硅气凝胶常压制备、表征及对狄氏剂吸附性能研究

以工业水玻璃为硅源,采用三甲基氯硅烷［(CH₃)₃SiCl,TMCS］/乙醇［CH₃CH₂OH,EtOH］/正己烷［C₆H₁₄］混合液对硅水凝胶进行溶剂交换和表面改性,在常压干燥条件下获得疏水硅气凝胶材料,并对其吸附狄氏剂性能进行了系统评价.BET、FTIR、热重等表征结果显示,制得的硅气凝胶材料接触角在135°～142°之间,比表面积在444～560 m²·g^-1之间,孔径范围为17.5～23.4 nm,孔隙率为94.8%～95.6%,材料在空气中的耐热温度约为380℃.改性剂用量与组成比例对材料性能有较大影响,在TMCS∶EtOH∶C₆H₁₄摩尔比为1∶1∶1时,材料疏水性、比表面积和孔容孔径等物理化学性质达到最大值.本方法制备的疏水硅气凝胶对狄氏剂表现出良好的吸附性能,4　h内狄氏剂去除率达到84%;吸附动力学符合准二级动力学模型,吸附速率常数随疏水性增强而增大;Freundlich系数K_f为30.22 μg·g^-1,是活性炭的11倍.     

MBR污水处理工艺中活性污泥动力学参数测定

缺乏可靠的污泥动力学设计参数是膜-生物反应器（membrane bioreactor,MBR）工艺在实际应用中遇到的主要问题之一.以某座处理城市污水的实际规模MBR工程的好氧活性污泥为对象,采用耗氧速率表征方法,测定计算得到以下动力学参数值：异养菌产率系数Y_H＝0.693、自养菌产率系数Y_A＝0.263、异养菌衰减系数K_dH＝0.108 d^-1、自养菌衰减系数K_dA＝0.089 d^-1、COD最大比去除速率v_mS＝1.94 mg·(mg·d)^-1、COD去除半饱和常数K_S＝34.6 mg·L^-1、氨氮最大比去除速率v_mN＝0.18 mg·(mg·d)^-1、氨氮去除半饱和常数K_N＝1.06 mg·L^-1.以上结果与传统活性污泥法工艺（CAS）中污泥的文献报道值相比,Y_H和K_dH较高,而v_mS和v_mN较低.MBR的高污泥浓度条件可能是导致上述差异出现的主要原因.     

Co(C3H6NS2)3·C6H12N2S3单晶的制备及催化性能的研究

采用常温饱和溶液蒸发法,一硫化四甲基秋兰姆与钴(Ⅱ)发生原位反应得到一种新型非均相Fenton催化剂单晶Co(C₃H₆NS₂)₃·C₆H₁₂N₂S₃;通过单晶X衍射、红外光谱和C、N和H元素分析对该单晶结构进行了表征;该单晶的空间群为P-1,在不对称单元中有1个Co(Ⅲ)中心,3个新配体C₃H₇NS₂和1个TMTM;Co(Ⅲ)呈现出稍微偏斜的八面体的配位几何构型.利用该单晶催化氧化降解了直接蓝6和直接绿28;结果显示,在酸性和碱性条件下,染料的降解率和矿化率都较高,这是因为活性中心Co(Ⅲ)提高了H₂O₂的效率.当投加量在1 200～1 600　mg·L^-1之间时,处理90　min后,直接蓝6和直接绿28的降解效率可分别达到94.39%和94.78%.相比之下,不加该单晶光催化剂,其它条件完全相同时,处理90　min后2种染料的降解率均不到45%,降解缓慢.使用后的单晶,通过过滤,可反复使用,有利于降低处理成本.此外还研究了催化反应的动力学,反应遵从Langmuir-Hinshelwood动力学模型;2种染料降解反应速率常数k分别为3.03×10²和6.25×10²　mg·(L·min)^-1,吸附常数K分别为1.52×10^-4和7.23×10^-5　L·mg^-1.     

