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Assessment by Simulation of Some Techniques for

Sustainable Carbon Dioxide Sequestration


Joo Tiago Costa Jacinto
joao.jacinto@tecnico.ulisboa.pt

Instituto Superior Tcnico, Lisbon, Portugal


December 2014

Abstract
Nowadays, global warming and carbon dioxide emissions are a worldwide concern. Since the cement
industry is one of the largest carbon dioxide producers and emitters, this subject is a special concern to
Cimpor.
Currently, the Carbon Capture and Storage technologies being developed, while useful to help
solving some emission problems, only represent a small fraction of the available options to sustainably
store carbon dioxide. Many entities are studying different technologies in order to use carbon dioxide to
generate added value, through its conversion to other chemicals or using its supercritical properties in
power generation.
Among the technologies available there are methanol and methane production. In the scope of this
work, a tool using Aspen to simulate these processes was developed. These processes were
implemented and using SustainPros functionalities were sustainably enhanced to assess if they
represent economically viable options as carbon dioxide emission reduction technologies. The
processes were submitted to the economic analysis functionalities of Aspen in order to verify their
applicability.
These two reactive pathways use hydrogen as a reactant and its cost proved to be the deciding
factor in this processes viability. Hydrogen consumption represents up to 97% of the operating costs. It
should be noted that the hydrogen is produced via the only carbon neutral available technology, water
electrolysis. This technology is still relatively inefficient and must be further developed to be more
competitive, thus reducing the hydrogen costs significantly, before these reuse technologies start to be
economically appealing.

Keywords: Carbon dioxide, Reuse, Methanol, Methane, Sustainability, Simulation, Aspen, SustainPro.

1. Introduction
The Global Warming has been a recurrent thematic in todays news. Ever since the Kyotos Protocol
signing (1997) the carbon dioxides emissions suffer from constant regulation and monitorization in order
to limit the Global Warming effect caused by this and other greenhouse gases.
In 2005 it was launched the European Union Emission Trading Scheme whose purpose is to set a
cap on the amount of greenhouse gases that can be emitted by the participating installations. There are
also some emission allowances that can be traded. Every installation that is a part of this system must
monitor their CO2 and report their emissions to the authorities to ensure that they respect their
allowances [1].
1

Although many measures are implemented in different regions of the world to decrease the GHG
emissions the emissions are still increasing since 1850. The main source of carbon dioxide emissions
are the combustion of fuels, both liquid and solid. Despite not being the main source of emissions, the
cement industry represents 5% of the 9000 million tonnes of carbon dioxide emitted per year [2].
In the cement production clinker, the main component of cement, produces 800 kg of CO 2 for each
tonne produced, being 35% of these generated from the use fuel and the remaining from the calcination
process [3]
The cement industries are trying to capture and store carbon dioxide to prevent emissions using two
main carbon capture and storage (CCS) technologies, the post combustion and the oxyfuel
technologies [4]. These technologies wont be commercially available until 2020, meaning that other
solutions might be tested in the meantime.
Cimpor is one of the largest producers of CO 2 in Portugal, producing about 2.4 million tonnes per
year of clinker which corresponds to 1.9 million tonnes of CO 2 per year, on their plant at Alhandra,
Lisbon, alone. As a member of the European Cement Research Association, Cimpor is especially
conscious of this subject and wants to study the different possibilities towards a more sustainable
capture of CO2, whether to produce another chemical or to apply it towards a different end [3].

2. State of Art
Carbon dioxide is a very special compound with a good set of unique properties that makes it suitable
to be applied in different types of processes whether they involve chemical reactions or not. However
only a few have the potential to demand large quantities of CO 2 and thus help accelerate the reduction
of emissions.
Of all the techniques available to reuse carbon dioxide only a few have the potential for being used
effectively, given that the technology to make these processes viable exists. The main ones are the
enhanced oil recovery (EOR) using carbon dioxide, the usage of carbon dioxide as a working fluid in
refrigeration plants, enhanced geothermal systems (EGS) or power generation, chemical production of
fuels such as methanol, dimethyl ether and methane, or in bioengineering processes like algal biofixation or microbial fuel production.

