Ex Situ CO2 capture by carbonation of steelmaking slag coupled with metalworking wastewater in a rotating packed bed.

Both basic oxygen furnace (BOF) slag and cold-rolling wastewater (CRW) exhibiting highly alkaline characteristics require stabilization and neutralization prior to utilization and/or final disposal. Using CO2 from flue gases as the stabilizing and neutralizing agents could also diminish CO2 emissions. In this investigation, ex situ hot stove gas containing 30 vol% CO2 in the steelmaking process was captured by accelerated carbonation of BOF slag coupled with CRW in a rotating packed bed (RPB). The developed RPB process exhibits superior results, with significant CO2 removal efficiency (η) of 96-99% in flue gas achieved within a short reaction time of 1 min at 25 °C and 1 atm. Calcite (CaCO3) was identified as the main product according to XRD and SEM-XEDS observations. In addition, the elimination of lime and Ca(OH)2 in the BOF slag during carbonation is beneficial to its further use as construction material. Consequently, the developed RPB process could capture the CO2 from the flue gas, neutralize the CRW, and demonstrate the utilization potential for BOF slag. It was also concluded that carbonation of BOF slag coupled with CRW in an RPB is a viable method for CO2 capture due to its higher mass transfer rate and CO2 removal efficiency in a short reaction time.

Systematic approach to determination of maximum achievable capture capacity via leaching and carbonation processes for alkaline steelmaking wastes in a rotating packed bed.

Accelerated carbonation of basic oxygen furnace slag (BOFS) coupled with cold-rolling wastewater (CRW) was performed in a rotating packed bed (RPB) as a promising process for both CO2 fixation and wastewater treatment. The maximum achievable capture capacity (MACC) via leaching and carbonation processes for BOFS in an RPB was systematically determined throughout this study. The leaching behavior of various metal ions from the BOFS into the CRW was investigated by a kinetic model. In addition, quantitative X-ray diffraction (QXRD) using the Rietveld method was carried out to determine the process chemistry of carbonation of BOFS with CRW in an RPB. According to the QXRD results, the major mineral phases reacting with CO2 in BOFS were Ca(OH)2, Ca2(HSiO4)(OH), CaSiO3, and Ca2Fe1.04Al0.986O5. Meanwhile, the carbonation product was identified as calcite according to the observations of SEM, XEDS, and mappings. Furthermore, the MACC of the lab-scale RPB process was determined by balancing the carbonation conversion and energy consumption. In that case, the overall energy consumption, including grinding, pumping, stirring, and rotating processes, was estimated to be 707 kWh/t-CO2. It was thus concluded that CO2 capture by accelerated carbonation of BOFS could be effectively and efficiently performed by coutilizing with CRW in an RPB.

Health risk assessment of exposure to selected volatile organic compounds emitted from an integrated iron and steel plant.

Workplace air samples from sintering, cokemaking, and hot and cold forming processes in the integrated iron and steel industry were analyzed to determine their volatile organic compound (VOC) concentration. Sixteen VOC species including three paraffins (cyclohexane, n-hexane, methylcyclohexane), five chlorinated VOC species (trichloroethylene, 1,1,1-trichloroethane, tetrachloroethylene, chlorobenzene, 1,4-dichlorobenzene), and eight aromatics (benzene, ethylbenzene, styrene, toluene, m,p-xylene, o-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene) were selected to measure their noncancer risk for workers. Concentrations of toluene, xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, dichlorobenzene, and trichloroethylene were high in all four processes. Carbon tetrachloride and tetrachloroethylene concentrations were high in the hot and cold forming processes. The noncancer risk followed the increasing order: cokemaking > sintering > hot forming > cold forming. 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene contributed 44% to 65% and 13% to 20% of noncancer risk, respectively, for the four processes. Benzene accounted for a high portion of the noncancer risk in cokemaking. The hazard index (HI: 17-108) of the average VOC concentrations suggests that health risks can be reduced by improving workplace air quality and protecting workers.

