Process Design of An Acrylic Acid Plant

Process Design Project 2007 Group 7
Process Design of an
Acrylic Acid Plant
Group 7
Group Members:
Jamillah David
Luke Elliott
Norwind Khor
Oluwatoyin Olaleye
Jason Sharp
Basel Siddiqi
Zengcun Zhu
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Abstract......................................................................................................................................................... 1
Level 0) Input Information............................................................................................................................. 1
Level 1) Batch or Continuous Operation....................................................................................................... 1
1.1) Production Rate.................................................................................................................................. 1
1.2) Market Forces.................................................................................................................................... 2
1.3) Operational Issues............................................................................................................................. 2
Level 2) Input-Output Flowsheet Structure.................................................................................................... 2
2.1) Feed Stream Purification.................................................................................................................... 2
2.2) Recycle by-products........................................................................................................................... 2
2.3) Gas Recycle and Purge..................................................................................................................... 2
2.4) Number of Product streams................................................................................................................ 2
2.3) Economic Potential............................................................................................................................. 3
2.4) Alternative Designs............................................................................................................................ 3
Level 3) Recycle Structure............................................................................................................................ 3
3.1) Number of reactors............................................................................................................................. 3
3.2) Number of Recycle Streams............................................................................................................... 3
3.3) Excess Reactant................................................................................................................................ 3
3.4) Material Balances............................................................................................................................... 4
3.5) Reactor Heat Effects.......................................................................................................................... 4
3.6) Compressor Design and Cost............................................................................................................ 4
3.7) Reactor Cost...................................................................................................................................... 5
3.8) Design Variable Optimisation............................................................................................................. 6
Level 4) General Separation System Structure............................................................................................. 7
4.1) General Structure............................................................................................................................... 7
4.2) Vapour Recovery System................................................................................................................... 7
4.3) Liquid Separation System.................................................................................................................. 7
5) Detailed Simulation using ASPEN............................................................................................................ 8
5.1) ASPEN Property Models.................................................................................................................... 9
5.2) Process Optimisation......................................................................................................................... 9
5.3) Process Adjustments........................................................................................................................... 11
6) Level 4 Economic Potential (EP4)........................................................................................................... 11
6.1) Capital cost of the separation system............................................................................................... 11
6.2) Operating cost of the separation system.......................................................................................... 12
7) Heat Exchanger Network Synthesis........................................................................................................ 12
7.1) Arrangement of Reactant Preheating............................................................................................... 12
7.2) Identification of Streams that can be Integrated...............................................................................12
7.3) Network Synthesis............................................................................................................................ 13
7.4) Integration of Distillation Columns and Process Streams.................................................................14
7.5) Final Heat Exchanger Network......................................................................................................... 14
8) Level 5 Economic Potential (EP5)........................................................................................................... 14
9) Process Sensitivity Analysis................................................................................................................... 14
10) Environmental considerations............................................................................................................... 15
References.................................................................................................................................................. 16
Appendix A – Selectivity Data..................................................................................................................... 17
Appendix B – Data Tables.......................................................................................................................... 18
Appendix C – Material balances required at level 2....................................................................................19
Appendix D – Material balances required at level 3....................................................................................20
Appendix E– Hess’s Law Calculation.......................................................................................................... 21
Appendix F – Pressure Sensitivity Analysis................................................................................................ 23
Appendix G – Selection of Column Type.................................................................................................... 24
Appendix H – Sample Calculation for Costing a Separation System Vessel...............................................25
Required Information Obtained from Aspen............................................................................................ 25
Installed Cost........................................................................................................................................... 25
Operating Cost........................................................................................................................................ 26
Appendix I – Sizing the Flash Vessel.......................................................................................................... 27
Appendix J– Heat Transfer Co-efficient Selection.......................................................................................28
Appendix K – Heat Integration.................................................................................................................... 29
Temperature Interval Grid....................................................................................................................... 29
Energy Cascade...................................................................................................................................... 30
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Minimum Number of Units for Maximum Energy Recovery.....................................................................30

Appendix L – EP4 Price Break-Down.......................................................................................................... 31
Appendix M – EP5 Price Break-Down......................................................................................................... 32
Appendix N – ASPEN................................................................................................................................. 34
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Abstract
This report outlines the details of designing a process to produce 50,000 tonnes.yr -1 of acrylic acid with a
mass purity greater than 95%. It was firstly decided that a continuous process should be used. Next, a level
2 analysis was carried out, where it was decided to employ a gas recycle and purge. The level 2 economic
potential was found to be in the region of 85×106$.yr-1, indicating that this chemical route has a high potential
to be profitable. Carrying this design through to level 3 it was found that the optimum conversion and
percentage loss of propylene in the purge was 0.85 and 5% respectively. Feed mass fractions of 0.09
propylene and 0.275 steam were chosen to maximise economic potential while maintaining safe operation.
Using design heuristics, the general separation system was decided to consist of a flash vessel, vapour
recovery (absorber using demineralised water) and a liquid separation system. Studying calculated binary
mixture ratios the liquid separation system was designed and consisted of a liquid-liquid extractor and two
distillation columns. Each of these units operating conditions were determined through optimisation using
ASPEN. Finally, a heat integration network was designed to reduce the processes utility costs. The level 5
economic potential of the designed process was estimated at 80.1×106 $.yr-1.
Level 0) Input Information

Acrylic acid is an industrially important compound that is mainly used as an intermediate in the formation of a
wide variety of products such as plastics and paints. A plant was to be designed with the aim of producing
acrylic acid (C3H4O2) and the input information is provided below.
0.1) Reactions and conditions

a) Reactions: C3 H 6 ( g )  1.5O2 ( g )  C3 H 4 O2 ( g )  H 2 O( g ) [R1]
C3 H 6 ( g )  2.5O2 ( g )  C 2 H 4 O2 ( g )  CO2 ( g )  H 2 O( g ) [R2]
C3 H 6 ( g )  4.5O2 ( g )  3CO2 ( g )  3H 2 O( g ) [R3]
b) Reactor conditions: Inlet Temperature = 310°C and pressure = 3.5 bar.

c) Phase of reaction system: Gas.
d) Catalyst: The number of catalysts required is discussed in level 3 section 3.1.
e) Product distribution: Selectivity data as a function of conversion is provided in Appendix A.
f) Kinetic information: At the reactor conditions the equilibrium of reactions R1, R2 and R3 lies far to
the right. Each reaction rate, r, can be evaluated using equation 1 and the values for Er and ko,r are
tabulated in Appendix B, Table 8.
 E 
 rr  ko ,r exp  r  Pprop PO2
 RTR  [1]
0.2) Required rate of production for acrylic acid: 50,000 metric tons per year.
0.3) Required purity of acrylic acid: minimum 95% purity by mass.
0.4) Raw materials specifications: Tabulated in Table 1.
Table 1: Raw material specifications.
Raw Mass Composition Available Available
Price ($/kg)
Material (%) Pressure (bar) Temperature (oC)
Propylene 6-9 3.50 -16.3 0.38
Steam 25-30 3.50 310 139.36 × 10-4
Air 61-69 1.01 25.0 0.00
0.5) Processing constraints: the feed mass composition must be within 6 – 9% propylene, 25 – 30% steam
and the remainder air to maintain operation outside the explosive limits of the combustion reactions.
Level 1) Batch or Continuous Operation

To determine whether batch or continuous operation should be applied to this process the following areas
have been considered.
1.1) Production Rate

Continuous operation is preferred to batch configuration for plants that are required to produce more than
5000 tonne.yr-1 because batch processes have increased operating costs at higher production levels. In this
case, 50,000 tonne.yr-1 of product is required, therefore continuous operation is favoured.
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1.2) Market Forces

Acrylic acid has a stable demand throughout the year due to its wide use in industrial applications. The plant
being designed is only required to produce a single product that has long term uses and demand. Therefore
the flexibility of a batch process is not required and continuous operation is more suitable.
1.3) Operational Issues

There are no operational issues that make a continuous process inappropriate. This is because the process
has a relatively high rate of conversion and does not involve the handling of solids and/or slurries. However,
care must be taken in the selection of vessel and piping materials to counter the corrosive properties of the
chemicals within the system which may weaken structures and result in solid deposits.
Level 2) Input-Output Flowsheet Structure

The level 2 flowsheet can be seen in Figure 1and the decisions made have been explained below.
Figure 1: Level 2 flowsheet
2.1) Feed Stream Purification

No feed purification is required as the propylene and air streams are pure. The oxygen feed is supplied to the
process as an air stream and hence contains a large proportion of inert nitrogen. It has been decided that
nitrogen will not be removed from this stream due to the high separation costs. In addition, the presence of
nitrogen reduces the amount of steam feed required to operate safely outside the explosive limits of the
exothermic combustion reactions and may be utilised as a heat carrier.
2.2) Recycle by-products

At the reactors operating conditions the equilibrium of each reaction lies far to the right, effectively making
them irreversible. Therefore, there is no benefit from recycling acetic acid (which has a monetary value) and
other by-products. As water is inexpensive and may contain impurities it will not be recycled.
2.3) Gas Recycle and Purge

In keeping with the level 2 rule of recovering or using more than 99% of valuable reactants, it was decided
that propylene should be recycled. As propylene has a boiling point of -48 oC it is the boarder line between
heavy and light components. In order to separate propylene from the lighter components exiting the reactor,
distillation with refrigeration or a membrane process would be required. As refrigeration is very expensive
and no cost correlations are available for membrane separators, it was decided to consider propylene as a
light component. Thus, a gas recycle and purge was utilised to recover the valuable reactant and prevent the
accumulation of light inert components and by-products in the process.
2.4) Number of Product streams

Every component’s boiling point and destination code can be seen in Table 2. Assuming distillation is the
primary separation process, product streams were determined by ordering the components by boiling point
and grouping neighbouring components with the same destination code. This results in four product streams,
which can be seen in Figure 1.
Table 2: Component destination codes

Component Stream Number Normal Boiling Point (oC) Destination Code
Nitrogen (N2) 8 -195.8 2. Recycle and Purge
Oxygen (O2) 8 -183.0 2. Recycle and Purge
Carbon Dioxide (CO2) 8 -78.5 2. Recycle and Purge
Propylene (C3H6) 8 -48.0 2. Recycle and Purge
Water (H2O) 7 100.0 6. Excess – Waste
Acetic Acid (C2H4O2) 6 118.1 8. Valuable by-product
Acrylic Acid (C3H4O2) 5 141.0 7. Primary Product
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2.3) Economic Potential

