Scholarly article on topic 'Process simulation of Ca-looping processes: review and guidelines'

Process simulation of Ca-looping processes: review and guidelines Academic research paper on "Chemical engineering"

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Energy Procedia
OECD Field of science
{CCS / "Calcium looping" / "Sorption enhanced reforming" / Cement}

Abstract of research paper on Chemical engineering, author of scientific article — Matteo C. Romano, Isabel Martínez, Ramón Murillo, Bjørnar Arstad, Richard Blom, et al.

Abstract Ca-looping is one of the most promising processes for CO2 capture in short to medium term plants, which can be applied for both post-combustion and pre-combustion layouts. The recent successful operations of MW-scale pilot plants are leading to an increased interest in this technology. In addition, the particularly advantageous applicability in cement plants, the main industrial contributors to CO2 emissions worldwide, can further lead to a forthcoming development of the technology. Quite a large amount of scientific papers on reactors and process modeling has been published in the recent years and more studies are expected to be published in the future. According to the experience of the authors in this field and on the basis of a literature review, suggestions and modeling needs for next works are provided in this paper.

Academic research paper on topic "Process simulation of Ca-looping processes: review and guidelines"

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Energy Procedía 37 (2013) 142- 150


Process simulation of Ca-looping processes: review and


Matteo C. Romanoa*, Isabel Martínezb, Ramón Murillob, Bj0rnar Arstadc, Richard Blomc, Dursun Can Ozcand, Hyungwoong Ahnd, Stefano Brandanid

a Politecnico di Milano, Energy Department, via Lambruschini 4, 20156 Milano, Italy b Instituto de Carboquímica (ICB-CSIC), C/Miguel Luesma Castán 4, 50018, Zaragoza, Spain c SINTEFMaterial and Chemistry, P.O. Box 124 Blindern, N-0314 Oslo, Norway _d IMP-SEE, The University of Edinburgh, Mayfield Road, Edinburgh, EH9 3JL, UK_


Ca-looping is one of the most promising processes for CO2 capture in short to medium term plants, which can be applied for both post-combustion and pre-combustion layouts. The recent successful operations of MW-scale pilot plants are leading to an increased interest in this technology. In addition, the particularly advantageous applicability in cement plants, the main industrial contributors to CO2 emissions worldwide, can further lead to a forthcoming development of the technology.

Quite a large amount of scientific papers on reactors and process modeling has been published in the recent years and more studies are expected to be published in the future. According to the experience of the authors in this field and on the basis of a literature review, suggestions and modeling needs for next works are provided in this paper.

© 2013 The Authors. Published by Elsevier Ltd. Selection and/or peer-review under responsibility of GHGT

Keywords: CCS, Calcium looping, sorption enhanced reforming, cement.

1. Introduction

Calcium (Ca)-looping is one of the most promising processes for CO2 capture in future short to medium term plants. Such regenerative processes are based on the capacity of calcium oxide (CaO)-based sorbents in the reaction with gaseous CO2 at high temperatures (600-750°C) by forming solid calcium carbonate (CaCO3). Since this carbonation reaction is highly exothermic, heat must be provided to decompose CaCO3 back into the CaO sorbent and a concentrated CO2 stream ready for sequestration. The Ca-looping concept can be integrated in a variety of plants, the most promising being: (i) coal fired PC or

* Corresponding author. Tel.: +39-02-239993846; fax: +39-02-23993913. E-mail address:

1876-6102 © 2013 The Authors. Published by Elsevier Ltd. Selection and/or peer-review under responsibility of GHGT doi:10.1016/j.egypro.2013.05.095

CFB power plants with post-combustion capture, (ii) natural gas-fed plants for power and hydrogen production with pre-combustion capture and (iii) cement production plants.

