Chapter 1 Correction LH

DECLERATION
“Thereby declare that this report is the result of my own work except for quotation
and summaries which have been duly acknowledge”
NUR AININA BINTI NAZMI NURUL ADZWIN BINTI NOORDIN

2014456536 2014420954
SITI SOLEHAH BINTI OMAR MUHAMMAD NOR ASYRAF BIN

2015834112 MUHAMAD
2015636532
DENNIS RODY ANAK HO KOK

SUNTING@SUNTING
2015694896
i
SUPERVISOR’S CERTIFICATION
“Thereby declare that I have read this thesis and in my own opinion this project
report is sufficient in terms of scope and quality for the award of the Bachelor in
Chemical Engineering (Hons).”
Signature : ………………………………….
Name : Siti Fatimah Abdul Halim
Date : ………………………………….
ii
TABLE OF CONTENTS
TITLE PAGE
DECLERATION i
SUPERVISOR’S CERTIFICATION ii
TABLE OF CONTENTS iii
LIST OF TABLES v
LIST OF FIGURES vi
LIST OF SYMBOLS vii
LIST OF ABBREVIATIONS viii
EXECUTIVE SUMMARY ix
PROCESS BACKGROUND AND SELECTION 1-1

1.1 Process Background 1-1
1.1.1 Physical Properties of Naphthalene, O-Xylene, Oxygen, Phthalic
Anhydride, Carbon Dioxide and Water 1-4
1.2 Objectives of Design Project 1-6
1.3 Process Selection Method for Carbon Dioxide Removal 1-6
1.3.1 Process selection factors Error! Bookmark not defined.
1.3.2 Physical absorption processes Error! Bookmark not defined.
1.3.3 Chemical absorption process Error! Bookmark not defined.
1.3.4 Membrane process Error! Bookmark not defined.
1.3.5 Adsorption Process Error! Bookmark not defined.
1.3.6 Cryogenic process Error! Bookmark not defined.
1.3.7 Hybrid Separation process Error! Bookmark not defined.
1.3.8 Process Selection Error! Bookmark not defined.
1.4 Process Selection Method for Phthalic Anhydride Production Error! Bookmark
not defined.
1.4.1 Processes for Production of Phthalic Anhydride Error! Bookmark not
defined.
1.4.2 Process Selection Error! Bookmark not defined.
1.4.3 Evaluation of the Process Selection Error! Bookmark not defined.
1.4.4 Scoring for the Evaluation Process Selection Error! Bookmark not
defined.
1.5 Conceptual Design and Flowsheeting Error! Bookmark not defined.
iii
1.6 Process Details 1-45
1.6.1 Chemistry 1-45
1.6.2 Reaction Kinetics 1-46
1.6.2 (a) The reaction Order, Rate Law and Rate Constant 1-46
1.6.2 (b) Stoichiometry 1-48
1.6.2 (c) Catalytic Reaction 1-49
1.6.3 Thermodynamics Properties 1-50
CONCLUSION 1-52
LIST OF REFERENCES 1-53
iv
LIST OF TABLES
PAGE
Table 1.1 Physical Properties [7] ........................................................................... 1-4
Table 1.2 Comparison of removal process...................Error! Bookmark not defined.
Table 1.3 Evaluation of removal process .....................Error! Bookmark not defined.
Table 1.4 Scoring for removal process ........................Error! Bookmark not defined.
Table 1.5 Comparison of the Processes ......................Error! Bookmark not defined.
Table 1.6 Evaluation of the Processes.........................Error! Bookmark not defined.
Table 1.7 Scoring for production of PA process ...........Error! Bookmark not defined.
Table 1.8: Reaction Conditions for production of phthalic anhydride ..................... 1-34
Table 1.9: Component analysis in production of phthalic anhydride ...................... 1-35
Table 1.12 Stoichiometric table for the main reaction .......................................... 1-48
Table 1.13 Relationship between Gibbs free energy and reaction spontaneity [50] .. 1-
50
Table 1.14 Magnitude of Kc .................................................................................. 1-50
Table 1.15 Properties of Species Involved in Production of Phthalic Anhydride at 25˚C.
................................................................................................. 1-51
v
LIST OF FIGURES
PAGE
Figure 1.1 Process flow for air oxidation of o-xylene [3] .......................................... 1-2
Figure 1.2 Process flow for air oxidation of naphthalene [3] .................................... 1-2
Figure 1.3 Main applications of PA in industry [2] ................................................... 1-3
Figure 1.4 Major product chain of phthalic anhydride in chemical industry. ............. 1-3
Figure 1.5 Concept diagram for production of Phthalic Anhydride ........................ 1-33
Figure 1.6 The input-output structure for production of Phthalic Anhydride ........... 1-35
Figure Error! Use the Home tab to apply 0 to the text that you want to appear
here..7 The oxidation of o-xylene to produce phthalic anhydride [46]
................................................................................................. 1-45
here..8 Activation energy pathway ........................................... 1-46
here..9 Steps in catalytic reaction ............................................ 1-49
vi
LIST OF SYMBOLS
Symbols
−𝑟𝐴 Rate of Disappearance
ΔG Free Gibbs Energy
ΔH Enthalpy
ΔS Entropy
Sort symbols according to alphabetical order
vii
LIST OF ABBREVIATIONS
CO2 Carbon Dioxide
H2S Hydrogen Sulfide
PA Phthalic Anhydride
Sort abbreviations according to alphabetical order
viii
EXECUTIVE SUMMARY
This project is to design a production of phthalic anhydride (PA) using o-xylene

and the treatment plant for pollutant that will be removing from the production process
which is carbon dioxide (CO2). The process selection is heavily influenced by general
cost, product yield, manufacturability and sustainability, by-product produced,
environmental impact and lastly, safety. In comparison to the other five process
production, catalytic vapor-phase oxidation of o-Xylene has been selected based on
scoring techniques. Because of its high process yield, it is chosen as the most effective
process with high profitability at a low manufacturing cost. The major concern of the
project is to reduce and treat the pollutant product from the production of phthalic
anhydride process and at the same to achieve the requirement by Malaysia
Department of Environment (DOE) in Environmental Quality Act 1974 (Clean Air).
Hazard Identification, Risk Assessment and Risk Control (HIRARC) are an integration
tool that can help identify, assess or measure and to control hazard and risk of any
workplace and its activities. It is important to know the hazard of chemicals used in this
process in order to eliminate, reduce or control the possibility for any accidents to occur.
Then, the other objective of this project is to produce the phthalic anhydride to fulfil the
public need as raw material to produce their product. Phthalic Anhydride is one of
importance material that used as raw material in manufacture of phthalate plasticizers,
the main product being dioctyl phthalate (DOP) which is used as a plasticizer in
polyvinyl chloride (PVC) industry. The other objective of this design project is to
produce 100, 000 tonnes per annum of phthalic anhydride to meet the increasing
market demand, thus being in line with another phthalic anhydride producer in Malaysia
and Asia. The site location for this production is the Gebeng Industrial Park, Pahang
which is selected due to consideration of several factors. The factors include the
strategic location, land price, facilities, transportation and environmental aspects. In
designing the production plant, environmental and safety is highly priority
consideration. Malaysia rules and regulations are taken into account in designing the
process and the whole plant. In this production of phthalic anhydride, the proposed
plant uses continuous process that the inputs and outputs flow continuously throughout
the process
ix
PROCESS BACKGROUND AND SELECTION
1.1 Process Background
Phthalic Anhydride (PA) is an organic product which can be obtained from

substances as o-xylene or naphthalene, through oxidation in presence of a catalyst,
usually a vanadium/titanium oxide. PA is an important chemical intermediate [1]. 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 [2]. 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 flexible PVC, which is sensitive to general economic
conditions as it is consumed in the construction and automobile industries.
The processes for producing PA by o-xylene or naphthalene are the same
except for reactors catalyst handling, and recovery facilities required for fluid bed
reactors. In PA production using o-xylene as the basic feedstock, filtered air is
preheated, compressed, and mixed with vaporized o-xylene and fed into the fixed-bed
tubular reactors [3]. The reactors contain the catalyst, vanadium pentoxide, and are
operated at 340 to 385⁰C. Small amounts of sulfur dioxide are added to the reactor
feed to maintain catalyst activity. Exothermic heat is removed by a molten salt bath
circulated around the reactor tubes and transferred to a steam generation system.
Moreover, Naphthalene-based feedstock is made up of vaporized naphthalene
and compressed air. It is transferred to the fluidized bed reactor and oxidized in the
presence of a catalyst, vanadium pentoxide, at 340⁰C to 385⁰C. Cooling tubes located
in the catalyst bed remove the exothermic heat, which is used to produce high-pressure
steam. The reactor effluent consists of PA vapors, entrained catalyst and various
byproducts and non-reactant gas. The catalyst is removed by filtering and returned to
the reactor
1-1
Figure 1.1 Process flow for air oxidation of o-xylene [3]
Figure 1.2 Process flow for air oxidation of naphthalene [3]
Figure 1.1 and Figure 1.2 show the process flow for air oxidation of o-xylene
and naphthalene, respectively.
The reactor effluent containing crude PA plus products from side reactions and excess
oxygen passes to a series of switch condensers where the crude PA cools and
crystallizes. The condensers are alternately cooled and then heated, allowing PA
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 PA are kept at 150⁰C and blanketed with dry nitrogen to prevent the
entry of oxygen fire or water vapor (hydrolysis to phthalic acid). Maleic anhydride is
currently the only byproduct being recovered.
Furthermore, Phthalic anhydride is widely used in industry for the production of
certain dyes. A well-known application of this reactivity is the preparation of the
anthroquinone dye quinizarin by reaction with para–chlorophenol followed by
hydrolysis of the chloride. Based on Figure 1.1-c, these are the application of PA in the
1-2
industries. The primary use of phthalic anhydride (PA) is as a chemical intermediate in
the production of plastics from vinyl chloride. Phthalate esters that function as
plasticizers are derived from phthalic anhydride. Phthalic anhydride has another major
use in the production of polyester resins and other minor uses in the production of alkyd
resins used in paints and lacquers, certain guys, insect repellents, and urethane
polyester polyols. Phthalic anhydride has also been used as a rubber scorch inhibitor
and retarder.
Figure 1.3 Main applications of PA in industry [2]
Figure 1.4 Major product chain of phthalic anhydride in chemical industry.
1-3
1.1.1 Physical Properties of Naphthalene, O-Xylene, Oxygen, Phthalic Anhydride, Carbon Dioxide and Water
Table 1.1
Physical Properties [4]
Property O-Xylene Oxygen Phthalic Carbon Dioxide Water

