Journal of CO Utilization 21 (2017) 5263

Contents lists available at ScienceDirect

Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Novel process technologies for conversion of carbon dioxide from industrial MARK
ue gas streams into methanol

Omar Y. Abdelaziza,b,1, Wafaa M. Hosnyc,1, Mamdouh A. Gadallac, , Fatma H. Ashourb,
Ibrahim A. Ashourd, Christian P. Hulteberga
a
Department of Chemical Engineering, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden
b
Department of Chemical Engineering, Cairo University, Giza 12613, Egypt
c
Department of Chemical Engineering, The British University in Egypt, El-Sherouk City, Cairo 11837, Egypt
d
Environmental Engineering Department, Zewail City of Science and Technology, Giza 12588, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: This research aims to develop ecient process technologies that are capable of converting/utilising CO2 streams
CO2 utilisation into energy-rich liquid products (fuels). This would result in better solutions with near-zero-carbon-emissions
CO2 abatement level. From an energetic and economic point of view, methanol synthesis from CO2 is a competitive alternate to
Synthetic fuel methanol production from biomass. Our work considers the CO2 balance for the technologies proposed, taking
Process design
into account all CO2 ows from/to the environment. Flue gas CO2 streams released from electric power stations,
Process simulation
Pinch analysis
steel industry, petroleum industry, and cement industry are good candidates for the developed technologies.
Three new processes are developed and modelled for converting CO2 streams into liquid methanol. The total cost
of equipment and utility for all process scenarios are evaluated and compared. The energy targets as well as the
CO2 emissions (balance) are determined. Heat integration is performed on the best selected process technology.
The case study employed for the present work is a power station plant burning natural gas for electricity pro-
duction with a capacity of 112 MW, releasing 328 t/h ue gases to the atmosphere, of which CO2 gas accounts
for 14%; hydrogen required for CO2 conversion comes from the chlor-alkali industry. The optimum process
technology reached in this contribution results in methanol production of 0.625 t-per-tonne of CO2 waste gas
supply, leading to an annual production of 222,507 tons methanol with a prot of 56.55 M$/y. Thus, the CO2
release to the environment is cut by about 62%.

1. Introduction
The 20th century can be considered as the century of rapid escala-
tion in energy consumption. The large dependence on fossil fuels and
their presence in limited amounts necessitates nding new alternatives.
Also, the need for protecting the environment from the greenhouse
gases (GHGs) that result from burning the carbon-based fuels urges us
to search for suitable solutions in order to decrease their concentrations
in the atmosphere. As a GHG, carbon dioxide (CO2) accords more than
60% to climatic changes due to its high emissions to the atmosphere,
where in the period between 2004 and 2013 global CO2 emissions have
had continued intense rise of about 2.5% per annum [1].
CO2 is a naturally occurring gas, emitted as a side gaseous product
during burning biomass and fossil fuels, and produced as a side-product
in some industrial processes. Combustion of various types of fuels in
dierent mobile and stationary energy systems results in emission of,
not only pollutants like NOx, SOx, and solid particulates, but also to
GHGs like CO2 and CH4. The natural carbon cycle can recycle 203 Gt of
CO2 each year, whereas the anthropogenic CO2 is emitted at an ap-
proximate rate of 7 Gt every year, representing about 3.4% of the total
CO2 converted in the natural cycle [2]. Although the manmade CO2
represents a small amount, the natural carbon cycle cannot recycle this
excess CO2, so it accumulates in the atmosphere leading to an increase
in the greenhouse eect and hence a strong impact on climate change.
Actually, CO2 is blamed to be the most important factor causing the
greenhouse eect, since it is the main inuential anthropogenic GHG. It
is believed that, the annual increase of the CO2 emissions is 1.2%, and
climate models predict that the CO2 concentration in the atmosphere
will reach about (540970) ppm by 2100 [3]. The increase in the CO2
concentration in the atmosphere has resulted in global warming,
however, the carbon-level increase is not only anthropogenic, but it is
also due to other natural processes such as the changes in the CO2

Corresponding author.
E-mail address: Mamdouh.Gadalla@bue.edu.eg (M.A. Gadalla).
1
Co-rst authorship.