Being Ca-looping an emerging technology, process modeling and simulation and economic evaluation are particularly important to understand its potential and to optimize operating parameters in the different possible applications. In such activity, in order to avoid misleading results, it is of primary importance to make correct calculation assumptions, taking into account the findings from the increasing modeling and experimental activity in this field.

This paper results from an activity carried out within the Joint Programme on Carbon Capture and Storage of the European Energy Research Alliance (EERA CCS-JP). The objective of this study is to make a brief review of the main process simulation studies available today on Ca-looping processes and propose some guidelines for future works on this subject. Further details on the analysis carried out and an extensive review of the literature can be accessed on the EERA CCS-JP web site [1].

2. Ca-looping for post-combustion capture applications

Coal-fired power plants including a post-combustion CO2 capture system using a Ca-based sorbent is the plant category most widely assessed, which is at the most advanced stage of development with the first MW-scale pilot installations [2,3]. As shown in Fig. 1, Ca-looping consist in removing CO2 from a flue gas of an air-blown boiler that is fed in a fluidized bed carbonator operating at 650-700° C at atmospheric pressure. CaCO3 formed in this reactor is then regenerated into CaO by oxy-fuel combustion in a calciner, which operates at high CO2 partial pressures to facilitate its later purification, compression and storage. The main thermodynamic advantage of the process is that a great amount of the energy introduced in the system can be recovered as not only carbonation reaction heat but also as gas and solid streams at high temperature. Therefore, it can be used to produce high pressure superheated steam instead of being released to the environment at low temperature like in solvent-based post-combustion capture plants. From another point of view, in these plants only the fraction of the input coal introduced in the calciner is burned with pure O2, with lower auxiliary power and investment costs for O2 production than in full oxy-fuel combustion power plants.

2.1. Reactor modeling

The great majority of the research on Ca-looping reactor modeling has focused on the most innovative component, i.e. the carbonator. Different carbonator models with different level of detail and complexity have been proposed in the literature during years either to explain the experimental results obtained from experimental rigs, or to design higher scale plants and carry out predictions about their performance.

After the first models considering

C02-r¡ch gasto

(Fc02) make-up (F0)

Fig. 1 - Scheme of the Ca-looping process focused on removing CO2 from the flue gas of an existing power plant

bubbling fluidized bed reactors [4-6], carbonator models proposed in the literature considered the reactor as a circulating fluidised bed where two zones were distinguished: a bottom dense zone and a lean one located above [7-10]. Almost every of these models concluded that the most influencing parameter on the carbonator efficiency is the fraction of particles reacting in the fast regime, determined mainly by the fresh sorbent make-up flow introduced in the system and the solid circulation between reactors.

2.2. Complete power plant simulation

Most of the works reviewed consider the integration of the Ca-looping system into a coal-fired power plant coupled with a high-efficiency supercritical steam cycle [4,6,8,11-14]. Conventionally, the capture system has been assumed to be working under fixed and reasonable operating conditions in both reactors: carbonator at 600-650°C with CO2 capture efficiency of 90%, and calciner at 900-950°C considering full calcination of the CaCO3 entering into the reactor, usually without CO2 recycle in the calciner. Romeo et al. and Martinez et al. carried out a sensitivity analysis to assess system performance under different operating conditions of the Ca-looping system, and determine the optimum fresh sorbent make-up flow and solid circulation for the Ca-looping from an economical [13] or an efficiency point of view [14]. Both works conclude that working with low purge percentages and high solid circulation between reactors lead to the highest electric efficiencies and the lowest costs per tCO2 captured.

