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2020-05

Process Simulation of Methanol Production from

Water Electrolysis and Tri-Reforming

Shi, Chenxu

Shi, C. (2020). Process simulation of methanol production from water electrolysis and
tri-reforming (Unpublished master's thesis). University of Calgary, Calgary, AB.
http://hdl.handle.net/1880/112061
master thesis

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 UNIVERSITY OF CALGARY

Process Simulation of Methanol Production from Water Electrolysis and Tri-Reforming

by

Chenxu Shi

A THESIS
SUBMITTED TO THE FACULTY OF GRADUATE STUDIES
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF MASTER OF SCIENCE

GRADUATE PROGRAM IN CHEMICAL ENGINEERING

CALGARY, ALBERTA

MAY, 2020

© Chenxu Shi 2020

Abstract

The alarmingly increase in anthropogenic CO2 emissions is widely considered as the root

cause of global warming. To mitigate this issue, CO2 utilization via methanol production

can be an effective approach. The present study develops an innovative process to

produce methanol by combining water electrolysis with tri-reforming of methane (TRM).

The proposed process utilizes carbon-free electricity to split water into O2 and H2; O2 is

collected for partial oxidation reaction in the TRM and H2 is collected for stoichiometric

number (SN) optimization. This process configuration eliminates the typical problem of

H2 deficiencies associated with methanol synthesis and allows for additional CO2 to be

converted. The main process flowsheet is developed with the well-known Aspen HYSYS

process simulator. Then the feasibility of this project is evaluated based on its techno-

economic performance as well as greenhouse gas (GHG) emissions. The estimated

capital expenditure (CAPEX), operating expenditure (OPEX) and GHG emissions of the

baseline plant are $774 million, $263 million/year and -0.14 kgCO2eq/kgMeOH,

respectively. In particular, water electrolysis process accounts for 34% of CAPEX and

54% of OPEX. A discounted cash flow (DCF) model combined with sensitivity analyses

show that a breakeven point can be reached with a methanol price of $491/ton. The

results from this study demonstrate that combining water electrolysis with TRM can

improve the sustainability and economic viability for methanol production. However, in

order for the process to become more financially attractive, further research and

development are necessary to drive down the costs of the current water electrolysis

technology.

i
Acknowledgements

I would like to express my most sincere gratitude to my supervisor Dr. Nader Mahinpey

for his continuous support and encouragements throughout my journey as an MSc

student. It has truly been a great learning experience to work under his supervision.

I would like to thank my supervisory committee members and examiners, Dr. Roman

Shor and Dr. Hua Song, for taking their valuable time to review my thesis and offering

their constructive feedbacks.

I would like to acknowledge Babak Labbaf for his continuous support on my research

project. His presence motivated me to push for progress everyday on my thesis.

I would like to thank the past and present members of the Energy and Environment

Research Group (EERG). I consider myself lucky to be surrounded by the most

supportive, engaging and knowledgeable peers. This journey certainly would not have

been the same without them.

I would also like to express my sincere appreciation to all the sponsors of our EERG

group including Natural Sciences and Engineering Research Council of Canada

(NSERC), Canadian Natural Resources Limited (CNRL) and Devon Energy Corporation,

for their kind financial support.

In addition, I would like to extend my gratitude to all the rest of the staff members in the

Chemical and Petroleum Engineering Department at the University of Calgary. Their

ii
day-to-day work behind the scenes created an efficient and welcoming environment for

all students.

Last, but most importantly, I would like to thank my parents, Wenqi Shi and Lihua Chen.

Without their constant love and support, I would not have been able to come this far.

iii
Dedication

I dedicate this work to the scientific community.

iv
Table of Contents
Abstract ................................................................................................................................ i
Acknowledgements ............................................................................................................. ii
Dedication .......................................................................................................................... iv
List of Tables .................................................................................................................... vii
List of Figures .................................................................................................................. viii
Nomenclature ..................................................................................................................... ix
Chapter One: Introduction .................................................................................................. 1
1.1 Background ............................................................................................................... 1
1.2 Objective ................................................................................................................... 4
1.3 Thesis Structure ......................................................................................................... 5
Chapter Two: Literature Review ........................................................................................ 6
2.1 Chapter Overview ..................................................................................................... 6
2.1 Syngas Generation..................................................................................................... 6
2.2.1 Steam Reforming of Methane............................................................................. 7
2.2.2 Dry Reforming of Methane ................................................................................ 8
2.2.3 Partial Oxidation of Methane ............................................................................. 8
2.2.4 Auto Thermal Reforming ................................................................................... 9
2.2.5 Tri-reforming of Methane ................................................................................. 11
2.3 Methanol Synthesis ................................................................................................. 11
2.3.1 Kinetics and Modeling...................................................................................... 11
Chapter Three: Process Modeling ..................................................................................... 14
3.1 Chapter Overview ................................................................................................... 14
3.2 Tri-reforming System .............................................................................................. 16
3.3 Water Electrolysis System ...................................................................................... 18
3.4 Compression System ............................................................................................... 18
3.5 Methanol Synthesis System .................................................................................... 19
3.6 Purification System ................................................................................................. 21
3.7 Boiler Feed Water System....................................................................................... 22
Chapter Four: Methanol Production from Water Electrolysis and Tri- Reforming: Process
Design and Technical-Economic Analysis ....................................................................... 23

v
 4.1 Chapter Overview ................................................................................................... 23
4.2 Abstract ................................................................................................................... 23
4.3 Introduction ............................................................................................................. 24
4.4 Technology Overview ............................................................................................. 27
4.4.1 Water electrolysis system ................................................................................. 29
4.4.2 Tri-reforming system ........................................................................................ 30
4.4.3 Compression system ......................................................................................... 31
4.4.4 Methanol synthesis system ............................................................................... 32
4.4.5 Purification system ........................................................................................... 34
4.5 Process Simulation and Results .............................................................................. 34
4.5.1 Process Description .......................................................................................... 34
4.5.2 Net energy efficiency........................................................................................ 42
4.6 Environmental Impact Evaluation ........................................................................... 44
4.7 Economic Evaluation .............................................................................................. 47
4.7.1 Economic Assumptions .................................................................................... 48
4.7.2 Capital Expenditure (CAPEX) ......................................................................... 49
4.7.3 Operating Expenditure (OPEX)........................................................................ 51
4.7.4 Revenue ............................................................................................................ 53
4.7.5 Economics Summary ........................................................................................ 54
4.7.6 Sensitivity Analysis .......................................................................................... 56
4.8 Conclusions and Recommendations........................................................................ 57
Acknowledgement ......................................................................................................... 58
Chapter Five: Conclusion and Recommendations ............................................................ 59
5.1 Conclusions ............................................................................................................. 59
5.2 Recommendations ................................................................................................... 60
5.2.1 Experimental evaluation ................................................................................... 60
5.2.2 Further cost reduction measures ....................................................................... 60
References ......................................................................................................................... 61
Appendix A: Re-arrangement of Kinetics Expression for Aspen HYSYS....................... 66
Appendix B: Discounted Cash Flow Analysis.................................................................. 82

vi
 List of Tables
Table 3. 1 Process information for the feed streams ......................................................... 14
Table 4. 1 Kinetic expressions for Cu/ZnO/Al2O3 catalyst .............................................. 32
Table 4. 2 Electricity, heat consumptions of each subsystem in the plant........................ 43
Table 4. 3 List of baseline economic assumptions for this project investment ................ 49
Table 4. 4 Raw materials and utilities prices considered in this project ........................... 52
Table 4. 5 Economic Results Summary ............................................................................ 54

vii
 List of Figures

Figure 1. 1 Basic block flow diagram of the conventional methanol synthesis process .... 3
Figure 2. 2 ATR reactor configuration ............................................................................. 10
Figure 3. 1 Main simulation flowsheet ............................................................................. 15
Figure 3. 2 Simulation sub-flowsheet: Tri-Reforming System ......................................... 17
Figure 3. 3 Simulation sub-flowsheet: Water Electrolysis System................................... 18
Figure 3. 4 Simulation sub-flowsheet: Compression System ........................................... 19
Figure 3. 5 Simulation sub-flowsheet: Methanol Synthesis ............................................. 20
Figure 3. 6 Simulation sub-flowsheet: Purification System ............................................. 21
Figure 3. 7 Simulation sub-flowsheet: Boiler Feed Water System ................................... 22
Figure 4. 1 Block flow diagram of the methanol synthesis process ................................. 29
Figure 4. 2 Process flow diagram of the methanol plant .................................................. 35
Figure 4. 3 BWR molar concentration profile (top) and temperature profile (btm.) ........ 39
Figure 4. 4 Column molar concentration profile (top) and temperature profile (btm.) .... 41
Figure 4. 5 Net energy efficiency comparison. ................................................................. 44
Figure 4. 6 Defined system boundary for direct and indirect GHG emissions ................. 46
Figure 4. 7 GHG emissions of the three different cases considered in this study ............ 47
Figure 4. 8 Distribution of CAPEX for the methanol plant .............................................. 51
Figure 4. 9 Distribution of OPEX for the methanol plant................................................. 53
Figure 4. 10 Cumulative discounted cash flow of this project ......................................... 55
Figure 4. 11 Sensitivity analysis using the tornado diagram ............................................ 57

viii
Nomenclature
AC alternating current
AR5 Fifth Assessment Report
ASU air separation unit
ATR auto-thermal reforming
AWE alkaline water electrolysis
BWR boiling water reactor
C&SU commissioning and start-up
CAPEX capital expenditure
CEPCI Chemical Engineering Plant Cost Index
CLC chemical looping combustion
DC direct current
DCF discounted cash flow
GHG greenhouse gas
GHSV Gas hourly space velocity
GHV gross heating value
GWP100 100-year global warming potential
HHV higher heating value
HPS high pressure steam
IGCC integrated gasification combined cycle
IPCC Intergovernmental Panel on Climate Change
IRR internal rate of return
LHHW Langmuir-Hinshelwood-Hougen-Watson
NPT net payout time
NPV net present value
NRTL non-random two-liquid
OPEX operating expenditure

ix
PEM proton exchange membrane
PFR plug flow reactor
POX partial oxidation
SN stoichiometric number
SRM steam reforming of methane
tkUCE ThyssenKrupp Uhde Chlorine Engineers
TRM tri-reforming of methane
WGS water gas shift
WHB waste heat boiler

x
 Chapter One: Introduction

1.1 Background
Methanol is one of the most useful chemical compounds in modern society. By

developing relevant chemistry, methanol can be used for a great variety of purposes from

making synthetic petrochemical products to energy related applications. Within the

petrochemical industry, methanol is frequently used as a precursor for a wide range of

synthetic materials and chemicals. Some common products derived from methanol

include adhesives, foams, solvents and windshield washer fluids [1]. More recently, there

has also been a growing demand for methanol in the energy sector. In comparison to most

energy carriers, methanol is a relatively cleaner fuel. The molecular structure of methanol

consists of a methyl group attached to a hydroxyl group with no carbon-carbon bonds.

Therefore, this allows methanol to generate much less air pollutants during combustion

[2]. Today, approximately 45% of the produced methanol worldwide is used for energy

related applications and this number is projected to grow in the upcoming years [1].

One of the renowned interests of using methanol is motivated by Professor George A

Olah with his original concept, the ―Methanol Economy‖ [3]. This concept is aimed to

gradually phase out fossil fuel consumption by switching to methanol as the default

energy carrier. On a human time-scale, fossil fuel is considered a non-renewable resource

[4]. The massive consumption of fossil fuel also generates a significant amount of air

pollutions including greenhouse gas (GHG) emissions. Therefore, for the long term

sustainability of global energy supply and prevention of climate change, it was identified

that methanol can be considered a suitable alternative. The volumetric energy density of

1
methanol is higher in comparison to hydrogen [5]. Methanol also has a relatively high

boiling point (64.7°C) and low freezing point (-97.6°C), which makes it relatively safe

for pipeline transportation and storage [6]. In the event of an accidental spill, methanol

would have less environmental impact compared to crude oil or gasoline since it can be

reduced through natural processes such as photo-oxidation and biodegradation [7].

Finally, the process of methanol production often involves CO2 as a precursor, which is a

promising solution to counter global GHG emissions.

In order to fully achieve the ―Methanol Economy‖, it is important to understand how

methanol is produced. The history of methanol production started with Robert Boyle

when he first isolated pure methanol using the process of wood distillation [8]. This

process was capable of producing relatively small volumes and is initially used for

lighting, cooking and heating purposes. However, as the demand for methanol grows for

industrial applications, a more economical approach was desired. In 1905, Paul Sabatier

and Jean-Baptiste Senderens discovered that copper can effectively catalyze the

decomposition of methanol. It was hypothesized that the same material under alternative

conditions can be equally effective for the production of methanol [9]. This work was

later expanded through patents to become the first synthetic pathway for large-scale

methanol production.

Since then, the methanol industry has evolved to become more diverse and efficient. A

variety of raw materials and pathways for methanol production are employed and many

more are under development for future applications [7], [8]. Figure 1.1 shows a generic

block flow diagram of the current process for methanol production. This process involves

2
the three basic steps of syngas generation, methanol synthesis and product purification.

The available feedstock used for the syngas generation process can include anything from

fossil fuels such as natural gas, crude oil and coal to renewable fuels such as biomass,

landfill and plant emissions [10]. The decision for choosing the appropriate feedstock

was vastly based on economic considerations. Since the early days, natural gas has been

the predominant feedstock for methanol production as they are relatively abundant and

inexpensive. With the recent commercialization of hydraulic fracturing, the price of

natural gas was further reduced [11]. As a result, currently about 90% of the world’s

methanol are derived from natural gas [12]. The cost advantage of natural gas does not

necessarily apply to all geographical locations. In areas where natural gas is scarce or

unavailable, the cost of shipping and transportation may render the process too expensive

for implementation. Under such scenarios, other types of feedstock may become the

preferred choice for methanol production. An example of this is in China where coal

became the predominant feedstock for methanol production [9], [13].

