CN4123R Final Year Design Project

Production of Formic Acid

Team Number: 15

Section Report
(1) Carbonylation Reaction

Submitted by: Goh Shu Ching

Matriculation No: A0161470M
Section Supervisor: Dr Sibudjing Kawi

This report is submitted in partial fulfilment

of the requirements for the Degree of Bachelor of Engineering

Department of Chemical and Biomolecular Engineering

National University of Singapore
2019/2020
Table of Contents
1. Executive Summary ............................................................................................................................. 4
2. Introduction ......................................................................................................................................... 4
3. Classification of Reactors .................................................................................................................... 5
3.1 Classification by the mode of operation ............................................................................................ 5
3.2 Classification by the phases present .................................................................................................. 5
3.3 Classification by process ................................................................................................................... 5
3.4 Classification by the Operating Pressure .......................................................................................... 5
3.5 Classification by the Operating Temperature.................................................................................... 6
3.6 Classification by the Operating Conditions ................................................................................. 6
3.7 Classification by the Geometrical Shape .......................................................................................... 6
3.8 Classification by the Orientation ....................................................................................................... 7
3.9 Classification by the Wall Thickness ................................................................................................ 7
3.10 Classification by Heating Method ................................................................................................... 7
3.11 Classification by the Fabricating Materials and Methods ............................................................... 7
3.12 Classification by the Location ......................................................................................................... 7
4. Reactor Design .................................................................................................................................... 8
4.1 General Design Overview ................................................................................................................. 8
4.2 Classification of the Reactor Process ................................................................................................ 8
4.3 Selection of Fluid Package ................................................................................................................ 9
4.4 Selection of the Reaction Kinetics and Catalyst ............................................................................... 9
4.5 Base Case Reactor Design............................................................................................................... 10
5. Optimization of Design Variables ..................................................................................................... 11
5.1 Objectives and Methodology .......................................................................................................... 11
5.2 Optimization Criteria and Restrictions ............................................................................................ 11
5.3 Sensitivity Analysis and Ranking of Design Variables .................................................................. 11
5.4 Optimization Iterations and Results ................................................................................................ 12
5.5 Results for Optimization ................................................................................................................. 16
6. Mechanical Design ............................................................................................................................ 17
6.1 Material Selection ........................................................................................................................... 17
6.2 Calculation of Design Pressure ....................................................................................................... 17
6.3 Calculation of Design Temperature ................................................................................................ 17
6.4 Determination of Design Stress....................................................................................................... 18

2
 6.5 Calculation of Wall Thickness of the Shell ..................................................................................... 18
6.6 Selection of Suitable End Closures ................................................................................................. 18
6.7 Calculations of Dimensions of the Reactor ..................................................................................... 19
6.8 Types of Other Equipment used in the Process............................................................................... 20
7. Safety Aspects ................................................................................................................................... 20
8. Summary of Reactor Specs and Energy Requirements ..................................................................... 21
9. Critique of Design ............................................................................................................................. 23
10. Highlights of Alternative Ideas ...................................................................................................... 24
10.1 Using Soluble Metal as an Alternative to Sodium Methoxide as Catalyst ................................... 24
11. References ...................................................................................................................................... 24

3
1. Executive Summary
A CSTR reactor is being designed for the carbonylation reaction as part of the production plant of Formic
Acid. The reactor is able to produce 11948 kg/h of Methyl Formate and achieved 10.57% conversion of
Methanol. Designing of CSTR is firstly done by classifying the reactors, followed by determination of
reaction kinetics, fluid packages, and catalyst for simulation. After listing a few assumptions, base case is
then simulated based on the parameters provided in the literature. Aspen HYSYS is used as the main
process simulation software.
Optimization of the base case is then executed to reduce the Total Annual Cost to the minimum. Design
Variables used in optimization includes CO Feed Flow Rate, Reactor Volume, Feed Temperature and
Pressure. Sensitivity analysis is first carried out on these variables to prioritize which variable to optimize
first. Final optimal conditions are to increase CO feed flow rate to 6900 kg/h, decrease volume of reactor
to 20𝑚3 , decrease feed pressure to 3500 kPa and temperature to 57°C.
Mechanical design of the reactor is then carried out where material of construction, design pressure and
temperature, maximum allowable stress and sizing of the reactor including ellipsoidal heads are evaluated.
Detailed costing is done for all units for optimized case assuming CEPCI of 397, resulting in Total Annual
Costs of $10.23 Million.

2. Introduction
Formic Acid (FA), a colorless liquid with distinctive pungent odor, is crucial in various industrial
applications. It is primarily used in textile dyeing, rubber production, intermediates in chemical and
pharmaceutical industries (Reutemann & Keiczka, 2000), also antibacterial agents in livestock feed
(Hietala et. Al, 2016). The demand for FA is rapidly increasing worldwide, as proven in production of
950,000 tonnes/year in 2014 (Hietala et. Al, 2016) as compared to 260,000 tonnes/year in 1987
(Reutemann & Keiczka, 2000).
The overall production of FA via Methyl Formate (MF) is described as the following reaction:

𝐶𝑂 + 𝐻2 𝑂 → 𝐻𝐶𝑂𝑂𝐻

However, there are two main reactions resulting in the overall reaction above. The first one being
carbonylation reaction of Methanol (MA) to produce MF. The reaction is given by:

𝐶𝐻3 𝑂𝐻 + 𝐶𝑂 ↔ 𝐻𝐶𝑂𝑂𝐶𝐻3
After separation, hydrolysis is carried out to produce FA and MA:

𝐻𝐶𝑂𝑂𝐶𝐻3 + 𝐻2 𝑂 ↔ 𝐻𝐶𝑂𝑂𝐻 + 𝐶𝐻3 𝑂𝐻

Carbonylation reaction will be focused in this section. To meet the overall production requirements of the
plant, at least 10.5% conversion of methanol is required. The product, MF will be sent downstream for
separation and recovery.

