CARBON DIOXIDE CAPTURE AND CONVERSION

MANPREET KAUR
B.E.MBA 4TH YEAR
ROLL NO. – CM15218
 INTRODUCTION
Rapid economic growth has contributed to today's ever increasing demand for
energy. An obvious consequence of this is an increase in the use of fossil fuels,
particularly conventional fossil fuels. However the abundant use of fossil fuels
has become a cause of concern due to their adverse effects on the environment
particularly related to the emission of CO2 a major anthropogenic greenhouse
gas(GHG).Carbon dioxide capture and storage (CCS) is considered a crucial
strategy for meeting CO2 emission reduction targets. The selection of specific
CO2 capture technology heavily depends on the type of CO2 generating plant
and fuel used.
CO2 capture technologies
• Post combustion : This process removes CO2 from the flue gas after combustion
has taken place. Post combustion technologies are the preferred. However the
major challenge for the post combustion CO@ capture is its large parasitic load.
Since the CO2 level in the combustion flue gas is normally quite low(i.e. 7-14%
for coal fired and as low as 4% for gas fired).
• Pre combustion : In this process the fuel is pretreated before combustion. For
coal, the pretreatment involve a gasification process conducted in a gasifier
under low oxygen level forming a syngas which consists mainly of CO and H2
and is mainly free from other pollutant gases. The syngas will undergo water gas
shift reaction with steam forming more H2 while the CO gas will be converted to
CO2.
CO2 capture technologies

