Process design and energy requirements for the capture of carbon dioxide from air

A process to capture carbon dioxide from air to reduce its atmospheric concentration and to mitigate climate change is studied. It is based on the absorption of carbon dioxide in a sodium hydroxide solution, its precipitation as calcium carbonate, and its release as pure gas stream through oxy-fuel calcination. The process utilizes existing commercial technologies wherever possible, particularly in the case of the absorber, whose design is carried out in detail. The analysis allows deriving material and energy balances for the whole process and determining energy demands that can be used for a technical, economical, and environmental feasibility evaluation of the technology. In particular, it indicates that the real specific energy demand is larger than the heat released to emit the same amount of CO₂ by the combustion of coal, and smaller than that of methane.     

The maximum capture efficiency of CO2 using a carbonation/calcination cycle of CaO/CaCO3

The use of natural calcium carbonates as regenerable CO₂ sorbents in industrial processes is limited by the rapid decay of the carbonation conversion with the number of cycles carbonation/calcination. However, new processes are emerging to capture CO₂ using these cycles, that can take advantage of the intrinsic benefits of high temperature separations in energy systems. This work presents an analysis of a general carbonation/calcination cycle to capture CO₂, incorporating a fresh feed of sorbent to compensate for the decay in activity during sorbent re-cycling. A general design equation for the maximum CO₂ capture efficiency is obtained by incorporating to the cycle mass balances a simple but realistic equation to estimate the decay in sorbent activity with the number of cycles.     

Preparation of high surface area CaCO3 by reacting CO2 with aqueous suspensions of Ca(OH)2: Effect of the addition of sodium polyacrylate

High surface area CaCO₃ was produced through the reaction between CO₂ and an aqueous suspension of Ca(OH)₂ with the addition of an additive, sodium polyacrylate. The surface area of CaCO₃ prepared was affected markedly by the amount of additive and the solution pH when adding the additive. The CaCO₃ with the highest surface area (87.7 ± 1.3 m²/g) was obtained under the conditions that the initial Ca(OH)₂ concentration was 2.4 wt.%, the amount of sodium polyacrylate added was 0.2 wt.%, and the solution pH at which the additive was added was in the range of 11.4-11.1. The high surface area CaCO₃ also had a high pore volume. The CaCO₃ was highly reactive toward SO₂, and a conversion of 0.95 was achieved when it was sulfated at 950 °C and 4000 ppm SO₂ in air for 1 min. Prior calcination reduced the reactivity of this high surface area CaCO₃.     

Characteristics of precipitated calcium carbonate by hydrothermal and carbonation processes with mega-crystalline calcite using rotary microwave kiln

In the conventional kiln, mega-crystalline calcite (m-CC) breaks apart easily during calcinations, and cannot be easily converted to CaO due to that it requiring a lot of heat. In this study, m-CC was calcined to CaO of around 1 mm using the rotary microwave kiln. Furthermore, CaCO₃ was produced by the carbonation process and hydrothermal process, and the form of CaCO₃ was characterized.Calcination of m-CC using the rotary microwave kiln resulted in CaO (97 wt%) of relatively fine size.CaCO₃ of colloidal-shaped and 6 μm in size could be prepared by applying the carbonation process to Ca(OH)₂ using a bubble reactor at 25 °C. As the carbonation temperature increased from 25 to 80 °C, the shape of prepared CaCO₃ changed from a colloidal-type to spindle-type of 1 μm due to self-assembly. Also, hexagonal-shaped aragonite could be prepared by the hydrothermal process with the supersaturated Ca(HCO₃)₂ solutions.     

Effect of calcination temperature on colorant behavior of cobalt-aluminate nano-particles synthesized by combustion technique

In this investigation, the normal nano-crystalline cobalt-aluminate spinel has been successfully synthesized by the combustion technique. In order to study the colorant behavior of powders after heat treatment, quantitative and qualitative experiments such as color spectroscopy, X-ray and Raman spectroscopy were applied. Transmission electron microscopy technique was used to estimate the particle size and observe the morphology of pigments. The green powder was identified as an inverse spinel structure whereas a normal spinel corresponding to blue color was produced at higher temperatures. For obtaining powder with the high colorant efficiency, it is better to carry out calcination at 1000 °C.     