Anhydride
Physical state Gas Gas Liquid Gas Liquid
and
appearance
Odor  Sweet  Odorless  Mild  Odorless  Odorless
 Aromatic  Faintly pungent
odor
Molecular 106.168 g/mol 31.998 g/mol 148.117 g/mol 44.009 g/mol 18.015 g/mol
Weight
Boiling Point 144°C -183°C 285.3°C -78.5°C (sublimes) 99.974°C
Melting Point -25.16°C -218.4°C 131.4°C -56.6°C 0°C
Critical 357.11°C -118.95°C 518°C 30.98°C 374.2°C
Temperature
Specific 0.88 1.105 1.53 1.52 1.00
Gravity
1-4
Vapor 0.7 kPa (at 20°C) < 0.0003 kPa 5720 kPa (at 20°C) 3.17 kPa (at 25°C)
Pressure (at 20°C)
Volatility Not available Non-volatile Not available Not available Water boil at higher
temperatures
making it less
volatile.
Odor 0.05 ppm Not available 0.053 ppm Not available Not available
Threshold
Solubility Water solubility at 25°C Water solubility at Water solubility Water solubility at 25°C is Low water solubility:
is at 180 mg/L and 25°C and pressure = at 20-25°C is at at 1480 mg/L. Miscible less than 10mg/L
soluble with most 1bar is at 40 mg/L 6200 to 6400 with hydrocarbons and Moderate water
organic solvents mg/L most organic liquids. solubility: 10-1000
mg/L
High water solubility:
more than 1000
mg/L
Colour Colourless liquid Colourless Clear Colourless Colourless liquid
colourless liquid
1-5
1.2 Objectives of Design Project
The objectives of this plant design are:

(a) To recover CO2 from 100,000 tonne/annum production of Phthalic
Anhydride
(b) To control any potential hazard in production of Phthalic Anhydride that
comply with Occupational Safety and Health Act 1994.
(c) To control the environment impact that comply with Environmental Quality
Act 1974.
1.3 Process Selection Method for Phthalic Anhydride Production
1.3.1 Processes for Production of Phthalic Anhydride
To select the optimum process for the production of phthalic anhydride, some
factors are considered to meet the requirements in producing the best quality of this
product with the least capital cost. Factors to consider are [5]:
 General cost (Including: Raw material, equipment, utilities)
 Product Yield
 By – product produced
 Environmental Impact
 Safety
1. General Cost
General cost is the most crucial and major concern in most of all design projects.
This is subdivided into two types: fixed costs and variable costs. Fixed costs are costs that
do not depend upon the production rate, and they must be paid even if no chemical is
produced. This include laboratory costs, operating labour, capital repayment charges,
insurance, etc. Variable costs, on the other hand, are dependent upon the amount of
chemical produced such as raw materials, utilities (services), shipping, etc. The types of
equipment to be used in the process should be kept as simple as possible. Major items of
1-6
equipment include reactors, heat exchangers, columns, pressure vessels, storage tanks,
etc. Ancillary equipment such as process piping, and insulation can be estimated after the
total cost of the major items is known [6]. The primary objective of every design project is
to gain profit while meeting the needs of the customers, so it is important to have the plant
in the least total cost as possible. Thus, the process to be used must be the most
economically viable.
2. Product Yield
The process to be used must have the greatest product yield. Having enormous
losses is due to the ineffective purification or separation processes used and this can
greatly affect the financial aspect of the plant [7]. A process should obtain high efficiency
to gain more profit at low manufacturing cost.
3. By-Product
By-product is a secondary product derived from a manufacturing process or
chemical reaction. It is not the primary product or service being produced. In the context
of production, a by-product is the 'output from a joint production process that is minor in
quantity and/or net realizable value (NRV) when compared with the main products'.
Because they are deemed to have no influence on reported financial results, by-products
do not receive allocations of joint costs. By-products also by convention are not
inventoried, but the NRV from by-products is typically recognized as 'other income' or as
a reduction of joint production processing costs when the by-product is produced. A by-
product can be useful and marketable, or it can be considered waste.
4. Environmental Impact
To select an optimum process, it is important to consider its environmental aspects.
The importance of this analysis is in making possible operation at a high-performance level
with reduced risks to the environment. This includes the presence of by products, harmful
emissions and waste generation. The presence of by product is inevitable, thus, this
should be controlled [8]. The concentrations of all chemicals to be discharged, including
gaseous emissions, must be determined and measures taken to ensure that these levels
conform to allowable legislative standards. It is prudent to ensure that not only are present
1-7
emission standards observed, but also that the plant could conform to any subsequent
legislative reductions in these emission levels (while still operating economically).
5. Safety
To ensure the plant able to operate in a safe manner, providing an acceptable