Removal of small trihalomethane precursors from aqueous solution by nanofiltration.

The removal of small trihalomethane precursors (THMPs) from aqueous solution by two commercial nanofiltration membranes (NF70 and NF270) was investigated. Resorcinol, phloroglucinol, and 3-hydroxybenzoic acid were selected as model compounds of small THMPs, while tannic acid was chosen as a medium molecular disinfection by-product (DBP) precursor for comparison. The performance of nanofiltration membranes were evaluated by introducing polyethylene glycol (PEG) solutions and uncharged saccharides to estimate molecular weight cut-off (MWCO) and membrane pore radii, respectively. The streaming potential was measured to estimate the membrane surface charge at different pH values, which reveals that the NF270 membrane is more pH-sensitive than the NF70 membrane. The rejections of the above selected THMPs were assessed under various pH values, and the removal efficiencies of THMPs for both membranes at high pH values are reasonably well. Charge exclusion is the prevailing mechanism for the selected small model compounds retended by the negatively charged nanofiltration membranes, while size exclusion and adsorption are controlled mechanisms but not sufficient for the rejection of unionized small organic molecules. In general, the NF270 membrane exhibits the superior permeation rate value, which takes an advantage over the NF70 membrane from the aspect of energy conservation.

Multiple model approach to evaluation of accelerated carbonation for steelmaking slag in a slurry reactor.

Basic oxygen furnace slag (BOFS) exhibits highly alkaline properties due to its high calcium content, which is beneficial to carbonation reaction. In this study, accelerated carbonation of BOFS was evaluated under different reaction times, temperatures, and liquid-to-solid (L/S) ratios in a slurry reactor. CO2 mass balance within the slurry reactor was carried out to validate the technical feasibility of fixing gaseous CO2 into solid precipitates. After that, a multiple model approach, i.e., theoretical kinetics and empirical surface model, for carbonation reaction was presented to determine the maximal carbonation conversion of BOFS in a slurry reactor. On one hand, the reaction kinetics of BOFS carbonation was evaluated by the shrinking core model (SCM). Calcite (CaCO3) was identified as a reaction product through the scanning electronic microscopy and X-ray diffraction analyses, which provided the rationale of applying the SCM in this study. The rate-limiting step of carbonation was found to be ash-diffusion controlled, and the effective diffusivity for carbonation of BOFS in a slurry reactor were determined accordingly. On the other hand, the carbonation conversion of BOFS was predicted by the response surface methodology (RSM) via a nonlinear mathematical programming. According to the experimental data, the highest carbonation conversion of BOFS achieved was 57% under an L/S ratio of 20 mL g(-1), a CO2 flow rate of 0.1 L min(-1), and a pressure of 101.3 kPa at 50 °C for 120 min. Furthermore, the applications and limitations of SCM and RSM were examined and exemplified by the carbonation of steelmaking slags.

Effects of polyelectrolytes on reduction of model compounds via coagulation.

The objective of this research work was to evaluate the performance of enhanced coagulation by alum and polymer. Synthetic source waters containing high molecular weight humic acids, medium molecular weight tannic acids and low molecular weight p-hydroxybenzoic acid were formulated by adjusting the concentration of turbidity and pH; and jar tests were used to study the effect of various types and dosages of polymer on reducing the above model compounds. At a specific pH condition, the applied alum dosage would efficiently decrease the turbidity to 2 NTU follows the order: humic>tannic>p-hydroxybenzoic acid. Adjustment of pH influenced the performance of alum obviously but not of p-DADMAC. High p-DADMAC dosage overwhelming the effects of alum is less affected by pH adjustment. The results of this investigation reveal that enhanced coagulation with p-DADMAC was founded to be very effective for removing high-molecular-weight THM precursors, i.e., humic acid and tannic acid, and markedly reduced the alum dosages required for turbidity removal. The other two polymers, i.e., cationic PAM and non-ionic PAM, which had higher molecular weight but lower charge density than p-DADMAC, were not capable of removing organic precursors. It was thus concluded that enhanced coagulation with polymer, p-DADMAC, could be considered as a promising technique for removal of NOMs with hydrophobic and higher-molar-mass (>1K) in water treatment plants.

