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1.
INTRODUCTION
Styrene, C
6
H
5
CH = CH
2
, is an unsaturated aromatic monomer, which
polymerizes to give polystyrene. Though, it was discovered way ac!in "#$6, its
commercial production and applications were developed in the nineteen thirties. %ost world
war period witnessed a oom instyrene demand due to its application in the manu&acture o&
synthetic ruer. This led to a dramatic increase in styrene capacity. Since then demand
and capacity have grown continuously.%olystyrene is manu&actured y the addition
polymerization o& styrene monomer unit. 'ow Chemical is the world(s largest producer
with a total capacity o& ".$ million metric tonne in the )S*, Canada, and +urope.
%olystyrene is a versatile thermoplastic availale in a wide range o&
&ormulations, &rom crystal and impact grades to highly specializedresins &or &oam
moulding and e,trusion, and resins that o&&er ignition -retardant properties.The wide range
in physical properties and relative ease o& processing, ma!es polystyrene an e,tremely
attractivematerial, capale o& competing &avoraly with more e,pensive resins in a numer
o& demanding applications.
Polystyrene. Indian Industry Scenario
%olystyrene is a &irst generation plastic. /ts ma0or advantages o& cost, low density
and easy mouldaility over the conventional materials have made it 1uite a success.
Consumption increased &rom "2,#33 4T in "2$5-$5 to aout 52,633 4T in "223-2"
registering a Cumulative *verage 6ate o& 7rowth 8C*679 o& aout "2:.
There are only two manu&acturers o& polystyrene in /ndia. They are.
". %olychem ;td, <omay
2. Hindustan %olymers 8now, ;7 %olymers %vt. ;td9, =isa!hapatnam
8* unit o& 4c'owell > Co. ;td9
These two companies together, have catered to appro,imately 63: o& the country(s
needs o& polystyrene in the Seventh %lan. /mports o& %S have increased over si, &old in the
Seventh %lan, &rom a mere ?#33 T in "2$5-$5 to aout 2?,333 T in "2$2-23 and "2,333 in
"223-2". 8"223-2" registered low consumption ecause o& the 7ul& @ar9. The ma0or
sectors in /ndia which consume general purpose %S > H/%S are the re&rigerator sector,
consumer electronic goods 8including audio and video cassettes9, pac!aging, the
"
automotive sector and household articles and miscellaneous uses which includes .
novelties, stationery items, toys, all pens, eads, toothrushes, uilding materials and
sanitary wares, structural &oam, crystal ware, wall cloc!s and the de&ence sector. +%S
production in the country in "223-2" was close to ?533 T with ;7 polymers producing
"?33 T and the alance eing produced y <*SA ;td.
Demand Projections:
The tale elow summarizes the demand pro0ections &or %S in the various sectors upto the
year 2333 *.'.
Table 1: Projected Demand for Polystyrene uto 1!!!"#$$$
Sector
%year&
Refri'erators Consumer
electronic
Cassette
s
Pac(a'in
'
Ot)ers Total
%tonne&
"223-2" 6333 2633 "5"33 5633 $333 52?33
"225-25 2533 "5"33 22233 2533 "6633 #2233
"222-
2333
"5333 22233 5#"33 "2233 ??533 "?5233
Polystyrene Suly Scenario:
The tale elow gives the e,pected indigenous supply o& %S upto 2333 *.'.
Table #: Polystyrene Indi'enous Suly Scenario
*ear Polyc)em +cDo,e
ll
Surem
e
Reliance Total
%tonne&
"225-25 "5,533 "2,$33 25,333 B 5$,333
"225-26 25,333 25,333 ?3,333 B #$,333
"226-2# ?3,333 ?3,333 ?6,333 25,333 "23,333
"22#-2$ ?6,333 ?6,333 ?6,333 ?3,333 "?$,333
"22$-22 ?6,333 ?6,333 ?6,333 ?6,333 "55,333
"222-2333 ?6,333 ?6,333 ?6,333 ?6,333 "55,333
Demand Suly -a:
2
The demand supply gap up to the year 2333 *.'. has een wor!ed out as &ollows.
Table .: Polystyrene. /stimated Demand - Suly -a
*ear Demand Indi'enous
suly
Demand 0 suly
'a1e2cess% &
"22"-22 52,?33 ?5,233 $,"33
"225-25 #2,233 5$,233 2",#33
"222-2333 "?5,233 "55,333 $,"33
Tec)nolo'y Selection by Indian Comanies:
The tale elow summarizes the technology selection y the /ndian manu&acturers.
Table 3: Tec)nolo'y Selection by Indian Comanies
S.no Comany4s name Collaborator Tye Remar(s
". %olychem ;td
%olychem ;td
'C@ chemical,
)S*
Huntsman
chemical corpn.
)S*
Technical
and
&inance
Collaoration
e,pired
Collaoration &or
their new %S
capacity o& 53333
T%*
2. ;7 polymers
;7 polymers
<D-plastic, )E
*tochem,
&rance
Technical
Technical
Collaoration
was &or the
e,isting plant
+,pansion o& %S
capacity to 53333
T%*
?. 6eliance industries Hunstan
chemical corpn.
Technical Few capacity o&
53,333 T%*
5. Supreme
petrochemicals
Hunstan
chemical corpn
Technical Few capacity o&
53,333 T%*
Polystyrene: International Scenario
7loal consumption o& %olystyrene has een increasing at a steady rate o&
appro,imately 5: p.a. Consumption, which stood at 6.6 million tons in "2$5 has increased
?
to aout $.5 million tons in "223. However, there was only a marginal rise in consumption
etween "223 and "22", with the developed countries showing a slight decrease.
<oth 7eneral %urpose %olystyrene and High /mpact %olystyrene have had an e1ual
share in the total consumption o& %olystyrene. 4anu&acturing capacity has increased y 2
million tons &rom $.5 million in "2$5 to aout "3.5 million in "223. The elow &igure
shows the world consumption o& polystyrene in 23"3.
Taiwan Canada
6ep. o& !orea me,ico Cceania
South *merica
Gapan china
others
*&rica @estern +urope
Central +urope
)nited states
5i'ure 1: 6orld Consumtion of Polystyrene in #$1$
#. PROP/RTI/S 7ND US/S O5 PO8*ST*R/N/
#.1. P)ysical Proerties:
Table 9: P)ysical Proerties of Polystyrene
*ppearance @hite crystalline solid
'ensity 3.26-".35
4olecular &ormula 8C
$
H
$
9
n
5
4elting point H 253
3
C
Thermal conductivity 3.3?? @I4!
6e&ractive inde, ".6
#.#.Processin' Proerties:
Alow properties may e the most important properties o& polystyrene processes.
There are two widely accepted industry methods &or the measurement o& processing
properties. These include the melt &low inde, and the solution viscosity.
The melt flo, inde2 is measured y *ST4 method as a measure o& the melt
viscosity at 233
3
C and a 5!g load. The melt &low inde, o& polystyrene is generally
controlled y ad0ustment o& the molecular weight o& the material and y the addition o&
such luricants as mineral oil. %olystyrenes are commercially produced with melt &low
ranges o& less than " to greater than 53, although the most widely availale gradesgenerally
have melt &lows etween 2.3 and 23g per "3min.
Solution :iscosity is another method &or measuring the molecular structure o& the
polystyrene. Solution viscosity can e measured as an $: solution in toluene and increases
with increasing molecular weight.%olystyrene is a non-Fewtonian &luid with :iscoelastic
properties. The viscosity o& polystyrene melts or solutions is de&ined as the ratio o& shear
stress to shear rate. 7enerally, as the molecular weight o& the polymer is increased or
mineral oil is decreased, melt viscosity increases.
#... +ec)anical Proerties:
Crystal polystyrenes have very low imact stren't)s o& less than 3.5&t-l.
Commercially availale impact polystyrene grades can e otained with values o& ".3 - 5.3
&t-l. 7enerally, polystyrenes are not produced with greater than "5: total ruer ecause
o& polymerization processing constraints. Fevertheless,impact properties can e increased
sustantially without additional ruer y the proper control o& ruer particle size,
percentage o& gra&ting, cross-lin!ing, and percentage o& gel.
Tensile and fle2ural roerties are also important representation o& the strength o&
polystyrenes. /ncreasing the ruer modi&ication o& polystyrene generally leads to lower
tensile strength, crystal grades eing sti&& and rittle. Tensile strength is also decreased y
the addition o& luricants, such as mineral oil. Ale,ural strengths &or polystyrenes can e
otained &rom 5333 to "$333psi and are also decreased y the addition o& ruer and other
5
additives to the polystyrene. +longations can e otained &rom ": &or crystal polystyrene
to "33: &or some impact polystyrene grades.
#.3. T)ermal Proerties:
7nnealed )eat distortion is one popular method &or measuring the resistance to
de&ormation under heat &or polystyrenes. The heat distortion temperature is decreased y
the addition o& ruer, mineral oil, or other additives to polystyrene. The glass transition
temperature &or unmodi&ied polystyrene is ?#? E, and the glass transition temperatures &or
poly utadienes are "6"-235 E, su0ect to the cis, trans and vinyl content.