碳负载富氧空位的NiCo2O4用于电催化还原硝酸盐

水体中硝酸盐是一种广泛存在的污染物,因此,开发用于水中硝酸盐还原的高效电催化剂受到广泛关注.采用溶胶-凝胶法耦合硼氢化钠还原法制备了碳负载富氧空位的NiCo₂O_4-x/C电催化剂,并研究其去除硝酸盐的性能.结果发现,在该体系中,耦合导电碳载体可改善半导体型电催化剂导电性,构建氧空位可促使原子H^*生成,最终实现硝酸盐高效还原.NiCo₂O_4-x/C阴极在电流密度为20 mA·cm^-2、pH=7的条件下,可于3 h内去除水中94.8%的NO₃^--N,相较于NiCo₂O₄及NiCo₂O₄/C阴极,NO₃^--N去除率分别提高了36.6%和12.2%.此外,NiCo₂O_4-x/C阴极在连续5次还原硝酸盐过程中性能并未有明显变化.结合掩蔽实验和电子顺磁共振波谱分析证实,NiCo₂O_4-x/C阴极除了可通过直接电子还原硝酸盐外,还可以通过生成原子H^*间接还原硝酸盐.通过对实际废水处理进一步验证其转化硝酸盐的性能,研究表明,NiCo₂O_4-x/C阴极可有效去除焦化废水生物出水中硝酸盐.     

·Cl引发α-蒎烯的大气氧化机制及动力学

α-蒎烯是大气中含量最丰富的单萜烯类挥发性有机化合物,与氯自由基（·Cl）反应是其重要的转化途径.然而,·Cl引发α-蒎烯大气氧化的分子机制尚不清楚.本研究采用量子化学计算与微观动力学模拟相结合的方法,研究了·Cl与α-蒎烯的引发反应以及引发反应生成的主要α-蒎烯自由基的后续转化机制与动力学.结果发现,·Cl反式加成到α-蒎烯的C₂位置生成加成中间体IM_1-9-a是最可行的反应途径.在298 K和1.013×10⁵ Pa条件下,计算得到·Cl与α-蒎烯的反应速率常数（k_Cl）为3.1×10^-10 cm³·molecule^-1·s^-1,与k_Cl的实验值（4.6±1.3）×10^-10 cm³·molecule^-1·s^-1一致.生成的IM_1-9-a进一步与O₂反应生成过氧自由基IM_3-1-a,在2.5×10⁹ cm^-3（100 ppt） NO和1.25×10⁹ cm^-3（50 ppt） HO₂·条件下,IM_3-1-a后续主要与NO和HO₂·反应生成有机硝酸酯（C₁₀H₁₆ClNO₃和C₁₀H₁₆ClNO₄）、氢过氧化物（C₁₀H₁₇ClO₂和C₁₀H₁₇ClO₃）和烷氧自由基（C₁₀H₁₆ClO₂·）.生成的 闭壳层产物与母体α-蒎烯相比具有较高的O∶C比,可能具有较低的蒸气压,进而贡献二次有机气溶胶.本研究结果可为全面评价α-蒎烯的 大气化学反应对大气质量的影响提供理论支撑.     

UV/氯联合处理含溴溶液中溴酸根的生成

研究了UV和氯联合作用下溴酸根离子(BrO^-₃)在低浓度含溴溶液中的生成,旨在探讨pH、次氯酸钠(NaOCl)浓度、溶解氧(DO)、光强和温度等因素对其生成的影响.研究表明,暗反应条件下H₂O-NaOCl-Br^-体系较稳定,而UV照射可使游离氯浓度持续降低,同时伴有部分Br^-（6 .6%～32%）被氧化成BrO^-₃离子;pH、温度和光强恒定时余氯的分解可用拟一级反应速率方程拟合;实验条件下（I为610～1 896 μW/cm²,T为12 .2～36 .1℃）,拟一级反应速率常数分别与体系温度和光强值有线性关系;BrO^-₃的生成大致可以分为快速、慢速和平缓3个阶段;在慢速生成阶段,BrO^-₃的生成量与余氯的分解量有良好的线性关系（绝大部分相关系数在0 .96以上）;实验范围内（pH为4 .41～11 .07,DO为1 .5～9 　mg/L,Cl₂为1 .23～4 .50 　mg/L）,低pH、低DO和高初始NaOCl（以氯计）浓度有利于溴酸根的生成,提高温度与光强均不同程度提高溴酸根生成速度,但同时因加速余氯的分解而减少了溴酸根的总生成时间.     

