改性小麦秸秆吸附Cu2+的动力学和热力学研究

本研究采用ZnCl2作为活化剂,用640W功率的微波照射5min的方法制备改性小麦秸秆。研究了改性小麦秸秆投加量、吸附时间、温度、pH对改性小麦秸秆吸附水溶液中Cu2+的影响,以及对其等温吸附特征、动力学和热力学进行了研究。试验结果表明:投加量为0.1g,pH为6,改性小麦秸秆对Cu2+有较好的吸附效果,吸附在10h后达到平衡。改性小麦秸秆对Cu2+吸附较好地符合Langmuir、Freundlich温吸附模型和准二级动力学方程,吸附过程中△G0,说明属于自发反应。     

Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.     

次氯酸钙溶液脱硫脱硝一体化过程热力学分析

烟气脱硫脱硝一体化技术已成为当前大气污染防治领域的研究热点,其中氧化剂液相吸收法极有可能率先实现产业化。文章理论上首次提出了次氯酸钙溶液脱硫脱硝一体化技术,利用热力学函数计算分析了脱硫脱硝反应的方向和限度,通过SO2和NO平衡分压计算推导了污染物的脱除效率,考察标准吉布斯函数变分析了该技术的优势。结果表明:脱硫脱硝反应的标准吉布斯函数变分别为-614.55和-888.21 kJ/mol,热力学角度上完全可行,反应限度极深,优于文献中介绍的尿素、NaClO2、KMnO4/NaOH溶液吸收法和臭氧结合氨水吸收法。同时,SO2和NO平衡分压很小,说明次氯酸钙溶液几乎可以完全脱除烟气中的SO2和NOX。     

雾天气下二次气溶胶均质成核生长过程

二次气溶胶的核化过程涉及分子杂乱运动和碰撞,在分子间的范德华力作用下,大气环境系统中产生分子聚合,形成分子团、胚胎和核.基于此建立二次气溶胶核化和生长模型,并且采用颗粒群平衡模拟和多重蒙特卡洛方法,对雾天气下水汽均质同分子核化及H₂O-H₂SO₄均质异分子核化的过程开展热力学和动力学数值研究. 结果表明:在水汽均质核化过程中,当水汽过饱和比从2增至10时,水汽的成核速率增加约73个数量级,形成临界胚胎所需的分子数降低了97.3%. 而对于H₂O-H₂SO₄均质异分子核化过程,在环境温度271.15 K,气态H₂SO₄分子数浓度为5×107cm-3条件下,当RH(相对湿度)由80%增至100%时,二次气溶胶成核速率增加1.4倍;在气态H₂SO₄分子数浓度较高、RH较大时,核化形成的临界胚胎粒径较小. 经过均质核化生长后,二次气溶胶粒径处于1.5～3.5 nm.      

Testing of chemical substances for environmental effects—an important task for the chemical industry

Recently the heterogeneous reactions are increasingly recognised as significant in polluted areas. In this work the reactions of gases with solid alkali‐halide crystals at temperatures 200K and 300K were examined by using a recently proposed thermodynamic model (Varotsos et al., 1988) which provides the interconnection of entropy and enthalpy for various processes with well known macroscopic properties of the bulk solid.     

Adsorption of phosphate ions from water using a novel cellulose-based adsorbent

A novel cellulose-based adsorbent, iron(III)-coordinated amino-functionalised poly(glycidylmethacrylate)-grafted cellulose [Fe(III)–AM-PGMACell] was developed for the removal of phosphate from water and wastewater. The scanning electron micrograph showed that AM-PGMACell has a rougher surface than cellulose and the adsorption of Fe(III) on AM-PGMACell made the surface even rougher. Infrared spectroscopy revealed that amino groups on the surface of AM-PGMACell complexed with Fe(III) played an important role in the removal of phosphate from solutions. X-Ray diffraction patterns showed a decrease in crystallinity after graft copolymerisation onto cellulose. The effects of contact time, initial sorbate concentration, pH, agitation speed, dose of adsorbent and temperature on the removal process were investigated. Maximum removal of 99.1% was observed for an initial concentration of 25 mg·L ^?1 at pH 6.0 and an adsorbent dose of 2.0 g·L ^?1. A two-step pseudo-first-order kinetic model and Sips isotherm model represented the measured data very well. Complete removal of 11.6 mg·L ^?1 phosphate from fertiliser industry wastewater was achieved by 1.6 g·L ^?1 Fe(III)–AM-PGMACell. The adsorbent exhibited very high reusability for several cycles. Overall, the study demonstrated that Fe(III)–AM-PGMACell can be used as an efficient adsorbent for the removal and recovery of phosphate from water and wastewater.     