#.9. C)emical Proerties:
Sol:ent cra;in' o& polystyrene is a commercially important phenomenon. High
impact polystyrenes are susceptile to solvent crazing at the inter&ace etween the ruer
particles and the polystyrene phase. The resistance o& polystyrene to this crazing is re&erred
to as environmental stress crac! resistance 8+SC69.
Aor &ood-pac!aging applications, such as utter tus and delicate containers,
polystyrene with high +SC6 properties are desirale. /ncreasing the percentage o& gel,
percentage gra&ting, and ruer particle size can increase stress crac! resistance.
Residual le:els o& low molecular weight materials are also important topolystyrene
per&ormance. Some o& the chemical impurities in the polystyrene are styrene monomer and
ethyl enzene solvent. 6esidual levels o& styrene elow 233 ppm and ethyl enzene levels
elow ?3 ppm are otainale &or very specialized applications.
#.<. US/S:
". +,truded &oam sheet o& polystyrene can e thermo&ormed into such parts as egg cartons
or carryout &ood containers. These are also used in cra&ts and model uilding, in particular
architectural models.
2. Crystal polystyrene materials have e,cellent thermal and electrical properties which
ma!e them use&ul as low cost insulating materials,envelope windows, cap layers &or glossy
sheet, orthermo&orming into &ood pac!aging applications.
6
?. *nother type o& polystyrene &oam is that produced &rom e,pandale polystyreneeads.
These eads can e molded to produce hot drin! cups, ice chests, disposale trays, plates,
owls, calm shells8&ood pac!aging9 and cushioned or &oampac!aging.
5. *lso, the e,pandale eads can e molded in very large loc!s that can then e cut into
sheets &or thermal insulation. These are supplied as compound with lowing agent and
other additives.
5. High /mpact %olystyrene is o&ten speci&ied &or low strength structural applications when
impact resistance, machineaility and low cost are re1uired.
6.Fatural H/%S is complaint &or use in &ood processing applications. Stero regular poly
utadiene elastomers are used &or impact modi&ications. /t can e processed easily y all
conventional thermoplastic &aricating techni1ues which include &ilm, sheet and pro&ile
e,trusion, thermo&orming, in0ection moulding, in0ection low moulding and structural
low moulding.
#. Cptical property o& polystyrene is used in manu&acture o& unrea!ale glasses &or
gauges, windows and lenses, as well as in countless specialties and novelties and also &or
edge lighting &or the edge lighting o& indicators and dials.
$. Solid or li1uid pigments and dies color high impact and crystal polystyrenes. This can e
accomplished in oth e,trusion and in0ection moulding processes. These colorants are
added and mi,ed during the melting stage o& oth the processes. *lso, polystyrene parts are
amenale to high 1uality printing. ;aels can eprinted directly on the polystyrene part to
produce attractive containers.
2.%olystyrenes are also used in &urniture, pac!aging, appliances, automoiles,construction,
radios, televisions, toys, house ware items, and luggage.
.. 8IT/R7TUR/ SUR=/* O5 DI55/R/NT PROC/SS/S
The di&&erent methods availale &or styrene polymerization are.
?.". <ul! polymerization.
?.2. Solution polymerization.
?.?. +mulsion polymerization.
?.5. Suspension polymerization.
..1. >ul( Polymeri;ation:
Solution 8ul!9 polymerization is commonly re&erred to as mass polymerization in
the industry. The vast ma0ority o& all polystyrene produced today is produced via this
#
technology. The common solvents used in this process are the styrene monomer itsel& and
ethyl enzene. The two types o& mass polymerization are atch and continuous, o& which
continuous mass is y &ar the most popular.
<ul! addition polymerization is a homogeneous process which uses an organic
initiator. The higher the temperature, the lower the molecular weight o& the polymer
produced. *t higher temperatures, the initiator decomposes to &orm radicals at a &aster rate,
then &or a given amount o& monomer with more radicals present more polymer chains will
e started 8initiated9, and the resulting polymers will have a lower molecular weight.
@e can have continuous polymerization at very low temperatures i& we use light toconvert
the initiator molecules to radicals 8which will start the polymerization9.
5i'ure #: Polystyrene +anufacture by >ul( Polymeri;ation
..#. Solution Polymeri;ation
Solution polymerization is a method o& industrial polymerization. /n this procedure,
monomer is dissolved in a non-reactive solvent that contains a catalyst. The reaction results
in a polymer which is also solule in the chosen solvent8either water or an organic
solvent9. +.g. polystyrene in toluenemonomer is solule and the polymer is insolule in the
$
diluent, acrylonitrile in chloro&orm. Heat released y the reaction is asored y the
solvent, and so the reaction rate is reduced. Cnce the ma,imum or desired conversion is
reached, e,cess solvent has to e removed in order to otain the pure polymer.
..../mulsion Polymeri;ation:
+mulsion polymerization is generally used &or polymerization o& styrene with other
monomers or polymers. /t is not a generally commercially accepted method o& producing
crystal polystyrene or high impactpolystyrene8H/%S9. +mulsion polymerization is carried
out similarly to suspension polymerization e,cept that the monomer droplets are
microscopic in size. +mulsion polymerization is also a heterogeneous polymerization with
water as the continuous phase. /n this system, however, monomer droplets are dispersed in
water using sur&actants or emulsi&ying agents, and a stale emulsion is produced.
+mulsion systems are characterized y sustantially smaller particle sizes than
suspension polymerizations, with particles in the range o& 3.35 to 3.2 Jm. *dditionally, a
water solule initiator rather than monomer-solule initiator is employed, and very
di&&erent !inetic &eatures are oserved. The end product o& an emulsion polymerization is a
stalelate,, an emulsion o& polymer in water.
..3. Susension Polymeri;ation:
This is also called pearl polymerization. /t has proved highly e&&icient &or large
scale production o& polymers o& high average molecular weight. <y variation o& the
polymerization condition it is possile to produce a range o& polymers with di&&erent
properties and processing characteristics so that a numer o& grades are o&&ered y the
manu&acturers to meet the di&&ering re1uirements o& the conversion process and the &inal
product.
There are many di&&erent ways o& ma!ing polystyrene using suspension process.
4ost producers use a atch process, although there is no technical reasons why a
continuous process could not wor!. /n the suspension process a numer o& small styrene
drops 3."5-3.53mm in diameter are suspended in water. The reaction occurs within these
drops. To aid in the &ormation o& proper size drops a suspending agent is used, and to !eep
them at that size a stailizing agent is added. * catalyst is used to control the reaction rate.
Table <: Polymeri;ation Systems Comarison
2
Tye of olymeri;ation 7d:anta'es Disad:anta'es
<ul! ;ow impurity levels
Fo solvent removal
Thermal control di&&icult
Side reactions, Khot spotsL
Thermal degradation
+,plosion ris!
Solution Thermal control
+asy mi,ing due to lower
viscosity
/mproved initiation
e&&iciency
'i&&icult to remove solvent and
other ingredients
Cost o& solvent recovery
Solvent environmental impact
%otential chain trans&er to
solvent
Suspension Thermal control
;ow viscosity throughout
reaction
High purity product
Simple polymer isolation
*gitation control
%article size di&&icult to control
%ossile contamination y
dispersing agents
polymer may re1uire washing
and drying.
+mulsion Thermal control
;ow viscosity throughout
reaction.
;ate, may e directly
usale.
High 4@ at high rates
with relatively narrower
4@'.
Small particle size
product.
'i&&icult to remove sur&actants,
emulsi&iers, coagulants.
6esiduals may degrade polymer
properties.
%olymer may re1uire washing
and drying.
5. S/8/CTION O5 T?/ PROC/SS
*mong the aove 5 processes suspension polymerization o&&ers considerale
advantages over the single phase techni1ues in so &ar that heat removal control is no longer
a prolem and a high purity product is otained, ut there are disadvantages such as the
need to use a dispersing agent. <ul! polymerization process is generally used to produce
"3
large amounts o& e,pandale polystyrene and highly thermal control process. /n solution
and emulsion processes solvent should e recovered and residues are &ormed which is not a
prolem in suspension polymerization. Ainally, ased on the aove considerations
suspension polymerization &or the manu&acture o& polystyrene is selected.
/t is used only in &ree radical type processes. The monomer is mechanically
dispersed in a media, usually water. There are cases where an organic media is used in
which neither the polymer nor the monomer are solule in the organic media. The initiator
used can e water solule or organic solule 8enzoyl pero,ide, */<F, or 8FH
5
9
2
8S,C
5
9y9.
)sually the initiator is organic solule. There are two separate phases throughout the whole
process. The droplets must e !ept &ar apart. This re1uires agitation. consistent, e&&icient,
andcontrolled. * suspending agent can e used. %olyvinyl alcoholdissolved in the
a1ueousphase is a typical suspending agent. The rate o& suspension polymerization is
similar to the rate o& ul! polymerization, ut the heat trans&er is much etter. +,amples
include the polymerization o& 44*, and vinyl chloride. The medium to monomer ratio is
"3.". %article size is a&&ect y the &ollowing &our &actors.