EP2  product values  by product value  raw material costs ($ / yr ) [2]
F9 y 9C3 H 6
Percentage Loss of C 3 H 6  L p    100 [3]where: Fi  molar flowrate of stream i ij
y 
F1 mole fraction of component j in stream i
The economic potential at level 2 was calculated using equation 2 and the component prices shown in
Appendix B. To determine the flowrates of the valuable components and raw materials in terms of the design
variables material balances were derived for the system assuming perfect separation, which can be seen in
Appendix C. The design variables at this level are
conversion and the feed mass fractions of steam and
propylene. The selectivity for acrylic acid and acetic acid in
reactions R1 and R2 have been determined as a function of
conversion by fitting a polynomial to the provided
experimental data, which can be seen in Appendix A. As
there is uncertainty in extrapolating beyond the range of the
selectivity data, only conversions between 0.60 and 0.85
will be considered. In order to use more than 99% of the
valuable reactant (propylene) a percentage loss of 1% in
the purge was defined for this component as shown by
equation 3. Figure 2 shows the resulting plot of economic
potential against conversion. From this it can be seen that
the most desirable conversion at this level is the lowest
value of 0.6, since this results in the largest economic
potential. Most importantly Figure 2 shows that the products
and by-products are worth more than the raw materials, so
Figure 2: Economic Potential at level 2 for this design and chemical route will be progressed to level 3.
Lp = 1% versus conversion
2.4) Alternative Designs

a) Remove propylene from the light gases and recycle this as a pure component. This would require
the cost of membrane separation to be lower than the loss of propylene in the purge.
Level 3) Recycle Structure
Figure 3: Level 3 flowsheet
3.1) Number of reactors

In industry a two step process is commonly used to produce acrylic acid from propylene as it has a higher
conversion and yield than a one step process. This process requires two reactors as each reaction takes
place over different catalysts and at different operating conditions. For simplicity it was assumed that the
desired conversion and yield can be achieved in a single step process where propylene is converted into
acrylic acid using one catalyst. Thus, only one reactor is required for the purpose of this design project.
3.2) Number of Recycle Streams

Since there is only one reactor N 2, O2, CO2 and C3H6 all have the same destinations. As these also have
boiling points in the same range, shown in Table 2, they will be grouped, resulting in one gaseous recycle
stream that will require a gas compressor.
3.3) Excess Reactant

An excess of oxygen will be used because air is relatively inexpensive and it can be seen from equation 1
that increasing the partial pressure of oxygen will increase the rate of all reactions and hence the conversion
of propylene. It can also be seen that this would not affect the selectivity as the rates of all three reactions
are directly proportional to the partial pressure of oxygen. Furthermore, increasing the flowrate of air to the
process will also increase the amount of cooling within the reactor by heat carriers.
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3.4) Material Balances

At level 3 an estimate of the recycle and internal flows are required to size the reactor and compressors,
which are needed to calculate the economic potential (EP 3). In the absence of a designed separation system,
perfect separation was assumed for this level 3 analysis. The material balances that have been performed
can be seen in appendix D. In addition to the design variables listed at level 2 (conversion (x) and the mass
fractions of steam and propylene in the feed), the percentage loss of propylene in the purge will also be
considered. This is because the percentage loss is directly related to the gas recycle flowrate and therefore
both the compressor’s and reactor’s size and cost. Hence, at level 3 the economic potential for a small loss
of valuable reactant may not be as high as a larger loss due to the fact that a larger compressor and reactor
will be required.
3.5) Reactor Heat Effects

In order to examine the reactors heat effects an energy balance was performed using equation 4 . As the
heats of each reaction were provided at 298K, Hess’s law was used to calculate the enthalpy change across
the reactor and this calculation can be seen in Appendix E.
H  Q  0 [4] where: H  enthalpy change and Q  heat removed

3.5.1) Adiabatic Temperature Change
Using Maple and the Hess’s law calculation the reactor

outlet temperature was determined in terms of the
design variables such that equation 4 was satisfied for
Q = 0. For adiabatic operation the temperature rise must
be less than 10 to 15% of the inlet temperature. Figure 4
shows that operation at low percentage propylene
losses in the purge and lower conversion results in
feasible adiabatic temperature rises. However,
economic analysis has shown that such operating
conditions are unfavourable, due to high compression
costs. As the adiabatic temperature rise is unacceptably
high for greater propylene losses and conversions it is
not economically desirable to operate the reactor
adiabatically.
Figure 4: Adiabatic Temperature Change for different conversions and losses of propylene.
3.5.2) Heating and Cooling

To determine the required cooling duty for isothermal operation equation 4 has been solved for a reactor exit
temperature of 310°C. This results in a cooling duty of 15000kW for a 1% loss of propylene in the purge and
conversion of 0.85. As this is greater than the maximum heat removal of 2550kW (~8×10 6 Btu/hr) by cooling
water (Douglas, 1988) isothermal operation is not feasible.
3.5.3) Heat Carriers

The inert steam added to the reactor to ensure operation outside of the explosive limits is also a dilutant and
heat carrier. An additional option to moderate the reactor temperature rise is to increase the gas recycle
flowrate. This results in a higher flow of heat removing inert components through the reactor. However, as
previously discussed in section 3.5.1 this results in high compressor costs which are economically
undesirable. Therefore, this option is also not favourable.
As all of these operation modes are either unfeasible or undesirable one of the design rules will have to be
compromised. By cooling the reactor with a molten salt it would be possible to remove 15000kW of heat.
Thus, it has been decided to use this form of cooling to operate the reactor isothermally. Cost information for
molten salts is not available so the cost of cooling water required was used instead to estimate the reactors
annual cooling cost.
3.6) Compressor Design and Cost

Two compressors are required for this process, one for the gas recycle and another for the inlet air stream.
It has been decided to use centrifugal compressors as these have few moving parts, high energy efficiency
and a small size relative to other types of compressors. The installed cost of these were calculated using
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Guthrie’s correlation (equation 5) where the Marshall and Swift equipment cost index (M & S) for this year is
1094 and Fc = 1.00 for centrifugal compressors (Douglas, 1988). The installed cost was converted to an
annualised cost by dividing by a capital charge factor, which is related to the project life, cost of capital and
has been estimated as 3.
M &S
 517.5 bhp   2.11  FC 
0.82
Compressor Installed Cost ($)   [5]
 280 
3.03  10 5 
 Pout 



hp  Pin Qin    1 [6] Where: P = Pressure (lb.ft -2)
  P  Q = Volumetric flowrate (ft3.min-1)
 in  
The brake horse power (bhp) was determined by dividing the isentropic power requirement (hp) by 0.9. This
allows for irreversibilities, such as fluid friction in valves, friction of moving parts and fluid turbulence. The
horse power (hp) was calculated using equation 6 and in doing so it was assumed that there is no pressure
drop across the mixer and heater preceding the reactor, such that Pout = 3.5 bar (7308 lb.ft -2) for both
compressors. For the inlet air compressor Pin is specified as 1.01 bar (2116 lb.ft -2). However, for the gas
recycle compressor Pin was assumed to be 0.8Pout to account for pressure drops across the reactor and
separation system, as this has yet to be designed. A sensitivity analysis, which can be seen in appendix F
indicates that the total annual cost of the gas recycle compressor varies significantly with the pressure drop
selected. Thus, if the gas recycle stream’s outlet pressure from the separation system determined at level 4
is notably different from 0.8Pout the cost of this compressor will need to be re-evaluated.
The molar flowrate of both streams being compressed were converted into volumetric flowrates assuming
perfect gas behaviour, where the temperature of the gas stream exiting the separation system was estimated
as 40°C. γ was estimated by taking a molar weighted average of appropriate γ values for each component,
which were selected from Table 10, appendix B.
The compressors annual operating cost was determined by multiplying their power requirement and
electricity cost (0.04 $.hp-1.hr-1). The power requirement is equal to the bhp divided by 0.9 to allow for
inefficiencies in converting input energy to shaft work.
3.7) Reactor Cost

The installed cost of the reactor is mainly dependent on its dimensions, as shown by Guthrie’s cost
correlation for pressure vessels (equation 7). Therefore the reactor needed to be designed in terms of the
design variables and the procedure by which this was done is outlined below.
 M & S  101.9 D1.066 L0.802  2.18  F  Where: Fc  Fm F p ,

R eactor Installed Cost ($)  c [7]D = reactor diameter (ft)
280 L = reactor length (ft)
It was decided to use a tubular reactor for this process as these operate at a high reaction rate, resulting in a
lower volume to achieve the same conversion as other types of reactors. Furthermore, tubular reactors are
usually more suitable for gas phase reactions. Due to the presence of H 2O and acidic chemicals within the
reactor it will be made out of stainless steel to counter corrosion.
When designing the reactor it was assumed that the total molar flowrate remained constant as the flowrate of
inert materials, such as H2O and N2, through it is much larger than that of the limiting reactant. Using this
simplification the reactor volume for a desired conversion was calculated by modelling it as a series of
CSTRs using an iterative procedure in Maple. The conversion of each CSTR was fixed at dx = 0.01,
maintaining a sufficient level of accuracy and the volume of each of these was calculated using equation 8,
where the rate of each reaction was evaluated at the exit conditions of the CSTR. This iteration was repeated
until dx × i was equal to the required conversion and the sum of dVi evaluated to calculate the corresponding
reactor volume. Assuming L / D  6 , the reactor’s length, diameter and hence installed cost (using equation
7) could be found in terms of the design variables. As the reactor operates at a pressure of 3.5 bar (50.75
lb.in-2) and is made out of stainless steel Fm = 3.67 and Fp = 1.05 (Douglas,1988). Similarly to section 3.6 this
cost was converted to an annualised cost by dividing by a capital charge factor of 3.
F4 y 4 p dx
dVi  [8] (Derived from the CSTR design equation (Metcalfe, 1997))
 r1  r2  r3  x idx
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The cooling cost of the reactor was estimated by calculating the flow rate of cooling water required to remove
the heat necessary for isothermal operation. By performing an energy balance on the cooling water stream
using the maximum cooling water temperature change ( ΔTmax=15°C) and its heat capacity (cp,w= 4.2 kJ.kg-
1
.°C-1) the cooling water flowrate was determined. By multiplying this by the cooling water utility cost,
tabulated in appendix B, the annual cooling cost in terms of the design variables was discovered.
3.8) Design Variable Optimisation

