Study on dechlorination salt characteristics of pickling sludge by a water-washing process.

Steel hydrochloric acid pickling sludge (SHPS), containing the heavy metals Fe, Zn, and Ni and a high chloride salt content, is considered a hazardous solid waste. With the gradual reduction of high-grade metal mineral resources such as Fe, Zn and Ni, it is particularly urgent to recycle valuable metals such as Fe, Zn and Ni in solid waste SHPS in order to realize the resource utilization of SHPS and reduce the environmental harm caused by SHPS. In addition, SHPS usually contains different amounts of alkali chloride, which will have a serious adverse impact on the subsequent extraction and smelting process of Fe, Zn and other metals. Therefore, the removal of chloride plays an important role in the resource utilization of valuable metals in SHPS. Thus, in this study, the effects of water washing dechlorination process parameters such as liquid-solid (L/S) ratio, SHPS particle size, washing time and washing frequency on the chloride removal rate were investigated. The best experimental parameters of SHPS washing were obtained. At the same time, the microscopic morphology and crystal phase composition of SHPS before and after washing were explored. The results showed that the optimized conditions were as follows: room temperature, a L/S ratio of 3 : 1, an SHPS particle size of 100 mesh, and 10 min of water washing, repeated two or three times; under these conditions, the removal rate of Cl, Na, Ca, K, Mg, and S reached 96.64-99.68%, 97.38-99.89%, 36.40-60.37%, 49.11-54.82%, 39.18-40.22%, and 36.98-42.13% respectively. The contents of Cl, K, and Na in filter residue (FR) meets the requirements in GB/T 36144-2018 and GB/T 32545-2016. Conversely, the contents of Fe, Zn, Mn and Ni in the FR are enriched, which is more conducive to the subsequent resource utilization of SHPS. The scanning electron microscope (SEM) image shows the particle size of the FR particles is reduced after washing. The X-ray diffractometer (XRD) results proved that the chlorine salt content in the FR after washing was significantly reduced, the diffraction peaks of Al2O3 appeared in the FR, and the diffraction peak intensity of CaCO3, Fe2O3 and SiO2 increased.

Reduction-Magnetic Separation of Pickling Sludge by Biomass Pyrolysis Reducing Gas.

The neutralization process of carbon steel pickling wastewater produces a large amount of steel hydrochloric acid pickling sludge (SHPS), and improper treatment of this sludge poses a serious threat to the environment. Considering that SHPS contains a large amount of iron oxide and given the huge demand for iron concentrate in China's ironmaking industry, refining iron oxide in SHPS into iron concentrate will have great environmental and economic benefits. This paper proposes a new method that uses biomass (corncob) to replace conventional coal-based reductants for the recovery of iron components in SHPS to simultaneously utilize two kinds of solid waste resources. Factors that affect the iron recovery rate and iron grade of SHPS, such as the reaction temperature, corncob dosage, residence time, and magnetic field strength, were studied using a fixed bed and a magnetic separator. These studies were combined with thermodynamic analysis, thermogravimetric analysis, X-ray diffraction, inductively coupled plasma-mass spectrometry, gas chromatography, etc. The results showed that when the reaction temperature was 680 °C, the corncob dosage was 5%, the residence time was 20 min, and the magnetic field strength was 200 mT, the recovery rate of iron reached 91.83%, and the iron grade of the recovered products was 67.72%, meeting the level I requirements in GB/T 32545-2016. Based on this result, a process involving SHPS reduction roasting with corncob pyrolysis reducing gas-magnetic separation was established to recover iron from SHPS. This process not only effectively utilizes the iron oxide in SHPS by converting it into iron concentrate powder for the ironmaking industry but also proves that the pyrolysis gas of corncob has good reduction ability.

Composition and Leaching Toxicity of Hydrochloric Acid Pickling Sludge Generated from the Hot-Dip Galvanized Steel Industry.

