MnO2/FeOOH复合材料对水中U(Ⅵ)的去除及机理试验研究

采用化学沉积法制备了二氧化锰/羟基氧化铁(MnO2/FeOOH)复合材料,并将其用于吸附去除水中的放射性重金属铀。通过静态吸附试验,考察了Fe/Mn物质的量比、pH值、吸附时间和干扰离子等因素对MnO2/FeOOH吸附U(Ⅵ)效果的影响,利用扫描电镜-能谱分析(SEM-EDS)、X射线衍射(XRD)、拉曼光谱(Raman)、红外光谱(FT-IR)和X射线光电子能谱(XPS)对材料结构和形貌进行表征,并分析其吸附机理。结果表明,在投加量为150 mg/L、温度为30℃、U(Ⅵ)初始质量浓度为10 mg/L、pH值为5、Fe/Mn物质的量比为1/2及吸附时间为120 min的条件下,MnO₂/FeOOH对U(Ⅵ)的去除率最大可达97.7%,且pH值对铀去除效果的影响最为明显。MnO₂/FeOOH对U(Ⅵ)吸附动力学符合准二级动力学模型,吸附等温线均能符合Langmuir和Freundlich模型,且最大吸附容量达260.34 mg/g。干扰离子试验表明,SO₄^2-、CO₃^2-和Fe³⁺对MnO₂/FeOOH吸附U (VI)几乎没有影响,而Ca²⁺和Cu²⁺具有明显的抑制作用,且抑制随浓度的增大而增强。FTIR和XPS分析表明MnO2/FeOOH对U(Ⅵ)的主要作用机制为表面羟基、Mn-O与铀的配位作用。因此,MnO2/FeOOH可作为一种潜在的铀吸附材料。     

Calorimetric behaviors of hydroxylamine and its salts caused by Fe(III)

The objective of this study is to obtain information on the calorimetric behaviors of aqueous solutions of hydroxylamine (HA), hydroxylamine chloride (HACl), and hydroxylamine nitrate(HAN) caused by different Fe(III) states (free Fe(III) from Fe(NH₄)(SO₄)₂, Fe(CN)₆³⁻, and Fe(EDTA)⁻). The calorimetric data were obtained with a small-scaled reaction calorimeter, Super-CRC.

In the mixing with Fe(III), HA showed the highest reactivity among three substrates. Free Fe(III) and Fe(EDTA)⁻ showed catalytic effects in the reactions. In the overall heat of reactions, Fe(EDTA)⁻ exceeded free Fe(III), which precipitated as Fe(OH)₃ and decreased the chances of interactions with HA. It was suggested that the generation of NH₃ had taken place in the process of reducing HA along with Fe(II) oxidation. Fe(CN)₆³⁻ was less reactive than free Fe(III) and Fe(EDTA)⁻.

The ability of masking Fe(III) was estimated for CyDTA. The HA including CyDTA had no exothermic peak; however, there was an endothermic peak of the heat flow at Fe(III) injection. CyDTA was found to have the ability to inhibit a violent exothermic reaction of HA.     

Development and physicochemical characterization of a new magnetic nanocomposite as an economic antibiotic remover

Maghemite (ϒ-Fe₂O₃) nanoparticles were impregnated to nanoporous carbon obtained from tomato waste (TWNC). The prepared magnetic composite (MTWNC) was characterized and used to remove tetracycline (TC) from water and then easily be separated from the medium by a magnetic technique. The morphologies and surface chemistries of both magnetic and non-magnetic nanoporous carbons were studied by FTIR, XRD, SEM, SEM-EDX, VSM, BET surface area, proximate and elemental analysis determinations. Batch adsorption studies were carried out and the effects of pH, initial TC concentration, adsorbent dose, ionic strength and temperature were investigated. The adsorption kinetics of TC on MTWNC could be expressed well by the pseudo-second order model, and sorption isotherms were described by Langmuir equation with maximum adsorption capacity of 60.60 mg/g at pH 4 and 50 °C. Thermodynamic parameters showed that the adsorption of TC onto MTWNC was feasible, spontaneous and endothermic. Furthermore, the recyclability of the adsorbent was tested with 0.01 M NaOH solution, and the results show that the synthesized composite adsorbent could be employed repeatedly in wastewater treatment.     

