硫酸盐还原菌处理酸性矿山废水的技术及思考

含高浓度硫酸盐酸性矿山废水的污染是一个全球性的问题。利用硫酸盐还原菌（SRB）可对含硫酸盐的酸性矿山废水进行生物处理．在厌氧条件下．SRB以碳源为电子供体将SO4^2-还原到S^2-并释放出碱度,使废水pH值提高．S^2-可用物化法或生化法从废水中除去。文章综述了SRB的特点及它的生长条件,重点分析了利用SRB处理酸性矿山废水中存在的问题,如碳源、生物反应器的选择,并对生物处理酸性矿山废水的技术进行了展望。     

Electrochemical remediation of acid mine drainage

Acid mine drainage (AMD), which has long been a significant environmental problem, results from the microbial oxidation of iron pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. Electrochemical treatment of AMD offers possible advantages in terms of operating costs and the opportunity to recover metals, along with cathodic reduction of protons to elemental hydrogen. This work describes the electrolysis of synthetic AMD solutions containing iron, copper and nickel and mixtures of these metals using a flow-through cell divided with an ion exchange membrane. Iron was successfully removed from a synthetic AMD solution composed of FeSO₄/H₂SO₄ via Fe(OH)₃ precipitation outside the electrochemical cell by sparging the electrolysed catholyte with air. The work was extended to acidic solutions of Fe²⁺, Cu²⁺, and Ni²⁺, both singly and in combination, and to an authentic AMD sample containing principally iron and nickel.     

德兴铜矿酸性矿山废水污染分析

本文对德兴铜矿的环境污染状况从污染物产生机理、污染水质水量以及污染源分布等进行了综合分析，为下一步铜矿的环境治理提供依据。     

人工湿地在酸性矿山废水中的应用

酸性矿山废水对环境污染和破坏较为突出,对酸性矿山废水进行治理越来越受到重视。文章介绍了酸性矿山废水的来源与危害,人工湿地治理酸性矿山废水的机理及在酸性矿山废水中治理的应用前景。     

硫酸盐还原菌法固定酸性矿山废水中重金属的研究进展

硫酸盐还原菌(SRB)法是一种极具潜力的酸性矿山废水(AMD)处理技术,如何将多种重金属分级沉淀并且分相分离出来,是SRB工艺走上工程应用的关键。本文综述了SRB法固定AMD中重金属的国内外研究进展,主要包括SRB法去除AMD中重金属的原理、SRB法分级沉淀AMD中多种重金属的工艺(分离式多级pH控制工艺及厌氧折流板反应器工艺)和SRB法厌氧污泥中金属硫化物的生物矿化(SRB介导的生物矿化成矿、生物矿化成矿影响因素及生物矿化过程微观机理),分析了此方面研究工作存在的问题。最后文章针对SRB法的深入研究及应用进行展望,认为硫酸盐还原体系中硫化物成矿的调控、成矿物相演变与微生物群落演替过程的解析以及矿化固定AMD中重金属成矿机理的探索将是今后重点关注的研究内容。     

Evaluation of municipal compost/limestone/iron mixtures as filling material for permeable reactive barriers for in‐situ acid mine drainage treatment

The aim of the present study was to assess the potential of municipal compost as a carbon source for sulfate‐reducing bacteria for acid mine drainage bioremediation for use in permeable reactive barriers at high flow rates (>0.1 m d^?1). Two different mixtures of municipal compost, limestone and zero‐valent iron were assessed in two column experiments. The effluent solution was systematically analysed throughout the experiments. At the end of the experiments precipitates from both columns were withdrawn for scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and X‐ray diffractometry examination and solid digestion and sequential extraction were carried out. Results showed that the effluent was free of metals and acidity. It seems that metal removal was not due to biogenic sulfide generation but to pH increase, ie metal (oxy)hydroxides precipitation. These precipitates can sorb other metals onto the surface. Sorption to organic matter could also contribute to metal removal. When zero‐valent iron was present, cementation of copper also occurred. It can be concluded that municipal compost was a poor carbon source to support continuous bacterial activity under high flow rates. Copyright © 2003 Society of Chemical Industry     

Inhibition of hematite on acid mine drainage caused by chalcopyrite biodissolution

Even though biodissolution of chalcopyrite is considered to be one of the key contributors in the formation of acid mine drainage (AMD), there are few studies to control AMD by inhibiting chalcopyrite biodissolution. Therefore, a novel method of using hematite to inhibit chalcopyrite biodissolution was proposed and verified. The results indicated that chalcopyrite biodissolution could be significantly inhibited by hematite, which consequently decreased the formation of AMD. In the presence of hematite, the final biodissolution rate of chalcopyrite decreased from 57.9% to 44.4% at 20 day. This in turn suggested that the formation of AMD was effectively suppressed under such condition. According to the biodissolution results, mineral composition and morphology analyses, and electrochemical analysis, it was shown that hematite promoted the formation and accumulation of passivation substances (jarosite and Cu_2-xS) on chalcopyrite surface, thus inhibiting the biodissolution of chalcopyrite and limiting the formation of AMD.     