Steel hydrochloric acid pickling sludge (SHPS), containing the heavy metals Fe, Zn, and Ni and a high chloride salt content, is considered a type of hazardous solid waste because of its potential harm to human health and the environment. In addition, the SHPS yield is large, but the main treatment currently used is only safe for landfills. Although studying the composition and leaching toxicity of SHPS is of great importance, only a small amount of related literature is available. This paper can help compensate for this deficiency. SHPS is analyzed from the aspects of its formation mechanism, pH, moisture content, elemental concentration, phase composition, microstructure, and leaching toxicity. The results show that its pH ranges from 2.25 to 11.11, and the moisture content ranges from 45.47% to 83.34%. Additionally, the concentration of Fe is the highest, with values from 29.80% to 50.65%, while other alkali metal elements, namely, Ca, K, and Na, have values of 0.36% to 23.07%, 0.02% to 19.82%, and 0.38% to 3.31%, respectively. Heavy metal elements, namely, Zn, Ni, Mn, Cr, and Pb, have values of 0.02% to 14.88%, 0.001% to 0.05%, 0.03% to 0.38%, 0.01% to 0.09%, and 0.02% to 0.19%, respectively. Anions, namely, SO4 2-, Cl-, F-, and NO3 -, have contents of 0.09% to 0.34%, 0.54% to 5.73%, 0.001% to 0.04%, and 0.01% to 0.15%, respectively. X-ray diffraction (XRD) analysis shows that Fe and Zn are mainly present in oxides, Ca is present as CaO and CaCO3, and chlorine is present in NaCl. Moreover, scanning electron microscopy (SEM) analysis shows that the microscopic structure consists mainly of bright and fluffy irregular spheres; stripes; flakes; and dark, very small irregular particles. The leaching toxicity test based on HJ/T 299-2007 (China) was performed, where SHPS samples were treated with a mixed solution of sulfuric acid, nitric acid, and pure water (pH = 3.20 ± 0.05) at a liquid-to-solid ratio of 10:1 for a period of 18 h. The leachate was filtered and analyzed for Cr, Ni, Mn, Zn, etc. The leaching results indicate that Zn and Ni are the main elements that cause SHPS to be hazardous to the environment. These research results can provide a reference for later researchers studying the effective treatment of SHPS, such as more effective treatments for reducing toxicity and resource utilization.

High-spatial-resolution VOCs emission from the petrochemical industries and its differential regional effect on soil in typical economic zones of China.

Volatile organic compounds (VOCs) are toxic to the ecological environment. The emission of VOCs into the atmosphere has already caused attention. However, few studies focus on their regional effects on soil. As a major VOCs source in China, research on the effect of petrochemical industry on the environment is urgent and essential for regional control and industrial layout. This study established national VOCs emission inventory of five petrochemical sub-industries and spatial distribution based on consumption of raw material or products' yield and 28,888 factories. The VOCs emissions showed continuously increasing trend from 2008 to 2019, with cumulative 1.83 × 107 t, wherein these from rapid economic development zones accounted for 66.10%. The detected concentrations of VOCs in various industries combined with meteorological parameters were used in Resistance Model to quantify regional dry deposition. Higher concentrations of 111 VOC species were 238.27, 260.01, 207.54 µg·m-3 from large-scale enterprises for crude oil and natural gas extraction, oil processing, synthetic rubber and resin, leading to higher deposition ratios of 0.81%-0.94%, 0.70%-0.81%, 1.50%-1.75% in rapid economic development zones, respectively. The regional climate condition played a dominant role. Annual VOCs dry deposition amount in rapid economic development zones was calculated to be totally 6.38 × 103 t using obtained deposition ratios and emissions, with 3.21 × 103 t in Bohai Economic Rim (BER), 2.42 × 103 t in Yangtze River Economic Belt (YREB), 748.43 t in Pearl River Delta (PRD). Generally, crude oil and natural gas extraction, oil processing, synthetic rubber and resin contributed 13.09%, 57.77% and 29.14%, respectively. The proportion of synthetic rubber and resin for dry deposition increased by 5.04%-18.81% compared with VOCs emissions in BER and YREB. In contrast, it declined from 45.52% for emission to 29.86% for deposition due to absolute dominance of small-scale enterprises in PRD. Overall, VOCs control from oil processing was significant, especially in BER.

A new method for evaluating air quality using an ideal grey close function cluster correlation analysis method.