4
3. Classification of Reactors
Classification of reactors is conducted by considering the characteristics of the chemical process as
mentioned below, and these characteristics should be identified respectively for a proper design.
3.1 Classification by the mode of operation
There are 3 modes of operation available: Batch, Continuous, and Semi-batch/Continuous.
In batch reactors, all the chemical regents are added in the beginning and after the reaction is done, the
process is stopped, and the product is removed.
In continuous reactors, reactants are added, and product are also withdrawn continuously. Hence,
continuous reactors usually operate under the steady state conditions.
Semi-batch is defined as processes which does not tally with the above two major processes. The process
will be interrupted periodically for some purpose, for instance, regeneration of catalysts.
3.2 Classification by the phases present
In homogeneous reactors, reactions will take place in the same phase, usually in liquid or gas phase.
Homogeneous gas phase reactors are usually operated in tubular reactors, while homogeneous liquid phase
reactors are operated in plug-flow and stirred tank reactors.
In heterogeneous reactors, two or more phases exist, and the possible combinations of those phases
includes liquid-liquid, liquid-solid, gas-solid, liquid-gas-solid phase reactions.
3.3 Classification by process
The chemical reactors are also categorized according to their processes. The four basic types of reactors
classified according to their processes are stirred tank reactors, tubular reactors, packed bed and fluidized
bed reactors. Packed bed and fluidized bed reactors are less common in industrial applications.
3.4 Classification by the Operating Pressure
Reactors can be classified according to their operating pressures. They are internal pressure vessels,
external pressure vessels and atmospheric pressure vessels.

If 𝑃𝑖𝑛𝑛𝑒𝑟 > 𝑃𝑜𝑢𝑡𝑒𝑟 – Internal Pressure Vessel

Low Pressure Vessel: 0.1 ≤ 𝑃 < 1.6𝑀𝑃𝑎

Medium Pressure Vessel: 1.6 ≤ 𝑃 < 10𝑀𝑃𝑎

High Pressure Vessel: 10 ≤ 𝑃 < 100𝑀𝑃𝑎

Ultra-High-Pressure Vessel: 𝑃 ≥ 100𝑀𝑃𝑎

If 𝑃𝑖𝑛𝑛𝑒𝑟 = 𝑃𝑜𝑢𝑡𝑒𝑟 – Atmospheric Pressure Vessel

If 𝑃𝑖𝑛𝑛𝑒𝑟 < 𝑃𝑜𝑢𝑡𝑒𝑟 – External Pressure Vessel

5
3.5 Classification by the Operating Temperature
Reactors can be classified according to their operating temperatures. They are low temperature, normal
temperature, medium temperature and high temperature reactors.

Low Temperature Vessel: 𝑇 < −20°𝐶

Normal Temperature Vessel: −20°𝐶 ≤ 𝑇 < 150°𝐶

Medium Temperature Vessel: 150°𝐶 ≤ 𝑇 < 450°𝐶

High Temperature Vessel: 𝑇 ≥ 450°𝐶

3.6 Classification by the Operating Conditions
Reactors can be classified according to their operating conditions.
Open reactors: Containing non-volatile and non-hazardous fluids, reactions under atmospheric
temperature and pressure.
Closed reactors: Containing volatile or hazardous fluids. Reactions under or over atmospheric temperature
and pressure conditions.
3.7 Classification by the Geometrical Shape
Reactors can be classified according to their geometrical shapes. They are cylindrical, spherical and
rectangular reactors. Shapes of the heads are also being considered as well.
Cylindrical reactors: most widely used type of reactors in process plants. Less expensive than fabricating
spherical reactors but not as strong as spherical ones. Different types of rounded heads are fixed in order
to increase the vessel strength.
Spherical reactors: most ideal type of reactors but not used widely because of their expensiveness.
Generally used for the storage of gasses and very high-pressure industrial processes.
Rectangular reactors: not used in most cases because the strain is not evenly distributed. Using for few
industrial applications in storage and mixing.
Hemispherical Head: Hemisphere is the
ideal shape for a head. The height of the
head is half of the diameter. The thickness
is half the thickness of the wall.
Ellipsoidal Head: This shape is more
economical than the hemi spherical head.
The height of the head is also a half of the
diameter, but the thickness is equal to the
thickness of the wall.
Figure 1: Different types of heads Torispherical head: This is the most
economical shape in manufacturing vessel
6
heads even though the strain would not be quite as evenly distributed, but it would be close. The height of
the head is close to a quarter of the diameter.
3.8 Classification by the Orientation
Reactors can be classified according to their orientation. They are vertical, horizontal, sloped reactors.
Orientation is specially considered in cylindrical reactors.
Vertical: Generally used for gaseous reactions.
Horizontal: Used for heavy liquid, solid reactions.
Sloped: Used for special purposes.
3.9 Classification by the Wall Thickness
Reactors can be classified according to their wall thickness. They are thin-walled and thick-walled reactors.
Thin-walled reactors: if thickness of reactor is less than 1/10th of the radius.
Thick-walled reactors: if thickness of reactor is more than 1/10th of the radius.
3.10 Classification by Heating Method
Reactors can be classified according to their heating method. They are fired and unfired reactors.
Fired reactors: if the reactor partially or totally open to an external heat source such as industrial gas burner
Unfired reactors: if the reactor is not exposed to an external heat source.
3.11 Classification by the Fabricating Materials and Methods
Reactors can be classified according to their fabricating material. They are steel, cast iron, aluminium etc.
Depending on the design parameters, the suitable material for the fabrication should be selected wisely.
3.12 Classification by the Location
Reactors can be classified according to their location. They are inside the plant equipment and outside the
plant field equipment. For the inside plant equipment, ventilation should be considered and for the field
equipment, the wind effect should be considered.

7
4. Reactor Design
4.1 General Design Overview
The approach taken for the design of reactor are shown below.