http://dx.doi.org/10.1016/j.jcou.2017.06.018
Received 23 August 2016; Received in revised form 18 June 2017; Accepted 24 June 2017
2212-9820/ 2017 Elsevier Ltd. All rights reserved.
O.Y. Abdelaziz et al.
solubility in the oceans [4].
At present, the atmospheric concentration of CO2 is about to surpass
the 400 ppm mark. So we can say that, the current CO2 concentration is
higher than that of the pre-industrial period (280 ppm) by over than
100 ppm [5]. In order to mitigate the global warming, the Kyoto Pro-
tocol forced the European Union and some other 37 industrial nations
to decrease their emissions on average to a level of 5.2%; this target is
lower than that of year 1990, within 2008 to 2012 time period. In this
framework, the Kyoto targets were peculiarly easy for Europe to
achieve [6]. The Copenhagen Accord seeks in addition to restrict the
global temperature increase to 2 C by the year 2100, above the pre-
industrial level [6]. Moreover and as pointed out by the International
Energy Agency (IEA), in order to successfully accomplish the 2 C
target, carbon capture and storage (CCS) advanced technologies are
needed; in this case the contribution of the total emissions reductions
shall rather be 19% by 2050 [7].
In principle, three well-dened technical options are used to miti-
gate the CO2 emissions; these approaches are basically energy e-
ciency, energy choices, and carbon capture. The captured CO2 can then
be subject to sequestration or utilisation. The former option requires
switching between the dierent energy forms seeking to a less carbon
intensive energy source. The latter option, on the other hand, requires
developing the chemical processes towards increasing the energy e-
ciency by dierent methods like choosing more selective catalyst, se-
lecting a more ecient process, or by performing a suitable energy
integration over the whole process in order to maximise heat recovery
and hence minimise the demand for fuels [8]. Controlling CO2 con-
centration in the atmosphere by the capture technology is costly and
energy intensive option. CO2 utilisation as a feedstock for chemicals
production is an excellent option since it does not only contribute to
attenuate the world climatic changes generated by the increased CO2
emissions, but also presents a great challenge in exploring novel con-
cepts and chances for catalytic, process-wise, and industrial develop-
ment.
During the past years, direct CO2 hydrogenation to methanol
(MeOH) involving process design activities has evidently attracted the
attention [911]. Here, it is worthy to point out the important role of
incorporating rigorous and robust simulation models in the decision
making process regarding such technologies as in the gas processing
industry [1216]. Finding innovative ways of producing MeOH from
these spent sources, subsequently upgrades the economic value of the
o-gases and reduces the specic CO2 emissions of industrial plants
[17]. According to literature studies and as a CO2 reduction measure,
CO2 gas can react with hydrogen (H2) to produce MeOH directly that
could be easily transported and is considered to be a future renewable
energy carrier [18]. In this way, MeOH can be produced at a lower
reaction temperature with higher selectivity.
Methanol (CH3OH) is an industrially important substrate that can be
used to produce several important chemicals, like acetic acid and for-
maldehyde, in addition to being a solvent on its own. This longer-chain
liquid petrochemical is in big demand, due to the ease in its storage and
transportation; it was anticipated for instance that the global methanol
consumption will reach up to 58.6 million metric tons (MMT) by 2012
[19]. According to the Methanol Institute (MI), the demand for MeOH
production is now increasing and expected to boost to well over 100
million tons by 2020, where the current emerging energy applications
only represent about 40% of methanol demand and are responsible for
much of that market growth [20]. As pointed out by Olah in his state-of-
the-art essay on the methanol economy, recycling of CO2 into MeOH
generation can be attributed as a feasible approach to tackle our carbon
conundrum, diminishing the dependence on fossil fuels while at the
same time helping in mitigating the matters associated with excessive
CO2 emissions [21]. The strong demand of MeOH is not only to be used
as a fuel, but also as an alternative starting raw materials for petro-
chemicals production [22].
The combustion of MeOH will result in neither NOx nor SOx to
53
Journal of CO Utilization 21 (2017) 5263
exhaust gases, turning it into a less polluting option in comparison to
conventional fossil fuels [23]. Fossil fuels are burned at higher tem-
peratures than that required for burning MeOH, thus the MeOH com-
bustion unit design is simpler [24]. To eciently replace fossil energy
sources and oil-derived transportation fuels, it is necessary to develop
highly protable and sustainable technologies for producing MeOH and
other alternative synthetic fuels. The utilisation of CO2 in MeOH
synthesis can reduce the intake from natural resources, because the fate
of CO2 from ue gas will eventually be emitted after a while by MeOH
combustion. More specic, the sustainability aspect of CO2 blending/
valorisation in MeOH synthesis emerges from the chaining of the
carbon atom in the MeOH molecule for longer time and also because of
the reduction in the resource intake, i.e. CH4, caused by such blending.
This approach carry a great potential as one of the possible/promising
transition strategies towards the methanol economy concept, mitigating
large amounts of CO2 and reducing the reliance on carbon-based feeds,
like natural gas and coal [25]. Such MeOH will then be a feedstock for
the key products of chemical and petrochemical synthesis and en-
vironmentally clean motor fuels [26].
The present contribution throws the light on the environmental
problems caused by CO2 accumulation in the atmosphere, together with
the energy crisis and the rapid depletion of the fossil fuels. In this paper,
solutions for both the aforementioned problems are introduced by
presenting new approaches for capturing/converting ue gas CO2
streams generated from power stations into liquid fuel methanol. The
introduced concepts seek to reduce both the fossil fuel consumption and
the atmospheric emissions by recycling the secondary CO2 as a carbon
source instead of using natural gas. Three chemical conversion process
technologies are developed for CO2 utilisation in MeOH synthesis and
modelling/simulation tasks are performed, employing the Aspen
HYSYS commercial software platform. Economic and environmental
implications are further assessed for the dierent proposed process
scenarios. Heat integration studies are also conducted for achieving
energy eciency in the process schemes. Results attained in this work
will shed light on the further development of diverse GTL processes.
2. Methods
The conventional way for MeOH production relies on the use of
natural gas as a source for synthesis gas (syngas) production. The rst
step includes desulphurisation of natural gas before introducing it to the
syngas production step to prevent the catalyst poisoning. After its
production, syngas is fed to the reactor at a certain temperature and
pressure. The euent of the reactor consists of MeOH product and
water, in addition to unconverted syngas. The reactor outlet is then
directed to a distillation tower to separate MeOH as a main product,
and recycle the unconverted syngas back to the MeOH convertor.
In this work, methanol is produced via the CO2 hydrogenation
route. The products of CO2 hydrogenation like MeOH and hydrocarbons
are excellent fuels in internal combustion engines, and are easily stored
and transported. Methanol is a raw material which feeds several che-
mical industries, however, a suitable source for H2 production should
be selected in order to support the chemical recycling of CO2 to MeOH
through an economic process. Most researchers suggested H2 genera-
tion either by using signicant sources of remaining fossil fuels, mainly
natural gas, or from splitting water (by electrolysis or other cleavage).
But our research proposes H2 generation through chlor-alkali industry.
The H2, in this context, is available at no cost since it is a by-product
from the chlor-alkali industry of an existing local plant. Thus, this ap-
proach is considered as a by-product valorisation option for an ecient
utilisation of H2 by-product streams of the aforementioned technology.
The H2 gure, which is available at such local industry, is assigned
according to the requirement of our developed processes (typically less
than the available H2 amount generated at the local facility). Also, as
pointed out earlier, most of research eorts preferred to produce MeOH
starting from natural gas, emitting large amounts of CO2 and
O.Y. Abdelaziz et al.
accelerating the consumption of the fossil fuels resources.
Taking into account all of the previous considerations, our new
research proposes a framework for process design, simulation, in-
tegration, and optimisation. This work again adopts the combination of
some technical options to solve the environmental impact of GHG
emissions. This combination involves process development of new
conversion processes, energy integration, waste streams recycle such as
H2 by-products, rigorous modelling/simulation, and parameters opti-
misation. Such combinations denitely bring a range of benets and
thus strengthen the work output. Further, simulation packages with
solid basis of energy integration capabilities are also adopted. All these
aspects from process development to rigorous parameter optimisation
hardly exist in a single research work/output. Innovative processes are
developed/suggested through in order to tackle the aforementioned
problems. According to this approach, natural gas is replaced by CO2
emitted from large scale industrial sources. Three process design
models are suggested, where each model has its own pros and cons that
will be discussed later. The ue gas stream emitted in power plants
burning natural gas is the CO2 source to all three processes. Basically,
the compositions of NOx and SOx gases within the ue gas streams in
comparison with the CO2 content were neglected. This is theoretically
valid especially when power stations/plants adopt techniques to control
the release of these emissions.
In the rst model, ue gas is directly used in the conversion reaction
as raw material for MeOH production. In the second one, water is se-
parated from the ue gases stream before processing. The third model
suggests capturing/separation of CO2 from the ue gases stream before
processing. Unlike the conventional method for MeOH production,
there is no need for the sulphur removal step and syngas production
step as well. Actually, production of MeOH through CO2 hydrogenation
made both natural gas desulphurisation and syngas production steps
dispensable. To add, the ue gas streams obtained from combustion
applications are assumed to have no NOx/SOx gases, providing that the
combustion plants will have control mechanisms for such emissions.
This fundamental assumption will ease the modelling and simulation of
conversion process technologies without the need of desulphurisation.
Fig. 1 presents the block ow diagrams of the three proposed scenarios
for MeOH production from ue gases, illustrating the process concepts
introduced.
The systematic approach applied here suggests passing through the
following steps:
Simulation of each suggested model using Aspen HYSYS software
tool.
Conducting mass and energy balance on each suggested process
scenario.
Performing an economic analysis on each process design scenario.
This step involves sizing and dimensioning of the various process
equipment and units.
Performing an environmental analysis on each process concept.
Comparing the three proposed process technologies from various
aspects.
Selection of the most suitable process from an economic and en-
vironmental point of view, taking into account the production rate
of the target product methanol.
Once the most suitable process is determined, its energy perfor-
mance is analysed and an optimised heat integration network (HEN)
is established, and the energy savings are nally calculated.
2.1. Process description
The input streams to the proposed processes are a ue gas stream
emitted from an existing natural gas red power plant fed at 95.2 C
and 91.3 kPa and a H2 gas stream produced from chlor-alkali industry
as a side-stream fed at 45 C and 1 bar. The data for ue gases and H2
streams are obtained from actual data at real conditions of an existing
54
Journal of CO Utilization 21 (2017) 5263
power station and chlor-alkali industry located in Egypt. The power
station plant produces about 112 MW by burning the corresponding
amount of natural gas as fuel. The ue gas and the H2 streams are
compressed separately to 75 bar in a series of compressors with inter-
mediate cooling. After compression, the two gaseous streams are mixed,
and then the resulting stream is heated to the reaction temperature of
210 C. Now, the resulting gaseous mixture containing both H2 and CO2
is available at 75 bar and 210 C; it is hence ready to be injected into a
xed bed adiabatic reactor. The gases leaving the reactor are rst
cooled by water. Water and methanol are almost completely separated
from the unreacted gases (mainly nitrogen) in a ash drum. The stream
leaving the ash drum, namely crude methanol (mainly composed of
methanol and water) is expanded to 1.2 bar in two throttling valves and
then heated up to 80 C. The hot crude MeOH stream is then sent to a
distillation column. Water comes out at the bottom of the column, while
MeOH is separated out at the top of the column, in a liquid form,
containing traces of water. This described process represents the
scheme proposed as the rst model (base case); see Fig. 1a.
The second model presented in this work, suggests the removal of
water from the ue gases stream before compression (Fig. 1b). This
suggestion has the capacity to decrease the compression ratio and the
temperature load on the compressors. Also, in this way, the size of the
equipment will be smaller relative to the process presented by the rst
model (base case), and hence, a lower capital cost is achieved. The third
process scenario (Fig. 1c) suggests using CO2 in a pure form to be mixed
afterwards with H2. In other words, the third candidate suggested di-
viding the plant into two parts. The rst part is designed to include a
CO2 capture unit, which is used to separate CO2 from the ue gases,
while the second part is designed to involve the CO2 hydrogenation to
liquid methanol. The simulation strategy and results of the three pro-
cesses are presented and discussed in upcoming sections.
2.2. Process simulation
Simulations in steady state are employed largely for the design,
analysis, and optimisation of chemical process industries. These simu-
lations give design and operation data for processes of mass and energy
balances that help in evaluating dierent plant scenarios or further
future studies. Typically, models in steady state modes are opted for at
early phases of design or to perform feasibility activities. Steady state-
based simulation models comprise of unit operations connected by
material and energy streams, and include calculations of physical and
thermodynamic properties of chemical components present in the
processes.
In this study, the models developed for the proposed processes are
applied for the optimisation and evaluation of the performances. This
eort includes a steady state simulation procedure in order to optimise
each process design by reducing capital and equipment costs, while
maximising process production. Three suggested process models are
simulated in order to be evaluated and to select the optimal process
design. The three suggested process alternatives are evaluated,
searching for the most ecient and protable design. The evaluation is
conducted taking into account the environment (CO2 emissions), and
achieving a satisfactory product quality. The next sections summarise
systematically the procedure for realising simulation models for any
given chemical plant. Main tasks to achieve process models are (1)
specify system of units, (2) describe simulation basis of components and
reactions, (3) specify process material and energy streams, (4) set up
process and operation equipment, and (5) simulate a complete process
ow sheet according to the proposed process scheme.
2.2.1. Selecting the unit set and simulation basis
Any process simulation using commercial simulators starts by spe-
cifying a system of units. The default one adopted by Aspen HYSYS is
the SI system of units. Most commercial simulators allow the option to
modify the system of units. In addition to selecting the units system,
O.Y. Abdelaziz et al. Journal of CO Utilization 21 (2017) 5263