以污泥酸性发酵产物为碳源生物处理模拟酸性矿山废水的工艺特性

以污水处理厂污泥的酸性发酵产物为硫酸盐还原菌(SRB)的碳源,在厌氧膨胀颗粒污泥床(EGSB)反应器中,研究了生物处理模拟酸性矿山废水(AMD)的工艺特性及影响因素。试验结果表明,污水厂污泥的酸性发酵产物可作为SRB的合适碳源。常温(20℃)条件下,当AMD中SO24-浓度为3000 mg.L-1,pH值3.0,EGSB反应器中液体升流速度为5.0 m.h-1,水力停留时间HRT=13.8 h,碳源COD/SO24-比值取1.0左右,进水SO24-负荷为5.22 kg SO24-.m-3.d-1时,SRB的还原能力可达到3.32 kg SO24-.m-3.d-1,SRB的比还原能力为0.356 kg SO24-.(kg VSS)-1.d-1。AMD处理出水pH值可达6.0,SO24-还原率达到63.6%,COD去除率为45.1%,重金属Fe2+、Mn2+、Ni2+、Zn2+、Cu2+去除率均在89%以上。出水pH值和重金属离子浓度均满足排放标准。     

Influence of sulphate-reducing bacteria on environmental parameters and marine corrosion behavior of Q235 steel in aerobic conditions

The growth cycle of sulphate-reducing bacteria (SRB), Desulfovibrio caledoniensis, and the effect of SRB on the environmental parameters and corrosion behavior of Q235 steel during a growth cycle in aerobic (air- and O₂-saturated culture solutions) and anaerobic (N₂⁻ saturated culture solutions) conditions were investigated. Oxygen dissolved in the culture solutions induced slow growth and fast decay of SRB. The growth process of SRB under anaerobic and aerobic conditions influenced sulphide anion concentration (Cs2−), pH, and conductivity (κ). The values of Cs2− and κ under aerobic conditions were lower than those under anaerobic conditions, and the pH values increased from O₂- to air- to N₂-saturated culture solutions. Aerobic conditions induced the open circuit potential (E_OC) to shift in the positive direction after the stationary phase of SRB growth. The charge transfer resistance (R_ct) increased quickly during the exponential growth phase, almost maintained stability during the stationary phase, and decreased after the stationary phase in all three conditions, and the impedance magnitude decreased from O₂- to air- to N₂-saturated culture solutions. The biofilms induced by SRB were observed by scanning electron microscopy (SEM) under aerobic and anaerobic conditions, and energy dispersive spectroscopy (EDS) was performed in abiotic and SRB-containing systems to distinguish the corrosion products. The reasons for the effects of SRB on the environmental parameters and corrosion behavior of carbon steel are discussed.     

以氢气为电子供体的硫酸盐还原菌处理酸性矿山废水

研究氢气作为唯一电子供体的硫酸盐还原菌对酸性矿山废水的处理效果。本文对反应过程中pH和氧化还原电位（ORP）,目标代谢产物H₂S和∑S^2-（HS^-、S^2-）,出水中重金属及总有机碳进行分析。研究表明,生物反应器pH可迅速上升至8.75～8.80,ORP下降至-330～-420mV;在4865mg/L \mathrm{S}{\mathrm{O}}_{\mathrm{4}}^{\mathrm{2}-}浓度下硫酸盐还原菌活性较好,其目标代谢产物H₂S与∑S^2-的积累量分别为88mg/L、172mg/L;Zn²⁺、Fe²⁺、Cu²⁺、Mn²⁺的去除率分别为94.3%、94.7%、97.5%、81.7%,重金属Cu²⁺、Zn²⁺的出水浓度分别为0.52mg/L、1.99mg/L,中和沉淀出水pH为6.9,其出水水质可达《污水综合排放标准》一级标准;出水残存总有机碳≤3mg/L,远低于以有机物为电子供体的出水水质;H₂培养生物反应器中主要以脱硫弧菌属为主导。     