• Oxyfuel combustion : In oxyfuel combustion, oxygen instead of air is

used for combustion .This reduces the amount of nitrogen present in
the exhaust gas that affects the subsequent separation process. With
the use of pure oxygen for the combustion the major composition of
the flue gases is co2,water,particulates and SO2.particulates and SO2
can be removed by conventional electrostatic precipitator and flue gas
desulphurization methods respectively. The remaining gases contain
high concentrations of CO2 (80-98 % depending on fuel used).this
process is technically feasible but consumes large amounts of oxygen
coming from an energy intensive air separation unit.
CO2 CAPTURE TECHNOLOGIES (D.Y.C Leung et al./Renewable and
sustainable energy reviews 39 (2014) 426-443)
Advantages and disadvantages of the different co2 capture
technologies
CAPTURE PROCESS APPLICATION AREA ADVANTAGES DISADVANTAGES
POST COMBUSTION COAL FIRED AND GAS FIRED TECHNOLOGY MORE MATURE
PLANTS THAN OTHER ALTERNATIVES;CAM
EASILY RETROFIT INTO EXISTING
PLANTS
PRE COMBUSTION COAL GASIFICATION PLANTS HIGH CO2 CONCENTRATION
ENHANCE SORPTION
EFFICIENCY;FULLY DEVELOPED
TECHNOLOGY
OXYFUEL COMBUSTION COAL FIRED AND GAS FIRED VERY HIH CO2 CONCENTRATION
PLANTS THAT NHANCES ABSORPTION
EFFICIENCY;MATURE AIR
SEPARATION TECHNOLOGIES
AVAILABLE
CHEMICAL LOOPING COAL GASIFICATION PLANTS CO2 IS THEMAIN
COMBUSTION COMBUSTION
PRODUCTWHICH REMAINS
UNMIXED WITH N2 THUS
AVOIDING ENERGY INTENSIVE
AIR SEPARATION
LOW CO2 CONCENTRATION AFFECTS
THE CAPTURE EFFICIENCY
TEMPERATURE ASSOCIATED HEAT
TRANSFER PROBLEM AND EFFICIENCY
DECAY ISSUES ASSOCIATED WITH THE
USE OF HYDROGEN RICH TURBINE
;HIGH CAPITAL AND OPERATING COSS
FOR CURRENT SORPTION SYSTEMS
HIGH EFFIECIENCY DROP AND ENERGY
PENALTY;CRYOGENIC O2 PRODUCTION
IS COSTLY ;CORROSION PROBLEM MAY
ARISE
PROCESS IS STILL UNDER
DEVELOPMENT AND INADEQUATE
LARGE SCALE OPERATION
EXPERIENCE
CO2 SEPARATION TECHNOLOGIES
• ABSORPTION:A liquid sorbent is used to separate the CO2 from the flue gas.
The sorbent can be regenerated through a stripping or regenerative process
by heating and/or depressurization. This process is the most mature method
for CO2 separation [30]. Typical sorbents include monoethanolamine (MEA),
diethanolamine (DEA) and potassium carbonate
• ADSORPTION: In contrast to absorption processes which use a liquid
absorbent, a solid sorbent is used to bind the CO2 on its surfaces. Large
specific surface area, high selectivity and high regeneration ability are the
main criteria for sorbent selection. Typical sorbents include molecular sieves,
activated carbon, zeolites, calcium oxides, hydrotalcites and lithium
zirconate.
CO2 SEPARATION TECHNOLOGIES
• CHEMICAL LOOPING COMBUSTION: A metal oxide is used as an
oxygen carrier instead of using pure oxygen directly for the
combustion as in the case of oxyfuel combustion. During the process
the metal oxide is reduced to metal while the fuel is being oxidized to
CO2 and water. The metal is then oxidized in another stage and
recycled in the process. Water, the process by-product, can be easily
removed by condensation, while pure CO2 can be obtained without
consumption of energy for separation. There are a wide variety of
metal oxides that are of low-cost and suitable for this process
including Fe2O3, NiO, CuO and Mn2O3
CO2 SEPARATION TECHNOLOGIES
• MEMBRANE SEPARATION :Membranes can be used to allow only CO2 to pass
through, while excluding other components of the flue gas. The most
important part of this process is the membrane which is made of a composite
polymer of which a thin selective layer is bonded to a thicker, non-selective
and low-cost layer that provides mechanical support to the membrane.
• HYDRATE BASED SEPARATION: Hydrate-based CO2 separation is a new
technology by which the exhaust gas containing CO2 is exposed to water
under high pressure forming hydrates. The CO2 in the exhaust gas is
selectively engaged in the cages of hydrate and is separated from other gases.
The mechanism is based on the differences of phase equilibrium of CO2 with
other gases, where CO2 can form hydrates easier than other gases such as N2
CO2 SEPARATION TECHNOLOGIES
• CRYOGENIC DISTILLATION : Cryogenic distillation is a gas separation
process using distillation at very low temperature and high pressure,
which is similar to other conventional distillation processes except
that it is used to separate components of gaseous mixture (due to
their different boiling points) instead of liquid. For CO2 separation,
flue gas containing CO2 is cooled to desublimation temperature (−100
to–135 °C) and then solidified CO2 is separated from other light gases
and compressed to a high pressure of 100–200 atmospheric pressure.
The amount of CO2 recovered can reach 90–95% of the flue gas.
CO2 UTILIZATION
• After capture, the high CO2 content stream can be transported for
geological storage, or for CO2 utilization.
• A demonstration plant in Luzhou, China was recently commissioned that
produces ammonia and urea using the CO2 captured (160 t/day) from its
production process
• CO2 can also be used in other areas such as food beverages, refrigerants
and fire extinguishing gases. Current CO2 utilization accounts for only 2%
of emissions, but forecasts predict chemical utilization could mitigate 700
megatons of CO2 per year, far greater than the combined potential of
nuclear, wind and cellulosic biofuel technologies.
CO2 UTILIZATION
• Enhanced oil recovery (EOR) using CO2 from capture processes can
significantly increase CO2 utilization. Other related new sectors include
the use of CO2 as a cushion gas for energy storage .
• CO2 can be utilized through mineralization, a process based on the
accelerated reaction of CO2 with Mg/Ca rich silicate rocks or inorganic
wastes to form stable carbonates which can be used.
• Large scale, economic photocatalytic conversion of CO2 into methane
(CH4) and/or methanol (CH3OH) represents a formidable scientific and
technical challenge . Recent progress in this area has focused mainly on
the development of novel catalysts through advances in nanotechnology
Dual function material for carbon
capture and conversion
Current CCs processes suffer from the fact that CO2 absorption by
corrosive liquids such as monoethanolamine (MEA) as well as
adsorption by solids such as alkaline metal oxides rely on a high
temperature thermal swing for their regeneration. These operations
constitute the large portion of cost of CO2 capture. The use of synthetic
fuels made from co2 as carriers for excess renewable electricity offers a
solution to manage fluctuating output of renewable energy while
mitigating co2 emissions .production of synthetic natural gas is a
promising option which has been demonstrated on an industrial scale
in Audi motor company’s ‘’e-gas’’ facility in Germany.
• Dual function materials offers a unique renewable energy storage
solution by producing SNG directly from industrial flue gas, while
eliminating the energy requirement, corrosion and transportation issues
associated with CCS.
• The dfm contains a sorbent as well as a catalyst component, allowing it
to both capture co2 and convert it to a fuel without an energy intensive
thermal swing process. The dfm process utilizes H2 produced via
electrolysis using renewable electricity(wind,hydro,geothermal,and/or
solar)to make synthetic natural gas via the methanation reaction
• Co2+4H2 CH4 +2H2O
PROCESS DIAGRAM FOR CO2 CAPTURE AND RECYCLE AS
SYNTHETIC NATURAL GAS BACK TO AN INDUSTRIAL FACILITY
( M.S. Duyer et.al/Applied Catalysis B:Environmental 168-
169(2015) 370-376)
MATERIAL SYNTHESIS
• Dual function materials were prepared by incipient wetness
impregnation of either Ru(NO)(NO3)2 on 10 wt.% CaO/γ-Al2O3 or of
Ca(NO3)2 on 10 wt.% Ru/γ-Al2O3. All samples were dried in air at 120
°C for 1 h and calcined in air at 320 °C for 2 h. This pretreatment
ensured the decomposition of Ru(NO)(NO3)2 to Ru. The DFMs
received in-situ pre-reduction in 4% H2/N2 at 320 °C for 2 h at the
beginning of each reactor test to ensure decomposition of Ca(NO3)2
to CaO.
REACTOR TESTING OF VARIOUS DFM COMPOSITIONS
( M.S. Duyer et.al/Applied Catalysis B:Environmental 168-
169(2015) 370-376)
ROW SAMPLE CH4/RU G-MOL CH4/KG DFM