Generally design variables are not all fixed at level 3 and are retained until level 4. However, it has been
decided to optimise the design variables at this stage as time constraints make it difficult to do this at level 4.
The inlet mass fractions of propylene and steam were optimised first, followed by the percentage loss of
propylene in the purge and conversion simultaneously. This approach was taken so that the factors affecting
the economic potential least were optimised first.
Figure 5: EP3 for different conversions and mass Figure 6: EP3 for different conversions and mass
fraction of propylene in the feed fraction of steam in feed
clearly shows that the level 3 economic potential (EP 3), which was calculated using equation 9,
Figure 5
increases as the inlet mass fraction of propylene is increased. Therefore the optimum inlet mass fraction of
propylene is the maximum value of 0.09. In contrast EP 3 is insensitive to changes in the inlet mass fraction of
steam, which can be seen in Figure 6. Since the mass fraction of propylene chosen is at the upper limit, a
steam mass fraction at the lower limit was avoided to ensure an adequate error margin from the explosive
limits. Thus, a mid-point inlet steam mass fraction of 0.275 was selected.
EP3  EP2  (compressor capital and operating cos t )  (reactor capital and operating cos t ) [9]
Figure 7 displays EP3 as a function of conversion for

various percentage losses of propylene in the purge
at the previously optimised inlet mass fractions. This
figure clearly indicates that the highest EP 3 is
produced by an optimum conversion of 0.85 and a
propylene loss of 4 or 5%. From closer examination
of this plot it was found that the optimum percentage
loss of propylene is 5%. These optimum design
variables result in a level 3 economic potential of
83×106 $/yr.
Figure 7: EP3 versus conversion for different Lp
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Level 4) General Separation System Structure

4.1) General Structure
The stream leaving the reactor is at 310°C and is gaseous. From design heuristics this stream is to be
cooled to 35°C and a phase split attempted. The outlet vapour is sent to a vapour recovery system and the
condensed liquid to a liquid recovery system. It has been decided to cool the stream exiting the reactor to
45°C, as cooling water is available at 30°C and a minimum approach of 10°C must be maintained.
4.1.1) Flash
As the stream exiting the reactor contains water and acidic compounds with dipoles, non-ideal behaviour
would be exhibited. Therefore the short cut method is not applicable for this situation and the flash vessel
was modelled in ASPEN. The results from this can be seen in Appendix N. It was decided to operate the
flash vessel adiabatically at a pressure of 2.8bar. This was because lower pressures increase the costs of
compressing the gas recycle and higher pressures are unfavourable for the subsequent separation units,
which operate more effectively at lower pressures. A joule-thompson valve will be added downstream to
further reduce the pressure to atmospheric. It was found that flashing to 2.8bar is a reasonable compromise,
which provides an acceptable vapour-liquid split.
4.2) Vapour Recovery System

4.2.1) Location
Using Aspen it has been found that a purge with a 5 percent loss of propylene results in acrylic and acetic
acid losses of 1.48×106 $/yr. This is significant and merits the use of a vapour recovery system on the purge.
Although no materials in the gas recycle affects the reactor operation or degrade the product distribution, the
presence of acidic components may cause corrosion. In addition, not using a vapour recovery system would
change the level 3 material balances and the previously optimised design variables. Due to time constraints
re-evaluation of the material balances was not possible and therefore a vapour recovery system was
required to meet the specified acrylic acid production rate. Since the purge and gas recycle both require a
vapour recovery system, a single system was placed on the flash outlet due to economies of scale.
4.2.2) Type
The only vapour recovery processes with available cost information in this project are condensation and
absorption with demineralised water. Other currently available technologies are adsorption, reaction systems
and membranes. As acrylic and acetic acid have an infinite solubility in water (Perry et al., 1997), absorption
is the more effective process and will be used. Using Table 16 in Appendix G it has been decided to use
sieve trays in all columns designed for this process. Sieve trays were also chosen as these have a similar
efficiency to bubble-cap trays but are simpler and cost 30 to 50% less (King,1980). Stainless steel is the
chosen design material for all columns due to the corrosive properties of acrylic and acetic acid in the
presence of water.
4.3) Liquid Separation System

4.3.1) Removal of light components
As Acrylic acid has a higher boiling point than all other components leaving the flash vessel it is expected
that the light impurities would not significantly contaminate this product, assuming distillation is used in the
liquid separation system. However, even if all the light components leaving the flash vessel remain in the
acrylic acid product stream it would contain 96% acrylic acid (using and neglecting the vapour recovery). As
this is greater than the product specification it is not necessary to remove the light ends.
4.3.2) Azeotropes and reactants

Propylene forms an azeotrope with water. This is not problematic since these components are mixed at the
reactor inlet and thus separation is not important. The acetic acid-acrylic acid-water mixture is azeotropic in
nature; a feature which must be considered in the liquid separation system design.
4.3.3) Structuring the Liquid Separation System

With the cost information provided in this project the processes that are available for separating components
in a liquid phase are flashing, distillation and liquid-liquid extraction with di-isopropyl ether (DIPE). The other
alternatives that have not been considered are crystallisation, ion exchange, liquid membranes and
microfiltration. To identify which technique and separation sequence is most suitable, binary property ratios
(rij) have been computed for each pairing of the three liquids required to be separated (H 2O, C3H4O2,
C2H4O2). The results from this are displayed in Table 3 and the properties used to compute these ratios can
be seen in appendix B. The table also displays μik (defined on the next page) and the higher this value is, the
better the separation.
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Table 3: Binary mixture ratios and separation analysis of different processes

Separation Process (k) rkg rkf Property (j) r1 j r2 j r3 j 1k  2k  3k
Distillation (1atm.) 1.02 1.01 b.p. 1.11 1.05 1.06 10 3.8 4.9
Distillation (1atm.) 1.50 1.05 Pvap 5.08 1.62 3.13 8.94 1.26 4.65
Flash (1atm.) 1.40 1.23 b.p. 1.11 1.05 1.06 NA NA NA
Flash (1atm.) 15.0 10.0 Pvap 5.08 1.62 3.13 NA NA NA
Liq-liq Exraction
(42.22°C, 2.5 bar) 2.0 1.2 solubility 100 135.6 1.35 123.5 168 0.188
(62.08°C, 2.5 bar) 2.0 1.2 solubility 38.4 65.4 1.70 46.5 80.2 0.626
Pair 1 = H2O-C3H4O2 Pair 2 = H2O-C2H4O2 Pair 3 = C2H4O2-C3H4O2
p jA pjA or B = value of property j for component A or B, where mixture i
where: rij 
p jB is made up of A and B
rij  rkf
 ik  if μik > 1 separation is better than ‘good’
rkg  rkf
indicates that each component pair can be separated by distillation or liquid-liquid extraction with DIPE.
Table 3
However, acrylic acid polymerises at temperatures greater than 90°C, which is undesirable. As all three
components have normal boiling points greater than 90°C atmospheric distillation would not be feasible and
vacuum distillation may need to be used. However, for the purpose of this project the polymerisation reaction
has been neglected for simplicity. Table 3 also shows that water can be separated from both acrylic and
acetic acid more effectively using liquid-liquid extraction with DIPE than distillation. This high effectiveness
justifies the cost of the solvent and will therefore be used rather than distillation. Furthermore, separating the
acids from water requires azeotropic distillation, which will be much more complicated and expensive due to
the necessary use of multiple columns. As this separation has the largest value of μ, indicating it is the
easiest, it will be performed first. In addition, water is corrosive which also favours its early removal.
Table 3 shows that separating acrylic and acetic acid by liquid-liquid extraction with DIPE is worse than
‘good’ and distillation is more effective. As distillation also does not require a solvent it is generally cheaper
than liquid-liquid extraction and was therefore used for this separation. However, the DIPE must also be
separated from the acids. This was performed by distillation as it was the only process available for this
separation. In addition, a difference in boiling points and vapour pressures exist (see appendix B, Table 12).
As the boiling point and vapour pressure difference between the DIPE and both acids is greater than that of
the two acids, removing DIPE is the easiest separation. Since this is also the most plentiful component and
lightest it was removed first. This conflicts with the rule of removing products as distillates but it agrees with
the rule of removing recycles as distillates as DIPE was recycled.
Thus, the liquid separation system consists of a liquid-liquid extractor using DIPE to separate water from the
flash liquid condensate, followed by a distillation column to remove DIPE from the acrylic and acetic acid
(DISTIL1). Then a second distillation column separates the acrylic and acetic acids (DISTIL2).
5) Detailed Simulation using ASPEN

DIPE TOP-UP
Figure 8: Final Process Flowsheet
- 11 -
The full stream table can be seen in Appendix N and specified values have been highlighted.
5.1) ASPEN Property Models

One key element of the Aspen simulation was the base and property methods which were used to
characterise the fluid behaviour. Through accurately modelling the process streams, precision in the choice
of operating conditions and vessel design was improved. Owing to the presence of the polar components,
namely water, acetic acid and acrylic acid, the system exhibited a high degree of non ideal behaviour. The
chosen base method was able to accurately model these particular stream characteristics. Additional fluid
property consideration had to be made in each separation vessel and a complimentary property method
chosen to best replicate the conditions that the solution would face in a given vessel. The chosen base
method was NRTL-RK and the property models employed were UNIF-LL, UNIFAC and UNIF-DMD in the
liquid-liquid extractor, absorber and distillation columns respectively.
NRTL-RK: NRTL-RK is an activity coefficient method used to represent highly non-ideal liquid mixtures at
low pressures (less than 10 atm, which applies for this process). R.K. which stands for the Redlich – Kwong
equation of state is able to calculate the vapour phase thermodynamic properties of the system provided that
the vapour phase non-ideality is small. This property is important for the modelling of N 2, O2 and C3H6, which
were the main components of the vapour phase. The NRTL component of the model describes vapour -
liquid equilibrium (VLE) and liquid-liquid equilibrium (LLE) of strongly non-ideal solutions. Thus, it is suitable
for modelling the acidic solution which, owing to its polar nature, exhibits a high degree of non-ideality. The
model requires binary parameters such as equilibrium phase data, many of which are included in the Aspen
Physical Property System databanks. The main disadvantage of this model is that it is not predictive; the
binary parameters are only valid over the temperature and pressure ranges under which they were collected.
UNIFAC: UNIFAC is used as a predictive model for the mixture’s behaviour in the event that the binary
parameters for the system are not included in the Aspen databanks. It is particularly accurate at modelling
VLE data. This feature is useful in the absorber since the system involves the dissolution of the acidic gases
in the water where accurate simulation of the acid gas into the water is vital.
UNIF-LL: UNIF-LL is based on the previously described UNIFAC property method and is able to accurately
model LLE data. This property is particularly important in the liquid-liquid extraction column for the accurate
modelling of the interactions between the organic solvent and acidic solution.
UNIF-DMD: Also based on the UNIFAC Method, it contains more temperature dependent terms of the group-
group interaction parameters. It is also able to predict both VLE and LLE with a single set of parameters and
to predict heats of mixing better. Thus, it is important in the distillation columns and flash vessel where both
VLE and LLE interactions are important and separation is based on relative volatility.
5.2) Process Optimisation

