Development of LnMnO3+σ perovskite on low temperature Hg0 removal

LnMnO_3+σ (Ln = La, Pr, Nd, Sm, Eu, Gd or Dy) perovskites synthesized by sol-gel method were employed for gaseous elemental mercury (Hg⁰) removal from coal-fired flue gas. Characterization results revealed the structure of the perovskites presented a phase transition process from rhombohedral system to O- and O'-orthorhombic structure with the change of A-site rare earth elements. The perovskites showed satisfactory Hg⁰ removal capacity in a narrow temperature range of 100–150°C. NdMnO_3+σ with an O-O’ orthorhombic structure presented the best Hg⁰ removal performance, which markedly depends on four factors: crystal structure, oxygen vacancy density, Mn⁴⁺/Mn³⁺ ratio and surface element segregation. The Hg⁰ removal mechanism was illustrated based on the mercury temperature programmed desorption experiment and X-ray photoelectron spectroscopy characterization. Both chemisorption and catalytic oxidation played a role in the Hg⁰ removal process. Chemisorption dominated the Hg⁰ removal, due to the slow catalytic oxidation rate at low temperature. This work preliminarily established the relation between the structure of rare earth manganese perovskite and Hg⁰ removal performance.     

Simultaneous removal of gaseous CO and elemental mercury over Cu-Co modified activated coke at low temperature

Cu-Co multiple-oxides modified on HNO₃-pretreated activated coke (AC_N) were optimized for the simultaneous removal of gaseous CO and elemental mercury (Hg⁰) at low temperature (< 200 °C). It was found that 2%CuOx-10%CoOx/AC_N catalyst calcined at 400°C resulted in the coexistence of complex oxides including CuO, Cu₂O, Co₃O₄, Co₂O₃ and CoO phases, which might be good for the simultaneous catalytic oxidation of CO by Co-species and removal of Hg⁰ by Cu-species, benefiting from the synergistic catalysis during the electro-interaction between Co and Cu cations (CoO ? Co₃O₄ and Cu₂O ? CuO). The catalysis removal of CO oxidation was obviously depended on the reaction temperature obtaining 94.7% at 200 °C, while no obvious promoting effect on the Hg⁰ removal (68.3%-78.7%). These materials were very substitute for the removal of CO and Hg° from the flue gas with the conditions of 8–20 vol.% O₂ and flue-gas temperature below 200 °C. The removal of Hg° followed the combination processes of adsorption and catalytic oxidation reaction via Langmuir-Hinshelwood mechanism, while the catalysis of CO abided by the Mars-van Krevelen mechanism with lattice oxygen species.     

Elemental mercury (Hg0) removal from coal syngas using magnetic tea-biochar: Experimental and theoretical insights

Mercury is ranked 3^rd as a global pollutant because of its long persistence in the environment. Approximately 65% of its anthropogenic emission (Hg⁰) to the atmosphere is from coal-thermal power plants. Thus, the Hg⁰ emission control from coal-thermal power plants is inevitable. Therefore, multiple sorbent materials were synthesized using a one-step pyrolysis method to capture the Hg⁰ from simulated coal syngas. Results showed, the Hg⁰ removal performance of the sorbents increased by the citric acid/ultrasonic application. T5CUF_0.3 demonstrated the highest Hg⁰ capturing performance with an adsorption capacity of 106.81 µg/g within 60 min at 200 °C under complex simulated syngas mixture (20% CO, 20% H₂, 10 ppmV HCl, 6% H₂O, and 400 ppmV H₂S). The Hg⁰ removal mechanism was proposed, revealing that the chemisorption governs the Hg⁰ removal process. Besides, the active Hg⁰ removal performance is attributed to the high dispersion of valence Fe₃O₄ and lattice oxygen (α) contents over the T5CUF_0.3 surface. In addition, the temperature programmed desorption (TPD) and XPS analysis confirmed that H₂S/HCl gases generate active sites over the sorbent surface, facilitating high Hg⁰ adsorption from syngas. This work represented a facile and practical pathway for utilizing cheap and eco-friendly tea waste to control the Hg⁰ emission.     

