Report
Report
INTRODUCTION
Phthalic anhydride was first reported by Lauret in 1836. In 1872, BASF developed
naphthalene oxidation process. Since then phthalic anhydride has been continuously
commercially produced. It was the first anhydride of a dicarboxylic acid to be
used commercially and its importance is comparable to acetic acid . The
most important derivatives of phthalic anhydride are polyesters, alkyl resins,
phthalocyanines and plasticizers like PVC . Till 1960, phthalic anhydride was
manufactured almost exclusively from naphthalene. The growing demand for
phthalic anhydride led to the search for alternative raw materials, such as o-
xylene, which is nowadays available in adequate quantities from cracking
plants and refineries.
Modern commercial processes for phthalic anhydride production are
based on the selective gas phase oxidation of o-xylene over V2O5/TiO2
catalysts, either in fixed or in fluidized bed reactors. The reaction proceeds at nearly
atmospheric pressure and in the temperature range of 360-400°C to give almost complete
conversion of o-xylene and selectivities for phthalic anhydride of 70-75%. This process is
complex, and involves different by-products resulting from the oxidation of
phthalic anhydride, such as o-tolualdehyde, phthalide and carbon oxides
(CO2 and CO). Due to the large exothermicity of the main reaction
(ΔH=−6800 kJ/mol), heat generation can produce hot spots, increasing the
risk of runaway reactions. Fluidized bed processes permit more efficient heat
removal and a better temperature control, avoiding yield losses and catalyst
degradation related with hot spots.
Phthalic anhydride is an important chemical intermediate. Its major outlets are phthalate
plasticizers, unsaturated polyesters and alkyd resins for surface coatings while its smaller volume
applications include polyester polyols, pigments, dyes, sweeteners and flame retardants.
It is traded in either molten form (requiring heated tankers) or as a white powder ('flake'). The
manufacture of phthalic anhydríde consumes almost all o-xylene produced so that sourcing a
suitable supply of high purity o-xylene is a critical consideration in the early stages of the
feasibility study.
1
Care must be taken in the process handling stages as explosive mixtures form easily
between phthalic anhydride dust and air, and spontaneous reaction occurs with many organic
compounds including skin tissue.
The first indigenous phthalic anhydride unit in India was put on stream by Herdillia
Chemicals Ltd. in a plant on the Thane-Belapur Road near Bombay in early 1968. The plant has
a capacity of 6000 tons/year.
1.1 Applications
2
The most important diester is bis(2-ethylhexyl) phthalate ("DEHP"), used in the manufacture of
polyvinyl chloride.
3
Phthalic anhydride can be produced using-
a) naphthalene
b) o-xylene
c) n-pentane
The first patent (BASF in 1896) used concentrated sulphuric acid in the presence of mercury
salts to perform the oxidation. The first vapour-phase process was patented in 1917. Since then,
there have been great improvements in the catalysts used, both in terms of increased yield and
reduced catalyst aging. Potassium-modified vanadium pentoxides (with promoters such as
molybdenum and manganese oxides) are now the most common catalysts used in PAN
production. The n-pentane process is the most recent development but requires a cheap supply of
raw material in order to be a viable option .
The main factors affecting the choice of feed stock are –
a] Yield (o-xylene gives more yield)
b] Availability ( naphthalene sources are becoming rarer)
c] Costs
d] Catalyst aging
e] Utility costs
f] Product quality
If o-xylene is preferred, a suitable source must also be determined. As nearly all the o-
xylene produced is used for phthalic anhydride manufacture there is unlikely to be an adequate
supply in the general market for a new plant. Therefore, a xylene separation plant, using a mixed
xylene feed, is often constructed on the same site as a PAN plant.
Apart from raw material selection, the main desígn consideration is the type of reactor.
Both fixed-bed and fluidized-bed processes are viable for the gas phase -process. The oxidation
reaction can be conducted at both high and low air ratios, which has significant implications for
the design of the reactor and downstream equipment. Plants throughout the world utilise a range
of technologies, including the liquid phase process which appears to be less viable.
The product typically needs to be purified to around 99.7%. The major contaminants are usually
maleic anhydride and single-ring aromatics. Both the raw materials and the product are skin, eye
and lung irritants. Appropriate safety equipment (overalls, face shield, long gloves) should be
worn by plant operators whenever they are likely to be in contact with any of the process hazard.
4
Phthalic Maleic
Anhydride Anhydride O-Xylene Oxygen
Molecular Formula C8H4O3 C4H2O3 C8H10 O2
Molar Mass (g/mol) 1.48 98.06 106.16 32
Appearance White Flakes White Crystals Colourless Liquid
Melting Point
(°C) 131 52.8 -24 -218.79
Boiling Point
(°C) 284.5 202 144 -182.95
Solubility in Water .62g/100g Reacts Insoluble
Flash Point
(°C) 152 102
Density
(gm/cc) 1.53 1.48 1.141
Viscosity 1.61 8.102
(cP) 0.55-1.2 at 60°C at 20°C -
Heat of Fusion 23.09 12.26 13.6
(kJ/mol) at 403.3K at 325.7K at 247.8K 0.444
Heat of Vaporization
(kJ/mol) - 54.8 36.24 at 417.6K 6.82
Specific Heat Capacity solid- 67.4, gas- 132.5(g)
(J/mole.K) 160 90.04 ,187(l) 29.378
Heat of Formation 19(g)
(kJ/mole) -460.37 -470 , -24.4(l) 0
Heat of Combustion
(kJ/mole) -3259.4 -1390.3 -4552.9 0
Entropy 353.6(g)
(J/mole.K) 180 ,247(l) 205.15
2. PHYSICO-CHEMICAL PROPERTIES
Table No.1 Physico-chemical properties
3. MARKET ASSESSMENT
5
3.1 World Consumption
Plasticizers account for the majority of world phthalic anhydride consumption, followed by
alkyd resins and unsaturated polyester resins (UPR). Other smaller-volume applications
include polyester polyols, saccharin, pigments, dyes and flame retardants. Demand for most
downstream markets for phthalic anhydride is greatly influenced by general economic
conditions. As a result, demand for phthalic anhydride largely follows the patterns of the
leading world economies. Consumption of phthalic anhydride depends heavily on
construction/remodeling activity (residential and nonresidential), automotive production and
original equipment manufacture (OEM).