ZnMnxCo2-xO4活化过一硫酸盐降解有机污染物

分别以Zn（CH₃COO）₂·2H₂O、Mn（CH₃COO）₃·2H₂O和Co（CH₃COO）₂·4H₂O为锌源、锰源和钴源,采用溶胶-凝胶自燃烧法成功制备了ZnMn_xCo_2-xO₄（x=0~2）复合物,并用X射线衍射和X射线光电子能谱对其进行表征.同时,还研究了Mn/Co物质的量比、催化剂用量及PMS用量对目标污染物降解的影响.结果表明,该复合物可催化活化过一硫酸钾（PMS）降解有机污染物,当催化剂中x=0.8,催化剂投加量为0.2 g·L^-1,PMS用量为0.4 mmol·L^-1（0.25 g·L^-1）时,20 μmol·L^-1（10 mg·L^-1）罗丹明B（RhB）可在15 min内完全降解.ZnMn_0.8Co_1.2O₄的高催化活性主要归功于Mn³⁺和Co²⁺的协同效应.将ZnMn_xCo_2-xO₄-PMS体系用于亚甲基蓝、结晶紫、金橙、双酚A、4-氯酚等其他污染物的降解,也取得了较好的效果.基于电子自旋共振ESR和自由基猝灭实验的结果,可以推测该反应体系中活性物种为硫酸根自由基和羟基自由基.     

辽东湾大气中多环芳烃的含量组成及气粒分配

2016年5月和8月对辽东湾大气环境中气相和颗粒相样品进行了走航和定点采集,并对24种PAHs在气相和颗粒相中的含量和组成进行探讨,对15种PAHs的气粒分配过程进行了分析.结果表明：5月和8月辽东湾大气气相和颗粒相中∑₂₄PAHs总平均含量分别为28.8 ng·m^-3和24.0 ng·m^-3,气相中∑₂₄PAHs含量5月小于8月,颗粒态∑₂₄PAHs含量5月大于8月,低分子量PAHs主要分布在气相中,高分子量PAHs组分主要分布在颗粒相,中等分子量PAHs的气粒分配更容易受到气温等环境条件影响;气粒分配系数K_p随着PAHs分子量增加而增加;lgK_p-lgP_L模型和lgK_p-lgK_OA模型的斜率m分别为-0.35和0.37,偏离平衡态m为-1或+1,辽东湾气粒分配未达到平衡;假设达到平衡态时的lgK_p-lgK_OA模型、lgK_p-lgP_L模型和碳黑-空气模型均表明,5环PAHs的模型预测结果与实际测定结果之间的吻合程度较好,15种PAHs的碳黑-空气模型能够更好地接近野外实际测定值,低分子量和中等分子量PAHs的气粒分配受到碳黑影响较大.     

