KMnO4/NaOH溶液吸收SO2/NO的动力学研究

在典型湿法烟气脱硫系统运行条件下,研究了平面传质搅拌反应器中KMnO₄/NaOH溶液同时吸收SO₂和NO的动力学,确定了反应级数、反应速率常数以及活化能.实验结果表明,NO的吸收速率随着入口NO分压和KMnO₄浓度的增加而提高.在吸收剂溶液中加入NaOH可以提高NO的吸收速率,烟气中O₂的体积分数对于NO和SO₂的吸收速率几乎没有影响.当同时吸收烟气中的SO₂和NO时,SO₂会降低NO的吸收速率,而NO对SO₂的吸收速率几乎没有影响.在KMnO4/NaOH溶液中NO的吸收速率对NO相间浓度和KMnO4浓度均为一级反应,平均反应速率常数为5.79×103 m³/(mol•s),活化能为26.85 kJ/mol.     

硅基高分散钴氧化物活化亚硫酸盐降解有机污染物的效能

近年来,基于硫酸根自由基（SO₄^·-）的高级氧化技术（SR-AOPs）迅速发展,高效稳定地产生SO₄^·-自由基的催化剂及相关机制成为新的研究重点。采用氨水改性吸附焙烧法制备非均相硅基高分散钴氧化物（CoNSi）催化剂,用于活化工业副产物亚硫酸盐（S（IV））,进而以废治污降解污染物。分别研究了不同pH值、不同CoNSi和亚硫酸钠（Na₂SO₃）投加量、不同橙黄Ⅱ（AO7）浓度以及氧气对底物降解效能的影响,分析了亚硫酸盐浓度和AO7浓度对AO7降解反应初始速率的影响。结果表明：当反应pH值为9.0,CoNSi和Na₂SO₃投加量分别为0.25 g/L和1.0 mM,AO7浓度为7 mg/L,氧气存在的条件下,AO7的降解率可达到79.4%。此外,序批实验证明了CoNSi活化亚硫酸盐的稳定性,自由基抑制实验证明了SO₄^·-自由基是降解AO7的主要活性物种。     

次氯酸钠对磺胺二甲氧嗪的降解与风险评价

自来水原水中新兴污染物的存在对饮用水水质安全提出新的挑战。采用氯消毒对典型磺胺类抗生素磺胺二甲氧嗪（Sulfadimethoxine,SDM）进行降解研究,考察余氯初始浓度、pH值、氨氮（NH₄-N）等因素对降解的影响,探究SDM氯氧化降解机理,评估其生态风险。结果表明：在SDM初始浓度为15 μmol/L、余氯初始浓度为60 μmol/L的条件下,120 s内SDM去除率达到95.9%,降解过程符合准二级反应动力学。反应速率常数随着余氯初始浓度增大而增大,随着NH₄⁺-N浓度增大而减小,背景阴离子Cl^-、NO₃^-、SO₄^2-对反应影响甚微,HCO₃^-、CO₃^2-对反应有抑制作用,中性条件下有利于SDM氯氧化反应。基于高分辨质谱HRMS Orbitrap解析出9种降解中间产物,降解过程中发生氯代反应、脱甲基反应和羟基加成反应等。在消毒过程中,SDM的完全去除并不意味着生态风险的有效削减,对饮用水水质安全构成潜在风险。     

低温等离子体处理甲酰胺溶液过程中活性粒子传质的数值模拟

采用一维漂移-扩散流体模型,对活性粒子在甲酰胺溶液中的传质进行了数值模拟。分析了等离子体处理甲酰胺溶液中5种主要活性氧粒子(OH、OH₂、O₃、O₂^- 、H₂O₂)的浓度和渗透深度。结果表明:在甲酰胺溶液中,O₃和OH的渗透深度可以达到13~14 μm,高于水中的7~9 μm;O₂^-渗透深度为580 μm,约为其在水溶液中的50%;甲酰胺浓度在10^-5~10^-3 mol/L内,对活性氧粒子传质过程的影响较明显;溶液中O₂对活性氧离子多样性有积极作用。这些现象表明,可以通过控制实际环境改变活性氧粒子的渗透深度。     