Figure 1 - Technologic Roadmap containing some carbon dioxide reuse applications.

3. Tools
To develop this work two main software were used. The Aspen Plus was used to simulate and model
the methanol and methane processes, as well as to economically evaluate the processes at hand, using
the Aspen Economic Analysis tool. This tool makes a rough estimative of the process costs, including
capital costs, operating costs and the revenue due to product sales, producing a financial balance of the
process.
The second software used was SustainPro. This tool was developed by Carvalho A. [5] and its
objective is to analyse a process and calculate, using some indicators, its most critical points where
energy and mass are being wasted, in order to improve the plants sustainability.

4. Modelling
The feed flue gas stream composition and flow rate are based on the Reference Document on Best
Available Techniques in the Cement, Lime and Magnesium Oxide Manufacturing Industries, adapted to
a production of 2.8 Mtpa [6].
Table 1 - General compostion of a cement plant flue gas.

Components mass per kg of cement produced


CO2

672 g

O2

389 g

N2

1975 g

H2O

132 g

TOTAL

3168 g

To evaluate the processes five Key Performance Indicators (KPI) were used.
Table 2 - KPI used description.

Indicator

Description

Hydrogen
Consumption

Indicates the amount of hydrogen spent per kilogram of


methanol/methane produced, expressed in kg H2/kg CH3OH
or CH4.

Hydrogen Efficiency

Quantifies how much hydrogen is being wasted in the


process, and is expressed in %.

Productivity

Expresses how much methanol or methane is produced per


kilogram of carbon dioxide consumed, measured in kg
CH3OH or CH4/kg CO2.

Electric Power
Consumption

Amounts the electric power consumed in MW per kilogram


of methanol/ methane produced.

Thermal Power
Consumption

States the amount of thermal power is needed in the process


to produce 1 kg of methanol/methane.

4.1 Methanol Production


Methanol is produced from five reactions according to the literature, being the first one the desired
reaction and the secondary occurring naturally inside the reactor [7]
CO2 + 3 H2 CH3 OH + H2 O

[eq. 1]

CO2 + H2 CO + H2 O

[eq. 2]

CO + 2 H2 CH3 OH

[eq. 3]

2 CH3 OH CH3 OCH3 + H2 O

[eq. 4]

CO2 + 4 H2 CH4 + 2 H2 O

[eq. 5]

The reaction occurs at the temperature of 260C, pressure of 330 bar, with a feed mixture of CO2:H2
of 1:10, resulting in a 95.3% conversion and 98.2% selectivity towards methanol [7].
4.1.1 Reactor Studies
In this study three reactor models were selected and reviewed, hereby named RStoic, REqui and
RGibbs. The RStoic is a stoichiometric reactor were the reactions conversions or molar extents are
known and supplied. The REqui, on the other hand, calculates the chemical and thermodynamic
equilibrium of the reactions based on the stoichiometry. Finally, the RGibbs calculates the equilibrium
as well, but based on Gibbs free energy minimization. The results produced by each model were
compared to the literature [7].
It should be noted that the results produced by the RGibbs model are similar to the ones produced
by REqui because the chemical and thermodynamic equilibrium is dislocated towards the methane
production if the conversion of each reaction isnt specified because it is a more stable compound than
methanol.
Table 3 - Side by side comparison of the results produced by the three models, for the methanol process.

Reactor Product
Stream Mass Flow

RStoic

REqui

RGibbs

CO2

10.13

0.000

22.87

O2

124.8

124.8

124.8

N2

633.4

633.4

633.4

H2O

126.7

166.3

15.14

CO

1.824

0.000

0.803

CH3OH

69.97

0.000

31.89

CH4

0.228

58.42

71.61

DME

112.8

77.94

0.000

(t/h)

It is obvious that the catalyst has an insurmountable importance on the dynamics of the reactions
occurring between this compounds. Trying to mimic the results presented in the RStoic or in the literature
[26] would imply the need to implement many restrictions to molar extents or temperature approaches
in the process simulator options in both REqui and RGibbs, to account for the lack of catalyst influence
on the reaction.

