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Manufacture of Acrylonitrile from Ammoxidation of Propylene 2016-17

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Table of Contents
1 INTRODUCTION .................................................................................................................. 1
1.1 Uses .................................................................................................................................. 2
1.2 Health Effects ................................................................................................................... 3
1.3 Market Prospects .............................................................................................................. 4
1.4 Acrylonitrile in India ........................................................................................................ 5
1.5 Demand of Acrylonitrile Past & Future ........................................................................... 5
1.6 Strength for Acrylonitrile Trade (Export Market)............................................................ 8
1.7 Financial Outlook ............................................................................................................. 8
2 PROCESS SELECTION ........................................................................................................ 9
2.1 AVAILABLE TECHNOLOGIES ................................................................................... 9
From propylene, ammonia and oxygen (sohio process) ......................................................... 9
From ethylene, hydrogen cyanide amd oxygen (asahi process) ........................................... 10
From acetylene and hydrogen cyanide (phillips petroleum process) .................................... 11
From Acrolein Cyanohydrin (KNAPSACK-Griesheim PROCESS) ................................... 13
By Dehydrogenation of Propionitrile (EASTMAN Kodak PROCESS)............................... 14
2.2 DETAILED COMPARISON ......................................................................................... 16
2.3 SELECTED TECHNOLOGY ....................................................................................... 17
3 SOHIO PROCESS ................................................................................................................ 19
3.1 Chemistry of the process ................................................................................................ 20
3.2 Raw Materials Used in the Process ................................................................................ 22
Propylene .............................................................................................................................. 22
AMMONIA........................................................................................................................... 24
3.3 VLE of Key Mixtures ..................................................................................................... 26
3.4 Properties of key components ........................................................................................ 28
3.5 CATALYST SELECTYION ......................................................................................... 28
Reaction System Analysis..................................................................................................... 30
3.6 Chemical ReactoR: SELECTION ANDAnalysis ....................................................... 31
3.7 FINAL FOWSHEET ...................................................................................................... 32
3.8 Further Developments .................................................................................................... 34
3.9 CONCLUSIONS ............................................................................................................ 34
4 CHEMICAL DESIGN OF EQUIPMENTS.......................................................................... 35

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4.1 REACTOR ..................................................................................................................... 35


EQUATION USED .............................................................................................................. 36
CALCULATION AND RESULT ........................................................................................ 37
4.2 Heat exchanger ............................................................................................................... 41
Heat exchanger between Reactor and Neutralizer ................................................................ 41
Heat exchanger between Neutralizer and Absorber.............................................................. 48
Heat exchanger between Absorber and Acrylonitrile Recovery Column ............................. 53
4.3 HCN removal multicomponent distillation column ....................................................... 60
4.4 Acrylonitrile Purification Column ................................................................................. 65
4.5 Pumps & Compressors ................................................................................................... 68
Compressors:......................................................................................................................... 68
Pumps:................................................................................................................................... 74
4.6 EQUIPMENT SPECIFICATION SHEET ..................................................................... 79
5 PROCESS CONTROL&INSTRUMENTATION ................................................................ 82
5.1 Control system for Reactor ............................................................................................ 85
5.2 Control System for Stripper ........................................................................................... 87
5.3 Control System for Distillation Column ........................................................................ 89
5.4 Control System for Total Condenser .............................................................................. 92
5.5 Control System for Heat Exchangers ............................................................................. 93
6 SITE SELECTION AND PROJECT LAYOUT .................................................................. 95
6.1 Site Selection .................................................................................................................. 95
6.2 Project Layout .............................................................................................................. 101
Plant layout consideration ................................................................................................... 101
Description: ......................................................................................................................... 102
7 PLANT UTILITIES ............................................................................................................ 106
8 ORGANIZATIONAL STRUCTURE AND MANPOWER REQUIREMENT ................. 116
8.1 ORGANIZATIONAL STRUCTURE .......................................................................... 116
8.2 MANPOWER REQUIREMENT ................................................................................. 118
9 ECONOMIC EVALUATION & PROFITABILITY ......................................................... 122
9.1 Estimation of EQUIPMENTS COST........................................................................... 122
9.2 Estimation of Direct & Indirect cost ............................................................................ 123
9.3 Estimation of Total Product Cost ................................................................................. 124

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Manufacturing cost ............................................................................................................. 124


General Expenses ................................................................................................................ 125
Total Product Cost .............................................................................................................. 126
Total Income ....................................................................................................................... 126
9.4 Rate of return ................................................................................................................ 126
9.5 Payback Period ............................................................................................................. 126
9.6 Implementation schedule.............................................................................................. 126
10 Material Storage, Handling & Safety.................................................................................. 128
10.1 Propylene .................................................................................................................. 128
10.2 AMMONIA .............................................................................................................. 133
10.3 SULPHURIC ACID ................................................................................................. 136
10.4 ACRYLONITRILE .................................................................................................. 137
11 ENVIRONMENTAL PROTECTION &ENERGY CONSERVATION............................ 146
12 References ........................................................................................................................... 159

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Table of Figures

Figure 1 Molecular Structure of Acrylonitrile ................................................................................ 1


Figure 2 Properties of acrylonitrile ................................................................................................. 2
Figure 3 Uses of acrylonitrile ......................................................................................................... 3
Figure 4 Hazards related to Acrylonitrile ....................................................................................... 4
Figure 5 Global Acrylonitrile Share by Company .......................................................................... 4
Figure 6 Production & Demand of Acrylonitrile in India. .............................................................. 5
Figure 7: Detailed comparison between available technologies ................................................... 16
Figure 8 VLE of binaries acrylonitrile/water & acetonitrile/water. .............................................. 27
Figure 9 Properties of key components ........................................................................................ 28
Figure 10: Reactor comparison for PFR, CSTR & FBR .............................................................. 31
Figure 11: SOHIO PROCESS FLOW SHEET ............................................................................. 33
Figure 12: Reactor design and sizing ............................................................................................ 39
Figure 13: REACTOR MODES OF OPERATION ..................................................................... 40
Figure 14Applications ranges of compressors. ............................................................................. 69
Figure 15 A Single Stage Centrifugal Pump................................................................................. 75
Figure 16Pump coverage chart based on normal ranges of operation. ......................................... 75
Figure 17 Location of Bharuch in Gujarat. ................................................................................... 99
Figure 18Locations of various industries in Gujarat................................................................... 100
Figure 19Dahej-Bharuch investment region ............................................................................... 100
Figure 20 Plant layout. ................................................................................................................ 105
Figure 21 Organizational structure. ............................................................................................ 118

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1 INTRODUCTION
Acrylonitrile is the chemical compound with the formula CH2CHCN. This pungent-smelling,
colorless liquid often appears yellow due to impurities. It is an important monomer for the
manufacture of useful plastics. In terms of its molecular structure, it consists of a vinyl group
linked to a nitrile.
It is also known as: 2-Propenenitrile, Vinyl cyanide; Cyanoethylene, ACN.
Acrylonitrile is the nitrile that is likely manufactured on the largest scale. Most industrial
acrylonitrile is produced through the Sohio process, the catalytic ammoxidation of propylene.
The global capacity of acrylonitrile in 2010 was 5.7 MMT against production of 5.1 MMT,
resulting in average operating rate of 90%. The demand for the 2010 was 5.08 MMT. RIL is the
sole producer of acrylonitrile in India with a capacity of 41 KTA. RIL's production in entirety is
sold in the domestic market and represents nearly 30% share with the rest being imported.

Figure 1 Molecular Structure of Acrylonitrile

Table 1 Identifiers of Acrylonitrile


Identifiers
CAS Number 107-131
PubChem 7855
ChemSpider 7567
UNII MP1U0D42PE
KEGG C01988
ChEBI CHEBI:28217
ChEMBL CHEMBL445612

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Figure 2 Properties of acrylonitrile


1.1 USES

Acrylonitrile has many uses:


1. In the manufacture of synthetic polymers, especially poly-acrylonitrile which comprises
acrylic fibers.
2. As a component of synthetic rubber.
3. Used in the synthesis of certain nylons.
4. As a fumigant.
5. Or, as in the case at the Dow Pittsburg Plant, used to make the glue that holds carpet to the
backing.

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Uses of acrylonitrile

Adiponitrile, 33%
Acrylic Fibres, 25%
ABS/SAN Resins, 23%
Acrylamide, 9%
Nitrile Elastomer, 3%
Miscellaneous, 7%

Figure 3 Uses of acrylonitrile


1.2 HEALTH EFFECTS

Acrylonitrile is highly flammable and toxic. It undergoes explosive polymerization. The burning
material releases fumes of hydrogen cyanide and oxides of nitrogen. It is classified as a Class 2B
carcinogen (possibly carcinogenic) by the International Agency for Research on
Cancer (IARC), and workers exposed to high levels of airborne acrylonitrile are diagnosed more
frequently with lung cancer than the rest of the population. Acrylonitrile increases cancer in high
dose tests in male and female rats and mice.
Pathways of exposure for humans include emissions, auto exhaust, and cigarette smoke that can
expose the human subject directly if they inhale or smoke. Routes of exposure include inhalation,
oral, and to a certain extent dermal uptake (tested with volunteer humans and in rat studies).
There are two main excretion processes of acrylonitrile. The primary method is excretion in urine
when acrylonitrile is metabolized by being directly conjugated to glutathione. The other method is
when acrylonitrile is metabolized with 2-cyanoethylene oxide to producecyanide end products that
ultimately forms thiocyanate, which is excreted via urine, or carbon dioxide and eliminated
through the lungs.

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Figure 4 Hazards related to Acrylonitrile

1.3 MARKET PROSPECTS


More than 90% of world Acrylonitrile capacity is based on the Sohio process i.e. ammoxidation
of chemical-grade propylene. In 1997, Monsanto spun off its industrial chemicals operation as
Solutia. Production at the Alvin plant is captive and used to make acrylic fibers and Adiponitrile.
Solutia put a new 550 million pound per year plant on stream in Alvin in 2003, raising the sites
nameplate to 1 billion products. The plants output is shared by Asahi and Bayer, both of which
have equity in the facility. In 1998, Amoco merged with British Petroleum to become BP Amoco.

Figure 5 Global Acrylonitrile Share by Company

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1.4 ACRYLONITRILE IN INDIA

RIL is the sole producer of acrylonitrile in India with a capacity of 41 KTA. RIL's production in
entirety is sold in the domestic market and represents nearly 30% share with the rest being
imported.

Figure 6 Production & Demand of Acrylonitrile in India.


1.5 DEMAND OF ACRYLONITRILE PAST & FUTURE

The following graphs give a brief overview on the growth of acrylonitrile demand over the period
2013-2018:

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From the graphs, we can see that the demand of Acrylonitrile in Asia-Pacific region is going to
increase in the coming 5 years. Thus, setting up an acrylonitrile plant is going to provide high
returns due to its high market cost.

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From the above figures, it clear that the growth in demand of acrylonitrile is going to increase
owing to an increase in the demand of products made by acrylonitrile like ABS/SAN resin,
Adiponitrile and fiber.

1.6 STRENGTH FOR ACRYLONITRILE TRADE (EXPORT MARKET)

The export market for Acrylonitrile, driven by strong demand from Asia, has improved
dramatically over past few years. Spot prices, led by both increased demand and pressure from
raw materials, have risen by 15 to 20 % during that period. In a market with endemically low
production rates and flat pricing since 1997, producers are looking at positive margins and
operating rates of more than 90% for the first time.

1.7 FINANCIAL OUTLOOK


Asia is recovering from the financial difficulties that disrupted acrylonitrile exports. Those
shipments are back up again, but not as high as in mid-1990s. New Acrylonitrile activity in the
region will continue to displace material exported from the US. The fastest growing market for
Acrylonitrile derivatives is for acrylic textile fibers, ABS/SAN, adiponitrile and nitrile rubber.
Although acrylamide constitute only 9 percent of total demand, other derivate, particularly ABS
resins and acrylic fibers, are also solid, following GDP growth.

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2 PROCESS SELECTION
By looking at the previous study we can easily conclude that setting up a facility to produce
Acrylonitrile is going to be beneficial for the producer. Thus hereby, I am giving a detailed
Techno-Economic Feasibility Report on Production of Acrylonitrile. The plant is proposed to
set up in Bharuch region in Gujarat.
Acrylonitrile is among the top 50 chemicals produced as a result of the tremendous growth in its
use as a starting material for a wide range of chemical and polymer products. Acrylic fibers remain
the largest use of Acrylonitrile; other significant uses are in resins and nitrile elastomers and as an
intermediate in the production of adiponitrile and acrylamide.
There are several processes for production of Acrylonitrile which were used previously but the
latest and the mostly used is the ammoxidation of propylene, popularly known as Sohio Process.
The process was developed by Sohio in 1960s which was later taken over by BP Amoco.
This process is generally used owing to its advantages over other processes in terms of profitability
as well as the ease of disposal and separation of by-products formed in the process. The process
involves ammoxidation of propylene in a fluidized bed reactor. However, an emerging technology
is the ammoxidation of propane, which offers the advantage of lower feedstock cost.

2.1 AVAILABLE TECHNOLOGIES

Prior to 1960, Acrylonitrile was produced commercially by processes based on either ethylene
oxide and hydrogen cyanide or acetylene and hydrogen cyanide. The growth in demand of acrylic
fibers, starting with introduction of Orlon Dupont around 1950, spurred efforts to develop
improved process technology for Acrylonitrile manufacturers to meet the demand. This resulted
in the discovery of Sohio process and by distillers of a heterogeneous vapor-phase catalytic process
for Acrylonitrile by selective oxidation of propylene and ammonia, commonly referred to as the
propylene ammoxidation process. Commercial introduction of this lower cost process by Sohio in
1960 resulted in the eventual displacement of all other Acrylonitrile manufacturing processes.
Today over 90% of the production of Acrylonitrile is based on Sohio-developed ammoxidation
process.

FROM PROPYLENE, AMMONIA AND OXYGEN (SOHIO PROCESS)


Acrylonitrile is produced in commercial quantities almost exclusively by the vapor-phase catalytic
propylene ammoxidation process developed by Sohio.
C3H6 + NH3 + (1/2) O2 C3H3N + 3 H2O
A schematic diagram of the commercial process is shown in fig. 1. The commercial process uses
a fluid-bed reactor in which propylene, ammonia and air contact a solid catalyst at 400-510C and
49-196kPa (0.5-0.2kg/cm) gauge. It is a single pass process with about 98% conversion of
propylene, and uses about 1.1. Kg propylene per kg of Acrylonitrile produced. Useful by-products

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from the process are HCN (0.1kg per Kg of Acrylonitrile), which is used primarily in the
manufacture of methyl methacrylate, and acetonitrile (about 0.03 kg per kg of acrylonitrile), a
common industrial solvent. In the commercial operation, the hot reactor effluent is quenched with
water in a counter current absorber and any unreacted ammonia is neutralizing with sulphuric acid.
The resulting ammonium sulphate can be recovered and used as a fertilizer. The absorber off-gas
containing primarily N2, CO, CO2 and unreacted hydrocarbon in either vented off directly, or first
passed through an incinerator to combust the hydrocarbon and CO. the Acrylonitrile containing
solution from the absorber is passed to a recovery column that produces a crude Acrylonitrile
steam overhead that contains HCN. The column bottoms are passed to a secondary recovery
column to remove water and produce a crude acetonitrile mixture. The crude acetonitrile is either
incinerated or further treated to produce solvent quality acetonitrile mixture. Acrylic fiber quality
(99.2% minimum) Acrylonitrile is obtained by fractionation of the crude Acrylonitrile mixture to
remove HCN, water, light ends and high ends, and high boiling impurities. Disposal of the process
impurities has become an increasingly important aspect of the overall process, with significant
attention being given to develop cost effective and environmentally acceptable methods for
treatment of the process waste streams. Current methods include deep-well disposal, wet air
oxidation, ammonium sulphate separation, biological treatment ad incineration.
Although Acrylonitrile manufacture from propylene and ammonia was first patented in 1949, it
was not until 1959, when Sohio developed a catalyst capable of producing Acrylonitrile with high
selectivity, that commercial manufacture from propylene became economically viable. Production
improvements over the past 30 years have stemmed largely from development of several
generations of increasingly more efficient catalysts. These catalysts are multi-component mixed
metal oxides. Other types of catalysts that have been used commercially are based on iron-
antimony oxide, uranium-antimony oxide, and tellurium-molybdenum oxide. Fundamental
understanding of these complex catalysts and the surface-reaction mechanism of propylene
ammoxidation have advanced substantially since the first commercial plant began operation.

FROM ETHYLENE, HYDROGEN CYANIDE AMD OXYGEN (ASAHI PROCESS)


The process comprises bringing a gaseous mixture consisting of olefinic hydrocarbon, hydrogen
cyanide and oxygen or an oxygen-containing gas into contact with a catalyst in presence of
halogenated aliphatic nitriles or a gaseous mixture of the halogenated aliphatic nitriles and
hydrogen halide.
Process Description:
The above flow diagram shows the reaction zone in which unsaturated aliphatic nitriles are
produced from olefinic hydrocarbon, hydrogen cyanide and oxygen. These are introducing to the
reaction zone via a line, whereas halogenated nitriles are introducing from another line as shown
in the diagram. A gaseous mixture discharged from the outlet of the reaction zone contains steam,
CO, CO2, N2, unreacted olefins hydrocarbons and usually a small amount of hydrogen cyanide in
addition to unsaturated aliphatic nitriles. This gaseous mixture is then introduced to an absorption
tower wherein the soluble materials are absorbed by an absorption medium and the separated
gaseous mixture of olefinic hydrocarbons, oxygen, CO, CO2, N2 are discharged from the top of the

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absorption tower. The gaseous mixture thus discharged from there contains no or very little
hydrogen halide, which is highly corrosive. If required, olefinic hydrocarbons may be recovered
there from by conventional methods and they may be recycled back to the first reaction zone and
reused. On the other hand, from the bottom of the absorption tower is obtained a mixture containing
unsaturated aliphatic nitriles to from halogenated aliphatic nitriles. The temperature of the
absorption tower is preferably 50 kPa under normal pressure. Under elevated pressure it can be
operated at above 50 kPa.
The mixture containing hydrogen halide fed to the addition reaction zone I then subjected at a
temperature of from room temperature to 150 kPa thereby converting hydrogen halide, nearly
completely, or, at least predominantly, to halogenated aliphatic nitriles. The effluent discharge
from the addition reaction zone contains unsaturated aliphatic nitriles, halogenated aliphatic
nitriles and, in addition, absorption medium, but it is substantially free from highly corrosive
hydrogen halide.
The effluent from the addition reaction zone is fed to the unsaturated aliphatic nitrile recovering
unit to obtain unsaturated aliphatic nitriles from its top and halogenated aliphatic from its bottom.
Halogenated aliphatic nitriles thus recovered may be recycled to the first reaction zone and, if
desired to the absorption tower for reuse.

FROM ACETYLENE AND HYDROGEN CYANIDE (PHILLIPS PETROLEUM


PROCESS)
The old traditional route to Acrylonitrile has been by the addition of acetylene to hydrogen cyanide,
usually in the presence of aqueous cuprous slat catalyst. The difficulties inherent in acetylene
handling together with the more favorable economics of the ammoxidation process based on

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propylene have resulted in substantial replacement of this process by propylene-ammonia-oxygen


process.

Phillips Petroleum Process


This process involves reducing Acrylonitrile by passing to a catalytic converter hydrocyanic acid
and acetylene formed by the action of a plasma stream on ammonia and a lower alkane
hydrocarbon such as methane or ethane, the yield of Acrylonitrile product is increased relative to
the yield of nitrogen containing by products such as succinonitrile, acetonitrile, and
propiononitrile, by passing at least a portion of the by-products from the catalytic converter to the
plasma stream as quench. The yield of Acrylonitrile is further increased by simultaneously passing
portions of the by-products from the catalytic converter respectively.

NH3
C2H2 + HCN
PLASMA REACTOR
STREAM

HCs, LOWER
PROD. + BYPROD.
ALKENES C1
C5

RECYCLED N2 -BYPRODUCT 2nd PORTION OF N2


BYPROD.

AN
SEPARATOR

N2 -BYPRODUCT

The above figure shows the essential features of the process. As shown there, a plasma stream
reactor having a feed of ammonia entering through a line and hydrocarbon entering through
another line produces acetylene and hydrocarbon acid.Which are removed through a line and
passed to a catalytic reactor. This reactor contains a catalyst suitable for converting the acetylene
and hydrocyanic acid to acrylonitrile. Preferred catalyst are alkali metal cyanides on suitable inert
catalytic supports such as charcoal ,silica ,natural and synthetic alumino silicates, clays ,refractory
metal oxides ,and the like, and mixtures thereof .A particularly preferred catalyst for fixed bed

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operation is one containing about 15 to 20 weight percent of equal parts by weight of sodium
cyanide and potassium cyanide supported on hard wood charcoal which is pre heated with hot
caustic solution to remove a portion of the ash content, and then with hot oxalic acid solution. In
this process, some unwanted nitrogen gas containing products are also formed in the catalytic
reactor. The products and by-products are removed from this reactor through a line and passed to
a separator wherein acrylonitrile is removed through a product line and at least a portion of the
nitrogen by-products are removed through a different line and recycled as quench to the plasma
stream within the first reactor via a conduit. The action of the nitrogen by-products on the plasma
stream will not only quench the stream but also result in the by-products decomposing to form
acetylene and hydrocyanic acid, which are passed back to catalytic reactor.
Thus, the contacting of hydrocarbon in plasma stream is ordinarily effected at a temperature above
30000F. Generally, the plasma stream is initially quenched with sufficient ammonia to reduce the
temperature of the stream to a temperature of the order of the 27000F.This temperature is low
enough to minimize the carbon-hydrogen reaction, but high enough for the reaction of acetylene
with ammonia to form hydrogen cyanide. After a very short reaction or residence time (0.0001 to
0.1 second), the resultant stream (ammonia quenched) containing hydrogen cyanide, acetylene,
etc., is given a final quench with nitrogen by-product and, if desired, another material such as water
to reduce the temperature to a point where no thermal reactions are experienced (a temperature of
1000 of or below).
If desired, a second portion of the nitrogen by products can be passed to the effluent from plasma
stream reactor via a conduit to further suppress the formation of undesired by products within
catalytic reactor.

FROM ACROLEIN CYANOHYDRIN (KNAPSACK-GRIESHEIM PROCESS)


This process involves polymerization manufacture using acrolein-cyanohydrin; especially the
acrolein-cyanohydrin obtained as a by-product I the manufacture of Acrylonitrile.
The preparation of Acrylonitrile by catalytically transformation of an olefin, preferably propylene,
with ammonia and oxygen in the gaseous phase at relatively high temperature gives rise to the
formation of varying amounts of acrolein as a by-product. During the workup of the reaction
products, the acrolein is entrained into the crude Acrylonitrile to imperatively react with the
permanently excess of hydrocyanic acid with the resultant formation of acrolein-cyanohydrin. On
purifying the Acrylonitrile, the acrolein-cyanohydrin is obtained in the sump portion of the
distillation means, and a useless and poisonous product was previously required to be destroyed.
This process unexpectedly provides a simple means for producing Acrylonitrile and hydrocyanic
acid by reacting acrolein-cyanohydrin with ammonia and oxygen or air in the following manner.
CH2=CH-CH(OH)CN + NH3 + 1/2O2 CH2=CH-CN + HCN + 2H2O
The reaction being carried at a temperature of 300-550 0C.With the use of catalysts, the same as
ordinarily used under analogous conditions for making Acrylonitrile from olefins, ammonia, air
and optionally steam.

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Process Description:
A suitable apparatus is used in carrying out the continuous transformation of acrolein-cyanohydrin
by this process into Acrylonitrile and hydrocyanic acid, the transformation being affected to form
a part of the conventional manufacture of Acrylonitrile from olefins, ammonia and air.
A portion of the gases i.e., olefin, preferably propylene, oxygen, preferably I the form of air, and
optionally steam, to be supplied to the reactor through a main line is caused to flow through a line
into saturator. Now this mixture is saturated at a certain temperature of 460 0C.A mixture of
acrolein-cyanohydrin and water coming from the crude acrylonitrile preparation unit, and the
resulting gas or vapor mixture is returned into main line. Ammonia is supplied in measured
quantities and the whole gas mixture is introduced into the reactor. The off-gas escaping from the
reactor in customary manner:
Acrylonitrile, hydrocyanic acid and acetonitrile can be removed by being washed with water and
ultimately separated from one another by distillation.
The transformation of acrolein-cyanohydrin into acrylonitrile and hydrocyanic acid by the process
results in the acrylonitrile yield being improved by some percent without special technical
expenditure being required. Furthermore, the continuous transformation of acrolein-cyanohydrin
into acrylonitrile and hydrocyanic acid after the actual acrylonitrile manufacture may result in the
proportion of ammonia consumers for acrylonitrile formation being reduced.
In most cases, ammonia has previously been used in a molar excess in order to increase the
propylene conversion rate or to suppress the formation of acrolein. In the preparation of
acrylonitrile, the ammonia in excess is, however, not easy to recover and thus adds to the
production costs. In contrast, there with, this process enables the acrolein or more accurately its
cyanohydrins, which is obtained in increased proportions without a large excess of ammonia being
used for acrylonitrile preparation, to be transformed into acrylonitrile and hydrocyanic acid which
has previously been impossible.