Step 1: Literature Review

Selection of Reaction Kinetics Reaction Conditions for Base Case

Step 2: Initial Design

Fluid Package Selection Base Case Simulation

Step 3: Process Optimization

Optimizing Design Variables

Step 4: Detailed Design

Mechanical Design Safety Considerations

Figure 2: Process Diagram of Design Methodology

Firstly, literature review is carried out to review the current reaction kinetics of carbonylation before
selecting the most suitable kinetics for simulation, as well as the reaction conditions needed as primary
reference for initial reactor design. Next, preliminary design of the reactor is carried out by selecting the
most appropriate fluid package and modelling using Aspen HYSYS with suitable assumptions. After base
case is produced, optimization is then done with different design variables. Lastly, detailed reactor design
is carried out and its operability limits are studied.
4.2 Classification of the Reactor Process
Based on section 3, the classification of the reactor is done below:
Table 1: Classification of the Reactor

Mode of Operation Continuous

Phases Present Homogeneous
Process Stirred-Tank Reactor
Operating Pressure Internal Medium Pressure (3.5-4MPa)
Operating Temperature Normal Temperature (Vessel Temperature 87°𝐶)
Operating Conditions Closed
Geometrical Shape Cylindrical
Orientation Vertical
Wall thickness Thin-walled
Heating Method None
Fabricating Material Stainless Steel
Location Field Equipment
Carbonylation process will be carried out in a closed Continuous Stirred-Tank Reactor (CSTR) with
internal medium pressure and normal temperature. Since methanol is present in bulk, and CO gas exists

8
as a supercritical fluid in pressure of 3.5MPa and temperature of −145°𝐶, it is assumed that CO is
considered as a liquid phase in this reaction, hence phases present in the reactor will be homogenous liquid.
4.3 Selection of Fluid Package
Selecting the appropriate fluid package is crucial in process simulation to successfully describing the
physical properties or known as thermodynamic properties of the fluid. According to Carlson (1996),
when choosing a suitable thermodynamic model, factors such as the nature of the properties, compositions
of the mixture, pressure and temperature range, and the availability of parameters in the database need to
be considered. Novita et. Al (2015) and Rangaiah et. Al (2019) had simulated the process using
UNIQUAC with Hayden O’ Connell Equation of State (UNIQUAC-HOC) because activity coefficients
are being used to describe non-ideal system, in this case methanol-water interaction, and Henry’s Law
was used to account for dissolution of CO in liquid phase.
However, based on the decision trees provided by Carlson (1996), Peng-Robinson with Modified Huron-
Vidal mixing rules (PR-MHV2) is being used in the design of carbonylation reaction instead. This is due
to PRMHV2 can deal with reactions occurring at high pressures (>10 bar). Furthermore, Modified Huron-
Vidal mixing rules can predict non-ideality at high pressure from low-pressure (group-contribution)
activity coefficient models (Wong-Sandler, MHV2, PSRK). This mixing rule has been used successfully
for polar mixtures at high pressures, such as systems containing light gases, in this case polar mixtures
would be Methanol and water, whereby light gases would be CO gas.
4.4 Selection of the Reaction Kinetics and Catalyst
The carbonylation reaction kinetics is determined using the kinetic data in literature. Both Bai.at Al (1996)
and Chen et. Al (2004) had conducted experimental studies on carbonylation of methanol with two
different kinetics. Bai et. Al (1996) has suggested the following kinetics as below:
70748 92059
𝑟 = 1.414 × 109 𝑒 −( )
− 2.507 × 1012 𝑒 −( )
𝑅𝑇 [𝑐𝑎𝑡]𝐿 [𝐶𝐻3 𝑂𝐻]𝐿 [𝐶𝑂]𝐿 𝑅𝑇 [𝑐𝑎𝑡]𝐿 [𝐻𝐶𝑂𝑂𝐶𝐻3 ]𝐿

Where r= reaction rate in mol/(L.min), [𝑐𝑎𝑡]𝐿 = liquid concentration of catalyst in mol/L, [𝐶𝐻3 𝑂𝐻]𝐿 =
liquid concentration of methanol in mol/L, [𝐶𝑂]𝐿 = liquid concentration of CO in mol/L, [𝐻𝐶𝑂𝑂𝐶𝐻3 ]𝐿 =
liquid concentration of MF in mol/L.

The kinetics is valid for temperature range of 60 − 110°𝐶 and pressure range of 2 − 4𝑀𝑃𝑎. Sodium
methoxide is chosen as the catalyst which is soluble in methanol to involve in the liquid phase reaction.
Whereby Chen at. Al (2004) had suggested the following kinetics:
67630
𝑟 = 9.96 × 106 𝑒 −( )
𝑅𝑇 [𝑐𝑎𝑡]𝐿 [𝐶𝐻3 𝑂𝐻]𝐿 𝑝𝐶𝑂

Where 𝑝𝐶𝑂 = partial pressure of CO in MPa

The differences between the two kinetics is that Chen at. Al (2004) assumes irreversible reaction and used
partial pressure of CO in the expression of rate kinetics compared to Bai et. Al (1996). The concentration
of catalyst is not explicitly included in the rate equation and it is assumed that it has been accounted in
pre-exponential factor (Rangaiah et. Al, 2019).
9
In this design, reaction kinetics from Bai et. Al was chosen instead for the following reasons: (i) Reversible
reactions are included in the rate equation, CO is expressed in liquid phase which is more suitable as the
carbonylation has been carried out in high pressure, and the concentration of catalyst is expressed
explicitly in the rate equation. However, a few assumptions have been made in Table 2 for the kinetics of
Bai et. Al (1996) to be valid in this simulation:
Table 2: List of assumptions for the rate kinetics

1 CO gas is in liquid phase (supercritical fluid) due to high pressure and excess MA
2 Catalyst is fully dissolved in methanol and assumed to be 0.408mol/L, which is the highest concentration of the
catalyst used by Bai et. Al (1996)
3 Concentration of catalyst will be kept constant and it will be accounted in the reaction kinetics

4 Deactivation of catalyst is non-existent as it is fully dissolved in MA

5 Formation of Carbon Dioxide gas, which will poison the catalyst is not possible in liquid phase of Carbon Monoxide
6 Reaction is in steady state

4.5 Base Case Reactor Design

Base Case for reactor is designed referring to work done by Rangaiah et. Al (2019), and the parameters
for simulation is shown in Table 3 below. The simulation for base case is done using Aspen HYSYS.
Table 3. Base Case Parameters

