Basic Design of Methanol Production Process 2019

KATHMANDU UNIVERSITY
SCHOOL OF ENGINEERING
DEPARTMENT OF CHEMICAL SCIENCE AND ENGINEERING
PROJECT REPORT
ON
BASIC DESIGN OF METHANOL PRODUCTION PROCESS BY CO2
HYDROGENATION
In Partial Fulfillment of the Requirements for the
Bachelor’s Degree in Chemical Engineering
Sagar Ban (019053-15)
Gaurav Khatiwada (019062-15)
Dipti Paudel (019065-15)
Rakesh Shrestha (019073-15)
October 2019
AUTHORIZATION
We hereby declare that we are the authors of this project.
We authorize the Kathmandu University to lend this report to other institutions or

individuals for the purpose of scholarly research. We further authorize the
Kathmandu University to reproduce the report by photocopying or by other means,
in total or in part, at the request of other institutions or individuals for the purpose
of scholarly research.
___________________________________________
Sagar Ban (019053-15)
Gaurav Khatiwada (019062-15)
Dipti Paudel (019065-15)
Rakesh Shrestha (019073-15)
October 2019
i
PROJECT EVALUATION
Basic design of methanol production process by CO2 hydrogenation
by
Sagar Ban
Gaurav Khatiwada
Dipti Paudel
Rakesh Shrestha
This is to certify that I have examined the above Project thesis and have found that
it is complete and satisfactory in all respects, and that any and all revisions
required by the thesis examination committee have been made.
_________________________________________
Prof. Dr. Kyun Young Park
_________________________________________
Head of Department
Department of Chemical Science and Engineering
October 2019
ii
ACKNOWLEDGMENTS
We owe our deepest gratitude to our supervisor, Prof. Dr. Kyun Young Park for his constant
guidance, support, and encouragement throughout our endeavor to complete this project.
We would also like to express our sincere gratitude towards Dr. Rajendra Joshi, Head of
Department, Chemical Science and Engineering, for his continuous motivation and guidance
throughout this challenging and exciting journey.
We are very thankful to Dr. Bibek Uprety, Dr. Dilip Kumar Rajak, Dr. Ziaul Haque Ansari,
Dr. Bishnu Pandey and Dr. Bhim Prasad Kafle for their helpfulness and leadership during our
years at Kathmandu University.
Last but not the least we are grateful towards all our friends and family for their constant
support, love and words of encouragement.
iii
Table of Contents
CHAPTER 1 ......................................................................................................................... 1
INTRODUCTION ................................................................................................................ 1
1.1 Global carbon dioxide scenario .................................................................................... 1
1.2 Methanol: Scopes ........................................................................................................ 2
CHAPTER 2 ......................................................................................................................... 3
LITERATURE REVIEW ...................................................................................................... 3
2.1 Overview..................................................................................................................... 3
2.2. Reaction Mechanism .................................................................................................. 4
2.3 Thermodynamics ......................................................................................................... 5
2.4 Catalyst Development.................................................................................................. 5
2.5 Kinetic Modeling......................................................................................................... 6
2.6 Kinetic expressions and constant factors ...................................................................... 8
2.6.1 For Two Reaction consideration ........................................................................... 8
2.6.2 For Three Reaction Consideration ......................................................................... 8
2.7 Reactors ...................................................................................................................... 9
2.7.1 Adiabatic Reactors .............................................................................................. 10
2.7.2 Isothermal reactors.............................................................................................. 11
CHAPTER 3 ....................................................................................................................... 12
REACTION SET SELECTION .......................................................................................... 12
CHAPTER 4 ....................................................................................................................... 18
PROCESS DESCRIPTION ................................................................................................. 18
4.1 Flow sheet description ............................................................................................... 18
4.2 Compressors .............................................................................................................. 18
4.3 Heat Exchangers ........................................................................................................ 18
4.4 Reactor ...................................................................................................................... 19
4.5 Vapor Liquid Separator ............................................................................................. 19
4.6 Flash Tank................................................................................................................. 19
4.7 Distillation................................................................................................................. 19
CHAPTER 5 ....................................................................................................................... 20
PROCESS FLOW DIAGRAM............................................................................................ 20
CHAPTER 6 ....................................................................................................................... 21
PIPING AND INSTRUMENTATION DIAGRAM ............................................................. 21
6.1 Pipe Size Calculation ................................................................................................. 21
CHAPTER 7 ....................................................................................................................... 31
iv
EQUIPMENT SPECIFICATION ........................................................................................ 31
7.1 Equipment Specification Calculations........................................................................ 32
7.1.1 Heat Exchanger .................................................................................................. 32
7.1.1.2 E-102 ............................................................................................................... 32
7.1.1.3 E-103 ............................................................................................................... 33
7.1.1.4 E-106 ............................................................................................................... 33
7.1.2 Vapor-Liquid Separator, TK-101 ........................................................................ 34
7.1.4 Distillation Column, T-101 ................................................................................. 37
7.1.5 Fixed Bed Reactor, R-101 ................................................................................... 38
7.2 Equipment Specification Sheets ................................................................................. 40
7.2.1 E-101 Specification Sheet ................................................................................... 41
7.2.2 E-102 Specification Sheet ....................................................................................... 42
7.2.8 C-101 Specification Sheet ................................................................................... 48
7.2.9 C-102 Specification Sheet ................................................................................... 49
7.2.10 C-103 Specification Sheet ................................................................................. 50
7.2.13 Flash Drum TK- 102 Specification Sheet .......................................................... 53
7.2.14 Vapor Liquid Separator, TK-101....................................................................... 54
7.2.15 Distillation Tower, T-101 Specification Sheet ................................................... 55
7.2.16 Reactor, R-101 Specification Sheet ................................................................... 56
CHAPTER 8 ....................................................................................................................... 57
ECONOMIC ANALYSIS ................................................................................................... 57
8.1 Total Capital Investment............................................................................................ 57
8.1.1 Manufacturing FCI (Direct Cost) ........................................................................ 57
8.1.1.1 Purchased Equipment (PE)............................................................................... 57
Equipment Cost Estimations ........................................................................................ 58
C-101 .......................................................................................................................... 58
C-102 .......................................................................................................................... 58
C-103 .......................................................................................................................... 58
v
C-104 .......................................................................................................................... 58
C-105 .......................................................................................................................... 58
E-101 .......................................................................................................................... 58
E-102 .......................................................................................................................... 59
E-103 .......................................................................................................................... 59
E-104 .......................................................................................................................... 59
E-105 .......................................................................................................................... 59
E-106 .......................................................................................................................... 60
E-107 .......................................................................................................................... 60
Cost of the Vertical Column without trays, packing or connection ............................... 61
Cost of steel Column connections ................................................................................ 61
Cost of Trays in Column.............................................................................................. 61
Cost of Packing including that for column internal support and distribution................. 61
8.1.1.2 Purchased-Equipment Delivery (DPE) ............................................................. 62
8.1.1.3 Purchased-Equipment Installation .................................................................... 62
8.1.1.4 Instrumentation and Controls ........................................................................... 62
8.1.1.5 Piping .............................................................................................................. 62
8.1.1.6 Electrical Systems ............................................................................................ 62
8.1.1.7 Buildings ......................................................................................................... 62
8.1.1.8 Yard Improvements ......................................................................................... 63
8.1.1.9 Service Facilities.............................................................................................. 63
8.1.1.10 Land .............................................................................................................. 63
8.1.2 Nonmanufacturing FCI (Indirect Cost) ................................................................ 63
8.1.2.1 Engineering and Supervision............................................................................ 64
8.1.2.2 Legal Expenses ................................................................................................ 64
8.1.2.3 Construction Expenses ..................................................................................... 64
8.1.2.4 Contractor’s Fee .............................................................................................. 64
8.1.2.5 Contingencies .................................................................................................. 64
8.1.3 Capital Investment Estimating Method ............................................................... 64
8.1.4 Calculation of the TCI ........................................................................................ 65
8.2 Revenue .................................................................................................................... 65
8.2.1 Total Revenue Calculation .................................................................................. 66
8.3 Total Product Cost (TPC) .......................................................................................... 66
8.3.1 Manufacturing Costs (Operating or Production Costs) ........................................ 66
8.3.1.1 Variable Production Costs ................................................................................ 66
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8.3.1.2 Fixed Charges .................................................................................................. 69
8.3.1.3 Plant Overhead Costs ....................................................................................... 70
8.3.2 General Expenses ............................................................................................... 70
8.3.2.1 Administrative Costs ........................................................................................ 70
8.3.2.2 Distribution and Marketing Costs..................................................................... 70
8.3.2.3 Research and Development Costs .................................................................... 70
8.3.3 TPC Calculation ................................................................................................. 71
8.4 Gross Profit ............................................................................................................... 71
8.5 Depreciation .............................................................................................................. 71
8.6 Net Profit without taxes ............................................................................................. 72
8.7 Payback period .......................................................................................................... 72
8.8 Comparing Return on Investment (ROI) with Minimum acceptable return (m ar) ........ 72
CHAPTER 9 ....................................................................................................................... 73
MATERIAL SAFETY DATA INFORMATIONS .............................................................. 73
9.1 METHANOL ............................................................................................................ 73
9.1.1 PRODUCT IDENTIFICATION ......................................................................... 73
9.1.2 HAZARD IDENTIFICATION ........................................................................... 73
9.1.3 FIRST AID MEASURES ................................................................................... 74
9.1.4 FIRE FIGHTING MEASURES .......................................................................... 74
9.1.5 ACCIDENTAL RELEASE MEASURES ........................................................... 75
9.1.6 STORAGE AND HANDLING ........................................................................... 75
9.1.7 EXPOSURE CONTROLS/PERSONAL PROTECTION .................................... 75
9.1.8 PHYSICAL AND CHEMICAL PROPERTIES .................................................. 75
9.1.9 STABILITY AND REACTIVITY ...................................................................... 76
9.1.10 TOXICOLOGICAL INFORMATION .............................................................. 76
9.1.11 ECOLOGICAL INFORMATION ..................................................................... 76
9.1.12 DISPOSAL CONSIDERATIONS..................................................................... 77
9.2 CARBON MONOXIDE ............................................................................................ 77
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9.3 CARBON DIOXIDE ................................................................................................. 81
9.3.3 FIRST AID MEASURE...................................................................................... 81
9.3.4 FIRE FIGHTING MEASURE ............................................................................ 81
9.3.5 ACCIDENTIAL RELEASE MEASURE ............................................................ 82
9.3.10 TOXICOLOGY INFORMATION .................................................................... 83
9.3.12 DISPOSABLE CONSIDERATION .................................................................. 83
9.4 WATER .................................................................................................................... 84
9.5 HYDROGEN ............................................................................................................ 87
9.5.3 FIRST AID MEASURE...................................................................................... 87
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CHAPTER 10 ..................................................................................................................... 90
CONCLUSION ................................................................................................................... 90
References....................................................................................................................... 91
Appendix 1...................................................................................................................... 95
Calculation of Equilibrium Constants .............................................................................. 95
APPENDIX 2.................................................................................................................. 98
PRO/II PROCEDURE DATA ......................................................................................... 98
ix
List of tables
Table 2.1 Several studies’ Methanol Carbon Source .............................................................. 6
Table 2.2 Parameter values of the kinetic model [B is given in J/mol] ................................... 8
Table 2.3 Parameter values for the kinetic model [B is given in J/mol] .................................. 9
Table 6.1 Density, Volumetric Flow rates, and calculated internal diameter for gas streams 22
Table 6.2 Average Density Calculation for all liquid streams .............................................. 22
Table 6.3 Volumetric Flowrates and Internal diameter for each liquid stream pipes ............. 23
Table 6.4 Standard Pipe Sizes, Thickness and ASME code for stream no. corresponding to
calculated internal diameter ................................................................................................. 23
Table 6.5 List of Instruments ............................................................................................... 30
Table 7.1 List of Equipments .............................................................................................. 31
Table 7.2 Each Component Compositions and their densities in the TK-101 ....................... 34
Table 7.3 Each Component Compositions and their densities in the TK-102 ....................... 36
Table 8.1 Information Required for Capital Cost Study Estimate ......................................... 57
Table 8.2 Typical Values of each Service facilities components as a percent of FCI ............ 63
Table 8.3 Skilled and Unskilled Worker hours per day for equipment operation .................. 68
Table 8.4 Annual Depreciation amount for straight line method .......................................... 72
Table 9.1 Flash point, Autoignition and flammable ranges for methanol .............................. 74
Table 9.2 Flash point, Autoignition and flammable ranges for Carbon Monoxide ................ 78
x
List of Figures
Fig 1.1 Methanol production and applications chart[10] .......................................................... 2
Fig 2.1 Quench reactor with quench gas inlet ...................................................................... 10

Fig 2.2 Spherical Reactor .................................................................................................... 10
Fig 2.3 Toyo MRF-Z® reactor ............................................................................................ 11
Fig 2.4 Linde Isothermal reactor.......................................................................................... 11
Fig 4.1 Comparison of CO2 Conversion, CO and CH3OH mole fraction involving 2 reactions
versus Temperature at 50 bar. .............................................................................................. 12
versus Temperature at 50 bar............................................................................................... 15
Fig 5.1 Process Flow Diagram for Methanol production by Carbon dioxide hydrogenation . 20
Fig 6.1 P & ID first part ...................................................................................................... 24

Fig 6.2 P & ID second part .................................................................................................. 25
Fig 6.3 P&ID Third Part ...................................................................................................... 26
xi
ABSTRACT
Over the past century, due to the excessive utilization of fossil fuels and increasing population
around the globe, the anthropogenic emissions of CO2 have increased drastically. The captured
CO2 can be utilized as to turn into a profitable business in addition to its positive impact of
controlling the CO2 concentration in the atmosphere. A production process of high purity
methanol from CO2 captured has been discussed in detail in this report.
The process is designed and simulated with Pro/II and Aspen Plus. A comparison is made of
the overall methanol yield resulting from consideration of only CO2 hydrogenation and the
reverse water gas shift reaction with the addition of CO hydrogenation reaction in the reactor.
A detailed selection and design calculation of the process equipments involved and process
control loop with their instruments has been done.
The Economic analysis and the safety data of all the components in the process has been
discussed resulting in the 17 % return on investment. The steam generation from the reactor
heat has been proposed and showed to increase the economic viability of the process. The
balance on CO2 in the process showed that it is possible to abate 2.12 t of CO2 per tonne of
methanol produced.
xii
CHAPTER 1
INTRODUCTION
1.1 Global carbon dioxide scenario

Technological advancements and rapid population growth have been causes for increase in the
global energy demand and its consumption. Fossil fuels, renewable energy and nuclear energy
are the sources of energy and amongst which fossil fuels are the primary and major source.
This primary dependence on fossil fuels has led to increasing carbon dioxide emission into the
atmosphere which has raised the alarming issues of global warming.
The large growth in global CO2 emissions has had a significant impact on its concentrations in
Earth’s atmosphere with fossil fuels being one of its major contributors. Carbon dioxide has
made up 76 percent of all global greenhouse gas emissions, followed by Methane at 16 percent
and Nitrous oxide at 6 percent[1]. Global warming and a changing climate have a range of
potential ecological, physical impacts including extreme weather events like floods, droughts,
rise in sea level, altered crop growth and disrupted water systems. Since the pre-industrial time,
the total temperature increment amounts to 1.2 °C[2].
Developed countries and major emerging economy nations possess a great share in total carbon
dioxide emissions. Developed nations typically have high carbon dioxide emissions per capita,
while some developing countries are increasing in the growth rate of carbon dioxide
emissions. China, Russia, USA, India and japan stand as top 5 countries contributing for global
carbon dioxide emission from fuel combustion[2].
Shifting the global energy balance in realistic time scales with a balanced use of oil, gas and
coal while protecting our environment is now a critical universal challenge. Until new, totally
renewable or sustainable energy sources supplant oil, coal and natural gas, the scientific,
technical and socio-economic challenge is clear: extract maximum energy from fossil fuels
while attempting to minimize harm to our environment. A recent opinion paper on emissions
pathways by Rogelj and co-workers shows that the scale of the CO2 emissions problem is not
being addressed quickly enough[3]. The atmospheric CO2 emission has increased drastically
after the industrial revolution with a concentration of 411 parts per million (ppm) to-date
considered its highest level in the last three million years. To begin to stabilize, or even reduce
atmospheric CO2 concentrations, our emissions need to not only stabilize but also decrease
significantly[1].
Greenhouse gases have helped in maintaining earth’s temperature by preventing heat from
escaping; however, excessive uses of these gases including CO2 have increased the average
earth’s temperature and caused global warming[4]. If the concentration of CO2 continues to
increase at the current rate, there will be a rise in temperature by 3.5 °F over the next century[5].
1
Carbon dioxide has direct use in wide applications such as food processing, preservation, coffee
decaffeination, fire suppression, beverage carbonation and production of coolants. In beverage
industry carbonation is done in order to provide sparkling appearance and refreshing bubbles
in the drinks[6]. Another approach of CO2 utilization is converting CO2 into fuels and chemicals
through various catalytic processes for synthesis of Methanol, Salicylic acid, and Urea[7]. The
conversion of CO2 to fuels can be an effective method for reduction in global net emission of
CO2. By converting CO2 into methanol, issues like depletion of fossil fuels and greenhouse gas
control can be solved, thus making methanol production a promising process for fuel
production and carbon reduction.
1.2 Methanol: Scopes

The industrial significance of methanol is huge. Globally, there are over 90 methanol plants
with combined capacity of 110 million metric tons[8]. Major application of methanol for the
production of formaldehyde and tert- butyl methyl ether which is used as a fuel or blended with
gasoline. Along with this, the use of methanol in plastic industries and as a direct fuel or
blended with petrol is gaining attention. Ease in storage and high energy density makes it a
convenient energy storage candidate. It holds excellent promise as an alternative source of
energy since it offers several advantages clean burning properties, low emissions, high octane
rating, high volatility, high energy density, easy transport and ability to be incorporated in the
existing engines without major modifications in the infrastructure. It has also been used in cell
research application as an energy carrier[9].
Fig 1.1 Methanol production and applications chart[10]
2
CHAPTER 2
LITERATURE REVIEW
2.1 Overview
In the Early 1913, Carbon Monoxide was reacted with Hydrogen using an iron-based catalyst
by German chemist A. Mittasch and M. Pier during ammonia synthesis developmental work at
BASF. Later development of a large-scale methanol production method using ZnO on Cr2O3-
based catalyst was done by M. Pier at high pressures (25-35 MPa) and 320 °C – 450 °C[11].
Later, in 1966, copper-based catalysts were introduced for methanol synthesis. This catalytic
process was operated at 50-100 bar pressure and 200-300 °C temperature[12]. Due to the high
purity of synthesis gas which was free from sulfur and carbonyl contaminants responsible for
catalyst contamination, the catalytic process was successful and a majority of the world’s
methanol production is based on this technology. First, methane or major component of natural
gas is reacted with water to produce a mixture of CO and H2 called syngas[13].
CH4 + H2O → CO + 3H2 ΔH (298K, 5MPa) = +206.3 kJ/mol
This syngas mixture is then used for methanol synthesis. An addition of small amount of CO2
to the syngas mixture was found to increase the catalytic activity and methanol yield. Thus, in
order to increase the yield by about 30 % CO2 is added in syngas mixture nowadays[14].
Methanol synthesis via CO2 hydrogenation is an excellent approach since it helps with CO2
mitigation as well as for renewable energy development.
Traditionally, the production of methanol comprises of three basic steps:
• Production of synthesis gas

• Conversion of synthesis gas to methanol
• Distillation of the reactor effluent
The synthesis gas (H2, CO and CO2) is mainly produced by reforming of natural gas. It can
also be produced by partial oxidation of carbon-based materials like petroleum, coal, petroleum
coke, heavy oil, asphalt or biogas. Syngas manufacturing and purification is a crucial part of
the overall process for methanol production. It usually represents more than half of the total
investment when the feedstock is natural gas and up to 70–80 % when the raw material is coal.
The composition of the syngas is usually characterized by the stoichiometric number M which
is defined as:
𝑦𝐻2 − 𝑦𝐶𝑂2
𝑀=
𝑦𝐶𝑂2 + 𝑦𝐶𝑂
For a stoichiometric CO/CO2/H2 mixture, the parameter M has a value of 2. A value larger than
2 indicates a mixture rich in H2, and reciprocally. Therefore, a syngas composition with a
stoichiometric number M slightly above 2 is the optimum for methanol synthesis[15]. Currently,
methanol is produced via synthesis processes operating at pressures of 50–100 atm and
3
temperatures of 200–300 °C. Most of the actual processes operate in gas phase and use copper-
based catalysts. The main differences among them are related to the reactor design and catalyst
arrangements.
The syngas is pressurized with a compressor and heated. Heating could also take place inside
the methanol converter. The mixed gases, having a H2/CO ratio from 3:1 to 5:1, are fed to the
reactor.
2.2. Reaction Mechanism

Methanol synthesis occurs by following reactions[16]:
Hydrogenation of Carbon monoxide
CO + 2H2 ↔ CH3OH Reaction (1)

(ΔH = -91 kJ/mol; ΔG = -25.34 kJ/mol)
Hydrogenation of Carbon dioxide
CO2 + 3H2 ↔ CH3OH + H2O Reaction (2)

(ΔH = -49.5 kJ/mol; ΔG = 3.30 kJ/mol)
Water gas shift reaction
CO + H2O ↔ CO2 + H2 Reaction (3)

