微波辅助紫外光催化氧化降解吲哚的研究

采用微波辅助紫外光催化氧化工艺处理吲哚污染物,并探讨了溶液pH值、TiO2用量、曝气时间和吲哚初始浓度对吲哚降解效果的影响。研究结果表明,曝气/MW/UV/TiO2系统中,当pH值为7、吲哚初始质量浓度为50 mg/L、催化剂质量浓度为0.2 g/L、曝气时间为60 min时,吲哚的降解效果最好,降解率为81.8%。微波辅助紫外光催化氧化工艺大大提高了TiO2的光催化性能,对难降解有机物吲哚具有良好的处理效果,对于解决目前日益严重的环境污染问题,具有一定的研究和实用价值。     

矿物均相酸催化剂催化甲醇和乙酸酯化反应动力学(英文)

In this work, esterification of acetic acid and methanol to synthesize methyl acetate in a batch stirred reactor is studied in the temperature range of 305.15–333.15 K. Sulfuric acid is used as the homogeneous catalyst with concentrations ranging from 0.0633 mol·L?1 to 0.3268 mol·L?1. The feed molar ratio of acetic acid to methanol is varied from 1:1 to 1:4. The influences of temperature, catalyst concentration and reactant concentration on the reaction rate are investigated. A second order kinetic rate equation is used to correlate the experimental data. The forward and backward reaction rate constants and activation energies are determined from the Arrhenius plot. The developed kinetic model is compared with the models in literature. The developed kinetic equation is useful for the simulation of reactive distillation column for the synthesis of methyl acetate.     

酸功能化离子液体催化合成仲丁醇的反应动力学(英文)

The acid-functionalized ionic liquid ([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) show that the synthesis method is feasible and high purity of ionic liquid can be obtained. Using [HSO3Pmim]HSO4 as the catalyst, we studied the reaction kinetics of synthesizing sec-butyl alcohol from sec-butyl acetate and methanol by transesterification in a high-pressure batch reactor. The effects of temperature, initial molar ratio of methanol to ester, and catalyst concentration on the conversion of sec-butyl acetate were studied. Based on its possible reaction mechanism, a ho-mogeneous kinetic model was established. The results show that the reaction heatΔH is 10.94 × 103 J·mol?1, so the reaction is an endothermic reaction. The activation energies Ea+and Ea?are 60.38 × 103 and 49.44 × 103 J·mol?1, respectively.     

掺杂改性TiO2紫外光催化降解甲苯的动力学研究

探索了用水热反应制备的锐钛型掺杂改性的TiO2(即A-TiO2)对甲苯的光催化降解作用.通过分析甲苯的初始浓度、TiO2用量、掺铁量和溶液的pH值对光催化速率的影响,研究改性TiO2催化甲苯的动力学行为;结果表明:甲苯溶液初始浓度为1.2 g/L(pH =5)、催化剂用量为2.0 g/L,掺铁量为4％(摩尔分数)、室温下紫外光照(λ=365 nm)反应2h,甲苯的降解率D％(47.93％)和表观反应速率常数k达到最大值0.2523 h-.光催化反应符合L-H动力学方程,降解过程表现为拟一级反应.     

催化湿式氧化山梨酸生产废水催化剂的研究

以过渡金属氧化物CuO为主活性组分通过对Cr2O3的复合和掺入电子助剂La2O3的考察,研制出适用于催化湿式氧化处理山梨酸生产废水的复合催化剂。考察了各组分浸渍液浓度、焙烧温度和焙烧时间等制备条件对催化剂的催化活性和稳定性的影响,确定了最佳制备条件。结果表明:优化制备的CuO-Cr2O3-La2O3/TiO2催化剂,用于处理山梨酸生产废水时具有良好的催化活性和稳定性,在θ=220℃,p(O2)=2.5 MPa,反应时间t=120 min,山梨酸生产废水初始CODCr=10 030 mg/L条件下CODCr去除率达到96.6%,而在相同条件下未加催化剂的湿式氧化CODCr去除率只有60.8%。     

对二甲苯液相催化氧化动力学(Ⅰ)反应机理和动力学模型

针对PX高温液相催化氧化过程的特点开发了一套气液固三相反应实验技术 ,进行了氧化过程的动力学实验研究 .根据自由基反应机理和Co Mn Br三元催化体系的作用机制对PX氧化过程进行了深入的剖析 ,分析了芳烃中甲基和醛基的各步氧化机理及其与催化剂循环之间的耦合作用 .在此基础上推导出关于反应物浓度的动力学模型 ,并根据实验数据计算出各动力学参数 .     

