Kinetics and the mass transfer mechanism of hydrogen sulfide removal by biochar derived from rice hull

The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperature has great influence on the adsorption of H₂S. At the different pyrolysis temperature, the H₂S removal efficiency of rice hull-derived biochar was different. The adsorption capacities of biochar were 2.09 mg·g^–1, 2.65 mg·g^–1, 16.30 mg·g^–1, 20.80 mg·g^–1, and 382.70 mg·g^–1, which their pyrolysis temperatures were 100 °C, 200 °C, 300 °C, 400 °C and 500 °C respectively. Based on the Yoon-Nelson model, it analyzed the mass transfer mechanism of hydrogen sulfide adsorption by biochar.

Implications: The paper focuses on the biochar derived from rice hull–removed hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperatures have great influence on the adsorption of H₂S. At the different pyrolysis temperatures, the H₂S removal efficiency of rice hull–derived biohar was different. The adsorption capacities of biochar were 2.09, 2.65, 16.30, 20.80, and 382.70 mg·g^?1, and their pyrolysis temperatures were 100, 200, 300, 400, and 500 °C, respectively. Based on the Yoon-Nelson model, the mass transfer mechanism of hydrogen sulfide adsorption by biochar was analyzed.     

弱碱性树脂吸附-解吸苦味酸

考察了水中苦味酸在弱碱性离子交换树脂D301R上的吸附与解吸。研究了吸附热力学、动力学特性及吸附机理。结果表明,树脂在pH=2.7～10.2时,吸附能力最好。等温平衡吸附遵循Freundlich模型。吸附过程为吸热、熵增的自发过程。吸附动力学符合Lagergren准二级速率方程,颗粒内扩散为吸附速率的主要控制步骤,吸附速率常数为7.23×10-5～1.20×10-4g/(mg.min),吸附活化能为19.4 kJ/mol。树脂上吸附的苦味酸可用HNO3+丙酮混合液定量洗脱,洗脱率达99%。静态吸附和脱附的比较结果证实了吸附过程中存在不可逆化学吸附。树脂对苦味酸的吸附主要是通过静电吸附、酸碱络合吸附、氢键吸附等协同作用来完成的。     

赋磁硅气凝胶的制备、表征和吸附异狄氏剂特性

以工业水玻璃为硅源,采用六甲基二硅胺烷(HMDZ)作为改性剂,掺杂纳米级Fe3O4,通过溶胶-凝胶、常压干燥技术,制备得到赋磁硅气凝胶吸附材料(MSA)。采用红外光谱(FTIR)、扫描电镜(SEM)、比表面分析(BET)及振动样品磁强计(VSM)等方法对其结构进行了表征,并对其吸附性能进行研究。结果表明,制得的赋磁硅气凝胶接触角在113°～116°之间,比表面积可达589.79 m2/g,密度约为0.192 g/cm3,饱和磁化强度约为0.44 emu/g,具有超顺磁性。赋磁硅气凝胶对疏水性有机物异狄氏剂表现出良好的吸附性能,符合Freundlich等温吸附模型,KF为42.91;吸附动力学符合准二级动力学模型,吸附速率常数为0.0341 g/(mg.min)。     

酸碱改性对氧化铁脱硫剂脱硫性能影响的研究

通过酸碱改性制备了酸式和碱式2种不同表面性质的常温氧化铁脱硫剂,并采用FT-IR技术对其表面酸碱性质和净化硫化氢废气活性进行了研究.结果表明,表面酸碱件质不同的脱硫剂其脱硫反应行为也不同,在脱硫过程中硫化氢氧化生成的硫酸及亚硫酸会影响脱硫剂的表面酸碱性质,造成酸式脱硫剂的表面酸性更强,从而抑制了硫化氢分子在酸式脱硫剂表...     

Removal of SO2 and NOX from Stack Gas by Reaction with Calcium Hydroxide Solids

Previous workers have shown that simultaneous SO₂/NO_X removal can be obtained in a dry scrubbing system with Ca(OH)₂ promoted by an additive such as NaOH, and that fly ash and product recycle improve the reactivity of the solids toward SO₂. To test SO₂/NO_X removal with fly ash and product recycle, bench-scale experiments with a packed bed reactor were performed at bag filter conditions. The most reactive solid for NO_X removal was prepared by slurrying Ca(OH)₂ with fly ash, CaSO₃, and NaOH. The best conditions for NO_X removal were the greatest temperature (125°C) and greatest concentrations of SO₂ (1500 ppm) and O₂ (20 percent). At the best conditions, NO_X removed in 1 hour was 3-4 moles per 100 moles Ca(OH)₂, compared to 5-10 moles SO₂ removed per 100 moles Ca(OH)₂. The best SO₂ removal was obtained at the highest relative humidities/lowest temperatures (55% RH/ 65°C) with solids prepared by slurrying Ca(OH)₂ with fly ash and NaOH. At these conditions, SO₂ removed In 1 hour was 60-80 moles per 100 moles Ca(OH)₂, compared to 0.5 to 1 moles NO_X removed per 100 moles Ca(OH)₂.     