Parameter Value Parameter Value

CO Feed Flow Rate 6500 kg/h Reactor Volume 100 𝑚3
CO Feed Pressure 4000 kPa Feed Temperature 65.0°C
Makeup MA Flow Rate 600 kg/h Reactor Temperature 95.59oC
Reactor Pressure 4000 kPa MA Flow Rate from Recycle 58134 kg/h

There is a missing parameter in Rangaiah et. Al (2019)’s simulation which is the volume of reactor, hence
it assumed that the volume is 100 𝑚3 with length to diameter ratio of 5. Furthermore, the reactor pressure
in Rangaiah et. Al (2019)’s simulation is at 40000kPa, which is out of the pressure range for reaction
kinetics to be valid. Therefore, reactor pressure is reduced to 4000kPa, which is the maximum pressure
desired for the reaction kinetics. Since the required production capacity of formic acid is higher than
Rangaiah et. Al (2019)’s work, CO feed flow rate is increased to 6500 kg/h, and desired conversion of
methanol is at 10.5%. With the base case parameters included, conversion of MA is at 11.15%, yield of
MF at 19.07% and MF flow rate is at 12582 kg/h.

10
5. Optimization of Design Variables
5.1 Objectives and Methodology
The objective of conducting optimization is to minimize total annual costs (TAC). TAC is calculated using
the formula below, assuming a payback period of 3 years.
𝑇𝑀𝐶
𝑇𝐴𝐶 = + 𝐶𝑂𝑀𝑑
3
Where
TMC= Total Module Cost (total grassroots cost in this case)

𝐶𝑂𝑀𝑑 = Annual Operating Costs excluding depreciation

Firstly, TAC of the base case will be calculated. After that, design variables and restrictions will be
determined. With the design variables available, sensitivity analysis will be carried out to determine the
level of the impact of the variables towards TAC. Optimization will then be carried out in descending
order starting from the variables with the heaviest influence towards TAC. This is done by varying the
variables by keeping others constant. The optimum value of the variable will be kept constant for
subsequent variables that will be changed accordingly. The process repeats until TAC does not decrease
by 1% for any variable in an iteration cycle. Cost estimation for the equipment is done using CAPCOST
program suggested by Turton et. Al (2013).
5.2 Optimization Criteria and Restrictions
The following variables will be adjusted: (1) CO Feed Flow Rate, (2) Reactor Volume, (3) Feed
Temperature, (4) Feed Pressure.
The restrictions and assumptions are listed below in Table 4 and 5 respectively.
Table 4: List of Restrictions

1 Conversion of Methanol cannot be lower than 10.5%

2 Height of Reactor <53m because of wind load and safety considerations
3 L/D =5 for process vessels of high pressure
4 Pressure of CO Feed cannot be lower than 3.5MPa because of supercritical fluid properties

Table 5: List of Assumptions

1 Cost is calculated at CEPCI of 397 (Turton et. Al, 2013)

2 There is no Waste Treatment and Operating Labor Costs involved

5.3 Sensitivity Analysis and Ranking of Design Variables

In conducting sensitivity analysis, design variables listed above is varied by ±5% of their base values to
estimate their effect on cost. The change in TAC is then compared and ranked accordingly. The results
are shown in Table 6 below.

11
 Table 6: Results of sensitivity analysis

Cost in Millions ($) %

Design Variable Rank
TMC 𝑪𝑶𝑴𝒅 TAC Change
Base Case 7.15 8.68 11.06
Feed Temperature 7.15 8.68 11.06 0.00 4
7.15 8.69 11.07 0.09
Feed Pressure 7.15 8.69 11.07 0.09 3
7.13 8.67 11.05 -0.15
Reactor Volume 7.34 8.68 11.13 0.57 2
6.97 8.68 11.00 -0.54
CO Feed Flow 7.15 8.92 11.30 2.17 1
Rate 7.14 8.44 10.82 -2.20

5.4 Optimization Iterations and Results

Following the results of the Sensitivity Analysis, the optimization was then carried out. A single design
variable was adjusted at a time with other variables fixed, and the effects on cost were investigated. The
order of which design variables were adjusted were (1) CO Feed Flow Rate (2) Reactor Volume, (3) Feed
Pressure, (4) Feed Temperature. The effects of each design variables on TAC was shown below.
Optimizing CO Feed Flow Rate

TMC against CO Flow Rate COMd against CO Flow Rate

9 9.2
COMd in millions ($)
TMC in millions ($)

9
7
8.8
5 8.6
8.4
3
8.2
1 8
7.8
-15500 6000 6500 7000 7500 5500 6000 6500 7000 7500
CO Feed Flow Rate (kg/h) CO Feed Flow Rate (kg/h)

(a) (b)

12
 TAC against CO Flow Rate Conversion of Methanol against
11.60 CO Flow Rate
TAC in millions ($)

11.40
15
11.20

Conversion (%)
11.00 10
10.80
10.60 5
10.40
10.20 0
5500 6000 6500 7000 7500 5500 6000 6500 7000 7500
CO Feed Flow Rate (kg/h) CO Feed Flow Rate (kg/h)

(c) (d)

Conversion of Methanol and TAC against CO Flow

Rate
11.60 14
11.40 12

TAC in millions ($)

11.20
Conversion (%)

10
11.00
8 TAC
10.80
6
10.60
10.40 4 Conversion of
2 Methanol
10.20
10.00 0
5500 6000 6500 7000 7500
CO Feed Flow Rate (kg/h)

(e)
Figure 3 (a), (b), (c), (d): Plots of costs against CO Flow Rate; (e) Plot of Conversion and TAC against CO Flow Rate

Based on Figure 3 (a), (b), (c) and (d), it was observed that TAC increases linearly with increase in CO
feed flow rate. This is due to the increase in the costs of raw materials, which will have greater impact on
𝐶𝑂𝑀𝑑 instead of TMC. However, TMC increases slightly with the increase in CO feed flow rate as well
because there are modifications of the specs being done on the compressor due to more CO feed flow
being present in the process stream. It is also seen that conversion of methanol increases significantly with
increase in CO flow rate as CO gas is the limiting reagent in carbonylation reaction. From Figure 3 (e), an
optimal point is found, which is CO feed flow rate of 6900 kg/h. Even though higher feed flow rate will
result in higher 𝐶𝑂𝑀𝑑 , it provides more freedom to reduce reactor volume which will cut down TMC to
a greater extent.
Optimizing Reactor Volume