After the reactor studies the separation processes were designed in order to purify the methanol
stream, using the results of the RStoic model.

Figure 2 - Methanol production diagram using the RStoic reactor model.

4.2 Methane Production


Methane is a more thermodynamic favourable compound, compared to methanol, which can be
produced from carbon dioxide. Using a specific zinc-zirconium catalyst conversions up to 98% can be
achieved with, practically, 100% methane selectivity, when the reaction occurs at 300C, atmospheric
pressure and a feed mixture ratio of CO2:H2 of 1:10 [8].
CO2 + 4 H2 CH4 + 2 H2 O

[eq. 6]

4.2.1 Reactor Studies


The three models tested for methanol were used once again in the methane production process. The
results produced are present on table 4.
Table 4 - Side by side comparison of the results produced by the three models, for the methanol process.

Reactor Product
Stream Mass Flow

RStoic

REqui

RGibbs

CO2

4.310

0.001

0.001

O2

124.8

124.8

124.8

N2

633.4

633.4

633.4

H2O

215.2

218.8

218.8

CH4

76.99

78.56

78.56

(t/h)

Its clear that the results produced are similar, ignoring a slight conversion reduction on the RStoic
model, that depicts the results from the literature [8]. This indicates that the models describe this
reaction, even without accounting the influence of the catalyst.
After the reactor studies the separation processes were designed in order to purify the methane
stream, using the results of the RStoic model.

Figure 3 - Methane production diagram.

5. Process Sustainability Analysis and Economic Evaluation


In order to produce better results the processes were submitted to a SustainPro analysis. The
SustainPro results allow to make more sustainable choices in the process towards reducing the costs
associated with material and energy waste. The analysis was run two times for each product.
5.1 Methanol Production
On the methanol process, the base case was analysed and the results obtained with SustainPro indicate
that theres too much energy being wasted by heating and cooling the non-reacting hydrogen along the
process separations. This could be corrected by using a smaller excess of hydrogen or by recycling it.
The other result obtained in this analysis is that theres too much energy being effortlessly by heating,
cooling and compressing the water vapour entering the process through the flue gas.
To correct this last result, a dehumidifier was introduced in the flue gas admission to remove the
water vapour, thus theoretically reducing the energy being wasted. This new scenario, scenario 1, was
submitted to another SustainPro analysis to be further enhanced. The results obtained indicate that the
main problems that affect the sustainability of the process are the hydrogen being wasted, that could be
corrected with a recycling unit, and the water produced in the reactor that is wasting energy in
downstreams separation units. A membrane separator was implemented in the process to obtain a pure
hydrogen stream (99%) and complete the recycling of this expensive raw material [9].
The three scenarios KPI were calculated in order to quantify the effects of each of the changes.
Table 5 - KPI for the methanol production process.

Indicator

Baseline

Scenario 1

Scenario 2

Hydrogen Consumption

0.689 kg H2 / kg CH3OH

0.693 kg H2 / kg CH3OH

0.340 kg H2 / kg CH3OH

Hydrogen Efficiency

28.6%

28.5%

58.3%

Productivity

0.659 kg CH3OH / kg CO2

0.657 kg CH3OH / kg CO2

0.656 kg CH3OH / kg CO2

Electric Power
Consumption

28.9 MW / kg CH3OH

27.0 MW / kg CH3OH

27.0 MW / kg CH3OH

Thermal Power
Consumption

33.4 MW / kg CH3OH

31.7 MW / kg CH3OH

31.7 MW / kg CH3OH

The KPI demonstrate that the introduction of the dehumidifier contribute to a lessened consumption
of power. The recycling of hydrogen greatly improves its efficiency and decreases the consumption. To
quantify how much these changes on the KPI account for the Aspen Economic Analysis tool was used.

Table 6 - Economic evaluation of the methanol production scenarios.