Physical,chemical and biological behaviour of fumigants on cottonseed

Fumigation is required to protect cottonseed in storage and pre-shipment from insect pests and/or microorganisms. Fumigation of cottonseed with carbon disulphide (CS₂), carbonyl sulphide (COS), ethanedinitrile (C₂N₂), ethyl formate (EF), methyl bromide (MB) and phosphine (PH₃) showed that >85% of the fumigants disappeared within 5?h of exposure. COS maintained >20?mg L^–1 for 24?h. After 1?day of aeration, 75%–85% of the absorbed COS and MB and 20%–40% of the absorbed CS₂, EF and PH₃ were released from treated cottonseed. The fumigant residues were reduced by 80% for COS, 50% for EF or MB and 25% for CS₂ after 1?day of aeration. After 13?days of aeration, fumigant residues were reduced by 95% for MB, 65% for EF, 55% for CS₂ and to natural levels in the COS residue. Carbon disulphide, COS, PH₃, EF and C₂N₂ had no effect on the germination of cottonseed, but germination was reduced to 50% by MB. COS has potential as a fumigant for control of insect pests in cottonseed because it dissipates quickly and does not negatively impact germination. On the other hand, MB appears to strongly absorb and requires an extended period for residues to dissipate, and it negatively impacts germination.     

Predicting Extents of Mercury Oxidation in Coal-Derived Flue Gases

Abstract

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O₂, H₂O, HCl), emissions (NO_X, SO_X, CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MW_t. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl₂ and CaCl₂ injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO_X, LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

Sequential electrochemical treatment of dairy wastewater using aluminum and DSA-type anodes

Dairy wastewater is characterized by a high content of hardly biodegradable dissolved, colloidal, and suspended organic matter. This work firstly investigates the performance of two individual electrochemical treatments, namely electrocoagulation (EC) and electro-oxidation (EO), in order to finally assess the mineralization ability of a sequential EC/EO process. EC with an Al anode was employed as a primary pretreatment for the conditioning of 800 mL of wastewater. A complete reduction of turbidity, as well as 90 and 81 % of chemical oxygen demand (COD) and total organic carbon (TOC) removal, respectively, were achieved after 120 min of EC at 9.09 mA cm^?2. For EO, two kinds of dimensionally stable anodes (DSA) electrodes (Ti/IrO₂-Ta₂O₅ and Ti/IrO₂-SnO₂–Sb₂O₅) were prepared by the Pechini method, obtaining homogeneous coatings with uniform composition and high roughness. The ^·OH formed at the DSA surface from H₂O oxidation were not detected by electron spin resonance. However, their indirect determination by means of H₂O₂ measurements revealed that Ti/IrO₂-SnO₂–Sb₂O₅ is able to produce partially physisorbed radicals. Since the characterization of the wastewater revealed the presence of indole derivatives, preliminary bulk electrolyses were done in ultrapure water containing 1 mM indole in sulfate and/or chloride media. The performance of EO with the Ti/IrO₂-Ta₂O₅ anode was evaluated from the TOC removal and the UV/Vis absorbance decay. The mineralization was very poor in 0.05 M Na₂SO₄, whereas it increased considerably at a greater Cl^? content, meaning that the oxidation mediated by electrogenerated species such as Cl₂, HClO, and/or ClO^? competes and even predominates over the ^·OH-mediated oxidation. The EO treatment of EC-pretreated dairy wastewater allowed obtaining a global 98 % TOC removal, decreasing from 1,062 to <30 mg L^?1.     

Kinetics of imidazolium-based ionic liquids degradation in aqueous solution by Fenton oxidation

In the last few years, several works dealing with Fenton oxidation of ionic liquids (ILs) have proved the capability of this technology for their degradation, achieving complete ILs removal and non-toxic effluents. Nevertheless, very little is known about the kinetics of this process, crucial for its potential application. In this work, the effect of several operating conditions, including reaction temperature (50–90 °C), catalyst load (10–50 mg L^?1 Fe³⁺), initial IL concentration (100–2000 mg L^?1), and hydrogen peroxide dose (10–200% of the stoichiometric amount for the complete IL mineralization) on 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl) oxidation has been investigated. Under the optimum operating conditions (T = 90 °C; [Fe³⁺]₀ = 50 mg L^?1; [H₂O₂]₀ = 100% of the stoichiometric amount), the complete removal of [C₄mim]Cl (1000 mg L^?1) was achieved at 1.5-min reaction time. From the experimental results, a potential kinetic model capable to describe the removal of imidazolium-based ILs by Fenton oxidation has been developed. By fitting the proposed model to the experimental data, the orders of the reaction with respect to IL initial concentration, Fe³⁺ amount and H₂O₂ dose were found to be close to 1, with an apparent activation energy of 43.3 kJ mol^?1. The model resulted in a reasonable fit within the wide range of operating conditions tested in this work.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