6
expected commissioning of large esterification units for the production of diphthalate (2-
propylheptyl) during 2009–2014 are the main factors for increased demand for phthalic
anhydride in these two regions. North American consumption of phthalic anhydride for
plasticizers is forecast to grow at an average annual rate of 1.0% during 2009–2014,
continued weak demand during 2010 in construction and automotive markets, especially in
the United States, will drag overall demand growth. Demand for phthalic anhydride in alkyd
resins is expected to decline in North America and Western Europe; most other regions are
forecast to experience moderate growth. Growth in phthalic anhydride demand for UPR is
also expected to vary by region; most Asian markets are forecast to see moderate-to-
significant growth in demand while moderate growth is forecast in North America and
Western Europe. World demand for phthalic anhydride is expected to start recovering in
2010–2012, largely as a result of improved construction/remodeling activity and stronger
OEM and automotive production. As a result, world consumption of phthalic anhydride is
forecast to grow at an average annual rate of 2.8% during 2009–2014.
Future concerns for the phthalic anhydride market include stricter environmental
regulations affecting and/or limiting the use of phthalates. Consumption of several phthalates
is forecast to diminish due to limits on use, they will be replaced largely by other phthalates,
benzoates, citrates and specialty plasticizers.
In the key China market, phthalic anhydride (PAN) spot market for imports were largely
subdued from early-September, falling from $990-1,030/tonne cost and freight (CFR), China
Main Port (CMP) in mid-August to $960-980/tonne, down $30-50/tonne. Buying appetite for
imports was thin as buyers continued to bypass such material for competitively-priced
domestic material. However, tighter-than-expected supply in the region due to maintenance
coupled with spiralling feedstock orthoxylene (OX) values led prices to reach a high of
$1,150-1,170/tonne CFR CMP in mid-November.
7
Market in the Asian region was weighed by poor conditions in the key China market.
After briefly exceeding the $1,000/tonne CFR mark in mid-August, prices fell by 3-5% to
$970-980/tonne for the week ended 3rd September. Spot prices rebounded in mid-September
in tandem with spiralling feedstock orthoxylene and limited availability to close at $1,220-
1,250/tonne CFR Southeast Asia for the week ended 12th November 2010.
There were signs of a seasonal slowdown in demand towards the end of the period and
producers bemoaned low margins between orthoxylene and Phthalic Anhydride. Spot prices
were stable throughout the period at €1,050-1,100/tonne FD NWE for liquid and €1,100-
1,200/tonne FD NWE for flake, in line with orthoxylene.
3.2.3 US Market:
US Phthalic Anhydride prices were at 64.50-73.00 cents/lb free on board (FOB) Molten
for November, and 65.50-73.00 cents/lb delivered (DEL) Flake, both up 3.50 cents/lb from
the previous month. Prices will move up another 2 cents in December. Phthalic Anhydride
contracts have moved higher since Q3, following feedstock ortho-xylene values upward.
The uptrend in ortho-xylene contract was also prompted by rising mixed xylene (MX)
prices, and other higher feedstock prices, as well as energy heading into Q4. Despite the
increase, Phthalic Anhydride market participants expect a quiet market in November and
December, due to weaker demand, and weaker downstream demand from unsaturated
polyester resins (UPS).
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3.3 Demand
The major outlet for phthalic anhydride (PA), accounting for just over half of
production, is in the manufacture of phthalate plasticisers, the main product being dioctyl
phthalate (DOP) which is used as a plasticiser in polyvinyl chloride (PVC). Hence, the
consumption of PA is mainly dependent on the growth of PVC, which is sensitive to general
economic conditions as it is consumed mainly in the construction and automobile industries.
The second largest use of PA, at around 18% of output, is in unsaturated polyester resins
(UPRs) which are used to produce fibreglass-reinforced resins. Their principal markets -
construction, marine and transportation are in the recreational area and so are also sensitive
to changes in economic conditions. In addition, UPR growth is tempered by the major
application areas having become saturated.
The third largest outlet is PA-based alkyd resins, which are used in solvent-based
coatings for architectural, machinery, furniture and fixture applications. They are in slow
decline due to limits in the level of volatile organic compounds in surface coatings. As a
result, there has been a switch to water-based and power coating technologies. In addition,
there is a trend towards decorative paints being based on vinyl acetate and acrylics. Small
volume uses for PA include the manufacture of dyes and pigments, detergents, herbicides
and insecticides, fire retardants, saccharin and polyester resin cross-linking agents.
