FACULTY OF CHEMICAL ENGINEERING AND NATURAL

RESOURCES

BKF 2343 MATERIAL AND ENERGY BALANCE

REPORT OF MINI PROJECT

LECTURER’S NAME: DR. SURIYATI BINTI SALEH

NAME MATRIC NO.

MUHAMMAD DANIAL BIN OTHMAN KA15163
MOHAMMAD FARID ISKANDAR BIN MOHD YUSRI KA15174
MUHAMMAD KHAIRUL AIZAT BIN ISMAIL KA15082
MOHD SHAFIQ BIN RASHID MUTALIB KA15181
 Content
List Page

Part 1
1.1 History
1.2 Application
1.3 Market survey
1.4 Screening synthesis route

Part 2
2.1 Process Flow Diagram
2.2 Calculation

References
Introduction of Styrene

Styrene, also known by the names of “phenylethane”, “vinyl benzene” or

“ethylbenzene”, is a colourless oily organic compound and a derivative of benzene.
Styrene evaporates easily and serves as a precursor to polystyrene and several
other copolymers.

In 1839, Styrene or the first name which is called as “Styrol” was discovered
by German apothecary Eduard Simon. He isolated a volatile oil from resin ( storax or
styrax ) of the American sweetgum tree. He called the oil “styrol” which now known
as Styrene. The actual founder of the Styrene was in 1827 by Bonastre during
experiment with alcohol extracts of Storax balsam. He separated the styrene as an
oil-like distillate of the balsam in 1831. The chemical reaction during the distillation is
a pyrolytic decarboxylation of organic acids. This proof that the existence of styrene
as natural product. Later the propensity to polymerize was observed by Simon. The
production didn’t stop at that point as Berthelot synthesized styrene by passing
acetylene and various aromatic hydrocarbons through the heated porcelain tube.

Styrene is named for "styrax" (also called "storax Levant"), the resin from a
Turkish tree, the Oriental sweetgum (Liquidambar orientalis), from which it was first
isolated and not for the tropical Styrax trees from which benzoin resin is produced.
Low levels of styrene occur naturally in many kinds of plants, as well as a variety of
foods such as fruits, vegetables, nuts, beverages, and meats. Its density 0.909
g/cm³ , Melting point -30 °C, 243 K, -22 °F, Boiling point 145 °C, 418 K, 293 °F,
Appearance is Colorless to yellow oily liquid, Penetrating odor and has a Negligible
Solubility (< 0.1%).

The discoveries of styrene were found in the 19th century but its commercial
production did not begin until 1925. In the beginning of 20 th century, styrene was
detected as impurities in industrial products. They maximize and monopolize the
usage as product like tar, tyre and carburetted water gas for daily life. Since the
news about the styrene started, many companies begin their research and tried to
operate on producing it. Naugatuck Chemical Co. in United State was the first one
producing styrene but stop after facing many difficulties in manufacture. Meanwhile,
in Germany I. G. Farbenindustrie carried the development work and reached to a
successful commercial. Even though they managed to become successful in the
commercial, but the one that become ultimately first company that managed to
produce styrene was Dow Chemical Co. in 1930.

As the news about styrene spread, the worldwide has huge demand and it
production increased from less than 30000 tons in 1938 to 2.5 million tons in 1965. It
reaches it peaks as it continued requested by worldwide as it get to 7 million tons in
1977. It can be concluded that the production rate growth 12% from 1965 to 1977.
The expansion of monomer production expands to the development production
facilities laid the groundwork for polystyrene and styrene copolymers.
 In addition the styrene in 1930 was mainly consumed in synthetic rubber
industry. The nation in Germany and United States has declared their trademark
which is Buna-S and GR-S rubber. Aside from the famous growth of styrene, the
polymers shows a positive impact as it demand continues from thousand tons in
1937 to 4.2 million tons in 1997. Unsaturated polyesters and reinforced plastics were
introduced for military used in 1942. Many methods and ways have been
approached for the manufacture and variation process of styrene. The commercial
uses of styrene were finalized for chemical reaction in polymerization and
copolymerization.

Another aspect was measured because the usage of styrene begins to take
effect and affect the surrounding even for human respiratory system. Some effect in
the irritation from the chemical reaction. Apart from that, human involve in the
process begin to have depression, tiredness, headache, fatigue and others sickness.
Safety measure and precaution have been released for preventing harm and
unnecessary result.