微波诱导热解制备小麦秸秆吸附剂及响应面优化工艺研究

以氯化锌为活化剂,通过微波诱导热解法制备小麦秸秆吸附剂,并以微波功率、热解时间和氯化锌质量分数为影响因素,碘吸附值为响应值,采用响应面法对小麦秸秆吸附剂的制备工艺进行优化。结果表明,热解时间和微波功率对碘吸附值的交互作用明显。响应面优化工艺分析,发现当热解时间4.03 min、微波功率569.0 W,氯化锌质量分数为31.24%时,碘吸附值最大,为643.33 mg/g。另外,小麦秸秆吸附等温线与I型相似,吸附剂的微孔容积为0.238 4cm³/g,吸附剂的BJH孔径分布表现窄小,最高峰出现在2.1nm左右。处理Cr(VI)废水的吸附试验,发现Cr(VI)的去除率可以达到70%以上。研究表明,微波诱导热解法及响应面优化工艺制备的小麦秸秆吸附剂技术可行且具有良好的重金属废水处理应用前景。     

Biosorption of Co(II) ions from aqueous solution using Chrysanthemum indicum: Kinetics,equilibrium and thermodynamics

The present study investigates the adsorption potential of Chrysanthemum indicum flower in its raw (CIF-R) and biochar (CIF-BC) form for the removal of cobalt ions from aqueous solution. The adsorbents were characterized for their surface area using BET analysis, surface morphology and elemental composition with SEM-EDAX and for the presence of functional groups by FTIR analysis. Batch adsorption experiments were carried out to evaluate the effect of process parameters, viz. pH, adsorbent dosage, initial metal ion concentration, contact time, stirring speed, presence of interfering ions and temperature on the adsorption of Co(II) ion using both the adsorbents. The optimum conditions for maximum removal of Co(II) ion was ascertained to be pH 5 for both adsorbents, adsorbent dose of 4 g/L and 3 g/L, equilibrium time of 60 min and 45 min, respectively, for CIF-R and CIF-BC. The maximum adsorption capacity of CIF-R and CIF-BC was found to be 14.84 mg/g and 45.44 mg/g, respectively, for the removal of Co(II) ion. The mechanism of adsorption was studied using different models of adsorption kinetics, isotherms and thermodynamics. It was inferred that Co(II) adsorption on both CIF-R and CIF-BC followed pseudo-second order kinetics and Langmuir isotherm model with the process being spontaneous and endothermic in nature.     

Fire and explosion risk assessment for large-scale oil export terminal

Now in Russian Federation and other countries large-scale oil terminals (volume of one tank exceeds 100 000 m³, total volume of tanks exceeds 300 000 m³) are designed and constructed. Therefore fire safety of such objects becomes a very important task, solution of which is hardly possible without detail fire risk assessment. This study is aimed to a solution of this problem. Potential, individual and social risks were calculated. The potential risk was defined as a frequency of occurrence of hazardous factors of fires and explosions in a given point of space (the so-called risk contours). The individual risk was defined as a frequency of injuring a given person by hazardous factors of fires and explosions. Time of presence of this person in hazardous zones (near the hazardous installation) is taken into account during calculations of the individual risk. Social risk was defined as a dependence of frequency of injuring a given number of people by hazardous factors of fires and explosions on this number. In practice the social risk is usually determined on injuring not less than 10 people.

The oil terminal under consideration includes the following main parts: crude oil storage consisting of three tanks of volume 100 000 m³ each, input crude oil pipeline of diameter 0.6 m, crude oil pumps, output crude oil pipeline of diameter 0.8 m, auxiliary buildings and facilities. The following main scenarios of tank fires have been considered: rim seal fire, pool fire on a surface of a floating roof, pool fire on a total cross-section surface of the tank, pool fire in a dyke, explosions in closed or semiclosed volumes. Fires and explosions in other parts of the terminal are also taken into account. Effects of escalation of accidents are considered.

Risk contours have been calculated both for the territory of the terminal and for the neighbouring space. The potential risk for the storage zone is near 10⁻⁴–10⁻⁵ year⁻¹, and at a distance 500 m from the terminal the potential risk values do not exceed 10⁻⁶ year⁻¹. The values of the individual risk for various categories of workers are in the range of 10⁻⁵–10⁻⁶ year⁻¹. Because of low number of the workers on the terminal and large distances to towns and villages the social risk value is negligible. These risk values are consistent with practice of the best oil companies, and fire hazard level of the terminal can be accepted as tolerable.     

Evaluation of the explosibility of malt grain dust based on static electrification during pneumatic transportation

The possibility of dust explosions by static electricity in a malt grain silo was investigated. Two kinds of experimental equipment were applied. One was to supply electrostatic charge in order to investigate the charge build up characteristics. The other was to transport the malt grain pneumatically in order to investigate the frictional charge accumulation in the transportation system.