Fig. 1. Block ow diagrams of proposed scenarios for methanol production from ue gases (a) base case (b) water removal case (c) CO2 capture case.

setting up the simulation basis is very important; and this implies de- 2.2.2. Dening feed streams and unit operations
ning the chemical components involved in the process and setting the For dening every material stream, temperature, pressure, owrate,
physical/thermodynamic model for properties calculation. The deni- and composition are fundamental properties to be specied. All other
tion of process reactions, types, kinetics data, stoichiometric coe- properties and conditions of the material streams are determined once
cients, etc., is also a signicant task for completing the simulation basis the simulation converges. Table 1 reports the data used for specifying
environment. In this work, PengRobinson-Stryjek-Vera equations of
state (PRSV EOS) is chosen as a uid package [27] due to the following:
Table 1
Data of the ue gas and H2 gas feed streams.
- PRSV EOS are characterised by high accuracy in predicting the
phase behaviour of hydrocarbon systems. Parameter Flue gas H2 gas
- It has the ability to deal with real systems in high accuracy. 5
Flowrate (kg/h) 3.28 10 9.33 103
- It is the correct choice when working at low vapour pressures.
Temperature (C) 95.2 45
- Is the equation of choice upon dealing with aqueous systems con- Pressure (kPa) 91.3 100
taining methanol.
Molar composition (%)
CO2 14.0
After selecting the suitable uid package, a component list is cre- H2O 6.6
ated. This component list contain all components that are involved in N2 75.6
the process; here they include H2, CO2, O2, N2, H2O, CH3OH, MEA, and O2 3.8
H2 100
CO.