Oxidation of a PAH polluted soil using modified Fenton reaction in unsaturated condition affects biological and physico-chemical properties

A batch experiment was conducted to assess the impact of chemical oxidation using modified Fenton reaction on PAH content and on physico-chemical and biological parameters of an industrial PAH contaminated soil in unsaturated condition. Two levels of oxidant (H₂O₂, 6 and 65 g kg⁻¹) and FeSO₄ were applied. Agronomic parameters, bacterial and fungal density, microbial activity, seed germination and ryegrass growth were assessed. Partial removal of PAHs (14% and 22%) was obtained with the addition of oxidant. The impact of chemical oxidation on PAH removal and soil physico-chemical and biological parameters differed depending on the level of reagent. The treatment with the highest concentration of oxidant decreased soil pH, cation exchange capacity and extractable phosphorus content. Bacterial, fungal, and PAH degrading bacteria densities were also lower in oxidized soil. However a rebound of microbial populations and an increased microbial activity in oxidized soil were measured after 5 weeks of incubation. Plant growth on soil treated by the highest level of oxidant was negatively affected.     

微电解-Fenton深度处理制药废水影响因素与参数控制

采用铁炭微电解-Fenton联合工艺深度处理制药废水生化出水,探讨了初始pH、曝气量、反应时间等因素对微电解出水Fe2+和Fe3+变化规律、COD降解速率以及后续Fenton氧化效果的影响,为优化微电解-Fenton氧化联合工艺提出了微电解间歇加酸的理论。间歇加酸可提高微电解系统中COD降解速率和Fe2+含量,使后续Fenton氧化无需投加FeSO4·7H2O即可达到较好的COD去除效果。结果表明,当初始pH=2.5,曝气量为0.6 m3/h,间歇加酸30 min/次,微电解反应2 h,出水投加1 mL/L的H2O2进行Fenton氧化2 h,COD总去除率可达81.33%;间歇加酸30 min/次可将微电解反应2 h出水Fe2+浓度从50 mg/L提高至151 mg/L,COD降解速率从10.6 mg COD/(L·h)提高至22.2 mg COD/(L·h)。     

Assessing the steady-state [·NO<Subscript>2</Subscript>] in environmental samples

Based on available literature data of [NO₂ ⁻], steady-state [·OH], and ·OH generation rate upon nitrate photolysis in environmental aqueous samples under sunlight, the steady-state [·NO₂], could be calculated. Interestingly, one to two orders of magnitude more ·NO₂ would be formed in photochemical processes in atmospheric water droplets compared to transfer from the gas phase. The relative importance of nitrite oxidation compared to nitrate photolysis as an ·NO₂ source would be higher in atmospheric than in surface waters. The calculated levels of ·NO₂ could lead to substantial transformation of phenol into nitrophenols in both atmospheric and surface waters.     

Protective role of a methanolic extract of spinach (Spinacia oleracea L.) against Pb toxicity in wheat (Triticum aestivum L.) seedlings: beneficial effects for a plant of a nutraceutical used with animals

Spinach extracts contain powerful natural antioxidants and have been used to improve the response of animal cells to various stress factors. The aim of the present study was to assess the effects of a methanolic extract of spinach (SE) used at two concentrations (21.7 and 217 ppm) on the growth, certain enzymes and antioxidant systems in wheat seedlings under lead stress. When wheat seedlings were grown for 7 days in a solution containing Pb(NO₃)₂ (3 mM), germination and growth were impaired, while signs of oxidative stress were observed. SE (217 ppm) pretreatment was able to protect seedlings from Pb toxicity by both reducing Pb uptake and Pb-induced oxidative stress. As a consequence, almost normal germination, elongation, biomass and α-amylase activity were restored by SE (217 ppm) pretreatment of wheat seedlings, in spite of the presence of Pb. Our results support the protective role and the antioxidant effect of SE against Pb. These results show an amazing similarity to the effects of SE in animals, which suggests that providing “nutraceuticals” to plants could improve their “health” status.     

