高效干法脱硫剂的研究与开发

煤炭燃烧过程中产生大量的SO2，对大气环境造成严重的污染，危害人体健康。烟气脱硫是解决SO2污染的主要方法，于法脱硫具有系统简单、投资省、占地面积小、运行费用低等优点。但目前此方法脱硫效率较低，即使在相当高的钙硫比条件下，吸收剂与SO2的反应也不完全。这主要是由于CaSO4的摩尔容积比Ca(OH)2或CaO的大，随着反应的进行，吸收剂的孔隙被堵塞，这个过程阻碍着内部反应的吸收剂与烟气中的SO2进一步发生反应，这样，脱硫效率不高，吸收剂的利用率也低，限制了此种方法的应用。     

烟气脱硫溶液中硫酸根的去除

分别采用石灰乳化学沉淀法和低温结晶法去除烟气脱硫溶液中的SO42-。实验结果表明：在室温、CaO溶液质量分数25%的条件下,石灰乳化学沉淀法对SO42-的去除率仅为59.51%,且向溶液中引入了Ca2+,产生的硫酸钙固体废物难以再生利用;采用低温结晶法处理烟气脱硫溶液,在结晶温度7 ℃、结晶时间3 h、NaOH加入量34.8 g/L的条件下,SO42-的去除率为82.04%、滤液中的ρ（Na+）为3.88 g/L。在现场工业应用试验中,采用低温结晶法去除烟气脱硫溶液中的SO42-,平均SO42-的去除率可达70.00%以上,滤液中的ρ（Na+）小于15.00 g/L。该法可有效抑制烟气脱硫溶液中SO42-含量的增加。     

过氧化钙降解有机污染物研究进展

CaO2具有很好的稳定性,可在水和土壤中逐步分解生成H2O2成为氧化反应的氧化剂,已作为H2O2的替代物用于环保领域的研究中.介绍了CaO2的作用机理,综述了CaO2用于处理含卤代物、染料、抗生素、苯系物等废水的研究进展,以及CaO2用于治理含石油烃、多环芳烃、苯系物和农药的污染土壤的研究进展.提出未来的研究方向:充分...     

天然气再燃添加有机酸盐同时降低SO2及NOx的机理研究

对天然气再燃过程中添加的有机酸盐同时脱硫、脱氮反应途径及机理进行了详细的分析.探讨了有机酸盐(钙镁醋酸盐CMA)分解的CHi还原NO的主要机理,研究了CMA固硫的反应机理,分析了脱硫过程影响HCN、NH3还原NO的因素.提出了天然气再燃添加CMA同时脱硫、脱氮时,也要综合考虑CaO对SO2的脱除和对NO生成的促进作用.     

Fe_2O_3和K_2CO_3对钙基添加剂脱硫脱硝的影响

在研究焦炭燃烧过程中使用钙基添加剂固硫的基础上,探讨了Fe_2O_3或K_2CO_3对CaO脱硫脱硝的影响。实验结果表明:添加剂的种类对焦炭燃烧过程中排放的SO_2和NO的浓度及总量均有一定的影响;加入Fe_2O_3或K_2CO_3替代部分CaO后,焦炭燃烧过程中排放的SO_2和NO比单独加入CaO时均有所下降;向焦炭中分别混合3.0%(w)CaO),1.5%(w)CaO+1.5%(w)Fe_2O_3,1.5%(w)CaO+1.5%(w)K_2CO_3的添加剂时,焦炭的SO_2排放总量分别降低了69.93%,75.98%,79.98%,NO排放总量分别降低了64.38%,79.73%,84.14%;加入Fe_2O_3或K_2CO_3后,钙基添加剂的表面性质发生了变化,同时增加了反应的活性中心数,因而复合添加剂能更有效地进行脱硫脱硝。     

氯氧化锆生产中废碱液的回收利用

建立了以 CaO 为沉淀剂去除废碱液中 SiO2回收 NaOH 的工艺,研究了各工艺因素对siO2去除效果的影响,实验结果表明,CaO 沉淀除去废碱液中 SiO2的最佳工艺条件为:CaO 与废碱液中 SiO2摩尔比 3.0,反应温度80～95℃,反应时间 40～60 min,搅拌转速 200 r/min.在此条件下,S...     