Unreacted Gas

Syngas Methanol Product

Fuel Methanol
Generation Synthesis Purification

Figure 1. 1 Basic block flow diagram of the conventional methanol synthesis process

As discussed, fossil fuels are considered non-renewable resources. Yet, it is still heavily

relied upon by the current methanol industry. In addition, the processes of converting

fossil fuels into methanol also typically generate a considerable amount of CO2

emissions. In order to achieve greater sustainability, there is now a growing interest in

3
alternative processes through green chemistry. An example of this can be found in

Iceland, where Carbon Recycling International (CRI) has constructed the world’s first

commercial methanol plant using only CO2 and hydrogen. The process implemented by

CRI is commonly referred to as the direct CO2 hydrogenation. The CO2 comes from an

adjacent geothermal power station where it is also supplying energy to make hydrogen.

This plant began operations early in 2012 and is currently able to produce 4000 tons of

methanol and recycle 5500 tons of CO2 annually [14]. One of the drawbacks of this

process is that it is limited by the costs of H2 manufacturing [8]. Although it can be

justified in Iceland due to its readily available geothermal energy, but for most other

places in the world, the process of making hydrogen through water electrolysis can be

highly expensive. Furthermore, many literature studies have suggested that direct CO2

hydrogenation would be less competitive overall in comparison to traditional syngas

process. The reason may be due to additional water formation on the commercial Cu/ZnO

catalyst which leads to inactivity and ultimately reduces the methanol yield [15], [16].

1.2 Objective
The main objective of this thesis is to develop a novel process for methanol production

that overcomes the challenges of direct CO2 hydrogenation. By using a combination of

tri-reforming of methane and water electrolysis, high quality syngas can be generated

while utilizing CO2 as a feedstock. This proposed design is set to achieve net negative

carbon emissions and reach far superior economic performance than direct CO2

hydrogenation.

4
1.3 Thesis Structure
This thesis contains elements of both manuscript-based and traditional thesis, all in

accordance with the University of Calgary FGS guidelines. The main body of this thesis

consists of three chapters (Chapters 2, 3 and 4). Chapter 2 is a literature review on the

current research progress and technologies available for syngas generation and methanol

synthesis. Chapter 3 highlights the design and conceptualization of a novel methanol

plant through process modeling. This chapter contains all the key elements on simulation

setup, flow sheet developments as well as results and outcomes. Based on the process

simulation, Chapter 4 is a recently published technical and economic analysis paper that

focuses on CO2 utilization and methanol production. This work was primarily carried out

by Chenxu Shi under the supervision of Dr. Nader Mahinpey and with the help and

support from Babak Labbaf and Ehsan Mostafavi.

5
 Chapter Two: Literature Review

2.1 Chapter Overview

The goal of this chapter is to gather the relevant information in support of the thesis

objective. Since methanol production is a highly integrated process with multiple unit

operations, this literature review is only focused on the most relevant topics which are

syngas generation and methanol synthesis. The first section of this chapter looks at a

variety of syngas generation processes including steam reforming, dry reforming, partial

oxidation, auto-thermal reforming, and tri-reforming. These processes are examined

based on their principal operations as well as advantages and disadvantages. The second

section is focused on methanol synthesis, which can be further divided into topics

focused on reaction mechanisms and kinetics as well as reactor design configurations. All

of the information obtained from this chapter is used to guide decisions in choosing the

appropriate technologies and parameters for process modeling.

2.1 Syngas Generation

Syngas is a mixture of H2, CO, and CO2. The specific molar ratio of syngas can vary

significantly based on the feedstock and manufacturing process. The method of syngas

characterization is mostly based on the stoichiometric number (SN), which is a molar

ratio between the difference of H2 and CO2 and the summation of CO and CO2 [8]:

(2.1)

6
Ideally for methanol synthesis, SN should be equal to 2 or slightly higher [8], [17]. This

is due to the reaction stoichiometry of methanol synthesis. If the SN value is greater than

2, excess hydrogen would be accumulated downstream in the methanol synthesis loop.

On the other hand, if the SN value is less than 2, this would result in hydrogen deficit.

Both cases are less than optimal for the overall productivity of methanol. In practice, it is

often difficult to achieve a SN value of 2 due to limitations of the existing technologies.

This point will be further elaborated in the following sections.

2.2.1 Steam Reforming of Methane

Steam reforming of methane (SRM) is the most widely adopted technology for syngas

generation. In this process, steam is co-fed together with natural gas to a reformer furnace

typically operated in the range of 800 – 1000°C and 20 – 30 atm. [18]. The main

reactions are [19]:

CH4 + H2O ↔ CO + 3H2, ΔH⁰ = 206 kJ mol-1 (2.2)

CO + H2O ↔ CO2 + H2, ΔH⁰ = -41 kJ mol-1 (2.3)

Since the overall reaction is highly endothermic, an external heat supply must be

available in order to drive the reaction forward. This is often achieved by burning a

portion of the natural gas feed, but this leads to substantial production and emission of

CO2 in the flue gas stream. Furthermore, the typical SRM process produces syngas at a

SN of approximately 3 [8], [20]. As a result, excess H2 is generated downstream in the

methanol synthesis loop and would have to be either purged or used as a plant fuel gas.

Nevertheless, SRM currently remains as the preferred choice for methanol production

due to its economic viability and level of technological maturity.

7
2.2.2 Dry Reforming of Methane
Dry reforming of methane (DRM) or also known as CO2 reforming of methane is a

syngas generation process that has received much attention in literatures. The main

benefit of this process is that CO2 can be utilized as a feedstock, which has the potential

to reduce the impact of GHG emissions. The main reactions for DRM are [21]:

CH4 + CO2 ↔ 2CO + 2H2, ΔH⁰ = 247 kJ mol-1 (2.4)

CO + H2O ↔ CO2 + H2, ΔH⁰ = -41 kJ mol-1 (2.5)

In many design aspects, DRM is similar to SRM. The overall reaction is also highly

endothermic which necessitates an external heat supply. Water gas shift is also present in

this process as a common side reaction. However, contrary to SRM, this process is more

susceptible to catalyst deactivation due to increased coke formation. Since CO2 is

introduced as a feed, the reduction of CO2 can result in additional coke formation [22].

Another drawback of this process is that the produced syngas has a low SN of 1. For

methanol synthesis, this would lead to H2 deficiency during operations and would

necessitate an additional source of H2 to balance the reaction stoichiometry and increase

productivity.

2.2.3 Partial Oxidation of Methane

Partial oxidation of methane (POX) is another potentially attractive option for syngas

generation. POX is a combustion process with limited amount of oxygen. As a result, this

creates incomplete combustion and produces carbon monoxide and hydrogen [23]. The

main reaction set for POX is [8]:

CH4 + ½ O2 ↔ CO + 2H2, ΔH⁰ = -35.6 kJ mol-1 (2.6)

8
 CO + ½ O2 ↔ CO2, ΔH⁰ = -283 kJ mol-1 (2.7)

H2 + ½ O2 ↔ H2O, ΔH⁰ = -241 kJ mol-1 (2.8)

The overall reaction is exothermic and the process can be either thermal (TPOX) or

catalytic (CPOX) [24]. No indirect heat supply is required. POX can be an attractive

option because it requires less energy and capital investment in comparison to SRM [25].

The produced syngas has a theoretical SN of 2, but the actual achievable SN is less than 2

because of unwanted oxidation reactions (2.7 and 2.8) that forms additional CO2 and H2O

[8], [26]. Nevertheless, the SN from POX is comparatively more suitable for methanol

production than either SRM or DRM. Despite the advantages, POX is not commonly

used by the methanol industry due to several drawbacks. First, POX generally requires

pure oxygen and the need for an air separation plant may offset the potential economic

advantage it brings. If air is used instead of oxygen, then nitrogen would have to be

separated downstream which can end up being more costly. Second, due to POX’s

exothermic nature, a lot of excess heat is produced and wasted which would result in

lower energy efficiency. Lastly, due to the typical high operating temperatures of POX,

process safety and reliability can be another major concern [23].

2.2.4 Auto Thermal Reforming

Auto thermal reforming (ATR) is a heat neutral process for syngas production[8], [26].

This process has gained much popularity in the current methanol industry because it

eliminates the need of external heat supply. The reaction stoichiometry of this process is

the combination between SRM and POX reactions. The ATR reactor is generally divided

into 3 reaction zones as shown in Figure 2.2 [27]:

1. Burner – where the inlet gases are mixed together in a turbulent flame
9
 2. Combustion zone – where the exothermic POX reaction takes place

3. Catalytic zone – where the endothermic SRM reaction takes place

The heat generated from the exothermic POX reactions are direct consumed in the

catalytic SRM reactions. The overall reaction can be expressed in the following manner

[28]:

CH4 +(2 – 2x) H2O + x (O2) ↔ CO2 + (4 – 2x) H2, ΔH⁰ = -35.6 kJ mol-1 (2.9)

Figure 2. 2 ATR reactor configuration

An advantage of ATR is that no flue gas is generated, which means the overall process

generates significantly less GHG emissions than the traditional SRM. Furthermore,

because the heat produced from the POX reaction in the combustion chamber is

immediately consumed for the steam reforming reactions, this allows the process to be

more energy efficient than standalone POX. Another major advantage of the ATR

10
process is that the SN can be adjusted by changing the oxygen-to-carbon (O/C) and

steam-to-carbon (S/C) ratios [29]. This allows the ATR to be flexible at producing syngas

for different types of applications including methanol synthesis. The disadvantage of

ATR is similar to POX in that it requires an air separation unit (ASU) and this will

require additional capital investment.

2.2.5 Tri-reforming of Methane

Tri-reforming of methane (TRM) can be seen as a variation of ATR. The main difference

is that CO2 is also introduced to the feed together with steam, oxygen and natural gas.

This reaction stoichiometry of TRM can be viewed as a combination between SRM,

DRM and POX put together. The SN can be adjusted by altering the feed ratios between

oxygen, steam, CO2 and natural gas. Since CO2 is also being introduced in the feed, the

resulting SN would be generally less than 2 [30]. Therefore, unless there is an additional

source of hydrogen, using this process for methanol synthesis would be less suitable than

the standard ATR.

2.3 Methanol Synthesis

The current methanol synthesis reaction is typically carried out in gas phase and using

copper based catalyst. The reaction conditions are generally between 200 – 300°C and 50

– 100 bar. In the whole methanol industry, about 60% uses the Johnson Matthey process

and another 27% uses the Lurgi process [8]. Process design variations are mostly

associated with catalyst arrangements and reactor configurations [31].

2.3.1 Kinetics and Modeling

Kinetics is one of the most important aspects of chemical reactor design. Understanding

the reaction kinetic mechanisms can help determine the optimal operating conditions and
11
catalyst arrangements. This study focuses on the commercial Cu/ZnO catalyst, which is

most widely used in the methanol industry. Currently in literatures, the reaction

mechanism involved in methanol synthesis is still an open issue for debate. It is generally

accepted that methanol is predominately formed by the hydrogenation of CO2. However,

the macro kinetics for methanol synthesis can be described by three overall reactions

[32]:

CO2 + 3H2 → CH3OH + H2O, ΔH⁰ = -49 kJ mol-1 (2.10)

CO + 2H2 → CH3OH, ΔH⁰ = -49 kJ mol-1 (2.11)
CO + H2O ↔ CO2 + H2, ΔH⁰ = -41 kJ mol-1 (2.12)

A large number of kinetic equations have been proposed in literature. Different studies

have looked at various feed gas compositions and operating conditions. Amongst the

literature sources, Vanden Bussche and Froment’s rate equation is one of the most widely

used models for methanol simulation studies. Based on this reaction scheme, H2 and CO2

are adsorbed onto the copper active sites forming carbonate structures [32].

Subsequently, these carbonate structures are converted through series of hydrogenation

reactions before forming methanol. Between 15 to 51 bar and 180 to 280°C, this model is

able to adequately describe the effect of pressure, temperature and feed composition on

product composition.

2.3.1 Reactors
Since methanol synthesis via CO and CO2 hydrogenation is a highly exothermic process,

therefore, temperature control is a necessary consideration in order to maximize yield.

Currently, the methanol industry has adopted two common types of reactors, adiabatic

and isothermal [8]. The most common type of adiabatic reactor used in industry is the

12
low pressure quench converter developed by Johnson Matthey. This type of reactor

consists of multiple adiabatic beds installed in series. The beds are loaded with catalyst,

generally consisting of Cu/ZnO/Al2O3. In between each bed, either water or gas can be

injected to cool the reactants. This reactor configuration can handle a maximum capacity

of 3000 t/d [8].

The Lurgi converter or commonly referred to as the boiling water reactor (BWR) is the

most widely adopted reactor in the entire methanol industry. The design is a fixed bed

reactor similar to that of a shell-and-tube heat exchanger. The catalyst is loaded inside the

reactor tubes and cooling water is injected on the shell side. This type of configuration

allows for tight control on the reactor temperature profile and is able to generate high

pressure steam (HPS) at the same time.

13
 Chapter Three: Process Modeling

3.1 Chapter Overview

This chapter is focused on the conceptualization of a methanol plant that combines the

technologies of tri-reforming of methane and water electrolysis. The simulation work is

carried out using Aspen HYSYS v10 simulator with 15 components and 3 different fluid

packages. Process information on the feed streams is shown in Table 3.1. Majority of the

process is modelled using the Peng-Robinson fluid package. For the purification system

in particular, the liquid phase separation between methanol and water is modelled using

the Non-random two-liquid (NRTL) fluid package. Lastly, the steam generation and

cooling water systems is modelled using the ASME steam fluid package. The simulation

converged with a mass balance error of 0.00% and an energy balance error of 0.04%. The

main simulation flowsheet is shown in Figure 3.1. Note that Figure 3.1 also contains 6

individual sub-flowsheets, each with a designed purpose.

Table 3. 1 Process information for the feed streams

Feed Natural gas [33] CO2 [34] Demineralized water

Feed rate (t/h) 36.1 29.8 45.0
Vapor Fraction 1 1 0
Temperature (⁰C) 40 300 25
Pressure (kPaa) 2749 2549 2500
Composition C1: 93.90 CO2: 99.5 H2O: 100.0
(mol%) C2: 4.20 H2O: 0.5
C3: 0.30
C4+: 0.10
N2: 1.0
O2: 0.01
H2O: 0.0
CO2: 0.50

14
Figure 3. 1 Main simulation flowsheet

15
3.2 Tri-reforming System
Figure 3.2 shows the tri-reforming system modeled in Aspen HYSYS. Pipeline natural

gas, steam, post combustion captured CO2 and oxygen are fed together to the process to

produce syngas. The major unit operations are fired heater, pre-reformer, tri-reformer and

waste heat boiler. Since pipeline natural gas has already been pre-treated with sulfur

removal, it is not necessary to be considered again in this simulation. The fired heater is

modeled using a Gibbs reactor. It is supplied with purged gas from the methanol

synthesis loop and combustion air. There is no required make-up fuel gas in this process.