5.2.1) Vapour Recovery System
If this unit was optimised solely on its own
economics then the best solution would be to use a 100.0%
small column with a large flowrate of demineralised
water. However, using large amounts of water at
this stage will lead to increased costs in 99.8%
subsequent separation units; due to the increased
Recovery of Acrylic Acid
size and solvent flowrate required to remove this

99.6% 7 Stages
additional water. Therefore, the column was
optimised to achieve a high recovery of the acids 9 Stages
with a low flowrate of water without neglecting the
size of the column required. 99.4%
5 Stages
From Figure 9 It can be seen that larger columns 3 Stages

achieve an extremely high recovery of acrylic acid 99.2%
for low water flowrates. However, due to the high
costs of larger columns this option is not as
economically promising. As a compromise it has 99.0%
been decided to use a 7 stage absorber with a 0.1 0.2 0.3 0.4 0.5 0.6
water flowrate of 0.167kmol/s (600kmol/hr). This Flowrate of water (kmol/s)
solution achieves an acrylic acid recovery greater
than 99.9% while using a low water flowrate and a Figure 9: Absorber acrylic acid recovery
versus flowrate of water
relatively inexpensive column.
- 12 -
5.2.2) Liquid-Liquid Extractor

In order to minimise the construction costs of separation units further downstream of the flash vessel it has
been decided to reduce the pressure from 2.8bar to 1atm using a valve. Furthermore, when the pressure is
dropped the stream will cool, which increases the effectiveness of the extraction process as seen in Table 3.
10 Stages 1.00000
98.705 9 Stages
Liq-Liq extractor EP x10 6 ($/yr)
11 Stages 0.99999
Acylic Acid Recovery

98.700
0.99998
98.695 11 Stages
0.99997 10 Stages
9 Stages
98.690
0.99996
98.685 0.99995
98.680 0.99994
2000 2200 2400 2600 2800 3000 2000 2200 2400 2600 2800 3000
DIPE flowrate (kmol/hr) DIPE flowrate (kmol/hr)
Figure 10: Economic Potential of the liquid-liquid Figure 11: Liquid-liquid extractor acrylic acid recovery
extractor for different DIPE flowrates and columns for different DIPE flowrates and columns
The DIPE will be recycled, reducing the total flow to the plant, as it is very expensive. However, as the
distillation columns further downstream had yet to be optimised, an estimate for the fresh DIPE feed had to
be used for an economic analysis to be preformed. The flowrate of fresh feed DIPE was estimated to be
equal to the flowrate of DIPE lost in the stream leaving the top of the extractor, as the majority was lost here.
The economic potential of this unit was estimated by subtracting the annualised installed costs of the
extractor and the annual cost of estimated fresh DIPE feed from the sale value of the acids leaving this unit
in the product stream (stream 17, Figure 8). Figure 10 illustrates that higher flowrates of DIPE and a smaller
column would give a slightly higher economic potential. It can also be seen that the extractor’s economic
potential is not very sensitive to the flowrate of DIPE within the range of data shown. Considering the fact
that the DIPE will have to be removed from the acid products in the next stage of the liquid separation
system a lower flowrate will be used; drastically reducing the size and cost of the following distillation
column. However, it is important not to neglect the fact that a high recovery of the acrylic acid is required, to
ensure the product specification is met. In order to achieve a high recovery with a lower flowrate of DIPE a
slightly larger column is required, which can be seen in Figure 11. Although this slightly increases the cost of
the extractor it is likely to reduce the distillation costs by a much bigger margin, as this extraction process is
vastly more effective than the distillation system, as shown in Table 3. Accounting for all these factors it has
been decided to use an 11 stage liquid-liquid extractor with an inlet DIPE flowrate of 2200kmol/hr
(0.611kmol/s), achieving a very high recovery of acrylic acid.
5.2.3) Distillation Columns
4.58 0.076
DISTIL1
Cost of DISTIL1 x106 ($/yr)
Cost of DISTIL2 x106($/yr)
4.56 0.074
DISTIL2
4.54 0.072
4.52 0.070
4.50 0.068
4.48 0.066
4.46 0.064
4.44 0.062
1.1 1.15 1.2 1.25 1.3
Reflux ratio divided by the minimum reflux ratio
Figure 12: Cost of both distillation columns against reflux ratio/minimum reflux ratio
- 13 -
The DIPE and acid mixture leaving the liquid-liquid extractor contained a significant fraction of light
components, which will readily vaporise in DISTIL1 and thus exit in the distillate. As refrigeration would be
required to totally condense the distillate a partial condenser will be used with a vapour fraction that is
achievable with cooling water. Since the majority of the light components are no longer present in the feed to
DISTIL2 a total condenser can be utilised, thus reducing the number of stages required. This is also
beneficial as a liquid distillate product is required. Initially the recoveries in both columns were set at a high
level of 0.99 for the light key (LK) and 0.01 for the heavy key (HK). These recoveries gave a high purity of
acrylic acid; however, the production rate was slightly below the requirement. In order to increase this
flowrate the light key recovery in DISTIL2 was reduced to 0.93. As these recoveries met acrylic acid’s
product specification the reflux ratio (RR) of each column was optimised at these conditions. This was done
purely on an economic basis where the annual installed column cost and utility costs of the condenser and
reboiler were minimised. Figure 12 shows that the optimum reflux ratio for DISTIL1 is in the region of 1.15
times the minimum reflux ratio (RR min). It can also be seen that the cost of DISTIL2 decreases with reflux
ratio and no minimum is achieved. As it is undesirable to operate distillation columns with a reflux ratio of
less 1.1 times the minimum it has been decided to set a reflux ratio of 1.15 times the minimum for both
columns. These reflux ratios result in DISTIL1 requiring 42 stages and DISTIL2 requiring 17 stages. It was
noticed that the diameters calculated using equation 16 (Appendix H) were mechanically infeasible. These
were therefore sized up to 3.66m and 2.13m for DISTIL1 and DISTIL2 respectively.
5.3) Process Adjustments

After completing the optimisation section the total process was reviewed. Although the acrylic acid had a
very high mass purity of 99.0% and a total flowrate meeting the product specification, the mass purity of the
acetic acid stream was only 52.3%. This purity of acetic acid was unacceptable for sale and must therefore
be improved. It was found that the main impurity in the acetic acid stream was DIPE. By reducing the
flowrate of DIPE into the liquid-liquid extractor to 1250kmol/hr and increasing the light key recovery in
DISTIL1 to 0.9997 a more acceptable acetic acid mass purity of 87.7% was achieved. The downside to doing
this is that the size of DISTIL1 increased to 48 stages. However, this additional cost is justified by the sale of
acetic acid. In order to meet the acrylic acid production rate the recovery of the light key in DISTIL2 had to be
decreased to 0.844 and the heavy key was decreased to 0.001. This increased the size of DISTIL2 to 23
stages due to the higher recovery of the bottom component. This resulted in an acrylic acid production rate of
50046tonnes/yr and mass purity of 99.0%.
Table 4: Final separation system set-up
Pressure Solvent Flowrate Number of RR LK HK Partial Condenser
Vessel
(bar) (kmol/hr) Stages (×RRmin-1) Recovery Recovery Vapour Fraction
FLASH 2.80 NA NA NA NA NA NA
ABSORB1 2.80 600 7 NA NA NA NA
LLEXT 1.01 1250 11 NA NA NA NA
DISTIL1 1.01 NA 48 1.15 0.9997 0.01 0.005
DISTIL2 1.01 NA 23 1.15 0.844 0.001 0.00 (total)
Table 5: Final key stream results
Stream Key Component Key Component mass purity (%) Total Stream Flowrate (tonne/yr)
5 Acrlic acid 99.0 50,000
6 Acetic acid 87.7 2,970
1 Propylene 100 33,800
2 Air 100 237,000
3 Steam 100 103,000
21 Demineralised water 100 88,100
Top - up DIPE 100 352
6) Level 4 Economic Potential (EP4)

EP4  EP3  capital co st of separationsystem  operating co st of separationsystem
[10]
Using equation 10 the economic potential at level 4 was found to be 77.2×106$/yr. The extra costs involved
in addition to level 3 have been explained below and example calculations can be seen in Appendix H and L.
6.1) Capital cost of the separation system

6.1.1) Base vessel installed cost
- 14 -
The installed cost of all the units enclosures in the separation system were calculated using Guthrie’s cost
correlation for pressure vessels, reactors and columns (equation 7). The flash vessel’s volume was
calculated by using the exiting vapour velocity and assuming a residence time of 10 seconds to allow for
liquid and vapour disengagement (Appendix I). The height and diameter of this vessel was deduced from the
volume by assuming a height to diameter ratio of 6, which applies for such a vessels. The height of the
absorber, distillation columns and liquid-liquid extractor were calculated from the number of stages by
assuming a 0.610m (2ft) standard tray spacing. In addition, extra height was added to the columns to
account for tray inefficiencies and extra space required at the top and bottom for effective separation. The
diameter of the absorber and distillation columns were calculated from the volumetric vapour flowrate within
these vessels using a correlation, which can be seen in Appendix H, equation 16. As this could not be
applied for the liquid-liquid extractor a height to diameter ratio of 6 was assumed to calculate its diameter.
6.1.2) Internal tray installed cost