锦界煤矿高浓度井下排水处理工程设计

锦界煤矿井下排水处理工程设计规模为4.32×104 m3/d,针对原水胶粒含量大、粒径小、比重轻等特点,矿井水处理采用预沉调节池+改良型机械搅拌澄清池+V型滤池的组合工艺,煤泥水处理采用直接离心脱水工艺,出水主要用作锦界煤矿周边电厂循环冷却用水及井下生产用水。介绍了该工程的工艺流程、设计参数及工艺特点,以期为同类煤矿井下排水处理工程的设计提供参考和借鉴。     

The role of sulfate as a competitive inhibitor of enzymatically‐mediated heavy metal uptake by Citrobacter sp: implications in the bioremediation of acid mine drainage water using biogenic phosphate precipitant

Heavy metals can be removed from solution via biocrystallization with enzymatically‐liberated inorganic phosphate, according to Michaelis–Menten kinetics, in free whole cells and cells immobilized within polyacrylamide gel in a flow‐through reactor. Sulfate is a competitive inhibitor of phosphate release and a predictive model was developed and shown to describe the effect of sulfate on the efficiency of phosphate release by flow‐through columns. The inhibitory effect was substantially less than anticipated in the case of metal removal by the columns. In the case of lanthanum removal metal removal efficiency was restored by increasing the substrate concentration in accordance with model predictions. In the case of uranyl ion its removal with an equivalent substrate supplement increased the activity by 20% over the initial value at a limiting flow rate. Since the initial loss in activity in the presence of 40 mmol dm⁻³ SO₄²⁻ (approximately twice the K_i value) was only approximately 20% with both metals this was considered to be a minor problem for bioprocess application. In confirmation, calculations made from a published ‘case history’ of application of the system to the bioremediation of acid mine drainage water (AMD) containing 0.22 mmol dm⁻³ of uranyl ion and 35 mmol dm⁻³ of SO showed that the benchscale model is a good representation of performance under actual load conditions. © 1999 Society of Chemical Industry     

Design parameters of boric acid production process from colemanite ore in the presence of propionic acid

In this study, three different boric acid production process alternatives which can be performed in the presence of propionic acid and/or calcium propionate were evaluated. The process in which calcium propionate is the recycling component was selected as the best alternative and modeled. Some of the design parameters were determined for the selected process. These parameters are solubility change of boric acid in the presence of calcium propionate at 25 °C, 35 °C and 75 °C, precipitation risk of calcium borate components in concentrated boric acid solutions containing calcium propionate, and the effect of calcium propionate on the solution pH with respect to free sulfuric acid concentration. According to the determined parameters, principal reactions occurred in the process, and other process parameters obtained by industrial practice, mass balances were conducted and all flow rates were calculated. In the process, calcium propionate concentration in production liquor must be kept lower than 3% and the reaction must be carried out without any free sulfuric acid in order to perform the process according to the model.     

Accelerated low water corrosion of carbon steel in the presence of a biofilm harbouring sulphate-reducing and sulphur-oxidising bacteria recovered from a marine sediment

Investigations were undertaken to elucidate causes of accelerated low water corrosion (ALWC) of steel piling in a harbour in Southern England. Visual inspection revealed features characteristic of ALWC such as the presence of poorly adherent, thick corrosion products of varying morphology, often seen as large blisters randomly located on sections of the structure at the low water mark. Upon the removal of blisters, a bright surface covered with shallow pits was exposed. Representative samples of the corrosion products were collected from the structure and water and sediment specimens were retrieved from selected areas in the harbour for microbiological, chemical and microscopy testing. In the laboratory, field samples were enriched to detect and enumerate communities of sulphur-oxidising bacteria (SOB) and sulphate-reducing bacteria (SRB). Biofilms, comprising SRB and SOB populations isolated from a sediment sample were grown under static conditions on surfaces of electrodes manufactured from steel piling material. Linear polarisation resistance (LPR) measurements revealed that the corrosion rate of steel with biofilms (0.518 mm y⁻¹) was higher than that recorded in sterile seawater alone (0.054 mm y⁻¹) and in sterile seawater to which nutrient was added (0.218 mm y⁻¹). Scanning electron microscopy (SEM) imaging demonstrated enhanced pitting under biofilms. The results of our investigation revealed for the first time that the attack on steel piling in the presence of sediment SRB and SOB populations was characteristic of ALWC.     