In a nutshell, the styrene process from the breaks down creates a new start
for human being to manipulate the nature product. The styrene was discovered for it
usage and all the characteristics being calculated for it production.
Application of styrene

Styrene is essential in the creation of many products that we use every

day. A few of the most familiar uses of styrene including such as solid and film
polystyrene, used in rigid food service containers, CD cases, appliance
housings, envelope windows and many other products. Next, polystyrene
foam, used in food service products and building insulation. Furthermore,
composite products, used in tub and shower enclosures, automobile body
panels, wind turbine parts, boats and many other applications. Moreover,
other styrene-based materials include the ABS plastic, used in refrigerator
liners, medical devices, small household appliances and luggage. The SAN
plastic, used for food containers and optical fibers. Next, SB Rubber (SBR),
which reduces dependence on natural rubbers and provides improved
performance in applications such as vehicle tires, leading to improved fuel
efficiency. Last but not least, SB latex (SBL) used in many paper coatings and
in more than 90% of the broadloom carpeting made in the United States to
attach carpet fibers to a backing material.

Strength, Durability, Comfort, Safety

Styrene is so widely used today because it enables a multitude of
products to deliver many benefits that are highly valued by consumers. These
benefits include strength, durability, comfort and safety. For example, styrene-
based products cushion bicycle helmets, strengthen military armor, create
wind power turbines, reduce coal plant emissions, enhance components that
make cars and trains lighter and more fuel-efficient, enable manufacturing
high-performance and cost-effective recreational products such as boats and
other watercraft, and reduce dependence on costly natural resources such as
tropical hardwoods used in boats and marble and granite used in homes and
buildings.
Market Survey
1. Supply and demand of the product worldwide

The market for styrene is highly diversified which includes various types of
derivatives, each having a wide range of applications across various sectors of the
market. Owing to this, large number of manufacturers present in the styrene market
engages in the production of different styrene-based products for various
applications. The global demand for styrene has been witnessing high growth on
account of the emerging packaging and construction industry which has led to
increasing demand for infrastructure facilities and consumer goods, especially in
emerging regions such as Asia Pacific. The overall global production of styrene has
been relocating to emerging economies, while developed industrialized regions such
as Western Europe and the U.S. have considerably reduced their production
capacities over the past few years.
 The global demand for styrene has been witnessing high growth on account of
the emerging packaging and construction industry which has led to increasing demand
for infrastructure facilities and consumer goods, especially in emerging regions such as
Asia Pacific. The overall global production of styrene has been relocating to emerging
economies, while developed industrialized regions such as Western Europe and the
U.S. have considerably reduced their production capacities over the past few years.
This trend occurred on account of the previous excessive increase in production at a
time when the global demand for styrene rose at less dynamic rates or even declined
during the global recession in 2008 - 09. Recent jump in benzene prices have led to
various styrene manufacturers increasing the cost of their styrene products. Moreover,
the collision of seasonally strong demand and low inventories with reduced styrene
supply from propylene oxide/styrene monomer (POSM) facilities has further propelled
styrene prices.

Growth in the end-user application industries such as automotive and construction is

anticipated to be one of the key factors driving the global styrene market. Automotive
industry has been the major end user of styrene butadiene rubber (SBR) particularly
used in tire manufacturing applications. However, increasing health and environmental
concerns due to usage of styrene and acceptance of other resins as substitute to
unsaturated polyester resin (UPR) are expected to the hamper the growth of the market.
Styrene when exposed to the atmosphere can be hazardous causing irritation to skin,
eyes, respiratory system and nervous system. It emits toxic vapors and produces
carbon monoxide on decomposition. Various manufacturers are planning to produce
styrenic polymers in the near future with the expansion of their production facilities and
increase in output. These factors are expected to provide new opportunities for the
growth of the market. Asia Pacific was the largest consumer for styrene, followed by
Europe. Future market growth is expected to be from Asia Pacific on account of growth
in wind energy applications of UPR and increased SBR demand due to increasing tire
labeling regulations.