基于双金属MOFs 制备Co3O4/In2O3 复合物及其气敏性能的研究

以硝酸铟(In(NO₃)₃·xH₂O)、对苯二甲酸(H₂BDC)、六水合硝酸钴(Co(NO₃)· 6H₂O) 为原料, 首先采用一锅油浴法合成了含有Co²⁺ 的铟基金属有机框架材料(MOFs) Co²⁺/CPP-3(In) 材料, 然后在450 ℃ 下焙烧制备Co₃O₄/In₂O₃ 复合物气敏材料, 将Co₃O₄/In₂O₃ 复合物的粉体制作成传感器, 并对其气敏性能进行研究。利用扫描电子显微镜和X 射线衍射仪(XRD) 对双金属MOFs Co²⁺/CPP-3(In) 材料和Co₃O₄/In₂O₃ 复合物进行表征, 采用静态配气法测试其气敏性能。结果表明, Co₃O₄/In₂O₃(n_Co : n_In = 0.4 : 1) 样品的形貌保留了其MOFs 前驱体的棒状结构, 棱柱形框架更为突出, 表面呈凹陷状, 棒体中间粗两边细, 六角截面和棒体均布满了孔洞。结合EDX 和XRD 表征结果, Co²⁺/CPP-3(In) MOFs 前驱体完全转化成Co₃O₄/In₂O₃ 复合物; Co₃O₄/In₂O₃(n_Co : n_In = 0.4 : 1) 复合物在 70 ℃ 下对5×10^-6 H₂S 的气敏性能最优, 响应值达到153, 是同条件下纯备In₂O₃对H₂S 响应值的5 倍, 并且有较好的重复性、选择性和稳定性。     

水热辅助溶胶凝胶法制备纳米钛酸锌及其光催化性能

采用水热辅助的溶胶凝胶法制备纳米钛酸锌（ZnTiO₃）光催化剂,以罗丹明B为目标降解物,运用动力学模型分析罗丹明B（RhB）初始浓度对降解效果的影响。通过SEM、XRD、XPS、UV-Vis DRS对ZnTiO₃进行表征,并使用自由基捕获试验分析其降解机理。结果表明,ZnTiO₃为纯六方相,形貌为类球形,粒径50 nm左右。在催化剂用量为1 g/L、RhB初始浓度为5 mg/L、pH值为3的条件下,光催化反应150 min后,RhB降解率为93.2%。其动力学方程为k=0.132C₀^-1.253。ZnTiO₃光催化剂降解过程中,·OH、h⁺、·O₂^-均起到催化作用,产生·OH、h⁺的量相近且多于·O₂^-,说明·OH、h⁺在催化反应中起主要作用。     

O3/NaOH同时脱硫脱硝的热力学研究

利用化学热力学基本原理,分别计算了O₃/NaOH溶液同时脱硫脱硝反应过程中的摩尔反应吉布斯自由能变、摩尔反应焓变、化学反应平衡常数,以及化学反应达到平衡时的SO₂和NO的分压力,结果表明:利用O₃/NaOH溶液同时脱除SO₂和NO是可行的.     

Fe(Ⅱ)活化亚硫酸盐降解卡马西平的动力学及机制研究

高级氧化技术是去除水中新型有机污染物的重要方法之一。研究Fe （Ⅱ）活化亚硫酸盐（Fe （Ⅱ）/亚硫酸盐）体系降解卡马西平（CBZ）的动力学及体系中活性氧化物种对CBZ降解的贡献。结果表明：当亚硫酸盐浓度由0.20 mmol/L增加至0.50 mmol/L时,反应20 min时Fe （Ⅱ）亚硫酸盐体系对CBZ的去除率不断增加,而进一步增加亚硫酸盐浓度时,卡马西平的去除率不再进一步增加。当反应初始pH值为3.0~7.0时,Fe （Ⅱ）/亚硫酸盐体系均可降解CBZ,在初始pH值为5.0时,此体系对CBZ的去除率最高,反应平衡时CBZ的去除率达87.3%。此外,铁盐中SO₄^2-和Cl^-对Fe （Ⅱ）/亚硫酸盐体系降解CBZ基本无影响。综合电子顺磁共振检测及淬灭剂实验的结果可知,Fe （Ⅱ）/亚硫酸盐体系中所产生的活性氧化物种包括硫酸根自由基（SO₄^-·）、羟基自由基（HO·）和过一硫酸根自由基（SO₅^-·）,它们均对卡马西平的降解起贡献作用,其中SO₄^-·和HO·起主要贡献作用。     