(ΔH = -41.2 kJ/mol; ΔG = -28.60 kJ/mol)
CO and H2 was considered as main reactants in methanol synthesis and the contribution of CO2
was neglected on the kinetic studies by Natta el al. and Leonov et al.[17] . Liu et al. showed that
methanol production rate increases with increasing CO2 pressure. Later they proposed that, in
the water absence case, hydrogenation of CO2 was the primary reaction in producing methanol
at low temperature with low conversion but with water presence at high temperature CO
hydrogenation was the primary reaction for methanol synthesis with high conversion[18].
Takagawa and Ohsugi, in 1987 determined the empirical rate equations with considering all
three methanol synthesis reactions. In their results, they showed that methanol production rate
increased with an increase in CO2/CO ratio in the beginning of the reaction but decreased as
the ratio increased and water started to form[19]. McNeil et al. found that that 2 molar percent
CO2 in the feed yielded optimum methanol production rate and the contribution of CO 2 to
methanol formation was greater at a lower temperature in their experimental study. In their rate
law, they included the effect of CO2 as methanol producer and as a rate inhibitor[20]. Methanol
synthesis and water gas shift reaction was studied by Sun and coworkers using IR technique in
1998. They found that CO2 hydrogenation was the principle pathway in methanol production
for both CO2 and CO2/CO hydrogenation reactions. Formate species hydrogenation was the
rate determining step and addition of CO lowered the activation energy of the production
process, in addition to affecting the reaction path[21].
4
2.3 Thermodynamics
Thermodynamic aspects of a chemical reaction, for understanding and predicting the stability
of the desired chemical species, yield, conversion and selectivity of the products, are very
important. It even provides information about reaction mixture phases, impact of temperature,
pressure and feed ratio. Carbon dioxide is a doubly bonded linear molecule having high
stability (ΔG° = -394.4 kJ mol-1) and requiring substantial energy input, highly active and stable
catalysts and its reaction conditions require optimization.
CO2 and H2 can react together to form methanol and water as in (2). The formed water
consumes one third the hydrogen that is charged for reaction, requiring more hydrogen than in
the methanol formation reaction from syngas (1). Both of the methanol formation reactions are
exothermic and take place with a loss in reaction volume. A Possibility exists for the reverse
water gas shift reaction to take place on the catalyst surface with CO2 as feed, as shown in (3).
The produced CO from this reaction undergoes hydrogenation to yield methanol as per (1). The
CO2 and CO hydrogenation to methanol are exothermic reactions and brings a loss of volume;
high pressure and low temperature hence should help to achieve a higher conversion as
predicted by Le Chatelier’s principle.
Graaf et al. performed a thermodynamic study on methanol synthesis by the reactions of CO,
CO2 and H2 and also calculated chemical equilibria for methanol synthesis using equilibrium
constants. Fugacity coefficients in the equilibrium constants were calculated using Soave-
Redlich-Kwong (SRK) equation of state (EOS) by taking non-ideal behavior of the gas mixture
into account [22].
Further, studies were performed to model the solubility of carbon dioxide in water with SRK
EOS with Huron-Vidal (HV) mixing rules. The model showed a capability of predicting highly
accurate water-gas solubility. This mixing rule with SRK also allowed accurate modelling of
solubilities of gases in liquid and vice versa. Despite the reported inapplicability at low
pressures due to differences of Gibbs energy near atmospheric pressure from that at infinite
pressures, this model with its high accuracy can be applied to model high pressure mixtures[23].
In our design study, methanol formation was compared between two cases: one case with
reactions (2) and (3) as in Vanden Bussche and Froment [17] and the other with all of the three
(1), (2) and (3) reactions in Graff et al..
2.4 Catalyst Development

Over the years, several catalysts for CO2 hydrogenation to methanol have been reported in the
literature. According to Lim et al.,[16] Cu, Zn, Cr, and Pd are commonly used to minimize by-
product formation (i.e. hydrocarbons) and maximize methanol yield and selectivity. An
optimum catalyst should have a high specific surface area that can be obtained with ultrafine
or nanostructured particles of the metal active sites. It is important to systematically
characterize the nature of the active sites and interactions among active components, support,
and promoter to be able to tailor the structure of the catalyst. The key to increasing the one-
pass conversion is to develop the optimum catalyst active for low-temperature synthesis.
The most commonly used catalysts are Cu, Pd, Zn and Cr. Among these CuO/ZnO/Al2O3
catalyst is well-known for its high activity and selectivity for the methanol synthesis reaction
and is highly adopted in industry. To improve the catalytic performance of methanol synthesis
5
from H2/CO2 feeding gas, CuO/ZnO catalysts have been widely modified by adding various
activators or other metals (Zr, Si, La, Ti, Cr, Ga, Ce, Fe, Nb, Pd, etc.) A support such as Al2O3
can further increase the activity and selectivity. Furthermore, a promoter such as Zr is known
to enhance the copper dispersion and catalytic activity of methanol synthesis catalysts. CuO
ranges between 20 to 80 percent, ZnO ranges between 15 to 50 percent and Al2O3 ranges from
4 to 30 percent. The investigation on enhancing the catalytic activity by the addition of supports
and promoters are increasing. Lachowska and Skrzypek found that CuO/ZnO/ZrO2 had a
catalyric activity higher than CuO/ZnO/Al2O3[24]. Nowadays, methanol is produced
industrially from synthesis gas mixtures (CO/CO2/H2) over Cu/ZnO/Al2O3 catalysts at 50 to
100 bar total pressure and at a temperature between 200 and 300 °C[25].
Many Cu-based catalysts like CuO/ZrO2, CuO/ZnO/ZrO2, CuO/ZnO/Ga2O3, modified

CuO/ZnO/Al2O3 and multi-component catalysts have been extensively studied. Furthermore,
many Cu-based catalysts promoted by B, V and Ga have been investigated, too. To investigate
the potential of catalysts containing Cu and Zr in methanol synthesis, Raudaskoski et al. (2009)
reviewed recent works done by various researchers.
In our present study, the catalyst used for methanol synthesis reaction is Cu/ZnO/Al2O3
(CuZA). The Cu/ZnO catalyst with ZrO2 as a promoter (CuZZ) can also be used. But the
apparent density of CuZZ is three times that of CuZA and has to be diluted with SiC in order
to meet the same catalytic bed volume.
2.5 Kinetic Modeling

Table 2.1 Several studies’ Methanol Carbon Source
Authors Carbon Source
[26]
Leonov et al., 1970-1973 CO
Rozovskii et al., 1975-1977[27, 28] CO2
Schermuly and Luft., 1977[29] CO
Denise and Sneeden., 1982[30] CO + CO2
Klier et al., 1982[31] CO + CO2
Monnier et al., 1984[32] CO
Bardet et al., 1984[33] CO + CO2
Chincen et al., 1984[34] CO2
Villa et al., 1985[35] CO
Liu et al., 1985[18] CO + CO2
Seyfert and Luft., 1985[36] CO
Dybkjaer., 1985[37] CO2
Takagawa and Ohsugi.,[19] CO
Chincen et al., 1987[38] CO + CO2
Graaf et al., 1988[39] CO + CO2
Shack et al., 1989[40] CO + CO2
McNeil et al., 1989[20] CO + CO2
Skrzypek et al., 1991[41] CO2
Askgaard et al., 1995[42] CO2
Vanden Bussche and Froment et al., 1996[17] CO2
Kubota et al., 2001[43] CO2
6
The work of Grabow and Mavrikakis[44] that is not mentioned in the above table describes a
microkinetic model, with 49 elementary steps, and considers the different intermediates
involved in the methanol synthesis. It deals with the density functional theory calculations and
provides an interesting result that the two-third of the methanol is produced from CO2
hydrogenation. Still there is a contradiction that whether the methanol synthesis and RWGS
(Reverse Water-Gas Shift) reaction are parallel pathways, shares a common intermediate, or
methanol formation proceeds by sequential RWGS and CO hydrogenation.
Van den Bussche and Froment[17] have established a kinetic model taking into account only the
water gas-shift reaction and the carbon dioxide hydrogenation for the catalyst of
CuO/ZnO/Al2O3 at 180 to 280 °C and pressure of 15 to 51 bar. The reactor taken was an
isothermal plug flow reactor and the effects of the operating conditions and the CO fractions
were studied.
Struis et al.[45] performed experiments for the single pass methanol production with CO2 and
H2 as a feed on the membrane reactor at 200 °C and 40 bar and GHSV of 5000 h-1. The catalyst
used was CuO/ZnO and the kinetic parameters (kinetic constants and adsorption constants)
were also determined through the experiments.
Kinetics of the low-pressure methanol synthesis over a commercial catalyst CuO/ZnO/Al2O3,

was investigated by Skrzypek et al.[41] The ranges of parameters were applied, especially
concerning inlet concentrations of reactants. It was found that methanol synthesis occurs from
CO2 rather than from CO. Langmuir-Hinshelwood type kinetic equations were also determined
based on the feed taken.
A kinetic model for the synthesis of methanol over commercial catalysts was developed by
Park et al.[46] based on the adsorption of CO and CO2 onto various active sites of Cu, while the
kinetic parameters were estimated by fitting 118 experimental sets of data under a variety of
conditions. Besides, dual site adsorption additional adsorption site for CO2 was taken into
account for determining the rate expressions and the kinetic parameters. The reaction
conditions were in the range of 220 to 340 °C and 50 and 90 bar.
The kinetics of low-pressure methanol synthesis with CO, CO2, and H2 as starting materials
were studied over a commercial CuO/ZnO/Al2O3 catalyst by Graaf et al. [39] at 15-50 bar and
210-245 °C. The results show that methanol can be formed from both CO and CO2. Besides
these two reactions, the water-gas-shift reaction takes place. Based on these three reactions and
the assumption of dual-site adsorption mechanism, 48 kinetic rate models are derived.
Hydrogen is believed to be adsorbed dissociatively. Experimental data supported their
assumptions.
Other different kinetic models are available based on the reactants available and the rate
determining steps. This kinetics was studied for decades and the improvement in the yield and
the selectivity over CO are the major factors considered. Based on the reaction kinetics the
optimization processes and also the catalyst activity is studied. As far today, different metal-
based catalysts are available and used for the production with so much more yet to come.
Beside the availability of different catalysts, Cu/ZnO/Al2O3 and Cu/ZnO/ZrO2 are used
commercially because of their high selectivity and operating performance.
7
On the basis of the analysis of literature data, we came to understand that both CO and CO2 are
involved in the synthesis of methanol. It could be interesting to compare the behavior of the
different proposed kinetic models in their application to real-reactor modeling. In fact, the
Graaf et al. and Van den Bussche and Froment rate equations are the only ones extensively
used in reactor modeling.
2.6 Kinetic expressions and constant factors

2.6.1 For Two Reaction consideration
Reactions[17]:
CO2 + 3H2 CH3OH
CO2 + H2 CO + H2O
1 PH O PCH OH
2 3
k1 PCO2 PH2 (1−K )
eq,1 P3 P
H2 CO2 mol
rCH3 OH = 3 [ ]
PH O
2 0.5
Kgcat s
(1+k2 +k3 PH2 +k4 PH2 O )
P H2
PH O PCO
2
k5 PCO2 (1−Keq,2 P )
CO2 PH2 mol
rRWGS = PH O
[ ]
Kgcat s
(1+k2 P 2 +k3 P0.5
H2 +k4 PH2O )
H2
B
ki = Ai exp ( i )
RT
3066
log10 K eq,1 = − 10.592
T
2073
log10 K eq,2 = − + 2.029
T
Table 2.2 Parameter values of the kinetic model [B is given in J/mol]

k1 A1 1.07
B1 40,000
k2 A2 3453.38
B2 -
k3 A3 0.499
B3 17,197
k4 A4 6.62×10-11
B4 124,119
k5 A5 1.22×1010
B5 -98,084
2.6.2 For Three Reaction Consideration

Reactions[47]:
CO + 2H2 CH3OH
CO2 + 3H2 CH3OH
8
CO2 + H2 CO + H2O
PCH OH
k1 KCO (PCO P1.5
H2 −
3
)
P0.5
H2 KP,A
rCO = KH O
(1+KCO PCO +KCO2 PCO2 )[P1.5 2
H2 + K0.5 PH2 O ]
H2
PCH OH PH O
k2 KCO2 (PCO2 P1.5
H2 −
3 2
)
P1.5
H2 KP,B
rCO2 = KH O
(1+KCO PCO +KCO2 PCO2 )[P1.5 2
H2 + K0.5 PH2 O ]
H2
PH OP
2 CO )
k3 KCO2 (PCO2 PH2 −
KP,B
rRWGS = KH O
(1+KCO PCO +KCO2 PCO2 )[P1.5
H +
2 P
H2 O ]
2 K0.5
H2
B
Parameter = Ai exp ( i )
RT
Table 2.3 Parameter values for the kinetic model [B is given in J/mol]
Parameters A B
k1 (kmol s-1 kg-1 Pa) 4.0638×10-6 -11,695
k2 (kmol s-1 kg-1 Pa) 1.5188×10-33 -266,010
k3 (kmol s-1 kg-1 Pa0.5) 9.0421×108 -112,860
KP,A (atm-2) 2.3717×10-13 98,438
KP,B (atm-2) 6.6688×10-11 54,499
KP,C 2.8118×102 -43,939
KCO (Pa-1) 8.3965×10-11 118,270
KCO2 (Pa-1) 1.7214×10-10 81,287
KH2 O 4.3676×10-12 115,080
(Pa-1/2)
K0.5
H2
2.7 Reactors
The design of a reactor should consider the control of reactor temperature since the methanol
synthesis reaction is exothermic in overall. The generated heat has to be recovered efficiently
and optimized for the economics of the process and high conversion is required to minimize
the cost involved in further separation processes[48]. The reactor technologies that are available
fall under two categories: namely gas phase technologies and liquid phase technologies. This
study is limited to the discussion of some of the gas phase technologies.
These reactors can be either adiabatic or isothermal. There is existing multi-bed quench direct
cooling or interstage heat exchange (indirect cooling) configuration available for adiabatic
units.
9
2.7.1 Adiabatic Reactors
There are multiple adiabatic beds installed inside a
pressurized shell quench converter. ICI low pressure
quench converter is among most commonly applied in
the industry[49]. The operating conditions are 50-100
bar and 270 °C. In a single bed, there exists a
Cu/ZnO/Al2O3 catalyst support and distributors to
inject cooling gas into the bed at multiple locations.
The fresh and recycled syngas helps for reaction
temperature mitigation which is a factor in optimizing
the reactor design. Here the heat of reaction is
recovered and reused, but due to the possible
irregularity in flux distribution the flow distribution
around catalyst pellets may not be uniform. Hence,
cold and hot zones exist inside the reactor, resulting in
lowering reaction rate and deactivation of catalyst or
byproducts formations. Fig 2.1 Quench reactor with quench gas
Kellogg, Brown and Root reactor, is another adiabatic inlet
fixed bed reactors’ series. It is spherical in shape and the
catalyst is loaded in between the external wall and an inner
spherical wall. The cost is lowered because the wall
thickness could be reduced to half due to the spherical
shape. The reactors provide flow radially from the outer
wall through the catalyst into the inner sphere. It is known
to lower cost of manufacturing, transportation and
installation[50].
The Toyo Engineering Corporation (TEC) reactor, called
MRF-Z® reactor, provides intermediate with multi-stage
radial flow reactor where heat is removed by means of
blade boiler tubes and the catalyst is loaded into concentric
beds. The maximum allowable reaction temperature is
Fig 2.2 Spherical Reactor
maintained with optimal conversion per pass[51].
10
2.7.2 Isothermal reactors
Fig 2.4 Linde Isothermal reactor

Linde isothermal reactor is equipped with
Fig 2.3 Toyo MRF-Z® reactor
helical tubes inserted in the catalyst bed
with indirect heat exchange which makes it suitable for both endothermic and exothermic
catalytic reactions and for gas/gas, gas/liquid or liquid/liquid systems[51].
Maximum reaction rate is possible and optimum temperature profile can be insured by heating
or cooling tubes resulting in higher productivity, increased catalyst life, fewer by-products,
efficient reaction heat recovery and lower operating costs.
The Air Liquide converter is among the most preferred reactors for methanol production in
large-scale plants[52-54]. Its design consists of a fixed bed reactor resembling a shell and tube
heat exchanger with the catalyst loaded inside the tubes and cooling water flowing through the
shell side to ensure a tight control of the temperature profile and to help in producing high-
pressure steam.
Typical operating conditions ranges 50–100 bar and 230–265 °C. Steam is produced at 40–50
bar and can be reused in the compression section in the distillation process. The high yields
and low recycle ratios allow attaining 1200 to 1400 ton/day productivity.
11
CHAPTER 3
REACTION SET SELECTION
Equilibrium conversion results for both two and three reactions.

To see the influence of varying temperature and pressure on resultant CO2 conversion, and CO
and CH3OH mole fractions, several simulations are performed by reacting CO2 with H2 in an
adiabatic equilibrium reactor. The feed is CO2 and H2 with 22:3 mass ratio.
A graph is plotted of CO2 conversion along with the resulting CO and CH3OH vapor mole
fractions from an adiabatic equilibrium reactor simulated with Pro/II for varying inlet pressures
and temperatures. The inlet pressure ranges from 50 bar to 80 bar with 10-bar increment and
the inlet temperature from 200 °C to 300 °C with 10 °C increment.
50 bar Results
0.59 0.14
0.58 0.12
CO2 Conversion
Mole Fractions
0.57
0.1
0.56
0.08
0.55
0.06
0.54
0.04
0.53
0.52 0.02
0.51 0
200 220 240 260 280 300
Inlet Temperature, °C
Carbon dioixde Conversion CO mole fraction Methanol Mole fraction
Fig 4.1 Comparison of CO2 Conversion, CO and CH3OH mole fraction involving 2 reactions versus
Temperature at 50 bar.
12
60 bar Results
0.6 0.16
0.59 0.14
0.12
0.58
CO2 Conversion
Mole Fractions
0.1
0.57
0.08
0.56
0.06
0.55
0.04
0.54 0.02
0.53 0
200 220 240 260 280 300
Carbon dioxide Conversion CO mole fraction Methanol Mole Fraction
70 bar Results
0.61 0.16
0.6 0.14
0.12
0.59
CO2 Conversion
Mole Fractions
0.1
0.58
0.08
0.57
0.06
0.56
0.04
0.55 0.02
0.54 0
200 210 220 230 240 250 260 270 280 290 300
Carbon dioxide Conversion CO mole fraction Methanol Mole Fraction
13
80 bar Results
200 210 220 230 240 250 260 270 280 290 300
0.62 0.16
0.61 0.14
0.12
0.6
CO2 Conversion
Mole Fractions
0.1
0.59
0.08
0.58
0.06
0.57
0.04
0.56 0.02
0.55 0
Carbon dioxide Conversion CO molefraction Methanol Mole Fraction
From the comparison of the graphs of Fig 4.1 through Fig 4.4, it can be deduced that with the
increasing temperature CO2 conversion increased while the mole fraction of CH3OH decreased
and that of CO increased, which means that most of the CO2 is being converted to CO rather
than CH3OH. The possible explanation for this phenomenon is that by increasing temperature
the RWGS reaction producing CO is endothermic reaction and favored but the exothermic
Methanol formation is suppressed. It can also be seen, with comparison among the graphs, the
CO2 conversion increased with increasing pressure. Even though there is an increase in
individual mole fractions of both CO and CH3OH with the increasing pressure, the results show
that the rate of CO formation is higher and dominant than Methanol formation and results are
unsatisfactory to be employed for the methanol production process design.
Similarly, by taking the CO to CH3OH formation reaction into consideration, the adiabatic
equilibrium simulation is performed once more and several results of CO2 conversion, CO and
CH3OH vapor mole fractions are shown against varying temperature and pressure. The
temperature and pressure variation scheme are similar to previously considered of 200 to 300
°C and 50 to 80 bars, respectively.
14
50 bar Results
0.22 0.05
0.045
0.21
0.04
CO2 Conversion
Mole Fractions
0.2 0.035
0.19 0.03
0.025
0.18
0.02
0.17 0.015
200 220 240 260 280 300
Carbon Dioxide Conversion CO mole Fraction Methanol Mole Fraction
Temperature at 50 bar
60 bar Results
0.23 0.05
0.22 0.045
CO2 Conversion
0.21 0.04
Mole Fractions
0.2 0.035
0.19 0.03
0.18 0.025
0.17 0.02
200 210 220 230 240 250 260 270 280 290 300
Carbon Dioxide Conversion CO mole Fractions Methanol Mole Fractions
15
70 bar Results
0.24 0.055
0.235
0.05
0.23
0.045
0.225
CO2 Conversion
Mole Fractions
0.22 0.04
0.215 0.035
0.21
0.03
0.205
0.025
0.2
0.195 0.02
200 210 220 230 240 250 260 270 280 290 300
Carbon Dioxide Conversion CO mole Fraction Methanol Mole Fraction
80 bar Results
0.25 0.055
0.245
0.05
0.24
0.045
0.235
CO2 Conversion
Mole Fractions
0.23 0.04
0.225 0.035
0.22
0.03
0.215
0.025
0.21
0.205 0.02
200 210 220 230 240 250 260 270 280 290 300
Carbon Dioxdie Conversion CO mole Fraction Methanol Mole Fraction
16
From the comparison of graphs of Fig 4.5 through 4.8, we see that CO2 conversion increases
almost linearly with increasing temperature and pressure similarly as in previous consideration
of only two reactions. It can also be seen that methanol mole fraction is higher than CO mole
fraction. This is different from previous simulation result with two reactions that CO mole
fraction is higher than that of methanol and the differences in mole fractions started to decrease
with increasing temperature, decreasing the CH3OH formation rate and increasing CO
formation rate. A point is reached in each of the graph, where CO and CH3OH mole fractions
are equal. This point shifts to the right or higher temperature as the pressure is increased. An
increase in pressure increased slightly all of CO2 conversion, CO and CH3OH mole fractions.
Thus, the comparison between two reactions and three reactions tells that the methanol
production process design is favored more by considering three reactions, yielding more
methanol. Since increasing pressure had little effect on CO2 conversion and resulting CH3OH
mole fraction, pressure may not be an important factor in the design as far as reaction
equilibrium is concerned. However, there was a great influence of increasing temperature on
increasing the resulting Methanol mole fraction and reaction temperature was seriously taken
into consideration in designing the process.
17
CHAPTER 4
PROCESS DESCRIPTION
4.1 Flow sheet description

CO2 is fed at 1 bar and hydrogen at 30 bar, both being at 25 °C. CO2 is compressed to 50 bar in
a series of compressors with intercooling and H2 is compressed to 50 bar in a single stage
compressor. The multi-stage compression of CO2 is employed to minimize the power
requirements.
The two streams of gases are mixed in a mixer M-101 and then the mixture of the gases is
heated to 513.15 K in a heat exchanger, E-104. Finally, this mixture of gases is mixed with the
recycle stream in a mixer M-102.
The stream is then injected into the fixed bed isothermal reactor where reaction takes place in
the reactor R-101. For maintaining the temperature inside the reactor constant, the cooling
water is used and steam is generated as a byproduct which can further be used in the heat
exchanger.
A gaseous mixture of methanol, water and unreacted reactants is formed. The mixture is then
cooled in a heat exchanger, E-106. The stream is then sent to a vapor liquid separator, TK-101
where the liquefied Methanol and water are removed from the bottom and the uncondensed
gases are passed through the top to a splitter where about 1% of the gases is removed as a purge
to minimize the accumulation and the remaining gases are passed through a heat exchanger to
the reactor as a recycle stream.
Further a small amount of unreacted gases is still left in the liquid products drawn from the
separator. A flash tank, TK-102 is used to remove the unreacted gases in the product. Before
the stream enters the flash tank, two valves BV-101 and BV-102 are used to reduce the pressure
to 1 bar. The residual amount of gases is removed from the top of the flash tank.
Now the bottom product of the flash tank contains only Methanol and water and trace amount
of gases. The product is then passed to the distillation column for the separation of methanol
and water. Finally, Finally, a methanol with about 98.9% purity is obtained as a distillate from
the distillation column..
4.2 Compressors
As the reaction takes place at 50 bar, the gases stream should also be available at 50 bar. Since
CO2 is available at 1 bar, a series of compressors with inter-stage cooling is used for the
compression of CO2 to 50 bar. The multi-stage compression was chosen to minimize total
power requirements. By comparison, Hydrogen is available at a relatively higher pressure of
30 bar, and a single stage compressor is enough to compress it.
4.3 Heat Exchangers

