Managed pathways for CO2 mineralisation: analogy with nature and potential contribution to CCUS-led reduction targets.

The managed mineralisation of CO2 on mineral substrates has significant potential to mitigate CO2 emissions to atmosphere, using processes that are analogous to the formation of limestone in nature. High-temperatures and pressures or ambient conditions can be applied in processes that compare with the natural chemical, hydrothermal or biological formation of limestone. In the UK, recent policy developments recognise the potential of carbon utilisation and a reduction target of 40 Mt by 2030 has been set. In the present work, the analogies between natural and managed carbonate-production are briefly reviewed and the potential gains for mineralisation technology employing flue-gas as a direct source of CO2 are presented. With reference to selected UK solid waste arisings, our high-level analysis indicates mineralisation is capable of permanently sequestrating 1.2 Mt per year of CO2 in carbonated construction products. At a European level, nearly 7.8 Mt of CO2 can be managed in the same way. If indicative indirect CO2 savings are also considered, maximum total CO2 reductions of up to 3 and 30 Mt per year are possible in the UK and Europe, respectively. In respect of the UK's CCUS-led CO2 reductions for the 8 years to 2030, our high-level assessment suggests that up to 24 Mt, representing 60% of the 'target', may be met by the mineralisation of selected industrial process residues.

Valorisation of agricultural biomass-ash with CO2.

This work is part of a study of different types of plant-based biomass to elucidate their capacity for valorisation via a managed carbonation step involving gaseous carbon dioxide (CO2). The perspectives for broader biomass waste valorisation was reviewed, followed by a proposed closed-loop process for the valorisation of wood in earlier works. The present work newly focusses on combining agricultural biomass with mineralised CO2. Here, the reactivity of selected agricultural biomass ashes with CO2 and their ability to be bound by mineralised carbonate in a hardened product is examined. Three categories of agricultural biomass residues, including shell, fibre and soft peel, were incinerated at 900 ± 25 °C. The biomass ashes were moistened (10% w/w) and moulded into cylindrical samples and exposed to 100% CO2 gas at 50% RH for 24 h, during which they cemented into hardened monolithic products. The calcia in ashes formed a negative relationship with ash yield and the microstructure of the carbonate-cementing phase was distinct and related to the particular biomass feedstock. This work shows that in common with woody biomass residues, carbonated agricultural biomass ash-based monoliths have potential as novel low-carbon construction products.

Offsetting anthropogenic carbon emissions from biomass waste and mineralised carbon dioxide.

The present work investigates biomass wastes and their ashes for re-use in combination with mineralised CO2 in cement-bound construction products. A range of biomass residues (e.g., wood-derived, nut shells, fibres, and fruit peels) sourced in India, Africa and the UK were ashed and exposed to CO2 gas. These CO2-reactive ashes could mineralise CO2 gas and be used to cement 'raw' biomass in solid carbonated monolithic composites. The CO2 sequestered in ashes (125-414 g CO2/kg) and that emitted after incineration (400-500 g CO2/kg) was within the same range (w/w). The CO2-reactive ashes embodied significant amounts of CO2 (147-424 g equivalent CO2/kg ash). Selected ashes were combined with raw biomass and Portland Cement, CEM 1 and exposed to CO2. The use of CEM 1 in the carbonated products was offset by the CO2 mineralised (i.e. samples were 'carbon negative', even when 10% w/w CEM 1 was used); furthermore, biomass ashes were a suitable substitute for CEM 1 up to 50% w/w. The approach is conceptually simple, scalable, and can be applicable to a wide range of biomass ashes in a closed 'emission-capture' process 'loop'. An extrapolation of potential for CO2 offset in Europe provides an estimate of CO2 sequestration potential to 2030.

Enhancement of accelerated carbonation of alkaline waste residues by ultrasound.

The continuous growth of anthropogenic CO2 emissions into the atmosphere and the disposal of hazardous wastes into landfills present serious economic and environmental issues. Reaction of CO2 with alkaline residues or cementitius materials, known as accelerated carbonation, occurs rapidly under ambient temperature and pressure and is a proven and effective process of sequestering the gas. Moreover, further improvement of the reaction efficiency would increase the amount of CO2 that could be permanently sequestered into solid products. This paper examines the potential of enhancing the accelerated carbonation of air pollution control residues, cement bypass dust and ladle slag by applying ultrasound at various water-to-solid (w/s) ratios. Experimental results showed that application of ultrasound increased the CO2 uptake by up to four times at high w/s ratios, whereas the reactivity at low water content showed little change compared with controls. Upon sonication, the particle size of the waste residues decreased and the amount of calcite precipitates increased. Finally, the sonicated particles exhibited a rounded morphology when observed by scanning electron microscopy.

Synergy between surface adsorption and photocatalysis during degradation of humic acid on TiO2/activated carbon composites.

