Review on treatment and utilization of barium slag in China.

Barium slag (BS) is generated as a by-product waste during the production of barium salts from barite. A large amount of BS is discharged annually threating the ecological environment and restricting the development of the barium salts industry. In China, BS is classified as hazardous waste due to its corrosivity, and more importantly because of its extraction toxicity of barium. Soluble barium is toxic and can result in barium poisoning for environment and human beings. The current review presents a detailed summary on general characteristics, discharge and disposal status, harmless treatment pathways and comprehensive utilization of BS in China. BaO, SiO2, CaO, and SO3 occur as main chemical compositions in BS, especially BaO accounting approximately for 35-40%. The mineral compositions include unreacted barite, quartz, clay minerals, newly-formed phases from the side reactions such as BaCO3, BaSiO3 and BaSO3, and residual carbon. A special attention is given to the assessment of the harmless treatment methods for BS from hazardous waste to general waste, which will decrease its management costs. Precipitation and solidification of soluble barium is the common pathway for harmless treatment of BS, and the using of other industrial waste can realize cost-saving. Methods for comprehensive utilization of BS include recovery of barium and carbon, application in building materials, and using as adsorbents for wastewater treatment. In particular, we analyzed and discussed the advantages and disadvantages of these existing process routes, intending to promote potentials for comprehensive utilization of BS in the future.

Bioleaching Performance of Titanium from Bauxite Residue Under a Continuous Mode Using Penicillium Tricolor.

The present study performed a continuous mode of bioleaching to investigate the leaching efficiency of Titanium (Ti) from bauxite residue using Penicillium Tricolor at between 4% and 12% pulp densities during a 120-day running. Obtained results of the current study showed that increased pulp density led to a decrease in biomass, dissolved oxygen, and amount of leaching Ti as well as an increase in pH value. Further, it was found that efficiency of bioleaching can be enhanced by increasing the rate of aeration, retention time, and concentration of carbon source. However, it was also evident that, at high pulp density, excessive agitation did not give an expected leaching efficiency but a collapse of biomass. In addition, results of the present study showed that the maximum leaching amount of Ti was 3202 mg/L with a corresponding leaching ratio of 50.35% during the whole bioleaching process. Moreover, it was noted that the biomass showed a significant negative correlation with the pH value and dissolved oxygen. However, the biomass showed a significant positive correlation with leaching amount of Ti and thus indicate that microbial metabolic activities are the uppermost factor affecting the continuous leaching performance.

Increasing phosphate sorption on barium slag by adding phosphogypsum for non-hazardous treatment.

Barium slag (BS) is a waste residue in the barium salt industrial procedure. Due to its high leaching concentration of Ba2+, BS is classified as a kind of hazardous waste. Industrial waste phosphogypsum (PG) is effective to immobilize barium ion in BS owing to the slightly soluble sulfate included. In this study, two different proportions of PG were selected for mixing with BS to solidify soluble barium ion. The non-hazardous BS samples treated with the proportions of PG (BS-PG1, BS-PG3) were then functionally used for phosphate removal in solution. Batch experiments for removal of phosphate were performed to evaluate the adsorption efficiency of BS-PG1 and BS-PG3. The effect of various factors such as contact time, initial pH, and reaction temperature on sorption performance was investigated. BS-PG1 and BS-PG3 reached adsorption equilibrium in approximately 3h at the initial concentration of 15 mg/L, and BS-PG1 exhibited adsorption capacity of 12.47 mg P/g, higher than that of BS (11.49 mg P/g) under the condition of solid:liquid, 1g:1L, 25 °C, natural pH. The results show that the adsorption processes of phosphates ions onto both BS-PG1 and BS-PG3 fitted well with the pseudo-second-order kinetic model. The Langmuir isothermal model was considered as the appropriate equation for experimental data, showing a maximum adsorption capacity for phosphate up to 13.67 mg P/g and 11.59 mg P/g for BS-PG1 and BS-PG3. In comparison with other adsorbents, BS-PG1 and BS-PG3 could be considered as efficient materials for the removal of phosphate.

Adsorptive removal of phosphate from aqueous solutions using different types of red mud.