hazard risk to the plant employees and the public, all process design activities, e.g.
process selection, plant layout, etc., and the equipment designs must be carried out with
the design objective of ensuring (within acceptable risk levels) the safe operation of the
plant [9].
1-8
1.3.2 Process Selection
Table 1.2.1
Comparison of the Processes
Production of
Production of Production of Phthalic
Production of Conversion of
Phthalic Phthalic Anhydride via
Phthalic Anhydride Phthalic Acid to
Anhydride via Anhydride via Catalytic Gas-
via Catalytic Gas- Phthalic
CRITERIA Catalytic Gas- Catalytic Gas- Phase Oxidation
Phase Oxidation of Anhydride
Phase Oxidation Phase Oxidation of a mixture of
Naphthalene
of n-Pentane of ortho-Xylene ortho-Xylene with
Naphthalene
Lower Cost
Lower Cost Higher Cost
Higher Cost Including: Lower Cost
Including: Including:
Including: 1. Equipment Including:
General Cost 1. Equipment 1. Equipment
1. Raw Material (Condenser) 1. Equipment
2. Utilities 2. Utilities
2. Equipment 2. Raw Material 2.Utilities
3. Raw Material 3. Raw Material
3. Utilities
Product Yield
85-90 [10] [11] 78-80 [12] 97 [13] 91-93 [14] 90 [15]
(%)
CO2, H2O, Maleic CO, CO2, Maleic CO, CO2, H2O,
By-Product CO2, H2O H2O
Anhydride Anhydride Maleic Anhydride
1. The major 1. The main 1. Uses fixed bed 1. The substances
1. Uses fluidized bed
contributor of environmental vapor phase are with high
reactor which
emissions is the concern of this reactor which probability
Environmental prodcued higher
reactor and process is the causes low CO2 acutely not
Aspect CO emission
condenser emission of emission. harmful to aquatic
(approximately 300
effluent which is certain products 2. Particulate, organisms and
lb/ton) [16]
vented from the of incomplete sulphur oxides are not expected
1-9
2. A thermal condenser unit. combustion. and carbon to accumulate in
incinerator alone is Releases CO2 Compared to monoxide make organisms [18].
approximately 95 emissions as well. using up the
percent efficient in 2. Emits particulates naphthalene and emissions, with
combustion of and hydrocarbons n-pentane as raw carbon monoxide
pollutants for o- in pre-treatment materials, it comprising over
xylene-based and distillation produces less half the total [16].
production, and 80 [12]. CO2 emission
percent efficient for (approximately
naphthalene-based 200lb/ton) [17].
production.
3. Particulate, sulphur
oxides and carbon
monoxide make up
the emissions, with
carbon monoxide
comprising over
half the total
1. The plant vessels 1. Exposure of 1. Hazardous in 1. Feed 1. Exposure can
could contain pentane can case of skin composition occur either in a
flammable mixtures cause drying and contact (irritant, must not exceed phthalic
of naphthalene or cracking of skin permeator), of 1 mole % of o- anhydride
phthalic anhydride with redness and eye contact xylene in air to manufacturing
vapours with air at blisters. (irritant), of avoid explosive facility or in the
Safety
high temperatures. 2. Pentane can ingestion, of mixture. various industrial
2. Acute (short-term) irritate the lungs. inhalation. or manufacturing
exposure of Repeated Repeated or facilities that use
humans to exposure may prolonged phthalic
naphthalene by cause bronchitis exposure to the anhydride [19].
inhalation, to develop with substance can
1-10
ingestion, and coughing, produce target
dermal contact is phlegm, and/or organs damage
associated with shortness of [13].
haemolytic breath [12].
anaemia, damage
to the liver, and
neurological
damage. Cataracts
have also been
reported in workers
acutely exposed to
naphthalene by
inhalation and
ingestion. [8]
For the evaluation of the three processes, equation 1 is used to calculate the score for each criterion for the five different
processes for the production of phthalic anhydride. Calculated score in each criterion is summed up to get the total score for
each process. The process that will have the highest total score will be the process to be used for the equipment design.
1-11
1.3.3 Evaluation of the Process Selection
Table 1.2.2
Evaluation of the Processes
Production of Production of
Production of Production of
Phthalic Phthalic Anhydride
Phthalic Phthalic Conversion of
Anhydride via via Catalytic Gas-
Anhydride via Anhydride via Phthalic Acid to
Catalytic Vapor- Phase Oxidation of
CRITERIA Catalytic Gas- Catalytic Gas- Phthalic
Phase Oxidation a mixture of ortho-
Phase Oxidation Phase Oxidation Anhydride
of o-Xylene Xylene with
of Naphthalene of n-Pentane
Naphthalene
General Cost 0 - + 0 0
Product Yield 0 - + 0 0
Manufacturability
+ + + + 0
and Sustainability
By-Product + 0 0 0 +
Environmental
- - - - +
Impact
Safety - + 0 + -
Total Score 0 -1 2 1 1
Rank 4 5 1 2 2
* Note : (+) : Better than, (-) : Worse than, (0) : Same as
1-12
1.3.4 Scoring for the Evaluation Process Selection
Table 1.2.3
Scoring for production of PA process based on the evaluation on Table 1.4.2 and the scoring number is based on the
possibility of the criteria to achieve the objective of production.
Production of
Production of Phthalic Anhydride Conversion of
Phthalic Anhydride
Weight via Catalytic Gas-Phase Oxidation Phthalic Acid
via Catalytic Vapor-
CRITERIA (%) of a mixture of ortho-Xylene with to Phthalic
Phase Oxidation of o-
Naphthalene Anhydride
Xylene
General Cost 25 4 3 3
Product Yield 10 5 4 4
Manufacturability
10 4 3 2
and Sustainability
By-Product 15 4 5 1
Environmental
20 2 2 2
Impact
Safety 20 1 1 1
Total Score 3.10 2.80 2.10
100
Rank 1 2 3
1-13
Justification of production of Phthalic Anhydride via Catalytic Vapor-Phase
Oxidation of o-Xylene
In recent years o-xylene has become the preferred raw material due to its
lower cost, availability, and ease transportation. The theoretical amount of air required
for oxidation of one mole of o-xylene is less than other process, the evaluation of heat
during the reaction is less, the product is of a higher purity compared to others product
from other reaction. Furthermore, being a vapor at ordinary temperature, o-xylene is
easier to handle in plant operation. Manufacturing PA from o-xylene by this recently
developed process offers a number of advantages over prior methods involving air
oxidation of o-xylene, with the most important being the relatively low cost.
Nevertheless present day fluid bed plants for producing PA from o-xylene incorporate
design features which obviously need substantial improvement, stemming from
product is separated out by means of solids condensers [20].
The main factors affecting the choice of feed stock are the yield (o-xylene is
higher yielding as all carbon atoms appear in the product), availability (naphthalene
sources are becoming rarer) and cost (naphthalene is only available at a competitive
cost in an impure form which is less suitable). Catalyst aging, utility costs (o-xylene
normally requires higher temperatures) and product quality (a wider range of by-
products are possible using naphthalene) also have potential to influence the final
choice. 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 o-xylene
separation plant, using a mixed o-xylene feed, is often constructed on the same site
as a PA plant.
Apart from raw material selection, the main design 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 utilize 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%[18]. 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 hazards.
1-14
1.4 Process Selection Method for Carbon Dioxide Removal
The removal of acid gases (CO2, H2S and other Sulphur components) from
petrochemical industry such as phthalic anhydride production industry is often
referred to as gas sweetening process. Carbon dioxide present in the production
reaction need to be removed in other to; increase the heating value of the gas, prevent
corrosion of pipeline and gas process equipment. The removal of carbon dioxide can
be accomplished in a number of ways. Varieties of processes and (improvement of
each) have been developed over the years to treat certain types of gas with the aim
of optimizing capital cost and operating cost, meet Gas specifications and for
environmental purpose [21]. The major processes available can be grouped as follows
[22]:
• Absorption Processes (Chemical and Physical absorption)
• Adsorption Process (Solid Surface)
• Physical Separation (Membrane, Cryogenic Separation)
• Hybrid Solution (Mixed Physical and Chemical Solvent)
1-15
1.4.1 Process selection factors
Today, the field of acid gas removal process is so wide and available processes
are so numerous, thus selection of an optimum process becomes an issue. Each of
the processes has advantages relatives to others for certain applications. Therefore,
in selection of the appropriate process, the following factors should be put into
consideration:
• Type and concentration of impurities in the feed gas
• The concentration of each contaminants and degree of removal required.
• Hydrocarbon composition of the gas
• Final specification
• Capital and operating cost
• Volume of gas to be processed
• Selectivity required for acid gas removal
• Conditions at which the feed gas is available for processing.
Decision in selecting a CO2 removal process can be simplified by gas composition

and operating conditions. High CO2 partial pressure in the feed gas (345 kpa)
enhances the possibilities of employing physical solvent, while the presence of
significant amount of heavy hydrocarbon discourages the use of physical solvent. Low
CO2 partial pressures and low outlet pressure of the product stream may favour
application of chemical solvents [23]. Process selection could prove difficult; a number
of variables must be weighed prior to making final process selection.
1-16
1.4.2 Physical absorption processes
Physical solvent processes use organic solvents to physically absorb acid gas
components rather than react chemically. Removal of CO2 by physical absorption
processes are based on the solubility of CO2 within the solvents. The solubility of CO2
depends on the partial pressure and on the temperature of the feed gas. Higher CO2 partial
pressure and lower temperature favours the solubility of CO2 in the solvents (absorbent),
at these conditions complete removal of gas from reaction of production is possible.
Selection of physical processes for the removal of CO2 from production of phthalic
anhydride is favoured on the following conditions [24];
i. The partial pressure of the CO2 in the feed should be 50 psi or higher
ii. The concentration of heavy hydrocarbon in the feed should be low. That is
the gas feed is lean in C3+.
iii. Only bulk removal of acid gas is required.
iv. Selective removal of CO2 is required.
There are various physical processes for the removal of CO2 from production industry but
not all the processes available are capable of removing CO2 in order to meet
Environmental Quality Act 1974 (Air Quality) specification of 50- 100 ppmv of 2.5% of CO2
in the product stream. The following physical processes will be discussed base on their
suitability/modification to treat acid gas with high or low concentration of CO 2 in the feed
gas and small – large scale processes will also be considered.
The processes are as follows [23];

 Selexol process
 Rectisol process
 Fluor process
i. Selexol process
The selexol process uses union Carbide selexol solvent, a physical solvent made of
dimethyl ether of polyethylene glycol [CH3 (CH2CH2O) nCH3] [25]. The solvent can be used
to selectively or simultaneously remove sulphur compounds, carbon dioxide, water as well
1-17
as aromatic compound. Dehydration of the feed gas is required before entering the Selexol
unit. Previous researchreport that initial runs on the dimethyl ether of tetra ethylene glycol
(DMTEG); shows that less expensive mixture of the dimethyl ether of polyethylene glycol
(DMPEG) ranging from diethylene glycol to hepta-glycol was just as effective as pure
DMPEG in absorption of CO2 [26].
Process Description of selexol process

The dehydrated sour gas enters the absorber and flow upward counter-currently
to the lean solvent which is introduced at the top of the absorber. The solvent enters the
absorber slightly below ambient temperature through the use of heat exchangers on
flashed solvent and lean solvent streams. Because of the high CO2 content in the feed
gas, a bottom- pump- around of solvent is used on the absorber and a two-stage solvent
introduction is employed [27]. The leanest solvent is introduced at the top of the absorber
and the semi-lean or partially stripped solvent is introduced in the mid-way of the absorber.
The rich solvent leaves the bottom of the absorber and flashed in a high-pressure
separator the vapour stream is recycled back to the absorber to reduce hydrocarbon
losses.
The rich solvent from the high-pressure separator is flashed in an intermediate
pressure separator to release a major portion of CO2 after passing through the rich solvent
sour gas exchanger. The low-pressure flash stage which is at atmospheric pressure
release the major portion of the remaining dissolved CO2, a portion of semi-lean solvent
stream from the flash is pumped back to the intermediate point in the absorber for
contacting the richest part of the sour gas stream, while the other portion is flow to the
stripper column where it is air/N2 stripped to remove the last traces of acid gas present
and then pumped through semi-lean-lean solvent heat exchanger to the top of the
absorber [28].
ii. Rectisol process
Rectisol process uses chilled methanol as a solvent, because of high vapour