The major markets for styrene are polystyrene, acrylonitrile-butadiene-styrene

(ABS)/styrene-acrylonitrile (SAN) resins, styrene-butadiene (S/B) copolymer latexes,
SBR elastomers and latexes, and unsaturated polyester resins (UPR). Polystyrene
drives styrene consumption worldwide. Of the total amount of styrene consumed in
2014, nearly 37% went into general-purpose/high-impact (GP/HI) polystyrene
production and 22% went into expandable polystyrene (EPS) production. Polystyrene
consumption continues to come under pressure from substitutes such as polypropylene
and PET from both a cost and performance perspective, and styrene consumption is
forecast to stay relatively flat, growing at an average rate of 1.6% per year in 2014–19.
Expandable polystyrene is doing better especially in construction where it is being
increasingly used as concrete forms and insulation where higher efficiency standards
are driving demand. Styrene consumption for EPS production is expected to grow at an
average rate of 2.3% per year in the next five years.
Styrene consumption into ABS resins and SBR is expected to see the highest annual
growth rates, at 3.6% and 4.1%, respectively.

The following Figure 1 shows world consumption of styrene:

Figure 1: World Consumption of Styrene 2014

Excess supply and a slowdown in global demand have recently marked

polystyrene (PS) markets. Mature markets (North America, Europe, and Japan) face
weaker demand, capacity rationalization, and an emphasis on profitability, while
developing markets (China, the Middle East, and Africa), are emphasizing capacity
addition and slightly better demand than that of the Western regions.

As a region, China drives demand for styrene and has supported global
demand growth in the last couple of years, while demand has declined in other major
regions like Western Europe and North America. General-purpose and high-impact
(GP/HIPS) polystyrene is the largest demand segment in most regions; in China and
Central Europe, expandable polystyrene (EPS) has the largest market share. In
Western Europe, demand into EPS is close to the GP/HIPS demand (as of 2014.
Consumption of styrene into ABS resins is particularly strong in Southeast Asia and
Northeast Asia.

Expandable polystyrene (EPS) is the second-largest styrene derivative. Styrene

consumption for EPS averaged nearly 4% annual growth from 2009 to 2014, making it
one of the fastest-growing styrene derivatives. However, growth for EPS is slowing,
especially in China—the largest market for EPS. The average growth rate over the next
five years will be only 2.3% per year. In general, demand in North America in 2014 was
strong owing to increased building/construction demand. But slowdowns in demand in
Asia and Europe, surplus capacity globally, higher feedstock prices, and lower producer
profitability marked the global EPS market in 2014. In terms of end uses, the EPS
market continues to have two speeds, because demand into packaging is not growing
as fast as construction applications. Globally, the world is awash in EPS capacity.
Low operating rates in China are the result of significant capacity additions combined
with demand declines in 2014.

Next the chemical compound ABS, the third-largest styrene derivative, is the
largest-volume engineering thermoplastic resin in the world. ABS is used in many
consumer-related end-use applications including appliances, electronics/electrical,
building and construction, and transportation. The ABS market is projected to grow at an
average rate of 3.6% per year over the next five years. The appliance sector will
continue to be the largest ABS enduse market. Global population growth, increases in
discretionary spending, and replacements will continue to influence ABS sector growth
during the forecast period. In 2012 and 2013, ABS capacity expansions outpaced
demand.

The fastest-growing region in the world will be the Middle East and Africa, which
will increase consumption at a rate of 12% per year during 2014–19. More significant,
but growing at a slower pace (3.5%) is China. China will account for 33% of global
demand in 2019; all other countries in Northeast Asia are expected to see low to flat
styrene demand growth.

With a global demand share of 2% in 2014, Brazilian styrene consumption is

expected to grow at an annual rate of 5.6% in the next five years with new derivative
capacity coming on stream. Styrene consumption in Southeast Asia has slowed and will
grow at an average rate of 2% per year through the forecast period.

Rising raw material prices and weakened demand for polystyrene in the United
States, Western Europe, and Japan have slowed overall styrene growth in these three
regions; growth will be flat over the forecast period.