55
O.Y. Abdelaziz et al. Journal of CO Utilization 21 (2017) 5263

the ue gas and H2 gas streams. It is evident from the table that the ue Table 2
gas stream does not have SOx and NOx gases. Kinetic model parameters.
In order to build the process ow sheet, all the equipment and the
Parameter A; Ba Value
material streams are specied. For every process unit, it is a must to
dene specic design/operation parameters to full its number of de- k1 A1 1.07
grees of freedom. Every parameter specication represents a single B1 40,000
degree of freedom. This means that an equivalent number of degrees of k2 A2 3453.38
freedom is required as parameters specications in order to fully solve B2
(simulate) a process equipment. In this eort, the installed unit op- k3 A3 0.499
erations are compressors, coolers, heaters, mixers, plug ow reactors, B3 17,197
and ash drums. The detailed modelling procedure of most process k4 A4 6.62 1011
equipment can be found in the simulation guide of Aspen HYSYS [28]. B4 124,119
For simulating the distillation column present in the process schemes, k5 A5 1.22 1010
the number of theoretical plates of 20, reux ratio of 3, column height B5 98,084
of 12.9 m, and column diameter of 3.96 m are set as column speci-
a
cations. B given in J/mol.

2.2.3. Reactor modelling
In the methanol synthesis reactor, generally two exothermic me-
thanol production reactions (Eqs. (1) and (2)) take place and a reverse
water gas shift (RWGS) reaction (Eq. (3)) occurs in parallel.
CO2(g) + 3H2(g) CH3OH(l) + H2O(g) H298K = 49.58 kJ/mol (1)
CO(g) + 2H2(g) CH3OH(l) H298K = 90.77 kJ/mol
CO(g) + H2O(g) CO2(g) + H2(g) H298K = + 41.19 kJ/mol
An adiabatic xed bed reactor, packed with 44,500 kg Cu/ZnO/
Al2O3 commercial catalyst is used for the reactor model. The kinetic
model [29] is employed, as shown by Eqs. (4)(8) below, and it is
considered the most suitable model for the catalyst selected after minor
rearrangement [10].
successive units, e.g. coolers. This implies that when a distillation
column comes rst, it should be simulated or modelled prior to any
equipment that successively depends on the outlet streams of this dis-
tillation unit. Subsequently, the other equipment can easily be simu-
lated.
Since the simulation results are the fundamental drivers for all
process development tasks/activities, models are checked out for ac-
(2) curacy and reliability. The more accurate the simulation results are, the
more reliable the simulation model is for future/further developments.
Therefore, the validation of simulation results is principal for this work.
(3)
Once the model is validated with an acceptable degree of accuracy
(usually less than 10% deviation), the simulation model is reliable for
better understanding the process performance, modifying the process
for better economic and environmental measures, and future develop-
ment.

1 P H2 O PCH3OH 2.3. Cost estimation

k1 PCO2 PH2 1 3 P
K eq1 P H
rCH3OH = 2CO2
mol
3 A complete economic analysis is performed for each suggested
kg cat .s
(1 + k P H2 O
2 P
H2
+ k3 PH0.5
2
+ k 4 PH2O ) (4) MeOH production route. Classical references are used in calculating the
xed cost of equipment and economic evaluation activities [31,32]. The

rRWGS =
(
k5 PCO2 1 K eq2 P
P H2 O PCO
CO2 P H2 ) mol
costs are further corrected with the Chemical Engineering's Plant Cost
Index. Economic evaluations in this study are based on the correlations
kg .s
(1 + k 2 P
P H2 O
H2
+ k3 PH0.5
2
+ k 4 PH2O ) cat
(5)
given by Douglas [31]. It is known that the cost of processing equip-
ment and plants increases with time and thus cost estimation proce-
B dures should take this into account by updating the values obtained
ki = Ai exp i
RT (6) from such correlations. Several methods are available in literature that
can be used for this purpose [31,32]. These methods are all similar in
3066 that they rely on multiplying the base cost from correlations in a certain
log10 K eq1 = 10.592
T (7)
year by the ratio of a cost index for some other year to the cost index for
1 2073 the base year. One of the most commonly used cost indices for cost
log10 = + 2.029
K eq2 T (8) scaling up is published by Marshall and Swift (M & S) and is updated
monthly by Chemical Engineering [31]. The cost correlations below
This model assumes that CO2 is the main source for carbon in the
MeOH synthesis. In addition, Ergun equation which is already built in Table 3
the Aspen HYSYS platform is used in calculating the pressure drop Specications of the reactor and catalyst for methanol synthesis.
across the catalyst bed. Specications of an industrial hydrogen-perm-
selective methanol synthesis reactor are also opted for [30]. Tables 2 Parameter Value Unit

and 3 summarise the parameters of the kinetic model and the char- Reactor tube diameter 5.5 m
acteristics of the reactor/catalyst, respectively, for methanol synthesis Tube inside diameter 21.2 mm
reaction. Tube outside diameter 25.4 mm
Tube length 10 m
Number of tubes 3026
2.2.4. Installing downstream unit operations and model validation Pressure inside the shell 71.2 bar
The sequential modular approach is adopted by most commercial Pressure inside tubes 76.98 bar
simulators, such as Aspen HYSYS or Aspen Plus. In this approach, any Particle diameter 0.00574 m
process plant is simulated (modelled) sequentially unit after unit. This Catalyst specic surface area 625.7 m2/m3
Void fraction of catalyst 0.39
means that upstream process equipment are modelled before moving
Void fraction of catalytic bed 0.39
onward to downstream process units. As an example for the proposed Catalyst density 1775 kgcat/m3cat
schemes, distillation column is to be simulated before modelling all

56
O.Y. Abdelaziz et al. Journal of CO Utilization 21 (2017) 5263

involve the cost upgrading, considering the M & S cost indices for es- $Cs H v
timating the capital costs. To give an instance, in case of calculating the ACof steam= V (8150)