Hg0 removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron (III) chloride were studied on alab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analy-ses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg⁰, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg⁰) into oxidized mercury (Hg²⁺). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg⁰. Therefore, the Hg⁰ removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl₃-HZSM-5 was mainly in the form of mercuric chloride(HgCl₂), while on FeCl₃-NaX and FeCl₃-NaA it was mainly mercuri coxide(HgO).     

Low-temperature (NO + O2) adsorption performance of alkaline earth metal-doped C-FDU-15

To improve the removal capacity of NO + O₂ effectively, the alkaline earth metal-doped order mesoporous carbon (A-C-FDU-15(0.001) (A = Mg, Ca, Sr and Ba)) and Mg-C-FDU-15(x) (x = 0.001?0.003) samples were prepared, and their physicochemical and NO + O₂ adsorption properties were determined by means of various techniques. The results show that the sequence in (NO + O₂) adsorption performance was as follows: Mg-C-FDU-15(0.001) (93.2 mg/g) > Ca-C-FDU-15(0.001) (82.2 mg/g) > Sr-C-FDU-15(0.001) (76.1 mg/g) > Ba-C-FDU-15(0.001) (72.9 mg/g) > C-FDU-15 (67.1 mg/g). Among all of the A-C-FDU-15(0.001) samples, Mg-C-FDU-15(0.001) possessed the highest (NO + O₂) adsorption capacity (106.2 mg/g). The species of alkaline earth metals and basic sites were important factors determining the adsorption of NO + O₂ on the A-C-FDU-15(x) samples, and (NO + O₂) adsorption on the samples was mainly chemical adsorption. Combined with the results of (NO + O₂)-temperature-programmed desorption ((NO + O₂)-TPD) and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization, we deduced that there were two main pathways of (NO + O₂) adsorption: one was first the conversion of NO and O₂ to NO₂ and then part of NO₂ was converted to NO₂^? and NO₃^?; and the other was the direct oxidation of NO to NO₂^? and NO₃^?.     

Mercury oxidation and adsorption characteristics of potassium permanganate modified lignite semi-coke

The adsorption characteristics of virgin and potassium permanganate modified lignite semi-coke (SC) for gaseous Hg⁰ were investigated in an attempt to produce more effective and lower price adsorbents for the control of elemental mercury emission. Brunauer-Emmett-Teller (BET) measurements, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to analyze the surface physical and chemical properties of SC, Mn-SC and Mn-H-SC before and after mercury adsorption. The results indicated that potassium permanganate modification had significant influence on the properties of semi-coke, such as the specific surface area, pore structure and surface chemical functional groups. The mercury adsorption efficiency of modified semi-coke was lower than that of SC at low temperature, but much higher at high temperature. Amorphous Mn⁷⁺, Mn⁶⁺ and Mn⁴⁺ on the surface of Mn-SC and Mn-H-SC were the active sites for oxidation and adsorption of gaseous Hg⁰, which oxidized the elemental mercury into Hg²⁺ and captured it. Thermal treatment reduced the average oxidation degree of Mn^x+ on the surface of Mn-SC from 3.80 to 3.46. However, due to the formation of amorphous MnO_x, the surface oxidation active sites for gaseous Hg⁰ increased, which gave Mn-H-SC higher mercury adsorption efficiency than that of Mn-SC at high temperature.     

