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CHEE 3004: Unit Operations Project Report 1

CHEE 3004: Unit Operations


Project 1 Report
The Design of a Gas-Liquid Absorber and
Distillation System

Due Date: 28th of September, 2014 (extension granted)

Authors
Faizzi Lokman
Robert OMalley
Masashi Date-Shappard

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Student Number
43115095
41185786
42932914

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CHEE 3004: Unit Operations Project Report 1


Executive Summary
This report provides an analysis of separation units in a methanol production plant. The
separation units include and absorber to remove carbon dioxide from exhaust gas, a flash
drum to remove light components from the methanol product and a distillation column to
remove water from the methanol product.
Manual calculations were used to describe the flow streams in the system as well as to
calculate absorber specifications. The program Aspen Plus was used to calculate the
specifications of the flash drum and the distillation column.
The exhaust gas stream entering the absorber was found to have a flow rate of 36.8 kmol/s
with the carbon dioxide having a mole fraction of 0.0978. We found that an absorber with the
following specifications provided below reduced the carbon dioxide mole fraction to 0.02 in
the exhaust gas.
Temperature
Pressure
Diameter
Height
Selected Solvent
Selected Random Packing Material

15C
5Mpa
11.16m
33.33m
Propylene Carbonate
50mm HiFlow Hyd (plastic)

The flash drum removing light components from the methanol product stream was best
operated under a temperature of 35oC and pressure of 1.6 MPa. Under these conditions
99.95% of the light components were removed and 93% of the methanol is recovered with
7% of the methanol in the vapour phase with the light components.
To obtain 99% pure methanol a distillation column was designed under the following
conditions:
Operating Parameters
Actual number of stages
13
Actual reflux ratio
0.859
Net heat duty of column (gW)
94.69
Condenser duty (gW)
-71.64
Reboiler duty (gW)
166.3
Minimum required steam flow in reboiler 76.91
(ton/s)
Distillate to feed ratio for methanol
0.99
Location of feed stage
9

With the separation units operating under these specifications the plant can obtain a product
purity of methanol at 99%mol and a combustion exhaust gas carbon dioxide concentration of
2%mol.

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Table of Contents
1.0 Introduction ....................................................................................................................................... 1
2.0 Methodology ..................................................................................................................................... 1
2.1 Mass Balance ................................................................................................................................ 1
2.1.1 Block Flow Diagram .............................................................................................................. 2
2.2 Absorber Design ........................................................................................................................... 3
2.2.1 Solvent Selection.................................................................................................................... 3
2.2.2 Minimum Required Liquid to Gas Ratio ............................................................................... 4
2.2.3 Design Diagram of Absorption Column ................................................................................ 4
2.2.4 Process Flow Diagram of the Absorber and Stripping System .............................................. 4
2.2.5 Random Packing Material Selection ...................................................................................... 5
2.2.6 Calculation of Tower Diameter.............................................................................................. 5
2.2.7 Estimation of Mass Transfer Coefficients, Height of Transfer Units for Liquid and Gas
Phases and Height of Overall Gas Transfer Units .......................................................................... 6
2.2.8 Calculation of Tower Height.................................................................................................. 6
2.2.9 Final Absorber Specifications ................................................................................................ 6
2.3 Distillation Design ........................................................................................................................ 7
2.3.1 Flash Separation Unit Design ................................................................................................ 7
2.3.2 Distillation Column Design ................................................................................................... 8
2.2.3 Selection of Property Method .............................................................................................. 10
3.0 Discussion and Analysis ................................................................................................................. 10
3.1 Absorber Design ......................................................................................................................... 10
3.1.1 Physical Solvent over Chemical Solvent ............................................................................. 10
3.1.2 Lowest CO2 Concentration .................................................................................................. 10
3.1.3 Amine Consideration ........................................................................................................... 11
3.1.4 Maximum Temperature Change across Column for Isothermal System ............................. 11
3.1.5 Validity of the Assumption of Insolubility of non-CO2 Components. ................................ 11
3.2 Distillation Design ...................................................................................................................... 12
3.2.1 Flash Drum........................................................................................................................... 12
3.2.3 Distillation Column .............................................................................................................. 12
4.0 Conclusions and Recommendations ............................................................................................... 13
4.1 Absorber...................................................................................................................................... 13
4.2 Distillation Process ..................................................................................................................... 13
References ............................................................................................................................................. 14

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Appendices
Appendix A: System Diagram, Stream table and Physical properties .............................................. 16
Appendix B: Master Microsoft Excel Sheets used for Absorber Calculations (Values) .................. 19
Appendix C: Master Microsoft Excel Sheets used for Absorber Calculations (Formulas) .............. 21
Appendix D: Working Steps Used to Calculate Height of Transfer Units for Liquid and Gas Phases
and Overall Gas Transfer Units and Mass Transfer Coefficients ..................................................... 23
Appendix E: Steam Requirement Calculations ................................................................................. 28
Appendix F Distillation Section Sensitivity Analyses ...................................................................... 29

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1.0 Introduction
This report presents an analysis of a methanol production plant. Specifically a mass balance to
determine the carbon dioxide emissions from the reforming gas exhaust, a proposed absorption tower
to reduce carbon dioxide emissions and a methanol separation system including a flash separation and
a distillation column.
The production of methanol has experienced rapid growth in recent years, with demand increasing 23
percent from 2010 to 2012. This demand growth has been majorly influenced by China which now
consumes just over half the worlds production of methanol (Manning, 2013). This is mainly due to
the population becoming increasingly industrialised and China being the only country so far to use it
as a blend for petrol. This supply is being fed with an increase in mining of feed methane in relatively
new sources such as shale and coal seam gas. To meet this increase in demand of methanol production
facilities will have to modify and optimise their processes, while keeping in mind current
environmental regulations. Set forth in this report is a design of a absorption tower to reduce carbon
dioxide concentration emissions to less than 2 percent and a methanol separation process to obtain 99
percent product purity.

2.0 Methodology
2.1 Mass Balance
As part of the initial calculations performed for this project, methodical mass balances were
performed on every unit in the methanol plant up to the methanol synthesis reactor. A diagram of the
overall methanol plant, marked with a red line, indicating the end point of mass balance calculations
is available in Appendix A.
Data provided by the project brief and assumptions made in order to solve the mass balances are
shown below:
Table 1 Key data and assumptions regarding mass balances

Data Provided
Methane feed rate of 2000 kmol/s
20% of methane feed used for combustion
Steam Feed rate is 3 times molar rate of methane
for reaction
Reaction 1,2 (reforming reactions) go to 70%
completion
Reaction 3 (combustion reaction) goes to 90%
completion
10% of Carbon monoxide produced in R1 is used
in R2
Temperatures at different stages of the process

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Assumptions made
Flow rate of air for combustion 5% more than
required
Relative humidity of air is 70%
Ambient air temperature is 30 degrees Celsius
Methane feed is 100% methane
Steam feed is pure water
No reactions occurring other than those specified.
Only water condenses out of the syn gas stream

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2.1.1 Block Flow Diagram

Figure 1: Block flow diagram for the reforming section of the methanol plant

An example mass balance calculation for the combustion reaction is shown below.
Combustion Reaction
The combustion reaction, shown below, uses 25% of feed methane and it is also an assumed that there
is 5% excess air than required for complete combustion.
Equation 1
An equation for the required flow rate of oxygen is derived.
Equation 2
Where the numbered subscripts denote the stream number in Figure 1 of Section 2.1.1.
The total flow rate of air is calculated based on the oxygen to nitrogen ratio of 21:79 along with the
water carried with it at 70% relative humidity at 300C, 1 atm. Which means partial pressure of water
in air equals 70% of vapour pressure of water at 300C, 1 atm, which is then turned into a mole fraction
of the airflow. The air flow is added to the combustion methane stream 7 to get stream 8. To calculate
the components of stream 9 the combustion reaction mentioned earlier is used to convert 90% of the
methane to its products, with the equation for each component listed below.
Equation 3
Equation 4
Equation 5
Equation 6
Equation 7
Condensing
As the temperature and pressure were specified in stream 12 the vapour pressure of water was used to
calculate the amount of water that was left in gas stream in which the remainder of water from stream
10 was removed in stream 11 due to the streams being in equilibrium.
Table 5 containing stream variable values are available in Appendix A.