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3.4 India’s Industry Scenario
The current price of the main raw material Orthoxylene is at US$1300/MT and the price
of Phthalic Anhydride is US$1500/MT. Variable operating costs are US$60/MT resulting in
a net margin of US$140/MT, which is substantially higher than the margin of US$50/MT
during the downturn.
There is a strong growth volume of Phthalic Anhydride in the Indian market as a result
of the demand and strong growth in its end user industries like paints and plasticizers.
The major outlet for phthalic anhydride (PA), accounting for just over half of production,
is in the manufacture of phthalate plasticizers, the main product being dioctyl phthalate
(DOP) which is used as a plasticizer in polyvinyl chloride (PVC). Hence, the consumption of
PA is mainly dependent on the growth of PVC, which is sensitive to general economic
conditions as it is consumed mainly in the construction and automobile industries. Health and
environmental issues that surround phthalates used in plasticizers for PVC could also hinder
future growth prospects.
10
Future concerns for the phthalic anhydride market include stricter environmental
regulations affecting and/or limiting the use of phthalates. Consumption of several phthalates
is forecast to diminish due to limits on use. They will be replaced largely by other phthalates,
benzoates, citrates and specialty plasticizers.
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4. MANUFACTURING PROCESS
…1
Other oxidation products include maleic anhydride, benzoic acid, carbon dioxide, etc.
Carbon dioxide is formed when the organic feedstock is completely oxidized. Historically,
naphthalene had been the feedstock for production of phthalic anhydride(PAN).It remained so
until after world war 2 when Oronite (now Chevron Phillips Chemcals Co.) commercialized
production of PAN using ortho-xylene.
The use of o-xylene as a feedstock was confined to the United States, until naphthalene
shortages in Europe promoted utilization of o-xylene. The switch to o-xylene was due to
diminishing supplies of naphthalene as a result of lower coke consumption and the increasing
availability of o-xylene from refinery operations.
In the United States, o-xylene became a more prominent feedstock as a result of a major
steel strike in 1959 that severely curtailed coal-tar naphthalene supplies. Despite the initially low
yields obtained , o-xylene became a preferred raw material because of its increasing supply
reliability compared to that of naphthalene. This spurred Research and Development activities to
improve the catalysts available.
So, Ortho-xylene is the clearly preferred modem day feedstock for phthalic anhydride
manufacture. Few naphthalene-based plants remain operational, and no new naphthalene plants
have been built since 1971. Ortho-xylene produces higher yie1ds , it is cheaper than naphthalene
and provides a more efficient process . Converting an existing plant to o-xylene can reduce raw
material costs by 25% and utility costs by 30%.
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4.1 Process Description
Phthalic anhydride processes can be classified according to the type of reactor used.
Three reactor configurations have been commercially developed: (a) fixed bed vapour-phase
reactor; (b) fluidised-bed vapour-phase reactor; and (c) liquid phase reactor.
In PAN production using o-xylene as the basic feedstock, filtered air is preheated,
compressed, and mixed with vaporized o-xylene and fed into the multiple reactors. The reactors
contain the catalyst, vanadium pentoxide, and are operated at 340°C to 385°C. Small amounts of
sulfur dioxide are added to the reactor feed to maintain catalyst activity.
C8H10+3O2→C8H4O3+3H2O ...2
C8H10+7.5O2→C4H2O3+ 4H2O+ 4CO2 ...3
C8H10+10.5O2→8CO2+5H2O ...4
C8H10+6.4O2→8CO+5H2O ...5
Reaction (2) is the main reaction and it is assumed a 70% selectivity. Reaction (3) refers
to the formation of the by-product MA and a 10% selectivity is considered. Reactions (4) and (5)
represent the complete and incomplete combustions of o-xylene with 15% and 5% selectivity,
respectively.
Exothermic heat is removed by a molten salt bath circulated around the reactor tubes and
transferred to a steam generation system. The reactor effluent containing crude PAN plus
products from side reactions and excess oxygen passes to a series of switch condensers where the
crude PAN cools and crystallizes. The condensers are alternately cooled and then heated,
allowing PAN crystals to form and then melt from the condenser tube fins. The crude liquid is
transferred to a pretreatment section in which phthalic acid is dehydrated to anhydride. Water,
maleic anhydride, and benzoic acid are partially evaporated. The liquid then goes to a vacuum
distillation section where pure PAN (99.8 wt. percent pure) is recovered. The product can be
stored and shipped either as a liquid or a solid (in which case it is dried, flaked, and packaged in
multi-wall paper bags). Tanks for holding liquid PAN are kept at 150°C and blanketed with dry
13
nitrogen to prevent the entry of oxygen (fire) or water vapor (hydrolysis to phthalic acid). Maleic
anhydride is currently the only byproduct being recovered.
Major developments in phthalic anhydride manufacture in recent years have been in the
area of catalyst activity. The above process uses a catalyst that requires an air: o –xylene ratio of
only 9.5: 1 (compared to around 20: 1 for other technologies). This increases the catalyst
productivity by 40% and dramatically reduces the reactor size, and lowers the cluty of other
critical equipment (including the switch condensers). Energy requirements for blowers and
pumps are reduced by about 60%. The reduced flow of inerts in the reactor allows more sensible
heat to be extracted via the cooling salts. The plant can become completely energy self-sufficient
and can export considerable quantities of steam to neighboring plants. An after-cooler can also
be added to remove about half of the product phthalic anhydride. This increases the product
quality by reducing the concentration of impurities entering the product stream in the condensers.