The particle charge of the pulverized malt grain was in the order of 10⁻¹⁴ C. The particle charge of the malt grain was in the order of 10⁻⁹ C and the pipe charge in the transport system was also in the order of 10⁻⁹ C. The charge accumulated on both the pulverized particle and the grain particle were small in view of the incendiary potentiality. However, attention must be paid when the particles are dumped into isolated space. There might be a charge accumulation that will lead to the ignition of the dust cloud.     

纳米γ-Fe2O3对汞离子的吸附行为研究

为了研究用于含汞离子废水处理的新型高效材料,研究了纳米γ-Fe₂O₃对汞离子的吸附行为。探讨pH值(3、8和12)、温度(288 K、298 K、308 K、318 K)和离子强度(Ca²⁺,0.001 mol/L、0.01 mol/L、0.1 mol/L)对该吸附的影响。使用吸附动力学方程(拉格朗日准一级、准二级)和等温吸附方程(Langmuir和Freundlich)分别对吸附数据进行拟合,并讨论吸附机理。结果表明:pH值为3、8、12时,纳米γ-Fe₂O₃对汞离子的吸附动力学方程符合准二级动力学模型(R2=0.997~0.999);288 K、298 K、308 K、318 K时,纳米γ-Fe₂O₃对汞离子的吸附过程更符合Langmuir吸附模型(R²=0.970~0.995),并且随温度升高,吸附量增加;在不同pH值下,纳米γ-Fe₂O₃对汞离子的吸附等温式可使用Langmuir模式(R²=0.983~0.996)进行表征,随p H值降低,吸附量减少,中性环境有利于吸附;在不同Ca²⁺浓度下,可用Langmuir等温吸附式拟合(R²=0.990~0.996)。通过Langmuir等温吸附式推算出最大吸附量随Ca²⁺浓度增加而减少。     

The effect of vent ducts on the reduced explosion pressures of vented dust explosions

An investigation into the effects of vent ducts on reduced explosion pressures is described. Experiments were made using an 18.5m³ explosion vessel and a modified 20 1 sphere, with dusts having K_st values ranging from 144 bar ms⁻¹ to 630 bar ms⁻¹. The vent area/vessel volume ratio bursting pressure of the vent cover, and the length to diameter ratio of the vent duct have been varied. Straight vent ducts, and ducts containing sharp 45° and 90° bends have been used.A simple model to describe the effect of vent ducts on the reduced explosion pressure has been derived and compared with the experimental results. Agreement is shown to be satisfactory in nearly all cases. A comparison between the experimental results and guidance on the effect of vent ducts already available in the literature is discussed.     

Adsorptive removal of basic dyes from aqueous solutions by surfactant modified bentonite clay (organoclay): Kinetic and competitive adsorption isotherm

Cationic surfactant (Hexadecyltrimenthylammonium chloride) modified bentonite clay was prepared and systematically studied for its adsorption behavior as an efficient adsorbent for the removal of basic dyes such as methylene blue (MB), crystal violet (CV) and Rhodamine B (RB) from aqueous phase. Organo modified clay shows better capacity for the removal of three dyes. The adsorption process was found to be dependent on pH and initial dye concentration. The maximum dye sorption was found to be at a pH of 9.0 (99.99% for MB, 95.0% for CV and 83.0% for RB). The adsorption capacity for the dyes was found to be 399.74, 365.11 and 324.36 μmol/g for MB, CV and RB, respectively at 30 °C. The equilibrium uptake was attained within 240 min. The kinetic studies were revealed that sorption follows a pseudo-second-order kinetic model which indicates chemisorption between adsorbent and adsorbate molecules. Adsorption isotherm indicates non-energetically adsorption sites which fit with Freundlich isotherm model. The fitness of kinetics and isotherm models was evaluated by using HYBRID error analysis function. Competitive adsorptions of dyes were studied by using binary component systems.     

Isotherm and kinetic studies for the biosorption of cadmium from aqueous solution by Alhaji maurorum seed

Cadmium is an extremely toxic metal commonly found in industrial regions. Anthropogenic activity is the most important factor causing its interference to water, soil and air resources. The aim of many researches is to present remediation strategy or to remove cadmium from contaminated resources through an economical and efficient method. Cadmium adsorption from aqueous solution using Alhaji maurorum seed adsorbent has been investigated and optimized in this study. Moreover, isotherm and kinetics of adsorption process was studied. The seeds are washed by distilled water after separation from the plant, and then dried in room temperature for 48 h. They are powdered by grinder and passed through sieve no.18 as well. Adsorption process was optimized in 4 steps regarding pH, contact time, adsorption dose and initial concentration of cadmium effects. The cadmium concentration in solution was measured using ICP-OES method. The results of optimization tests showed that the optimum condition of cadmium adsorption (85.5% removal) occurs at pH of 6.5 with 20 g/L of adsorption dose for 45 min. In addition, the efficiency of adsorption process increases as the cadmium concentration reduces in the initial solution. Adsorption process follows the pseudo second-order kinetics and Freundlich isotherm with correlation coefficients of 0.999 and 0.99, respectively. According to the findings of this analysis, it was concluded that A. maurorum seed is a good biological adsorbent for adsorbing cadmium from aqueous solution.     

