催化湿式氧化技术处理高浓度有机废水催化剂研究

以CuO为主话性组分,ZrO2为第二话性组分,并掺入电子助剂La2O3,研制出适用于催化湿式氧化处理高浓度乙酰基丁二酸二甲酯(DMAS)生产废水的复合催化剂.在固定床连续鼓泡式反应器装置上对高浓度DMAS生产废水进行处理,考察了各活性组分用量、焙烧温度、焙烧时间等条件对催化剂活性的影响,确定最佳制备条件为:采用ZSM-5为载体,Cu、Zr、La质量分数分别为4%、3%、2%,焙烧温度为550℃,焙烧时间为10 h.结果表明,优化制备的CuO-ZrO2-La2O3/ZSM-5催化剂,用于处理高浓度DMAS生产废水时具有较好的催化活性,在反应温度为240℃.反应压力为3.5 MPa,空速为2.0 h-1,气/水(体积比)=250:1,进水PH=7条件下,COD去除率达98.7%,而在相同条件下未加催化剂时,COD去除率只有35.8%.     

Fe_2O_3/TiO_2/γ-Al_2O_3催化剂同时脱硫脱硝性能

以溶胶凝胶法制备的15%TiO_2/γ-Al_2O_3为载体,通过浸渍法制备12%Fe_2O_3/15%TiO_2/γ-A_l2O_3催化剂,采用XRD和TPR对催化剂结构和性质进行表征,并考察不同焙烧温度、焙烧时间和载体对催化剂脱硫脱硝性能的影响。结果显示,最佳焙烧条件为500℃下焙烧3 h,12%Fe_2O_3/15%TiO_2/γ-Al_2O_3催化剂达到的最高脱硝脱硫率分别为98.2%和95.4%。     

Fe掺杂Mn-Ce/AC催化剂的制备及其低温脱硝

以活性炭为载体,采用浸渍法制备了一系列Fe掺杂Mn-Ce/AC催化剂,研究了Fe的添加量、焙烧温度对催化剂低温脱硝活性的影响;采用了XRD、SEM和N2吸附-脱附技术对催化剂进行了表征。结果表明,Fe的添加能有效提高Mn-Ce/AC的低温脱硝活性,当Fe的添加量为Fe/Mn(摩尔比)为0.1时,催化剂比表面积大,活性组分的分散程度较高,催化剂低温脱硝性能最优,添加量大于0.1时,更多的Fe沉积在载体表面,催化剂活性降低。焙烧温度影响负载氧化物的价态和晶体的分散度,在400℃温度下焙烧时,催化剂低温脱硝性能最佳,此时催化剂孔隙结构较优,活性组分的分散程度也较高。     

Y_2O_3/AC催化剂的烟气同时脱硫脱硝性能

采用等体积浸渍法制备了一系列不同负载量的x%Y_2O_3/AC(x=2、4、6、8和10)同时脱硫脱硝催化剂,以CO为还原气,考察该催化剂同时脱硫脱硝催化活性。采用X射线衍射仪(XRD)、H2-程序升温还原(H2-TPR)、比表面积(BET)对催化剂进行了表征。在不同负载量的催化剂中,6%Y_2O_3/AC表现出较好脱硫脱硝效果,SO_2和NO的T90%分别约为365℃和367℃。经HNO_3预处理过的活性炭载体制备的催化剂脱硝效果明显改善,催化剂预硫化可以显著提高脱硫脱硝活性,在550℃硫化的催化剂效果最好,NO和SO_2的T90%分别约为368和362℃,在380℃时脱硫脱硝率均可达到95%以上。     

金属负载型催化剂对烟气脱硫性能的影响

介绍了国内外烟气脱硫催化剂的研究现状,研究了金属氧化物负载型催化剂对烟气脱硫性能的影响。以活性炭(AC)为载体,选用8种不同的金属硝酸盐作为浸渍液,采用等体积浸渍法制备金属氧化物负载型催化剂。以脱硫效果较好的Fe2O3/AC为例,研究了不同焙烧温度、金属负载量以及焙烧时间对催化剂脱硫性能的影响。实验结果表明,Fe2O3/AC催化剂脱硫率随着金属负载量的增加呈递增趋势,最优金属负载量为10.0%(质量分数);脱硫率随着焙烧温度的增加显著提高,最优焙烧温度为350℃;脱硫率随着焙烧时间的增加而提高,最优焙烧时间为3.0h。     