M Stirring rate
M 6atio o& reactants
M Suspension agent
M Temperature
/& the particle size gets to large, the particle will asor too much heat. %article size
may e 3.3" to 3.5 cm, or as low as " micron. * suspension agentis a material that gives a
sur&ace activation that !eeps droplets &rom ecome larger 8droplets coming together to
&orm larger droplets is called coalescence9. Suspension polymerization is similar to ul!
polymerization, and it could e considered Nul! polymerization within a droplet.N
5. PROC/SS D/T7I8S
Suspension polymerization is a atch system popular &or special grades o&
polystyrene. /t can e used to produce either crystal or high impact grades. /n impact
production, the styrene and ruer solution is ul! polymerized eyond phase inversion
and is then suspended in water to create oil in water suspension utilizing soaps and
""
suspending agents. The suspended droplets are then polymerized to completion, utilizing
initiator and a staged heating pro&ile. The water phase is used as a heat sin! and heat
trans&er medium to a temperature controlled 0ac!et. Aor the production o& crystal
polystyrene the styrene monomer itsel& is suspended and polymerized via the same
mechanism.
Reaction conditions:
The reaction mi,ture consists o& two phases, a li1uid matri, and monomer droplets.
The monomer and initiator are insolule in the li1uid phase, so they &orm drops within the
li1uid matri,. * suspension agent is usually added to stailize the monomer droplets and
hinder monomer drops &rom coming together. The reaction mi,ture usually has a volume
ratio o& monomer to li1uid phase o& 3." to 3.5. The li1uid phase acts as a heat trans&er
agent, enaling high rates o& polymerization with little change in the temperature o& the
polymerizing solution.
The reactions are usually done in a stirred tan! reactor that continuously mi,es the
solution using turulent pressure or viscous shear &orces. The stirring action helps to !eep
the monomer droplets separated and creates a more uni&orm suspension, which leads to a
more narrow size distriution o& the &inal polymer eads. The polymerization is usually
carried to completion.The !inetics o& the polymerization within an individual ead are
similar to those o& typical radical polymerization.
Particle roerties:
Suspension polymerization is divided into two main types, depending on the
morphology o& the particles that result. /n ead polymerization, the polymer is solule in
its monomer and the result is a smooth, translucent ead. /n powder polymerization, the
polymer is not solule in its monomer and the resultant ead will e porous and irregular.
The morphology o& the polymer can e changed y adding a monomer diluent, an
inert li1uid that is insolule with the li1uid matri,. The diluentschanges the soluility o&
the polymer in the monomer and gives a measure o& control over the porosity o& the
resulting polymer.
The polymer eads that result can range in size &rom "33 nm to 5 mm. The size is
controlled y the stirring speed, the volume &raction o& monomer, the concentration and
"2
identity o& the stailizers used, and the viscosities o& the di&&erent components. The
&ollowing e1uation derived empirically summarizes some o& these interactions.
d = ! 8'
v
O6Ov
m
OP9 I8'
s
OFOv
t
OC
s
9
where, d is the average particle size, ! includes parameters related to the reaction
vessel design, '
v
is the reaction vessel diameter, '
s
is the diameter o& the stirrer, 6 is the
volume ratio o& the monomer to the li1uid matri,, F is the stirring speed, Q
m
and Q
l
are the
viscosity o& the monomer phase and li1uid matri, respectively, R is the inter&acial tension
o& the two phases, and C
s
is the concentration o& stailizer. The most common way to
control the particle size is to change the stirring speed.
The re1uirements o& polymerization are.
a. /nitiator
. Suspending agent
c. Stailizing agent
d. Catalyst
e. %olymerization temperature
a. Initiators: The initiators generally used are enzoyl pero,ide and t-utyl hydro
pero,ide.
b. Susendin' a'ent: To aid in the &ormation o& the proper size drops a suspending agent
is added. Some typical suspending agents are methylcellulose, ethyl cellulose and
polyacrylic acids. Their concentration in the suspension is etween 3.3"-3.5: o& monomer
charged.
c. Stabili;in' a'ent: To !eep the drops at proper size, a stailizing agent is added. The
stailizing agents are o&ten insolule inorganic such as calcium caronate, calcium
phosphates or entonite clay. They are present in small amount than the suspending agents.
d. Catalyst: * catalyst is used to control the reaction rate. The catalysts are usually
pero,ides. The most common ones are enzoyl, diacetyl, lauroyl, caproyl and tert-utyl.
Their concentration varies &rom 3."-3.5: o& the monomer charged.The ratio o& monomer
to dispersing medium is etween "3 and 53:.
e. Polymeri;ation temerature:%olymerization o& styrene occurs at temperature range o&
23-25
3
C.
Process descrition.
"?
The main manu&acturing route to styrene is the direct catalytic dehydrogenation o&
ethyl enzene.
CH
?
CH
2
catalyst CH
2
CH S H
2
+thyl enzene styrene
The reaction shown aove has a heat o& reaction o& -"2" !GImol 8endothermic9.
The suspension method is carried out in large reactors e1uipped with agitators, the
styrene monomer eing maintained in the a1ueous phase as droplets with a diameter
varying etween 3.5-"mm y use o& a dispersing agent such as partially hydrolyzed
polyvinyl acetate, inorganic phosphates or magnesium silicates.
To reduce the cycle time o& the reactors, the entering water and styrene will e
preheated. The temperatures o& the input streams will e sent so as to otain the desired
reaction temperature. The water entering the reactor will e heated to 25
3
C. The ul! o& the
styrene is to e heated to $5
3
C e&ore eing charged. This is done in a vertical doulepipe
heat e,changer, which is directly aove the reactor. To prevent the polymerization&rom
occurring in the heat e,changer or piping system, there are to e no ostructions etween
this heat e,changer and the reactor.
Fearly 65: o& all styrene is used to produce polystyrene. The overall reaction
descriing the styrene polymerization is.
initiator
D CH
2
CH CH
2
CH
D
Styrene %olystyrene
"5
This reaction is carried out in an inert organic solvent environment, which provides
the reaction medium &or this cationic polymerization reaction. The catalyst, ruer
stailizer, and suspending agent are premi,ed in styrene and discharged y gravity into the
reactor. This mi,ture will not e preheated, since it might polymerize. Typical water to
monomer ratios is "." to ?.". * comination o& two or moreinitiators is used with a
programmed reaction temperature to reduce the polymerization time to a minimum &or a
given amount o& residual styrene.
Purification Stes and /2trusion:
/& the water can e removed using physical separation processes, then the styrene
and the other impurities dissolved in it will also e discharged. * centri&uge with a washing
step will e used to do this. The material leaving the centri&uge has "-5: water.The &inal
puri&ication step is drying.
The polystyrene leaving this unit must meet the speci&ications set 83.3?: water9.
Then it is passed through a devolatization e,truder to remove the volatile residues and to
convert the polymer into pellets./t was assumed that ?: o& polystyrene would e removed
&rom the process in airvying, drying, centri&uging, trans&erring, or as ad as ad product. *t
least 25: o& that which is lost in processing must e intercepted e&ore it leaves the plant.
4ost o& it can e removed and sold as o&&-grade material. This waste is split among the
various streams leaving the processing area.
"5
5i'ure .: 5lo, s)eet of susension olymeri;ation
<. +7T/RI78 >787NC/
>asis:*mount o& polystyrene produced per day = 253 T%'
= 253O"3
?
I25
= "35"6.6#EgIhr
7ssumtions:
"6
". /t will e assumed that 22.$: o& the styrene is reacted and this can e accomplished y
using an average o& the temperatures and cycle time given.
2. Temperature o& reaction = 23-25C
?. Cycle time o& reactor=5.5hrs.
Reactor.
Reactor
'odecyl enzene enzoyl pero,ide S
sulphonate miscellaneous
styrene8".3?2 !gI!g %S9
polystyrene
water S tricalcium
phosphate styrene
water miscellaneous
5i'ure 3: +aterial >alance o:er reactor
Inut to t)e reactor:
Styrene = ".3?2 !g styreneI!g polystyrene
= ".3?2O"35"6.6#
= "3#53!g
@ater = 2.3 !g waterI!g polystyrene
= 2.3O"35"6.6#
= 23$??.?5!g.
Tricalcium phosphate = 3.335 !g tricalcium phosphateI!g polystyrene
= 3.335O"35"6.6#
= 52.3$?!g.
'odecyl enzene sulphonate = 3.33336 !g dodecyl enzene sulphonateI!g %S
= 3.33336O"35"6.6#
= 3.625!g.
<enzoyl pero,ide = 3.3325 !g enzoyl pero,ideI!g polystyrene
= 3.3325O"35"6.6#
"#
= 26.352!g.
4iscellaneous = 3.335
= 3.335O"35"6.6#
= 5".6#!g.
Total input to reactor = ?"#3?.#5!g.
Outut from t)e rector:
%olystyrene =".3?3 !g polystyrene I !g o& polystyrene
= ".3?3O"35"6.6#
= "3#22."#!g.
Styrene = 3.332 !g styreneI!g polystyrene
= 3.332O"35"6.6#
= 23.$?!g
@ater = 2.3 !g waterI!g polystyrene
= 2.3O"35"6.6#
= 23$??.?5!g.
4iscellaneous = 3.3""56 !g I!g polystyrene
= 3.3""56O"35"6.6#
= "23.5" !g.