生物质热裂解实验和模型研究(英文)

The analysis on the feedstock pyrolysis characteristic and the impacts of process parameters on pyrolysis outcomes can assist in the designing,operating and optimizing pyrolysis processes.This work aims to utilize both experimental and modelling approaches to perform the analysis on three biomass feedstocks—wood sawdust,bamboo shred and Jatropha Curcas seed cake residue,and to provide insights for the design and operation of pyrolysis processes.For the experimental part,the study investigated the effect of heating rate,final pyrolysis temperature and sample size on pyrolysis using common thermal analysis techniques.For the modelling part,a transient mathematical model that integrates the feedstock characteristic from the experimental study was used to simulate the pyrolysis progress of selected biomass feedstock particles for reactor scenarios.The model composes of several sub-models that describe pyrolysis kinetic and heat flow,particle heat transfer,particle shrinking and reactor operation.With better understanding of the effects of process conditions and feedstock characteristics on pyrolysis through both experimental and modelling studies,this work discusses on the considerations of and interrelation between feedstock size,pyrolysis energy usage,processing time and product quality for the design and operation of pyrolysis processes.     

用自热式高温好氧消化工艺预处理肺炎杆菌生物降解动力学研究(英文)

Biodegradation parameters and kinetic characteristics for pre-treating waste strains of Klebsiella pneu-moniae were studied in laboratory scale with an insulated reactor by an innovative technique,autothermal thermo-philic aerobic digestion(ATAD) . Based on an Arrhenius-type equation,an empirical model was developed to corre-late the removal of total suspended solid(TSS) with the initial TSS concentration,influent reaction temperature,aeration rate and stirring rate. The reaction temperatures of the ATAD system could be raised from the ambient temperatures of 25 °C to a maximum temperature of 65 °C. The exponentials for the initial TSS concentration,aeration rate and stirring rate were 1.579,-0.8175 and-0.6549,respectively,and the apparent activation energy was 6.8774 kJ·mol-1. The correlation coefficient for the pre-exponential factor was 0.9223. The TSS removal effi-ciency predicted by the model was validated with an actual test,showing a maximum relative deviation of 10.79%. The new model has a good practicability.     

选择性催化还原(SCR)脱硝催化剂的性能研究

文章开展了工艺条件对选择性催化还原(SCR)脱硝催化剂的性能研究,采用自行研制开发的V2O5-WO3/TiO2-Al2O3催化剂,考察了温度、空速、NH3与NO摩尔比、NO初始浓度、氧浓度等对这种催化剂脱硝性能的影响,为选择性催化还原(SCR)脱硝催化剂的应用提供科学的实验数据。     

消除油垢热分析实验噪音方法和热动力学研究

利用自行设计的较大物量的热质量损失(TG)分析装置,获得餐饮业油烟道油垢燃烧特性曲线。根据实验结果,将小波去噪方法引入到TG数据的平滑处理,通过正交化实验得到了最佳的小波参数,通过与常规的移动平均法、高斯平滑法、Vondrak平滑法比较,发现自适应小波变换在TG数据平滑处理提高了信噪比,均方根误差减小。最后通过比较微分法和积分法计算得到的动力学参数,发现原始TG数据计算的动力学参数和小波变换处理得到的微分热质量损失(DTG)数据计算得到的参数符合得很好,表明文中方法是有效的,可以直接地应用于热动力学分析中。     

Experimental study and kinetic analysis of oxidant-free thermal-assisted UV digestion utilizing supported nano-TiO2 photocatalyst for detection of total phosphorous

A novel thermal-assisted ultra-violet (UV) photocatalysis digestion method for the determination of total phos-phorus (TP) in water samples was introduced in this work. The photocatalytic experiments f...     

