical Plants . . . . . . . . . . . . . . . . . . . . . . 16
1.8.1 Alkylation . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.8.2 Esterfications . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.8.3 Neutralisation . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.8.4 Formulation . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.8.5 Sulphation . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.9 Glycol Ether . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.9.1 Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.9.2 Dryer Section . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.9.3 Reaction Section . . . . . . . . . . . . . . . . . . . . . . . 18
1.9.4 Alcohol Recovery Section . . . . . . . . . . . . . . . . . . 18
1.9.5 Distillation Sections . . . . . . . . . . . . . . . . . . . . . 18
1.10 Glycol Ether Acetate . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.10.1 Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.11 Liquor Bottling Plant . . . . . . . . . . . . . . . . . . . . . . . . 21
1.11.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.11.2 Raw Material Used . . . . . . . . . . . . . . . . . . . . . . 21
1.12 Guar Gum Plant . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.12.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . 22

II Ethylene Oxide and its Purification 23


1.13 Ethylene Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.13.1 Production . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.13.2 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.13.3 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.14 Purification of Ethylene Oxide . . . . . . . . . . . . . . . . . . . 26
1.14.1 Description of Purification Equipment . . . . . . . . . . . 28
CONTENTS 3

1.15 Column Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31


1.15.1 Components . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.15.2 Material Balance of Existing Column . . . . . . . . . . . . 31
1.15.3 Defining the Streams . . . . . . . . . . . . . . . . . . . . . 31
1.15.4 Determining Number of Stages . . . . . . . . . . . . . . . 33
1.15.5 Column Operational Parameters . . . . . . . . . . . . . . 33
1.15.6 Simulation of the Column . . . . . . . . . . . . . . . . . . 33
1.15.7 Sensitivity Analysis . . . . . . . . . . . . . . . . . . . . . 44
1.16 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Part I

Manufacturing Processes at
India Glycols Limited
1.1 About India Glycols Limited 5

1.1 About India Glycols Limited


India Glycols holds the distinction of being the only green petrochemical
company of its kind. It is one of the leading manufacturers of glycols, ethoxylates
and PEGs, performance chemicals, glycol ethers and acetates, natural gums and
potable alcohol.
It is the first and only company in the world to have commercialised the
production of ethylene oxide, its derivatives and glycols from renewable agri-
cultural resources, namely molasses or sugar cane.
The company was established as a single mono-ethylene glycol plant in 1983.
Since then, IGL has brought together cutting-edge technology, innovation and
an unflagging commitment to quality, to manufacture a wide range of products
that have found global demand.
IGL’s state-of-the-art, integrated facilities manufacture chemicals including
glycols, ethoxylates, glycol ethers and acetates, and various performance chem-
icals. Its product range spans the chemicals, spirits, herbal and other phyto-
chemical extracts and guar gum, industrial gases and realty sectors, and finds
application across an increasing number of industries.
These products are manufactured in compliance with stringent global stan-
dards of plant operations, quality and safety. The company’s facilities have been
approved and certified by international agencies including Det Norske Veritas
(DNV). The operations at all plants are closely monitored through distributed
control systems (DCS), which facilitate a high degree of control over the quality
of products.
1.1 About India Glycols Limited 6

Figure 1.1: Manufacturing Processes


1.2 Plant Information 7

1.2 Plant Information

S.No Unit/Plant Product Design Capacity

1 Distillery Ethanol 400 KL/Day


2 Bio-gas Bio-gas (Fuel) 150 KNm3 /Day
3 Industrial Gases O2 /N2 /CO2 /Ar 4200/1740 Nm3 /h
4 MEG1 MEG, DEG & TEG 140000 MTP.A.(MEG)
5 Ethoxylates EO Derivatives 20000 MTP.A.
6 Formulation Specialty Chemicals 10000 MTP.A.
7 Sulphation Specialty Chemicals 4000 MTP.A.
8 Guar Gum Guar Gum Powder 12000 MTP.A.
9 Glycol Ether Industrial Solvents 40000 MTPA.
10 Bottling Plant IMFL/Country Liquor 1 lac cases per month
11 Rab Unit Rab 1250 T.C.D.2

Table 1.1: Plant Information


1.3 Distillery 8

1.3 Distillery
Here, molasses3 are converted to alcohol by the fermentation and distilla-
tion process.

1.3.1 Conversion Process


Fermentable sugar present in the molasses is converted into alcohol by fermen-
tation with the help of living microorganisms called yeasts.
Large quantity of molasses containing about 42-46% of total reducible sugars
(TRS) is diluted with process water in the ratio of 1:3 to the required spe-
cific gravity, 0.1. The diluted molasses (called wort) is taken to fermenters.
Syrup (RAB) from Rab unit is diluted with process water and is taken to the
fermenters.
In the fermenters a predetermined quantity of yeast is added. The activation
of yeast is done in a pre-fermenter. Here molasses of specific gravity 1.06 is fed
and yeast is added. Sulphuric acid is added to maintain pH of wort at 4.8-5.2.
Urea is added as nutrient. Continuous aeration is done by means of compressed
air to speed up the activation process.
After activation the wort is transferred to one of the fermenters, undergoing
fermentation process. In the fermenter the conversion of fermentable sugar of
molasses to ethyl alcohol takes place and carbon dioxide is liberated as co-
product. Considerable amount of heat is evolved during fermentation causing
the temperature of wort to rise. This is controlled to keep the wort at 30-35
‰by spraying water on the outer surface. After fermentation, the wash in the
fermenters contains alcohol at a strength of approximately 7-8% by volume.
The fermented wash from fermenters is sent to the Distillation Section.
The following reactions represent the conversion process:
Inversion
C12 H22 O11 + H2 O −−−−−−→ 2 C6 H12 O6
Sucrose Water Glucose

C6 H12 O6 −−→ 2 C2 H5 OH + 2 CO2

After the fermentation is complete, the wash will contain alcohol at a strength
of 7-8% by volume. By distillation process, alcohol is recovered from fermented
wash and concentrated under the action of reflux. The product alcohol (95%
v/v) is drawn from the top of the Rectifying Column.

1.3.2 Distillation
The fermented wash is fed through the pre-heater condensers and then through
the spent wash plate heat exchanger (PHE) to the top of degassifying
column. In the condensers, the wash gets heated to about 70 ‰by means of
condensing vapours from the rectifying column top and then further heated up
to 85 ‰by means of spent wash in the plate heat exchanger. In the degassifying
column the wash flows down and is completely freed of carbon dioxide and some
aldehydes are also removed here. It then passes down to analyzer column where
direct steam is used to strip all the alcohol from the wash. The spent wash
3 A thick syrup produced in refining raw sugar and ranging from light to dark brown in

colour.
1.3 Distillery 9

discharged from the bottom of analyzer column is passed through the spent
wash PHE where it heats the feed wash. The alcohol vapours (50% v/v) from
the 12th plate are fed to the rectifying column. The vapours from top of the
column are condensed in a series of condensers and a reflux is sent back to the
top of the column.
The product alcohol (95% v/v) is drawn as liquid from column and is cooled
in cooler before being sent in alcohol receivers.
The heavy ends, mainly higher alcohols, are stripped off alcohol using direct
steam at the base of column.
1.4 Bio-Gas Plant 10

1.4 Bio-Gas Plant


In the bio-gas plant,

1. The spent wash of distillery is treated in two stages i.e. Anaerobic and
Aerobic to produce bio-gas, and
2. The effluent is treated to meet the Uttarakhand Pollution Control
Board’s norms.