Three heat exchangers E-101, E-102 and E-103 are used for the cooling purpose as the
compression leads to the increase in temperature. Water at 25 °C is used as coolant. The reaction
takes place at 240 °C. Hence, the heat exchangers E-104 and E-105 are used to heat the mixture
of gases to the reaction temperature. In order to condense the mixture and separate the vapor
18
from the liquid the mixture is cooled to around 35 °C in a heat exchanger, E-106. The boiling
point of methanol is around 65 °C. So, the mixture of methanol and water from the flash tank
is heated to around the boiling point of methanol which in our case it was actually heated up to
80 °C in heat exchanger E-107.
4.4 Reactor
The reactor used is a fixed bed isothermal reactor. As the pressure inside the reactor is 50 bar,
the thermodynamic model used is Redlich-Kwong-Soave equation of state with modified
Huron-Vidal mixing rules (RKSMHV2). First of all, we used the model proposed by Vanden
Bussche. Because this model does not account for the CO hydrogenation. We found that the
yield of methanol was calculated to be extremely low, implying that CO hydrogenation is not
negligible. Next, we used the model developed by An et. al.[47] that accounts for all the three
reactions (CO hydrogenation, CO2 hydrogenation and RWGS). The kinetic expressions used
are given by Lim et. al[16]. Both the kinetic and the rate expressions were discussed in the above
sections. In the conventional methanol synthesis process, the catalyst used is the
Cu/ZnO/Al2O3. In our case we used the catalyst developed for CO2 hydrogenation by An et.
Al, which is a fibrous Cu/Zn/Al/Zr. The pressure drop in the reactor was neglected. Cooling
water is used in the reactor in order to maintain the temperature of the reactor.
4.5 Vapor Liquid Separator

The outlet stream of the reactor contains methanol, water and the unreacted gases. This stream
is condensed to 35 °C in the heat exchanger E-106 and passed to a vapor liquid separator TK-
101. Most of the gases are separated from the mixture of methanol and water. The gases are
then passed to a splitter where about 1% of the gases are removed as a purge in order to
minimize the accumulation in the reactor and the remaining gases are sent to the reactor as the
recycle.
4.6 Flash Tank

Some of the residual gases still exist in the liquid stream exiting vapor liquid separator. The
pressure is reduced to 1 bar using the two valve BV-102 and BV-103. Due to the
depressurization, the residual gases are separated from the mixture of methanol and water in
the flash tank TK-102. The operating temperature of the flash tank is 35 °C.
4.7 Distillation
A distillation column is used to purify methanol. The column was simulated using a rigorous
distillation model, RADFRAC in ASPEN plus V.10. The boiling point of methanol is about 65
°
C. The mixture of methanol and water is heated to 80 °C which is above the boiling point of
methanol in the heat exchanger E-107 and passed to the distillation column T-101. The
optimum reflux ratio and the number of plates were found to be 1.5 and 57 respectively. The
column was set to have 44 rectification plates and 13 stripping plates. These optimum values
were set in order to meet the desired purity. The obtained methanol in the distillate was around
98.9 % pure.
19
CHAPTER 5
PROCESS FLOW DIAGRAM
Fig 5.1 Process Flow Diagram for Methanol production by Carbon dioxide hydrogenation
20
CHAPTER 6
PIPING AND INSTRUMENTATION DIAGRAM
6.1 Pipe Size Calculation

For gas streams at various temperatures and pressures, the pipe size is calculated using the ideal
gas equation, while for the liquid streams the pipe size is calculated using online density
relation and with the individual mass streams and then the size was calculated.
Using the ideal gas equation as,
P1 V1 = n1 RT1 …… (1)
P2 V2 = n2 RT2 ……. (2)
where P1, V1, n1, and T1 are the Pressure, Volume, no. of moles and Temperature at STP.
similarly, P2, V2, n2, and T2 are the Pressure, Volume, no. of moles and Temperature at stream
condition. And R is the universal gas constant.
Dividing (1) by (2), we obtain
P1 V1 n1 T1
= …. (3)
P2 V2 n2 T2
m2 g
With P1 = 1.01325 bar, V1 = 22.4 L, n1 = 1 gmol, T1 = 273.15 K, n2 = g and rearranging
M gmol
m2
for ρ =
V2
, (3) becomes
1 m3
1.01325 bar ×22.4 L × 1000 L 1 gmol 273.15 K
= m2 × ……. (4)
P2 × V2 T2
M
Kg
m2 1 gmol ×M ×273.15 K ×P2 ×1000 L × 10−3 g
Now, Density, ρ = = …(5)
V2 T2 ×1.01325 bar ×1 m3 ×22.4 L
Evaluating ρ for each stream and calculating volumetric flow rates and also using the rule of
thumb for wet basis gas velocity as 18.288 m/s, 1.8288 m/s for liquid velocity for calculating
internal pipe diameter (ID) and evaluating a table we get,
21
Table 6.1 Density, Volumetric Flow rates, and calculated internal diameter for gas streams
Stream Molecular Pressure, Temperature, Density, Gas Mass Volumetric ID, mm
no. Weight, bar K Kg/m3 Flowrates, Flow rates,
g/gmol Kg/s m3/s
1 44 1 298.15 1.78 2.44 1.376 309
2 44 3 377.39 4.21 2.44 0.581 201
3 44 3 311.15 5.11 2.44 0.479 182
4 44 9 393.51 12.11 2.44 0.202 118
5 44 9 311.15 15.32 2.44 0.160 105
6 44 26 393.63 34.98 2.44 0.070 68
7 44 26 311.15 44.26 2.44 0.055 62
8 44 50 364.55 72.64 2.44 0.034 48
9 2 30 298.15 2.44 0.33 0.136 97
10 2 50 345.34 3.52 0.33 0.095 81
11 12.6 50 347.23 21.79 2.78 0.127 94
12 12.6 50 513.15 14.75 2.78 0.188 114
13 11 50 513.15 13.20 79.61 6.032 648
14 11 50 513.15 13.15 76.83 5.844 638
15 11.4 50 513.15 13.34 79.61 5.969 645
16 11 50 308.15 21.89 77.58 3.544 497
17 11 50 308.15 21.89 77.58 3.544 497
19 11 50 308.15 21.89 0.78 0.035 50
20 11 50 308.15 21.89 76.81 3.508 494
21 26.6 10 307.17 10.43 0.08 0.007 22
22 32.6 1 300.93 1.31 0.18 0.138 98
23 32.6 1 304.15 1.29 0.18 0.143 100
25 28.6 1 353.15 0.98 0.43 0.443 175
26 32.1 1 337.3 1.14 1.16 1.015 266
For liquid streams density calculation,
Table 6.2 Average Density Calculation for all liquid streams

Stream Mass Water, Methanol, Temperature, Pressure, Water Methanol 𝜌𝑠𝑡𝑟𝑒𝑎𝑚
no. flowrates, Xw % Xm % K bar Density, Density, 𝜌𝑤 × 𝑋𝑤 + 𝜌𝑚 × 𝑋𝑚
= ,
Kg/s 𝜌𝑤 , 𝜌𝑚 , 100
Kg/m3 Kg/m3
16 2.03 33.17 58.27 308.15 50 994.035 776.7 782.30
18 2.03 33.17 58.27 308.15 50 994.035 776.7 782.30
21 1.95 34.45 60.47 307.15 10 994.3745 777.7 812.837
22 1.85 36.3 63.06 301.15 1 996.2365 783.4 855.646
24 1.84 36.37 63 304.15 1 995.344 780.5 853.73
25 1.41 42.6 57.39 353.15 1 971.8007 1.137 414.640
27 0.68 98.23 1.76 372.37 1 996.5162 1.064 978.896
22
Liquid Streams Pipe size calculation,
Table 6.3 Volumetric Flowrates and Internal diameter for each liquid stream pipes
Stream no. Volumetric Flowrates, × 10-3 ID, mm
m3/s
16 2.592 42
18 2.59 42
21 2.4017 41
22 2.1599 39
24 2.159 39
25 3.40 49
27 0.6598 22
For Streams containing both gas and liquid streams, the square of the pipe sizes for both the
streams are added and a square root of the result is taken.
Standard Pipe sizes and thicknesses[55],
Table 6.4 Standard Pipe Sizes, Thickness and ASME code for stream no. corresponding to calculated
internal diameter
Stream no. Internal Thickness Standard Pipe ASME
Diameter, mm sizes, in.
1 311.10 6.35 12 20
2 202.74 8.18 8 40S
3 182.58 18.26 8 120
4 122.24 9.53 5 80S
5 106.38 3.96 4
6 68.78 2.11 3 5S
7 62.68 5.16 2-1/2 40S
8 49.22 5.54 2 80S
9 97.38 2.11 3-1/2 5S
10 82.80 3.05 3 10S
11 95.50 3.05 3-1/2 10S
12 114.46 6.27 4-1/2 40S
13 679.24 15.88 28 30
14 640.94 9.53 26 40S
15 679.24 15.88 28 30
16 501.84 28.58 22 80
17 501.84 28.58 22 80
18 42.76 2.77 1-1/2 10S
19 52.48 3.91 2 40S
20 495.30 6.35 20 10
21 49.22 5.54 2 80S
22 106.38 3.96 4
23 102.26 6.02 4 40S
24 40.94 3.68 1-1/2 40S
25 182.58 18.26 8 120
26 266.20 3.40 10 5S
27 22.48 2.11 3/4 10S
23
Fig 6.1 P & ID first part
24
Fig 6.2 P & ID second part
25
Fig 6.3 P&ID Third Part
26
LINE
OPERATING CONDITIONS SPECIFICATIONS P&ID REFERENCES
NUMBER
SER
PRESS TEMP FLOW RATE
TAG NO. VIC FLUID MOL SIG. RANGE CONN.
MA NO MA Density VISC. RFQ MATERIAL CONT.
E (STAT NOR. MAX. MIN. WT Cv INSTRUMENT LOC. OF SET SIZE
NOR. X. R X. (kg/m3) Cp NO./MAKER BODY/ELEMENT ACTION
E) (g/gmol) POINT (in.)
BAR CELSIUS KG/HR
CV-101 C- CO2 1 1.1 25 28 Globe Valve L
1 8800 9680 8800 1.78 44 Min-max 12 18 Cr-8Ni PID-1
101 (G)
FIC-101 C- CO2 1 1.1 25 28 44 Flow Indicator Controller D
2 101 (G) 8800 9680 8800 1.78 12 PID-1
FT-101 C- CO2 1 1.1 25 28 1.78 44 PID-1

3 8800 9680 8800 Flow Transducer L 12 PPS Body
101 (G)
FE-101 C- CO2 1 1.1 25 28 1.78 44 Flow meter (orifice PID-1
4 8800 9680 8800 L Min-Max 12 S/S-316
101 (G) meter)
TI-101 C- CO2 1 1.1 25 28 1.78 44 Temperature Indicator L PID-1
5 8800 9680 8800 12
101 (G)
PI-101 C- CO2 1 1.1 25 28 Pressure Indicator (Strain L 3 in H2O – PID-1
6 8800 9680 8800 4.21 44 12 S/S-316
101 (G) Gauge) 1400 MPa
TI-102 E- CO2 3 3.3 65 71.5 4.21 44 Temperature Indicator L PID-1
7 8800 9680 8800 8
101 (G)
PI-102 E- CO2 3 3.3 65 71.5 4.21 44 Pressure Indicator (Strain L 3 in H2O – PID-1
8 8800 9680 8800 8 S/S-316
101 (G) Gauge) 1400 MPa
FI-102 E- CO2 3 3.3 65 71.5 4.21 44 Flow Indicator L PID-1
9 8800 9680 8800 8
101 (G)
CV-103 E- CO2 3 3.3 39 43 44 Globe Valve L PID-1
10 8800 9680 8800 5.11 Min-Max 8 18 Cr-8Ni
101 (G)
TIC- C- CO2 3 3.3 38 43 5.11 44 Temperature Indicator D PID-
11 8800 9680 8800 8
103 102 (G) Controller 1
TT-103 C- CO2 3 3.3 38 43 5.11 44 Temperature L PID-
12 8800 9680 8800 8 PPS Body
102 (G) Transducer 1
TE-103 CO2 3 3.3 38 43 5.11 44 Temperature element L Nickel PID-
C- -270 to
13 (G) 8800 9680 8800 (K-type thermocouple) 8 Chromium/Nickel 1
102 1260 oF
Alumel
TI-104 E- CO2 9 9.9 121 133 44 Temperature Indicator L PID-
14 8800 9680 8800 12.11 5
102 (G) 1
15 FI-104 E- CO2 9 9.9 121 133 12.11 44 Flow Indicator L PID-
8800 9680 8800 5
102 (G) 1
16 PI-104 CO2 9 9.9 121 133 12.11 44 Pressure Indicator L 3 in H2O PID-
E-
(G) 8800 9680 8800 (Strain Gauge) – 1400 5 S/S-316 1
102
MPa
17 CV-105 E- CO2 9 9.9 41 45 44 Globe Valve L PID-
8800 9680 8800 15.32 Min-Max 4 18 Cr-8Ni
102 (G) 1
18 TIC- C- CO2 9 9.9 38 43 15.32 44 Temperature Indicator D PID-
8800 9680 8800 4
19 TE-105 CO2 9 9.9 38 43 15.32 44 Temperature element L Nickel PID-
C- -270 to
(G) 8800 9680 8800 (K-type 4 Chromium/Nickel 1
103 1260oC
Thermocouple) Alumel
20 TT-105 C- CO2 9 9.9 38 43 44 Temperature L PID-
8800 9680 8800 15.32 4 PPS Body
103 (G) Transducer 1
21 TI-106 E- CO2 26 29 121 133 44 Temperature Indicator L PID-
8800 9680 8800 34.98 3
103 (G) 1
22 FI-106 E- CO2 26 29 121 133 34.98 44 Flow Indicator L PID-
8800 9680 8800 3
103 (G) 1
23 PI-106 CO2 26 29 121 133 34.98 44 Pressure Indicator L 3 in H2O PID-
E-
(G) 8800 9680 8800 (Strain Gauge) – 1400 3 S/S-316 1
103
MPa
24 CV-107 E- CO2 1 1.1 40 44 44 Globe Valve L PID-
8800 9680 8800 44.26 Min-Max 2.5 18 Cr-8Ni
103 (G) 1
25 TIC- C- CO2 26 29 38 43 44.26 44 Temperature Indicator D PID-
8800 9680 8800 2.5
26 TT-107 C- CO2 26 29 38 43 44.26 44 Temperature L PID-
8800 9680 8800 2.5 PPS Body
104 (G) transducer 1
27 TE-107 CO2 26 29 38 43 44.26 44 Temperature element L Nickel PID-
C- -270 to
(G) 8800 9680 8800 (K-type 2.5 Chromium/Nickel 1
104 1260oC
28 TI-108 M- CO2 50 55 92 101 44 Temperature Indicator L PID-
8800 9680 8800 72.64 2
101 (G) 1
27
29 FI-108 M- CO2 50 55 92 101 72.64 44 Flow Indicator L PID-
8800 9680 8800 2
101 (G) 1
30 PI-108 CO2 50 55 92 101 72.64 44 Pressure Indicator L 3 in H2O PID-
M-
(G) 8800 9680 8800 (Strain Gauge) – 1400 2 S/S-316 1
101
MPa
31 FIC- C- H2 (G) 30 33 25 28 Flow Indicator D PID-
1200 1320 1200 2.44 2 3.5
109 105 Controller 1
32 FT-109 C- H2 (G) 30 33 25 28 2.44 2 Flow Transducer L PID-
1200 1320 1200 3.5 PPS Body
105 1
33 FE-109 C- H2 (G) 30 33 25 28 2.44 2 Flow element (orifice L PID-
1200 1320 1200 Min-Max 3.5 S/S-316
105 meter) 1
34 CV-109 C- H2 (G) 30 33 25 28 2.44 2 Globe valve L PID-
1200 1320 1200 3.5 18 Cr-8Ni
105 1
35 PI-109 H2 (G) 30 33 25 28 2.44 2 Pressure Indicator L 3 in H2O PID-
C-
1200 1320 1200 (Strain Gauge) – 1400 3.5 S/S-316 1
105
MPa
36 TI-109 C- H2 (G) 30 33 25 28 2 Temperature Indicator L PID-
1200 1320 1200 2.44 3.5
105 1
37 FI-110 M- H2 (G) 50 55 73 80 2 Flow Indicator L PID-
1200 1320 1200 3.52 3
101 1
38 PI-110 H2 (G) 50 55 73 80 3.52 2 Pressure Indicator L 3 in H2O PID-
M-
1200 1320 1200 (Strain Gauge) – 1400 3 1
101
MPa
39 TI-110 M- H2 (G) 50 55 73 80 3.52 2 Temperature Indicator L PID-
1200 1320 1200 3
101 1
40 TI-111 E- Gas 50 55 74 82 Temperature Indicator L PID-
10000 11000 10000 21.79 12.6 3.5
104 2
41 PI-111 Gas 50 55 74 82 21.79 12.6 Pressure Indicator L 3 in H2O PID-
E-
10000 11000 10000 (Strain Gauge) – 1400 3.5 S/S-316 2
104
MPa
42 FIC- E- Gas 50 55 74 82 21.79 12.6 Flow Indicator D PID-
10000 11000 10000 3.5
43 FT-111 E- Gas 50 55 74 82 21.79 12.6 Flow Transducer L PID-
10000 11000 10000 3.5 PPS Body
104 2
44 CV-111 E- Gas 50 55 74 82 21.79 12.6 Globe Valve L PID-
10000 11000 10000 Min-Max 3.5 18 Cr-8Ni
104 2
45 FE-111 E- Gas 50 55 74 82 12.6 Flow element (orifice L PID-
10000 11000 10000 21.79 Min-Max 3.5 S/S-316
104 meter) 2
46 CV-112 E- Gas 11.36 12.5 185 204 12.6 Globe Valve L PID-
11500 12650 11500 14.75 Min-Max 4
104 2
47 TIC- E- Gas 50 55 241 265 14.75 12.6 Temperature Indicator D PID-
10000 11000 10000 4
48 TT-112 E- Gas 50 55 241 265 14.75 12.6 Temperature L PID-
10000 11000 10000 4 PPS Body
104 Transducer 2
49 TE-112 Gas 50 55 241 265 14.75 12.6 Temperature element L Nickel PID-
E- -270 to
10000 11000 10000 (K-type 4 Chromium/Nickel 2
104 1260oC
50 PI-113 Gas 50 55 240 264 Pressure Indicator L 3 in H2O PID-
R-
281571.4 309728 281571.4 13.2 11 (Strain Gauge) – 1400 28 S/S-316 2
101
MPa
51 TI-113 R- Gas 50 55 240 264 13.2 11 Temperature Indicator L PID-
281571.4 309728 281571.4 28
101 2
52 FE-113 R- Gas 50 55 240 264 13.2 11 Flow element (orifice L 28 PID-
281571.4 309728 281571.4 Min-Max S/S-316
101 meter) 2
53 CV-113 R- Gas 50 55 240 264 13.2 11 Globe Valve L 28 PID-
281571.4 309728 281571.4 Mi 18 Cr-8Ni
101 2
54 FIC- R- Gas 50 55 240 264 13.2 11 Flow Indicator D 28 PID-
281571.4 309728 281571.4
55 FT-113 R- Gas 50 55 240 264 11 Flow Transducer L 28 PID-
281571.4 309728 281571.4 13.2 PPS Body
101 2
56 TE-114 Gas 50 55 241 265 11 Temperature element L Nickel PID-
E- -270 to
271670 298837 271670 13.15 (K-type 26 Chromium/Nickel 2
105 1260oC
57 TT_114 E- Gas 50 55 241 265 13.15 11 Temperature L 26 PID-
271670 298837 271670
105 Transducer 2
28
58 TIC- E- Gas 50 55 241 265 13.15 11 Temperature Indicator D 26 PID-
271670 298837 271670
59 CV-114 E- Gas 11.36 12.5 185 204 13.15 11 Globe Valve L 26 PID-
350000 385000 350000 Min-Max 18 Cr-8Ni
105 2
60 CV-115 R- Gas 1 1.1 25 28 2450000 269500 2450000 Globe Valve L PID-
13.34 11.4 Min-Max 28 18 Cr-8Ni
101 0 00 0 2
61 TIC- R- Gas 50 55 240 264 11.4 Temperature Indicator D 28 PID-
281571.4 309728 281571.4 13.34
62 TT-115 R- Gas 50 55 240 264 11.4 Temperature L 28 PID-
281571.4 309728 281571.4 13.34 PPS Body
101 Transducer 2
63 TE-115 Gas 50 55 240 264 11.4 Temperature element L 28 Nickel PID-
R- -270 to
281571.4 309728 281571.4 13.34 (K-type Chromium/Nickel 2
101 1260oC
64 PI-115 Gas 50 55 240 264 11.4 Pressure Indicator L 3 in H2O 28 PID-
R-
281571.4 309728 281571.4 13.34 (Strain Gauge) – 1400 S/S-316 2
101
MPa
65 PSV- R- Gas 50 55 240 264 11.4 Pressure Safety Valve L 28 PID-
281571.4 309728 281571.4 13.34
115 101 2
66 CV-116 E- Gas 1 1.1 79 87 Globe Valve L PID-
514231 565654 514231 21.89 11 Min-Max 22 18 Cr-8Ni
106 2
67 TIC- E- Gas 50 55 35 39 21.89 11 Temperature Indicator D 22 PID-
281571.4 309728 281571.4
68 TT-116 E- Gas 50 55 35 39 21.89 11 Temperature L 22 PID-
281571.4 309728 281571.4 PPS Body
106 Transducer 2
69 TE-116 Gas 50 55 35 39 21.89 11 Temperature element L 22 Nickel PID-
E- -270 to
281571.4 309728 281571.4 (K-type Chromium/Nickel 2
106 1260oC
70 CV-117 TK- Vapor 50 55 35 39 21.89 11 Globe Valve L 22 PID-
281571.4 309728 281571.4 Min-Max 18 Cr-8Ni
101 Liquid 2
71 FIC- TK- Vapor 50 55 35 39 21.89 11 Flow Indicator D 22 PID-
281571.4 309728 281571.4
117 101 Liquid Controller 2
72 FT-117 TK- Vapor 50 55 35 39 21.89 11 Flow Transducer L 22 PID-
281571.4 309728 281571.4 PPS Body
101 Liquid 2
73 FE-117 TK- Vapor 50 55 35 39 21.89 11 Flow element (orifice L PID-
281571.4 309728 281571.4 Min-Max 22 S/S-316
101 Liquid meter) 2
74 PI-118 Vapor 50 55 35 39 21.89 11 Pressure Indicator L 3 in H2O PID-
TK-
Liquid 281571.4 309728 281571.4 (Strain Gauge) – 1400 S/S-316 2
101
MPa
75 PSV- TK- Vapor 50 55 35 39 21.89 11 Pressure Safety Valve L PID-
281571.4 309728 281571.4
118 101 Liquid 3
76 PI-119 Vapor 50 55 35 39 21.89 11 Pressure Indicator L 3 in H2O PID-
S-
Liquid 2744.14 3018 2744.14 (Strain Gauge) – 1400 1.5 S/S-316 3
101
MPa
77 BV-101 S- Vapor 1 1.1 35 39 21.89 11 L PID-
2744.14 3018 2744.14
101 Liquid 3
78 HA-101 S- Vapor 1 1.1 35 39 21.89 11 L PID-
2744.14 3018 2744.14
101 Liquid 3
79 CV-118 TK- Vapor 50 55 35 39 21.89 11 Globe Valve L PID-
7157 7873 7157 Min-Max 1.5 18 Cr-8Ni
102 Liquid 3
80 FIC- TK- Vapor 50 55 35 39 21.89 11 Flow Indicator D PID-
7157 7873 7157 1.5
81 FT-118 TK- Vapor 50 55 35 39 21.89 11 Flow Transducer L PID-
7157 7873 7157 1.5 PPS Body
102 Liquid 3
82 FE-118 TK- Vapor 50 55 35 39 21.89 11 Flow element (orifice L PID-
7157 7873 7157 Min-Max 1.5 S/S-316
102 Liquid meter) 3
83 CV-122 TK- Vapor 1 1.1 28 31 Globe Valve L PID-
7157 7873 7157 1.31 32.6 Min-Max 4 18 Cr-8Ni
102 Liquid 3
84 FE-122 Vapor 1 1.1 28 31 32.6 L PID-
TK- Liquid 3
7157 7873 7157 1.31 Flow element (orifice Min-Max 4 S/S-316
102
meter)
85 FT-122 TK- Vapor 1 1.1 28 31 1.31 32.6 Flow Transducer L PID-
7157 7873 7157 4 PPS Body
102 Liquid 3
86 FIC- TK- Vapor 1 1.1 28 31 1.31 32.6 Flow Indicator D PID-
7157 7873 7157 4
29
Table 6.5 List of Instruments
87 HA-123 TK- Vapor 1 1.1 31 34 L PID-