Total output &rom reactor = ?"#3?.#5 !g.
Table @: Reactor +aterial >alance
Comonents inut%('1(' PS& outut%('1(s PS&
Styrene ".3?2 3.332
%olystyrene - ".3?3
@ater 2 2
tri calcium phosphate 3.335 -
dodecyl enzene sulphonate 3.33336 -
enzoyl pero,ide 3.3325 -
4iscellaneous 3.335 -
Total ?.35?56 ?.35?56
6as) tan(
6as) tan(: output &rom the reactor
?.35?56 !gI!g o& %S
2.3 !g o& waterI!g o& %S
"$
3.335 !g o& HClI!g o& %S
".3?3 polystyrene 8unit ratio9
3.332 styrene 8unit ratio9
5.3 water
3.3"56 miscellaneous
5i'ure 9: +aterial >alance o:er 6as) tan(
Inut to ,as) tan(:
Cutput &rom reactor = ?.35?56O"35"6.6#
= ?"#3?.#6!g.
@ater =2.3 !g waterI !g polystyrene
= 2.3O"35"6.6#
=23$??.?5!g.
Hydrochloric acid = 3.335 !g HClI !g polystyrene
= 3.335O"35"6.6#
= 5".6# !g.
Total input to wash tan! =?"#3?.#5 S 23$??.?5 S 5".6#
= 525#$.#5!g.
Outut from ,as) tan(:
%olystyrene = ".3?3 !g polystyreneI !g polystyrene desired
=".3?3O"35"6.6#
= "3#22."#!g
Styrene = 3.332 !g styreneI!g polystyrene
= 3.332O"35"6.6#
= 23.$?!g.
@ater = 5.3 !g waterI !g polystyrene
= 5.3O"35"6.6#
= 5"666.6$!g.
4iscellaneous = 3.3"556 !gI!g o& polystyrene
= 3.3"56O"35"6.6#
= "62.3$!g
"2
Total output &rom wash tan! = "3#22."#S 23.$?S5"666.6$S"62.3$
= 525#$.#5 !g
Table A: 6as) Tan( +aterial >alance
Comonents inut%('1(' PS& outut%('1(' PS&
%olystyrene ".3?3 ".3?3
Styrene 3.332 3.332
@ater 5 5
4iscellaneous 3.3""56 3.3"556
HCl 3.335 -
Total 5.35#56 5.35#56
Centrifu'e
Centrifu'e:
Cutput &rom wash tan!
3.3" !g o& %SI!g o& %S
3.332 !g o& styreneI!g o& %S
".3 !g o& waterI!g o& %S 5.25 !g o& H
2
CI!g o& %S
3.3"556 misc.I!g o& %S
8desired9
".32 !g o& %S I !g o& %S
3.35 !g o& waterI !g o& %S
3.333" !g o& misc.I!g o& %S
5i'ure <: +aterial >alance o:er Centrifu'e
Inut to t)e centrifu'e:
Cutput &rom wash tan! = 525#$.#5 !g
@ater =".3 !g waterI!g polystyrene
="35"6.6# !g water.
Outut from centrifu'e:
The output &rom centri&uge comprises o& two layers. Cne is the desired and theother is ad
product.
'esired product composition.
23
%olystyrene = ".32 !g polystyreneI!g o& desired polystyrene
= ".32O"35"6.6#
= "3625!g
@ater = 3.35 !g waterI !g polystyrene
= 3.35O"35"6.6#
= 523.$?!g
4iscellaneous = 3.333" !gI !g polystyrene
= 3.333"O"35"6.6#
=".35"66# !g
)ndesired product composition.
%olystyrene = 3.3"!g polystyreneI!g polystyrene
= 3.3"O"35"6.6#
="35."66# !g
Styrene = 3.332 !g styrene I!g polystyrene
= 3.332O"35"6.6#
=23.$?!g
@ater = 5.25 !g water I !g polystyrene
= 5.25O"35"6.6# = 5"562.5"!g
4iscellaneous = 3.3"556 !gI !g polystyrene
=3.3"55O"35"6.6#
="6".352 !g.
Table !: Centrifu'e +aterial >alance
comonents inut%('1('
PS&
Desiredoutut%('1('PS& undesired outut%('1('
PS&
polystyrene ".3?3 ".32 3.3"
styrene 3.332 - 3.332
water 5 3.35 5.25
miscellaneous 3.3"556 3.333" 3.3"556
total 6.35#56 ".3#3" 5.2##56
Dryer:
Dryer
*ir 8".?5$6 !gI !g %S9 S output&rom centri&uge
3.3"5 !g o& %SI!g o& %S 3.335 !g o& %SI !g o& %S
2"
8ad product9 ".?2$5" !g o& moist airI !g o& %S
8desired product9
".3 !g o& %SI!g o& %S
3.333" !g o& waterI !g o& %S
5i'ure @: +aterial >alance o:er Dryer
Inut to t)e dryer:
Cutput &rom the centri&uge = "3625 S 523.$? S ".35"66#
= """56.$#!g
*ir = ".?5$6 !g I !g %S
= ".?5$6O"35"6.6#
= "535$ !g
Outut from t)e dryer:
Cutput &rom dryer comprises o& three parts
". 'esired polystyrene with composition.
%olystyrene =".3 !gI!g polystyrene
= "35"6.6# !g o& polystyrene
@ater = 3.333" !gI!g polystyrene
= 3.333"O"35"6.6#
= ".35"66#!g
2. )ndesired %roduct with %olystyrene = 3.335 !gI!g polystyrene
= 3.335O"35"6.6#
= 52.3$?!g
4oist air = ".?2$5" !gI!g polystyrene
= ".?2$5"O"35"6.6#
= "556#.$2 !g
?. <ad product otained has a composition o& polystyrene
= 3.3"5 !gI!g polystyrene
= 3.3"5O"35"6.6#
= "56.25!g
Table 1$: Dryer +aterial >alance
22
comonents inut%('1(' PS& desired outut%('1(' PS& undesired outut%('1(' PS&
polystyrene ".32 ".3 3.32
water 3.35 3.333" -
miscellaneous 3.333" -
*ir ".?5$ -
moist air - - ".?2$
Total 2.5"$" ".333" ".5"$
/2truder:
/2truder
output &rom dryer
".3 !g o& %olystyrene
3.333" !g waterI !g %S
5i'ure A: +aterial >alance o:er /2truder
/nput to e,truder =output &rom dryer = "35"6.6# S ".35"#66#
= "35"#.#"2 !g
Cutput &rom e,truder = "35"#.#"2 !g
@. /N/R-* >787NC/
7ssumtions:
". *ssume 2!g o& styrene are to e used to carry each !g o& additive into the reactor.
2. Steam at "53 psi is used as heating medium.
?. The reaction is ta!ing place in a atch reactor.
5. *ssume heat losses o& aout "3:.
5. Cycle time o& the reactor = 5.5 hrs.
6. *ssume 2 reactors were used.
Styrene )eat e2c)an'er.
Temeratures Inlet Outlet
Styrene ?3
o
C 2?
o
C
2?
The additive &eed tan! must e large enough to handle all additive plus a carrier solution o&
styrene. The amount o& dodecyl enzene sulphonate, tricalcium phosphate and enzoyl
pero,ide used per atch are.
= 83.335 S 3.33336 S 2 O 3.33259 O "35"6.6# O 5.5 I 2
=65.3?2 !g.
Aor 2 !g o& styrene used = 65.3?2 O 2 8assumption "9
= "2$.3#$!g.
@hen 7%%S is made, all ut "2$.3#$!g o& styrene are heated to 2?C. Aor theother
products less is used. T
s
= m
s
C
ps
T
s
where, T
s
is the rate o& heat trans&er
m
s
is the &low rate o& styrene through e,changer
= 88".3?2 !g styreneI!g %S9O"35"6.6# !g %S O5.5hrsI2 U "2$.3#$ !g styrene9 I 85minI639
= ##226.5 !gIhr.
C
ps
= heat capacity o& styrene = 3.5? <tuI l
o
A = ".#22 !GI !g
o
C
T
s
= temperature di&&erence o& styrene entering at ?3
o
C and leaving e,changer at 2?
o
C
= 2? U ?3 = 6?
o
C
T
s
= ##226.5O".#22O6?
= $#63.55O"3
?
!GIhr.
*t "53 psi, T
s
="$2
o
C. 8assumption29
= latent heat o& vaporization = "225.2$!GIhr.
T
s
=m
s
C
ps
T
s
= m O
There&ore, mass &low rate o& steam re1uired, m = $#63.55O"3
?
I"225.2$
= 5?$2.32!gIhr.
7ir )eat e2c)an'er:
Temeratures Inlet Outlet
air ?3
o
C "53
o
C
The air is to e heated to "53C using "53psi steam.
The amount o& energy re1uired = T
a
= m
a.
C
p.
T = m
@here,
m
a
= &low rate o& air used in dryer
= "535$ !gIhr
C
p
= heat capacity o& air entering and leaving the e,changer
25
= ".356$ !GI!g C
T = temperature di&&erence o& air entering at ?3
o
C and leaving the e,changer at "53
o
C
= "53 U ?3 = "23C.
