Hydrotalcite-Derived Copper-Based Oxygen Carrier Materials for Efficient Chemical-Looping Combustion of Solid Fuels with CO2 Capture.

Chemical-looping combustion (CLC) is a promising technology that utilizes metal oxides as oxygen carriers for the combustion of fossil fuels to CO2 and H2O, with CO2 readily sequestrated after the condensation of steam. Thermally stable and reactive metal oxides are desirable as oxygen carrier materials for the CLC processes. Here, we report the performance of Cu-based mixed oxides derived from hydrotalcite (also known as layered double hydroxides) precursors as oxygen carriers for the combustion of solid fuels. Two types of CLC processes were demonstrated, including chemical looping oxygen uncoupling (CLOU) and in situ gasification (iG-CLC) in the presence of steam. The Cu-based oxygen carriers showed high performance for the combustion of two solid fuels (a lignite and a bituminous coal), maintaining high thermal stability, fast reaction kinetics, and reversible oxygen release and storage over multiple redox cycles. Slight deactivation and sintering of the oxygen carrier occurred after redox cycles at an very high operation temperature of 985 °C. We expect that our material design strategy will inspire the development of better oxygen carrier materials for a variety of chemical looping processes for the clean conversion of fossil fuels with efficient CO2 capture.

Precursor engineering of hydrotalcite-derived redox sorbents for reversible and stable thermochemical oxygen storage.

Chemical looping processes based on multiple-step reduction and oxidation of metal oxides hold great promise for a variety of energy applications, such as CO2 capture and conversion, gas separation, energy storage, and redox catalytic processes. Copper-based mixed oxides are one of the most promising candidate materials with a high oxygen storage capacity. However, the structural deterioration and sintering at high temperatures is one key scientific challenge. Herein, we report a precursor engineering approach to prepare durable copper-based redox sorbents for use in thermochemical looping processes for combustion and gas purification. Calcination of the CuMgAl hydrotalcite precursors formed mixed metal oxides consisting of CuO nanoparticles dispersed in the Mg-Al oxide support which inhibited the formation of copper aluminates during redox cycling. The copper-based redox sorbents demonstrated enhanced reaction rates, stable O2 storage capacity over 500 redox cycles at 900 °C, and efficient gas purification over a broad temperature range. We expect that our materials design strategy has broad implications on synthesis and engineering of mixed metal oxides for a range of thermochemical processes and redox catalytic applications.

Modeling and Evaluation of Ash-Forming Element Fate and Occurrence in Woody Biomass Combustion in an Entrained-Flow Burner.

Biomass combustion equipment is often susceptible to ash deposition due to the relatively significant quantities of potassium, silicon, and other ash-forming elements in biomass. To evaluate the propensity for ash deposition resulting from biomass combustion, a biomass combustion model was integrated with a chemical equilibrium model to predict the fate and occurrence of ash-forming elements in a pilot-scale entrained-flow burner. The integrated model simulated the combustion of white wood (virgin wood) and recycled wood (treated wood) previously combusted in the burner. The key advantage of this model in comparison to a model with general equilibrium assumed is that it was able to consider the rate of release of trace and minor species with time, the local equilibrium in the particles, and separately, that in the continuum phase (which also included any solid or liquid materials nucleating). The simulation generated the fate and occurrence profiles of each ash-forming element along the burner. The qualitative comparisons between the modeled profiles and the previous experimental findings under similar operating conditions show reasonable agreement. The concentrations of ash-forming elements released from the burner were also compared with the experimental online inductively coupled plasma readings. However, the latter comparison shows overestimation using the modeled results and might suggest that further considerations of other parameters such as ash nucleation and coagulation are required. Nonetheless, based on the ongoing performance of the integrated model, future use of the model might be expanded to a broader range of problematic solid fuels such as herbaceous biomass or municipal solid waste.

Process intensification of the ionoSolv pretreatment: effects of biomass loading, particle size and scale-up from 10 mL to 1 L.