673 740 673 1.29 32.6
102 3
88 CV-124 TK- Liquid 1 1.1 31 34 Globe Valve L PID-
6484 7132 6484 854 Min-Max 1.5 18 Cr-8Ni
102 3
89 FE-124 TK- Liquid 1 1.1 31 34 854 Flow element (orifice L PID-
6484 7132 6484 Min-Max 1.5 S/S-316
102 meter) 3
90 FT-124 TK- Liquid 1 1.1 31 34 854 Flow Transducer L PID-
6484 7132 6484 1.5 PPS Body
102 3
91 FIC- TK- Liquid 1 1.1 31 34 854 Flow Indicator D PID-
6484 7132 6484 1.5
92 CV-125 E- Liquid 11.36 12.5 54 60 Globe Valve L PID-
20000 22000 20000 415 Min-Max 6 18 Cr-8Ni
107 3
93 TE-125 Liquid 1 1.1 76 84 415 Temperature element L Nickel PID-
E- -270 to
6484 7132 6484 (K-type 6 Chromium/Nickel 3
107 1260oC
94 TT-125 E- Liquid 1 1.1 76 84 415 Temperature L PID-
6484 7132 6484 6 PPS Body
107 Transducer 3
95 TIC- E- Liquid 1 1.1 76 84 415 Temperature Indicator D PID-
6484 7132 6484 6
96 TC-127 T- Liquid 1 1.1 99 109 Temperature D PID-
2402.42 2643 2402.42 979 3/4
101 Controller 3
97 CV-127 T- Liquid 1 1.1 99 109 Globe Valve L 18 Cr-8Ni PID-
2402.42 2643 2402.42 979 Min-Max 3/4
101 3
98 CV-126 T- Liquid 1 1.1 64 70 Globe Valve L 18 Cr-8Ni PID-
6122.73 6735 6122.73 1.14 Min-Max 10
101 3
99 FE-126 T- Liquid 1 1.1 64 70 1.14 Flow element (orifice- L 10 PID-
6122.73 6735 6122.73 Min-Max S/S-316
101 meter) 3
100 FC-126 T- Liquid 1 1.1 64 70 1.14 Flow Controller D 10 PID-
6122.73 6735 6122.73
101 3
101 LE-128 T- Liquid 1 1.1 64 70 Level element L 10 PID-
4081.82 4490 4081.82
101 3
102 LT-128 T- Liquid 1 1.1 64 70 Level Transducer L 10 PID-
4081.82 4490 4081.82 PPS Body
101 3
103 LC-128 T- Liquid 1 1.1 64 70 Level Controller D 10 PID-
4081.82 4490 4081.82
101 3
104 CV-128 T- Liquid 1 1.1 64 70 Globe Valve L 10 PID-
4081.82 4490 4081.82 Min-Max 18 Cr-8Ni
101 3
105 CV-129 T- Liquid 1 1.1 64 70 Globe Valve L 10 PID-
4081.82 4490 4081.82 Min-Max 18 Cr-8Ni
101 3
106 FC-129 T- Liquid 1 1.1 64 70 Flow Controller D 10 PID-
4081.82 4490 4081.82
101 3
107 LC-130 T- Liquid 1 1.1 99 109 Level Controller D 3/4 PID-
2402.42 2643 2402.42
101 3
108 CV-130 T- Liquid 1 1.1 99 109 Globe Valve L 3/4 PID-
2402.42 2643 2402.42 Min-Max 18 Cr-8Ni
101 3
(1) Fluid State (2) Location (3) Signal
G: Gas or Vapor L: Local E: Electric

D: DCS AI: Analog Input
DO: Digital Output
30
CHAPTER 7
EQUIPMENT SPECIFICATION
S. ITEM EQUIPMENT NAME QTY SPEC AND SIZE MATERIAL OPERATION DESIGN INSULATION REMARKS
NO. NO. Temp Press. Temp Press.
(C) (bar) (C) (bar)
1 C-101 Compressor 1 Type: Centrifugal 25 1 209 3.3 Isentropic
2 C-102 Compressor 1 Type: Centrifugal 38 3 133 9.9 Isentropic
3 C-103 Compressor 1 Type: Centrifugal 38 9 132.5 29 Isentropic
4 C-104 Compressor 1 Type: Centrifugal 38 26 100.5 55 Isentropic
5 C-105 Compressor 1 Type: Centrifugal 25 30 136 55 Isentropic
6 E-101 Heat Exchanger 1 Type: Shell and Tube Carbon Steel 104 3 115 3.3
Shell OD = 12.75 in
7 E-102 Heat Exchanger 1 Type: Shell and Tube Carbon Steel 120 9 132 9.9
Shell OD = 14 in
8 E-103 Heat Exchanger 1 Type: Shell and Tube Carbon Steel 120.5 26 132.5 29
Shell OD = 8.625 in
9 E-104 Heat Exchanger 1 Type: Shell and Tube Carbon Steel 74 50 275 55
Shell OD = 26.378 in
10 E-105 Heat Exchanger 1 Type Shell and Tube Carbon Steel 35 50 275 55
Shell OD = 82.874 in
11 E-106 Heat Exchanger 1 Type: Shell and Tube Carbon Steel 240 50 264 55
Shell OD = 30.47 in
12 E-107 Heat Exchanger 1 Type: Shell and Tube 31 1 165 12.5
Shell OD = 18 in Carbon Steel
13 R-101 Fixed Bed Reactor 1 Type Fixed Bed catalytic Stainless 13Cr 240 50 264 55 Isothermal
reactor (Grade 410)
Capacity: 78.82 m3 (D = 2.8m,
L = 12.8m)
Domed end: Ellipsoidal
14 TK-101 Vapor Liquid Separator 1 Type: Vertical (Hemispherical) Carbon Steel 35 50 100 55 Isothermal
Capacity: 196.86 m3 (D =
5.4m, L = 8.6m)
15 TK-102 Flash Tank 1 Type: Horizontal (Ellipsoidal) Carbon Steel 31 1 62 1.1 Isothermal
Capacity: 2.6 m3 (D = 1.03m, L
= 3.1m)
16 T-101 Distillation Column 1 Type: Sieve tray column Column material = 80 1 88 1.1
Capacity: 55.62 m3 (D = Carbon Steel
1.62m, L = 27m) Tray material =
SS314
Table 7.1 List of Equipments
31
7.1 Equipment Specification Calculations
7.1.1 Heat Exchanger
7.1.1.1 E-101
The heat exchanger used is shell and tube heat exchanger where the coolant (water) is used
on the tube side and the hot gas (CO2) is used on the shell side.
For shell side,
mass flow rate = 8800 Kg/h
Inlet temperature = 377.389 K
Outlet temperature = 311.15 K
For tube side,
Outlet temperature =313.15 K
Here,
Heat capacity of CO2 = 0.889 KJ/Kg·K
(The heat capacity is taken at the average of inlet and outlet temperature i.e. 344.27 K)
Heat load = 8800 · 0.889 · (377.389 − 311.15)
= 518200.9448 KJ/h
Now, we fix the inlet and outlet temperature of the coolant in order to find the mass flow rate
of water.
Heat capacity of water = 4.2 KJ/Kg·K
The same amount of heat is gained by the water so,
518200.9448 = m·4.2·(313.15-298.15)
m = 8139.67 Kg/h
For sizing the heat exchanger, ASPEN V.10 is used. The obtained mass flow rate of coolant
and the required parameters are used as an input in ASPEN V.10 to meet the desired outlet
temperature of the hot gas.
The configuration is fixed as default in the heat exchanger and the geometry are presented in
the specification sheet of the heat exchanger.
7.1.1.2 E-102
For shell side,
For tube side,
Here,
Heat load = 8800 · 0.897 · (393.15 − 311.15)
= 650140.57 KJ/h
of water.
32
650140.57 = m·4.2·(313.15-298.15)
m = 9221.85 Kg/h
7.1.1.3 E-103
For shell side,
For tube side,
Here,
Heat load = 8800 · 0.897 · (393.63 − 311.15)
= 651064.128 KJ/h
of water.
651064.128 = m·4.2·(313.15-298.15)
m = 10334.35 Kg/h
7.1.1.4 E-106
on the tube side and the hot fluid is used on the shell side.
For shell side,
mass flow rate = 281571.4 Kg/h
Compositions:
CO2 = 0.8239
CO = 0.0073891
H2O = 0.0098863
H2 = 0.1317
CH3OH = 0.0272
33
For tube side,
Here,
Heat load = 281571.4 · 2.871 · (513.15 − 308.15)
= 165720259.7 KJ/h
of water.
165720259.7 = m·4.2·(375.15-298.15)
m = 512431.23 Kg/h
7.1.2 Vapor-Liquid Separator, TK-101
The compositions along with their densities in the feed are:
Table 7.2 Each Component Compositions and their densities in the TK-101
Component Composition Density (Kg/m3)
CO2 0.2184 1.96E-6
CO 3.08E-3 1.14
H2 0.7622 0.08988
CH3OH 9.89E-3 792
H2O 6.40E-3 997
Here, the density of liquid at STP = (9.89E-3×792) + (6.40E-3×997)

= 14.21 Kg/m3
The density of vapor at STP = (0.2184×1.96E-6) + (3.08E-3×1.14) + (0.7622×0.08988)
= 0.072 Kg/m3
Now, we will find the density of liquid and vapor at T = 308.15 K and P = 50 bar.
We have,
P1 ρ1 T1
= ×
P2 ρ2 T2
For liquid,
1 14.21 273.15
= ×
50 ρl 308.15
ρl = 629.8 Kg/m3
For liquid,
1 0.072 273.15
= ×
50 ρv 308.15
34
ρv = 3.19 Kg/m3
Now, we will estimate the settling velocity of the liquid.
1⁄
ρl −ρv 2
ut = 0.07[ ]
ρv
1
629.8−3.19 ⁄2
ut = 0.07[ ]
3.19
ut = 0.98 m/s
Here, with specifying the demister pad the same settling velocity is used.
For the vapor volumetric flow rate,
274414.1136
V=
3600×3.19
V = 23.895 m3 /s
The minimum allowable diameter of the separator is given by
4×V
Dv = √( )
π×ut
4×23.895
Dv = √( )
π×0.98
Dv = 5.4 m
For the calculation of liquid level,
7157.2939
Liquid volumetric flow rate, L =
3600×629.8
L = 3.16 × 10−3
Allowing a minimum of 10 min hold up
Volume held in vessel = 3.16 × 10−3 · (10 × 60)
= 1.896 m3
volume held up
Liquid depth required, hv =
vessel cross sectional area
1.896
hv = 2
π×5.4 ⁄4
hv = 0.08 m
From the nozzle of the feed below to the liquid level it is taken minimum D v/2 and above the
nozzle to the demister pad, it is taken as minimum Dv. The thickness or the height of the
demister pad is also taken as the minimum value of 0.4 m.
Hence, the height of the separator = hv + Dv/2 + Dv + 0.4
= 8.6 m
For the design of domed end,
As the diameter of the vessel is greater than 4500 mm, the hemispherical head is used.
The minimum wall thickness is given by,
Pi ·Di
t=
4·SE−0.4·Pi
Here, the operating pressure is 50 bar.
Hence, the design pressure is 55 bar (5.5 N/mm2) which is 10 p above the operating pressure.
The material used for the construction is Carbon Steel.
35
Hence, from ASME BPV Code Sec. VIII D.1, corresponding to the operating temperature,
the maximum allowable stress = 12.9×103 psi = 88.9 N/mm2
So,
5.5×5.4×103
t=
4×88.9×1−0.4∗5.5
t = 84 mm
7.1.3 Flash Separator, TK-102

The compositions along with their densities in the feed are:
Table 7.3 Each Component Compositions and their densities in the TK-102
Component Composition Density (Kg/m3)
CO2 0.0505 1.96E-6
CO 1.47E-4 1.14
H2 0.0161 0.08988
CH3OH 0.4635 792
H2O 0.4697 997
Here, the density of liquid at STP = (0.4635 × 792) + (0.4697 × 997)

= 835.38 Kg/m3
The density of vapor at STP = (0.0505 × 1.96E-6) + (1.47E-4 × 1.14) + (0.0161 × 0.08988)
= 1.61 × 10-3 Kg/m3
Now, we will find the density of liquid and vapor at T = 308.15 K and P = 50 bar.
We have,
P1 ρ1 T1
= ×
P2 ρ2 T2
For liquid,
1 835.38 273.15
= ×
1 ρl 304.15
Kg
ρl = 750.23 m3
For liquid,
1 0.00161 273.15
= 𝜌 × 308.15
1 𝑣
Kg
ρv = 0.00145 m3
Now, we will estimate the settling velocity of the liquid.
1⁄
ρl −ρv 2
ut = 0.07 [ ]
ρv
1⁄
750.23−0.00145 2
ut = 0.07 [ ]
0.00145
m
ut = 50.35 s
Here, with specifying the demister pad the same settling velocity is used.
For the vapor volumetric flow rate,
654.686
V = 3600×0.00145
m3
V = 125.42 s
Taking, liquid height at half the vessel diameter,
hv = 0.5Dv and corresponding to the operating pressure Lv/Dv = 3
36
πD2v
Now, the cross sectional area for the vapor flow = × 0.5
4
Vapor volumetric flow rate
Vapor velocity, uv = Cross sectional area for vapor flow
125.42
uv = πD2
v ∗0.5
4
Vapor residence time required for the droplets to settle to liquid surface
ℎ𝑣 0.5𝐷
= 50.35𝑣
𝑢𝑡
vessel length
Now, Actual residence time = vapor velocity
Lv 3Dv
= 125.42
uv
πD2 v ∗0.5
4
Lv
= 0.0094D3v
uv
For the separation, required residence time = actual
0.5Dv
= 0.0094D3v
50.35
Dv = 1.03 m
we have,
Lv
=3
Dv
Hence, Lv = 3.1 m
In this case also, we are using the same thickness of the demister pad (0.4 m) as used in the
vapor-liquid separator.
For the design of domed end,
As the diameter of the vessel is less than 4500 mm, the ellipsoidal head is used.
The minimum wall thickness is given by,
𝑃𝑖 𝐷𝑖
𝑡 = 2𝑆𝐸−0.2𝑃
𝑖
Here, the operating pressure is 1 bar.
Hence, the design pressure is 1.1 bar (0.11 N/mm2) which is 10% above the operating
pressure.
The material used for the construction is Carbon Steel.
Hence, from ASME BPV Code Sec. VIII D.1, corresponding to the operating temperature,
the maximum allowable stress = 12.9*103 psi = 88.9 N/mm2
So,
0.11∗1.03∗103
𝑡 = 2∗88.9∗1−0.2∗0.11
𝑡 = 0.64 𝑚𝑚
7.1.4 Distillation Column, T-101

For methanol,
32
ρv,STP = 22.4
ρv,STP = 1.43 Kg/m3
The inlet temperature in the column is 353.15 K. So, the density of vapor at this temperature
is
ρv,STP 273.15
= 1.43 ∗ 353.15
ρv
37
ρv = 1.105 Kg/m3
The density of liquid methanol at 353.15 K is 732.3 Kg/m3.
For finding the column diameter,
A plot from Unit Operation of Chemical Engineering, Figure 21.26 is taken as a reference to
calculate the vapor velocity[56].
So,
L R
= (R+1)
V
The reflux in the column is taken as 1.5.
1⁄ 1⁄
L ρv 2 1.5 1.105 2
(ρ ) = 2.5 (732.3) = 0.0233
V l
For the plate spacing of 18 in.
1⁄
ρv 2 20 0.2
K v = uc (ρ −ρ ) (σ) = 0.29
l v
The surface tension of methanol at 353.25 K is 17.5 dyne/cm.
1⁄
732.3−1.105 2 17.5 0.2
uc = 0.29 ( ) ( 20 )
1.105
uc = 7.26 ft/s
uc = 2.21 m/s
Now, for vapor flow rate,
V = D(R + 1) = 2.5D
2.5∗4179.1063
V = 1.105∗3600
V = 2.63 m3 /s
For the cross sectional area of the column,
2.63
Bubbling area = 2.21 = 1.19 m2
For the bubbling area to be the 70% of the column area,
1.19
Column area = 0.7 = 1.7 m2
1⁄
4∗1.7 2
Hence, Column diameter = ( ) = 1.47 m
π
Considering the safety we are adding the 10% in the column diameter and obtain it to be 1.62
m.
7.1.5 Fixed Bed Reactor, R-101

As the fixed bed reactor is the tubular reactor, for the calculation of the diameter of the
reactor
we use the same concept.
First of all, we will calculate the bundle diameter and with some clearance we calculate the
diameter of the reactor.
The bundle diameter is given by
1
Nt ⁄n1
Db = do ( )
K1
We have,
Number of tubes (Nt) = 4000
Thickness of the tube (t1) = 3.38 mm
38
Inside diameter of the tube (di) = 26.64 mm
Outside diameter of the tube (do) = di + 2 × t1 = 33.4 mm
Now,
The reactor is like the one shell pass and one tube pass heat exchanger. So,
K1 = 0.319
n1 = 2.142
Then,
1
4000 ⁄2.142
Db = 33.4( ) = 2735.5 mm
0.319
With the clearance of 100 mm
Diameter of the reactor (D) = 2835.5 mm = 2.8 m
For the domed ends,
As the diameter of the reactor is less than 4500 mm, the head is the ellipsoidal type.
So,
Pi Di
t=
2SE−0.2Pi
For the material of Stainless steel 13 Cr Grade 410,
the maximum allowable stress (S) = 119.3 N/mm2
Design pressure (Pi) = 5.5 N/mm2
So,
5.5∗2.8∗1000
t= = 64.84 mm
2∗119.33−0.2∗5.5
For the cylindrical shell,

Pi Di
t=
2SE−1.2Pi
5.5∗2.8∗1000
t= = 66.4 mm
2∗119.33−1.2∗5.5
For the length of the reactor,

We assume that the tube support is 50% of the reactor diameter.
So,
Length of the reactor (L) = Tube length + 2 × (50% of D)

= 10 + 2 × (50% od 2.8)
= 12.8 m
For the volume of the reactor,
Volume of the reactor,V = Cross sectional area × Length
πD2
V= ×L
4
π×2.82
V= × 12.8
4
V = 78.82 m3
For the calculation of catalyst weight,

We have,
39
Particle density of catalyst = 1775 Kg/m3
Void fraction = 0.5
Bulk density of catalyst = Void fraction × Particle density of catalyst
= 0.5 × 1775
= 887.5 Kg/m3
Weight of catalyst (mc) = Bulk density of catalyst ×Volume of the reactor
= 887.5 × 78.82
= 69,952 Kg
As the reactor used needs to be isothermal, and the reactor releases a lot of heat we use the
water to cool the reactor and to maintain the reactor temperature. The rector generates steam
in the course of maintaining the temperature.
Here, we are about to calculate the amount of steam generated.
Reactor heat duty = amount of heat required to boil + Latent heat of vaporization +
Amount of heat required to reach 185 o C
Reactor heat duty = mw Cp dt + ms Lv + ms Cp dt
Here, reactor heat duty = 8.354 × 109 KJ/h
we assume,
mass of water (mw) = 25,272,610.7 Kg/h
Inlet water temperature = 25 oC
Specific heat capacity of water (Cp) = 4.2 KJ/Kg·K[57]
Latent heat of vaporization (Lv) = 2013.56 KJ/Kg[58] ,Specific heat of steam = 2.5944 KJ/Kg
Now,
8.354 × 109 KJ/h = mw × 4.2 × (100 − 25) + ms × 2013.56 + ms × 2.5944 × (185 −
100)
ms = 175965 Kg/h
The heat exchanger E-104, E-105 and E-107 are simulated using ASPEN V.10. The flow rate
of the steam is assumed in each heat exchanger in order to meet the desired cold stream outlet
temperature.
7.2 Equipment Specification Sheets