2. Major Producer of Styrene

Styrene demand remains dominated by its main derivative, polystyrene (59%),

which has reached maturity in most developed countries. Other styrene consumption
is for the production of acrylonitrile-butadiene-styrene (ABS) and styrene-acrylonitrile
(SAN) resins (16%), styrene-butadiene (S/B) copolymer latexes (6%) and
unsaturated polyester, accounting for an additional 6% of world styrene demand,
while SBR and SBR latexes production accounted for 4% of world demand.
 Styrene finds application in the manufacture of diverse products including
coatings, adhesives, packaging, paints and inks, floor wax, lubricants and many more.
In 2012, the annual global styrene capacity was estimated at over 32.7 million tonnes.
Asia holds around half of the world styrene capacity.

Figure 2: Styrene Capacity Broken Down by Region

Styrolution, Total Petrochemicals, CNPC, Shell, LyondellBasell Chemical Co, Chemicals
and Fibre Corp (FCFC), Formosa, Saudi Petrochemical Co (Sadaf) and Americas
Styrenics are some of the leading companies active in the worldwide styrene market.

In 2012, the global styrene production recorded slight growth of nearly 175,000
tonnes and exceeded 26.4 million tonnes. Asia is an unrivalled styrene producer,
accounting for approximately 50% of the world styrene output. It is followed by Europe
and North America.

Figure 3: World Styrene Production by Country

The countries which are China, USA and Japan are the top styrene manufacturing
countries. In 2012, their combined share in the world styrene production amounted to
more than 44% (over 11.7 million tonnes). In 2012, the global styrene consumption
recorded stable growth, driven by surging demand from the major styrene end-users
such as polystyrene, SB latex, ABS/SAN resins industries. In the past several years,
the highest growth in the demand for styrene has been registered in Asia.
In 2011, the world styrene foreign trade was worth more than 14.5 billion. Asia is the
leading styrene exporter and importer, with styrene imports, though, prevailing over
exports in the region.

The global styrene capacity utilization rates are poised to grow from
approximately 85% in 2012 to over 90% by 2017. Styrene markets in Asia, Latin
America and the Middle East are predicted to grow fastest. The global styrene
production is forecast to go beyond 29.7 million tonnes by 2015.
 3. Prices

In the year 2013, the market price of styrene was approximately in the range
between USD 1,675.51 – 1,697.56 per metric tonne in average. However, over the
years the market price has dropped gradually and currently, the average market price of
styrene is between USD 1,021.50 – 1,048.50 per metric tonne. The reason behind the
fall of styrene market price is mainly due to a large production of styrene itself. Demand
of styrene from around the world has increased significantly over the past few years and
thus, this may have caused overproduction. In the future, the market price of styrene is
expected to fall slightly even more in between USD 800.00 – 950.00 per metric tonne
because the demand of styrene will keep on increasing. In addition, there will be higher
competition amongst producers in attracting customers to buy their product. Hence, this
is one of the key reasons for producers to reduce the price of styrene.

Figure 1: Styrene Price Range 2013

 Figure 2: Styrene Price Range 2016

Table : Price for Styrene in November 2015

 By November 27, Asian styrene monomer (SM) market shed USD37-39.5/mt
since October 30. FOB South Korea was USD874/mt, CFR China was USD898/mt,
CFR Taiwan lost USD38/mt to USD899/mt. At early the month, SM market was
declining at slow pace due to dull domestic demand. FOB South Korea broke below
USDF900/mt for the first time, before SM's USD market offer rose on the back of
firm benzene's price and marginal climbing ethylene, combined with favorable
Chinese demand. SM market offer held firm on news heard of turnaround plan in
2016 of some Asian SM units which expects a tight supply next year, in addition to
low inventory in China.

