Marcin Broda

Synthesis of Highly Efficient, Ca‐Based, Al2O3‐Stabilized, Carbon Gel‐Templated CO2 Sorbents

www.MaterialsViews.com C O M M U Synthesis of Highly Effi cient, Ca-Based, Al 2 O 3 -Stabilized, Carbon Gel-Templated CO 2 Sorbents N IC A Marcin Broda and Christoph R. Müller * IO N The increasing concentration of greenhouse gases in the atmosphere is most likely linked to climate change. [ 1 ] Considering that the use of fossil energy carriers will continue and may even increase over the next decades, it is imperative to fi nd ways of using fossil fuels that limit the release of CO 2 into the atmosphere. One of the most promising short to mid-term strategies for mitigating climate change is CO 2 capture and storage (CCS). [ 2 ] However, the currently available CO 2 capture technology, i.e. scrubbing with amines, comes with a large penalty on plant effi ciency. Thus, there is a pressing need to develop more effi cient, less energy intensive CO 2 capture technologies. A promising, 2 nd generation CO 2 capture technology is the use of alkaline earth metal based CO 2 sorbents. [ 3 ] The selective capture and release of CO 2 is achieved by the following, theoretically reversible, reaction:

Highly efficient CO2 sorbents: development of synthetic, calcium-rich dolomites.

The reaction of CaO with CO(2) is a promising approach for separating CO(2) from hot flue gases. The main issue associated with the use of naturally occurring CaCO(3), that is, limestone, is the rapid decay of its CO(2) capture capacity over repeated cycles of carbonation and calcination. Interestingly, dolomite, a naturally occurring equimolar mixture of CaCO(3) and MgCO(3), possesses a CO(2) uptake that remains almost constant with cycle number. However, owing to the large quantity of MgCO(3) in dolomite, the total CO(2) uptake is comparatively small. Here, we report the development of a synthetic Ca-rich dolomite using a coprecipitation technique, which shows both a very high and a stable CO(2) uptake over repeated cycles of calcination and carbonation. To obtain such an excellent CO(2) uptake characteristic it was found to be crucial to mix the Ca(2+) and Mg(2+) on a molecular level, that is, within the crystalline lattice. For sorbents which were composed of mixtures of microscopic crystals of CaCO(3) and MgCO(3), a decay behavior similar to natural limestone was observed. After 15 cycles, the CO(2) uptake of the best sorbent was 0.51 g CO(2)/g sorbent exceeding the CO(2) uptake of limestone by almost 100%.

High-Purity Hydrogen via the Sorption-Enhanced Steam Methane Reforming Reaction over a Synthetic CaO-Based Sorbent and a Ni Catalyst

Sorbent-enhanced steam methane reforming (SE-SMR) is an emerging technology for the production of high-purity hydrogen from hydrocarbons with in situ CO2 capture. Here, SE-SMR was studied using a mixture containing a Ni-hydrotalcite-derived catalyst and a synthetic, Ca-based, calcium aluminate supported CO2 sorbent. The fresh and cycled materials were characterized using N2 physisorption, X-ray diffraction, and scanning and transmission electron microscopy. The combination of a Ni-hydrotalcite catalyst and the synthetic CO2 sorbent produced a stream of high-purity hydrogen, that is, 99 vol % (H2O- and N2-free basis). The CaO conversion of the synthetic CO2 sorbent was 0.58 mol CO2/mol CaO after 10 cycles, which was more than double the value achieved by limestone. The favorable CO2 capture characteristics of the synthetic CO2 sorbent were attributed to the uniform dispersion of CaO on a stable nanosized mayenite framework, thus retarding thermal sintering of the material. On the other hand, the cycled limestone lost its nanostructured morphology completely over 10 SE-SMR cycles due to its intrinsic lack of a support component.