中国SO2减排控制指标体系与减排控制对策研究

通过建立SO2减排控制指标体系的方法,分析了中国减排SO2的影响因素,建立了SO2减排量函数关系表达式,并对中国SO2减排提出了相关建议.     

可见光下氮掺杂罗丹明B分子印迹TiO_2的选择性光催化性能

采用溶胶-凝胶法和分子印迹技术,以尿素为氮源、罗丹明B为模板分子制备了氮掺杂罗丹明B分子印迹TiO_2粉末(N-TiO_2-RhB),并对样品进行了XRD、UV-Vis DRS和BET表征。表征结果显示:氮掺杂和分子印迹一定程度改善了样品的孔隙结构和孔径分布,N-TiO_2-RhB的比表面积和孔体积分别为TiO_2的1.9倍和1.5倍;氮掺杂使TiO_2的光吸收带边发生红移,而分子印迹不能改变催化剂的光吸收带边。N-TiO_2-RhB具有最佳的可见光活性和选择性,对罗丹明B的降解率高达92.7%。对罗丹明B、罗丹明6G、甲基紫和甲基绿的降解过程均符合一级反应动力学方程。     

磁性铁矿石对CO还原SO2的催化活性

采用磁性强弱不同的铁矿石以及制备的Fe3O4作为催化剂,催化CO还原SO2。实验结果表明:在3种催化剂中弱磁性铁矿石对CO还原SO2的催化活性最好;当反应温度为700℃时,在弱磁性铁矿石催化作用下的SO2转化率达84.3%。该方法既可以有效去除炼油厂催化裂化再生装置排放的SO2,同时又利用了低品位的磁性铁矿石,实现了SO2的治理和资源的综合利用。     

硫酸尾气中SO2超标原因分析及改进措施

浙江巨化股份有限公司硫酸厂采用二段氨法处理硫酸尾气,在执行GB4282－84时SO2可以达到排放标准,在执行GB12697－1996时,SO2排放速率低于标准规定限值,但因受处理装置SO2吸收效率的限制,SO2排放浓度时有超标。为此,1999年该厂对影响硫酸尾气中SO2排放质量提高的因素进行了全面分析,找出了超标原因,并通过完善处理装置、优化工艺指标等措施,提高了处理装置的SO2吸收效率,做到了达标排放。     

Role of aluminous component of fly ash on the durability of Portland cement-fly ash pastes in marine environment

The durability, of mixtures of two kinds of Spanish fly ashes from coal combustion (ASTM class F) with 0, 15 and 35% replacement of Portland cement by fly ash, in a simulated marine environment (Na(2)SO(4)+NaCl solution of equivalent concentration to that of sea water: 0.03 and 0.45 M for sulphate and chloride, respectively), has been studied for a period of 90 days. The resistance of the different mixtures to the attack was evaluated by means of the Koch-Steinegger test. The results showed that all the mixtures were resistant, in spite of the great amount of Al(2)O(3) content of the fly ash. The diffusion of SO(4)(2-), Na+ and Cl- ions through the pore solution activated the pozzolanic reactivity of the fly ashes causing the corresponding microstructure changes, which were characterized by X-ray diffraction (XRD), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). As a result, the flexural strength of the mixtures increased, principally for the fly ash of a lower particle size and 35% of addition.     

Modelling of long-term dynamic leaching tests applied to solidified/stabilised waste

The paper aims at simulating the closed-system dynamic leaching of a cement-based monolith containing lead with the numerical reactive transport code HYTEC in a 3D-cylindrical geometry. The model considers, simultaneously, the chemical evolution of pore water, the progression of mineralogical alteration fronts, and the concomitant release of elements from the S/S waste. In good agreement with the experiment, element releases were found to be mainly controlled by either diffusion (Na, K, and, to a lesser extent, Cl), by surface dissolution (Ca, Si) or by a mixed evolution (Pb, SO4). All of the calculated mineralogical transformations take place in a thin layer beyond the monolith surface. Consequently, modelling of Ca, Si and SO4 releases was quite sensitive to the node size of the simulation grid and was improved by taking into account the increase of porosity and effective diffusion coefficient due to mineral dissolution in the leached layer. In agreement with experimental results, the deepest front corresponds under closed-system conditions to portlandite dissolution and calcium silicate hydrates CSH 1.8 transformation into CSH of lower Ca/Si ratio. A second, distinct and intermediate, front is made by ettringite dissolution. The network of CSH is globally preserved in the leached layer, complete dissolution occurring over a very small thickness only. Finally, hydrotalcite precipitation in the leached layer is expected by modelling due to pH drop.     