BY DEHYDROGENATION OF PROPIONITRILE (EASTMAN KODAK PROCESS)


This process involves the production of acrylonitrile from propionitrile by thermal cracking.
Process Description:
Dry propionitrile may be a cracked in a stainless-steel tube at 700-710 0C. Contact time is 0.92-
1.1 seconds and a linear velocity of the vaporized feed is 150-200 f/s in the cracking tube. The
cracked-up product is quenched with chilled, cracked product. Quench temperature is maintained
at 35-40 0C.Vapors from the quench are scrubbed with cracked product which has been chilled to
5-10 0C. The quench product is fed into the HCN stripper column to remove all the HCN as an
overhead product. Base product is washed at the wash column with 5% aqueous NaOH to remove
residual HCN.
Organic layer from the wash column is fed into an extractive distillation column. Water is
introduced on the top plate to extract acetonitrile. Acrylonitrile and propionitrile are distilled
overhead as the water azeotrope. The overhead product is decanted and the water layer is recycled
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to the top plate of the extractive column. The organic layer is fed into the drying column. Sodium
propionate, the preferred polymerization inhibitor, is added to the organic layer to maintain a
concentration of 100 ppm. Overhead from the drying column is continuously decanted to remove
water.
The organic layer is returned to the column as reflux. Dry nitriles from the base of this column are
fed into the acrylonitrile column. This column is operated at reduced pressure, about 100 mm Hg,
to prevent thermally induced polymerization. Acrylonitrile is the overhead product. The base
product, propionitrile, is recycled to the cracking furnace. The conversion of propionitrile to
cracked products is 16-20% per pass. The yields in mol percents are 55% to acrylonitrile, 42% to
HCN, and 2% to acetoniterile.

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2.2 DETAILED COMPARISON

PHILPPS PETROLEUM
NAME OF TECHNOLOGY SOHIO PROCESS ASAHI PROCESS KNAPSACK PROCESS EASTMAN PROCESS
PROCESS
RAW MATERIAL Propylene,Ammonia,oxygen Ethylene,HCN,Oxygen Acetylene, HCN Acrolein,Cynohydrin Propionitrile
CH2=CH2 + H2 + CH2=CH-CH(OH)CN + NH3
C3H6 + NH3 + (1/2) O2 ---> C2H2 + HCN + NH3 ---> C3H3N THERMAL CRACKING OF
REACTIONS HCN+O2 ---> C3H3N + + 1/2O2 ---> CH2=CH-CN +
C3H3N + 3 H2O +N2 BYPROD propionitrile
impurites HCN + 2H2O
AVILABILITY OF RAW Rawal wasi industry, shiv sakti Delhi cyyogenic productions pvt. Ltd, Acuro organics Ltd, Choice
Dulex indutires,Pune Alphchemical Ltd
MATERIAL traders,RIL Universal industrial plants organisation Ltd

COST OF RAW MATERIAL Rs. 38/Kg of PP Rs 783.537/kg Rs 463/kg Rs 9.5/kg Rs 250/ml


Cost of Production
due to difficulty in seperation 55% to acrylonitrile, 42% to HCN,
YIELD 80- 99.2 % 90% 90%
low yield and 2% to acetonitrile
T: 24 - 50C , P: 50 - residence t: 0.0001 - 0.1sec , T:2700 - Contact T:0.92 - 1.1 sec , T: 700 -
CONTROL VARIABLES T: 400 - 510C , P: 49 - 196KPa T: 300 - 550C
150KPa 1000C or below 710C
OTHERS Utilises Fluidised Bed Reactor Fixed Bed reactor Stainless Steel Tube
Single Pass Process Linear Velocity 150-200 f/s
1.1 kg propylene/ 1 kg ACN
BYPRODUCTS 0.1 kg HCN / 1 kg CAN Succinonitrile Hydrogen Cyanide Acetonitrile
Acetonitrile 0.3 kg/kg CAN Propionitrile Acetonitrile Propionitrile
Hydrogen Cyanide
CATALYST USED Iron Antimony Oxide Aq Cuprous Chloride Alkali Metal Cyanides
Uranium Antibody Oxide Support : Charcoal, Silica
Tellurium Molybednum Oxide

Figure 7: Detailed comparison between available technologies

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2.3 SELECTED TECHNOLOGY

On literature survey and data collection, 5 technologies where discovered which where/are being
used in the commercial scale production of Acrylonitrile process through propylene. Fig-1 shows
detailed analysis of these technologies in a tabulated manner. On studying this table, it becomes
very evident that the cost of raw material for ASAHAI process and PHILPPS PETROLEUM
PROCESS in comparison to the other three process/technologies are high. Among the remaining
three process NAPSACK has the lowest raw material cost and SOHIO AND EASTMAN have a
moderate raw material purchase, it was also noted that the cost for ASAHAI process is almost
double in comparison to PHILPPS PETROLEUM although it is being produces at a comparatively
lower temperature. Furthermore, both ASAHAI process and PHILPPS PETROLEUM PROCESS
produces HCN as a product off their main reaction which is a toxic and harmful substance and can
lead to many health and safety hazards thus ASAHAI process was discarded as a potential
technology which we could had used for the production process. Philips process when further
accessed showed a great advantage of low residence times but at the same time it has very high
temperature condition range and used an expensive catalyst hence we may avoid using it for large
scale commercial production.
On further analysis, it was observed that the EASTMAN PROCESS had a comparatively lower
yield than SOHIO, KNAPSACK, PHILPPS PETROLEUM process. EASTMAN PROCESS and
KNAPSACK, also gives out a large no of by products which makes their separation and treatment
process difficult and their entire process costly. Thus, KNAPSACK process can be deemed not
feasible on economic grounds and the same can be said for EASTTMAN process because along
with almost all the short comings of EASTMAN process it is also has a very high operating
temperature condition.
The propylene based process developed by Sohio could displace all over commercial production
technologies because of its substantial advantage in overall production costs, primarily due to
lower raw materials costs. Raw material costs less by-product credits account for about 60% of the
total Acrylonitrile production cost for a world-scale plant. The process has remained economically
advantageous over other process technologies since the first commercial plant in 1960 because of
the higher Acrylonitrile yields resulting from the introduction of improved commercial catalysts.
Reported per-pass conversions of propylene to Acrylonitrile have increased from about 65% to
over 80%. Thus, we are selecting Sohio Process for study.
During a course of years after the development of Sohio Process, a lot of research has been done
in this field to increase the yield of process by a change of catalyst, reactor type etc.
By changing the reactor from a fixed bed to a fluidized bed reactor yield of the process has been
improved. Also, we found that using advanced catalyst, developed by numerous improvements
upon the original catalyst i.e. Bismuth Phosphomolybate and yield of 82.3 % is even obtainable.
(US Patent 6420307 B1) and this improvement clearly satisfies the growing demand of propylene
in the market.
Since this catalyst is not tested under industrial condition, so we are using a yield of 73% for study.

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3 SOHIO PROCESS
Most industrial acrylonitrile is produced by catalytic ammoxidation of propylene, also known as
the Sohio process. In 2002, world production capacity was estimated at 5 million tonnes per
annum. Acetonitrile and hydrogen cyanide are significant byproducts that are recovered for sale. In
fact, the 2008-2009 acetonitrile shortage was caused by a decrease in demand for acrylonitrile.

23 = 2 + 23 + 32 22 = + 62
In the standard SOHIO process, air, ammonia, and propylene are introduced into a fluid-bed
catalytic reactor operating at 50-200 kPag and ~400-510C (750-950F). Ammonia and air are fed
to the reactor in slight excess of stoichiometric proportions because excess ammonia drives the
reaction closer to completion and air continually regenerates the catalyst. A significant feature of
the process is the high conversion of reactants on a once-through basis with only a few seconds
residence time. The heat generated from the exothermic reaction is recovered via a waste-heat-
recovery boiler.

The reactor effluent is routed to a water quench tower, where sulfuric acid is introduced to
neutralize any unconverted ammonia. The product stream then flows through a counter-current
water absorber-stripper to reject inert gases and recover reaction products. The operation yields a
mixture of ACN, acetonitrile, and water and then is sent to a fractionator to remove hydrogen
cyanide.
The final two steps involve the drying of the ACN stream and the final distillation to remove heavy
ends. The fiber-grade ACN obtained from the process is 99% pure. Historically, one of the first
successful catalysts was bismuth phosphomolybdate supported on silica as a heterogeneous
catalyst. Further improvements have since been made.
The catalyst employed makes the difference in technologies. The first commercial plant built by
Sohio (now BP International) used a catalyst based on Bi2O3MoO3. Since then, numerous chemical
formulations have been patented. The catalyst should be multifunctional and possess redox
properties. The most commonly employed contain molybdenum or antimonium oxides mixed with
transition metals, such as Fe, Ni, Co and V, activated by alkali - and rare - earth elements. The
reaction rate is high enough to achieve almost total per - pass conversion at ratios of reactants close
to stoichiometry. High selectivity in acrylonitrile remains a challenge. Today the best catalysts can
give a yield in acrylonitrile of 80 82%, mainly because of losses in propene by combustion.
Significant amounts of highly toxic species form, such as HCN, acetonitrile (ACN) and heavy
nitriles. Their removal from aqueous mixtures is difficult, as reflected in elevated water - treatment
and energy costs.

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3.1 CHEMISTRY OF THE PROCESS

The ammoxidation of propene to acrylonitrile described by the global equation given above
actually involves a very complex reaction mechanism. More generally, the reaction of
ammoxidation refers to the interaction of ammonia with a hydrocarbon partner (alkene, alkane or
aromatic) in the presence of oxygen and suitable catalyst. An ammoxidation catalyst must fulfil
two conditions: possess redox properties and be multifunctional.

Figure 7 Mechanistic cycle for alkene ammoxidation


Figure 7, shows the major steps in a catalytic cycle. Firstly, ammonia interacts with the bifunctional
active centers, here M1and M2, generating an extended ammoxidation site. The first active
species forms from ammonia as = NH, then on this site the alkene inserts as an allylic complex
by hydrogen abstraction. After the rearrangement of atoms, the surface complex is transformed in
the product H2C = CH - CN, which further desorbs from the surface. The result of this process is
a reduced surface site whose regeneration takes place by the oxygen coming exclusively from the
catalyst lattice. Subsequently, the lattice must be filled - in with oxygen coming from the gas phase.
Thus, the overall reaction takes place via a common solid - state lattice capable of exchanging
electrons, anion vacancies and oxygen transmission. The above mechanism is consistent with the

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concept of site isolation proposed by Grasselli and Callahan the inventors of the SOHIO catalyst,
which states that an ammoxidation catalyst becomes selective when the reacting oxygen species
at the active centers are spatially isolated from each other. The knowledge of the reaction
mechanism is important for process design. Firstly, only olefins with activated methyl groups may
undergo ammoxidation reactions to nitriles. Otherwise, oxidative dehydrogenation takes place
preferentially. For example, from the isomers = C 4 only isobutene can give methacrylic nitrile.
Toluene and xylenes can be converted to the corresponding nitriles too. Secondly, the role of
ammonia as chemisorbed species = NH is primordial in reaction, because they start the catalytic
cycle before propene. Therefore, sufficient ammonia must be present in the reaction mixture,
slightly above the stoichiometric amount thus, the reaction mechanism suggests that propane and
ammonia should be mixed and fed together, while the oxygen should enter the reaction
stoichiometric amount. Otherwise, the sites are occupied by oxygen and the combustion prevails.
The oxygen should be fed to replace only the amount consumed in the lattice, in slight excess
above the stoichiometry space independently to fill the lattice. This principle is applied in the
reactor technology. Among secondary reactions the most important losses are by oxidations,
namely by propene combustion:
3
2 3 + 32 + 32
2 2
2 3 + 32 3 + 32
Therefore, the overall exothermic effect rises to about 160 kcal/mol propene. In the absence of
ammonia, the active sites are oxidized leading to acrolein:
1
2 3 + 2 2 + 2
2
Partially, the oxidation may progress to allylic alcohol. Other byproducts of significance are HCN
and acetonitrile, whose formation may be expressed by the overall reactions:
2 3 + 33 + 32 3 + 62
3
22 3 + 33 + 2 33 + 32
2
The stoichiometry indicates a complex reaction mechanism. The amount of HCN is generally
larger than that of acetonitrile, the ratio depending on the catalyst formulation and reaction
conditions. Both reactions are favored by higher temperature and pressure, as well as by longer
residence time. It is interesting to note that supplementary reactions leading to impurities may take
place outside the reaction space, mostly in the aqueous phase during the first separation steps of
quench and absorption in water. Typical examples are the formation of propion-cyanohydrin and
dinitrile-succinate favored by a basic pH:
2 + 2 2
2 + 2 2

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The reaction may be exploited to convert acrolein, which is difficult to remove, into heavier
species. Reaction may take place during the distillation of acrylonitrile. More generally, the
separation/purification of acrylonitrile is complicated by secondary chemical reactions in which
the pH of liquid phase plays an important role. These aspects will be examined later. In addition,
undesired species may originate from reactions with impurities present in the fresh feed, such as
ethylene giving acetaldehyde and acetic acid, or butenes leading to heavies. For this reason, the
concentration of non - C 3 alkene in the fresh propylene feed must be limited to a maximum of
0.5%.

3.2 RAW MATERIALS USED IN THE PROCESS

The raw materials used in the acrylonitrile manufacturing process are propylene, ammonia, and
air. We discuss them one by one under the following stated headings.

PROPYLENE
Propylene is perhaps the oldest petrochemical feed stock and is one of the principle light olefins.
It is used widely as an alkylation or polymer gasoline feedstock for octane improvement. In
addition, large quantities of propylene are used in plastics as polypropylene, and in chemicals, e.g.,
acrylonitrile, propylene oxide, 2- propanol, and Cumene. Propylene is produced primarily as a by-
product of petroleum refining and of ethylene production by steam Pyrolysis.
Table 2 Physical Properties of Acrylonitrile
Property Value

Molecular weight 42.081

Freezing temperature, K 87.9

Boiling point ,K 225.4

Critical temperature ,K 365.0

Critical pressure, MPa 4.6

Critical volume, cm3/mol 181.0

Liquid density, at 223 K, g/cm3 0.612

Standard enthalpy of formation, kJ/mol 20.42

Property Value

Heat of vaporization at bp,kJ/mol 18.41

Solubility, at 200C, 101.3 kPa (1 atm),mL gas/100 mL solvent

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In water 44.6

In ethanol 1250

In acetic acid 524.5

Manufacture:
Steam cracking:
In steam cracking, a mixture of hydrocarbons and steam is preheated to 870 K in the convective
section of a pyrolysis furnace.
Refinery production:
Refinery propylene is formed as a by-product of fluid cracking of gas oils, and to a far extent, of
thermal processes, e.g., coking. The total amount of propylene produced depends on the mix of
these processes and the specific refinery product state.
Table 3Product Specification for Chemical-Grade propylene
Component Specification, wt% ASTM Test method

Propylene 92-94 D2163

Ethane and lighter <0.4 D2163


Ethylene <0.2 D2723

Hydrocarbons C4 and above


C5 and above <0.2 D2712
<0.005 D2162
Propane <8.0 D2163

Impurities
Acetylene + methyl acetylene <100 D2712
+ propadiene
Total H2, O2, CO, CO2 and N2 <100 D2504
Sulphur <10 D3120
Water <50 D2713
Halides <10
Alcohols <50
Amines <5
Butadiene <20 D2712

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Butanes <125
Dimethyl formamide 0.3
a
Values are in ppm wt.

Table 4Product Specifications for Polymer-Grade Propylene


Component Specification, ASTM Test method
wt.%
Propylene 99.5a D2163

Ethane <1000 D2163

Total acetylenes ,dienes , and other unsaturates <10 D2712

Hydrogen <2 D2504

Oxygen <8 D2504

CO <4 D2504

Water <10

Sulphur <5 D3120

Total nitrogen, aldehydes, ketones, and <10 D2504


alcohols
aValues is wt%

AMMONIA
Physical Properties:
Ammonia is a colourless alkaline gas, is lighter than air and possesses a unique, penetrating odour.
Ammonia is readily absorbed in water to make ammonia liquor.Considerable amount of heat is
evolved during the solution of ammonia in water.It is an excellent solvent for salts, and has an
exceptional capacity to ionize electrolysis. The alkali metals and alkaline earth metals are readily
soluble in ammonia bar beryllium.
Table 5 Physical Properties of Ammonia
Property Value
Molecular weight 17.03
Freezing temperature,0C -33.5
Boiling point, 0C -77.7
Critical temperature, 0C 133.0
Critical pressure, MPa 11.425

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Heat of formation,kJ/mol -39222,at 00K


-46222,at 2980K
Solubility in water, wt% 42.8, at 00C
33.1 at 200C
23.4, at 400C
14.1, at 600C
Specefic heat, J/kg K 2097.2 at 00C
2226.2, at 1000C
2105.6, at 2000C
Specific Gravity 0.690, at -400C
0.639, at 00C
0.580, at 400C
Butanes <125
Dimethyl formamide 0.3

Specification and Analysis:


Anhydrous and aqua ammonia are manufactured in various grades depending on use,
Specifications are given in the following tables:
Table 6Anhydrous Ammonia Specification
Material content Commercial or Refrigeration Metallurgical
fertilizer grade grade gradewt
Ammonia,min wt% 99.5 9.98 99.99
Water , max ppm by 5000 150 33
Oil, max ppm by wt 5 3 2
Noncondensable gases, max - 0.2 10
ml/g

Ammonia and ammonium ion in industrial water streams, including waste water streams, can be
determined by either of two methods (ASTM Procedure D1426). In the first, the sample is buffered
to a pH of 7.4 and distilled into a solution of boric acid where the ammonia nitrogen is determined
calorimetrically with regents or titrated using sulphuric acid.
The other method is less accurate but more rapid and involves direct Nesslerizaton of the sample
for colorimetric determination. Other calorimetric indicators with more sensitivity, such as
indophenols, have been also find use in analysis for trace ammonia.

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3.3 VLE OF KEY MIXTURES

The VLE of acrylonitrile/acetonitrile indicates a quasi - ideal system, but very low relative
volatility, below 1.15, which makes necessary a large number of stages and high reux. Actually,
both components are involved in the process as mixtures with water. Figure 5 presents T x y
phase diagrams for the binaries acrylonitrile/water and acetonitrile/water calculated by Aspen Plus
with Uniquac/Redlich Kwong as the thermodynamic option. Note that acrylonitrile/water forms
a heterogeneous azeotrope, while the azeotrope acetonitrile/water is homogeneous. Both
azeotropes show close compositions (0.68 vs. 0.65 mole fraction nitrile) and narrow boiling points
(345 vs. 350 K). The prediction of VLE is accurate. Although the solubility of water in
acrylonitrile at higher temperature is somewhat underestimated, this will not alter the conceptual
design.
The conclusion is that the separation by simple distillation of the ternary mixture
acrylonitrile/acetonitrile/water is not possible because of azeotropes. Changing the VLE behaviour
by a mass - separation agent is desirable. The literature search indicates that water itself may play
this role, which is quite surprising! Some ash calculations help to understand this phenomenon.
Consider a mixture AN/ACN in ratio 10:1 and variable water amount. At lower water/organic ratio
there are two-liquid phases, while the composition of the vapour phase is xed by the binary
azeotrope. At ratios larger than 10 the heterogeneous azeotrope acrylonitrile/water disappears
since there is only one liquid phase. The K values for AN and ACN are about 20 and 4,
respectively, giving a relative volatility of 5, while the K value for water is below 1. The increase
in the relative volatility AN/ACN is sensible up to water/mixture ratios of about 20. As a result,
the separation of the acrylonitrile/acetonitrile mixture by extractive distillation with water may be
feasible in a single column but with a large amount of entrainer.

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Figure 8 VLE of binaries acrylonitrile/water & acetonitrile/water.

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3.4 PROPERTIES OF KEY COMPONENTS

Figure 9 Properties of key components

3.5 CATALYST SELECTYION

The possibility of producing acrylonitrile by the reaction of propylene and ammonia was first
revealed in 1949 in a patent assigned to Allied Chemical. However, the reaction when catalyzed
by a VMoPO mixed oxide produced acrylonitrile in less than 10% yield. The
commercialization of a propylene-to-acrylonitrile process only became possible with the invention
of catalysts that effectively change the mechanism from that dictated by gas-phase kinetics to one
in which the surface reaction provides a pathway, giving a higher yield of acrylonitrile than is
possible from the uncatalyzed thermalreaction.
Selective catalytic ammoxidation of alkenes grew out of the discoveries in the 1950s of catalysts
that oxidize propylene (then an underutilized by-product of petroleum refining) to acrylonitrile. In
the United States, researchers at The Standard Oil Co. (Ohio) (also called SOHIO) discovered a
bismuthphosphomolybdate catalyst, Bi9PMo12O5250 wt% SiO2, for this reaction, which gave
yields of acrolein of up to 70% (2).

Bismuth molybdate system: Catalysts based on bismuth molybdates are the most efficient class of
catalyst for oxidation and ammoxidation of propylene and olefin. They are also most thoroughly
investigated.Among several bismuth molybdate catalysts studied (11), the rates of catalyst
reduction by a feed consisting of propylene and ammonia in the absence of gaseous oxygen (i.e.,
reduction cycle) at 430C decrease in the following order: multicomponent system > Bi,MoO
>BiFeMoO,, 2Bi&OO,(y).

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Primary bismuth molybdate system: These catalysts are mixed oxide constituted from Bi2O3
and MoO3 at specified ratios. Multicomponent bismuth molybdates system: These catalysts
were developed by the modification of primary bismuth molybdates by replacing or adding other
metal elements. The first replacement of half the amount of the bismuth molybdate by iron in
Bi9P1Mo12O52 increased the catalytic activity for the ammoxidation of propylene noticeably.
The Bi-Fe-Mo-O system consists of several different composite oxide including bismuth
molybdate, iron molybdate and Bi3FeMo2O12.

In the catalytic cycle, the activation of propylene via a-hydrogen abstraction is rate determining.
The re-oxidation step, while it is essential to the catalytic cycle, is usually much faster for all
bismuth molybdate-based catalysts. Therefore, a catalyst possessing a large number of active
surface sites of proper structure and composition for selective oxidation, and one that is capable of
reconstituting these surface sites rapidly with bulk lattice oxygen, which in turn are rapidly
replenished by gaseous oxygen, will be the most efficient catalyst. Among those enumerated here,
the multicomponent system is clearly the best but its complexity and availability is an issue as still
it is not being used in the mass production of acrylonitrile and further the required data and
information it is not easily available. A case study on WASTE MINIMIZATION BY PROCESS
MODIFICATION which had used acrylonitrile as a test sample showed how alteration of reactor
design and distillation parameter selection can reduce waste generation for the acrylonitrile
process. The catalyst used for the reaction in the study process was Bi-Mo-O. It was observed that
at operating condition of 1-2 tam and 350-600 the reaction yields a conversion of 75-91% and
hence Bi-Mo-O was selected as the catalyst to be employed in this process.
The following is the main reaction and all the possible side reaction which my takes place when
we use the selected Bi-Mo-O catalyst for the process.
Main Reaction
2 = 3 + 3 + 3/2 2 2 = + 32
Side Reaction
= 3 + 3 + 9/4 2 3 + 1/2 2 + 1/2 + 32
2 = 3 + 2 2 = + 20
2 = + 3 + 2 2 = + 220
2 = + 22 2 + + + 20
3 + 3/2 2 2 + + 2
Total Reaction
35 1 2 5 1 11
CH = CH CH3 + NH3 + 12 O2 3 CH2=CH-CN + 3 HCN + 6 CO2 + 2 CO + H20\
3

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REACTION SYSTEM ANALYSIS


The rate equation for the ammoxidation ofpropyleneover Bi-Mo-O has a first-order dependence
with respect to propylene and a zero-order dependence forboth oxygen and ammonia when they
are supplied inat least stoichiometric amounts . The rateequations are

1 = 1 3 6

2 = 2 3 6

3 = 3 3 6

= 2

5 = 5 2

6 = 6 3

where the rate constants are expressed in the Arrhenius form by

From Callahan's studies, the activation energies for Rate Eqs.1,2, 3,4 and 5 were estimated to be
Ene rgy Value Te mp C K
E1 19000 T1 470 743
E2 19000 T2 450 723
E3 7000 T3 350 623
E4 7000 T4 400 673
E5 19800 T5 500 773
E6 7000 T6 550 823

Table 7: Table 6: Activation Energy for Rate Equations


The above date can be used to calculate rate constants at diffrent tremperatures by Arrhenius eq.
Gas Constant ( R ) 1.98
Rate Constant (k) Initial (T1) Final (T2) At T3 At T4 At T5 At T6
k1 0.40556 0.28372 0.03370 0.10584 0.66948 1.42324
k2 0.00973 0.00681 0.00081 0.00254 0.01606 0.03415
k3 0.01744 0.01529 0.00697 0.01063 0.02098 0.02770
k4 6.81341 5.97311 2.72477 4.15363 8.19528 10.82022
k5 0.16222 0.11179 0.01214 0.04001 0.27350 0.60018
k6 0.07300 0.06400 0.02919 0.04450 0.08781 0.11593

Table 8: Rate constants at different temperatures

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3.6 CHEMICAL REACTOR: SELECTION ANDANALYSIS

In the study done on the waste minimization of acrylonitrile production (mentioned in the previous
section) different types of reactor where tested under different operating conditions such as
residence time and conversion AT 400C and 2 atm in the presence of selected catalyst and the
following results were obtained

Figure 10: Reactor comparison for PFR, CSTR & FBR


On analysis, the data given above it is very evident that the conversion of rate in case of Fluidized
bed reactor (FBR) is clearly more than Continuously Stirred Tank Reactor (CSTR) or Plug flow
reactor (PFR). Further the byproducts to ACN ratio is also minimum (i.e. Production of ACN and
byproduct like HCN and ACE are produced less) in case of FBR.00C and pressure of 2 atm.
A comparison of the mole ratio of HCN/ACN and the mole ratio of ACE/ACN for each of the
reactors at constant residence times of 2, 10, and 15 sec in table shows that the FBR has the lowest
values. The greatest difference in these ratios is for HCN/ACN. The highest ratio of HCN/ACN
occurs in the CSTR which also has the lowest conversion. The mole ratios of both HCN/ACN and
ACE/ACN are higher with the PFR than the FBR but the conversion in the PFR is also higher.
Further it also shows the ratio of HCN/ACN and ACE/ACN at three different conversions for three
reactors. The residence time used for each reactor varies with the type of the reactor. The FBR
again generates less waste than the other two reactors.
Hence due to this discreet and detailed comparison between the three reactors it becomes clear that
that using a Fixed Bed Reactor would be the most profitable and effective choice. Efficiency of
the reactor for this process can be given in the following order:
Fluidized bed reactor (FBR) > Plug flow reactor (PFR) > Continuous stirred tank reactor (CSTR)
A bubbling bed model has been used for the FBR. This model has a rising bubble surrounded by
a cloud-wake and enclosed by an emulsion catalyst bed. To minimize the byproducts in the
production of acrylonitrile by modification of the reaction parameters in the process, the following
conditions would be recommended

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Temperature: 400-480C
Residence Time: 2-10 sec
Pressure: 1-2 atm

There is an optimum temperature for minimizing the waste and that it is in the range of 400-480C
for each type of reactor. For this temperature range, a high conversion can be obtained by selecting
the correct residence time. A higher conversion can be obtained by choosing a longer residence
time, but the ratio of waste to acrylonitrile produced will also increase marginally. The reactor
effluent from the operation of the reactor at 450C and the residence time of 7 seconds.