40
7.2.1 E-101 Specification Sheet
1 Company
2 Service of unit
3 Item No.
4 Date:
5 Size Type: BEM
6 PERFORMANCE OF UNIT
7 Fluid Allocation Shell Side Tube Side
8 Fluid Name Gas Water
9 Fluid Quantity, Total 8800 Kg/h 8200 Kg/h
10 Vapor 8800 Kg/h
11 Liquid 8200 Kg/h
12 Inlet Outlet Inlet Outlet
13 Temperature, K 377.39 311.16 298.15 311.5
14 Pressure, bar 3 2.78 1 0.97
15 Density, g/cc 0.0042 0.0052 0.961 0.1943
16 Molecular weight, g/mol 44.01 18.02
17 Heat Duty, KW 146.3
18 CONSTRUCTION OF ONE SHELL
19 Shell Tube SKETCH
Side Side
20 Design Pressure 3.3 1.1
21 Design Temperature 416 344
22 Number of Passes 1 1
23 Corrosion Allowance,
mm
24 Fouling Resistance,
m2-K/W
25 Connections
26 Size/Rating
27 Allowable Pressure 0.26 0.2
drop, bar
28 Calculated Pressure 0.217 0.032
drop, bar
29 Dp ratio 0.84 0.16
30 Tube Pattern 30-Triangular
31 Baffle Type Single Segmental
32 Baffle cut orientation Horizontal
33 Exchanger Material Carbon Steel
34 Tube Length, in 118.11
35 Baffle Spacing, in 13.189
36 Number of Baffles 6
37 Number of Tubes 98
38 Tube OD, in 0.75 Tube Pitch, in 0.9375
39 Shell ID, in 12.09 Shell OD, in 12.75
41
1 Company
2 Service of Unit
3 Item No.
4 Date
5 Size Type: BEM
10 Vapor 8800 Kg/h
11 Liquid 9222 Kg/h
13 Temperature, K 393.51 311.26 298.15 313.4
14 Pressure, bar 9 8.78 1 0.96
15 Density, g/cc 0.0123 0.0159 0.961 0.0169
17 Heat Duty, KW 188
Side Side
20 Design Pressure 10 1.1
22 Number of Passes per shell 1 2
23 Corrosion Allowance, mm
24 Fouling Resistance, m2-
K/W
25 Connections
26 Size/Rating
27 Allowable Pressure drop, 0.26 0.2
bar
28 Calculated Pressure drop, 0.22 0.036
bar
29 Dp ratio 0.84 0.18
39 Shell ID, in 13.25 Shell OD, in 14
42
1 Company
2 Service of Unit
3 Item No.
4 Date
5 Size Type: BEM
10 Vapor 8800 Kg/h
11 Liquid 10334 Kg/h
13 Temperature, K 393.63 311.43 298.15 312.93
14 Pressure, bar 26 25.91 1 0.97
15 Density, g/cc 0.0042 0.0052 0.961 0.1943
Side Side
K/W
25 Connections
26 Size/Rating
bar
bar
29 Dp ratio 0.14 0.0.24
43
1 Company
2 Location
3 Item No.
4 Date
5 Size Type: BEM
8 Fluid Name Steam Gas
10 Vapor 11500 Kg/h 10000 Kg/h
11 Liquid
13 Temperature, K 523.15 457.54 347.23 513.85
14 Pressure, bar 11.36 11.09 50 49.94
15 Density, g/cc 0.96107 0.002317 0.01345 0.02286
Side Side
20 Design Pressure 13 55
K/W
25 Connections
26 Size/Rating
bar
bar
29 Dp ratio 0.99 0.093
44
1 Company
2 Service of unit
3 Item No.
4 Date
5 Size Type: BEM
10 Vapor 350000 Kg/h 271670 Kg/h
11 Liquid
13 Temperature, K 523.15 457.75 308.15 514.78
14 Pressure, bar 11.36 11.15 50 49.93
15 Density, g/cc 0.0048 0.0067 0.022 0.0132
Side Side
20 Design Pressure 13 55
K/W
25 Connections
26 Size/Rating
bar
bar
29 Dp ratio 0.798 0.1156
35 Baffle Spacing, in 27
45
1 Company
2 Service of Unit
3 Item No.
4 Date
5 Size Type: BEM
8 Fluid Name Hot fluid Water
9 Fluid Quantity, Total 281571.4 Kg/h 514231 Kg/h
10 Vapor
11 Liquid
13 Temperature, K 513.15 308.1 298.15 352.4
14 Pressure, bar 50 49.91 1 0.9
15 Density, g/cc 0.96107 0.002317 0.01345 0.02286
Side Side
K/W
25 Connections
26 Size/Rating
bar
bar
29 Dp ratio 0.49 0.147
46
1 Company
2 Service of unit
3 Item No.
4 Date
5 Size Type: BEM
10 Vapor 20000 Kg/h 6484 Kg/h
11 Liquid
13 Temperature, K 423.15 326.66 304.15 349.02
14 Pressure, bar 11.36 11.29 1 0.835
15 Density, g/cc 0.83049 0.936 0.379 0.00103
16 Molecular weight, 18.01 24.99
g/mol
Side Side
22 Number of Passes 1 1
per shell
23 Corrosion
Allowance, mm
24 Fouling Resistance,
m2-K/W
25 Connections
26 Size/Rating
27 Allowable Pressure 0.26 0.2
drop, bar
28 Calculated Pressure 0.06228 0.164
drop, bar
29 Dp ratio 0.8216 0.2396
39 Shell ID, in 17.25 Shell OD, in 18
47
7.2.8 C-101 Specification Sheet
1 Company
2 Location
3 Service of Unit
4 Item No.
5 Date
7 Gas Handled
8 Molecular Weight, g/mol
9 Inlet Outlet
10 Temperature, K 298.15 377.39
11 Pressure, bar 1 3
12 Enthalpy, MM KJ/hr 2.6861 3.2977
13 Entropy, KJ/Kg-mol-K 187.1274 187.1274
14 Cp, KJ/Kg-mol-K 37.4612 41.2037
15 Cv, KJ/Kg-mol-K 28.9838 32.5813
16 Cp/Cv 1.2925 1.2646
17 Mass flow rate, Kg/hr 8.800 8.800
18 Z (from actual density) 0.9951 0.9937
19 Molecular weight 44.010 44.010
20 Isentropic coefficient 1.2711
21 Polytropic Coefficient 1.2711
22 Isentropic Head 7087.42
23 Polytropic Head 7087.42
24 Theoretical Work, HP 227.84
48
1 Company
2 Location
3 Service of Unit
4 Item No.
5 Date
7 Gas Handled
9 Inlet Outlet
10 Temperature, K 311.15 393.51
11 Pressure, bar 3.00 9.00
14 Cp, KJ/Kg-mol-K 38.5088 42.5180
15 Cv, KJ/Kg-mol-K 29.6934 33.3067
16 Cp/Cv 1.2969 1.2766
49
1 Company
2 Location
3 Service of Unit
4 Item No.
5 Date
7 Gas Handled
9 Inlet Outlet
10 Temperature, K 311.15 393.63
11 Pressure, bar 9.00 26.00
14 Cp, KJ/Kg-mol-K 39.8675 44.8783
15 Cv, KJ/Kg-mol-K 29.8631 33.6743
16 Cp/Cv 1.3350 1.3327
50
1 Company
2 Location
3 Service of Unit
4 Item No.
5 Date
7 Gas Handled
9 Inlet Outlet
10 Temperature, K 311.15 364.55
11 Pressure, bar 26.00 50.00
14 Cp, KJ/Kg-mol-K 45.2104 50.2985
15 Cv, KJ/Kg-mol-K 30.3967 33.2269
16 Cp/Cv 1.4873 1.5138
51
1 Company
2 Location
3 Service of Unit
4 Item No.
5 Date
7 Gas Handled
9 Inlet Outlet
10 Temperature, K 298.15 345.34
11 Pressure, bar 30.00 50.00
14 Cp, KJ/Kg-mol-K 28.9251 29.1866
15 Cv, KJ/Kg-mol-K 20.5219 20.7829
16 Cp/Cv 1.4095 1.4044
52
7.2.13 Flash Drum TK- 102 Specification Sheet
1 Company
2 Location
3 Service of Unit: Separation of gas and liquid
4 Item No.
5 Date
6 Flash Type: Isothermal
8 Operating Temperature, [K] 304.15
9 Operating Pressure, [bar] 1
10 Maximum Allowable Temperature, 335
[K]
11 Maximum Allowable Pressure, [bar] 1.1
12 Feed Upstream Product
13 Flow rate, Vapor Liquid Vapor Liquid
[Kg/h] 654.686 6502.608 673.0508 6484.2431
14 Compositions
15 CO2 0.0505 0.6486 3.42E-3
16 CO 1.47E-4 1.99E-3 1.84E-6
17 H2 0.0161 0.219 8.41E-5
18 CH3OH 0.4635 0.1091 0.4915
19 H2O 0.4697 0.0213 0.505
20 DESIGN SPECIFICATION
21 Diameter, [m] 1.03
22 Height, [m] 3.1
23 Material Carbon Steel
24 Design Code ASME BPVC, Section VIII,
Division I
25 Nozzle rating
26 Head Type Ellipsoidal
27 Thickness of 0.64
head, [mm]
28 Shell Type Cylindrical
shell, [mm]
30 REMARKS
31 The demister pad of thickness 0.4 m is used
32
33
53
7.2.14 Vapor Liquid Separator, TK-101
1 Company
2 Location
3 Service of Unit: Separation of gas and liquid
4 Item No.
5 Date
6 Flash Type: Isothermal
8 Operating Temperature, [K] 308.15
9 Operating Pressure, [bar] 50
10 Maximum Allowable Temperature, 373
[K]
11 Maximum Allowable Pressure, [bar] 55
12 Feed Upstream Product
13 Flow rate, Vapor Liquid Vapor Liquid
[Kg/h] 274414.11 7157.29 274414.11 7157.29
14 Compositions
15 CO2 0.2184 0.2204 0.0505
16 CO 3.08E-3 3.11E-3 1.47E-4
17 H2 0.7622 0.771 0.0161
18 CH3OH 9.89E-3 4.57E-3 0.4635
19 H2O 6.40E-3 9.68E-4 0.4697
20 DESIGN SPECIFICATION
21 Diameter, 5.4
[m]
22 Height, [m] 8.6
23 Material Carbon Steel
24 Design Code ASME BPV Code Sec. VIII
Div. 1
25 Nozzle rating
26 Head Type Hemispherical
27 Thickness of 84
wall, [mm]
28 Shell Type Cylindrical
Shell, [mm]
30 REMARKS
31 hv, [m] = 0.08
32 h1, [m] = 5.4
h2, [m] = 2.7
33
h3 [m] = 0.4
34
54
7.2.15 Distillation Tower, T-101 Specification Sheet
EQUIPMENT NUMBER:
NAME :
General Data
Service : Distillation
Column Type : Tray
Tray Type : Sieve
Number of trays : 57
Tray Distance : 0.46 m Tray material : SS314
Column Diameter : 1.62 m Column material : CS
Column Height : 27 m
Heating : Reboiler
Process Conditions
Stream Details Feed Top Bottom
Temperature [K] 353.15 337 373.37
Pressure 1 1 1
[bara]
Density
[Kg/m3]
Mass flow rate 6636.03 4179.11 2456.92
[Kg/h]
Compositions
[mol%]
CO2 0.34 0.69 9.9E-26
CO 1.8E-4 3.7E-4 1E-28
H2 8.7E-3 1.8E-2 1E-28
CH3OH 49.2 99.3 1
H2O 50.5 2.6E-11 99
Reflux Ratio [mole basis] 1.5
Condenser Duty [Kj/hr] 7.15
Reboiler Duty [Kj/hr] 9.90
Column Internals
Trays Packing Not Applicable
Hole Diameter [in] : Type :
0.25 Material :
Tray Thickness [in] : Volume [m3] :
0.125 Length [m] :
2
Active Tray Area [m ] : Width [m] :
Weir height [mm] : Height [m] :
50.8
Diameter of chute pipe/hole [mm] :
Remarks:
(1) Trays are numbered from top to bottom.
(2) SS = Stainless Steel and CS = Carbon Steel
(3) Reboiler is
55
7.2.16 Reactor, R-101 Specification Sheet
Company Name Project Name Reactor Specification Sheet
Project Number Sheet
ADDRESS Rev Date By Apv. Rev Date By Apv.
Packed Bed Reactor
Specification Sheet
Form
6 Plant Packed Bed Reactor Item Numbers
7 Location
8 Service
9 Size 78.82 m3 Diameter 2.8 m
3
10 Capacity 78.82 m
11 Standard Reference Drawing Design Data
12 CODE ASME SEC. VIII DIV. Stamp
I
13 Design 55 bar Design 565 K
Pressure Temperature
14 Operating 55 bar Operating 513.15 K
Pressure Temperature
15 Operating 281571.41 Kg/hr
Flowrate
16 Molecular 11.55 g
Weight
17 Inlet CO2 (0.2147), CO (0.003), H2O (0.00094),
Composition H2 (0.77), CH3OH (0.0044)
18 Outlet CO2 (0.2116), CO (0.0031), H2O (0.0064),
Composition H2 (0.762), CH3OH (0.00989)
19 Corrosion Allowance
20 Allowable Stress 119.3 N/mm2
21 Mass of Catalyst 69952 Kg
22 Wind load Seismic Factor
23 Comments Tests
24 X-Ray
25 Item Thickness Material Type Comments
26 Shell 66.4 mm SS 13Cr (Grade 410) Cylindrical
27 Head 64.8 mm SS 13Cr (Grade 410) Ellipsoidal
28 Insulation
29 Tube Support 1.4 m
30 Nozzle Schedule
31 Tag No. Service No. Size Rating Facing Projection
32 N-1 Feed Inlet 1 28” 725 Narrow Faced
33 N-2 Product Outlet 2 28” 725 Narrow Faced
34 N-3 Water Inlet 3 1” 15 Narrow Faced
35 N-4 Steam Outlet 4 5” 150 Narrow Faced
REMARKS
Catalysts are randomly packed
56
CHAPTER 8
ECONOMIC ANALYSIS
Investors need to be made assured that a project is worth consideration with economic
assessment of the project. Calculation of the Total Capital Investment (TCI), Total Product
Cost (TPC) and Total Revenue (TR) of an engineering project for its feasibility analysis has
been carried out with the determination of the payback period and cumulative cash flow
prediction at the end of our study period. Several factors have been taken into consideration
before the calculation of each parameters, corresponding to all TCI, TPC and TR calculation.
Among several categories of capital cost estimation types, Study Estimate (Factored Estimate)
with ±30% error has been selected as a reasonable choice for the economic analysis of our
design project since it is based on the major equipment items’ knowledge[59]. Some of the
information necessary for the preparation of this level of estimate are listed as:
Table 8.1 Information Required for Capital Cost Study Estimate
Required Information
Site Location
Process Flowsheet Rough Sketches
Equipment list Preliminary sizing and material specifications
Buildings and Structures Approximate sizes and type of construction
Utilities Rough quantities (steam, water, electricity,
etc.)
Piping Preliminary flowsheet and specifications
Electrical Preliminary motor list – approximate sizes
Worker-hours Engineering and drafting
8.1 Total Capital Investment
Purchasing and installing the required machinery and equipment needs allocation of a large
sum of money with addition of land, service facilities and complete erection of the plant with
piping, controls and services also. All the necessary manufacturing and plant facilities are
supplied under the fixed-capital investment (FCI) while that necessary for its operation is
supplied under working capital (WC) and their total is the total capital investment (TCI). FCI
is further subdivided as manufacturing FCI (direct cost) and nonmanufacturing FCI (indirect
cost) and each of these costs are allocated and calculated.
8.1.1 Manufacturing FCI (Direct Cost)
Manufacturing FCI represents the allocated amount needed for process equipments installation
with all the necessary components for a complete process operation. Direct cost components
major in the FCI are listed below with certain percentage allocated based on a careful
interpretation from sources based on industrial experience for our design project.
8.1.1.1 Purchased Equipment (PE)
Capital investment estimation can be done with the purchased equipment cost and with the
equipment prices sources, with price adjustment to capacity and with auxiliary process
equipment estimation. Division of the equipments can be done as processing equipments,
equipments for raw materials handling and storage, and equipments for finished-products
handling and storage.
57
Estimation of the equipment cost is often necessary when cost data for respective size or
capacity involved are not available. When capacity range does not exceed beyond the 10-fold
range, a cost capacity concept can be used, known as six-tenths factor rule. According to this
rule, the cost of a unit a is X0.6 times the known cost of unit b with X as the ratio of capacity of
a to the capacity of the unit b.
For avoiding oversimplification, the above-mentioned rule of thumb should only be used when
there is absence of other information, for others, typical exponents for equipment cost as a
function of capacity are available.
Equipment Cost Estimations
Compressors Cost
The cost of compressor including drive, gear mounting, baseplate, and normal auxiliary
equipment can be calculated using Fig 12-28[59]. The cost estimation requires power required
with material adjustment factor. All the compressor material is selected as Carbon Steel with
adjustment factor equal to 1.
C-101
For the Power required (KW) = 167.57, we obtained $ 90,000 as its compressor cost.
C-102
C-103
C-104
C-105
For the Power required (KW) = 228, we obtained $ 140,000 as its compressor cost.
Total Cost of all the five compressors equal to $ 472,000
Heat Exchangers Costs
The cost of heat exchangers can be calculated using Fig 14.18, Fig 14.21-14.23 of Ref[59]. The
required information is the heat transfer area, tube outside diameter, tube length and safe
operating pressure of each exchangers. The cost has been calculated and a sum is made as
below.
E-101
Heat transfer area = 5.24351 m2
Cost = $ 3000
Tube outside diameter = 0.019 m; Cost adjustment factor = 0.9
Tube Length = 3 m; Cost adjustment factor = 1.2
Safe Operating pressure, Tube side = 1.1 bar;
Shell side = 3.3 bar; average Cost adjustment factor = 0.96
Total cost = $ 3110.4
58
E-102
Cost = $ 3000
Tube Length = 2.55 m; Cost adjustment factor = 1.31
Shell side = 10 bar; average Cost adjustment factor = 0.975
Total Cost = $ 3448.575
E-103
Cost = $ 3200
Total Cost = $ 3143.232
E-104
Cost = $ 15000
Safe Operating pressure, Tube side = 55 bar;
Total Cost = $ 15503.4
E-105
The heat transfer area exceeds the maximum area that can express the purchase cost in Fig.
14-18 of Ref[59] so summation of cost with areas has been done as
3 × Cost of 1000 m2 + Cost of 754 m2 = 3 × $ 65000 + $ 50000 = $ 245000
Safe Operating pressure, Tube side = 55 bar;
Total Cost = $ 255780
59
E-106
Cost = $ 60000
Total Cost = $ 63443.25
E-107
Cost = $ 10000
Total Cost = $ 8467.2
Totaled sum of all heat exchangers = $ 3110.4 + $ 3448.575 + $ 3143.232 + $ 15503.4 + $
255780 + $ 63443.25 + $ 8467.2
= $ 352896.0
Reactor Cost
The cost of the reactor can be calculated similar to the heat exchanger since it is fixed tubular
packed bed reactor with material made of 304 Stainless Steel.
Tube Outside diameter of the packed bed reactor = 0.0334 m
No. of tubes = 4000
Length of tube = 10 m
Heat transfer area of single tube = 1.0493 m2
Total Heat transfer area = 4197.2 m2
The heat transfer area exceeds the maximum area that can express the purchase cost in Fig.
14-18 of Ref[59] so summation of cost with areas has been done as
4 × Cost of 1000 m2 + Cost of 197.2 m2 = 4 × $ 65000 + $ 20000 = $ 280,000
Tube Length = 10 m; Cost adjustment factor = 0.92
Safe Operating pressure, Tube and Shell Pressure = 1.6
60
Total Cost = $ 494592
Distillation Column Cost
Tray and Packed columns’ cost can be divided as:
• Cost for column shell, including heads, skirts, manholes, and nozzles,
• Cost for internals, including trays and accessories, packing, supports, and distributor
plates, and
• Cost for auxiliaries, such as platforms, ladders, handrails, and insulation
All of the costs are calculated as shown:
Cost of the Vertical Column without trays, packing or connection
The vertical height of the column is 27 m and using available diameter of 2 m we get an
approximate cost of the tower from Fig 15-11 of Ref [59], and it corresponds to $ 90,000 with
material adjustment factor for carbon steel equal to 1.
Cost of steel Column connections
The cost of Flanged manholes, flanged nozzles and couplings was obtained with Fig 15-12 [59]
using Column wall thickness of 0.015 m assumed as the thickness of the pipe from Ref. [55].
The cost corresponds to $ 7,000 for Flanged Manholes, $ 4,000 for Flanged nozzles, and $700
for couplings with total cost of steel column connections equal to $ 11,700
Cost of Trays in Column
The tray cost, including tray deck, bubble caps, risers, down comers and structural-steel parts,
can be calculated from Fig 15-13[59] using Stainless steel sieve trays and available diameter of
2 m, we obtain installation cost of $ 1,200 per tray and taking into account for 57 trays and
applying quantity factors of 0.97 we get the total installation cost = 1,200 × 57 × 0.97 = $
66,348.
Cost of Packing including that for column internal support and distribution
From Fig 15-14[59] using packed-height of 27 m and inside diameter of 2 m we obtain purchased
cost $ 60,000 and using 2.2 as the Packing material adjustment factor corresponding to SS304
we get a total of $ 132,000.
Total cost of the Distillation Column
$ 90,000 + $ 11,700 + $ 66,348 + $ 132,000 = $ 300,048
Vapor/Liquid Separator cost
The cost of the vapor liquid separator is used as $ 1000 as per the ref [60].
The total cost of the Purchased-Equipment has been estimated from the calculation in
Equipments cost calculation section from the reference dating to 2002 with cost index = 390.4
and using 617.8 as CEPI for 2018, we can calculate the actual total cost of equipment as
617.8
Equipments cost (2018) = $ 2,562,882.533 × = $ 4,055,709.09
390.4
Adding the cost of Vapor/liquid separator to this cost, we obtain the total cost of equipments
for 2018 = $ 4,056,709.09
61
8.1.1.2 Purchased-Equipment Delivery (DPE)
With predesign estimates consideration, 10 percent of purchased-equipment cost is taken as a
delivery allowance as recommended. Hence, the purchased-equipment Delivery cost is 0.1 ×
PE.
8.1.1.3 Purchased-Equipment Installation
This cost includes the costs for labor, foundations, platforms, supports, construction expenses
and other factors. Installation costs for equipment are estimated to vary from 25 to 55 percent
with additional total cost for the labor and materials involved for insulating equipment and
piping is approximated 8 to 9 percent of the delivered purchased-equipment cost, hence an
average of 40 percent plus additional 8.5 percent of delivered purchased equipment cost is
taken. Hence, the total purchased-equipment installation cost is 0.485 × DPE = 0.485×1.1× PE.
8.1.1.4 Instrumentation and Controls
Cost of instruments, its installation labor and auxiliary equipment and materials expenses are
included in the cost allocation for instrumentation and control and its proportion in the capital
investment depends upon the amount of control required. Averaging between 8 to 50 percent
of the delivered purchased-equipment cost, 29 percent is used in our predesign estimation.
Hence, its total cost is 0.29 × DPE = 0.29×1.1×PE.
8.1.1.5 Piping
The cost of piping covers labor, valves, fittings, pipe, supports and items involved directly in
the complete process pipe erection and includes process piping for raw materials, intermediate-
product, finished product, steam, water, air, sewer and others. Datas are available based on the
experience gained from piping cost obtained from previous chemical process plants and
factoring by percentage of purchased-equipment cost gives a rough estimate of the cost. For a
typical fluid process plants, the material and labor cost of piping amounts equal to 68 percent
of purchased-equipment cost. An additional average of 15 to 25 percent that is 20 percent of
total installed cost of the piping is accounted for labor and material for pipe insulation and
extremes in temperature greatly influences this cost. Hence, Piping cost is 0.88 × PE.
8.1.1.6 Electrical Systems
Power wiring, lighting, transformation and service with the instrumentation and control wiring
cost are included inside the cost for electrical systems. As recommended for our study estimate,
an average between 15 to 30 percent that is 22.5 percent of the delivered purchased-equipment
cost is used for estimation which is estimated for the most chemical plants. Hence, cost for
electrical systems is 0.225 × DPE = 0.225 × 1.1 × PE.
8.1.1.7 Buildings
The cost of buildings, including services, consists of labor expenses, materials and supplies
involved in the erection of all buildings connected with the plant, and also plumbing, heating,
lighting, ventilation, and other services are estimated depending on the types of process plant.
It can be a new plant at a new site or new unit at an existing site or even expansion at existing
site. For our study estimate, we can consider a fluid processing plant and as a new unit erection
at an existing site averaging between 5 to 18 percent and taking 11.5 percent of purchased-
equipment cost. Hence, its cost is estimated as 0.115 × PE.
62
8.1.1.8 Yard Improvements
Most chemical plants approximate cost for the yard improvements between 10 to 20 percent
that is an average 15 percent of the purchased-equipment cost which includes fencing, grading,
sidewalks, railroad sidings, landscaping and other similar items. Hence, its cost is estimated to
be 0.15 × PE.
8.1.1.9 Service Facilities
Service facilities for a chemical process plant include steam, water, power, compressed air, and
fuel supplying utilities along with waste disposal, fire protection and miscellaneous items. The
cost of all mentioned and more are included under the general heading of service facilities cost.
General range for total cost for service facilities is 30 to 80 percent of the purchased-equipment
cost averaging 55 percent for a normal solid-fluid processing plant. As recommended the total
cost are included as the percent of FCI as estimated in the table 7.2. A sum of all the service
facilities is made and it is equal to 0.175 × FCI.
Table 8.2 Typical Values of each Service facilities components as a percent of FCI
Service Facilities Range, % Typical Value, %
Steam generation 2.6-6.0 3.0
Steam distribution 0.2-2.0 1.0
Water supply, cooling, and pumping 0.4-3.7 1.8
Water treatment 0.5-2.1 1.3
Water distribution 0.1-2.0 0.8
Electric Substation 0.9-2.6 1.3
Electric Distribution 0.4-2.1 1.0
Gas supply and distribution 0.2-0.4 0.3
Air compression and distribution 0.2-0.3 1.0
Refrigeration including distribution 0.5-2.0 1.0
Process waste disposal 0.6-2.4 1.5
Sanitary Waste Disposal 0.2-0.6 0.4
Communications 0.1-0.3 0.2
Raw Material Storage 0.3-3.2 0.5
Finished-product Storage 0.7-2.4 1.5
Fire Protection Systems 0.3-1.0 0.5
Safety Installations 0.2-0.6 0.4
8.1.1.10 Land
Depending on the location of the property, the land cost and the cost for accompanying surveys
and fees can vary significantly. As recommended a rough average of land costs for industrial
plants averaging 4 to 8 percent that is 6 percent of the purchased equipment cost is used for our
study estimate. Since this cost cannot be depreciated, it is not included in FCI but is shown as
a one-time investment at the beginning of the plant operation and is equal to 0.06 × PE.
8.1.2 Nonmanufacturing FCI (Indirect Cost)
Costs that not directly related to process operation but are involved in construction overhead
and other plant components are designated nonmanufacturing FCI. Indirect costs include
processing buildings, administrative and other offices, warehouses, laboratories,
transportation, shipping, and receiving facilities, utilities and waste disposal facilities and
others. Components listed below are added to the indirect cost for the TCI calculation with
careful allocation of factors based on delivered purchased-equipment cost or FCI.
63
8.1.2.1 Engineering and Supervision
This cost includes cost for construction design and engineering, including internal or licensed
software, computer-based drawings, purchasing, accounting, travel, communications, home
office expenses with overhead, construction and cost engineering and others that cannot be
charged directly to the equipment, materials, or labor, is considered in indirect cost. From the
typical values presented based on the experience, this cost amounts to approximately 30 percent
of the delivered purchased-equipment cost for the process plant. Hence, its cost is 0.3×DPE =
0.3 × 1.1 × PE.
8.1.2.2 Legal Expenses
Land purchases, equipment purchases, and contracts of construction, proving compliance with
government, environmental and safety requirements are major sources of the legal expenses
and usually are in 1 to 3 percent averaging 2 percent of the FCI i.e. 0.02 × FCI.
8.1.2.3 Construction Expenses
Items of Construction or field expense including temporary construction and operation,
construction tools and rentals, home office personnel located at the construction site,
construction payroll, travel and living, insurances and other make up to this indirect cost. 8 to
10 percent or an average of 9 percent of the FCI is estimated for the ordinary chemical process
plants. Hence, this is equal to 0.09 × FCI.
8.1.2.4 Contractor’s Fee
Different situation results in varying contractor’s fee but experiences has suggested 1.5 to 6
percent averaging 3.75 percent of the FCI for this cost i.e. 0.0375 × FCI.
8.1.2.5 Contingencies
Experiences has shown possibility of unexpected events and changes that increase the cost of
the project inevitably. These events can be storms, floods, transportation accidents, strikes,
price changes, small design changes, errors in estimates and other unforeseen expenses and
factors for these types of contingencies ranges from 5 to 15 percent of the FCI with an average
8 percent been considered for our study estimate i.e. 0.08 × FCI.
8.1.3 Capital Investment Estimating Method
Although various methods for estimating are available, their dependence on the amount of the
detailed information makes us choose a method based on percentage of the delivered-
equipment cost. The method requires the determination of the delivered-equipment cost and
other items included are estimated as percentages of the delivered-equipment cost. The
expected accuracy has been recorded to ±20 to 30 percent range. The method is summarized
if f1, f2, f3,..,fn are the factors for piping, electrical, indirect costs, etc. and Cn is the FCI and E
is the delivered purchased-equipment then
Cn = ∑(E + f1 E + f2 E + f3 E + ⋯ + fn E) = E ∑(1 + f1 + f2 + f3 + ⋯ + fn )
64
8.1.4 Calculation of the TCI
At first, taking into account all of the factors described we get,
FCI = Direct Cost + Indirect Cost
→ FCI = PE + 0.1 × PE + 0.485 × 1.1 × PE + 0.29 × 1.1 × PE + 0.88 × PE + 0.225 × 1.1 × PE
+ 0.115 × PE + 0.15 × PE + 0.175 × FCI + 0.06 × PE + 0.3 × 1.1 × PE + 0.02 × FCI + 0.09 ×
FCI + 0.0375 × FCI + 0.08 × FCI
→ FCI × (1 - 0.175 - 0.02 - 0.09 - 0.0375 - 0.08) = PE × (1 + 0.1 + 0.485 × 1.1 + 0.29 × 1.1 +
0.88 + 0.225 × 1.1 + 0.115 + 0.15 + 0.06 + 0.3 × 1.1)
→ FCI × (0.5975) = PE × (3.735)
3.735
→ FCI = 4,056,709.09 × 0.5975
Therefore, Fixed Capital Investment, FCI = $ 25,358,675.23