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2.2 Absorber Design
The exhaust gas from the combustion chamber is to be sent to a stack for release to the atmosphere.
However, before the gas is released, the carbon dioxide composition of the gas must be reduced to 2%
to meet a design specification set by the client (Kotta, 2014). To achieve this goal, an absorption
process was designed and analysed as part of this project.
The inlet gas stream mole fractions, molar flows, kinematic viscosity and density are shown in the
Table 6 of Appendix A.
It was assumed that the solubility of non-CO2 components in the exhaust gas were negligible, so the
only component being removed in the absorber is CO2, which has a concentration of 9.78% as shown
in Table 1.
Sections 2.2.1 to 2.2.7 of the report detail the design steps undertaken for the absorber design and also
include justification on design decisions made.
The master Microsoft Excel worksheet used for all the calculations in Section 2.1.1 to 2.2.7 is
available in Appendix B and C on Table 7, Table 8, Table 9, and Table 10.
2.2.1 Solvent Selection
The first phase of designing an absorber required the selection of the most appropriate solvent to use
for carbon dioxide removal. In order to select the solvent, Henrys constant data for three solvents:
water, propylene carbonate and propylene glycol were used to determine which had the greatest value
of equilibrium CO2 concentration in the outlet solvent stream. Equilibrium CO2 concentrations were
calculated using the following equation:
Equation 8
Where:
is the CO2 mole fraction of the inlet gas stream (-), is the Henrys constant (MPa), PTotal
is the operating pressure of the absorber (MPa) and xout,max is the equilibrium CO2 mole fraction in the
outlet solvent stream (-).
The chosen operating pressure for the column is 5 MPa, as having it high allows for more effective
CO2 removal from the gas stream without requiring a large solvent flow rate (Cameron, 2014) and
this is pressure is very good for the solvent, propylene carbonate (Higman, 2006). This occurs due to
the fact that the solubility of CO2 in physical solvent such as propylene carbonate increases fairly
linearly with increasing operating pressure (Cameron, 2014).
Table 11, containing all the equilibrium outlet mole fractions of CO2 dissolved in the solvent is
available in Appendix D.
By calculating the equilibrium concentration of CO2 in the outlet solvent stream, the minimum solvent
flow rate can also be found using the following equation, which is a rearrangement of a mass balance
performed over the column:
Equation 9
Where: Lmin is the minimum molar flow of solvent (kmol/s), V is the molar flow of vapour (kmol/s)
and
is the mole fraction of CO2 in the inlet gas (-).

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From Table 11 of Appendix D, it can be seen that the solvent which exhibits the highest solubility for
carbon dioxide is propylene carbonate at a temperature of 288K or 15 oC. A greater solubility results
in a lower solvent flow requirement as seen on the equation above, and this decreases the operational
costs related to solvent regeneration, pumping and heating. Therefore, propylene carbonate is the most
suitable solvent to use for the CO2 absorber. The operating temperature of 15 oC was chosen because
the value of xout,max was the greatest at that temperature.
2.2.2 Minimum Required Liquid to Gas Ratio
Using the equations shown in Section 2.2.1 of the report, the minimum gas to liquid ratio for the
solvent, propylene carbonate was calculated to be 1.018.
The project brief specified that the actual flow rate of solvent is 1.2 times the minimum required
amount. At a temperature of 288K, the minimum flow rate of propylene carbonate required to meet
the CO2 concentration of 2% in the outlet gas steam is 37.47 kmol/s, therefore the actual flow rate is
44.97kmol/s.
2.2.3 Design Diagram of Absorption Column
In addition to calculating the minimum liquid to gas ratio and the actual flow rate of solvent, a design
diagram, which display the equilibrium line, minimum liquid to gas ratio line and operating line has
been generated using calculated values and is shown below:

Absorption Column X-Y Plot


CO2 Mole Fraction in Gas (-)

0.12
0.1
0.08
0.06

Equilibrium line

0.04

Operating Line

0.02

Lmin

0
0

0.02

0.04

0.06

0.08

0.1

CO2 Mole Fraction in Solvent (-)


Figure 2 Design Diagram of Absorption Column

2.2.4 Process Flow Diagram of the Absorber and Stripping System


To regenerate the propylene carbonate used to remove CO2 from the exhaust gas stream, additional
equipment must be installed alongside it. Propylene carbonate is a physical solvent, so a stripping
column is not required (Keskes, 2008). Instead, two flash drums in series is sufficient to allow the
solvent to release the CO2 is captured in the absorber and be regenerated (Keskes, 2008).

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Figure 3 Process flow diagram of the absorber and stripping system

2.2.5 Random Packing Material Selection


Three possible random packing materials: metal, ceramic and plastic were available, so research was
performed to determine which had the most suitable properties for this application. Additionally, the
cost of the materials was also taken into account. The material selected is plastic it is a cheap material
(Intalox, 2010) and also because the column is operating at a low temperature and does not contain
corrosive fluids, so there is no point to using ceramic or metal packing. After plastic was selected as
the material which the packing is to be made of, the shape and size of the packing were determined.
Packing shapes which had a high value of a, the surface area available per unit volume of packing
was desired as the gas and liquid would have more contract area, thereby reducing the packing height
required to perform the separation (Kotta, 2014). The reduction in packing height required decreases
the capital cost of the tower (Kotta, 2014), which is economically favourable. Another requirement for
the packing material is to not cause a large pressure drop, or undesired operational limits may be
reached, causing a decrease in separation efficiency (Cameron, 2014). The packing material, 50mm
Hiflow Hyd plastic packing exhibited a decent a value of 118.4 (Billet and Schultes, 1993) and did
not cause much of a pressure drop, so it was chosen as the packing material.
2.2.6 Calculation of Tower Diameter
The diameter of the tower was calculated using equations and charts provided on the book, Coulson
& Richardson's Chemical Engineering, by Coulson, J.M., Sinott, R.K. & Richardson, J.F.
Firstly, FLV, the flow parameter of the absorber had to be calculated using the following equation:
Equation 10
Where:
is the density of gas (kg/m3),
is the density of solvent (kg/m3), L is the solvent mass
flow rate (kg/s) and V is the gas mass flow rate (kg/s). *Values for
and
at 5Mpa were gathered
from the NIST thermophysical property databanks.
Calculations yielded an FLV value of 1.013 and by combining this with the given maximum gas-phase
pressure drop of 0.35 kPa or 35.69 mmH2O per metre of packing, the corresponding K4 value was
found from looking at the K4 vs FLV provided in Figure 6 of Appendix D. This K4 value was found to
be approximately 0.35. Also from the graph, the K4 value associated with flooding was determined to
be approximately 0.6.

