Study on phase evolution and promoting the pozzolanic activity of electrolytic manganese residue during calcination.

Electrolytic manganese residue (EMR) is a harmful by-product in the electrolytic manganese industry. Calcination is an efficient method for disposing EMR. In this study, thermogravimetric-mass spectrometry (TG-MS) combined with X-ray diffraction (XRD) was used for analysing the thermal reactions and phase transitions during calcination. The pozzolanic activity of calcined EMR was determined by the potential hydraulicity test and strength activity index (SAI) test. The leaching characteristics of Mn were determined by TCLP test and BCR SE method. The results showed that MnSO4 was converted into stable MnO2 during calcination. Meanwhile, Mn-rich bustamite (Ca0.228Mn0.772SiO3) was converted into Ca(Mn, Ca)Si2O6. The gypsum was transformed into anhydrite and then decomposed into CaO and SO2. Additionally, the organic pollutants and ammonia were completely removed following calcination at 700 °C. The leaching concentration of Mn decreased from 819.9 mg L-1 to 339.6 mg L-1 following calcination at 1100 °C. The chemical forms of Mn were transformed from acid-soluble fraction to residual fraction. The pozzolanic activity tests indicated that EMR1100-Gy maintained a complete shape. The compressive strength of EMR1100-PO reached 33.83 MPa. Finally, the leaching concentrations of heavy metals met the standard limits. This study provides a better understanding for the treatment and utilization of EMR.

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.

Harmless treatment technology of phosphogypsum: Directional stabilization of toxic and harmful substances.

Phosphogypsum is one of the typical by-products of phosphorus chemical industry. As a strategic industry related to the national livelihood of China, phosphorus chemical industry has accumulated and produced a significant amount of phosphogypsum. In general, phosphogypsum contains approximately 80%-95% calcium sulfate dihydrate, and less than 5% toxic and harmful elements. In this paper, toxic and hazardous components in phosphogypsum were efficiently solidified and stabilized by highly targeted solidification and stabilization technology. Calcium carbide slag or lime was used as an alkali-base neutralizer of phosphogypsum, and polymeric ferric sulfate or polymeric aluminum chloride as a directional solidification stabilizer to analyze the leaching toxicity of the mixed powder in 1, 3, 5 and 15 days. The experimental results demonstrate excellent solidification and stabilization effect with the leaching pH of 6-9, the leaching concentration of P, F and heavy metals of less than 0.5 mg/L, 10 mg/L and 0.1 mg/L, respectively, which meets the requirements of relevant international standards. Mechanistic analysis indicates that the solidification and stabilization of toxic and hazardous substances in phosphogypsum is perfectly achieved owing to the generation, adsorption and encapsulation of insoluble substances. This technology can reduce the costs and difficulty in the phosphogypsum treatment, and has extensive application potentials.

Study on harmless treatment of electrolytic manganese residue by low temperature thermochemical method.

The Electrolytic Manganese Residue (EMR) is a by-product of the electrolytic manganese metal (EMM) industry, containing high concentrations of potential pollutants such as NH4+-N and soluble Mn2+. These components pose a serious threat to the ecological environment. To explore accurate, efficient, and harmless treatment methods for EMR, this study proposes a low-temperature thermochemical approach. The orthogonal experiment design investigates the effects of reaction temperature, reaction time, quicklime (CaO), sodium carbonate (Na2CO3), sodium phosphate (Na3PO4) (Reviewer #3), and water consumption on manganese solidified and ammonia removal from EMR. The results indicate that optimal conditions are a reaction temperature of 60 ℃ (Reviewer #3) and a reaction time of 10 min. CaO precipitates Mn2+ as manganese hydroxide (Mn(OH)2) (Reviewer #3), achieving effective manganese solidified and ammonia removal. The addition of Na2CO3 causes Mn2+ to form manganesecarbonate (MnCO3) (Reviewer #3)precipitate, while Na3PO4 makes Mn2+ form Manganese phosphate trihydrate (Mn3(PO4)2·3H2O) (Reviewer #3). Increased water consumption enhances the interaction adequacy between ions. Under optimal conditions (CaO 10%, Na2CO3 1%, Na3PO4 0.5%, and 80% water consumption), the removal rate of ammonium ions reaches 98.5%, and the solidification rate of soluble Mn2+ is 99.9%. The order of influence on ammonium ion removal is CaO > water consumption > Na3PO4 > Na2CO3. Therefore, this study provides a new method for low-cost process disposal and efficient harmless treatment of EMR (Reviewer #3).