13
 Conversion and TAC against Reactor Volume
11.9 11.60
11.8
11.40

TAC in millions ($)

11.7
Conversion (%) 11.6 11.20
11.5 11.00
11.4
11.3 10.80
11.2 10.60
11.1
11 10.40
10.9 10.20
0 20 40 60 80 100 120
Reactor Volume (m3)

Conversion TAC

Figure 4: Plot of Conversion and TAC against Reactor Volume

Reactor volume of base case (100𝑚3 ) is considered unrealistic because for L/D=5, vessel diameter of
2.94m and height of 14.71m is not feasible and the fabrication cost would be extremely high. Therefore,
to minimize TAC, there is a need to reduce the volume of to a more reasonable sizing. From Figure 4, it
can be deduced that TAC increases significantly with reactor volume as reactor is the most expensive
equipment calculated in TMC. However, conversion declines sharply with decrease in reactor volume as
the residence time is reduced, hence there is lesser time for the reaction to take place in the reactor. Since
the objective of optimization is reducing TAC while keeping conversion of methanol at 10.5%, the reactor
volume is decided to be at the lowest bound of optimization value, which is 20𝑚3 , with reactor diameter
of 1.72m and height of 8.60m.
Optimizing Feed Pressure

TMC against Feed Pressure COMd against Feed Pressure

5 8.98
COMd in millions ($)
TMC in millions ($)

4 8.97
3 8.96
2 8.95
1 8.94
0 8.93
3500 3600 3700 3800 3900 4000 4100 3500 3600 3700 3800 3900 4000 4100
Feed Pressure (kPa) Feed Pressure (kPa)

(a) (b)

14
 Conversion and TAC against Feed Pressure
11.001 10.29
11.0005 10.28

TAC in millions ($)

Conversion (%)

11
10.27
10.26
10.9995
10.25
10.999
10.24
10.9985 10.23
10.998 10.22
3400 3500 3600 3700 3800 3900 4000 4100
Feed Pressure (kPa)

Conversion TAC

(c)
Figure 5 (a), (b): Plot of costs against Feed Pressure; (c): Plot of Conversion and TAC against Feed Pressure

In this design, feed pressure is regarded as the pressure inside the CSTR reactor. From Figure 5 (c), TAC
generally decreases linearly with feed pressure. While 𝐶𝑂𝑀𝑑 decreases linearly with feed pressure due to
reduction in utilities to power up the pumps and compressors, TMC and conversion only decrease slightly
with decrease in feed pressure. Hence, it can be deduced that reactor pressure will not have high influence
towards the rate of reaction as the reactants present in liquid phase. Therefore, the optimum feed pressure
is determined at the lower bound of optimization which is at 3500kPa.
Optimizing Feed Temperature

Conversion and TAC against Feed Temperature

11.2 10.236
11
TAC in millions ($)

10.234
Conversion (%)

10.8
10.6 10.232
10.4
10.2 10.230
10
10.228
9.8
9.6 10.226
50 52 54 56 58 60 62 64 66
Feed Temperature (degC)

Conversion TAC

Figure 6: Plot of Conversion and TAC against Feed Temperature

15
Based on Figure 6, decrease in feed temperature will have significant decrease on conversion of methanol.
Such phenomenon is normal because reaction kinetics are dependent on temperature. However, the
increase in TAC is very minimal and the values are fluctuating. This is because although the increase in
TAC is due to increase in utilities to cool down hot stream even further when temperature decreases,
utilities in heating up makeup MA stream decreases because lesser heat required to heat up the stream to
the desired temperature. The optimum feed temperature will be at 57.0°C, resulting in reaction temperature
of 87.26°C in the vessel.

5.5 Results for Optimization

The summary of parameters for optimization are shown in Table 7.
Table 7: Summary of design variables and respective ranges of operation, plus chosen optimal solution

Design Variables Base Case Lower Bound Upper Bound Optimal Value
CO Feed Flow (kg/h) 6500 5500 7000 6900
Reactor Volume (𝑚3 ) 100.0 20.0 100.0 20.0
Feed Pressure (kPa) 4000 3500 4000 3500
Feed Temperature 65.0 50.0 65.0 57.0
(°C)

The simulation for optimized case is then conducted with optimized parameters as shown below in
Table 8.
Table 8: Cost of Process during Optimization

Cost in Millions ($)

Case
TMC AUC TAC
Base 7.15 8.68 11.06
Optimized 3.87 8.94 10.23

Overall, the optimization process is successful with reduction in TAC of approximately 7.50%.

16
6. Mechanical Design
6.1 Material Selection
Material selection in the mechanical design of the reactor is the most important factor which considers its
safety and economical aspects. If the material selected is not suitable enough to withstand in the process
operating temperature, operating pressure and etc., there will be a huge catastrophe while if the material
selected is far beyond the expected material requirement, the payback period of the plant will be very
higher. The below considerations are very important in the material selection. (1) Operating conditions
(temperature, pressure, corrosion resistance), (2) Ease of fabrication, (3) High service performance, (4)
Good market availability, (5) Design life.
For all equipment, material of construction (MOC) is Stainless Steel (SS). While Carbon Steel (CS) is
more commonly used in process industry due to its lower costs, it is not suitable to be used in synthesis of
MF as the chemical is not compatible to CS due to its corrosive nature (‘Chemical Compatibility’, 2012).
Therefore, the next cheapest alternative to CS will be SS. In addition, SS can withstand stronger resistance
to chemical corrosion caused by MF. Therefore, final MOC used for designing carbonylation process will
be SS304.
6.2 Calculation of Design Pressure
Design pressure is usually overdesigned relative to operating pressure for safety purposes. It shall be
designed for handling the most severe condition of pressure and temperature in normal operating situations.
The maximum pressure difference between the internal and external part of the vessel should be
considered while designing pressure vessels, especially CSTR reactor in this case.
According to Turton et. Al (2013), the formula for calculating design pressure for operating pressure
higher than 100psig will be:

𝑃𝑑 = 1.1𝑃𝑜

Where 𝑃𝑑 is the design pressure and 𝑃𝑜 is the operating pressure in kPa

Since 𝑃𝑜 = 3625kPa, Therefore, Design Pressure = 3987.5kPa.