pressure of methanol the process is normally operated at temperature range of -30 to -
100oF. The process is best suited where there are limited quantities of ethane and heavier
components [26]. There are many possible processes configurations for Rectisol process
depending on process requirement/specifications and scalability. Rectisol process is now
extensively used in natural gas industry to remove CO2.
1-18
Process Description of rectisol process
In this process the methanol solvent contacting the feed gas in the first stage of the
absorber is stripped in two stages of flashing via pressure reduction. The regenerated
solvent is virtually free of sulphur compounds but contains some CO2 [26]. The acid gas
leaving the first stage solvent regenerator is suitable for Claus plant. The second stage of
absorption then removes the remaining CO2 present. The rich solvent from the bottom of
the second stage of the absorber is stripped deeply in a steam-heated regenerator and
return to the top of the absorption column after cooling and refrigeration.
iii. Fluor Process
The Fluor solvent process is one of the most attractive processes for gas treating
when the feed gas CO2 partial pressure is high (> 60 psia), or where the sour feed gas is
primarily CO2. The process is based on the physical solvent propylene carbonate for the
removal of CO2 [29]. Propylene carbonate (C4H6O3), is a polar solvent with high affinity for
CO2 and αij values of C1 or C2 to CO2 are high, therefore hydrocarbon pickup in the rich
solvent and subsequent hydrocarbon losses in the CO2 vent stream are minimal. The early
fluor solvent process configurations were limited to treating a narrow range of feed gas
compositions, which is application, were limited to feed gas stream with low C5+
hydrocarbon [26]. Recently new configurations have been developed for treating; A low to
medium and high CO2 content sour gas.
a) Process description for low-medium CO2 content
For gas with CO2 partial pressure of about 60-120 psia and the feed gas is at 1000
psig and ambient temperature. The feed gas is first dried in a TEG contactor to remove
almost all the water, this prevent water build-up in the solvent. The dehydrated feed gas is
then cooled by cold treated gas from the absorber and further cooled by external
refrigeration. The cooling process minimizes the temperature rise in the bottom of the
absorber cause by heat of solution of CO2, which results in a close isothermal absorber
temperature profile [26]. Also, it aids the removal of heavy hydrocarbon, thus minimized
co-absorption of heavy hydrocarbon by solvent and reduces the recycle gas flow and
hydrocarbon losses in the CO2 vent. The near isothermal temperature profile of fluor
process improves both mass transfer and rich solvent CO2 loading [29].
1-19
The rich solvent is regenerated by series of flashes. The flash drums are stacked
one on top of the other. The flash gases from the high-pressure, medium and low-pressure
flash drums are recycled back to the front end of the plant via a recycle gas compressor.
Flash gas recycle typically reduces hydrocarbon losses to less than 0.5% of the feed gas
[28]. Losses can be reduced further with an increase in recycle compression horsepower.
Over 90% of the CO2 desorbed in the atmospheric flash and residual CO2 is desorbed in
a vacuum flash. The flash drums are stacked one on top of the other. The flash gases from
the high-pressure, medium and low-pressure flash drums are recycled back to the front
end of the plant via a recycle gas compressor. Flash gas recycle typically reduces
hydrocarbon losses to less than 0.5% of the feed gas. Losses can be reduced further with
an increase in recycle compression horsepower. Over 90% of the CO 2 desorbed in the
atmospheric flash and residual CO2 is desorbed in a vacuum flash [29].
b) High CO2 content fluor solvent application
The feed gas pressure in this case varies from 400 – 1200 psig with the CO2 content
varying from 30-70 % and more [26]. High CO2 content in the feed gas increases the
amount of refrigeration produced by the flash regeneration of the rich solvent. At very high
CO2 partial pressures, the cooling effect from flash regeneration will exceed the cooling
required for CO2 absorption [25]. Also, the viscosity and surface tension of propylene
carbonate increases dramatically, and the absorber mass transfer rate drops drastically.
This negatively impact the process, therefore overcooling of the solvent should be avoided.
The excess refrigeration is harness in this application by lower the absorption column
temperature with refrigeration generated from flashing the rich solvent from high to
medium pressure [30]. This allows the absorber to operate at a lower temperature and
increases the solvent loading. The flashed gasses are compressed and recycled to reduce
hydrocarbon losses in the CO2 vent. Excess refrigeration generated by flashing of the rich
solvent flowing to the first stage flash drum is used to cool and condense the CO2 vent
stream from the atmospheric and vacuum flashes [29].
1.4.3 Chemical absorption process
Chemical absorption processes are based on exothermic reaction of the solvent with
the gas stream to remove the CO2 present. Most chemical reaction are reversible, in this
case reactive material (solvent) removes CO2 in the contactor at high pressure and
1-20
preferably at low temperature [31]. The reaction is then reversed by endothermic stripping
process at high temperature and low pressure. Chemical absorption processes are
particularly applicable where acid gas (CO2) partial pressure are low and for low level of
acid gas requirement in the residue gas. The water content of the solution minimizes heavy
hydrocarbon absorption, thus making the solvent more suitable for feed sour gas rich in
heavy hydrocarbon. Majorities of chemical solvent processes use either an amine or
carbonate solution.
i. Potassium Carbonate process
Carbonate process uses potassium carbonate (K2CO3) to remove CO2 from natural
gas. It works best in a gas with CO2 partial pressure ranges between 30 – 90 psi [32]. The
high pressure of natural gas transmission lines yields relatively high acid gas partial
pressure. As a result, the hot potassium carbonate is now frequently use for the
economical sweetening of natural gases having medium to high acid gas contents [28].
The reaction with carbon dioxide gives two parts of potassium bicarbonate for each part
of potassium carbonate reacted. Therefore, the concentration of the solution of the solvent
use (K2CO3) for CO2 removal is controlled by potassium bicarbonate solubility rather than
by potassium carbonate solubility.
Process description of carbonate process

For carbonate process the sour gas flows through a separator and to sour gas -
sweet gas heat exchanger. The heated sour gas enters the bottom of the absorber and
flow counter-currently with the descending lean hot potassium carbonate stream. The
sweet gas exits the top of the absorber and through a gas-gas exchanger. Typically, the
absorber is operated at about 230oF [33]. The sour gas-sweet gas exchanger is using to
recover sensible heat and decrease the heat requirement for the system. The acid rich
potassium carbonate from the bottom of the absorber is flashed to remove some part of
acid gas absorbed while the remaining is stripped at low pressure (Patm) and high
temperature at the stripper which operate at approximately 245oF [25]. The regenerated
solvent from the bottom of the stripper is pumped back to the absorber for re-use. The
entire system is operated at high temperature to increase potassium carbonate solubility,
therefore a dead spot where the solution is likely to cool, and precipitate should be avoided;
hence the system suffers from plugging, erosion or foaming.
1-21
ii. Amine Base process
The alkanolamines are the most generally accepted and widely used of the various
available solvents for removal of CO2 from natural gas stream [34].Their reactivity and
availability at low cost especially Monoethanolamine (MDEA), and Diethanolamone (DEA),
have made the solvent achieved a pinnacle position in the gas processing industry [26].
At elevated temperature (as obtained in the stripper column) the reaction is reversed that
is backward reaction is favoured where the carbonate salt formed is decomposed to
release the acid gas absorbed, therefore stringent control of stripper column temperature
should be adopted to reduce the release of carbonate salt. Methyldiethanolamine (MDEA)
and diethanolamine (DEA) are today the most tertiary amines for acid gas removal [26].
Other amine solutions that can be used are diglycoamine, diisopropanaolamine and
methyldiethanolamine [25].
Amine solutions are basic, and hence non-corrosive. They are sometime use as
corrosion inhibitors. In the presence of acid gases, significant corrosion may occur at
points where the concentration and temperature of acid gas is high. The primary amines
are the most corrosive. Therefore, the application of primary solution requires the use of
corrosion inhibitors and the unit may be made of special steels [35]. Foaming is a frequent
problem in these installations due the following;
 Suspended solids
 Condensed hydrocarbon
 Amine-degradation products.
 Foreign matter from corrosion inhibitors.
The foaming tendency in these installations can be prevented by good design and
operation; also, anti-foaming agents can be used [34] . Filtration of the solvent recycled to
the absorber step is essentially important. Filter that retain particle sizes larger than 10μm
is recommended [35]. Degradation of amine solvents occur when get in contact with the
air or oxygen, and the oxidation products often cause corrosion. Oxidation can be reduced
by placing the amine solutions under an inert gas blanket in the storage tanks.
1-22
Process description of amine-based process
The gas (CO2) enters the plant through a separator to remove any free liquid or
entrainment solids. The gas leaves the top of the scrubber and enters the bottom of the
absorber in counter-current contact with aqueous lean amine solution. Sweet gas leaves
the top of the absorber and flow to a dehydration unit before being considered ready for
liquefaction [34]. Lean amine flows downward counter currently to the sour gas and
absorbed the CO2 constituent and become rich solution. The rich solvent from the bottom
of the absorber is flashed in a separator to recover some absorbed hydrocarbon in the rich
solvent and then pass through amine-amine heat exchanger to the stripper where the acid
gas absorbed is stripped off at a very high temperature and low pressure. The acid gas
then leaves the top of the stripper column. The lean amine from the bottom of the reboiler
attached to the stripper flow through amine-amine heat exchanger and through a water air
cooler before being introduced back to the top of the absorber.
The amine-amine heat exchanger serves as a heat conservation device. A part of
absorbed acid gas is flashed from the heated rich solution on the top tray of the stripper.
The reminder of the rich solution flows downward through the stripper in counter-current
contact with vapour generated in the reboiler; which strips the acid gas from the rich
solution. The stripper overhead products (acid gas and steam) pass through a condenser
where the steam is condensed and cooled and returned to the top of the stripper as a
reflux, while the acid gas is separated in a separator and sent to the flare or compressed
for sequestration process [36].
1.4.4 Membrane process
Polymer membranes systems are a commercially proven technology for natural gas
treating application. Membranes are being used more frequently in gas field operations in
removing carbon dioxide and water vapour to meet pipeline and petrochemical project
specification. For a gas to permeate through a membrane surface the gas must first
dissolve in the high-pressure side of the membrane, diffuse across the membrane wall,
and evaporate from the low-pressure side [25]. Gas separation therefore works on the
principle that some gases are more soluble in, and pass more readily through polymeric
membrane than other gases. Each particular gas species encounters a unique resistance
to gas transport exhibit by a specific membrane. This resistance is dependent on two
factors; first, the size and shape of the gas molecules, this control the diffusivity of the gas
1-23
through the membrane and secondly, the extent of the molecular interaction between
membrane and the gas characterizes the solubility of the gas molecule in the membrane.
The overall selectivity of the membrane process is dependent on the resistance in

series of the boundary layer, selective film and porous substructure. A gas encountering
low resistance to transport is called “fast” gas which selectively permeates through the
membrane, while gas with high resistance is called “slow” gas [37]. In natural gas carbon
dioxide (CO2) species is said to be fast gas because of it linear molecular orientation and
high solubility in some polymeric membrane especially “polysulfone membrane” [38].
Membrane permeation is pressure driven process. The partial pressure difference
between the feed side and the permeate side has by far the greatest impact on the
performance of a membrane separator. The driving force for transportation through a
membrane is the difference in the partial pressure of the feed gas across the membrane.
The greater the partial pressure, the greater the driven force. This pressure difference
influences the membrane area required to achieve the desired separation at a given feed
conditions. Another important process criteria are the ratio of feed pressure over permeate
pressure, this has to be established in accordance to the membrane selectivity in order to
achieve an efficient separation.
Process description of membrane process

