烟气中N2O生成反应的动力学研究

采用静态法 模拟道气中对Ｎ２Ｏ生成有影响的组分ＮＯ,ＳＯ２和Ｈ２Ｏ,以及温度进行了动力学研究。结果表明,随着ＮＯ,ＳＯ２和Ｈ２Ｏ浓度的增加反反应时间的加长,Ｎ２Ｏ的生态量增加,反应温升高,Ｎ２Ｏ的生成速率下降。将实验数据用尝试法和微分法进行处理,得到如下结果在Ｎ２Ｏ的生成反中对ＮＯ,ＳＯ２和Ｈ２Ｏ均为一级反应,反应速率常数分别为：２．０＊１０＾－５,８．９＊１０＾－６,８．８＊１０＾－８ｍ＾３．ｍ     

SO2在Co—Mo／AC催化剂上的还原

本文研究了活性焦（ＡＣ）担载Ｃｏ－Ｍｏ催化剂对ＳＯ２还原的催化性能。考查了催化剂不同的预处理方法,Ｈ２／ＳＯ２摩尔比和还原温度对还原过程硫产率的影响,并就硫化后的Ｃｏ－Ｍｏ和活性焦在催化床不同的构成对硫产率的影响进行了研究。结果表明,经硫化后的催化剂在ＳＯ２＋２Ｈ２→Ｓ＋２Ｈ２Ｏ反应有较高的催化活性,在最佳反应温度３００℃,Ｈ／ＳＯ摩尔比为３,空速６０００Ｌ;ｋｇ＾－１．ｈ＾－１条件下,生成硫的产     

氧气和水蒸气对球状活性炭吸附SO2能力的影响

研究了Ｏ２和Ｈ２Ｏ对沥青基球状活性炭（ＰＳＡＣ）吸附ＳＯ２能力的影响。结果表明,Ｏ２和ＳＯ２占据不同的活性中心,而Ｈ２Ｏ和ＳＯ２占据同一类活性中心,且ＳＯ２与活性中心的结合能力比Ｈ２Ｏ强得多。Ｏ２或Ｈ２Ｏ均能提高ＰＳＡＣ对ＳＯ２的吸附能力。ＳＯ２吸附量的增加来源于ＳＯ２的化学吸附量。     

潮湿气氛下Ca（OH）2与SO2反应动力学研究

本文用固定床积分反应器研究潮湿气氛下Ｃａ（ＯＨ）２与ＳＯ２的反应动力学。     

固定燃烧源排放N2O的采样,分析方法及其监测

烟道气是一含有多种哗合物的复杂体系，除Ｎ２，Ｏ２外，还含有燃烧产物Ｈ２Ｏ，ＣＯ２ＣＯ，ＮＯｘ，ＳＯ２和Ｈ２Ｓ等，烟气样在贮放过程中它们之间相互影响，使各自的浓度发生变化，为了得到烟气中Ｎ２Ｏ含量的准确测定值，分别研究了Ｈ２Ｏ，ＳＯ２和ＮＯ的含量，放置时间对Ｎ２Ｏ生成量的影响，试验结果表明，玻璃注射器不适于贮放烟气样，样品中只有Ｈ２Ｏ，ＳＯ２和ＮＯ三种化合物同时存在时，才会有进一步的Ｎ２Ｏ的生成，其     

红壤对SO_4~（2－）和H_2PO_4~－的吸附与竞争吸附研究

研究红壤对ＳＯ４（２－）和Ｈ_２ＰＯ(４－)的吸附与竞争吸附机理．实验结果表明，红壤吸附Ｈ２ＰＯ４－的量远远大于ＳＯ４（２－），前者几乎是后者的２倍．在两种阴离子共存体系中，Ｈ２ＰＯ４－使ＳＯ４（２－）吸附量明显减少，在浓度低时甚至出现负吸附；ＳＯ４（２－）对Ｈ２ＰＯ４－吸附量的影响很小．说明土壤对Ｈ２ＰＯ４－的吸持力较强，为高强度专性吸附，不易于被其它阴离子解吸；土壤对ＳＯ４（２－）的吸持力则较弱，为低强度专性吸附或非专性物理吸附，能够被吸持力更强的阴离子完全解吸．     