1 γ-Al2O3 0.00 0.00

2 10% Ru/γ-Al2O3 0.10 0.10
3 1% CaO 10% Ru/γ-Al2O3 0.19 0.19
4 5% CaO 10% Ru/γ-Al2O3 0.27 0.27
5 10% CaO 10% Ru/γ-Al2O3 0.31 0.30
6 1.1% Ru 10% CaO/γ-Al2O3 2.46 0.27
7 2% Ru, 10% CaO/γ-Al2O3 1.79 0.35
8 5% Ru 10% CaO/γ-Al2O3 1.01 0.50
9 6.8% Ru,10% CaO/γ-Al2O3 0.65 0.44
10 10.6% Ru, 10% CaO/γ-Al2O3 0.44 0.46
11 10% Ru/γ-Al2O3 +10% CaO/γ-Al2O3 0.25 0.12
Dual function materials (DFMs) for CO2 capture and conversion couple
the endothermic CO2 desorption step of a traditional adsorbent with
the exothermic hydrogenation of CO2 over a catalyst in a unique way; a
single reactor operating at an isothermal temperature (320 °C) and
pressure (1 atm) can capture CO2 from flue gas, and release it as
methane upon exposure to renewable hydrogen. This combined CO2
capture and utilization eliminates the energy intensive CO2 desorption
step associated with conventional CO2 capture systems as well as
avoiding the problem of transporting concentrated CO2 to another site
for storage or utilization.
( M.S. Duyer et.al/journal of CO2 utilization 15 (2016) 65-71)
The operation of a Ru CaO/γ-Al2O3 DFM is proposed to
follow the steps outlined in Eqs. (1)–(4) given below.

• Adsorption of CO2 from flue gas onto CaO sites:

• (1)CO2 + CaO/γ-Al2O3 → CO2⋯CaO/γ-Al2O3

• Spillover of CO2 from CaO sites and adsorption on Ru sites:

• (2)CO2⋯CaO/γ-Al2O3 → CO2 + CaO/γ-Al2O3
• (3)CO2 + Ru/γ-Al2O3 → CO2⋯Ru/γ-Al2O3

• Methanation of CO2 on Ru sites upon exposure to hydrogen:

• (4)CO2 + 4 H2 → CH4 + 2 H2O ΔH = −164 kJ/mol
CO2 UTILIZATION WITH A NOVEL
DUAL FUNCTION MATERIAL
• The present work focuses on improving our first generation dual
function material by
• Investigating a series of alternative methanation catalyst to be
compared with (Ru)
• Replacing Cao with new adsorbents to address the challenges of
increasing CO2 capture capacity and enhancing methane production.
Concentratio
n of CH4 in
the product
stream for
various
supported
metal
catalyst
( M.S. Duyer et.al/journal of
CO2 utilization 15 (2016) 65-
71)
 sample G-mol
CH4/Kg dfm
Methanation capacities 5% Ru 10% 0.50
of dfm containg CaO/Al2O3
different adsorbent
components measured 5% Ru 10% 0.91
during hydrogenation
of captured co2 in a K2CO3/Al2O3
microreactor
( M.S. Duyer et.al/journal of 5% Ru 10% 1.05
CO2 utilization 15 (2016) 65-
71)
Na2CO3/Al2O3
CONCLUSIONS
• Novel dual function materials (DFM) have been developed for CO2 capture
and conversion in a single reactor. Dual function materials consist of a
catalyst and adsorbent component, both of which play a critical role in
determining the methanation capacity of the final material.
• In this work, precious and base metals have been screened for their CO2
methanation activity and Rh was identified as a catalyst candidate along with
the preferred Ru, which was the catalyst component of the original DFM.
0.1% Rh 10% CaO/γ-Al2O3 had a methanation capacity of 0.4 g-mol/kg DFM
and was identified as a promising candidate for applications requiring higher
resistance to oxidizing conditions. Ruthenium is still the preferred catalyst
based on price, stability in the aging tests and low temperature performance.
CONCLUSIONS
• Alkali and alkali earth metal oxides supported on γ-Al2O3 were investigated as CO2
adsorbents for improving the performance of DFMs, which originally contained
dispersed CaO (10% CaO/γ-Al2O3) as the CO2 capture component. 10% K2CO3/γ-
Al2O3 and 10% Na2CO3/γ-Al2O3 showed much greater CO2 capture capacities
compared to 10% CaO/γ-Al2O3 (used in initial DFMs) which also corresponded to
enhanced methanation capacities in the new DFMs.
• The optimized materials based on these sorbents outperformed the 5% Ru 10%
CaO/γ-Al2O3 which was the previous highest methanation capacity DFM. 5% Ru 10%
Na2CO3 had the highest methanation capacity and is a promising DFM for future
CO2 capture and direct utilization applications. Overall this work highlights the
importance of both catalyst and CO2 adsorbent development for engineering dual
function material systems that combine CO2 capture and utilization in a single
reactor.
REFERENCES
[1]M.D. Porosoff, B. Yan, J.G. ChenCatalytic reduction of CO2 by H2 for synthesis of CO, methanol
and hydrocarbons: challenges and opportunities
Energy Environ. Sci., 9 (2016), pp. 62-73
[2]S. Saeidi, N.A.S. Amin, M.R. Rahimpour
J. CO2 Util., 5 (2014), pp. 66-81
[3]W. Wang, S. Wang, X. Ma, J. Gong
Chem. Soc. Rev., 40 (2011), pp. 3703-3727
[4]C. Janke, M.S. Duyar, M. Hoskins, R. Farrauto
Appl. Catal. B Environ., 152–153 (2014), pp. 184-191
[5]M.S. Duyar, M.A.A. Treviño, R.J. Farrauto
Appl. Catal. B Environ., 168–169 (2015), pp. 370-376
[6]G. Centi, S. Perathoner
Catal. Today, 148 (2009), pp. 191-2ArticleDownload PDFView Record in Scopus
[7]G. Centi, E.A. Quadrelli, S. Perathoner
Energy Environ. Sci., 6 (2013), pp. 1711-17305