锰铁复合磁性材料制备及其对零价汞吸附性能研究

燃煤工业是我国人为汞排放的主要来源,寻求合理有效的途径来控制汞排放至关重要.本文将氧化性强的过渡金属锰离子引入Mn/γ-Fe₂O₃晶格中,制备出锰铁复合磁性材料（Fe_3-xMn_x）_1-δO₄,以其来模拟Hg⁰在燃煤废气中的吸附过程,并通过比表面积和孔隙率、X衍射分析、SEM、磁性分析、氧化还原等材料表征方法研究（Fe_3-xMn_x）_1-δO₄的吸附性能,同时重点研究（Fe_3-xMn_x）_1-δO₄在不同掺杂量、温度、空速等操作条件下对Hg⁰的吸附能力.结果显示,制备所得的（Fe_3-xMn_x）_1-δO₄的比表面积均在120 m²·g^-1以上,较大的比表面积和孔体积可以为Hg⁰的吸附反应提供更多的活性区域,促进反应进行.SEM表征也显示（Fe_3-xMn_x）_1-δO₄的微观特征呈现球状颗粒物,拥有较大的表面积,能够提供更多的吸附活性位.在磁性铁氧化物中引入过渡金属锰,其对汞的氧化能力明显增强;在100~200℃的反应温度窗口,此时温度大小与（Fe_3-xMn_x）_1-δO₄对汞的吸附能力成正比,达到200℃时,500 min内平均穿透率可达到9%;空速对（Fe_3-xMn_x）_1-δO₄吸附汞的能力影响较小.     

Self-catalytic degradation of ortho-chlorophenol with Fenton's reagent studied by chemiluminescence

The degradation of ortho-chlorophenol using Fenton's reagent was studied by chemiluminescence (CL). Without a special CL reagent, a weak CL emission from the mixture of ferrous ion and hydrogen peroxide was observed at room temperature. The CL intensity was increased by the addition of ortho-chlorophenol into the mixed solution. When the temperature was raised to 65℃, the CL intensity was enhanced strongly. The CL mechanisms for the system H₂O₂-Fe²⁺ with and without ortho-chlorophenol were studied by examining the CL spectrum, gas chromatography-mass spectrometry and electron spin resonance spectrum. The effects of various free radical scavengers, surfactants and fluorescence compounds on the CL intensity were also investigated. A self-catalytic oxidation mechanism was proposed. The results showed that singlet oxygen was the main emitter for the system H₂O₂-Fe²⁺. The strong CL from the system H₂O₂-Fe²⁺-ortho-chlorophenol was due to singlet oxygen and electronically excited quinone. The benzenediol-like intermediate product formed during the phenol oxidation process greatly promoted the Fenton's reaction and led to higher CL intensity. Chemiluninescence is a novel approach for the investigation of the oxidation of some organic pollutants by Fenton's reagent.     

回转窑热解气化炉处理生活垃圾特性

基于目前固定床热解气化法在常温下进行存在燃气热值和气化效率较低、燃料适用范围小和预处理复杂等问题,采用控制变量法设计探究了不同预热空气温度和过量空气系数对小型回转窑式热解气化炉处理村镇生活垃圾的影响.结果表明:预热空气温度升高有利于垃圾热解气化产气,但有一定的局限性,当温度超过600 ℃时垃圾的气化产气明显下降;当过量空气系数为0.4时,垃圾的热解气化效率达到最大值,并且焦油产量最小.垃圾原样在过量空气系数为0.4、空气预热温度为500 ℃下对底渣、飞灰进行重金属含量的分析测试结果显示,飞灰中的铅含量远高于GB 18598—2001《危险废物填埋污染控制标准》相关标准限值,需要经过处理才能排放,二英采样分析结果显示其含量均低于GB 18485—2014《生活垃圾焚烧污染控制标准》限值.研究显示,该回转窑式热解气化工艺处理生活垃圾的最佳过量空气系数为0.4,最佳空气预热温度为500 ℃,在此最佳工况条件下焦油产量小,飞灰及焦渣中重金属含量小,ρ(二英)低于0.10 ng/m3.      

灰分对高硫煤热解部分气化硫变迁的影响

采用分步脱除矿物质方法,对义马原煤及HCl,HCl-HF,HCl-HNO₃处理后煤样,分别在固定床反应器中考察了热解部分气化下硫的脱除规律.结果表明:一方面在热解过程中原煤及酸处理煤样H₂S和COS的析出均呈双峰趋势,其析出值主要受温度、原煤中灰分和HNO₃氧化作用;另一方面,在部分气化和酸处理后煤样热解半焦在600℃～900℃范围内硫脱除率可达50%～80%,800℃时,无机硫可完全脱除.而原煤热解半焦总硫,无机硫的脱除率在700℃时最大.气化温度的升高,加强了碱性矿物质的固硫作用,其结果是900℃气化时,总硫和无机硫脱除率降低.酸处理后有机硫含量基本保持不变,其噻吩结构只随碳骨架的气化而析出.     