6.3 Calculation of Design Temperature

Design Temperature is required for providing additional safety and loss prevention. According to ASME
Boiler and Pressure Vessel Code, the design temperature should not be lower than the mean temperature
at the outer surface of the metal part. Based on the calculation of design temperature suggested by Turton
et. Al (2013):

𝑇𝑑 = 𝑇𝑜,𝑚𝑎𝑥 + 25°𝐶

Where 𝑇𝑑 is the design temperature in °𝐶, 𝑇𝑜,𝑚𝑎𝑥 is the maximum operating temperature of the vessel.

Maximum temperature inside the vessel: 86.0°C

For safety reasons, additional 25°C is added, hence design temperature = 111.0°C

17
6.4 Determination of Design Stress
Design Stress is defined as the maximum allowable stress at the most severe operating conditions. Since
maximum allowable stress will change with temperature, hence design stress is determined based on
design temperature.
Maximum allowable stress for stainless steel SS304 is shown in tables below, based on ASME Boiler and
Pressure Vessel Code (2017):
Table 9: Material Data for Stainless Steel SS304

Nominal Spec Type/Grade Min. Tensile Strength Min. Yield Max. Temperature
Composition No. (MPa) Strength Limit
(MPa) (°𝐶)
18%Cr-8%Ni SA-240 304 515 205 816

Table 10: Maximum Allowable Stress Values for Stainless Steel SS304 at Different Temperatures

65°C (MPa) 100°C (MPa) 125°C (MPa) 150°C (MPa) 200°C (MPa) 250°C (MPa)
138 137 134 130 126 122

Since design temperature of the vessel lies in between the range of 100°C to 125°C, hence design stress
is determined to be 134MPa.
6.5 Calculation of Wall Thickness of the Shell
According to ASME Boiler and Pressure Vessel Code (2017), the formula for calculating wall thickness
is shown below:
𝑃𝑑 𝐷
𝑡=
2𝑆𝐸 − 0.2𝑃𝑑

Where 𝑡 is the theoretical thickness of the shell, 𝑃𝑑 is the design pressure, D is the internal diameter of
the reactor, S is the maximum allowable stress and E is the joint efficiency (which is assumed to be 1 in
this case)

With the information given from the previous sections: 𝑃𝑑 = 3987.5𝑘𝑃𝑎; D=2m; S=138MPa; and E=1
Design Wall Thickness of the shell = 2.9cm
6.6 Selection of Suitable End Closures
Considering the classification of reactors by geometrical shape, ellipsoidal head is used for the designing
of the top and bottom heads of the reactor, which is shown in Figure 7 below.

18
 Figure 7: Overview Design of Ellipsoidal Head

Ellipsoidal head is chosen because: (1) the design pressure is more than 15 bars, (2) cheaper alternative of
hemispherical heads, (3) having same thickness as the reactor wall hence it is relatively easy to be
fabricated.
Therefore, design thickness of the head = 2.9cm.
6.7 Calculations of Dimensions of the Reactor
According to Turton et. Al (2013), classification of the optimum vessel length to diameter ratio according
to the pressure is mentioned below. The design pressure for the CSTR reactor is 3625kPa (525.76 psig)
Therefore, the most suitable L/D Ratio for the reactor = 5.
Table 11: Length to Diameter Ratio (Turton et. Al, 2013)

Pressure (psig) L/D Ratio

0-250 3
250-500 4
>500 5

The volume of the reactor is evaluated according to ASME Boiler and Pressure Vessel Code (2017), by
considering the diagram shown in Figure 8.
2ℎ
The effective length of the reactor, L should be calculated as 𝑙 + .
3

𝐷
Since the ratio of diameter to height of the head is 2:1, 𝐿 = 𝑙 + 3 .

Total volume of the vessel is then calculated as:

𝜋𝐷2 𝐿 5𝜋𝐷3
𝑉= =
4 4
Where V is the volume of the vessel, D is the diameter of vessel, L is the effective
Figure 8: Geometry of length of the vessel.
the Vessel (Turton et. Al,
2013) Given D = 1.72m, 𝑉 = 20𝑚3, 𝑙 = 8.03𝑚.

19
6.8 Types of Other Equipment used in the Process
Compressor
Compressors are widely applied in transporting gases with compression ratios higher than 2. Based on the
guidelines for the selection of compressors as suggested by Seider at. Al (2009), centrifugal compressors
are being selected as it can be easily controlled, able to handle large flow rate up to 150,000 actual cubic
metres per minute (ACFM) and pressure up to 15,000psig, even though it is more expensive and less
efficient (70-75%). It can handle high pressure and large flowrate of CO gas very well.
Heat Exchanger
Heat exchanger is being used for heating or cooling process streams to a desired temperature. In this
design, double-pipe heat exchanger will be selected for this design because it is the most common heat
exchanger in market and heat exchange areas are lesser than 200𝑓𝑡 2 throughout the carbonylation process.
Pump
Pump are utilized vastly in chemical processing plants to transport liquid reactants or products through
piping systems. Pump selection is done using the guidelines suggested by Seider et. Al (2009). Since the
operating requirements for all the pumps fall in the recommended ranges: (1) Volumetric flow rate of less
than 5000gpm; (2) Head between 15.24m to 975.5m; (3) Kinematic viscosity less than 100cs; (4)
Available NPSH greater than 1.52m, radial centrifugal pump will be selected in this design as it is
relatively inexpensive to install and maintain, widely available in market, and it operates at high speed
hence can be driven directly with electric motor (Seider et. Al, 2009).