The first phase of the biochemical reaction of anaerobic process takes place
in the Biologically Conditioned and Controlled Reactor (BCCR). Here, organic
compounds are solubilised, hydrolyzed and converted to Volatile Fatty Acids
(Formic, Acetic, Butyric Lactic Acids, etc.), with the help of microorganisms.
Biogas is collected from the BCCR and sent to a gas cooler. After cooling it
goes to a cyclone water separator and finally it is sent to boilers through blower
via gas filter for use as a fuel.
Secondary aerobic treatment is carried out in a series of aeration tanks,
Conventional Aeration Tanks I and II, and Extended Aeration Tank.
Supernated4 sludge generated in aerobic process is removed through clar-
ifiers and the effluent is partially sent to tertiary treatment plant (Reverse Os-
mosis). Clean water is reused in the plant premises & rest of the reject is sent
to storage lagoon.

4 Supernate is the liquid which remains above the solid produced by a precipitation reac-
tion.
1.5 Industrial Gases Unit/Air Separation Unit 11

1.5 Industrial Gases Unit/Air Separation Unit


Here, atmospheric air is passed through an air filter to remove solids and.
Then, it is compressed to 5.8 Kg/cm2 g by air compressor. Feed air is cooled
in the reactivation preheater and trickling cooler with the help of cooling water
and chilled water.
Cooled air is then fed to one of two adsorber vessels packed with Neobead
SA (Alumina) and molecular sieves where moisture and CO2 is absorbed from
the air by neobead-SA and molecular sieves respectively.
Two adsorbers (air driers) are operated alternately. One adsorber is under
operation the other is regenerated by dry waste nitrogen returning from the cold
box.
Most of the air from the adsorber is directly fed to the cold box and cooled
to cryogenic temperature in the Air Heat Exchanger against pure oxygen,
pure nitrogen and waste nitrogen.
The cold air leaving the air heat exchanger is fed directly into the bottom
of lower rectifying column.
Some of the cold air from the adsorber is compressed by the air blower
connected to expansion turbine and cooled by pre-cooler and after cooler.
The boosted air is introduced to the cold box and cooled down in the Air Heat
Exchanger. The boosted cold air is withdrawn from the middle part of the
Air heat exchanger and then expanded through Expansion turbine to provide
refrigeration.
Initial separation of the air into an oxygen rich liquid fraction (liquid air)
and a gaseous nitrogen fraction is accomplished in the lower rectifying column
while final separation into pure oxygen and waste nitrogen is done in the upper
rectifying column. After passing through liquid air super cooler, liquid air is
expanded and introduced as feed into the upper rectifying column. Liquid nitro-
gen is extracted from the middle part of the lower rectifying column, expanded
and fed to the upper rectifying column as reflux.
In the upper rectifying column, the liquid air and reflux nitrogen are sepa-
rated into product pure oxygen and waste nitrogen.
Oxygen is taken out from the bottom of the upper rectifying column and
nitrogen from the top of the lower rectifying column.
1.6 Mono-Ethylene Glycol Plant (MEG) 12

1.6 Mono-Ethylene Glycol Plant (MEG)


Here, ethanol is converted to Mono-Ethylene Glycol (MEG).

1.6.1 Conversion Process


Ethanol Dehydration
Main Reaction:
Catalyst

Ethanol ‰
C2 H5 OH −−−−−→ C2 H4 + H2 O
300 Ethylene W ater

Side Reactions:
C2 H5 OH −−→ CH3 CHO + H2
2 C2 H5 OH −−→ C2 H5 −O−C2 H5 + H2 O

Ethanol (95% vol.%) is vapourised in the Ethanol Feed Vapouriser. The


ethanol vapour is combined with steam from the Third Effect Condenser and the
resulting dehydration feed mixture is preheated to reaction temperature through
a feed/effluent exchanger and then a furnace. The hot vapour mixture flows
through the Ethanol Dehydration Reactor where ethanol is converted to
ethylene. It is an adiabatic operation using SYNDOL catalyst.
Heat is recovered from the reactor effluent in the Feed/Effluent Exchanger.
A portion of the reactor effluent containing a mixture of ethylene and steam
is sent to the Stripping column. Another portion flows to the Glycol Feed
Stripper Reboiler and the remainder passes through the Ethanol Feed Vaporizer
and then to the Dehydration Excess Steam Condenser.

Ethylene Oxide Reaction and Recovery


Main reaction:
1 Oxidation
CH2 −CH2 +
Ethylene
2 O2 −
Oxygen 200-300 ‰
−−−−−→ C2 H4 O2
EthyleneOxide
+∆

TT 
O

Ethylene Oxide Structure

Side reactions:
C2 H4 + 3 O2 −−→ 2 CO2 + 2 H2 O
C2 H4 + 21 O2 −−→ CH3 −CHO

Temperature 200–300 ‰
Pressure 10–30 Kg/cm2

Ethylene, formed in the Ethanol Dehydration Reactor enters the rich


cycle gas line before the Scrubber and K.O. Drum.
Oxygen enters from battery limits and is mixed with lean cycle gas before
entering a preheating unit (the Gas-Gas Exchanger). The gas mixture flows
1.6 Mono-Ethylene Glycol Plant (MEG) 13

from the Gas-Gas Exchanger to the Reactor where a partial conversion of ethy-
lene to ethylene oxide occurs over solid silver based catalyst.
After heat is recovered in the reactor effluent gas cooler and gas-gas ex-
changer, ethylene oxide (EO) is scrubbed from the reactor effluent gas using
lean cycle water and the EO rich cycle water is sent to the EO stripper and re-
absorption section. A small stream of lean (scrubbed) cycle gas is sent through
the carbon dioxide removal system and then combined with the lean cycle gas.
Boiling water circulating on the shell side of the multi-tubular reactor removes
the heat of reaction with the production of H.P. steam which is sent to the H.P.
Heater and used in the plant.

Ethylene Oxide Purification


Dilute Ethylene Oxide is taken and purified in Ethylene Oxide Purification
Column. The column bottom stream containing the stripped EO-free water is
recycled to the plant. Pure ethylene oxide is then taken into buffer vessel (EO
Storage Tank) in Ethoxylate Plant. It is stored in EO storage tank and is cooled
to -5 ‰, using a refrigeration system.

Carbon Dioxide Removal System


Carbon dioxide produced by the reaction is removed by treating a portion of
the cycle gas from the recycle compressor with a hot potassium carbonate
solution. The carbonate is converted to potassium bicarbonate by reaction with
the carbon dioxide at system pressure. The carbon dioxide rich solution is then
regenerated at atmospheric pressure using stripping steam. The carbon dioxide
lean cycle gas is then recombined with the bulk of the oxide-lean cycle gas.

Absorption:

K2 CO3 + CO2 + H2 O −−→ 2 KHCO3


P otassiumCarbonate CarbonDioxide Steam P otassiumBicarbonate

Regeneration:

2 KHCO3 −−→ K2 CO3 + H2 O + CO2

Around 24 MT/h carbon dioxide rich solution with an estimated composition


of 12.5 mole % water & 81.5 mole % CO2 at 1.1 Kg/cm2 is consumed and the
condensate is used as recycle water.

