Complex Engineering Activity Process

Modeling and Simulation

“Production of Methanol from Syngas”

Submitted
to:
Dr.A.N.Tabish
Submitted
by:

Ameer Hamza 2021-CH-221

Shamir Zahoor 2021-CH-265
Sameer Arshad 2021-CH-267
Fahad Hussain 2021-CH-283

DDepartment of Chemical, Polymer, and Composite

Materials Engineering

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1: Production of methanol from syngas.................................................................................................................................3
INTRODUCTION...................................................................................................................................................................... 3
2:DESIGN PROBLEM / PROJECT DEFINITION:..........................................................................................................................3
2.1: LITERATURE REVIEW:.......................................................................................................................................................3
2.1.1: Manufacturing Routs:...................................................................................................................................................3
Equations:...............................................................................................................................................................................3
Partial Oxidation:....................................................................................................................................................................3
Equations:...............................................................................................................................................................................3
Biomass Gasification:..............................................................................................................................................................4
Equations:...............................................................................................................................................................................4
Equations:...............................................................................................................................................................................4
2.2:Thermo-physical property information:...........................................................................................................................4
2.3:Health and Safety data.....................................................................................................................................................5
2.4:Reaction kinetics:..............................................................................................................................................................7
2.5:PROCESS CREATION / FLOWSHEET DEVELOPMENT..........................................................................................................8
Input/output Diagram:........................................................................................................................................................... 8
Operation diagram:................................................................................................................................................................ 9
Alternative Process:................................................................................................................................................................9
2.6:Process flow Diagram:....................................................................................................................................................10
ALTERNATIVE PROCESS DIAGRAM:.......................................................................................................................................11
3:METHODOLOGY / PROCESS DESCRIPTION.......................................................................................................................12
4:DESIGN OF REACTOR.........................................................................................................................................................16
CO+2H2⇌ CH3OH.................................................................................................................................................................16
CO2+3H2⇌ CH3OH+H2O......................................................................................................................................................16
CO+H2O⇌ CO2+H2...............................................................................................................................................................16
4.1: DESIGN OF HEAT EXCHANGER.......................................................................................................................................16
4.2: DESIGN OF MASS TRANSFER EQUIPMENT “RadFrac”....................................................................................................16
4.3: DESIGN OF Distillation Column......................................................................................................................................17
4.4: RadFrac Design Results..................................................................................................................................................19

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 PHASE-I
1: Production of methanol from syngas
PHASE-II
INTRODUCTION

2:DESIGN PROBLEM / PROJECT DEFINITION:

Methanol needs to be synthesized from 1000kmol/hr syngas, consisting of 6%CO,27%CO2 and
67%H2at 60oC and 1atm pressure. An isothermal equilibrium based CSTR of size 4.5m3 will be
used which will operate at 45 bar and 280oC.
A simple mixer unit will be used for recycling purpose.
For distillation of methanol, use DSTWU for shortcut calculation followed by "RADFRAC" column for
more rigorous calculation. We possess one isentropic compressor with 90% isentropic and 80%
mechanical efficiencies at our disposal. We also have a second isentropic compressor (using
ASME method) with 70% isentropic and 80% mechanical efficiencies that can be used for our
work. We have two valves which work as "adiabatic flash for specified outlet
Pressure”. We also have three simple exchangers which can be used as a heater or cooler, as and when
the need arises.

2.1: LITERATURE REVIEW:

A brief literature review about process is:

2.1.1: Manufacturing Routs:

Steam Reforming:
Process: Steam reforming is the most common method for producing syngas, which is the precursor for
methanol production. In this process, natural gas (primarily methane) reacts with steam at high
temperatures (700-1000°C) and moderate pressures (20-30 bar) in the presence of a catalyst
(usually nickel-based) to produce hydrogen and carbon monoxide.
Equations:
CH4 + H2O → CO + 3H2 CO2 + CH4 → 2CO + 2H2
Catalysis: Catalysts such as nickel or nickel oxide supported on alumina or other materials facilitate the
reaction by providing active sites for the dissociation of methane and water molecules.
Purification: The resulting syngas is then purified to remove impurities such as sulfur compounds and
carbon dioxide before undergoing methanol synthesis.
Partial Oxidation:
Process: Partial oxidation involves the reaction of a hydrocarbon feedstock (such as natural gas or liquid
hydrocarbons) with a limited amount of oxygen or air at high temperatures (800-1500°C) in a
controlled environment to produce syngas.
Equations:
CH4 + 0.5O2 → CO + 2H2 CnHm + 0.5O2 →nCO + (m/2)H2
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Advantages: Partial oxidation can be advantageous in situations where steam or water availability is
limited, and it can also produce a syngas with a higher hydrogen- to-carbon monoxide ratio
compared to steam reforming.
Disadvantages: However, this process requires careful control of oxygen levels to prevent complete
combustion, which would result in the formation of carbon dioxide rather than carbon monoxide.
Biomass Gasification:
Process: Biomass gasification involves the thermal decomposition of biomass materials (such as wood,
agricultural residues, or municipal solid waste) in a controlled environment (typically with limited
oxygen or steam) to produce syngas.
Equations:
CnHmOp → nCO + (m/2)H2 CO2 + C →2CO
Advantages: Biomass gasification is a renewable and potentially carbon-neutral method for producing
syngas, as the carbon dioxide released during combustion is offset by the carbon dioxide absorbed
during biomass growth.
Disadvantages: However, biomass gasification can be more complex and costly compared to fossil fuel-
based methods, and it requires careful management of feedstock composition and gasification
conditions.

Coal Gasification:

Process: Coal gasification involves the reaction of coal with oxygen or steam at high temperatures (700-
1500°C) in a controlled environment to produce syngas.
Equations:
C + H2O → CO + H2 C + O2 → CO2
Advantages: Coal gasification can utilize abundant coal reserves for syngas production, potentially
providing a more diverse feedstock compared to natural gas or biomass.
Disadvantages: However, coal gasification can produce significant amounts of carbon dioxide and other
pollutants, making it less environmentally friendly compared to other methods. Additionally, coal
gasification plants are generally more complex and expensive to build and operate.

2.2:Thermo-physical property information:

The production of methanol from synthesis gas (syngas) involves several important thermophysical
properties. Syngas, typically a mixture of carbon monoxide (CO) and hydrogen (H2), is converted
into methanol through a catalytic process known as methanol synthesis. Here are some key thermo
physical properties relevant to this process:
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 1. Heat of Reaction: The heat of reaction, or enthalpy change (∆H), of the methanol
synthesis reaction is crucial for understanding the energy requirements of the process. It describes
the amount of heat released or absorbed during the conversion of CO and H2 into methanol.
2. Reaction Equilibrium Constant: The equilibrium constant (K) for the methanol synthesis
reaction determines the extent to which the reaction proceeds under given conditions of temperature
and pressure. It's essential for optimizing reactor conditions to achieve maximum methanol yield.
3. Heat Capacity: The heat capacities of reactants, intermediates, and products play a
significant role in determining the temperature profile within the reactor. They influence the energy
balance of the process and help in designing efficient heat exchange systems.

Density and Viscosity: Density and viscosity of the reactants, intermediates, and products affect the
fluid dynamics within the reactor and the associated mass transfer processes. These properties
impact reactor design and performance.
4. Thermal Conductivity: Thermal conductivity is important for heat transfer within the
reactor and associated equipment. Understanding the thermal conductivity of the reaction mixture
and catalyst bed helps in optimizing reactor design for efficient heat management.
5. Vapor Pressure: Vapor pressure of methanol is important for separation and purification
processes, particularly in distillation or vapor-phase separation units. It determines the conditions
under which methanol can be recovered from the reaction mixture.
6. Solubility: Solubility of methanol in water and other solvents affects downstream
separation processes, especially when methanol purification involves liquid-liquid extraction or other
solvent-based techniques.
7. Reaction Kinetics: While not strictly a thermophysical property, understanding the
kinetics of the methanol synthesis reaction is crucial for reactor design and operation. Kinetic
parameters such as rate constants and activation energies govern the rate of methanol formation and
help optimize catalyst performance.

These properties, along with others, are essential for the design, optimization, and operation of methanol
production plants from syngas. They provide insights into the behavior of the system under various
conditions and aid in achieving high efficiency and productivity.