3.7 FINAL FOWSHEET


Approximately stoichiometric quantities of propylene, ammonia, and oxygen (as air) are
introduced to a fluidized-bed catalytic reactor at 2 atm and a contact time in the range of several
seconds, and a temperature of 350-600C is maintained. The use of polymerization-grade
propylene is unnecessary. Once-through-flow is used because conversion of propylene is
practically complete. The reaction is exothermic, so heat removal must be provided. The reactor
effluent from the fluid bed reactor is neutralized to remove unconverted ammonia in the form of
ammonium sulphate with the help of H2SO4. The stream is then send into an absorber column
where it is washed with water to yield an unabsorbed stream of inert gases/tail gases (CO, CO2,
O2,etc) and the solution of acetonitrile, acrylonitrile, and HCN. This solution is then made to enter
in a stripper where it is stripped of the dissolved products and the water and unreacted products
are removed from the bottom. A part of the bottom water is send back to the neutralizer as recycled
water stream and the rest is disposed as waste water, the stripped products are then send in the first
fractionation column where they are fractionated to remove pure HCN as distillate and the bottom
is sent to the main purification section. The main fractionator consists of an extractive distillation
column which yields two stream one wet acrylonitrile rich stream leaving as distillate and another
wet acetonitrile rich stream discharged as bottom. The bottoms wet acetonitrile is dried, and
fractionated to give high purity product of acetonitrile (ACE), and bottom product of acrylonitrile
and water which are recycled to extractive distillation column to improve its efficiency and reduce
potential wastes. The overhead of extractive distillation column consisting of wet acrylonitrile, is
dried and purified in a two-stage process first by azeotropic and then conventional distillation to
give highly pure acrylonitrile (ACN) distillate.

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Figure 11: SOHIO PROCESS FLOW SHEET

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3.8 FURTHER DEVELOPMENTS


An economic analysis can show that the most effective factor in reducing the manufacturing costs
could be replacing the propene by propane, which is 30% cheaper. An industrial process is
attributed to Asahi. The key competitive element is the availability of a suitable catalyst. Despite
intensive research the performance of todays catalysts remains rather modest. The conversion
should be kept low, below 50%, while the selectivity cannot be pushed beyond 60%. Because the
recycle of unconverted propane and larger spectrum of by-products the advantage of lower price
seems to be not sufficient for a technological breakthrough.
An interesting non-petrochemical alternative developed by Monsanto is based on synthesis gas
and NH3. In the first step, acetonitrile is obtained with selectivity of 85% at 300 600 C and
pressures up to 35 bar by using Mo/Fe oxide catalysts:
NH3 + 2CO + 2H2 CH3CN + 2H2O
In the second step acetonitrile is converted to acrylonitrile by catalytic oxidative methylation, as
described by the global reaction:
CH3CN + CH4 + O2 H2C=CHCN + 2H2O
At this stage the conversion is of 45% and selectivity up to 70%. An additional advantage is the
vaporization of acetonitrile by-product directly in aqueous solution.

3.9 CONCLUSIONS

The manufacturing of acrylonitrile by ammoxidation of propene remains highly competitive


because of the high performance achieved with the modern catalysts based on
molybdenum/antimonium oxides. The conversion of propene is practically complete, while the
ammonia and oxygen are used in amounts close to stoichiometry. Fluid - bed - reactor technology
allows short reaction times and very high heat - transfer coefficients to be achieved, by preserving
safety despite the potential explosive reaction mixture and very high exothermic effect.
The conceptual interest of this case study is the development of a complex separation scheme. The
absorption of acrylonitrile in water, apparently trivial, needs a large amount of cold water, and
accordingly a large amount of low temperature energy. Important saving can be achieved by a
two - stage scheme. The first step is a simple flash at lower temperature by which a substantial
amount of acrylonitrile is separated. In the second step, the remaining gas is compressed to 4.5 bar
before water absorption. In this way the water consumption can drop up to 60% with the
supplementary advantage of much lower energy in the distillations implying water solutions.
The separation of acetonitrile from acetonitrile by extractive distillation with water can be done in
a more efficient two - column heat integrated setup. The separation of acrylonitrile from water,
which is hindered by the existence of an azeotrope, can actually take advantage of the large
immiscibility gap. Valuable by-products, such as HCN and acetonitrile can be efficiently
separated. Chemical conversion can solve the separation of difficult impurities, such as acrolein.

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4 CHEMICAL DESIGN OF EQUIPMENTS


4.1 REACTOR
Main Reaction
2 = 3 + 3 + 3/2 2 2 = + 32
Side Reaction
= 3 + 3 + 9/4 2 3 + 1/2 2 + 1/2 + 32
2 = 3 + 2 2 = + 20
2 = + 3 + 2 2 = + 220
2 = + 22 2 + + + 20
3 + 3/2 2 2 + + 2
Total Reaction
35 1 2 5 1 11
CH = CH CH3 + NH3 + 12 O2 3 CH2=CH-CN + 3 HCN + 6 CO2 + 2 CO + H20\
3

The rate equation for the ammoxidation ofpropyleneover Bi-Mo-O has a first-order dependence
with respect to propylene and a zero-order dependence forboth oxygen and ammonia when they
are supplied inat least stoichiometric amounts . The rateequations are

1 = 1 3 6

2 = 2 3 6

3 = 3 3 6

= 2

5 = 5 2

6 = 6 3

where the rate constants are expressed in the Arrhenius form by

From Callahan's studies, the activation energies for Rate Eqs.1,2, 3,4 and 5 were estimated to be

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Table 9: Activation Energy for Rate Equations


Ene rgy Value Te mp C K
E1 19000 T1 470 743
E2 19000 T2 450 723
E3 7000 T3 350 623
E4 7000 T4 400 673
E5 19800 T5 500 773
E6 7000 T6 550 823

The above date can be used to calculate rate constants at diffrent tremperatures by Arrhenius eq.
Gas Constant ( R ) 1.98
Rate Constant (k) Initial (T1) Final (T2) At T3 At T4 At T5 At T6
k1 0.40556 0.28372 0.03370 0.10584 0.66948 1.42324
k2 0.00973 0.00681 0.00081 0.00254 0.01606 0.03415
k3 0.01744 0.01529 0.00697 0.01063 0.02098 0.02770
k4 6.81341 5.97311 2.72477 4.15363 8.19528 10.82022
k5 0.16222 0.11179 0.01214 0.04001 0.27350 0.60018
k6 0.07300 0.06400 0.02919 0.04450 0.08781 0.11593

Table 10: Rate constants at different temperatures


As the incoming stream from the reactor contains

Propylene = 129.951 kmol/hr


Ammonia = 166.770 kmol/hr
Air = 1079.546kmol/hr

Thus total amount entering into the reactor = 1376.261 kmol/hr


= 40638.450 m3/hr
Initial concentration of propylene, C PR0 = 129.951 *1000/40638.4508
= 3.1977 mol/m3

A Bubbling Flow Reactor (BFR) gives 99% conversion of propylene, so the concentration of
propylene in the outgoing stream of the reactor can be given by,

EQUATION USED
= + +

2 3
=
150 1
1- )
1 = =
1

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Manufacture of Acrylonitrile from Ammoxidation of Propylene 2016-17

1 = 1 = 1- )
1
= + + 1
+ 1
+ 1
+

1 1 1
W= 1
+

CALCULATION AND RESULT

INPUT/ASUMMPTIONS
E 0.5
Emf 0.6
Ef 0.8
Ac 6.1544 m2
D 2.8
Density (Cat) 2500 Kg/m3
Cp (Cat) 0.25 cal/GSEC
Bulk Density (Cat) 1250
Pr 0.77
De 0.39
air 0.00036 poise
C3h6 0.0025 poise
Nh3 0.00021 poise
Avg 0.0003254 poise
0.00003254 kg/ms
0.000076223
Db 13.34 mm
Db 0.01334 m
D 0.000039
0.5
b 0.005

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Reactor condition
Conversion 81.05%
Pressure 2 atm
Teperature 450 C
Reactor Inlet
Propylene 21.82 Kmol/hr
Ammonia 21.82 Kmol/hr
Air 63.64 Kmol/hr
TOTAL 107.28 Kmol/hr

Ds 76.22335732
Delta, 0.5
Mavg in 29.37
Density (Gas) 0.9777 Kg/m3

Actual Bubble Velocity


Umf 0.015757821 m/s
Ubr 0.257206547 m/s
U0 0.241448726
Ub 0.482897452
Ut 0.24

weight of catalyst
Kbc 17.93527375 sec-1
kce 10.7796302
c 0.336464724
mc 0.84116181
mb 0.0125
me 0.14633819
Ye 0.058535276
Kr 2.760482474
w 765.61 kg
Lf 3.035 m
Lm 1.214 m
Tdh 4.452 m
total hight 8.701 m

Volume 53.5494344 m3

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Figure 12: Reactor design and sizing

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Figure 13: REACTOR MODES OF OPERATION

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4.2 HEAT EXCHANGER

HEAT EXCHANGER BETWEEN REACTOR AND NEUTRALIZER

Calculation of heat load


Component Flow rate Cp Temp diff Q
kJ/hr
kg/hr kJ/kg K
K

Nitrogen 23890.94806 1.06464 350 8902340.63


CO 73.16296 1.07456 350 27516.2966
O2 204.704 0.98736 350 70740.7895
CO2 114.92932 1.04472 350 42024.13572
HCN 1264.533678 1.597 350 706811.0993
Acetonitrile 960.212865 1.781 350 598548.6894
Acrylonitrile 5037.32088 1.74 350 3067728.416
Ammonia 29.4901177 2.512 350 25927.71148
Water Vapor 7765.13155 1.9828 350 5388845.993
Acrylic Acid 62.7371772 1.625 350 35681.76953

Total V=39403.17061 Total Q=18866165.53

Hot Fluid Cold Fluid Difference

Hot Side 450 C 25 C 400 C

Cold Side 100 C

Difference 350 C

Since the flow rate of vapour stream is too high, we shall use 4 heat exchangers connected in
parallel to each other.
(Source: Wolverine Tube Heat Transfer Databook, page 49)
39403.17061
Thus, Vapor flow rate in each heat exchanger = = 9850.803 kg/hr
4

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Manufacture of Acrylonitrile from Ammoxidation of Propylene 2016-17

18866165.53
Heat flow rate in each exchanger = = 4716541.383 kJ/hr
4

Q 4716541.383
Water flow rate, m = =
C p T 3600* 4.187 * 20

= 15.705 kg/s
450 20 100 40
= 30
= 187.003
[ 70 ]

T1 T2
R= = 20
t 2 t1

Where, T1 =Inlet Temperature of Hot Feed


T2 = Outlet Temperature of Cooled feed
t1 = Inlet Temperature of cold water
t2 = Outlet Temperature of cold water

t 2 t1
S= = 0.0476
T1 t1

1 S
R 2 1 ln
1 RS

FT =
2 S R 1 R2 1
R 1 ln

2 S R 1 R 1
2

= 0.8442
We shall use 1-2 Shell and Tube Heat Exchanger

(T ) ln = FT*LMTD
= 158.60C
Assumption:
At atmospheric pressure and 2psi allowable pressure drop a fouling friction factor of 5000
may be anticipated. Since the flow rate is too high we will have to take four heat exchangers

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connected in parallel with each other. Below is the calculation shown for one such type of
heat exchanger, rest heat exchangers being the same as this. Uassumed = 200 W/m2K
Q
A=
U D T

= 39.120 m2
Taking tubes of 16mm inner diameter and 20mm outer diameter and length as 2.44m.
Tube outside surface area = 0.1534 m2
39.120
Number of tubes = = 255.
0.1530
We are assuming two tube passes and 1.25 triangular pitch.

Tube side coefficients


Mean water temperature = 40 C
Tube per pass = 255/2 =128
Cross sectional area for a single tube = di2/4
= *(0.008)2
= 0.000201 m2
Total flow area = 128*0.000201 = 0.0257 m2
15.64545479
Water mass velocity = 727.234674 kg/m2s
0.021513626
Density of water, = 992.2 kg/m3
Water linear velocity, ut = 0.613 m/s

4200 * (1.35 0.02 * t ) * u t


0.8

hi 0.2
di

Where, hi= coefficient of water


t = Average water temperature, C
di = Inner tube diameter, mm
hi = 3504.800W/m2 C

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Shell side heat transfer coefficient


Using 1.25 triangular pitch,
1/n1
Nt
Bundle Diameter = Db do
K1
For Triangular Pitch K1 =0.249 & n1 = 2.207 (Ref Table 12.4 , Coulson & Richardsons
Chemical Engineering, Vol 6, 4th Edition )
Db = 462.500 mm
Clearance = 11 mm (Ref Table 12.4 , Coulson & Richardsons
Chemical Engineering, Vol 6, 4th Edition )
Therefore, Diameter of the shell, Ds = 473.500mm
Baffle spacing, lb = Ds/5 = 94.700 mm

( p t d o ) * Ds * l b
As = = 0.008965 m2
pt

9850.792653
Mass velocity = = 356.414 kg/m2s
3600*0.007677403
= 1.255246 kg/m3
356.4136587
Linear velocity = 283.9392905 m/s
1.255246

1.1 * ( p t 0.917d o )
2 2

Equivalent diameter, de = = 0.0142 m


do

Mean Shell side temperature = 275 C


Properties:
Specific Heat Cp = 1.274217327 J/kg-K
Thermal Conductivity k = 0.0549342 W/mK
Viscosity = 1.86086*10-5 Ns/m2

Gs * d e
Reynolds number, Re = = 185573

Cp
Prandtl Number, Pr = = 0.000431
k

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Choose 25% baffle cut,


jh = 0.003 (Ref Fig 12.29, Coulson & Richardsons
Chemical Engineering, Vol 6, 4th Edition )
Therefore, by using the equation given below, we can calculate the heat transfer coefficient for the
shell side.

k f * j h * Re* Pr
0.33

hs = 167.01 W/m2 C
de

Overall heat transfer coefficient


K for metal = 40 W/m K
Fouling Coefficient = 5000 W/m2K

1 1 1 20*103 ln 20 16 20 20

U 5000 222.9604992 2* 40 16*5000 16* 4045.051336
U = 144.514 W/m2K
which is close to the assumed value of 200 W/m2K

Pressure drop calculations

Tube side
= 6.71112*10-4 Ns/m2
* di * u
Re = = 14493.430

jh = 5*10-3

L u t 2
Pt N p 8 j f 2.5
di 2

3 6.05 992.2 *(0.732951697) 2


= 2 8*3.5*10 2.5
17.4 2

= 3203.25Pa
= 3.203 kPa

Shell Side

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D L u 2
Ps 8 j f s
de l b 2
= 76532.58 Pa
= 76.53 kPa
Summary:
Tube Dimension: 16 mm (I.D) x 20 mm (O.D) x 2.44 m
Number of Tubes: 255
Diameter of Shell: 473 mm
Tube side pressure drop = 3.203 kPa
Shell side pressure drop = 76.53 kPa

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Table 11: CALCULATION: HEAT EXCHANGER-1


HOT (Tubel-effluent) COLD(shell-colent)
INPUT DATA
TEMP(*C)
INPUT 450 25
OUTPUT 100 413.9438291
U 235
DIAMETER(m) inner 0.06 0.01905
DIAMETER(m) outer 0.02
Q 2544802.146
r,s 0.899872871 0.915161951

FLOW RATE(kg/hr) 10663.35 10663.35


SPECIFIC HEAT(KCAL/Kg) 35.56057866 125.83032
VISCOSITY(Kg.m/hr) 0.0504 0.80928
LENGTH OF TUBES(m) 2.77
THERMAL CONDUCTIVITY OF TUBE 14.02
SURFACE AREA OF THE TUBES(m^2) 193.9844024
OUTPUT DATA
T1 36.06
T2 75
LMTD 53.17
NTU 7.31480162
Heat rransfer area 203.6581653
Ft 0.945
CORR.LMTD 50.24769469
Surface area of one tube (m2) 0.173956
No. OF TUBE 1170.745276

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HEAT EXCHANGER BETWEEN NEUTRALIZER AND ABSORBER

Calculation of Heat Load

Component Flow rate(kg/hr) Cp(kj/kg k) Temp diff Q(kj/hr)

Nitrogen 10892 1.131 30 739131.12

Carbon dioxide 104.44 3.40 30 21407.80

Carbon monoxide 66.70 1.04 30 4158.336

Oxygen 186.90 .929 30 10416.70

HCN 1153.50 1.59 30 110038.20

Acetonitrile 875.80 2.3 30 120854.90

Acrylonitrile 4591.40 2.20 30 606063.50

Ammonia 0 0 30 0

Total V=17870.80 Total Q=1612060.50


Hot Fluid Cold Fluid Difference
Hot Side 90C 40C 50C
Cold Side 60C 20C 40C
Difference 30C 20 C 10C

Thus, Vapor flow rate in each heat exchanger = 17870.80kg/hr


Heat flow rate in each exchanger =1612060.50 kJ/hr

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Q
Water flow rate, m =
C p T

4716541.383
=
3600* 4.187 * 20
= 15.64545479 kg/s
90 20 60 40
= 9020
= 47.20
[60 0]

T1 T2
R= =6
t 2 t1

Where, T1 =Inlet Temperature of Hot Feed


T2 = Outlet Temperature of Cooled feed
t1 = Inlet Temperature of cold water
t2 = Outlet Temperature of cold water

t 2 t1
S= = 0.143
T1 t1

1 S
R 2 1 ln
1 RS
FT =

2 S R 1 R2 1
R 1ln

2 S R 1 R 1
2

= 0.82
We shall use 1-2 Shell and Tube Heat Exchanger

(T ) ln = FT*LMTD
= 38.74C
Assumption:
At atmospheric pressure and 2psi allowable pressure drop a fouling friction factor of 5000
may be anticipated. Since the flow rate is too high we will have to take four heat exchangers
connected in parallel with each other. Below is the calculation shown for one such type of
heat exchanger, rest heat exchangers being the same.

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Uassumed = 200 W/m2K


Q
A=
U D T

= 57.80 m2
Taking tubes of 16mm inner diameter and 20mm outer diameter and length as 2.44m.
Tube outside surface area = 0.153309721m2
57.80
Number of tubes = = 376.96 = 377
0.153309721
We are assuming two tube passes and 1.25 triangular pitch.

Tube side coefficients


Mean water temperature = 40 C
377
Tube per pass = 189
2
Cross sectional area for a single tube = di2/4
= *(0.008)2
= 0.00020 m2
Total flow area = 189*0.000201 = 0.038 m2
15.64545479
Water mass velocity = 727.234674 kg/m2s
0.021513626
Density of water, = 9965.4 kg/m3
Water linear velocity, ut = 0.291 m/s

4200 * (1.35 0.02 * t ) * u t


0.8

hi 0.2
di

Where, hi= coefficient of water


t = Average water temperature, C
di = Inner tube diameter, mm
hi = 1627 W/m2 C

Shell side heat transfer coefficient

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Using 1.25 triangular pitch,


1/n1
Nt
Bundle Diameter = Db do
K1
For Triangular Pitch K1 =0.249 & n1 = 2.207 (Ref Table 12.4 , Coulson & Richardsons
Chemical Engineering, Vol 6, 4th Edition )
Db = 552 mm
Clearance = 11 mm (Ref Table 12.4 , Coulson & Richardsons
Chemical Engineering, Vol 6, 4th Edition )
Therefore, Diameter of the shell, Ds = 563mm
Baffle spacing, lb = Ds/5 = 112.60 mm

( p t d o ) * Ds * l b
As = = 0.0124 m2
pt

9850.792653
Mass velocity = = 399.330 kg/m2s
3600*0.007677403
= 1.22 kg/m3
356.4136587
Linear velocity = 283.9392905 m/s
1.255246

1.1 * ( p t 0.917d o )
2 2

Equivalent diameter, de = = 0.0142 m


do

Mean Shell side temperature = 75 C


Properties:
Specific Heat Cp = 1.363 J/kg-K
Thermal Conductivity k = 0.0549342 W/mK
Viscosity = 3.9*10-5 Ns/m2

Gs * d e
Reynolds number, Re = = 244638

Cp
Prandtl Number, Pr = = 0.0004714
k

Choose 25% baffle cut,

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jh = 1.1*10^-3 (Ref Fig 12.29, Coulson & Richardsons


Chemical Engineering, Vol 6, 4th Edition )
Therefore, by using the equation given below, we can calculate the heat transfer coefficient for the
shell side.

k f * j h * Re* Pr
0.33

hs = 83 W/m2 C
de

Overall heat transfer coefficient


K for metal = 45 W/m K
Fouling Coefficient = 5000 W/m2K

1 1 1 20*103 ln 20 16 20 20

U 5000 222.9604992 2* 40 16*5000 16* 4045.051336
U = 75.09 W/m2K
which is close to the assumed value of 200 W/m2K

Pressure drop calculations

Tube side
= 8.222*10-4 Ns/m2
* di * u
Re = = 5645.67

jh = 5.5*10-3

L u t 2
Pt N p 8 j f 2.5
di 2

6.05 992.2 *(0.732951697) 2


= 2 8*3.5*103 2.5
17.4 2

=211.84Pa
= .211 kPa

Shell Side
D L u 2
Ps 8 j f s
de l b 2

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= 494.05 Pa
= .494 kPa
Summary:
Tube Dimension: 16 mm (I.D) x 20 mm (O.D) x 2.44 m
Number of Tubes: 377
Diameter of Shell: 563 mm
Tube side pressure drop = .211 kPa
Shell side pressure drop = .494 kPa

HEAT EXCHANGER BETWEEN ABSORBER AND ACRYLONITRILE RECOVERY


COLUMN

Heat Load Calculation

Component Mol. Fraction Mass flow Cp(KJ/kg k) Temp diff Q(KJ/hr)


rate(kg/hr)

Acrylonitrile 0.123 4977.50 2.231 76 844154.135

Acetonitrile 0.030 949.15 2.423 76 174798.501

HCN 0.0611 1250.478 2.805 76 266576.90

Water 0.784 10703.10 4.222 76 3434325.103

Total V=17880.228 Total Q=4719854.640

Hot Fluid Cold Fluid Difference


Hot Side 100C 30C 70C
Cold Side 24C 20C 4C
Difference 76C 10C 66C

Thus, Vapor flow rate in heat exchanger =17880.228 kg/hr

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Heat flow rate in exchanger = 4719854.640 kJ/hr


Q
Water flow rate, m =
C p T

4716541.383
=
3600* 4.187 * 20
= 31.310 kg/s
100 20 30 24
= 10020
= 28.56
[ 302 ]

T1 T2
R= = 7.6
t 2 t1

Where, T1 =Inlet Temperature of Hot Feed


T2 = Outlet Temperature of Cooled feed
t1 = Inlet Temperature of cold water
t2 = Outlet Temperature of cold water

t 2 t1
S= = 0.125
T1 t1

1 S
R 2 1 ln
1 RS
FT =

R 1ln 2 S R 1 R 2 1
2


2 S R 1 R 1
= 0.950
We shall use 1-2 Shell and Tube Heat Exchanger

(T ) ln = FT*LMTD
= 27.36C
Assumption:
At atmospheric pressure and 2psi allowable pressure drop a fouling friction factor of 5000
may be anticipated. Since the flow rate is too high we will have to take four heat exchangers

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connected in parallel with each other. Below is the calculation shown for one such type of
heat exchanger, rest heat exchangers being the same.
Uassumed = 200 W/m2K
Q
A=
U D T

= 23.95 m2
Taking tubes of 16mm inner diameter and 20mm outer diameter and length as 2.44m.
Tube outside surface area = 0.153309721m2
23.950
Number of tubes = = 156.190
0.153309721
We are assuming two tube passes and 1.25 triangular pitch.