Ethylene Oxide Stripping and Reabsorption


Rich cycle water containing ethylene oxide in solution is preheated before passing
into the stripping column where the ethylene oxide is stripped out. The lean
cycle water is then pumped through a series of heat exchangers where the water
is cooled prior to being returned to the scrubber. At this point a bleed steam
is taken and sent to the Cycle Water Treating Unit to purge the glycol which is
made in the cycle water loop.
1.6 Mono-Ethylene Glycol Plant (MEG) 14

The vapour necessary to strip ethylene oxide from cycle water is provided by
steam generated from the lean cycle water in the MEG column condenser and
by a portion of the steam/ethylene mixture from the Ethanol Dehydration Re-
actor. Overhead vapour from the stripping column consists mainly of ethylene,
ethylene oxide and steam. The ethylene oxide is reabsorbed and steam is con-
densed by direct contact with cooled process water in the Reabsorber. Overhead
vapour from the Reabsorber consisting mainly of ethylene is combined with the
ethylene from the Dehydration Excess Steam Condenser, the make-up nitrogen
ballast gas from OSBL and the flash vapour from the Regenerator Flash Drum.
The combined steam is then compressed and fed to the Scrubber. From the
Reabsorber bottoms a solution of ethylene oxide in water is sent to the Glycol
Reaction and Evaporation Section.

Glycol Reaction And Recovery


Reactions

C2 H4 O + H2 O −−→ HO−CH2 −CH2 −OH


M EG

C2 H4 O + MEG −−→ HO−(CH2 )2 −O−(CH2 )2 −OH


DEG

C2 H4 O + DEG −−→ HO−(CH2 )2 −O−(CH2 )2 −O−(CH2 )2 −OH


T EG

Ethylene oxide solution from the Reabsorber bottoms is sent to the Glycol
Feed Stripper for removal of carbon dioxide. The carbon dioxide-free stream is
then preheated and fed to the Glycol Reactor. The reactor effluent is fed in to
the first stage of a triple effect evaporator system. The water purge from the
cycle water loop is treated in the Cycle Water Treating Unit and then used in
the evaporator system as reflux. The condensate from the Second and Third
Effect Reboiler and the Third Effect Condenser is used to preheat the feed to
the Glycol Reactor. The overhead vapour from the Third Effect Evaporator
is used to generate L.P. Steam (in the third Effect Condenser) for the ethanol
dehydration. The crude glycol from the bottom of the third effect evaporator
is sent to the Drying Column for further processing.

Glycol Drying And Purification


The crude wet glycol is dried by vacuum distillation in the Drying Column.
The Drying Column bottoms are fed to the MEG Column where Mono-ethylene
Glycol product is taken as overheads. The product is cooled and stored in the
MEG Rundown Tanks for subsequent pumping to MEG Storage OSBL.
The MEG Column bottoms are sent to the MEG/DEG Spiltter.

MEG/DEG And Heavy Glycol Separation


The mixture of glycols from the MEG Column bottoms is distilled in the
MEG/DEG Splitter where MEG is taken overhead and recycled to the Dry-
ing Column.
1.6 Mono-Ethylene Glycol Plant (MEG) 15

While taking MEG overhead for recycle, the MEG/DEG Splitter bottoms
containing DEG and higher glycols are stored and cooled in the Crude DEG
Tank. Contents of the Crude DEG Tank are later distilled in the MEG/DEG
Splitter, taking DEG product overhead. DEG product is cooled and stored
in the DEG Rundown Tanks for subsequent pumping to DEG storage OSBL.
Triethylene Glycols (TEG) and heavier glycols from the MEG/DEG splitter
bottoms are pumped OSBL and the MEG Column bottoms are accumulated in
the MEG Column Bottoms Tank.
1.7 Ethoxylate Plant 16

1.7 Ethoxylate Plant


The Ethoxylation5 unit is designed to manufacture all products of condensation
of EO with any type of starter provided that the chain starter the product of
condensation are liquid at the operating conditions. The maximum allowable
viscosity is 500 cp at operating conditions.

Ethoxylation Reaction
150 ‰
ROH + nC2 H4 O −−−−−−→ R(OC2 H4 )n OH
Catalyst

The raw materials, Nonyl Phenol, Castor Oil, Lauryl Alcohol, DEG, Stearic
Acid etc. which are to be ethoxylated are directly fed from raw material storage
to reactor which is a “gas liquid contactor”. After raw material loading, catalyst
is charged into the reactor. Water is removed by dehydration under vacuum.
Before starting the reaction, the reactor is inertised with nitrogen and raw ma-
terial is heated up to reaction initiation temperature. After above preparation
cold ethylene oxide is fed from buffer vessel to reactor. The reaction occurs in
the Gas Liquid Contactor. EO and raw material are completely converted
into the ethoxylated product. After stripping with nitrogen and cooling the
raw product is neutralized in reactor itself. The final neutralized product is
discharged to the intermediate process vessel for analysis and finally pumped to
the final product storage tank for filling and packing.

5 Ethoxylation is an industrial process in which ethylene oxide is added to fatty acid

alcohols to give them detergent properties.


1.8 Specialty Chemical Plants 17

1.8 Specialty Chemical Plants


This has the following plants:

ˆ Blending/Formulation Plant

ˆ Sulphation Plant
Specialty chemicals are manufactured through the following processes:

ˆ Alkylation

ˆ Esterification
ˆ Neutralization
ˆ Formulation/Blending
ˆ Sulphation

1.8.1 Alkylation
This process is a reaction of Alkenes and Alcohols/aromatic alcohols to man-
ufacture major specialty chemicals such as Styrenated Phenols and Ethoxy-
lated/Propoxylated Styrenated Phenol, which are used as Agro emulsifiers.
R1 R1 R-CH=CH2 +
CH2-CH2-R’ R = Alkyl and/or Aryl Group R’ = Methyl/Hydroxyl

1.8.2 Esterfications
This process is carried out between fatty alcohol and fatty acids to produce
fatty acid esters such as Sorbitan Mono Oleate, Sorbitan Distearates etc., which
are used in Textile, Personal Care Products, and Industrial Cleaning.

C6 H14 O6 + RCOOH −−→ Sorbitan + 2 H2 O


Sorbitol

1.8.3 Neutralisation
Organic acids like Linear Alkyl Benzene Sulphonic Acid react with alkali e.g.,
Ca(OH)2 and convert into salt e.g. CABS, which are mainly used in the man-
ufacture of emulisifiers.

1.8.4 Formulation
It is a process of blending of various specialty chemicals/surfactants to achieve
specified requirements of the consumer.
1.8 Specialty Chemical Plants 18

1.8.5 Sulphation
O

Cl S O

OH
Cholorosulphuric Acid

Sulphation Reaction
ROH + ClSO3 H −−→ R−O−SO3 H + HCl

Sulphation is the process of reaction of Alcohols and Ethoxylated alcohols


with Chlorosulphuric acid in a glasslined reactor. These sulphonated products
are mainly used in personal care finished products such as shampoos, toothpaste
and quality detergents.
1.9 Glycol Ether 19

1.9 Glycol Ether


Glycol ethers are a group of solvents based on alkyl ethers of ethylene glycol
commonly used in paints. These solvents typically have higher boiling point,
together with the favorable solvent properties of lower molecular weight of ethers
and alcohols.
Glycol ethers are produced by reaction of alcohol and Ethylene oxide in the
presence of catalyst. There are different type of Glycol ethers i.e. Methyl alcohol
base, Ethyl alcohol base etc..

1.9.1 Reaction
The production of glycol ether from alcohol and ethylene oxide is obtained by
a series of consecutive competitive and irreversible reactions:
Catalyst
ROH + nC2 H4 O −−−−−−→ R−O−(C2 H4 O)n −H

n=1 Mono Ethylene Glycol Ether


n=2 Diethylene Ethylene Glycol Ether
n=3 Triethylene Glycol Ether
n=4/5 Higher Ethylene Glycol Ether

1.9.2 Dryer Section


Adsorption of water from a 95 vol. % ethanol solution is carried out in a
molecular sieve-based adsorption tower. Dry ethanol is obtained. Regenera-
tion of the bed is done by heating with nitrogen. This process is not applicable
for methanol.