Preparation and performances of mesoporous TiO2 film photocatalyst supported on stainless steel

Mesoporous TiO₂ film photocatalysts supported on stainless steel substrates were prepared using the sol–gel method with Ti(OC₄H₉)₄ as a precursor and poly ethylene glycol (PEG) as a structure-directing agent. Mesoporous TiO₂ film with a pore diameter of about 15 nm was obtained with the addition of PEG (molecular WEIGHT =400). The pore diameter of TiO₂film was varied with molecular weight of PEG additive. The structure-directing process was also discussed. Mesoscopically ordered inorganic/polymer composites were believed to form during the process. Compared to conventional TiO₂ film photocatalyst, the mesoporous TiO₂ film showed a good performance for the photo degradation of rhodamine B (RB) solution irradiated with UV light of 365 nm. The photo degradation constant of rhodamine B for mesoporous TiO₂ film photocatalyst can arrive at 22 times of that for conventional TiO₂ film photocatalyst. Also an excellent performance for the degradation of gaseous formaldehyde with mesoporous film photocatalyst was obtained. The photo degradation rate of gaseous formaldehyde for mesoporous TiO₂ film photocatalyst can arrive at six times of that for conventional TiO₂ film photocatalyst.     

Photocatalytic degradation of imazapyr in water: Comparison of activities of different supported and unsupported TiO2-based catalysts

Photocatalytic oxidation in aqueous phase of imazapyr, a systemic herbicide characterized by its high persistence and mobility in soils, has been investigated using two different titania photocatalysts: commercial Degussa P-25 and industrial Millennium PC-500. Despite potentially better textural and crystalline properties of PC-500, its photocatalytic activity is smaller than that of P-25 for that reaction. A less efficiency of PC-500 powders absorbing the irradiated photons, as well as a low substrate adsorption capacity, has been attributed as the main responsible for such behaviour. Variables such as concentration of imazapyr, amount of catalyst and the physical state of TiO₂ (as a powder or deposited on an Ahlstrom paper) have been studied to elucidate their influence on the efficiency of the photocatalyzed degradation of imazapyr. It has been determined that both adsorption capacities of the catalyst and the reaction rates are strongly affected by the above mentioned parameters. They are even able to modify both the mechanism and kinetic order of the process, by affecting the interfacial substrate–TiO₂ interactions.     

High temperature CO2 capture performance and kinetic analysis of Na4SiO4 ceramics

Alkali silicate-based ceramics sorbents were regarded as particularly suitable materials for CO₂ capture at high temperatures, however, the CO₂ capture behaviors of Na₄SiO₄ had been seldom investigated. In this work, the Na₄SiO₄ ceramics samples were prepared using the one-step synthesized method, and the CO₂ sorption/desorption performances at high temperatures, the thermal stability, and the cycling stability of Na₄SiO₄ were systematically investigated. It was demonstrated that the maximum CO₂ sorption capacity of SO-3 sample reached 19.4 wt% at 725 °C, and the optimal condition of cycling tests were 750 °C for sorption and 800 °C for desorption based on the sorption/desorption capacity and rate, which exhibited good thermal stability and high cyclic stability. Besides, the kinetic analysis results showed that the diffusion process was the rate-determining step of CO₂ adsorption, which was more dependent on temperature than the chemisorption process. The structure and surface morphology variations were also investigated, it was interesting that there was a special “fish scale” surface structure after the sorption process, revealing that the melting phenomenon happened during the chemisorption reaction process. By comparing with common sorbent Li₄SiO₄, the material and CO₂ capture costs of Na₄SiO₄ were much lower. These results proved that Na₄SiO₄ was expected to be a suitable high temperature CO₂ capture material as a good supplement to alkali silicate-based ceramics sorbents.     

纳米TiO2-粉煤灰／UV催化臭氧化处理苯胺的研究

采用纳米TiO2-粉煤灰／UV催化臭氧化处理苯胺溶液,考察了反应时间、pH值、催化剂投加量、光照强度、温度、负载次数等因素对苯胺降解率的影响。研究结果表明,苯胺初始质量浓度100mg／L、紫外灯功率10W、pH=7．0、温度（20±2）℃、催化剂涂膜层数4层、光照时问8min时,苯胺去除率达到97％以上。     

Photocatalytic oxidation of ketones in the gas phase over TiO2 thin films: a kinetic study on the influence of water vapor