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 2. Results From Three Sites

The data mining/groundwater modeling methodology developed in McDade et al. (2013) was performed to determine if matrix diffusion is a plausible explanation for the lower‐concentration but persistent chlorinated solvent plumes in the groundwater‐bearing units at three different pump‐and‐treat systems. Capture‐zone maps were evaluated, and eight wells were identified that did not draw water from any of the historical source areas but captured water from the sides of the plume. Two groundwater models were applied to study the persistence of the plumes in the absence of contributions from the historical source zones. In the wells modeled, the observed mass discharge generally decreased by about one order of magnitude or less over 4 to 10 years of pumping, and 1.8 to 17 pore volumes were extracted. In five of the eight wells, the matrix diffusion model fit the data much better than the advection dispersion retardation model, indicating that matrix diffusion better explains the persistent plume. In the three other wells, confounding factors, such as a changing capture zone over time (caused by changes in pumping rates in adjacent extraction wells); potential interference from a high‐concentration unremediated source zone; and limited number of pore volumes removed made it difficult to confirm that matrix diffusion processes were active in these areas. Overall, the results from the five wells indicate that mass discharge rates from the pumping wells will continue to show a characteristic “long tail'' of mass removal from zones affected by active matrix diffusion processes. Future site management activities should include matrix diffusion processes in the conceptual site models for these three sites. © 2013 Wiley Periodicals, Inc.     

Demobilisation of critical contaminants in four typical waste-to-energy ashes by carbonation

Two bottom ashes, one air pollution control (APC) residue and one fly ash from three different Swedish municipal solid waste incineration (MSWI) plants were characterised regarding the leaching of environmentally relevant components. Characterisation was performed using a diffusion tank leaching test. The impact of carbonation on the release of eight critical components, i.e., Cl(-), Cr, Cu, Mo, Pb, Sb, Se, SO(4)(2-) and Zn, was assessed at a lab-scale and showed carbonation to have a more pronounced demobilising effect on critical components in bottom ashes than in APC residue and fly ash. From grate type incinerator bottom ash, the release of Cr decreased by 97%, by 63% for Cu and by 45% for Sb. In the investigated APC residue, the releases of Cr, Se and Pb were defined as critical, although they either remained unaffected or increased after carbonation. Cl(-) and SO(4)(2-) remained mobile after carbonation in all investigated residues.     

水性油墨废水絮凝污泥制备吸附剂及阳离子染料的吸附

以水性油墨废水絮凝污泥为原料、采用一步炭化活化法制备了吸附剂,并将其用于阳离子蓝X-GRRL溶液(300 mg/L)的吸附处理。考察了吸附剂投加量、吸附时间、吸附温度和吸附pH对吸附效果的影响,并对吸附动力学进行了探讨。结果表明:所制得吸附剂的总孔体积为0.5 cm~3/g,平均孔径为7.12 nm;在吸附剂投加量0.6g/L、吸附时间420 min、吸附温度25℃、吸附pH 5.4的条件下,吸附量高达486.21 mg/g,脱色率达97.24%;该吸附剂对于阳离子蓝X-GRRL的吸附过程可用准二级动力学模型和颗粒内扩散效应模型很好地描述。     

软锰矿浆催化氧化烟气中二氧化硫产酸过程研究

采用软锰矿浆催化氧化烟气中的SO2,使其生成硫酸。考察了软锰矿浆液固比、软锰矿浆初始pH、气体流量、进口SO2浓度、气体中氧浓度和反应温度对硫酸浓度的影响。试验结果表明,软锰矿浆的液固比和气体中的氧浓度对产酸速率的影响最大。软锰矿浆与SO2反应生成硫酸的过程分为线性阶段和幂函数两个阶段,符合Pasiuk提出的反应动力学模型。     

Migration of inorganic ions from the leachate of the Rio das Ostras landfill: A comparison of three different configurations of protective barriers