1.9.3 Reaction Section


Dry alcohol is mixed with recycle alcohol from distillation section and with the
catalyst by the catalyst mixers and is fed to the reactor. Glycol ether forma-
tion is exothermic. Hence, in order to keep the temperature in the reaction
temperature range, the reaction section is designed with multiple EO injection
and intermediate intercoolers. The reactors are tubular type reactors. After
the reaction, reactor effluent is collected in an effluent drum.

1.9.4 Alcohol Recovery Section


The reactor effluent is fed to a distillation column where the alcohol is separated
from glycol ethers.

1.9.5 Distillation Sections


The crude glycol ethers are fed to the distillation column. The mono ethylene
glycol ether leaves from the top as pure product. The column is operated under
vacuum.
The heavy glycols (from the bottoms) are then fed to another distillation
column where diethylene glycol ether leaves from the top as pure product. The
column is operated under vacuum.
1.9 Glycol Ether 20

The bottom glycol separation is achieved in a one step flash evaporation.


The flash box is operated under vacuum and the top product is mixture of tri-
and tetraethylene glycol ether.
1.10 Glycol Ether Acetate 21

1.10 Glycol Ether Acetate


1.10.1 Reaction
Ethyl cellosolve acetate is formed by reaction of ethyl cellosolve with acetic
acid. During reaction LABSA is used as catalyst. The reaction is as given be-
low:

LABSA
−−
C2 H5 −O−C2 H4 OH+CH3 COOH )−−−−
−−
−*
− C2 H5 −O−C2 H4 −OCOCH3 + H2 O
Ethyl Cellosolve Acetic Acid Ethyl Cellosolve Acetate Water
1.11 Liquor Bottling Plant 22

1.11 Liquor Bottling Plant


1.11.1 Description
Rectified spirit/ENA produced in distillery is transferred to the bottling
section for blending and bottling. It is diluted by mixing appropriate quantity
of demineralized water. Thereafter, caramel and essence are added to produce
specific type of blends like Country Liquor, Whisky, Brandy, Gin and Rum.
Separate tanks are used to store different type of blends to avoid washing of the
tanks.
The blended liquor is bottled in bottling section, packed and will be sent to
market.

1.11.2 Raw Material Used


Molasses/Rectified Spirit Rectified spirit is the produce of fermentation and
distillation and can be made from saccharine material and starch.

ENA Extra neutral alcohol is the alcohol produced by taking extraordinary


precaution during the process of redistribution of rectified spirit after the
addition of chemicals, and treatment by activated carbon. The spirit is
made neutral.
DM Water Demineralized (DM) water is another name for deionized (DI)
water. It is water from which the (mineral) ions have been removed.
Essences for giving odour.
Caramel is burnt sugar; a brown or black porous substance obtained by heat-
ing sugar. It is soluble in water, and is used for colouring spirits, gravies,
etc.
1.12 Guar Gum Plant 23

1.12 Guar Gum Plant


1.12.1 Description
Raw Guar seed is emptied in hoppers and sent to temporary storage silos. After
cleaning it goes to crushers which divide the guar seeds into portions. Sieving
removes the fines generated and the remaining goes to milling for protein sepa-
ration. Uncrushed guar is recycled.
After milling, the whole material is sieved to separate protein which goes
to storage. Remains of seed (Endosperm6 + husk) is traditionally known as
Chhala now goes to roasting process in which it is heated upto 90‰for 30 s.
This hot chhala goes to dehusking machine where endosperm (dal) and husk is
separated which is then sieved to two different segments i.e. Guar Churi (Husk)
and Guar Dal.

6 Endosperm is the tissue produced under the seeds of most flowering plants
Part II

Ethylene Oxide and its


Purification
1.13 Ethylene Oxide 25

1.13 Ethylene Oxide


Ethylene oxide (EtO) is a flammable, colorless gas at temperatures above
10.7‰that smells like ether at toxic levels. EtO is found in the production
of solvents, antifreeze, textiles, detergents, adhesives, polyurethane foam, and
pharmaceuticals. Smaller amounts are present in fumigants, as well as during
hospital sterilization of surgical equipment.

1.13.1 Production
Ethylene oxide is produced by the direct vapour-phase oxidation process, in
which ethylene is oxidized to ethylene oxide with air or oxygen and a silver
catalyst at 10–30 atm (1–3 MPa) and 200–300‰.

1.13.2 Uses
Ethylene oxide is an important raw material used in the manufacture of chemical
derivatives that are the basis for major consumer goods in virtually all indus-
trialized countries. More than half of the ethylene oxide produced worldwide is
used in the manufacture of monoethylene glycol.
Other derivatives of ethylene oxide include: diethylene glycol, which is used
in the production of polyurethanes, polyesters, softeners (cork, glue, casein and
paper), plasticizers and solvents and in gas drying; triethylene glycol, which
is used in the manufacture of lacquers, solvents, plasticizers and humectants
(moisture-retaining agents) and in gas drying; poly(ethylene) glycols, which are
reacted with other materials and used in cosmetics, ointments, pharmaceutical
preparations, lubricants (finishing of textiles, ceramics), solvents (paints and
drugs) and plasticizers (adhesives and printing inks); ethylene glycol ethers,
which are frequently a component of brake fluids, detergents and solvents (paints
and lacquers) and are used to treat natural and refinery gas; ethanolamines,
which are used in textile finishing, cosmetics, soaps, detergents and natural gas
purification; and ethoxylation products of fatty alcohols, fatty amines, alkyl
phenols, cellulose and poly(propylene) glycol, which are used in the production
of detergents and surfactants (non-ionic), biodegradable detergents, emulsifiers
and dispersants.

1.13.3 Properties
Description Colourless gas
Boiling-point 13.2‰at 746 mm Hg [99.4 kPa]; 10.4–10.8‰at 760 mm Hg
[101.3 kPa]
Freezing-point -111‰

Density (liquid) 0.8824 at 10‰/10‰


Solubility Soluble in water, acetone, benzene, ethanol and diethyl ether
Vapour pressure 145.6 kPa at 20‰

Relative vapour density (air = 1) 1.5 at 20‰


1.13 Ethylene Oxide 26

Stability Reacts readily with acids; reactions proceed mainly via ring opening
and are highly exothermic; explosive decomposition of vapour may occur
at higher temperatures if dissipation of heat is inadequate.
Lower explosive limit 2.6–3.0% by volume in air
Inflammability limits in air 2.6–99.99% (V)
1.14 Purification of Ethylene Oxide 27

1.14 Purification of Ethylene Oxide


The purification of the ethylene oxide-water stream to a product stream of
around 99.95% purity in EO is carried out in a distillation column, T-1410, the
EO Purification Column.
The theoretical number of stages required for purification of the EO-water
mixture without any other impurities is only around 9 or 10. However, aldehy-
des, namely formaldehyde and acetaldehyde are also present in the feed stream.
They constitute around 20 ppm of the feed by weight. The product is desired
to have minimal amount of aldehydes, and the actual column contains around
90 stages, most of which perform the task of separation of ethylene oxide and
acetaldehyde.
1.14 Purification of Ethylene Oxide 28

Figure 1.2: T-1410, EO Purification Column


1.14 Purification of Ethylene Oxide 29

1.14.1 Description of Purification Equipment


The feed consisting of around 7-10% ethylene oxide in water (from G-3512A/B
parallel system and EOP column feed pumps, G-512A/B), at 58 deg. C, is
preheated using two parallel feed-bottoms exchangers, E-1412 and E-1414 to
around 95‰.
The preheated feed is then sent to the lower part of the column.
Hot DM water from E-150/A/B is sent near the middle of the column. This is
primarily used for the separation of aldehydes. Addition of this water, however,
increases the heat requirement from the reboilers.
A side stream near the middle is taken as aldehyde purge. This is done to
prevent the accumulation of impurities (aldehydes) in the product. This stream
is sent back to the Glycol Feed Stripper, T-510, where it is purified and again
sent to the Ethylene Oxide Purification Column.