In membrane process feed gas is normally pre-treated/conditioned before entering
the membrane system to ensure efficient operation. The pre-treatment equipment varies
depending on the feed gas composition and conditions [37]. Generally, for natural gas the
feed gas is filtered through a high coalescing filter for removal of entrained particulates or
aerosols including sand, pipe scale. The feed gas is cooled in a cooler. Any condensed
liquids are removed in the gas/liquid separator and flashed back to the inlet compressor
third stage discharge scrubber. After liquid removal, the feed gas enters the feed
preheater; tri-ethylene glycol is sometime used as a heat medium to increase the gas
temperature [39]. The temperature control is provided to maintain the gas at the desired
operating temperature of the membrane fibres. The heated gas then enters the membrane
gas separators where it is separated into two streams; the permeate or CO2 product a-low
pressure, CO2-rich stream and the non-permeate or residue, a high-pressure hydrocarbon
rich stream.
1-24
1.4.5 Adsorption Process
Adsorption process involves the absorption of acid gas components by solid

adsorbent. The removal processes are either by chemical reaction or by ionic bonding of
solid particles with the acid gas. Commonly use adsorption processes are; the iron oxide,
Zinc oxide and molecular sieve (Zeolite) process [26]. The adsorbent is generally
characterized by a micro-porous structure which selectively retains the components to be
separated, once the bed is saturated with the acid gas the vessel is removed from the
system for regeneration by flowing hot sweet gas through the bed. Among the adsorption
processes mention above only the molecular sieve is more suitable for removal of small
concentration of CO2 from natural gas. The sieve makes use of the synthetically solid
crystalline Zeolite to remove the gas impurities. The crystal structure creates a large
number of localized polar charges called active site [40]. The polar gas molecule such as
H2S and H2O form weak ionic bond at the active site. Non-polar molecules such as
hydrocarbon will not bond at the active site. Though carbon dioxide molecules are non-
polar and will not bond to the active site, but due to CO2 linear structure, small
concentration of CO2 will be trapped in the pores. The process is therefore more applicable
for feed gas with low concentration of CO2 [31].
1.4.6 Cryogenic process
Low temperature distillation (Cryogenic separation) is a commercial process

commonly use to liquefy and purify carbon dioxide from relatively high purity (>90%)
sources. It involves cooling the gases to a very low temperature (lower than -73.3oC) so
that the carbon dioxide can freeze-out / liquefied and separated [38].
1.4.7 Hybrid Separation process
The hybrid separation processes combine the properties of physical and chemical
solvent for effective and selective removal of acid gas from natural gas. One of the well
acclaimed successful hybrid separation process uses in the oil and gas industry is Sulfinol
process licensed by shell E&P. Sulfinol is a mixture of sulfolane (tetrahydrothiophene1-1
dioxide a physical solvent), water and either diisopropanolamine (DIPA) or
Methyldiethanolamine (MDEA) (both chemical solvent) [25]. The dual functionality and
1-25
capacity of physical and chemical solvents mixture of sulfinol make the solvent more
efficient. The physical solvent for instance provides the system for bulk removal of acid
gas and also allows much greater solution loading of acid gas than most pure base
solvents. Typically, a sulfinol solution of 40% sulfolane, 40% DIPA and 20% water can
remove 1.5 moles of acid gas per mole of sulfinol solution [28]. The technology can be
used to remove H2S, CO2, COS, CS2 Mercaptans etc. For complete removal of CO2 from
natural gas sulfinol-M is (a combination of sulfinol with MDEA).
1-26
1.4.8 Process Selection
Table 1.4.1
Comparison of removal process
CRITERIA Removal
General Cost Solvent Advantages Disadvantages
PROCESS Element
1. The heat rise of the solvent in 1. The solvent has high affinity to
Fair Cost
the absorber is low since there heavy hydrocarbon which will be
Including:
is no heat of chemical reaction removed with CO2 and
1.Equipment
[27]. essentially result to hydrocarbon
Selexol (absorber, Sulphur, Carbide
2. Regeneration of the solvent is losses [41].
Process separator, Heat CO2, H2O Selexol
by air stripping, it’s required no 2. The process is more efficient at
Exchanger)
re-boiler’s heat. high operating pressure.
3. The process could be operated
at low pressure [41]
1. The solvent (methanol) does 1. Chilled methanol solvent used is
Lower Cost
not foam and completely capable of absorbing metallic
Including:
miscible with water thus trace components such as
Rectisol 1. Solvent Chilled
CO2 reduces losses [25]. mercury (Hg) to form amalgams
Process (Methanol) Methanol
2. The have high thermal and in the low temperature of the
2.Equipment
chemical stability. process [32].
(Absorber)
3. It’s non-corrosive.
1-27
4. There are no degradation 2. Rectisol complex scheme and
problems the need to refrigerate the
5. The rich solvent can be easily solvent result in high capital and
regenerated by flashing at low operating cost of the plant [41].
pressure therefore eliminate
the need for re-boiler’s heat.
1. Process required no fired duty 1. Solvent circulation for the Fluor
for solvent regeneration. solvent process is high.
Lower Cost 2. Solvent has high CO2 solubility 2. Solvent is very expensive
Including: and enhance CO2 loading. 3. The solvent has high affinity to
Fluor Propylene
1. Less CO2 3. It’s required no make-up water. heavy hydrocarbon which will be
Process Carbonate
equipment used. 4. The operation is simple and a removed with CO2 and
dry gas as output product. essentially results to
5. Modification for increasing CO2 hydrocarbon losses
in the feed is low.
Higher Cost 1. Steam requirement for the
1. Potassium carbonate causes
Including: system is low since absorber
general stress corrosion of the
Potassium 1.Material (High and stripper are operated at
Potassium units.
Carbonate acid gas) CO2 nearly the same temperature
Carbonate 2. The solvent reacts with some
Process 2. Equipment (isothermal system) [31].
corrosion inhibitors and cause
(Absorber, gas- 2. Degradation of the solvent is
erosion of the unit.
gas exchanger) minimal.
1-28
3. It is a continuous circulating 3. Tendency for foaming and solid
system employing an suspension is high thus reduce
inexpensive chemical. CO2 solvent loading
1. CO2 to be absorbed at ambient
temperature
2. Antifouling agent
Lower Cost
3. Good design and operation
Including:
4. Recommended process
Amine 1. Solvent 1. The primary amines are the
Alkanoala 5. The CO2 concentration of the
Based (MDEA and CO2 most corrosive
mines feed gas to be treated is
Process DEA) 2. Degradation of amine solvents
relatively low
2. Less
6. The CO2 recovery rates from
Equipment used
amine base solvent can be as
high as 98% and purity can be
in excess of 99% [35].
1. Membrane has good weight 1. Separated CO2 is at low
and space efficiency, which pressure and requires additional
Higher Cost
make it more applicable off compression to meet pipeline
Including:
Membrane shore environment [38] pressure requirement.
1. Equipment CO2, H2O -
Process 2. It has high adaptability to 2. Compression of the feed gas is
2. Utilities
variation of CO2 content in the necessary to provide the driving
3. Membrane
feed gas force for permeation, the energy
required for compression is high
1-29
3. Membrane has limited / No especially is high pressure is
moving parts thus make the require thus contributing to the
process riskier to operate. cost of operation [42].
3. The hydrocarbon loss is high.
Lower Cost: 1. Tendency for blockage of
1. Suitable for feed gas with high
Including: process equipment is high
Cryogenic concentration of CO2
1. Less CO2 - 2. Some cryogenic fluids are
Process 2. It produces a liquid CO2 ready
Equipment used flammable and toxic such as
for transportation by pipeline
(acetylene, ethane) [38]
1. Higher co-absorption of heavy
Higher Cost Tetra-
1. Low energy requirement hydrocarbon
Hybrid Including: hydrothiop
H2S, CO2, 2. Low foaming and non-corrosive 2. A reclaimer is required to
Solution 1. Material hene
COS, CS2 nature of the solvent remove the oxazolidones
Process (Sulfolane) 1-1
3. High acid gas loading produced in a side reaction of
2. Equipment dioxide
DIPA with CO2 [29]
1-30
Table 1.4.2 Evaluation of removal process
CRITERIA General Removal

Solvent Advantages Disadvantages Total Score Rank
PROCESS Cost Element
Selexol Process 0 + 0 0 - 0 6
Rectisol Process - 0 + + 0 1 4
Fluor Process - 0 + + 0 1 4
Potassium Carbonate
+ 0 + 0 0 2 2
Process
Amine Based Process + 0 + + 0 3 1
Membrane Process + 0 + 0 0 2 2
Cryogenic Process - 0 0 + - -1 8
Hybrid Solution Process 0 + - 0 - -1 8
* Note: (+) : Better than, (-) : Worse than, (0) : Same as
1-31
Table 1.4.3 Scoring for removal process
Score Potassium Amine