The fired heater acts as a multi-pass preheater for the reactants that provides a total heat

duty of 42 MW. Due to the absence of reliable kinetic data for reforming reactions in

literature, both the pre-reformer and the ATR are also modeled using the Gibbs reactor.

The pre-reforming reaction is an endothermic process and it is operated at a temperature

of 550°C. This process eliminates the C2+ hydrocarbons in the feed before it is sent to

the ATR. The ATR is an energy neutral process. The partial oxidation reaction provides

the heat required for SRM and DRM. The effluent from the ATR consists of mostly

syngas and is at a high temperature of 1046°C. A waste heat boiler is used to cool the

effluent down to 265°C while generating high pressure steam.

16
Figure 3. 2 Simulation sub-flowsheet: Tri-Reforming System

17
3.3 Water Electrolysis System
Figure 3.3 shows the water electrolysis system modeled in Aspen HYSYS. Since HYSYS

has limited capabilities with modeling electrolytes, only a simplified model was built to

represent the actual process. The major unit operations are a conversion reactor followed

by a component splitter. Demineralized water is fed to the conversion reactor with a

specified 100% conversion to form H2 and O2. Since the reaction is highly endothermic,

energy is supplied in the form of electricity to the reactor. It is worth mentioning that the

efficiency cannot be explicitly specified in this reactor, which means that in order to

account for the total energy consumption of this process, it is necessary to carry out

manual energy calculations. Using the efficiency factor provided in literature [35], it was

determined that the total energy consumption for this process is 300 MW. The component

splitter separates the produced gases into separate streams of H2 and O2 at 99.95% purity.

Figure 3. 3 Simulation sub-flowsheet: Water Electrolysis System

3.4 Compression System

Figure 3.4 shows the compression system modeled in Aspen HYSYS. ATR effluent is

dehydrated before it is mixed with hydrogen from water electrolysis. After the mix, the

syngas feed has a SN of 2.0 and is ready to be send for compression. The main unit

operations of the compression system are the two-staged centrifugal compressor for the

18
syngas feed and a single-staged centrifugal compressor for the recycled gas. The syngas

compressor is set to a pressure ratio of 2.2 per stage and a polytrophic efficiency of 80%.

The recycled gas compressor is set to match the outlet pressure from the syngas

compressor. Based on this configuration, the final outlet pressure is at 10670 kPa and the

recycling ratio is 4.67.

Figure 3. 4 Simulation sub-flowsheet: Compression System

3.5 Methanol Synthesis System

Figure 3.4 shows the methanol synthesis system modeled in Aspen HYSYS. The two

main unit operations are the feed/effluent exchanger (E-400) and the boiling water reactor

(BWR). E-400 is a standard shell and tube heat exchanger that heats up the syngas to

250°C while cooling down the BWR effluent. The BWR is modeled using a plug flow

reactor with a heterogeneous catalyst reaction set. The selected catalyst for this model is

19
Cu/ZnO/Al2O3 with the well-known kinetics expression developed by Bussche and

Froment [32]. However, due to the specific input template on HYSYS, the kinetic

expressions had to be re-arranged in order to be modeled correctly. Please see Appendix

A for more details on the kinetics expression re-arrangement steps. The overall reactor

design of the BWR is similar to a shell-and-tube exchanger. The methanol synthesis

reaction occurs on the tube side and saturated water passes on the shell side to keep the

temperature profile under control. There are a total of 2700 tubes, each with a length of

7.0 m and a diameter of 0.035 m. This makes up the total volume of the reactor to be 18.2

m3 with a void fraction of 0.4. The single pass conversion for H2, CO, and CO2 are

15.7%, 27.3%, and 9.0%, respectively. The BWR effluent exits at a temperature of

275°C.

Figure 3. 5 Simulation sub-flowsheet: Methanol Synthesis

20
3.6 Purification System
Figure 3.6 shows the purification system modeled in Aspen HYSYS. The main unit

operations are the two separators (V-501 and V-502) and the distillation column (T-100).

V-501 is the main separator of the unreacted gases from the BWR effluent. It is operated

at 40°C and 10200 kPa. 96% of methanol and 98% of water is condensed and separated

from the unreacted gases. V-502 is a secondary separator operated at 40°C and at a

reduced pressure of 250 kPa. With this condition, most of the unreacted gases are

vaporized and separated from the methanol/water mixture. The last step of purification is

at T-100 where the methanol is separated from water. T-100 is contains 22 equilibrium

stages, a partial condenser and a partial reboiler. The feed is introduced at stage 12,

methanol is collected at the top and water is collected at the bottom. The final recovery

rate of methanol is at 99.5% with 99.9wt% purity.

Figure 3. 6 Simulation sub-flowsheet: Purification System

21
3.7 Boiler Feed Water System
Figure 3.7 shows the boiler feed water return system. Boiler feed water in this process is

sent to the WHB in the tri-reforming system and the BWR in the methanol synthesis

system. The water gets converted to steam and is mostly used for the distillation column

reboiler. Another small portion of the steam is used for syngas generation. There is an

excess amount of steam which can be used for auxiliary heating purposes. Once the

steam is used for heating, the returned condensate is pumped back to the BFW surge

drum and ready to be re-used. A make-up water stream is necessary since the BFW

system is not entirely kept in a closed loop, part of the steam is consumed for syngas

generation.

Figure 3. 7 Simulation sub-flowsheet: Boiler Feed Water System

22
 Chapter Four: Methanol Production from Water Electrolysis and Tri-
Reforming: Process Design and Technical-Economic Analysis
Accepted on Dec. 27, 2019 in the Journal of CO2 Utilization

4.1 Chapter Overview

This chapter is a manuscript titled ―Methanol Production from Water Electrolysis:

Process Design and Technical-Economic Analysis‖, which was recently published in the

Journal of CO2 Utilization. No changes were made on the original contents aside from

page formatting and word editing. For more information on the estimation of CAPEX and

OPEX from this study, please refer to Appendix B and Appendix C. This study was

carried out at the EERG group supervised by Dr. Nader Mahinpey. He also provided

support on methodology development and technical reviews. Babak labbaf and Ehsan

Mostafavi provided useful feedbacks and suggestions on the process simulation. Chenxu

Shi was responsible for overall project conceptualization and implementation. This

manuscript proposed a novel concept for methanol production and completed with

environmental and economic feasibility studies.

4.2 Abstract
CO2 utilization via methanol synthesis can be an effective approach to mitigate the issue

of global warming. This study developed an innovative process to produce methanol by

combining water electrolysis with tri-reforming of methane (TRM). The proposed design

utilized carbon-free electricity to split water into O2 and H2; O2 is collected for partial

oxidation reaction in the TRM and H2 is collected for stoichiometric number (SN)

optimization. This process configuration eliminates the typical problems of H2 surplus or

deficit associated with methanol synthesis and allows a substantial amount of CO2 to be

converted. The main process flowsheet was developed with Aspen HYSYS process

23
simulator and then the feasibility of this project was evaluated based on its technical,

environmental, and economic performances. The estimated capital expenditure

(CAPEX), operating expenditure (OPEX) and GHG emissions of the baseline plant are

US$774 million, US$263 million/yr. and -0.14 kgCO2eq/kgMeOH, respectively. In

particular, water electrolysis process accounted for 34% of CAPEX and 51% of OPEX. A

discounted cash flow (DCF) model combined with sensitivity analyses showed that a

breakeven point could be reached with a methanol price of US$491/ton. The results

demonstrated that combining water electrolysis with TRM could achieve a sustainable

carbon-sink process for methanol production.

4.3 Introduction
The methanol economy proposed by Nobel Prize winner, Professor George A. Olah is a

concept that aims to ensure the long-term stability of global energy supply and the

environment [7]. Through the development of relevant chemistry, methanol can be

adapted as a transportation fuel, an energy storage medium, and as a raw material for

various petrochemical products [3]. Methanol is a relatively clean fuel in comparison to

most other energy carriers. The molecular structure of methanol consists of mostly

hydrogen atoms and no carbon-carbon bonds [36]. This allows methanol to generate

significantly less air pollutants such as NOx, SO2 and particulate matters during

combustion. In the case of an accidental spill into the environment, methanol would have

lower impact compared to the counterpart of crude oil or gasoline. This is because

methanol can degrade more rapidly through the processes of photo-oxidation and

biodegradation [8]. Owing to its wide range of industrial applications and environmental

benefits, it is of great interest for society to adopt methanol as the main energy carrier.

24
Today, about 90% of the world’s methanol comes from natural gas [12], a non-renewable

energy resource. For the long-term sustainability of the methanol industry and the world

at large, it is imperative to come up with feasible process designs that utilize renewable

energy. Methanol synthesis through green chemistry is a widely studied topic in

literatures. One of the commonly suggested pathways is the direct hydrogenation of CO2

to methanol, where the CO2 comes from a carbon capture process and the H2 comes from

water electrolysis using renewable electricity (wind, solar, geothermal, biomass, etc.).

Van-Dal and Bouallou studied such a process configuration through the development of

an Aspen Plus simulation model [37]. Their work concluded that as long as the H2

produced is carbon-free, the methanol plant itself is able to mitigate large amounts of

CO2 emissions. In support of this finding, other feasibility studies have also led to similar

conclusions that CO2 hydrogenation can be a promising approach to counter global

emissions [38], [39]. In fact, the concept of direct CO2 hydrogenation is not new to

industry as well. Some of the earliest methanol plants in the US used byproducts of

fermentation, which consisted of CO2 and H2, for methanol production [40]. In 2011,

Carbon Recycling International (CRI) of Iceland commercialized the world’s first CO2-

to-methanol plant using its readily available geothermal energy [41]. The same company

has already announced plans to construct additional pilot plants throughout Europe [42],

[43]. In Japan, CO2-to-methanol process was also demonstrated by Mitsui Chemicals

using a pilot plant in order to assess its feasibility [44].

Despite having all the environmental benefits, direct CO2 hydrogenation to methanol has

its own challenges to overcome. Through a comprehensive review study by Bozzano and

Manenti, it was suggested that methanol synthesis based on water electrolysis is not an

25
attractive option due to its high energy consumptions associated with H2 manufacturing

[8]. Likewise, Perez-Fortes et al. have also identified that the current H2 production costs

would be too high for this process to be financially attractive [39]. The economic

viability of this process is based on the premises that electricity is available at extremely

low cost, which, for the short to medium term, is an unrealistic condition to achieve in

most geographic locations. In addition to the high costs associated with H2 production,

several studies have also pointed out other technical challenges associated with direct

CO2 hydrogenation. Pontzen et al. performed a study on the commercial Cu/ZnO catalyst

(Süd-Chemie) and reported that CO2 hydrogenation is slower and less competitive

compare to CO hydrogenation under typical process conditions [15]. Tijm et al. also

identified that higher CO2 concentration creates irreversible damages to the commercial

Cu/ZnO catalyst and the root cause of the problem is may be due to water formation

during the synthesis reaction [16]. Therefore, in order to prolong the lifespan of the

catalysts, the presence of CO plays an important role by actively consuming water via

water gas shift (WGS) to form additional CO2 and H2. This is also reflected during

industrial operations when Haldor Topsoe reported that a higher ratio of CO to CO2 can

increase reaction rate and conversion per pass and decrease catalyst deactivation rate

[17].

In order to overcome the challenges of direct CO2 hydrogenation, one of the new areas

being studied is oxidative methane reforming process coupled with water electrolysis.

Combining these two processes enables the generation of high quality syngas that is

optimal for methanol synthesis. Since water electrolysis generates oxygen as a byproduct,

it can be directly used in the natural gas reforming process through partial oxidation.

26
With this configuration, the costly air separation unit (ASU) can be eliminated.

Furthermore, since there is additional H2 available from water electrolysis, this allows

more CO2 to be utilized in the reforming process in order to balance the syngas

composition. Li et al. proposed this configuration through their study of plasma catalytic

reforming coupled with water electrolysis [45]. Despite being mostly focused on the lab-

scale performance of the plasma catalytic reformer (PCR), their work demonstrated that

high energy efficiencies can be achieved with this configuration. In this current project,

we are focused on combining the state-of-the-art technologies of tri-reforming of

methane and alkaline water electrolysis for methanol synthesis. The combined

technologies are investigated through process development and technical-economic

analysis. It is predicted that such a configuration can achieve significantly better

economic performance than direct CO2 hydrogenation. The main portion of this work is

performed utilizing Aspen HYSYS process simulator and the results from the simulation

are used to conduct further assessments on the technical, economic and environmental

performance. Specifically, the technical metrics are focused on overall CO2 conversion

and net energy efficiency, the economical metrics are focused on the capital expenditure

(CAPEX), operating expenditure (OPEX) and net present value (NPV), and the

environmental metrics are geared towards greenhouse gas (GHG) emissions. The results

obtained are placed in parallel comparison with published data of direct CO2

hydrogenation in order to identify areas of strengths and weaknesses.

4.4 Technology Overview

When considering the design criteria for methanol synthesis, one of the key aspects to

consider is the composition of syngas. This is often characterized by the stoichiometric

27
number (SN), which is a molar ratio of the difference between H2 and CO2 to the

summation of CO and CO2:

(4.2)

For methanol production under ideal conditions, SN should be equal to a value of 2 or

slightly higher [8], [17]. Any significant deviation from a SN of 2 would lead to cases of

hydrogen surplus (SN >2) or hydrogen deficiency (SN<2). In the traditional steam

reforming of methane (SMR) process, the generated syngas typically has a SN of 2.8 to 3

[8]. As a result, this creates excess H2, which is then usually recycled to the reformer as

fuel gas. Another emerging trend in the methanol industry is to consider the possibility of

a stand-alone auto-thermal reforming (ATR) for syngas generation. However, since this

arrangement produces syngas at a lower SN of 1.7, it was suggested that an additional

source of H2 to balance the stoichiometry would make the process more effective [9].