Then as replenished by shipment cargoes and market demand resumed dull, SM

market went downstrend low. FOB S. Korea again broke below USD900/mt.
N.W.Europe market gained USD64.5/mt in November, with a jump of USD43/mt in a
single day, mostly due to a force majeure occured to Shell's unit, combined with few
replenishment shipment from US. In addition, as winter's coming, Rhine River's level
was too low to run freight. At present the spread price between between FOB
N.W.Europe and CFR China is at USD16.5/mt, with no arbitrage window for trades.
Screening of Synthesis Route
Screening for synthesis route for Styrene, C8H8. The route processes for
synthesis Styrene is the oxidative dehydrogenation of ethylbenzene. The
availability of the raw materials as we know that ethylbenzene is the product
from the ethylene or ethene that reacted with benzene. The majority of
monomers are used to produce the products that are tied with the olefin
plants. In this case, benzene and ethelyne need to be purchased and
transported to the site of the styrene plant.
Therefore, the prices at which benzene and ethene might be purchased
needs to be determined. Also, the cost of transportation needs to be included
in this material cost. Another material that needs to be purchased is the
catalyst. The process includes a method of replenishing the catalyst as an
example decoking it, but some catalyst will be lost over time and more will
need to be purchased. Another material cost includes the processing of any
wastes that are produced. This includes waste water or other streams that
need to be treated. The complexity of this process, as the technical synthesis
styrene is usually run at 600°C with the excess of steam ethylbenzene, the
ethylbenzene steam has the molar ratio 5:1 and 12:1. Styrene plants must run
their reactors under thermal and adiabatic conditions with flow rates that
ensure short contacts times to prevent the polymerization of styrene. The
major reaction is the reversible, endothermic conversion of ethylbenzene to
styrene and hydrogen:

C6H5CH2CH3 ↔ C6H5CH=CH2 + H2

Competing thermal reactions degrade ethylbenzene to benzene, and also to

carbon:

C6H5CH2CH3 ↔ C6H6 + C2H4

C6H5CH2CH3 ↔ 8C + 5H2

Styrene also reacts catalytically to toluene:

C6H5CH2CH3 + H2 ↔ C6H5CH3 + CH4

The complexity for this route also involved of formation of coke. This
formation of coke are used to deactivate the catalyst. The coke is remove by
combustion with steam. The effectiveness of this route, the conversion of
ethylbenzene is the between 50% to 60% that obtained in the technical
reactor. The typical byproduct of the 1% of benzene and 2% of toluene that
formed by catalytic dealkyation and hydrodealkylation of ethylbenzene. The
dilution of ethylbenzene with the superheated steam give more efficiency for
the route to produce styrene. It gived the shifts of equilibrium of ethylbenzene
towards to the higher conversion to products styrene that reduced educts
partial pressure.
 Another route for the production of styrene is from ethylbenzene and also
involved co-production of propylene oxide (Oxirane process, ca. 15% of the
styrene production.) The first step is direct air oxidation of ethylbenzene at ca.
130 °C and 0.2 MPa to form ethylbenzene hydroperoxide. In the next step this
is able to oxidize propylene to propylene oxide in presence of a metallic
catalyst (example: molybdenium or titanium at Temperature 110 °C, Pressure
4 MPa). Ethylbenzene hydroperoxide itself is reduced to α-methylbenzyl
alcohol (methyl phenyl carbinol) which finally is dehydrated to styrene at
250 °C and low pressure over a suitable metal oxide contact (often Al2O3).

For the health and safety, the styrene products is totally mildy toxic and
inflammable. Styrene has an odor threshold 0.05-0.15 ppmv. Both liquid and
vapor can irritate the eyes and respiratory system. The high concentration of
styrene can cause depression of central nervous system. Styrene is usually
stored and transported which contains TBC, which is skin sensitizer. Styrene
monomer is flammable and can form explosive mixture with air at atmospheric
ambient condition. It is suggested to store the styrene below or at the
atmopheric temperature. One major by product is carbon dioxide.

This is created from the incineration of gaseous hydrocarbon side

products and the burning of coke on the catalyst. Streams are to be
combustion to carbon dioxide and water. Purge stream also contains carbon
dioxide. All products are to be sent though scrubbers to reduce the carbon
monoxide content from side combustion reactions and bring the limits within
the National Ambient Air Quality standards. There are three major variables
that affect equipment safety. They are the operating pressures, temperatures,
and the chemicals present. Choosing the appropriate materials of construction
reduces the dangers associated with temperature and certain chemicals. For
example, carbon steel cannot be used above 455°C or with hydrogen gas,
thus stainless steel is the appropriate material in streams which carbon steel
cannot be used. For equipment operating at high pressures, the thickness of
equipment must be increased. This is taken into account as a pressure factor
used when costing equipment.
 Process Flow Diagram

Flowchart

Recycle Ethylbenzene

Benzene Toluene

Styrene
Ethylbenzene
Condenser Separator 1 Separator 2
Heater Reactor

Boiler
Calculation at reactor.