2.3:Health and Safety data

Health and safety considerations are paramount in the production of methanol from syngas due to the
potentially hazardous nature of the materials and processes involved. Here are some key health and

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 safety data points relevant to methanol production: 1.Toxicity: Methanol is toxic to humans and
can cause severe health effects, including blindness or death, if ingested, inhaled, or absorbed
through the skin. Workers must be trained in handling procedures, including the use of personal
protective equipment (PPE) such as gloves, goggles, and respiratory protection.

1.Flammability: Methanol is highly flammable and can form explosive vapor-air mixtures. Proper
measures must be in place to control ignition sources and prevent the accumulation of
flammable vapors. Facilities should have adequate ventilation and explosion-proof equipment
where necessary.
2.Exposure Limits: Regulatory agencies such as OSHA (Occupational Safety and Health Administration)
and ACGIH (American Conference of Governmental Industrial Hygienists) have established
permissible exposure limits (PELs) and threshold limit values (TLVs) for methanol exposure in the
workplace. Monitoring of air concentrations is essential to ensure compliance with these limits.
3.Emergency Response: Facilities must have comprehensive emergency response plans in place, including
procedures for spills, leaks, fires, and exposure incidents. Employees should be trained in emergency
response protocols, and appropriate firefighting equipment and spill containment materials should be
readily available.
4.Corrosivity: Methanol can be corrosive to certain metals and materials. Compatibility assessments
should be conducted to ensure that equipment and storage vessels are constructed from suitable
materials that can withstand exposure to methanol and its byproducts.
5.Catalyst Handling: Catalysts used in methanol synthesis processes may pose additional health and
safety risks due to their composition and handling requirements. Workers should be trained in safe
handling practices and provided with appropriate PPE to minimize exposure.
6.Pressure Hazards: Methanol synthesis reactors operate at high pressures to promote the desired
chemical reactions. Proper design, maintenance, and inspection of pressure vessels and piping
systems are essential to prevent leaks, ruptures, and other pressure-related incidents.
7.Hydrogen Sulfide (H2S): Syngas derived from certain feedstocks may contain hydrogen sulfide, a highly
toxic and flammable gas. Proper precautions, such as H2S monitoring, ventilation, and the use of
scavengers, may be necessary to mitigate the risks associated with H2S exposure.
8.Waste Management: Proper disposal of waste streams, including spent catalysts and byproducts, is
essential to prevent environmental contamination and ensure compliance with regulations.

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Worker Training: Comprehensive training programs should be implemented to educate
workers about the hazards associated with methanol production and the proper procedures for
handling, storage, and emergency response.
By addressing these health and safety considerations proactively, methanol production facilities can
minimize risks to workers, the surrounding community, and the environment. Regular monitoring,
maintenance, and ongoing safety training are essential components of a robust safety management
system.
2.4:Reaction kinetics:
The reaction kinetics for the production of methanol from syngas involve understanding the rate at
which the chemical reactions occur and the factors that influence this rate.
The reactor will be governed by the following equilibrium reaction kinetics:

CO+2H2⇌ CH3OH CO2+3H2⇌ CH3OH+H2O

and supported by water-gas shift reaction
CO+H2O⇌ CO2+H2
The equilibrium constants of the above reactions are given by the following:
lnk1,eq = -29.03+(11820)/(T)

lnk2,eq = -24.36+(7052)/(T)

lnk3,eq = -4.67+(477)/(T)

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 2.5:PROCESS CREATION / FLOWSHEET DEVELOPMENT

Input/output Diagram:

1.1.1

Function diagram:

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 Operation diagram:

Alternative Process:

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2.6:Process flow Diagram:

Hydrogen

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ALTERNATIVE PROCESS DIAGRAM:

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 PHASE-III

3:METHODOLOGY / PROCESS DESCRIPTION

Brief description how simulation proceed;

3.1:Thermophysical method used for the simulation

The method used is PENG-ROB

3.2:Brief description of the process flowsheet?