Brilliant red X-3B uptake by a novel polycyclodextrin-modified magnetic cationic hydrogel: Performance, kinetics and mechanism

A novel polycyclodextrin-modified magnetic cationic hydrogel (PCD-MCH) was developed and its performance, kinetics and mechanism for the removal of reactive brilliant red X-3B (X-3B) were studied. The results showed that the zeta-potential of PCD-MCH was 32.8 to 16.7 mV at pH 3.0–10.5. The maximum X-3B adsorption capacity of PCD-MCH was 2792.3 mg/g. The adsorption kinetics could be well-described by the Weber–Morris model and the homogeneous surface diffusion model (HSDM). Diffusion stages corresponding to surface or film diffusion, intra-particle or wide mesopore diffusion, and narrow mesopore/micropore diffusion occurred at 0–120, 120–480 and 480–1200 min, respectively. The latter two diffusion stages were rate-controlling for X-3B adsorption kinetics. At the initial X-3B concentration of 600 mg/L, the diffusion coefficient (D_s) and external mass transfer coefficient in the liquid phase (k_F) were 3 × 10^?11 cm²/min and 4.68 × 10^?6 cm/min, respectively. X-3B approaching the center of PCD-MCH particles could be observed at 360 min. At the end of the third diffusion stage, the C_p at q/q_e = 0 was 45.20 mg/L, which was close to the homogeneous C_p value of 46 mg/L along the radius of PCD-MCH particles. At pH 3.0–10.0, PCD-MCH showed stable X-3B adsorption capacities. After five regeneration-reuse cycles, the residual adsorption capacity of regenerated PCD-MCH was higher than 892.7 mg/g. The corresponding adsorption mechanism was identified as involving electrostatic interactions, cyclodextrin cavities and hydrogen bonds, of which cyclodextrin cavities showed prominent capture performance towards dye molecules through the formation of inclusion complexes.     

Effect of alkaline earth metal promoter on catalytic activity of MnO2 for the complete oxidation of toluene

Herein, Na⁺ and Ca²⁺ are introduced to MnO₂ through cation-exchange method. The presence of Na⁺ and Ca²⁺ significantly enhance the catalytic activity of MnO₂ in toluene oxidation. Among them, the Ca-MnO₂ catalyst exhibits the best catalytic activity (T₅₀ = 194°C, T₉₀ = 215°C, E_a = 57.2 kJ/mol, reaction rate 8.40 × 10^?10 mol/(sec?m²) at 210°C. T₅₀ and T₉₀: the temperature of 50% and 90% toluene conversion; E_a: apparent activation energy) and possess high tolerance against 2.0 vol.% water vapor. Results reveal that the increased acidic sites of the MnO₂ sample can enhance the adsorption of gaseous toluene, and the mobility of oxygen species and the content of reactive oxygen species in the catalyst are significantly improved due to the formed oxygen vacancy. Thus these two factors result in excellent catalytic performance for toluene oxidation combining with the weak CO₂ adsorption ability.     

Nb2O5 nanowires in-situ grown on carbon fiber: A high-efficiency material for the photocatalytic reduction of Cr(VI)

Niobium oxide nanowire-deposited carbon fiber (CF) samples were prepared using a hydrothermal method with amorphous Nb₂O₅·nH₂O as precursor. The physical properties of the samples were characterized by means of numerous techniques, including X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), UV–visible spectroscopy (UV–vis), N₂ adsorption–desorption, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy. The efficiency for the removal of Cr(VI) was determined. Parameters such as pH value and initial Cr(VI) concentration could influence the Cr(VI) removal efficiency or adsorption capacity of the Nb₂O₅/carbon fiber sample obtained after hydrothermal treatment at 160°C for 14 hr. The maximal Cr(VI) adsorption capacity of the Nb₂O₅ nanowire/CF sample was 115 mg/g. This Nb₂O₅/CF sample also showed excellent photocatalytic activity and stability for the reduction of Cr(VI) under UV-light irradiation: the Cr(VI) removal efficiency reached 99.9% after UV-light irradiation for 1 hr and there was no significant decrease in photocatalytic performance after the use of the sample for 10 repeated cycles. Such excellent Cr(VI) adsorption capacity and photocatalytic performance was related to its high surface area, abundant surface hydroxyl groups, and good UV-light absorption ability.     