Tube side coefficients


Mean water temperature = 25C
156.190
Tube per pass = 78
2
Cross sectional area for a single tube = di2/4
= *(0.008)2
= 0.000201 m2
Total flow area = 78*0.000201062= 0.0156 m2
15.64545479
Water mass velocity 727.234674 kg/m2s
0.021513626
Density of water, = 995.940 kg/m3
Water linear velocity, ut = 2 m/s

4200 * (1.35 0.02 * t ) * u t


0.8

hi 0.2
di

Where, hi= coefficient of water


t = Average water temperature, C
di = Inner tube diameter, mm
hi = 7770 W/m2 C

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Shell side heat transfer coefficient


Using 1.25 triangular pitch,
1/n1
Nt
Bundle Diameter = Db do
K1
For Triangular Pitch K1 =0.249 & n1 = 2.207 (Ref Table 12.4, Coulson & Richardsons
Chemical Engineering, Vol 6, 4th Edition )
Db = 370 mm
Clearance = 11 mm (Ref Table 12.4, Coulson & Richardsons
Chemical Engineering, Vol 6, 4th Edition)
Therefore, Diameter of the shell, Ds = 381mm
Baffle spacing, lb = Ds/5 = 76.200 mm

( p t d o ) * Ds * l b
As = = 0.0058 m2
pt

9850.792653
Mass velocity = = 856.330kg/m2s
3600*0.007677403
= 708.600 kg/m3
356.4136587
Linear velocity = 283.9392905 m/s
1.255246

1.1 * ( p t 0.917d o )
2 2

Equivalent diameter, de = = 0.014 m


do

Mean Shell side temperature = 62C


Properties:
Specific Heat Cp = 3.832 J/kg-K
Thermal Conductivity k = 0.0549342 W/mK
Viscosity = 2.718*10-4 Ns/m2

Gs * d e
Reynolds number, Re = = 247739.3784

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Cp
Prandtl Number, Pr = = 0.000431633
k

Choose 25% baffle cut,


jh = 0.007 (Ref Fig 12.29, Coulson & Richardsons
Chemical Engineering, Vol 6, 4th Edition )
Therefore, by using the equation given below, we can calculate the heat transfer coefficient for the
shell side.

k f * j h * Re* Pr
0.33

hs = 180 W/m2 C
de

Overall heat transfer coefficient


K for metal = 40 W/m K
Fouling Coefficient = 5000 W/m2K

1 1 1 20*103 ln 20 16 20 20

U 5000 222.9604992 2* 40 16*5000 16* 4045.051336
U = 160.870 W/m2K
which is close to the assumed value of 200 W/m2K

Pressure drop calculations

Tube side
= 8.223*10-4 Ns/m2
* di * u
Re = = 38757

jh = 3.6*10-3

L u 2
Pt N p 8 j f 2.5 t
di 2

6.05 992.2 *(0.732951697) 2


= 2 8*3.5*103 2.5
17.4 2

= 1399.220Pa

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= 1.399 kPa

Shell Side
D L u 2
Ps 8 j f s
de l b 2
= 24.860 Pa
=0.024 kPa
Summary:
Tube Dimension: 16 mm (I.D) x 20 mm (O.D) x 2.44 m
Number of Tubes: 156
Diameter of Shell: 381 mm
Tube side pressure drop = 1.399 kPa
Shell side pressure drop = 0.024 kPa

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Table 12: CALCULATION: HEAT EXCHANGER-2


HOT (Tubel-effluent) COLD(shell-colent)
INPUT DATA
TEMP(*C)
INPUT 100 25
OUTPUT 60 69.45072332
U 200
DIAMETER(m) inner 0.016 0.01905
DIAMETER(m) outer 0.02
Q 1293519.605
r,s 0.899872871 0.592676311

FLOW RATE(kg/hr) 10663.35 10663.35


SPECIFIC HEAT(KCAL/Kg) 35.56057866 125.83032
VISCOSITY(Kg.m/hr) 0.0504 0.80928
LENGTH OF TUBES(m) 2.77
THERMAL CONDUCTIVITY OF TUBE 14.02
SURFACE AREA OF THE TUBES(m^2) 188.2516696
OUTPUT DATA
T1 30.55
T2 35
LMTD 32.72
NTU 1.358343675
Heat rransfer area 197.6395481
Ft 0.945
CORR.LMTD 30.9243782
Surface area of one tube (m2) 0.173956
No. OF TUBE 1136.146773

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4.3 HCN REMOVAL MULTICOMPONENT DISTILLATION COLUMN

Feed Composition (kmol/hr)


Acrylonitrile 92.976
Acetonitrile 22.925
HCN 45.851
Water 5.946
Total 167.70

Data
Top Plate Temperature 35 C
Bottom Plate Temperature 100 C
Column Pressure 1 atm

Assuming feed at bubble point


D = (92.9769* 0.01) + (22.9258* 0.01) + (45.851* 0.99)
= 46.55 kmol/hr

B = (92.976* 0.99) + (22.925* 0.99) + (45.851* 0.01) + 5.946


= 121.148kmol/hr

Component Molar flow Xf Psat at 35 top Psat at bottom avg avg*Xf


rate C mm 100C
(kmol/hr) Hg mm Hg
HCN 45.851 0.273 1140 7.523 7218.58 6.307 6.88 1.883
ACRYLONITRILE 92.976 0.554 151.52 1 1144.43 1 1 0.554
ACETONITRILE 1108.38
22.925 0.136 147.905 0.976 1 0.968 0.972 0.132
WATER 5.946 0.0354 42.175 0.278 760 0.685 0.436 0.0154

i X if

0
i

1.883 0.554 0.132 0.0154


0
(6.88 ) (1.0 ) (0.972 ) (0.436 )
By iterations,
= 0.446

Rm XD *XD - *XD/ -
HCN 0.97 7.297 6.442 1.031
Acrylonitrile 0.0251 0.0251 0.553 0.0453
Acetonitrile 0.0049 0.00478 0.525 0.0090
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Water 0 0 0 0

Underwood Minimum Reflux Equation


*X
( D) Rm 1
Rm + 1 = 1.085
Rm = 0. 0855
Actual Reflux Ratio = R = 0.128
For Minimum Number of Stages:
D = 46.552 kmol/hr
B = 121.148 kmol/hr
FDHCN = 45.851
FBHCN = 0.4585
FDAcrylonitrile = 0.929
FBAcrylonitrile = 92.04

Fenske Equation:

DX D
N m DX D
FX DX BX (r refers to Acrylonitrile, i refers to HCN)
f D i B r
Therefore Nm = 4.762
No. of Stages
Gilliland Correlation
N Nm
0.5 (From Graph)
N 1
N = 11.259 12
Assuming plate efficiency = 50%
(12 1)
Actual No of Stages =
0.5
= 22
Tower Diameter:
L / D = 0.1283= Actual Reflux Rate
D = 46.55 kmol/hr
L = 5.97kmol/hr

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Bottom:
L = L+F
= 5.97+ 167.70= 173.674kmol/hr
V = L B
= 173.674 121.148
= 52.526kmol/hr

Calculating Top Diameter:

Top temperature: 35 C
PM avg
Density of Vapour (v) =
RT
Mavg = X HCN * M HCN X Acrylonitrile * M Acrylonitrile X Acetonitrile * M Acetonitrile
= 0.97 *27.030 + 0.0251 *53.1 + 0.0049 * 41.05
= 27.61kg/kmol
101325 * 27.619
v
8.314 * 308 *1000
= 1.093kg/m3
Density of liquid (l):
X X X
l Acrlonitrile Acetonitrile HCN
Acrylonitrile Acetonitrile HCN
0.0251 0.0049 0.97
=
789.367 768.87 688
= 690.127 kg/m3
Maximum volumetric flow rate,
V * M avg
Qv =
v * 3600
49.984 * 27.61
Qv =
1.093 * 3600
= 0.3508 m3/s
Lw v
Liquid vapor flow factor Flv
Vw L
Flv = 0.127
Assuming tray spacing of 0.5 m between each plate we get from the graph on Page 567, Coulson
& Richardsons Chemical Engineering, Volume 6, 3rd Edition
K1 = 0.078
l v
Flooding velocity u f K1
v
Uf = 1.95 m/s

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Now designing for 60% flooding velocity


u v u f * Flooding Coefficient

= 1.958 * 0.6
= 1.175 m/s
Qv
Effective hole area, Ah =
uv

0.351
=
1.175
= 0.298 m2
Now selecting downcomer area AD = 10% of the total area
AD = 0.1 * A
Since Ah = A - AD = 0.9A
A = Ah/0.9
= 0.332 m2

4* A
Diameter =

D = 0.65 m

Calculating base diameter


Assuming 100 mm water, pressure drop per plate
Column pressure drop = 100*0.001*1000*9.81*12 = 11772 Pa
Top Pressure, 1 atm = 101325 Pa
Estimated Bottom Pressure = 101325 + 11772 = 113097 Pa
For Bottom temperature 100 C
113097 * 49.025
Density of Vapour = v
8.314 * 373 *1000
= 1.787934509 kg/m3
X X X X H 2O
Density of Liquid = l Acrlonitrile Acetonitrile HCN
Acrylonitrile Acetonitrile HCN H 2O

= 803.43 kg/m3
Maximum volumetric flow rate,

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V * M avg
Qv =
v * 3600
Qv = 0.3813 m3/s
Lw v
Liquid vapor flow factor Flv
Vw L
Flv = 0.1514
Assuming tray spacing of 0.5 m between each plate we get from the graph on Page 567, Coulson
& Richardsons Chemical Engineering, Volume 6, 3rd Edition
K1 = 0.05
l v
Flooding velocity u f K1
v
Uf = 1.059 m/s
Now designing for 60% flooding velocity
u v u f * Flooding Coefficient

= 1.059 * 0.6
= 0.64 m/s
Qv
Effective hole area, Ah =
uv

0.38131
=
0.64
= 0.6 m2
Now selecting downcomer area AD = 10% of the total area
AD = 0.1 * A
Since AN = A - AD = 0.9A
A = Ah/0.9
= 0.67 m2

4* A
Diameter =

D = 0.922 m
Using same diameter above and below feed, reducing the perforated area for plates above the feed.

D = 0.922 m
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Height of column = (total space between trays * tray spacing) + (Actual trays * tray thickness)
= (11 * 0.5 + 12 * 0.005)
= 5.56 m
Keeping 1m for top disengagement height and 2.75m below the last tray,
Total height H = 5.56 + 1 + 1 + 2.75 = 10.31 11 m

H = 11 m

SPECIFICATIONS
TOTAL TRAYS = 22
TRAY SPACING = 0.5 m
HEIGHT = 11 m
DIAMETER = 0.922 m

4.4 ACRYLONITRILE PURIFICATION COLUMN

Feed:

Molar flow rate Flow rate in weight


Molecular wt
(kmol/hr) (Kg/hr)
Acrylonitrile 91.12 53.1 4838.83
Water 220 18 3960
TOTAL 311.12

Distillate:

Molar flow rate


(kmol/hr)
Acrylonitrile 90.21
water 2.2
TOTAL 92.41

Since we have 99% molar flow Acrylonitrile in distillate, Thus

XD = (0.99/53.1)/(0.99/53.1+0.01/18)=0.971

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XB = (.01*16.8)/( .01*16.)+ 68.966= 0.03924

By drawing graph according to McCabe-Thiele Method


for minimun get intercept (xd/Rm+1) = 0.44
Thus, Rm =(0.971/.44)-1 = 1.20
Assuming, R = 1.5Rm Thus, R= 1.5* 1.20 = 1.81
Intercept (XD/(R+1)) of operating line = 0.345

From graph no of plates = 16


Taking tray efficiency to be 0.6
no of ideal plates = 16/0.6 = 26.666
Thus taking no of plates to be 27.

Taking tray spacing = 0.5 m, Tray


thickness = 0.005m = (No. of trays-1)*0.5+No.of trays*tray
Height of Column, m thickness = 13.135

keeping 1 m for top disengagement and 3 m below botom tray


Thus height = 13.135 + 4
= 17.135 = 18m

Tower Diameter:
L / D = 1.81= Actual Reflux Rate
D = 92.415 kmol/hr
L = 167.27 kmol/hr
Assuming saturated liquid feed, q = 1
Bottom:
L = L+F
= 167.27 + 311.127 = 478.397kmol/hr
V = L B
= 478.397 218.51
= 259. 887kmol/hr = 2801.96 kg/hr
PM avg
Density of Vapour (v) =
RT
Mavg = X Hwater * M water X Acrylonitrile * M Acrylonitrile
= 18*0.197 + 53.1*0.883

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= 46.198 kg/kmol
v = 1.093kg/m3
Density of liquid (l):
X Acrlonitrile X water
l
Acrylonitrile water
0.01 0.99
=
806 998.2
= 995.825 kg/m3
Maximum volumetric flow rate,
V * M avg
Qv =
v * 3600
2801.96 * 46.198
Qv =
1.899 * 3600
= 18.93 m3/s
Lw v
Liquid vapour flow factor Flv
Vw L
Flv = 0.047
Assuming tray spacing of 0.5 m between each plate we get from the graph on Page 567,
Coulson & Richardsons Chemical Engineering, Volume 6, 3rd Edition
K1 = 0.85
l v
Flooding velocity u f K1
v
Uf = 1.944 m/s
Now designing for 60% flooding velocity
u v u f * Flooding Coefficient

= 1.944* 0.6
= 1.167 m/s
Qv
Effective hole area, Ah =
uv

= 1.623 m2
Now selecting downcomer area AD = 10% of the total area
AD = 0.1 * A
Since Ah = A - AD = 0.9A
A = Ah/0.9

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= 1.803 m2

4* A
Diameter =

D = 1.52 m
Taking tray spacing= 0.5 m, Tray thickness = 0.005 m
Height of Column = (No. of trays-1)*0.5+No.of trays*tray thickness = 13.135
keeping 1 m for top disengagement and 3 m below botom tray
Thus height = 13.135 + 4
= 17.135 = 18m

Specification
TOTAL TRAYS = 27
TRAY SPACING = 0.5 m
HEIGHT = 18 m
DIAMETER = 1.52 m

4.5 PUMPS & COMPRESSORS

COMPRESSORS:
The several kinds of commercial compressors are identified in this classification :
1. Rotodynamic:
a. Centrifugal (radial flow)
b. Axial flow

2. Positive displacemnet
a. Reciprocating piston
b. Rotary (screws, blades, lobes, etc.).
Centrifugal Compressor:
The head-flow rate curve of a centrifugal. compressor often has a maximum as shown on
Figure , similar to the pump curve of Figure.
To the left the developed head increases with flow, but to the right the head decreases
with increasing flow rate.

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At the peak the flow pulsates and the machine vibrates. This operating point is called the surge
limit and is always identified by the manufacturer of the equipment, as shown on figure for
centrifugal machines.

Figure 14Applications ranges of compressors.

Table 13Specifications of Centrifugal Compressors

Stable operation exists anywhere right of the surge limit. Another kind of flow limitation occurs
when the velocity of the gas somewhere in the compressor approaches sonic velocity. The resulting

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shock waves restrict the flow; a slight increase in flow then causes a sharp decline in the developed
pressure.
Table 7.6 shows as many as 12 stages in a single case. These machines are rated at either 10K or
12K ft/stage. The higher value corresponds to about 850 ft/sec impeller tip speed which is near the
limit for structural reasons. The limitation of head/stage depends on 7.26.

Maximum compression ratios of 3-4.5 per stage with a maximum of 8-12 per machine are
commonly used. Discharge pressures as high as 3000-5000 psia can be developed by centrifugal
compressors.
Compressor 1:
Between the Propylene storage tank and Reactor.
Molar flow rate = 129.95 Kmol/hr
= 1779.89 ft3/min
At this value from the above graph we require a Centrifugal Compressor.
Operating temperature = 87 = 648.2R
Inlet Pressure = 1 atm
Outlet Pressure = 2 atm
From Table 7.6, the smallest compressor for this gas rate is #38M.
Its characteristics are
N = 8100 rpm at 10-12K ft / stage
Np = 0.77
K = Cp / Cv = 1.157
1
2
Head (Hp) = 1 Z [1 1]

0.157
1 21.1570.77
Head (Hp) = 1.15715440.9648.2 0.157 [1 1]
2.08

Head (Hp) = 20495.23 ft


Maximum Head = 10200 ft
No. of stages = 4.2
Accordingly, the five stages with standard 10,000 ft/ stage impeller.
The required speed with the data of table 7.6 is :

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20 95.23
Speed = 810010000 5

=5186 RPM


Pgas = 33000

200.520 95.23
= 330000.77

= 161.72 Horse Power

161.72
Total Horse Power Input = 0.97

= 166.72 Horse Power Max

Compressor No. 2:
Between the Ammonia storage tank and Reactor.
Molar flow rate = 166.77 Kmol/hr
= 2168 ft3/min
At this value from the above graph we require a Centrifugal Compressor
Operating temperature = 87 = 648.2R
Inlet Pressure = 1 atm
Outlet Pressure = 2 atm
From Table 7.6, the smallest compressor for this gas rate is #38M.
Its characteristics are
N = 8100 rpm at 10-12K ft / stage
Np = 0.77
K = Cp / Cv = 1.316
1
2
Head (Hp) = 1 Z [1 1]

Head (Hp) = 52864.51 ft

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Maximum Head = 10200 ft


No. of stages = 4.2
Accordingly, the five stages with standard 10,000 ft/ stage impeller.
The required speed with the data of table 7.6 is :

5286 .51
Speed = 810010000 5

= 8329 RPM


Pgas = 33000

= 216.66 Horse Power

216.66
Total Horse Power Input = 0.97

= 223.36 Horse Power Max

Compressor 3:
Between the Oxygen storage tank and Reactor.
Molar flow rate = 220.31 Kmol/hr
= 1817.19 ft3/min
At this value from the above graph we require a Centrifugal Compressor
Operating temperature = 87 = 648.2R
Inlet Pressure = 1 atm
Outlet Pressure = 2 atm
From Table 7.6, The smallest compressor for this gas rate is #38M.
Its characteristics are
N = 8100 rpm at 10-12K ft / stage
Np = 0.77

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K = Cp / Cv = 1.39
1
2
Head (Hp) = 1 Z [1 1]

Head (Hp) = 57827.07 ft


Maximum Head = 10200 ft
No. of stages = 4.2
Accordingly, the five stages with standard 10,000 ft/ stage impeller.
The required speed with the data of table 7.6 is :

57827.07
Speed = 810010000 5

= 8711 RPM

Pgas = 33000

= 293.96 Horse Power

293.96
Total Horse Power Input = 0.97

= 303.05 Horse Power Max


Compressor No. 4 :
Between the Neutraliser and absorber.
Molar flow rate = 852.84 Kmol/hr
= 3845.20 ft3/min
At this value from the above graph we require a Centrifugal Compressor
Operating temperature = 100 = 671.33R
Inlet Pressure = 1 atm
Outlet Pressure = 1.1 atm
From Table 7.6, the smallest compressor for this gas rate is #38M.
Its characteristics are

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N = 8100 rpm at 10-12K ft / stage


Np = 0.77
K = Cp / Cv = 1.40

1
2
Head (Hp) = 1 Z [1 1]

Head (Hp) = 4897.40 ft


Maximum Head = 10200 ft
No. of stages = 4.2
Accordingly, the five stages with standard 10,000 ft/ stage impeller.
The required speed with the data of table 7.6 is :

897. 0
Speed = 810010000 5

= 2535 RPM


Pgas = 33000

= 144.55 Horse Power

1 .55
Total Horse Power Input = 0.97

= 149.02 Horse Power Max

PUMPS:
When selecting pumps for any service, it is necessary to know the liquid to be handled, the total
dynamic head, the suction and discharge heads, and, in most cases, the temperature, viscosity,
vapour pressure, and specific gravity. In the chemical industry, the task of pump selection is
frequently further complicated by the presence of solids in the liquid and liquid corrosion
characteristics requiring special materials of construction. Solids may accelerate erosion and
corrosion, have a tendency to agglomerate, or require delicate handling to prevent undesirable
degradation.

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Figure 15 A Single Stage Centrifugal Pump.

Range of Operation
Because of the wide variety of pump types and the number of factors which determine the selection
of any one type for a specific installation, the designer must first eliminate all but those types of
reasonable possibility. Since range of operation is always an important consideration, Fig. 10-26
should be of assistance. The boundaries shown for each pump type are at best approximate. In
most cases, however, Fig. 10-26 will prove useful in limiting consideration to two or three types
of pumps. this type, guide vanes or diffusers are interposed between the impeller discharge and
the casing chamber. Losses are kept to a minimum in a well-designed pump of this type, and
improved efficiency is obtained over a wider range of capacities. This construction is often used
in multistage high-head pumps.

Figure 16Pump coverage chart based on normal ranges of operation.

Action of a Centrifugal Pump


Briefly, the action of a centrifugal pump may be shown by Fig.6. Power from an outside source is
applied to shaft A, rotating the impeller B within the stationary casing C. The blades of the impeller
in revolving produce a reduction in pressure at the entrance or eye of the impeller. This causes

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liquid to flow into the impeller from the suction pipe D. This liquid is forced outward along the
blades at increasing tangential velocity. The velocity head it has acquired when it leaves the blade
tips is changed to pressure head as the liquid passes into the volute chamber and thence out the
discharge E.
Pumps can be classified into two general types:
1. Dynamic pumps, such as centrifugal pumps.
2. Positive displacement pumps, such as reciprocating and diaphragm pumps.

The single-stage, horizontal, overhung, centrifugal pump is by far the most commonly used type
in the chemical process industry. Other types are used where a high head or other special process
considerations are specified.
Pump selection is made on the flow rate and head required, together with other process
considerations, such as corrosion or the presence of solids in the fluid. The chart shown in Figure
can be used to determine the type of pump required for a particular head and flow rate.

The Static Head corresponding to any specific pressure is dependent upon the weight of
the liquid according to the following formula:
2.31 Presurre psi
=
Specific Gravity
A Centrifugal pump imparts velocity to a liquid.
This velocity energy is transformed largely into pressure energy as the liquid leaves the
pump.

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The relationship between the head developed in pump and its velocity is expressed by:
v2
=
2g
H - Total head developed (feet)
V - Velocity of impeller (feet/sec)
g - 32.2 feet/sec2
The approximate head of any centrifugal pump can predicted by calculating the velocity
of the impeller. Use the next equation to calculate the impeller velocity in case the
impeller diameter is given:

=
229
D - Impeller diameter (inch)
V - Velocity (ft/sec)

All pumps are centrifugal pumps.


Pump 1:
To pump feed from absorber to stripper.
Flow rate = 16.35 m3/hr
= 71.99 gallons/min
At this value from the graph given in Perrys hand book we require a single stage centrifugal pump
& the specification of the pump are:
Total Head: 45.78 ft.
RPM: 3500
Efficiency = 77%
.
Power = 3960

= 7 hp
Pump 2:
To pump feed from Stripper to HCN removal column:
Flow rate = 9.29 m3/hr
= 40.90 gallons/min

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At this value from the graph given in Perrys hand book we require a single stage centrifugal pump
& the specification of the pump are:
Total Head: 13.56 ft.
RPM : 3500
Efficiency = 77%
Power = 4 hp
Pump 3:
To pump feed from HCN removal column to Azeotropic Distillation column.
Flow rate = 46.908 m3/hr
= 206.53 gallons/min
At this value from the graph given in Perrys hand book we require a single stage centrifugal pump
& the specification of the pump are:
Total Head: 89.594 ft.
RPM : 3500
Efficiency = 77%
Power = 10 hp
Pump 4:
To pump feed from Azeotropic Distillation column to Acrylonitrile purification column.
Flow rate = 10.004 m3/hr
= 44.05 gallons/min
At this value from the graph given in Perrys hand book we require a single stage centrifugal pump
& the specification of the pump are:
Total Head: 47.19 ft.
RPM : 3500
Efficiency = 77%
Power = 4 hp

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4.6 EQUIPMENT SPECIFICATION SHEET

Table 14 Equipment specification sheet for reactor

REACTOR, RT 101

Type Fluidized bed reactor


Identification RT 101
Function Reaction
Operating Pressure (Top) 2 atm
Temperature(Top) 450 C
Height of Reactor 9.45 m
Diameter 4.91 m

Table 15 Equipment specification sheet for HCN removal column


HCN REMOVAL COLUMN, DC 101
Identification DC 101
Function Removal of HCN
Operating Pressure 1 atm
Temperature top 308 K
Temperature bottom 373 K
No. of Trays 22
Tray Spacing 0.5 m
Height 11 m
Diameter 0.922 m
IS 1570-1961 04 Cr 19 Ni 9 (Austenitic
Material of construction
Steel)

Table 16 Equipment specification sheet for Acrylonitrile purification column

ACRYLONITRILE PURIFICATION COLUMN, DC 103


Identification DC 103
Operating Pressure (Top) 1 atm
Operating Pressure (bottom) 1.361 atm

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Temperature(Top) 353 K
Temperature(Bottom) 373 K
No. of Trays 22
Tray Spacing 0.5 m
Height 18 m
Diameter 1.52 m
Material of construction IS 1570-1961 04 Cr 19 Ni 9

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5 PROCESS CONTROL&INSTRUMENTATION
Process Control and Instrumentation
Instruments are used in the chemical industry to measure process variables, such as temperature,
pressure, density, viscosity, specific heat, conductivity, pH, humidity, dew point, liquid level, flow
rate, chemical composition and moisture content. By use of instruments having varying degrees of
complexity, the values of these variables can be recorded continuously and controlled within
narrow limits.
Automatic control has been accepted generally throughout the chemical industry, thats why we
have chosen automatic control. The resultant savings in labor combined with improved ease and
efficiency of operations has more than offset the added expense for instrumentation. We have also
used high speed computers as they serve vital tool in the operation of the plant. Effective utilization
of the many instruments that we have employed in our plant is achieved by centralized control,
whereby one centrally located control room is used for the indication, recording and regulation of
the process variables. Panel boards have been developed which present a graphical representation
of the process and have the instrument controls and indicators mounted at the appropriate locations
in the overall process. This helps a new operator to quickly become familiar with the significance
of the instrument reading and rapid location of any operational variance is possible. We have
planned to design the control system correctly so that the problems of transmission lags, cycling
due to slow or uncompensated response, radiation errors, or similar factors are tackled easily.
The primary objectives of the designer when specifying instrumentation and control schemes are:
1. Safe plant Operation:
To keep the process variables within known safe operating limits.
To detect dangerous situations as they develop and to provide alarms and automatic shut- down
systems.
To provide interlocks and alarms to prevent dangerous operating procedures.
2. Production rate: To achieve the design product output.
3. Product quality: To maintain the product composition with the specified quality standards.
4. Cost: To operate the lowest production cost, commensurate with the other objectives.
Each process has its key process variables which directly impact the production and operations.
Instrumentation is provided to monitor the key process variables during plant operation. They may
be incorporated in automatic control loops or used for the manual monitoring of the process
operation. Instruments monitoring critical process variables will be fitted with automatic alarms to
alert the operators to critical and hazardous situations.