FEED

CO-CO2
C2

H3
H3-OUT C2-OUT
HYDROGEN
SEP-2
VAP

DSTWU
C1 D-VAP
MIX CSTR V-1 H2 SEP-1
H1
C1-OUT H1-OUT MIX-OUT CSTR-OUT V1-OUT H2-OUT LIQ
Errors

D-LIQ

Our Feed is at low pressure level so we passed the feed through compressor(C-1) that
increased the pressure but also temperature was increases than required temperature. For this
we put a cooler(H-1) to decrease the temperature than the feed is put into the CSTR. Then
again temperature is above the required temperature so we passed it through another cooler(H-
2) and then passed the product through separation column(SEP-1) to separate the liquid
methanol and vapors. Liquid is passed through DSTWU to separate the vapor and liquid phase.
The product moved out from separator is totally vapor but at low pressure. So it is compressed
by compressor(C-2) that also increased the temperature for which third cooler(H-3) is used to
maintain the temperature. Then again the product is passed through another separator(sep-2)
from where carbon monoxide and carbon dioxide is removed and hydrogen is recycled. A
random error also occurred in the reactor but it does not effect the conversion or product
composition. So, it can be ignored.

3.3: Describe how individual units of the process flowsheet are modeled in Aspen Plus
(e.g. what appropriate Aspen Plus block was used to simulate the fixed bed catalytic
reactor etc.)
3.4: Provide all input conditions used for the process simulation including inlet
streams properties and unit operations input conditions etc.
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Following below template to summarize the information of point 3 & 4.

Sr. # Unit in the flowsheet Block in the simulation Input specifications of the
diagram block
1 Pressure Changer Compressor(C-1) Type: Isentropic
Discharge Pressure: 45 bar
Isentropic Efficiency: 90%
Mechanical Efficiency: 80%

2 Heat Exchanger Heater(H-1) Temperature: 280 C

Pressure: 45 bar
Phase: vapor-Liquid

3 Mixer Mixer(Mix) Max Iteration: 30

Error Tolerance: 0.0001

4 Reactor CSTR Temperature: 280 C

Pressure: 45 bar
Phase: vapor only
Volume: 4.5 cum
5 Heat Exchanger Heater(H-2) Temperature: 60 C
Pressure: 0 bar
Phase: vapor-Liquid

Sr. # Unit in the flowsheet Block in the simulation Input specifications of the
diagram block
6 Separator Sep(Sep-1) Outlet Stream: LIQ
Sub-Stream: Mixed
CH3OH Split Fraction: 1
H2O Split Fraction: 1

7 Pressure Changer Compressor(C-2) Type: Isentropic(ASME

Method)
Discharge Pressure: 45 bar
Isentropic Efficiency: 70%
Mechanical Efficiency: 80%

8 Heat Exchanger Heater(H-3) Temperature: 280 C

Pressure: 45 bar
Phase: vapor-Liquid

9 Separator Sep(Sep-2) Outlet Stream: Hydrogen

Sub-Stream: Mixed
H2 Split Fraction: 1
10 Distillation Column DSTWU Condenser Pressure: 1.5 bar
Reboiler Pressure: 1.7 bar
Reflux Ratio: 1.6
Light Key: CH3OH
Heavy Key: H2O

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3.5: PROCESS SIMULATION RESULTS
Mass and energy balance in tabulated format as per below provided template

Parameter FEED C1-OUT H1-OUT MIX-OUT CSTR-OUT

Temperature (⁰C) 60 629.54 280 279.99 280
Pressure (bar) 1.01 45 45 45 45
Vapor fraction 1 1 1 1 1
Mass flow (kg/hr) 14913.90 14913.90 14913.90 14916.6 14916.60
Mole flow (kmol/hr) 1000 1000 1000 1001.33 533.35
CO(kg/hr) 1680.62 1680.62 1680.62 1680.62 785.44
CO2(kg/hr) 11882.64 11882.64 11882.64 11882.64 2991.46
H2 (kg/hr) 1350.63 1350.64 1350.63 1353.32 2.68
CH3OH (kg/hr) 0 0 0 0 7497.43
H2O (kg/hr) 0 0 0 0 3639.58
Parameter V1-OUT H2-OUT VAP C2-OUT H3-OUT
Temperature (⁰C) 250.03 60 60 220.59 280
Pressure (bar) 12 12 12 45 45
Vapor fraction 1 0.18 1 1 1
Mass flow (kg/hr) 14916.60 14916.60 3779.59 3779.59 3779.59
Mole flow (kmol/hr) 533.35 533.35 97.34 97.34 97.34
CO(kg/hr) 785.44 785.44 785.44 785.44 785.44
CO2(kg/hr) 2991.46 2991.46 2991.46 2991.46 2991.46
H2 (kg/hr) 2.6825 2.68 2.6825 2.68 2.68
CH3OH (kg/hr) 7497.43 7497.43 0 0 0
H2O (kg/hr) 3639.58 3639.58 0 0 0
Parameter CO-CO2 HYDROGE LIQ DISTLL BOTTOM
N
Temperature (⁰C) 280 280 60 75.61 100.78
Pressure (bar) 45 45 12 1.5 1.7
Vapor fraction 1 1 0 0 0
Mass flow (kg/hr) 3779.59 2.68 11137 7111.64 4025.36
Mole flow (kmol/hr) 96.01 1.33 436.01 230.79 205.22
CO(kg/hr) 785.44 0 0 0 0
CO2(kg/hr) 2991.46 0 0 0 0
H2 (kg/hr) 0 2.68 0 0 0
CH3OH (kg/hr) 0 0 7497.43 6747.68 749.74
H2O (kg/hr) 0 0 3639.58 363.958 3275.62