温度对干化污泥水蒸气气化产气特性的影响

采用固定床气化装置,在水蒸气流量为0.32 kg/h条件下进行了污泥水蒸气气化实验。研究了温度对污泥气化气体产率、氢气产率、气体成分与低位热值、气体能源转化率的影响。结果表明:随着反应温度从700℃上升到1 000℃;气体产率从0.39 m3/kg升至0.61 m3/kg;氢气产率从0.18 m3/kg升至0.34 m3/kg;气体能源转化率从54%升至88%;产气的低位热值从10 688.1 kJ/m3提高至11 168.9 kJ/m3。同时产气中H2和CO含量随着温度的升高而增加,CH4、CO2和CnHm含量随温度的升高而减少。因此,为了获得更多的可燃气体,建议在污泥水蒸气气化工艺中,气化温度必须大于800℃。     

Supercritical gasification for the treatment of o-cresol wastewater

The supercritical water gasification of phenolic wastewater without oxidant was performed to degrade pollutants and produce hydrogen-enriched gases. The simulated o-cresol wastewater was gasified at 440-650℃ and 27.6 MPa in a continuous Inconel 625 reactor with the residence time of 0.42-1.25 min. The influence of the reaction temperature, residence time, pressure, catalyst, oxidant and the pollutant concentration on the gasification efficiency was investigated. Higher temperature and longer residence time enhanced the o-cresol gasification. The TOC removal rate and hydrogen gasification rate were 90.6% and 194.6%, respectively, at the temperature of 650℃ and the residence time of 0.83 min. The product gas was mainly composed of H2, CO2, CFL and CO, among which the total molar percentage of H2 and CFL was higher than 50%. The gasification efficiency decreased with the pollutant concentration increasing. Both the catalyst and oxidant could accelerate the hydrocarbon gasification at a lower reaction temperature, in which the catalyst promoted H2 production and the oxidant enhanced CO2 generation. The intermediates of liquid effluents were analyzed and phenol was found to be the main composition. The results indicate that the supercritical gasification is a promising way for the treatment of hazardous organic wastewater.     

Experimental study on MSW gasification and melting technology

In order to develop municipal solid waste (MSW) gasification and melting technology, two preliminary experiments and a principle integrated experiment were fulfilled respectively. The gasification characteristics of MSW are studied at 500-750℃ when equivalence ratio (ER) was 0.2-0.5 using a fluidized-bed gasifier. When temperature was 550-700℃ and ER was 0.2-0.4, low heat value (LHV) of syngas reaches 4000-12000 kJ/Nm3. The melting characteristics of fly ash were investigated at 1100-1460℃ using a fixed-bed furnace. It was proved that over 99.9% of dioxins could be decomposed and most heavy-metals could be solidified when temperature was 1100-1300℃. The principle integrated experiment was carried out in a fluidized-bed gasification and swirl-melting system. MSW was gasified efficiently at 550-650℃, swirl-melting furnace maintains at 1200-1300℃ stably and over 95% of fly ash could be caught by the swirl-melting furnace. The results provided much practical experience and basic data to develop MSW gasification and melting technology.     

基于Aspen Plus的生活垃圾热解气化模拟及正交优化

热解气化技术作为一种城市固体废弃物(municipal solid waste,MSW)无害化处理的方式,其相关研究具有现实意义.利用Aspen Plus软件建立了 MSW固定床热解气化模型,在模型验证的基础上探讨了气化温度、气化压力和空气当量比对MSW热解气化过程的影响.通过二次回归正交试验法得出MSW热解气化过程中...     