Improving Energetic Performance and Water Usage in an Industrial Ethanol Distillery

In this paper, a case study based on an industrial process of ethanol distillation was undertaken. It was aimed to improve the energy and water usage in the process. Pinch Analysis concepts were used to propose a new heat exchanger network and a study was undertaken to the water reuse. The minimization of wastewater is achieved through the exploitation of recycle and reuse opportunities by process modifications. Through these studies, a new streams circuit was obtained, which resulted in a lower consumption of steam and in a reduction in the volume of water collecting of 12 m³ to 1 m³ per tons of crushed sugar cane. Process changes and economical viability were presented. Two kinds of equipment were studied, cooling towers and aspersion tanks.     

Removal of a cationic bisbiguanide using Functionalized Activated Carbons (FACs)

Functionalized Granular Activated Carbons (FACs) are used as adsorbents for treating pharmaceutical wastewaters containing Chlorhexidine Gluconate. Chemical modifications of Granular Activated Carbons (GACs) using functionalizing agents like HCl and HF produce FACs. The adsorption capacity of each of FAC-HCl and FAC-HF is found to be higher than GAC. The modelled maximum adsorption capacity for FAC-HCl is 1.02 g/g of adsorbent, 3.49 g/g of adsorbent for FAC-HF and 0.0682 g/g of adsorbent for GAC. This is mainly due to the additional chemisorptions by surface complexation at the functionalized surface sites of the modified GACs. This is also supported by the well-known pseudo-second-order kinetic model. Formation of surface complexes with the functional groups and weakly polar Chlorhexidine Gluconate is well supported by the physical characterization using Energy dispersive X-ray spectroscopy (EDAX), Brunner–Emmett–Teller (BET) test and Fourier Transform Infrared spectroscopy (FTIR) analysis after adsorption. The adsorption capacity of GAC and the FACs increases in the order of FAC-HF > FAC-HCl > GAC conforming to the proportion of the total acidity of the carbon surfaces. Intra-particle diffusion is not the sole rate-controlling factor. An agreement to pseudo-second-order kinetic model, Elovich kinetic model and Boyd's film diffusion model proves that chemisorption is the rate-controlling parameter in this adsorption study.     

Equilibrium study and kinetics of Cu removal from water by zeolite prepared from oil shale ash

Engineered zeolite was produced from oil shale ash by reaction with sodium hydroxide in a closed vessel reactor. This adsorbent was used for removal of copper ions from aqueous solution. The maximum adsorption capacity was 504.6 mg Cu²⁺/g zeolite. Kinetic studies showed that the rate of adsorption of copper is increased with increasing the solution pH and temperature, quantity of the zeolite and agitation speed. The kinetic data were fitted to homogeneous micropore model and found that the mass transfer coefficient and diffusivity of the Cu²⁺ are directly affected by the kinetic parameters. The increase in solution concentration will decrease the mass transfer coefficient while diffusivity is increased.     

Kinetics and equilibrium adsorption study of lead(II) onto the low cost adsorbent—Eupatorium adenophorum spreng

Adsorption of Pb(II) ions from aqueous solution onto a low cost adsorbent—the Eupatorium adenophorum spreng has been investigated to evaluate the effects of initial lead ion concentration, contact time, pH and temperature on the removal of Pb(II) systematically. The optimal pH value for Pb(II) adsorption onto the E. adenophorum spreng was found to be 5.0. Thermodynamic parameters such as standard Gibbs free energy (ΔG°), standard enthalpy (ΔH°), and standard entropy (ΔS°) were evaluated by applying the van’t Hoff equation, which describes the dependence of equilibrium constant on temperature. The thermodynamics of Pb(II) adsorption onto the E. adenophorum spreng indicated that the adsorption was spontaneous and endothermic. Langmuir and Freundlich isotherms were used to analyze the equilibrium data at different temperatures and the equilibrium data were found to fit Freundlich isotherm equation better than Langmuir isotherm. The adsorption was analyzed using pseudo-second-order kinetic models.     