Modeling of in-line low-NOx calciners—a parametric study

Simulations with a heterogeneous model of an in-line low-NO_x calciner, based on non-isothermal diffusion-reaction models for char combustion and limestone calcination combined with a kinetic model for NO formation and reduction, are reported. The analysis shows that the most important hydrodynamic parameter is the mixing rate of preheated combustion air into the sub-stoichiometric suspension leaving the reducing zone and the most important combustion parameter is the char reactivity. Also, the calcination rate modifies very much the temperature in the calciner, char and limestone conversion and NO emission. Carbon monoxide is a key component for the reduction of NO and reliable data for the kinetics of NO reduction by CO over CaO are very important for the prediction of the NO emission. The internal surface area of char and limestone particles influences the combustion and calcination rates and thereby the char and limestone conversion and the NO emission.     

Latest developments on application of heterogenous basic catalysts for an efficient and eco friendly synthesis of biodiesel: A review

Heterogeneous catalysts are now being tried extensively for biodiesel synthesis. These catalysts are poised to play an important role and are perspective catalysts in future for biodiesel production at industrial level. The review deals with a comprehensive list of these heterogeneous catalysts which has been reported recently. The mechanisms of these catalysts in the transesterification reaction have been discussed. The conditions for the reaction and optimized parameters along with preparation of the catalyst, and their leaching aspects are discussed. The heterogeneous basic catalyst discussed in the review includes oxides of magnesium and calcium; hydrotalcite/layered double hydroxide; alumina; and zeolites. Yield and conversion of biodiesel obtained from the triglycerides with various heterogeneous catalysts have been studied.     

An apparent kinetic model for the carbonation of calcium oxide by carbon dioxide

For the apparent kinetics of the carbonation reaction of calcium oxide by carbon dioxide, as a kind of noncatalytic gas–solid reaction, a model equation has been proposed as follows: X=kbt/(b+t), where X is the conversion of CaO; k, a kinetic rate constant (time⁻¹); b, a constant (time) equivalent to the time taken to attain half the ultimate conversion of CaO, and t, the time. As a result of analyses for some literature-reported data of CaO-carbonation conversion, it has been found that the rate of the carbonation can be well represented by dX/dt=k(1−X/X_u)², where X_u is the ultimate conversion of CaO, which is given by the product of two parametric constants, k and b. The constants k and b in the two rate control regimes of CaO-carbonation, chemical reaction control and diffusion control, have been determined as functions of temperature, respectively. The activation energy in the carbonation of surface CaO with CO₂ is estimated to about 72 kJ/mol regardless of the sources of CaO, however, that in the diffusion control regime appears differently as 102.5 (mesoporous CaO) or 189.3 kJ/mol (commercial-available CaO), possibly due to the morphological differences of the two CaO samples. From a practical point of view, the simple model equation proposed in this study deserves attention in that the CaO-carbonation behavior at working temperatures higher than 700 °C could be closely predicted.     

CO2 uptake of modified calcium-based sorbents in a pressurized carbonation-calcination looping

This study focuses on enhancing CO₂ uptake by modifying limestone with acetate solutions under pressurized carbonation condition. The multicycle tests were carried out in an atmospheric calcination/pressurized carbonation reactor system at different temperatures and pressures. The pore structure characteristics (BET and BJH) were measured as a supplement to the reaction studies. Compared with the raw limestone, the modified sorbent showed a great improvement in CO₂ uptake at the same reaction condition. The highest CO₂ uptake was obtained at 700 °C and 0.5 MPa, by 88.5% increase over the limestone at 0.1 MPa after 10 cycles. The structure characteristics of the sorbents on N₂ absorption and SEM confirm that compared with the modified sorbent, the effective pores of limestone are greatly driven off by sintering, which hinders the easy access of CO₂ molecules to the unreacted-active sites of CaO. The morphological and structural properties of the modified sorbent did not reveal significant differences after multiple cycles. This would explain its superior performance of CO₂ uptake under pressurized carbonation. Even after 10 cycles, the modified sorbent still achieved a CO₂ uptake of 0.88.     