镍基催化剂的制备及其对垃圾气化产氢的催化活性

以陶粒为载体,采用常温浸渍法制备了负载型镍基催化剂,并利用X射线衍射分析(XRD)、X射线荧光分析(XRF)、BET、环境扫描电镜-能谱仪分析(ESEM-EDX)和元素分析等对其进行了表征,该催化剂BET表面积为101.3m2/g.活性组分NiO颗粒平均粒径约为2μm,均匀分散在载体表面.并在下吸式固定床气化炉中,进行水蒸气催化气化城市生活垃圾有机组分的实验来评价镍基催化剂的催化活性.结果表明,在镍基催化剂的作用下,H2和CO含量明显增加,H2含量最高达43.22%,CO2、CH4、C2H4和C2H6.平均含量降至1%以下.催化气化过程的产氢率远远高于气化过程,最高达19.9mol H2/kg,低温段催化气化的潜在产氢率高于气化过程,但高温段低于气化过程;高温有利于气化产气中H2和CO的生成,还可以促进CH4、C2H4和C2H6的分解.催化气化过程的焦油产率、灰渣产率明显低于气化过程,特别是焦油产率降至2%以下,而产气率则高于气化过程.     

Structural and photocatalytic properties of TiO2 films fabricated on silicon substrates by MOCVD method

Silicon(111) and Silicon(100) were employed for fabrication of TiO2 films by metal organic chemical vapor deposition( MOCVD).Titanium(Ⅳ) isopropoxide(Ti[O(C3H7)4]) was used as a precursor. The as-deposited TiO2 films were characterized with FE-SEM, XRD and AFM. The photocatalytic properties were investigated by decomposition of aqueous Orange Ⅱ. And UV-VlS photospectrometer was used for checking the absorption characteristics and photocatalytic degradation activity. The crystalline and structural properties of TiO2 film had crucial influences on the photodegradation efficiency. For MOCVD in-situ deposited films on Si substrates, the photoactivities varied following a shape of “M”: at Iower(350℃ ), middle(500℃ ) and higher(800℃ ) temperature of deposition, relative lower photodegradation activities were observed. At 400% and 700% of deposition, relative higher efficiencies of degradation were obtained, because one predominant crystallite orientation could be obtained as deposition at the temperature of two levels, especially a single anatase crystalline TiO2 film could be obtained at 700℃.     

Research on low emission MSW gasification and melting system

In order to eliminate secondary pollution caused by municipal solid waste (MSW) incineration, a MSW gasification and melting process is proposed. The process is expected to reduce the emission of pollutants, especially heavy-metals and dioxins. In this paper, the combustible components of MSW and simulated MSW were gasified in a lab-scale fluidized bed at 400°C–700°C when the excess air ratio (ER) was between 0.2 and 0.8. The experimental results indicated that the MSW could be gasified effectively in a fluidized bed at approximately 600°C–700°C when excess air ratio was 0.2–0.4. The melting characteristics of two typical fly ash samples from MSW incinerators were investigated. The results indicated that fly ash of pure MSW incineration could be melted at approximately 1,300°C and that of MSW and coal co-combustion could be melted at approximately 1,400°C. When temperature was over 1,100°C, more than 99.9% of the dioxins could be decomposed and most of the heavy-metals could be solidified in the slag. Based on the above experiments, two feasible MSW gasification and melting processes were proposed for low calorific value MSW: (1) sieved MSW gasification and melting system, which was based on an idea of multi-recycle; (2) gasification and melting scheme of MSW adding coal as assistant fuel. __________ Translated from Environmental Science, 2006, 27(1): 69–73 [译自: 环境科学]     

城市生活垃圾热解产气特性的试验研究

在外热式固定床试验台上,针对城市生活垃圾中的典型组分,进行了不同条件下的热解试验研究。试验测量不同条件下产物的产气量和产气速率,分析了热解气的组分和气体热值。分析发现,物料的挥发分、加热方式以及热解终温等对产气影响大,随温度的增加产气中H2含量逐渐增多,C2H4和C2H6的含量逐渐下降,气体热值有一个最大值。