Reactivation of Limestone-Derived Sorbents using Hydration: Preliminary Results From a Fluidised Bed

A simple method of CO~2~ capture is by using the calcium looping cycle. The calcium looping cycle uses CaCO~3~ as a CO~2~ carrier, via the reversible reaction CaO(s) + CO~2~(g) = CaCO~3~(s), to extract CO2 from the exhaust stream and provide a pure stream of CO~2~ suitable for sequestration. 
A problem associated with the technology is that the capacity of the sorbent to absorb CO~2~ reduces significantly with the number of cycles of carbonation and calcination. The energy penalty of the cycle is considerably increased by cycling unreacted sorbent: hydration of unreactive sorbent has emerged as a promising strategy of reducing this penalty by regenerating the reactivity of exhausted sorbent.
A small atmospheric pressure fluidised bed reactor has been built and tested, that allows repeated cycling between two temperatures up to 1000 °C. 
Work presented here focuses on the effects of variation of the calcination temperature before hydration. Hydration has been found to more than double the reactivity of a spent sorbent cycled under the mildest conditions studied (calcination temperature of 840 °C). However, as calcination temperature is increased the observed reactivation decreases until little reactivation is observed for the sorbent cycled at 950 °C. The primary reason for this appears to be a substantial increase in friability of particles, with reactivity normalised for mass losses appearing similar independent of cycling temperature

A shrinking core model for steam hydration of CaO-based sorbents cycled for CO2 capture

Calcium looping is a developing CO2 capture technology. It is based on the reversible carbonation of CaO sorbent, which becomes less reactive upon cycling. One method of increasing the reactivity of unreactive sorbent is by hydration in the calcined (CaO) form. Here, sorbent has been subjected to repeated cycles of carbonation and calcination within a small fluidised bed reactor. Cycle numbers of 0 (i.e., one calcination), 2, 6 and 13 have been studied to generate sorbents that have been deactivated to different extents. Subsequently, the sorbent generated was subjected to steam hydration tests within a thermogravimetric analyser, using hydration temperatures of 473, 573 and 673 K. Sorbents that had been cycled less prior to hydration hydrated rapidly. However, the more cycled sorbents exhibited behaviour where the hydration conversion tended towards an asymptotic value, which is likely to be associated with pore blockage. This asymptotic value tended to be lower at higher hydration temperatures; however, the maximum rate of hydration was found to increase with increasing hydration temperature. A shrinking core model has been developed and applied to the data. It fits data from experiments that did not exhibit extensive pore blockage well, but fits data from experiments that exhibited pore blockage less well

An overview of advances in biomass gasification

Biomass gasification is a widely used thermochemical process for obtaining products with more value and potential applications than the raw material itself. Cutting-edge, innovative and economical gasification techniques with high efficiencies are a prerequisite for the development of this technology. This paper delivers an assessment on the fundamentals such as feedstock types, the impact of different operating parameters, tar formation and cracking, and modelling approaches for biomass gasification. Furthermore, the authors comparatively discuss various conventional mechanisms for gasification as well as recent advances in biomass gasification. Unique gasifiers along with multi-generation strategies are discussed as a means to promote this technology into alternative applications, which require higher flexibility and greater efficiency. A strategy to improve the feasibility and sustainability of biomass gasification is via technological advancement and the minimization of socio-environmental effects. This paper sheds light on diverse areas of biomass gasification as a potentially sustainable and environmentally friendly technology

Progress in biofuel production from gasification

Biofuels from biomass gasification are reviewed here, and demonstrated to be an attractive option. Recent progress in gasification techniques and key generation pathways for biofuels production, process design and integration and socio-environmental impacts of biofuel generation are discussed, with the goal of investigating gasification-to-biofuels’ credentials as a sustainable and eco-friendly technology. The synthesis of important biofuels such as bio-methanol, bio-ethanol and higher alcohols, bio-dimethyl ether, Fischer Tropsch fuels, bio-methane, bio-hydrogen and algae-based fuels is reviewed, together with recent technologies, catalysts and reactors. Significant thermodynamic studies for each biofuel are also examined. Syngas cleaning is demonstrated to be a critical issue for biofuel production, and innovative pathways such as those employed by Choren Industrietechnik, Germany, and BioMCN, the Netherlands, are shown to allow efficient methanol generation. The conversion of syngas to FT transportation fuels such as gasoline and diesel over Co or Fe catalysts is reviewed and demonstrated to be a promising option for the future of biofuels. Bio-methane has emerged as a lucrative alternative for conventional transportation fuel with all the advantages of natural gas including a dense distribution, trade and supply network. Routes to produce H2 are discussed, though critical issues such as storage, expensive production routes with low efficiencies remain. Algae-based fuels are in the research and development stage, but are shown to have immense potential to become commercially important because of their capability to fix large amounts of CO2, to rapidly grow in many environments and versatile end uses. However, suitable process configurations resulting in optimal plant designs are crucial, so detailed process integration is a powerful tool to optimize current and develop new processes. LCA and ethical issues are also discussed in brief. It is clear that the use of food crops, as opposed to food wastes represents an area fraught with challenges, which must be resolved on a case by case basis