The ionoSolv process is one of the most promising technologies for biomass pretreatment in a biorefinery context. In order to evaluate the transition of the ionoSolv pretreatment of biomass from bench-scale experiments to commercial scale, there is a need to get better insight in process intensification. In this work, the effects of biomass loading, particle size, pulp washing protocols and 100-fold scale up for the pretreatment of the grassy biomass Miscanthus giganteus with the IL triethylammonium hydrogen sulfate, [TEA][HSO4], are presented as a necessary step in that direction. At the bench scale, increasing biomass loading from 10 to 50 wt% reduced glucose yields from 68 to 23% due to re-precipitation of lignin onto the pulp surface. Omitting the pulp air-drying step maintained saccharification yields at 66% at 50 wt% loading due to reduced fiber hornification. 100-fold scale-up (from 10 mL to 1 L) improved the efficacy of ionoSolv pretreatment and increasing loadings from 10 to 20 wt% reduced lignin reprecipitation and led to higher glucose yields due to the improved heat and mass transfer caused by efficient slurry mixing in the reactor. Pretreatment of particle sizes of 1-3 mm was more effective than fine powders (0.18-0.85 mm) giving higher glucose yields due to reduced surface area available for lignin re-precipitation while reducing grinding energy needs. Stirred ionoSolv pretreatment showed great potential for industrialization and further process intensification after optimization of the pretreatment conditions (temperature, residence time, stirring speed), particle size and biomass loading. Pulp washing protocols need further improvement to reduce the incidence of lignin precipitation and the water requirements of lignin washing.

Demetallization of Sewage Sludge Using Low-Cost Ionic Liquids.

Sludge produced from wastewater treatment has little to no value and is typically treated through volume reduction techniques, such as dewatering, thickening, or digestion. However, these methods inherently increase heavy metal concentrations, which makes the sludge unsuitable for land spreading and difficult to dispose of, owing to strict legal requirements/regulations concerning these metals. We addressed this problem, for the first time, by using recyclable low-cost protic ionic liquids to complex these toxic metals through a chemical fractionation process. Sewage sludge samples collected from wastewater plants in the UK were heated with methylimidazolium chloride ([Hmim]Cl, triethylammonium hydrogen sulfate ([TEA][HSO4]) and dimethylbutylammonium hydrogen sulfate ([DMBA][HSO4]) under various operating temperatures, times and solids loadings to separate the sludge from its metal contaminants. Analysis of the residual solid product and metal-rich ionic liquid liquor using inductively coupled plasma-emission spectrometry showed that [Hmim]Cl extracted >90% of CdII, NiII, ZnII, and PbII without altering the phosphorus content, while other toxic metals such as CrIII, CrVI and AsIII were more readily removed (>80%) with [TEA][HSO4]. We test the recyclability of [Hmim]Cl, showing insignificant efficiency losses over 6 cycles and discuss the possibilities of using electrochemical deposition to prevent the buildup of metal in the IL. This approach opens up new avenues for sewage sludge valorization, including potential applications in emulsion fuels or fertilizer development, accessed by techno-economic analysis.

Rhododendron and Japanese Knotweed: invasive species as innovative crops for second generation biofuels for the ionoSolv process.

We investigated the potential of two terrestrial biomass invasive species in the United-Kingdom as lignocellulosic biofuel feedstocks: Japanese Knotweed (Fallopia japonica) and Rhododendron (Rhododendron ponticum). We demonstrate that a pretreatment technique using a low-cost protic ionic liquid, the ionoSolv process, can be used for such types of plant species considered as waste, to allow their integration into a biorefinery. N,N,N-Dimethylbutylammonium hydrogen sulfate ([DMBA][HSO4]) was able to fractionate the biomass into a cellulose-rich pulp and a lignin stream at high temperatures (150-170 °C) and short reaction times (15-60 minutes). More than 70-80% of the subsequent cellulose was hydrolysed into fermentable sugars, which were fermented into the renewable energy vector bioethanol.

Efficient Fractionation of Lignin- and Ash-Rich Agricultural Residues Following Treatment With a Low-Cost Protic Ionic Liquid.