Similarly, From table 16-17 of ref.[59]. We estimate the working capital as ranging from 10 to
20 percent of TCI and taking average value of 15 percent of TCI. Hence,
From, TCI = FCI + WC
→ TCI = FCI + 0.15 × TCI
→ TCI × (1-0.15) = FCI
FCI 25,358,675.23
→ TCI = 0.85 = $ = $ 29,833,735.57
0.85
8.2 Revenue
Revenue is obtained from the sales of products produced by the plant and in our case it’s the
sale of the Methanol and Steam generated. When price of each product is multiplied by the rate
of the sales and a sum of each is made, we obtain the total annual revenue from the sale of
products. The Method can be expressed as:
Annual Sales revenue, $/yr = ∑( sales of Product, kg/yr )(Product sales price, $/kg)
As suggested for our preliminary economic studies, a 50 percent of the design annual capacity
is taken as the production and sales rate and for the subsequent years, the design annual capacity
of the plant is used as the production and sales rate. An allowance is to be made for the
downtime with typical downtime ranging between 10 to 20 percent for the continuous process.
Hence the actual operating time is taken after allowance of an average downtime of 15 percent
that is 310 days per year.
65
8.2.1 Total Revenue Calculation
Methanol Revenue
Price of Methanol is set at $ 800 per metric ton[61].
During first year of operation, plant is operated at half its capacity hence, the total revenue that
Kg 24 hr 310 days $ tonne
can be for this year is 4140 × × × 0.5 × 800 × 1000 kg
hr day year tonne
= $ 12,320,640 per year at half capacity
During later years of operation, plant is operated at its full capacity hence, the total revenue
that can be for this year is 4140 × × × 800 ×
hr day year tonne 1000 kg
= $ 24,641,280 per year at full capacity

Steam Revenue
Price of Steam is set at $ 27.61 per metric ton[15] with 2016’s cost index = 533.9 and using
2018’s cost index 617.8. We can estimate the price of steam per tonne as,
617.8
Price of steam (2018) = $ 27.61 × = $ 31.95
533.9
During first year of operation, plant is operated at half its capacity hence, the total revenue that
can be for this year is 175,965 × × × 0.5 × 31.95 ×
= $ 20,914,144.11 per year at half capacity

During later years of operation, plant is operated at its full capacity hence, the total revenue
that can be for this year is 175,965 × × × 31.95 ×
= $ 41,828,288.22 per year at full capacity
8.3 Total Product Cost (TPC)

Plant operating cost, product selling cost, capital investment recovery and corporate functions
contribution such as management and R&D all make up to the Total Product Cost (TPC).
Division of the TPC is done as cost involved in manufacturing and general expenses. The
former is further subdivided into variable production costs, fixed charges and plant overhead
costs.
8.3.1 Manufacturing Costs (Operating or Production Costs)
Manufacturing operation expenses or that related to the process plant physical equipment are
included in the manufacturing costs.
8.3.1.1 Variable Production Costs
These are directly associated with the manufacturing operation which include raw materials
expenditures (with transportation, unloading, etc.), direct operating labor, supervisory and
clerical labor applicable to manufacturing operation, utilities, plant maintenance and so forth.
66
Raw Materials Cost
Carbon dioxide and Hydrogen are the materials that are directly consumed in making of our
methanol. The Cost of each is listed with 50 percent of the annual capacity for the first year
and the actual annual capacity cost for the subsequent years. The cost of transportation must
be added to the raw materials cost, even though they are highly variable, as recommended 10
percent of the raw materials is added as shown in the calculation below.
Carbon dioxide cost
The cost of Carbon dioxide $15 per metric ton of CO2-equivalent greenhouse gases in the study
of 2019 [62]. This is used as the basis for our study estimate. So,
Kg 24 hr 310 days 15
Cost of CO2 at full capacity operation = 8800 × × × $ 1000 Kg
hr day yr
$
→ 982,080 yr
$
Also, the cost for the first year of operation at 50 percent capacity = 0.5 × 982,080 yr
$
→ 491,040 yr
Hydrogen Cost
The Hydrogen is produced mostly on site and its cost ranged $ 0.70/ kg as of 2002 [63] with
390.4 as Chemical Engineering plant cost index and 617.8 as CEPI for 2018 we can obtain the
Hydrogen cost as
2018 CEPI
Cost of Hydrogen ($/kg) = Cost of Hydrogen at 2002 × 2002 CEPI
617.8
= 0.7 × 390.4
= 1.11 $/kg
Kg 24 hr 310 days 1.11
Cost of H2 at full capacity operation = 1200 × × × $ 1 Kg
hr day yr
$
→ 9,910,080 yr
$
Also, the cost for the first year of operation at 50 percent capacity = 0.5 × 9,910,080 yr
$
→ 4,955,040 yr
Operating Labor
The labor can be divided as skilled or unskilled and although there is the presence of the
variation in the hourly wages of the operating labor in different industries at various locations,
literature shows that cost of operating labor usually amounts to 10 to 20 percent of the TPC.
For our study estimate, the cost of skilled and unskilled labor has been estimated as per the
guidelines of ref[59].
67
Taking our design capacity of methanol production of 4140 kg/hr or 99360 kg/day, from the
employee hours
fig 6-9 of ref[59], we obtain the operating labor required equal to 33 day ×processing step
corresponding to our highly automated processing.
Allocating the number of workers, skilled and unskilled, for each processing step with 12
working hours per shift, for both skilled and unskilled workers, as
employee hours
Unskilled workers = 33 day ×processing step × 11 processing steps
unskilled employee hours

= 363
day
employee hours
Skilled workers = 33 day ×processing step × 4 processing steps
skilled employee hours

= 132 day
Table 8.3 Skilled and Unskilled Worker hours per day for equipment operation
Equipment No. of Skilled Worker Unskilled Worker
Equipments hours hours
Compressors 5
Heat Exchangers 7
Reactors 1 132 363
Vapor-Liquid Separator 1
Flash Drum 1
Distillation tower 1
With the aid of table 6-15 of ref[59] and ref[64], we obtain the labor cost for both unskilled and
skilled employee hours as
$ 23038.90 $
Unskilled Labor cost (2018) = 25.58 hr× = 40.75 hr
14461
And,
$ 10254.20 $
Skilled Labor cost (2018) = 33.67 hr× = 56.91 hr
6067
Hence, the total annual labor cost for the plant operating at full capacity is the sum of labor
cost for both skilled and unskilled labor.
$ unskilled employee hours days
Total operating unskilled labor cost = 40.75 hr × 363 × 310 year
day
= $ 4,585,597.5
$ skilled employee hours days
Total operating skilled labor cost = 56.91 hr × 132 × 310 year
day
= $ 2,328,757.2
And total operating labor cost = $ 4,585,597.5 + $ 2,328,757.2 = $ 6,914,354.7
68
Operating Supervision and Clerical Assistance
The operating labor amount, operation complexity and quality standards of the product
determines this cost and an average of 15 percent of the cost of operating labor has been
suggested which equals to 0.15 × operating labor cost.
Utilities
The cost for steam, electricity, process and cooling water, compressed air, refrigeration and
waste treatment even when varying depending upon the amount needed, plant location and
source, as a rough approximation for ordinary chemical processes, an average of 15 percent of
TPC is used for our study estimate which equals to 0.15 × TPC.
Maintenance and Repairs
The total plant cost for maintenance and repairs in the process industries has been reported to
range from 2 to 10 percent of the FCI with 7 percent being a reasonable approximation for
average processes with normal operating conditions. Also, taking into account that when plant
is operating at 50 percent plant capacity, 75 percent value of the 100 percent maintenance and
repairs value at full capacity has been taken.
Hence, for full capacity operation the cost is 0.07 × FCI. And for that at half the capacity
operation is 0.75 × 0.07 × FCI.
Operating Supplies
Lubricants, test chemicals, custodial supplies, charts etc. make up the cost equal to 15 percent
of total cost for maintenance and repairs and is equal to 0.15 × 0.07 × FCI for full capacity and
0.15 × 0.07 × 0.075 × FCI when operating at half the full capacity.
Laboratory Charges
In this manufacturing cost, the laboratory tests for control of operations and product quality
control cost is covered. For quick study estimates, this amounts to 10 to 20 percent of the
operating labor averaging 15 percent and is equal to 0.15 × operating labor.
Patents and Royalties
After bearing a certain amount included in the development and procurement of the patent
rights, this amount corresponds to 0 to 6 percent of the TPC averaging 3 percent and is equal
to 0.03 × TPC.
Catalysts Price
The cost of catalyst is taken as the price for CuO/ZnO/Al2O3 as a study estimate because of its
$
availability in ref[65]. The cost is 200 Kg and total catalyst needed in our Packed bed reactor is
69,953 Kg resulting in a total cost of $ 13,990,600. With the typical lifetime of the catalyst
being 2 years[66]. We get an annual catalyst cost of $ 6,995,300 for the full capacity operation.
And for the first year of operation with plant operating at only half the capacity the cost of
catalyst is 0.5 × $ 6,995,300 = $ 3,497,650.
8.3.1.2 Fixed Charges
These are the cost that do not change at all or not to a significant amount with the amount of
production are fixed costs. Included in the cost are depreciation, insurance, loan interest and so
forth. As a rough approximation for study estimation suggested average of 10 to 20 percent of
the TPC that is 15 percent has been used.
69
Depreciation
Since the depreciation amount changes from year to year, it has been calculated separately.
Financing
At the investment time, a fixed rate of interest is established and the capital borrowed. Annual
interest rates amount to 5 to 10 percent of the total burrowed capital. For Estimation we have
used 0.15 × TCI as of Table 6-18 from ref[59].
Local Taxes
For our study estimate, it is considered that plant is established at a sparsely populated area and
as suggested the charges amount to 1 to 2 percent or an average 1.5 percent of the FCI = 0.015
× FCI.
Property Insurance
Depending upon the type of process being carried out and protection facilities availability fixed
charges are made and as recommended amount to 1 percent of FCI per year = 0.01 × FCI.
8.3.1.3 Plant Overhead Costs
These include the expenditures for routine plant services. Nonmanufacturing equipments and
buildings, medical, packaging, restaurant, recreation, storage facilities costs for chemical plants
have been suggested to amount to 50 to 70 percent of the total expenses for operating labor,
supervision and maintenance with an average amount of 60 percent.
Hence, the total plant overhead costs = 0.6 × (0.15 × TPC + 0.15 × 0.15 × TPC + 0.07 × FCI)
which is for full capacity operation. And that for half the capacity operation
= 0.6 × (0.15 × TPC + 0.15 × 0.15 × TPC + 0.75 × 0.07 × FCI)
8.3.2 General Expenses
8.3.2.1 Administrative Costs
Salaries and wages of the administrators, secretaries, accountants, computer support staff,
engineering and legal personnel comes under administrative expenses along with the need
supplies. For our study estimate, 15 to 25 percent averaging 20 percent of the operating labor
is added under this cost and equals to 0.2 × operating labor.
8.3.2.2 Distribution and Marketing Costs
These costs include salaries, wages, supplies and other expenses for sales offices, salaries,
commissions, and traveling expenses for sales representative, shipping expenses, containers’
cost, advertising expenses, and technical sales services. For most chemical plants the cost
ranges from 2 to 20 percent and hence an average of 11 percent of TPC is used and equals to
0.11 × TPC.
8.3.2.3 Research and Development Costs
These include salaries and wages for all the personnel directly connected, fixed and operating
expenses for all machinery and equipment involved, materials and supplies cost and
consultant’s fees. In the chemical industry, these costs have been suggested to amount to about
5 percent of TPC i.e. 0.05 × TPC.
70
8.3.3 TPC Calculation
For the first year at half the plant capacity operation,
TPC = variable cost + fixed charges + plant overhead cost + general expenses
→ TPC = $ 491,040 + $ 4,955,040 + 0.5 × OLC + 0.15 × 0.5 × OLC + 0.15 × 0.5 × TPC +
0.75 × 0.07 × FCI + 0.15 × 0.75 × 0.07 × FCI + 0.5 × 0.15 × OLC + 0.03 × TPC + $ 3,497,650
+ 0.05 × TCI + 0.015 × FCI + 0.01 × FCI + 0.6 × (0.5 × OLC + 0.5 × 0.15 × OLC + 0.75 ×
0.07 × FCI) + 0.2 × 0.5 × OLC + 0.11 × 0.5 × TPC + 0.05 × TPC
→ TPC = $ 5,446,080 + OLC × (0.5 + 0.075 + 0.075 + 0.3 + 0.045 +0.1) + TPC × (0.075 +
0.03 + 0.055 + 0.05) + FCI × (0.0525 + 0.007875 + 0.015 + 0.01 + 0.0315) + TCI × 0.05 +
$3,497,650
→ TPC × (1- 0.21) = $ 8,943,730 + FCI × 0.116875 + TCI × 0.05 + OLC × 1.095
→ TPC × 0.79 = $ 8,943,730 + $ 2,963,795.17 + $ 1,491,686.78 + $ 7,571,218.40
20,970,430.35
→ TPC = $ = $ 26,544,848.54
0.79
For the later years, the plant operates at its full capacity, hence
TPC = variable cost + fixed charges + plant overhead cost + general expenses
→ TPC = $ 982,080 + $ 9,910,080 + OLC + 0.15 × OLC + 0.15 × TPC + 0.07 × FCI + 0.15 ×
0.07 × FCI + 0.15 × OLC + 0.03 × TPC + $ 6,995,300 + 0.05 × TCI + 0.015 × FCI + 0.01 ×
FCI + 0.6 × ( OLC + 0.15 × OLC + 0.07 × FCI) + 0.2 × OLC + 0.11 × TPC + 0.05 × TPC
→ TPC = $ 17,887,460 + OLC × (1 + 0.15 + 0.15 + 0.6 + 0.09 +0.2) + TPC × (0.15 + 0.03 +
0.11 + 0.05) + FCI × (0.07 + 0.0105 + 0.015 + 0.01 + 0.042) + TCI × 0.05
→ TPC × (1- 0.34) = $ 17,887,460 + FCI × 0.116875 + TCI × 0.05 + OLC × 2.19
→ TPC × 0.66 = $ 17,887,460 + $ 2,963,795.17 + $ 1,491,686.78 + $ 15,142,436.79
37,485,378.74
→ TPC = $ = $ 56,796,028.39
0.66
8.4 Gross Profit