The installed costs of the absorber’s and distillation columns’ trays were calculated using equation 11.
M &S
Tray Installed Cost , $   1.55
4.7 D HFc [11] where: Fc  Fs  Ft  Fm
 280 
6.1.3) Reboiler and condenser installed costs for the distillation columns
The installed costs of both of these units were calculated using equation 12, where A is the heat transfer
area (ft2). Simple and commonly used kettle reboilers are to be installed on both distillation columns. For
such units UΔT can be assumed as 11250 Btu.(hr.ft2)-1 (Douglas, 1988), which allowed the heat transfer area
to be calculated. Shell and tube heat exchangers are to be used as condensers for both distillation columns,
as these apply for the operating pressure and temperature ranges (Hewitt, 2007). These heat exchangers
were sized using known log-mean temperature differences and heat transfer coefficients displayed in
Appendix J (Hewitt, 2007). This method of costing was also applied to all coolers in the process.
M &S
Heat Exchanger Installed Cost , $   101.3 A  2.29  Fc 
0.65
[12] where:
 280 
Fc   Fd  Fp  Fm
6.1.4) Furnace installed cost

The furnaces’ installed costs were calculated using equation 13, where Q is the required duty in 10 6 Btu.hr-1.
M &S
Furnace Installed Cost, $    3 0.85

 5.52  10 Q 1.27  Fc  [13] where:
 280 
Fc  Fd  Fm  Fp
6.2) Operating cost of the separation system

The DIPE and demineralised water annular costs were calculated using the flowrates displayed in Table 5
and their utility costs (Appendix B). The cooling water, steam and fuel oil utility costs were calculated for
each heat exchanger, furnace and reboiler by performing an energy balance on each of these units.
7) Heat Exchanger Network Synthesis

7.1) Arrangement of Reactant Preheating
The reactant preheating and mixing system’s structure can be seen in Figure 8. First the compressed air and
steam streams were mixed together. This was to ensure that when propylene is added the resulting mixture
is outside of its explosive limits. The air and steam stream was then heated to avoid any steam
condensation. Following this, propylene was safely added and the entire stream was heated to 310 °C. The
propylene stream was not heated before being mixed as an explosion could occur if any propylene leaks in
the furnace. Before this stream is fed to the reactor it was mixed with the gas recycle, which was also heated
to 310°C.
7.2) Identification of Streams that can be Integrated

All process streams that require a heater or cooler have been considered for heat integration in order to
minimise the process utility costs. These can be seen in, where the supply temperatures were either
provided in Table 1 or calculated in ASPEN, see Appendix N. The heating or cooling requirements (duties) of
each of these streams were also determined using APSEN and by dividing by the corresponding streams
- 15 -
temperature change, heat capacity flowrates were calculated. The heat released by the reactor was also
considered in the heat integration (stream R) as this is also an available energy source. The reactor was
modelled as a hot stream with a target temperature of 1°C lower than its operating temperature, such that its
heat capacity flowrate is equal to its duty, which was calculated in Maple at level 3.
Table 6: Heat Integration streams information

Supply Target Heating or Heat Capacity Flowrate
Stream
Temperature (°C) Temperature (°C) Cooling Duty (W) (Fcp) (W/°C)
24 “cold” 231 310 1230000 -15500
22 “cold” 269 310 749000 -18400
10C “cold” 64.4 310 4340000 -17700
R “hot” 310 309 14900000 14900000
11 “hot” 310 45.0 19400000 73200
6 “hot” 100 40.0 11900 198
5 “hot” 141 40.0 197000 1960
7.3) Network Synthesis

The maximum energy recovery design was the first to be considered, where counter-current shell and tube
heat exchangers with a minimum approach temperature of 10°C were used. The available utilities were
cooling water at 30°C (with a maximum temperature rise of 15°C), saturated steam at various pressures and
fuel oil (see appendix B, Table 11). The first stage in this design was to determine the temperature intervals.
The temperature interval grid can be seen in appendix K and the results have been summarised in Table 7.
Table 7: Energy surplus or deficit in each temperature interval

Temperature Interval (°C) ΣFcphot - ΣFcpcold (W/°C) Energy Surplus or Deficit in Interval (W)
310 – 300 -51500 -515000
300 – 299 14900000 14900000
299 – 269 21700 648000
269 – 231 40100 1540000
231 – 131 55600 5550000
131 – 90.0 57500 2340000
90.0 – 64.4 57700 1480000
64.4 – 35.0 75400 2220000
35.0 – 30.0 2160 10800
Using Table 7 a cascade view of the temperature intervals, which can be seen in Appendix K, was
constructed. From analysing this energy cascade diagram it was found that the minimum hot utility duty to
produce a feasible cascade was 515kW, which resulted in a minimum cold utility duty of 28700kW. From this
a cold stream pinch temperature (temperature at which no heat is transferred between intervals) of 300°C
(310°C hot stream) was also determined. For the maximum energy recovery design only hot utilities are
required above the pinch temperature (hot side) and only cold utilities are required below the pinch (cold
side). Thus, the heat integration network designs of the hot and cold sides were carried out separately.
7.3.1) Cold Side Design

Immediately below the pinch temperature hot and cold streams can only be integrated if Fcp hot ≥Fcpcold, so
that the minimum approach temperature is maintained. At the pinch either stream 11 or the reactor can be
used to heat streams 24, 22 and 10C. However, in order to do this the hot stream will need to be split. By
weighting the split fraction by streams 24, 22 and 10C’s duties the outlet temperature of the stream used to
heat these will be equal and cause less stresses within materials when the split streams are mixed back
together. This results in molar hot stream split fractions of 0.185, 0.097 and 0.718 to heat streams 24, 22 and
10C respectively. When the heat capacity flowrates of each split was considered it was found that Fcphot ≤
Fcpcold for some split fractions of stream 11, which is not feasible, but this was not the case for the reactor.
Thus, the reactor will be used to fully heat streams 24, 22 and 10C to the cold stream pinch temperature
(300°C). A cooler of duty 9080kW will be required to remove the remainder of the reactors heat and streams
11, 6 and 5 will require coolers of duty 19400kW, 11.9kW and 197kW respectively. This results in a total cold
utility duty of 28700kW. As this is equal to the minimum cooling duty previously determined, the number of
units (7) is equal to the minimum (see Appendix K) and only cold utilities are required this meets all three
criteria of the maximum energy recovery system.
7.3.2) Hot Side Design
- 16 -
As the hot side only contains cold streams requiring heating from the cold stream pinch temperature (300°C)
to 310°C no integration can be performed. Thus, streams 24, 22 and 10C require heaters of duty 155kW,
184kW and 177kW respectively. This results in a total hot utility requirement of 515kW. As this is equal to the
previously discovered minimum heating duty, the number of units (3) is equal to the minimum (see Appendix
K) and only hot utilities are required this meets all three criteria of the maximum energy recovery system.
7.3.3) Reducing the number of units

In order to reduce the total number of units used in this system loops between heat exchangers and utilities
have been studied. Although loops do exist between the reactor heat exchangers and the hot utility, no
heaters could be removed as the reactor cannot heat the cold streams above 300°C due to the minimum
approach temperature. The elimination of a heat exchanger is not economically beneficial as all heat
exchangers have significantly high duties, which merit the units installed cost.
7.4) Integration of Distillation Columns and Process Streams

350 GCC The grand composite curve (GCC), which is
Distil 1 generated from the cascade, is a graph of
300 Distil 2
temperature against enthalpy and indicates how
much surplus energy there is over each temperature
Temperature (°C)
250
interval. The grand composite curve for this process
200 is displayed in Table 7. From this it can be seen that
150
the temperature – enthalpy representation of both
distillation columns fit within the process stream
100 grand composite curve. This indicates that surplus
energy can be used by the distillation columns
50
reboilers at high temperatures and returned by the
0 condensers at lower temperatures. Hence, the
0 5 10 15 20 25 30 heating and cooling of both distillation columns is
eliminated.
Enthalpy x106 (W)
Figure 13: Grand composite curve and distillation columns temperature – enthalpy diagrams
7.5) Final Heat Exchanger Network
Figure 14: Heat exchanger network
8) Level 5 Economic Potential (EP5)

EP5  EP4  utility co st savings due to heat integration
[14]
Using equation 14 the level 5 economic potential was found to be 80.1×106$/yr. The utility costs of both the
reboilers and condensers for the two distillation columns were completely eliminated by heat integration. In
addition, the heat integration network also reduced the duty required to be supplied by the hot utility for
heating streams 24, 22 and 10C. The costs of the additional heat exchangers required for this network have
been calculated using the method described previously in section 6.1.3 and a cost break down is shown in
Appendix M.
9) Process Sensitivity Analysis