多相氧化组合反应器与耦合分离新技术的研究构想与前景展望

目前大量化学品经过氧化反应制造,如重要的有机化工原料环氧丙烷(PO)、环氧氯丙烷(ECH)和盐酸羟胺等,现有工艺存在严重的“三高”问题,环保、经济和安全性方面需全面提升。国内自主创新的H₂O₂氧化工艺是以H₂O₂为氧化剂、在钛硅分子筛催化下的氧化反应,具有原子经济、环境友好等优点。但该过程是强放热的多相快反应,反应器设计与工程放大亟需解决高效混合、快速换热和安全性等问题,而氧化副产物的高效分离则是另一共性问题。基于以上问题,本项目进行了从基础研究到工业应用的全链条设计和一体化实施,重点解决H₂O₂氧化体系的分子混合与界面传递机理、跨尺度传递与反应耦合机制和反应器放大规律及过程强化新途径三个共性科学问题。项目完成后将形成多个自主产业化成套技术,建成两个H₂O₂绿色氧化体系工业示范装置(环氧丙烷工业示范装置、盐酸羟胺工业示范装置)以及环氧氯丙烷成套新技术工艺包,同时打破国外技术的封锁与垄断,颠覆和淘汰污染环境严重的现有工艺,实现节能环保绿色清洁生产。     

海水环境下MICP的反应机理与影响因素

为了探讨海水环境下微生物矿化反应过程与影响因素,在海水和去离子水环境下,通过改变营养盐浓度、菌液与营养盐体积比、环境温度等条件进行微生物诱导碳酸钙沉淀(Microbially Induced Carbonate Precipitation,MICP)水溶液试验,然后通过SEM、XRD和EDS测试对水溶液生成物进行检测,并推测海水环境下MICP的反应机理。结果表明:不同水环境条件下,营养盐浓度为1 mol/L、菌液与营养盐体积比为30:120时,反应速率最快,且生成沉淀物质量最大;温度对于碳酸钙沉淀反应影响明显,与低温(4℃)条件相比,室温(25℃)下反应速率更大,且反应进行得较充分;海水环境水溶液试验中,高pH值可以加速反应的进行,同时,由于海水中存在Mg²⁺、Ba²⁺等离子,使得沉淀物中除CaCO₃外,还含有少量的碱式碳酸镁(Mg₅(CO₃)₄(OH)₂·4H₂O)、BaCO₃等矿物成分。     

Kinetics of Fe3O4 formation by air oxidation

The kinetics of Fe₃O₄ formation by air oxidation of slightly acidic suspension of Fe(OH)₂ was studied. The effects of initial concentration of Fe(II), temperature, partial pressure of oxygen, air flow rate and stirring rate on the oxidation rate were investigated. The results show that Fe₃O₄ formation is composed of two-step reaction, the first step is the formation of Fe(OH) ₂ ⁺ by oxidation of Fe(OH)⁺ complex ions, the second step is the formation of magnetite by dehydration and deprotonation of Fe(OH)⁺ and Fe(OH) ₂ ⁺ . The oxidation reaction is zero-order with respect to the concentration of Fe(II) and around 0.5-order with respect to partial pressure of oxygen, and oxygen transfer process is rate-limiting step of oxidation reaction with apparent activation energy of 2.74 kJ · mol⁻¹.     

Selective leaching of vanadium from V-Ti magnetite concentrates by pellet calcification roasting-H_2SO_4 leaching process

A novel method of pellet calcification roasting-H_2 SO_4 leaching was proposed to efficiently separate and extract vanadium(V) from vanadium-titanium(V-Ti) magnetite concentrates.The leaching rate of V is as high as 88.98%,while the leaching rate of impurity iron is only 1.79%.Moreover,the leached pellets can be used as raw materials for blast furnace ironmaking after secondary roasting.X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy with energy dispersive X-ray spectrometry(SEMEDS) analyses showed that V~(3+) was oxidized to V~(5+) after roasting at 1200℃,and V~(5+) was then leached by H_2 SO_4.X-ray diffraction(XRD) analyses and single factor experiment revealed a minimal amount of dissolved Fe_2 O_3 during H_2 SO_4 leaching.Therefore,a high separation degree of V and iron(Fe) from V-Ti magnetite concentrate was achieved through H_2 SO_4 leaching.Compared with the traditional roastingleaching process,this process can achieve a high selectivity of V and Fe,and has excellent prospects for industrial production.     