= latent heat o& vaporization = "225.2$!GIhr.
T
a
= "535$O".356$O"23
= ".#6565O"3
6
!GIhr.
*mount o& steam re1uired, m = T
a
I = 8".#6565O"3
6
9 I "225.2$
= $$5."!gIhr.
Reactor coolin' system:
Arom e1uation 829, 8$9 o& reactor design,
'iameter, ' = 2.5#2m
*verage energy removed per hour= ##.2$2O"3
?
'
?
!GIhr.
= ##.2$2O"3
?
O82.5#29
?
.
= ""$.$"?O"3
5
!GIhr
= ??3.3?6!GIs.
/nlet temperature o& cooling water = ?3C.
Cutlet temperature o& cooling water = 6$C.
Speci&ic heat o& cooling water, C
p
=5."$#!GI!g
o
C
;et m
w
e the amount o& cooling water re1uired to remove the heat.
Heat released in the reaction = heat gained y the cooling water
T = m
w
. Cp. T.
m
w
B5."$#O86$-?39 = ??3.3?6 !GIs
m
w
= 2.3#5? !gIs in each reactor.
There&ore amount o& water re1uired in total &or 2 reactors = 2.3#5?O2
="$.66$ !gIs.
Dryer:
Temeratures Inlet Outlet
%olystyrene ?3C. $3C.
*ir "53C. $5C.
Speci&ic heat o& polystyrene, C
apps
=".??#!GI!g
o
C
Heat re1uired to raise polystyrene product entering the dryer to discharge temperature,
= mO C
pps
O T
25
= "3625!gIhrO".??#O"3
?
O8$3-?39I?633s
= ".2#?33O"3
5
@
Speci&ic heat o& water, C
pw
= 5."$# !GI!g
o
C
Heat re1uired &or removing water entering the dryer,
= mOC
pw
O T
= 523.$?!gIhrO5."$#O"3
?
O8$3-?39I?633s
= 3.?32$##O"3
5
@.
There&ore total heat re1uired,
= #."32$O"3
5
S ".323?5O"3
5
@.
= $."2?"5O"3
5
@.
The amount o& air re1uired is determined y the amount o& energy "53C. *irmust supply
to remove the moisture &rom the polystyrene.
m = T
t
I8 C
p
.T9.
@here, Cp= heat capacity o& air = 3.2?# <tuI l
o
C = 3.222? GI!g
o
C.
T = di&&erence in air temperature entering and leaving dryer, C.
Tt = heat trans&erred in dryer =$.23$3?O"3
5
@.
m = mass &low rate o& air.
m = 8$."2?"5O"3
5
9 I83.222?O8"53-$599O?633
= "2#32.656!gIhr.
The amount o& air is ade1uate. *dd "3: to account &or possile heat losses. 8assumption 59
There&ore mass &low rate = "."O "2#32.656
= "?2#2.222 !gIhr.
A. SP/CI5IC /CUIP+/NT D/SI-N
7ssumtions:
". Heat o& the reaction = ?33 <T)Il.
2. *ssume 23: o& the reactor is &ull and height o& the reactor is 2 times o& its
diameter
?. 'ensity o& the mi,ture is "I? o& the way etween water and styrene.
5. *ssume ma,imum reaction rate is nearly twice the average rate.
5. *ssume cycle time &or 7%%S is 5.5 hrs and it ta!es 3.5 hrs &or 4%%S and ".3 hrs
&or H/%S longer than 7%%S and time ta!en &or charge and discharge is "hr and
3.5hr to initiate the reaction.
6. The reaction is ta!ing place in a atch reactor.
26
Process desi'n of t)e reactor:
The polymerization o& styrene is an e,othermic reaction. The amount o& energy
released at any time is dependent on the volume o& the reactor, and the rate o& removal o&
that heat is dependent on the sur&ace area. )nless the heat is removed, the temperature will
rise and the reaction rate will increase. The result will e an uncontrolled reaction that not
only may ruin the atch ut could also damage the reactor and might cause &ire or
e,plosion to occur. There&ore there is a ma,imum size o& the reactor &or each set o&
reaction condition which will e calculated. The ma,imum rate o& heat production will e
&irst calculated.
The heat o& polymerization = ?33 <tuI l 8assumption "9
= ?33O".355I3.55?6
= 62#.#2 !GI!g.
4ass &raction o& the styrene = ".3?2I8".3?2S29
= ".3?2I?.3?2
= 3.?53?#
The weight o& styrene in the reactor = VO=O mass &raction o& styrene 8"9
@here, V = 'ensity o& mi,ture 8assumption 59
= 222.3$6 !gIm
?
= = volume o& reactor=areaOlength = W'
2
I5 O;
@here, ' = diameter o& reactor
; = length o& reactor.
There&ore e1uation 8"9 ecomes,
@eight o& styrene in the reactor = 3.2O222.3$6O3.?53?#OWO'
2
I 5O82O'9 8assumption 29
= 55#.36?O'
?
!g.
There&ore the energy released y polymerization
= @eight o& styrene in reactorOheat o& polymerization
= 55#.36?O'
?
O 62#.#2
= ?"".256O"3
?
O'
?
!G
*ll this energy must e removed as it is &ormed.
The cycle time &or 7%%S = 5.5 hrs 8assumption 59
/& the time ta!en &or charge and discharge = " hr
*nd time ta!en to initiate the reaction = 3.5hr
2#
Then all the energy released must e removed in 5.5-"-3.5 = 5.3hr.
There&ore average energy produced per hour = ?"".256O"3
?
O'
?
I 5
= ##.2$2O"3
?
'
?
!GIhr. 829
However, the reaction rate is not uni&orm. The ma,imum reaction rate must e !nown to
calculate the area needed &or heat e,change.
The ma,imum heat produced per hour = 2O average energy producedIhr.8assumption 59
= 2O##.2$2O"3
?
O'
?
!GIhr
= "55.2#$O"3
?
O'
?
O"3
?
GI?633 s
= 5??2#.22 '
?
GIs 8?9
The rate o& heat removed,
T = ).*.XT
Y
859
@here, ) = overall heat trans&er coe&&icient.
* = area o& heat trans&er.
XT
Y
= average temperature driving &orce etween coolant and suspension.
Since 25: o& the time, the air temperature is elow ?3
Y
C. /t will e assumed that inlet
cooling water temperature never e,ceeds ?3
Y
C.
The reaction temperature = 2?
Y
C.
*ssume the ma,imum cooling water outlet temperature rise is5
Y
C.
There&ore outlet temperature o& cooling water =?5
Y
C
There&ore the average temperature o& cooling water =8?3S?59I2 = ?2.5
Y
C.
XT
Y
= 2?-?2.5 = 63.5
Y
C.
Cverall heat trans&er coe&&icient at 63.5
o
C = 53<tuIhr.&t
2
E =2$?.2 @Im
2
E
The area o& heat trans&er is thearea covered y the suspension. This can e estimatedto e
the ottom sur&ace are S 23: o& the sides. 8 assumption 29
*rea, * = 3.2W'; S W'
2
I5
= 6.55'
2
Sustituting values o& *, XT
Y
and ) in e1uation 8?9, we get,
T = 2$?.2O6.55'
2
O63.5 859
Comparing e1uation 8?9 and e1uation 859, we get,
5??2#.22O'
?
= 2$?.2O6.55'
2
O63.5
' = 2$?.2O6.55O63.5I 5??2#.22
= 2.55? m.
*s, ; = 2' 8assumption 29
2$
= 2O2.55?
= 5."36 m.
*nd, = = W'
2
;I 5
= WO82.55?9
2
O5."36I5
= 26."?$ m
?
= 6235.2? gal.
/n Zencyclopedia o& polymer technology and science[, the &ollowing statement appears.
K/n a suspension polymerization o& styrene in a 5333 gal reactor, the lowest coolant
temperature re1uired is "23\A 852\ C9L.
Hence now the average coolant temperature is ta!en as 52\C instead o& ?2.5\C.
49 = (30+)/2
Cutlet temperature o& cooling water, T = 6$\C.
*nd, average temperature = 86$ S ?39I2 = 52\C.
XT
Y
= 2? - 52 = 55\C.
*lso Z)[ at XT
Y
=55
o
C is 63 <T)I hr.&t
2
.\A =?5".22 @Im
2
E and a ma,imum reaction rate
o& ".$ times theaverage would e etter estimates.
Ta!ing ma,imum heat released per hour = ".$ times average value.
8e1uation2,assumption 59
= ".$O##.2$2 O'
?
O"3
6
I ?633
= ?$225O'
?
GIs 869
6ate o& heat removed T =).*.XT
Y
= ?5".22O6.55O'
2
O55 8#9
Heat released in the reactor = heat gained y cooling water
Arom e1uations 869,8#9
?$225O'
?
= 63O5.6$#O6.55'
2
O55
' = ?5".22O6.55O55I?$225 = 2.5#2m 8$9
; = 2O' =2O2.5#2 = 5.26m
= = W'
2
;I 5
= WO82.5#292O5.26I5
= 2?.25 m
?