Hence, the general approach considered in this study is the combination of water

electrolysis with tri-reforming (TRM) to produce syngas followed by conversion to

methanol. The process utilizes carbon-free electricity to split water into O2 and H2; O2 is

collected for the partial oxidation reaction in tri-reforming and H2 is collected for the

optimization of SN for methanol production. Figure 4.1 shows the block flow diagram of

the conceptual design. Within the battery limit of the central processing facility contains

five main subsystems: water electrolysis, tri-reforming, syngas compression, methanol

synthesis reaction, and methanol purification. Technology selections of each subsystem

are discussed in details in the sections below.

28
Figure 4. 1 Block flow diagram of the methanol synthesis process

4.4.1 Water electrolysis system

Water electrolysis using carbon-free electricity is a sustainable way to produce H2 and

O2. The two most common types of commercially available technologies are alkaline

water electrolysis (AWE) and proton exchange membrane (PEM). AWE is a more

established technology in comparison to PEM. Despite having relatively lower power

density than PEM, AWE offers longer stability, lower cost and higher power capacity

[46]. From a technical and economic standpoint, this study selected AWE to be the more

appropriate technology for the generation of H2 and O2.

A typical AWE system consists of anode and cathode, electrolyte, diaphragm and power

supply. In general, caustic electrolytes such as potassium hydroxide solution are used to

avoid corrosion problems. The electrodes are typically made of nickel due to its

operational reliability and low cost [47]–[49]. The purpose of the diaphragm is to

separate the produced H2 and O2; this prevents the formation of an explosive gas mixture

29
and maintain high product purities. When a sufficient direct current (DC) is applied, the

following reactions occur simultaneously on both the cathode and anode,

Cathode: 2H+ + 2e → H2 (4.2)

Anode: 2OH- → 1/2O2 + H2O + 2e (4.3)

The overall reaction of the water electrolysis process is:

H2O → H2 + 1/2 O2 (4.4)

This study considers the nominal 20-MW AWE module developed by ThyssenKrupp

Uhde Chlorine Engineers (tkUCE). Each module produces 4000 Nm3/h of H2. The

tkUCE AWE cells also have a wide operating range of 10% to 100%, which makes it

suitable for the intermittent nature of wind and solar electricity. The designed operating

pressure is slightly above atmospheric pressure and the cells are able to generate products

at >99.95% purity [35]. The complete installation package also includes an AC/DC

converter, gas compressors and temporary storage vessels for H2 and O2.

4.4.2 Tri-reforming system

Syngas can be generated from a variety of different processes. However, considering the

objectives of this study, tri-reforming of methane (TRM) was selected as the suitable

technology. The TRM process is designed to convert natural gas together with steam,

CO2 and O2. Instead of using an air separation unit (ASU), this process can take full

advantage of the available O2 generated from water electrolysis. Furthermore, the

produced syngas ratio can be adjusted by altering the amount of steam and CO2 fed to the

system [50], [51]. In comparison to dry reforming which also converts CO2, coke

formation is significantly suppressed due to the presence of steam [26], [52].

30
The main reactor of TRM takes the identical form of an auto-thermal reformer (ATR)

with three reaction zones [27]: the burner where the inlet feed mixes in a turbulent

diffusion flame, the combustion zone where partial oxidation reaction (POX) occurs and

the catalytic zone where steam and dry reforming reactions (SRM and DRM) occur. For

the purpose of this study, a commercial Ni/Al2O3 catalyst is used in the main reactor and

the reactions considered herein are,

POX: CH4 + 1/2O2 → CO + 2H2, ΔH⁰ = -35.6 kJ mol-1 (4.5)

SRM: CH4 + H2O ↔ CO + 3H2, ΔH⁰ = 206.8 kJ mol-1 (4.6)

DRM: CH4 + CO2 ↔ 2CO + 2H2, ΔH⁰ = 247.3 kJ mol-1 (4.7)

To maximize the operating life expectancy of such a reactor, inlet natural gas must go

through feed pre-treatment. This process typically consists of desulfurization and pre-

reforming reactions. During desulfurization, H2 is reacted with sulfur compounds

contained in the feed to form H2S and is separated it from the main process. This prevents

catalyst poisoning in the main reactor and allows for longer operations without catalyst

replacement. In the pre-reforming process, C2+ hydrocarbons are eliminated through

reactions with steam thereby preventing soot formation and deposition in the main

reactor. Like the main TRM reactor, the same Ni/Al2O3 catalyst is also used in the pre-

reformer.

4.4.3 Compression system

The compression system follows a standardized industry approach. In order to handle a

large quantity of syngas, the most common design is to use multi-staged centrifugal

compressor with inter-stage cooling. To prevent liquid entrainment and damage to the

compressor bearings, a liquid knockout drum with demister pad is installed.

31
4.4.4 Methanol synthesis system
The methanol synthesis process converts syngas into methanol. The reaction kinetics

considered in this study is based on the commercial Cu/ZnO catalyst commonly used in

industry. Through wide consensus in literatures, methanol is predominately formed by

the hydrogenation of CO2 [8]. Any presence of CO must first undergoes water gas shift

(WGS) to form CO2 and H2 before it can be converted to methanol [26]. For this reason,

the Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic expression developed by

Bussche and Froment [32] is adopted for reactor modeling. These kinetic expressions are

shown in Table 4.1. The overall kinetic reactions considered in this study are,

CO2 hydrogenation: CO2 + 3H2 → CH3OH + H2O, ΔH⁰ = -49 kJ mol-1 (4.8)

WGS: CO + H2O ↔ CO2 + H2, ΔH⁰ = -41 kJ mol-1 (4.9)

The study selected the widely used boiling water reactor (BWR) for methanol synthesis.

Since the overall reaction is highly exothermic, heat energy must be removed to

maximize product yield. The BWR is similar in design to that of a shell-and-tube heat

exchanger by which methanol synthesis reaction occurs on the tube side and water

vaporizes on the shell side. The tubes are filled with Cu/ZnO/Al2O3 commercial catalyst

pellets to speed up the reaction and the water from the shell side absorbs the heat

released. Such a reactor design keeps the temperature under control and generates high-

pressure steam (HPS) at the same time.

Table 4. 1 Kinetic expressions for Cu/ZnO/Al2O3 catalyst

32
 WGS:
Methanol Synthesis:

( ) [ ]
( )
( )
( )

T [K]
( ) ( )
P[bar]

( ) ( )

33
4.4.5 Purification system
The purification system separates the light end components and water from the methanol

product. In general, the system consists of a series of separator, flash drum and a

distillation column. Similar to the compression system, a standardized industry approach

was followed to design the purification system. By altering the process conditions

(temperature and pressure), methanol can be isolated at high purity.

4.5 Process Simulation and Results

4.5.1 Process Description
Figure 4.2 shows the process flow diagram of the methanol plant. The entire flowsheet is

developed with Aspen HYSYS v10 [53] using a combination of 3 different fluid

packages. Majority of the process is modeled using Peng-Robinson. NRTL is selected for

modeling the methanol-water liquid phase interactions in the purification system and

ASME steam is used for modeling the steam generation and cooling water systems. The

baseline production rate is 2095 ton/day, which is equivalent to the size of a commercial

scale plant. The final product stream contains grade A methanol (99.9wt%), which can be

used for various industrial purposes. The designed overall conversion of C1 and CO2 are

97% and 87%, respectively. In order to meet the designed specifications, the tri-

reforming system must work synergistically with the water electrolysis system and

deliver syngas at an optimum stoichiometric number (SN) of 2.0.

34
Figure 4. 2 Process flow diagram of the methanol plant

35
At the tri-reforming system, pipeline spec. natural gas [33] (1) is fed together with

superheated steam (2), post-combustion captured CO2 (5) and oxygen (11) from water

electrolysis. In this process, it is assumed that sulfur contents are negligible since the

natural gas feed composition follows pipeline specifications. The multi-pass fired-heater

initially heats the combined stream of natural gas and steam to 550⁰C in order for the pre-

reformer reactions to take place. The pre-reformed gas then gets combined with CO2 and

goes for a 2nd pass in the fired-heater to reach 650⁰C before it is sent to the TRM reactor.

Oxygen from water electrolysis is also pre-heated to 650⁰C and sent to the TRM reactor.

The total required duty of the fired heater is 42 MW which is met by burning the purged

gas from the methanol synthesis loop. Both the pre-reformer and the TRM reactor are

operated adiabatically and assumed to reach thermodynamic equilibrium over the catalyst

Ni/Al2O3 [27]. In order to determine the required catalyst volume for the reactors, a

conservative assumption of 3000h-1 gas hourly space velocity (GHSV) is applied [54].

The main difference is that for pre-reformer, the reaction is driven by the enthalpy of the

inlet feed whereas for TRM reactor, the reactions are driven by the heat released from

partial oxidation. In HYSYS, both of these reactors are modeled using the Gibbs reactor

block in order to calculate the equilibrium compositions. The pre-reformer outlet

composition shows that all of the C2+ hydrocarbons are consumed at the specified inlet

temperature. As for the TRM reactor, the equilibrium composition shows that 97% of the

C1 and 39% of the CO2 are converted. Reactor effluent (8) consists of mostly syngas in

the CO/CO2/H2 molar ratio of 0.29/0.06/0.47. This is equivalent to a stoichiometric

number (SN) of 1.2, which indicates that additional H2 is needed for methanol synthesis.

Temperature of the reactor effluent is 1046⁰C. Heat energy is recovered by cooling the

36
reactor effluent down to 265⁰C through a waste heat boiler (WHB) to generate high-

pressure steam (HPS).

The water electrolysis system is designed to supply O2 and H2 for the main process. The

main component of this system is a set of 15 modules of tkUCE 20 MW AWE. The entire

system has a total power consumption of 300 MW. Each AWE module is operated at

66.6% efficiency. Demineralized water (10) is initially fed to the 15 modules. With

carbon-free electricity, the water is split into O2 (11) and H2 (12) and the gases are

collected based on the designed specification of 99.95mol% purity. Since carbon-free

electricity is often derived from renewable energy source such as wind and solar,

temporary storage vessels are necessary to ensure that the plant can be operated at steady

state. Compressors will be included in the system to deliver the produced gas at 2500

kPa. In HYSYS simulation, a simplified model is developed using a conversion reactor

and a component splitter.

H2 from water electrolysis is added to the TRM reactor effluent to create the optimal SN

of 2.0. The syngas (15) is fed through a two-staged centrifugal compressor with a

compression ratio of 2.2 per stage. An inter-stage cooler is used to prevent temperature

from going above 200 ⁰C during the second stage compression. In addition to syngas

compression, recycled gas (19) from the purification system is also sent here for re-

compression. The recycling ratio (stream 19/stream 15) is 4.67. The recycled gas

compressor has a compression ratio of 1.05. All compressors designed in the simulation

are centrifugal type and has a polytropic efficiency of 80%. The total power consumption

of the compression system is 19.3 MW. Together, the syngas and recycled gas are

37
combined (21) and delivered to the methanol synthesis system at a pressure of 10,670

kPa.

The combined feed gas (22) is preheated to 250 ⁰C through a feed gas/effluent heat

exchanger before introduced to the BWR. The BWR is modelled using a plug flow

reactor (PFR) with a heterogeneous reaction set (LHHW). The reactor contains 2700

tubes with uniform diameters and lengths of 0.035 m and 7.0 m, respectively. The total

volume of the reactor tube side is 18 m3. Inside each tube contains the commercial

Cu/ZnO/Al2O3 spherical catalyst pellets with an average diameter of 0.005 m. These

pellets have a bulk density of 1140 kg/m3 and make up 60% of the total reactor volume.

During operations, the BWR is oriented vertically with the feed gas introduced at the

bottom. Temperature is controlled by injecting 128 t/h of high-pressure saturated water

on the shell side of the BWR. 61MW of heat energy is absorbed from the reactions to

generate high-pressure steam. The BWR components’ molar concentration and

temperature profiles are shown in Figure 4.3. In a single pass, 15.7% of H2, 27.3% of CO

and 9.0% of CO2 are converted. The BWR effluent (23) at 275 ⁰C is cooled against the

reactor feed gas stream down to 113 ⁰C (24) before it is sent to the purification system.

38
 0.20 0.70

0.15 CO
0.68
Molar Concentration
H2
0.10
CO2
0.66
0.05 CH3OH

H2O
0.00 0.64
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00
Reactor Axial Distance (m)

280

275

270
Temperature (°C)

265

260

255

250
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00
Reactor Axial Distance (m)

Figure 4. 3 BWR molar concentration profile (top) and temperature profile (btm.)

39
At the purification system, the BWR effluent is initially cooled down to 40⁰C (25) and

sent to the separator. 96% of methanol and 98% of water is condensed and separated (28)

from the unreacted gas. To prevent inert concentration build-up in the recycle loop, 98%

of the unreacted gas (26) is sent back for re-compression while the remainder 2% (27) is

purged and sent to the pre-heater as fuel gas (36). Downstream of the two-phase

separator, a throttling valve is used to reduce the pressure down to 250 kPa (29). Then a

flash drum is used to separate most of the remaining dissolved gas in the stream (31). The

remaining methanol and water mixture (30) is then preheated to 78⁰C (32) and sent to the

distillation column for final separations. The distillation column has 22 stages, a partial

reboiler and a partial condenser. The required heating duty of the reboiler is 65.0 MW,

which is supplied by the high-pressure steam generated in the earlier processes. The

required cooling duty of the condenser is 64.1 MW, which is supplied by 3,688 t/h of

cooling water. The feed is introduced at stage 12, water (34) is separated to the bottom

and methanol (33) is collected at the top. A vent gas stream (35) is also introduced at the

top of the partial condenser to separate trace amounts of impurities from the methanol

product. The molar concentration and temperature profile of the distillation column is

shown in Figure 4.4. Overall, the distillation column delivers methanol at 99.5% recovery

and 99.9wt% purity.

40
 1.00
CH3OH

0.80

Molar Concentration
0.60

0.40

0.20
H2O
0.00
0 2 4 6 8 10 12 14 16 18 20 22
Distillation Column Stages

120

110

100
Temperature (C)

90

80

70

60

50
0 2 4 6 8 10 12 14 16 18 20 22
Distillation Column Stages

Figure 4. 4 Column molar concentration profile (top) and temperature profile (btm.)