Effects of polydiallyldimethyl ammonium chloride coagulant on formation of chlorinated by products in drinking water.

The objectives of this research work was to evaluate the reduction of THM precursors by cationic p-DADMAC and determine the correlations between the chlorine demand and trihalomethane formation in the presence of electrolyte solutions and ambient light. The chlorine demand was found to be significantly reduced provided that the H2SO4 electrolyte was fed to the sample solutions. The amount of CHCl3 formation was also decreased when the Na2SO4 electrolyte was introduced in spite of the levels of light intensity. The p-DADMAC can not only effectively remove the turbidity but also reduce the formation of CHCl3. The optimum dosage of p-DADMAC for reducing the turbidity, TOC and CHCl3 in the humic acid and source water samples was determined and depended upon the nature of organics.

Kinetic modeling on CO2 capture using basic oxygen furnace slag coupled with cold-rolling wastewater in a rotating packed bed.

In this study, direct and indirect carbonation of basic oxygen furnace slag (BOFS) coupled with cold-rolling wastewater (CRW) was carried out via a rotating packed bed (RPB). The solid products were qualitatively characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) and quantitatively analyzed with thermogravimetric analysis (TGA). The leachate was analyzed with inductively coupled plasma-optical emission spectroscopy (ICP-OES). The results indicate that the maximum achievable carbonation conversion (MACC) of BOFS was 90.7%, corresponding to a capture capacity of 0.277 g CO2/g of BOFS, by direct carbonation with CRW under a rotation speed of 750 rpm at 30 °C for 20 min. In addition, CO2 mass balance among the gas, liquid, and solid phases within an RPB was well-developed, with an error less than 10%, to confirm the actual CO2 capture capacity of BOFS with precision and accuracy. Furthermore, a reaction kinetic model based on mass balance was established to determine the reaction rate constant for various liquid agents (CRW and pure water). It was concluded that co-utilization of alkaline wastes including BOFS and CRW via the RPB is a novel approach for both enhancing CO2 capture capacity and reducing the environmental impacts of alkaline wastes.

Accelerated carbonation of steelmaking slags in a high-gravity rotating packed bed.

Carbon dioxide (CO(2)) sequestration using the accelerated carbonation of basic oxygen furnace (BOF) slag in a high-gravity rotating packed bed (RPB) under various operational conditions was investigated. The effects of reaction time, reaction temperature, rotation speed and slurry flow rate on the CO(2) sequestration process were evaluated. The samples of reacted slurry were analyzed quantitatively using thermogravimetric analysis (TGA) and atomic absorption spectrometry (AAS) and qualitatively using X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), and transmission electron microscopy (TEM). The sequestration experiments were performed at a liquid-to-solid ratio of 20:1 with a flow rate of 2.5 L min(-1) of a pure CO(2) stream under atmospheric temperature and pressure. The results show that a maximum conversion of BOF slag was 93.5% at a reaction time of 30 min and a rotation speed of 750 rpm at 65°C. The experimental data were utilized to determine the rate-limiting mechanism based on the shrinking core model (SCM), which was validated by the observations of SEM and TEM. Accelerated carbonation in a RPB was confirmed to be a viable method due to its higher mass-transfer rate.

Identifying the rejection mechanism for nanofiltration membranes fouled by humic acid and calcium ions exemplified by acetaminophen, sulfamethoxazole, and triclosan.

This research investigated the fouling effect of humic acid and humic acid/calcium ions on the rejection of three target compounds, i.e., acetaminophen, sulfamethoxazole, and triclosan, by two nanofiltration (NF) membranes. A modified Hermia fouling model was used to describe the fouling process. The effects of solute and membrane characteristics on the rejection and flux decline at various pH levels and with various foulants were also investigated. Results show that fouling mechanisms include complete blocking and gel layer formation. The presence of humic acid and humic acid/calcium ions may positively influence the rejection of hydrophilic compounds and neutral compounds rejected only by size exclusion. The experimental rejections of solute by the NF270 membrane correlate well with the theoretical rejection model in which only size exclusion was considered. For NF membranes with pore sizes larger than the solutes (e.g., the NTR7450 membrane), the rejection could be determined from the model combining both size exclusion and electrostatic exclusion.