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

Pilot testing of enhanced sorbents for calcium looping with cement production

One of the main challenges for commercialising calcium looping (CaL) as a CO2 capture technology is maintaining a high level of sorbent reactivity during long-term cycling. In order to mitigate the decay in carrying capacity, research has moved towards producing enhanced sorbents. However, this creates potential problems related to ease of scaling up production techniques and production costs, and raises the question as to whether such approaches can be used at large scale. On the other hand, a key advantage of CaL over other carbon capture technologies is synergy with the cement industry, i.e., use of spent sorbent as a feedstock for clinker production. In this work two enhanced materials: (i) limestone doped with HBr through a particle surface impregnation technique; and (ii) pellets prepared from limestone and calcium aluminate cement, were tested in a 25 kWth dual fluidised bed pilot-scale reactor in order to investigate their capture performance and mechanical stability under realistic CaL conditions. Moreover, the spent sorbent was then used as a raw material to make cement, which was characterised for phase and chemical composition as well as compressive strength. The HBr-doped limestone showed better performance in terms of both mechanical strength and stability of the CO2 uptake when compared to that of pellets. Furthermore, it was shown that the cement produced has similar characteristics and performance as those of commercial CEM 1 cement. This indicates the advantages of using the spent sorbent as feedstock for cement manufacture and shows the benefits of synthetic sorbents in CaL and suitability of end-use of spent sorbents for the cement industry, validating their synergy at pilot scale. Finally, this study demonstrates the possibility of using several practical techniques to improve the performance of CaL at the pilot scale, and more importantly demonstrates that commercial-grade cement can be made from the lime product from this technology

High CO2 absorption in new amine based-transition-temperature mixtures (deep eutectic analogues) and reporting thermal stability, viscosity and surface tension: Response surface methodology (RSM)

To study CO2 capture potential, three types of transition-temperature mixtures (TTMs) were prepared by mixing ethyltriphenylphosphonium bromide (MTPPB) as a hydrogen bond acceptor (HBA) and n-methyl diethanolamine (MDEA) as a hydrogen bond donor (HBD) in different molar ratios (1:7, 1:10 and 1:16). Fourier transform infrared spectroscopy (FT-IR) results showed that TTMs have almost similar spectra to their HBD (MDEA) with different levels of transmittance and exhibit similar behavior. From the experimental results, it was found that the thermal stability, viscosity and surface tension of TTMs decreased as the concentration of MDEA in the mixture increased. According to response surface methodology (RSM) models and analysis of variance (ANOVA), temperature and molar ratio had a great effect on the viscosity and surface tension of TTMs. Finally, it was found that CO2 solubility in TTMs (at 303.15 K at pressure up to 1.35 MPa) was enhanced as the MDEA quantity increased in the mixture up to 1:10 mol ratio. However, by increasing MDEA concentration to 16:1 mol ratio, there was a decreasing trend in the CO2 solubility data. Also, all TTMs, particularly TTM containing 10:1 mol MDEA (MTPPB-MDEA 1:10) exhibited an equilibrium loading capacity approaching 1 mol CO2 per mole solvent at high pressure, revealing their high potential for CO2 capture. A comparison showed that the CO2 solubility in the studied solvents was higher than that of existing deep eutectic solvents (DESs) and other TTMs as well as several ionic liquids (ILs) to date. To the best of our knowledge, this is the first study to report the CO2 solubility in phosphonium-base TTMs containing MDE

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: characterizations and DFT analysis

Is it possible to improve CO2 solubility in potassium carbonate (K2CO3)-based transition temperature mixtures (TTMs)? To assess this possibility, a ternary transition-temperature mixture (TTTM) was prepared by using a hindered amine, 2-amino-2-methyl-1,3-propanediol (AMPD). Fourier transform infrared spectroscopy (FT-IR) was employed to detect the functional groups including hydroxyl, amine, carbonate ion, and aliphatic functional groups in the prepared solvents. From thermogravimetric analysis (TGA), it was found that the addition of AMPD to the binary mixture can increase the thermal stability of TTTM. The viscosity findings showed that TTTM has a higher viscosity than TTM while their difference was decreased by increasing temperature. In addition, Eyring’s absolute rate theory was used to compute the activation parameters (∆G*, ∆H*, and ∆S*). The CO2 solubility in liquids was measured at a temperature of 303.15 K and pressures up to 1.8 MPa. The results disclosed that the CO2 solubility of TTTM was improved by the addition of AMPD. At the pressure of about 1.8 MPa, the CO2 mole fractions of TTM and TTTM were 0.1697 and 0.2022, respectively. To confirm the experimental data, density functional theory (DFT) was employed. From the DFT analysis, it was found that the TTTM + CO2 system has higher interaction energy (|∆E|) than the TTM + CO2 system indicating the higher CO2 affinity of the former system. This study might help scientists to better understand and to improve CO2 solubility in these types of solvents by choosing a suitable amine as HBD and finding the best combination of HBA and HBD

Micro-Symposium on Orin Kerr\u27s \u27A Theory of Law\u27

For more than a century, careful readers of the Green Bag have known that “[t]here is nothing sacred in a theory of law...which has outlived its usefulness or which was radically wrong from the beginning...The question is What is the law and what is the true public policy?” Professor Orin Kerr bravely, creatively, and eloquently answered that question in his article, “A Theory of Law,” in the Autumn 2012 issue of the Green Bag. Uniquely among all theories of law that I know of, Kerr’s answer to the fundamental question of law and true public policy enables all scholars to answer that same question in their own ways. The Green Bag is pleased to be featuring his “A Theory of Law” in its first micro-symposium, and just as pleased with the quality, quantity, and diversity of the responses to the call for papers. Blessed with an abundance of good work but cursed by a shortage of space, we were compelled to select a small set – representative and excellent – of those essays to publish in the Green Bag or its sibling publication, the Journal of Law. We regret that we cannot do full justice to the outpouring of first-rate legal-theoretical commentary we received

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