41
4.5.2 Net energy efficiency
The net energy efficiency of this process is defined as the ratio between total energy

output and total energy input:

(30)

In this study, the total energy output is the gross heating value of methanol (GHV MeOH)

calculated using the higher heating value (HHV) property. At full plant capacity,

GHVMeOH is 546 MW. On the other hand, the total energy input includes a combination

of electricity, heat and natural gas consumptions. The gross heating value of consumed

natural gas (GHVNG) is 566 MW. The rest of the energy input coming from electricity

and heat consumptions in the plant are summarized in Table 4.2. As previously discussed,

heat energy is recovered from the waste heat boiler (WHB) and boiling water reactor

(BWR) by generating high pressure steam. Majority of this steam is used to provide

heating duty for the distillation column reboiler. Another portion is consumed as

reactants in the TRM reactor. The rest of the excess steam is not considered in the energy

efficiency calculations, but can be used for various on-site heating purposes.

The net energy efficiency of the baseline process was determined to be 62%. Figure 4.5

shows a comparative study with other processes reported in literatures. While the

baseline process implemented in this study is more energy efficient compared to direct

CO2 hydrogenation, there is still a considerable gap from the commercial natural gas

process. One of the key bottlenecks of the current design is the efficiency of water

electrolysis, which has significant potentials for improvements. In addition, further

42
developments can still be made on the process design by carrying out energy

optimizations to reduce the overall energy consumptions.

Table 4. 2 Electricity, heat consumptions of each subsystem in the plant

Energy Consumptions (+) and Productions (-)

Plant Subsystems
Electricity (kW) Heat (kW)

Water Electrolysis System:

20-MW AWEs x 15 300000 -

Tri-Reforming System:
TRM Pre-heater Air Blower 967 -
Waste Heat Boiler - -63360
Steam Consumption (Gen. Energy) - 13650

Compression System:
Syngas Feed 1st Stage Compressor 7936 -
Syngas Feed 2nd Stage Compressor 8971 -
Recycle Gas Compressor 2363 -

Methanol Synthesis System:

Boiling Water Reactor - -61000
Boiler Feed Water Circulation Pump 23 -
Make-Up Water Pump 28 -

Purification System:
Distillation Column Reboiler - 64760
Cooling Water Circulation Pump 295 -

Net Energy Consumption:

320288 -45950

43
 100%

Net Energy Effciency, ղ 80% 75%

62% 63%
60%
52%

40%

20%

0%
Baseline process Coal to MeOH* NG to MeOH** CO₂/H₂ to
MeOH***

Figure 4. 5 Net energy efficiency comparison of various methanol synthesis processes.

*The coal to methanol process is based on the gasification technology simulated using
Pro/II [55]. **The natural gas to methanol process is based on the conventional steam
reforming technology [8]. ***The CO2/H2 to methanol process is based on direct CO2
hydrogenation where H2 comes from water electrolysis [37].

4.6 Environmental Impact Evaluation

The two species of greenhouse gases considered in this project are CO2 and CH4. The

metrics used for determination of 100-year global warming potential (GWP100) are in

accordance with IPCC 2014 AR5 [56]. Figure 4.6 shows the defined system boundary of

this study, which include direct emissions from the methanol plant and indirect emissions

from natural gas extraction and processing, electricity generation and heat generation. In

order to estimate the indirect emissions, the following data were retrieved from an LCA

analysis performed by Kim et al. [57]:

44
1. Conventional electricity generation is 0.407 kg CO2 eq./kWh

2. Conventional heat generation is 0.233 kg CO2 eq./kWh

3. Natural gas extraction and processing is 0.178 kg CO2 eq./kg NG

The total emitted CO2 is then calculated based on the following equation:

(41)

A comparative case study was conducted to evaluate the GWP100 differences between the

baseline process configuration and the conventional methanol production process. Three

different cases were considered as follows:

• Case 1: Conventional methanol production using natural gas and steam. This

process consists of three major steps: steam methane reforming, methanol

synthesis and product purification. The emission data for this process were

retrieved from literature [57].

• Case 2: Baseline process configuration using electricity from the power grid. It is

assumed that energy source for electricity generation is based on the US fuel mix

of 2009 [57], [58].

• Case 3: Baseline process configuration using electricity from carbon-free

generation processes only (i.e. wind, solar and nuclear) where zero emissions can

be assumed.

The results from the case study are shown in Figure 4.7. In this study, it is assumed that

CO2 fed to the process as raw material is counted as negative emissions. The

45
conventional process (case 1) emits GHG from all sources defined in the system

boundary and the total GWP100 is 0.67 tCO2eq./tMeOH. On the other hand, the baseline

process configuration (case 2 and case 3) use CO2 as raw material, require less natural

gas and does not require external heat supply. Nevertheless, despite having these

advantages, the overall GWP100 for the baseline process configuration would still be

higher than the conventional process if the electricity consumption is drawn directly from

the power grid. In order to realize the target of net negative carbon emissions, electricity

supply must be entirely based on carbon-free generation technologies. It was determined

that a GWP100 of -0.14 tCO2eq./tMeOH can be achieved if the baseline process uses

carbon-free electricity. In comparison to the conventional methanol process, this is about

570,000 ton of CO2 mitigated annually when the plant is operating at full capacity.

Indirect
emissions

electricity generation

Direct
emissions
Indirect
emissions

Natural Gas
Extraction/Processing Methanol Plant

Indirect
emissions

Heat generation

Figure 4. 6 Defined system boundary for direct and indirect GHG emissions

46
 1.60 1.49

1.40

1.20

1.00
GHG Emissions (kg CO2 eq./kg MeOH)

0.80

0.60
0.40
0.40

0.20 0.12 0.09 0.08 0.08

0.07
0.00 0.00 0.00
0.00
Case 1 Case 2 Case 3
-0.20
-0.22 -0.22
-0.40

Plant emissions Natural Gas Production Electricity Generation Heat Generation

Figure 4. 7 GHG emissions of the three different cases considered in this study

4.7 Economic Evaluation

An economic study was conducted to determine the financial feasibility under various

market conditions. Results from the process simulation flowsheet were used to estimate

the capital expenditure (CAPEX), operating expenditure (OPEX) and revenue. Based on

these estimations, a discounted cash flow (DCF) model was developed to determine the

net present value (NPV) of this process. A sensitivity analysis was performed on the DCF

model to determine the impact of different variables on the NPV.

47
4.7.1 Economic Assumptions
The main economic assumptions used for this study are shown in Table 4.3. This is a

grass roots plant based in North America. The specific location is set in the Gulf Coast,

Texas, United States for favorable economic conditions such as market access, utilities

prices and corporate income tax. This project is set to initiate in 2018 with 3 years for

construction and 1 year for commissioning and start-up (C&SU). During the

construction phase, it is assumed that 1st and 2nd year will use 50% of the CAPEX and

the 3rd year will use the remainder CAPEX. Once construction reaches 100%

completion, operations can be initiated. The start-up year is assumed to reach 50% of the

plant capacity and the following years are assumed to reach full plant capacity. The life

expectancy of this project is assumed to be 20 years, which is consistent to other similar

processes and technologies. In order to account for the time value of money, an annual

discount rate of 8.0% was applied. On top of that, an inflation rate of 1.9% retrieved from

the US Bureau of labor statistics in 2018 was assumed over the project lifespan [59]. In

terms of asset depreciation, a straight line method was adopted with 20% salvage value.

The plant asset is assumed to be liquidated after 20 years of operation. For pre-design

estimates, the working capital of this project was assumed to be 15.0% of fixed capital

expense, which is a typical value for traditional chemical plant operation [60], [61]. In

order to account for plant turnarounds and unplanned outages, an on-stream factor of

91% is assumed (The equivalence of 7,992 operating hours per year). The revenue

generated from the production and sales of methanol is subject to a 21.0% corporate

income tax for the state of Texas [62].

48
Table 4. 3 List of baseline economic assumptions for this project investment
Referenced Year of Project Initiation 2018
Project Life 20 years
Project Location Texas, US
Inflation rate 1.9%
Depreciation type Straight line with 20% salvage value
Income tax 21.0%
Annual discount rate, i 8.0%
Working capital (WC) 15.0% of fixed capital
Construction period 3 years
Start-up (C&SU) period 1 Year
Operating hours per year 7992 hours (91% on-stream factor)

4.7.2 Capital Expenditure (CAPEX)

The steps followed for the determination of CAPEX are mostly in accordance with

―Chemical Engineering Process Design and Economics: A Practical Guide‖ handbook

[61]. The main project expenses are associated with the plant bare module cost, which

includes the purchase and installation of all process equipment within the battery limit.

Cost data were retrieved for standardized process equipment and adjusted based on size,

material of construction, pressure rating and the Chemical Engineering Plant Cost Index

(CEPCI) of 2018 [63]. For water electrolysis system and tri-reforming system, price

estimations had to be obtained from specific vendors [35], [64], because specialized

process equipment were used. The offsite facilities, project contingency and working

capital were considered based on the following:

49
• Offsite facilities: 30% of plant bare module. This includes any auxiliary buildings,

product storage tanks, chemical supplies and miscellaneous utilities.

• Project contingency: 30% of plant bare module. This accounts for unforeseen

expenses, unexpected delays, disruptive weather etc.

• Working capital: 15% of fixed capital (See section 4.6.1). The fixed capital cost is

the summation of plant bare module, offsite facilities and project contingency.

The total CAPEX of this project is calculated to be US$774 million. Figure 4.8 shows the

break-down of CAPEX associated with each major portion of project investment. While

offsite facilities, project contingency and working capital are fixed percentages based on

the main project expenses, CAPEX reduction measures can be considered for each of the

plant subsystems. Among the subsystems, water electrolysis accounts for the most

significant portion of capital investment (about 62% of the plant bare module

investment).

50
 0.12% 2.21%

6.45% 13.04% Working Capital

Contingency
11.56%
Off-site
16.30% Utility System
Water Electrolysis
Tri-Reforming
Compression
33.92% 16.30% Methanol Synthesis
Purification

0.08%

Figure 4. 8 Distribution of CAPEX for the methanol plant

4.7.3 Operating Expenditure (OPEX)

The annual OPEX can be divided into direct and indirect expenses. Direct expenses

include raw materials, utilities, catalysts, operating labor, supervision, maintenance,

supplies, laboratory charges, patents and royalties. The indirect expenses include

overhead, local taxes and insurance. The prices of raw materials and utilities used in this

study are listed in Table 4.4. The catalysts used during plant operation include Ni/Al2O3

and Cu/ZnO and their price information were retrieved from NREL [65]. Since catalysts

degrade over time, they are assumed to be replaced every 5 years. Based on the size and

scale of this methanol plant, it was estimated that a total of 30 plant operators are

required for daily operations and the annual salary for each operator is US$62,380

51
according to the US Bureau of Labor Statistics [66]. The rest of the operating expenses

were calculated as follows: supervision is 10% of operating labor costs, maintenance is

2% of fixed capital, plant supplies is 10% of maintenance, laboratory charges is 10% of

operating labor, patents and royalties is 2% of direct expense, plant overhead is 50% of

operating labor, supervision and maintenance, local taxes is 2% of fixed capital and

insurance is 1% of fixed capital. The annual OPEX of this project is calculated to be

US$263 million/yr. Figure 4.9 shows that OPEX distribution for this project is dominated

by the cost of electricity consumption at 54.2%. This is an expected outcome since the

water electrolysis system along consumes about 300 MW of electricity.

Table 4. 4 Raw materials and utilities prices considered in this project

Raw Materials

Natural Gas (US$/mmBtu) [67] 3.17

CO2 (US$/ton) [34] 86.40

Water (US$/m3) [61] 5.95

Utilities

Electricity (US$/kWh) [68] 0.06

Cooling Water (US$/m3) [61] 0.05

52
 Electricity
2.95% 5.12% 2.56%
Cooling water
1.75%
0.78% Natural Gas
0.20% Demineralized Water
5.71%
CO2

7.77% Catalysts

54.19% Labor and supervision

Maintenance, supplies
0.81% 16.85% and lab
Patents&Royalties

Overhead

Local Taxes
1.30%

Figure 4. 9 Distribution of OPEX for the methanol plant

4.7.4 Revenue
Based on the current design considerations, methanol is the only source of revenue for

this project. From the historical data, it can be observed that the price of methanol is

highly volatile. For the purpose of this study, US$493.25/t was assumed based on the

average methanol price of 2018 according to Methanex [69]. When the plant is operating

at full capacity, the annual product sales revenue generated is US$343 million.

53
4.7.5 Economics Summary
A DCF model is developed incorporating all results and assumptions. The steps followed

in the DCF analysis are presented in Appendix D. Figure 4.10 illustrates the net cash flow

of this project over the entire lifespan from construction to full-scale operation. It is

determined from DCF that this project will have a net payout time (NPT) of 19.8 years

and a positive net present value (NPV) of US$11.4 million after 20 years of operation.

The internal rate of return (IRR) for this project is at 8.17%. Table 5.3 provides a

summary of the economic performance of this project. In comparison to direct CO2

hydrogenation [8], the economic feasibility of this process is far superior.

Table 4. 5 Economic Results Summary

Total capital expenditure US$774 million

Total operating expenditure US$263 million/yr.
Total product sales revenue US$343 million/yr.
Net payout time (NPT) 19.8 years
Net present value (NPV) US$11.4 million
Internal rate of return (IRR) 8.17%

54
Figure 4. 10 Cumulative discounted cash flow of this project over 20 years of operation

55
4.7.6 Sensitivity Analysis
A sensitivity analysis is performed to determine the relative impacts of raw materials,

utilities and product prices on the NPV. The prices of each variable are deviated by +/-

20% from their baseline values and the respective impacts are reflected in the tornado

diagram in Figure 4.11. The order of significance is shown from the top (selling price of

methanol) to bottom (purchase cost of demineralized water). Based on the current model,

the breakeven selling price of methanol is US$491/t which is lower than the average price

of 2018. However, a drop of only US$2/t would take this project to an unprofitable

condition.

Several areas can be considered to improve the economic feasibility of this project. One

of the key driving factors is process improvements related to water electrolysis. Further

R&D efforts focused on improving the energy efficiency can lead to reductions in both

electricity consumption and equipment purchase cost. Another consideration for cost

reduction is through further developments in clean energy processes. Progress in wind,

solar and nuclear energy sectors can reduce the cost of carbon free electricity generation

down to a more affordable level. Lastly, improvements in carbon capture processes can

also provide additional savings. The current price of CO2 capture is US$86.40/t using the

amine absorption technology from a post combustion capture plant. However, with the

new integrated gasification combined cycle (IGCC) plants, the cost of CO2 capture can be

as low as US$11.00/t [70].