Influence of the Calcination and Carbonation Conditions on the CO2 Uptake of Synthetic Ca-Based CO2 Sorbents

In this work we report the development of a Ca-based, Al(2)O(3)-stabilized sorbent using a sol-gel technique. The CO(2) uptake of the synthetic materials as a function of carbonation and calcination temperature and CO(2) partial pressure was critically assessed. In addition, performing the carbonation and calcination reactions in a gas-fluidized bed allowed the attrition characteristics of the new material to be investigated. After 30 cycles of calcination and carbonation conducted in a fluidized bed, the CO(2) uptake of the best sorbent was 0.31 g CO(2)/g sorbent, which is 60% higher than that measured for Rheinkalk limestone. A detailed characterization of the morphology of the sol-gel derived material confirmed that the nanostructure of the synthetic material is responsible for its high, cyclic CO(2) uptake. The sol-gel method ensured that Ca(2+) and Al(3+) were homogenously mixed (mostly in the form of the mixed oxide mayenite). The formation of a finely and homogeneously dispersed, high Tammann temperature support stabilized the nanostructured morphology over multiple reaction cycles, whereas limestone lost its initial nanostructured morphology rapidly due to its intrinsic lack of a support component.

Effect of Pelletization and Addition of Steam on the Cyclic Performance of Carbon-Templated, CaO-Based CO2 Sorbents

In this work, we report the development of a synthetic CO2 sorbent that possesses a high cyclic CO2 uptake capacity and, in addition, sufficient mechanical strength to allow it to be used in fluidized-bed reactors. To overcome the problem of elutriation of the original powdered material, the synthetic CO2 sorbent was pelletized. An important aspect of this work was to assess the effect of steam on the cyclic CO2 capture capacity of the original, powdered CO2 sorbent and the pelletized material. After 30 cycles of repeated calcination and carbonation reactions conducted in a fluidized bed, the CO2 uptake of the pellets was 0.29 g of CO2/g of sorbent, a value that is 45% higher than that measured for the reference limestone. For the case that carbonation/calcination cycles were conducted in a thermogravimetric analyzer under steam-free carbonation conditions, the CO2 uptake of the best sorbent was 0.33 g of CO2/g of sorbent (after 10 cycles). Importantly, it should be noted that, after 10 cycles using wet carbonation conditions, the CO2 uptake of this material increased by 55% when compared to dry conditions. This observation was attributed to enhanced solid-state diffusion in the CaCO3 product layer under wet conditions. However, independent of the reaction conditions, the pelletized material showed a lower cyclic CO2 uptake when compared to the original powder. A detailed morphological characterization of the pellets indicated that the destruction of the primary, hollow micrometer-sized spheres during pelletization was responsible for the lower cyclic CO2 uptake of the pellets.

Synthesis of Cu-Rich, Al2O3-Stabilized Oxygen Carriers Using a Coprecipitation Technique: Redox and Carbon Formation Characteristics

Chemical looping combustion (CLC) is an emerging, new technology for carbon capture and storage (CCS). Copper-based oxygen carriers are of particular interest due to their high oxygen carrying capacity and reactivity, low tendency for carbon deposition, and exothermic reduction reactions. In this work, CuO-based and Al(2)O(3)-stabilized oxygen carriers with high CuO loadings were developed using a coprecipitation technique. The cyclic redox performance of the synthesized oxygen carriers was evaluated at 800 °C in a laboratory-scale fluidized bed reactor using a reducing atmosphere comprising 10 vol. % CH(4) and 90 vol. % N(2). The CuO content in the oxygen carrier was found to increase with the pH value at which the coprecipitation was performed. The oxygen carrying capacity of the oxygen carrier containing 87.8 wt % CuO was found to be high (5.5 mmol O(2)/g oxygen carrier) and stable over 25 redox cycles. Increasing the CuO content further, i.e. > 90 wt %, resulted in materials which showed a decreasing oxygen carrying capacity with cycle number. It was also shown that the incorporation of K(+) ions in the oxygen carrier can avoid the formation of the spinel CuAl(2)O(4) and significantly reduce carbon deposition.