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With the K4 value, the equation below was rearranged and used to find the gas mass velocity,
which has the units (kg/m2.s).
Equation 11
Where:
is the Packing factor (52m-1) (Perry, 2008) and Y is kinematic viscosity of solvent
(2.561*10-6 m2/s) (NIST WebBook)
The actual and flooding value of
was calculated to be 13.41 and 17.56 kg/m2.s, respectively,
giving a flooding percent of 76.4% and this is between the recommended range of 60 to 80% (Kotta,
2014), giving further justification for the operating pressure. From the actual , the tower diameter
was also calculated using the two equations below:
Equation 12
Where: A is the cross sectional area of the column and D is the diameter of the column (m).
Calculations have yielded a cross sectional area of 81.14 m2 and an absorber column diameter of
10.16m.
2.2.7 Estimation of Mass Transfer Coefficients, Height of Transfer Units for Liquid and Gas
Phases and Height of Overall Gas Transfer Units
The working steps used to calculate the height of transfer units (HL, HG) in and mass transfer
coefficients (Kxa, Kya) in liquid and gas phases as well as height of overall gas transfer units (Hoy)
are shown in Appendix D due to the large number of steps.
The key data values used to calculate Hoy is provided in Table 13 of the Appendix D
The final calculated values of HL, HG and Hoy were 3.74m, 3.832m and 7.749m, respectively.
The calculated values of Kya and Kxa are 5.82*10-2 kmol/m3.s and 7.49*10-2 kmol/m3.s. If there
were uncertainties in these parameters, the calculated tower height and column cross sectional area
and therefore diameter may be underestimated, causing the separation process to be less efficient.
2.2.8 Calculation of Tower Height
The number of overall gas transfer units, (Noy) was calculated using the equation below.
Equation 13

Noy, the number of overall gas transfer units, was calculated to be 4.301.
With a Hoy value of 7.749m and a Noy value of 4.301, the height of packing required was calculated
to be approximately 33.33m as it is Hoy multiplied by Noy. This gives the column a height to
diameter ratio of 3.28, which is greater than the rule of thumb ratio of 2-3:1, but it is still an
acceptable value (Kotta, 2014)
2.2.9 Final Absorber Specifications

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Table 2 shows the final specification of the absorber needed to reduce the concentration of CO2 to 2%
before being released into atmosphere.

Table 2 Final absorber specifications

Temperature
Pressure
Diameter
Height
Selected Solvent
Selected Random Packing Material

15C
5Mpa
11.16m
33.33m
Propylene Carbonate
50mm HiFlow Hyd (plastic)

The gas released to the atmosphere after passing through the absorber meets the 2% carbon dioxide
mole fraction specification, and the total adjusted flow of the exiting gas is 33.88 kmol/s.

2.3 Distillation Design


The stream exiting the methanol converter is sent into a flash separation unit and then to a distillation
column to produce a methanol stream of 99% purity by removing other components present in the
reactor product stream.
The reactor product stream composition is shown in Table 14 of Appendix D.
Calculations were required in order to determine the operating conditions for the flash separation unit
and distillation column at which a methanol stream with the desired purity of 99% could be produced.
To perform these calculations, the process simulation package, ASPEN PLUS was used to create a
simulated model of the system and the layout of this model is displayed below:

Figure 4 ASPEN PLUS model of the flash separation unit and distillation column system

The design steps used to determine the operating conditions for the flash separation unit and the
distillation column will now be explained in detail.
2.3.1 Flash Separation Unit Design
The purpose of the flash separation unit or flash drum was to separate the light gases (carbon dioxide,
carbon monoxide, hydrogen, and methane) from methanol and water, which are the less volatile
components.

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The ASPEN PLUS block used to represent the flash drum was Flash2, which is a two outlet flash
tank which utilises rigorous vapour-liquid equilibrium to calculate separation of the inlet stream into
outlet vapour and liquid streams (Washington University, n.d). The operating conditions for the flash
separation unit, fraction vapour of total outlet and vapour and liquid mole fractions of each
component are listed below:
Table 3 Operating conditions of flash drum and outlet total and component vapour/liquid fractions

Operating Conditions
Flash Drum Temperature (oC)
Flash Drum Pressure (MPa)

35
1.6

Outlet Conditions
Fraction Vapour (Total)

0.791

Mole Fraction
Component
Vapour
Liquid
Carbon Dioxide
0.99982
1.84E-04
Carbon Monoxide
0.98951
0.0105
Hydrogen
0.99992
8.35E-05
Methane
0.99889
1.11E-03
Methanol
0.0685
0.93149
Water
0.0175
0.98253
The operating temperature of 35 oC was specified in the project brief Appendix (The University of
Queensland, 2014), but the operating pressure was not. In order to find the optimal operating pressure
for the flash drum, a sensitivity analysis was performed to quantify how the amount of methanol being
lost in the light gas vapour stream changed as the operating pressure was varied.
The graph of the sensitivity analysis is provided in Figure 7 of Appendix D:
As it can be seen in Figure 7 in the Appendix D, the amount of methanol lost in the vapour stream is
very high at low operating pressures, but falls as the pressure increases. Initially, the rate of change is
great, but beings to decrease with increasing pressure. If the pressure is too high, more light gases
leave in the liquid stream, compromising its purity, but conversely, low pressure results in more
methanol loss. Therefore an optimal operating pressure of 1.6 MPa, which balances these two factors,
was selected. At this pressure, only 6.85% of the methanol entering the flash drum is lost to the
vapour stream and the amount of light gases leaving with the liquid is 1% or less for each component.
Another sensitivity analysis performed on the flash drum operating conditions was the temperature at
which the separation process was taking place. The effect on operating temperature was observed by
plotting the methanol loss rate into the vapour product stream of the flash drum to determine if the
original temperature of 35 oC is acceptable. The graph of the resulting sensitivity analysis is shown in
Figure 8 the Appendix D:
The data curve in Figure 8 of Appendix D shows that at the operating temperature of 35 oC, the
methanol loss is only 6.85%, so this operating pressure was deemed to be acceptable.
2.3.2 Distillation Column Design
The process used to design the distillation column was of a much greater complexity and it required
the use of two column blocks in ASPEN PLUS, as shown in Figure 4 of Section 2.3. Initially, the
block DSTWU was used to calculate the number and configuration of stages as well as a minimum
reflux ratio and operating pressures for the condenser and reboiler. DSTWU was only used for initial

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calculations because it uses a shortcut method for calculations and works under the assumption of
constant molar overflow and constant relative volatilities (Washington University, n.d) and this may
not be the case through the entire column. In order to obtain results of a greater accuracy, the Radfrac
column, which utilises a much more rigorous calculation process, should be used (Washington
University, n.d). The calculated operating parameters for the DSTWU column are provided in Table
15 of Appendix D:
The initial reflux ratio was set to 1.5 as it is a reasonable starting value (Washington University, n.d)
and after ASPEN performed column calculations, a minimum reflux ratio of 0.307 was found. From
the minimum reflux ratio, an economic reflux ratio was calculated by multiplying it by 1.5, because
that is the reflux ratio at which the total cost of the system, a combination of operational and capital
costs typically reaches a minimum (Treybal, 2005).
Operating pressure for the reboiler and condenser were set to be 0.1 and 0.103 MPa, as the separation
of methanol from water is requires less energy to perform at low pressure due to the higher tendency
for methanol to transform into a vapour (Perry, 2008). Another reason for these pressures is that the
difference in methanol and water boiling temperatures is greater than 35 degrees (NIST, 2014), which
is beneficial for high quality separation to occur.
After inputting the operating parameters in Table 15 into the Radfrac column block, the final
methanol product purity fell to 95.7%, so a design specification was placed on the column, which
varied the reflux ratio until a product purity of 99% was met. ASPEN PLUS was able to meet this
specification, and the operating parameters at that condition are shown below:
Table 4 Final distillation column operating parameters gained from Radfrac

