Qasim Imtiaz

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.

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.

Coprecipitated, Copper‐Based, Alumina‐Stabilized Materials for Carbon Dioxide Capture by Chemical Looping Combustion

Chemical looping combustion (CLC) has emerged as a carbon dioxide capture and storage (CCS) process to produce a pure stream of CO(2) at very low costs when compared with alternative CCS technologies, such as scrubbing with amines. From a thermodynamic point of view, copper oxide is arguably the most promising candidate for the oxygen carrier owing to its exothermic reduction and oxidation reactions and high oxygen-carrying capacity. However, the low melting point of pure copper of only 1085 °C has so far prohibited the synthesis of copper-rich oxygen carriers. This paper is concerned with the development of copper-based and Al(2)O(3)-stabilized oxygen carriers that contain a high mass fraction of CuO, namely, 82.4 wt %. The oxygen carriers were synthesized by using a coprecipitation technique. The synthesized oxygen carriers were characterized in detail with regards to their morphological properties, chemical composition, and surface topography. It was found that both the precipitating agent and the pH at which the precipitation was performed strongly influenced the structure and chemical composition of the oxygen carriers. In addition, XRD analysis confirmed that, for the majority of the precipitation conditions investigated, CuO reacted with Al(2)O(3) to form fully reducible CuAl(2)O(4). The redox characteristics of the synthesized materials were evaluated at 800 °C by using methane as the fuel and air for reoxidation. It was found that the oxygen-carrying capacity of the synthesized oxygen carriers was strongly influenced by both the precipitating agent and the pH at which the precipitation was performed; however, all oxygen carriers tested showed a stable cyclic oxygen-carrying capacity. The oxygen carriers synthesized at pH 5.5 using NaOH or Na(2)CO(3) as the precipitating agents were the best oxygen carriers synthesized owing to their high and stable oxygen transfer and uncoupling capacities. The excellent redox characteristics of the best oxygen carrier were interpreted in light of the detailed morphological characterization of the synthesized material and a synthesis-structure-performance relationship was developed.

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.

CuO promoted Mn2O3-based materials for solid fuel combustion with inherent CO2 capture

We experimentally demonstrate the promising redox and oxygen release characteristics of a novel bimetallic Cu–Mn oxygen carrier for chemical-looping with oxygen uncoupling (CLOU) based CO2 capture. The new material was prepared via a co-precipitation technique and showed a higher oxygen partial pressure than pure CuO and a higher oxygen carrying capacity than Mn2O3, thus, synergistically combining the advantages of the individual metal oxides. The promising CLOU characteristics of the new material were demonstrated further by combusting charcoal fully in a fluidized bed and producing a pure stream of CO2.

Highly Efficient Oxygen‐Storage Material with Intrinsic Coke Resistance for Chemical Looping Combustion‐Based CO2 Capture

Chemical looping combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) are emerging thermochemical CO2 capture cycles that allow the capture of CO2 with a small energy penalty. Here, the development of suitable oxygen carrier materials is a key aspect to transfer these promising concepts to practical installations. CuO is an attractive material for CLC and CLOU because of its high oxygen-storage capacity (20 wt %), fast reaction kinetics, and high equilibrium partial pressure of oxygen at typical operating temperatures (850-1000 °C). However, despite its promising characteristics, its low Tammann temperature requires the development of new strategies to phase-stabilize CuO-based oxygen carriers. In this work, we report a strategy based on stabilization by co-precipitated ceria (CeO2-x ), which allowed us to increase the oxygen capacity, coke resistance, and redox stability of CuO-based oxygen carriers substantially. The performance of the new oxygen carriers was evaluated in detail and compared to the current state-of-the-art materials, that is, Al2 O3 -stabilized CuO with similar CuO loadings. We also demonstrate that the higher intrinsic oxygen uptake, release, and mobility in CeO2-x -stabilized CuO leads to a three times higher carbon deposition resistance compared to that of Al2 O3 -stabilized CuO. Moreover, we report a high cyclic stability without phase intermixing for CeO2-x -supported CuO. This was accompanied by a lower reduction temperature compared to state-of-the-art Al2 O3 -supported CuO. As a result of its high resistance towards carbon deposition and fast oxygen uncoupling kinetics, CeO2-x -stabilized CuO is identified as a very promising material for CLC- and CLOU-based CO2 capture architectures.