Baseline

Scenario 1

Scenario 2

218 M$

178 M$

180 M$

Total Operating Cost

1820 M$/year

1820 M$/year

870 M$/year

Total Raw Materials Cost

1720 M$/year

1720 M$/year

841 M$/year

Total Utilities Cost

-50 M$/year

-47 M$/year

-51 M$/year

440 M$/year

437 M$/year

436 M$/year

-1402 M$/year

-1401 M$/year

-452 M$/year

Total Project Capital Cost

Total Product Sales


Margin

The introduction of a dehumidifier in the methanol process conduces to a small increase in the
margin, this is due to the fact that the main contributor to this processs deficit is the capital being
funnelled into the raw materials purchase. As can be seen when looking towards the changes in the
economic results of the scenario 2 when the hydrogen recycling unit is introduced, the hydrogen is in
fact the deciding and limiting factor in this processs viability.
5.2 Methane Production
On the methane process, a similar procedure was taken. The first SustainPro results indicate that on
the methane production process theres too much methane being wasted, due to inefficient separation
processes implemented. This can be corrected by completely overhauling the process and trying
different approaches to the methane/air separation. The other results are similar to the methanol
process, in the sense that both the hydrogen wasted and the water entering the reactor represent
problems to this processs sustainability.
In the methane case, the corrections implemented were in reverse order. On the first scenario was
introduced the hydrogen recycling unit in order to reduce the material waste. On the second scenario
the pre-feed dehumidifier was introduced, reducing the costs associated with the separation processes,
in theory.
In addition, it was created a scenario were the flue gas from the cement plant was pure in carbon
dioxide, mimicking the theoretically results obtained using the oxyfuel technology.
Table 7 Key Performance Indicators for the methane process.

Indicator

Baseline

Scenario 1

Scenario 2

Pure CO2

Hydrogen
Consumption

1.27 kg H2 / kg CH4

0.727 kg H2 / kg CH4

0.728 kg H2 / kg CH4

1.273kg H2 / kg CH4

Hydrogen
Efficiency

39.5%

69.1%

68.9.1%

39.5%

Productivity

0.357 kg CH4 / kg
CO2

0.357 kg CH4 / kg
CO2

0.357 kg CH4 / kg
CO2

0.357 kg CH4 / kg
CO2

Electric Power
Consumption

12.4 MW / kg CH4

13.3 MW / kg CH4

13.0 MW / kg CH4

0 MW / kg CH4

Thermal Power
Consumption

33.1 MW / kg CH4

35.4 MW / kg CH4

33.7 MW / kg CH4

14.2MW / kg CH4

In the methane process, the recycling of hydrogen (implemented in Scenario 1) contribute to an


increase on power consumption. This is due to the fact that the hydrogen recycled in this process is at
such low temperature (-200C) due to it being separated from methane, a much harder separation than
the methanol/hydrogen one. With this decrease in temperature in the reactors feed theres more power
being consumed in order to maintain the reactions conditions. Despite this fact, the hydrogen
consumption decreases substantially and the efficiency increases.
When comparing the baseline scenario to the pure CO2 its clear that the purity of the flue gas affects
the quality of the separation processes. This supports the notion that the oxyfuel technology, while
expensive, might be a great help to enhance the sustainability of the cement plants carbon dioxide
reuse application possibilities.

The economic evaluation of the methane production yield the following results.
Table 8 - Economic evaluation results of the methane production.