Name Description

E-1412/E-1414 Purification Column Feed Bottoms Exchanger


G-1410A/B Purification Column Bottom Pumps
E-1413 Purification Column Side Stream Reboiler
E-1410/X Purification Column Reboiler
T-1410 Ethylene Oxide Purification Column
E-1411/X Purification Column Condenser
G-1411A/B Purification Column Reflux Pumps
D-1410 Purification Column Reflux Drum
G-1412A/B Purification Column Product Pumps
G-1413 EO Booster Pump

Table 1.2: Ethylene Oxide Purification Equipment

The feed consisting of around 7-10% ethylene oxide in water (from G-3512A/B
parallel system and EOP column feed pumps, G-512A/B), at 58 ‰, is preheated
using two parallel feed-bottoms exchangers, E-1412 and E-1414 to around 95‰.
The preheated feed is then sent to the lower part of the column.
Hot DM water from E-150/A/B is sent near the middle of the column. This is
primarily used for the separation of aldehydes. Addition of this water, however,
increases the heat requirement from the reboilers.
A side stream near the middle is taken as aldehyde purge. This is done to
prevent the accumulation of impurities (aldehydes) in the product. This stream
is sent back to the Glycol Feed Stripper, T-510, where it is purified and again
sent to the Ethylene Oxide Purification Column.

Side Stream Reboiler, E-1413


A side stream at around 54‰is taken from a point a little above the vapour
distributor and sent to the Purification Column Side Stream Reboiler, E-1413.
1.14 Purification of Ethylene Oxide 30

Basically, the objective is to reduce the steam requirement of the Purification


Column Reboiler, E-1410/X. For this purpose, heat from the bottoms is utilized
in the Purification Column Side Stream Reboiler, E-1413. The side stream at
54‰gets vapourized at the same temperature and is sent back to the column
below the vapour distributor.
Before the use of this side stream reboiler, steam requirement of the Pu-
rification Column Reboiler, E-1410/X was around 10 tonnes/hour. The side
stream reboiler was successfully operated after the 2009 annual shutdown, and
has reduced the steam requirement of Purification Column Reboiler, E-1410/X
by around 2 tonnes/hour.
The side stream reboiler was not operational, though installed, previously
probably due to a problem in the control valve (HV-145TX). This valve controls
the flow in the feed line of the reboiler.

Bottoms
Bottoms consist of mainly water and leaves around 130‰and around 3 kg/cm2
pressure.
Surprisingly, a large part of formaldehyde in the feed also exited from
the bottoms. Formaldehyde is the most volatile of all the components in the
columns, and it was expected that it would be present in the overheads.

Utilization of Bottoms Heat The heat from the bottoms is utilized first in
the Purification Column Feed Bottoms Exchangers, E-1412/E-1414 (bot-
toms are pumped by G-1410A/B). Here, the feed is preheated to around
95‰from 58‰. The bottoms exit at around 100-110‰.
This 100‰stream is sent to Purification Column Side Stream Reboiler,
E-1413, where the side stream is vapourized and sent back to the column.
The bottoms exit at around 60-70‰, and are sent to the Reabsorber Water
Coolers, E-430, E-2430 and E-3430.

Purification Column Reboilers One part of the bottoms from the EOP col-
umn is sent to two parallel reboilers, Purification Column Reboiler, E-
1410/X. Here, MP steam is used to heat the bottoms and the heated
bottoms are sent back to the column. Condensed steam (nearly at satu-
ration) at around 191‰, is sent to the High Pressure Condensate Flash
Drum, D-830.

Top Vapours
The top vapours consist of around 90% ethylene oxide, but contain aldehydes
as impurity. Hence, they cannot be directly condensed and sent downstream.
The vapours exit at around 48‰and 2 kg/cm2 pressure. They are sent to
two parallel condensers, Purification Column Condenser, E-1411/X.

Purification Column Condensers Cooling Water Supply (CWS) at 33‰is


used for condensation. It exits (Cooling Water Return, CWR) at 43 ‰.
The top vapours at 48‰get condensed and leave at around 45‰.
The exit streams are combined and sent to Purification Column Reflux
Drum, D-1410. From here, a reflux with R approximately equal to 6.5 is
maintained using a pump, G-1411A/B.
1.14 Purification of Ethylene Oxide 31

Ethylene Oxide purge is taken and sent to the glycol ether plant.

Ethylene Oxide Product


Ethylene Oxide product is withdrawn as a side stream (near tray 83 in the
old arrangement), and pumped by G-1412A/B to the Oxide Product Cooler,
E-18101 for cooling and storage in Ethylene Oxide bullets.
The Ethylene Oxide from the Ethylene Oxide bullets are distributed for use
internally.
Ethylene Oxide is known to be hazardous, and its presence is monitored
very carefully even to the order of around 30-40 ppm. Ethylene Oxide can
cause explosions if not properly handled.
1.15 Column Design 32

1.15 Column Design


In this tower, the bottoms stream should be exclusively water, while the tops
stream will contain most of the formaldehyde, as these components are the least
and most volatile in the system, respectively. Thus, two additional side product
streams are required: a low-purity stream containing almost all of the acetalde-
hyde, and a high-purity stream containing approximately 99.95% ethylene oxide.
This project will aim to optimize the total number of trays in this column, as
well as the location of all feed and product streams.
A small amount of water is added since this facilitates better separation of
acetaldehyde, since acetaldehyde dissolves in water.

1.15.1 Components
The major components separated in the column are:

Component Formula Molecular Weight (kg/kmol) Boiling Point (‰)


Ethylene Oxide C2 H 4 O 2 44.05 10.5
Water H2 O 18 100.0
Formaldehyde HCHO 30.03 -19.0
Acetaldehyde CH3 CHO 44.05 20.6

Table 1.3: Major Components in the Column

1.15.2 Material Balance of Existing Column

Service Feed Bottoms Overheads


Component kg/h wt% kg/h wt% kg/h wt%
Ethylene Oxide 11663.6 10.00 2.0 20 ppm 32470.2 100.00
MEG 698.0 0.68
Formaldehyde 1.7 15 ppm 1.6 16 ppm 0.7 20 ppm
Acetaldehyde 0.6 5 ppm 0.2 2 ppm 0.1 3 ppm

Service Reflux Purge Pure EO


Component kg/h wt% kg/h wt% kg/h wt%
Ethylene Oxide 29570.3 100.00 2899.9 100.00 7099.9 100.00
MEG
Formaldehyde 0.6 20 ppm 0.1 20 ppm
Acetaldehyde 0.1 3 ppm 0.0 3 ppm 0.1 10 ppm

Table 1.4: Material Balance with 10T/h Product Basis

1.15.3 Defining the Streams


The inlet and outlet streams were defined using the material balance of the
column in operation.
1.15 Column Design 33

Figure 1.3: Stream Compositions


1.15 Column Design 34

1.15.4 Determining Number of Stages


The approximate number of stages was determined using the “Shortcut Col-
umn” in CHEMCAD, which uses the Fenske equation to predict the number
of trays. In this column, the major separation is not between ethylene oxide
and water, but rather between ethylene oxide and acetaldehyde. Running the
“shortcut column” tray analysis for ethylene oxide-water separation with around
99.99% purity of ethylene oxide predicted the minimum number of stages of
around 10, with a reflux ratio of around 6. However, this calculation does not
take into account separation of aldehydes. Considering the separation of alde-
hydes resulted in prediction of around 60 stages. This was taken as the initial
approximation.

