Conversion of calcium sulphide to calcium carbonate during the process of recovery of elemental sulphur from gypsum waste

The production of elemental sulphur and calcium carbonate (CaCO₃) from gypsum waste can be achieved by thermally reducing the waste into calcium sulphide (CaS), which is then subjected to a direct aqueous carbonation step for the generation of hydrogen sulphide (H₂S) and CaCO₃. H₂S can subsequently be converted to elemental sulphur via the commercially available chemical catalytic Claus process. This study investigated the carbonation of CaS by examining both the solution chemistry of the process and the properties of the formed carbonated product. CaS was successfully converted into CaCO₃; however, the reaction yielded low-grade carbonate products (i.e. <90 mass% as CaCO₃) which comprised a mixture of two CaCO₃ polymorphs (calcite and vaterite), as well as trace minerals originating from the starting material. These products could replace the Sappi Enstra CaCO₃ (69 mass% CaCO₃), a by-product from the paper industry which is used in many full-scale AMD neutralisation plants but is becoming insufficient. The insight gained is now also being used to develop and optimize an indirect aqueous CaS carbonation process for the production of high-grade CaCO₃ (i.e. >99 mass% as CaCO₃) or precipitated calcium carbonate (PCC).     

Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

CO2 emissions in calcium carbide industry: An analysis of China's mitigation potential

China's calcium carbide output has dominated the global market for several years, driven by the demand for PVC (polyvinyl chloride), a fundamental polymer material and also the primary downstream product of calcium carbide in China. The fast growth of this energy-intensive industry leads to an inevitable increase in CO₂ emissions. However, there is a large reduction potential with process improvement in this industry which is currently characterized by widespread outdated facilities. In this study, we attempt to assess the reduction potential of CO₂ emissions in China's calcium carbide production, based on the analysis of CO₂ emission patterns and estimation of the emission amount. Three scenarios regarding process improvement are employed to conduct this assessment. The results imply that the cumulative CO₂ abatement in the Current Policy Scenario and in the Strengthened Policy Scenario from 2008 to 2020, compared with the Baseline Scenario, are 89.0 and 107.6 million t, respectively. The specific measures and policy implications to achieve this potential are also discussed in the article.     

The effects of phosphorus-free inhibitors on the ignition of lycopodium dust

The minimum ignition temperature of dust suspension (MIT) and the hot surface ignition temperature of the dust layer (LIT) are essential safety parameters for the process industry. However, the knowledge of the ignition behavior when solid mixtures of flammable fuels and phosphorous-free inhibitors are considered is still scarce and further experimental and theoretical analyses are requested. In this work, the ignition temperature of phosphorous-free inhibitors (coal fly ash and calcium carbonate) mixed with lycopodium dust have been studied in terms of LIT analysis (hot plate thickness: 5 mm, 12.5 mm and 15 mm), and by the Godbert-Greenwald test for the MIT. Both coal fly ash and calcium carbonate have been tested at different concentrations and particle sizes.Results show that the effects of the inhibitor can be counter-productive when layer ignition temperature is considered even if the minimum ignition temperature of the dust suspension shows a positive effect from the safety point of view. This behavior has been analyzed in the terms of thermal conductivity and diffusivity of the mixture, by using Maxwell's equation for two-phase solid mixtures. Standard empirical correlations for the ignition temperature of solid mixtures have been also tested, showing their weakness in reproducing mixture behavior.     

过磷酸钙与石灰混施对污染农田低累积玉米生长和重金属含量的影响

通过田间实验,研究了过磷酸钙和石灰混施对重金属污染农田上低累积玉米产量以及籽粒、茎叶重金属含量的影响,并分析了施用过磷酸钙和石灰后土壤pH和有效重金属含量的变化。结果表明,与单施过磷酸钙和单施石灰相比,过磷酸钙和石灰混施更能显著提高玉米生物产量,且过磷酸钙和石灰均有一定的后效。单施石灰处理、石灰与过磷酸钙混施处理都均显著降低玉米籽粒Cd、Zn和Cu含量,其中以中量(0.4 kg/m2)、高量石灰(0.6 kg/m2)+中量过磷酸钙(0.2kg/m2)处理效果最佳,其玉米籽粒Cd、Zn和Cu含量降低到了国家食品卫生标准允许的含量水平。石灰处理均不同程度地提高了玉米籽粒Pb含量,配施过磷酸钙也不能明显降低玉米籽粒Pb含量,但仍低于饲料卫生标准允许的含量水平。另外,单施石灰处理和石灰与过磷酸钙混施处理均显著降低了玉米茎叶Cd、Pb、Zn和Cu含量,可以安全用作有机肥。     