Quantitatively, when comparing with a reference plant without capture, a broad range of electric efficiencies has been reported. Lower efficiency penalties of the order of 3 percentage points have been assessed in [12] that do not include CO2 compression or fan consumption in the calciner. Abanades et al. analysed the efficiency obtained for different configuration schemes of the Ca-looping system, and assessed a penalty of 5.75 percentage points with respect to a reference plant of 46% of electric generation efficiency, being 2.85 and 3.17 percentage points attributed to the CO2 compressor and the ASU, respectively [11]. In the rest of the reviewed works, efficiency penalties are typically between 6.5 and 8.5 percentage points with respect to the reference plant. Reasons for these differences are the electric efficiency for the reference plant assumed, the different qualities of the thermal integration proposed, the fact that in some cases no thermal integration has been carried out and a reasonable electric efficiency has been applied to the total heat recovered from the Ca-looping system, or the different power consumptions assumed for the auxiliaries, compressors and fans with respect to other works.

2.3. Guidelines for future works

On the basis of the different works reviewed of carbonator and process modeling in the Ca-looping system, the following needs of research and consideration are highlighted in this field:

■ Accurate models on the CO2 carrying capacity of the sorbent should be taken into account to improve the reliability of the carbonator models proposed and, therefore, contribute to a better assessment of the whole performance of the plant. Moreover, this accuracy on sorbent reactivity would also contribute to a better understanding of experimental results from pilot scale plants. CO2 carrying capacity of the Ca-sorbent entering the carbonator will be different from that predicted because it depends on carbonation conditions [15-17], on the partial conversion achieved in the carbonator and calciner [18] and on the possible reactivation mechanism carried out in the process [19,20]. It is necessary to include an accurate model that considers the real "age" of the Ca particles in the system according to their carrying capacity, irrespective of their previous history of partial or complete cycles experimented in the Ca-looping system. Accurate results would be obtained in this way about the carbonator and plant performance.

■ CaSO4 formation should be included in the models proposed. Sulphur reacts not only with the

CaO active for the carbonation reaction, but also can form CaSO4 with the non-active CaO [21]. It is important to quantify this effect and determine the fraction of non-active CaO that reacts with sulphur to form CaSO4 for not being excessively conservative when considering sulphur.

■ Ashes from coal burnt in the calciner should be included in the process modeling of Ca-looping systems as thermal balances and operational issues are going to be affected.

Coal ashes act as inerts in the Ca-looping system and influence the heat required in the calciner to heat up solids up to calcination temperature.

■ Auxiliaries power consumption should be properly taken into account in the efficiency assessment. In particular, the consumption of the fan needed to offset the flue gas pressure losses in the carbonator should be included, since it may provide a relevant contribution to the auxiliary electric consumption. For a reliable estimation of this consumption, it is important to consider the presence of inactive solids (inactive sorbent, ash from coal and CaSO4) as part of the carbonator inventory and to use a carbonator model to estimate the link between the fundamental Ca-looping process parameters (carbonator inventory, sorbent make-up and sorbent recycle rate) and CO2 capture efficiency.

■ Improvements on the calculation methodology of the oxy-fuel combustion side should be made with respect to the existing literature, where it is often treated in a simplified way. For example, flue gas recycle and CO2 compression and purification unit should be considered in future works.

3. Ca-looping for pre-combustion capture applications

Although several applications on coal fed plants have been considered [22-25], the process most widely assessed for pre-combustion CO2 capture by CaO sorption is sorption-enhanced steam methane reforming (SE-SMR). According to this concept, methane is converted in a single reactor where CO2 is adsorbed over a solid sorbent while steam methane reforming (SMR) and water gas shift (WGS) reactions occur (1). Therefore, progression of the SMR and WGS gaseous phase reactions is not limited to equilibrium set by CO2 formation and can proceed almost to a complete depletion of reactants.

CH4 + 2H2O + CaO ^ 4H2 + CaCO3 AH°r = -14.5 kJ/mol (1)

The enthalpy balance of the overall reaction is only 14.5 kJ/mol, meaning that it is thermally balanced, and therefore not only the carbonation reaction facilitates H2 production by removing CO2 from the gaseous phase, but also provides the heat required for the SMR reaction, allowing for the use of adiabatic reformers.