1.15.5 Column Operational Parameters


The operating pressure of the column was selected to be 2.8 bar (absolute) so
that an additional cooling mechanism is not required for ethylene oxide, since
an increase in pressure causes an increase in boiling point. Diameter of the
column was taken as 1.6 m, the same as the actual column.

1.15.6 Simulation of the Column


The UNIQUAC thermodynamic model was chosen for the system.

Figure 1.4: CHEMCAD Model


1.15 Column Design 35

Material and Energy Balances - CHEMCAD

CHEMCAD 6.2.0 Page 1

Simulation: eop_actual Date: 06/25/2010 Time: 16:52:16


FLOW SUMMARIES:

Calculation mode : Sequential


Flash algorithm : Normal

Equipment Calculation Sequence


2

No recycle loops in the flowsheet.

Warning: Stream 6 may form two liquid phases. VLL option is recommended.
CHEMCAD 6.2.0 Page 2

Simulation: eop_actual Date: 06/25/2010 Time: 16:52:16


FLOW SUMMARIES:

Overall Mass Balance kmol/h kg/h


Input Output Input Output
Ethylene Oxide 259.983 259.982 11453.011 11453.004
Water 5777.095 5777.092 104074.356 104074.316
Acetaldehyde 0.031 0.031 1.374 1.374
Formaldehyde 0.046 0.046 1.374 1.374

Total 6037.154 6037.151 115530.118 115530.069

Overall Energy Balance kcal/h


Input Output
Feed Streams -3.90742e+008
Product Streams -3.87642e+008
Total Heating 8.00907e+006
Total Cooling -4.90907e+006
Power Added 0
Power Generated 0

Total -3.87642e+008 -3.87642e+008

Consolidated Report - CHEMCAD

CHEMCAD 6.2.0 Page 1


1.15 Column Design 36

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36

FLOWSHEET SUMMARY

Equipment Label Stream Numbers

2 SCDS 4 2 -3 -1 -5 -6

Stream Connections

Stream Equipment Stream Equipment Stream Equipment


From To From To From To
1 2 3 2 5 2
2 2 4 2 6 2

CHEMCAD 6.2.0 Page 2

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36

Calculation mode : Sequential


Flash algorithm : Normal

Equipment Calculation Sequence


2

No recycle loops in the flowsheet.

Warning: Stream 6 may form two liquid phases. VLL option is recommended.
CHEMCAD 6.2.0 Page 3

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36

Overall Mass Balance kmol/h kg/h


Input Output Input Output
Ethylene Oxide 259.983 259.982 11453.011 11453.004
Water 5777.095 5777.092 104074.356 104074.316
Acetaldehyde 0.031 0.031 1.374 1.374
Formaldehyde 0.046 0.046 1.374 1.374

Total 6037.154 6037.151 115530.118 115530.069

CHEMCAD 6.2.0 Page 4

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1.15 Column Design 37

Overall Energy Balance kcal/h


Input Output
Feed Streams -3.90742e+008
Product Streams -3.87642e+008
Total Heating 8.00907e+006
Total Cooling -4.90907e+006
Power Added 0
Power Generated 0

Total -3.87642e+008 -3.87642e+008

CHEMCAD 6.2.0 Page 5

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36

COMPONENTS
ID # Name Formula
1 129 Ethylene Oxide C2H4O
2 62 Water H2O
3 128 Acetaldehyde C2H4O
4 114 Formaldehyde CH2O

THERMODYNAMICS

K-value model : UNIQUAC


No correction for vapor fugacity
Enthalpy model : Latent Heat
Liquid density : Library

Std vapor rate reference temperature is 0 C.


Atmospheric pressure is 1.0332 kg/cm2.

UNIQUAC Parameters: Tij = Aij -(Uij-Uji)/RT + Cij*Ln(T) + Dij*T (T Deg K)

I J Uij-Ujj Uji-Uii Aij Aji Cij Cji Dij Dji


1 2 878.06 104.56 0.000 0.000 0.000 0.000 0.000 0.000
1 3 -422.43 607.76 0.000 0.000 0.000 0.000 0.000 0.000
2 3 271.58 106.01 0.000 0.000 0.000 0.000 0.000 0.000
2 4 22768.00 -3243.40 0.000 0.000 0.000 0.000 0.000 0.000
CHEMCAD 6.2.0 Page 6

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36


EQUIPMENT SUMMARIES

Scds Rigorous Distillation Summary

Equip. No. 2
Name
1.15 Column Design 38

No. of stages 90
1st feed stage 76
2nd feed stage 82
Condenser mode 1
Condenser spec 11.0000
Reboiler mode 7
Reboiler spec. 1.0000e-005
Reboiler comp i 1
Est. dist. rate 79.5000
(kmol/h)
Est. T top C 40.0000
Est. T bottom C 140.0000
Calc cond duty kcal/h -4.9091e+006
Calc rebr duty kcal/h 8.0091e+006
Side 1 stage no. 6
Side 1 spec. 7100.0000
Side product 1 mode -3
Side 2 stage no. 76
Side 2 spec. 1290.0000
Side product 2 mode -3
Calc Reflux mole 781.8317
(kmol/h)
Calc Reflux ratio 11.0000
Calc Reflux mass kg/h 34442.0313
Column type 1
Column diameter m 1.6233
Thickness (top) m 0.0032
Thickness (bot) m 0.0032
No of sections 1
Calc. tolerance 0.0651

CHEMCAD 6.2.0 Page 7

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36


STREAM PROPERTIES

Stream No. 1 2 3 4
Name Bottoms Feed Top Product DM Water
- - Overall - -
Molar flow kmol/h 5773.3888 5981.6444 71.0756 55.5093
Mass flow kg/h 104009.0000 114530.1173 3131.0941 1000.0000
Temp C 133.2882 90.0000 40.9198 70.0000
Pres kg/cm2-G 2.0000 2.0000 2.0000 2.0000
Vapor mole fraction 0.0000 0.03145 0.0000 0.0000
Enth kcal/h -3.8264E+008 -3.8700E+008 -1.2971E+006 -3.7429E+006
Tc C 374.1945 357.9358 196.0000 374.2000
Pc kg/cm2-G 224.5008 196.0543 72.2844 224.5099
Std. sp gr. wtr = 1 1.000 0.986 0.878 1.000
Std. sp gr. air = 1 0.622 0.661 1.521 0.622
Degree API 10.0011 11.9646 29.6364 10.0000
1.15 Column Design 39

Average mol wt 18.0152 19.1469 44.0530 18.0150


Actual dens kg/m3 931.4030 58.3174 843.8225 977.4476
Actual vol ft3/hr 3943.5591 69354.8125 131.0389 36.1295
Std liq m3/h 104.0099 116.1204 3.5656 1.0000
Std vap 0 C scfh 4569813.0000 4734654.0000 56258.5117 43937.3047
- - Vapor only - -
Molar flow kmol/h 188.1353
Mass flow kg/h 7154.4367
Average mol wt 38.0281
Actual dens kg/m3 3.8647
Actual vol ft3/hr 65376.1953
Std liq m3/h 8.0385
Std vap 0 C scfh 148914.8438
Cp kcal/kg-C 0.3269
Z factor 0.9695
Visc cP 0.01179
Th cond kcal/h-m-C 0.0169
- - Liquid only - -
Molar flow kmol/h 5773.3888 5793.5099 71.0756 55.5093
Mass flow kg/h 104009.0000 107375.6828 3131.0941 1000.0000
Average mol wt 18.0152 18.5338 44.0530 18.0150
Actual dens kg/m3 931.4029 953.0792 843.8225 977.4476
Actual vol m3/h 111.6692 112.6619 3.7106 1.0231
Std liq m3/h 104.0099 108.0819 3.5656 1.0000
Std vap 0 C scfh 4569813.0000 4585739.5000 56258.5117 43937.3047
Cp kcal/kg-C 1.0209 0.9816 0.4890 1.0000
Z factor 0.0023 0.0025 0.0070 0.0026
Visc cP 0.2038 0.3110 0.2233 0.4109
Th cond kcal/h-m-C 0.5891 0.5311 0.1242 0.5644
Surf. tens. dyne/cm 52.1069 56.1867 21.1326 64.1657
CHEMCAD 6.2.0 Page 8