Agricultural residues from rice, wheat and sugarcane production are annually available at the gigaton-scale worldwide, particularly in Asia. Due to their high sugar content and ash compositions, their conversion to bioethanol is an attractive alternative to their present disposal by open-field burning and landfilling. In this work, we demonstrate application of the low-cost protic ionic liquid triethylammonium hydrogen sulfate ([TEA][HSO4]) for pretreatment of rice straw, rice husk, wheat straw and sugarcane bagasse. The feedstocks had high ash (up to 13 wt%) and lignin content (up to 28 wt%). Pretreatment effectiveness was examined at 150 and 170°C and an optimal pretreatment time was identified and characterized by glucose release following enzymatic saccharification (i.e., hydrolysis), biomass delignification observed by compositional analysis, and lignin recovery. The isolated lignin fractions were analyzed by 2D HSQC NMR to obtain insights into the structural changes occurring following ionic liquid pretreatment. After treatment at 170°C for 30-45 min, enzymatic hydrolysis of three agroresidues gave near-quantitative glucose yields approaching 90% while rice husk gave 73% yield. Glucose release from the pulps was enhanced by saccharifying wet pulps without an air-drying step to reduce hornification. According to pulp compositional analysis, up to 82% of lignin was removed from biomass during pretreatment, producing highly digestible cellulose-rich pulps. HSQC NMR of the extracted lignins showed that delignification proceeded via extensive cleavage of ß-O-4' aryl ether linkages which was accompanied by condensation reactions in the isolated lignins. The high saccharification yields obtained indicate excellent potential for valorization of low-cost agroresidues in large volumes, which is promising for commercialization of biofuels production using the ionoSolv pretreatment technology.

Pretreatment of South African sugarcane bagasse using a low-cost protic ionic liquid: a comparison of whole, depithed, fibrous and pith bagasse fractions.

BACKGROUND: Sugarcane bagasse is an abundant and geographically widespread agro-industrial residue with high carbohydrate content, making it a strong candidate feedstock for the bio-based economy. This study examines the use of the low-cost protic ionic liquid triethylammonium hydrogen sulfate ([TEA][HSO4]) to fractionate a range of South African sugarcane bagasse preparations into a cellulose-rich pulp and lignin. The study seeks to optimize pretreatment conditions and examine the necessity of applying a depithing step on bagasse prior to pretreatment. RESULTS: Pretreatment of five bagasse preparations, namely whole, industrially depithed, laboratory depithed (short and long fiber) and pith bagasse with [TEA][HSO4]:[H2O] (4:1 w/w) solutions produced highly digestible cellulose-rich pulps, as assessed by residual lignin analysis and enzymatic hydrolysis. Pretreatment under the optimized condition of 120 °C for 4 h produced a pretreated cellulose pulp with up to 90% of the lignin removed and enabled the release of up to 69% glucose contained in the bagasse via enzymatic hydrolysis. Glucose yields from whole and depithed bagasse preparations were very similar. Significant differences in lignin recovery were obtained for laboratory depithed bagasse compared with whole and industrially depithed bagasse. The silica-rich ash components of bagasse were seen to partition mainly with the pulp, from where they could be easily recovered in the post-hydrolysis solids. CONCLUSIONS: The five bagasse preparations were compared but did not show substantial differences in composition or cellulose digestibility after pretreatment. Evidence was presented that a depithing step appears to be unnecessary prior to ionoSolv fractionation, potentially affording significant cost and energy savings. Instead, lignin re-deposition onto the pulp surface (and, in turn, particle size and shape) appeared to be major factors affecting the conditioning of bagasse with the applied IL. We show that pith bagasse, a common by-product of paper making, can be successfully conditioned for high glucose release while allowing recovery of lignin and silica-rich ash. The glucose yields obtained for bagasse using [TEA][HSO4]-water mixtures were ~ 75% as high as for conventional aprotic ionic liquids such as [Emim][OAc]; this result is highly promising for commercialization of ionoSolv processing given [TEA][HSO4] is 40 times less expensive, thermally stable and recyclable.

Net-zero emissions energy systems.

Some energy services and industrial processes-such as long-distance freight transport, air travel, highly reliable electricity, and steel and cement manufacturing-are particularly difficult to provide without adding carbon dioxide (CO2) to the atmosphere. Rapidly growing demand for these services, combined with long lead times for technology development and long lifetimes of energy infrastructure, make decarbonization of these services both essential and urgent. We examine barriers and opportunities associated with these difficult-to-decarbonize services and processes, including possible technological solutions and research and development priorities. A range of existing technologies could meet future demands for these services and processes without net addition of CO2 to the atmosphere, but their use may depend on a combination of cost reductions via research and innovation, as well as coordinated deployment and integration of operations across currently discrete energy industries.