Development of MgAl2O4-stabilized, Cu-doped, Fe2O3-based oxygen carriers for thermochemical water-splitting

The commercially dominating technology for hydrogen production (i.e. steam methane reforming) emits large quantities of CO2 into the atmosphere. On the other hand, emerging thermochemical water splitting cycles allow the production of a pure stream of H2 while simultaneously capturing CO2. From a thermodynamic point of view, the Fe2O3–Fe couple is arguably the most attractive candidate for thermochemical water splitting owing to its high H2 yield and H2 equilibrium partial pressure. However, the low reactivity of Fe2O3 with methane and the high activity of Fe for methane decomposition (leading to carbon deposition and in turn COx poisoning of the H2 stream) are major drawbacks. Here, we report the development of MgAl2O4-stabilized, Cu-modified, Fe2O3-based redox materials for thermochemical water-splitting that show a high reactivity towards CH4 and low rates of carbon deposition. To elucidate the effect of Cu doping on reducing significantly the rate of carbon deposition (while not affecting negatively the high redox activity of the material) extended X-ray absorption fine structure spectroscopy and energy dispersive X-ray spectroscopy was employed.

The development of effective CaO-based CO2 sorbents via a sacrificial templating technique

A carbon-based sacrificial templating approach was employed to realize single-pot synthesis of cyclically stable CaO-based CO2 sorbents. The sacrificial carbonaceous template was formed through resorcinol-formaldehyde polymerization reaction. The resultant sorbents following the thermal decomposition of the carbonaceous template featured an inverse opal-like macrostructure composed of a highly porous nanostructured backbone. In addition to pure CaO, sorbents supported with Al2O3, MgO, Y2O3, and ZrO2 were synthesized. SEM and XRD were utilized to characterize the morphology and the chemical composition of the synthetic CO2 sorbents, respectively. The cyclic CO2 uptake performance of the synthetic sorbents was assessed by TGA and compared to limestone. All of the synthetic sorbents exhibited an improved CO2 uptake performance when compared to limestone. The performance enhancement became more pronounced in the case of supported sorbents. The sorbent with the best CO2 uptake performance was supported by a mixture of Al2O3 and Y2O3, and exhibited a CO2 uptake of 0.61 g CO2/g CaO after 10 cycles of calcination and carbonation under practically relevant operating temperatures, which exceeded the CO2 uptake of limestone by more than 350%.

Development of a Steel‐Slag‐Based, Iron‐Functionalized Sorbent for an Autothermal Carbon Dioxide Capture Process

We propose a new class of autothermal CO2 -capture process that relies on the integration of chemical looping combustion (CLC) into calcium looping (CaL). In the new process, the heat released during the oxidation of a reduced metallic oxide is utilized to drive the endothermic calcination of CaCO3 (the regeneration step in CaL). Such a process is potentially very attractive (both economically and technically) as it can be applied to a variety of oxygen carriers and CaO is not in direct contact with coal (and the impurities associated with it) in the calciner (regeneration step). To demonstrate the practical feasibility of the process, we developed a low-cost, steel-slag-based, Fe-functionalized CO2 sorbent. Using this material, we confirm experimentally the feasibility to heat-integrate CaCO3 calcination with a Fe(II)/Fe(III) redox cycle (with regards to the heat of reaction and kinetics). The autothermal calcination of CaCO3 could be achieved for a material that contained a Ca/Fe ratio of 5:4. The uniform distribution of Ca and Fe in a solid matrix provides excellent heat transfer characteristics. The cyclic CO2 uptake and redox stability of the material is good, but there is room for further improvement.

Mechanochemically Activated, Calcium Oxide-Based, Magnesium Oxide-Stabilized Carbon Dioxide Sorbents

Carbon dioxide capture and storage (CCS) is a promising approach to reduce anthropogenic CO2 emissions and mitigate climate change. However, the costs associated with the capture of CO2 using the currently available technology, that is, amine scrubbing, are considered prohibitive. In this context, the so-called calcium looping process, which relies on the reversible carbonation of CaO, is an attractive alternative. The main disadvantage of naturally occurring CaO-based CO2 sorbents, such as limestone, is their rapid deactivation caused by thermal sintering. Here, we report a scalable route based on wet mechanochemical activation to prepare MgO-stabilized, CaO-based CO2 sorbents. We optimized the synthesis conditions through a fundamental understanding of the underlying stabilization mechanism, and the quantity of MgO required to stabilize CaO could be reduced to as little as 15 wt %. This allowed the preparation of CO2 sorbents that exceed the CO2 uptake of the reference limestone by 200 %.