A photocatalyst comprising nano-sized TiO(2) particles on granular activated carbon (GAC) was prepared by a sol-dipping-gel process. The TiO(2)/GAC composite was characterized by scanning electron microscopy (SEM), X-ray diffractiometry (XRD) and nitrogen sorptometry, and its photocatalytic activity was studied through the degradation of humic acid (HA) in a quartz glass reactor. The factors influencing photocatalysis were investigated and the GAC was found to be an ideal substrate for nano-sized TiO(2) immobilization. A 99.5% removal efficiency for HA from solution was achieved at an initial concentration of 15 mg/L in a period of 3h. It was found that degradation of HA on the TiO(2)/GAC composite was facilitated by the synergistic relationship between surface adsorption characteristics and photocatalytic potential. The fitting of experimental results with the Langmuir-Hinshelwood (L-H) model showed that the reaction rate constant and the adsorption constant values were 0.1124 mg/(L min) and 0.3402 L/mg. The latter is 1.7 times of the calculated value by fitting the adsorption equilibrium data into the Langmuir equation.

Long-term performance of aged waste forms treated by stabilization/solidification.

Current regulatory testing of stabilized/solidified (S/S) soils is based on short-term performance tests and is insufficient to determine their long-term stability or expected service life. In view of this, and the significant lack of data on long-term field performance in the literature, S/S material has been extracted from full-scale remedial operations and examined using a variety of analytical techniques to evaluate field performance. The results, including those from X-ray analytical techniques, optical and electron microscopy and leaching tests are presented and discussed. The microstructure of retrieved samples was found to be analogous to other cement-based materials, but varied according to the soil type, the contaminants present, the treatment applied and the field exposure conditions. Summary of the key microstructural features in the USA and UK is presented in this work. The work has shown that during 16 years of service the S/S wastes investigated performed satisfactorily.

Accelerated carbonation treatment of industrial wastes.

The disposal of industrial waste presents major logistical, financial and environmental issues. Technologies that can reduce the hazardous properties of wastes are urgently required. In the present work, a number of industrial wastes arising from the cement, metallurgical, paper, waste disposal and energy industries were treated with accelerated carbonation. In this process carbonation was effected by exposing the waste to pure carbon dioxide gas. The paper and cement wastes chemically combined with up to 25% by weight of gas. The reactivity of the wastes to carbon dioxide was controlled by their constituent minerals, and not by their elemental composition, as previously postulated. Similarly, microstructural alteration upon carbonation was primarily influenced by mineralogy. Many of the thermal wastes tested were classified as hazardous, based upon regulated metal content and pH. Treatment by accelerated carbonation reduced the leaching of certain metals, aiding the disposal of many as stable non-reactive wastes. Significant volumes of carbon dioxide were sequestrated into the accelerated carbonated treated wastes.

Production of lightweight aggregate from industrial waste and carbon dioxide.

The concomitant recycling of waste and carbon dioxide emissions is the subject of developing technology designed to close the industrial process loop and facilitate the bulk-re-use of waste in, for example, construction. The present work discusses a treatment step that employs accelerated carbonation to convert gaseous carbon dioxide into solid calcium carbonate through a reaction with industrial thermal residues. Treatment by accelerated carbonation enabled a synthetic aggregate to be made from thermal residues and waste quarry fines. The aggregates produced had a bulk density below 1000 kg/m(3) and a high water absorption capacity. Aggregate crushing strengths were between 30% and 90% stronger than the proprietary lightweight expanded clay aggregate available in the UK. Cast concrete blocks containing the carbonated aggregate achieve compressive strengths of 24 MPa, making them suitable for use with concrete exposed to non-aggressive service environments. The energy intensive firing and sintering processes traditionally required to produce lightweight aggregates can now be augmented by a cold-bonding, low energy method that contributes to the reduction of green house gases to the atmosphere.

Precipitation of heavy metals from wastewater using simulated flue gas: sequent additions of fly ash, lime and carbon dioxide.

Lime is a preferred precipitant for the removal of heavy metals from industrial wastewater due to its relatively low cost. To reduce heavy metal concentration to an acceptable level for discharge, in this work, fly ash was added as a seed material to enhance lime precipitation and the suspension was exposed to CO2 gas. The fly ash-lime-carbonation treatment increased the particle size of the precipitate and significantly improved sedimentation of sludge and the efficiency of heavy metal removal. The residual concentrations of chromium, copper, lead and zinc in effluents can be reduced to (mg L(-1)) 0.08, 0.14, 0.03 and 0.45, respectively. Examination of the precipitates by XRD and thermal analysis techniques showed that calcium-heavy metal double hydroxides and carbonates were present. The precipitate agglomerated and hardened naturally, facilitating disposal without the need for additional solidification/stabilization measures prior to landfill. It is suggested that fly ash, lime and CO2, captured directly from flue gas, may have potential as a method for wastewater treatment. This method could allow the ex-situ sequestration of CO2, particularly where flue-gas derived CO2 is available near wastewater treatment facilities.