3.6: Key results related to individual unit operation such as heat duty in case of heat exchangers

Unit Operations Key Result

Compressor(C-1) Net work required: 6795.70 kW

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 Power loss: 1359.14 kW
Heat exchanger(H-1) Heat duty: -3424.59 kW
Mixer(MIX) Outlet temperature: 279.9 C
Vapor fraction: 1
Reactor(CSTR) Heat duty: -4533.09 kW
Valve(V-1) Pressure drop: 33 bar
Heat exchanger(H-2) Heat duty: -5996.38 KW
Separator(SEP-1) Heat duty: -55.95 KW
Compressor(C-2) Net work required: 200.96kW
Power loss: 40.19 kW
Heat exchanger((H-3) Heat duty: 68.45 KW
Separator(SEP-2) Heat duty: -0.14284 KW
Distillation column(DSTWU) Minimum reflux ratio: 0.23
Actual reflux ratio: 1.6
Mini number of stages: 3.05
Number of actual stage: 4.05
Feed stage: 3.50

3.7: KEY FINDINGS:

Mass flow of our feed is 14913 kg/hr Vapor fraction is 1 throughout except the cooler 2 named
as H-2 where vapor fraction is 0.1849 and distillation column DSTWU where vapor fraction is
0 and total product is in liquid phase. It means almost all the streams are in vapor phase. Mass
flow rate of CO, CO2 and H2 in the feed is 1680, 11882.646 ,and 1350.63 kg/hr respectively.
There is no CH3OH and H2O in feed. Then after the reaction in CSTR,7497.43 kg/hr of
methanol is produced. CO, CO2, H2 produced after reaction are 785.44, 2991.46 and 2.6828
kg/hr respectively. 3639.58 kg/hr water is also produced in the reaction. When this product is
passed from the separation column methanol is separated and is put into another distillation
column named as DSTWU. From where 6747.68 kg/hr of methanol goes into the distillate and
749.743 kg/hr methanol goes in the bottom as bottom product. The purity of ethanol is 90
percent. water goes mainly in the bottom while 363.958 kg/hr also goes to distillate. CO, CO 2
produced is separated by using second separation column and hydrogen is recycled again.

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 PHASE-IV

4:DESIGN OF REACTOR

Description and purpose of the reactor:

Reactor is the most vital Equipment in any chemical process where Reaction is taking place. In our problem, we
have used Continuous Stirred Tank Reactor(CSTR) operating as an isothermal equilibrium CSTR(according to
the problem statement) for the production of methanol from syngas. For Given Condition this is the best suited
equipment for reaction given as:

CO+2H2⇌ CH3OH
CO2+3H2⇌ CH3OH+H2O
and supported by water-gas shift reaction

CO+H2O⇌ CO2+H2

Note: All other parameters are provided in table 1 for example input conditions and results and design
results are provided in specification sheet named as table 2.

4.1: DESIGN OF HEAT EXCHANGER

Description and purpose of the Heater:

Heat exchanger is the equipment used for heating or cooling. If we need to cool the process or heat the
process we use heater(it acts as heater as well as cooler).In our problem, when the feed is compressed
by compressor ,its temperature also increases than the required conditions of temperature .so we use
heater to cool the feed and meet the condition of temperature given. Similarly other two are also used
to cool the streams according to the conditions.

Note: All other parameters are provided in table 1 for example input conditions and results and design
results are provided in specification sheet named as table 2.