n1 mol EB (v)/h Reactor

n2 mol EB(v)/h
T=600°C n3 mol St(v)/h
P=1 atm n4 mol B(v)/h
n5 mol T(v)/h
n6 mol H2(v)/h
Boiler T= 600°C
P= 1 atm

Selectivity EB to Styrene = 95%

Fractional conversion for EB = 65%

C 8 H 10  C 8 H 8  H 2
C 8 H 10  C 6 H 6  C 2 H 4
Basis = 2192.13 mol St(v)/h = n3 mol St(v)/h

(2192.13)
n1 mol EB (v)/h = = 3550 mol EB (v)/h
(0.65)(0.95)
n2 mol EB(v)/h = nunconverted = (1-0.65)(3550)
= 1242.5 mol EB (v)/h

*By using the extent of reaction

n3 mol St(v)/h =   1 = 2192.13 mol St(v)/h
n2 mol EB(v)/h = n1 mol EB (v)/h   1   2
  2 = 3550-1242.5-2190.13
= 115.37 mol/h
n6 mol H2(v)/h =   1 = 2192.13 mol H2(v)/h
n4 mol B(v)/h =   2 = 115.37 mol B(v)/h
n5 mol T(v)/h =   2 = 115.37 mol T(v)/h
References state = C(s),H2(g) 25℃ at 1 atm
Species Nin (mol/h) Hin (kj/mol) Nout (mol/h) Hout (kj/mol)
EB 3550 H1 = 151.144 1242.5 H2 = 151.144
Styrene, St - - 2192.13 H3 = 258.68
Benzene, B - - 115.37 H4 =168.29
Toluene, T - - 115.37 H5 =154.98

873
EB(v,600℃,1 atm) : H1 = H1°f +  CpdT
298

873
H1 = 29.79 +  0.21105dT
298
H1 = 151.144 kj/mol

873
EB(v,600℃,1 atm) : H2 = H2°f +  CpdT
298

873
H2 = 29.79 +  0.21105dT
298
H2 = 151.144 kj/mol

873
St(v,600℃,1atm) : H3 = H3°f +  CpdT
298

873
H3 = 146.9 +  0.1945dT
298
H3 = 258.68 kj/mol

600
B(v,600℃,1atm) : H4 = H4°f +  CpdT
25

H4=82.93+
600

 (74.06x10
3
)  (32.95x105 )T  (25.20 x108 )T 2  (77.57 x1012 )T 3dT
25

H4 = 168.29 kj/mol
 600
T(v,600℃,1atm) : H5 = H5°f +  CpdT
25

H5=50.00+
600

 (94.18x10
3
)  (38.00 x105 )T  (27.86 x108 )T 2  (80.33x1012 )T 3dT
25

H4 = 154.98 kj/mol

H   noutHout   ninHin

H =
[(1242.5)(151.144)+(2192.13)(258.68)+(155.37)(168.29)+(155.37)(154.98)] -
[(3550)(151.144)]

H = 254.32x103 kj/h
Calculation at mixing point

n2 mol EB(v)/h = 1242.5 mol/h

T=138°C
P=1atm

n0 mol EB(l)/h Mixing Point

n1 mol EB (l)/h =3550 mol/h
T=25°C T=82°C
P=1atm P=1atm

Material balance on Ethylbenzene

n0 + n2 = n1

n0 mol EB(l)/h = 3550 - 1242.5

= 2307.5 mol/h

References state= EB (liquid) at 25°C , 1 atm

Species Nin = (mol/h) Hin = (kj/mol) Nout =(mol/h) Hout = (kj/mol)
EB(v) 1242.5 H1 = 53.33 - -
EB(l) 2307.5 0 3550 H2 = 8.125

EB(l,25°C,1atm) EB(v,138°C,1atm)

H1a H1c

EB(l,136.2°C,1atm) EB(v,136.2°C,1atm)
H1b
 409.2
H1a =  CpdT
298

H1a =
409.2

 (20.527)  (5.9578x10
1
)T  (3.0849 x104 )T 2  (3.5621x108 )T 3  (1.2409 x1011 )T 4 dT
298