7. Safety Aspects
In design of process plants, safety and loss prevention should be taken into consideration to avoid
catastrophes or accidents. Reactor is known to prone to fail if it is not well-designed. Therefore, safety
aspects of reactor should be prioritized favorably. The recommended testing methodology is Non-
destructive Testing (NDT) to ensure the reactors are operating normally and how often the equipment
should be replaced (“Overview of Non-destructive Testing”, 2020). Some of the conventional NDT
methods include:
Visual Inspection – Inspection of a piece of equipment with naked eyes.
Acoustic Emission Testing – Detects the generation of waves produced by sudden stress redistribution of
equipment due to change in reaction conditions. Particularly useful for inspecting abnormalities present
in the reactor.
Magnetic Particle Testing – Detects flaws on the surface and subsurface of a metallic equipment by
running AC/DC current. If leaks or flaws are detected, ferrous ion particles will interrupt the current,
generating electromagnetic field at the site of damage. This is relatively simple to implement especially
reactors made of metal.

20
Radiography Testing – Evaluate flaws on the equipment using X-ray or gamma rays. It is often used on
inspecting pressure vessels such as reactor, and it is an effective tool without much preparation work
required.
Considering one of the raw materials, CO gas and the product generated, MF are hazardous, Hazard and
Operability Analysis (HAZOP) should be conducted for safety and loss prevention. By doing HAZOP
analysis, permissible levels of inhalation of raw materials and products can be evaluated. Furthermore, the
Material Safety Data Sheets (MSDS) of all raw materials and products and NFPA 704: Standard System
for the Identification of the Hazards of Materials for Emergency Response by National Fire Protection
Association should studied thoroughly and factory workers should be briefed for safety precautions and
basic first-aid skills before plant operation.
Besides HAZOP analysis, Layer of
Protection Analysis (LOPA) should be
conducted as well and it can be seen in
Figure 9. LOPA is a simplified, yet
comprehensive risk assessment
developed by American Institute of
Chemical Engineers (AIChE) which is
widely used in process industry. By
having the seven layers of protection on
the reactor, the safety aspects of the
reactor can be enhanced further.
Figure 9: Layers of Protection Analysis (AIChE, 2001)

8. Summary of Reactor Specs and Energy Requirements

The final parameters and energy requirements are shown in Table 12 and 13 below.
Table 12: Final Reactor Specifications

Parameter Value Parameter Value

CO Feed Flow Rate (kg/h) 6900 kg/h Reactor Height (m) 8.60 m
CO Feed Pressure (kPa) 3500 kPa Feed Temperature (°C) 57.0°C
Makeup MA Flow Rate (kg/h) 600 kg/h Reactor Temperature (°C) 87.26°C
Reactor Pressure (kPa) 3500 kPa MA Flow Rate from Recycle (kg/h) 58134 kg/h
Reactor Diameter (m) 1.72 m TMC ($) 3,870,000

Table 13: Energy Requirements

Equipment No. Equipment Name Utility Type Duty (kJ/h) AUC ($)
P-1 Feed Pump Electricity 5.472 × 103 77,700
P-8 Feed Pump Electricity 554.0 × 103 765
K-1 Compressor Electricity 723.6 × 103 101,200
K-2 Compressor Electricity 590.4 × 103 82,300

21
 E-1 Cooler Cooling Water at 30°C 5.960 × 107 1,760
E-2 Cooler Cooling Water at 30°C 4.260 × 107 1,250
E-3 Heater Low Pressure Steam (5 barg, 160°C) 4.450 × 107 2,250
E-4 Cooler Cooling Water at 30°C 5.490 × 109 16,200
Subtotal 283,000

Total Module Costs of the Auxiliary Equipment are summarized in the table below.
Table 14: Costs of Auxiliary Equipment

Equipment No. Equipment Name Capacity Material TMC ($)

P-1 Feed Pump 1.137 kW SS304 24,100
P-8 Feed Pump 115.8 kW SS304 140,000
K-1 Compressor 181 kW SS304 1,220,000
K-2 Compressor 147 kW SS304 1,220,000
E-1 Cooler 156.8 kW SS304 19,200
E-2 Cooler 116.2 kW SS304 19,300
E-3 Heater 12.36 kW SS304 19,300
E-4 Cooler 1526 kW SS304 19,300
Subtotal 2,804,000

Process Flow Diagram and Stream Data are shown in Figure 10 and Table 15.

Figure 10: Process Flow Diagram for Design of Carbonylation Reactor

Table 15: Stream Data

Stream CO Feed MA Feed P1_1 P1_2 P1_3 P1_4

Temperature (°C) 30 30 120.4898 40 113.2983 57
Pressure (kPa) 1000 120 2034.474 2000 3534.474 3500
Molar Flow (kgmole/h) 246.3369 18.7472 246.3369 246.3369 246.3369 246.3369
Mass Flow (kg/h) 6900 600 6900 6900 6900 6900
Liquid Volume Flow (𝑚3 /h) 13.19326 0.755047 13.19326 13.19326 13.19326 13.19326

22
 Mass Fraction
CO 0.995 0.000 0.995 0.995 0.995 0.995
FA 0.000 0.000 0.000 0.000 0.000 0.000
MA 0.000 0.998 0.000 0.000 0.000 0.000
MF 0.000 0.000 0.000 0.000 0.000 0.000
Nitrogen 0.005 0.000 0.005 0.005 0.005 0.005
Water 0.000 0.002 0.000 0.000 0.000 0.000

Stream P1_5 P1_6 P1_7 P1_9 P1_10 P1_11

Temperature (°C) 31.20625 57 87.26427 85.61 87.11146 57
Pressure (kPa) 3534.474 3500 3500 231.9 3534.47 3500
Molar Flow (kgmole/h) 18.7472 18.7472 1914.787 1843.471 1843.471 1843.471
Mass Flow (kg/h) 600 600 66378.7 58878.7 58878.7 58878.7
Liquid Volume Flow (𝑚3 /h) 0.755047 0.755047 81.72379 73.93505 73.93505 73.93505
Mass Fraction
CO 0.000 0.000 0.022 0.000 0.000 0.000
FA 0.000 0.000 0.000 0.000 0.000 0.000
MA 0.998 0.998 0.791 0.987 0.987 0.987
MF 0.000 0.000 0.180 0.005 0.005 0.005
Nitrogen 0.000 0.000 0.001 0.000 0.000 0.000
Water 0.002 0.002 0.007 0.007 0.007 0.007