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36


STREAM PROPERTIES

Stream No. 5 6
Name Side Product Ald Purge
- - Overall - -
Molar flow kmol/h 161.1695 31.5179
Mass flow kg/h 7100.0000 1290.0000
Temp C 40.9198 42.1959
Pres kg/cm2-G 2.0000 2.0000
Vapor mole fraction 0.0000 0.0000
Enth kcal/h -2.9413E+006 -7.6233E+005
Tc C 196.0000 206.3552
Pc kg/cm2-G 72.2844 76.4065
Std. sp gr. wtr = 1 0.878 0.884
Std. sp gr. air = 1 1.521 1.413
Degree API 29.6364 28.6006
Average mol wt 44.0530 40.9291
1.15 Column Design 40

Actual dens kg/m3 843.8225 848.6874


Actual vol ft3/hr 297.1408 53.6781
Std liq m3/h 8.0853 1.4596
Std vap 0 C scfh 127570.5625 24947.3809
- - Liquid only - -
Molar flow kmol/h 161.1695 31.5179
Mass flow kg/h 7100.0000 1290.0000
Average mol wt 44.0530 40.9291
Actual dens kg/m3 843.8225 848.6873
Actual vol m3/h 8.4141 1.5200
Std liq m3/h 8.0853 1.4596
Std vap 0 C scfh 127570.5625 24947.3809
Cp kcal/kg-C 0.4890 0.5166
Z factor 0.0070 0.0065
Visc cP 0.2233 0.2517
Th cond kcal/h-m-C 0.1242 0.1313
Surf. tens. dyne/cm 21.1326 22.2830

CHEMCAD 6.2.0 Page 9

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36


FLOW SUMMARIES:

Stream No. 1 2 3 4
Stream Name Bottoms Feed Top Product DM Water
Temp C 133.2882 90.0000* 40.9198 70.0000*
Pres kg/cm2-G 2.0000 2.0000* 2.0000 2.0000*
Enth kcal/h -3.8264E+008 -3.8700E+008 -1.2971E+006 -3.7429E+006
Vapor mass frac. 0.00000 0.00000 0.00000 0.00000
Total kmol/h 5773.3888 5981.6448 71.0756 55.5093
Total kg/h 104009.0000 114530.1173 3131.0941 1000.0000
Total std L m3/h 104.0099 116.1205 3.5656 1.0000
Total std V scfh 4569813.00 4734654.00 56258.51 43937.30
Flowrates in kg/h
Ethylene Oxide 0.1145 11453.0116 3131.0941 0.0000
Water 104006.2002 103074.3585 0.0000 1000.0000
Acetaldehyde 1.2904 1.3744 0.0000 0.0000
Formaldehyde 1.3744 1.3744 0.0000 0.0000

Stream No. 5 6
Stream Name Side Product Ald Purge
Temp C 40.9198 42.1959
Pres kg/cm2-G 2.0000 2.0000
Enth kcal/h -2.9413E+006 -7.6233E+005
Vapor mass frac. 0.00000 0.00000
Total kmol/h 161.1695 31.5179
Total kg/h 7100.0000 1290.0000
Total std L m3/h 8.0853 1.4596
Total std V scfh 127570.56 24947.38
Flowrates in kg/h
1.15 Column Design 41

Ethylene Oxide 7100.0000 1221.7950


Water 0.0000 68.1208
Acetaldehyde 0.0000 0.0840
Formaldehyde 0.0000 0.0000

CHEMCAD 6.2.0 Page 10

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36


DISTILLATION PROFILE

Unit type : SCDS Unit name: Eqp # 2

* Net Flows *
Temp Pres Liquid Vapor Feeds Product Duties
Stg C kg/cm2-G kmol/h kmol/h kmol/h kmol/h kcal/h
1 40.9 2.00 781.83 71.08 -4.909E+006
2 40.9 2.00 781.83 852.91
3 40.9 2.00 781.83 852.91
4 40.9 2.00 781.83 852.91
5 40.9 2.00 781.83 852.91
6 40.9 2.00 620.66 852.91
161.17 side pr
7 40.9 2.00 620.66 852.91
8 40.9 2.00 620.66 852.91
9 40.9 2.00 620.66 852.91
10 40.9 2.00 620.66 852.91
11 40.9 2.00 620.66 852.91
12 40.9 2.00 620.66 852.91
13 40.9 2.00 620.66 852.91
14 40.9 2.00 620.66 852.91
15 40.9 2.00 620.66 852.91
16 40.9 2.00 620.66 852.91
17 40.9 2.00 620.66 852.91
18 40.9 2.00 620.66 852.91
19 40.9 2.00 620.66 852.91
20 40.9 2.00 620.66 852.91
21 40.9 2.00 620.66 852.91
22 40.9 2.00 620.66 852.91
23 40.9 2.00 620.66 852.91
24 40.9 2.00 620.66 852.91
25 40.9 2.00 620.66 852.91
26 40.9 2.00 620.66 852.91
27 40.9 2.00 620.66 852.91
28 40.9 2.00 620.66 852.91
29 40.9 2.00 620.66 852.91
30 40.9 2.00 620.66 852.91
31 40.9 2.00 620.66 852.91
32 40.9 2.00 620.66 852.91
33 40.9 2.00 620.66 852.91
34 40.9 2.00 620.66 852.91
1.15 Column Design 42

35 40.9 2.00 620.66 852.91


36 40.9 2.00 620.66 852.91
37 40.9 2.00 620.66 852.90
38 40.9 2.00 620.66 852.90
39 40.9 2.00 620.66 852.90
40 40.9 2.00 620.66 852.90
41 40.9 2.00 620.66 852.90
CHEMCAD 6.2.0 Page 11

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36


DISTILLATION PROFILE

42 40.9 2.00 620.65 852.90


43 40.9 2.00 620.65 852.90
44 40.9 2.00 620.65 852.90
45 40.9 2.00 620.65 852.90
46 40.9 2.00 620.64 852.89
47 40.9 2.00 620.64 852.89
48 40.9 2.00 620.64 852.89
49 40.9 2.00 620.63 852.88
50 40.9 2.00 620.62 852.88
51 40.9 2.00 620.62 852.87
52 40.9 2.00 620.60 852.86
53 40.9 2.00 620.59 852.85
54 40.9 2.00 620.58 852.84
55 40.9 2.00 620.56 852.82
56 40.9 2.00 620.53 852.80
57 40.9 2.00 620.51 852.78
58 40.9 2.00 620.47 852.75
59 40.9 2.00 620.43 852.72
60 40.9 2.00 620.37 852.67
61 40.9 2.00 620.30 852.62
62 40.9 2.00 620.22 852.55
63 40.9 2.00 620.12 852.47
64 40.9 2.00 619.98 852.36
65 40.9 2.00 619.82 852.23
66 40.9 2.00 619.61 852.06
67 41.0 2.00 619.33 851.85
68 41.0 2.00 618.98 851.58
69 41.0 2.00 618.50 851.22
70 41.0 2.00 617.86 850.75
71 41.0 2.00 616.97 850.11
72 41.1 2.00 615.65 849.21
73 41.1 2.00 613.58 847.90
74 41.2 2.00 609.92 845.83
75 41.4 2.00 601.51 842.17
76 42.2 2.00 622.47 833.75 55.51
31.52 side pr
77 42.2 2.00 622.47 830.72
78 42.2 2.00 622.47 830.72
1.15 Column Design 43