Preparation and electrochemical properties of Pb-0.3wt%Ag/Pb-WC composite inert anodes

We prepared Pb-0.3wt%Ag/Pb-WC(WC stands for tungsten carbide,the same below) composite inert anodes by double-pulse electrodeposition on the surface of Pb-0.3wt%Ag substrates,and investigated the electrochemical properties of the composite inert anodes,which were obtained under different forward pulse average current densities from 2 A/dm~2 to 5 A/dm~2 and WC concentrations from 0 g/L to 40 g/L in bath.The kinetic parameters of oxygen evolution,corrosion potential and corrosion current of the composite inert anodes were obtained in a synthetic zinc electrowinning electrolyte of 50 g/L Zn~(2+) and 150 g/L H_2SO_4 at 35 ℃,by measuring the anodic polarization curves,Tafel polarization curves and cyclic voltammetry curves.The results show that Pb-0.3wt% Ag/Pb-WC composite inert anodes obtained under forward pulse average current density of 3 A/dm~2 and WC concentration of 30 g/L in an original acid plating bath,possess higher electrocatalytic activity of oxygen evolution,lower overpotential of oxygen evolution,better reversibility of electrode reaction and corrosion resistance in [ZnSO_4+H_2SO_4] solution.The overpotential of oxygen evolution of the composite inert anode is 0.926 V under 500 A/m~2 in [ZnSO_4+H_2SO_4] solution,and 245 mV lower than that of Pb-1% Ag alloy;the corrosion current of the composite inert anode is 0.95×10~(-4)A which is distinctly lower than that of Pb-1%Ag alloy,showing the excellent corrosion resistance.     

Insights into the adsorption performance and mechanism of hydrated Ca ion on talc (0 0 1) basal surface from DFT calculation

The utilization of Ca ion as assistant depressant of CMC on talc has been widely reported. Thus, the study on the adsorption mechanism of Ca ion on talc surface is very crucial for understanding the performance of CMC on talc depression. In this paper, mechanism insights into hydrated Ca ion adsorption on talc (0 0 1) basal surface were creatively provided using DFT calculation. [Ca(H₂O)₆]²⁺ and [Ca(OH)(H₂O)₃]⁺ were determined as the effective hydrate components for Ca ion adsorption, and the top O site was the most favorable position for their adsorptions on talc surface. Furthermore, the adsorption mechanisms of [Ca(H₂O)₆]²⁺ and [Ca(OH)(H₂O)₃]⁺ on talc surface were found to be not the Ca—O chemical bond, but the hydrogen bonding formed by the H atom of the H₂O ligand and the surface O atom. H₂O acted like a bridge to connect them to the talc surface. Moreover, the hydrogen bonding was formed due to the hybridization of H 1s orbital with the O 2s, O 2p orbitals. Simultaneously, electrons transferred between the H atom and the surface O atom. This work provides theoretical insights into the Ca ion adsorption on talc surface, which can help deeply understand the talc flotation using CMC as depression.     

Recovery of copper sulfate after treating As-containing wastewater by precipitation method

The solid sodium hydroxide neutralized acidic As-containing wastewater till pH value was 6. Green copper arsenite was prepared after copper sulfate was added into the neutralized wastewater when the molar ratio of Cu to As was 2:1 and pH value of the neutralized wastewater was adjusted to 8.0 by sodium hydroxide. The arsenious acid solution and red residue were produced after copper arsenite mixed with water according to the ratio of liquid to solid of 4:1 and copper arsenite was reduced by SO₂ at 60 °C for 1 h. The white powder was gained after the arsenious acid solution was evaporated and cooled. Copper sulfate solution was obtained after the red residue was leached by H₂SO₄ solution under the action of air. The results show that red residue is Cu₃(SO₃)₂·2H₂O and the white powder is As₂O₃. The leaching rate of Cu reaches 99.00% when the leaching time is 1.5 h, molar ratio of H₂SO₄ to Cu is 1.70, H₂SO₄ concentration is 24% and the leaching temperature is 80 °C. The direct recovery rate of copper sulfate is 79.11% and the content of CuSO₄·5H₂O is up to 98.33% in the product after evaporating and cooling the copper sulfate solution.     