Transformation and Detoxification of Typical Metallurgical Hazardous Waste into a Resource: A Review of the Development of Harmless Treatment and Utilization in China.

The production process of the metallurgical industry generates a significant quantity of hazardous waste. At present, the common disposal method for metallurgical hazardous waste is landfilling, which synchronously leads to the leaching of toxic elements and the loss of valuable metals. This paper presents a comprehensive review of the research progress in the harmless treatment and resource utilization of stainless steel dust/sludge (including stainless steel dust and stainless steel pickling sludge) and aluminum ash (including primary aluminum ash and secondary aluminum dross), which serve as representative hazardous wastes in ferrous metallurgy and nonferrous metallurgy, respectively. Additionally, the general steps involved in the comprehensive utilization of metallurgical hazardous waste are summarized. Finally, this paper provides a prospective analysis on the future development and research trends of comprehensive utilization for metallurgical hazardous waste, aiming to offer a basis for the future harmless, high-value, resource-based treatment of metallurgical hazardous waste and the realization of industrial applications in China.

A clean approach for detoxification of industrial chromium-bearing stainless steel slag: Selective crystallization control and binary basicity effect.

The complete detoxification and resource utilization of stainless steel slag are still facing challenges. In this paper, the harmless treatment of industrial stainless steel slag was realized by using a high temperature modification-crystallization control approach, and the influence of binary basicity (B) on selective enrichment of Cr-containing spinel in the slag and corresponding detoxification effect were systematically explored. Results demonstrated that the enrichment degree of Cr and the amount of Cr-bearing spinel separately reached 98.62 wt% and 13.32 wt% when B= 1.2. The reason was that low alkalinity promoted the reaction of Cr in slag to form Cr-containing spinel, thus improving the enrichment of Cr in the spinel and reducing the occurrence probability of Cr in the matrix phase. Furthermore, the toxicity test of modified slag powder was proceeded according to Chinese standard HJ/T 299-2007 and American standard EPA (Toxicity Characteristic Leaching Procedure, TCLP), and the feasibility of using modified slags as admixture for producing cement was discussed. Even if TCLP was adopted, the Cr leaching concentration in modified slag powder with B= 1.2 was only 1.59 mg/L, which was far lower than the national limit of heavy metal leaching concentration (15 mg/L) of solid waste. Remarkably, when the powder was formed as cement, the Cr leaching concentration was even lower than ICP-OES detection line. Meanwhile, its mechanical property was better than that of cement prepared without powder, indicating the detoxified slag powder met the requirements of concrete admixture. This paper provides a new way with certain economic value for detoxification and large-scale utilization of stainless steel slag.

Study on mutual harmless treatment of electrolytic manganese residue and red mud.

Electrolytic manganese residue (EMR) and red mud (RM) are solid waste by-products of the metal manganese and alumina industries, respectively. Under long-term open storage, ammonia nitrogen and soluble manganese ions in EMR and alkaline substances in RM severely pollute and harm the environment. In order to alleviate the pollution problem of EMR and RM. In this study, the alkaline substances in RM were used to treat ammonia nitrogen and soluble manganese ions in EMR. The results confirm the following suitable treatment conditions for the mutual treatment of EMR and RM: EMR-RM mass ratio = 1:1, liquid-solid ratio = 1.4:1, and stirring time = 320 min. Under these conditions, the elimination ratios of ammonia nitrogen (emitted in the form of ammonia gas) and soluble manganese ions (solidified in the form of Mn3.88O7(OH) and KMn8O16) are 85.87 and 86.63%, respectively. Moreover, the alkaline substances in RM are converted into neutral salts (Na2SO4 and Mg3O(CO3)2), achieving de-alkalinisation. The treatment method can also solidify the heavy metal ions-Cr3+, Cu2+, Ni2+, and Zn2+-present in the waste residue with leaching concentrations of 1.45 mg/L, 0.099 mg/L, 0.294 mg/L, and 0.449 mg/L, respectively. This satisfies the requirements of the Chinese standard GB5085.3-2007. In the mutual treatment of EMR and RM, the kinetics of ammonia nitrogen removal and manganese-ion solidification reactions are controlled via a combination of membrane diffusion and chemical reaction mechanisms.

Fenton oxidation treatment of oxytetracycline fermentation residues: Harmless performance and bioresource properties.