REFERENCES
• [8]J.C.M. Pires, F.G. Martins, M.C.M. Alvim-Ferraz, M. Simoes Chem. Eng. Res. Des., 89
(2011), pp. 1446-1460
• [9]G.T. Rochelle Science, 325 (2009), pp. 1652-1654
• [10]A. Veawab, A. Aroonwilas, P. Tontiwachwuthikul Fuel Chem. Div. Reprints, 47 (2002),
pp. 49-50
• [11]D.Y.C. Leung, G. Caramanna, M.M. Maroto-Valer Renew. Sustain. Energy Rev., 39
(2014), pp. 426-443
• [12]A. Samanta, A. Zhao, G.K.H. Shimizu, P. Sarkar, R. Gupta Ind. Eng. Chem. Res., 51
(2012), pp. 1438-1463
• [13]P.A. Webley Adsorption, 20 (2014), pp. 225-231
• [14]A. Trovarelli, C. Deleitenburg, G. Dolcetti, J.L. Lorca J. Catal., 151 (1995), pp. 111-124
REFERENCES
• [15]J.C. Medina, S.J. Butala, C.H. Bartholomew, M.L. Lee Geochim. Cosmochim. Acta, 64 (2000), pp. 643-649
• [16]L. Mendelovici, M. Steinberg J. Catal., 96 (1985), pp. 285-287
• [17]H.Y. Kim, H.M. Lee, J.-N. ParkJ. Phys. Chem. C, 114 (2010), pp. 7128-7131
• [18]H. Habazaki, M. Yamasaki, B.-P. Zhang, A. Kawashima, S. Kohno, T. Takai, K. Hashimoto Appl. Catal. A Gen., 172 (1998), pp. 131-140
• [19]C. Zhao, X. Chen, C. Zhao Energy Fuels, 26 (2012), pp. 1401-1405
• [20]C. Zhao, X. Chen, C. Zhao Ind. Eng. Chem. Res., 51 (2012), pp. 14361-14366
• [21]J.B. Lee, T.H. Eom, B.S. Oh, J.-I. Baek, J. Ryu, W.S. Jeon, Y.H. Wi, C.K. Ryu Energy Procedia, 4 (2011), pp. 1494-1499
• [22]S.C. Lee, H.J. Chae, S.J. Lee, B.Y. Choi, C.K. Yi, J.B. Lee, C.K. Ryu, J.C. Kim Environ. Sci. Technol., 42 (2008), pp. 2736-2741
• [23]L. Li, X. Wen, X. Fu, F. Wang, N. Zhao, F. Xiao, W. Wei, Y. Sun Energy Fuels, 24 (2010), pp. 5773-5780
• [24]L. Li, Y. Li, X. Wen, F. Wang, N. Zhao, F. Xiao, W. Wei, Y. Sun Energy Fuels, 25 (2011), pp. 3835-3842
• [25]P. Gruene, A.G. Belova, T.M. Yegulalp, R.J. Farrauto, M.J. Castaldi Ind. Eng. Chem. Res., 50 (2011), pp. 4042-4049
• [26]J. Yu, Q. Ge, W. Fang, H. Xu Appl. Catal. A Gen., 395 (2011), pp. 114-119
• [27]Y.-J. Tu, Y.-W. Chen Ind. Eng. Chem. Res., 37 (1998), pp. 2618-2622
• [28]K. Aika, A. Ohya, A. Ozaki, Y. Inoue, I. Yasumori J. Catal., 92 (1985), pp. 305-311
• [29]A. Beuls, C. Swalus, M. Jacquemin, G. Heyen, A. Karelovic, P. Ruiz Appl. Catal. B Environ., 113–114 (2012), pp. 2-10
• [30]A. Karelovic, P. Ruiz J. Catal., 301 (2013), pp. 141-153
REFERENCES
• [31]A. Karelovic, P. Ruiz Appl. Catal. B Environ., 113–114 (2012), pp. 237-249
• [32]M. Jacquemin, P. Ruiz Catal. Today, 157 (2010), pp. 462-466
• [33]H. Hayashi, J. Taniuchi, N. Furuyashiki, S. Sugiyama, S. Hirano, N. Shigemoto, T. Nonaka Ind. Eng. Chem. Res.,
37 (1998), pp. 185-191
• [34]S.C. Lee, B.Y. Choi, T.J. Lee, C.K. Ryu, Y.S. Ahn, J.C. Kim Catal. Today, 111 (2006), pp. 385-390
• [35]S.C. Lee, J.C. Kim Catal. Surv. Asia, 11 (2007), pp. 171-185
• [36]S.C. Lee, H.J. Chae, S.J. Lee, Y.H. Park, C.K. Ryu, C.K. Yi, J.C. Kim J. Mol. Catal. B Enzym., 56 (2009), pp. 179-
184
• [37]S.C. Lee, B.Y. Choi, C.K. Ryu, Y.S. Ahn, T.J. Lee, J.C. Kim Korean J. Chem. Eng., 23 (2016), pp. 374-379
• [38]S.C. Lee, Y.M. Kwon, C.Y. Ryu, H.J. Chae, D. Ragupathy, S.Y. Jung, J.B. Lee, C.K. Ryu, J.C. Kim Fuel, 90 (2011),
pp. 1465-1470
• [39]C. Zhao, X. Chen, C. Zhao Energy Fuels, 23 (2009), pp. 4683-4687
• [40]A. Silaban, M. Narcida, D.P. Harrison Chem. Eng. Commun., 146 (1996), pp. 149-162
• [41]A. Tsuneto, A. Kudo, N. Saito, T. Sakata Chem. Lett., 21 (1992), pp. 831-834
THANK YOU