Red mud (RM) is an industrial waste generated during production of alumina from using the Bayer process or the sintering process. Four types of red mud from China were characterized for their diverse chemical and mineral compositions using inductively coupled plasma-atomic emission spectroscopy (ICP-AES), inductively coupled plasma-mass spectrometry (ICP-MS) and X-ray diffraction (XRD). Acid treatment was employed to obtain activated red mud (ARM), posing increased surface areas from 10-28 m2/g to 220-350 m2/g. RMs and ARMs were used to adsorb phosphate in solution to compare the adsorption capacity. Sample GZ3, a red mud from the sintering process, presented the highest adsorption capacity among the four raw RMs, posing an adsorption capacity of 0.37 mg P/g in the solution of 1 mg P/L with a solid/solution ratio of 0.5 g: 1 L. Whereas, activated GX (AGX), a high iron Bayer red mud from diaspore bauxite, showed the highest adsorption capacity of all the ARMs, with an adsorption capacity of 1.92 mg P/g in the same condition. The dynamic studies indicate that the adsorption mainly followed the pseudo second-order model. The models of Freundlich and Langmuir were used to simulate the sorption equilibrium on GZ3 and AGX. It suggests that the Freundlich model had a better correlation with GZ3 while the Langmuir model fitted well with AGX.

Hydrothermal chemical modification of red mud for efficient adsorption of methylene blue.

Red mud (RM) is the industrial solid waste produced after alumina extraction from bauxite, and most RM is directly discharged to the landfill yards without any treatment. In this study, modified red mud (MRM) was synthesized by a hydrothermal chemical modification method as an efficient adsorbent for methylene blue (MB) removal. The prepared MRM was characterized by X-ray fluorescence spectroscopy, X-ray diffraction, scanning electron microscope, transmission electron microscope, and Fourier transform infrared spectrometer. The effects of reaction time, initial MB concentrations, MRM dosage, temperature, and system pH were investigated in the MB batch adsorption experiments. The results showed that the modification method increased the specific surface area of RM material from 16.72 to 414.47 m2/g. The maximum adsorption capacity of MRM for MB was 280.18 mg/g under the conditions of initial MB concentration of 1000 mg/L, reaction time of 300 min, temperature of 25 ℃, and natural pH of 6.06. Meanwhile, the adsorption kinetics and equilibrium isotherms were demonstrated to fit well with the pseudo-second-order kinetic model and Temkin isotherm, respectively. This study provides a new method for the valorization of RM and demonstrates that MRM can be used as a low cost and environmentally friendly potential adsorbent for the removal of MB from wastewater.

Synthesis of submicron ferrous oxalate from red mud with high Fenton catalytic performance on degradation of methylene blue.

Ferrous oxalate dihydrate (FOD) can be used as a photo-Fenton catalyst with remarkable photo-Fenton catalytic and photocatalytic performances on organic pollutant degradation. Various reduction processes were compared in the current study to synthesize FODs from ferric oxalate solution utilizing the iron source in alumina waste red mud (RM), including natural light exposure (NL-FOD), UV light irradiation (UV-FOD), and hydroxylamine hydrochloride hydrothermal method (HA-FOD). The FODs were characterized and employed as photo-Fenton catalysts for methylene blue (MB) degradation, and the effects of HA-FOD dosage, H2O2 dosage, MB concentration, and the initial pH were investigated. The results show that HA-FOD has submicron sizes and lower impurity contents with more rapid degradation rates and higher degradation efficiencies compared with the other two FOD products. When using 0.1 g/L of each obtained FOD, 50 mg/L of MB can be rapidly degraded by HA-FOD by 97.64% within 10 min with 20 mg/L of H2O2 at pH of 5.0, while NL-FOD and UV-FOD achieve 95.52% in 30 min and 96.72% in 15 min at the same conditions, respectively. Meanwhile, HA-FOD exhibits strong cyclic stability after two recycling experiments. Scavenger experiments reveal that the predominant reactive oxygen species responsible for MB degradation are hydroxyl radicals. These findings demonstrate that submicron FOD catalyst can be synthesized using hydroxylamine hydrochloride hydrothermal process from ferric oxalate solution with high photo-Fenton degradation efficiency and reduced reaction time for wastewater treatment. The study also provides a new pathway of efficient utilization for RM.

Radiological restrictions of using red mud as building material additive.

Red mud remains as residue from the processing of bauxite using different methods. The chemical composition of red mud varies widely with respect to the types of bauxite ore and processing parameters. Red mud samples from Guizhou, China, were investigated using a X-ray fluorescence spectroscope, a quadrupole inductively coupled plasma mass spectrometer and a electron probe micro-analyzer. The results showed that red mud consisted of eight main chemical components--CaO, Al(2)O(3), SiO(2), Fe(2)O(3), TiO(2), Na(2)O, K(2)O and MgO--and dozens of trace elements, including natural radioactive elements, such as uranium and thorium. Gamma spectrometric analysis showed that the values of internal exposure index I (Ra) and external exposure index I (γ) of Guizhou red mud were 1.1-2.4 and 2.3-3.5 respectively. Thus, it should not be used as a main building material indiscriminately. The amount of red mud from Guizhou when it is used for main building materials in China should be less than 28-44%.