Operating Parameters
Actual number of stages (-)
13
Actual reflux ratio (-)
0.859
Methanol Recovery (-)
0.98
Methanol product purity (%)
99.0 Specification Achievable
Net heat duty of column (gW)
94.69
Condenser duty (gW)
-71.64
Reboiler duty (gW)
166.3
Minimum required steam flow in reboiler 76.91
(ton/s)
Distillate to feed ratio for methanol
0.99
Location of feed stage (-)
9
At these operating conditions, the flow rate of methanol product is 2214 kmol/s.
The minimum steam flow required in the reboiler to provide the heat duty was calculated by using the
heat of vaporisation of steam at 30 PSIG obtained from the NIST thermo-physical property databanks
and the required reboiler duty. This calculation was performed under the assumption that all the
energy lost by the steam is gained by the reboiler. In reality, this would not be the case due to
efficiencies and losses, so the actual amount is greater. Working steps used for this calculation are
provided in the report Appendix E.
It is recommended that the type of plate used for this tray column should be sieve trays. This
recommendation was made because the operating pressure of the column is approximately one bar,
which means that sieve trays are suitable as long as excessive weeping is not occurring in the column
(GBH Enterprises, N.D). In addition to this, sieve trays are one of the cheapest plate types available

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on the market (GBH Enterprises, N.D), so its economically favourable to use them due to their low
replacement costs.
2.2.3 Selection of Property Method
The property method used for the ASPEN PLUS calculations was the Peng-Robinson equation of
state because of its simplicity and ease of use. It is known that for highly non-ideal systems such as
alcohol-water mixtures, there are better alternatives to use instead of the PR EOS, such as PR EOS
with Wong-Sandler mixing rules (Aspen Technology Inc, 2006), but the attempted use of this
property method resulted in high amount of converging errors and was generally more difficult to use.
If more time was available and a greater accuracy was required, the PRWS property method would
have been used instead.

3.0 Discussion and Analysis


3.1 Absorber Design
3.1.1 Physical Solvent over Chemical Solvent
Regardless of physical or chemical solvent, the objective of the solvent in this absorber is to remove
carbon dioxide before being released into the atmosphere. Both physical and chemical solvent have
their advantages and disadvantages, here is the justification on why physical solvent is more
preferable.
Although physical solvent performs weaker in capturing carbon dioxide compared to chemical
solvent, the operating conditions of the absorber in which at high pressure and lower temperature will
increase the absorptive capacity of the physical solvent, hence making it more favourable in this case
(Kothandaraman, 2010). Besides for any chemical reactions to occur at faster rate, the absorber must
operate at opposite conditions of current absorber. Hence, chemical solvent generally would not be
suitable to be used into this absorber.
Solvents are usually recycled later after the carbon dioxide has been absorbed. For chemical solvent,
heat must be applied to break its chemical bond between carbon dioxide and hence separate it into
another stream (Anderson, et al, 2003). Moreover, other pollutants absorbed by the chemical solvent
must be removed as well as they will later inhibit the carbon dioxide capture. High energy
requirement for solvent recovery causes it to be more expensive than physical solvent. A common
method for regenerating physical solvents is to simply reduce the operating pressure (Burr, et al,
2008).
For this system, propylene carbonate is chosen over the other two physical solvents. It has higher
carbon dioxide dissolving capacity compared to propylene glycol and water. The plant size and cost
required for any certain carbon dioxide removal capacity then will be significantly less. Furthermore,
propylene carbonate holds more advantages compared to the other two solvents such as high thermal
stability, low hydrocarbon (other impurities) solubility and recoverability of any small amounts
entrained in the purified gas (Kohl, et al, 1960).
3.1.2 Lowest CO2 Concentration
The lowest CO2 concentration in the treated gas can be reduced to zero theoretically if the flow rate of
the solvent is extremely large which then leads to more capital and operational cost. Since the
environmental regulations state that the safe concentration of CO2 to be released into atmosphere is
2%, this is the constraint to be considered. To lower the CO2 concentration in the gas the most

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effective way to change parameters of the absorber is to lower the temperature or increase the
pressure of the operation.
3.1.3 Amine Consideration
If a chemical solvent such as amine is used, a few other considerations involving mass and energy
balances, column diameter and height of packing calculations must be taken into account, this is due
to the amines viscosity and reaction kinetics.
The current operating conditions of absorber will likely not be suitable for the performance of amine
solvent. Chemical solvents work more efficiently at higher temperatures and in this case increased
alkalinity; these will increase the mass transfer coefficient of solute within the solvent. (Wilcox 2012).
Using amines as a solvent is a popular choice among sites with a CO2 concentration around 10%,
though there are many downsides with selecting amines as a solvent. These downsides include the
reaction having a high heat of reaction, requiring cooling equipment, and high regeneration energy
required. The latter probably has the biggest impact as these increases the amount of low pressure
steam in the stripping absorber which requires a large flow of solvent to compensate. This cascades
due to the viscosity of amines, into requiring large columns for the amount of flow, and large power
requirements to regain the large pressure drops over the columns. These factors take up a large chunk
of the operating and capital cost of CO2 capture (Fang, 2012).
3.1.4 Maximum Temperature Change across Column for Isothermal System
The column was initially assumed to operate isothermally to aid the calculation process. However,
there is a slight temperature gradient across the column mainly due to the absorption of carbon
dioxide in the liquid phase.
The temperature of solvent input gives only little impact on the internal temperature change, but its
flow rate has a more significant impact (Perry, et al, 1997). A high ratio of liquid to gas flow will
generally results in less changes of temperature due to the higher heat capacity of liquid phase.
Lowering the ratio would results in less carbon dioxide absorbed and hence, causing the point of
maximum temperature to move up the column where a higher concentration of carbon dioxide will
build up (Perry, et al, 1997).
Solute absorption would take place more rapidly near the bottom of the column. Since the absorption
of carbon dioxide releases heat, hence the rate of heat liberation would be the highest there. Going
down the column, the temperature change should be more significant. To minimise that, the feed gas
is often cooled by heat exchanger before entering the column. Hence, it will result in a temperature
profile that is closer to isothermal (Ebenezer, 2005).
3.1.5 Validity of the Assumption of Insolubility of non-CO2 Components.
The ratio of solubility of nitrogen and oxygen to the solubility of carbon dioxide in propylene
carbonate are 0.0084 and 0.026 respectively (Burr, et al, 2008). Hence, this shows that the solubility
of carbon dioxide is far greater than the other components. The assumption is said to be valid.
The assumption made will slightly underestimate the height of packing calculated. As there will be
some mass transfer of the other components into the liquid solvent, the rate of carbon dioxide
absorption will be hindered. Hence, it would require a marginally taller packing to allow more solute
absorption time to reach the specification of maximum 2% carbon dioxide in the treated gas flow. If
the assumption was proven to be invalid this packing height would be required to be significantly
taller.