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It is desirable that the process variable to be monitored and dependents variable-that is easier to
measure-is monitored in its place. For e.g. in the control of the distillation columns, the continuous,
on line analysis of the overhead products is desirable but difficult and expensive to achieve reliably
so temperature is often monitored as an indicator of composition. The temperature instrument may
form part of a control loop controlling, say reflux flow, with the composition of the overhead
checked frequently by sampling and lab analysis.
Instrumentation claims the following advantages:
o Control: It controls all those parameters, which control the process and do not allow them to
cross safe limit thereby enabling smooth and safe operation.
o Safety: An efficient controlled plant possesses high safety by carefully monitoring potential
hazards like fire, explosion, toxicity etc.
o Product Quality: By the monitoring of the process parameters like temperature, pressure and
composition streams of reaction vessel, it guarantees the quality of the product.

Motivation behind process control

An industrial process consists of a number of unit operations interconnected to produce the desired
result: conversion of feedstock into product. Equipment is chosen to carry out the required unit
operations. It is the performance of these pieces of equipment that is controlled by the control
system. During its operation, the plant must satisfy several requirements imposed by its designers
and the general technical, economic and social conditions in the presence of ever-changing
external influences or disturbances.
We know in this era of highly cost competitiveness, there is always requirement of automation of
the process operations to reduce the manual labor. The main advantage of automation also lies in
the decrement of hazard exposure and increased process and equipment safety. Following are some
of the reasons behind process control and instrumentation in industries:
1. Production Specifications & Optimization: A plant should produce the desired amount and
quality of the final products. To maintain the final product composition desired, chemical process
control is essential.
2. Process Safety & Human Safety: The safe operation of a chemical process is a primary
requirement for the well being of the people in the plant and for its continued contribution to the
economical development. Every type of equipment has its particular weaknesses. These must be
addressed by appropriate instrumentation. In some cases the strategy is to avoid trespassing into
damaging regimes. In others it is possible to prevent damage from occurring.
3. Environmental Safety & Regulations: Various central and state laws may specify the
allowable limits of temperatures, concentration and flow rates of effluents from the plant.
Environmental pollution must be minimized using various pollution control strategies.
Levels of process control and optimization:

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5) Planning and
(Days-months) scheduling Demanding forecasting, supply
chain management,raw materials
and product planning

4) Real time
(Hours-days) optimization Plant wide and individual unit
real- time optimization, parameter
estimation, supervisory control,
data reconciliation

3b) Multivariable
(Minutes-hours) Multivariable control, model
and constraint
predictive control
control

PID control, advanced control


3a) Regulatory
(Seconds-minutes) techniques, control loop
control
performance monitoring

(< 1 second) 2) Safety, environment Alarm management, emergency,


and equipment
protection

1) Measurement and Sensor and actuator validation,


(< 1 second) actuation limit checking

PROCESS

4. Operational Limits of Equipments: The various types of equipments used in plants have
constraint inherent to their operation. Such constraint should be satisfied throughout the operation
of the plant. For e.g. pumps must maintain a certain NPSH, tanks should not overflow or go dry,
distillation columns should not be flooded, the temperature in catalytic reactors should not exceed
the range of the catalyst. The control systems are needed to satisfy all these operational constraints.
Every type of equipment has a variety of options available for controlling it. There are various
types of control that are possible to control specific equipment. To decide among the best way that
suits the process comes under this heading. Of all the possible control options some will simply
not work and some will have undesirable side effects. Those that do work will have different
secondary effects.

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5. Measurement Aspects:Every type of equipment has its special measurement


requirements. The guiding principle is to determine the actual value that is to be controlled and to
install instrumentation that will measure that precise value. This is very much dependent on the
specific purpose of the equipment. When this is not possible, adequate alternatives must be
found. Such issues are addressed in these articles. They are not always self-evident.
6 Cost Competitiveness: The operation of a plant must confirm to the market condition, i.e. the
availability of raw materials and demand of the final products. Further it should be as economical
as a possible in the utilization of raw materials, energy, capital and labor. Thus, it is required that
the operating conditions are controlled at given optimal levels of minimum operating cost,
maximum profit, and so on.
The main process of the plant consists of the reactor system, separation system, and the distillation
columns. Following is the list of main equipments for which process control and instrumentation
has been done for our plant:
1) Fluidized bed reactor (Reactor)
2) Absorber and Stripper
3) Distillation Columns
4) Total Condenser
5) Heat Exchangers
6) Storage tank

5.1 CONTROL SYSTEM FOR REACTOR

RT-101: Feed (Propylene, ammonia and air) is entering at Temperature 360.15 K and we have to
maintain the required temperature. The temperature condition for the reaction is important to be
controlled for carrying out ammoxidation reaction. We have put three controllers for temperature
control. The temperatures of propylene and air are controlled by manipulating the flow rate of
water in Heat exchanger.
It is used to have following control scheme:
1. Flow of cooling water into the reactor is maintained and controlled by using temperature
controller which is measuring the temperature of product stream.

2. It is desired to maintain a constant pH for the reaction to happen. Thats why we have
employed a pH controller to control the flow of buffer solution into the reactor.

3. A flow controller is used to maintain the flow of cooling water into the reactor.

Different Variables:

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Manipulated Type of
Controlled Variable Instrumentation
Variable controllers

Temperature PID
Temperature Cooling water flow in
Measurement

Flow Flow Measurement Cooling water flow in PI

pH pH measurement Buffer flow in PI

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5.2 CONTROL SYSTEM FOR STRIPPER

Following scheme has been adopted for control system of strippers:


1. Pressure control has been employed to maintain and control the flow of the top product .
2. Cascading of temperature controller is employed to maintain and control the flow of steam
in reboiler.
3. A minimum level has to be maintained in the stripper, therefore level controller has been
employed to maintain and control the flow of the bottom product (stream 8).
Table of different variables to be controlled in stripper:

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Manipulated Type of
Controlled Variable Instrumentation
Variable controllers
Temperature PID
Temperature Steam Flow in
Measurement
Bottom product flow P
Level Level Measurement
out
Bottom Product flow PI
Flow Flow Measurement
out

Considering equipment safety:


1. Pressure, temperature and flow measurements must be appropriately done and controlled
in design limits.
2. The level controller must be placed properly.

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5.3 CONTROL SYSTEM FOR DISTILLATION COLUMN

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Three distillation columns are being used in the process which is controlled by the following
scheme:
1. Pressure drop across the column is a crucial factor in the distillation. To maintain and
control it properly we employed PI controllers. The flow of feed stream and the flow of
steam in reboiler are controlled by this.
2. The flow of cooling water into the condenser is maintained and controlled via pressure
controller employed at the top.
3. Flow of top product (output from condenser) is maintained and controlled by using Flow
controller and reflux is maintained by using temperature controller (PID) which measures
the column temperature.
4. Ratio controller is employed to maintain and control the flow of bottom stream (24)
between feed stream and bottom stream.

Manipulated Type of
Controlled Variable Instrumentation
Variable controllers
Temperature Cooling water & steam PID
Temperature
Measurement flow in
Pressure drop P Measurement P across column PI
Pressure Pressure Measurement Cooling water flow in P
Flow of different PI
Flow Flow Measurement
streams
Ratio of feed & bottom Bottom product flow PI
Ratio controller (FFC)
product out
Considering equipment safety:
1. Pressure drop limits must be kept in mind by using PI controller.
2. Flow of cooling water must be controlled appropriately using Proportional controller for
pressure.
3. Advanced control strategies must be applied for required distillation like we are using ratio
controller (PI) between feed and bottom stream.
4. Reboiler must be controlled carefully to avoid accidents.

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5.4 CONTROL SYSTEM FOR TOTAL CONDENSER

Control scheme

1. Flow of the vapor product is maintained and controlled by pressure controller which is
measuring the pressure of stream coming from top of the column.
2. Flow of cooling water into the condenser is maintained and controlled by using temperature
controller which is measuring the temperature of recycle stream into the column.
3.
Manipulated Type of
Controlled Variable Instrumentation
Variable controllers
Temperature PID
Temperature Cooling water flow in
Measurement

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Vapor product flow P


Pressure Pressure Measurement
out

5.5 CONTROL SYSTEM FOR HEAT EXCHANGERS

Two types of advanced control strategies can be employed in designing the control system of a
heat exchanger:

Using feed forward controller

Type of Controlled Manipulated


Measurements
Controller Variable Variable
Feed Temperature
Temperature Steam inflow
Forward and Flow

Using feed backward controller

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Type of Controlled Manipulated


Measurements
Controller Variable Variable
Feed
Temperature Steam inflow Temperature
Backward

Considering equipment safety:


1. Control system for Maximum Pressure Drop can be in place as is in the case of Heat
Exchanger

2. The Maximum Pressure on the shell side is controlled by a simple feedback control using
a proportional controller.

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3.

6 SITE SELECTION AND PROJECT LAYOUT


6.1 SITE SELECTION
The feasibility of the plant & site selection is mainly based upon the following:-
1. Raw materials availability.
2. Markets.
3. Energy availability.
4. Climate.
5. Transportation facilities.
6. Water supply.
7. Waste disposal.
8. Labor supply.
9. Taxation and legal restrictions.
10. Site characteristics.
11. Flood and fire protection.

Based upon all the above factors, we have chosen Bharuch (SEZ), Gujarat as a potential site for
the project. Following are the names of leading suppliers for the raw materials in Gujarat
GACL (Gujarat Alkalies and Chemicals Limited)(for Propylene)
Vadilal Chemicals Limited-(for Propylene)
Ramdev corporation-(for Propylene)
Purnima metal and plastic works-(for Propylene)
Aerochem Industries, Ankleshwar-(for Ammonia)

Alternative sites may be Vadodara, Ahmedabad and Surat (Gujarat), but due to the
availability of SEZ (160 Ha) for chemicals in Bharuch and being a PCPIR (petroleum,
chemicals and petrochemicals investment region), it is the best suited for our project.
Advantage Gujarat
The advantages in selecting Gujarat as the site for the project are described below:
1. Raw material supply:

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As mentioned above, these all suppliers are situated in Gujarat, near our project site. The
availability of raw materials makes the selection of Bharuch as the project site very
obvious. Handling and transportation of the raw materials will be eased due to the lesser
distance between the supplier and project site.

2. Robust Infrastructure:
a. Dependable Power Supply: This factor is a key to industrial development. Present
power generation capacity of Gujarat is 9,628 MW, plans afoot to raise it to 25,000
MW by 2012. per capita power consumption is 1354 units against the national average
of 665 units. Also there is rich availability of natural gas (34 MMCD) and lignite (1,072
MMT) in Gujarat.

b. Transportation facilities: Total road length in Gujarat is 74,018 Km, whereas rail
length is 5,188 Km (8.25 % of India). 13 airports and 42 ports along 1,600 Km coastline
also make Gujarat as a favorite location for industries and businesses. Bharuch (itself
a large seaport city), situated between Vadodara and Surat, is well connected through
roadways, railways and airways.

c. Utilities: Bharuch has always been prosperous because of its location on the Narmada
River. Although water tends to be scarce in Gujarat, one never finds difficulty in getting
water in Bharuch. As a result of this, agriculture and other linked commercial activities
have flourished in Bharuch.

3. Initiatives by Government:

a. Licensing policy:
In Chemical sector, 100% FDI is permissible.
The entrepreneurs need tosubmit only IEM with the Department ofIndustrial
Policy and Promotion provided no locational angle is applicable.

b. Customs duty:
The peak rate of customs duty on most Chemicals is 7.5%.

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On basic raw materials like acid grade fluorspar. Sulphur. Rock phosphate,
natural borates is 5%.
On most building blocks and feedstock the duty is 5% (ethylene, propylene,
crude, naphtha, benzene, toluene, xylene, Ethyl benzene)
c. Excise duty:
On almost all chemicals the excise duty is 16%.

4. SEZ Advantage:
For SEZ units-
Income tax incentives: 10 year corporate tax holiday on export profit, 100% for the
initial five years and 50% for the next five years.
Other benefits:
o Exemption of electricity duty 10 Years.
o Duty-free procurement of capital goods (including second hand capital
goods), raw materials and consumable spares from domestic markets.
o Full freedom for sub-contracting.
o Facility to realize and repatriate export proceeds within 12 months.
o Facility to retain 100% foreign exchange receipts in the export earners
foreign currency account.
Indirect tax incentives (for both SEZ units & Developers):
o Nil customs duty.
o Nil excise duty.
o Exemption from central sales tax.
o Exemption from service tax.
o Exemption from securities transaction tax.
o Exemption from tax on sale of electricity for self generated and purchased
power.
Besides above, Gujarat has very Liberal labour policies for SEZ and also SEZ
Development committee monitors infrastructure development for each SEZ.

5. Global Competitiveness:

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The chemical industry in Gujarat is a significant component of the States economy,


contributing to more than 51% of Indian production of major chemicals with
revenues at approximately more than INR US$ 3 billion. Gujarat contributes 15%
of the total national chemical exports.
Petrochemical Industry in Gujarat produces 13.048 Million Tonnes of
petrochemical products and also contributes around 62% to the total production of
the country.
Bulk of the exports from this sector goes to markets such as USA, Europe and other
developed nations- a clear sign of the global competitiveness.
Gujarat has been the ideal destination for several leading MNCs including BASF,
Bayer, DuPont, GE Plastics, Cairn Energy, Solvay, Shell, British Gas, Perstrop,
Huber, Heubach Colours and Cheminova.

6. Market Advantages:
While the State chemicals industry exhibits several similarities to the global chemical
industry, there are several characteristics specific to the Gujarat across sub-segments. At
the industry level, Gujarat chemical industry is characterized by:
High domestic demand potential, as the Indian markets develop and per capita
consumption levels increase.
High degree of fragmentation and small-scale operations.
Limited emphasis on exports due to domestic market focus and smaller scale of
operation.
Low cost competitiveness as compared to other countries.

7. Quality Workforce and Educational Infrastructure:


Gujarat is also famous for its educational infrastructure and quality workforce.
Least man days lost due to industrial unrest.
Large pool of skilled technical personnel available.
39 engineering colleges offering courses in chemical Engg.

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49 Polytechnics offering diploma courses in chemical engineering (eg. K. J.


Polytechnic, Bharuch).

Figure 17 Location of Bharuch in Gujarat.

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Figure 18Locations of various industries in Gujarat.

Figure 19Dahej-Bharuch investment region

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6.2 PROJECT LAYOUT

PLANT LAYOUT CONSIDERATION


After selecting a site for the plant, plant layout is a crucial factor in the economics and safety of process
plant. Some of the ways, in which plant layout contributes to safety and loss prevention (SLP), & which
are included in the layout design are:

(1)Economic considerations: construction and operation cost.


(2) Segregation of different risks.
(3) Minimization of vulnerable pipe work.
(4) Containment of accidents.
(5) Limitation of exposure.
(6) Efficient and safe construction.
(7) Efficient and safe operation.
(8) Efficient and safe maintenance.
(9) Safe control room design.
(10) Emergency control facilities.
(11) Fire fighting facilities.
(12) Access for emergency services.
(13) Security.
(14) Future Expansion.
(15) Modular construction.

Our plant layout mainly includes the following buildings and construction as per the process requirements
and support activities:
1. Plant Area (including boiler house, pump house, cooling tower, water treatment plant etc.).
2. Power Plant.
3. Storage.
4. Repair & Maintenance Workshop.
5. Plant Utilities.
6. Loading Area (train, tankers, trucks etc.).
7. Stores.
8. R & D Centre.
9. Laboratories.

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10. Quality Control Wing.


11. Pollution Control Wing.
12. Fire & Safety Station.
13. Medical Centre.
14. Bank & Post Office.
15. Recreation & Staff Facilities.
16. Administrative Block.
17. Marketing Block.
18. Training Centre.
19. Petrol Pump.
20. Security Wing.
21. Canteen.
22. Parking (Light Vehicles & Heavy Vehicles)
23. Lawns & Fountains.
24. Green Belt Area.
25. Space for Future Expansion.

A site layout for the plant is provided on the next page. Considerations have been given for the future
expansions. Some area has been marked for Green Belt. Hazardous materials are kept at a safe distance
from the offices and other staff facilities.

DESCRIPTION:

6.2.1.1 Location of buildings


o Buildings which are the work base for a number of people should be located so as to limit their
exposure to hazards. Analytical laboratories should be in a safe area, but otherwise as close as
possible to the plants served. So should workshops and general stores. The main office block should
always be near the main entrance and other administration buildings should be near this entrance if
possible.
o Other buildings, such as medical centers, canteens, etc., should also be in a safe area and the latter
should have ready access for food supplies.
o All buildings should be upwind of plants which may give rise to objectionable features. Water drift
from cooling towers can restrict visibility and cause corrosion or ice formation on plants or
transport routes, and towers should be sited to minimize this.

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o Another problem is recycling of air from the discharge of one tower to the suction of another, which
is countered by placing towers cross-wise to the prevailing wind. The entrainment of effluents from
stacks and of corrosive vapors from plants into the cooling towers should be avoided, as should the
siting of buildings near the tower intakes.
o The positioning of natural draught cooling towers should also take into account resonance caused
by wind between the towers. The problem of air recirculation should also be borne in mind in siting
air-cooled heat exchangers.

6.2.1.2 Economic Considerations


o The cost of construction can be minimized by adopting a layout that gives the shortest run of
connecting pipe between equipment, and the least amount of structural steel work. However, this
will not necessarily be best arrangement for operation and maintenance.
o Some features which have a particularly strong influence on costs are foundations, structures,
piping and electrical cabling. This creates the incentive to locate items on the ground, to group
items so that they can share a foundation or a structure, and to keep pipe and cable runs to a
minimum.

6.2.1.3 Safety Considerations


o Plants which may leak flammables should generally be built in the open or, if necessary, in a
structure with a roof but no walls. If a closed building cannot be avoided, it should have explosion
relief panels in the walls or roof with relief venting to a safe area. Open air construction ventilates
plants and disperses flammables but, as already indicated, scenarios of leakage and dispersion
should be investigated for the plant concerned.
o Fire spread in buildings should be limited by design, as should fire spread on open structures.
Sprinklers and other protective systems should be provided as appropriate. Plants which may leak
toxics should also generally be built in the open air. The hazardous concentrations for toxics are
much lower than those for flammables, however, and it cannot be assumed that an open structure
is always sufficiently ventilated.
o Ventilation is necessary for buildings housing plants processing flammables or toxics. Air inlets
should be sited so that they do not draw in contaminated air. The relative position of air inlets and
outlets should be such that short circuiting does not occur. Exhaust air may need to be treated before
discharge by scrubbing or filtering.
o Blast walls may be needed to isolate potentially hazardous equipment, and confine the effect of the
explosion. At least two escape routes for operators must be provided from each level in the process
building.

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6.2.1.4 Operations
o Access and operability are important to plant operation. The routine activities performed by the
operator should be studied with a view to providing the shortest and most direct routes from the
control room to items requiring most frequent attention.
o Equipment that needs to have frequent operator attention should be located convenient to the
control room. Valves, sample points and instruments should be located at convenient positions and
heights. Sufficient working space and headroom must be provided to allow easy access to
equipment.
o Good lighting on the plant is important, particularly on access routes, near hazards and for
instrument reading. Operations involving manipulation of equipment while observing an indicator
should be considered so that the layout permits this.

6.2.1.5 Maintenance
o Maintenance costs are very large in the chemical industry. In some cases the cost of maintenance
exceeds the companys profit. The engineer must design to reduce these costs.
o Heat exchangers must be sited such that tube bundle can be easily withdrawn for cleaning and tube
replacement.
o Vessels that require frequent replacement of catalyst or packing should be located on the outside
of the building.
o Equipment that requires dismantling for maintenance, such as compressors and large pumps, should
be placed under cover.

6.2.1.6 Modular Construction


o For convenience of efficient management the whole plant is assembled section wise at the plant
manufacturers site in the form of modules. These modules will include the equipment, structural
steel, piping and instrumentation. Modules are then transported to the plant site, by road or sea.

6.2.1.7 Future Expansion


o We know that technology is improving day by day. Thats why keeping future expansion in mind,
equipment should be located so that it can be conveniently tied in with any future expansion of the
process.

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Figure 20 Plant layout.

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7 PLANT UTILITIES

Air for process and instrumentation


AIR:
Dry air is required for instrumentation systems, for nitrogen supply and as plant air.
The specifications for plant air are:
Flow: 800 N/M3
Pressure: 8KG/cm2
Temperature: Ambient
Dew point: 20 C below ambient
Specifications for instrument air are:
Flow: 400N/M3
Pressure: 5KG/cm2
Temperature: Ambient
Dew point: -400 C below ambient
AMBIENT AIR QUALITY STANDARDS (NATIONAL)-INDIA
Time Concentration in ambient air
weighted
Industrial Residential Sensitive
Pollutants average Areas Rural & other Areas
Areas

Sulphur Dioxide (SO2) Annual 80 g/m3 60 g/m3 15 g/m3


Average
24 hours** 120 g/m3 80 g/m3 30 g/m3

Oxides of Nitrogen Annual 80 g/m3 60 g/m3 15 g/m3


Average
NO2 24 hours 120 g/m3 80 g/m3 30 g/m3

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Suspended Particulate Annual 360 g/m3 140 g/m3 70 g/m3


Matter (SPM) Average*
24 hours** 500 g/m3 200 g/m3 100 g/m3

Respirable Particulate Annual 120 g/m3 60 g/m3 50 g/m3


Matter (RPM) (size less Average*
than 10 microns)
24 hours** 150 g/m3 100 g/m3 75 g/m3

Lead (Pb) Annual 1.0 g/m3 0.75 g/m3 0.50 g/m3


Average*
24 hours** 1.5 g/m3 1.0 g/m3 0.75 g/m3

Ammonia (NH3) Annual 0.1 mg/m3 0.1 mg/m3 0.1 mg/m3


Average*
24 hours** 0.4 mg/m3 0.4 mg/m3 0.4 mg/m3

Carbon Monoxide (CO) 8 hours** 5 mg/m3 2 mg/m3 1.0 mg/m3

1 hour 10 mg/m3 4 mg/m3 2 mg/m3

*Annual Airthmetic mean of minimum 104 measurements in a year taken twice a week 24
hourly at uniform interval.
**24 hourly/8 hourly values should be met 98% of the time in a year. However, 2% of the
time, it may exceed but not on two consecutive days.

Nitrogen
We require nitrogen for production of acrylonitrile. The nitrogen specifications for plant
nitrogen are:
Hydrogen: 5 10 N/M3
Oxygen: 20ppm

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Carbon monoxide: nil


Carbon dioxide: <20ppm
Nitrogen + Argon: balance
Dew point: -55 at atm. pressure
Pressure: 7.0kg/cm2
Temperature: ambient

Heat Transfer Media

Liquids and solids are used to transport heat and give it up to process require a unique combination
of properties.
In this acrylonitrile plant we are using steam and water as a heat transfer media.
Their properties are given below:
Fluid Temperature,0F Pressure,lb./in2.gauge
Steam 200-1100 0-4500
Water 300-1100 90-2300

Steam

Steam is vaporized water. It is a transparent gas. At standard temperature and pressure, pure steam
(unmixed with air, but in equilibrium with liquid water) occupies about 1,600 times the volume of
an equal mass of liquid water. In the atmosphere, the partial pressure of water is much lower than
1 atm, therefore gaseous water can exist at temperatures much lower than 100 C (212 F) (see
water vapor and humidity).

In common speech, steam most often refers to the visible white mist that condenses above boiling
water as the hot vapor mixes with the cooler air. This mist consists of tiny droplets of liquid water.
Pure steam emerges at the base of the spout of a steaming kettle where there is no visible vapor.

Detailed Specifications

Product Steam
CAS# Not applicable
RTECS 1003161VN
Synonyms vapor, condensation, mist, haze, fog .