The pharmaceutical factories of oxytetracycline (OTC) massively produce OTC fermentation residues (OFRs). The high content of residual OTC and antibiotic resistance genes in OFRs must to be considered and controlled at an acceptable level. This study therefore investigated the applicability of Fenton oxidation in OTC degradation and resistant gene inactivation of OFRs. The results revealed that Fe2+ as catalyzer could very rapidly activate H2O2 to produce HO•, leading to instantaneous degradation of OTC. The optimum conditions for OTC removal were 60 mM H2O2 and 140 mg/L Fe2+ under pH 7. After Fenton oxidation treatment, the release of water-soluble polysaccharides, NO3-N, and PO4-P was enhanced, whereas for proteins and NH3-N were reduced. Three soluble fluorescence components (humic, tryptophan-like, and humic acid-like substances) were identified through fluorescence spectra with parallel factor analysis, and their reduction exceeded 50% after Fenton oxidation. There were twelve intermediates and three degradation pathways of OTC in OFRs during Fenton process. According to toxicity prediction, the comprehensive toxicity of OTC in OFRs was alleviated via Fenton oxidation treatment. In addition, Fenton oxidation showed the ability to reduce antibiotic resistance genes and mobile genetic elements, and even tetO, tetG, intI1, and intI2 were eliminated completely. These results suggested that Fenton oxidation treatment could be an efficient strategy for removing OTC and resistance genes in OFRs.

Novel conditioner for efficient dewaterability and modification of oily sludge with high water content.

The oily sludge with high water content (OS) was dewatered, modified, and converted into solid fuel by a novel chemical conditioner (OSO-101). The effect of OSO-101 dosage on the dewaterability of OS was studied, showing that OSO-101 dosage of 15% (wt.) could achieve the best dewaterability efficiency of OS (98.18%). Meanwhile, compared with some conventional conditioners, OSO-101 developed by our team was more effective in improving OS dewaterability efficiency. And OSO-101 may have free radical reaction, polar reaction, and redox reaction with petroleum hydrocarbons in OS, thereby polymerizing and forming condensed solid structures. The calorific value change of OS after conditioning, heavy metal content, and dioxin content of fly ash leached from incinerated product were measured for resource analysis and environmental assessment. Results showed that the resultant OS fuel blocks had extremely low content of heavy metals, dioxins, and other toxic and hazardous substances leached from fly ash. And this process did not require secondary treatment and fully met environmental protection emission standards. Additionally, OSO-101 had certain economic rationality and could effectively recover the calorific value contained in OS. This research is expected to provide new insights for efficient dewaterability and modification of OS, as well as subsequent resource utilization and harmless treatment, bringing potential environmental and economic benefits.

Role of hypochlorite in the harmless treatment of cyanide tailings through slurry electrolysis.

The efficient and harmless treatment of cyanide tailings is necessary for gold extraction processes. The present study reports the effects of ClO- generation in a slurry electrolysis system containing NaCl on the removal rate of cyanide and heavy metal ions in cyanide tailings. The chemical dissolution of metallic minerals and the reaction mechanisms were investigated by Fourier-transform infrared (FT-IR) and X-ray diffraction (XRD) analyses. The obtained results evidenced the key role of ClO- in the removal of cyanide and heavy metal ions through the slurry electrolysis system with NaCl addition. Furthermore, ClO- formation increased with the NaCl concentration, resulting in a higher removal rate of cyanide and heavy metal ions and enhanced metallic mineral dissolution. The cyanide tailings showed the best harmless effect with a NaCl concentration of 15 g/L. With this condition, the removal rates of CNT, CN-, Cu, Zn and Fe were 96.15%, 98.34%, 98.62%, 99.32% and 79.31%, respectively; furthermore, Cu and Fe precipitated at the cathode. The relative hematite content decreased by 3.12%. Under the effect of an electric field, the cyanide and metal cyanide complexes in the cyanide tailings oxidised and decomposed to release metal cations by the strongly oxidising ClO- generated at the anode. The metal cations and hematite were reduced at the cathode, while the metal oxide mineral hematite in the electrolyte underwent chemical dissolution. In the toxic degradation of cyanide tailings, the comprehensive recovery of metals and destruction of metallic minerals in tailings will provide favourable conditions for subsequent comprehensive utilisation.

Enhanced removal of tetracycline via advanced oxidation of sodium persulfate and biochar adsorption.