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3.2 Distillation Design
There are several variables in the separation system (flash drum and distillation column) which had a
noticeable effect on the recovery and purity of the methanol. Two key variables were put through a
sensitivity analysis in the flash drum and three for the distillation column.
3.2.1 Flash Drum
The two key variables analysed for the flash drum was the operating pressure and temperature. As
shown in Figure 7 and Figure 8 of Appendix D, the increase in pressure and the increase in
temperature had opposite effects on the amount of methanol being lost to the light gas vapour stream
of the flash drum. Low pressure or high temperature caused more methanol to be lost and as a result
of its increased volatility and reduced the amount sent to the distillation column, thereby lowering
methanol recovery in the system. While the removal of light gases such as: carbon monoxide, carbon
dioxide, hydrogen and methane would increases as a result of this, the reduction of impurities in the
liquid product stream was insignificant to the loss of methanol. Due to this fact, operating the flash
drum at high pressure and low temperature was deemed to be the best course of action, even if it
resulted in a higher light gas concentration in the liquid product stream.
3.2.3 Distillation Column
The Radfrac distillation column block used for ASPEN PLUS simulations had three key variables put
through sensitivity analyses.
The first variable to be analysed was the reflux ratio, which is the split fraction of top product being
put back into the column over the distillate product leaving the column. Methanol product purity and
flow rate are plotted against the reflux ratio a graph below:
From Figure 9 of Appendix F, it can be seen that the methanol product purity rose very rapidly with
increased reflux rate, and then reached a peak with barely any change. If greater product purity and
flow are desired, the reflux ratio could be set higher, but this means that the column capital and
operating costs would increase. The elevation in costs is attributed to the fact that the flow rates
through the column rise proportionally with reflux rate as more fluid is sent back into the column at
higher reflux rates. This change requires a wider column and greater steam flow into the reboiler for
the separation to occur (Kotta, 2014). Therefore, it is economically unfavourable to have the reflux
ratio high than the value that allows the set product purity specification to be met.
The second analysed variable was the location of feed stage in the column, where the liquid stream
leaving the flash drum enters the column for its final separation into methanol in the top and water in
the bottom product streams. Methanol product purity and flow rate are graphed against feed stage
location (note that stages are counted from the top to bottom of column) in Figure 11 of Appendix F.
The data curves in Figure 11 of Appendix F show that the feed stage location has a noticeable effect
on the methanol product purity and flow rate when it is between the 2nd and 11th stages, then both
values drastically drop after this range. The peak product purity and recovery was achieved between
the 8th and 9th stages, but stages are always rounded to the closest whole number as it is physically
impossible to have half a stage, which is why the 9th stage was chosen as the actual feed stage. From
these results, it can be concluded that the location of feed stage is a variable which greatly affect the
product purity and recovery.
Finally, the last sensitivity analysis performed was regarding the change in methanol product purity
and flow rate as the number of stages present in the distillation column was altered. Results of this
analysis are shown in a graphical format below:

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Data curves in Figure 10 of Appendix F show that increasing the number of stages also increases
methanol product purity and flow rate. The rate of increase is large initially, but then reaches a peak
with very little change. This agrees with the notion that having more stages increases the ability of the
column to separate the bottom and top products from each other (Perry, 2008). However, as shown in
the graph above, the operational benefit of having more stages diminishes very rapidly after a certain
value, while the capital cost required to add additional stages continues to rise (Perry, 2008). As a
result of this, the construction of further stages becomes a waste of capital and is not recommended.
Analysis of stage numbers below the 9th and above the 13th stages could not be performed due to the
former being designated as the feed stage and the latter as the total number of stages in the Radfrac
block specifications.

4.0 Conclusions and Recommendations


After performing a considerable amount of research, calculations and analysis on the given methanol
production process, several conclusions were arrived at.

4.1 Absorber
The carbon dioxide mole fraction was able to be reduced to the specified amount of 2% by passing it
through a random packed absorber and contacting it with propylene carbonate, the solvent. The
operating temperature and pressure for the column was 15 oC and 5Mpa, respectively, and at these
conditions, the actual scaled flow rate of solvent was calculated to be 44.97 kmol/s.

4.2 Distillation Process


The aim of the distillation process was to purify the product methanol to 99% purity this was obtained
by using a flash drum to remove the light components and a distillation column to remove the water.
The flash drum removed 99.98% of the light components from the product stream. This leaves a
concentration of 0.1% of light components in the stream. This was achieved under an operating
pressure of 1.6 MPa and an operating temperature of 35C.
The distillation column removes 99% of the water leaving the methanol in the product stream 99%
pure. To achieve this the distillation column was found to operate under the following conditions
gleaned from table 4:
Operating Parameters
Actual number of stages (-)
13
Actual reflux ratio (-)
0.859
Net heat duty of column (gW)
94.69
Condenser duty (gW)
-71.64
Reboiler duty (gW)
166.3
Minimum required steam flow in reboiler 76.91
(ton/s)
Distillate to feed ratio for methanol
0.99
Location of feed stage (-)
9

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CHEE 3004: Unit Operations Project Report 1

References
Anderson, S. & Newell, R., January 2003, Prospects for Carbon Capture and Storage Technologies.
Billet, R. & Schultes, M., Predication of Mass Transfer Columns wit Dumped and Arranged
Packings Volume 77, Institute of Chemical Engineers
Burr, B. & Lyddon, L., 2010, A Comparison of Physical Solvents For Acid Gas Removal, Bryan
Research & Engineering, Inc
Cameron, I. 2014, Gas Liquid Absorption, lecture notes for CHEE3004: Unit Operations course at
The University of Queensland, distributed on 26/08/14.
Coulson, J.M., Sinott, R.K. & Richardson, J.F., 1999, Coulson & Richardson's Chemical
Engineering, Volume 6, Oxford, Butterworth-Heinemann.
Ebenezer, S 2005, Removal Of Carbon Dioxide From Natural Gas For LNG Production, Norwegian
University of Science and Tec hnology, Trondheim available at
http://www.google.com/patents/US2926751#forward-citations (viewed on 20/05/14)
Fang, M.& Zhu, D. 2012. Chemical Absorption. Handbook of Climate Change Mitigation. W.-Y.
Chen, J. Seiner, T. Suzuki and M. Lackner, Springer, US, pp. 1441-1514.
GBH Enterprises, Selection of Internals for Distillation Columns, [Online], available on
https://www.academia.edu/3641162/Selection_of_Internals_for_Distillation_Columns (viewed
19/09/14)
Higman, C. 2006, Chapter 13: Gas Treating, Elsevier
Intalox Packing Tower Systems, 2010, Plastic Random Packing, Koch-Glitsch
Keskes. E. et al, 2008, A Ohysical Absorption Process For the Capture of CO2 From CO2-Rich
Natural Gas Streams Chemical Engineering Department, Imperial College London
Kohl, A. & Miller, F., 1960, Organic carbonate process for carbon dioxide, United States Patent.
Kothandaraman, A., June 2010, Carbon Dioxide Capture by Chemical Absorption: A Solvent
Comparison Study, Massachusetts Institute of Technology.
Kotta, L. 2014, CHEE3004 Project 1 Final Thoughts, supplementary information provided for
CHEE3004: Unit Operations course at The University of Queensland, distributed on 13/09/14.
Kotta, L. 2014, Multistage binary distillation, lecture notes for CHEE3004: Unit Operations course
at The University of Queensland, distributed on 19/08/14.
Kotta, L. 2014, Project 1: The design of a gas-liquid absorber and distillation system, provided for
The University of Queensland CHEE3004 project.
Manning, M. 2013, ' Driven By China, Global Methanol Demand Rises 23 Percent in Two Years,
Unprecedented Demand Growth Expected for 2012 to 2022, Says New IHS Study', IHS Press release,
Houston, 11 March.

