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 CO2 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 0.10 mg/L and 5 mg/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 Na2CO3 and CO2 may practically apply to cement-based s/s of heavy metal-bearing sediment. (C) 2008 Elsevier B.V. All rights reserved.

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. (C) 2009 Elsevier Ltd. All rights reserved.

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition Of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of Si-29 solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research oil the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique. (C) 2008 Elsevier Ltd. All rights reserved.

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.

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/m3 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.

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.

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.

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.

Characterisation of products of tricalcium silicate hydration in the presence of heavy metals

The hydration of tricalcium silicate (C(3)S) in the presence of heavy metal is very important to cement-based solidification/stabilisation (s/s) of waste. In this work, tricalcium silicate pastes and aqueous suspensions doped with nitrate salts of Zn(2+), Pb(2+), Cu(2+) and Cr(3+) were examined at different ages by X-ray powder diffraction (XRD), thermal analysis (DTA/TG) and (29)Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). It was found that heavy metal doping accelerated C(3)S hydration, even though Zn(2+) doping exhibited a severe retardation effect at an early period of time of C(3)S hydration. Heavy metals retarded the precipitation of portlandite due to the reduction of pH resulted from the hydrolysis of heavy metal ions during C(3)S hydration. The contents of portlandite in the control, Cr(3+)-doped, Cu(2+)-doped, Pb(2+)-doped and Zn(2+)-doped C(3)S pastes aged 28 days were 16.7, 5.5, 5.5, 5.5, and <0.7%, respectively. Heavy metals co-precipitated with calcium as double hydroxides such as (Ca(2)Cr(OH)(7).3H(2)O, Ca(2)(OH)(4)4Cu(OH)(2).2H(2)O and CaZn(2)(OH)(6).2H(2)O). These compounds were identified as crystalline phases in heavy metal doping C(3)S suspensions and amorphous phases in heavy metal doping C(3)S pastes. (29)Si NMR data confirmed that heavy metals promoted the polymerisation of C-S-H gel in 1-year-old of C(3)S pastes. The average numbers of Si in C-S-H gel for the Zn(2+)-doped, Cu(2+)-doped, Cr(3+)-doped, control, and Pb(2+)-doped C(3)S pastes were 5.86, 5.11, 3.66, 3.62, and 3.52. And the corresponding Ca/Si ratios were 1.36, 1.41, 1.56, 1.57 and 1.56, respectively. This study also revealed that the presence of heavy metal facilitated the formation of calcium carbonate during C(3)S hydration process in the presence of carbon dioxide.

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, CO2 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 CO2 emissions. In particular, the modification of ash properties that occur upon carbonation and the CO2 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 CO2 emissions.