1kj
H1a = 17036x
1000 j
H1a = 17.04 kj/mol

H1b = Hv = 35.98 kj/mol

411
H1c =  CpdT
409.2

H1c =
411

 (20.527)  (5.9578x10
1
)T  (3.0849 x104 )T 2  (3.5621x108 )T 3  (1.2409 x1011 )T 4 dT
409.2

1kj
H1c = 314.81x
1000 j
H1c = 0.3148 kj/mol

H  17.04 + 35.98 + 0.3148

= 53.33 kj/mol
EB(l,25°C,1atm) EB(l,82°C,1atm)

355

EB(l,82°C,1atm) = H2 =
298
 CpdT
H2 =
355

 (20.527)  (5.9578x10
1
)T  (3.0849 x104 )T 2  (3.5621x108 )T 3  (1.2409 x1011 )T 4 dT
298

1kj
H2 = 81248x
1000 j
H2 = 8.125 kj/mol

H   noutHout   ninHin
H = (8.125)(3550) - (53.33)(1242.5)
= -37.42x103 kj/h
Condenser
T=600℃ n=benzene T=85℃
P=1 atm n=H2 P=1 atm

n=EB n=EB
n=ST n=ST
n=B n=T
n=T CONDENSER
T=85℃
P=1 atm

REFERENT:EB,ST,B,T (VAPOR,600℃,1 ATM)

NIN(KJ/MOL) HIN(KJ/MOL) NOUT(KJ/MOL) HOUT(KJ/MOL)

Ethylbenzene 42.5 0 42.5 Ĥ1

Styrene 2192.13 0 2192.13 Ĥ2

Benzene 115.37 0 115.37 Ĥ3

115.37 0 115.37 Ĥ4
Toluene
2192.13 2192.13 Ĥ5
Hydrogen
gas

for Ethylbenzene
(vap,600℃,1 ATM) (LIQ,85℃,1 ATM)

Ĥa Ĥb

(vap,136℃,1 ATM) (liq,136℃,1 ATM)

Ĥc
Ĥ1= For Ĥ1 (EB)
Ĥ1= Ĥa+ Ĥb+ ĤC
136℃
Ĥa= ∫600℃ 𝐶𝑃𝐷𝑇
Ĥa=283.8276KJ/MOL

Ĥb= -9.1818kj/mol
 85℃
Ĥc= ∫136℃ 𝐶𝑃𝐷𝑇
Ĥc= -9.5246kj/mol
Ĥ1= -302.5341 kj/mol

For Styrene
for Ĥ2
(vap,600℃,1 ATM) (LIQ,85℃,1 ATM)

Ĥa Ĥb

(vap,146℃,1 ATM) (liq,146℃,1 ATM)

Ĥc

Ĥ2= For Ĥ2 (st)

Ĥ2 =Ĥa+ Ĥb+ ĤC
146℃
Ĥa= ∫600℃ 𝐶𝑃𝐷𝑇
Ĥa=2544.47KJ/MOL
Ĥb= -43.9kj/mol
85℃
Ĥc= ∫146℃ 𝐶𝑃𝐷𝑇
Ĥc= -107.235kj/mol

Ĥ2= -2695.61 kj/mol

for Benzene
for Ĥ3
Ĥ3
(vap,600℃,1 ATM) (vap,85℃,1 ATM)

Ĥ3= For Ĥ3 (benzene)

85℃
Ĥ3= ∫600℃ 𝐶𝑃𝐷𝑇
Ĥ3= -80.68KJ/MOL
For Toluene
for Ĥ4
(vap,600℃,1 ATM) (LIQ,85℃,1 ATM)

Ĥa Ĥb

(vap,110℃,1 ATM) (liq,110℃,1 ATM)

ĤC

Ĥ4= For Ĥ4 (toluene)

Ĥ4 =Ĥa+ Ĥb+ ĤC
110℃
Ĥa= ∫600℃ 𝐶𝑃𝐷𝑇
Ĥa=-94.9133KJ/MOL
Ĥb= -33.18kj/mol
85℃
Ĥc= ∫110℃ 𝐶𝑃𝐷𝑇
Ĥc= -3.216kj/mol

Ĥ4= -131.3093 kj/mol

for Hydrogen gas

for Ĥ5
Ĥ5
(vap,600℃,1 ATM) (vap,85℃,1 ATM)

Ĥ5= For Ĥ5 (benzene)