1000lb Hs (18)
cost of the pressure vessels, reactors, and columns ($) involved in each
model, Eq. (9) can be used, while Eq. (10) can be used when calculating Such that Cs is the cost of steam, Hv (Btu/mol) is the latent heat of
the installation cost ($). vapourisation (heat duty), Hs (Btu/mol) is the latent heat of steam,
and V (lb/h) is the mass owrate of the stream to be heated. The cost of
M &S
Purchasedcost= (101.9)D1.066H0.82Fc electricity in $/y is calculated as follows:
280 (9)
1kW
M &S ACof electricity=Ce (Qp) (8150)
Installed cost= (101.9)D1.066H0.82 (2.18 + Fc) 1.341hp (19)
280 (10)
Where, Ce is the cost of one kWh ($/kWh) and Qp is the electric power
Where D is the diameter of the column in ft, H is the column height in ft, consumption (hp).
and Fc is a correction factor and can be obtained as function of vessel The compressor type is determined by knowing its capacity.
pressure and material of construction, as given by Douglas [31]. M & S According to the capacities, all the compressors present in the three
is the Marshall and Swift ination index. models are proposed to be of centrifugal type. Centrifugal pumps are
For distillation columns, the installation cost of trays and tower like giant electric fans and involve only rotary motion. They are
internals ($) are calculated from Eq. (11), where H = tray stack height, cheaper than reciprocating pumps, require less frequent maintenance,
ft (24-in spacing) and correction factors as Eq. (12) below. and do not require lubrication. Their single drawback is that they are
M&S limited to pressures of about 250 bar. The cost of the centrifugal pump
Installedcost= (4.7)D
1.55HF
c ($) is determined using Eq. (20):
280 (11)
M &S
Purchasedcost= (517.5)(bhp)0.82Fc
280 (20)
Fc = Fs + Fr + Fm (12) Where the brake horse power, bhp lies in the range: 30 < bhp <
The correction factors Fs, Fr and Fm are related to tray spacing, tray type 10,000, and the installation cost ($) is calculated using Eq. (21):
and material of construction, respectively, and again can be found in M &S
the book by Douglas. Installedcost= (517.5)(bhp)
0.82 (2.11 + F )
c
After the temperatures of all streams are xed, the cost of these 280 (21)
equipment are calculated with the aid of charts. In case of calculating Fc here is a correction factor based on design and type of pumps, and
the cost of shell & tube heat exchangers, Eqs. (13) and (14) are used to can be found in the book of Douglas.
calculate the purchased cost ($) and the installation cost ($), respec- The cost estimation correlations presented above certainly do not
tively, and then modied to 2015 using the cost indices. account for the time-changes of costs and process as these values vary
M&S with time. The results attained based on the estimations of the above
Purchasedcost= (101.3A0.65Fc) calculations may not be valid for other times. Therefore, a complete
280 (13)
economic analysis should consider uncertainty analysis in order to get
more realistic results. Although the current study does not discuss this
M&S
Installedcost= (101.3A
0.65 (2.29 + F ))
c issue, it is advisable to involve the issue for more robust conclusion and
280 (14) results. Therefore, a complete economic analysis would need an un-
2
Where A is the heat transfer area in ft ; 200 < A < 5000, and the certainty analysis. Despite having said that, the current study is valu-
factor Fc is calculated using tables provided in the aforementioned text able for cost comparison and decision-making practices.
books following Eq. (15). The Fd factor is based on the design type of
the heat exchanger, while Fp is function of the pressure and Fm is de- 2.4. Environmental analysis
pendent on the material of construction.
CO2 is emitted through the process in three dierent ways: un-
Fc = (Fd + Fp) Fm (15) reacted CO2, CO2 emitted due to production of steam necessary for
In order to calculate the cost of cooling water and steam, the supplying the thermal energy, and CO2 emitted due to electricity con-
owrates of cooling water and steam are determined at rst by per- sumption. The rate of CO2 emission is hence determined, and accord-
forming an energy balance, according to Eq. (16). ingly the CO2 emissions due to the electricity consumption are calcu-
lated by knowing the total electricity consumption in the process plant.
Q = w Cp (Tf- Ti) (16) The amount of CO2 emitted (kg/s) as a result of burning a certain
amount of fuel, QFuel (kW), is estimated using the equation below:
Where, w: stream mass owrate, Cp: heat capacity, Tf: nal tem-
perature and Ti: initial temperature. Once the amount of each utility is Q C
(CO2)Emission = Fuel %
determined, the utilities cost are calculated using empirical equations. NHV 100 (22)
For example, if the cooling water costs $Cw/103 gal, the annual cost
Where, is the ratio of the molar masses of CO2 and carbon. Net
(AC) of cooling water in $/y is calculated using the following equation,
heating values (NHV) are assigned as 39,771 kJ/kg and 51,600 kJ/kg,
considering the number of operating hours per year is 8150 as proposed
while%C are set as 86.5 and 75.4 for heavy fuel oil and natural gas,
by Douglas:
respectively [33,34].
$0.01 C w 1 gal Hv Going forward, the credits of carbon resulting from the sale of O2
ACofC w = V (8150) separated in the process to another plant that uses oxygen as a feedstock
1000 gal 8.34 lb T (17)
are estimated. Oxygen is industrially produced via cryogenic air dis-
Where Cw is the cost of cooling water, Hv (Btu/mol) is the latent heat tillation in industrial plants. It is found that O2 production and com-
of vapourisation (heat duty), T is temperature driving force for cooling pression to 35 bar requires about 0.42 kWh electricity per each kg of O2
water and V (lb/h) is the vapour mass owrate. Similarly, the annual produced [35]. Thus, if the electricity necessary for oxygen compres-
cost of steam in $/y is calculated using the following equation: sion are generated from a coal power plant, typically 723 g/kWhel, CO2