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.

Na+ doping induced changes in the reduction and charge transport characteristics of Al2O3-stabilized, CuO-based materials for CO2 capture

Chemical looping combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) are emerging CO2 capture technologies that could reduce appreciably the costs associated with the capture of CO2. In CLC and CLOU, the oxygen required to combust a hydrocarbon is provided by a solid oxygen carrier. Among the transition metal oxides typically considered for CLC and CLOU, copper oxide (CuO) stands out owing to its high oxygen carrying capacity, exothermic reduction reactions and fast reduction kinetics. However, the low Tammann (sintering) temperature of CuO is a serious drawback. In this context, it has been proposed to support CuO on high Tammann temperature and low cost alumina (Al2O3), thus, reducing the morphological changes occurring over multiple CLC or CLOU redox cycles and stabilizing, in turn, the high activity of CuO. However, in CuO-Al2O3 systems, phase stabilization and avoiding the formation of the CuAl2O4 spinel is key to obtaining a material with a high redox stability and activity. Here, we report a Na(+) doping strategy to phase stabilize Al2O3-supported CuO, yielding in turn an inexpensive material with a high redox stability and CO2 capture efficiency. We also demonstrate that doping CuO-Al2O3 with Na(+) improves the oxygen uncoupling characteristics and coke resistance of the oxygen carriers. Utilizing in situ and ex situ X-ray absorption spectroscopy (XAS), the local structure of Cu and the reduction pathways of CuO were determined as a function of the Na(+) content and cycle number. Finally, using 4-point conductivity measurements, we confirm that doping of Al2O3-supported CuO with Na(+) lowers the activation energy for charge transport explaining conclusively the improved redox characteristics of the new oxygen carriers developed.

Platform Chemicals via Zeolite‐Catalyzed Fast Pyrolysis of Glucose

Furan derivatives, such as 5‐hydroxymethylfurfural (HMF) and furfural, obtained from renewable feedstocks are sustainable alternatives to petroleum‐based building blocks for the manufacture of chemical products. This study shows for the first time the applicability of the catalytic fast pyrolysis (CFP) of glucose over tailored zeolites for the production of HMF and furfural. In particular, we demonstrate that Lewis‐acid‐containing faujasite zeolites attained by alkali metal–cation exchange exhibit combined yields to these platform molecules of 17 %. Despite the fact that further research is required on the process assessment at a larger scale and under more realistic conditions, CFP has potential for the production of biomass‐derived commodity chemicals.

CaO-Based CO2 Sorbents Effectively Stabilized by Metal Oxides

Calcium looping (i.e., CO2 capture by CaO) is a promising second-generation CO2 capture technology. CaO, derived from naturally occurring limestone, offers an inexpensive solution, but due to the harsh operating conditions of the process, limestone-derived sorbents undergo a rapid capacity decay induced by the sintering of CaCO3 . Here, we report a Pechini method to synthesize cyclically stable, CaO-based CO2 sorbents with a high CO2 uptake capacity. The sorbents synthesized feature compositional homogeneity in combination with a nanostructured and highly porous morphology. The presence of a single (Al2 O3 or Y2 O3 ) or bimetal oxide (Al2 O3 -Y2 O3 ) provides cyclic stability, except for MgO which undergoes a significant increase in its particle size with the cycle number. We also demonstrate a direct relationship between the CO2 uptake and the morphology of the synthesized sorbents. After 30 cycles of calcination and carbonation, the best performing sorbent, containing an equimolar mixture of Al2 O3 and Y2 O3 , exhibits a CO2 uptake capacity of 8.7 mmol CO2  g-1 sorbent, which is approximately 360 % higher than that of the reference limestone.