A sensitivity analysis was preformed on the ASPEN simulation to analyse the effects of changing the
flowrates of the inputs to the system. The input flowrates of Propylene (1), DIPE (18) and water (21) were
increased and decreased by 10% and the purity and flowrates of the acid products were calculated. From
- 17 -
this analysis, it was observed that the purity of the acrylic acid stream is only drastically changed by reducing
the flowrate of propylene by 10%. Thus, strict control over this flowrate is important. The full table can be
seen in Appendix O.
10) Environmental considerations
- 18 -
References
 Douglas, J., M., 1988, Conceptual Design of Chemical Processes (McGraw-Hill, Singapore)
 Felder, R., M. and Rousseau, R., W., 1986, Elementary principles of chemical processes (Wiley, New
York, Chichester)
 Happel, J. and Jordan, D.G., 1975, Chemical Process Economics, 2 nd Edition (Dekker, New York), pp
454
 Hewitt, G., F., 2007, Process Heat Transfer Imperial College Option Course Lecture Notes
 King, C.J., 1980, Separation Processes, 2nd Edition (McGraw-Hill, USA), pp 604 - 605
 Metcalfe, I.S., 1997, Chemical Reaction Engineering A First Course (Oxford University Press, Great
Britain), pp 11
 Perry, R.H., Green, D.W., 1997, Perry’s Chemical Engineers’ Handbook, 7 th Edition (McGraw-Hill, USA)
pp 2-28
 {1} www.cheric.org/kdb/ (23-01-07)
 {2} www.chrismanual.com/A/ACR.pdf (23-01-07)
 {3} en.wikipedia.org/wiki/Acetic_acid_(data_page) (23-01-07)
Nomenclature
bhp Break horse power hp
Cpi Heat capacity of component i j.mol-1.k-1
D Diameter m
EPi Economic potential at level i $.yr-1
Er Activation energy of reaction r kJ/kmol
Fi Molar flowrate of stream i mol.s-1
flp Feed mass fraction of propylene NA
fls Feed mass fraction of steam NA
H Entalpy W
H Height m
HK Heavy key NA
ko,r Rate constant of reaction r kmol/(m3.(kPa)2.yr)
L Length m
LK Light key NA
M&S Marshall and swift equipment cost index NA
P Pressure kPa, bar, atm
Pprop Partial pressure of propylene kPa
Po2 Partial pressure of Oxygen kPa
Q Heat W
R Universal gas constant J.mol-1.K-1
RRmin Minimum reflux ratio NA
RR Reflux ratio NA
rr Rate of reaction r kmol.m-3.yr-1
T Temperature °C, K
TR Temperature of reaction K
yij Mole fraction of componet j in stream i NA
- 19 -
Appendix A – Selectivity Data
0.915
0.910
Selectivity of Reaction 1 (s1)
0.905
0.900
0.895
0.890 y = -0.2036x 2 + 0.4441x + 0.6799
0.885
0.880
0.875
0.870
0.60 0.65 0.70 0.75 0.80 0.85 0.90
Conversion (x)
Figure 15: Relationship of the selectivity of reaction 1 with respect to conversion
0.12
Selectivity of Reaction 2 (s2)
0.10
0.08
0.06
0.04 y = 0.1516x 2 - 0.3335x + 0.2424
0.02
0.00
0.60 0.65 0.70 0.75 0.80 0.85 0.90
Conversion (x)
Figure 16: Relationship of the selectivity of reaction 2 with respect to conversion
- 20 -
Appendix B – Data Tables

Table 8: Kinetic data for equation 1
Reaction Er (kJ/kmol) k0,r (kmol/(m3.(kPa)2.yr))
R1 63000 1.30 x 109
R2 84000 7.20 x 109
R3 100000 1.48 x 109
Table 9: Commodity Prices

Component Price ($/kg)
Propylene 0.38
Process Steam 139.36 x 10-4
Acrylic Acid 1.92
Acetic Acid 0.97
Table 10: γ values for different gas structures (Happel et al., 1975)
Gases γ
Monatomic 0.4
Diatomic 0.29
More complex gases (CO2, CH4) 0.23
Other R/Cp
Table 11: Utility Costs

Utility Cost Units
Cooling Water 8.12×10-6 $.kg -1
Saturated steam at 41.4bar and 253°C 9.97×10-3 $.kg-1
Compressor power cost 0.04 $.(hp.hr)-1
Fuel oil for combustion in furnaces 3.79×10-9 $.J-1
Demineralised water 16.132 $.(kmol.hr-1.yr)-1
Di-isopropyl Ether (DIPE) 0.89 $.kg-1
Table 12: Properties of the components in the liquid separation system (Perry et al., 1997)
Property Components
H2O C3H4O2 C2H4O2 DIPE
Boiling point (b.p.) at 1 atm. (°C) 100 141 118 69
Vapour Pressure (Pvap) at 50°C (mmHg) 91.7 18.1 56.6 401
Solubility in DIPE (KD)
(42.22°C, 2.5 bar) 0.02039 2.048 2.765 3459
(62.08°C, 2.5 bar) 0.02869 1.102 1.875 1226
- 21 -
Appendix C – Material balances required at level 2
Figure 17: Level 2 process diagram with the mix and feed stream to the reactor displayed
Subscript p has been used to represent propylene.
Mole balance around the reactor and separation system for:

 C3H4O2: 0  0  F5  s1 xF4 y 4 p
 C2H4O2: 0  0  F6  s 2 xF4 y 4 p
Defining the feed mass fraction design variables:

18 F3
 H2O(g): m s 
42 F1  29 F2  18F3
42 F1
 C3H6: m p 
42 F1  29 F2  18 F3
Define a term for 99.5% percentage loss of propylene in the purge:

F1  xF4 y 4C3 H 6
 Lp   100
F1
These 5 equations have been solved in Maple to find the molar flowrates of acrylic acid, acetic acid,
propylene feed and input steam in terms of the design variables. Converting these flowrates into mass
flowrates allows the economic potential to be found in terms of the design variables. The Maple code for this
can be seen on the attached CD.
- 22 -
Appendix D – Material balances required at level 3

Perfect separation in the separation system has been assumed at this level.
Mole balance around the whole process for:

 C3H4O2: 0  0  F5  S1 xF4 y 4 C3 H 6
 C2H4O2: 0  0  F6  S 2 xF4 y 4C3 H 6
 C3H6: 0  F1  F9 y 9 C3 H 6  xF4 y 4 C3 H 6
 H2O: 0  F3  F7  S1 xF4 y 4C3 H 6  S 2 xF4 y 4C3 H 6  3(1  S1  S 2 ) xF4 y 4C3 H 6
 N2: 0  F2 y 2 N 2  F9 y 9 N 2
0  F 2 y2O2  F 9 y9 N 2  (3 / 2) S1 xF4 y4 C3 H 6  (5 / 2) S 2 xF4 y4C3 H 6
 O2 :
 (9 / 2)(1  S1  S 2 ) xF4 y4C3 H 6
 CO2: 0  0  F9 y 9CO2  S 2 xF4 y 4C3 H 6  3(1  S1  S 2 ) xF4 y 4C3 H 6
Mole balance around the mixer for:

 C3H6: 0  F1  F4 y 4C3 H 6  F10 y10 C3 H 6
 N2: 0  F2 y 2 N 2  F4 y 4 N 2  F10 y10 N 2
 O2: 0  F2 y 2O2  F4 y 4O2  F10 y10O2
 H2O: 0  F 3  F 4 y H 2O
 CO2: 0  0  F4 y 4CO2  F10 y10CO2
Physical Constraints:
 Stream 9: y 9 N 2  y 9O2  y 9CO2  y 9C3 H 6  1
 Stream 4: y 4 N 2  y 4O2  y 4CO2  y 4C3 H 6  1
Equations of the splitter:

 Total mole balance: 0  F8  F10  F9
 N2 mole fraction: y 8 N 2  y 9 N 2  y10 N 2
 O2 mole fraction: y 8O2  y 9O2  y10O2
 CO2 mole fraction: y8CO2  y 9 CO2  y10 CO2
 C3H6: mole fraction: y 8O2  y 9O2  y10O2
Taking the mid-point of the allowable mass fraction ranges for the feed to the reactor:
18F3
 H2O(g): m s   0.275
42 F1  29 F2  18F3
42 F1
 C3H6: mC3 H 6   0.075
42 F1  29 F2  18F3
Define a term for the percentage loss of propylene in the purge:

F1  xF4 y 4C3 H 6
 LC3 H 6   100
F1
- 23 -
Appendix E– Hess’s Law Calculation
The enthalpy diagram, shown in Figure 18, was constructed assuming the gas stream behaves ideally so the
enthalpy only varies with temperature.
Figure 18: Enthalpy Diagram for the reactions that occur within the reactor
Table 13: Conditions for each point displayed in the above enthalpy diagram
Letter Components Temperature (°C) Phase
a N2, O2, CO2, H2O, C3H6 (or p) 310 g
b H2O 100 g
c H2O 100 l
d N2, O2, CO2, H2O, C3H6 25 l&g
e N2, O2, CO2, H2O, C3H6, C3H6O2, 25 l&g
C2H6O2
f H2O 100 l
g C2H6O2 118.1 l
h C3H6O2 141 l
i H2O 100 g
j C2H6O2 118.1 g
k C3H6O2 141 g
l N2, O2, CO2, H2O, C3H6 Tout g
Enthalpy balance equations for each change shown in Figure 18, where the variable heat capacities can be
seen in Table 14 and the heats of vaporisation can be seen in Table 15.
 25 25 25 25

H 1  F4  y4 co2  CpCO2 dT  y4O2  CpO2 dT  y4 N 2  Cp N 2 dT  y4 p  Cp p dT 
 310 310 310 310 
100
H 2  F4 y4 H 2O
310
 Cp H 2O dT

H 3  F4 y4 H 2O  H Hvap2O 
25
H 4  F4 y4 H 2O
100
 Cp H 2O dT
H 5  1 H R1   2 H R 2   3 H R 3
 T T T T

H 6  F8  y8co2  CpCO2 dT  y8O2  CpO2 dT  y8 N 2  Cp N 2 dT  y8 p  Cp p dT 
 25 25 25 25 
141
H 7  F5  CpC3 H 4O2 dT
15

H 8  F5 H Cvap
3 H 4 O2

T
H 9  F5
141
 Cp C3 H 4 O2 dT
- 24 -
118 .1
H 10  F6  Cp
15
C 2 H 4 O2 dT
H 11  F6  H Cvap
2 H 4 O2

T
H 12  F6  Cp
118 .1
C 2 H 4O2 dT
100
H 13  F7  Cp
25
H 2O dT
H 14  F7  H Hvap
2O