Photocatalytic oxidation of two ketones having different hydrophilicity, acetone and methyl isobutyl ketone (MIBK), over TiO₂ thin films supported on glass rings was studied under different relative humidity (RH) conditions. Adsorption isotherms of both ketones in the dark under different concentrations of water vapor were also measured and modeled considering a two-site Langmuir model. As expected, an increase in RH resulted in a decrease in the surface concentration of the organic molecules, but the photocatalytic oxidation rates did not show a parallel variation. In the case of acetone, almost total mineralization was achieved, and the kinetic constants obtained from fitting the data to the Langmuir–Hinselwood–Hougen–Watson (LHHW) model, were significantly larger in the presence of water vapor. Photocatalytic elimination of methyl isobutyl ketone (MIBK) is proposed to take place simultaneously by a direct oxidation route and by a sequential mechanism. Acetone is a stable intermediate in this last reaction pathway. Photodegradation of MIBK at different levels of RH was also modeled using LHHW kinetic expressions, and the rates obtained were slightly lower than those obtained for the photooxidation of acetone. However, a carbon balance was not achieved for MIBK, very likely due to the accumulation of partially oxidized products on the surface of the photocatalyst. The influence of water vapor on the photocatalytic oxidation rate of this larger ketone is more complex, and both inhibition and promotion effects can be envisaged. In addition, experimental results show that humidity exerts a significant influence in the mineralization efficiency of MIBK.     

聚硅硫酸钛制备复合光催化剂及降解甲基橙的研究

以无机钛盐、硅酸盐为原料,制备了聚硅硫酸钛絮凝剂,然后利用其水溶液水解产物制备复合光催化剂,考察了钛与硅摩尔比、水解pH值、调节pH值所用碱的种类、煅烧温度和煅烧时间对该复合光催化剂降解甲基橙时活性的影响,并利用扫描电镜（SEM）和X射线衍射（XRD）对其进行了物性测试分析。结果表明：n（Ti）：n（Si）=12：1的聚硅酸硫酸钛,以NH3.H2O调节pH值,在pH值为6时水解,产物在650℃煅烧1.5h后制得的复合光催化剂活性最高,当其投加量为0.5g.L-1时,光催化反应30min后,甲基橙的脱色率可达100%。物性分析表明,聚硅钛制备的复合光催化剂是一种以锐钛矿为主、分散均匀的纳米级球形颗粒。     

负载型TiO2 制备及其对茜素红的降解研究

以钛酸四丁酯和正硅酸乙酯为前驱体、冰醋酸为水解抑制剂，用溶胶-凝胶法制备纳米TiO₂/SiO₂复合物。通过X-射线衍射、红外光谱和比表面积仪等测试手段进行了分析，结果表明，纳米TiO₂ /SiO₂粒子焙烧后主要以锐钛型存在，有Ti—O—Si键的产生，复合粒子的比表面积达到389 m²·g^－1。光催化结果表明，n(Ti)∶n(Si)=3和焙烧温度为700 ℃的TiO₂/SiO₂粒子对茜素红溶液的降解性能最好。利用气质联用仪对降解产物进行了分析。     

Preparation and characterization of a novel activated carbon‐supported N‐doped visible light response photocatalyst (TiO2−xNy/AC)

A photocatalyst, TiO_2?xN_y/AC (activated carbon (AC) supported N‐doped TiO₂), highly active in both the Vis and UV range, was prepared by calcination of the TiO₂ precursor prepared by acid‐catalyzed hydrolysis in an ammonia atmosphere. The powders were characterized by diffuse reflectance spectroscopy, scanning electron microscopy, X‐ray diffraction, N₂ adsorption, Fourier transform infrared spectroscopy and phenol degradation. The doped N in the TiO₂ crystal lattice creates an electron‐occupied intra‐band gap allowing electron‐hole pair generation under Vis irradiation (500–560 nm). The TiO_2?xN_y/AC exhibited high levels of activity and the same activity trends for phenol degradation under both Vis and UV irradiation: TiO_2?xN_y/AC calcined at 500 °C for 4 h exhibited the highest activity. The band‐gap level newly formed by doped N can act as a center for the photo‐generated holes and is beneficial for the UV activity enhancement. The performance of the prepared TiO_2?xN_y/AC photocatalyst revealed its practical potential in the field of solar photocatalytic degradation of aqueous contaminants. Copyright © 2007 Society of Chemical Industry     

TiO2/AC复合材料的制备及其对孔雀石绿的光催化降解

以活性炭为载体,用溶胶-凝胶法制备了不同TiO2负载量的TiO2/AC复合光催化剂,运用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和红外光谱仪(FT-IR)对该催化剂进行表征.探讨了TiO2的负载量、光催化剂质量浓度、溶液的初始质量浓度等因素对孔雀石绿降解效率的影响,并对催化剂进行了回收再生实验.结果表明,TiO2负载量为30％时的复合催化剂为锐钛矿相,对孔雀石绿的降解具有良好的光催化活性,且回收7次重复使用降解效果仍在95％以上.