57
O.Y. Abdelaziz et al.
would be rather emitted; hence, carbon credits generated are equal to
the savings in CO2 emissions. Carbon credits are calculated using the
following equation:
C credits = 0.42 (WO2) 723 106 (23)
Where, C credits is the carbon credits (t/h) and WO2 is oxygen mass
owrate (kg/h).
After calculating the amount of CO2 rejected by the MeOH process
plant, the carbon credits generated, and CO2 generated due to thermal
energy and electricity, CO2 balance is performed. CO2 balance is in this
context conducted by subtracting the amount of CO2 fed to each plant
from the total amount of CO2 generated from it.
2.5. Process integration
Process integration is a holistic approach that can be applied on
integrated chemical systems in order to boost and reconcile various
process parameters/objectives, such as cost eectiveness/protability,
product enhancement, energy recovery, and pollution prevention [36].
Among dierent process integration methodologies, Pinch Analysis is
certainly the most widely adopted method that was developed in the
late 70s by Linnho and Flower [37]. Comprehensive guides to Pinch
Analysis from the fundamentals to recent advances are provided by
Smith [38] and Kleme [39] in their text books.
Heat integration activities and heat exchanger network (HEN) de-
signs are performed on the selected process scenario based on Pinch
Analysis principles and with the aid of Aspen Energy Analyser soft-
ware. This helped in maximising energy recovery and utilisation via
exchanging the heat between hot and cold streams after determining
the minimum heating and cooling utilities (targets). These targets are
estimated from the minimum temperature approach dierence between
hot and cold streams (Tmin) that is set at 10 C.
3. Results and discussion
The process ow diagrams of the three developed processes are
depicted in Fig. 2. In the rst scheme, base case (Fig. 2a), the ue gases
stream is fed at 95.2 C and 91.3 kPa, while the H2 gas is fed at 45 C
and 1 bar (Table 1).
Both the ue gases stream and the H2 gas stream are compressed
separately to 75 bar in a series of compressors with an intermediate
cooling. After compression, the two gaseous streams are mixed (Mix-
100), and then the resulting stream is heated (E-101) to the reaction
temperature of 210 C. The gaseous stream, containing both H2 and
CO2, is available at 75 bar and 210 C, so it is ready to be fed into the
xed bed reactor. Typical reactor feed data are reported in Table 4.
The reactor outlet stream is cooled to 35 C using water in (E-105).
Methanol and water, which were condensed in the (E-105), are now
ready to be separated from the unreacted gases (mainly N2 gas) in a
ash drum (V-100). The liquid stream out from the ash drum contains
mainly MeOH, H2O, and some dissolved gases. The pressure of this
stream is decreased to 1.2 bar in two throttling valves (VLV-100 and
VLV-101) and then directed to (E-106) in order to be heated up to 80 C.
After heating the crude methanol stream to 80 C, the stream is then
sent to the distillation tower (T-100) in order to separate MeOH from
water. Water leaves at the column bottom, while MeOH comes out as a
liquid at the top with a small amount of water vapour and some un-
reacted gases. Water is separated from MeOH in a multistage purica-
tion system, distillation column. Only small amount of water (0.96 mol
%) will leave with MeOH, and this percent will not aect the MeOH use
as a liquid fuel.
In the second proposed scenario, water removal case (Fig. 2b), the
ue gases stream is fed at same conditions stated (see Table 1). The
pressure of the H2 gas is increased again to 75 bar in a series of com-
pressors with intermediate cooling. But, here, the ue gases are rst
cooled, and then enter a ash drum in order to separate water from the
58
Journal of CO Utilization 21 (2017) 5263
ue gases mixture. After separating water, the pressure of the ue gases
stream is increased to 75 bar. Post compression, the ue gases stream
and the H2 gas stream are mixed (Mix-100); the resulting stream has the
reaction temperature of 210 C. The gaseous stream containing both H2
and CO2 is hence fed to the reactor at the conditions available in
Table 4 for water removal case. Again, the reactor outlet stream is
cooled to 35 C using water in (E-105). Methanol and water, which
were condensed in the (E-105), are now ready to be separated from the
unreacted gases (mainly nitrogen gas) in a ash drum (V-100). After
heating the crude methanol stream to 80 C, the stream is then sent to
the distillation tower (T-100) in order to separate MeOH from water.
Water leaves the column at the bottom, while MeOH leaves the column
at the top as a liquid with a small amounts of water vapour and some
unreacted gases. Water is separated from MeOH in a distillation
column. A small amount of water (0.94 mol%) leaves at the top of the
column with MeOH, oering the highest product purity.
In the third scenario, CO2 capture case (Fig. 2c), the ue gases
stream is once more fed at same conditions stated (Table 1). In another
way, CO2 is separated here from the ue gases stream in a CO2 capture
unit, and then subjected to a compression with intermediate cooling
cycle. The H2 gas stream is compressed separately to 75 bar in a series
of compressors with intermediate cooling. After compression, the CO2
stream and the H2 gas stream are mixed (Mix-100), and then the re-
sulting stream is fed to the reactor at conditions available in Table 4 for
CO2 capture case. The reactor outlet stream is cooled to 35 C using
water in (E-105). Methanol and water, which were condensed in the (E-
105), are now ready to be separated from the unreacted gases (mainly
nitrogen gas) in a ash drum (V-100). The pressure of the liquid stream
leaving the ash drum is decreased to 1.2 bar in (VLV-100 and VLV-
101), then the resulting stream is directed to (E-106) in order to be
heated up to 80 C. After heating the crude methanol stream to 80 C,
the stream is then sent to the distillation tower (T-100) in order to se-
parate MeOH from water. Water leaves the bottom of the column, while
MeOH leaves at the top with a small amounts of water vapour and some
unreacted gases. Only small amount of water (0.99 mol%) leaves the
top of the column with MeOH. It must be noted that the methanol
product purity of the second scenario is higher than the other two
scenarios (0.94 mol% water).
For the carbon capture installation, the ue gases stream is com-
pressed to 1.75 and then introduced to the absorption column at the
bottom, while the 30 wt% MEA solvent is introduced to the column at
the top. The CO2 rich-solvent leaving the absorption tower at the
bottom is rst preheated by the regenerated solvent and then sent to the
regeneration column. The regeneration column reboiler recovers the
heat from low pressure steam in favour of reversing the reaction be-
tween MEA and CO2. The regenerated MEA solvent (lean amine) is
preheated by exchanging heat with the CO2 rich solvent (rich amine),
and then fed back to the absorption tower. The gas stream exiting at the
top of the regeneration tower consists mainly of CO2 and water vapour.
This gaseous stream is fed to a ash drum (V-101) in order to separate
water from CO2. The CO2 gaseous stream is then directed to a com-
pression cycle with intermediate cooling in order to prepare it to the
reaction conditions of 75 bar.
3.1. Comparative analysis
To compare between the three proposed scenarios, the coolers and
heaters details are listed in Table 5 for the developed processes. During
this work, water is generally used as a cooling medium beside re-
frigerant, while steam is used for heating. The overall material balance
is presented in Table 6 for the three proposed process schemes/sce-
narios.
The results show that, the reaction yield is about 60% for the base
case. Considering an operation of 7200 h/y, about 212,950 t of liquid
methanol will be produced annually. After performing an overall en-
ergy balance also for the base case, it was found that, the process
O.Y. Abdelaziz et al. Journal of CO Utilization 21 (2017) 5263