It equals to the total product sales revenue minus the total product cost and in our design is
given as, Gross profit (g1) = $ 12,320,640 + $ 20,914,144.11- $ 26,544,848.54 = $ 6,689,935.57
Gross profit (g2…) = $ 24,641,280 + $ 41,828,288.22 - $ 56,796,028.39 = $ 9,673,539.83
8.5 Depreciation
Here we are going to employ a straight-line depreciating method, with 6 years as the recovery
period as recommended for the chemical plants[59]. The depreciation amount for each year in
V
recovery period is d = , n = 6 years and V = $ 25,358,675.23, is fixed capital investment.
n
71
Table 8.4 Annual Depreciation amount for straight line method
Recovery years Depreciation amount ($) Book Value ($)
0 0 25,358,675.23
1 4,226,445.87 21,132,229.36
2 4,226,445.87 16,905,783.49
3 4,226,445.87 12,679,337.62
4 4,226,445.87 8,452,891.75
5 4,226,445.87 4,226,445.88
6 4,226,445.87 0
8.6 Net Profit without taxes
It equals to the total gross profit per year minus yearly depreciation amount, and in our design
is given as, Net Profit (Np1) = $ 6,689,935.57 - 4,226,445.87 = $ 2,463,489.7
Net profit (Np2…) = $ 9,673,539.83 - 4,226,445.87 = $ 5,447,093.96
8.7 Payback period

Here, the payback period is estimated without considering the time value of money.
Total capital investment (TCI) = $ 29,833,735.57
Deducting first year net profit, the remaining amount = $ 29,833,735.57 - $ 2,463,489.7
= $ 27,370,245.87
$ 27,370,245.87
Hence, the total payback period = 1 + = 6.02 years
$ 5,447,093.96
8.8 Comparing Return on Investment (ROI) with Minimum acceptable

return (mar)
For our low level of risk, with new capacity with the established corporate market position,
suggested mar = 12 percent per year from table 8-1 of ref[59].
(1⁄N) ∑10
j=1(Np,j ) (1⁄10) (($ 2,463,489.7)+( $ 5,447,093.96 ×9 ))
ROI = = = 0.17
TCI $ 29,833,735.57
Which is higher than mar, so investment offers acceptable rate of return.
72
CHAPTER 9
MATERIAL SAFETY DATA INFORMATIONS
9.1 METHANOL
9.1.1 PRODUCT IDENTIFICATION
Product Name: Methanol
Formula: CH3OH
Generic ID for Methanol: Carbinol; Methyl alcohol; Methyl hydroxide; Monohydroxy
methane; Wood alcohol; Wood naphtha; Wood spirits; Columbian spirits; Methanol
9.1.2 HAZARD IDENTIFICATION
1. Appearance: Colorless liquid
2. Flash Point: 12 °C,
3. Danger! Poison! May be fatal or cause blindness if swallowed. harmful Vapors.
4. Flammable liquid and vapor: Harmful if swallowed, inhaled, or absorbed through the skin.
Causes eye, skin, and respiratory tract irritation. May cause central nervous system depression.
Cannot be made non-poisonous.
5. Target Organs: Eyes, nervous system, optic nerve.
6. Potential Health Effects:
• Eye: May cause painful sensitization to light. Methanol is a mild to moderate eye
irritant. Inhalation, ingestion or skin absorption of methanol can cause significant
disturbance in vision, including blindness.
• Skin: Causes moderate skin irritation. May be absorbed through the skin in harmful
amounts. Prolonged and or repeated contact may cause defatting of skin and dermatitis.
Methanol can be absorbed through the skin, producing systemic effects that include
visual disturbances.
• Ingestion: May be fatal or cause blindness if swallowed. Aspiration hazard. Cannot be
made nonpoisonous. May cause gastrointestinal irritation with nausea, vomiting and
diarrhea. May cause systematic toxicity with acidosis. May cause central nervous
system depression, characterized by excitement, followed by headache, dizziness,
drowsiness, and nausea. Advanced stages may cause collapse, unconsciousness, coma,
and possible death due to failed respiratory failure. May cause cardiopulmonary system
effects.
• Inhalation: Methanol is toxic and can very readily form extremely high vapor
concentrations at room temperature. Inhalation is the most common route of
occupational exposure. At first, methanol causes CNS depression with nausea,
headache, vomiting, dizziness and incoordination. A time period with no obvious
symptoms follows (typically 8-24 hrs.). This latent period is followed by metabolic
acidosis and severe visual effects which may include reduced reactivity and/or
increased sensitivity to light, blurred, doubt and/or snowy vision, and blindness.
73
Depending on the severity of exposure and the promptness of treatment, survivors may
recover completely or may have permanent blindness, vision disturbances and/or
nervous system effects.
• Chronic: Prolonged or repeated skin contact may cause dermatitis. Chronic exposure
may cause effects similar to those of acute exposure. Methanol is only very slowly
eliminated from the body. Because of this slow elimination, methanol should be
regarded as a cumulative poison. Though a single exposure may cause no effect, daily
exposures may result in the accumulation of a harmful amount. Methanol has produced
fetotoxicity in rats and teratogenicity in mice exposed by inhalation to high
concentrations that did not produce significant maternal toxicity.
9.1.3 FIRST AID MEASURES
1. Eyes: In case of contact, immediately flush eyes with plenty of water for at least 15 minutes.
Get medical aid.
2. Skin: In case of contact, immediately flush skin with plenty of water for at least 15 minutes
while removing contaminated clothing and shoes. Get medical aid immediately. Wash clothing
before reuse.
3. Ingestion: Potential for aspiration if swallowed. Get medical aid immediately. Do not induce
vomiting unless directed to do so by medical personnel. Never give anything by mouth to an
unconscious person. If vomiting occurs naturally, have victim lean forward.
4. Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial respiration. If
breathing is difficult, give oxygen. Get medical aid.
5. Notes to Physician: Effects may be delayed.
6. Antidote: Ethanol may inhibit methanol metabolism.
9.1.4 FIRE FIGHTING MEASURES
Table 9.1 Flash point, Autoignition and flammable ranges for methanol
FLASH POINT AUTOIGINITION FLAMMABLE
RANGE
12 °C 455 °C 6.0 – 31.0 Vol %
1. General Information: Ethanol may inhibit methanol metabolism. As in any fire, wear a
self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or
equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be
generated by thermal decomposition or combustion. Use water spray to keep fire-exposed
containers cool. Water may be ineffective. Material is lighter than water and a fire may be
spread by the use of water. Vapors are heavier than air and may travel to a source of ignition
and flash back. Vapors can spread along the ground and collect in low or confined areas.
2. Extinguishing Media: For small fires, use dry chemical, carbon dioxide, water spray or
alcohol-resistant foam. Water may be ineffective. For large fires, use water spray, fog or
alcohol-resistant foam. Do not use straight streams of water.
74
9.1.5 ACCIDENTAL RELEASE MEASURES
• Spills/Leaks: Use water spray to disperse the gas/vapor. Remove all sources of
ignition. Absorb spill using an absorbent, non-combustible material such as earth, sand,
or vermiculite. Do not use combustible materials such as sawdust. Use a spark-proof
tool. Provide ventilation. A vapor suppressing foam may be used to reduce vapors.
Water spray may reduce vapor but may not prevent ignition in closed spaces
9.1.6 STORAGE AND HANDLING
• HANDLING: Wash thoroughly after handling. Remove contaminated clothing and
wash before reuse. Ground and bond containers when transferring material. Use spark-
proof tools and explosion proof equipment. Avoid contact with eyes, skin, and clothing.
Empty containers retain product residue, (liquid and/or vapor), and can be dangerous.
Keep container tightly closed. Do not ingest or inhale. Do not pressurize, cut, weld,
braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames.
• STORAGE: Keep away from heat, sparks, and flame. Keep away from sources of
ignition. Store in a cool, dry, well-ventilated area away from incompatible substances.
Flammables-area. Keep containers tightly.
9.1.7 EXPOSURE CONTROLS/PERSONAL PROTECTION
1. Engineering Controls: Use explosion-proof ventilation equipment. Facilities storing or
utilizing this material should be equipped with an eyewash facility and a safety shower. Use
adequate general or local exhaust ventilation to keep airborne concentrations below the
permissible exposure limits.
OSHA Vacated PELs: Methanol: 200 ppm TWA; 260 mg/m3 TWA
2. Personal Protective Equipment:
• Eyes: Wear chemical splash goggles.
• Skin: Wear butyl rubber gloves, apron, and/or clothing
• Clothing: Wear appropriate protective clothing to prevent skin exposure.
• Respirators: Follow the OSHA respirator regulations found in 29 CFR 1910.134 or
European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149
approved respirator if exposure limits are exceeded or if irritation or other symptoms
are experienced.
9.1.8 PHYSICAL AND CHEMICAL PROPERTIES
• Appearance, odor and state: clear, colorless - APHA: max 10
• Molecular weight: 32.04 g/gmol
• Boiling point: 64.7 °C at 760 mmHg
• Specific gravity: 7910 g/cm3 at 20 °C
• Freezing point/Melting point: 98 °C
• Vapor pressure (At 200C): 128mm Hg
• Gas density: 1.11 (Air=1)
• Solubility in water: miscible
75
9.1.9 STABILITY AND REACTIVITY
• Chemical stability: Stable under normal temperatures and pressures
• Conditions to avoid: High temperatures, ignition sources, confined spaces.
• Incompatibility (Materials to Avoid): Oxidizing agents, reducing agents, acids, alkali
metals, potassium, sodium, metals as powders (e.g. hafnium, raney nickel), acid
anhydrides, acid chlorides, powdered aluminum, powdered magnesium.
• Hazardous decomposition products: Carbon monoxide, irritating and toxic fumes
and gases, carbon dioxide, formaldehyde.
• Hazardous polymerization: Will not occur
9.1.10 TOXICOLOGICAL INFORMATION
LD50/LC50:
Draize test, rabbit, eye: 40 mg Moderate;
Draize test, rabbit, eye: 100 mg/24H Moderate;
Draize test, rabbit, skin: 20 mg/24H Moderate;
Inhalation, rabbit: LC50 = 81000 mg/m3/14H;
Inhalation, rat: LC50 = 64000 ppm/4H;
Oral, mouse: LD50 = 7300 mg/kg;
Oral, rabbit: LD50 = 14200 mg/kg;
Oral, rat: LD50 = 5600 mg/kg;
Skin, rabbit: LD50 = 15800 mg/kg;
1. Teratogenicity: There is no human information available. Methanol is considered to be a
potential developmental hazard based on animal data. In animal experiments, methanol has
caused fetotoxic or teratogenic effects without maternal toxicity.
2. Reproductive Effects: See actual entry in RTECS for complete information.
3. Mutagenicity: See actual entry in RTECS for complete information.
4. Neurotoxicity: ACGIH cites neuropathy, vision and CNS under TLV basis.
9.1.11 ECOLOGICAL INFORMATION
1. Ecotoxicity:
• Fish: Fathead Minnow: 29.4 g/L; 96 Hr; LC50 (unspecified)
• Fish: Goldfish: 250 ppm; 11 Hr; resulted in death
• Fish: Rainbow trout: 8000 mg/L; 48 Hr; LC50 (unspecified)
• Fish: Rainbow trout: LC50 = 13-68 mg/L; 96 Hr.; 12 °C
• Fish: Fathead Minnow: LC50 = 29400 mg/L; 96 Hr.; 25 °C, pH 7.63
• Fish: Rainbow trout: LC50 = 8000 mg/L; 48 Hr.;
• Unspecified Bacteria: Phytobacterium phosphoreum: EC50 = 51,000-320,000 mg/L;
30 minutes;
76
2. Environmental: Dangerous to aquatic life in high concentrations.
• Aquatic toxicity rating: TLM 96>1000 ppm.
• May be dangerous if it enters water intakes.
• Methyl alcohol is expected to biodegrade in soil and water very rapidly. This product
will show high soil mobility and will be degraded from the ambient atmosphere by the
reaction with photochemically produced hydroxyl radicals with an estimated half-life
of 17.8 days.
• Bioconcentration factor (BCF) for fish (golden ide) < 10. Based on a log Kow of -0.77,
the BCF value for methanol can be estimated to be 0.2.
3. Physical: No information available.
4. Other: No information available.
9.1.12 DISPOSAL CONSIDERATIONS
US EPA guidelines for the classification determination are listed in 40 CFR Parts 261.3.
Additionally, waste generators must consult state and local hazardous waste regulations to
ensure complete and accurate classification.
1. RCRA P-Series: None listed.
2. RCRA U-Series:
CAS# 67-56-1: waste number U154 (Ignitable waste).
9.2 CARBON MONOXIDE

Product Name: Carbon Monoxide
Formula: CO
Synonyms or Generic ID for Carbon Monoxide (CO): CO; Exhaust Gas; Flue gas; Carbonic
oxide; Carbon oxide; Carbone
1. Appearance: Colorless gas [may be liquid at low temperature or high pressure]
2. Emergency overview:
WARNING!
FLAMMABLE GAS.
MAY CAUSE FLASH FIRE.
MAY BE FATAL IF INHALED.
MAY CAUSE TARGET ORGAN DAMAGE, BASED ON ANIMAL DATA, CONTENTS
UNDER PRESSURE.
Keep away from heat, sparks and flame. Do not puncture or incinerate container. Avoid
breathing gas. May cause target organ damage, based on animal data. Use only with adequate
ventilation. Keep container closed. Contact with rapidly expanding gases can cause frostbite.
3. Target organs: May cause damage to the following organs:
blood, lungs, cardiovascular system, central nervous system (CNS).
77
4. Entry Route: Inhalation
5. Potential acute health effects:
• Eyes: Contact with rapidly expanding gas may cause burns or frostbite.
• Skin: Contact with rapidly expanding gas may cause burns or frostbite.
• Inhalation: Toxic by inhalation.
• Ingestion: Ingestion is not a normal route of exposure for gases
6. Potential chronic health effect:

• CARCINOGENIC EFFECTS: Not available.
• MUTAGENIC EFFECTS: Not available.
• TERATOGENIC EFFECTS: Classified 1 by European Union.
7. Medical conditions aggravated by overexposure:

Pre-existing disorders involving any target organs mentioned in this MSDS as being at risk
may be aggravated by over-exposure to this product.
No action shall be taken involving any personal risk or without suitable training. If it is
suspected that fumes are still present, the rescuer should wear an appropriate mask or self-
contained breathing apparatus. It may be dangerous to the person providing aid to give mouth-
to-mouth resuscitation.
1. Eye contact: Check for and remove any contact lenses. Immediately flush eyes with plenty
of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical
attention immediately
2. Skin contact: In case of contact, immediately flush skin with plenty of water for at least 15
minutes while removing contaminated clothing and shoes. To avoid the risk of static discharges
and gas ignition, soak contaminated clothing thoroughly with water before removing it. Wash
clothing before reuse. Clean shoes thoroughly before reuse. Get medical attention immediately.
3. Frostbite: Try to warm up the frozen tissue and seek medical attention.
4. Inhalation: Move exposed person to fresh air. If not breathing, if breathing is irregular or if
respiratory arrest occurs, provide artificial respiration or oxygen by trained personnel. Loosen
tight clothing such as a collar, tie, belt or waistband. Get medical attention immediately.
5. Ingestion: As this product is a gas, refer to the inhalation section.
Table 9.2 Flash point, Autoignition and flammable ranges for Carbon Monoxide
FLASH POINT AUTOIGINITION FLAMMABLE
RANGE
12 °C 608.89 °C 12.5 – 74.0Vol %
1. Products of combustion: Decomposition products may include the following materials:
carbon dioxide & carbon monoxide.
78
2. Fire hazards in presence of various substances: Extremely flammable in the presence of
the following materials or conditions: open flames, sparks and static discharge and oxidizing
materials.
3. Fire- fighting media & instructions: In case of fire, use water spray (fog), foam or dry
chemical. A safe distance to cool container and protects surrounding area. If involved in fire,
shut off flow immediately if it can be done without risk. Contain gas under pressure. Flammable
gas. In a fire or if heated, a pressure increase will occur and the container may burst, with the
risk of a subsequent explosion.
1. Personal Precautions: Immediately contact emergency personnel. Keep unnecessary
personnel away. Use suitable protective equipment. Shut off gas supply if this can be done
safely. Isolate area until gas has dispersed.
2. Environmental Precautions: Avoid dispersal of spilled material and runoff and contact
with soil, waterways, drains and sewers.
3. Method for cleaning up: Immediately contact emergency personnel. Stop leak if without
risk. Use spark-proof tools and explosion proof equipment. Note: see section 1 for emergency
contact information and section 13 for waste disposal.
• HANDLING: Use only with adequate ventilation. Use explosion-proof electrical
(ventilating, lighting and material handling) equipment. High pressure gas. Do not
puncture or incinerate container. Use equipment rated for cylinder pressure. Close valve
after each use and when empty. Keep container closed. Keep away from heat, sparks
and flame. To avoid fire, eliminate ignition sources. Protect cylinders from physical
damage; do not drag, roll, slide, or drop. Use a suitable hand truck for cylinder
movement.
• STORAGE: Keep container in a cool, well-ventilated area. Keep container tightly
closed and sealed until ready for use. Avoid all possible sources of ignition (spark or
flame). Segregate from oxidizing materials. Cylinders should be stored upright, with
valve protection cap in place, and firmly secured to prevent falling or being knocked
over. Cylinder temperatures should not exceed 52 °C.
1. Engineering Controls: Use only with adequate ventilation. Use process enclosures, local
exhaust ventilation or other engineering controls to keep worker exposure to airborne
contaminants below any recommended or statutory limits. The engineering controls also need
to keep gas, vapor or dust concentrations below any lower explosive limits. Use explosion-
proof ventilation equipment.
79
2. Personal Protective Equipment:
• Eyes: Safety eyewear complying with an approved standard should be used when a risk
assessment indicates this is necessary to avoid exposure to liquid splashes, mists or
dusts.
• Skin: Personal protective equipment for the body should be selected based on the task
being performed and the risks involved and should be approved by a specialist before
handling this product.
• Respirators: Use a properly fitted, air-purifying or air-fed respirator complying with an
approved standard if a risk assessment indicates this is necessary. Respirator selection
must be based on known or anticipated exposure levels, the hazards of the product and
the safe working limits of the selected respirator
• Hands: Chemical-resistant, impervious gloves complying with an approved standard
should be worn at all times when handling chemical products if a risk assessment
indicates this is necessary.
• In case of large spill: Self-contained breathing apparatus (SCBA) should be used to
avoid inhalation of the product. Full chemical-resistant suit and self-contained
breathing apparatus should be worn only by trained and authorized persons.
• Boiling point: -191.7°C
• Specific volume: 13.8889 ft3/lb
• Freezing point/melting point: -198.9°C
• Vapor density: 0.97 (Air = 1)
• Gas density: 0.072 lb/ft3
• Critical temperature: -140.1°C
• Chemical stability: Stable under normal temperatures and pressures
• Incompatibility (Materials to Avoid): Oxidizing agents
• Hazardous decomposition products: Under normal conditions of storage and use,
hazardous decomposition products should not be produced.
• Hazardous polymerization: Will not occur
• IDLH: 1200 ppm
• Chronic effects on humans: TERATOGENIC EFFECTS: Classified 1 by European
Union. May cause damage to the following organs: blood, lungs, cardiovascular
system, central nervous system (CNS).
• Carcinogenic: no known significant effects or critical hazards
• Reproductive Effects: No known significant effect or critical hazard.
• Mutagenicity: No known significant effect or critical hazard.
• Other toxic effects on humans: No specific information is available in our database
regarding the other toxic effects of this material to humans.
80
• Aquatic ecotoxicity: Not available.
• Products of degradation: carbon oxides (CO, CO2)
• Environmental fate: Not available
• Environmental hazards: No known significant effects or critical hazards
• Toxicity to the environment: Not available
Product removed from the cylinder must be disposed of in accordance with appropriate Federal,
State, local regulation. Return cylinders with residual product to Airgas, Inc. Do not dispose of
locally.
9.3 CARBON DIOXIDE

Material name: Carbon dioxide
Chemical formula: CO2
Appearance, Odor & State: At room temperature and atmospheric pressure, carbon dioxide
is a colorless, odorless, slightly acidic gas. Carbon Dioxide is shipped as a liquefied gas under
its own vapor pressure.
9.3.3 FIRST AID MEASURE
No action shall be taken involving any personal risk or without suitable training. If fumes are
still suspected to be present, the rescuer should wear an appropriate mask or a self-contained
breathing apparatus. It may be dangerous to the person providing aid to give mouth-to-mouth
resuscitation.
• Eye contact: In case of contact, immediately flush eyes with plenty of water for at least
15 minutes. Get medical attentions immediately.
• Skin contact: In case of contact, immediately flush skin with plenty of water. Remove
contaminated clothing and shoes. Wash clothing before reuse. Thoroughly clean shoes
before reuse. Get medical attention.
• Frostbite: Try to warm up the frozen tissues and seek medical attention.
• Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial respiration.
If breathing is difficult, give oxygen. Get medical attention.
9.3.4 FIRE FIGHTING MEASURE
Flammability of the product
Firefighting media and instructions. If involved in fire, shut off flow immediately if it can be
done without risk. Apply water from a safe distance to cool container and protect surrounding
area. No specific hazard.
Special protective equipment for fire-fighters
Fire fighters should wear appropriate protective equipment and self-contained breathing
apparatus (SCBA) with a full-face piece operated in positive pressure mode.
81
9.3.5 ACCIDENTIAL RELEASE MEASURE
• Personal precautions: Immediately contact emergency personnel. Keep unnecessary
personnel away. Use suitable protective equipment. Shut off gas supply if this can be
done safely. Isolate area until gas has dispersed.
• Environmental precautions: Avoid dispersal of spilled material and runoff and
contact with soil, waterways, drains and sewers.
• STORAGE: Keep container tightly closed. Keep container in a cool, well-ventilated
area. Cylinders should be stored upright, with valve protection cap in place, and firmly
secured to prevent falling or being knocked over. Cylinder temperatures should not
exceed 52 °C.
• HANDLING: Avoid contact with eyes, skin and clothing. Keep container closed. Use
only with adequate ventilation. Do not puncture or incinerate container. Wash
thoroughly after handling. High pressure gas. Use equipment rated for cylinder
pressure. Close valve after each use and when empty. Protect cylinders from physical
movement. Never allow any unprotected part of the body to touch insulated pipes or
vessels that contain cryogenic liquids. Prevent entrapment of liquid in closed systems
or piping without pressure relief devices. Some materials may become brittle at low
temperatures and will easily fracture.
Engineering controls: Use only with adequate ventilation. Use process enclosures, local
exhaust ventilation, or other engineering controls to keep airborne levels below recommended
exposure limits.
Personal protection
dusts.
• Respiratory: Use a properly fitted, air-purifying or air-fed respirator complying with an
approved standard if a risk assessment indicates this is necessary. Respirator selection
must be based on known or anticipated exposure levels, the hazards of the product and
the safe working limits of the selected respirator.
• Hand: Chemical-resistant, impervious gloves or gauntlets complying with an approved
standard should be worn at all times when handling chemical products if a risk
assessment indicates this is necessary.
82
• Molecular weight: 44.01 g/gmole
• Molecular formula: CO2
• Boiling/condensation point: -78.55°C
• Melting/freezing point: Sublimation temperature: -78.5°C
• Critical temperature: 30.9°C (87.6°F)
• Vapor pressure: 830 psig
• Vapor density: 1.53 (Air = 1)
• Physical chemical comments: Not available.
The product is stable.
9.3.10 TOXICOLOGY INFORMATION
Toxicity data
IDLH: 40000 ppm
Chronic effects on humans: Causes damage to the following organs: lungs, cardiovascular
system, skin, eyes, central nervous system (CNS), eye, lens or cornea.
Other toxic effects on humans: No specific information is available in our database regarding
the other toxic effects of this material for humans.
Specific effects
• Carcinogenic effects: No known significant effects or critical hazards.
• Mutagenic effects: No known significant effects or critical hazards.
• Reproduction toxicity: No known significant effects or critical hazards.