Total Project Capital Cost


Total Operating Cost

Baseline

Scenario 1

Scenario 2

Pure CO2

172 M$

191.2 M$

335 M$

4.91 M$

2030 M$/year

1284 M$/year

1400 M$/year

1856 M$/year

Total Raw Materials Cost

1720 M$/year

982 M$/year

982 M$/year

1717 M$/year

Total Utilities Cost

158 M$/year

203 M$/year

310 M$/year

0.04 M$/year

122 M$/year

121 M$/year

280 M$/year

129 M$/year

-1924 M$/year

-1182 M$/year

-1154 M$/year

-1727 M$/year

Total Product Sales


Margin

Contrary to what happens in the methanol process, these changes dont improve this processes
viability greatly. When considering the changes occurring from the baseline to the first scenario, the
introduction of the hydrogen recycling produces the biggest improvements. Although theres a reduction
in the raw materials cost, the utilities cost increases due to the aforementioned fact. Since the
hydrogens price is so influent, this increase in the utilities cost is negligible to the fact that the hydrogen
efficiency improved.
In the second scenario, the introduction of a dehumidifier in the flue gas accounts for an increase in
the operating costs due to the fact that in this process the reactor is the equipment that heats the reactive
mixture, meaning that it must be larger to allow the thermal fluid to maintain the reactors conditions.
This doesnt occur in the methanol production because the reactive mixture is being conditioned before
entering the reactor.
In addition, the water removed in the process makes the separation processes more efficient
resulting in better product sales. These factors balance out and the margin increases slightly, making a
less effective change to increase the processs sustainability.
The Pure CO2 clear shows that what was concluded when the KPI were compared. The utilities cost
is reduced greatly. When combined with a proper hydrogen recycling unit, certainly the margin will
increase drastically.
6. Results Discussion and Conclusions
The results of the second scenario for each process were compared to the literature, where a similar
study was done [10].
Table 9 - Comparison of the results of this work with the literature, for the methanol process [10].

Daily Financial Balance

Scenario 2

ECRA results

Costs

0.78 k$/tpd

0.83 k$/tpd

Income

0.39 k$/tpd

0.41 k$/tpd

Balance

-0.39 k$/tpd

- 0.42 k$/tpd

Its clear that the balance is negative in either case. In relative values, the income in the second
scenario represents 50% of the costs associated with the methanol production. For the ECRA results,
the income is 49% of the costs, meaning that the results obtained through this work and ECRA are
roughly the same.
Table 10 - Comparison of the results produced in this work with the literature, for the methane production [10].

Daily Financial Balance

Scenario 2

ECRA results

Costs

3.3 k$/tpd

2.18 k$/tpd

Income

0.49 k$/tpd

0.60 k$/tpd

Balance

-2.8 k$/tpd

- 1.6 k$/tpd

In the second scenario, generated using SustainPro, the income represents 15% of the costs, a
considerable decrease when compared to the methanol production. The ECRA results are less alarming
but still a huge decrease when methanol production is considered. The ECRA report shows that the
income represents 28% of the costs. This works results are clearly inferior, both in the excessive unitary
costs and the revenue generated by the product. This bears a 75% decrease in the financial balance.
The reasons behind this difference might be associated with the separation processes implemented. In
this works case, these separations are very power demanding and inefficient, increasing the costs
greatly while reducing the income considerably.
Creating a hypothetic scenario, assuming that the cost reduction, in percentage, that occurs with the
introduction of a recycling unit in the Pure CO 2 process is the same as the one happening when
considering the baseline and the first scenario, yields the following results.
Table 11 - Comparison of the Pure CO2 scenario with the literature [10].

Pure CO2 with recycling

ECRA results

Costs

1.92 k$/tpd

2.18 k$/tpd

Income

0.22 k$/tpd

0.60 k$/tpd

Balance

-1.7 k$/tpd

- 1.6 k$/tpd

Daily Financial Balance

Without verifying the consequences of the introduction of the recycling in the income, only
considering the raw material cost reduction, the results become similar to the ones on the literature,
specially the financial balance.
In 2014, the average price for 1 tonne of CO2 emitted was 8.3 $/t [11]. Since hydrogens price is the
major factor when considering the viability of the reuse applications, a graph to calculate the price at
which the cement plant should start to produce methanol instead of paying the emission allowances
was made.
40

CO2 Emission
Cost

30

Economic
Balance

10
1

0.98

0.96

0.94

0.92

0.9

0
0.88
-10

M$/year

20

-20
-30

Hydrogen Price in $/t

-40

Figure 4 - Influence of the hydrogen price on the Economic Balance of the methanol production process.

