煤液化催化剂生产废水处理工艺设计和运行

采用斜板沉降-流砂过滤-蒸发器-结晶器工艺来处理煤液化催化剂生产废水。本文对该项目的催化剂生产废水处理工艺路线进行了详细介绍,并对实际生产期间的运行数据做了总结分析。通过运行数据表明:该工艺线路技术可靠,产品水的各项指标均能稳定达到再生水用作工业用水水源的水质标准,满足了生产回用的目的,且能够实现长期连续稳定运行。     

催化剂Ru/ZrO2-CeO2催化湿式氧化苯酚

催化剂Ru/ZrO₂-CeO₂催化湿式氧化苯酚的过程表明,Ru/ZrO₂-CeO₂可以显著提高COD和苯酚去除效果,当反应温度为170℃,压力为3 MPa,反应120 min后,COD和苯酚的去除率分别达到了99％和100％.试验还考察了不同反应条件对苯酚溶液COD去除的影响,并获得了最优的反应条件：温度为170℃,压力为3 MPa,催化剂的投加量为5　g/Ｌ,搅拌速度为500 r/min.通过对中间产物的分析,本研究提出了催化湿式氧化苯酚的简单路径图,认为苯酚首先被氧化成小分子有机酸,接着小分子有机酸被氧化成二氧化碳和水.前一个过程是快速反应,后一个过程中的乙酸氧化是慢速过程,需要在高温下才能完成.乙酸的氧化主要是自由基攻击α碳上的C—H键,先生成甲酸,并最终生成二氧化碳和水.     

Pd/C气体扩散电极用于电生成H2O2降解苯酚的研究

采用自制的Pd/C气体扩散阴极和Ti/IrO2/RuO2阳极,在无隔膜电解槽中对苯酚模拟废水降解效果及机制进行了研究,采用电子自旋共振法(ESR)对电解体系中产生的羟自由基(·OH)进行了检测.结果表明,在Pd/C气体扩散体系中掺杂Pd催化剂可以促进H2 O2的生成(H2 O2的稳定浓度是7.5 mg/L),有利于·OH的产生.经电化学氧化处理120 min后,苯酚和COD的去除率分别达到97.2%和50%,表明在电催化氧化过程中苯酚被氧化生成了大量低分子量中间产物.废水的BOD5/COD值达到0.73是处理前的9.1倍,苯酚废水的可生化降解性通过电化学氧化处理后显著提高.在该电化学体系中苯酚的降解是在阳极直接、间接氧化及阴极产生的H2 O2、·OH的氧化共同作用下完成的.通过对紫外扫描光谱图的分析推断出苯酚在电解过程中有醌类物质生成;由GC-MS检测到了邻苯二酚、对苯二酚、苯醌等芳香族化合物和己二酸、顺丁烯二酸、反丁烯二酸、丁二酸、丙二酸、乙二酸等短链羧酸,据此提出了苯酚降解的可能历程.     

实车三效催化剂表面成分分析

对主要在北京行驶的总里程在34×104～59×104km的6辆轻型出租车用三效催化剂,利用X射线荧光光谱仪(XRF)分析了其表面元素的种类、含量,以及污染物元素含量与行驶里程的关系.结果表明,在催化剂表面检测到的元素种类近30种,含量较高的元素种类基本相同.前后级催化剂上检测到的共同污染物元素有P、Ca、Zn和Mn等,主要来自于机油和汽油,34×104km行驶里程后,P在催化剂的累积速度已非常缓慢,Ca、Zn和Mn在催化剂表面的沉积经过56×104km后仍有增加的趋势.在后级催化剂上还检测到了明显的S含量,说明S更容易在后级催化剂上沉积.经过40×104km行驶里程后,S在催化剂表面的沉积量基本达到平衡状态.累积规律说明经过40×104km行驶里程后,容易使催化剂中毒的P和S对催化剂活性影响已较小,而Ca、Zn和Mn的持续累积,将会继续降低催化剂的活性.     