3.1. Reactor modeling

Different reactor concepts (packed bed [26-29] and fluid bed [30-35]) have been studied. Fixed bed SE-SMR is typically modeled for temperatures from 500 to 650°C, pressures from 1 to 15 atm and for steam-to-methane ratios (S/M) from 2.0 to 5.5. In [26,28], simple modeling of breakthrough curves have been carried out where the parameters needed for the particle conversion expressions have been derived from their own or literature thermo gravimetric measurements or isotherm data of the various sorbents. The temperature and pressure dependencies on the enhancement in H2 production are analyzed and H2 and CO2 concentrations in the reactor effluent with time are modeled showing different behavior of the various sorbents. Li et al. also considered sorbent capacity decay with cycle number and compared different CaO sorbents such as limestone, dolomite and impregnated CaO systems [27]. Zagoruiko et al. focused on modeling the thermal effects by using a "moving heat wave" generated by in situ catalytic

combustion of methane for regeneration of the sorbent [29].

Fluid bed SE-SMR reactor modeling has been developed through a series of papers from Wang et al. using a 3D two fluid Eulerian hydrodynamic model together with kinetic parameters of the reactions taking place [30-32]. Neither details on catalyst nor sorbent particle structure were included assuming only that reactions take place on the particle surface without diffusion limitations. CO2 sorption is fast compared with the rate of the reforming reactions while the CO2 desorption rate is slow due to the increased CO2 concentration in the gas phase making higher temperature needed to achieve the necessary kinetics of sorbents regeneration. Di Carlo et al. include both intra- and extra-particle mass transfer effects in their study of SE-SMR using a similar two fluid Eulerian model as Wang et al. [30,33]. A Ni-catalyst/dolomite powder mixture was used. At sorbent-to-catalyst mass ratios larger than 2, autothermal conditions in the reactor were simulated where the heat produced upon sorption compensated the endothermicity of the reforming reaction.

Jakobsen et al. studied the SE-SMR process by using a linear plug flow model for fluid bed reactor using different flow regimes and sorbents [35]. Their results indicate that the contact time in a riser is too short to reach high methane conversion and CO2 capture rates, while high H2 yield and capture rates can be obtained in a bubbling bed.

3.2. Complete power plant simulation

The main issue related to the integration of a SE-SMR reactor in a complete plant depends on how the regeneration process is carried out. The most feasible option is to consider low pressure interconnected fluidized bed reactors. The limit of this layout is related to the low pressure of the H2 delivered, which would require relevant energy penalty associated to cooling and compression in case of a high pressure final utilization (e.g. combustion in a gas turbine, utilization in high pressure refinery processes).

The use of pressurized interconnected fluidized bed is an alternative investigated in some works. However, two kind of problems arise with such a configuration: (i) stable operation of interconnected pressurized fluidized beds has not been demonstrated yet and requires technology breakthrough and (ii) regeneration temperatures rise with pressure up to values at which the activity of the catalyst and the capacity of the sorbent are compromised (roughly 1100-1200°C, at 20-30 bar).

A further alternative are packed beds, which allow operating reforming and calcination at different pressures by keeping the solid material always in the same reactor, periodically exposed to atmospheres favorable to carbonation and to calcination. The intrinsic dynamic behavior of the system, the difficult control of peak temperatures and the complexity and cost of high temperature valve system represent the limits of the packed bed-based process.

Two studies assessed only the SE-SMR reactors system [28,36]. Chen et al. focused on interconnected fluidized beds [28]. Fernandez et al. considered the innovative Ca-Cu looping process based on fixed beds, where calcination is sustained by oxidation of fuel by means of a CLC loop using Cu/CuO as oxygen carrier [36]. Ochoa-Fernandez et al. assessed a complete plant for H2 production based on high pressure (10 bar) reforming and low pressure (1 bar) regeneration [37]. Solieman et al. and Romano et al. considered the integration of SE-SMR process into a combined cycle based power plant [38,39]. In the first case [38], a packed bed system was considered, while pressurized interconnected fluidized beds were adopted in the second case [39]. Finally, Meyer et al. assessed the process based on the ZEG concept, where the H2-rich gas is converted in a high temperature SOFC and the waste heat from the fuel cell is used to regenerate the Ca-based sorbent [40].