+1uation 8"9 ecomes
*mount o& styrene produced per reactor per hour
= 83.2OV O=Omass &raction9Icycle time
22
= 83.2O222.3$6O2?.25O3.?53?#9I5.5 8assumption 2,59
= "2?$.$? !gIhr.
Fumer o& 7%%S reactors re1uired &or 63: conversion is.
= 8"35"6.6#!g %SO".3?2 !g styreneI!g %SO : o& conversion9Iamount o& styrene
produced per reactor = 8"35"6.6#O".3?2O3.69I"2?$.$?
= 5.236 rectors.
*ll the aove calculations have een done using 7%%S. /t will e assumed that the same
conditions apply to 4%%S and H/%S e,cept that the reaction times are di&&erent. Aor
economic purpose, the same size reactor will e used &or each product.
Aor 4%%S the reaction ta!es 3.5hrs longer = 5.5S3.5 =6hrs.
Aor H/%S the reaction ta!es ".3 hrs longer = 5.5S" = 6.5 hrs.
Fumer o& 4%%S reactors re1uired &or 23: conversion = 85.236O3.2O 69I83.6O5.59
= ".$2? reactors.
Fumer o& H/%S reactors re1uired &or 23: conversion = 85.236O3.2O6.59I83.6O5.59
= 2.35 reactors.
There&ore together we need 5 reactors &or 4%%S, H/%S and 5 reactors &or 7%%S ma!ing a
total o& 2reactors needed. * "3
th
reactor will e installed as a spare. This will allow &ull
production to continue i& cleaning out the reactors ecomes more o& a prolem
thane,pected.
+ec)anical desi'n:
'ata &rom literature.
'esign pressure &or the reactor = 223psi = "6.5# !gIcm
2
.
'esign pressure &or 0ac!et = #5psi = 6.2# !gIcm
2
.
%ermissile stress o& reactor = 253!gIcm
2
.
Shell internal diameter = 2.5$6m.
*gitator horse power &or 5333gal = 53hp
'iameter o& agitator = "3?5mm.
Speed = 233rpm.
*gitator lades 8&lat9 = 6
@idth o& lade =#5mm.
?3
Thic!ness o& lades =$mm.
Sha&t material U commercial cold rolled steel.
%ermissile shear stress in sha&t = 553!gIcm
2
.
+lastic limit in tension = 2563!gIcm
2
.
4odulus o& elasticity ="2.5O"35!gIcm
2
.
%ermissile stresses &or !ey 8caron steel9
Shear = 653!gIcm
2
.
Crushing = "?33!gIcm
2
.
Stu&&ing o, 8caron steel9
%ermissile stress = 253!gIcm
2
.
Studs and olts 8hot rolled caron steel9
%ermissile stress = 5$#!gIcm
2
.
Goint e&&iciency = 3.$5.
%oisons ratio = 3.?.
!. +7T/RI78S O5 CONSTRUCTION
The choice o& construction material &or a polymerization reactor will depend on a
variety o& &actors, most importantly the speci&ic polymerization to e per&ormed. Stainless
steel construction o&&ers a lot more options and has many things to consider. The particular
alloy o& stainless steel to e used involves a alance o& economics, corrosion engineering,
and pressure vessel mechanical design. %rocess heat trans&er issues may also enter the
decision. Type ?35 has a higher allowale stress than ?"6 ut a somewhat narrower
spectrum o& corrosion resistance. /t is also a little less e,pensive material. So it may e
indicated &or plants that re1uire large, higher pressure reactors. However i& there is a
component o& the polymerization that is corrosive to ?35 then ?"6 might e pre&erred.
+aterial Proerties:
*C53$ gives consideration to ma,imum replacement volume, and ma,imum size
and density o& synthetic particles that will e recognized in the evaluation report. *C53$
?"
re1uires synthetic particle properties, including ma,imum diameter and gradation, ul!
density, and water asorption to e tested in accordance with *ST4 C "?6, *ST4 C 22
and *ST4 C "2$, respectively. * series o& tests is also re1uired y *C53$ to determine
density and compressive strength o& concrete that is to e evaluated under *C53$.
Concrete compressive strength measurement is to e in accordance with *ST4 C ?2.
*ST4 C 56# and *ST4 C "?$ are used to measure the e1uilirium concrete density and
unit weight, respectively. These properties are measured and reported to e used &or
&le,ural strength, splitting tensile strength and modulus o& elasticity calculations.
+ec)anical Proerties:
*s re1uired y *C53$, concrete &le,ural strength is to e determined using *ST4
C#$, and average test results are to e e1ual to or higher than the value otained &rom
#.5]&c, where &
c
is the measured compressive strength o& the concrete in accordance with
*ST4 C ?2.
5ire"resistance and Combustibility:
*C53$ also contains two optional tests. noncomustile uilding material
evaluation y testing in accordance with *ST4 + "?6 to show that concrete with
lightweight synthetic particles can e classi&ied as noncomustile material and &ire-
resistance-rated construction tests conducted in accordance with *ST4 + ""2 to determine
the &ire-resistance ratings o& assemlies with concrete containing the light weight synthetic
particles in the concrete mi,ture.
7ccetance Criteria Statements:
/& a product demonstrates through tests that it satis&ies all re1uirements o& *C53$,
an evaluation report is issued veri&ying that the product can e used as an alternative to
uilding code-speci&ied materials.
"9 +valuation reports must state the ma,imum replacement amount o& the light weight
synthetic particles that was utilized during the 1uali&ication tests, along with particle
density and ma,imum water asorption values.
29 To maintain product consistency, *C53$ re1uires third-party &ollow-up inspections y
an approved inspection agency &or the manu&acture o& the light weight synthetic particles.
?2
This is re1uired so that the manu&acturer will continue to produce the same product used
during the 1uali&ication tests.
?9 Aor structural design purposes, concrete containing light weight synthetic particles
must e considered as structural lightweight concrete. This re1uires use o& *C/ ?"$
parameters and design coe&&icients speci&ied &or structural light weight concrete. <ecause
the density o& concrete produced using light weight synthetic particles as aggregate
replacement may vary, implementing light weight concrete coe&&icients and parameters is
considered to e a conservative approach &or design o& reduced-weight concrete with
synthetic light weight particles.
59 /n addition to the items o& *ST4 C 25, the delivery tic!et &rom the ready- mi, plant
must include the type and amount o& lightweight synthetic particles added to the concrete
mi,ture.
59 <ecause o& the presence o& compressile +%S eads in the concrete mi,ture, the creep
o& the concrete was o& concern. There&ore, &or applications where computed de&lections
contain long-term de&lections due to sustained loads, creep e&&ects ased on creep test
results must e considered in design, which must e sumitted to the code o&&icial &or
approval.
69 Chloride content o& +%S eads was o& concern &or corrosion o& rein&orcement.
1$. ?/78T?D S75/T* 7ND /N=IRON+/NT78 7SP/CTS
6aste roducts:
%olystyrene manu&acture is a relatively clean process. Small volumes o& li1uidand
gaseous wastes are generated and these are treated within the plants. @aste polystyrene
generated during production is reprocessed or sent to a recycler. %olystyrene manu&acture
is a relatively clean process. Small volumes o& li1uid and gaseous wastes are generated and
these are treated within the plants. @aste polystyrene generated during production is
reprocessed or sent to a recycler. This is a 4ost +nergy-+&&icient%ac!aging 4aterial.
%olystyrene is Sa&e, Hygienic %olystyrene and the +nemy o&<acteria.
/ase of disosal:
??
*ccording to the ).S. +nvironmental %rotection *gency 8+%*9 in the "222 update
o& theNCharacterization o& 4unicipal Solid @aste in the ).S.N report, less than one
percent8aout 3.6 percent9 o& solid waste disposed o& in the ).S. is polystyrene pac!aging
-including oth &ood service pac!aging 8cups, plates, owls, trays, clam shells, meat trays,
egg cartons, yogurt and cottage cheese containers, and cutlery9 and protective
pac!aging8shaped end pieces used to ship electronic goods and loose &ill NpeanutsN9.
The disposal o& polystyrene is managed sa&ely and e&&ectively through the
integrated system advocated y the ).S. +%*, which includes. Source 6eduction, 6euse,
6ecycling, @aste-to-+nergy 6ecovery, and ;and&illing.
Polystyrene safe to use in contact ,it) food:
Aor more than 53 years, polystyrene has een in wide spread use as a hygienic
material &or protecting and preserving &ood. /n &act, one-reason polystyrene single use &ood
containers are so widely used in hospitals and other sensitive environment is that they are
signi&icantly more hygienic than the alternatives. %olystyrene does not haror acteria,
which is a ma0or concern among health specialists.
* recent *merican study shows that " in # reusale dishes haror a level o& acteria
which e,ceeds )S health standards. /n contrast, no disposale &ood service items e,ceeded
the standards.
5oam Polystyrene 0 Presence of C5C4s:
+,truded &oam polystyrene produced in &or meat, chic!en and vegetale trays and
ta!e away &ood containers, does not use CAC lowing agents. %roducers converted
away&rom CAC(s in "2$2 and now operate on recycled caron dio,ide or hydrocaron
gases.+,pandale or ead polystyrene 8+%S9 such as in produce o,es has always used a
hydrocaron lowing agent.