Hydrogen Production by Sorption Enhanced Steam Reforming (SESR) of Biomass in a Fluidised-Bed Reactor Using Combined Multifunctional Particles.

The performance of combined CO2-sorbent/catalyst particles for sorption enhanced steam reforming (SESR), prepared via a simple mechanical mixing protocol, was studied using a spout-fluidised bed reactor capable of continuous solid fuel (biomass) feeding. The influence of particle size (300⁻500 and 710⁻1000 µm), CaO loading (60⁻100 wt %), Ni-loading (10⁻40 wt %) and presence of dicalcium silicate support (22.6 wt %) on SESR process performance were investigated. The combined particles were characterised by their density, porosity and CO2 carrying capacity with the analysis by thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH) and mercury intrusion porosimetry (MIP). All experiments were conducted with continuous oak biomass feeding at a rate of 0.9 g/min ± 10%, and the reactor was operated at 660 ± 5 °C, 1 atm and 20 ± 2 vol % steam which corresponds to a steam-to-carbon ratio of 1.2:1. Unsupported combined particles containing 21.0 wt % Ni and 79 wt % CaO were the best performing sorbent/catalyst particle screened in this study, when accounting for the cost of Ni and the improvement in H2 produced by high Ni content particles. SESR tests with these combined particles produced 61 mmol H2/gbiomass (122 g H2/kgbiomass) at a purity of 61 vol %. Significant coke formation within the feeding tube and on the surfaces of the particles was observed which was attributed to the low steam to carbon ratio utilised.

Impact of Flue Gas Compounds on Microalgae and Mechanisms for Carbon Assimilation and Utilization.

To shift the world to a more sustainable future, it is necessary to phase out the use of fossil fuels and focus on the development of low-carbon alternatives. However, this transition has been slow, so there is still a large dependence on fossil-derived power, and therefore, carbon dioxide is released continuously. Owing to the potential for assimilating and utilizing carbon dioxide to generate carbon-neutral products, such as biodiesel, the application of microalgae technology to capture CO2 from flue gases has gained significant attention over the past decade. Microalgae offer a more sustainable source of biomass, which can be converted into energy, over conventional fuel crops because they grow more quickly and do not adversely affect the food supply. This review focuses on the technical feasibility of combined carbon fixation and microalgae cultivation for carbon reuse. A range of different carbon metabolisms and the impact of flue gas compounds on microalgae are appraised. Fixation of flue gas carbon dioxide is dependent on the selected microalgae strain and on flue gas compounds/concentrations. Additionally, current pilot-scale demonstrations of microalgae technology for carbon dioxide capture are assessed and its future prospects are discussed. Practical implementation of this technology at an industrial scale still requires significant research, which necessitates multidisciplinary research and development to demonstrate its viability for carbon dioxide capture from flue gases at the commercial level.

Phase evolution, characterisation, and performance of cement prepared in an oxy-fuel atmosphere.

Cement manufacture is one of the major contributors (7-10%) to global anthropogenic CO2 emissions. Carbon capture and storage (CCS) has been identified as a vital technology for decarbonising the sector. Oxy-fuel combustion, involving burning fuel in a mixture of recycled CO2 and pure O2 instead of air, makes CO2 capture much easier. Since it combines a theoretically lower energy penalty with an increase in production, it is attractive as a CCS technology in cement plants. However, it is necessary to demonstrate that changes in the clinkering atmosphere do not reduce the quality of the clinker produced. Clinkers were successfully produced in an oxy-fuel atmosphere using only pure oxides as raw materials as well as a mixture of oxides and clay. Then, CEM I cements were prepared by the addition of 5 wt% gypsum to the clinkers. Quantitative XRD and XRF were used to obtain the phase and elemental compositions of the clinkers. The particle size distribution and compressive strength of the cements at 3, 7, 14, and 28 days' ages were tested, and the effect of the particle size distribution on the compressive strength was investigated. Additionally, the compressive strength of the cements produced in oxy-fuel atmospheres was compared with those of the cement produced in air and commercially available CEMEX CEM I. The results show that good-quality cement can be successfully produced in an oxy-fuel atmosphere and it has similar phase and chemical compositions to CEM I. Additionally, it has a comparable compressive strength to the cement produced in air and to commercially available CEMEX CEM I.