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Molecular Formula Steam is essentially water in a gas-like state


Molecular Weight 18.02
UN Number 2735

Physical Properties

Property Value
Molecular Weight 18.02
Freezing Temperature -25 0C
Boiling Point Above 1000C
Critical Temperature 3740C
Critical Pressure, bar 220.6
Critical Volume, m3/kmol 323.82
Compressibility at 400 K 0.988970
Liquid Density,at 400 K,kg/m3 0.554985
Dipole Moment,10-3 1.69 D
Standard Enthalpy of Formation J/kg 2.72995E06
Heat of Vaporization at bp, J/kg.K 1499.84
Refractive index 1.330
Hazardous decomposition products Hydrogen peroxide (H2O2), magnesium
hydroxide,
Hazardous Polymerization Will not occur

Benefits

Steam Baths - Special Benefits A steam bath is excellent for respiratory ailments since
steam can remove allergens and mucus from the lungs.
Doctors have been advising that patients breathe steam
for various respiratory problems for a long time now. The
steam bath allows the user to inhale a larger concentration
of steam than by using a vaporizer. This allows maximum
benefits to those with breathing problems.

Steam has a soothing quality for the breathing passages


since it raises the moisture level in the lungs, throat and
nose. People that suffer from the problems of asthma or
the common cold will find they feel much better after
indulging in a steam bath.

No matter how good the sauna bath might feel by


relieving symptoms it is not cure for respiratory diseases.

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The temporary benefits of relief from the symptoms are


good enough that many sufferers go back to the steam
bath again and again.

Skin Benefits . A good sweat is excellent for healthy skin.


Dermatologists understand the benefits of steam to create
a beautiful, healthy glow. Serious sweating washes the
skin better than soap and water since it unlocks the pores
and lets deep-seated grime along with dead cells to be
washed out. Also a steam bath increases the blood
circulation to the skin contributing to a healthy, glowing
manifestation, you will glisten!
Pain Relief Benefits Heat is a useful tool for management of muscular pain.
Taking a steam bath after a substantial bodily workout is
an excellent method of speeding up the healing
progression of hurt tissues and muscles. Heat allows the
blood vessels to enlarge which boosts the blood
circulation, letting increased oxygen to arrive at injured
parts of the body. This has the twofold effect of pain
reduction and improving the healing speed.
Relaxation Benefits Deep sleep is one of the best medicinal ways to heal the
body. Our contemporary life is filled with daily stresses,
and these stresses will build up over time and can induce
stress linked illnesses such as high blood pressure and
hypertension. A sauna bath is a excellent method of
unwinding and help relieve the daily stresses. The heat of
the sauna allows the muscles to loosen up, and the steam
makes available a comforting atmosphere for calming the
mind.
Method of Testing

Dryness Value Test:

Wet steam is undesirable as it has less energy than dry steam and more importantly can cause wet
loads. The packaging used for sterile products prevents reinfection when dry, but its bacterial
retentive properties will be adversely affected by the presence ofmoisture . Wet loads can be
considered to be un-sterile. The dryness fraction describes how dry steam is, with a value of 1
representing steam that is 100% dry, and therefore free of entrainedmoisture . Steam with a dryness
fraction of 0.99 consists of 99% steam and 1% water. If we measure the latent heat present in steam
that has a dryness fraction of 0.99 we will find that it possesses 99% of the full quotient of latent
heat.

Bring Pure Steam Testing In House:

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The draw back to carrying out steam quality testing has always been the lack of the correct Pitot
and Expansion Tubes, along with difficulty of generating a quality protocol for qualification
purposes. Now these excuses are gone, a quantity of the tubes have been manufactured to a tried
and tested design, and are now in stock. The Pure Steam Quality protocol is also available for
direct download. This document is not a template, it is a finished document. There is a prefixed S
OP which will auto populate the document for you, with your companys names and addresses,
other than that the document is ready to execute.

Steam Quality:

A continuous supply of saturated steam is required for steam sterilization and for humidification
in certain EO sterilizers. Too high a level of non condensible gases will prevent the attainment of
sterilization; too littlemoisture carried in suspension may allow the steam to become superheated
during expansion into the chamber, while excess moisture may cause damp loads. Where steam
systems are either routinely or irregularly shut down, large quantities of air will be present in the
distribution system on restarting. It is recommended that in such circumstances a comprehensive
and validated venting procedure should be applied and testing for steam quality is appropriate.

Water
PROCESS AND GENERAL WATER REQUIREMENT AND STANDARDS:
The principal uses of water in industry are:
1. For steam raising, the steam being used for electrical or mechanical power generation,
heating, or chemical reaction.
2. As a cooling medium
3. For hot water supply and hot water heating systems.
4. As a solvent and reactant in chemical process.
5. As a suspending medium in process of mechanical separation such as coal washing.
6. For drinking.

Process and general water requirement and standards.


1. COOLING WATER:
Cooling water is used to cool acrylonitrile and other products.The specification for cooling
water are as follows.

Total hardening as CaCO3 21mg/l

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M alkalinity as CaCO3 11mg/l


P alkalinity as CaCO3 2mg/l
Free carbon dioxide nil
Free acid as CaCO3 nil
Fluoride 4mg/l
Sulfates 8mg/l
Iron 2mg/l
Copper 1mg/l
TDB 11mg/l
pH 9.3
Cooling water supply temp. 250C
Cooling water return temp. 500C
Supply pressure 4.5kg/sp.cm

2. PROCESS WATER:
The process water is required in acrylonitrile plant as a solvent. Specification for cooling
water are as follows:

M alkalinity as CaCO3 93mg/l


P alkalinity as CaCO3 0mg/l
Chloride 51mg/l
Calcium as CaCO3 135mg/l
Magnesium as CaCO3 53mg/l
Hardness as CaCO3 188mg/l
Sodium 29mg/l
Silica 7mg/l
Nitrate 13mg/l
Sulfates 97mg/l
TDS 315mg/l
pH 6.5

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BOILER FEED WATER: The specification of boiler feed water are:


Iron: 0.1ppm
Hardness: less than 0.2ppm
Copper: 0.05ppm
Caustic alkaline: 0.15-0.45ppm
Soda alkaline: 0.45-1ppm
Excess soda ash: 0.3-0.55ppm

WATER TREATMENT AND STORAGE FACILITIES:


Water treatment is done through a process involving ion exchange resins. The feed water is
supplied through bore wells, filtered and then send to cation exchange unit. After being d-gasified,
it is sent to anion exchange unit and then utilized.The ion exchange resins are dispatched in most
conditions in drums and are to be stored as such. The vessel should not be kept drained for long as
it may cause resin to dry up. The resins are to be regenerated using acids and bases.
EQUIPMENT REQUIRED:
Boiler feed water treatment unit:
S.No. Description Size/capacity Quantity

1. Storage tanks 5m*5m*2m 4

2. Weak acid cation unit 1

3. Strong acid cation unit 1

4. Strong base cation unit 1

5. Degasser 1

6. Pumps 0-100ppm 4

Refrigeration
The basic application of refrigeration systems includes air conditioning, which is dominating by
centrigugal and reciprocating water chillers. Centrifugal water cillers (CWC) are high capacity

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2000 tons satisfy most requirements. CWC are used normally if electric power is utilized and
tonnage is greater than 100 tons.
The types of machines available are:
1. Direct-drive, two stage,hermetic balanced thrust.
2. Direct-drive,two stage,hermetic with in-line impellers.
3. Direct-drive,single stage,high speed,hermetic.
4. Gear-drive,single stage,high speed,hermetic.
5. High speed,single stage,hermetic,high frequency.
6. Open design,external drive, either single or two stage,either direc or gear drive.

The electric, ermetic, CWC direct drive design has proved itself to be one of the most reliable
piece of air conditioning equipment. In this CWCs have automatic capacity modulation through
the use of inlet guide vanes.The compressor operates by utilizing an impeller,which imparts
velocity energy to refrigerant gas. The velocity energy is converted into pressureenergy in the
diffuser section of the compressor.The inlet guide vanes can vary the machine capacity by
simultaneously throttling and causing a pre-rotation of the gas that enters the impeller.The pre
rotaion of the gas causes the relative between the gas and impeller inlet to be less, and
consequently, the impeller picks u less gas. The tonnage is roughly proportional to the volume
handled.
Design capacity for comfort cooling is usually determined by a method of heat load calculations.
The design capacity for the refrigeration equipment is based on the maximum load in tons that
occurs at a specific time in the operation of the equipment.Since, for industrial process the
equipment requirements vary greatly, selection is based on meeting a predetermined tonnage or
Btu.
An economical selection of condenser-water supply must be made from several available
sources.Among many sources, any low temperature city or well water can be economical.An
economical balance between cost of water and that of electric power must be found to arrive at
lowest overall cost.Cooling towers are normally the most popular condenser water source.
Air conditioning:
General requirements:
Necessary consideration while designing an environmental control system are ventilation
requirements, adequacy of controls,minimizing the other contaminants, freeze protection and good
air distribution.
Clean air requirements:
The definition of air conditioning is said to encompass cooling,dehumidification and air
cleaning.Atmosphere dust to be removed by air filter can be reports in three different ways.

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1. On weight basis
2. By area
3. By count

Ventilation requirements:
It is done by reduce body odors and maintaining comfortable conditions.It is concerned with
control of dust,fumes,vapors and gases.
Air distribution requirements:
Distribution of air is specific to an application. The application may include from general
ventilation,spot cooling,make up air and dilution ventilation.The equipments include
diffusers,which come in many types and sizes.The selection depends upon the particular
application.Which causes warm air to fall quickly in the coling season,causing drafts.

Electricity

The power required for the chemical process I motor drives,lighting and general use,may be
generated on site,but will more usually be purchased from the local supply company and state
grid.It may be possible to obtain steam for processing and heatins as a byproduct from the self-
generation of electricity, and this factor may influence the final decision. In some cases, it may be
justified to provide power to the plant from two independent sources to permit continued operation
of the plant facilities if one of the power sorces fails. The voltage at which the supply will be taken
at very high voltage, typically 11000 or 33000 V.Transfrmers will be used to step down the supply
voltage to the voltage used on site.

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8 ORGANIZATIONAL STRUCTURE AND MANPOWER


REQUIREMENT

8.1 ORGANIZATIONAL STRUCTURE

The main purpose of this selection is to establish a suitable framework within which the employees
can function. Design of such an appropriate structure for the organizational channels the effort of
the members towards the goal concordant with the company policy.
In this section we:
Define an organization
Take a look at the various factors desirable in organizational structure.
List the advantages and disadvantages of common organizational structure.
Keep in mind the needs of an entrepreneur and suggest the best organizational structure
available to him, and show the possible organizational structure the company may take as
it grows.

INTRODUCTION
An organization is a system of roles designed to accomplish shared purposes. Selecting an
organizational structure is not a simple matter of applying a few well known universal principles.
The organization structure factors such as:
Activity
Authority
Accountability
Responsibility
Power and
Communication

But an organization that works well in one type of environment (environment being defined as a
combination of markets, customers products and technologies) may fail miserably in another. This
failure may arise due to contingency factors, which are:
Take uncertainty, technology and environment.
Power and conflict
Growth and size
Goals and effectiveness

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Here task uncertainty ids the degree to which information necessary for the performance is
unpredictable. Technology and environment are the source of this unpredictability. An
organization structure that works well in an industry, technology and market demand & does not
change rapidly would not go well in an industry where innovations are rapid.
Organization structures should manage conflicts so that it help the industry rather than tear it apart.
It is helpful to understand the basic determinants of power in an organization and how conflict and
power are related.
Having sated that organizations are desired to accomplish shared purposes we must understand
how these goals are formed and the implications of multiple goals for organizational effectiveness.
No single criteria for effectiveness can be found.
Organizational effectiveness includes at a minimum the following criteria:
Organizational efficiency
Adaptability to external changes
Satisfaction of individual needs.

DIVISIONS OF ORGANIZATIONS
Keeping the above factors in mind the organization can be divided into the following categories.
1. General Administration
2. Production Division
3. Marketing Division
4. Personnel Division
5. Technical Services Division

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Figure 21 Organizational structure.

8.2 MANPOWER REQUIREMENT

1. General Administration:

The general Manager heads the factory organization. He has to perform the following duties:
Administration of various Departments.
To ensure smooth running of the factory with the maximum profits.
To plan and implement diversification programs.
To take prompt and important decisions so as to simplify the execution of work.

2. Production Division:

A production manager assisted by a Plant Superintendent heads the department. He is a technical


man and is responsible for the overall production and smooth running of the plant. This division
is divided into a few subdivisions. Skilled personnel such as engineers look after the functioning
of the plant.
3. Marketing Division:

The Marketing Manager heads this division. He is responsible for developing new marketing
strategies and also publicity, advertising and sales of the product.

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4. Commercial Division:

A Commercial Manager is in charge of this section. He is supreme controller of accounts and


budgeting. The Chief Accountant and his staff assist him in his work.
5. Personnel Division:

It is headed the Personnel officer. He is concerned with overseeing recruitment, training, welfare,
medical facilities and an overall maintenance of harmony within the employees of the
organization.
6. Technical Service Department:

This department offers technical services and expertise to the production and maintenance
department. It is engaged in R&D and providing innovative solutions.
7. Staff and Labor

Staff and labor can be divided into:


Technical: Skilled (Engineers)
Unskilled (operators)
Non Technical

Every chemical industry requires a proper mixture of both to ensure the smooth operation of the
plant. The Vessels rule and the rule of the thumb are two methods that have been suggested to
determine the labor requirement.
The table, which follows, gives the requirement of the staff, their salaries and experience as
required for the setting up our Acrylonitrile manufacturing plant.

DESIGNATION NO. QUALIFICATIONS EXPER- SALARY


IENCE (Rs. Month)
(year)
1.General Manager 1 B.Tech & M.B.A.(Chemical) 20 1,20,000/-

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2.Research and Development


Superintendents 4 B.Tech, M.Tech, 10 1,00,000/-
Ph.D.(chemical)
5 75,000/-
Chemists 5 B.Tech, M.Tech (chemical)
3.Training
Personnel Officers 4 M.B.A. 10 75,000/-
4 B.Tech (chemical) 5 50,000/-
Training Officers
4 M.A. (public relations) 5 35,000/-
Labor Officers

4.Maintenance Division
Supervisors 5 B.Tech (chemical) 10 75,000/-
Maintenance 15 B.Tech (mechanical) 5 50,000/-
Engineers
Electrical Engineers 15 B.Tech (Electrical) 5 50,000/-
labor 30 Middle School 10 20,000/-

5.Administrative Division
Administration 4 B.Tech (chemical), M.B.A. 10 90,000/-
Officers 4 Private Group Officers 5 25,000
Security Officers
Medical Officers 4 Graduate 10 35,000
Other staff 25 M.B.B.S., M.D.Graduate 2 75,000

6.Production Division
Manager 1 B.Tech (chemical),M.B.A. 15 1,00,000/-
Plants Divisional 5 B.Tech, M.Tech (chemical) 10 75,000/-
Incharge
Production Engineers 15 B.Tech(chemical) 5 50,000/-

7.Marketing Division
Manager 1 M.B.A. 15 1,00,000/-
Personnel 10 M.B.A. 5 50,000/-
Staff

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25 Graduate(B.Com,M.Com) 2 25,000/-

8.Accounts
Commercial Manager 1 B.Tech (chemical) M.B.A. 15 1,00,000/-
Chief Accountants 5 C.A. 10 75,000/-
Accountants
Clerks 10 B.Com,M.Com 5 35,000/-
25 Graduate 2 25,000/-
9.Technical Services
Department
1 B.Tech, M.tech. Ph.D(chemical) 10 1,00,000/-
Chief Chemist
15 M.Sc. Ph.D(chemistry) 5 50,000/-
Chemists
Project Engineers 15 B.Tech,M.tech(chemical) 5 50,000/-
Staff 20 M.Sc (chemistry) 2 25,000/-
10.Canteen Services
Incharge 1 Graduate 5 20,000/-
Labor 15 Middle School 2 10,000/-
11.Technical library
Librarian 1 Post Graduate(Library Science) 4 20,000/-
Staff 5 Graduate 1 7,500/-

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9 ECONOMIC EVALUATION & PROFITABILITY


Project cost evaluation:
Assumption: Plant is running at its installed capacity.
METHODOLOGY OF CALCULATION:
Cost of various equipments for a suitable base capacity will be determined from the graphs and
nomographs available in literature ,in case of non-availability of existing costs .Cost will be
determined using capacity exponent method .From this cost (i.e. calculated for the base year) using
Marshall and Swift index ,and the dollar to rupees conversion rate ,the present cost of equipment
will be calculated.
General strategy is as follows:
Capacity of equipment b = Cost of equipment a (Capacity of equipment a Capacity of
equipment b)m
Where m = capacity exponent
For Heat Exchanger:
Cost = Base cost of the equipment M & S Index (Present)/ M& S Index (Base) (capacity b/
capacity a)m
Total cost = overall correction factor cost
For tower and drums:
Cost = cost of the equipment M & S Index (Present) / M &S Index (Base)
Data Used:
Marshall & swift equipment cost index
1514.3
2015
Marshall & swift equipment cost index
1300
2007

9.1 ESTIMATION OF EQUIPMENTS COST

Table 17Cost of Equipments


COST (MM $) COST (MM $)
EQUIPMENTS
2002 2010
Propylene Tank(ST 101) 0.257 0.968
Ammonia Tank (ST102) 0.200 0.754

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Reactor (RT 101) 0.100 0.376


Heat Exchanger (HX 101) 0.024 0.090
Heat Exchanger (3) (HX 102 to HX
104) 0.071 0.270
Neutralizer (NE 101) 0.045 0.169
Gas absorber (AB 101) 0.039 0.146
Stripper (ST 101) 0.099 0.374
HCN removal tower (DC 101) 0.034 0.129
Azeotropic distillation tower (DC
102) 0.054 0.205
Acrylonitrile column (DC 103) 0.112 0.421
Condenser (HE 101 to 103) 0.071 0.270
Reboiler (HE 101 to 103) 0.071 0.270
Acrylonitrile Storage tank(ST 103) 0.120 0.452
Pumps 0.040 0.151
Compressors 0.100 0.377
TOTAL 1.438 5.420

9.2 ESTIMATION OF DIRECT & INDIRECT COST

Table 18 Direct & Indirect costs


COMPONENTS COST (million $)
DIRECT COST
Purchased equipment, E 5.420
Purchased equipment installation, 47%E 2.547
Instrumentation and control,18% E 0.976
Piping (Installation), 66% E 3.577
Electrical, 11% E 0.596
Building, process & auxilary, 40% E 2.168
Yard Improvement, 10% E 0.542
Service facilities,70% E 3.794
Land, 6% E 0.325
Total direct cost (DC) 19.946

INDIRECT COST
Engineering and supervision,10% DC 1.995
Construction expenses & Contractor's fee, 18% DC 3.590

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Contingency, 12% DC 2.394


Total indirect cost 7.978
Fixed capital investment (FCI) 27.924
Working capital, 15% FCI 4.93

Total capital investment, (TCI) 32.852


Depreciable fixed capital investment 27.924

9.3 ESTIMATION OF TOTAL PRODUCT COST


Financial aspects:
Assumption taken for calculation of product include the following
1) Personnel cost includes executives and clerical salaries, operating, supervision and labor
expenses.
2) Maintenance & repair charges are taken as 5% of the fixed capital investment.
3) Operating supplies cost are taken as 15% of Maintenance & repair charges.
4) For the calculation of depreciation, straight-line method is used and salvage value is taken
as zero .Plant life has been assumed to be of 20 years.
5) Local taxes (Property) are taken as 1% of the fixed capital investment.
6) Insurance charges are taken as 0.5% of the fixed capital investment.
7) Plant overhead cost is taken as 10% of the total raw material cost.
8) Rent is taken as 10% of the rented land & building.
9) Operating labour cost is taken as 12% of the total product charges.
10) Direct & clerical labour cost is taken as 12% of the operating labour cost.
11) Utilities cost is taken as 12% of the total product charges.
12) Laboratory charges are taken as 15% of the operating labour.
13) Plant overhead cost is taken as 13% of the total product charges.

Total product cost = Total manufacturing cost + General expenses.

MANUFACTURING COST

Table 19 Manufacturing costs


COMPONENTS COST (Million $)
Local taxes, 1% FCI 0.279
Insurance, 0.5% FCI 0.14
Depreciation 0.915

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Total fixed charges 2.064


Total product charges, TPC 13.761
Operating labour, 12% TPC 1.651
Direct supervisory & clerical labour, 12% OL 0.198
Utilities, 12% TPC 1.651
Maintainence & Repair, 5% FCI 1.396
Operating supplies cost, 15% M&R 0.21
Laboratory charges, 15% OL 0.248
Plant overhead cost, 13% TPC 1.789

Table 20 Raw material costs

Raw Material Cost


Component Cost( $/kg) Amount(kg/annum) Total Cost (Million $)
Propylene 0.6 6721010.065 4.03
Ammonia 1 2720028.55 2.72
TOTAL 6.75

Total manufacturing cost = Direct production cost + fixed charges + Plant overhead cost
= 12.104+1.334+1.789
= 15.227 Million $
= 978.639 million Rs

GENERAL EXPENSES

Table 21 General expenses


NATURE OF EXPENSES COST (million
$)
Administrative costs, 5% TPC 0.688
Distribution & marketing cost, 15% 2.064
TPC
Research & Development cost, 5% 0.688
TPC
Financial (Interest), 7% FCI 1.955
TOTAL 5.395

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TOTAL PRODUCT COST


Total Product cost = Manufacturing cost + General expenses
= 15.227 + 5.395
= 20.622 Million $
= 1325.376 Million Rs

TOTAL INCOME
We fix the selling price of the product according to current market price which is at $6/kg.

Table 22 Income & Profit data


Selling price($/kg) 6
Gross sale (tonnes/yr) 4100
Total Income(Million $/yr) 24.6
Gross profit (Million $/yr) 3.978
Income Tax rate 35%
Income tax (Million $/yr) 1.392
Net profit after tax (Million $/yr) 2.586

9.4 RATE OF RETURN


Rate of return after tax = net profit after tax / Total capital investment 100
= 7.87%

9.5 PAYBACK PERIOD


Payout period = Depreciable fixed capital investment / (Profit / yr + Depreciation / yr)
= 7.976 years

9.6 IMPLEMENTATION SCHEDULE

The land is acquired approximately 2 years before the time when production is expected to
start.The development of the land will take approximately two months after which the equipment
erection work will start .The total time for the erection of the plant and consequent commissioning
is expected to be 2 years after which production will start.
Since all the equipments required for the plant are indigenous, the orders for the same shall be
placed about 1 year before they have to be erected in the plant.

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The recruitment of labour and personnel of the plant will start about 2 months before the plant is
to be commissioned.

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10 MATERIAL STORAGE, HANDLING & SAFETY


10.1 PROPYLENE

Hazard identification

HMIS Ratings:

Health: 2
Fire: 4
Physical Hazard: 1
Personal Protection: chemical goggles ,gloves, respirator
NFPA Ratings:

Health: 2
Fire: 4
Reactivity: 1
Emergency Overview:

Propylene is Extremely flammable liquefied gas. It is a colorless liquefied gas with a sweet
hydrocarbon odor. Propylene is highly volatile, when released it will disperse as a highly
flammable vapour cloud. Consider need for immediate emergency isolation and evacuation.
Vapors are heavier than air and may travel along ground to some distant source and flash back.
Do not attempt to extinguish a gas fire unless leak source can be isolated and shut off.
Contact with liquefied gas may cause frostbite. Excessive inhalation of this material causes
headache, dizziness, nausea and loss of coordination and in extreme conditions coma and possibly
death.
Potential Health Effects:

Eye: Contact of the eye with the liquefied gas may cause severe injury or frostbite. Gas may be
mildly irritating.

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Skin: Contact of the skin with the liquefied gas may result in frostbite and blistering. Gas
may be mildly irritating .Product does not penetrate through the skin.
Ingestion: Ingestion of this product is extremely unlikely. However, contact of the mouth
or throat with the liquefied gas may result in serious injury or frostbite.
Inhalation: It is a mildly narcotic asphyxiant gas that can cause unconsciousness/death if
OXYGEN levels are sufficiently reduced. Excessive inhalation of this material causes headache,
dizziness, nausea and loss of coordination, and in extreme conditions coma and possibly death.
High concentrations may trigger heartbeat irregularities, and possible cardiac sensitization.

Handling And Storage

Handling Procedures:

Keep locked up or secured. Handle in fully enclosed, grounded, properly designed and approved
flammable gas systems. Use with adequate ventilation. Avoid inhalation. Keep away from
uncontrolled heat and incompatible materials. Ground all material handling and transfer
equipment to dissipate build-up of static electricity. Wear suitable protective equipment including
thermally protective gloves. No smoking or open flames permitted in storage, use or handling
areas. Check for accumulation of liquids when breaking into pipelines.
Storage Procedures:

Storage area should be clearly identified, well illuminated, clear of obstruction and accessible
only to trained and authorized personnel. Store in grounded properly designed and approved
pressure containers and away from incompatible materials. Store and use away from heat, sparks,
open flame, or any other ignition source. Store according to applicable codes or regulations for
liquefied pressurized gases as applicable to cylinders, vessels ,piping, buildings, rooms, cabinets,
allowable quantities and minimum storage distances. Have appropriate extinguishing capability
in storage area (e.g. sprinkler system, portable fire extinguishers) and flammable gas detectors.
Keep cylinders secure while in storage or in transportation.