Reuse:
6euse, the practice o& utilizing polystyrene products in the same &orm, is important
notonly ecause it delays the &inal disposal o& a product, ut also ecause it reduces
themanu&acture and purchase o& new products. *s a result, reuse prevents waste. Fearly
?3percent o& polystyrene loose &ill 8sometimes called NpeanutsN ecause o& its shape9
isused again, ma!ing it one o& the most commonly reused pac!aging materials in
?5
someretail locations. Aor mailing services, the reuse rate o& loose &ill is as high as 53
percent.
The success&ul application o& reused loose &ill polystyrene reduced the demand &or
virgin polystyrene y 25 percent in "22# alone and, to this day, continues to directly reduce
waste.Cther pac!aging and disposales commonly reused y the polystyrene industry
include.pallets, insulated shipping o,es, test tue trays, auto part trays, ice chests and
coolers.
Recyclin':
The recycling o& polystyrene protective pac!aging and non-pac!aging polystyrene
materials, 8such as audioIvisual cassettes and agricultural nursery traysIcontainers9 has
increased dramatically during the last decade and there has een a decrease in the amount
o& polystyrene &ood service pac!aging recycled during this period. Fon-&ood
servicepac!aging is not contaminated with &ood and other wastes as is &ood service
polystyrene pac!aging, and there&ore is more cost-e&&ective to recycle. %resently, &ood
service polystyrene pac!aging is generally not recycled ecause it is not economically
sustainale. /t is important to note that ecause o& un&avorale economics, no other post
consumer &ood service disposale material, including paper and paperoard, is recycled in
a measurale way.
<e&ore "2$$, there was essentially no recovery o& post-consumer polystyrene &or
recycling, ut as o& 2333, 0ust twelve years later, more than ?2# million pounds o&
polystyrene pac!aging were recycled. * portion o& this material came &rom durale
polystyrene products such as coat hangers, compact disc N0ewel cases,N single-use cameras
and agricultural nursery trays.
Some companies that ma!e protective pac!aging are collecting it ac! &orrecycling
through the *lliance o& Aoam %ac!aging 6ecyclers. /n addition, some ma!es o& loose &ill
NpeanutsN have set up a networ! o& collection sites &or reuse and recycling o& their
polystyrene products. %roducts that have incorporated recycled-content polystyrene
include. &oam eggcartons, lunch trays, transport pac!aging, audio and videocassette cases,
o&&ice supplies and uilding materials.
?5
6aste"to"/ner'y Reco:ery:
/n many overseas countries polystyrene is recycled through incineration o&
municipal waste &or energy recovery. The urning o& polystyrene is no more hazardous
than comustion o& many natural organic materials.
%olystyrene consists solely o& caronand hydrogen. @hen comustion is complete,
water and caron dio,ide are given o&&, leaving trace levels o& ash, the same comustion
products as &rom paper or wood. @hile some polystyrene in medical an municipal wastes
is currently incinerated in *ustralia, the energy recovery option has not yet een
implemented.
@hen incinerated, polystyrene produces energy, which compares &avoraly
withcoal and oil. <ecause o& its high &uel value, polystyrene in properly designed
incineratorshelps to urn wet garage more e&&iciently, and maintain the high urning
temperaturesnecessary &or sa&e comustion.The incineration o& plastics can also generate
energy and this potential is alreadyeing harnessed in some overseas countries, particularly
in @estern +urope, The )nitedStated and Gapan.
8and fillin':
@hile recycling and reuse continue to grow in popularity, most o& the waste in this
country still goes to land&ills. %eople assume the waste inside a land &ill iodegrades. <ut
the &act is that very little - not paper, not polystyrene, not even &ood waste - degrades in a
meaning&ul way.
%olystyrene is e&&ectively and sa&ely disposed o& in land&ills. 4odern land&ills are
designed to protect the environment &rom the li1uids and gases produced during the very
slow rea!down y reducing the e,posure o& garage to air, water and sunlight -conditions
needed &or degradation. There&ore, y design, modern land&ills greatly retardthe
?6
degradation process to reduce the y-products that might otherwise contaminate
groundwater and the air.
Pre:entin' 8itter:
The polystyrene industry cares aout the environment. * widely held
misconception is that litter is a prolem caused y speci&ic materials themselves rather than
aerrant consumer ehavior. The reality is that some people improperly dispose o&
materials y littering. ;ittering is a matter o& ehavior, people who discard materials into
theenvironment usually do so ecause they don(t thin! or don(t care. *ttriuting the litter
issue to one particular pac!aging material does not solve the prolem ecause another type
o& pac!aging will ta!e its place as litter unless ehavior changes.
+SDS S?//T
+SDS Name: %olystyrene
C)emical 5amily: %olymer.
?a;ards Identification:
P)ysical State
7earance
/mer'ency O:er:ie,
Routes of /ntry
Potential 7cute ?ealt)
/ffects:
/yes
S(in
In)alation
Solid
%ellets
/rritating vapors to respiratory system and eyes may
&orm when polymer is processed at high temperatures.
4olten or heated material in s!in contact can cause
severe urns.
Aor Hot 4aterial. s!in contact, eye contact, and
inhalation.
'ust may cause mechanical irritation to eye.
?eated Polymer: +ye contact can cause serious
thermal urns.
=apours &ormed when polymer is heated may e
irritating to the eye.
Fo !nown acute e&&ects o& this product resulting &rom
s!in contact at room temperature.
Fegligile at room temperature. Fuisance dusts can e
?#
In'estion
5irst 7id +easures:
/ye Contact
S(in Contact
In)alation
In'estion
5ire 5i')tin' +easures:
5lammability of t)e Product
7uto"i'nition Temerature
5las) Points
5lammable 8imits
Products of Combustion
/2losion ?a;ards in
Presence of =arious
Substances
5ire 5i')tin' +edia and
Instructions
Protecti:e Clot)in' %5ire&
irritating to the upper respiratory tract.
/rritating vapors may &orm when the polymer is
processed at high temperatures.
Fo e&&ects are e,pected &or ingestion o& small amounts.
4ay e a cho!ing hazard.
6inse with water &or a &ew minutes. See! medical
attention i& necessary.
Polymer: FC !nown e&&ect on s!in contact, rinse with
water &or &ew minutes.
?eated Polymer:Aor serious urns &rom heated
polymer, get medical attention. /n case o& s!in contact,
immediately immerse in or &lush with clean, cold water.
*llow the victim to rest in a well-ventilated area.
Fo Airst *id procedures are needed.
4ay e comustile at high temperature.
553\C 8$25\A9
^233\C 8^?22\A9
Fot availale
Caron o,ides 8CC, CC29 and soot.
6is!s o& e,plosion o& the product in presence o&
mechanical impact. Fot e,pected.
6is!s o& e,plosion o& the product in presence o& static
discharge. %ossile.
6is! o& e,plosion &rom dust accumulation o& this
product is possile.
S4*;; A/6+. 'ry chemical e,tinguisher 8*<C or
*<9. )se water spray or &og.
;*67+ A/6+. )se water spray or &og. 'o not use
water 0et.
4ay re-ignite itsel& a&ter &ire is e,tinguished.
@ear 4SH*IF/CSH approved sel&-contained
reathing apparatus or e1uivalent and &ull protective
?$
Secial Remar(s on
5ire?a;ards
Secial Remar(s on
/2losion ?a;ards
?andlin' and Stora'e:
?andlin'
Stora'e
Personal Protection:
/yes
>ody
Resiratory
gear.
Aire may produce irritating gases and dense smo!e.
Alowing material may produce static discharge, igniting
dust accumulations.
%rocessing or material handling e1uipment may
generate dust o& su&&iciently small particlesize, that
when suspended in air may e e,plosive.
*void Temperatures o& 633\A 8?"6\C9 or aove.
Handling o& plastic may &orm nuisance dust. %rotect
personnel.
%neumatic material handling and processing e1uipment
may generate dust o& su&&iciently small particle size
that, when suspended in air, may e e,plosive. 'ust
accumulations should e controlled through a
comprehensive dust control program that includes, ut
is not limited to,source capture, inspection and repair o&
lea!ing e1uipment, routine house!eeping and employee
training in hazards.
@hen handled in ul! 1uantities, this product and its
associated pac!aging may present a crushing hazard
due to the large masses involved, possily resulting in
severe in0ury or death.
Eeep container dry. Eeep in a cool place. 7round all
e1uipment containing material. Eeepcontainer tightly
closed. Eeep in a cool, well-ventilated place.
Comustile materials shoulde stored away &rom
e,treme heat and away &rom strong o,idizing agents.
Sa&ety glasses
Coveralls.
=entilation is normally re1uired when handling this
product at high temperatures. @ear appropriate
respirator when ventilation is inade1uate.
?2
?ands
5eet
Stability and Reacti:ity:
Stability and Reacti:ity
Incomatibility ,it)
=arious Substances
?a;ardous Decomosition
Products
?a;ardous
Polymeri;ation
Thermally insulated gloves re1uired when handling hot
material.
Shoes.
The product is stale. *void Temperatures o& 633\A
8?"6\C9 or aove.
6eactive with strong o,idizing agents.