SiO_2掺杂对V_2O_5-WO_3/TiO_2脱硝催化性能的影响

采用溶胶凝胶法制备TiO_2-SiO_2载体,浸渍法制备出V_2O_5-WO_3/TiO_2-SiO_2催化剂,利用BET、FESEM、XRD、TGA和激光拉曼对催化剂进行表征,研究催化剂的理化性质。以NH_3为还原剂,考察反应温度、SiO_2掺杂量、焙烧温度、空速和使用时间对SCR催化还原NO的性能影响。结果表明,V_2O_5-WO_3/TiO_2-SiO_2催化剂最佳反应温度在250~350℃。SiO_2掺杂能提高活性组分V_2O_5和WO_3在载体表面的分散性,制备出的催化剂具有更大的比表面积和更宽的温度区间,提高脱硝活性及稳定性。SiO_2掺杂量对催化剂性能影响较大,制备的催化剂中,TiO_2/SiO_2=2显示了最大催化活性,脱硝率均在60%以上,TiO_2/SiO_2=0.5制备的催化剂稳定性最差。焙烧温度对催化剂性能也有影响,焙烧温度在500和600℃时,最低脱硝率为58%和23%,最佳焙烧温度为400℃,脱硝率均在80%以上,具有优越的脱硝性能。实验结果还表明,空速对V_2O_5-WO_3/TiO_2-SiO_2催化剂的影响不大,在20 000 h~(-1)空速下催化剂的使用时间对脱硝率的影响也不大,48 h内能保持在99%左右,非常稳定。     

钒硅催化脱硫脱硝的研究

考察了经10% H2-90% Ar(体积分数)还原的钒硅催化剂在固定床石英玻璃反应器中的脱硫脱硝活性,研究了反应温度、SO2/NO摩尔比及O2浓度对SO2和NO脱除率的影响.结果表明,还原后的钒硅催化剂的平均NO脱除率提高了15%左右;反应温度对脱硫脱硝影响较大,当温度为400℃以上时SO2和NO脱除率基本保持稳定;SO2/NO摩尔比为2和5时,钒硅催化剂的NO脱除率较高;模拟烟气中有O2条件下的脱硫脱硝活性明显高于无O2条件,O2体积分数为6.00%时SO2和NO脱除率达到最大.     

水热老化条件对Cu/ZSM-5催化剂NH3-SCR反应的影响

针对Cu/ZSM-5高温水热失活的问题,通过浸渍法合成了Cu/ZSM-5催化剂,并对该催化剂进行了不同温度和不同H_2O(g)含量的水热老化。采用比表面积分析、SEM观察、X射线衍射分析、H_2-程序升温还原、X射线光电子能谱分析对Cu/ZSM-5催化剂的理化性能进行了表征。分别研究了不同水热老化条件下Cu/ZSM-5催化剂的NH_3-SCR性能和水热失活机理。结果表明,经水热处理后,各Cu/ZSM-5催化剂的NH_3-SCR性能均有所降低。随着老化温度的提高,催化剂的分子筛载体出现结构坍塌,比表面积减小,孔容积增大,但仍保持MFI结构,老化温度的提高同样使催化剂活性Cu~(2+)减少并一部分转化为CuO微晶,而H_2O(g)含量的变化对催化剂的物理化学结构的影响较小。在高温水热老化过程中,温度对催化性能劣化的影响大于水蒸汽含量,是催化剂失活的主要原因。     

负载型磷酸氧钒低温脱硝催化剂的制备及其抗硫抗水性能

针对目前低温脱硝催化剂抗硫抗水性较差的不足,以TiO_2为载体负载活性组分V_2O_5,利用磷酸调控表面酸性,制备了磷酸氧钒催化剂VPO/TiO_2,并实验研究了SO_2和水蒸气对其脱硝活性的影响。结果表明:控制P与V的摩尔比为1/5,活性组分(VPO)负载量为10%,焙烧温度为400℃时,催化剂脱硝性能最好,180～400℃温度范围内脱硝率高于98%;反应温度为200℃,烟气中SO_2体积分数为200×10~(-6)～800×10~(-6)和水蒸气体积分数为4%时,催化剂的活性无明显下降。添加磷酸能够促使催化剂表面生成VOPO_4、(VO)_2P_2O_7及V~(4+)/V~(5+)氧化还原电对,提高了催化剂的低温脱硝活性。磷酸可增强催化剂的表面酸性,减少了SO_2的表面吸附及其与活性组分的反应。另外,催化剂表面以介孔为主,可提高未被水分子占据的活性位点量,FT-IR图谱显示抗硫抗水测试后的VPO/TiO_2表面未发现有硫酸根生成,VPO/TiO_2表现出较强的抗SO_2和水蒸气毒化的性能。负载型磷酸氧钒催化剂具有较高的脱硝活性和较强的抗硫抗水性能。     