Carbon Capture in the Cement Industry: Technologies, Progress, and Retrofitting.

Several different carbon-capture technologies have been proposed for use in the cement industry. This paper reviews their attributes, the progress that has been made toward their commercialization, and the major challenges facing their retrofitting to existing cement plants. A technology readiness level (TRL) scale for carbon capture in the cement industry is developed. For application at cement plants, partial oxy-fuel combustion, amine scrubbing, and calcium looping are the most developed (TRL 6 being the pilot system demonstrated in relevant environment), followed by direct capture (TRL 4-5 being the component and system validation at lab-scale in a relevant environment) and full oxy-fuel combustion (TRL 4 being the component and system validation at lab-scale in a lab environment). Our review suggests that advancing to TRL 7 (demonstration in plant environment) seems to be a challenge for the industry, representing a major step up from TRL 6. The important attributes that a cement plant must have to be "carbon-capture ready" for each capture technology selection is evaluated. Common requirements are space around the preheater and precalciner section, access to CO2 transport infrastructure, and a retrofittable preheater tower. Evidence from the electricity generation sector suggests that carbon capture readiness is not always cost-effective. The similar durations of cement-plant renovation and capture-plant construction suggests that synchronizing these two actions may save considerable time and money.

Comparative Assessment of Gasification Based Coal Power Plants with Various CO2 Capture Technologies Producing Electricity and Hydrogen.

Seven different types of gasification-based coal conversion processes for producing mainly electricity and in some cases hydrogen (H2), with and without carbon dioxide (CO2) capture, were compared on a consistent basis through simulation studies. The flowsheet for each process was developed in a chemical process simulation tool "Aspen Plus". The pressure swing adsorption (PSA), physical absorption (Selexol), and chemical looping combustion (CLC) technologies were separately analyzed for processes with CO2 capture. The performances of the above three capture technologies were compared with respect to energetic and exergetic efficiencies, and the level of CO2 emission. The effect of air separation unit (ASU) and gas turbine (GT) integration on the power output of all the CO2 capture cases is assessed. Sensitivity analysis was carried out for the CLC process (electricity-only case) to examine the effect of temperature and water-cooling of the air reactor on the overall efficiency of the process. The results show that, when only electricity production in considered, the case using CLC technology has an electrical efficiency 1.3% and 2.3% higher than the PSA and Selexol based cases, respectively. The CLC based process achieves an overall CO2 capture efficiency of 99.9% in contrast to 89.9% for PSA and 93.5% for Selexol based processes. The overall efficiency of the CLC case for combined electricity and H2 production is marginally higher (by 0.3%) than Selexol and lower (by 0.6%) than PSA cases. The integration between the ASU and GT units benefits all three technologies in terms of electrical efficiency. Furthermore, our results suggest that it is favorable to operate the air reactor of the CLC process at higher temperatures with excess air supply in order to achieve higher power efficiency.

Comparison of the structural motifs and packing arrangements of six novel derivatives and one polymorph of 2-(1-phenyl-1H-1,2,3-triazol-4-yl)pyridine.

The crystal structures of a new polymorph and seven new derivatives of 2-(1-phenyl-1H-1,2,3-triazol-4-yl)pyridine have been characterized and examined along with three structures from the literature to identify trends in their intermolecular contact patterns and packing arrangements in order to develop an insight into the crystallization behaviour of this class of compound. Seven unique C-H···X contacts were identified in the structures and three of these are present in four or more structures, indicating that these are reliable supramolecular synthons. Analysis of the packing arrangements of the molecules using XPac identified two closely related supramolecular constructs that are present in eight of the 11 structures; in all cases, the structures feature at least one of the three most common intermolecular contacts, suggesting a clear relationship between the intermolecular contacts and the packing arrangements of the structures. Both the intermolecular contacts and packing arrangements appear to be remarkably consistent between structures featuring different functional groups, with the expected exception of the carboxylic acid derivative 4-(4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl) benzoic acid (L11), where the introduction of a strong hydrogen-bonding group results in a markedly different supramolecular structure being adopted. The occurrence of these structural features has been compared with the packing efficiency of the structures and their melting points in order to assess the relative favourability of the supramolecular structural features in stabilizing the crystal structures.