This process has a lower capital cost and a higher operating efficiency compared with other
processes. This is a direct result of the low air to o-xylene ratio in the reactor. No electricity or
fuel is required and a significant steam credit can be exported. The final selling price for
phthalic anhydride produced by this process is likely to be lower than by competitive processes.
14
15
5. THERMODYNAMIC FEASIBILTY
Chemical thermodynamics is the study of the interrelation of heat and work with
chemical reactions or with physical changes of state within the confines of the laws of
thermodynamics. Chemical thermodynamics involves not only laboratory measurements of
various thermodynamic properties, but also the application of mathematical methods to the study
of chemical questions and the spontaneity of processes. The structure of Chemical
Thermodynamics is based on the first two laws of thermodynamics.
The primary objective of chemical thermodynamics is the establishment of a criterion for
the determination of the feasibility or spontaneity of a given transformation. In this manner,
chemical thermodynamics is typically used to predict the energy exchanges that occur in the
following processes:
1. Chemical reactions
2. Phase changes
3. The formation of solutions
The following state functions are of primary concern in chemical thermodynamics:
• Internal energy (U)
• Enthalpy (H).
• Entropy (S)
• Gibbs free energy (G)
Most identities in chemical thermodynamics arise from application of the first and second laws
of thermodynamics, particularly the law of conservation of energy, to these state functions.
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Phthalic
Components O-xylene Water Anhydride
g=19
ΔHf (kJ/mole) l=-24.4 l=-285.83 s=-460.37
g=353.6
S (J/mole.K) l=247 l=69.95 s=180
g=132.5
Cp (J/mole.K) l=187 s=160
As oxygen is in its pure form, its entropy and enthalpy will be zero.
Calculating enthalpy, entropy and Gibb’s free energy for the above reaction,i.e. checking its
thermodynamic feasibility at room temperature, i.e.25°C
• ENTHALPY of reaction-
= [-460.37+(-285.83)]-[19+0]
ΔH = -765.2 kJ/mole
• ENTROPY of reaction-
ΔS = (S)products – (S)reactants
= [180+69.95] – [353.6+0]
17
ΔS = -103.65 J/(mole.K) = - 0.10365 kJ/(mole.K)
ΔG = ΔH - TΔS
ΔG = -734.31 kJ/mole
6. KINETICS
18
The vapour-phase oxidation of o-xylene over a vanadium pentoxide catalyst is
essentially first order with respect to the o-xylene concentration. However, above a maximum o-
xylene concentration (which depends only on the specific type of catalyst and is independent of
temperature while the catalyst remains activated) the catalyst deactivates irreversibly and the
reaction rate decreases rapidly. Deactivation occurs when the valence-state of vanadium changes.
New developments have focussed on finding additives to prevent this from happening. The low
air ratio (LAR) catalyst can sustain the reaction up to a concentration of 2.77 mole % o-xylene,
compared with only 1.0-1.4% in other catalysts.
There are at least three significant reaction mechanisms which occur at the temperatures
encountered within the reactor. Below 370°C, the reaction is first order with respect to the
oxygen concentration and the rate constant is low. The selectivity for phthalic anhydride is high
but conversion of the feed may not be complete and the product is likely to undergo further
combustion.
Between 370°C and 440°C, the reaction is first order with respect to the hydrocarbon.
The rate constant is significantly higher, the selectivity remains high and the o-xylene conversion
is essentially complete.
Above 440°C (and below 550°C), the reaction is also first order with respect to
hydrocarbon concentration but conforms to a third reaction mechanism. The activation energy is
substantially less, the rate constant is higher and, because the activation energy is low, the
reaction rate is almost independent of temperature. The selectivity for phthalic anhydride begins
to decrease at higher temperatures as side reactions and complete oxidation become more
likely. The catalyst is irreversibly deactivated if the surface temperature exceeds 500°C. There
will be a temperature drop from the gas to the catalyst surface of 10-50°C.
Thus, the maximum allowable gas temperature is 510-550°C. The gas temperature in the
reactor should, therefore, be controlled so that the bulk of the reaction occurs from
440-510°C.
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7.1 MSDS – Phthalic Anhydride
7.1.1 Chemical Product
MSDS Name – Phthalic Anhydride
Synonym- 1,3-Isobenzofurandione , 1,2-Benzene Carboxylic Acid Anhydride
7.1.2 Composition
Hazards Symbol-XN
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the
upper and lower eyelids. Get medical aid.
Skin: Get medical aid. Flush skin with plenty of water for at least 15 minutes while
removing contaminated clothing and shoes.
20
Ingestion: Get medical aid. Wash mouth out with water.
Inhalation: Get medical aid immediately. Remove from exposure and move to fresh air
immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.
Get medical aid.