复合型异质结催化剂AgI-BiOI/ZSM-5可见光催化氧化NO

采用液相浸渍沉淀法制备AgI-BiOI/ZSM-5异质结催化剂,通过X-射线衍射(XRD)、紫外-可见光漫反射光谱(DRS)、扫描电镜(SEM)和交流阻抗(EIS)等表征技术对样品进行表征分析,研究AgI-BiOI/ZSM-5催化剂在可见光条件(λ＞ 420 nm)下催化氧化NO的可行性及异质结催化剂的稳定性.研究结果表明,所制备的AgI-BiOI/ZSM-5催化剂在可见光下催化氧化NO的效率达到90％,表现出良好的催化活性,而且AgI-BiOI/ZSM-5在反复使用5次后其催化活性基本保持不变.EIS测试结果表明,AgI-BiOI/ZSM-5异质结的形成有利于光生电子和空穴的分离,从而提高了AgI-BiOI/ZSM-5的催化活性和稳定性.     

次氯酸钠发生器的研制

介绍了电解法生产次氯酸钠的原理 ,并在原有生产工艺的基础上进行了重新设计和对设备的重新选择、改造 ,得出了各个工艺参数的最佳值 ,生产出高品质的次氯酸钠     

Estimation of uncertainty of sampling for analysis of pesticide residues

Abstract

A computer model was used to take random samples from primary sample populations obtained from field trials to simulate the uncertainty of sampling for residue analysis of plant commodities and soil. The results indicate about 40%, 30% and 20% relative uncertainty when random samples of size 5, 10 and 25 are taken respectively, from a single lot. Therefore the sample size should be the same for establishing and enforcing legal limits.     

不同泥源对厌氧氨氧化反应器启动的影响

采用2套上流式生物膜反应器,分别接种少量厌氧氨氧化污泥和大量硝化污泥,考察其对厌氧氨氧化反应器启动的影响。污泥接种入反应器后,测得接种厌氧氨氧化污泥的反应器(R1)内MLSS为0.22 g/L,另一个反应器(R2)MLSS为2.7 g/L。与直接接种厌氧氨氧化污泥相比,R1经过72 d的运行才显现出厌氧氨氧化特性。经过114 d的培养,前者氮去除速率由0.23 kg/(m3.d)提升到5.29 kg/(m3.d),总氮去除率大于89%;R2的氮去除速率由0.01 kg/(m3.d)提升到1.1 kg/(m3.d),总氮去除率大于84.6%。说明普通污泥启动需要一个较长的筛选过程,直接接种少量的厌氧氨氧化污泥比接种普通的污泥能够更快启动厌氧氨氧化反应器。     

Evaluation of the presence of drugs of abuse in tap waters

A total of seventy samples of drinking water were tested for non-controlled and illicit drugs. Of these, 43 were from Spanish cities, 15 from seven other European countries, three from Japan and nine from seven different Latin American countries. The most frequently detected compounds were caffeine, nicotine, cotinine, cocaine and its metabolite benzoylecgonine, methadone and its metabolite EDDP. The mean concentrations of non-controlled drugs were: for caffeine 50 and 19 ng L⁻¹, in Spanish and worldwide drinking water respectively and for nicotine 13 and 19 ng L⁻¹. Illicit drugs were sparsely present and usually at ultratrace level (<1 ng L⁻¹). For example, cocaine has mean values of 0.4 (Spain) and 0.3 ng L⁻¹ (worldwide), whereas for benzoylecgonine, these mean values were 0.4 and 1.8 ng L⁻¹, respectively. Higher concentrations of benzoylecgonine were found in Latin American samples (up to 15 ng L⁻¹). No opiates were identified in any sample but the presence of methadone and EDDP was frequently detected. Total mean values for EDDP were 0.4 ng L⁻¹ (Spain) and 0.3 ng L⁻¹ (worldwide). Very few samples tested positive for amphetamines, in line with the reactivity of chlorine with these compounds. No cannabinoids, LSD, ketamine, fentanyl and PCP were detected.     