Removal of F− and organic matter from coking wastewater by coupling dosing FeCl3 and AlCl3

Coagulation and precipitation is a widely applied method to remove F^? from wastewater. In this work, the effect of coagulation on the removal of F^? and organic matter from coking wastewater was studied using AlCl₃ and FeCl₃ as compound coagulants. The removal rates of F^? and organic matter under different coagulant doses and pH conditions were investigated. The results show that the highest removal rates of F^? by AlCl₃ and FeCl₃ are 94.4% and 25.4%, respectively; when the dosage is 10 mmol/L, the TOC removal rates of FeCl₃ and AlCl₃ reach 20.4% and 34.7%, respectively. Therefore, the removal rate of F^? by AlCl₃ is higher than that of FeCl₃, but the removal rate of organic matter by FeCl₃ is relatively higher. The addition of Ca²⁺ can promote the removal of F^?, but the removal rate of organic matter decreases. In addition, by investigating the effects of different pH and Fe–Al ratio on the removal rate, the removal effect of adding FeCl₃ and AlCl₃ at the same time was discussed. The results show that the most suitable working condition for the removal of organic matter and F^? is that the pH is 6.5 and the molar ratio of Al/Fe is 8:2. Overall, the removal mechanism of F^? and organic matter in coking wastewater by FeCl₃ and AlCl₃ was explored in this study. The experimental results can provide reference for the advanced treatment of coking wastewater.     

国际化学危险品分类体系简介

介绍了当前国际化学危险品的各种分类体系,对比了GHS与TDG、EU_CLP、DOT、WHMIS等对化学危险品的具体分类。有助于GHS的理解与掌握,全面推进GHS在我国的实施。     

土壤整体质量的生态毒性评价

土壤样品采自沈阳西部污灌区 .进行了污染物 (重金属和矿物油 )含量分析和生态毒性试验 .重金属采用原子吸收分光光度仪测定 ,矿物油采用紫外分光光度计测定 .生态毒性试验分别参照国际标准组织 (ISO)和OECD指南 ,进行了植物毒性试验、蚯蚓毒性试验和蚕豆根尖微核试验 .植物试验以小麦种子发芽根伸长抑制率为试验终点 ,试验周期50h ,蚯蚓毒性试验以蚯蚓死亡率、体重增长抑制率为试验终点 ,试验周期28d .土壤中矿物油含量在145mg/kg～1121mg/kg ,重金属Cd为0.34mg/kg～1.81mg/kg .土壤对植物和蚯蚓显示不同程度的毒性效应 ,土壤的蚕豆根尖微核率明显高于对照 .种子发芽根伸长抑制率为2.0%至-35.1% ,蚯蚓死亡率为0%～40%.体重增长抑制率由14d的-2.3%～-19.4%在28d增加到-2.1%～10.7% ,蚕豆根尖微核率最高达6.62/100.研究表明 ,土壤中的污染物积累较低 ,但具有明显的生态毒性 .     

多目标规划在预测区域总产值-排污-水质协调解中的应用研究

以某区域水环境－经济系统为研究实例，寻求值－排污－水质综合协调解方法，寻求净收益最大时的总体规划方案。建立目标参数规划模型，寻求不同生产规模条件下的产值－排污－水质协调解，又探讨了水环境标准约束下的某化工区废水治理费用的计算方法，提出了以供决策者选择的方案。     

滇池富营养化特性评价

介绍了滇池水质状况,对滇池富营养化特性进行了分析和评价,并提出了对策.     