21
France VLE: 6 mg/m3 VLE
Germany: 1 mg/m3 TWA (inhalable fraction)
Japan: 0.33 ppm Ceiling; 0.2 mg/m3 Ceiling
Malaysia: 1 ppm TWA; 6.1 mg/m3 TWA
Netherlands: 2 mg/m3 STEL Netherlands: 1 mg/m3 MAC
Spain: 1 ppm VLAED; 6 mg/m3 VLAED
7.2.2 Composition
CAS# Chemical Name %
108-31-6 Maleic Anhydride 99.5 min
Table No.6 CAS Details-MAN
24
7.2.5 Fire Fighting Measures
Extinguishing Media: Small fire: Carbon dioxide, water, foam.
Large fire: Water spray, fog or foam, do not use water jet.
DO NOT USE DRY CHEMICAL: Large volumes of gases could
be produced by reaction with Maleic Anhydride.
Special Fire-Fighting Procedures: Wear self-contained breathing apparatus with full face
piece operated in the positive pressure demand mode and full body protection when fighting fires
Hazardous Combustion Products: Carbon Dioxide, Carbon Monoxide.
Unusual Fire and Explosion Hazards: Unstable, or air-reactive or water-reactive chemical
involved . Vapors from melted material can be ignited. Keep melted material away from ignition
sources. May form flammable dust-air mixtures when finely divided. Prevent dust buildup by
providing adequate ventilation during grinding or milling
26
Hazardous Decomposition Products : Toxic levels of Carbon monoxide, carbon dioxide,
irritating aldehydes and ketones may be formed on burning. Heating in air may produce irritating
aldehydes, acids, and ketones.
Hazardous Polymerization : Will not self-polymerize but can undergo uncontrolled co-
polymerization in the presence of other monomers and catalysts.
27
Aquatic Toxicity LC50 - 96hr 230 mg/liter (mosquito fish) practically nontoxic LC50 -
24hr 150 mg/liter (blue gill sunfish) practically nontoxic
Mobility This product is not likely to volatilize rapidly into the air because of its low
vapor pressure.
Bio-accumulative potential This product is not expected to bio-accumulate through food
chains in the environment.
7.3.2 Composition
Eyes: Irritant .Symptoms may include tearing, blurring, and sensitivity to light.
Inhalation: Can cause central nervous system depression. Irritation including naus,
headache, dizziness, drowsiness, loss of coordination, fatigue, lung congestion and lowered body
temperature.
Ingestion: Can cause digestive disorders, bloody vomit, intoxication, liver and kidney
damage.
Skin: Wash with soap and water and flush with water. Remove contaminated clothing
and wash before reuse. Get medical attention
Eyes: Immediately wash eyes with water for atleast 15 minutes
Inhalation: Move towards fresh air.
Ingestion: Do not induce vomiting.
29
immediately in case of rising sound from venting safety device or any discoloration of tanks due
to fire. For tank, rail car or tank truck: Evacuation radius: 800 meters (1/2 mile). Water may be
ineffective.
32
8. MATERIAL BALANCE
Let us assume that 10 kmol of o-xylene is fed to a reactor.
Selectivity for PAN reaction= 0.7
C8H10 + 3O2 C8H4O3 + 3 H2O ...from equation (8)
O-xylene reacted = 7 kmol
Oxygen reacted = 21 kmol
PAN formed = 7 kmol
Water (g) formed = 21 kmol
33
Material Balance around the reactor :
Reactants entering:
O-xylene = 10 kmol = 10*106 = 1060 kg
Oxygen fed = 77.18 kmol = 77.18*32 = 2469.76 kg
Nitrogen fed = 290.37 kmol = 290.37*28 = 8130.36 kg
Total weight = 1060+10600=11660 kg
Products leaving:
PAN = 7 kmol = 7*148 = 1036 kg
H2O(g) = 35 kmol=35*18 = 630 kg
CO2 = 20 kmol =20*44 = 880 kg
MAN = 1 kmol = 1*98 = 98 kg
O2 = 27.68 kmol = 27.68*32 = 885.76 kg
N2 = 290.37 kmol = 290.37 *28 = 8130.36 kg
Total weight = 11660.12 kg
Law of Conservation of mass is satisfied.
PAN
O-xylene H2O
REACTOR MAN
Air
O2
N2
CO2
34
Material Balance around the Switch Condenser:
Feed to switch condenser:
PAN = 7 kmol
H2O (g) = 35 kmol
CO2 = 20 kmol
MAN = 1 kmol
O2 = 27.68 kmol
N2 = 290.37 kmol
Assume that 2 mol% and 0.2 mol% of MAN and PAN present in the feed leave in the top stream.
Top Stream Leaving the Condenser:
PAN = (0.2/100)*7 = 0.014 kmol
H2O (g) = 35 kmol
CO2 = 20 kmol
MAN = (2/100)*1= 0.02 kmol CO2
O2 = 27.68 kmol
O2
N2 = 290.37 kmol
N2
Bottom stream Leaving the Condenser:
MAN = 0.98 kmol = 0.98*98 = 96kg H2O
PAN
PA N = 6.986 kmol = 6.986*148 = 1034 kg
MAN
H2O
N2
O2
SWITCH
CONDENSOR
MAN
PAN
CO2 MAN
PAN
Fig No. Reactants and Products entering and leaving the Switch Condensor
35
Material Balance around the Distillation Column:
Feed to Distillation Column:
MAN = 96 kg
PA N = 1034 kg
Total (F) = 1130 kg
PAN composition (weight basis) in Distillate (D) and Residue (W) are 2% and 98% respectively
Overall Material Balance: F = D + W where F= 1130 kg (wt. basis)
PAN balance (wt. Basis) : xF*F = xD*D + x W* W
Where xF*F = 1034 kg
xD = 0.002
xW = 0.998
Solving above two equations, we get
D = 94.116 kg; W = 1035.88 kg
DISTILLATE
MAN
DISTILLATION
COLUMN
PAN
BOTTOMS
Fig No. Reactants and Products entering and leaving the Distillation Column
36
Aim: To produce PAN product, 60000 metric tons/year, 99.8 wt% purity.