Environmental effects of nanosilver: impact on castor seed germination, seedling growth, and plant physiology

Increasing use of nanoparticles in daily products is of great concern today, especially when their positive and negative impact on environment is not known. Hence, in current research, we have studied the impact of silver nanoparticle (AgNPs) and silver nitrate (AgNO₃) application on seed germination, root, and shoot length of castor bean, Ricinus communis L. plant. Silver nanoparticles had no significant effects on seedling growth even at higher concentration of 4,000 mg L^?1, while the silver in bulk form as AgNO₃ applied on the castor bean seeds inhibited the seed germination. Silver uptake in seedlings of the castor seeds on treatment with both the forms of silver was confirmed through atomic absorption spectroscopy studies. The silver nanoparticle and silver nitrate application to castor seeds also caused an enhanced enzymatic activity of ROS enzymes and phenolic content in castor seedlings. High-performance liquid chromatography analysis of individual phenols indicated enhanced content of parahydroxy benzoic acid. These kinds of studies are of great interest in order to unveil the movement and accumulation of nanoparticles in plant tissues for assessing future applications in the field or laboratory.     

氯离子对氨氮电化学氧化的影响

以自制的二氧化铅粉末多孔电极为阳极,不锈钢为阴极,探讨了投加Cl-对氨氮电化学氧化反应速率、途径及产物等的影响。结果表明,投加Cl-能显著提高氨氮的电化学氧化速率;有氯离子存在的条件下,氨氮的去除主要靠电催化过程中产生的强氧化性物质.OH,HClO的作用,其去除率随着电流密度的增大呈增高的趋势,随初始pH的增大而增大;投加氯离子后,NO3--N的生成量增加,但氧化产物主要是以N2为主的含氮气体。     

不同改性方式对竹炭净化气态氮氧化物效果的影响

为了研究不同表面改性方法对竹炭空气净化效果的影响,测定了化学药剂活化、超声处理、微波处理后的改性竹炭对低浓度氮氧化物的净化效果。结果表明:活化剂浸渍后的竹炭,对氮氧化物净化效率降低,净化速度减慢;微波功率越大、辐照时间越长,改性后竹炭对氮氧化物处理效率越大,但辐照时间达到一定程度后,竹炭对氮氧化物的处理效率增大变得缓慢;超声处理后的竹炭对NO的处理效率比改性前有明显提高。BET测试结果表明,竹炭产品用微波和超声处理后,平均孔径、微孔表面积和比表面积均比活化前增大;而经过活化剂浸渍后,微孔面积和比表面积都显著下降。因此建议采用微波及超声方式对竹炭进行活化。     

呼吸测量法测定废水中活性异养菌COD组分

废水中的活性异养菌(XH)会影响废水生物处理过程动力学,过程模拟需要对其定量表征.通过2种方法对城市污水中XH进行呼吸测量,分别结合XH最大比呼吸速率参数(P方法)和细胞生长过程模型拟合(F方法)测定其中的XH-COD组分.结果表明,F方法的测量结果是P方法的0.6～0.9倍,两者存在一定的丰廿关性;对于含高XH、低易生物降解基质(RBCOD)的废水,呼吸测量得不到明显的呼吸速率指数上升段,影响F方法的测定结果,水样稀释和外加RBCOD是可行的改进办法.使用P方法得到某城市污水厂进水的XH-COD占总COD的23%～46%(平均31%),高于多数文献报道结果.     

Microwave irradiation and citric acid assisted seed germination and phytoextraction of nickel (Ni) by <Emphasis Type="Italic">Brassica napus</Emphasis> L.: morpho-physiological and biochemical alterations under Ni stress

The complex bio-geochemistry of soil allows pollutant to persist for a longer period of time which further decreased the fertility and natural composition of land. Nickel, an inorganic pollutant, coming from a wide range of industrial and manufacturing units possesses serious threat to soil degradation and crop productivity around the world. The present study was carried to evaluate the combined role of microwave irradiation (MR) and citric acid (CA) on the phytoextraction potential of Brassica napus L. under Ni stress. An initial seed germination test was conducted to select effective time scale of MR exposure. Highest seed germination was observed at exposure of 2.45 GHz frequency for 30 s. Healthy seeds of B. napus L. genotype Faisal Canola (RBN-03060) treated with MR at 2.45 GHz for 30 s were sown in plastic pots filled with 5 kg of soil. Nickel and CA applied exogenously in solution form with different combinations to both MR-treated and untreated B. napus plants. The MR-treated plants showed higher growth, biomass, photosynthetic pigments (Chl a, b, total, and carotenoids) and activities of antioxidant enzymes (SOD, POD, APX, CAT) as compared to untreated plants who showed higher reactive oxygen species (MDA, H₂O₂) and electrolyte leakage. Increasing Ni concentration significantly decreased the physiological and biochemical attributes of B. napus both in MR-treated and untreated plants. The addition of CA alleviated Ni-induced toxic effects in both MR-treated and untreated plants by improving antioxidant defense system. The degree of Ni stress mitigation was higher in MR-treated plants. The Ni concentration was higher in root, stem, and leaves of MR-treated plants under CA application as compared to untreated plants. The present study concluded that seeds treated with MR before sowing showed higher accumulation and concentration of Ni from soil, and this phenomenon boosted with the application of CA.