4.2: DESIGN OF MASS TRANSFER EQUIPMENT “RadFrac”

Description and purpose of the RadFrac:

Radfrac column is the separation column used for rigorous calculations. In our problem, we used
DSTWU to separate methanol and water. We cannot design DSTWU as it is used only for rating. So
we design RadFrac Column by using the data from DSTWU column. Data like No. of stages and flow
rate of distillate are used for the design of Radfrac Column.

Note: All other parameters are provided in table 1 for example input conditions and results and design
results are provided in specification sheet named as table 2.

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4.3: DESIGN OF Distillation Column

Description and purpose of the Distillation Column:

Distil column is the separation column used for shortcut calculations. In our problem, we use distl to
separate methanol and water. We cannot design DSTWU as it is used only for rating. So we design
dstil Column by using the data from DSTWU column. Data like No. of stages and flow rate of
distillate are used for the design of distl Column.

Note: All other parameters are provided in table 1 for example input conditions and results and
design results are provided in specification sheet named as table 2.
Equipment Name Distillation Reactor Compressor Heater
Column (CSTR)
(RadFrac)
Operating
60 280 60 629.54
Conditions 12 12 45
Temperature (C) 45
436.01 1001.33 97.34
Pressure (bar) 1000
Flow Rate 0 0.06 0.28 0.06
Composition 0 0.27 0.69 0.27
CO 0 0.67 0.01 0.67
CO2 0.53 0 0 0
H2 0.46 0 0 0
CH3OH
H2O
Results Distill Bottom
Temperature (⁰C) 76.37 94.178 280 221 280
Pressure (bar) 1.5 1.5 45 45 45
Vapor fraction 0 0 1 1 1
Mass flow (kg/hr) 6974.11 4162.9 14916.60 3779.58 14913.90
Mole flow (kmol/hr) 230.79 205.223 533.35 97.34 1000
CO (kg/hr) 0 0 775.44 0.28 1680.62
CO2 (kg/hr) 0 0 2991.46 0.69 11882.64
H2 (kg/hr) 0 0 2.6825 0.014 1350.63
CH3OH (kg/hr) 6433.50 1063.92 7497.42 0 0
H2O (kg/hr) 540.60 3098.97 3639.50 0 0
Indicated horsepower (kW) N/A N/A 160.7 N/A
Brake horsepower(kW) N/A N/A 200.96 N/A
Power loss(kW) N/A N/A 40.19 N/A
Isentropic outlet N/A N/A 178.284 N/A
temperature(⁰C)

Table 1:

Table 2:

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Equipment Name Distillation Column Reactor Compressor Heat exchanger
(CSTR) (Heater)
(RadFrac)
Temperature (C) 76.37 280 221 280
Pressure (bar) 1.5 45 45 45
Internals N/A N/A N/A
Tray type Sieve
No of passes 1
Hole Dia. (mm) 12.7
Wear Height (mm) 50.8
Downcomer Clearance 38.1
(mm) 0.60
Tray Spacing (m) 1.47
Diameter (m) 0.02
Max. Acceptable
Pressure drop (bar) 0.16
Total residence time 1.21
(min) 0.02
Total height (m)
Total pressure drop (bar)
Volume Flow (liter/min) 231.26 8027.24 1459.01 17261.69

Pot Orientation N/A Vertical N/A N/A

Pot Head Type N/A Elliptical N/A N/A
Volume (cum) N/A 4.5 N/A N/A
Phase N/A Vapor N/A vapor
Specification type N/A Reactor- N/A N/A
Volume
Model N/A N/A Compressor
Type N/A N/A Isentropic Simple cooler
using ASME
method
Isentropic Efficiency N/A N/A 0.7 N/A
Mechanical Efficiency N/A N/A 0.8 N/A
Heat capacity calculation N/A N/A Rigorous N/A
method
Molar Entropy N/A N/A N/A 0.282
Molar enthalpy N/A N/A N/A -24969.40
Critical N/A N/A N/A 0.074
volume(cum/kmol)
Molar volume(cum/kmol) N/A N/A N/A 1.035

Heat duty(cal/sec) N/A N/A N/A -817949.186

Net duty(cal/sec) N/A N/A N/A -817949.186

4.4: RadFrac Design Results

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