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CHEE 3004: Unit Operations Project Report 1


McCabe WL, Smith JC & Harriott P., 1993, Unit Operations of Chemical Engineering, 5th Ed,
McGraw-Hill, New York
National Institute for Standards and Technology, Thermophysical Properties of Fluid Systems,
available at http://webbook.nist.gov/chemistry/fluid/ (viewed 01/09/14)
National Institute for Standards and Technology, Chemistry WebBook, available at
http://webbook.nist.gov/chemistry/, (viewed 29/08/14)
Physical Property Methods and Models. 2006, Aspen Technology, Inc. Cambridge.
Perry, RH & Green DW, 2008, Perrys Chemical Engineers Handbook , 8th Ed, McGraw-Hill, New
York
Treybal, RE, 2005, Mass Transfer Operations, 3rd Ed, McGraw-Hill, New York
Washington University, ASPEN Tutorial #6: Aspen Distillation available at
http://courses.washington.edu/overney/Aspen/Aspen_Tutorial_Unit_6.pdf (viewed 28/08/14)
Wilcox, J 2012, Chapter 3: Absorption, in Carbon Capture, Stanford University, Springer New York.

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Appendices
Appendix A: System Diagram, Stream table and Physical properties

Figure 5 Flow chart of the entire methanol production plant, marked with end of mass balances

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CHEE 3004: Unit Operations Project Report 1


Table 5 Stream flows corresponding to the block flow diagram

Stream
1
200
Total flow
0
(kmol/s)
Temperatur 30
e (C)
1.6
Pressure
(MPa)
200
Methane
0
(kmol/s)
1
Methane
mole
fraction
0
Water
(kmol/s)
0
Water mole
fraction
0
Carbon
monoxide
(kmol/s)
0
Carbon
monoxide
mole faction
0
Carbon
dioxide
(kmol/s)
0
Carbon
dioxide mole
fraction
0
Hydrogen
(kmol/s)
0
Hydrogen
mol fraction
0
Oxygen
(kmol/s)
Oxygen mole 0
fraction
0
Nitrogen
(kmol/s)
0
Nitrogen
mole
fraction

Group 31

10

11

12

13

14

480
0

160
0

640
0

640
0

8640

40
0

4516

4516

8640

358
4

5056

5056

4516

210

30

145

450

855

30

255

960

855

35

35

100

150

1.6

1.6

1.6

1.6

1.6

1.6

1.6

1.6

1.6

1.6

1.6

7.5

0.1

160
0

160
0

160
0

480

40
0

400

40

480

480

480

40

0.25

0.25

0.05
6

0.08
9

0.009

0.05
6

0.09
5

0.09
5

0.009

480
0

480
0

480
0

3680

116

836

3602

358
4

18

18

836

0.75

0.75

0.42
6

0.02
6

0.185

0.41
7

0.00
4

0.00
4

0.185

1120

1042

1042

1042

0.13

0.12

0.12

0.12

360

78

78

78

360

0.079
7

0.00
9

0.00
9

0.00
9

0.079
7

3360

3438

3438

3438

0.38
9

0.39
8

0.39
8

0.39
8

840

120

120

0.18
6

0.027

0.027

3160

3160

3160

0.7

0.7

0.7

Page 17

CHEE 3004: Unit Operations Project Report 1


Table 6: Inlet gas data including kinematic viscosity and density courtesy of NIST WebBook
Components
Methane

Mole Fraction
(-)
0.01087

Molar Flow
(kmol/s)
0.4

Carbon Dioxide

0.0978

3.6

Nitrogen

0.8587

31.6

Oxygen

0.0326

.2

Group 31

Kinematic Viscosity
(m2/s)

Density
(kg/m3)

3.21E-07

36.98

1.09E-07

154.1

3.10E-07

58.94

3.06E-07

69.15

Page 18

CHEE 3004: Unit Operations Project Report 1


Appendix B: Master Microsoft Excel Sheets used for Absorber Calculations (Values)
Table 7 Master Excel Sheet used for Absorber Calculations (Values) (Part 1)

Total
Temp (deg C)
Pressure (Mpa)
Gas flow in (rescaled) kmol/s
Total
CO2
Other

Solvent
Water
Propylene Carbonate
Propylene Glycol

Solvent
Water
Propylene Carbonate
Propylene Glycol

Group 31

3680
15 CH4
5 CO2
N2
36.8 O2
3.6
33.2

288
125.1
6.4
30.2

288
3.91E-03
0.076
0.016192053

mol flow rate


(kmol/s)

mw kg/kmol
16.04
44.01
28
32

henry's constant (MPa)


Temperature
298
156
8.7
38.1

Xmax out
Temperature
298
3.13E-03
0.056
0.013

308
184.8
10.6
45.6

308
2.65E-03
0.046
0.011

kinematic
Dynamic Visc
mass fraction mol fraction density kg/m3 total density
viscosity (m2/s) total viscosity (m2/s)
40
0.174
0.0109
36.98
0.4019
4.02E-07
3.21E-07
3.49E-09
360
4.305
0.0978
154.1
15.0770
1.51E-05
1.09E-07
1.06E-08
3160
24.04
0.8587
58.94
50.6141
5.06E-05
3.10E-07
2.66E-07
120
1.043
0.0326
69.15
2.2548
2.25E-06
3.06E-07
9.97E-09
29.57
1
68.3478 avg
2.90E-07

318
243
12.4
52.6

318
2.01E-03
0.039
9.30E-03

Solvent
Water
Propylene Carbonate
Propylene Glycol

Solvent
Water
Propylene Carbonate
Propylene Glycol

288
25.02
1.28
6.04

288
732.4
37.47
176.8

henry's constant (-)


Temperature
298
308
31.2
36.96
1.74
2.12
7.62
9.12

Lmin (kmol/s)
Temperature
298
913.4
50.9
223.1

308
1082.0
62.1
267.0

318
48.6
2.48
10.52

318
1422.7
72.6
308.0

Page 19

CHEE 3004: Unit Operations Project Report 1


Table 8 Master Excel Sheet used for Absorber Calculations (Values) (Part 2)
Yin
Yout
Y*in

Best Temperature
Best Solvent

Propylene carbonate
288K
Non solute fraction
L actual (kmol/s)
X out actual
Out
CO2 Absorbed
44.97
0.0637
0.98
0.678
Change in CO2
2.922
CO2 in outlet gas
0.678
Lmin/G Ratio
1.018
Hoy Calculations

0.0978
0.020
0.082

Y*out
Log Mean
Noy

K4

0.350

xin*
xout
xout*
log mean x
Nox
Kxa
Packing Parameters

0.0156
0.0637
0.0764
-0.0141
4.5060
7.49E-02

packing surface
area
a
m^3/m^3
E

118.4
0.925

2.561E-06

characteristic

Ch

0.881

rohG

68.35

characteristic

CL

1.553

rohL

1205

characteristic

Cv

0.369

1088
4627
1.013
35.69
81.14

Packing Factor Fp

52

4627
1.28

GdotY

henry's constant

mass flow
m

Vapour Flow Rate

36.8

Liquid Flow Rate

44.97

height of gas tu

Hg

3.832

13.410

height of liquid tu
HL
specific liquid hold up hL
diffusity of Co2 in liquidDL
liquid velocity
uL
aPh
liquid froude number NfrL
reynold number liq
NreL