Mechanisms of biodegradation of dibenzoate plasticizers

Biodegradation mechanisms were elucidated for three dibenzoate plasticizers: diethylene glycol dibenzoate (D(EG)DB), dipropylene glycol dibenzoate (D(PG)DB), both of which are commercially available, and 1,6-hexanediol dibenzoate, a potential green plasticizer. Degradation studies were done using Rhodococcus rhodochrous in the presence of pure alkanes as a co-substrate. As expected, the first degradation step for all of these systems was the hydrolysis of one ester bond with the release of benzoic acid and a monoester. Subsequent biodegradation of the monobenzoates of diethylene glycol (D(EG)MB) and dipropylene glycol (D(PG)MB) was very slow, leading to significant accumulation of these monoesters. In contrast, 1,6-hexanediol monobenzoate was quickly degraded and characterization of the metabolites indicated that the biodegradation proceeded by way of the oxidation of the alcohol group to generate 6-(benzoyloxy) hexanoic acid followed by β-oxidation steps. This pathway was blocked for D(EG)MB and D(PG)MB by the presence of an ether function.The use of a pure hydrocarbon as a co-substrate resulted in the formation of another class of metabolites; namely the esters of the alcohols formed by the oxidation of the alkanes and the benzoic acid released by hydrolysis of the original diesters. These metabolites were biodegraded without the accumulation of any intermediates.     

混凝试验搅拌器的研制

影响混凝效果的因素众多,混凝沉淀烧杯试验是进行水的混合、絮凝、沉淀工艺研究、设计和生产指导的最有效方法之一,阐述了智能型混凝试验搅拌器的设计原理和技术性能.     

生物质快速热裂解主要参数对生物油产率的影响

以松木木屑为原料,在自制的小型流化床上,开展了生物质热裂解温度、生物质粒径和进料速率对生物油产率的影响实验研究.结果表明,在热裂解温度分别为450、475、500、525和550℃条件下,当热裂解温度为500℃时,生物油产率最高,平均产率达到53.33%（质量百分比）.反应温度越高,炭产量越低,不可冷凝气体产量越高,气体发热值越高;粒径＜1 mm的生物质其粒径对生物油产率影响不大;生物质进料速率增加时,生物油产率增加.本研究为生物能的利用提供了新的途径.     

An application of the theory of kinematics of mixing to the study of tropospheric dispersion

The most common technique used for numerical simulations of tracer mixing is that of the numerical solution of the advection–diffusion equation with the unresolved fluxes parameterized using the similarity theory. Despite correct predictions of the overall directions of transport, models based on a numerical solution of the advection–diffusion equation lack sufficient accuracy to correctly reproduce the coupling of mixing with small scale processes which are sensitive to the microstructure of the tracer distribution. The objective of this paper is to revisit the basic formalism employed in numerical models used to investigate atmospheric tracers. The main mathematical method proposed here is the theory of kinematics of mixing which could be applied effectively for simulations of atmospheric transport processes. At the beginning of the paper, we introduce simple mathematical transformations in order to demonstrate how complex topological structures are created by mixing processes. These idealistic flow systems are essential to explain transport properties of much more complex three-dimensional geophysical flows. An example of the application of the kinematics of mixing to the analysis of tracer transport on a planetary scale is presented in the following sections. The complex filamentary structures simulated in the numerical experiment are evaluated using some commonly applied statistical measures in order to compare the results with the data published in the literature. The results of the experiment are also analysed with the help of simple conceptual models of fluid filaments. The microstructure of the tracer distribution introduced in the paper is essential to increase our understanding of atmospheric transport and to develop more realistic parameterizations of small-scale mixing. The presented results could also be used to improve calculations of the coupling between microphysical processes and tracer mixing.     

造纸废水混凝处理中SFT助凝替代性研究

中小造纸厂废水处理常用PAC作混凝剂 ,PAM作助凝剂。由于PAM成本很高 ,影响了处理设备的投运率。用超细滑石粉 (SFT)替代PAM助凝 ,与混凝剂PAC配合 ,其混凝处理效果基本相当 ,但是处理成本降低 0 .10元 /m3 。由于SFT属环境无害材料 ,不会给排泥带来二次污染     

产油微藻培养与回收的关键技术研究进展

寻找廉价而高效的替代原料是实现生物柴油产业化的关键所在.微藻以含油量高、生长周期短、环境适应能力强、生物产量高等优点,有望成为一种极具潜力的生物柴油生产原料.然而,目前尚存在微藻培养低效成本高和微藻回收效率低两大难题.综述了微藻培养与回收过程中的关键技术,并对存在的两大难题及其改进技术进行了详细的探讨.最后,总结并展望了微藻培养、回收技术未来的发展趋势.