Toxicological Information

Acute Toxicity - General Product Information

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Similar hydrocarbon mixtures were tested under the EPA's High Production Volume (HPV)
Chemical Challenge Program. Propylene has been tested under the HPV test plan for the Olefins
Panel of the ACC Propylene Streams Category. Based on testing, propylene has a low order of
acute toxicity. Inhalation of propylene can produce narcosis and anesthesia; however, these
effects are only seen at very high concentrations (reports indicate >46,000ppm to induce narcosis
in humans). Excessive exposures may cause headache, dizziness, nausea, loss of coordination,
and in extreme conditions, coma and possibly death. High concentrations may trigger heartbeat
irregularities and possible cardiac sensitization. In the gaseous state propylene is not expected to
be irritating to the skin or eyes. However, should skin or eye contact occur with this product in
its liquid state ,tissue freezing ,severe cold burns, and/or frostbite may result.
Acute Toxicity - LD50/LC50

Propylene (115-07-1)
Inhalation LC50 Rat: >65,000 ppm/4H
Propane (74-98-6)
Dermal LD50 Rat: >800,000 ppm/4H
Chronic Toxicity - General Product Information

Similar hydrocarbon mixtures were tested under the EPA's High Production Volume (HPV)
Chemical Challenge Program. Propylene has been tested under the HPV test plan for the Olefins
Panel of the ACC Propylene Streams Category. Repeated exposure to propylene produces no
clinical effects in animals exposed to concentrations up to 10,000 ppm, one half of the lower
flammability limit, for 103 weeks. In the nasal cavity ,propylene induced nasal lesions of
relatively mild nature and relatively few animals were affected. Results indicated no carcinogenic
effects found. A weak mutagenic response was observed with Salmonella typhimurium strains
TA1535 exposed to propylene in the presence of S9 mix but not in the absence of S9. It was not
mutagenic in the other Salmonella strains (TA100, TA98 and TA1537) or in E.coli WP2uvrA
(pKM101). Propane was negative for mutagenicity when tested in the in vitro Ames assay in five
strains of Salmonella typhimurium.
Chronic Toxicity - Carcinogenic Effects

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ACGIH, EPA, IARC, OSHA, and NTP carcinogen lists have been checked forselected
similar materials or those components with CAS registry numbers.
Propylene (115-07-1)
ACGIH: A4 - Not Classifiable as a Human Carcinogen
IARC: Monograph 60 [1994]; Supplement 7 [1987] (Group 3 (not classifiable))
Special Remarks on Other Toxic Effects on Humans

Propylene that is inhaled is largely exhaled unchanged. A small fraction may be metabolized and
transported in blood as propylene oxide. There is no known health effect found to be associated
with this metabolism in 2-year cancer studies or in studies of potential adverse genetic effects.

FIRE FIGHTING

Conditions of Flammability: Flammable liquid and vapor


Flash point: Method: Autoignition
o
-162 F (- TCC Temperature: 927oF (460oC)
o
108 C)
LEL(%): 2.0 UEL(%): 11.1
Hazardous combustion products: Carbon monoxide, Carbon dioxide
Sensitivity to mechanical shock: None
Sensitivity to static discharge: Not Available

FIRE AND EXPLOSION HAZARDS:


This product will ignite at ambient temperatures and can be expected to form a flammable mixture
upon release to the atmosphere. May burn with an almost invisible flame in bright light.

EXTINGUISHING MEDIA:
Water, carbon dioxide, dry chemical.

FIRE FIGHTING INSTRUCTIONS:


If possible, stop the flow of gas with a remote valve. Use water spray to cool fire exposed
containers. If fire is extinguished and flow of gas is continued, increase ventilation to prevent a
build up of a flammable/explosive atmosphere. Extinguish sources of ignition. Be cautious of a
Boiling Liquid Evaporating Vapor Explosion, BLEVE, if flame is impinging on surrounding
containers. Direct 500 GPM water stream onto containers above the liquid level with remote
monitors. Limit the number of personnel in proximity to the fire. Evacuate surrounding areas to
at least 3000 feet in all directions.

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First Aid Measures

EYES:
Never introduce oil or ointment into the eyes without medical advice! If pain is present, refer the
victim to an ophthalmologist for further treatment and follow up.

SKIN:
Remove contaminated clothing and flush affected area with cold water and soap. DO NOT USE
HOT WATER.

INGESTION:
Not normally required. Seek immediate medical attention.

INHALATION:
Prompt medical attention is mandatory in all cases of overexposure to product. Rescue personnel
should be equipped with self-contained breathing apparatus. Conscious persons should be assisted
to an uncontaminated area and inhale fresh air. Quick removal from the contaminated area is most
important. Unconscious persons should be moved to an uncontaminated area, given assisted
(artificial) respiration and supplemental oxygen. Further treatment should be symptomatic and
supportive.

Safety instructions:
Earth bond and ground all lines and equipment associated with the product system. Electrical
equipment should be non-sparking and explosion proof.
Propylene is non-corrosive and may be used with any common structural material. Use only in
well-ventilated areas. Valve protection caps must remain in place unless container is secured with
valve outlet piped to use point. Do not drag, slide or roll cylinders. Use a suitable hand truck for
cylinder movement. Use a pressure regulator when connecting cylinder to lower pressure (<250
psig) piping or systems. Flammable Limits of propylene in air is 2.0 11.1% by volume with Auto-
Ignition Temperature is 480C (896F) and flash point is -108C (-162F).
Do not heat cylinder by any means to increase the discharge rate of product from the cylinder.
Use a check valve or trap in the discharge line to prevent hazardous back flow into the cylinder.
Protect cylinders from physical damage. Store in cool, dry, well-ventilated area away from heavily
trafficked areas and emergency exits. Do not allow the temperature where cylinders are stored to
exceed 130F (54C). Cylinders should be stored upright and firmly secured to prevent falling or
being knocked over. Full and empty cylinders should be segregated. Use a "first in-first out"
inventory system to prevent full cylinders from being stored for excessive periods of time.
Post "No Smoking" signs in storage or use areas.

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Never carry a compressed gas cylinder or a container of a gas in cryogenic liquid form in an
enclosed space such as a car trunk, van or station wagon. A leak can result in a fire, explosion,
asphyxiation or a toxic exposure.

10.2 AMMONIA

Hazards Identification

EMERGENCY OVERVIEW:

Irritating or corrosive to exposed tissues. Inhalation of vapors may result in pulmonary


edema and chemical pneumonitis .Slightly flammable.
ROUTE OF ENTRY:

Skin Skin Eye Contact Inhalation Ingestion


Contact Absorption

Yes No Yes Yes No

HEALTH EFFECTS:

Mutagen Yes

Exposure Limits Yes

Irritant Yes

Sensitization No

Teratogen No

Reproductive Hazard No

Synergistic Effects None Reported


Carcinogenicity: -- NTP: No IARC: No OSHA: No
EYE EFFECTS:

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Mild concentrations of product will cause conjunctivitis. Contact with higher concentrations of
product will cause swelling of the eyes and lesions with a possible loss of vision.
SKIN EFFECTS: Mild concentrations of product will cause dermatitis or conjunctivitis.
Contact with higher concentrations of product will cause caustic-like dermal burns and
inflammation. Toxic level exposure may cause skin lesions resulting in early necrosis and
scarring.

INGESTION EFFECTS:

Since product is a gas at room temperature, ingestion is unlikely.


INHALATION EFFECTS:

Corrosive and irritating to the upper respiratory system and all mucous type tissue .Depending on
the concentration inhaled, it may cause burning sensations, coughing, wheezing, shortness of
breath, headache ,nausea, with eventual collapse .Inhalation of excessive amounts affects the
upper airway (larynx and bronchi) by causing caustic-like burning resulting in edema and
chemical pneumonitis. If it enters the deep lung, pulmonary edema will result.Pulmonary
edema and chemical pneumonitis are potentially fatal conditions.

Handling And Storage

Electrical Classification:

Class 1, Group D.
Earth-ground and bond all lines and equipment associated with the ammonia system.
Electrical equipment should be non-sparking or explosion proof.
Gaseous or liquid anhydrous ammonia corrodes certain metals at ambient temperatures.
The presence of oxygen enhances the corrosion of ordinary or semi-alloy steels. The addition of
water inhibits this enhancement. Keep anhydrous ammonia systems scrupulously dry.
Use only in well-ventilated areas. Valve protection caps must remain in place unless
container is secured with valve outlet piped to use point. Do not drag, slide or roll cylinders. Use
a suitable hand truck for cylinder movement. Use a pressure regulator when connecting cylinder
to lower pressure (<500 psig)piping or systems .Do not heat cylinder by any means to increase the
discharge rate of product from the cylinder.
Use a check valve to trap in the discharge line to prevent hazardous back flow into the
cylinder. Protect cylinders from physical damage. Store in cool, dry, well-ventilated area away

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from heavily trafficked areas and emergency exits .Do not allow the temperature where cylinders
are stored to exceed 125oF (52oC).Cylinders should be stored upright and firmly secured to prevent
falling or being knocked over. Full and empty cylinders should be segregated. Use a "first in-first
out" inventory system to prevent full cylinders from being stored for excessive periods of time.
Never carry a compressed gas cylinder or a container of a gas in cryogenic liquid form in
an enclosed space such as a car trunk, van or station wagon. A leak can result in a fire, explosion,
asphyxiation or a toxic exposure.

Fire Fighting Measures

Conditions of Flammability: Nonflammable


Flash point: Method: Autoignition
None Not Applicable Temperature: 1274 oF (690
o
C)
LEL(%):16 UEL(%):25
Hazardous combustion products: None
Sensitivity to mechanical shock: None
Sensitivity to static discharge: None

First Aid Measures

EYES:
Flush contaminated eye(s) with copious quantities of water. Part eyelids to assure complete
flushing. Continue for a minimum of 15 minutes. PERSONS WITH POTENTIAL EXPOSURE
TO AMMONIA SHOULD NOT WEAR CONTACT LENSES.
SKIN:
Remove contaminated clothing as rapidly as possible. Flush affected area with copious quantities
of water. In cases of frostbite or cryogenic "burns" flush area with lukewarm water. DO NOT
USE HOT WATER. Aphysician should see the patient promptly if the cryogenic "burn" has
resulted in blistering of the dermal surface or deep tissue freezing.
INGESTION:
Not specified. Seek immediate medical attention.
INHALATION
Prompt medical attention is mandatory in all cases of overexposure. Rescue personnel should be
equipped with self-contained breathing apparatus. Conscious persons should be assisted to an
uncontaminated area and inhale fresh air. Quick removal from the contaminated area is most
important. Unconscious persons should be moved to an uncontaminated area, given mouth-to-
mouth resuscitation and supplemental oxygen. Keep victim warm and quiet. Assure that mucus or
vomited material does not obstruct the airway by positional drainage.

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10.3 SULPHURIC ACID

Hazard Identification

PHYSICAL STATE AND APPEARANCE:

Odorless, clear to amber, heavy, oily liquid .A pungent odor may exist if certain impurities are
present in the acid.
EMERGENCY OVERVIEW:

Danger! Extremely corrosive. Causes severe burns and / or eye damage.


Mist: Causes respiratory irritation. Harmful if inhaled. Harmful or fatal if swallowed. Reacts
violently with water .Concentrated Sulfuric Acid will react with many organic materials and may
cause fire due to the heat of the reaction. Not flammable, but reacts with most metals to form
explosive/flammable hydrogen gas.
This product contains ingredients that are considered to be hazardous as defined by the OSHA
Hazard
Skin contact . Eye contact. Ingestion. Inhalation.
Routes of entry :Potential acute health effects
EYE CONTACT: Immediate pain, severe burns and corneal damage, which may result in
permanent blindness.
SKIN CONTACT: Causes burns, and brownish or yellow stains. Concentrated solutions
may cause second or third degree burns with severe necrosis. Prolonged and repeated
exposure to dilute solutions may cause irritation, redness, pain and drying and cracking of
the skin.
INHALATION: Causes respiratory irritation and at high concentrations may cause severe
injury, burns, or death. Effects of exposure may be delayed.
INGESTION: Causes severe irritation or burns of the mouth, throat, and esophagus.
EXISTING MEDICAL CONDITIONS POSSIBLY AGGRAVATED BY EXPOSURE:
Skin irritation maybe aggravated in individuals with existing skin lesions. Breathing of
vapors or sprays (mists) may aggravate acute or chronic asthma and chronic pulmonary
disease such as emphysema and bronchitis.
Handling and Storage:

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Good general ventilation should be provided to keep vapor and mist concentrations below the
exposure limits. Have available and wear as appropriate: Chemical splash goggles; full-length
faceshield /chemical splash goggle combination; acid-proof gauntlet gloves, apron, and boots;
acid proofsuit and hood; and appropriate NIOSH/MSHA respiratory protection. In case of
emergency or where there is a strong possibility of considerable exposure, wear a complete
acid suit with hood, boots and gloves. If acid vapor or mist are present and exposure limits may
be exceeded, wear appropriate NOISH/MSHA respiratory protection.
HANDLING: Wear appropriate Personal Protection Equipment. Do not breathe sprays or mists.
Do not ingest. Do not get in eyes, on skin or on clothing. Keep ignition sources away from
sulfuric acid storage ,handling and transportation equipment. Locate safety shower and eyewash
station close to chemical handling area. Use EXTREME care when diluting with water. Always
add acid to water never the reverse .CAUTION: Hydrogen, a highly flammable gas, can
accumulate to explosive concentrations inside drums, or any types of steel containers or tanks
upon storage. Carbon steel storage tanks must be vented. People working with this chemical
should be properly trained regarding its hazards and its safe use.
STORAGE: If stored in non-reactive container, keep container tightly closed. Metal and,
specifically carbonsteel, storage tanks must be vented due to hydrogen release as noted above.

10.4 ACRYLONITRILE

Hazards Identification

NFPA RATINGS (SCALE 0-4):

HEALTH=4
FIRE=3
REACTIVITY=2

EMERGENCY OVERVIEW:

COLOR: colorless
PHYSICAL FORM: liquid

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ODOR: pungent odor


MAJOR HEALTH HAZARDS: harmful (if inhaled, on contact with the skin, or swallowed), eye
burns ,respiratory tract irritation, skin irritation, allergic reactions, cancer hazard (in humans)
PHYSICAL HAZARDS: Flammable liquid and vapor. Vapor may cause flash fire. May
polymerize. Containers may rupture or explode.

Potential Health Effects:

INHALATION:
SHORT TERM EXPOSURE: irritation, itching, nausea, vomiting, diarrhea, stomach pain,
irregular heartbeat, headache, drowsiness, dizziness, bluish skin color, suffocation, convulsions,
coma
LONG TERM EXPOSURE: digestive disorders, reproductive effects, cancer
SKIN CONTACT:
SHORT TERM EXPOSURE: irritation (possibly severe), allergic reactions, blisters, suffocation
LONG TERM EXPOSURE: same as effects reported in short term exposure
EYE CONTACT:
SHORT TERM EXPOSURE: burns, tearing, eye damage
LONG TERM EXPOSURE: same as effects reported in short term exposure
INGESTION:
SHORT TERM EXPOSURE: suffocation
LONG TERM EXPOSURE: reproductive effects, cancer

Handling And Storage


STORAGE:
Store and handle in accordance with all current regulations and standards. Notify State Emergency
Response Commission for storage or use at amounts greater than or equal to the TPQ (U.S. EPA
SARA Section 302). SARA Section 303 requires facilities storing a material with a TPQ to
participate in local emergency response planning (U.S. EPA 40 CFR 355 Part B). Protect from
physical damage. Store outside or in a detached building .Store with flammable liquids. Keep
separated from incompatible substances. Monitor inhibitor content. Secure to prevent tipping.

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Use diking sufficient to contain total contents plus 10%. Keep separated from incompatible
substances.

Fire Fighting Measures

General Hazard
Severe fire hazard.
Highly flammable and volatile liquid.
Highly flammable vapours emitted.
The vapour is heavier than air.
Vapours or gases may ignite at distant ignition sources and flash back.
May be ignited by heat, sparks, static electrical discharge or flame.

Suitable Extinguishing Media


Dry chemical powder, alcohol foam, water spray (fog), CO2.After fire is extinguished re-ignition
may occur from hot surfaces. Cool containing vessels with flooding quantities of water until well
after fire is out.
Extinguishing Media NOT to be used
Water jet (solid water stream may scatter and spread fire).
Special Exposure Hazards
If involved in a fire acrylonitrile produces very toxic fumes and dense, black, acrid smoke
clouds.Liquid will float and may re-ignite on surface water.
Special Protective Equipment for Fire-fighters
Fire-fighters must wear breathing apparatus and full chemical protection.
Further Information
Contaminated fire water must be contained and prevented from entering water courses.
If the fire is impossible to control withdraw and let it burn.

First Aid Measures


General Advice
The ready availability of oxygen is essential for First Aid treatment in cases of acrylonitrile
poisoning. Take off all contaminated clothing and shower immediately. Symptoms include
headache, vomiting, dizziness, larger doses may result in unconsciousness, paralysis/cramp,
cessation of breathing, death.
Anyone affected by acrylonitrile, significantly exposed to acrylonitrile but not yet showing
symptoms or suspected of being significantly exposed to acrylonitrile must be referred promptly
to a doctor following any necessary first aid.

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First aiders must protect themselves against acrylonitrile.


Mouth-to-mouth resuscitation should not be used.
If a patient stops breathing, mechanical means should be used to inflate the lungs e.g. oxygen
resuscitator.
Transfer patient to hospital. Delayed effects may occur up to 8 hours after exposure.

Inhalation
Remove patient to fresh air.
Administer oxygen continuously even if patient appears healthy.
Keep patient quiet and warm.
Follow up with Medical treatment.

Skin Contact
Remove patient to fresh air.
Remove contaminated clothing including underwear and shoes.
Wash affected area with plenty of water until irritation has stopped.
Keep patient quiet and warm.
Follow up with medical treatment.

Eye Contact
Flush the eye immediately with plenty of water protecting the unaffected eye, until irritation has
stopped.
Follow up with medical/ophthalmic treatment.

Ingestion
Conscious patients should drink at least 1 pint of water.
If patient vomits, take care to prevent inhalation of any vomit.
Keep patient quiet and warm.
Follow up with medical treatment.

Ecological Information

Ecotoxicity

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Freshwater data suggests that Acrylonitrile is of moderate toxicity to aquatic organisms with
reported 48 hour LC50 values ranging from 7.6 mg/l (water flea Daphnia Magna) to 70 mg/l
(Rainbow trout Oncorhynchus mykiss).
Mobility
Limited solubility in water.
Persistence and Degradability
Standard degradation tests indicate that this material will degrade in the aquatic environment but
not readily. Acrylonitrile is readily degraded in acclimatised aerobic systems; anaerobic systems
display greater sensitivity and may be inhibited. Atmospheric degradation occurs via photo-
oxidation.
Bioaccumulative Potential
Acrylonitrile is not expected to bioaccumulate due to its degradability and low octanol/water
partition coefficient.

Loading, Unloading and transport of Acrylonitrile.

LOADING OPERATIONS
The operations of filling any road tanker, tank container, Rail Tank Cars or ship tank with
Acrylonitrile is a potential hazard. It is therefore important that loading facilities and transport
equipment are correctly designed and constructed, properly used and maintained.
It is recommended to have the loading facilities inspected by the supplier every few years to ensure
sharing of experience and best practice.
Be also aware that static electricity can build up during loading and unloading operations.
Approved and regularly tested earth connection shall be installed and connected before the
loading/unloading connection is made. The installation of an Earth Proofing Device is strongly
recommended.

Loading facilities must be designed and located having due regard to the potential hazards
associated with acrylonitrile. The design and construction of storage, handling and transport
equipment is described in Section 3 and appendices 1 to 4 of these Guidelines. As far as transport
is concerned, equipment which meets the requirements of the ADR, RID, ADNR and IMO
Regulations is subject to periodic inspection and testing requirements as laid down in these
regulations. Normally official inspection and testing is carried out by competent authorities in the
particular country of registration.

Written operating instructions must be available at all filling points covering the procedures for
loading of Acrylonitrile, and personnel involved must be fully trained in their implementation. The
instructions must recognize the specific hazards of Acrylonitrile and outline the correct operations
of the filling equipment in both normal and emergency situations. It is not the intention in this

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Section of these Guidelines to attempt to set detailed operating instructions for filling Acrylonitrile
vehicles, since these will necessarily depend upon local operating conditions.
All necessary protective clothing and emergency equipment must be available for loading
operations. Personnel must be trained in the correct use of this clothing and equipment.
A visual inspection of the transport equipment must be carried out by the loading terminal
personnel before, during and after loading. This inspection does not replace or diminish the
responsibility of the owner of the road tanker, tank container, ship or to ensure that the equipment
is properly tested, maintained and fit for purpose. It is meant to ensure that the transport of
Acrylonitrile is conducted as safely as possible.
The inspection list detailed in appendix 5 is recommended for use by the loader to check the
condition of Acrylonitrile transport equipment.
In addition to the routine inspection of all transport equipment prior to each loading operation, a
responsible person from the loading company must carry out a check on each road tanker, tank
container or Rail Tank Cars prior to initial introduction into service, or reintroduction to service
after maintenance or repair.
The Routine Inspection List assumes that Acrylonitrile is to be conveyed by international transport.
In circumstances where Acrylonitrile is to be conveyed nationally (more usually), in accordance
with international regulations, the inspection list must be modified as appropriate.
It is necessary that all loading facilities are properly equipped for safe unloading operations.

UNLOADING OPERATIONS

The operation of unloading any road tanker, tank container, Rail Tank Cars or ship tank containing
Acrylonitrile is a potential hazard.
It is therefore important that unloading facilities are correctly designed, constructed, properly used
and maintained.
It is recommended that the supplier inspects the unloading facilities before the first delivery and
every few years to ensure sharing of experience and best practice.
Unloading facilities must be designed and located having due regard to the potential hazards
associated with Acrylonitrile. The equipment must be subject to regular checks to ensure the
maintenance of the standards set. The installation of Earth Proofing Devices is strongly
recommended.
Written operating instructions must be available for unloading Acrylonitrile from road tankers,
tank containers, Rail Tank Cars and ship tankers, and personnel involved must be fully trained in
their implementation.
The instructions must recognize the specific hazards of Acrylonitrile, and ensure the correct
operation of unloading equipment in both normal and emergency situations.
All necessary protective clothing and emergency equipment must be available for unloading
operations. Personnel must be trained in the correct use of this clothing and equipment.
An inspection of the transport equipment is recommended and must be carried out at the unloading
terminal at the customers site.

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This inspection does not replace or diminish the responsibility of the Acrylonitrile supplier and the
owner of the road tanker, tank container, Rail Tank Cars or ship to ensure that the equipment and
transport documentation are in correct conditions and issued properly.
Unloading of Acrylonitrile at a customers premises is the customers responsibility. If requested,
the consignor or Acrylonitrile supplier may provide the customer with technical advice and safety
service which in principle may include a safety visit.

Acrylonitrile transport by road

General requirements for Acrylonitrile Transport by Road


Acrylonitrile road transport is under ADR or national regulations which are obligatory and must
be met in all countries.
In certain countries specific transport permission issued by the authorities is required.
The haulier is responsible for the safe transport of Acrylonitrile by road from the loading point to
the discharge point. The following points are important and need to be included in standards related
to land transport and must be complied with.
The Haulage Company should be assessed to SQAS (Safety and Quality Assessment System under
the auspices of Cefic) with good results. Regular review meetings on the SQAS assessment should
be done by the supplier.
Acrylonitrile must only be transported on defined routes. The route to be followed must be selected
carefully and must be known to both the haulier and the consignor or supplier. In countries where
specific transport permission is required, the route is part of the permission.
As far as possible, the route must: a) Utilize motorways b) Be planned to avoid major centres
of population or areas of high population density. c) Avoid use of tunnels or passenger ferries.
Safe Parking
Drivers of Acrylonitrile road tankers en route must ensure that the vehicle, when not being driven,
is either supervised at all times or is parked in a safe parking location.
Use an authorized parking area for dangerous chemicals products when available. If the above is
not available, the parking area must be in an isolated position in the open, in an area which is
preferably lit at night. A secure depot or secure factory premises must be utilized as far as possible.
Severe Weather Conditions
When severe weather conditions are experienced during transport, for example icy roads, snow or
poor visibility caused by fog, the delivery must be stopped at the next suitable parking place. The
delivery must not resume until weather conditions improve. Local rules may apply. (The present
requirement for minimum visibility is 200 meters in The Netherlands
Delays or Accidents
All delays during transport caused by severe weather conditions, breakdowns or other reasons must
be reported to the consignor immediately.
Transport accidents must also be reported to the consignor immediately. An on-board telephone is
highly recommended.
Emergency Procedure

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If emergency action needs to be taken by drivers when leaks, spills or fire occur during transport,
then the instructions given in the Instructions in writing must be followed. See appendix 11.
Note that the European Acrylonitrile producers cooperate to assist in emergency situations.