To scientifically and reasonably evaluate air quality with a large amount of monitored data, this paper proposes a new evaluation method called ideal grey close function cluster correlation analysis (IGCFCCA). Taking the air quality in Ningxia Province, China, as an example, according to China's air quality standard, SO2, NO2, PM10, PM2.5 and O3 are selected as evaluation indexes to perform the evaluation. The results show that the air quality in this region in 2018 can be divided into three classifications, among which the relatively poor air quality in March, April and May is the first classification, the better air quality in August and September is the third classification, and the air quality in other months falls under the second classification. Correlation analysis is used to qualitatively determine that these three classifications correspond to first-level air quality in China's air quality standard, and the correlation degree, which is the distance between the three classifications and the first-level air quality, is quantitatively determined. Specifically, the correlation degrees of the first-classification, second-classification and third-classification of air quality are 0.674, 0.697 and 0.71, respectively. The research results indicate potential directions and objectives for air quality management to achieve scientific management.

Characteristics of biochars prepared by co-pyrolysis of sewage sludge and cotton stalk intended for use as soil amendments.

The safe disposal and utilisation of sewage sludge can be challenging because of the potential environmental risks posed by heavy metals in the sludge. Conversion of sewage sludge and agriculture biomass into biochars that can be used to improve or remediate contaminated soils is a promising solution to this problem. In this study, biochars were produced via co-pyrolysis of sewage sludge and cotton stalk (1:1, w/w) at temperatures ranging from 300°C to 600°C. Then, the potential environmental risks of heavy metals and properties of the biochars were investigated. The addition of cotton stalk promoted the migration and transformation of heavy metals from bioavailable to stable fractions, which significantly reduced the potential environmental risks of heavy metals in biochars. Moreover, compared with biochars obtained via pyrolysis of sewage sludge alone, the pH values, C contents, and adsorption capacities of biochars increased, while the yields, ash contents, specific surface areas and molar H/C ratios decreased. In summary, co-pyrolysis of sewage sludge and cotton stalk is a feasible method for alleviating the potential environmental risks of heavy metals in biochars used to treat soils.

Co-pyrolysis of sewage sludge and cotton stalks.

Proper disposal of ever-increasing amounts sewage sludge and cotton stalks is a challenge around the world, and conversion of these wastes into biochars via co-pyrolysis may be a promising solution. In this study, biochars were prepared via co-pyrolysis of sewage sludge and cotton stalks with different mixing ratios (cotton stalks/sewage sludge, w/w) at 650 °C for 2.0 h, and then, biochars were characterized to identify their potential agronomic and environmental benefits as soil amendments. Biochars prepared with higher mixing ratios had higher C contents and lower H/C and N/C ratios, which suggests that this approach has potential for improving C storage in biochar-treated soils to help offset greenhouse gas emissions. All biochars were mesoporous materials with an average pore size of 3-4 nm. The specific surface area increases indicated that these biochars would have relatively high water holding capacities and heavy metal adsorption capacities in heavy metal contaminated soils. The high ash contents and cation exchange capacity values in biochars prepared with lower mixing ratios indicate that these products would be useful for enhancing the nutrient supply and nutrient retention capacity in degraded soils. Moreover, the addition of more cotton stalks efficiently decreased the mobility and bioavailability of heavy metals in the biochars. At a certain level, co-pyrolysis of sewage sludge and cotton stalks to produce biochars would have both economic and environmental benefits.

Effects of various additives on the pyrolysis characteristics of municipal solid waste.

Additives can have a significant impact on the pyrolysis process. The effects of three additives (CaO, MSW char and biomass) on the pyrolysis characteristics of municipal solid waste (MSW) were investigated using a fixed-bed reactor. In addition, the effects of additives and temperature on the MSW pyrolysis product yield, the composition of MSW pyrolysis gases, and the composition of MSW pyrolysis tar were investigated using fixed bed reactor, GC-MS and FTIR, respectively. The results showed that the maximum tar yield of the MSW reached 28.73% at 600 °C and the tar yield decreased with increasing amounts of CaO and MSW. The tar yield began to decrease when the additive amount of CaO was 5% and decreased to 23.05% when the additive amount of MSW char (C) was 30%. Synergistic pyrolysis of the biomass and MSW was observed when the additive amount of the pine increased to 75% (with a tar yield of 37.91%). Regarding gas composition, with increasing additives content, the CO2 yield decreased, while the CO yield increased. According to the FTIR analysis of the tar, CaO enhanced the condensation of the aromatic rings and converted the aliphatic hydrocarbons, while C reduced the oxygenic groups of the tar. The GC-MS results revealed that the additives decreased the yield of carboxylic acid and ethanol, and increased the ester yield. The additives were also found to have a deoxidation effect that decreased the acid content, potentially improving the quality and stability of the tar.