56
 MeOH Price

Electricity Price

Natural Gas Price

Category

+20%
CO2 Price -20%

Cooling Water Price

Demineralized water Price

-800 -600 -400 -200 0 200 400 600 800

NPV ($ million)

Figure 4. 11 Sensitivity analysis using the tornado diagram

4.8 Conclusions and Recommendations

Methanol production with CO2 utilization can be a sustainable pathway to meet future

global energy demands. In order to overcome the technical and economic challenges of

direct CO2 hydrogenation, this study investigated the combined state-of-the-art

technologies of water electrolysis with tri-reforming for methanol production. The

primary objective was reached by the conceptual design of a commercial scale methanol

plant with net negative carbon emissions. Project feasibility was then evaluated based on

the technical, environmental and economic performance.

The major steps took in process design consisted of technology selections and flowsheet

developments using Aspen HYSYS v10. The heat and material balance data obtained

from simulation results were used to perform equipment sizing, reactor conversions, and

net energy efficiency calculations. Through the combined processes of tri-reforming,

57
water electrolysis and methanol synthesis, the overall conversions of CH4 and CO2 are

97% and 87%, respectively. The net energy efficiency of this process was determined to

be 62%, which is distinctively higher in comparison to direct CO2 hydrogenation.

The environmental impact of this project was evaluated by considering the GHG

emissions of CO2 and CH4. The method of calculation included both direct emissions

from the methanol plant and indirect emissions from the consumption of raw materials

and utilities. Results have shown that if carbon-free electricity is used, this process is

capable of reaching net negative carbon emissions of -0.14 tCO2eq./tMeOH. In

comparison to a traditional methanol plant, this is a net reduction of CO2 emissions by

570,000 tons annually.

The economic feasibility of this project was evaluated with DCF analysis using standard

project assumptions. The estimated CAPEX and OPEX of this project are US$774

million and US$263 million/yr., respectively. From the DCF model, it was determined

that a positive NPV of US$11.4 million can be achieved after 20 years of operation. From

the sensitivity analysis, it was shown that the selling price of methanol has the highest

impact on NPV and the breakeven point is at US$491/ton. With better technologies

available for water electrolysis, electricity generation, and CO2 capture, the economics of

this project is anticipated to reach much greater improvements.

Acknowledgement
The authors would like to extend their gratitude to the Natural Sciences and Engineering

Research Council (NSERC) of Canada for funding this research, through its Industrial

Research Chairs (IRC) program.

58
 Chapter Five: Conclusion and Recommendations

5.1 Conclusions
The ―Methanol Economy‖ is a promising concept that ensures the long term stability of

global energy supply. The main challenge is to figure out a cost-effective solution in

producing renewable methanol. Direct CO2 hydrogenation demonstrated great potentials

in terms of sustainability and environmental benefits. However, the high costs of this

process may prevent it from further large scale implementations by the industry. To

overcome the challenges of direct CO2 hydrogenation, this study investigated the

combination of tri-reforming of methane (TRM) and water electrolysis for methanol

synthesis.

Through process simulation and economic analysis, this study was able to demonstrate

several advantages of combining TRM with water electrolysis. One of the main

advantages is that an increased amount of CO2 can be converted to syngas without

concerns on the stoichiometric number (SN). Since syngas produced by TRM on its own

would typically be deficient in H2 for methanol synthesis, but with the addition of H2

from water electrolysis, this problem can be effectively alleviated. The other main

advantage is that O2 from water electrolysis can be fully utilized in TRM. In direct CO2

hydrogenation, O2 from water electrolysis is typically considered a by-product and is

vented to the atmosphere. By using the O2 for partial oxidation reactions in TRM, this

eliminates the need for an air separation unit (ASU), thereby effectively reducing the

capital and operating expenses. With these advantageous, the economic feasibility of this

process has significantly improved in comparison to direct CO2 hydrogenation. Using

59
economic parameters from 2018, this design is capable to achieve a positive NPV of

$11.4 million with a breakeven methanol price of $491/t.

5.2 Recommendations
For the continuation and further expansion of this conceptual design, the author would

like to make the following recommendations as future steps.

5.2.1 Experimental evaluation

The combination of TRM with water electrolysis is only a theoretical concept. Before the

commercialization of this process, it is recommended to perform additional testing

through laboratories and pilot plants. The idea of performing tests is to identify any

potential operating concerns. For instance, if the water electrolysis process is operated

based on solar or wind energy, then the whole process would be subject to a high degree

of fluctuation. It is important to analyze the impact of process fluctuations so that

adequate control measures can be implemented.

5.2.2 Further cost reduction measures

In order for this process to gain further attractions within the methanol industry, it is

highly recommended to look for additional steps to reduce costs. In the process, the main

costs are associated with the water electrolysis process, which accounted for roughly 34%

of CAPEX and 54% of OPEX. With further improvements on water electrolysis energy

efficiency, both the CAPEX and OPEX can be significantly reduced.

60
 References

[1] ―How Methanol is Used | Methanex Corporation.‖ [Online]. Available:

https://www.methanex.com/about-methanol/how-methanol-used. [Accessed: 12-
Mar-2020].
[2] ―OECD iLibrary | World Energy Outlook 2014.‖ [Online]. Available:
https://www.oecd-ilibrary.org/energy/world-energy-outlook-2014_weo-2014-en.
[Accessed: 24-Feb-2020].
[3] G. A. Olah, ―Towards Oil Independence Through Renewable Methanol
Chemistry,‖ pp. 104–107, 2013.
[4] I. ~ Nigo Capell An-P Erez, M. Mediavilla, C. De Castro, O. Carpintero, and L. J.
Miguel, ―Fossil fuel depletion and socio-economic scenarios: An integrated
approach,‖ Energy, pp. 641–666, 2014.
[5] ―Alternative Fuels Data Center - Fuel Properties Comparison.‖ [Online].
Available: https://afdc.energy.gov/fuels/fuel_comparison_chart.pdf. [Accessed:
21-Mar-2020].
[6] PubChem, ―METHANOL | CH3OH,‖ National Center for Biotechnology
Information, 2004. [Online]. Available:
https://pubchem.ncbi.nlm.nih.gov/compound/methanol#section=Top. [Accessed:
04-Mar-2020].
[7] G. A. (George A. Olah, A. Goeppert, and G. K. S. Prakash, Beyond oil and gas :
the methanol economy. Wiley-VCH, 2009.
[8] G. Bozzano and F. Manenti, ―Efficient methanol synthesis : Perspectives ,
technologies and optimization strategies,‖ Prog. Energy Combust. Sci., vol. 56, pp.
71–105, 2016.
[9] J. Matthey, P. O. Box, and B. Avenue, ―Methanol Production – A Technical
History,‖ no. 3, pp. 172–182, 2017.
[10] ―How is Methanol Produced|Methanol Institute.‖ [Online]. Available:
https://www.methanol.org/methanol-production/. [Accessed: 24-Feb-2020].
[11] R. Fukui, C. Greenfield, K. Pogue, and B. van der Zwaan, ―Experience curve for
natural gas production by hydraulic fracturing,‖ Energy Policy, vol. 105, pp. 263–
268, Mar. 2017.
[12] M. Bertau, H. Offermanns, L. Plass, F. Schmidt, and W. Hans Jurgen, Methanol:
The Basic Chemical and Energy Feedstock of the Future. 2014.
[13] X. Xu, Y. Liu, F. Zhang, W. Di, and Y. Zhang, ―Clean coal technologies in China
based on methanol platform,‖ Catal. Today, vol. 298, pp. 61–68, 2017.
[14] ―Projects: Emissions-to-Liquids Technology — CRI - Carbon Recycling

61
 International.‖ [Online]. Available:
https://www.carbonrecycling.is/projects#project-goplant. [Accessed: 26-Feb-
2020].
[15] F. Pontzen, W. Liebner, V. Gronemann, M. Rothaemel, and B. Ahlers, ―CO2-
based methanol and DME - Efficient technologies for industrial scale production,‖
Catal. Today, vol. 171, no. 1, pp. 242–250, 2011.
[16] P. J. A. Tijm, F. J. Waller, and D. M. Brown, ―Methanol technology developments
for the new millennium,‖ Applied Catalysis A: General, vol. 221, no. 1–2. pp.
275–282, 2001.
[17] Kim Aasberg-Petersen, Charlotte Stub Nielsen, Dybkjær, and Jens Perregaard,
―Large Scale Methanol Production from Natural Gas,‖ Haldor Topsoe, pp. 1–14,
2013.
[18] F. Schuth and J. Weitkamp, Handbook of Heterogeneous Catalysis, vol. 5.
WILEY-VCH, 1999.
[19] S. A. Bhat and J. Sadhukhan, ―Process intensification aspects for steam methane
reforming: An overview,‖ AIChE J., vol. 55, no. 2, pp. 408–422, Feb. 2009.
[20] J. P. Lange, ―Methanol synthesis: A short review of technology improvements,‖
Catal. Today, vol. 64, no. 1–2, pp. 3–8, Jan. 2001.
[21] J. M. Lavoie, ―Review on dry reforming of methane, a potentially more
environmentally-friendly approach to the increasing natural gas exploitation,‖
Front. Chem., vol. 2, no. NOV, pp. 1–17, 2014.
[22] M. K. Nikoo and N. A. S. Amin, ―Thermodynamic analysis of carbon dioxide
reforming of methane in view of solid carbon formation,‖ Fuel Process. Technol.,
2011.
[23] R. Luque and J. G. Speight, Gasification for Synthetic Fuel Production:
Fundamentals, Processes and Applications. Elsevier Ltd, 2014.
[24] J. Oakey, Fuel Flexible Energy Generation: Solid, Liquid and Gaseous Fuels.
Elsevier Inc., 2015.
[25] J. Zhu, D. Zhang, and K. D. King, ―Reforming of CH4 by partial oxidation:
Thermodynamic and kinetic analyses,‖ Fuel, 2001.
[26] A. Goeppert, G. K. S. Prakash, and G. A. Olah, ―Recycling of carbon dioxide to
methanol and derived products &#x2013; closing the loop,‖ vol. 43, no. 23, 2014.
[27] J. G. Speight, Gasification of Unconventional Feedstocks. 2014.
[28] M. H. Halabi, M. H. J. M. de Croon, J. van der Schaaf, P. D. Cobden, and J. C.
Schouten, ―Modeling and analysis of autothermal reforming of methane to
hydrogen in a fixed bed reformer,‖ Chem. Eng. J., vol. 137, no. 3, pp. 568–578,
2008.
[29] P. Dahl, T. Christensen, S. Winter-Madsen, and S. King, ―Proven autothermal
62
 reforming technology for modern large- scale methanol plants,‖ Proven
autothermal reforming Technol. Mod. large-scale methanol plants, pp. 1–12,
2014.
[30] C. Shi, B. Labbaf, E. Mostafavi, and N. Mahinpey, ―Methanol production from
water electrolysis and tri-reforming: Process design and technical-economic
analysis,‖ J. CO2 Util., vol. 38, pp. 241–251, May 2020.
[31] F. Dalena, A. Senatore, A. Marino, A. Gordano, M. Basile, and A. Basile,
―Methanol Production and Applications: An Overview,‖ in Methanol: Science and
Engineering, Elsevier, 2018, pp. 3–28.
[32] K. M. Vanden Bussche and G. F. Froment, ―A Steady-State Kinetic Model for
Methanol Synthesis and the Water Gas Shift Reaction on a Commercial
Cu/ZnO/Al2O3Catalyst,‖ J. Catal., vol. 161, no. 1, pp. 1–10, 1996.
[33] Uniongas, ―Chemical Composition of Natural Gas - Union Gas,‖ 2017. [Online].
Available: https://www.uniongas.com/about-us/about-natural-gas/chemical-
composition-of-natural-gas. [Accessed: 25-Mar-2019].
[34] K. Li, W. Leigh, P. Feron, H. Yu, and M. Tade, ―Systematic study of aqueous
monoethanolamine (MEA)-based CO2 capture process: Techno-economic
assessment of the MEA process and its improvements,‖ Appl. Energy, vol. 165, pp.
648–659, 2016.
[35] Thyssenkrupp, ―Hydrogen from large-scale electrolysis,‖ 2018.
[36] ―World Energy Outlook 2014,‖ 2014.
[37] É. S. Van-Dal and C. Bouallou, ―Design and simulation of a methanol production
plant from CO2hydrogenation,‖ J. Clean. Prod., vol. 57, pp. 38–45, 2013.
[38] D. Bellotti, M. Rivarolo, L. Magistri, and A. F. Massardo, ―Feasibility study of
methanol production plant from hydrogen and captured carbon dioxide,‖ J. CO2
Util., vol. 21, no. July, pp. 132–138, 2017.
[39] M. Pérez-fortes, J. C. Schöneberger, A. Boulamanti, and E. Tzimas, ―Methanol
synthesis using captured CO 2 as raw material : Techno-economic and
environmental assessment,‖ Appl. Energy, vol. 161, pp. 718–732, 2016.
[40] W.-H. Cheng, H. H. Kung, and M. Dekker, Methanol Production and Use. New
York, 1994.
[41] K. C. Shulenberger, A.M., Jonsson, F.R., Ingolfsson, O., Tran, ―Process for
producing liquid fuel from carbon dioxide and water,‖ 2011.
[42] ―MefCO2 (Methanol fuel from CO2) - Synthesis of methanol from captured
carbon dioxide using surplus electricity. | SPIRE.‖ [Online]. Available:
https://www.spire2030.eu/mefco2. [Accessed: 24-Jun-2019].
[43] ―FReSMe (From Residual Steel Gases to Methanol).‖ [Online]. Available:
http://www.fresme.eu/. [Accessed: 24-Jun-2019].