后勤装备防腐涂层加速试验环境谱研究

结合后勤装备服役特点,综合考虑亚热带沿海地区湿热、紫外光照、盐雾等主要腐蚀因素的影响,建立了适用于后勤装备表面涂层的加速试验环境谱,给出了各环境块的具体确定方法,并且提出了建立加速谱与装备实际使用环境的当量加速关系的方法。为后勤装备外露关键部位涂层使用寿命评定、涂层有效性检验和腐蚀修理方案制定提供了重要的依据。     

乌海市城区环境噪声现状分析

对乌海市《城市区域环境噪声标准》适用区域进行了划分,以乌海市2011年城区环境噪声监测统计数据为基础,分析了乌海市暴露在不同等效声级下的城区面积分布状况和达标情况。     

烟气脱硫副产物的综合利用

通过分析烟气脱硫石膏的性能 ,介绍了脱硫石膏的利用情况和研究进展 ,利用脱硫石膏生产建筑材料 ,如 β石膏和α石膏的工艺日臻成熟 ,利用脱硫石膏生产水泥辅料已进入工业化 ,而利用脱硫石膏生产充填尾砂胶结剂已经完成试验阶段 ,脱硫石膏在农业上也有很广泛的用途。     

生态保护地协同管控成效评估

分区分类管理是我国生态保护的重要管控制度,生态保护地是事关国家生态安全的关键区域,开展生态保护地保护成效评估及不同类型生态保护地之间的协同管控成效评估具有重要意义。以吉林省自然保护地和重点生态功能区等生态保护地（即禁止开发区和限制开发区）为研究对象,以重要生态空间、植被生态、水源涵养功能为主要内容,基于“禁止开发区—限制开发区—省域”的管控梯度差异,评估分析了生态保护地的协同管控成效。结果表明：（1）从重要生态空间协同管控成效来看,自然保护地的重要生态空间面积比例最高、人类活动干扰指数最低,这与生态保护管控严格程度呈现很好地正相关。但是1980—2015年间重要生态空间面积比例均有所减少,减少幅度与管控严格程度没有表现出正相关。（2）从植被生态协同管控成效来看,植被覆盖总体呈现出自东向西逐步降低的特点,与东部分布有重点生态功能区和森林类自然保护区、西部分布较多的湿地类自然保护地的空间特征一致。但是,由于湿地及水域类型自然保护地面积占比较高,且分布在吉林西部草原和平原区的面积比例较高,自然保护地的年际变化较大、且植被覆盖稳定度低于重点生态功能区。（3）从水源涵养功能协同管控成效来看,水源涵养能力呈现出东部和西部高、中部低的特点,与这两个区域主要分布有森林、草地和湿地等重要生态空间密切相关,也与分布着大面积的重点生态功能区和各类自然保护地密切相关。自然保护区的水源涵养能力最高,且年际变化最小、稳定性最高。     

哈尔滨松北区城市湿地的生态安全分析

以哈尔滨松北区城市湿地为研究对象,选择10个指标,采用因子分析法和聚类分析法,研究了松花江发生污染事故前后城市湿地的生态安全状况.结果表明:发生污染前哈尔滨松北区城市湿地东区的生态安全程度最高,发生污染后中区的生态安全程度最低;西区的抗干扰能力较差.各主因子中以水因子的下降幅度最大,说明水污染直接影响了哈尔滨松北区城市湿地的生态安全.最后有针对性地提出了哈尔滨松北区城市湿地的生态安全对策.      

氯苯类化合物的生物降解

经过2个月的驯化,从某染料厂和某毛纺厂活性污泥中分离出能够生长于1,4-二氯苯、1,2,4-三氯苯和六氯苯的4种微生物.通过测定该混合菌降解氯苯类化合物过程中的累积好氧量、微生物生长曲线及降解产物Cl^-的释放,证明在好氧条件下该混合菌能够以1,4二氯苯和1,2,4-三氯苯为唯一碳源和能源,降解产物Cl^-浓度的变化与微生物生长周期有关.通过好氧振荡瓶培养法测得3种氯苯的生物降解顺序为:1,4-二氯苯[356.7μg/(L·d)]>1,2,4-三氯苯[110.4μg/(L·d)]>六氯苯[～6μg/(L·d)],说明氯取代数越多,氯苯类化合物越难被好氧降解.