Ĥ5=
85℃
∫ 28.84𝑥10−3 + 0.00765𝑥10−5 𝑇 + 0.3288𝑥10−8 𝑇 2 + (−0.8696𝑥10−12 )𝑇 3 𝑑𝑇
600℃

Ĥ5= -15.07 KJ/MOL

Q=ṅĤ1+ ṅĤ2+ ṅĤ3 + ṅĤ4 + ṅĤ5

ΔH=Q= -5979.87x103 kj/h
 n1 mol T(v)/h
Calculation at separator 1 T = 120⁰c
P = 1 atm
n3 mol EB (l)/h
n2 mol St (l)/h n3 mol EB (v)/h
n1 mol T (l)/h n2 mol St (v)/h

T = 85⁰c Separator 1 T = 120⁰c

P = 1 atm P = 1 atm

Reference state EB(l) and ST(l) at 85⁰c at 1 atm

Species Nin (mol/h) Hin (kJ/mol) Nout (mol/h) Hout (kJ/mol)
EB 1242.5 0 1242.5 6.8075
Styrene 2192.13 0 2192.13 3.68
Toluene 115.37 0 115.37 38.03

Toluene
H1a H1b H1c

( l,85⁰c,1atm) ( l,110⁰c,1 atm) ( g, 110⁰c, 1 atm) ( g, 120⁰c,1

atm )
110
T ( l, 110⁰c,1 atm) = H1a = ∫85 𝐶𝑝𝑑𝑡
110
= ∫85 (94.18 × 10⁻3 ) + (38 × 10−5 )𝑇 + (−27.86 × 10−8 )𝑇 2 +
(80.33 × 10−12 )𝑇 3 𝑑𝑇
= 3.216 kJ/mol
T ( g, 110⁰c, 1 atm) = H1b = Hvapor = 33.47 kJ/mol
120
T ( g, 120⁰c,1 atm ) = H1c = ∫110 (94.18 × 10⁻3 ) + (38 × 10−5 )𝑇 + (−27.86 ×
10−8 )𝑇 2 + (80.33 × 10−12 )𝑇 3 𝑑𝑇
= 1.343 kJ/mol
H1 = H1a + H1b + H1c
= 38.03 kJ/mol

Styrene
H2a

( l,85⁰c,1atm) ( l, 120⁰c,1 atm)

120
St ( l, 120⁰c,1 atm) = H2a = ∫85 0.1945𝑑𝑇 = 6.8075 kJ/mol
H2 = H2a
= 6.8075 kJ/mol
Ethylbenzene

H3a

( l,85⁰c,1atm) ( l, 120⁰c,1 atm)

120
Eb ( g, 120⁰c,1 atm) = H3c =∫85 (74.06𝑥10−3 ) + (32.95𝑥10−5 )𝑇 +
(−25.20𝑥10−8 )𝑇 2 + (77.57𝑥10−12 )𝑇³𝑑𝑇
=3.68 kJ/mol
H3 = H3c
= 3.68 kJ/mol
ΔH = n1H1 + n2H2 +n3H3
= 20.912×10³ kJ/h
 T=
138°C
ETHYL P= 1
BENZENE atm
T= (1242.5
120°C mol/h)
P= 1 atm
ETHYL
BENZEN
E (1242.5
mol/h)
STYREN
E (2192.3
mol/h)

STYRENE
(2192.3 T= 138°C
mol/h) P=1 atm

Styrene

(L,120°c,1atm)(L,138°c,1atm)
411
∫393 0.1816𝑇 = 3.2688 kj/mol
3.2688*1242.5 =4061.484 kJ/mol

Ethylbenzene
(L,120°c,1atm)(L,136°c,1atm) (v,136°c,1atm)(v,138°c,1atm)
409 411
∫393 0.2356𝑇 + 35.98+∫409 0.2356𝑇 = 40.221 kj/mol
40.221*2192.15 =88170.47 kj/mol

References state: EB(l), ST(l) at 120˚C , 1 atm

Species Nin(mol/h) Hin(kj/mol) Nout(mol/h) Hout(kj/mol)

Ethylbenzene 1242.5 0 1242.5 3.2688

Styrene 2192.13 0 2192.13 40.221

ΔH = n1H1 + n2H2 = 92.231x103 kj.mol