H2O2对抗旱性不同玉米品种愈伤组织抗氧化系统的影响

两个玉米品种愈伤组织经１０－４ｍｏｌＬ－１、１０－３ｍｏｌＬ－１和１０－２ｍｏｌＬ－１Ｈ２Ｏ２处理３ｈ后,电解质泄漏率加大;Ｈ２Ｏ２和ＭＤＡ含量增加;ＡｓＡ和ＣＡＲ含量的减少．１０－４ｍｏｌＬ－１的Ｈ２Ｏ２处理对愈伤组织产生的氧化伤害较小．抗旱性较强品种ＰＡＮ６０４３愈伤组织的抗氧化酶（ＳＯＤ、ＰＯＤ、ＡＰ和ＧＲ）活性高于抗旱性较弱品种ＳＣ７０１,ＡｓＡ和ＣＡＲ含量的下降程度低于ＳＣ７０１．ＰＡＮ６０４３愈伤组织具有较强的抗Ｈ２Ｏ２能力,与含高活力抗氧化系统密切相关     

高温脱除H2S的Mn—Fe／Al2O3脱硫剂研究

本文在热力学分析的基础上,制备了Ｍｎ－Ｆｅ／Ａｌ２Ｏ３脱硫剂,原料气中Ｈ２Ｓ浓度约为０．３％,空速约为３０００ｈ＾－１,在５５０－６５０℃的反应条件下,进行了脱硫反应实验,当出口Ｈ２Ｓ浓度大于０．０１％时,结束脱硫反应,在７１０℃,２４００ｈ＾－１空速的条件下,用１０．８３％的Ｏ２对脱硫剂进行再生,当出口ＳＯ２浓度低于０．００２％时,结束再生反应。     

NOx分解还原催化研究进展

介绍和评价了ＮＯ_ｘ分解还原的３类催化剂：贵金属催化剂、氧化物催化剂、金属离子置换的分子筛。在ＮＯ_ｘ的碳氢化合物选择性催化还原反应（ＨＣ－ＳＣＲ反应）中，同样有３类催化剂，即金属氧化物、贵金属和分子筛。由于Ｃｕ－ＺＳＭ－５是目前最有希望投入实际使用的一种，故本文重点介绍了它对ＮＯ_ｘ的ＨＣ－ＳＣＲ反应的催化机理，以及温度、Ｏ_２含量、Ｃｕ~（２＋）的置换度、不同种类ＨＣ及ＨＣ含量等各种因素对Ｃｕ－ＺＳＭ－５的影响，并对其工作台试验进行了评价，指出了其存在的问题及当前的研究热点。     

二氧化硫与1—己烯的光化学反应动力学

利用ＧＣ／ＭＳ方法研究了ＳＯ２与１－己烯在无氧和有氧体系中光化学反应动力学，确定了ＳＯ２与１－己烯光化学反应的级数，给出了２９３－３３３Ｋ温度范围内总的反应速度常数Ｋ，以及Ｋ与温度的关系、反应的活化能和指前因子。另外，对反应物己醛和２－己酮的生成反应速度常数及其活化能也进行了计算和讨论。     

过碳酸钠/钼酸钠体系对2-氯乙基乙基硫醚的降解机理与动力学研究

研究了不同温度下过碳酸钠/钼酸钠体系和单一过碳酸钠对芥子气模拟剂2-氯乙基乙基硫醚（2-CEES）降解动力学规律,建立了相应的反应速率方程;利用液质联用技术分析了降解产物,并利用顺磁共振技术检测了过碳酸钠/钼酸钠体系产生的活性成分,推测了反应机理.结果表明,两种体系对2-CEES降解反应均为一级反应,过碳酸钠/钼酸钠体...     