Advanced oxidation of antibiotic tetracycline (TC) is becoming an accessible and efficient technology. The removal of TC from the complex wastewater needs to be lucubrated. In this study, a TC removal system involving degradation and adsorption was established. TC degradation was accomplished by enhanced advanced oxidation via the addition of sodium persulfate (SP) and biochar into simulated wastewater containing Mn2+ and TC wastewater. The adsorption of TC and its derivatives was removed by biochar. The results indicate that the optimized reaction parameters were 3.0 g/L of biochar prepared at 600 °C (B600) and 400 mg/L of SP under acidic condition, and the removal percentage of TC was 87.48%, including 74.23% of degradation and 13.28% of adsorption; the anions Cl-, NO3-, and H2PO4- had negligible effects on the removal of TC in this Mn2+/B600/SP system. The system also functioned well with an aqueous solution with a high chemical oxygen demand (COD) concentration. Electron paramagnetic resonance (EPR) analysis indicated that ·OH and SO4- free radicals were present in the Mn2+/B600/SP system. Based on the testing and analysis results, a removal mechanism and potential TC degradation pathway for this system were proposed. TC can be degraded by ·OH and SO4- via three degradation pathways. Mn2+ can be precipitated as MnO2, and a part of the TC and its derivatives can be adsorbed on the biochar surface. The Mn2+/B600/SP system also performed satisfactorily for a complex aqueous solution with various cations and antibiotics.

Oily sludge treatment in subcritical and supercritical water: A review.

Oily sludge, an inherent byproduct of the petroleum industry, presents dual characteristics of petroleum resources and hazardous waste. Owing to the unique physicochemical properties of sub-/supercritical water, hydrothermal technologies have been increasingly used for oily sludge treatment. This review is the first to focus on oily sludge treatment using sub-/supercritical water. Eight hydrothermal technologies used for different purposes are summarized herein: pressurized hot water extraction (PHWE) for hydrocarbon separation, thermal hydrolysis (TH) for dewaterability improvement, hydrothermal carbonization (HTC) for hydrochar production, wet air oxidation (WAO) for biodegradability improvement, hydrothermal liquefaction (HTL) for bio-oil production, supercritical water upgrading (SCWU) for light oil production, supercritical water oxidation (SCWO) for complete degradation, and supercritical water gasification (SCWG) for H2-rich syngas production. Moreover, a general reaction pathway for sub-/supercritical water treatment of oily sludge is presented, with a particular focus on the chemical mechanism at temperatures above 350 °C. Lastly, two reaction maps are included to illustrate the reaction pathways of two groups of identifiable model compounds in oily sludge: aliphatic and aromatic hydrocarbons. This review provides detailed information that can promote a better understanding of various hydrothermal technologies, a guideline for selecting the suitable hydrothermal process for a particular oily sludge, and recommendations for further researches.

Synergistic solidification/stabilization of electrolytic manganese residue and carbide slag.

Electrolytic manganese residue (EMR) contains high concentrations of NH4+ and heavy metals, such as Mn2+, Zn2+, Cu2+, Pb2+, Ni2+ and Co2+, while carbide slag (CS) contains high amount of OH- and CO32-, both posing a serious threat to the ecosystem. In this study, EMR and CS synergistic stabilization/solidification (S/S) was discussed science CS could stabilize or solidify EMR and simultaneously reduce its corrosive. The results showed that after the synergistic S/S for 24 h when liquid-solid ratio was 17.5% and CS dosage was 7%, Mn2+ and NH4+ leaching concentrations of the S/S EMR were below the detection limits (0.02 mg/L and 0.10 mg/L) with a pH value of 8.8, meeting the requirements of the Chinese integrated wastewater discharge standard (GB 8978-1996). Mn2+ was stabilized as MnFe2O4, Mn2SiO4, CaMnSi2O6, and NH4+ escaped as NH3. Zn2+, Cu2+, Pb2+, Ni2+ and Co2+ in EMR can also be stabilized/solidified because of the react with OH- and CO32- in CS. Chemical cost was only $ 0.54 for per ton of EMR synergistic harmless treatment with CS. This study provided a new idea for EMR cost-effective and environment-friendly harmless treatment.

Optimize the Preparation of Novel Pyrite Tailings Based Non-sintered Ceramsite by Plackett-Burman Design Combined With Response Surface Method for Phosphorus Removal.