Alteration of shell nacre micromorphology in blue mussel Mytilus edulis after exposure to free-ionic silver and silver nanoparticles

This study describes the morphology of inner shell surface (ISS) of the blue mussel Mytilus edulis Linnaeus after short-term exposures to radiolabeled silver in free-ionic (^110mAg⁺) and engineered nanoparticulate (^110mAgNPs, <40 nm) phases. Radiolabeled silver in starting solutions was used in a similar low concentration (∼15 Bq mL⁻¹) for both treatments. After exposure experiments radiolabeled silver was leached from the ISS using HCl. It concentration for shells from both treatments was ∼0.5 Bq mL⁻¹. Whole ISS of young individuals and prismatic layer of adults showed no evidence of any major alteration process after silver uptake. However, the nacre portion of adult mussels exposed to both treatments revealed distinct doughnut shape structures (DSS) formed by calcium carbonate micrograins that covered the surface of aragonite tablets. Scanning electron microscope (SEM) imaging revealed the existence of only minor differences in DSS morphology between mussels exposed to Ag⁺ and AgNPs. From literature survey, DSS were also found in bivalves exposed to Cd²⁺. The DSS occurring in a specimen of a field-collected bivalve is also shown. Formation of distinctive DSS can be explained by a disturbance of the shell calcification mechanism. Although the occurrence of DSS is not exclusively associated with metal bioavailability to the mussels, the morphology of DSS seems to be linked to the speciation of the metal used in the uptake experiments.     

Fe(II)-mediated transformation of schwertmannite associated with calcium from acid mine drainage treatment

Schwertmannite is an important Fe(III)-oxyhydroxysulfate in acid mine drainage (AMD) polluted areas and its stability depends on surrounding environmental factors and previously bound elements. The treatment and neutralization of AMD normally involve the use of lime, which leads to the discharge of abundant Ca in the mining area. Such an environmental disturbance brings up an important and less considered problem of how the reductive transformation of schwertmannite associated with coexisting Ca occurred. Here, the Fe(II)-mediated transformation of Ca-adsorbed schwertmannite and subsequent Ca repartitioning behaviors were investigated. Results showed that adsorbed Ca had a weak inhibitory effect on Fe(II)-mediated schwertmannite transformation. Release of SO₄²⁻ and SEM images both indicated that transformation rates of schwertmannite decreased under the influence of adsorbed Ca. XRD patterns indicated that adsorbed Ca altered schwertmannite transformation pathways and product compositions upon treatment with 0.4 mmol/L Fe(II). The end products of Sch notably contained both goethite and lepidocrocite; however, transformation products of SchCa only contained goethite all along. Approximately 33.5% of the surface adsorbed-Ca was released into solution within 6 hr after Fe(II) injection. Aqueous Ca behaved in a “first release and then im-mobilization” manner, which indicated dissolution and secondary mineralization drove Ca migration during the Fe(II)-mediated transformation of SchCa. Adsorbed Ca blocked the surface sites for subsequent Fe(II) adsorption, limited the Fe(II)-Fe(III) ETAE, and decreased the transformation rates. This work sheds light on the complex geochemical behavior of schwertmannite under the influences of environmental perturbations in AMD environments.     