Hazardous decomposition products are caron
mono,ide, caron dio,ide, dense smo!e, and various
hydrocarons. +,posure o& polystyrene to e,tremely
high temperatures 8633
o
A orhigher9 may cause partial
decomposition. Chemicals that may e released include
styrenemonomer, enzene, and other hydrocarons.
Fo.
11. P87NT 8OC7TION 7ND 87*OUT
Plant 8ocation
The geographical location o& the plant can have a crucial e&&ect on the pro&itaility
o& a pro0ect, and the scope &or &uture e,pansion. 4any &actors must e considered when
selecting a suitale site, and o& the plant on studying many &actors =isa!hapatnam in
*ndhra %radesh is selected as the est place. The principal &actors to e considered are.
4ar!eting area.
6aw material supply.
Transport &acilities.
*vailaility o& laour.
*vailaility o& utilities. water, &uel, power.
*vailaility o& suitale land.
+nvironmental impact, and e&&luent disposal.
53
;ocal community considerations.
Climate.
%olitical strategic considerations.
+ar(etin' 7rea
Aor materials that are produced in ul! 1uantities. such as cement, mineral acids
and &ertilizers, where the cost o& the product per ton is relatively low and the cost o&
transport a signi&icant &raction o& the sales price, the plant should e located close to the
primary mar!et. This consideration will e less important &or low volume production, high-
priced products_ such as pharmaceuticals. /n an international mar!et, there may e an
advantage to e gained y locating the plant within an area with pre&erential tari&&.
Ra, +aterials
The availaility and price o& suitale raw materials will o&ten determine the site
location. %lants producing ul! chemicals are est located close to the source o& the ma0or
raw material_ where this is also close to the mar!eting area. Soda ash plant should e
located near the salt la!es or near sea, where sodium chloride is availale aundantly.
Transort
The transport o& materials and products to and &rom plant will e an over riding
consideration in site selection. /& practicale, a site should e selected that is close at least
two ma0or &orms o& transport. road, rail, waterway or a seaport. 6oad transport is eing
increasingly used, and is suitale &or local distriution &rom a central warehouse. 6ail
transport will e cheaper &or the long-distance transport o& ul! chemicals. *ir transport is
convenient and e&&icient &or the movement o& personnel and essential e1uipment and
supplies, and the pro,imity o& the site to a ma0or airport should e considered.
7:ailability of 8abor
;aor will e needed &or construction o& the plant and its operation. S!illed
construction wor!ers will usually e rought in &rom outside the site, ut there should e
an ade1uate pool o& uns!illed laor availale locally and laor suitale &or training to
operate the plant. S!illed trades men will e needed &or plant maintenance. ;ocal trade
5"
union customs and restrictive practices will have to e considered when assessing the
availaility and suitaility o& the laor &or recruitment and training.
Utilities %ser:ices&
The word KutilitiesL is now generally used &or the au,iliary services needed in the
operation o& any production process. These services will normally e supplied &rom a
central &acility and will include.
M +lectricity - %ower re1uired &or electrochemical processes, motors, lightings and general
use.
M Steam &or process heating - The steams re1uired &or the process are generated in the tue
oilers using most economic &uel.
M Cooling water - Fatural and &orced dra&t cooling towers are generally used to provide the
cooling water re1uired on site.
M @ater &or general use - The water re1uired &or the general purpose will e ta!en &rom
local water supplies li!e rivers, la!es and seas. <ecause o& this reason all the plants located
on the an!s o& river.
M 'ematerialized water - 'ematerialized water, &rom which all the minerals have een
removed y ion-e,change is used where pure water is needed &or the process use, in oiler
&eed water.
M 6e&rigeration - 6e&rigeration is needed &or the processes, which re1uire temperatures
elow that are provided y the cooling water.
M /nert-gas supplies.
M Compressed air - /n a polystyrene plant compressed air is one o& the raw materials. /t is
also needed &or pneumatic controllers etc.
M +&&luent disposal &acilities - Aacilities must e provided &or the e&&ective disposal o& the
e&&luent without any pulic nuisance.
/n:ironmental Imact and /ffluent Disosal
*ll industrial processes produce waste products, and &ull consideration must e
given to the di&&iculties and coat o& their disposal. The disposal o& to,ic and harm&ul
e&&luents will e covered y local regulations, and the appropriate authorities must e
consulted during the initial site survey to determine the standards that must e met.
8ocal Community Considerations
52
The proposed plant must &it in with and e acceptale to the local community. Aull
consideration must e given to the sa&e location o& the plant so that it does not impose a
signi&icant additional ris! to the community. ;and 8site considerations9 su&&icient suitale
land must e availale &or the proposed plant and &uture e,pansion. The land should e
ideally &lat, well drained and have load-earing characteristics. * &ull site evaluation should
e made to determine the need &or piling or other &oundations.
Climate
*dverse climatic conditions at site will increase costs. *normally low
temperatures will re1uire the provision o& additional insulation and special heating &or
e1uipment and piping. Stronger locations will e needed at locations su0ect to high wind
loads or earth1ua!es.
Political and Strate'ic Considerations
Capital grants, ta, concessions, and other inducements are o&ten given y
governments to direct new investment to pre&erred locations_ such as areas o& high
unemployment. The availaility o& such grants can e the overriding consideration in site
selection.
Plant 8ay Out
The economic construction and e&&icient operation o& a process unit will depend on
how well the plant and e1uipment speci&ied on the process &low sheet is laid out. The
principal &actors are considered are.
+conomic considerations. construction and operating costs.
The process re1uirements.
Convenience o& operation.
Convenience o& maintenance.
Sa&ety.
Auture e,pansion.
4odular construction.
Costs
5?
The cost o& construction can e minimized y adopting a layout that gives the
shortest run o& connecting pipe etween e1uipment, and at least amount o& structural steel
wor!. However, this will not necessarily e the est arrangement &or operation and
maintenance.
Process ReEuirements
*n e,ample o& the need to ta!e into account process consideration is the need to
elevate the ase o& columns to provide the necessary net positive suction head to a pump or
the operating head &or a thermo siphon reoiler.
Oerations
+1uipment that needs to have &re1uent attention should e located convenient to the
control room. =alves, sample points, and instruments should e located at convenient
positions and heights. Su&&icient wor!ing space and headroom must e provided to allow
easy access to e1uipment.
+aintenance
Heat e,changers need to e sited so that the tue undles can e easily with drawn
&or cleaning and tue replacement. =essels that re1uire &re1uent replacement o& catalyst or
pac!ing should e located on the outsideo& uildings. +1uipment that re1uires dismantling
&or maintenance, such as compressors and large pumps, should e places under cover.
Safety
<last walls may e needed to isolate potentially hazardous e1uipment, and con&ine
the e&&ects o& an e,plosion. *t least two escape routes &or operators must e provided &rom
each level in process uildings.
Plant e2ansion
+1uipment should e located so that it can e conveniently tied in with any &uture
e,pansion o& the process. Space should e le&t on pipe alleys &or &uture needs, and service
pipes over-sized to allow &or &uture re1uirements.
+odular construction
55
/n recent years there has een a move to assemle sections o& plant at the plant
manu&acturer[s site. These modules will include the e1uipment, structural steel, piping and
instrumentation. The modules are then transported to the plant site, y road or sea.
The advantages o& modular construction are.
/mproved 1uality control.
6educed construction cost.
;ess need &or s!illed laour on site.
Some o& the disadvantages are.
Higher design costs > more structural steel wor!.
4ore &langed constructions > possile prolems with assemly, on site.
T)e Plant 8ayout Fey 6ords
". 6aw material Storage
2. %roduct Storage
?. %rocess Site
5. ;aoratories
5. @or!shop
6. Canteen > Change house
#. Aire <rigade
$. Central Control 6oom
2. Security o&&ice
"3. *dministrative <uilding
"". Site &or +,pansion %ro0ect.
"2. +&&luent treatment plant
"?. %ower house
"5. +mergency water storage
"5. %lant utilities
* detailed plant layout is drawn and some general considerations that in&luenced the plans
&ollow.
". Space was set aside &or a whole new train.
2. The prevailing wind in the summer comes &rom the northwest and in the winter comes
&rom the west.
55
?. The low down tan! is located on the south side o& the plant where winds will
notgenerally carry any spills over the plant.
5. The utilities and the waste treatment areas are located on the north side o& theplant where
they will e upwind o& the plant.
5. The styrene storage will e located on the south side o& the plant ?33&t &rom the river and
the doc!. /t will e ?33&t &rom the processing area.
6. The warehouse and the ul! storage will e located on the west side, upwind &rom the
plant and styrene storage. They will e at least 253&t &rom reactor area.
#. The reactor and the &eed preparation area will e on the east side o& the plant 233&t &rom
the river.
$. The other processing areas will e etween the reactor area and the warehouse. They
will e over 233&t &rom the reactor area.
Some speci&ic considerations &ollow.
". There must e enough headroom aove the reactor to remove the agitator.
2. There must e enough room to remove the screw &rom the e,truder.
?.7ravity &eed is to e used &or charging additives to the reactor, &or discharging the reactor
to the hold tan!s, and &or &eeding the dryer.
5. +ach o& the styrene storage tan!s will have a di!e around it that is capale o& containing
the tan