3.74E+00
0.101
2.20E-09
0.0473
29.6
0.027
933.35

V
L
FLV
pressure drop
A
Adjusted diffusivity
Dg
viscosity of gas mewG

hydraulic/packing area ah/a


acceleration
g
reynold number gas NreG
schmidt number
NscG
gas velocity
uG
diffusity of Co2 in gas DG

1.713
9.81
3.41E+04
0.000
0.196
1.60E-05

density of gas

Group 31

0.000
0.018
4.301

Mass Transfer Coefficients


Kya
5.85E-02
xin
0.0000

rohG
dp
K
Height of TransferHoy
Units

4.28E-07
2.90E-07
68.35
3.80E-03
0.9967
7.749

Visc ^0.1
py(px-py)^-1
Diameter
Height
Height to
Diameter Ratio

2.22E-01
1.28721E-05
10.16
33.33
3.280

Page 20

CHEE 3004: Unit Operations Project Report 1


Appendix C: Master Microsoft Excel Sheets used for Absorber Calculations (Formulas)
Table 9 Master Excel Sheet used for Absorber Calculations (Formulas) (Part 1)

Total
Temp (deg C)

=SUM(E2:E5)
15

CH4

mol flow rate


mw kg/kmol (kmol/s)
mass fraction mol fraction density kg/m3
16.04
40
=G2*D2
=E2/$B$1
36.976

Pressure (Mpa)

CO2

44.01

360

=G3*D3

=E3/$B$1

Gas flow in (rescaled)


Total
CO2
Other

kmol/s
=B1/100
=E3/100
=B5-B6

N2
O2

28

3160
120

=G4*D4
=G5*D5
=SUM(F2:F5)

=E4/$B$1
58.943
=E5/$B$1
69.148
=SUM(G2:G5)

32

154.12

henry's constant (MPa)


Temperature
298
308
318
156
184.8
243

Solvent
Water

288
=B12/$B$3

Propylene Carbonate 6.4

8.7

10.6

12.4

Propylene
Carbonate

Propylene Glycol

30.2

38.1

45.6

52.6

Propylene
Glycol

288
=$G$25/H12

Xmax out
Temperature
298
308
=$G$25/I12=$G$25/J12

318
=$G$25/K12

Propylene Carbonate =$G$25/H13

=$G$25/I13=$G$25/J13

Propylene Glycol

=$G$25/I14=$G$25/J14

Solvent
Water

Solvent
Water

Group 31

288
125.1

=$G$25/H14

total density
=H2*G2

Dynamic Visc

kinematic viscosity (m2/s)

=I2*10^-6

=N83/H2

total viscosity
(m2/s)
=K2*G2

=H3*G3

=I3*10^-6

=N84/H3

=K3*G3

=H4*G4
=H5*G5
=SUM(I2:I5)

=I4*10^-6

=N85/H4

=I5*10^-6

=N86/H5

=K4*G4
=K5*G5
=SUM(L2:L5)

avg

298
=C12/$B$3

henry's constant (-)


Temperature
308
=D12/$B$3

318
=E12/$B$3

=B13/$B$3

=C13/$B$3

=D13/$B$3

=E13/$B$3

=B14/$B$3

=C14/$B$3

=D14/$B$3

=E14/$B$3

Solvent
Water

288
=($B$5*($G$25-$G$26))/B20

Lmin (kmol/s)
Temperature
298
308
=($B$5*($G$25-$G$26))/C20
=($B$5*($G$25-$G$26))/D20

318
=($B$5*($G$25-$G$26))/E20

=$G$25/K13

Propylene
Carbonate

=($B$5*($G$25-$G$26))/B21

=($B$5*($G$25-$G$26))/C21

=($B$5*($G$25-$G$26))/D21

=($B$5*($G$25-$G$26))/E21

=$G$25/K14

Propylene
Glycol

=($B$5*($G$25-$G$26))/B22

=($B$5*($G$25-$G$26))/C22

=($B$5*($G$25-$G$26))/D22

=($B$5*($G$25-$G$26))/E22

Page 21

CHEE 3004: Unit Operations Project Report 1


Table 10 Master Excel Sheet used for Absorber Calculations (Formulas) (Part 2)

Best Temperature
Best Solvent

Propylene carbonate
288K

L actual (kmol/s)
=H21*1.2

X out actual
=((B5*($G$25-$G$26))/A29)

Lmin/G Ratio

Non solute fraction Out


0.98
Change in CO2
CO2 in outlet gas
=$H$21/$B$5

CO2 Absorbed
=($B$7/$C$29)*0.02
=$B$6-$D$29
=B6-D30

Hoy Calculations

Yin
Yout
Y*in

0.0978
0.02
=H13*B29

Mass Transfer Coefficients


Kya
xin

=((B5/F44)/G50)
0

Y*out
Log Mean
Noy

0
=((G25-G27)-(G26-G28))/(LN((G25-G27)/(G26-G28)))
=(G25-G26)/G29

xin*
xout
xout*
log mean x
Nox
Kxa

=(0.02/H13)
=B29
=B21
=((J27-J28)-(J29-J30))/(LN((J27-J28)/(J29-J30)))
=(J27-J29)/J31
=((A29/F44)/(J46/J32))

K4

0.35

Packing Parameters

mass flow
m

=B87*102.9
=H13

GdotY

=SQRT(F34/(J43*J44*J40*13.1))

henry's constant

packing surface area


m^3/m^3

a
E

118.4
0.925

Vapour Flow Rate

=B5

=H87

characteristic

Ch

0.881

Liquid Flow Rate

=A29

rohG

=I6

characteristic

CL

1.553

height of gas tu

Hg

=(1/J39)*(J36-C41)^(1/2)*(4*J36/(J35^4))^(1/2)*C49^(-3/4)*C50^(-1/3)*C51/G45*4
rohL

=F87

characteristic

Cv

0.369

height of liquid tu
specific liquid hold up
diffusity of Co2 in liquid
liquid velocity

=1/J38*(1/12)^(1/6)*(4*C41*J36/C42/J35/C43)^(1/2)*C43/J35*4
=(12*C45/C46)^(1/3)*(C47)^(2/3)
0.0000000022
=C35/F39/F44
=0.25*J35
=C43^2*J35/C48
=C43*G48*G49/(1-J36)/H87

V
L
FLV
pressure drop
A
Adjusted diffusivity
viscosity of gas

=K84
=C35
=F41/F40*(F38/F39)^0.5
35.6900674542274
=K84/F35
Dg
mewG

Packing Factor

Fp

52

liquid froude number


reynold number liq

HL
hL
DL
uL
aPh
NfrL
NreL

Visc ^0.1
py(px-py)^-1
Diameter
Height

=L6^0.1
=(F38*(F39-F38))^-1
=(F44*4/PI())^0.5
=G50*G30

hydraulic/packing area
acceleration
reynold number gas
schmidt number
gas velocity
diffusity of Co2 in gas

ah/a
g
NreG
NscG
uG
DG

=J37*C46^0.15*C45^0.1
9.81
=C51*G48*G49/(1-J36)/L6
=G46/(G47*C52)
=K84/I6/F44
0.000016

density of gas

Height to Diameter Ratio

=J46/J45

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rohG
dp
K
Height of Transfer Units Hoy