Fig. 2. Process ow diagrams of proposed scenarios for methanol production from ue gases (a) base case (b) water removal case (c) CO2 capture case.

requires a heating duty (Qh) of 1.86 108 kJ/h which is equivalent to In the second model, the water removal case, it was deduced that
6.77 105 t/y steam, a cooling duty (Qc) of 6.49 108 kJ/h which the reaction yields about 0.6256 t of MeOH per each tonne of CO2
can be supplied in the form of 62.48 105 t/y cooling water, and supplied, (62.56%) yield. Taking into account an operation of 7200 h/
8.63 104 kW electricity. y, the plant will the produce 222,507 t of liquid methanol per annum.

59
O.Y. Abdelaziz et al. Journal of CO Utilization 21 (2017) 5263

Table 4 Table 7
The reactor feed data. Comparison between the three proposed process scenarios.

Property Base case Water removal case CO2 capture case Parameter Base case Water removal CO2 capture
case case
Molar owrate (kmol/h) 15.7 103 15 103 6.4 103
Pressure (bar) 75 75 75 Conversion (%) 65.4 67.6 99.74
Temperature (C) 210 210 210 Methanol production (kmol/ 923 964 1260
h)
Molar feed composition (%)
Qh (MW) 51.67 52.5 99.72
CO 0.0 0.0 0.0
Qc (MW) 180.28 151.94 99.44
H2O 4.70 0.51 0.19
N2 53.24 55.56 6.16 Utility consumption
CO2 9.90 10.29 20.95 Electricity (MW) 86.3 72.1 38.7
H2 29.60 30.86 71.91 Cooling water (Mt/y) 248 209 1123
O2 0.0 2.79 0.80 Steam (kt/y) 677 689 32340
Refrigerant (Mt/y) 131.4 492750

Environmental analysis
Table 5 CO2 emissions (t/h) 11.35 11.54 120.6
Heaters and coolers details. C credits 4.07 4.07 0.50
CO2 abatement (t/h) 1.7 8.33 +106.5
Equipment Base case Water removal case CO2 capture case
Economic analysis
Heat Utility Heat Utility Heat Utility Total annualised cost ($M) 80.31 72.23 78.6
duty duty duty Total cost per kg methanol 0.38 0.33 0.27
(MW) (MW) (MW) ($)
Prot ($M) 44.69 56.55 88.36
E-100 6.13 Water 6.13 Water 6.13 Water Payback period (y) 1.39 1.17 1.09
E-101 6.34 Water 53750 Water ROI (%) 71.93 85.41 91.34
E-102 19.36 Water 5.91 Water 0.89 Water
E-103 12.48 Water 13.74 Water 2.37 Water
E-104 13.05 Water 9.87 Water 0.45 Water three process scenarios is however presented in Table 7. The compar-
E-105 65.06 Water 56.26 Water 42.55 Water ison is comprehensive and tackles the utility requirement, process
E-106 4.01 Steam 4.01 Steam 4.62 Steam
performance, economic, and environmental perspectives/evaluations.
E-107 16.62 Refrigerant 2700 Steam
E-108 5.56 Water 5.56 Water 5.56 Water Technically speaking, there are three process alternatives that can
E-109 6.52 Water 6.52 Water 6.52 Water be selected to process the CO2 emitted with ue gases to useful liquid
E-110 62490 Refrigerant methanol fuel. Only the one that oers larger energy savings, lower CO2
E-111 16.27 Water emissions, and satisfactory MeOH production and performance will be
T-100 REB. 47.54 Steam 48.51 Steam 36.27 Steam
T-100 COND. 45.70 Water 47.51 Water 35.07 Water
rather selected. Referring to the results obtained from the economic
T-102 REB. 59750 Water study, environmental study, and energy balance (Table 7), it is obvious
that the third model, CO2 capture case, shows the highest conversion,
MeOH production owrate, prot, and return on investment (ROI).
The overall energy balance over the process shows that the process Albeit, it has the highest capital cost, operating cost, and CO2 emissions.
requires a heating duty (Qh) of 1.89 108 kJ/h which is equivalent to This is due to the presence of the CO2 capture unit in its process ow
6.89 105 t/y steam, a cooling duty (Qc) of 5.47 108 kJ/h which sheet unlike models one and two. Furthermore, the CO2 capture process
can be supplied in the form of 2.09 108 t/y cooling water and is an energy intensive process, so it emits large amounts of CO2 emis-
1.5 107 kg/h refrigerant, and 7.21 104 kW electricity. sions in accordance. So, if we started the process with highly con-
The results for the third scenario, CO2 capture case, reveal that the centrated CO2 stream, or if CO2 can be captured from the ue gases
reaction yield is about 0.82 t methanol per tonne CO2, i.e. 82% yield. stream through a less energy intensive unit, the emissions will be highly
On that account, considering an operation of 7200 h/y, this plant will decreased and the third model will rather be the best. Since decreasing
produce about 291,648 t of liquid methanol annually. The energy bal- the GHG emissions is very important in our case from an environmental
ance results show that the process requires a heating duty (Qh) of concern, this model will thus be rejected.
3.59 108 kJ/h which is equivalent to 32.34 106 t/y steam, a On the other hand, the second model, water removal case, has
cooling duty (Qc) of 3.58 108 kJ/h which can be supplied in the form higher conversion, MeOH production rate, ROI, and prot than the base
of 1.123 109 t/y cooling water and 5.625 1010 kg/h refrigerant, case. Nevertheless, the second scenario is characterised by lower uti-
and 3.87 104 kW electricity. A detailed comparison between the lities consumption, capital cost, operating cost, and MeOH production
cost than the base case. Also, the amounts of CO2 emitted from the rst
Table 6 two process scenarios are nearly the same. Over and above that, the
Overall material balance for the three scenarios (CO2 emissions due to the energy con- energy integration results showed that the second model requires lower
sumption are not included). cooling duty (116 MW) than that required for base case (129 MW). The
Compound Base case Water removal case CO2 capture case
superiority of model number two involving water removal unit over
base case model is due to the installation of a ash drum that separate
Inlet (t/h) Outlet Inlet (t/h) Outlet Inlet (t/h) Outlet water from the ue gases stream initially before entering the methanol
(t/h) (t/h) (t/h) synthesis reactor. Removal of water before further processing resulted
in lower compression ratios and decreased the heating load on the
CO2 67.94 23.51 67.94 22.01 67.94 0.16
CO 0.0 31.30 0.0 0.0 0.0 0.0 compressors, entailing signicant economic savings besides the com-
H2O 13.11 0.0 1.37 20.17 13.11 24.46 petitive environmental performance.
H2 9.33 3.23 9.33 3.02 9.33 1.20
O2 13.41 13.41 13.41 13.41 13.41 1.65
N2 233.51 233.51 233.51 233.51 233.51 11.04
3.2. Heat integration design
MeOH 0.0 32.35 0.0 33.44 0.0 43.11
MEA 0.0 0.0 0.0 0.0 180 180
To this end, the objective is to design an integrated energy network