In all the cases, reactors have been calculated at equilibrium, which is a reasonable assumption according to experimental data and outputs from reactor modeling studies. Reforming was assumed to be carried out at 550-600°C and S/C=2.5-3.5 for low pressure (1-2 bar) reformers cases and at 600-700°C

and S/C=4.2-4.8 for high pressure (17-35 bar) cases. In none of these plants sorbent purging and makeup have been considered. This appears to be a reasonable assumption when feeding a clean gaseous fuel as natural gas, with no ash and negligible sulfur, considering that no impurity is expected to accumulate in the Ca-looping system or to affect the capacity and the activity of the Ca-sorbent (in case of CaO, sorbent capacity loss is a consequence of calcination conditions, there is no need of using a fuel with sulfur or ashes). Conversion between 10 and 53% has been adopted in these studies, significantly higher than the residual capacity of natural sorbents, but acceptable considering the possible advancements in the development of synthetic sorbents and reactivation techniques.

Overall H2 yields of 2.4-2.7 molH2/molCH4-eq (or 0.60-0.68 molH2/molH2-eq) and cold gas efficiencies of 81-83% have been obtained in all the cases. In cases for power production, net efficiencies of 50-51% have been obtained when using state of the art combined cycles, while and efficiency of 76.9% is claimed for the SOFC-based ZEG concept.

3.3. Guidelines for future works

On the basis of the modeling and experimental findings, the following modeling guidelines and needs of experimental investigation can be highlighted:

■ In plants for H2 production, it is important to include the PSA process for H2 purification within the process model as done in [37]. As a matter of facts, PSA process can have a relevant effect on the mass and energy balance since PSA off-gas, rich of CO, CO2, CH4 and a part of the H2 (10-20% of the total, according to the hydrogen recovery factors of commercial PSA) can be recycled to the calciner. These gases provide part of the heat for regeneration in case of oxycombustion-based regeneration, reducing the required primary fuel input.

■ When comparing SE-SMR with conventional processes for H2 production, it is important to consider the pressure at which H2 is needed by the final user. As a matter of facts, homogeneous H2 delivery pressures should be assumed when comparing different technologies. Penalties for SE-SMR-based layouts using low pressure reactors will arise when high pressure H2 is needed.

■ Ca/catalyst ratio can be important for the mass and energy balance. Ni-based catalysts are thermal ballast and can behave as oxygen carriers between calciner and reformer. This phenomenon should be minimized since O2 produced at high cost with ASU may react with Ni in the calciner to form NiO and eventually oxidize part H2-rich syngas in the reformer. Therefore, low catalyst/Ca ratios are desirable. A lack of modeling and experimental activity to find the minimum catalyst/sorbent ratio can be highlighted.

■ In case of regeneration by heat exchange, it is important to provide sufficient details on the heat and mass balances. As a matter of facts, heat transfer of high thermal power at high temperature under relatively low ATs is a critical process which can lead to large heat transfer surface operating at high temperature and relatively low fuel utilizations, voltages and efficiency of the fuel cell of the ZEC/ZECA concepts.

■ When calculating power plants based on gas turbines, it is important to use a reliable model for the gas turbine. As reported in [25], considering blades cooling flows can have a really important effect on the estimated overall plant efficiency when adopting advanced high TIT gas turbines (of the order of 4-5% points).

4. Ca-looping applications on cement production plants

Cement is a key construction material, and global demand is expected to grow at around six percent in 2012, amounting to 3.8 billion tons [41]. The cement industry, which is one of major industrial sources of

CO2 emissions, accounts for 8% out of global CO2 emission in 2011 [42]. Reduction in it carbon emissions can be achieved only in part by more efficient use of fuels but over half of its CO2 is generated by calcination reaction. Therefore, it is essential to retrofit a carbon capture process into a cement plant if more than 90% reduction of carbon emission is to be achieved.