T
H 15  F7  Cp
100
H 2O dT
From Figure 18 it can be deduced that the change in enthalpy across the reactor (moving from position a to l)
can be found by summing all of the enthalpies shown above (H1 to H15).
Table 14: Heat capacities of each component required in the above enthalpy equations
Component Phase Heat Capacity (kJ.(kmol.K)-1) Reference
H2O Gas 33.46+0.688*10 T+0.7604*10^-5T2-3.593*10-9T3
-2
N2 Gas 29+0.2199×10-2T+0.5723×10-5T2-2.871×10-9T3
(Felder et al.,
O2 Gas 29.1+1.158×10-2T-0.6076×10-5T2+1.311×10-9T3
1986)
C3H6 Gas 59.58+17.71×10-2T-10.17×10-5T2+24.6×10-9T3
CO2 Gas 36.11+4.233×10-2T-2.887×10-5T2+7.464×10-9T3
C2H4O2 Gas 4.949×10-8(T+273)3-1.753×10-4(T+273)2+2.549×10-1(T+273) + 4.84 {1}
C3H4O2 Gas 6.975×10-8(T+273)3-2.352×10-4(T+273)2 + 0.3191(T+273) + 1.742 {1}
H2O Liquid 75.4 (Felder et al.,
1986)
C3H4O2 Liquid 138.7 {2}
C2H4O2 Liquid 123.1 {3}
Table 15: Heats of vaporisation required for the above enthalpy equations
Component Heat of vaporisation at 298K (kJ/kmol) Reference
H2O 40650 (Felder et al., 1986)
C3H4O2 46024 {1}
C2H4O2 23681 {1}
- 25 -
Appendix F – Pressure Sensitivity Analysis
Figure 19: Gas recycle compressor cost against conversion for

different inlet pressures at a 1% loss of propylene
Figure 1 indicates that the gas recycle compressors cost varies significantly with the selected inlet pressure
and hence the assumed pressure drop across the reactor and separation system. It can also be seen that
the cost is more sensitive at lower conversions. This sensitivity must be kept in mind when analysing the
economic potentials at level 3.
- 26 -
Appendix G – Selection of Column Type

Table 16: Selection Guide* for distillation-column internals (King, 1980)
Tray Packed Column
Application
Condition for this Sieve
Bubble- Disk and
process or Counterflow Random Stacked
cap doughnut
valve
Low Pressure (<13 Yes 2 1 0 2 3 1
kPa)
Moderate Pressure Yes 3 2 1 2 1 1
High Pressure No 3 2 2 2 0 0
(>50% of critical)
High turndown ratio No 2 3 0 1 2 1
Low Liquid flow No 1 3 0 1 2 0
rates
Foaming Systems No 2 1 2 3 0 1
Internal tower No 2 3 1 1 0 0
cooling
Suspended solids No 2 1 3 1 0 1
Dirty or No 2 1 3 1 0 2
polymerizing (neglected)
solution
Multiple feeds or No 3 3 2 1 0 1
sidestreams
High liquid flow No 2 1 3 3 0 2
rates
Small-diameter No 1 1 1 3 2 1
columns
Column diameter Yes 3 2 2 2 2 1
1 to 3m
Larger-diameter No 3 1 2 2 1 1
columns
Corrosive fluids Yes 2 1 2 3 1 2
Viscous fluids No 2 1 1 3 0 0
Low pressure drop No 1 0 0 2 2 3
(efficiency
unimportant)
Expanded column No 2 0 2 2 3 0
capacity
Low cost Yes 2 1 3 2 1 3
(performance
unimportant)
Reliability of design Yes 3 2 1 2 1 1
* 0 = do not use, 1 = evaluate carefully, 2 = usually applicable, 3 = best selection
- 27 -
Appendix H – Sample Calculation for Costing a Separation System Vessel

For this example both the annualised installed cost and operating cost of the second distillation column
DISTIL2 has been shown.
Required Information Obtained from Aspen
Table 17: Required information to cost the second distillation column DISTIL2
Reflux Heat
Cooling Distillate
ratio/ Actual Number Duty of Reboiler Condenser Density of Molecular
Duty of the flowrate
min Reflux of the Temp. Temp. gas weight gas
Condenser (kmol/s)
reflux Ratio Stages Reboiler (°C) (°C) (kmol/m3) (g/mol)
(W)
ratio (W)
1.1 6.80 19 480000 141 475000 100 7.19 0.00240 73.4
Installed Cost
First the distillation column was required to be sized. The calculations for the height also apply for the
absorber and liquid-liquid extractor but the diameter calculations only apply for the distillation columns and
absorber.
Calculating the column height

The column height was initially calculated by multiplying the tray spacing of 0.610m (2ft) by the number of
stages, which neglects the extra space required in the ends and plate efficiency. This is equal to 11.6m for
the example being considered.
The extra spacing for the ends was than accounted for by adding an additional 15% to the previously
calculated height (Douglas,1988). The plate efficiency was assumed to be 90% and this was included in the
height by dividing through by 0.9.
11 .6m  1.15 N  1.15  0.610

Actual column height   14.8m , in general H  , N = number of
0 .9 0 .9
stages
Calculating the Column Diameter

The diameter of the distillation column was calculated using equation 16, where V = molar vapour flowrate
(mol.hr-1), MG = molecular mass of the gas (lb.mol-1) and ρm = gas molar density (mol/ft3). The molar vapour
flowrate was determined by performing material balances on the top of the column using the reflux ratio. By
converting units it was found that D is equal to 0.715ft for this example.
1
M  4
D  0.0164 V  G 
 m 
[16]
Calculating the base vessel installed cost

This method for calculating the installed cost of the vessel enclosure applies for all units in the separation
system. Now the distillation columns height and diameter are known equation 7, which has been shown
below, can be used to calculate the installed cost of the basic vessel enclosure. As the distillation column is
made out of stainless steel and operates at a pressure of 1atm Fm = 3.67 and Fp = 1 (Douglas,1988). For this
example the installed cost is equal to $36700.
 M & S  101.9 D1.066 H 0.802  2.18  F  Where: Fc  Fm F p ,

Veseel Installed Cost ($)  c [7] D = diameter (ft)
280
H = height length (ft)
Calculating the tray installed cost
The following calculations apply for both distillation columns and the absorber. Using equation 11, shown on
the next page, the installed tray cost can be calculated. For the considered example Fs = 1, as the tray
spacing is equal to 24in. (0.610m), Ft = 0.0, as sieve trays are being used and Fm = 1.7, as the trays will be
- 28 -
made out of stainless steel (Douglas,1988). Thus, Fc = 2.7 and the tray installed cost is for this example is
$1430.
M &S
Tray Installed Cost , $   1.55
4.7 D HFc [11] where: Fc  Fs  Ft  Fm
 280 
Calculating the reboiler installed cost

Firstly the reboiler was sized using equation 17, where UΔT has been estimated as 11250 Btu.(hr.ft2)-1
(Douglas, 1988). By converting the heat duty displayed in Table 17 into the appropriate units, the heat
exchange area in the reboiler was found to be 146ft 2 for this example. Using equation 12, shown below, the
installed cost of the reboiler was found to be $61440, as Fd = 1.35 for a kettle reboiler, Fp = 0 as the pressure
is at 1 atm. and Fm = 2.81 as stainless steel and carbon steel would be used for each side of the heat
exchanger (Douglas).
Q
A [17]
UT
M &S
Heat Exchanger Installed Cost , $   101.3 A  2.29  Fc 
0.65
[12] where:
 280 
Fc   Fd  Fp  Fm
Calculating the condenser installed cost

Similarly to the reboiler, the installed cost of the condenser can also be calculated using equation 12, where
Fp and Fm remain the same but Fd would change to 1 as floating head shell and tube heat exchangers are to
be employed (Douglas). The area of these heat exchangers were found using equation 17 but with a log-
mean temperature difference, as the cooling water would change in temperature. The heat transfer co-
efficient selection has been discussed in Appendix J. For this example, a heat transfer co-efficient of
764W.m-2.K-1 has been selected and the log-mean temperature difference is equal to 62.3°C, resulting in a
heat transfer area of 9.98m2 (107ft2). Using equation 12 it can be deduced that the condenser installed cost
is equal to $42086. This cost calculation was also applied to all other coolers in the process and heat
exchangers.
All of these installed costs for the distillation column were then summed and divided by a capital charge
factor of three to convert these into an annualised cost, which results in a total annualised installed cost of
47200$.yr-1. This can also be applied to all units in the separation system.
Operating Cost
The distillation columns operating costs are made up of both the heating and cooling utilities required for the
reboiler and condenser. Other units that involve the use of solvents such as the absorber and liquid-liquid
extractor also need to include the cost of these.
Reboiler operating cost

As the reboiler in DISTIL2 operates at a temperature of 140.75°C saturated steam at 10.3 bar was the
chosen utility as this has a temperature of 186°C, which is required to ensure the minimum approach
temperature is maintained. By performing an energy balance for this utility and using the cost information
displayed in Table 11 the flowrate of steam required to supply 480000W of energy was found to be
0.241kg.s-1. This corresponds to an annualised cost of 52900$/yr, which was calculated using the
assumption that the plant operates 8150 hours in a year.
Condenser operating cost

The flowrate of the cooling water can be calculated through an energy balance using the maximum cooling
water temperature change (ΔTmax=15°C) (if this is feasible for the condenser’s operating temperature) and its
heat capacity (cp,w= 4.2 kJ.kg-1.°C-1). For this examples condenser duty of 475000W, 7.54kg.s-1 of cooling
water would be required. Using Table 11 this can be converted to an annualised cost, which was found to be
1800$.yr-1.
Thus, the total operating cost for DISTIL2 is 54700$.yr -1 for these example conditions. By summing the
annualised installed cost and operating cost a unit’s total annualised cost can be found. For this example the
total annualised cost is equal to 97400$.yr -1. Although this example was for a distillation column it covers
nearly all of the additional utility costing required at level 4 and the same methods have been applied to other
units.
- 29 -
Appendix I – Sizing the Flash Vessel
From ASPEN it was found that the:

3 1
 Volumetric flow rate of the gas within the flash vessel, V g  7.90 m s
 Vapour fraction within the flash vessel, x g  0.778
To size the flash vessel a residence time, τ, of 10 seconds was assumed. This should be sufficient for the
liquid and vapour phases to separate as the mixture fed to the flash vessel is two phase from the quenching.
The volume of the vapour within the flash vessel, V g  V g  V g  79m

3
Vg
The total volume of the flash vessel, V   V  102m 3
xg
To ensure the flash vessel would operated as it is required, this volume was sized up to 150 m3
H
Assume that the height to diameter ratio is 6, 6
D
4V
Solving for the diameter results in D  3  D  3.17 m
6
Thus, H  19.0m
- 30 -
Appendix J– Heat Transfer Co-efficient Selection