Self-catalytic pyrolysis thermodynamics of waste printed circuit boards with co-existing metals

● The co-existing metals in WPCBs has positive catalytic influence in pyrolysis. ● Cu, Fe, Ni can promote reaction progress and reduce the apparent activation energy. ● Ni play better role in promoting WPCB pyrolysis reaction. Waste printed circuit boards (WPCBs) are generated increasingly recent years with the rapid replacement of electric and electronic products. Pyrolysis is considered to be a potential environmentally-friendly technology for recovering organic and metal resources from WPCBs. Thermogravimetric analysis and kinetic analysis of WPCBs were carried out in this study. It showed that the co-existing metals (Cu, Fe, Ni) in WPCBs have positive self-catalytic influence during the pyrolysis process. To illustrate their catalytic effects, the apparent activation energy was calculated by differential model. Contributions of different reactions during catalytic pyrolysis process was studied and the mechanism function was obtained by Šesták-Berggren model. The results showed that Cu, Fe, Ni can promote the reaction progress and reduce the apparent activation energy. Among the three metals, Ni plays better catalytic role than Cu, then Fe. This work provides theoretical base for understanding the three metals’ catalytic influence during the pyrolysis of non-metal powders in WPCBs.     

温度和砷酸根对砖红壤中Cd（II）吸附动力学的影响

土壤中砷和镉同时存在的现象普遍存在,但目前对砷酸根与Cd(II)在可变电荷土壤表面协同作用的机制还了解不多。用一次平衡法研究了288 K和308 K温度条件下Cd(II)在昆明砖红壤表面的吸附动力学,比较了加入砷酸根对Cd(II)吸附动力学的影响。结果显示,加As(V)和升高温度均不仅增加Cd(II)的吸附量,而且提高了吸附反应的速率。Cd(II)在砖红壤表面的吸附反应进行的特别快,几乎在30 min内达到准平衡,假二级动力学方程能很好拟合30 min内的吸附动力学数据(r2>0.999 5)。从反应速率常数计算得到的活化能的结果表明,加As(V)显著降低了Cd(II)吸附反应的活化能,这是As(V)促进可变电荷土壤吸附Cd(II)的根本原因。     

CO2+MEA反应在CaCO3催化下Eley-Rideal模型及混合胺溶液体系协同效应的机理研究

研究混合胺溶液吸收二氧化碳(CO₂)的反应机理对低碳环保具有重要意义.本文以碳酸钙(CaCO₃)为催化剂,在Eley-Rideal模型下通过Gaussian09软件模拟计算乙醇胺(MEA)+CO₂反应机理,,同时计算混合胺溶液体系乙醇胺(MEA)+二乙醇胺(DEA)/2-氨基-2-甲基-1-丙醇(AMP)/N-甲基二乙醇胺(MDEA)吸收CO₂中经实验证明的协同效应.本文在CCSD(T)/6-311++G(d,p)水平上计算在两性离子机理下中间步骤的自由能和几何振动频率.模拟结果表明,在固体催化剂CaCO₃作用下,反应活化能降低了14.9%,但是自由能没有降低.混合胺盐能量(MEA-DEA-CO₂,MEA-AMP-CO₂)低于MEA-CO₂-MEA能量,差距分别为-18.25%和-14.5%,而MEA-MDEA-CO₂体系能量与单一溶液体系差距仅为-5.88%.这表明二级胺,空间位阻胺的协同效应大于三级胺.     

PVC的热解脱氯动力学分析

采用动态热重法对PVC热解脱氯反应动力学进行了研究，对不同升温速率下TG曲线采用下同方法分析，计算出反应速率常数、反应级数、活化能等脱氯反应动力学参数，并推断出反应机制，分析结果表明，PVC热解存在两个阶段，氯原子主要在250℃-300℃之间以HCl的形式释放，且反应为一级反应。     

Removal of Cr(VI) from aqueous solution using waste weed, Salvinia cucullata

Biosorption studies of Cr(VI) were carried out using waste weed, Salvinia cucullata. Various adsorption parameters were studied, such as agitation speed, contact time, pH, particle size, and concentrations of adsorbent and adsorbate. The equilibrium was achieved in 12 h. A lower pH favoured adsorption of Cr(VI). The kinetics followed pseudo-second-order rate equations. The adsorption isotherm obeyed both the Langmuir and Freundlich models. The calculated activation energy (1.1 kJ mol^-1) suggested that the adsorption followed a diffusion-controlled mechanism. Various thermodynamic parameters such as Δ G^°, Δ H^°, and Δ S^° were also calculated. The positive values of enthalpy indicated the endothermic nature of the reaction, and Δ S^° showed the increasing randomness at the solid liquid interface of Cr(VI) on the adsorbent, which revealed the ease of adsorption reaction. These thermo-dynamic parameters showed the spontaneity of the reaction. The maximum adsorption of uptake (232 mg g^-1) compared well with reported values of similar adsorbents. The rate-determining step was observed to follow an intra-particle diffusion model.     