Weight Membrane
CRITERIA Max:5 Carbonate Based
(%) Process
Min: 1 Process Process
General Cost 25 5 5 5 5
Removal
20 5 4 4 4
Element
Solvent 20 5 3 4 1
Advantages 20 5 4 5 3
Disadvantages 15 5 3 4 3
Scoring 3.90 4.45 3.30
100 25
Rank 2 1 3
Justification of amine-based process

Amine base solvent (DEA) was chosen in this project to establish the operating conditions
at which the CO2 removal process from the petrochemical and natural gas industry can be
operated to meet the environmental regulation specifications and to minimized emission
to the environment. The process justification was based on the following conditions;
 The CO2 concentration of the feed gas to be treated is relatively low (5.23%) with
high hydrocarbon contents, the amine process is considered more suitable
(Tennyson et al, 1977) [34].
 The solvent applies (DEA) is considered to be chemically stable; DEA can be
heated to its normal boiling point (269oC at 760mmHg) before decomposition.
Therefore, reduce the solvent degradation during stripping and reduce solvent loss
and accumulation in the units [25].
 The heat of reaction of DEA with CO2 is low compared to other amines the heat
generated in the absorber is low which increase the solvent loading capacity in the
absorber. Since solubility/loading of CO2 increases at low temperature [35].
 The CO2 recovery rates from amine base solvent can be as high as 98% and purity
can be in excess of 99%. Amine base solvent process is more efficient for acid gas
available at high or low partial pressure and with low or relatively high partial
pressure acid gas product [36]
1-32
1.5 Conceptual Design and Flow sheeting
This report covers the conceptual design of the Design Project to produce 100,000 metric
tonne of phthalic anhydride per annum. Conceptual design is an early stage of the design
process which is the broad outlines of function and form of something articulated. Based on
Douglas’ Hierarchy, there are four levels in the hierarchy which are (1) Selection of Process
Mode, (2) Selection of Input-Output Structure, (3) Selection of Recycle Structure, and (4)
Selection of Separation and Purification Structure.
Step 1: Batch versus Continuous Process
There are three types of process modes that can be chosen which are either
continuous, non-isothermal or non-adiabatic process. For the production of 100,000 tonne per
annum of phthalic anhydride, the most suitable process would be continuous process.
Continuous process has a lot of advantages as it increase productivity as it produces more unit
in less time compared to the other processes. Furthermore, high scale production can be
achieved as well as reducing labor costs by automating many activities that was traditionally
done by hand.
Step 2: The Input/Output Structure of the Process
The purposed of this section is to investigate the input/output structure of the process.
Then, identify the main reaction pathway to identify the feed and the product chemicals.
Phthalic anhydride
(main product)
Carbon dioxide
O-xylene (treatment)
C6H4(CH3)2 (l) + 3O2 (g) -> C6H4(CO)2O (l) + 3H2O (l) Maleic anhydride
(by-product)
C6H4(CH3)2 (l) + 7.5O2 (g) -> C2H2(CO)2O (l) + 4CO2 (g) + Water (treatment)
Oxygen 3H2O (l)
O-Xylene (recycle)
Oxygen (recycle)
Nitrogen (purge)
Figure 1.5 Concept diagram for production of Phthalic Anhydride
1-33
Figure 1.5 shows the concept diagram for the production of phthalic anhydride. The
reactions involved in this process are shown as the figure above. Firstly, o-xylene undergo a
catalytic oxidation to produce phthalic anhydride. The side reaction produced from the catalytic
oxidation of o-xylene are carbon dioxide and maleic anhydride.
Table 1.4: Reaction Conditions for production of phthalic anhydride

Limiting Reactant O-Xylene
Excess Reactant Air/Oxygen
Feed ratio (O-Xylene: Air) 1:3
Reaction Temperature and Pressure 250-400oC and 1.0-6.0 atm
Reaction Phase Vapor Phase
Kinetic or Thermodynamic In a chemical reaction of phthalic anhydride production
controlled? shown the thermodynamically controlled based on the
condition of the reaction such as temperature, pressure
and the solvent/catalyst had used.
Catalyst Vanadium Pentoxide/Titanium Oxide
Conversion of limiting reactant 79%
Product Yield 99% PA, 0.9% MA, 0.06% Phthalic, 0.04% Other
Feed preparation for reactor feed Preheating and pressure preparation
The input-output structure focuses solely on the reactor. The raw material has
undergone preheating and compression in the feed preparation reactor in order to compliment
the operating conditions; which are then being fed to the packed bed reactor. Figure 1.6 shows
the input-output structure for the production of phthalic anhydride and Table 1.9 shows the
component analysis for the production process of phthalic anhydride.
1-34
Recycle:
O-xylene
O-xylene Phthalic Anhydride

Reactor feed
Oxygen Reactor
preparation
Water
Maleic Anhydride
O2, N2, CO2
Figure 1.6 The input-output structure for production of Phthalic Anhydride
Table 1.5: Component analysis in production of phthalic anhydride
Component Normal Boiling Point Light/Heavy Destination

(oC)
O-Xylene 144.4 Heavy Recycle
Phthalic Anhydride 284 Heavy Main Product
Maleic Anhydride 202 Heavy By-product
Carbon Dioxide -56.6 Light Treatment (waste)
Water 100 Heavy Treatment (waste)
Oxygen -182.96 Light Recycle
Nitrogen -195.80 Light Purge
Step 3: The Recycle Structure of the Process
The recycle block represents the return of unreacted feed chemical that will be
separated from the reactor effluent and feed back to the reactor for further reaction. The recycle
stream is to ensure a full utilization of o-xylene for a higher product yield of Phthalic Anhydride.
The unreacted raw material will re-enter the feed preparation reactor in order to comply the
operating condition of the next equipment. For the production of phthalic anhydride, a
compressor is chosen for the recycling process to take place. Figure 1.7 illustrates the process
block diagram of the production of phthalic anhydride with recycle stream.
1-35
Recycle:
O-xylene
O-xylene Water
Reactor Separator
Preparation Reactor Separator
Oxygen Preparation
Phthalic
Anhydride
Figure 1.7: Recycle structure
Number and type of reactor: 1 and Fixed Bed Reactor Multitube

Recycle compressor/pump: 1 pump
Economic Potential Analysis

EP = Profit Margin – Reactor Cost – Pump
Price of O-Xylene = $ 0.35/kg
Price of Phthalic Anhydride = $ 1.20/kg
Price of Maleic Anhydride = $ 0.90/kg
Price of Carbon Dioxide = $ 0.12/kg
Feed rate of o-xylene to process = 10,828.93kg/h
Product rate of phthalic anhydride + Maleic Anhydride + Carbon Dioxide
= 11,537.49kg/h + 594.55kg/h + 1584.36 kg/h
= 13,716.40kg/h
Profit Margin = [(11,537.49kg/h x $1.20/kg) +(594.55kg/h x $0.90) + (1584.36kg/h x $0.12)] –

[(10,828.93kg/h x $0.35/kg)]
= ($ 10,780.08/h) / (13,716.40kg/h) = $ 0.78/kg of all product (average)
= $ 10,780.08/h = $ 89,711,832/year
Reactor Cost: $ 2,490,000

Pump: $21,800
EP = $ 89,711,832 - $2,490,000 - $21,800 = $ 87,200,032
1-36
Step 4: General Structure of the Separation System
i. Alternative Scheme 1
MEA Absorber CO2
O-xylene
Reactor Separator
Preparation Reactor Flash
Oxygen Preparation
Distillation
Recycle: Column
Phthalic
O-xylene, oxygen,
nitrogen Distillation Anhydride
Column Maleic
Distillation Anhydride
Water
Column
Figure 1.8 Conceptual Design for Scheme 1
The alternative scheme 1 shown the separation system that consisted of three distillation
columns and one flash to separate the desired product and undesired product.

Separator: 1 flash and 3 Distillation Column
Economic Potential Analysis (Based on Scheme 1)

EP = Profit Margin – reactor cost – compressor cost – separator cost
1-37
= 11,537.49kg/h + 594.55kg/h + 1584.36 kg/h
= 13,716.40kg/h
[(10,828.93kg/h x $0.35/kg)]
= $ 10,780.08/h = $ 89,711,832/year

Pump: $21,800
Separator: $116,000 (T701) + $316,000(T702) + $281,000(T703) +$ 40,700(V701)
EP = $ 89,711,832 - $2,490,000 - $21,800 - $753,700 = $ 86,446,332
ii. Alternative Scheme 2
MEA Absorber CO2
O-xylene
Reactor Separator
Preparation Reactor Flash
Oxygen Preparation
Distillation
Recycle: Column
Phthalic
O-xylene, oxygen,
Column Maleic
Anhydride
Water
Flash
1-38
The conceptual design for alternative scheme 2 slightly different from scheme 1 because its
consisted with 2 unit of flash at the initial and last separation section in order to reduce the cost
of equipment.

Separator: 2 flash and 2 Distillation Column

= 11,537.49kg/h + 594.55kg/h + 1584.36 kg/h
= 13,716.40kg/h
[(10,828.93kg/h x $0.35/kg)]
= $ 10,780.08/h = $ 89,711,832/year

Pump: $21,800
Separator: $116,000 (T701) + $316,000(T702) + $40,000 (V702) +$ 40,700(V701)
EP = $ 89,711,832 - $2,490,000 - $21,800 - $512,700 = $ 86,687,332
1-39
iii. Alternative Scheme 3
MEA Absorber CO2
O-xylene
Reactor Separator Distillation
Preparation Reactor
Oxygen Preparation Column
Distillation
Recycle: Column
Phthalic
O-xylene, oxygen,
Column Maleic
Distillation Anhydride
Water
Column
Conceptual design scheme 3 shown that, in the separation section, four unit of
distillation column have been used in order to get an effective separation process compared to
scheme 1 and 2. Even tough, this scheme will have consumed high cost in purchasing of
equipment and the maintenance.