Effect of platinum on the photocatalytic degradation of chlorinated organic compound

TiO2 nanoparticles, doped with di erent Pt contents, were prepared by a modified photodeposition method using Degussa P-25 TiO2, H2PtCl6 6H2O and methanol as the solvents. The physicochemical properties of Pt/TiO2 were investigated by the nitrogen adsorption and desorption isotherm measurement technique, X-ray di raction analysis and photoluminescence spectra, respectively. Reaction rates from photocatalytic removal of dichloromethane over Degussa P-25 TiO2 and Pt/TiO2 were evaluated. The average diameter and BET surface area of the TiO2 catalyst particles were 300 nm and 50 m2/g, respectively. The degradation e ciency was 99.0%, 82.7%, 55.2%, and 57.9% with TiO2 at inlet concentrations of 50, 100, 200, and 300 ppm, respectively. And the degradation e ciency was 99.3%, 79.7%, 76.5%, and 73.4% with a 0.005 wt.% Pt/TiO2 at inlet concentrations of 50, 100, 200, and 300 ppm, respectively. In addition, we found that the photoluminescence emission peak intensities decreased with increases in the doping amount of Pt, which indicates that the irradiative recombination was weakened. Furthermore, the results showed that the UV/0.005 wt.% Pt/TiO2 process was capable of e ciently decomposing gaseous DCM in air.     

Effect of manufacturing methods of AgCl/Al2O3 catalyst on selective catalytic reduction of NOx

The AgCl/Al2O3 catalyst has potential for use in the selective catalytic reduction (SCR) of NOx. A compound hydrocarbon, following oxygenation is used as a type of reducing agent. In this experiment, the AgCl/Al2O3 catalyst was produced by four different methods, and the differences among their reduction catalysis of NOx were compared. Ethanol was used as a type of reducing agent. X-ray diffraction analysis was performed to study the crystalline structure and scanning electron microscope and transmission electron microscope (TEM) were applied to determine the microindentation. The results indicated that, in the range of 350–400°C, there was no significant difference on the NOx reduction rate; however, there was dispersion at high and low temperature ranges. The size of the AgCl particles was about 20–100 nm.     

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Experimental study on filtration and continuous regeneration of a particulate filter system for heavy-duty diesel engines

This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（CDPF）. Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number（SPN） was close to100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.     

Unregulated emissions from diesel engine with particulate filter using Fe-based fuel borne catalyst

The alteration and formation of toxic compounds and potential changes in the toxicity of emissions when using after-treatment technologies have gained wide attention. Volatile organic compound（VOC）, carbonyl compound and particle-phase polycyclic aromatic hydrocarbon（PAH） emissions were tested at European Steady State Cycle（ESC） to study unregulated emissions from a diesel engine with a fuel-borne catalyst and diesel particulate filter（FBC–DPF）. An Fe-based fuel-borne catalyst was used for this study. According to the results, brake specific emissions of total VOCs without and with DPF were 4.7 and4.9 mg/kWh, respectively, showing a 4.3% increase. Benzene and n-undecane emissions increased and toluene emission decreased, while other individual VOC emissions basically had no change. When retrofitted with the FBC–DPF, total carbonyl compound emission decreased 15.7%, from 25.8 to 21.8 mg/kWh. The two highest carbonyls, formaldehyde and acetaldehyde, were reduced from 20.0 and 3.7 to 16.5 and 3.3 mg/kWh respectively. The specific reactivity（SR） with DPF was reduced from 6.68 to 6.64 mg/kWh. Total particle-phase PAH emissions decreased 66.4% with DPF compared to that without DPF. However, the Benzo[a]pyrene equivalent（BaPeq） with DPF had increased from 0.016 to 0.030 mg/kWh.Fluoranthene and Pyrene had the greatest decrease, 91.1% and 88.4% respectively. The increase of two- and three-ring PAHs with DPF indicates that the fuel-borne catalyst caused some gas-phase PAHs to adsorb on particles. The results of this study expand the knowledge of the effects of using a particulate filter and a Fe-based fuel-borne catalyst on diesel engine unregulated emissions.