Here 1 year = 300 days
60,000 tons/yr = 200 tons/day=25/3 tons/hr=25000/3 kg/hr;
37
Selectivity for complete combustion reaction=0.2
C8H10 + 10.5º2 5 H2O + 8CO2
o-xylene reacted = 80*0.2 =16 kmol/hr
Oxygen reacted =10.5*16 = 168 kmol/hr
Carbon dioxide formed = 8*16 = 128 kmol/hr
Water (g) formed = 5*16 = 80 kmol/hr
H2O=5040kg/hr
N2 =65041.2kg/hr
38
O-xylene =8480kg/hr
O2 = 7088kg/hr
REACTOR
MAN=784kg/hr
Air= 84801.2 kg/hr
PAN=8288kg/hr
CO2 = 7040kg/hr
Fig No. Reactants & Products in a Reactor along with Massflow Rates
H20=5040kg/hr
PAN=16.576kg/hr
MAN=15.68kg/hr
N2=65041.2kg/hr
O2=7088kg/hr
CO2=7040kg/hr
H20=5040kg/hr
N2=65041.2kg/hr
SWITCH
CONDENSOR
O2=7088kg/hr
PAN=8288kg/hr
MAN=784kg/hr
MAN=768.3kg/hr
PAN=8271.4kg/hr
Where xF*F=8271.44 kg
xD= 0.002
xW= 0.998
Solving above two equations, we get
D= 753.19 kg/hr; W= 8286.50 kg/hr
Rounding Off: DISTILLATE=753.19kg/hr
PAN=8271.4kg/hr
DISTILLATION
COLUMN
MAN=768.3kg/hr
PAN=8286.5kg/hr
Fig No. Massflow rates of reactants & products in Distillation Column
9. ENERGY BALANCE
DATA:
Vapor Heat Capacities (range 150°C - 450°C)
Cp (cal/moleK) = a + bT + cT 2 + dT3 , T in (K)
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Liquid Heat Capacity (range 125°C - 200°C)
for any organic: Cp (cal/mole°C) = 41.69 + 7.773 10−2 , T in (°C)
Vapor Pressures (range 100°C - 300°C)
form:
Since the gases are at high temperature and low pressure, the gases can be assumed to be ideal .
Compound mole fraction
o-xylene 0.0265
air 0.9735
Complete Combustion:
C8H10 + 10.5O2 5 H2O + 8CO2
Let us assume that latent heat of vaporization of feed varies linearly with composition
λ feed = (55.888*49601.73 +7.84 *24486.93)/(55.888+7.84)
= 46511.66 kJ/kmol
The environmental impact due to day-to-day operation and the potential environmental
damage that results from a plant accident or spill have been considered. Potential emissions to
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the environment from the proposed phthalic anhydride plant have been assessed in three
categories:
(a) Airborne emissions
(b) Waterborne emissions and
(c) Solid waste.
The main process hazard which may occur during normal operation of phthalic anhydride
plants is the risk of PAN dust clouds forming from minor process breaches. PAN dust clouds are
both toxic and explosive. Air quality monitoring will be utilized to identify process breaches
producing dust clouds before they become hazardous. Appropriate breathing equipment will
always be available.
Safety will be a priority and detailed policies will be developed to ensure safe working
practices are cultivated. Employees from all groups and levels will be involved in safety on a
day-to-day basis. The use of appropriate protective equipment will be mandatory for both
employees and visitors in all process areas. Noise will be controlled through good design and
appropriate insulation, and will not exceed recommended levels.
The Low Air Ratio process is the cleanest of the processes for phthalic anhydride
production. Normal operating conditions will produce only two significant discharges to the
environment which are shown in Figure.
(a) Non-condensable reaction by-products that remain with the air as it is rejected from the
process to the environment.
(b) Heavy residue from the bottoms of the rectification column.
The reaction by-products are mostly light organic vapours. A scrubbing unit will be
installed in order to reduce the concentrations of contaminants to less than 25 ppm PAN, 10 ppm
maleic anhydride and 3 ppm benzoic acid prior to discharge to the atmosphere. A 50 m stack
should disperse these concentrations to acceptable levels. The total amount of PAN vented to the
atmosphere will be less than 1 kg/hr. However approximately 15 T/hr of carbon dioxide will be
produced as a by-product of the main synthesis reaction and this gas will need to be vented to the
atmosphere. This is a negligible quantity when compared with the discharges from other local
industries.
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10.2 Waterborne Emissions
Water is not part of the phthalic anhydride process and will not come into direct contact
with any process stream in the system. Air coolers will be used to satisfy most of the process
cooling requirements so that cooling water usage will be minimal. The cooling-water circuit is a
closed system and does not use either sea or river water, and it makes only small discharges of
pH-neutral water to the environment. Biological fouling is controlled with phosphate additives
rather than the more environmentally hazardous chromate additives. Steam requirements will be
essentially met by the process itself using the heat generated by the PAN reaction. An
interconnection with the adjoining utilities plant will be installed but will generally only be used
to export steam. Process contaminants that might enter the steam system through exchanger leaks
or other process disturbances will be scrubbed at the shared utilities plant, so that condensate can
be recycled to reduce energy consumption and chemical treatment costs.