页岩气压裂返排液的分析与双效MVR处理

对西南地区某页岩气田压裂返排液进行了分析,在此基础上采用双效机械蒸汽再压缩(MVR)系统对其进行处理,建立了完整的计算模型,并对影响系统的主要参数进行了探讨。压裂返排液分析结果表明:蒸发浓缩液黏度与相同浓度氯化钠溶液的黏度相近,可排除因有机物富集导致其在蒸发器内壁附着而影响传热系数及堵塞蒸发器的可能。模型计算结果表明:进料含盐率由2%增至6%时,压缩机比功耗与压缩机进气量的降幅均小于4.0%,两效蒸发器面积分别减小约4.3%和18.5%;传热温差由4℃升至8℃时,压缩机比功耗增加约51.0%,两效蒸发器面积均减小约49.6%;在系统安全运行的前提下,提高蒸发温度可降低系统能耗。     

活性炭对含铅废水吸附特性研究

采用静态法用活性炭吸附处理含铅废水,考察了活性炭对含铅废水的吸附特性。结果表明:活性炭对铅离子吸附平衡时间为100 m in;吸附等温方程为:Ce/qe=0.4298+0.0594Ce(25℃),该方程符合Langmu ir型吸附模式,不同温度下吸附平衡参数0RL1,表示该吸附为有利吸附。实验数据应用数学模型拟合,二级相关系数R2=0.9998,显示吸附过程动力学与二级动力学模型相关性较好;计算不同温度下各热力学参数:△Hθ大于零、△Gθ小于零,证实该吸附过程是一个自发吸热过程。△Sθ大于零,表明铅离子在固液界面有序性减小、混乱度增大。△Hθ值很小,说明该过程为物理吸附。     

污泥焚烧中Cd形态转化的热力学平衡模拟

采用热力学平衡分析方法,结合典型污泥成分和焚烧条件预测了污泥焚烧过程中重金属Cd的转化和迁移规律。模拟计算中考虑了主量矿物质与Cl、S对Cd的形态转化的影响。研究结果表明,污泥焚烧过程中,在低温的条件下Cd主要以固体碳酸盐形式存在,随着温度升高,碳酸盐分解为固态CdO,随后有气态Cd(OH)2、Cd和CdO生成,并且在较高温度主要以气态Cd存在。焚烧体系中,矿物质SiO2对Cd的形态转化影响大于其他矿物质,SiO2能与Cd结合生成稳定的CdSiO3,从而可有效抑制含Cd气态污染物的排放。焚烧体系中Cl较易与Cd结合形成CdCl2而导致Cd的挥发,Cl含量的增加促进了Cd在焚烧体系中的挥发。在低温阶段,Cd易与S结合形成固态硫酸盐,抑制了金属的挥发;在高温阶段,金属的形态转化基本不受S的影响,但是可以影响气态金属Cd的生成温度。根据污泥在不同焚烧温度、Cl含量、S含量条件下Cd的不同产物形态,可以对Cd的污染进行有效控制。     

天然土壤对水溶液中Pb~(2+)的吸附

以天然土壤为吸附材料,处理水溶液中的Pb2+,研究3种土壤对水溶液中Pb2+的吸附过程并结合土壤的理化性质对吸附规律进行初步分析。结果表明,棕壤和钙层土对Pb2+的吸附能力远大于红壤,3种土壤对Pb2+的吸附动力学曲线与二次动力学方程有较好的拟合性;3种土壤吸附Pb2+的吸附等温线用Langmuir方程描述最为合适,其次是Temkin方程,再次是Frenudlich方程,钙层土对Pb2+的吸附受温度影响较为明显;由实验数据得出的反应热力学参数说明3种土壤对Pb2+的吸附是自发的吸热过程;Pb2+在饱和吸附的土壤表面覆盖率并不高;土壤对Pb2+的吸附能力受各种土壤理化性质的综合影响。