The heat transfer co-efficients were determined for each heat exchanger using ESDU data tables (Hewitt,
2007). The following information was used to determine the heat transfer co-efficients:
 type of heat exchanger (this was always shell and tube)
 duty divided by appropriate temperature difference (Q/ΔT)
 cold side fluid
 hot side fluid
Table 18: Heat transfer co-efficients selected for each heat exchanger
Closest Cold Closest Hot Heat Transfer
Heat Exchanger Q/ΔT (W.K-1) Side Fluid Side Fluid Co-efficient
Match Match (W.m-2.K-1)
DISTIL1 Condenser Treated Cooling Condensing
1750000 764
Water Hyrdro-carbon
DISTIL2 Condenser Treated Cooling Condensing
8900 764
Water Hyrdro-carbon
ACECOOL Treated Cooling Low Viscosity
450 714
Water Organic Liquid
ACRCOOL Treated Cooling Low Viscosity
15500 714
Water Organic Liquid
QUENCH Treated Cooling Medium
223000 484
Water Pressure Gas
10C – R (HE) Medium Medium
5660 300
Pressure Gas Pressure Gas
22 – R (HE) Medium Medium
25800 300
24 – R (HE) Medium Medium
32000 300
Reactor Cooler Treated Cooling Medium
33300 484
Water Pressure Gas
- 31 -
Appendix K – Heat Integration

Temperature Interval Grid
Figure 20: Temperature interval grid (where the hot streams account for the minimum approach temperature)
The corresponding cascade is displayed on the next page.
- 32 -
Energy Cascade
Figure 21: Cascade view of the temperature intervals, where energy flows are in W
From Figure 21 it can be seen that the minimum hot utility duty is 515,000W and the minimum cold utility
duty is 28,700,000W. This figure also displays that the cold stream pinch temperature is 300 °C, which
corresponds to a hot stream pinch temperature of 310°C.
Minimum Number of Units for Maximum Energy Recovery

The minimum number of units for maximum energy recovery can be calculated using equation 15. Where
x x
U min is the minimum number of units for the x side design (hot or cold), N s is the number of streams on
x
the x side design and N ut is the number of utilities available on the x side design.
x
U min  N sx  N utx  1 [15]
cold
For the code side design: U min  7  1  1  U min
cold
7
hot
For the hot side design: U min  3  1  1  U min
hot
3
- 33 -
Appendix L – EP4 Price Break-Down

EP4 77,242,720.83
EP3 83,079,692.78
Annualised
Annual
installed cost Total cost
solvent
of column and ($/yr)
cost ($/yr)
trays ($/yr)
ABSORB1 111,024.77 9,679.20 120,703.97
Annualised Cost of Cost of DIPE

installed cost DIPE lost lost in Total cost
of column in stream stream 7 ($/yr)
($/yr) 20 ($/yr) ($/yr)
371,455.0
LLEXT 58,492.82 92,460.23 220,501.95 0
Annualised Cost
Reboiler Condenser Total
installed cost Reboiler Cost Cooling Reboiler Condense
Installed installed cost cost
of column and Utility Utility ($yr) area (ft2) r area (ft2)
cost ($/yr) ($/yr) ($/yr)
trays ($/yr) ($/yr)
2,060,643. 5669.6610 220,959.7 3,443,39
DISTIL1 615,006.84 08 66,013.28 04 2 24592.5 480,772.26 5.19
168.85214 288,638.
DISTIL2 181,962.53 66,341.16 2,265.86 67 22,510.25 125.469 15,558.45 25
Annualised
Heat Total
Utility cost installed cost
exchange costs
($/yr) of column
area (ft2) ($/yr)
($/yr)
243,164.3
QUENCH 73,396.42 4957.8 169,767.87 0
ACECOOL 45.01 6.794 2,337.76 2,382.76
ACRCOOL 746.18 232.986 23,263.87 24,010.05
Annualise
6 d installed Total
Utility cost Duty x10
Duty (w) cost of costs
($/yr) (BTU/hr)
furnace ($/yr)
($/yr)
136,419.5 4.18597362 209,737.6
HEAT1 1226809.93 5 6 73,318.08 2
2.55619578 131,515.8
HEAT2 749160.567 83,305.61 7 48,210.21 2
482,512.8 14.8056953 214,559.8 697,072.7
HEAT3 4339199.35 9 2 9 9
Annualised
Diameter
Height (ft) installed cost
(ft)
($/yr)
FLASH 62.37 10.37 304,896.20
- 34 -
Appendix M – EP5 Price Break-Down

EP5 80,099,616.39
EP3 83,079,692.78
Annualised Annual
installed cost solvent Total cost
of column and cost ($/yr)
trays ($/yr) ($/yr)
ABSORB1 111,024.77 9,679.20 120,703.97
Cost of
Annualised Cost of DIPE
DIPE
installed cost lost in Total cost
lost in
of column stream 7 ($/yr)
stream
($/yr) ($/yr)
20 ($/yr)
92,460.2 371,455.0
LLEXT 58,492.82 3 220,501.95 0
Annualised Cost Total

Reboiler Condenser
installed cost Reboiler Cost Cooling Reboiler Condense
of column and Utility Utility ($yr) area (ft2)
Installed
r area (ft2)
installed cost cost
cost ($/yr) ($/yr) ($/yr)
trays ($/yr) ($/yr)
5669.6610 220,959.7 1,316,7

DISTIL1 615,006.84 04 2 24592.5 480,772.26 38.82
168.85214 220,03
DISTIL2 181,962.53 67 22,510.25 125.469 15,558.45 1.23
Heat Annualised
Total
Utility cost exchang installed cost
costs
($/yr) e area of column
($/yr)
(ft2) ($/yr)
275,902.8
QUENCH 73,396.42 4957.8 202,506.44 7
ACECOOL 45.01 6.794 2,788.58 2,833.58
ACRCOOL 746.18 232.986 27,750.15 28,496.33
Annualise
Utility 6 d installed Total
Duty x10
Duty (w) cost cost of costs
(BTU/hr)
($/yr) furnace ($/yr)
($/yr)
17,201.3 0.52781494
HEAT1 154690.0839 2 1 12,612.28 29,813.60
20,410.6 0.62629292
HEAT2 183551.6534 9 6 14,586.29 34,996.98
19,648.5 0.60290624
HEAT3 176697.5707 2 7 14,122.01 33,770.53
Annualised
Diameter
Height (ft) installed cost
(ft)
($/yr)
FLASH 62.37 10.37 304,896.20
Annualis
Heat ed
exchange installed
area (ft2) cost
($/yr)
10C-R 2029.59 113,322.
- 35 -
57
68,062.0
22-R 926.35 2
78,309.0
24-R 1149.42 9
Annualis
Heat ed Total
Utility cost
exchange installed costs
($/yr)
area (ft2) cost ($/yr)
($/yr)
Reactor
Cooling 6.396 2,681.28 34,338.03 37,019.30
- 36 -
Appendix N – ASPEN
Table 19: Flowrate of species leaving the flash vessel
Component Flowrate of component in stream (kmol/s) 8A
13 (Liquid) 8 (Vapour)
Propylene 0.0000139 0.00458
Water 0.205449 0.0267006 12 FLA S H
Oxygen 0.000171 0.0529626

Nitrogen 0.000781 0.7340154
Carbon Dioxide 0.0000784 0.011143 13
Acrylic acid 0.0225514 0.00111
Acetic Acid 0.00152 0.000253 Figure 22: Flash Vessel Schematic
This is continued on the next page.
Appendix O – Process Sensitivity Analysis
Acrylic acid Acetic Acid

Mass Production Production
Mass purity
purity rate rate
(%)
(%) (tonnes/yr) (tonnes/yr)
Standard Conditions 99.0 50,000 87.7 29,700
10% Increase 98.9 53,050 88.6 3,230
Propylene (1)
10% Decrease 82.5 45,299 86.7 2,701
10% Increase 99.0 50,418 86.9 2,994
DIPE (18)
10% Decrease 98.9 45,820 88.8 2,929
Demineralised 10% Increase 98.9 49,430 87.7 2,966
Water (21) 10% Decrease 99.0 50,298 87.7 2,967
- 37 -

Process Design of An Acrylic Acid Plant

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Process Design of An Acrylic Acid Plant

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Process Design Project 2007 Group 7

Minimum Number of Units for Maximum Energy Recovery.....................................................................30

Level 0) Input Information

0.1) Reactions and conditions

b) Reactor conditions: Inlet Temperature = 310°C and pressure = 3.5 bar.

Level 1) Batch or Continuous Operation

1.1) Production Rate

1.2) Market Forces

1.3) Operational Issues

Level 2) Input-Output Flowsheet Structure

Figure 1: Level 2 flowsheet

2.1) Feed Stream Purification

2.2) Recycle by-products

2.3) Gas Recycle and Purge

2.4) Number of Product streams

Table 2: Component destination codes

2.3) Economic Potential

2.4) Alternative Designs

Level 3) Recycle Structure

Figure 3: Level 3 flowsheet

3.1) Number of reactors

3.2) Number of Recycle Streams

3.3) Excess Reactant

3.4) Material Balances

3.5) Reactor Heat Effects

H  Q  0 [4] where: H  enthalpy change and Q  heat removed

Using Maple and the Hess’s law calculation the reactor

3.5.2) Heating and Cooling

3.5.3) Heat Carriers

3.6) Compressor Design and Cost

3.7) Reactor Cost

 M & S  101.9 D1.066 L0.802  2.18  F  Where: Fc  Fm F p ,

3.8) Design Variable Optimisation

Figure 7 displays EP3 as a function of conversion for

Figure 7: EP3 versus conversion for different Lp

Level 4) General Separation System Structure

4.2) Vapour Recovery System

4.3) Liquid Separation System

4.3.2) Azeotropes and reactants

4.3.3) Structuring the Liquid Separation System

Table 3: Binary mixture ratios and separation analysis of different processes

5) Detailed Simulation using ASPEN

Figure 8: Final Process Flowsheet

5.1) ASPEN Property Models

5.2) Process Optimisation

size and solvent flowrate required to remove this

From Figure 9 It can be seen that larger columns 3 Stages

5.2.2) Liquid-Liquid Extractor

Acylic Acid Recovery

5.2.3) Distillation Columns

Cost of DISTIL2 x106($/yr)

5.3) Process Adjustments

6) Level 4 Economic Potential (EP4)

6.1) Capital cost of the separation system

6.1.2) Internal tray installed cost

6.1.4) Furnace installed cost

6.2) Operating cost of the separation system

7) Heat Exchanger Network Synthesis

7.2) Identification of Streams that can be Integrated

Table 6: Heat Integration streams information

7.3) Network Synthesis

Table 7: Energy surplus or deficit in each temperature interval