This chart shows how the hydrogen price affects the profitability of the methanol process. At the price
of 0.963 $/t it becomes more cost-effective to produce methanol instead of emitting carbon dioxide to
the atmosphere. At the price of 0.925 /t, it becomes profitable to produce methanol.
This is good news for the methanol production technology. This indicates that if the electrolysis
technology develops sufficiently to become more efficient or the energy cost to produce hydrogen
decrease enough, the methanol production might be a more sustainable, profitable and clean way to
handle the carbon dioxide emissions.
The methane process is more dependent on other operating costs, making it so that even if the
hydrogen was free the process would still not be profitable. In order to make this process more effective,
there would have to exist a major overhaul in the separations involved so that the fixed costs would
lower and make it a more appealing choice.

6.1 Conclusions
From the reuse technology options evaluated its clear that the methanol production is a more
sustainable option, being able to generate revenue if the hydrogen production price is low enough (at
0.925 /t). On the other hand, the methane production is a more expensive process, due to the increased
hydrogen consumption and an inefficient separation design.
Although the final results produced are unable to generate revenue, it is clear that the SustainPro is
a great tool to enhance a chemical process. The improvements generated with only two iterations of
each process are great.
The final note is that with the current carbon dioxide emission allowance prices, at 8.3 /t, its
pointless to try to chemically convert carbon dioxide to methanol or methane, from an economic point
of view. If the global awareness increases and the importance of diminishing the emissions of carbon
dioxide increases then there will be a point in time where the carbon dioxide reuse technologies will
become far more appealing and desirable.
6.2 Future Work
Its clear that theres no economic incentives to reuse carbon dioxide in order to produce either methanol
or methane. Although theres work to be done in order to improve this tool and achieve a less unattractive
scenario. The plants modelled in this work werent energetically integrated, meaning that the utilities
cost or revenue can be improved.
Also, the separation processes can be chosen in a fashion that would greatly reduce the operating
costs and utility consumption. For example, a membrane separation, while less effective than a
cryogenic distillation, used in the methane process, is less energy demanding. This fact might make it a
better solution in an economic standpoint.
Procedural choices aside, its clear that the future of the worlds cement production originated carbon
dioxide relies on the Oxyfuel process development, having a huge effect in simplifying the reuse
technologies and making them more attractive.
The last and more important detail is the hydrogen production technologies. The carbon neutral ways
to produce hydrogen are very expensive and inefficient to be commercially viable. Theres research and
development to be made in this field for the cement industry to consider reducing their carbon dioxide
emissions by sustainably reusing this gas.
7. References
[1] Wagner, M.: Firms, the Framework Convention on Climate Change & the EU Emissions Trading
System. Corporate Energy Management Strategies to Address Climate Change and GHG Emissions in
the European Union., CSM, 2004.
[2] How much carbon dioxide is produced per kilowatt-hour when generating electricity with fossil
fuels?, 2014, http://www.eia.gov, last accessed in: April 2014.
[3] Data supplied by Cimpor.
[4] Cement Technology Roadmap 2009. Carbon emissions reductions up to 2050., IEA, 2009
[5] Carvalho, A. Design of Sustainable Chemical Processes: Systematic Retrofit Analysis Generation
and Evaluation of Alternatives., IST, 2009
[6] European Commission, Reference Document on Best Available Techniques in Cement, Lime and
Magnesium Oxide Manufacturing Industries, 2010.
[7] Bansode, A., Urakawa, A., Towards Full One-pass Conversion of Carbon Dioxide to Methanol and
Methanol-derived Products., Institute of Chemical Research of California, 2013.
[8] Yamasaki, M. et al, CO2 methanation catalysts prepared from amorphous Ni-Zr-Sm and Ni-Z-misch
metal alloy precursors., Tohoku University, 1999.
[9] Hy9, H2 purifiers, http://www.hy9.com/purifier-technology, last accessed in: September 2014.
[10] Corcoran, R.: ECRA Project Report about CO2 reuse from cement production/ MeOH and
Methane Synthesis., ECRA, 2013.
[11] Energy Exchange Group, https://www.eex.com/en/market-data/emission-allowances/spotmarket/european-emission-allowances#!/2014/12/05, last accessed in: December 2014.
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