CO2 sequestration by carbonation of steelmaking slags in an autoclave reactor.

Carbon dioxide (CO(2)) sequestration experiments using the accelerated carbonation of three types of steelmaking slags, i.e., ultra-fine (UF) slag, fly-ash (FA) slag, and blended hydraulic slag cement (BHC), were performed in an autoclave reactor. The effects of reaction time, liquid-to-solid ratio (L/S), temperature, CO(2) pressure, and initial pH on CO(2) sequestration were evaluated. Two different CO(2) pressures were chosen: the normal condition (700 psig) and the supercritical condition (1300 psig). The carbonation conversion was determined quantitatively by using thermo-gravimetric analysis (TGA). The major factors that affected the conversion were reaction time (5 min to 12h) and temperature (40-160°C). The BHC was found to have the highest carbonation conversion of approximately 68%, corresponding to a capacity of 0.283 kg CO(2)/kg BHC, in 12h at 700 psig and 160°C. In addition, the carbonation products were confirmed to be mainly in CaCO(3), which was determined by using scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) to analyze samples before and after carbonation. Furthermore, reaction kinetics were expressed with a surface coverage model, and the carbon footprint of the developed technology in this investigation was calculated by a life cycle assessment (LCA).

Performance evaluation for carbonation of steel-making slags in a slurry reactor.

CO(2) sequestration by the aqueous carbonation of steel-making slag under various operational conditions was investigated in this study. The effects of the operational conditions, including type of steel-making slag, reaction time, reaction temperature, and CO(2) flow rate, on the performance of the carbonation process were evaluated. The results indicated that the BOF slag had the highest carbonation conversion, approximately 72%, at a reaction time of 1h, an operating pressure of 101 kPa and a temperature of 60°C due to its higher BET surface area of BOF slag compared to UF, FA, and BHC slags. The major factors affecting the carbonation conversion are reaction time and temperature. The reaction kinetics of the carbonation conversion can be expressed by the shrinking-core model. The measurements of the carbonated material by the SEM and XRD instruments provide evidence indicating the suitability of using the shrinking-core model in this investigation. Comparison of the results with other studies suggests that aqueous carbonation by slurry reactor is viable due to its higher mass transfer rate.

Reduction of natural organic matter by nanofiltration process.

The objectives of this investigation were to characterize natural organic matter (NOM) in Kin-men raw water, to evaluate the performance of the nanofiltration (NF) membrane process for NOM removal, and to determine the good engineering practice (GEP) of the NF 270 membrane filtration performance. Three different samples: (1) raw water collected from the Tai Lake in Kin-men, Taiwan; (2) ultrafiltration (UF) pre-treated water; and (3) sand filtration (SF) treated water after the coagulation and sedimentation processes were employed in this study. The hydrophobic component (58%) was the predominant NOM fraction, and the NOM molecular weight was distributed broadly, i.e., lower than 1 kDa (30%), 1-5 kDa (32%) and larger than 5 kDa (38%). Hydrophobic NOM easily accumulated on the NF membrane surface and resulted in flux decline. The SF-NF was the proposed treatment process because it can reduce the NOMs effectively with lower energy consumption than UF-NF. It was noted that the dissolved organic carbon (DOC) rejection ratio was not affected by changing cross-flow velocity. However, at lower cross-flow velocity (0.15 ms(-1)), the reduction of organic matter in water sample was higher than that at higher cross-flow velocity (0.30 ms(-1)). By integrating the experimental results, it was concluded that a transmembrane pressure of 690 kPa and a cross-flow velocity of 0.30 ms(-1) exhibited the GEP, yielding about 94% of both DOC and UV(254) reduction.