The most serious process hazard is the potential for phthalic anhydride dust clouds to
form following process breaches. The condensers will be the primary point of risk but other
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equipment; including the storage tanks and the reactor are also possible sources. At low
concentrations (less than 1%), PAN dust is a serious health risk. At higher levels (1.5-10.5%),
PAN dust is a major explosion hazard. A level of 10,000 ppm (1 %) PAN in the atmosphere is
immediately dangerous to life, but a lower concentration also poses a health risk and is an eye,
nose and skin irritant. Health and safety standards require a minimum of 3 ppm PAN and 0.05
ppm MAN for safe working environments before acute or chronic effects are detectable. These
standards will be met through appropriate process design and operating precautions. Phthalic
anhydride dust is explosive at concentrations of 1.5-10.5% in air. As there is always the
possibility of process leaks, all sources of ignition and non-intrinsically safe equipment will be
excluded from the site, except within the main buildings. High-risk zones will be identified and
equipped with air quality monitors to detect dust before it reaches a hazardous level. The three
areas of highest risk are the condensers, reactor and storage vessels. The areas where these items
are located are separated from other items of equipment to prevent an explosion in one area
triggering an explosion in another. Major fires in the plant will burn hot and be difficult to
extinguish, but will not release large quantities of harmful vapours. A fire station, manned by
specially trained process operators, will be located near the process equipment in order to access
and contain any fires before they become difficult to manage.
Significant volumes of reactants, products and intermediates will be held on site in the
three product storage tanks, two reactant storage tanks and an intermediate PAN pretreatment
tank. Spills from these sources are clearly the most serious due to the potential volume of
material that could be lost. Subsequently, all of these vessels require containing walls (or bunds)
to be built around them to prevent loss of hazardous materials in the event of a tank breach.
Ortho-xylene is a flammable and moderately toxic liquid at ambient temperatures and represents
a serious hazard if a significant volume is spilled. Process operations will be paused during a
spill until satisfactory recovery can be completed using temporary storage facilities which will be
readily available on the site. Phthalic anhydride is solid up to 131oC, although it will be held as a
liquid in the main product tanks and intermediate pretreatment tank. Consequently, any spill will
solidify quickly after contact with cool air. This helps to contain spills and aids the recovery
process, but increases the risk of dust cloud formation and may block drains. Recovery can be
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affected with shovels and drums, but adequate protective equipment must be provided for the
workers. The recovered product can then be returned to the pretreatment tank to avoid any
discharge to the environment. Hot water will be used to clean up any remaining residue.
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FIGURE: Phthalic anhydride process block diagram with emission sources.
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The major requirements for an Ethylene Glycol plant are ethylene oxide and water.
Glycol plants are almost always located very close to Ethylene oxide plants to reduce
transportation expenses, as the transportation of ethylene oxide is expensive due to its explosive
tendencies. The plant considered here is located adjacent to an Ethylene oxide plant. The most
optimum location would be in a petrochemical industrial area where there is a market for fiber
grade glycol.
Probably the location of the raw materials of an industry contributes more toward the
choice of plant site than any other factor in most chemical operations low delivered cost of raw
materials must be weighed up against other operating costs.
This is especially noticeable in those industries in which the raw materials are
inexpensive and bulky and is made more compact and obtain a high bulk value during the
process of manufacture. The supply of basic raw materials should be controlled directly be user.
Physical distance is not the only controlling factor in source of raw materials, for purchase price
and buying expense, base point procuring, reserve stock and reliability of supply are also
determinants.
The existence of transportation facilities has given too many of the greatest track centers
of world. A location should be chosen, if possible which has several competitions will help to
maintain low rates and give better service. Often times, a location is selected outside the city in
order to have a rail road siding available and thus eliminate trucking costs to freight years from
excessive costs of transportation. There will be more long distance water transportation used in
the future to reduce the cost of freight years from excessive costs of transportation.
There will be long-distance water transportation used in the future to reduce the cost of freight,
with the spread between production cost and sales cost constantly narrowing. We would see that
the product has a ready market at a close distance from the plant site so that transportation will
not become a big problem. Also we have to see that the product has as a ready market so that
there will be demand throughout the year for the product.
11.1.3 Climate
The plant site should be at a place where the climate is mild. Excessive cold, torrid heat
and excessive humidity should not be present where the plant is situated for this will reduce the
productivity part of the workmen. Also if excessive of conditions is present then the air
conditioning and other facilities also will increase the expenditure.
The Chemical Engineering industries are the largest users of electric power equipment
among the industries today because the modern demand is for extreme flexibility that sometimes
errors on the side of too many individual drives. Power for chemical industry is primarily from
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coal water and oil: in as much as they provide for the generation of steam both for processing
and of electricity production. A plant should establish near a hydraulic power generated project.
By keeping the availability of power and deep water transportation overweight all other
considerations including that of extremely severe winter weather making for difficult operating
conditions.