MCM-41吸附法脱除烟气中二氧化硫的研究

基于活性炭吸附剂存在再生成本高、高温吸附能力差以及在高湿高温下脱附后性能严重下降等问题,研究采用MCM-41材料作为新型烟气脱硫吸附材料,该材料具有表观均匀、比表面积大、耐高温、脱附后能高效利用等优点,该研究设计了一种基于MCM-41材料的烟气脱硫吸附装置。介绍了该烟气脱硫吸附装置的结构、工作原理,并对MCM-41材料和活性炭在烟气中二氧化硫吸附效果进行了对比实验研究。研究结果表明:MCM-41吸附剂脱硫性能优异,相比活性炭吸附剂,脱硫效率提高了4%~8.4%,基于MCM-41材料的烟气脱硫吸附装置结构紧凑、占地面积小、吸附剂更换方便、脱硫效率高,在烟气排放量较小的各类工业企业脱硫系统中具有广泛的应用前景。     

毛竹遗态Fe_2O_3/Fe_3O_4/C复合材料吸附水中砷(Ⅴ)的工艺优化组合研究

以自制毛竹遗态Fe_2O_3/Fe_3O_4/C复合材料为吸附剂,选取溶液初始p H值、吸附剂粒径、吸附剂投加量、砷(V)初始浓度、吸附时间和温度为影响因素开展工艺优化组合寻求的正交实验研究,结果显示,工艺优化组合为:砷(V)初始浓度10 mg/L,溶液初始p H=3,温度为35℃,吸附剂粒径小于100目,吸附剂用量为0.6 mg/50 m L,吸附时间为7 h。     

改性沸石吸附氨氮及电化学再生研究

研究了改性沸石对氨氮的吸附效能、动力学机制以及电化学再生效果。间歇和连续试验结果表明:沸石经改性后,能高效去除水中的氨氮,其吸附等温式更符合Langmuir模型,沸石、改性沸石的饱和吸附量分别为8.09 mg/g和13.55 mg/g,沸石的钠型改性能显著提高吸附容量约40.3%;颗粒内扩散是改性沸石吸附氨氮的控制性步骤,可以利用Vermeulen的内扩散模型进行描述;利用电化学再生吸附饱和后的沸石,再生液为NaCl溶液,阳极涂覆RuO2-Ti,再生时间为3h,可高效地再生沸石,无二次污染物排出,对环境冲击较小。     

苯乙烯系双腈胺螯合树脂对水相中As(Ⅴ)的吸附性能研究

将PS-DCDA树脂用于水相中As(Ⅴ)的吸附净化处理,探讨了溶液的pH值、初始As(Ⅴ)质量浓度、接触时间、温度、NaCl、竞争性阴离子等因素对吸附性能的影响,并研究了其对As(Ⅴ)的吸附等温线、动力学和热力学。结果表明,NaCl和竞争性阴离子(Cl-、SO24-、CO23-、NO3-、HPO24-等)明显地抑制了PS-DCDA树脂对As(Ⅴ)的吸附。PS-DCDA树脂对As(Ⅴ)的吸附符合Langmuir等温式,准二级吸附动力学方程能够很好地描述As(Ⅴ)在树脂上的吸附动力学行为。粒子内扩散方程表明,表面吸附和内部扩散参与到As(Ⅴ)的吸附过程当中。PS-DCDA树脂对As(Ⅴ)的热力学参数表明,PS-DCDA树脂对As(Ⅴ)的吸附是自发的、吸热的过程。已吸附As(Ⅴ)的PS-DCDA树脂可以用0.1 mol/L NaOH有效解吸,解吸后的树脂对As(Ⅴ)仍具有较高的吸附量。     

纳米α - Fe2O3微球对U(Ⅵ)的吸附特性研究

将海藻酸钠与纳米α-Fe2O3制成微球,用于吸附U(Ⅵ)。探讨了纳米α-Fe2O3含量、交联时间、pH值、投加量、浓度、温度等对吸附的影响。结果表明,pH值对U(Ⅵ)的吸附过程影响显著,适宜pH值为3。U(Ⅵ)在微球上的吸附量随着吸附时间的增加而增大,初始阶段(1.5 h)反应进行得很快,9 h时达到吸附平衡。当U(Ⅵ)初始质量浓度为10mg/L时,其饱和吸附量为2.64mg/g。准二级动力方程很好地拟合了吸附动力学数据,且R2>0.99。吸附率与温度呈正相关,Lang-muir与Freundlich吸附等温方程均能较好地拟合固定化微球对U(Ⅵ)的吸附过程(R2>0.99),但Freundlich等温线效果更好。吸附反应中ΔG<0,ΔH>0且小于40 kJ/mol,ΔS>0,这表明吸附过程能自发进行,为吸热反应。