9. Critique of Design
The proposed design was limited in accuracy due to the list of assumptions listed in Table 2 of Section 4.
Assuming constant concentration of catalyst is a great concern because according to the reaction kinetics
proposed by Bai et. Al (1996), concentration of catalyst plays an important part in the overall rate of
reaction. This would result in inaccuracies of the simulation results. However, there are not much literature
on activation and deactivation mechanism of sodium methoxide catalyst being published, hence
experimental studies can be conducted on this area of interest. Besides that, assuming the plant is operating
at steady state compromises the accuracy of reactor simulation because in actual industrial processes, there
are startup and shutdown procedures involved and these operations are not in steady state. Furthermore,
there are limitations in HYSYS whereby vapor fraction of CO gas might not be accurate due to being
supercritical fluid.
There are several improvements that can be done to improve the accuracy of the design:
1. Design of the Impellers in CSTR
Impellers is a type of agitator mounted on the top of CSTR and it is driven by electrical motor. There are
a few common impeller types available such as Straight Blade, Pitched Blade, Turbine, Helical Ribbon
and many more. It is known that characteristics of impellers, such are its sizing and rotational speed would

23
affect the extent of mixing inside the reactor. Sophisticated analysis of mixing can be done using
Computational Fluid Dynamics (CFD) simulation.
2. Replace CSTR with Bubbling Reactor
Carbonylation is a heterogeneous catalytic reaction, therefore using a bubble column reactor for
carbonylation simulation is more accurate as compared to CSTR. Even though there are various aspects
such as sphericity of the catalyst, minimum fluidization velocities, minimum fluidized height need to be
calculated and considered, plus its economical costs to install a reactor with the given specifications.
Modelling of bubble column reactor is possible with CFD using ANSYS Fluent.
3. Using Multi-Objective Differential Evolution (I-Mode) to Optimize Design Variables
I-Mode is a program designed by Sharma et. Al (2017) optimize multiple design variables based on
differential evolution of multiple objectives, hence optimization can be carried out more effectively and
efficiently. However, it is limited for using with Aspen Plus simulator only.

10. Highlights of Alternative Ideas

10.1 Using Soluble Metal as an Alternative to Sodium Methoxide as Catalyst
Sodium Methoxide, or any alkali metal alkoxide are the most common catalysts used in carbonylation
processes because it has high conversions of CO and MF selectivity. However, according to He et. Al
(2008), using metal alkoxides are not environmentally friendly and potentially causes problem such as
generation of waste byproducts and corrosion. Therefore, soluble metal nanocluster catalysts are being
introduced as the alternative to replace sodium methoxide as catalyst. In He et. Al (2008)’s work, catalytic
performances of different soluble metal nanocluster crystals are being studied, with copper being the most
effective metal with CO conversion of 30%. Further studies on the properties of such soluble metal
nanocluster crystals are required because the conversion of CO is still not on par with Sodium Methoxide,
and such nanocrystals are still not commercially available in the market, hence the cost of purchasing will
be relatively higher.

11. References
American Society of Mechanical Engineers. (2017). ASME boiler & pressure vessel code. New York,
NY.
Bai, L., Zhao, Y., Hu, Y., Zhong, B., & Peng, S. (1996). Kinetics of the carbonylation of methanol in a
mechanically agitated reactor. Fuel And Energy Abstracts, 38(2), 120. doi: 10.1016/s0140-
6701(97)84352-4
Chemical Compatibility. (2012). Retrieved 22 March 2020, from
http://www.fnwvalve.com/FNWValve/assets/images/PDFs/FNW/tech_ChemChart.pdf
Chen, L., Zhang, J., Ning, P., Chen, Y., & Wu, W. (2004). Kinetics of Methanol Carbonylation to
Methyl Formate Catalyzed by Sodium Methoxide. Journal Of Natural Gas Chemistry, 13(4). Retrieved
from

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https://www.researchgate.net/publication/266457383_Kinetics_of_Methanol_Carbonylation_to_Methyl
_Formate_Catalyzed_by_Sodium_Methoxide
Chua, W., da Cunha, S., Rangaiah, G., & Hidajat, K. (2019). Design and optimization of Kemira-
Leonard process for formic acid production. Chemical Engineering Science: X, 2, 100021. doi:
10.1016/j.cesx.2019.100021
da Cunha, S., Rangaiah, G., & Hidajat, K. (2018). Design, Optimization, and Retrofit of the Formic
Acid Process I: Base Case Design and Dividing-Wall Column Retrofit. Industrial & Engineering
Chemistry Research, 57(29), 9554-9570. doi: 10.1021/acs.iecr.8b00883
He, L., Liu, H., Xiao, C., & Kou, Y. (2008). Liquid-phase synthesis of methyl formate via
heterogeneous carbonylation of methanol over a soluble copper nanocluster catalyst. Green
Chemistry, 10(6), 619. doi: 10.1039/b804459g
Hietala, J., Vuori, A., Johnsson, P., Pollari, I., Reutemann, W., & Kieczka, H. (2016). Formic
Acid. Ullmann's Encyclopedia Of Industrial Chemistry, 1-22. doi: 10.1002/14356007.a12_013.pub3
Overview of Nondestructive Testing (NDT). (2020). Retrieved 23 March 2020, from
https://inspectioneering.com/tag/nondestructive+testing
Reutemann, W., & Kieczka, H. (2000). Formic Acid. Ullmann's Encyclopedia Of Industrial Chemistry.
doi: 10.1002/14356007.a12_013
Seider, W., Lewin, D., Seader, J., Widagdo, S., Gani, R., & Ng, K. (2009). Product and process design
principles.
Sharma, S., Rangaiah, G., & Maréchal, F. (2017). Integrated Multi-Objective Differential Evolution and
its Application to Amine Absorption Process for Natural Gas Sweetening. Differential Evolution In
Chemical Engineering, 128-155. doi: 10.1142/9789813207523_0005
Turton, R., Bailie, R., Whiting, W., Shaeiwitz, J., & Bhattacharyya, D. (2013). Analysis, Synthesis, and
Design of Chemical Processes, Fourth Edition.
Willey, R. (2014). Layer of Protection Analysis. Procedia Engineering, 84, 12-22. doi:
10.1016/j.proeng.2014.10.405

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