The large amount of untreated pyrite tailings has caused serious environmental problems, and the recycling of pyrite tailings is considered as an attractive strategy. Here, we reported a novel non-sintered ceramsite prepared with pyrite tailings (PTNC) as the main active raw material for phosphorus control, and the dosage effect of ingredients on total phosphorus (TP) removal ability was investigated. The results from Plackett-Burman Design (PBD) suggested the dosages of dehydrated sludge, sodium bicarbonate, and cement were the factors which significantly affect the TP removal ability. The Box-Behnken Design (BBD) based response surface methodology was further employed, and it indicated the interactions between different factors, and the optimized recipe for PTNC was 84.5 g (pyrite tailings), 10 g (cement), 1 g (calcined lime), 1 g (anhydrous gypsum), 3 g (dehydrated sludge), and 0.5 g (sodium bicarbonate). The optimized PTNC was characterized and which presented much higher specific area (7.21 m2/g) than the standard limitation (0.5 m2/g), as well as a lower wear rate (2.08%) rather than 6%. Additionally, the leaching metal concentrations of PTNC were far below the limitation of Chinese National Standard. The adsorption behavior of TP on PTNC was subsequently investigated with batch and dynamic experiments. It was found that the calculated max adsorption amount (qmax) was about 7 mg/g, and PTNC was able to offer a stable TP removal ability under different hydraulic retention time (HRT). The adsorption mechanism was discussed by model fitting analysis combined with XRD and SEM characterization, and cobalt phosphide sulfide was observed as the newly formed substance through the adsorption process, which suggested the existing of both physical and chemical adsorption effect. Our research not only offered an economic preparation method of ceramsite, but also broadened the recycling pathway of pyrite tailings.

Extractive removal of micro and trace nitrofen, 2, 4-dichlorophenol and p-nitrotrophenol from water/soil by humic acid ester ether.

The amphiphilic humic acid ester ether (HAEE), as a kind of solid-phase extractant with characteristics of easy separation and hydrophilic-hydrophobic amphiphilic property, was prepared and used to extract micro or trace nitrofen, 2,4-dichlorophenol and p-nitrotrophenol (NIPs) from water and soil. Degradation of NIPs and extractant regeneration were carried out by simple photocatalysis. The adsorption equilibrium of the mono- or three mixed NIPs by HAEE in aqueous could be quickly reached within 20 min. The adsorption process was fit to quasi-second-order kinetics model and Friendlich thermodynamics model. The possible adsorption interaction was discussed. Results suggested that the adsorption of NIPs onto HAEE predominated by hydrogen bonding, hydrophobic interaction and π-π interaction. The extraction capacity of mixed NIPs (80 µg/L each component) by HAEE was up to 0.38 mg/g and tended to be multi-layer adsorption, in which p-nitrotrophenol had higher adsorption competitiveness because of lower resistance to HAEE. When HAEE-NIPs were degraded by photo-catalyst Fe0/F-TiO2 for 8 h, not only the adsorbed NIPs could be totally degraded and mineralized, but also the HAEE could be effectively regenerated. When the NIPs were continuously extracted from 40-year aging soil for three times (regenerative twice) by combined extractant (48 mL H2O + 2 mL n-hexane + 0.1 g HAEE), the total extraction efficiency of NIPs could reach to 84.66%. This research could supplement the theory and technique for harmless treatment of NIPs contaminated water and soil.

Harmless treatment of municipal solid waste incinerator fly ash through shaft furnace.

Municipal solid waste incinerator fly ash (MSWI FA) is a type of waste that is harmful to the environment, and the melting treatment methods can treat MSWI FA, removing its potential negative impacts. However, special equipment is required for the FA melting process, which necessitates high costs. Metallurgical shaft furnaces (MSF) can melt MSWI FA efficiently. Therefore, the feasibility of using an MSF for FA treatment was studied herein. First, the fundamental physicochemical properties of the FA were analyzed. Then, the appearance and internal morphology of the FA were examined using a scanning electron microscope. Finally, melting experiments were designed according to the conditions of the MSF. The results show that slag changes into a glassy state under rapid cooling, which is beneficial to the solidification of harmful elements. These harmful elements, including Pb, Zn, and Cu, are thus reduced and volatilized into the flue gas under the MSF's reducing atmosphere. The harmful elements that enter the slag are solidified, causing its leaching toxicity to achieve the national standard requirements. Further, under the simulated MSF smelting conditions, the FA dioxin destroy removal efficiency realized more than 99.99% efficiency. Therefore, the harmless treatment of MAWI FA can be realized through MSF process.