Synthesis and Characterization of a Proton-transfer Complex of 1,2,4,5-benzenetetracarboxylic Acid with 1,10-phenanthroline

1Introduction Uptonow,manyproton transfercomplexesofaro maticcarboxylicacidsandLewisbaseshavebeen reported[19].Theproton transferfromorganicacidsto aminesmaytakeplacereadilywithaverylowactivation energyincontrastwiththeattackoftheaminetothecar bonylcarbon…     

Preparation of AgSnO2 composite powders by hydrothermal process

Silver-tin oxide powders were synthesized by the hydrothermal method with Ag（NH3）2^＋ solution and Na2SnO3 solution as raw materials and Na2SO3 as reductant. The precipitation conditions of Na2SnO3 solution and the reduction conditions of Ag（NH3）2^＋ were also investigated. The powders prepared were characterized by differential thermal analysis （DTA）, X-ray diffraction analysis （XRD）, scanning electron microscope （SEM） and energy spectrum analysis, The results show that pH value of the solution is a key parameter in the formation of Sn（OH）4 precipitate and the reduction reaction of Ag（NH3）2^＋ can release H^＋ ions, which results in synchronous precipitation of Sn（OH）6^2- as Sn（OH）4. The reduction of Ag（NH3）2^＋ and precipitation of Na2SnO3 occur simultaneously and the coprecipitation of silver and tin oxide is reached by the hydrothermal method. The silver-tin oxide composite powders have mainly flake shape of about 0.3 μm in thickness and there exists homogeneous distribution of tin oxide and silver in the powder synthesized.     

Estimation of kinetics parameters in Beckmann rearrangement of cyclohexanone oxime using genetic algorithm

Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrangement of OXH^＋ while the SO3 acts as dehydrating agent and OXSO3 can turn to CPLSO3 ultimately. Considering self-catalyzed reaction between OXSO3 and CPLH^＋ , kinetic model for Beckmann rearrangement was established. Corresponding parameters were estimated by using float genetic algorithm （GA） and simulation results agree well with the experimental data below -19.3 ℃. Industrial equipment was simulated and analyzed. Effects of key process parameters such as molar ratio of sulfuric acid to oxime and circulation ratio on the residual oxime are also discussed. The results show that the caprolactam exists as CPLH^＋ finally in oleum and the minimum molecular ratio of sulfuric acid to oxime can be 0.5 theoretically.     

Changes of hydrochemical composition and heavy metals concentration in shallow groundwater from karst hilly areas in Guiyang region, China

The quality changes of shallow groundwater from karst hilly areas in Guiyang region of China impacted by the urbanization were investigated. The results show that the major ions in shallow groundwater from the karst hilly areas are mainly composed of HCO₃ ⁻, SO₄ ²⁻, Ca²⁺ and Mg²⁺, and the concentrations scopes of NO₃ ⁻, Cl⁻, K⁺ and Na⁺ of the groundwater in agricultural, residential and industrial areas are 4.5–9.6, 2.8–7.1, 3.9–6.3 and 2.5–4.9 times higher than those in the forest areas, respectively. The concentrations of As, Pb and Cd of shallow groundwater in the industrial areas are also significantly enhanced, followed by those in the residential areas and the agricultural areas. The concentrations of NO₃ ⁻, SO₄ ²⁻, As, Pb and Cd of the groundwater in the industrial areas and those of NO₃ ⁻, SO₄ ²⁻, As and Cd of shallow groundwater in the residential areas reach grade III of the Groundwater Quality Standard of China (GB/T 14848-93), while the concentration of NO₃ ⁻ in the groundwater from the industrial areas exceeds grade V. With the process of urbanization, NO₃ ⁻ is the key factor to influence the groundwater quality in karst hilly areas, followed by SO₄ ²⁻, As, Pb and Cd.