63
[44] T. Haganuma and D. Fujita, ―(12) Patent Application Publication (10) Pub. No.:
US 2013/0237618 A1,‖ vol. 1, no. 19, 2013.
[45] K. Li, J. Liu, X. Li, H. Lian, and X. Zhu, ―Novel power-to-syngas concept for
plasma catalytic reforming coupled with water electrolysis,‖ Chem. Eng. J., vol.
353, no. July, pp. 297–304, 2018.
[46] M. Carmo, D. Fritz, J. Mergel, and D. Stolten, ―A Comprehensive review on PEM
water electrolysis. Int J Hydrogen Energy ;38:4901-34.,‖ vol. 8, no. 1, 2013.
[47] R. L. Leroy, ―I n d u s t r i a l w a t e r electrolysis: present a n d f u t u r e,‖ vol. 8,
no. 6, pp. 401–417, 1983.
[48] N. Guillet and P. Millet, ―4 Alkaline Water Electrolysis,‖ pp. 117–166, 2018.
[49] K. Zeng and D. Zhang, ―Recent progress in alkaline water electrolysis for
hydrogen production and applications,‖ Prog. Energy Combust. Sci., vol. 36, no. 3,
pp. 307–326, 2010.
[50] C. Song and W. Pan, ―Tri-reforming of methane: A novel concept for catalytic
production of industrially useful synthesis gas with desired H2/CO ratios,‖ Catal.
Today, pp. 463–484, 2004.
[51] W. Cho et al., ―Optimal design and operation of a natural gas tri-reforming reactor
for DME synthesis,‖ Catal. Today, 2009.
[52] S. Arora and R. Prasad, ―RSC Advances An overview on dry reforming of
methane : strategies to reduce carbonaceous deactivation of,‖ pp. 108668–108688,
2016.
[53] Aspen Technology Inc., ―Aspen HYSYS Version 10.0,‖ 2017. [Online]. Available:
https://www.aspentech.com. [Accessed: 26-Mar-2019].
[54] J. R. Couper, W. R. Penney, J. R. Fair, and S. M. Walas, Chemical process
equipment selection and design. Gulf Professional Publishing, 2012.
[55] Po-Chuang C., Hsiu-Mei C., Yau-Pin C., Chiou-Shia Y., ―Process simulation study
of coal to methanol based on gasification technology.,‖ World Acad. ofScience,
Eng. Technol., vol. 41, no. 5, pp. 988–996, 2010.
[56] ―IPCC, 2014: Climate Change 2014: Synthesis Report. Contribution of Working
Groups I, II and III to the Fifth Assessment Report of the Intergovernmental Panel
on Climate Change [Core Writing Team, R.K. Pachauri and L.A. Meyer (eds.)].
IPCC, Geneva, Switzer.‖
[57] J. Kim et al., ―Methanol production from CO 2 using solar-thermal energy:
Process development and techno-economic analysis,‖ Energy Environ. Sci., vol. 4,
no. 9, pp. 3122–3132, 2011.
[58] ―Net Generation by Energy Source: Total (All Sectors),‖ U.S. Energy Information
Administration, 2019. [Online]. Available:
https://www.eia.gov/electricity/monthly/epm_table_grapher.php?t=epmt_1_01.

64
 [Accessed: 13-Jun-2019].
[59] U.S. BUREAU OF LABOR STATISTICS, ―United States Core Inflation Rate |
2019 | Data | Chart | Calendar.‖ [Online]. Available:
https://tradingeconomics.com/united-states/core-inflation-rate. [Accessed: 03-Jun-
2019].
[60] M. S. Peters and K. D. Timmerhaus, Plant Design and Economics for Chemical
Engineers. Mcgraw-Hill College Division, 1990.
[61] G. D. Ulrich and P. T. Vasudevan, Chemical Engineering: Process Design and
Economics A Practical Guide, 2nd ed. Durham, NH: Process Publishing, 2004.
[62] K. Pomerleau, ―US Corporate Income Tax Now More Competitive | Tax
Foundation,‖ 2018. [Online]. Available: https://taxfoundation.org/us-corporate-
income-tax-more-competitive/. [Accessed: 04-Jun-2019].
[63] Scott Jenkins, ―Chemical Engineering Plant Cost Index: 2018 Annual Value -
Chemical Engineering | Page 1,‖ 2019. [Online]. Available:
https://www.chemengonline.com/2019-cepci-updates-january-prelim-and-
december-2018-final/. [Accessed: 06-Jun-2019].
[64] ―Technology Handbook - Air Liquide Engineering & Construction,‖ 2018.
[65] Nexant Inc., ―Equipment Design and Cost Estimation for Small Modular Biomass
Systems , Synthesis Gas Cleanup , and Oxygen Separation Equipment,‖ NREL
Rep. SR-510-39945, no. May, pp. 1–117, 2006.
[66] BUREAU OF LABOR STATISTICS, ―Occupational Employment and Wages,
May 2018 51-8091 Chemical Plant and System Operators,‖ 2019. [Online].
Available: https://www.bls.gov/oes/current/oes518091.htm. [Accessed: 07-Jun-
2019].
[67] ―Henry Hub Natural Gas Spot Price (Dollars per Million Btu),‖ 2018. [Online].
Available: https://www.eia.gov/dnav/ng/hist/rngwhhdm.htm. [Accessed: 26-Mar-
2019].
[68] ―Industrial Price Comparison,‖ 2018. [Online]. Available:
https://www.rockymountainpower.net/about/rar/ipc.html. [Accessed: 26-Mar-
2019].
[69] ―Pricing | Methanex Corporation,‖ 2019. [Online]. Available:
https://www.methanex.com/our-business/pricing. [Accessed: 22-Mar-2019].
[70] H. Herzog and K. Smekens, ―IPCC Special Report on Carbon Dioxide Capture and
Storage,‖ 2018.

65
 Appendix A: Re-arrangement of Kinetics Expression for Aspen HYSYS

Original Kinetics:

The governing equations and kinetic rate expressions for methanol synthesis are retrieved
from Vanden Bussche and G.F. Froment:

CO2 hydrogenation: CO2 + 3H2 → CH3OH + H2O, ΔH⁰ = -49 kJ mol-1

WGS: CO + H2O ↔ CO2 + H2, ΔH⁰ = -41 kJ mol-1

WGS:
Methanol Synthesis:

[ ]

( )
( )
( )
( )

T [K]
( ) ( )
P[bar]

( ) ( )

Table A1 Kinetic expressions

66
In order to model this LHHW expression in Aspen HYSYS, the kinetic data must be re-
arranged in the following manner:

Re-arrangements:

Equilibrium Constants (

( ) ( (

67
CO2 hydrogenation:

( )

( )

( )

( )
( )

( ( ) ( ) )

( ) ( )

( ( ) ( ) )

The reaction rate by default from literature is expressed in . In HYSYS, the reaction

rate is commonly expressed in . Therefore further unit conversions are necessary:

( ) ( )

( ( ) ( ) )

( ) ( )

( ( ) ( ) )

68
Water Gas Shift (WGS):

( )

( )

( )

( ) ( )

( )

( ) ( )

( )

( ) ( )

( )

( ) ( )

( )

Lastly, the kinetic parameters in the highlighted equations are used for HYSYS reactor
modeling.

69
 Appendix B: Capital Cost Estimation

Calculation steps:

1. Compile a list of equipment from process simulation

2. Equipment sizing and purchase cost estimation
3. Factor in offsite costs, contingency and working capital
List of equipment:

Water Electrolysis Alkaline Water Electrolysis Plant

Tri-reforming Tri-Reformer
Feed Gas Pre-Heater
Pre-Reformer
Waste Heat Boiler
ATR Effluent Cooler
Pre-heater Air Blower
Compression Syngas Compressor Stage 1
Syngas Compressor Stage 2
Recycled Gas Compressor
Syngas Compressor Stage 1 Turbine
Syngas Compressor Stage 2 Turbine
Recycled Gas Compressor Turbine
Syngas Compressor Inter-stage Cooler
Syngas Compressor Suction Scrubber
Methanol Synthesis Methanol Reactor
Methanol Reactor Feed/Effluent Exchanger
Purification Methanol/Water Distillation Tower
Recycle Gas Flash Drum
Purge Gas Flash Drum
Reactor Effluent/Column feed exchanger
Reactor Effluent Cooler
Methanol/Water Tower Condenser
Methanol/Water Tower Reboiler
Utilities Boiler Feed Water Surge Vessel
BFW Pump
Make-up Water Pump
Cooling Water Circulation Pump
Make-up Water Preheater

70
Equipment Sizing and Cost Estimation:

Water Electrolysis Cost for the water electrolysis system is taken directly from
System: tKUCE:
$375 million ±35%
Alkaline Water Off-site facilities such as water treatment, utilities and gas
Electrolyser compression are assumed to be 30% of the total cost. They are
subtracted from the total cost in order to get an estimate on the
bare module cost.
375 – 0.30*375 = 262
Bare module cost = $262,500,000
Tri-Reforming System: To account for economy of scale, the following formula is used
in the cost estimation of the tri-reforming system:
Tri-reformer New cost = Base cost * (New capacity/Base capacity)^n
Feed Gas Pre-Heater Cost data from Air Liquide are used:
Pre-Reformer 500,000 Nm3/h of syngas (160 mil)
Waste Heat Boiler 1,000,000 Nm3/h of syngas (280 mil)
ATR Effluent Cooler n = 0.637
Pre-heater Air Blower The tri-reforming system in the process has a net syngas
production of 207,000 Nm3/h
Bare module cost = $92,000,000
Syngas Compressor - Purchase price at $5.0 mil for 7936 kW (U&V Figure 5.30)
Stage 1 - cost index for 2018 is 603.1, U&V reference is 400
- Bare module factor for centrifugal carbon steel compressor is
2.5
Bare module cost = $18,843,750
Syngas Compressor - Purchase price at $5.5 mil for 8971kW (extrapolated from
Stage 2 U&V Fig 5.30)
- cost index for 2018 is 603.1, U&V reference is 400
- Bare module factor for centrifugal carbon steel compressor is
2.5
Bare module cost = $20,728,125
Recycled Gas - Purchase price at $1.75 mil for 2363 kW (extrapolated from
Compressor U&V Fig 5.30)
- cost index for 2018 is 603.1, U&V reference is 400
- Bare module factor for centrifugal carbon steel compressor is
2.5
Bare module cost = $6,595,313
Syngas Compressor - Purchase price at $450,000 for 7936 kW (extrapolated from
Stage 1 Turbine U&V Fig 5.20)
- cost index for 2018 is 603.1, U&V reference is 400
- Bare module factor for centrifugal carbon steel compressor
turbine is 1.5
Bare module cost = $1,017,563
Syngas Compressor - Purchase price at $500,000 for 8971 kW (extrapolated from

71
Stage 2 Turbine U&V Fig 5.20)
- cost index for 2018 is 603.1, U&V reference is 400
- Bare module factor for centrifugal carbon steel compressor
turbine is 1.5
Bare module cost = $1,130,625
Recycled Gas - Purchase price at $500,000 for 2363 kW (extrapolated from
Compressor Turbine U&V Fig 5.20)
- cost index for 2018 is 603.1, U&V reference is 400
- Bare module factor for centrifugal carbon steel compressor
turbine is 1.5
Bare module cost = $339,188
Syngas Compressor U = 1206W/m2K (from U&V Table 4-15a)
Inter-stage Cooler Overall UA [kJ/C-h] = 4.811E5 (from HYSYS)
Total heat transfer area = 111 m2
From U&V Figure 5.44:
Take fixed tube sheet HEX at 111 m2 with purchase cost at
$13,000
This process requires 1 HEX
Total purchase cost is $13,000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor = 1.25
Bare Module factor = 3
Bare module cost = $58,793
Syngas Compressor Vessel Size (From HYSYS sizing calc.):
Suction Scrubber L: 8.0m x D: 2.3m V: 33m^3
From U&V Figure 5.44:
Equipment purchase cost = $13,000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor = 2.5
Material factor (Stainless Steel) = 4.0
FBM = 20
Bare module cost = $1,206,000
Methanol Reactor Assume the reactor internal design is similar to a shell and tube
heat exchanger
# of tubes = 2700
Tube length = 7 m
Tube diameter = 0.035 m
Total estimated area is 2078 m2
extrapolate graph on U&V Fig 5.36
Purchase cost of equipment is $100,000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor = 1.2
FBM = 3.5
Bare module cost = $527,625
Methanol Reactor U = 1859 W/m2K (from U&V Table 4-15a)
Feed/Effluent Overall UA [kJ/C-h] = 1.03E7 (From HYSYS)

72
Exchanger The total heat transfer area is estimated to be 1541 m2
Referenced from U&V 5.36:
2 fixed tube sheet HEX at 800 m2.
purchase cost at $40000 per HEX
Total purchase cost is $80000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor = 1.15
Bare Module factor = 3.5
Bare module cost = $422,100
Methanol/Water Tower cost = Vessel + trays
Distillation Tower Estimated Height and Diameter (from HYSYS Sizing calc.):
29 m x 5.3 m
From U&V Figure 5.44
Vessel Purchase cost: $250,000
Tray purchase cost: 35 * $1,200
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor = 1.2
Material factor (Stainless Steel) = 4.0
Bare module factor = 11
Bare module cost = $4,842,090
Recycle Gas Flash Vessel Size (From HYSYS sizing calc.):
Drum L: 13.3 m x D: 3.8 m V: 152 m^3
From U&V Figure 5.44:
Equipment purchase cost = $90,000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor (1.02E4 kPa) = 5.5
Material Factor (Stainless Steel) = 4.0
Bare Module factor = 40
Bare module cost = $5,427,000
Purge Gas Flash Drum Vessel Size (From HYSYS sizing calc.):
L: 8.4 m x D: 1.5 m V: 15.3 m^3
From U&V Figure 5.44:
Equipment purchase cost = $25,000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor (250 kPa) = 1.2
Material Factor (Stainless Steel) = 4.0
Bare Module factor = 11
Bare module cost = $414,563
Reactor U = 200 W/m2K (from U&V Table 4-15a)
Effluent/Column feed Overall UA [kJ/C-h] = 3.06E6 (From HYSYS)
exchanger The total heat transfer area is estimated to be 4260 m2
Referenced from U&V Figure 5.36:
Total purchase cost is $250,000 (5 HEX)
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor (1.04E4 kPa) = 1.15
Material factor (Stainless Steel) = 3.00