=(C52*1.83)/F38
=L6
=I6
=6*(1-J36)/J35
=1/(1+2/3*1*G48/(1-J36)/J45)
=C39+C36*(C37/C38)*C40

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CHEE 3004: Unit Operations Project Report 1


Appendix D: Working Steps Used to Calculate Height of Transfer Units for Liquid and Gas
Phases and Overall Gas Transfer Units and Mass Transfer Coefficients
Table 11 Maximum mole fraction of carbon dioxide in outlet solvent stream

Solvent

Temperature (K)
288
298
308
318
Equilibrium CO2 mole fractions in solvent outlet (-)
3.91E-03
3.14E-03
2.65E-03
2.01E-3

Water
0.076

0.056

0.046

0.039

0.016

0.013

0.011

9.3E-3

Propylene Carbonate
Propylene Glycol
Table 12 Minimum solvent flow rate required to absorb CO2

Solvent
Water
Propylene
Carbonate
Propylene Glycol

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288
732.4

Temperature (K)
Lmin (kmol/s)
298
308
913.4
1082.0

37.47
176.8

50.9
223.1

62.1
267.0

318
1422.7
72.6
308.0

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CHEE 3004: Unit Operations Project Report 1

Figure 6 The K4 vs FLV chart with the operating value and flooding values marked

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CHEE 3004: Unit Operations Project Report 1


Table 13 Parameters and values used to calculate height of overall gas transfer units, Hoy

Parameters
a (surface area per unit
volume of packing)
(voidage)
Ch, CL, Cv
(packing characteristics)
Fp
(packing factor)
DL (diffusivity of CO2 in
solvent)
DG (diffusivity of CO2 in gas
at 1atm)
Dg (modified gas diffusivity at
5 MPa)
g (gravitational acceleration)
Velocity of liquid
Velocity of gas

Values
118.4 m2/m3

Sources
Billet and Schultes, Table 2a.

0.925
0.881, 1.553, 0.369

Billet and Schultes, Table 2a.


Billet and Schultes, Table 2a.

52
2.2E-09m2/s

Perrys Chemical
Handbook
Cussler, Diffusion

1.6E-5 m2/s

Cussler, Diffusion

4.28E-07 m2/s

Calculated

9.81 m/s2
0.059 m/s
0.264 m/s

Calculated
Calculated

Engineering

Equation 14
Where HL is the height of transfer units in the liquid phase
Equation 15
Where

, the ratio of phase interface area to the packing surface area is assumed to be 0.25 (Kotta,

2014). The specific liquid holdup, hL, can be calculated from


Equation 16
Where
Equation 17
And the Froude number Nfr is computed with
Equation 18
Height of gas phase transfer unit, HG
Equation 19
The Schmidt number, NSc,G is given by
Equation 20
Mass transfer coefficients can be calculated by using the following equations (University of
Queensland, 2014):

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CHEE 3004: Unit Operations Project Report 1


Equation 21
Equation 22
Where:

Equation 23

Where: Zt is the height of packing (m), Nox is the number of transfer units in the liquid phase, xout is
the mole fraction of CO2 in outlet solvent and xin is the mole fraction of CO2 in the inlet.

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CHEE 3004: Unit Operations Project Report 1

Table 14Reactor product stream composition, flow rate, temperature and pressure

Phase:
Component Mole Fraction
Carbon Dioxide
Carbon Monoxide
Hydrogen
Methane
Methanol
Water
Mole Flow (Kmol/s)
Temperature (oC)
Pressure (MPa)

Vapour Feed
Zi
0.10
0.01
0.56
0.11
0.15
0.07
16000
150
2

Methanol Loss in Vapour (Kmol/s)

Methanol Loss vs Operating Pressure (Temperature: 35oC)


1400
1200
1000
800
600
400
200
0
0.2

0.7

1.2

1.7

Operating Pressure (MPa)

Figure 7 Graph of methanol loss in vapour against flash drum operating pressure

Methanol Loss to Light Gas Stream


(Kmol/s)

Methanol Loss vs Temperature (Pressure: 1.6 MPa)


2500
2000
1500
1000

500
0
0

20

40

60

80

100

120

140

160

Temperature (oC)

Figure 8Graph of methanol loss against flash drum operating temperature

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CHEE 3004: Unit Operations Project Report 1


Table 15 Distillation column operating parameters gained from DSTWU calculations

Operating Parameters
Minimum reflux ratio (-)
Optimum reflux ratio (-)
Actual number of stages (-)
Feed stage (-)
Condenser pressure (MPa)
Reboiler pressure (MPa)
Distillate to feed ratio for methanol (-)
Methanol product purity (%)

0.307
0.46
13
9
0.1
0.103
0.99
99.3

Appendix E: Steam Requirement Calculations


Minimum required steam flow in reboiler working steps:
Table 16 Reboiler and steam property data required for steam flow calculations

Data
Heat duty of reboiler (kJ/s)
Steam heat of vaporisation at 30 PSIG (kJ/mol)
Molecular weight of steam/water (kg/kmol)

Value
166323925
38.93
18

Source
ASPEN PLUS
NIST
NIST

To calculate the minimum required flow of steam, several design assumptions were impletmented.
Assumptions

Steady state operation


No reaction
All energy lost by steam is gained by reboiler
Steam enters as a saturated vapour and is condensed to a saturated liquid after transferring
heat to reboiler
Steam is pure water vapour

Perform an energy balance on the reboiler:


Equation 24
Where:
and

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is the molar flow of steam,


is the reboiler heat duty.

is the heat of vaporisation for 1 mole of steam

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CHEE 3004: Unit Operations Project Report 1

Convert the mass flow rate of steam to tonnes per second to reduce significant digits:

Therefore, the minimum required steam flow rate is 76.91 ton/s.

Appendix F Distillation Section Sensitivity Analyses

1.01
1
0.99
0.98
0.97
0.96
0.95
0.94
0.93
0.92
0.91
0.9

2250
2200
2150
2100
2050

Methanol Product Flow (kmol/s)

Methanol Product Purity (-)

Methanol Product Purity/Flow vs Reflux Ratio

2000
0

0.5

1.5

Reflux Ratio (-)

2.5
Methanol Product Purity
Methanol Product Flow

Figure 9 Graph of methanol product purity and flow against reflux ratio

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CHEE 3004: Unit Operations Project Report 1

0.98

2150

0.96

2100

0.94

2050

0.92
2000
0.9
1950

0.88

1900

0.86
0.84

Methanol Product Flow (kmol/s)

Methanol Product Purity (-)

Methanol Product Purity/Flow vs Number of Stages

1850
8

10

11

12

13

Number of Stages (-)

14

Methanol Product Purity


Methanol Product Flow

Figure 10 Graph of methanol product purity and flow against number of stages

0.98

2150

0.96

2100

0.94

2050

0.92

2000
0.9
1950

0.88

1900

0.86

0.84
0

Feed Stage (-)

10

Methanol Product Flow (kmol/s)

Methanol Product Purity (-)

Methanol Product Purity/Flow vs Feed Stage

1850
12
14
Methanol Product Purity
Methanol Product Flow

Figure 11 Graph of methanol product purity and flow against location of feed stage

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