Acrylonitrile transport by rail

Acrylonitrile railway transport is under RID regulations or national regulations which are
obligatory and must be met in all countries.
The appropriate railway authorities are responsible for the safe transport of Acrylonitrile by rail
from the dispatch siding to the final reception siding. The selection of route, intermediate stopping
locations and cessation of traffic due to severe weather conditions are matters to be decided by the
railway authorities or the railway company owning the rail network.
The appropriate railway authorities will normally intervene in the event of a transport emergency
involving Acrylonitrile Rail Tank Cars. Railway authorities must be made aware of the
information contained in these guidelines as an aid for railway hazardous cargo intervention teams.
In some cases rail wagons are transported over the public road by lorries from the final rail siding
to the eventual customer by a Piggyback arrangement, and such movements may be arranged
by railway authorities as part of their overall service. This way of transport poses additional
hazards (load stability) and therefore is strongly discouraged.
Emergency Procedure
In the event of derailment, leak, or other problem involving rail tank cars of acrylonitrile the
railway personnel must inform the consignor immediately. In addition under the ICE scheme, the
National Emergency Centre for the country in which the accident has occurred must be contacted.
Acrylonitrile transport by sea
Transport of Acrylonitrile by sea is generally made by cargo chemical ships. Acrylonitrile sea
transport is under
IMO regulations, which are standard and adopted by all major countries that transport
dangerous goods by sea.
Because of the nature of the activity, a number of different parties may be involved in the operation
of sea transportation from consignor to customer.
These may include the:
Shipping Company
Port or harbour authorities
Surveyors
Hauliers (road or rail)
Chemical terminal storage company All these parties are involved in both loading and unloading
the product.
Prior to the commencement of each new traffic flow, a safety audit of critical aspects of the
transport operation should be carried out by the consignor as recommended

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This audit may include, as appropriate: a) The shipping company (type and technical information
about the chemical cargo tanker). b) Loading/Unloading and storage facilities at the chemical
terminals at the port. c) Emergency handling procedures within hazardous cargo yards at the
chemical terminals. d) Responsibility for emergency response arrangements between consignor
and customer.

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11 ENVIRONMENTAL PROTECTION &ENERGY


CONSERVATION
The International Standards are based on the methodology known as Plan-Do-Check-Act (PDCA).
PDCA can be briefly described as follows.
Plan: establish the objectives and processes necessary to deliver results in accordance with
the organizations environmental policy.
Do: implement the processes.
Check: monitor and measure processes against environmental policy, objectives, targets,
legal and other requirements, and report the results.
Act: take actions to continually improve performance of the environmental management
system,
Many organizations manage their operations via the application of a system of processes and their
interactions, which can be referred to as the process approach. ISO 9001 promotes the use of the
process approach. Since PDCA can be applied to all processes, the two methodologies are
considered to be compatible.
This International Standard contains only those requirements that can be objectively audited.
Those organizations requiring more general guidance on a broad range of environmental
management system issues are referred to ISO 14004. This International Standard does not
establish absolute requirements for environmental management.

AIR POLLUTION

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Acrylonitrile is a colorless, liquid, man-made chemical with a sharp, onion- or garlic-like odor.It
can be dissolved in water and evaporates quickly. Acrylonitrile is used to make other chemicals
such as plastic, synthetic rubber, and acrylic fibers. A mixture of Acrylonitrile and carbon
tetrachloride was used as a pesticide in the past, however, all pesticides uses have stopped.
Acrylonitrile may be found in the soil, water, or air near industrial sites where it is made, or at
hazardous waste sites where it has been disposed of. Because Acrylonitrile evaporates easily, most
of it is released to the air from the faciliries where it is produced and used. In air, Acrylonitrile
breaks down quickly (about half will disappear within 5 to 50 hours ) by reacting with other
chemicals and sunlight. Acrylonitrile can enter groundwater by filtering through the soil, but it is
not commonly found in ground water.
It is broken down by bacteria in surface water. When it is released to soil, some of it will be broken
down by bacteria, but most of it will evaporate to the air or filter to groundwater. Acrylonitrile
does not build up in the food chain.
Exposer to Acrylonitrile can take place if you live near a factory where Acrylonitrile is made or
near a hazardous waste site that contains Acrylonitrile, you are unlikely to be exposed to it. Also
by breathing contaminated air near hazardous waste sites. That contain Acrylonitrile you can get
exposed to Acrylonitrile. Working in, or living near industries where it is manufactured or used.
Swallowing food and water that contains small amount of Acrylonitrile are few other reasons that
lead to exposure to Acrylonitrile.

Effect of Acrylonitrile on human beings


Effect of Acrylonitrile on human health will depend on how much Acrylonitrile is present and the
length an frequency of exposure. Effect also depends on the health of a person or condition of the
environment when exposure occurs. Breathing Acrylonitrile for short periods of time adversely
affects the nervous system, the kidney, the blood and the liver breathing high concentrations of
Acrylonitrile will cause nose and throat irritation, tightness in the chest, difficulty breathing ,
nausea, dizziness, weakness, headache, impaired judgment, and convulsions. These symptoms
usually disappear when exposure is stopped. If spilled on the skin, Acrylonitrile will burn the skin
and produce redness and blisters.
Animal studies show effects from breathing Acrylonitrile.These effects include irritation to the
nasal cavity and lungs, changes in the brathing rate , fluid accumulation in thr lungs, weakness,
and paralysis. Decreased fertility and birth defects have been observed in some laboratory animals
exposed to high concentrations of Acrylonitrile in air or drinking water. There is evidence that
children are much more sensitive to Acrylonitrile than adults. In a few cases, children have died
following exposure to acrylonirile vapors that caused only nceminor nose and throat irritation in
adults.

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The Department of Health and Human Services (DHHS) has determined that Acrylonitrile may
reasonable be anticipated to cause cancer in people. Studies of people are inconclusive, while
animal studies have shown cancers of the brain and mammary glands.

Medical tests to show exposure to Acrylonitrile


There is a test that can-detect Acrylonitrile in blood. Other tests can be used to measure the
breakdown products (metabolites) of Acrylonitrile in urine. One of the metabolites (cyanide) could
come from other chemicals you might have been exposed to, so it is not a definite indicator of
Acrylonitrile exposure. The results of these tests could also be affected by cigarette smoking.
Special equipment is needed for these tests, and they are not routinely available in a doctors office.

Recommendations
The EPA recommends that leaves in lakes and streams should be limited to 0.058 parts of
Acrylonitrile per billion parts of water (0.058 ppb) to prevent possible health effects from drinking
water or eating fish contaminated with Acrylonitrile. Any release to the environment greater than
100 pounds of Acrylonitrile must be reported to the EPA.
The Occupational Safety and Health Administration (OSHA) has set a limit of 2 ppmover an 8
hour workday, 40-hour workweek. The National Institute of Occupational Safety and Health
(NIOSH) recommends that average workplace air should not exceed 1 part per million (1 ppm)
Acrylonitrile averaged oer a 10-our period. The federal recommendations have been pdated as of
July 1999.

Various Limits
1) TLV-TWA : Time Weighted-Average concentration for a normal 8-hr workday and a 0-
hr workweek to which nearly all workers may be repeatedly exposed without adverse
effects.
Skin: air sampling alone is insufficient to accurately quantitative exposure.
Measures to prevent significant cutaneous absorption may be required. A2: suspected
human carcinogen (ACGIH 1993-94).

2) TWA : Time-Weighted-Average concentration for up a 10-hr workday during a 40-hr


workweek. Ca: potential human carcinogens. LF: Reduce exposure to lowest feasible
concentration; when Ca designation accompanies lowest feasible designation, use of only
the most reliable and protective respirators is recommended (NIOSH 1990,92).

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3) TWA : Time-Weighted-Average concentrations that must not be exceeded during any 8-


hr work shift of a 40-our workweek. Skin: air sampling alone is insufficient to accurately
quantitative exposure. Measures to prevent significant cutaneous absorption may be
required. OSHA standards promulgated pursuant to Occupational Safety and Health Act,
29 CFR 1910 (OSHA 1993).

4) TLV-Ceiling: Airborne concentration that must not be exceeded as averaged over a 15-
minute period during the work day.

TLV Values for Acetonitrile


OSHA Permissible exposure limit (PEL) for acetonitrile is 40 ppm, 70 mg/m3
NIOSH Recommended exposure limit (REL) for acetonitrile is 20 ppm TWA
ACGIH Threshold limit value (TLV) of 40 ppm, 67 mg/m3 TWA; 60 ppm, 101 mg/m3 STEL
JCAHO Follows OSHA Law
Exposure Limits:TWA: 40 (ppm) from ACGIH, (LV-STEL: 60 from ACGIH, TLV- TWA: 20
(ppm) from NIOSH.
TWA: 40 ;STEL: 60 (ppm) from OSHA (PEL)

Prevention Of Pollution In Manufacturing Of Acrylonitrile


Emissions of acrylonitrile produced via the sohio process may occure from several sources
including the absorber vent, column purge vents, storage tanks, transport and loading facilities,
and deep well ponds. Fugitive emissions may also occure from leaks in pumps, compressors, and
valves. Acrylonitrile emissions represent only a small fraction of the total VOC emitted from these
sources, accounting for approximately 6 weight percent of the total uncontrolled VOC emissions
and 15 weight percent of the total VOC emissions after typical controls.
Acrylonitrile process emissions from the sohio process occur from the obsorber vent during normal
operation, the absorber vent during startup, and the distillation column purge vents during normal
operation.During normal operation, the absorber vent gas contains only about 0.001 weight percent
acrylonitrile and 1.25 weight percent total VOC.8 The absorber gases are usually incinerated at
removal efficiencies of 98 percent or higher.The majority of the acrylonitrile production facilities
utilize thermal incineration, although one facility has employed catalytic incineration on the
absorber vent.2 Because of the large percentage (97+ percent ) of nitrogen and other non
combustibles normally present in the absorber vent gas stream, supplemental fuel must be added
to ensure proper combustion.

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Incineration may be an acceptable method of control for startup emissions but is not generally used
due to the potentially high NOx emissions which could result from the combustion of stream
containing a large percentage of acrylonitrile, hydrogen cyanide, and Acetonitrile.
Seven ways by which pollution occurs during manufacture of acrylonitrile

1. Absorber vent gas


2. Column purge waste gas
3. Fugitive emissions
4. Incinerator stack gas
5. Deep well/pond emissions
6. Storage tank emissions
7. Product transport loading facility vent
Wastewater for disposal is generated mainly from the wastewater and acetonitrile columns.

VOC and Acrylonitrile Emissions From ACN Manufacturing

Control Efficiency
Emission Point Emission Rate (kg/hr) Control Method (%)
Acrylonitrile Total VOC

Absorber
Vents 2.05 2050 Thermal Incineration 95-97
Catalytic Oxidation

Column Vents 103 205 Flare 98-99

Storage Tanks 13.5 14.8 Double Seal Floating Roof 99

Loading 3.44 3.98 Flare Incinerator 98-99

Fugitive 9.5 19.5 Leak Detection /Maintenance N/A


Incinerator
Stack 7.4 N/A N/A
Deep
Well/Pond 267 Water Scrubber N/A

Above for a plant of 180 million kg AN per annum capacity

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POLLUTANTS AND THEIR CONTROL

1. Air Pollution

Absorber Vent Gas. The absorber vent gas stream contains nitrogen, oxygen, un-reacted
propylene, hydrocarbon impurities from the propylene feed stream, CO, CO, water vapor, and
small quantities of ACN, acetonitrile, and hydrogen cyanide. Two control methods are used to
treat this stream: thermal incineration and catalytic oxidation.
The thermal incineration units have demonstrated VOC destruction efficiencies of 99.9% or
greater, while most catalytic units can achieve destruction efficiencies only in the 95-97% range.
Destruction efficiencies in the 99% and greater range can be achieved with catalytic oxidizers, but
these are not achieved on a long-term basis because of deactivation of the catalyst by a number of
causes. The advantage of catalytic oxidation is low fuel usage, but emissions of NO x formed in
the reactors and not destroyed across the catalyst can pose problems.
Column Waste Purge Gas. Waste gas releases from the recovery column, light-ends column,
product column, and the Acetonitrile column are frequently tied together and vented to a flare.
The estimated VOC destruction efficiency of the flare is 98-99% for all streams with a heat content
of 300 Btu/scf or greater. The use of a flare is ideally suited for streams that are intermittent and
having heating values of 300 Btu/scf.
Fugitive emissions. Fugitive emissions from piping, valves, pumps, and compressors are
controlled by periodic monitoring by leak checking with a VOC detector and a directed
maintenance program.
Incinerator Stack Gas. Staged combustion and ammonia injection are used to control the
emissions of NO x from the incinerator that treats the absorber off-gas vent, the crude Acetonitrile
waste gas stream, and the by-product liquid HCN stream. Staged combustion suppresses the
formation of NO x by operating under fuel-rich conditions in the flame zone where most of the
NO x is formed and oxygen-rich conditions downstream at lower temperatures where NO x is not
appreciably formed.

Ammonia injection reduces NO x by selectively reacting ammonia with NO x. The reaction occurs
at temperatures in the range of 870-980 C (1600-1800 F) and, as such, the ammonia must be
injected in the post-flame zone of the combustion chamber. Residence times of 0.5- 1.0 second
are required for NO x destruction efficiencies in the range of 80%, which is compatible with the
residence time required for VOC destruction.

Deep Well/Pond Emissions. Emissions of acrolein and other odorous components in vents from
wastewater treatment steps are controlled with water scrubbers. In some cases, pond emissions

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are controlled by adding a layer of low-vapor-pressure oil on the surface of the pond to limit
volatilization.

Storage Tank Emissions. Product storage tank emissions are controlled with double-seal floating
roofs or, in some cases, water scrubbers. Field experience indicates that a removal efficiency of
99% can be achieved with water scrubbing.

Product Transport Loading. Emissions from product transport loading vents are gathered and
sent to a flare or incinerator for VOC control. Destruction efficiencies of 98-99% are achieved
using the flare and greater than 99% using incineration.
2. Solid/Liquid Waste

Wastes include salts of hydrogen cyanide, metal cyanide complexes, and organic cyanides
(cyanohydrins) as solutions or solids. The wastewater from the wastewater column contains
ammonium sulfate and heavy hydrocarbons, while the wastewater from the acetonitrile column
mainly contains heavy bottoms. The wastewater from both these columns is typically discharged
to a deep well pond . Other methods of waste treatment include alkaline chlorination in a recycle
lagoon system, and incineration.
3. Disposal of wastes

HCN being highly toxic, thus it is not suitable for transport. Thus it is converted into acetone
cyanohydrins for shipping.
Acetonitrile has only industrial use as a solvent. So there is no demand it is generally incinerated
because it cannot be dumped under the regulatory conditions.
Ammonium sulphate derived from neutralization of unreacted ammonia can be recovered and sold
into fertilizer market. Generally the cost of this conversion exceeds the recovery made by selling
the product.

Potentially Hazardous Wastes Generated From Acrylonitrile Production


Waste Source Pollutant Amount Disposal Method

Wastewater
Column Ammonium Sulfate N/A Deep well pond
Heavy
Hydrocarbons N/A Deep well pond

Acetonitrile
Column Heavy Bottoms N/A Deep well pond

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EMISSION STANDARDS FOR PROCESS EMISSION (SPECIFIC ORGANIC


POLLUTANTS)
3
S. No. Parameter Source Maximum emission Limit (mg/Nm )
1 Chlorine EDC / VCM plant and incinerator 10
2 HCl EDC / VCM plant and incinerator 30
3 Ammonia Process vent (wastewater stripper 75
acrylonitrile plant, caprolactum plant
4 H2S Naphtha pre-treatment plant, olefin plant 05

5 Phosgene Generated in TDI and MDI plants 01


6 HCN Acrylonitrile plant 10

EMISSION STANDARDS FOR VOC-HAPS FROM PROCESS VENTS


S.No. Parameters Maximum emission Limit

Existing plant New plants/ Expansion


3 3
(mg/Nm ) (mg/Nm ) (gm/hr)

1. (Toluene Di- 0.1 0.1 0.5


isocyanate) TDI,
Methylenediphenyl
Di-isocyanate
(MDI)

2. Benzene, 5.0 5.0 25.0


Butadiene

3. EO, VCM, EDC, 20.0 10.0 50.0


ACN, PO

Water Pollution Related To Acrylonitrile


Acrylonitirle is a monomer made from the vapor phase amoxidation of propylene.It is used in the
production of acrylic fibers, nitrile rubber and Acrylonitrile butadiene styrene (ABS). The
amoxidation reaction produces water, containing to the volume of wastewater that contains
relatively high concentrations of cyanides, a number of nitriles, nitrile polymers and ammonium

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sulfate. The presence of cyanides and nitriles in this waste make it hazardous, but it is not a RCRA
hazardous waste.
A number of improvements have been made in the acrylonitrile process to maximize wastes,
including new catalysts that improve the yield and therefore reduce the volme of waste. In the
1970s, a process was developed to recover a fertilizer-grade ammonium sulfates as a by-product
from acrylonitrile waste. This reduced quantities of pollutants in th waste.
The acrylonitrile process is an example of a class of processes that produce water that needs to be
treated. In the case of acrylonitrile , when propylene is ammoxidized to form acrylonitrile, water
is formed along with the product.Unless the basic chemistry of the ammoxidation reaction is
changed, or wastewater is reused in a cooling tower and evaporated, the volume of wastewater
cannot be reduced beyond the amount of water made in the acrylonitrile reaction.
A number of chemical process produce waters of reaction. Some are hazardous and some are not,
but recognizing that water is being produced in the process is important when addressing water
and waste balances in a process plant.
NOISE POLLUTION
Noise has recently been recognized as a pollutant.It is a great means in thickly ppulatde area. There
is simple evidence that it affects speech, hearing and general health of people exposed to it over
an extended period of time.
In our process noise is produced from various types of columns and various mechanical
equipments like compressors etc.This type of noise poses a potential damage to the various plant
personnel who work very close to these equipments.
Protection for the above can be achieved by providing ear guards. Also the period for which the
personnel is exposed to noise should be minimized and kept within limits.

Energy Conservation
With the rising population of the world and rapidly increasing per capita energy consumption in
the developing countries, energy conservation has become the focus of attention all around the
world, particularly in energy intensive petrochemical industry.

The fast depleting petroleum resources, which are estimated to be just around 89 *
109 barrels as reserves (sufficient for just another 30 years) have led to the
exploration of new energy resources. In this context, both conventional and
nonconventional sources of energy are to be studied.

Alternate Energy Resources

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Renewable energy resources have become more important now a day in process plants. The major
renewable energy forms and their present use and future prospectshave been tabulated below.
S. Sources Energy(J*109) Energy(J*109) Energy(J*109)
No. 1980 2002 Long Term
Potential

1. SOLAR ENERGY 0.1 3.5 - 7 20 30


(Passive Dosing)

2. SOLAR ENERGY 0.1 1.7 58


(Residential Collectors)

3. SOURCE ENERGY 0.1 2.9 10 20


(Industrial Collectors)

4. SOLAR ENERGY 0.1 2.4 10 30


(Solar Ponds)

5. WOOD 35 48 100

6. CROP RESIDUES 6.5 7 -

7. ANIMAL DUNG 2 2 -

8. BIO GAS 0.2 2.5 9.8

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9. URBAN SEWAGE & SOLID 0.3 1.5 15


WASTE

10. METHANOL FROM WOOD 0.1 1.5 15 20

11. ENERGY CROPS 0.1 1.5 21 30

12. HYDROPOWER 19.1 38 48 90

13. WIND POWER 0.1 12 10

14. SHOLAR POTOVOLATIC 0.1 0.0 20

15. GEOTHERMAL 0.3 13 10 20

TOTAL 33.5 135 334 406

Solar Energy:
Electrical / thermal conversion of solar energy in which electricity is generated through the use of
solar concentrating mirrors, absorbers and high temperature thermodynamic cycle can be used for
both industrial and domestic use. In industry, much of the energy required is used for relatively
low temperature applications such as space heating, dehydration of food,heating water for
production and processing of low-pressure steam.

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Biomass conversion:
Heat, fuel, electricity or chemical feed stocks undergo cultivation and chemical processing under
the action of terrestrial and aquatic plants. Other sources from which energy can be derived include
industrial. Agricultural, human and animal wastes. The final products of thes processes may be
methane, ethylene, hydrogen, alcohol, heat, steam, charcoal, other solid fuels and synthetic oils.

Wind energy:
Wind is utilized to propel turbines and air foils, which convert it to electrical or mechanical energy.
A 3.5 m diameter rotor develops about 0.16 BHP in a 15 mph wind and can pump to 35 gallons
of water per minute to a eight of about 10 cm.
Tidal energy:
Ocean thermal energy conversion into electricity is another possible source of energy. This is due
to the fact that oceans are the largest solar collectors and storage and storage system. We can also
make use of the thermal gradients that exist beneath the water surface and derive heat from these.
Nuclear energy:
More than 1900 tons of uranium reserves are present in the earth. Given proper masures, this form
of energy is very competitive and an excellent substitute for fossile fuels. However, this form of
energy is viewed with some reservations due to the inherent hazards of radioactive pollution.

Energy Conservation Measures


The increasing cost of primary fuel has broadened the range of the heat recovery applications that
can be economically justified. In a typical chemical concern with a profit margin of Rs.4 per Rs.
100 sales, a saving of Rs. 1 in energy cost is approximately equivalent to an increase of Rs. 25 in
sales.
The entire gamut of energy conservation operations can be classified into two broad categories:
a) Energy concept:
The term energy has its origins in the last of thermodynamics. It can be redefined in termas of
enthalpy or entropy change or temperature difference. In a given process, the sum all the inputs
are always greater than the sum of all the outputs, the differences being the energy losses. The
endeavor of all energy conservation steps is to minimize this energy loss.
b) Pinch concept:
Every chemical industry used hot and cold streams. The hot streams are cooled while the cold
streams get heated up. However there is a limit to which the can cool down and the cold stream is
heated up.These are called the hot and cold end Approach. T, i.e. the temperature difference

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,between the hot and cold ends need not remain same through the temperature range. In a grand
composites curve, all the hot cold streams are combined to from the ot composite and cold
composites respectively. There is a situation when T becomes minimum.This point of closest
approach is called the pinch of the integrated heat exchanger network (HEN) and signifies zero
heat transfer in the grand composite curve. To achieve energy conservation , the following three
rules must be followed:
No heat transfer across the pinch
No cooling above the pinch
No heating below the pinch

Apart from the above , some more measures taken for energy conservation in plants are:
1.Boiler & Steam systems
Increase the efficiency of the condense system
Replace improperly sized steam traps
Upgrade the quality of insulation in the plant
Reuse the hot water stream previously served

2. Recovery from the process


Reuse the bottoms of the distillation columns and to preheat the feed to the distillation
columns.

3. Select pump to save energy: To save energy and operating cost, pumps are selected as clse to
the best efficiency point (BEP) as possible.
4. Select piping to save energy: Large diameter piping should be installed to reduce unnecessary
pressure drop.
5. Computer control: Computer control of critical parameters in the plant provides another
opportunity for saving energy and increasing the capacity utilization. With the help of optimum
control, energy consumption can be minimized.

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12 REFERENCES
Max S. Peters & Klaus D. Timmerhaus, Plant Design & Economics for Chemical
Engineers, McGraw Hill.
Gavin Towler & Ray Sinnott, Chemical Engineering Design-Principles, Practice &
Economics of Plant & Process Design, Elsevier.
H. Silla, Chemical Process Engineering-Design & Economics, Marcel Dekker Inc.
Richardson & Coulson, Chemical Engineering Design, Vol. 6, Elsevier, Butterworth.
William D. Baasel, Preliminiary Chemical Engineering Plant Design, Elsevier.
Levenspil,O.S., Chemical Reaction Engineering, 3rd Edition, John Wiley &Sons.
Henley, E.J., & Rosen, E.M., Material and energy balance calculations John Wiley &
sons (1969).
Perrys Chemical Engineers Handbook McGraw-Hill Book Company (7th edition).
Bhattacharya,B.C, Introduction to chemical equipment design, mechanical aspects
Coughanowr & Koppel, Process systems analysis and control, McGraw Hill.
Stanley M. Walas, Chemical Process Equipment-Selection & Design, Butterworth-
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William L. Luyben, Chemical Reactor Design & Control, John Wiley & Sons.
Ernest,E.Ludwig Applied process design for chemical and petrochemical plants, 3rd
Edition, Gulf Publishing.
James G. Speight, Chemical & Process Design Handbook, McGraw Hill.
Bruce E. Poling, Properties of Gases & Liquids, 5th Edition.
Douglas, Conceptual Design of Chemical Processes, McGraw Hill.
Erwin, Industrial Chemical Process Design
James R. Couper & Stanley Walas, Chemical Process Equipment-Selection & Design,
Elsevier.
H. Scott Fogler Elements of Chemical Reaction Engineering, 4th edition, Prentice Hall.
Kern.D.Q. Process heat transfer
Shreve, Chemical Process Industries
Henry Kister, Distillation design, McGraw Hill.
Evans, F.L. Equipment design handbook, Gulf publishing (1971)
Marshall & Sittig, Vinyl and Acrylic Fibers(1968)
M. Podhorsky & H. Krips, Heat Exchangers-A Practical Approach to Mechanical
Construction, Design & Calculations, Begell House Inc.
T. Kuppan, Heat Exchanger Design Handbook, Marcel Dekker Inc.
Ramesh K. Shah, Fundamentals of Heat Exchanger Design, John Wiley & Sons.
Igor J. Karassik, Pump Handbook, 4th edition, McGraw Hill.

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Barton, D.H.K, Kinetics of the dehydrochlorination of substituted hydrocarbons


Kharbanda,O.P., Process plant and equipment cost estimation
Othmer,Kirk & others,Encyclopedia of chemical technology
Mcketta,J.M., Encyclopedia of chemical engineering
Geankoplis, Transport Processes & Unit Operations, 3rd Edition, Prentice Hall.
Robin Smith, Chemical Process Design & Intergration, John Wiley & Sons.
McCabe & Smith, Unit operations of Chemical Engineering
A report on Locating and estimating air emissions from sources of acrylonitrile,
EPA-450/4-84-007a (March 1984)
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www.hydrocarbonprocessing.com
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