Application of accelerated carbonation with a combination of Na2CO3 and CO2 in cement-based solidification/stabilization of heavy metal-bearing sediment.

The efficient remediation of heavy metal-bearing sediment has been one of top priorities of ecosystem protection. Cement-based solidification/stabilization (s/s) is an option for reducing the mobility of heavy metals in the sediment and the subsequent hazard for human beings and animals. This work uses sodium carbonate as an internal carbon source of accelerated carbonation and gaseous CO(2) as an external carbon source to overcome deleterious effects of heavy metals on strength development and improve the effectiveness of s/s of heavy metal-bearing sediment. In addition to the compressive strength and porosity measurements, leaching tests followed the Chinese solid waste extraction procedure for leaching toxicity - sulfuric acid and nitric acid method (HJ/T299-2007), German leaching procedure (DIN38414-S4) and US toxicity characteristic leaching procedures (TCLP) have been conducted. The experimental results indicated that the solidified sediment by accelerated carbonation was capable of reaching all performance criteria for the disposal at a Portland cement dosage of 10 wt.% and a solid/water ratio of 1:1. The concentrations of mercury and other heavy metals in the leachates were below 0.10mg/L and 5mg/L, respectively, complying with Chinese regulatory level (GB5085-2007). Compared to the hydration, accelerated carbonation improved the compressive strength of the solidified sediment by more than 100% and reduced leaching concentrations of heavy metals significantly. It is considered that accelerated carbonation technology with a combination of Na(2)CO(3) and CO(2) may practically apply to cement-based s/s of heavy metal-bearing sediment.

Influence of carbonation on the acid neutralization capacity of cements and cement-solidified/stabilized electroplating sludge.

Portland cement (PC) and blended cements containing pulverized fuel ash (PFA) or granulated blast-furnace slag (GGBS) were used to solidify/stabilize an electroplating sludge in this work. The acid neutralization capacity (ANC) of the hydrated pastes increased in the order of PC > PC/GGBS > PC/PFA. The GGBS or PFA replacement (80 wt%) reduced the ANC of the hydrated pastes by 30-50%. The ANC of the blended cement-solidified electroplating sludge (cement/sludge 1:2) was 20-30% higher than that of the hydrated blended cement pastes. Upon carbonation, there was little difference in the ANC of the three cement pastes, but the presence of electroplating sludge (cement/sludge 1:2) increased the ANC by 20%. Blended cements were more effective binders for immobilization of Ni, Cr and Cu, compared with PC, whereas Zn was encapsulated more effectively in the latter. Accelerated carbonation improved the immobilization of Cr, Cu and Zn, but not Ni. The geochemical code PHREEQC, with the edited database from EQ3/6 and HATCHES, was used to calculate the saturation index and solubility of likely heavy metal precipitates in cement-based solidification/stabilization systems. The release of heavy metals could be related to the disruption of cement matrices and the remarkable variation of solubility of heavy metal precipitates at different pH values.

Comparison of properties of traditional and accelerated carbonated solidified/stabilized contaminated soils.

The investigation of the long-term performance of solidified/stabilized (S/S) contaminated soils was carried out in a trial site in southeast UK. The soils were exposed to the maximum natural weathering for four years and sampled at various depths in a controlled manner. The chemical properties (e.g., degree of carbonation (DOC), pH, electrical conductivity (EC)) and physical properties (e.g., moisture content (MC), liquid limit (LL), plastic limit (PL), plasticity index (PI)) of the samples untreated and treated with the traditional and accelerated carbonated S/S processes were analyzed. Their variations on the depths of the soils were also studied. The result showed that the broad geotechnical properties of the soils, manifested in their PIs, were related to the concentration of the water soluble ions and in particular the free calcium ions. The samples treated with the accelerated carbonation technology (ACT), and the untreated samples contained limited number of free calcium ions in solutions and consequently interacted with waters in a similar way. Compared with the traditional cement-based S/S technology, e.g., treatment with ordinary portland cement (OPC) or EnvirOceM, ACT caused the increase of the PI of the treated soil and made it more stable during long-term weathering. The PI values for the four soils ascended according to the order: the EnvirOceM soil, the OPC soil, the ACT soil, and the untreated soil while their pH and EC values descended according to the same order.

Characterization of carbonated tricalcium silicate and its sorption capacity for heavy metals: a micron-scale composite adsorbent of active silicate gel and calcite.