• Products of degradation: These products are carbon oxides (CO, CO2).
• Toxicity of the products of biodegradation: The product itself and its products of
degradation are not toxic.
• Environmental fate: Not available
• Environmental hazards: No known significant effects or critical hazards
• Toxicity to the environment: Not available
9.3.12 DISPOSABLE CONSIDERATION

locally.
83
9.4 WATER
Material name: Water
Synonyms: Dehydrogenase Monoxide: H2O
• Inhalation:
Acute overexposure: Inhalation can result in asphyxiation and is often fatal.
Chronic overexposure: Chronic inhalation overexposure not encountered.
• Skin Contact:
Acute overexposure: Prolonged but constant contact with liquid may cause a mild
dermatitis. Chronic overexposure: Mild to severe dermatitis.
• Skin Absorption:
Acute overexposure: No effects noted.
Chronic overexposure: No effects noted.
• Eye Contact:
Acute overexposure: No effects noted.
• Ingestion:
Acute overexposure: Excessive ingestion of liquid form can cause gastric distress and
mild diarrhea.
• Eyes: None
• Skin: None
• Inhalation: Remove to fresh air; provide artificial respiration; Provide oxygen.
• Ingestion: None
• Small Spill: Mop up, or absorb with an inert dry material and place in an appropriate
waste disposal container.
• Large Spill: Absorb with an inert material and put the spilled material in an appropriate
waste disposal.
• Conditions contributing to instability: Exposure to direct current electricity.
• Incompatibility: Strong acids and bases can cause rapid heating. Reaction with sodium
metal can result in explosion.
• Hazardous decomposition products: Hydrogen - Explosive gas Oxygen - Supports
rapid combustion
• Conditions contributing to hazardous polymerization: None
84
Flammability of the product
Firefighting media and instructions
If involved in fire, shut off flow immediately if it can be done without risk. Apply water from
a safe distance to cool container and protect surrounding area. No specific hazard.
Special protective equipment for fire-fighters
Fire fighters should wear appropriate protective equipment and self-contained breathing
apparatus (SCBA) with a full facepiece operated in positive pressure mode.
• STORAGE: Keep container tightly closed. Keep container in a cool, well-ventilated
area. Cylinders should be stored upright, with valve protection cap in place, and firmly
secured to prevent falling or being knocked over. Cylinder temperatures should not
exceed 52 °C.
• HANDLING: Avoid contact with eyes, skin and clothing. Keep container closed. Use
only with adequate ventilation. Do not puncture or incinerate container. Wash
thoroughly after handling. High pressure gas. Use equipment rated for cylinder
pressure. Close valve after each use and when empty. Protect cylinders from physical
movement. Never allow any unprotected part of the body to touch insulated pipes or
vessels that contain cryogenic liquids. Prevent entrapment of liquid in closed systems
or piping without pressure relief devices. Some materials may become brittle at low
temperatures and will easily fracture.
dusts. When working with cryogenic liquids, wear a full-face shield.
• Respiratory: Use a properly fitted, air-purifying or air-fed respirator complying with
an approved standard if a risk assessment indicates this is necessary. Respirator
selection must be based on known or anticipated exposure levels, the hazards of the
product and the safe working limits of the selected respirator.
• Hands: Chemical-resistant, impervious gloves or gauntlets complying with an
approved standard should be worn at all times when handling chemical products if a
risk assessment indicates this is necessary. Insulated gloves suitable for low
temperatures.
85
• Physical state and appearance: Liquid.
• Odor: Odorless.
• Taste: Not available.
• Molecular Weight: 18.02 g/gmol
• Color: Colorless.
• pH (1% solution/water): 7 [Neutral].
• Boiling Point: 100°C.
• Melting Point: Not available.
• Critical Temperature: Not available.
• Specific Gravity: 1 (Water = 1)
• Vapor Pressure: 2.3 kPa at 20°C
• Vapor Density: 0.62 (Air = 1)
• Volatility: Not available.
• Odor Threshold: Not available.
• Water/Oil Dist. Coefficient: Not available.
• Ionicity (in Water): Not available.
• Dispersion Properties: Not applicable
• Solubility: Not Applicable
• Stability: The product is stable.
• Instability Temperature: Not available.
• Conditions of Instability: Not available.
• Incompatibility with various substances: Not available.
• Corrosivity: Not available.
• Special Remarks on Reactivity: Not available.
• Special Remarks on Corrosivity: Not available.
• Polymerization: Will not occur.
Toxicity data, IDLH: 40000 ppm
Chronic effects on humans: Causes damage to the following organs: lungs, cardiovascular
system, skin, eyes, central nervous system (CNS), eye, lens or cornea.
Other toxic effects on humans: No specific information is available in our database regarding
the other toxic effects of this material for humans.
Specific effects
• Carcinogenic effects: No known significant effects or critical hazards.
• Mutagenic effects: No known significant effects or critical hazards.
• Reproduction toxicity: No known significant effects or critical hazards.
86
• Ecotoxicity: Not available.
• BOD5 and COD: Not available.
• Products of Biodegradation: Possibly hazardous short-term degradation products are
not likely. However, long term degradation products may arise.
• Toxicity of the Products of Biodegradation: The product itself and its products of
degradation are not toxic.
• Special Remarks on the Products of Biodegradation: Not available.

locally.
9.5 HYDROGEN
Product name: Hydrogen, compressed
Chemical name: Hydrogen formula: H2
Synonyms: none
Hydrogen is a flammable, colorless, odorless, compressed gas packaged in cylinders at high
pressure. It poses an immediate fire and explosive hazard when concentrations exceed 4%. It
is much lighter than air and burns with an invisible flame. High concentrations that will cause
suffocation are within the flammable range and must not be centered.
9.5.3 FIRST AID MEASURE
• Inhalation: Persons suffering from lack of oxygen should be removed to fresh air. If
victim is not breathing, administer artificial respiration. If breathing is difficult,
administer oxygen. Obtain prompt medical attention.
• Skin contact: None
• Eye contact: None
• Ingestion: None
• Notes to physician: None
Flammable gas: 565.5 °C Lower: 4% Upper: 74%
Extinguishing media: CO2, dry chemical water spray or fog for surrounding area. Do not
extinguish until hydrogen source is shut off.
Hazardous combustion products: none
Special firefighting instructions: evacuate all personnel from danger area. Immediately cool
container with water spray from maximum distance, taking care not to extinguish flames. If
flames are accidentally extinguished, explosive re-ignition may occur. Stop flow of gas if
without risk while continuing cooling water spray.
87
Unusual fire and explosion hazards: burns with a pale blue, nearly invisible flame. Hydrogen
is easily ignited with low-ignition energy, including static electricity. Hydrogen is lighter than
air and can accumulate in the upper sections of enclosed spaces. Pressure in a container can
build up due to heat, and it may rupture if pressure relief devices should fail to function.
Evacuate immediate area. Eliminate any possible sources of ignition, and provide maximum
explosion proof ventilation. Shut off source of hydrogen, if possible. If leaking from cylinder,
or valve, call the Air Products' emergency phone number. The presence of a hydrogen flame
can be detected by approaching cautiously with an outstretched straw broom to make the flame
visible.
• STORAGE: Specific requirements are listed in NFPA 50A. Cylinder storage locations
should be well protected, well-ventilated, dry, and separated from combustible
materials. Cylinders should never knowingly be allowed to reach a temperature
exceeding 52 °C). Cylinders of hydrogen should be separated from oxygen cylinders or
other oxidizers by a minimum distance of 20 ft., or by a barrier of noncombustible
material at least 5 ft. Cylinders should be stored upright with valve protection cap in
place and firmly secured to prevent falling or being knocked over. Protect cylinders
from physical damage; do not drag, roll, slide or drop. Use a suitable hand truck for
cylinder movement. Post "No Smoking or Open Flames" signs in the storage areas.
There should be no sources of ignition. All electrical equipment should be explosion
proof in the storage and use areas. Storage areas must meet national electric codes for
class 1 hazardous areas.
• HANDLING: Do not "open" hydrogen cylinder valve before connecting it, since self-
ignition may occur. Hydrogen is the lightest gas known and may collect in the top of
buildings without proper ventilation. It may leak out of a system which is gas-tight for
air or other gases. Leak check system with leak detection solution, never with flame. If
user experiences difficulty operating cylinder valve, discontinue use and contact
supplier. Use only approved CGA connections. DO NOT USE ADAPTERS. Never
insert an object (e.g., wrench, screwdriver, pry bar, etc.) into valve cap openings. Doing
so may damage valve, causing a leak to occur. Use an adjustable strap wrench to remove
over-tight or rusted caps. Never strike an arc on a compressed gas cylinder or make a
cylinder a part of an electrical circuit.
• Engineering controls: Provide natural or explosion-proof ventilation adequate to
ensure Hydrogen does not reach its lower explosive limit of 4%.
• Respiratory protection
General Use: None
Emergency Use: Air supplied respirators are required in oxygen-deficient
atmospheres. Before entering area, you must check for flammable or oxygen-deficient
atmospheres.
• Protective gloves: Work gloves are recommended when handling cylinders.
• Eye protection: Safety glasses are recommended when handling cylinders.
88
• Appearance and state: Colorless gas at normal temperature and pressure.
• Odor: Odorless
• Boiling point: -252.8 °C
• Specific gravity (Air =1): 0.06960
• Freezing point/melting point: -259.2 °C
• Vapor pressure: Not applicable
• Gas density (At 21.1°C) and 1 atm: 0.00521 lb/ft3
• Solubility in water (Vol/Vol at 15.6 °C): 0.019
• Specific volume (At 21.1°C and 1 atm): 192 ft3/lb
• Chemical stability: Stable
• Conditions to avoid: None
• Incompatibility (Materials to Avoid): Oxidizing agents. Some steels are susceptible
to hydrogen embrittlement at high pressures and temperatures.
• Reactivity:
A) hazardous decomposition products: None
B) hazardous polymerization: Will not occur.
Hydrogen is a simple asphyxiant.
No adverse ecological effects are expected. Hydrogen does not contain any Class I or Class II
ozone depleting chemicals (40 CFR Part 82). Hydrogen is not listed as a marine pollutant by
DOT (49 CFR Part 171).
Waste disposal method: Do not attempt to dispose of residual or unused product in the cylinder.
Return to supplier for safe disposal. Residual product within process system may be vented at
a controlled rate, to the atmosphere through a vent stack that discharges to an elevated point.
This stack should be in an isolated area away from ignition sources
89
CHAPTER 10
CONCLUSION
Considering the two reactions (CO and CO2 hydrogenation), methanol was obtained in lesser
amount with some amount of CO that cannot be neglected than when the three reactions (CO
and CO2 hydrogenation and RWGS), was considered. The optimum temperature and pressure
were found to be 240 °C and 50 bar respectively, with a series of simulation done in Pro/II.
Hence, the kinetic model involving the three set of reactions favored the yield of methanol
which was used in our simulation.
The processing units were optimized in order to obtain around 99 % pure methanol. The process
was run with and without the recycle and we found the yield to be higher with recycle inclusion.
The recycle stream was used with the purge of about 1% to minimize the accumulation in the
reaction loop. The reactor produced significant amount of heat hence the cooling water was
used to maintain the reactor temperature to its optimum value. The steam so produced from the
reactor was at 185 °C and can be used, as a utility, in the heat exchangers and in the reboiler of
the distillation which makes our process more economic.
The vapor-liquid separator was used in order to separate the gas mixture and the liquid. But
because of the residual gases entrained in the liquid stream, we further used a flash tank
employed under reduced pressure and hence even the residual gases were separated. Finally,
the distillation column was employed for the separation of methanol and water. The number of
plates, feed location and the reflux ratio were optimized and found to be 57 plates, 14th from
top and 1.5 respectively. The methanol so obtained was 4139 Kg/h (Overall Yield of 0.47) with
99 % purity.
The piping of the entire process with pipe sizes, insulation and materials of construction has
been designed with process control loop along with their respective instruments needed.
Equipments needed and the design parameters of each have been specified. Material safety
study was carried out, in detail, for each component involved in the process. Finally, the
economic analysis was done successfully with the ROI of 17 % making our process
economically feasible.
90
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94
Appendix 1
Calculation of Equilibrium Constants
Methanol Formation Reaction
CO2 + 3H2 CH3 OH + H2 O
Reverse Water Gas Shift Reaction
CO2 + H2 CO + H2 O
Cpig D
= A + BT + CT 2 +
R T2
Table A.1 Constants for Cp calculations for different components

Component A 103 B 106 C 10-5 D O O
∆Hf,298 ∆Gf,298
CO2 5.457 1.045 - -1.157 -393509 -394359
CO 3.376 0.557 - -0.031 -110525 -137169
H2 O 3.470 1.450 - 0.121 -241818 -228572
H2 3.249 0.422 - 0.083 - -
CH3 OH 2.211 12.216 -3.450 - -200660 -161960
O O
∆Hf,298 ,∆Gf,298 : Units are in J/mol
∆GO ∆GO − ∆H0O ∆H0O 1 T ∆CPO T

∆CPO dT
= + + ∫ dT − ∫
RT RT0 RT T T0 R T0 R T
Table A.2 Equilibrium Constants for Methanol Formation Reaction, relation with temperature
T(K) 1 −∆GO
T ln K eq1 =
RT
298.15 0.003354 -1.544809
323.15 0.0030945 -3.101933009
348.15 0.0028723 -4.455229203
373.15 0.00267989 -5.651849355
398.15 0.00251162 -6.719487381
423.15 0.00236323 -7.679142058
448.15 0.002231396 -8.547314721
473.15 0.00211349 -9.337515643
498.15 0.00200743 -10.06006842
523.15 0.001911498 -10.72385458
548.15 0.00182433 -11.33627591
573.15 0.001744744 -11.90321897
95
ln Keq1 vs. 1/T for methanol formation
0.0015 0.0017 0.0019 0.0021 0.0023 0.0025 0.0027 0.0029 0.0031 0.0033 0.0035
0
-2
-4
-6 ln Keq1 = 6446.8/T - 23.011

ln Keq1
-8
-10
-12
-14
1/T
Fig A. 1: a graph showing equilibrium constant relationship with abs. temperature for rxn 1
Table A.3 Equilibrium Constants for Reverse Water Gas Shift Reaction relation with temperature
T(K) 1 −∆GO
T ln K eq2 =
RT
298.15 0.003354 -11.55196
323.15 0.0030945 -10.26797748
348.15 0.0028723 -9.171409906
373.15 0.00267989 -8.22518645
398.15 0.00251162 -7.40122504
423.15 0.00236323 -6.67798714
448.15 0.002231396 -6.038747893
473.15 0.00211349 -5.470104016
498.15 0.00200743 -4.96134593
523.15 0.001911498 -4.503908411
548.15 0.00182433 -4.090748609
573.15 0.001744744 -3.715948137
96
ln Keq2 vs 1/T
0.0015 0.0017 0.0019 0.0021 0.0023 0.0025 0.0027 0.0029 0.0031 0.0033 0.0035
0
-2
-4
-6
ln Keq2
-8
-10 ln Keq2 = -4870.2/T + 4.8116
-12
-14
1/T
Fig A. 2: a graph showing equilibrium constant relationship with abs. temperature for rxn 2
97
APPENDIX 2
PRO/II PROCEDURE DATA
The Procedure Data used in the program for two reactions simulation is written as:
T = RTEMP + 273.15
R = 8.314
XK1 = 1.07*EXP(40000/(R*T))
XK2 = 3453.38
XK3 = 0.499*EXP(17197/(R*T))
XK4 = (6.62E-11)*EXP(124119/(R*T))
XK5 = (1.22E10)*EXP(-98084/(R*T))
P1 = XVAP(1)*RPRES
P2 = XVAP(2)*RPRES
P3 = XVAP(3)*RPRES
P4 = XVAP(4)*RPRES
P5 = XVAP(5)*RPRES
XKEQ1 = EXP(-22.902+(6407.5/T))
XKEQ2 = EXP(4.8116-(4870.2/T))
BETA = 1 + XK2*(P3/P4) + XK3*(P4**0.5) +XK4*P3
RRATES(1) = 887.5*XK1*P1*P4*(1-P3*P5/(XKEQ1*P1*P4**3))/BETA**3
RRATES(2) = 887.5*XK5*P1*(1-XKEQ2*P3*P2/(P1*P4))/BETA
RETURN
98
The Procedure Data used in the program for three reactions simulation is written as:
R=8.314
XK1=4.0638E-6*EXP(-11695/(R*RTEMP))
XK2=1.5188E-33*EXP(-266010/(R*RTEMP))
XK3=9.0421E8*EXP(-112860/(R*RTEMP))
XKPA=2.3710077E-23*EXP(98438/(R*RTEMP))
XKPB=6.495528E-21*EXP(54499/(R*RTEMP))
XKPC=2.8118E2*EXP(-43939/(R*RTEMP))
XKCO=8.3965E-11*EXP(118270/(R*RTEMP))
XKCO2=1.724E-10*EXP(81287/(R*RTEMP))
XK=4.3676E-12*EXP(115080/(R*RTEMP))
P1=XVAP(1)*RPRES*1E5
BETA=(1+XKCO*P2+XKCO2*P1)*(P4**0.5+XK*P3)
RHOB=1775/2
RRATES(1)=RHOB*XK1*XKCO*(P2*P4**1.5-P5/(P4**0.5*XKPA))/BETA
RRATES(2)=RHOB*XK2*XKCO2*(P1*P4**1.5-P5*P3/(P4**1.5*XKPB))/BETA
RRATES(3)=RHOB*XK3*XKCO2*(P1*P4-P3*P2/XKPC)/BETA
RETURN
99

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KATHMANDU UNIVERSITY

DEPARTMENT OF CHEMICAL SCIENCE AND ENGINEERING

BASIC DESIGN OF METHANOL PRODUCTION PROCESS BY CO2

In Partial Fulfillment of the Requirements for the

Bachelor’s Degree in Chemical Engineering

Sagar Ban (019053-15)

Gaurav Khatiwada (019062-15)

Dipti Paudel (019065-15)

Rakesh Shrestha (019073-15)

We hereby declare that we are the authors of this project.

We authorize the Kathmandu University to lend this report to other institutions or

Sagar Ban (019053-15)

Gaurav Khatiwada (019062-15)

Dipti Paudel (019065-15)

Rakesh Shrestha (019073-15)

Basic design of methanol production process by CO2 hydrogenation

Fig 2.1 Quench reactor with quench gas inlet ...................................................................... 10

Fig 6.1 P & ID first part ...................................................................................................... 24

1.1 Global carbon dioxide scenario

1.2 Methanol: Scopes

Fig 1.1 Methanol production and applications chart[10]

CH4 + H2O → CO + 3H2 ΔH (298K, 5MPa) = +206.3 kJ/mol

Traditionally, the production of methanol comprises of three basic steps:

• Production of synthesis gas

2.2. Reaction Mechanism

Hydrogenation of Carbon monoxide

CO + 2H2 ↔ CH3OH Reaction (1)

CO2 + 3H2 ↔ CH3OH + H2O Reaction (2)

Water gas shift reaction

CO + H2O ↔ CO2 + H2 Reaction (3)

2.4 Catalyst Development

Many Cu-based catalysts like CuO/ZrO2, CuO/ZnO/ZrO2, CuO/ZnO/Ga2O3, modified

2.5 Kinetic Modeling

Kinetics of the low-pressure methanol synthesis over a commercial catalyst CuO/ZnO/Al2O3,

2.6 Kinetic expressions and constant factors

Table 2.2 Parameter values of the kinetic model [B is given in J/mol]

2.6.2 For Three Reaction Consideration

Fig 2.4 Linde Isothermal reactor

Equilibrium conversion results for both two and three reactions.

Carbon dioxide Conversion CO mole fraction Methanol Mole Fraction

Carbon Dioxide Conversion CO mole Fractions Methanol Mole Fractions

Carbon Dioxide Conversion CO mole Fraction Methanol Mole Fraction

Carbon Dioxdie Conversion CO mole Fraction Methanol Mole Fraction

4.1 Flow sheet description

4.3 Heat Exchangers

4.5 Vapor Liquid Separator

4.6 Flash Tank

6.1 Pipe Size Calculation

For liquid streams density calculation,

Table 6.2 Average Density Calculation for all liquid streams

FT-101 C- CO2 1 1.1 25 28 1.78 44 PID-1

87 HA-123 TK- Vapor 1 1.1 31 34 L PID-

G: Gas or Vapor L: Local E: Electric

Here, the density of liquid at STP = (9.89E-3×792) + (6.40E-3×997)

7.1.3 Flash Separator, TK-102

Here, the density of liquid at STP = (0.4635 × 792) + (0.4697 × 997)

7.1.4 Distillation Column, T-101

7.1.5 Fixed Bed Reactor, R-101

For the cylindrical shell,

For the length of the reactor,

Length of the reactor (L) = Tube length + 2 × (50% of D)

For the calculation of catalyst weight,

7.2 Equipment Specification Sheets

BETA = 1 + XK2(P3/P4) + XK3(P4**0.5) +XK4*P3