79 42.2 2.00 622.40 830.72


80 42.2 2.00 621.49 830.66
81 42.3 2.00 531.46 829.75
82 71.7 2.00 6032.22 739.71 5981.64
83 72.1 2.00 6034.36 258.83
84 75.0 2.00 6051.89 260.97
85 92.1 2.00 6191.46 278.50
86 122.3 2.00 6503.64 418.07
87 132.1 2.00 6615.89 730.26
88 133.2 2.00 6628.72 842.51
CHEMCAD 6.2.0 Page 12

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36


DISTILLATION PROFILE

89 133.3 2.00 6629.97 855.33


90 133.3 2.00 856.58 5773.39 8.009E+006

Mole Reflux ratio 11.000

Total liquid entering stage 76 at 42.196 C, 653.963 kmol/h.


Total liquid entering stage 82 at 71.674 C, 6031.949 kmol/h.
CHEMCAD 6.2.0 Page 13

Simulation: eop_actual Date: 06/25/2010 Time: 16:49:36


HEATING CURVES SUMMARY

Eqp # 2 Unit type : SCDS Unit name:

Condenser

NP Temp Pres Del H Vapor Liquid Vap mole Vap mass


C kg/cm2-G kcal/h kg/h kg/h frac. frac.
1 40.9 2.0 4.91E+006 37573 0 1.0000 1.0000 Dew
2 40.9 2.0 4.42E+006 33816 3757 0.9000 0.9000
3 40.9 2.0 3.93E+006 30058 7515 0.8000 0.8000
4 40.9 2.0 3.44E+006 26301 11272 0.7000 0.7000
5 40.9 2.0 2.95E+006 22544 15029 0.6000 0.6000
6 40.9 2.0 2.45E+006 18787 18787 0.5000 0.5000
7 40.9 2.0 1.96E+006 15029 22544 0.4000 0.4000
8 40.9 2.0 1.47E+006 11272 26301 0.3000 0.3000
9 40.9 2.0 9.82E+005 7515 30059 0.2000 0.2000
10 40.9 2.0 4.91E+005 3757 33816 0.1000 0.1000
11 40.9 2.0 0.000 0 37573 0.0000 0.0000 Bub

Reboiler

NP Temp Pres Del H Vapor Liquid Vap mole Vap mass


1.15 Column Design 44

C kg/cm2-G kcal/h kg/h kg/h frac. frac.


1 133.3 2.0 0.000 0 119442 0.0000 0.0000 Bub
2 133.3 2.0 8.01E+005 1543 117900 0.0129 0.0129
3 133.3 2.0 1.60E+006 3086 116356 0.0258 0.0258
4 133.3 2.0 2.40E+006 4630 114813 0.0387 0.0388
5 133.3 2.0 3.20E+006 6173 113269 0.0517 0.0517
6 133.3 2.0 4.00E+006 7716 111726 0.0646 0.0646
7 133.3 2.0 4.81E+006 9260 110183 0.0775 0.0775
8 133.3 2.0 5.61E+006 10803 108639 0.0904 0.0904
9 133.3 2.0 6.41E+006 12347 107096 0.1034 0.1034
10 133.3 2.0 7.21E+006 13890 105552 0.1163 0.1163
11 133.3 2.0 8.01E+006 15433 104009 0.1292 0.1292
1.15 Column Design 45

1.15.7 Sensitivity Analysis


Sensitivity analysis was carried out in CHEMCAD, which is used to study the
variation in dependent parameter by variation of other independent parameters.
Sensitivity analysis was used to determine:
ˆ The Optimal Number of Stages
ˆ The Optimal Side Product Withdrawal Stage

Number of Stages

CHEMCAD 6.2.0 Page 1

Simulation: EOP_final Date: 06/25/2010 Time: 10:58:42

Title Stages
Y_Title Mass Fraction

Line 1
Number of Stages Top Product
10 0.837447
28 0.999965
46 0.999966
64 0.999961
82 0.999968
0 0

Line 2
Number of Stages Side Stream
10 0.25385
28 0.999944
46 0.999946
64 0.999938
82 0.99995
0 0

Line 3
Number of Stages Aldehyde Purge
10 -1
28 0.617817
46 0.91846
64 0.874263
82 0.990885
0 0

Hence, the number of stages may be kept at around 90.

Side Product Withdrawal Stage


1.15 Column Design 46

CHEMCAD 6.2.0 Page 1

Simulation: EOP_170809_6 Date: 06/25/2010 Time: 15:48:20

Sensitivity Analysis Report


Product Stage

Run Side Product Sta EO Mass Fraction Acetaldehyde Formaldehyde


#
0 2 0.918686 0.0813136 2.02168e-011
1 3 1 5.25169e-010 0
2 4 0.999989 1.08283e-005 3.44277e-013
3 5 1 7.26189e-010 4.58568e-021
4 6 1 8.42276e-010 0
5 7 0.44435 0.000222292 0.165478
6 8 0.175291 0.00617798 1.28301e-007
7 9 1 1.27905e-009 7.82895e-023
8 10 0.703521 0.0497549 0.232759

Sensitivity Analysis Run Time Messages


--------------------------------------
[Variable] Side Product Stage Number = 2.00000e+000
* Equip. 2: SCDS/EXTR did not converge.
[Variable] Side Product Stage Number = 3.00000e+000
Normal termination.
[Variable] Side Product Stage Number = 4.00000e+000
* Equip. 2: SCDS/EXTR did not converge.
[Variable] Side Product Stage Number = 5.00000e+000
Normal termination.
[Variable] Side Product Stage Number = 6.00000e+000
Normal termination.
[Variable] Side Product Stage Number = 7.00000e+000
* Equip. 2: SCDS/EXTR did not converge.
[Variable] Side Product Stage Number = 8.00000e+000
* Equip. 2: SCDS/EXTR did not converge.
[Variable] Side Product Stage Number = 9.00000e+000
Normal termination.
[Variable] Side Product Stage Number = 1.00000e+001
* Equip. 2: SCDS/EXTR did not converge.

The simulation did not converge for a few values of side product withdrawal
stage. From the above results, the side product may be withdrawn from stage
6 for good purity of the product.
1.16 Conclusion 47

1.16 Conclusion
Hence, the T-1410 Ethylene Oxide Purification Column was simulated on CHEM-
CAD. We could not, however, find a reasonable explanation for the formaldehyde
exiting from the bottoms, though being the most volatile component. Acetalde-
hyde separation required the most number of theoretical stages, around 80.
The side stream reboiler, E-1413, was not included in the simulation.
The purpose of this reboiler is to vapourize the liquid and redistribute the
vapours into the rectification section.
To include this reboiler, the column could be modelled as two separate
columns, one being the ethylene oxide/aldehydes-water separation column (the
stripping section), and the other being the ethylene oxde-aldehydes separation
column (the rectification section of T-1410). E-1413 could be used as the re-
boiler of the latter column, and a more accurate simulation could be performed.
The stripping section would consist of few stages, as EO and water are easily
separated. The rectification section would consist of majority of the stages. This
technique could probably give a better insight into the problem of formaldehyde
coming from the bottoms as well.