Cyclic calcination/carbonation looping of dolomite modified with acetic acid for CO2 capture

The dolomite modified with acetic acid solution was proposed as a CO₂ sorbent for calcination/carbonation cycles. The carbonation conversions for modified and original dolomites in a twin fixed-bed reactor system with increasing the numbers of cycles were investigated. The carbonation temperature in the range of 630 °C–700 °C is beneficial to the carbonation reaction of modified dolomite. The carbonation conversion for modified dolomite is significantly higher than that for original sorbent at the same reaction conditions with increasing numbers of reaction cycles. The modified dolomite exhibits a carbonation conversion of 0.6 after 20 cycles, while the unmodified sorbent shows a conversion of 0.26 at the same reaction conditions, which is calcined at 920 °C and carbonated at 650 °C. At the high calcination temperature over 920 °C modified dolomite can maintain much higher conversion than unmodified sorbent. The mean grain size of CaO derived from modified dolomite is smaller than that from original sorbent with increasing numbers of reaction cycles. The calcined modified dolomite possesses greater surface area and pore volume than calcined original sorbent during the multiple cycles. The pore volume and pore area distributions for calcined modified dolomite are also superior to those for calcined unmodified sorbent during the looping cycle. The modified dolomite is proved as a new and promising type of regenerable CO₂ sorbent for industrial applications.     

Degradation of concrete by flue gases from coal combustion

The effect of flue gases from coal combustion on the concrete shell of a power plant stack was analyzed and the damage to the concrete was evaluated. The compressive and tensile strengths of concrete were determined by rebound hammer test and pull-off test on the site. Samples of concrete taken from various zones of the stack shell were analyzed in detail. The examination techniques used included chemical analysis, water suspension analyses, XRD, thermal analysis, SEM and EDS. It was found that the flue gases and the acid condensate, acted very aggressively at an elevated temperature and caused severe degradation of the inside surface zone of the concrete shell. The binding material in this zone was converted into sulfur-bearing compounds. Gypsum was identified as the dominant compound in the degraded zone of concrete in the upper parts, while anhydrite in the lower parts of the stack. Carbonated zone was located below the clearly delimitated sulfated zone of the concrete. The aggressive environment in the stack did not affect the internal zones in the concrete.     

Nanostructured Ca-based sorbents with high CO2 uptake efficiency

Calcium-based carbon dioxide sorbents were made in the gas phase by scalable flame spray pyrolysis (FSP) and compared to the ones made by calcination (CAL) of selected calcium precursors. Such flame-made sorbents consisted of nanostructured CaO and CaCO₃ with twice as much specific surface area (40-60 m²/g) as the CAL-made sorbents. All FSP-made sorbents exhibited faster and higher CO₂ uptake capacity than all CAL-made sorbents at intermediate temperatures. CAL of calcium acetate monohydrate resulted in sorbents with the best CO₂ uptake among all CAL-made ones. At higher temperatures both FSP- and CAL-made sorbents (esp. from CaAc₂·H₂O) exhibited very high initial molar conversions (95%) but sintering contributed to grain growth that reduced the molar conversion down to 50%. In multiple carbonation/decarbonation cycles, the nanostructured FSP-made sorbents demonstrated stable, reversible and high CO₂ uptake capacity sustaining maximum molar conversion at about 50% even after 60 such cycles, indicating high potential for CO₂ uptake. The top performance of flame-made sorbents is best attributed to their nanostructure (30-50 nm grain size) that allows operation in the reaction-controlled carbonation regime rather than in the diffusion-controlled one when sorbents made with larger particles are employed.     

二氧化碳催化还原成碳的进展

介绍了二氧化碳催化还原成碳的最新研究成果和发展趋势，以及它的基本反应原理和应用，并对这方面的开发研究提出了建议。