Separator: 4 Distillation Column

1-40
= 11,537.49kg/h + 594.55kg/h + 1584.36 kg/h
= 13,716.40kg/h
[(10,828.93kg/h x $0.35/kg)]
= $ 10,780.08/h = $ 89,711,832/year
Pump: $21,800
Separator: $116,000 (T701) + $316,000(T702) + $281,000(T703) +$ 281,000 (T704)
EP = $ 89,711,832 - $2,490,000 - $21,800 - $ = $ 86,206,032
Step 5: Environmental Control

i. Wastewater Treatment Process
Figure 1.11 Block flow diagram of wastewater treatment process
Generally, all chemical processes produce waste streams. These include gases, liquids and
solids that must be treated prior to being discharged into the atmosphere, sequestered in
landfills and so on. These waste streams may contain unreacted materials, chemicals produced
by side reactions, fugitive emissions and impurities coming in with the feed chemicals and the
reactions products of these chemicals. Not all the unwanted emissions come directly from the
process streams. From the Figure 1.11 above shown the wastewater process flow that will be
use in production process. Next, continue with solid waste treatment process and gas treatment
process.
1-41
ii. Solid Waste Treatment Process
Sludge produced from wastewater treatment process will be treated as scheduled
wastes and also solid wastes from operation, maintenance, handling and other sections will be
sent to landfill management for further treatment.
iii. Gas Waste Treatment Process
Figure 1.12 Process flow diagram of gas sweetening
Carbon dioxide is one of the several dangerous greenhouse gases in the atmosphere.
Hence, it is important for carbon dioxide to be treated before being release to the environment.
In this project, the removal of carbon dioxide is done based on amine base solvent (DEA)
process. In this process, alkanamine will be utilized as a chemical solvent to remove acid
gases.
Step 6: Heat Exchanger and their utilities

The main objective of the process energy recovery is to optimize the energy that a
process exchanger with the utilities. At the expense of capital investment, the utility usage can
be decreased by exchanging energy between process stream. The amount of energy
integration is a function of the relative costs of the utilities. In additional, the process becomes
more complex and more difficult to control. This lost in flexibility must be weighed against the
savings in operating costs.
1-42
1-43
Process Flow Diagram
P-701 E-701 C-701 M-701 E-702 R-701 E-703 E-704 E-705 V-705 E-706 V-702 S-701 M-703 E-707 E-708 T-701 T-702 T-703
P-702
OX Inlet OX Heater Air OX and OX Recycle Reactor Product Product Product CO2 CO2 CO2 Spliter Mixer Heater Heater PA and MA and H2O and
OX
Pump Compressor Compressed and Mixture Cooler Cooler Cooler Flash Cooler Flash MA Dis- OX Dist- OX Dist-
Recycle
Figure 1.13 Process Flow Diagram of production of Phthalic Anhydride
1-44
1.6 Process Details
1.6.1 Chemistry
Catalytic oxidation is the oxidation process that occur with the aid of a catalyst.
Catalytic oxidation has been widely used in the destruction of organic compounds due
to its high efficiency (or conversion of reactants), its economic benefits and good
applicability [43]. The catalyst will not have changes during the reaction and it will help
to promote the oxidation reaction, allowing efficient reaction or to lower reaction
temperature. A faster reaction requires a smaller vessel, thus reducing capital costs
and low operating temperatures generally and reduced auxiliary requirements, thus
can reduce operating costs. Generally, oxidation process is the process where electron
is losing during the reaction and oxygen being added and products from this reaction
are main product, carbon dioxide and water.
This reaction concept is similar to the oxidation of o-xylene in order to
produce phthalic anhydride with the help of vanadium catalyst. O-xylene, which is
available in abundant quantities from petroleum refineries appears to be the most
suitable. Phthalic anhydride may be produced from o-xylene according to the following
chemical equation.
Figure 1.14 The oxidation of o-xylene to produce phthalic anhydride [44]
In catalytic oxidation process, the catalyst affect the rate of reaction by lowering
the activation energy during the reaction of o-xylene with oxygen in order to yield
product desired. When less energy is needed for molecules to collide each other, the
faster the reaction will take place. The diagram below show the pathway of activation
energy with and without catalyst. From the diagram, it shows that high energy is
required to yield products when there is no catalyst used and low energy is needed
when there is aid of catalyst.
1-45
Figure 1.15 Activation energy pathway
1.6.2 Reaction Kinetics
Chemical reaction kinetic study deals with rate of chemical processes such as
the rate law, the rate constant, the stoichiometry and the catalytic reaction.
1.6.2 (a) The reaction Order, Rate Law and Rate Constant
The substances that influence the rate of reaction are usually one or more of
the reactants, but can occasionally include products. The rate law is experimentally
determined and can be used to predict the relationship between the rate of a reaction
and the concentrations of reactants Limiting reactant in this process is o-xylene and
usually chosen as basis of calculation.
During this reaction occur, the major initial product is o-tolualdehyde (TAL),
which is subsequently converted via o-phthalide (PL) to phthalic anhydride (PA): o-
toluic acid is a minor intermediate, while maleic anhydride (MA) is a significant by-
product resulting from the over oxidation of PA. Other minor by-products have also
been reported, and carbon oxides are formed at all stages of the reaction [45]. Carbon
dioxide formed will be treated as a pollutant before releasing to the atmosphere as high
concentration of carbon dioxide in the atmosphere will increase the potential of
greenhouse effect.
1-46
Figure 1.16 Generalized reaction network for ortho-xylene oxidation [46]
The reaction that usually involved in the production of phthalic anhydride is

demonstrated by following equations:
𝐶6 𝐻4 (𝐶𝐻3 )2 + 3𝑂2 → 𝐶6 𝐻4 (𝐶𝑂)2 𝑂 + 3𝐻2 𝑂 (desired reaction) (1.1)
𝐶6 𝐻4 (𝐶𝐻3 )2 + 7.5𝑂2 → 𝐶2 𝐻2 (𝐶𝑂)2 𝑂 + 4𝐶𝑂2 + 3𝐻2 𝑂 (undesired reaction) (1.2)
From the equations above, the rate law of the reaction can be determine as
follow:
−𝑟𝐴 = 𝑘𝐶𝐴 (1.3)
Where;
−𝑟𝐴 = rate of disappearance of naphthalene (s-1)
𝑘 = rate constant for naphthalene (s-1)
𝐶𝐴 = final concentration of naphthalene (mol/L)
The exponent of the concentration in the equation (1.4) lead to the concept of
reaction order. The order of a reaction refers to the powers to which the concentrations
are raised in the kinetic rate law. From the equation above, the reaction of naphthalene
to phthalic anhydride is a second order reaction. The reaction rate constant, k is not
truly a constant and merely independent of the concentration of species involved and
also strongly dependent on temperature.
The kinetic constant used for the desired reaction to produce PA is 𝑘 =
4.12 × 1011 [17] while for undesired reaction to produce MA is 𝑘 = 2.25 × 1011 [17].
1-47
1.6.2 (b) Stoichiometry
Table 1.6
Stoichiometric table for the main reaction
Substance Species Initial Change Remaining

O-xylene A FAO - FAOX FA=FAO(1-X)
Oxygen B FBO -3FAOX FB=FAO(𝜃B-3X)
Phthalic C FCO FAOX FC=FAO(𝜃C+X)
anhydride
Water D FEO 3FAOX FD=FAO(𝜃D+3X)
Where,
𝐹 𝐶 𝑦𝐵𝑂
𝜃𝐵 = 𝐹 𝐵0 = 𝐶𝐵𝑂 = 𝑦𝐶𝑂
(1.4)
𝐴𝑂 𝐴𝑂
And 𝜃𝐶 , and 𝜃𝐷 , 𝜃𝐸 , are defined similarly. The reaction involved the change of phase
and for the liquid phase, the volume change with reaction is negligible and for the gas
phase, the change in volume is considered.
𝑃 𝑇
𝜐 = 𝜐𝑂 ( 𝑂 ) (1 + 𝜀𝑋) (1.5)
𝑃 𝑇𝑂
Where,
change in total number of moles for complete conversion
𝜀= (1.6)
total moles fed
𝜀 = 𝑦𝐴𝑂 𝛿 (1.7)
9
𝐸 𝐷 𝐶 𝐵 2 2 1 2
𝛿 =𝐴+𝐴+𝐴−𝐴−1=1+1+1− 2
− 1 = 1.75 (1.8)
From the equation above, the concentration of reactants and products can be
generated:
FA FAO (1−X) CAO (1−X) TO P
CA (o − xylene) = υ
= υO (1+εX)
= 1+εX
( T )P (1.9)
O
FB
CB (oxygen) = υ
=
FAO (1−3X) CAO (1−3X) TO P
( ) (1.10)
υO (1+εX) 1+εX T PO
FC FAO (1+X) CAO (1+X) TO P
CC (phthalic anhydride) = υ
= υO (1+εX)
= 1+εX
( T )P (1.11)
O
FD FAO (1+3X) CAO (1+3X) TO P