73
 Bare Module factor = 6.5
Bare module cost = $2,449,688
Reactor Effluent U = 200 W/m2K (from U&V Table 4-15a)
Cooler Overall UA [kJ/C-h] = 6.95E6 (From HYSYS)
Estimated heat transfer area = 8241m2
Referenced from U&V Figure 5.36:
Max area for fixed tube sheet HEX is 900 m2 with purchase
cost at $55000
Total purchase cost is $440,000 (8 HEX)
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor (1.04E4 kPa) = 1.15
Material factor (Stainless Steel) = 3
Bare Module factor = 6
Bare module cost = $3,979,800
Distillation Tower U = 950 W/m2K (from U&V Table 4-15a)
Condenser Assume LMTD = 20
Overall duty [kJ/C-h] = 2.42E8 (From HYSYS)
Estimated heat transfer area is 3538 m2
Referenced from U&V 5.36:
Using graph extrapolation:
purchase cost is at ~$180,000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor = 1.15
Material factor (CS/SS) = 1.7
Bare Module factor = 4.5
Bare module cost = $1,221,075
Distillation Tower U = 1400 W/m2K (from U&V Table 4-15a)
Reboiler Assume LMTD = 110
Overall duty [kJ/C-h] = 2.43E8 (From HYSYS)
Estimated heat transfer area is 438 m2
Referenced from U&V 5.36:
Extrapolate graph with purchase cost at $25,000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor = 1.15
Material factor (SS) = 3
Bare Module factor = 6
Bare module cost = $316,575
Boiler Feed Water Vessel Size (From HYSYS sizing calc.):
Surge Vessel L: 6.5 m x D: 2.5 m V: 32 m^3
From U&V Figure 5.44:
Equipment purchase cost = $33,000
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor (4250 kPa) = 3.5
Material Factor (Stainless Steel) = 4.0
Bare Module factor = 8.5
Bare module cost = $422,854

74
BFW Pump - Purchase price at $12000 for 22 kW (U&V Figure 5.49)
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor (2300 kPa) = 2.5
Material factor (SS) = 1.9
Bare module factor = 9
Bare module cost = $162,810
Make-up Water Pump - Purchase price at $15000 for 28 kW (U&V Figure 5.49)
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor (2300 kPa) = 2.5
Material factor (SS) = 1.9
Bare module factor = 9
Bare module cost = $162,810
Cooling Water - Purchase price at $40000 for 295 kW (U&V Figure 5.49)
Circulation Pump - cost index for 2018 is 603.1, U&V reference is 400
Pressure factor (400 kPa) = 1
Material factor (SS) = 1.9
Bare module factor = 5
Bare module cost = $301,500
Make-up Water U = 1300 W/m2K (from U&V Table 4-15a)
Preheater Assume LMTD = 112C
Overall duty [kJ/C-h] = 1.78E7 (From HYSYS)
Estimated heat transfer area is 34 m2
Referenced from U&V 5.36:
purchase cost is at ~$600
- cost index for 2018 is 603.1, U&V reference is 400
Pressure factor = 1.15
Material factor (SS) = 3.0
Bare Module factor = 6
Bare module cost = $54,270

75
Cost Summary:

Water Electrolysis $262,500,000

Tri-reforming $92,000,000
Syngas Compressor Stage 1 $18,843,750
Syngas Compressor Stage 2 $20,728,125
Recycled Gas Compressor $6,595,313
Syngas Compressor Stage 1 Turbine $1,017,563
Syngas Compressor Stage 2 Turbine $1,130,625
Recycled Gas Compressor Turbine $339,188
Syngas Compressor Inter-stage Cooler $58,793
Syngas Compressor Suction Scrubber $1,206,000
Methanol Reactor $527,625
Methanol Reactor Feed/Effluent Exchanger $422,100
Methanol/Water Distillation Tower $4,842,090
Recycle Gas Flash Drum $5,427,000
Purge Gas Flash Drum $414,563
Reactor Effluent/Column feed exchanger $2,449,688
Reactor Effluent Cooler $3,979,800
Methanol/Water Tower Condenser $1,221,075
Methanol/Water Tower Reboiler $316,575
Boiler Feed Water Surge Vessel $422,854
BFW Pump $162,810
Make-up Water Pump $203,513
Cooling Water Circulation Pump $301,500
Make-up Water Preheater $54,270
Total $420,535,406

76
Other Cost Factors:

 Offsite facilities: 30% of plant bare module. This includes any auxiliary buildings,
product storage tanks, chemical supplies and miscellaneous utilities.
Offsite cost = 0.30 * $420,535,406 = $126,160,622

 Project contingency: 30% of plant bare module. This accounts for unforeseen
expenses, unexpected delays, disruptive weather etc.

Contingency cost = 0.30 * $420,535,406 = $126,160,622

 Fixed capital is the summation of plant bare module, offsite and contingency costs

Fixed capital = $420,535,406 + $126,160,622 + $126,160,622 = $672,856,649

 Working capital: 15% of fixed capital. The fixed capital cost is the summation of
plant bare module, offsite facilities and project contingency.

Working capital = 0.15 * $672,856,649 = $100,928,497

 Total capital cost is the summation of fixed capital and working capital.

CAPEX = $672,856,649 + $100,928,497 = $773,785,147 = $ 774 million

77
 Appendix C: Operating Cost Estimation

Calculation steps:

Operating cost is divided into direct and indirect expenses.

Direct expenses include: Raw materials (natural gas, demineralized water, carbon
dioxide), catalysts (Ni/Al2O3, Cu/ZnO), operating labor, supervision, utilities (Electricity,
steam, cooling water), maintenance and repairs, operating supplies, laboratory charges,
patents and royalties.

Indirect expenses include: Overhead, local taxes, insurance

Base assumptions and method of calculation for each expense item:

Location US Texas
Time 2018
Currency US Dollar
On Stream Factor 0.91
Direct expenses:
Natural gas Annual Consumption (from HYSYS):
3.05E8 kg/year

Natural gas composition is obtained from Union Gas

Price is retrieved from Henry Hub Data 2018

3.17 $/MMBtu (3.00$/GJ)

HYSYS LHV of Natural Gas: 48320 KJ/kg

(0.048320 GJ/kg)

Unit Price: 3*0.048320 = 0.145$/kg

Demineralized water Annual Consumption (from HYSYS):
3.59E5 m3/year

Reference according to U&V Equation 6.1:

Csu = a * CEI + b * Csf
For demineralized water grassroot:
a = 0.007+2.5e-4*q^-0.6
b = 0.004
CEI = 567
Csf = 3.10 $/GJ
q = 45.09 m3/h = 0.013 m3/s
Unit price = Csu = 5.95$/m3
Carbon dioxide Annual Consumption (from HYSYS):
2.36E8 kg/year
78
 $86.40/t - The current price of CO2 capture from a coal combustion
plant using amine absorption technology ( Li et al. 2016)
Ni/Al2O3 Catalyst GHSV = reactant std, volumetric flow/catalyst volume

Pre-reformer Reactor
Assume GHSV = 3000 h-1
std volumetric flow = 77140 m3/h
Catalyst volume = 26m3

TRM reactor
Assume GHSV = 3000 h-1
Std volumetric flow = 200700 m3/h
Catalyst volume = 67m3

total catalyst volume = ~93 m3

Assume catalyst density = 2000 kg/m3
Void fraction = 0.4

Total catalyst loading: 111.6 Mt

Assume 5 year replacement
Annual catalyst assumption: 22.3 Mt/year

Catalyst price taken from NREL (2011): $21.36/kg

2011 CEI = 585.7
2018 CEI = 567
Catalyst price for 2018: $20.6/kg
Cu/ZnO Catalyst Bulk Density: 1140 kg/m3
Total reactor tube side volume: 18.18 m3

Total catalyst loading is 20.7 Mt

Assume catalyst lifetime = 5 yrs
Annual catalyst consumption:4 Mt/year

Catalyst price taken from NREL (2011): $21.36/kg

2011 CEI = 585.7
2018 CEI = 567
Catalyst price for 2018: $20.6/kg
Operating labor Total number of operators per shift:
Water Electrolysis = 4
ATR = 2
Compression = 1
Methanol reactor = 1
Purification = 1
Utilities = 1

79
 Total = 10

Assume 3 shifts per day

According to the US Bureau of Labor Statistics, annual salary per

worker is $62380
Supervision 10% of operating labor
Electricity Annual Consumption (from HYSYS):
2.56E9 kWh/year

Rocky Mountain Power electricity rates of 2018: 5.57 cents/kWh

Steam Annual Consumption (from HYSYS):
0 kg/year

Reference U&V Equation 6.1:

Csu = a * CEI + b * Csf
For Process Steam Grassroot:
a = 2.3 * ms^(-0.9)
b = 0.0034*P^(0.05)
CEI = 567
ms =24.675 kg/s
P = 39.13 bar
Csu = 0.013 $/kg
Cooling water Annual Consumption (from HYSYS):
6.30E7 m3/year

Reference U&V Equation 6.1:

Csu = a * CEI + b * Csf
For cooling water grassroot:
a = 0.00007+2.5e-5*q^-1
b = 0.003
CEI = 567
Csf = 3.10 $/GJ
q = 2556 m3/h + 6488 m3/h = 9044 m3/h = 2.51 m3/s
Csu = 0.054$/m3
Maintenance and repairs 2% of fixed capital
Operating supplies 10% of maintenance
Laboratory charges 10% of operating labor
Patents and royalties 2% of direct expense
Indirect expenses:
Overhead 50% of operating labour supervision and maintenance
Local taxes 2% of fixed capital
Insurance 1% of fixed capital

80
Operating cost summary:

Date 2019-11-28
Job Title Electrolysis + ATR Methanol Facility
Location US/CAN
Currency USD
On Stream Factor 0.91 333 days

Direct Annual Cost ($/yr) Unit Price

1. Raw Materials
Natural Gas $ 44,266,610.13 145.00 $/Mt
Demineralized Water $ 2,139,858.00 5.95 $/m3
Carbon dioxide (CO2) $ 20,399,848.32 86.40 $/Mt
2. Catalysts
Ni/Al2O3 (ATR + pre-
reformer) $ 446,000.00 20000 $/Mt
Cu/ZnO (MeOH Reactor) $ 80,000.00 20000 $/Mt
3. Operating Labor $ 1,871,400.00 62,380.00 $/yr
4. Supervision $ 187,140.00
5. Utilities
Electricity $ 142,341,552.84 0.0557 $/kWh
Steam $ - 0.013 $/kg
Cooling Water $ 3,411,015.75 0.054 $/m3
6. Maintenance and repairs $ 13,457,132.98
7. Operating supplies $ 1,345,713.30
8. Laboratory Charges $ 187,140.00
9. Patents and royalties $ 4,602,668.23
Subtotal $ 234,736,079.55

Indirect Annual Cost ($/yr) Unit Price

1. Overhead $ 7,757,836.49
2. Local Taxes $ 13,457,132.98
3. Insurance $ 6,728,566.49
Subtotal $ 27,943,535.97

Total Operating Cost $ 262,679,615.52

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 Appendix D: Discounted Cash Flow Analysis

Table B1 Assumed parameters for the DCF Analysis

Project Life (years) 20

Inflation 1.9%

Depreciation ($M) 31.0

Income Tax 21%

Annual Sales Revenue ($M/yr) 343.3

Annual Operating Cost ($M/yr) 262.7

Annual Discount Rate 8.0%

Fixed Capital ($M/yr) 672.9

Working Capital ($M/yr) 100.9

Total Investment ($M/yr) 773.8

Construction period (Years) 3

Start-up (C&SU) period (Years) 1

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DCF formulas:

1. Net Income = (Annual Sales Revenue – Operating Cost ) * ( 1 + Inflation) ^(

Year – 1)
(Net income for the initial 3 years is 0 due to constructions. During the start-up
year, net income is halved because it is assumed production will only reach 50%
of its designed capacity)
2. Cash Flow =
Fixed Capital + Working Capital (Year -2: 25%, Year -1: 25%, Year 0: 50%)
Net income (From year 1 to 19)
Net income + Depreciated Value (Year 20)
3. Depreciated Value = Fixed Capital – Depreciation * Year Count
(Depreciation is calculated by assuming straight line depreciation with 20%
salvage value)
4. Taxable Income = Net Income – Depreciation
5. Tax = Income Tax * Taxable Income
6. Cash Flow After Tax = Cash Flow – Tax
7. Discount Factor = (1 + Annual Discount Rate) ^(-Year)
8. Discounted Cash Flow (DCF) = Cash Flow After Tax * Discount Factor
9. Cumulative DCF = Adding DCFs from previous years

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Table B2. Discounted Cash Flow Table

Net Cash Depreciate Taxable Cash Flow Cum.

Tax Disc. DCF
Income Flow d Value Income After Tax
Year DCF
Factor
($M) ($M)
($M) ($M) ($M) ($M) ($M) ($M)

-2 0.0 -193.4 0.0 0.0 0.0 -193.4 N/A -193 -193

-1 0.0 -193.4 0.0 0.0 0.0 -193.4 N/A -193 -387

0 0.0 -386.9 773.8 0.0 0.0 -386.9 0.00 -387 -774

1 40.3 40.3 742.8 9.4 2.0 38.3 0.00 36 -738

2 82.1 82.1 711.9 51.2 10.8 71.4 0.00 61 -677

3 83.7 83.7 680.9 52.8 11.1 72.6 0.00 58 -619

4 85.3 85.3 650.0 54.3 11.4 73.9 0.00 54 -565

5 86.9 86.9 619.0 56.0 11.8 75.2 0.00 51 -514

6 88.6 88.6 588.1 57.6 12.1 76.5 0.00 48 -466

7 90.2 90.2 557.1 59.3 12.5 77.8 0.00 45 -420

8 92.0 92.0 526.2 61.0 12.8 79.2 0.00 43 -378

9 93.7 93.7 495.2 62.8 13.2 80.5 0.00 40 -337

10 95.5 95.5 464.3 64.5 13.6 81.9 0.00 38 -299

11 97.3 97.3 433.3 66.4 13.9 83.4 0.00 36 -264

12 99.2 99.2 402.4 68.2 14.3 84.8 0.00 34 -230

13 101.0 101.0 371.4 70.1 14.7 86.3 0.00 32 -198

14 103.0 103.0 340.5 72.0 15.1 87.8 0.00 30 -168

15 104.9 104.9 309.5 74.0 15.5 89.4 0.00 28 -140

16 106.9 106.9 278.6 76.0 16.0 91.0 0.00 27 -114

17 108.9 108.9 247.6 78.0 16.4 92.6 0.00 25 -89

18 111.0 111.0 216.7 80.1 16.8 94.2 0.00 24 -65

19 113.1 113.1 185.7 82.2 17.3 95.9 0.00 22 -43

20 115.3 115.3 154.8 84.3 17.7 252.3 0.00 54 11

84