Adsorption-based processes are widely used in the treatment of dilute metal-bearing wastewaters. The development of versatile, low-cost adsorbents is the subject of continuing interest. This paper examines the preparation, characterization and performance of a micro-scale composite adsorbent composed of silica gel (15.9 w/w%), calcium silicate hydrate gel (8.2 w/w%) and calcite (75.9 w/w%), produced by the accelerated carbonation of tricalcium silicate (C(3)S, Ca(3)SiO(5)). The Ca/Si ratio of calcium silicate hydrate gel (C-S-H) was determined at 0.12 (DTA/TG), 0.17 ((29)Si solid-state MAS/NMR) and 0.18 (SEM/EDS). The metals-retention capacity for selected Cu(II), Pb(II), Zn(II) and Cr(III) was determined by batch and column sorption experiments utilizing nitrate solutions. The effects of metal ion concentration, pH and contact time on binding ability was investigated by kinetic and equilibrium adsorption isotherm studies. The adsorption capacity for Pb(II), Cr(III), Zn(II) and Cu(II) was found to be 94.4 mg/g, 83.0 mg/g, 52.1 mg/g and 31.4 mg/g, respectively. It is concluded that the composite adsorbent has considerable potential for the treatment of industrial wastewater containing heavy metals.

Current status and perspectives of accelerated carbonation processes on municipal waste combustion residues.

The increasing volumes of municipal solid waste produced worldwide are encouraging the development of processes to reduce the environmental impact of this waste stream. Combustion technology can facilitate volume reduction of up to 90%, with the inorganic contaminants being captured in furnace bottom ash, and fly ash/APC residues. The disposal or reuse of these residues is however governed by the potential release of constituent contaminants into the environment. Accelerated carbonation has been shown to have a potential for improving the chemical stability and leaching behaviour of both bottom ash and fly ash/APC residues. However, the efficacy of carbonation depends on whether the method of gas application is direct or indirect. Also important are the mineralogy, chemistry and physical properties of the fresh ash, the carbonation reaction conditions such as temperature, contact time, CO(2) partial pressure and relative humidity. This paper reviews the main issues pertaining to the application of accelerated carbonation to municipal waste combustion residues to elucidate the potential benefits on the stabilization of such residues and for reducing CO(2) emissions. In particular, the modification of ash properties that occur upon carbonation and the CO(2) sequestration potential possible under different conditions are discussed. Although accelerated carbonation is a developing technology, it could be introduced in new incinerator facilities as a "finishing step" for both ash treatment and reduction of CO(2) emissions.

Accelerated carbonation of municipal solid waste incineration fly ashes.

As a result of the EU Landfill Directive, the disposal of municipal solid waste incineration (MSWI) fly ash is restricted to only a few landfill sites in the UK. Alternative options for the management of fly ash, such as sintering, vitrification or stabilization/solidification, are either costly or not fully developed. In this paper an accelerated carbonation step is investigated for use with fly ash. The carbonation reaction involving fly ash was found to be optimum at a water/solid ratio of 0.3 under ambient temperature conditions. The study of ash mineralogy showed the disappearance of lime/portlandite/calcium chloride hydroxide and the formation of calcite as carbonation proceeded. The leaching properties of carbonated ash were examined. Release of soluble salts, such as SO4, Cl, was reduced after carbonation, but is still higher than the landfill acceptance limits for hazardous waste. It was also found that carbonation had a significant influence on lead leachability. The lead release from carbonated ash, with the exception of one of the fly ashes studied, was reduced by 2-3 orders of magnitude.

Characterization and preliminary assessment of a sorbent produced by accelerated mineral carbonation.

This study shows that calcium silicate/aluminate-based materials can be carbonated to produce sorbents for metal removal. The material chosen for investigation, cement clinker, was accelerated carbonated, and its structural properties were investigated using X-ray diffraction (XRD), scanning electron microscopy, thermal gravimetric and differential thermal analysis, nuclear magnetic resonance spectroscopy, and nitrogen gas adsorption techniques. The principal carbonation reactions involved the transformation of dicalcium silicate, tricalcium silicate, and tricalcium aluminate into a Ca/Al-modified amorphous silica and calcium carbonate. It was found that carbonated cement had high acid buffering capacity, and maintained its structural integrity within a wide pH range. The uptake of Pb(II), Cd(II), Zn(II), Ni(II), Cr(II), Sr(II), Mo(VI), Cs(II), Co(II), and Cu(II) from concentrated (1000 mg L(-1)) single-metal solutions varied from 35 to 170 mg g(-1) of the carbonate cement. The removal of metals was hardly effected by the initial solution pH due to the buffering capability of the carbonated material. The kinetics of Pb, Cd, Cr, Sr, Cs, and Co removal followed a pseudo-second-order kinetic model, whereas the equilibrium batch data for Cu fitted the pseudo-first-order rate equation. PHREEQC simulation supported by XRD analysis suggested the formation of metal carbonates and silicates, calcium molybdate, and chromium (hydro)oxide. Cesium was likely to be adsorbed by Ca/Al-modified amorphous silica.