CD (water) = υ
= υO (1+εX)
= 1+εX
( T )P (1.12)
O
1-48
1.6.2 (c) Catalytic Reaction
Catalytic oxidation of o-xylene by using vanadium oxide catalyst can be broken

down into the sequence of individual steps.
1. Mass transfer of the reactant from bulk fluid to the external surface of
the catalyst pellet.
2. Diffusion of the reactant from the pore mouth through the catalyst pores
to the immediate vicinity of the internal catalytic surface.
3. Adsorption of reactant onto the catalyst surface.
4. Reaction on the surface of the catalyst.
5. Desorption of the products from the surface.
6. Diffusion of the products from the interior of the pellet to the mouth at
the external surface.
7. Mass transfer of the products from the external pellet surface to the bulk
fluid.
Figure 1.17 Steps in catalytic reaction
As the reaction is heterogeneous catalytic reaction, the mechanisms are written

as follow:
i. Adsorption: A + S ↔ A. S
S represent an active site and will dente a vacant site which no atom, molecule or
complex adsorbed on it. The combination of A.S is when species A will be adsorbed
on the site S. Species A can be an atom, a molecule or an atomic combination.
Rate of adsorption = rate of attachment – rate of detachment (1.13)
𝑟𝐴𝐷 = 𝑘𝐴 𝑃𝐴 𝐶𝑣 − 𝑘−𝐴 𝐶𝐴.𝑆 (1.14)
ii. Surface reaction: A. S ↔ B + S
After A is adsorbed onto the surface, the reaction will occur to form a product.
Surface reaction = rate of attachment – rate of detachment (1.15)
𝑟𝑆 = 𝑘𝑆 𝐶𝐴.𝑆 − 𝑘−𝑆 (1.16)
i. Desorption: B + S ↔ B. S
After that, the products of the surface reaction adsorbed on the surface will desorbed
into the gas phase and produce the product. This is known as desorption process.
Rate of adsorption = rate of attachment – rate of detachment (1.17)
𝑟𝐷 = 𝑘𝐷 𝐶𝐵.𝑆 − 𝑘−𝐷 𝑃𝐵 𝐶𝑉 (1.18)
1-49
1.6.3 Thermodynamics Properties
To determine the rate of forward and reverse reaction is the same the
concentration of reactant and product must be constant by using chemical equilibrium.
Floger [47] stated the relationship between the change in Gibbs free energy, ΔG,
enthalpy, ΔH and entropy, ΔS is by the equation 1.8. The relationship between Gibbs
free energy with spontaneity is shown in Table 1.12
∆𝐺 = ∆𝐻 − 𝑇∆𝑆
Table 1.7
Relationship between Gibbs free energy and reaction spontaneity [48]
ΔG=0 A Reaction is at equilibrium where forward or reverse direction will be
no net change.
ΔG>0 A reaction that in the forward direction where it is not spontaneous
where it is spontaneous in the reverse direction.
ΔG<0 A reaction that in the forward direction which is spontaneous.
Smith et al [49] stated that equilibrium, KC can be evaluated by the following equation
1.1:
ln 𝐾𝑐 = −∆𝐺°/𝑅𝑇
Table 1.8
Magnitude of Kc
Kc>>1 The equilibrium lies to the right and the reaction mixture contains
mostly products.
Kc<<1 The equilibrium lies to the left and the reaction mixture contains mostly
reactants.
0.10<Kc<10 The mixture contains same amounts of both reactants and products.
According to Fogler [47] the equilibrium constant Kc ant any temperature can be
evaluated if Kc at one temperature and heat 1of reaction, ΔHRX is known as show in
equation 1.2
𝛥𝐻𝑅𝑋 1 1
𝐾𝑐(𝑇) = 𝐾𝑐(𝑇1) exp[ ( − )]
𝑅 𝑇1 𝑇
From the reaction of the production of Phthalic anhydride the molecular weight, boiling
point, melting point, Heat of formation and entropy of each component at standard
temperature are shown in Table 1.14 below:
1-50
Table 1.9
Properties of Species Involved in Production of Phthalic Anhydride at 25˚C.
Material Molecular Boiling Melting Heat of Enthrophy,

Weight (g/mol) Point Point Formation, ΔS,
(0C) (0C) ΔHf, (J/mol.k)
(kJ/mol)
O-Xylene 106.168 144.5 -25.16 19.00 244.04

Phthalic 148.12 285.3 131.4 -297.65 174.62
Anhydride
Water 18.02 100 0 -288.83 6.62
Oxygen 32.00 -182.96 -218.79 0 205.02
At standard Temperature:
𝑘𝐽 𝑘𝐽 𝑘𝐽
∆𝐻°(25℃) = [3(−288.83) + − 297.65] − [19.00 ] = −1183.14
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
𝐽 𝐽
∆𝑆°(25℃) = [3(6.62) + 174.62] − [244.04 + 3(205.04)]
𝑚𝑜𝑙. 𝐾 𝑚𝑜𝑙. 𝐾
𝐽
= −664.68
𝑚𝑜𝑙. 𝐾
𝐽 𝐽 𝐾𝐽
𝑐° = −1183.14 × 103 − [(298 𝐾) (−664.68 )] = −940.81
𝑚𝑜𝑙 𝑚𝑜𝑙. 𝐾 𝑚𝑜𝑙
𝑘𝐽
−940.81
ln 𝐾𝑐 = 𝑚𝑜𝑙
𝑘𝐽
(8.3145 × 10−3 ) × 298 𝐾
𝑚𝑜𝑙. 𝐾
𝐾𝑐 = 0
The calculation above shows negative value of ΔG that indicated the
reaction is in a forward direction which is spontaneous. While the value of Kc is less
than 1 where the reaction is mostly lies to reactant. At 250C reaction of phthalic
anhydride production is favoured as reactant and not to the product. The selectivity of
phthalic anhydride production will decrease as the product consumed and the reaction
is not in equilibrium where the concentration of reactant will be increased. To ensure
the desired reaction the value of ΔG must be positive in insurance that it will favoured
more to product.
1-51
CONCLUSION
Process background and selection are the most crucial part in any plant design
project. It is crucial to select the most profitable process for the production of Phthalic
Anhydride (PA), and in this case it is via catalytic vapor-phase oxidation of o-Xylene
process. The advantages of using catalytic oxidation to produce PA has outshine the
other four processes. Because of its high process yield, it is chosen as the most
effective process with high profitability at a low manufacturing cost. The additional help
from a catalyst has sped up the oxidation reaction thus allowing an efficient reaction.
A faster reaction will reduce the capital costs and also operating cost. O-xylene will
react with vanadium catalyst to produce PA.
1-52
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DECLERATION

NUR AININA BINTI NAZMI NURUL ADZWIN BINTI NOORDIN

SITI SOLEHAH BINTI OMAR MUHAMMAD NOR ASYRAF BIN

DENNIS RODY ANAK HO KOK

PROCESS BACKGROUND AND SELECTION 1-1

Sort symbols according to alphabetical order

CO2 Carbon Dioxide

H2S Hydrogen Sulfide

Sort abbreviations according to alphabetical order

This project is to design a production of phthalic anhydride (PA) using o-xylene

1.1 Process Background

Phthalic Anhydride (PA) is an organic product which can be obtained from

Figure 1.2 Process flow for air oxidation of naphthalene [3]

Figure 1.3 Main applications of PA in industry [2]

Figure 1.4 Major product chain of phthalic anhydride in chemical industry.

Property O-Xylene Oxygen Phthalic Carbon Dioxide Water

The objectives of this plant design are:

1.3 Process Selection Method for Phthalic Anhydride Production

1.3.1 Processes for Production of Phthalic Anhydride

To ensure the plant able to operate in a safe manner, providing an acceptable

* Note : (+) : Better than, (-) : Worse than, (0) : Same as

Decision in selecting a CO2 removal process can be simplified by gas composition

The processes are as follows [23];

Process Description of selexol process

ii. Rectisol process

Rectisol process uses chilled methanol as a solvent, because of high vapour

iii. Fluor Process

a) Process description for low-medium CO2 content

b) High CO2 content fluor solvent application

1.4.3 Chemical absorption process

i. Potassium Carbonate process

Process description of carbonate process

1.4.4 Membrane process

The overall selectivity of the membrane process is dependent on the resistance in

Process description of membrane process

Adsorption process involves the absorption of acid gas components by solid

1.4.6 Cryogenic process

Low temperature distillation (Cryogenic separation) is a commercial process

1.4.7 Hybrid Separation process

CRITERIA General Removal

* Note: (+) : Better than, (-) : Worse than, (0) : Same as

Score Potassium Amine

Justification of amine-based process

Step 1: Batch versus Continuous Process

Step 2: The Input/Output Structure of the Process

Figure 1.5 Concept diagram for production of Phthalic Anhydride

Table 1.4: Reaction Conditions for production of phthalic anhydride

O-xylene Phthalic Anhydride

Table 1.5: Component analysis in production of phthalic anhydride

Component Normal Boiling Point Light/Heavy Destination

Step 3: The Recycle Structure of the Process

Number and type of reactor: 1 and Fixed Bed Reactor Multitube

Economic Potential Analysis

Profit Margin = [(11,537.49kg/h x $1.20/kg) +(594.55kg/h x $0.90) + (1584.36kg/h x $0.12)] –

Reactor Cost: $ 2,490,000

MEA Absorber CO2

Figure 1.8 Conceptual Design for Scheme 1

Number and type of reactor: 1 and Fixed Bed Reactor Multitube

Economic Potential Analysis (Based on Scheme 1)

Reactor Cost: $ 2,490,000

ii. Alternative Scheme 2

MEA Absorber CO2

Figure 1.9 Conceptual Design for Scheme 2