Batch tests and diffusion tests were performed to analyze the efficiency of a protective barrier in a landfill consisting of compacted soil with 10% bentonite compared to the results obtained for only compacted soil and for compacted soil covered with a 1-mm-thick HDPE geomembrane; the soil and leachate were collected from the Rio das Ostras Landfill in Rio de Janeiro, Brazil. The diffusion tests were performed for periods of 3, 10 and 60 days. After the test period, the soil pore water was analyzed and the profiles for chloride, potassium and ammonium were determined along a 6-cm soil depth. The results of the batch tests performed to define sorption parameters were used to adjust the profiles obtained in the diffusion cell experiment by applying an ion transfer model between the interstitial solution and the soil particles. The MPHMTP model (Multi Phase Heat and Mass Transfer Program), which is based upon the solution of the transport equations of the ionic contaminants, was used to solve the inverse problem of simultaneously determining the effective diffusion coefficients. The results of the experimental tests and of the model simulation confirmed that the compacted soil with 10% bentonite was moderately efficient in the retention of chloride, potassium and ammonium ions compared to the configurations of compacted soil with a geomembrane and compacted soil alone, representing a solution that is technically feasible and requires potentially lower costs for implementation in landfills.     

Gas permeability and tortuosity for packed layers of processed municipal solid wastes and incinerator residue.

To make a proper evaluation of gas component movement inside a landfill site, it is important to investigate the different parameters related to gas flow. In this work gas-filled porosity, intrinsic permeability, tortuosity and equivalent pore radius were determined for various packed wastes, such as incineration ash, shredded bulky waste and shredded incombustible waste. These parameters were measured/inferred for samples packed in a column and exposed to a controlled gas flow. The effect of waste conditions, especially the moisture content, on these parameters was also investigated. The intrinsic permeability of such packed wastes was generally in the order of 10(-10) to 10(-9) m2, except for some ash that was one to two orders lower. The tortuosity of waste layer was greater than that of a particulate material and ranged between 2 and 10. The equivalent pore radius was generally in the order of 10(-4) m, which means that gas diffusion is still ordinary in such packed waste layer. The obtained results will be utilized when simulating gas flow inside a landfill site for biogas extraction or site aeration.     

Characteristics of mercury desorption from sorbents at elevated temperatures

This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. Elemental mercury and mercuric chloride were tested with activated carbon and bauxite. The experimental results indicated that mercury desoption from sorbents was strongly affected by the desorption temperature and the mercury–sorbent pair. Elemental mercury was observed to desorb faster than mercuric chloride and activated carbon appeared to have higher desorption limits than bauxite at low temperatures. A kinetic model considering the mechanisms of surface equilibrium, pore diffusion and external mass transfer was proposed to simulate the observed desorption profiles. The model was found to describe reasonably well the experimental results.     

Solid-liquid distribution of selected concrete admixtures in hardened cement pastes

The distribution between hardened cement paste and cement pore water of selected concrete admixtures (BZMs), i.e., sulfonated naphthalene-formaldehyde condensate (NS), lignosulfonate (LS) and a gluconate-containing plasticiser used at the Paul Scherrer Institute for waste conditioning, was measured. Sorption data were fitted to a single-site Langmuir isotherm with affinity constants K=(19+/-4)dm(3)g(-1) for NS, K=(2.1+/-0.6) dm(3)g(-1) for LS and sorption capacities q=(81+/-16)g kg(-1) for NS, q=(43+/-8)g kg(-1) for LS. In the case of gluconate, a two-site Langmuir sorption model was necessary to fit the data satisfactorily. Sorption parameters for gluconate were K(1)=(2+/-1)x10(6)dm(3)mol(-1) and q(1)=(0.04+/-0.02)mol kg(-1) for the stronger binding site and K(2)=(2.6+/-1.1)x10(3)dm(3)mol(-1) and q(2)=(0.7+/-0.3)mol kg(-1) for the weaker binding site. Desorption of these BZMs from cement pastes and pore water in cement specimens prepared in the presence of the BZMs were then used to test the model. It was found that only minor parts of NS and LS could be mobilised as long as the cement composition was intact, whereas the sorption of gluconate was found to be reversible. The Langmuir model makes valuable predictions in the qualitative sense in that the pore water concentration of the BZMs is reduced by several orders of magnitude as compared to the initial concentrations. In view of the necessity for conservative predictions used in the safety analysis for disposal of radioactive waste, however, the predictions are unsatisfactory in that the measured pore water concentrations of NS and LS were considerably larger than the predicted values. This conclusion does not apply for gluconate, because its concentration in cement pore water was below the detection limit of approximately 50 nM.