Froth flotation separation of carbon from barium slag: Recycling of carbon and minimize the slag.

Barium slag is a kind of solid waste derived from the carbon reduction process of producing barium salt. Carbon is one of the main components in barium slag with a content of more than 10%. In this study, a barium slag was characterized using XRF, XRD and SEM-EDS, and froth flotation test was introduced to recover the carbon in the barium slag. In the process of froth flotation test, diesel was selected as a collector and terpenic oil was selected as a frother for carbon separation. The flotation influences of pulp pH, collector dosage, frother dosage and flotation time were investigated. The results showed that the obtained carbon concentrate had a carbon grade of 63.25% and its recovery was 82.70% under the conditions of pH 8.50, diesel 600 g/t, terpenic oil 500 g/t, and flotation time 5 min. SEM-EDS analysis results revealed that the flotation concentrate was coarse and its particle sizes had a homogeneous distribution. The findings of this research provide a new pathway for barium slag utilization. The carbon obtained from the flotation test in this study can be recycled as raw materials, while the reduction of the remaining tailings can be utilized as building material additives.

A critical review on approaches for electrolytic manganese residue treatment and disposal technology: Reduction, pretreatment, and reuse.

Electrolytic manganese residue (EMR) has become a barrier to the sustainable development of the electrolytic metallic manganese (EMM) industry. EMR has a great potential to harm local ecosystems and human health, due to it contains high concentrations of soluble pollutant, especially NH4+ and Mn2+, and also the possible dam break risk because of its huge storage. There seems to be not a mature and stable industrial solution for EMR, though a lot of researches have been done in this area. Hence, by fully considering the EMM ecosystem, we analyzed the characteristics and eco-environmental impact of EMR, highlighted state-of-the-art technologies for EMR reduction, pretreatment, and reuse; indicated the factors that block EMR treatment and disposal; and proposed plausible and feasible suggestions to solve this problem. We hope that the results of this review could help solve the problem of EMR and thus promote the sustainable development of EMM industry.

Conversion synthesis of manganese sulfate residue into iron hydroxide adsorbent for Cu(II) removal from aqueous solution.

Manganese sulfate residue (MSR) is a by-product derived from the manganese sulfate production process. In this study, an iron hydroxide adsorbent was prepared from MSR using the hydrothermal conversion method. The adsorbent was characterized and used to remove copper(II) ions from aqueous solution. Batch experiments were performed to investigate the adsorption efficiency of copper ions at different contact times, initial concentrations, solution pH levels, and reaction temperatures. Adsorption equilibrium was observed in 3 h, and the best pH was under natural conditions (pH ∼ 5.5). Increasing the initial Cu2+ concentration and reaction temperature can increase the adsorption quantity. The adsorption capacity of iron hydroxide at an initial concentration of 50 mg L-1 was 14.515 mg g-1 Cu(II) under the conditions of a nature pH and room temperature. According to the adsorption data, the pseudo-second-order model can describe the adsorption kinetics of copper ions well, and the Freundlich model provides an excellent fit to the adsorption isotherm. XRD and FTIR were applied to characterize the raw materials and adsorbents to reveal the adsorption mechanism. The results suggest that the adsorbent converted from MSR is a promising material for the removal of Cu(II) in aqueous solutions.

Theoretical-molar Fe3+ recovering lithium from spent LiFePO4 batteries: an acid-free, efficient, and selective process.

In spent lithium iron phosphate batteries, lithium has a considerable recovery value but its content is quite low, thus a low-cost and efficient recycling process has become a challenging research topic. In this paper, two methods about using the non-oxidizing inorganic iron salt - Fe2(SO4)3 to recover lithium from LiFePO4 are proposed. The method-1 is theoretical-molar Fe2(SO4)3 (Fe2(SO4)3 : LiFePO4 =1:2) dosage is added and more than 97% of lithium can be leached in just 30 min even under a pretty high solid-liquid ratio of 500 g/L. Spectrophotometry provides the evidence of Fe2+/Fe3+ substitution in the leaching process. In the method-2, the generated Fe2+ originating from LiFePO4 is fully utilized with the addition of H2O2, and the dosage of Fe2(SO4)3 is decreased by two thirds (Fe2(SO4)3 : LiFePO4 =1:6). Several sulphates (CuSO4, NiSO4, MgSO4) are employed to explore the leaching mechanism. All the results reveal that the reaction of Fe3+ substituting Fe2+ has a powerful driving force. In addition, these two leaching processes simultaneously present superior selectivity for the impurities. The Fe2(SO4)3 in two methods does not cause pollution and is easily regenerated by adding H2SO4. The proposed rapid, efficient and selective leaching thought would be a competitive candidate for recycling spent LiFePO4 batteries.