Water for industrial purpose can be obtained from one of two general sources: the plant’s
own source of municipal supply, if the demand for water is large it is more economical for the
industry to supply its own water. Such supply may be obtained from drilled wells, rivers, lakes,
dammed steams, or other impounded supplier, before a company enters upon any project, it must
ensure itself if a sufficient supply of water for all industrial, sanitary and fire demand, both
present and future. Data on temperature of water and on maximum, minimum and average rain
fall can be obtained from governmental agencies if surface water is to be pounded or the date on
stream flow of reverse can be acquired likewise if wells are to be relied on, Geologists and
practical well drillers should be consulted.
A certain careful study of the supply of a cheap labor should be made. Factors to be
considered in labor studies are supply, kind diversity, intelligence, wage scales regulation
efficiency and costs. The success of many of organizations depends upon the means by which its
labor gets to and from their works. A cheap site may have to be avoided if the laborers cone a
long distance they will be tired in coming to the plant. Also technical skill should be given due
importance.
The nature of the sub soil is very important while considering the plant of the industry.
Also due consideration should be given for the expansion of the plant. The cost of the land is
important, as well as local building costs and living conditions. Also even if there is no
immediate plan for expanding, a new plant should be constructed at a location where additional
space is available.
Plant layout in its broadest sense is a part of the overall system. It includes everything
from the original of the building to the location and movement of a small component. It is an
integral part of:
• PRODUCTION PLANNING: It allows, promotes and aids the creation of utility.
• MAINTENANCE: It affects the amount, difficulty and time required for it.
• MATERIAL HANDLING: This is necessitated by the design & layout of the
plant.
• ORGANIZATION: Physical layout often determines areas of authority, spheres
of personnel influence.
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Obviously machines, equipment, materials, employees, fixtures and all the necessary facilities
for engaging in an activity must be given a place of work. How they are located and where they
are located, may well determine the firm’s efficiency, its profit potential and its existence. Noise,
color, tight and dictate work environment. Proper work environment will increase the
productivity to optimum levels, boost the morale and job satisfaction.
Good layout design requires through knowledge of work flow, product flow and information
flow. Engineering, management & future expansion are to be imbibed into the layout design.
Technology is continuously upgrading making better manufacturing techniques available and
correct layout will accommodate these challenges.
Consideration is to be given for backward integration and forward integration of the product.
Further the arrangement of the equipment and facilities specified in the process flow sheet is a
necessary requirement for accurate pre-construction cost estimation of future detailed design
involving piping, structural and electrical facilities. Careful attention to the development of the
plot and the elevation plans will point out unusual plant requirements and therefore, give reliable
information on building site costs required for precise pre-construction cost accounting.
The following list will suggest some of the reasons for what good layout is about:
1. Reduce manufacturing costs.
2. Increase employee safety.
3. Better service to the customer.
4. Reduce capital investment.
5. Increase flexibility.
6. Improve employee morale through improved employee comforts and
conveniences in work area.
7. Better quality of the product.
8. Effective utilization of floor space.
9. Reduce work in process to a minimum.
10. Reduce work delays and stoppages.
11. Better work methods and utilization of labor.
12. Improve control and supervision.
13. Easier maintenance.
14. Reduce manufacturing cycle.
15. Better utilization of equipment and facilities.
16. Eliminate congestion points.
The following are among the major fundamentals most often citied:
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Storage facilities for raw materials, intermediate and finished products may be located in
isolated areas or in adjoining areas. Hazardous materials become a menace to life and property
when stored in large quantities and should be kept isolated. Arranging storage of materials so as
to facilitate or simplify handling is a point to be considered in design. Where it is possible to
pump a single material to an elevation so that subsequent handling can be accomplished by
gravity into intermediate reaction storage units.
Necessary because liquids can be transported by blowing or by pumping and solids can
be moved by mechanical means. Access for initial construction and maintenance is a necessary
part of planning, for example, over head equipment must have space for lowering into place, and
heat exchange equipment should be located near access areas here trucks or hoists can be placed
for pulling and replacing tube bundles. Thus space should be provided for movement of cranes
and fork trucks as well as access way around doors and underground hatches. Therefore each
plant presents its own challenges that need to be incorporated in the layout.
Expansion must always be kept in mind. The question of multiplying the number of units
or increasing the size of the prevailing unit or units merit more study than it can be given here.
Suffice it to say that one must exercise engineering judgment. Correcting inconsiderate layout
plan may involve scrapping the serviceable equipment or shut down the running equipment.
Nevertheless the cost of change must be borne for economics of large units and in the end make
replacement inevitable.
Floor space mayor may not be major factor in the design of a particular plant. The value
of land may be considerable item. The engineer should, however, follow the rule of practicing
economy of floor space, consistent with good house keeping in the plant and with proper
consideration given to line flow of materials, space to permit working on parts of equipment that
need servicing , safety and comfort to the operators.
The distribution of gas, air, water, steam, power and electricity is not always a major item
of consideration but flexibility of designing these items should permit to meet almost any
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condition. Regard to the proper placement of each of these services practicing good design
reduces the cost of maintenance.
11.8 Workshop
A workshop is also provided to supply tools on demand from laboratory and process.
Therefore, this is laid out nearer to the process area.
These are located to the processing area, because probably accidents occur at the
processing. Thus they can be easily controlled.
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FIGURE: PHTHALIC ANHYDRIDE PLANT LAYOUT WITH RELEVANT
ENVIRONMENT AND SAFETY ADDITION
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