Sequential experimental design for estimation and analysis of thermal parameters in a fixed bed

The analysis of the effective radial thermal conductivity and the film heat transfer coefficient were carried out in a fixed bed. The temperature profiles were described by two‐dimensional pseudo‐homogeneous model. The thermal parameters were estimated using a sequential experimental design technique. The minimum volume criterion was used to design the next point for temperature measurement in the bed. The utilization of T = T₀ (constant) as the boundary condition at the bed inlet resulted in an axial variation of thermal parameters, which was the factor responsible for the inadequacy of the model in fitting experimental data of different bed heights simultaneously. Using T = T(r) as the boundary condition makes the thermal parameters independent of the axial position and the model statiscally adequate to describe the axial and radial temperature profiles throughout the bed.     

阴极冷却固定床反应器电合成乙醛酸

以过饱和草酸水溶液为阴极液,盐酸溶液为阳极液,在阴极冷却固定床电化学反应器内草酸电解合成乙醛酸。考察了电流密度、电极和电解液温度、阴极材料对合成乙醛酸时空产率和电流效率的影响。结果表明,阴极冷却固定床反应器是一种较理想的反应器,用石墨板作阳极,铅作阴极,电流密度为400.5A/m2,阴极空速u0=0.505m/s,电解温度为20℃左右时,电解1.5h,在阴极可得到质量分数为5.45%的乙醛酸溶液,平均时空产率可达0.12kg/dm3·h以上。     

Determination of thermal parameters of non-spherical particles in a packed bed from svstem response analysis in the time domain

The thermal conductivity and the particle-to-fluid heat-transfer coefficient for peanut-shaped polyester particles in a packed bed were determined simultaneously using the pseudo-random binary noise sequence (PRBNS) response technique. The modified Dispersion-Concentric (D-C) model was applied to beds packed with the non-spherical particles. A time domain method, using the convolution integral, was developed for removing the effects of the bed ends and the transducer time lag on the experimental responses. Parameter estimation was performed in the time domain, using a simplex method to fit the thermal response calculated from the parametric D-C model to the experimental response curve. The particle-to-fluid heat transfer coefficient in the bed was determined to be 106 W/m². K at an interstitial fluid velocity of 2.0 m/s. The thermal conductivity of polyester was 0.22 W/m. K at 313 K.     

晋城矿区煤层气发电现状及规划

晋城矿区赋有丰富的煤层气资源 ,为充分利用这部分煤层气资源 ,晋城无烟煤矿业集团利用美国的打钻、压裂、排采技术实施煤层气开发示范工程 ,经潘庄、寺河两矿煤层初步发电试验 ,取得成功 ,2 0 0 2年初运转的 1 1× 1 0 4kW发电示范工程 ,取得良好的经济效益 ,为后续煤层气资源利用积累了宝贵的经验。     

Sampling method for studying the activity of lactic acid bacteria during spray drying

In this study, a novel sampling method was established to study changes in the activity of lactic acid bacteria during spray drying. Before spray drying, a sampling device with a refrigerant and a magnet was pre-cooled and positioned in a spray-drying tower. Carbonyl iron powder (CIP) was added to the drying media to increase the sampling mass by the magnetic effect. During drying, a temperature sensor measured the particle contact temperature. After drying, the sample in the sampling device was taken out to analyze the characteristics, including the mass, water content, and bacteria livability in the sample. The sampling device and method were optimized with a sampling cup with a depth of 3.5?cm (for contact temperatures below 79.1°C) or 5?cm (for contact temperatures below 89.1°C). The ratio of CIP to reconstituted skim milk (RSM) was 1:10, and RSM concentration was not lower than 20% (w/w). This method was then applied to spray drying of Lactobacillus bulgaricus sp1.1. Furthermore, it was demonstrated that 2?mL of sterile water placed in the sampling cup prior to drying resulted in a more accurate measurement of cell viability. This sampling method can be used in practical spray drying applications for biological materials without using a special instrument or drying tower.     

薄层稠油油藏SAGD物理模拟研究

紧密围绕杜84块兴Ⅰ组油藏的地质特点与开发现状,依据相似原理设计建立了比例物理模型,开展SAGD比例物理模拟实验,探讨了薄层稠油双水平井SAGD开采中蒸汽腔的形成和发育过程,生产特征和开发效果,预测了盖层的热损失,可为开发方案编制提供借鉴。