Sorption of hazardous metals from single and multi-element solutions by saltbush biomass in batch and continuous mode: interference of calcium and magnesium in batch mode

Batch studies were performed to determine the interference of calcium (Ca) and magnesium (Mg) on the sorption of Cu(II), Cd(II), Cr(III), Cr(VI), Pb(II), and Zn(II) [from CuSO(4), K(2)Cr(2)O(7), Pb(NO(3))(2), Cr(NO(3))(3), ZnCl(2), and Cd(NO(3))(2)] by saltbush (Atriplex canescens) biomass. The results demonstrated that Ca and Mg at concentrations of at least 20 times higher than the concentration of most of the target metals did not interfere with the metal binding. The data show that the batch binding capacity from a multimetal solution at pH 5.0 was (micromol/g) about 260 for Cr(III) and Pb, and about 117, 54, and 49 for Cu, Zn, and Cd, respectively. The use of 0.1M HCl allowed the recovery of 85-100% of the bound Cu, Cr(III), and Pb, and more than 37% of the bound Cd and Zn. The column binding capacity for Pb was about 49 micromol/g from both the single and multimetal solutions, while it was, respectively about 35 and 23 micromol/g for Cr(III). The binding capacity for Cu and Zn from the single and multimetal column experiments was 35 micromol/g and less than 10 micromol/g, respectively. The stripping data from the single column experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and Zn, 90% and 74% of the bound Pb and Cr(VI), respectively, and less than 25% of the bound Cd and Cr(III), while the stripping from the multimetal experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and about 74%, 54%, 43%, and 40% of the bound Pb, Zn, Cd, and Cr(III), respectively.     

Study on the influence of additives in an industrial calcium fluoride and waterworks sludge co-melting system

This work explores the effect of additives on the pouring temperature in a waterworks and industrial calcium fluoride sludge co-melting system. Two kinds of sludge were mixed in various ratios to find a mixing ratio at which the operating temperature for subsequent additive tests was relatively low. Various proportions of either sodium carbonate (Na2CO3) or potassium carbonate (K2CO3) reagent were added to the mixed-sludge samples to elucidate the consequent changes in pouring temperature. The experimental results revealed that the pouring temperature was lowest when calcium fluoride was mixed with waterworks sludge in a ratio of 4:6 (w/w). Adding sodium carbonate or potassium carbonate reagent to the mixed-sludge samples further reduced the pouring temperature. Increasing the amount of sodium carbonate did not significantly reduce the pouring temperature beyond that observed when 2% was added, suggesting that 2% was the optimal additional percentage of sodium carbonate. In contrast, the pouring temperature was increased when over 2% potassium carbonate was added to the mixed-sludge samples, revealing that the optimal additional percentage of potassium carbonate was also 2%. These findings indicate that both sodium carbonate and potassium carbonate can be used as additives to increase the energy efficiency of the melting process, but sodium carbonate is more operationally convenient.     

过磷酸钙和腐烂苹果联合添加对猪粪堆肥过程中碳素转化和腐熟的影响

调控堆肥过程中CO_2的排放,对于保证堆肥进程的有效进行和减少碳素损失具有重要意义.本文以过磷酸钙和腐烂苹果为添加剂,共设置4个处理:不添加添加剂(CK)、过磷酸钙处理(P)、腐烂苹果处理(A)及混合添加处理(1/2过磷酸钙+1/2腐烂苹果,PA),研究在自制堆肥反应箱猪粪堆肥过程中碳素转化特征及其对堆肥腐熟的影响.结果表明,单加过磷酸钙处理进入高温期的时间晚于其他处理3～4 d,而混合添加处理并没有出现高温期推迟的现象.整个堆肥过程中,CK、P、A和PA处理CO_2-C的累积排放量分别占起始碳素的37.0%、33.0%、40.1%和36.7%,碳素损失分别为54.1%、50.3%、59.4%和55.7%.虽然单加过磷酸钙处理降低了堆肥中碳素损失,但却抑制了有机质的降解,增加了电导率值,而混合添加处理促进了有机质的降解,并使腐殖质含量较对照提高了11.8%.此外,单加过磷酸钙处理的种子发芽指数在40 d时才达到80%,而混合添加处理在24 d时已达到80%.综上分析,1/2过磷酸钙+1/2腐烂苹果联合添加是一种可行的畜禽粪便堆肥添加剂使用方法.