60
O.Y. Abdelaziz et al. Journal of CO Utilization 21 (2017) 5263

Table 8 data are found to be helpful in determining the energy cost and capital
Stream data of selected process. investment. The extracted data of the selected process are given in
Table 8.
Stream Stream type Supply Target Duty (kW) Cp (kW/C)
temperature temperature Heat integration studies are performed for the process ow diagram
(C) (C) shown priory in Fig. 2b. In the beginning of the analysis, data are ex-
tracted from the steady state process and the grid diagram is con-
1 Hot 284 35 56260 255.92
structed. The process contains nine hot streams and two cold streams. In
2 Hot 214.6 38 6520 36.92
3 Hot 204.3 38 6130 36.86 the current process scheme, four hot streams are segmented to satisfy
4 Hot 188.9 38 5560 36.85 the condition of phase change followed by large temperature change in
5 Hot 188.4 38 13740 91.37 a single phase. Results are explained with Composite Curves (Fig. 3a)
6 Hot 178.7 73 9872 93.40 and Grand Composite Curves (Fig. 3b), analysing current process en-
7 Hot 104 38 5909 89.52
ergetic performance and potentials of improvement and further savings.
8 Hot 95.2 5 16620 184.22
9 Hot 72 60.1 47970 4041.47 Composite Curves represent the heating and cooling demand of the
10 Cold 100.6 106.8 48510 7822.58 process corresponding to the temperature range. Such curves set the
11 Cold 36.5 80 4008 92.23 energy targets prior to design and quantity of maximum energy re-
covery can be thereby calculated. The close gap in the diagram shows
the Tmin, the minimum driving force for heat exchange, where the
for the selected model for methanol production (water removal case),
Pinch point is the point where the two curves approach closest and the
applying the established Pinch Analysis principles in designing an al-
temperature dierence between two composite curves is Tmin.
ternative energy-ecient HEN by using Aspen Energy Analyser com-
Economic eciency is decided by Tmin and it aects heat exchange
mercial software. Energy streams data are extracted from the developed
area. For the present case, the Tmin is identied as 10 C.
process design. The extracted data consist of temperature, heat duty,
At this stage, an alternative design for the existing one is developed
and heat capacity of each process stream. The utility data and the cost
and it is introduced as Fig. 4. Hot streams are represented by red colour

Fig. 3. Energy performance for water removal case (a)

Composite Curves (b) Grand Composite Curves.

61
O.Y. Abdelaziz et al.
Fig. 4. The HEN alternative design for water removal case.
lines in the upper portion of the grid diagram and the cold streams are
represented by blue lines in the lower portion.
Before energy integration, the total cooling and heating require-
ments are found to be 168.57 MW and 52.5 MW, respectively. Aside
from that, the process consumes about 209 Mt/y cooling water,
131.4 Mt/y refrigerant, and 689 kt/y steam. Energy targets identied
from the Composite Curves are estimated as heating load of zero MW
and cooling load of 116 MW. After performing heat integration tasks,
the current process requires zero heating utilities and two cooling uti-
lities (cooling water and refrigerant). Now, the integrated process
consumes 146.47 Mt/y of cooling water (43% reduction), 36.3 Mt/y of
refrigerant (72.4% reduction), and no steam is required (100% reduc-
tion). In addition, the process can generate about 138 kt/y of medium
pressure steam and 104.6 kt/y of high pressure steam, attaining more
economic benets.
4. Conclusions and outlook
The mitigation of GHG emissions, particularly CO2, and their e-
cient utilisation represent to the globe both a serious challenge and a
great opportunity for continual blooming concerning energy and en-
vironment matters. In the light of sustainable development, CO2 va-
lorisation and utilisation research is critical and should thus be an in-
tegral part of R & D activity for eective carbon and energy
management. When applicable, exploiting CO2 in concentrated sources
without its separation is primarily favoured. Meanwhile, and for ap-
plications where pure CO2 is required, more ecient gas separation
techniques are thus desired.
In this contribution, three process technologies have been devel-
oped for CO2 conversion into MeOH and evaluated from an energetic,
economic, and environmental perspective. Process design/simulation,
heat integration, and methods of economics and environmental per-
formance analysis have been evaluated. Results have shown that among
the three process technologies proposed, the water removal process
turned to be optimum. Methanol liquid fuel has been produced at the
rate 0.625 t per each tonne of CO2 in the ue gas released to the at-
mosphere. Process prot has been estimated at 56.55 M$/y for a pay-
back time of 1.17 year. Considerably, CO2 emissions have been cut by
more than 60% in overall. Since our process schemes appeared to
produce a considerable amount of N2, therefore this nitrogen can be
further puried in order to be used for ammonia synthesis and hence
urea production. In this context, urea production process can be con-
sidered as a sink for CO2. Expanding applications of urea based poly-
mers can create more demand on CO2 and NH3 for urea synthesis. Gas-
to-methanol technologies can oer the potential to diversify the energy
62
Journal of CO Utilization 21 (2017) 5263
markets and minimise global rely on crude oil-derived transportation
fuels.
Acknowledgments
O.Y. Abdelaziz acknowledges the Swedish Foundation for Strategic
Research (RBP14-0052) and Cairo University for nance and support.
W.M. Hosny also thanks the British University in Egypt for the nancial
support.
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