It has been argued that Ca-looping processes would have lower net energy consumption than amine processes since they can be better integrated with cement plants. Since ECRA [43] listed Ca-looping technologies as one of the promising capture technologies for cement plants, there have been conceptual studies which proposed various integration models, such as utilization of purge flow for the cement clinker and synergy between cement and power plants [44,45].

Given that the calciner purge can be used as kiln feed, a symbiosis model of a power plant, a Ca-looping process and a cement plant has been proposed with its mass and energy balances [10]. The flue gases from both plants are sent to the Ca-looping process, and the CaO purge of this capture unit is returned to cement plant, mixed with CaO from fresh raw material, and used as kiln feed. In this way, the CO2 emission and energy consumption of the cement plant can be drastically reduced due to reduced calcination loads. The surplus energy from the capture unit can be utilized to generate electricity by running a separate steam cycle. The total thermal energy consumption increases by about 6.7% for the integrated system due to addition of capture unit. CO2 emission avoided was estimated to be 94% on a basis of total CO2 emission at both industries by this integration system, which would add about 12.4 €/ton of avoided CO2.

A similar assessment has been performed in [46], where the effect of the actual composition of the purge on the maximum "substitution rate" of the cement plant raw meal has been considered. As a matter of fact, large amount of CaSO4 and ashes from coal combustion in the calciner can limit the maximum amount of Ca-looping purge that can be used in the cement plant. Such a maximum "substitution rate" strongly depends on the fuel used in the calciner and on the parameters of the Ca-looping process.

As a direct integration of Ca-looping with a cement plant, Rodriguez et al. [47] investigated two alternative processes, including an economic study. One is a retrofit replacing the existing pre-calciner with an oxy-calciner which can achieve 89% CO2 capture and the other is capturing CO2 from the kiln gas using a carbonator in addition to capturing CO2 by oxy-calciner to improve capture rate up to 99%. Similarly with other Ca-looping processes, the surplus energy from high temperature streams is recovered by an integrated steam cycle. It is reported that the total energy consumption of the cement plant increases from 2.93 GJ/ton of cement covering the electricity demand to 5.45 GJ/ton of cement by retrofit for carbon capture.

Ca-looping process can also be applied to a gas stream downstream of the pre-calciner to achieve over 90% capture. The flue gas stream leaving the 3rd preheater stage has been identified to be an optimum feed for a carbonator rather than the end-of-pipe flue gas since it does not require preheating, has higher CO2 partial pressure and lower volumetric flow rate [48]. The CO2-depleted gas is routed back to 2nd preheater for raw material heating. The effects of sulfidation and ash have been taken into account in the carbonator model. It has been represented that this process is capable of achieving more than 90% CO2 capture with additional energy consumption of 2.3 to 3.0 GJ/ton CO2 avoided by considering heat recovery.

4.1. Guidelines for future works

Modeling of Ca-looping process for CO2 capture in cement plants has many similarities with the postcombustion capture from power plant flue gases case. Therefore, the suggestions described in section 2.3 can be extended to this case for both Ca-looping reactors modeling and process simulation. An additional issue should however be considered for cement plants, related to the limited variability of the composition

of the final clinker, which may limit the maximum amount of Ca-looping purge to be used in the plant if too rich of CaSO4 and ash.

5. Conclusions

This paper originates from an activity carried out within the Joint Programme on Carbon Capture and Storage of the European Energy Research Alliance (EERA CCS-JP). The main works in the open literature dealing with modeling and simulation of Ca-looping processes have been reviewed. On the basis of this review and the recent experimental findings on this technology, guidelines and suggestions for future modeling studies have been provided.


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