A kinetic study of Mn(II) precipitation of leached aqueous solution from electrolytic manganese residues

Electrolytic manganese residue (EMR) is a type of solid waste discharged from the process that converts solid manganese carbonate of rhodochrosite into soluble Mn(II) and generates anode mud under electrolysis. The experimental material was a filtrate created by using distilled water as a dispersal agent for the EMR, followed by simple filtration. A calculated amount of sodium carbonate was added to recover the soluble Mn(II) via precipitation into manganese carbonate. Data showed that Mn concentration may be markedly decreased from 2069 to 36 mg/L, thereby reaching a recovery rate as high as 98%. Analysis demonstrated that precipitation of Mn(II) from a leached aqueous solution followed first-order kinetics. The findings indicate that the reaction rate constant decreased as temperature gradually rose and that its apparent activation energy E_a was ?10.48 kJ/mol.     

Formic acid fractionation towards highly efficient cellulose-derived PdAg bimetallic catalyst for H2 evolution

The present work, in which cellulose isolated from formic acid fractionation (FAC) is decorated with polyetherimide (PEI) to attain highly efficient cellulose-derived PdAgbimetallic catalyst (PdAg-PEI-FAC), has been investigated, and the catalyst properties are characterized by XRD, XPS, BET, ICP-AES and HAADF-STEM. The as-obtained Pd3.75Ag3.75-PEI-FAC exhibits excellent catalytic performance for H2 evo-lution from a sodium formate-free formic acid (FA) aqueous medium at ambient temperature and the turnover frequency (TOF) reaches a high value of 2875 h-1, which is superior to most of the previously reported Pd-based heterogeneous catalysts supported on a carbon matrix in the literature. The remarkable catalytic activities of PdAg-PEI-FAC result from high dispersion Pd and synergistic effects between the PdAg bimetallic system. Furthermore, the amide (-NH) group in PEI coated on cellulose acting as a proton scavenger efficiently improves the catalytic property of catalyst. In addition, the critical factors affecting H2 release, such as FA concentration, reaction temperature, PdAg compositions and support matrix type, are also evaluated. Based on the experimental results, the probable three-step mechanism of H2 evolution from FA over Pd3.75Ag3.75-PEI-FAC is proposed. In the end, the activation energy (Ea) of Pd3.75Ag3.75-PEI-FAC catalyst is calculated to 53.97 kJ mol-1, and this catalyst shows unique robustness and satisfactory re-usability with no loss of catalytic activity after five recycles. The findings in this work provide a novel routine from lignocellulose fractionation towards cellulose-derived catalyst for H2 evolution.     

Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst in the catalytic wet air oxidation (CWAO) of cationic red GTL under mild reaction conditions

Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃, an environmental friendly material, was investigated. The catalyst exhibited good catalytic performance in the CWAO of cationic red GTL. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. HO₂· and O₂·⁻ appeared as the main reactive species in the reaction. The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst, a novel environmental-friendly material, was used to investigate the catalytic wet air oxidation (CWAO) of cationic red GTL under mild operating conditions in a batch reactor. The catalyst was prepared by wet impregnation, and characterized by special surface area (BET measurement), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst exhibited good catalytic activity and stability in the CWAO under atmosphere pressure. The effect of the reaction conditions (catalyst loading, degradation temperature, solution concentration and initial solution pH value) was studied. The result showed that the decolorization efficiency of cationic red GTL was improved with increasing the initial solution pH value and the degradation temperature. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. Hydroperoxy radicals (HO₂·) and superoxide radicals (O₂⁻·) appeared as the main reactive species upon the CWAO of cationic red GTL.