钒钛SCR脱硝催化剂低温研究进展

由于商用钒钛SCR催化剂存在活性温度偏高等缺点,开发低温高活性的催化剂体系已成为国内外研究的热点。分析了钒钛催化剂低温SCR反应的脱硝机理,探讨了催化剂性能的低温改性方法和努力方向,介绍了催化剂中毒方面的研究进展,为催化剂的完善和低温SCR的深入研究提供参考。     

High-throughput screening of dioxins in sediment and soil using selective pressurized liquid extraction with immunochemical detection

A high-throughput screening method using selective pressurized liquid extraction (SPLE) and enzyme-linked immunosorbent assay (ELISA) for monitoring dioxins in sediment and soil is described. SPLE conditions were developed by extracting sediment or soil together with alumina, 10% AgNO₃ in silica, and sulfuric acid impregnated silica (acid silica) using dichloromethane (DCM) as the solvent at 100 °C and 2000 psi. Post-extraction cleanups were not required for ELISA. Two reference sediments (National Institute of Standards and Technology SRM 1944 and Wellington Laboratories WMS01) were analyzed by the SPLE–ELISA method. The ELISA utilized a polyclonal antibody and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as the calibrant. Recoveries of ELISA-derived TCDD equivalents (EQ) relative to the expected gas chromatography/high resolution mass spectrometry (GC/HRMS) derived dioxin toxic equivalent (TEQ) values were 116 ± 11% for SRM 1944 and 102 ± 13% for WMS01. ELISA TCDD EQs were consistent with the dioxin TEQs as measured by GC/HRMS for 25 soil/sediment samples from seven different contaminated sites. The ELISA had an approximate method detection limit of 10 pg g⁻¹ with a precision of 2.6–29% based on the relative percentage difference (%RPD) for duplicate samples. Estimated sample throughput for the SPLE–ELISA was three times or more than that of the GC/HRMS method employing PLE with a multi-column cleanup.     

Selective recovery of Cu(II) from strongly acidic wastewater by zinc dimethyldithiocarbamate: Affecting factors, efficiency and mechanism

The selective recovery of copper from strongly acidic wastewater containing mixed metal ions remains a significant challenge. In this study, a novel reagent zinc dimethyldithiocarbamate (Zn(DMDC)₂) was developed for the selective removal of Cu(II). The removal efficiency of Cu(II) reached 99.6% after 120 min reaction at 30°C when the mole ratio Zn(DMDC)₂/Cu(II) was 1:1. The mechanism investigation indicates that the Cu(DMDC)₂ products formed as a result of the displacement of Zn(II) from the added Zn(DMDC)₂ by Cu(II) in wastewater, due to the formation of stronger coordination bonds between Cu(II) and the dithiocarbamate groups of Zn(DMDC)₂. Subsequently, we put forward an innovative process of resource recovery for strongly acidic wastewater. Firstly, the selective removal of Cu(II) from actual wastewater using Zn(DMDC)₂, with a removal efficiency of 99.7%. Secondly, high-value CuO was recovered by calcining the Cu(DMDC)₂ at 800°C, with a copper recovery efficiency of 98.3%. Moreover, the residual As(III) and Cd(II) were removed by introducing H₂S gas, and the purified acidic wastewater was used to dissolve ZnO for preparation of valuable ZnSO₄·H₂O. The total economic benefit of resource recovery is estimated to be 11.54 $/m³. Accordingly, this study provides a new route for the resource recovery of the treatment of copper-containing acidic wastewater.     

不同海岸梯度上短枝木麻黄小枝金属元素含量及其再吸收率动态

对福建东山赤山林场不同海岸梯度上短枝木麻黄小枝中的钾(K)、钙(Ca)、镁(Mg)、钠(Na)、铁(Fe)、锰(Mn)和锌(Zn)元素含量及其再吸收率动态进行了研究.结果表明,海岸梯度对短枝木麻黄小枝中各元素含量及其再吸收率均具有显著影响.在各海岸梯度上,K再吸收率为正值,且基干林带的再吸收率显著低于其它样地,Fe和Zn为负值,Ca、Mg和Na再吸收率在防护林带前沿为负值,而在后沿林为正值,Mn则相反.这表明,基干林带严重的环境胁迫显著降低了短枝木麻黄小枝的养分再吸收率.短枝木麻黄成熟小枝中的K、Mg含量与其再吸收率存在显著正相关,而Na和Fe与其再吸收率存在显著负相关,其它元素与其再吸收率之间没有显著相关性.除K外,各元素在衰老小枝中的含量与相应元素再吸收率之间均存在显著负相关,表明元素再吸收程度越高,其再吸收率就越高.Ca、Mg、Na和Fe再吸收率之间具有显著的正相关关系(P<0.01),Zn除与Mn再吸收率呈显著正相关外,与其它元素均表现为负相关,Mn则与其它元素再吸收率之间没有显著相关性.因而短枝木麻黄小枝中不同类型的养分状况对其再吸收率具有不同的影响.表5参42     

Investigation on the urea deposit formation and thermal decomposition characteristics in the SCR aftertreatment system of a diesel engine

Selective catalytic reduction is the most efficient and reliable equipment for NOx control in current diesel engines. However, the issue of urea crystallization becomes increasingly serious with the implement of the new emissions standards. In this paper, urea deposit samples collected from engine test bed and tube furnace were characterized by thermogravimetric analysis and Fourier transform-infrared analysis to aid the comprehension of urea deposit formation. Moreover, thermogravimetric tests were conducted to disclose the effects of catalyst on the thermal decomposition processes of urea deposit. The results indicated that less temperature resistant species are formed in the engine test bed than in the tube furnace at conditions with the same temperatures. The main compositions in the World Harmonized Transient Cycle (WHTC) urea deposits are urea, cyanuric acid (CYA) and ammelide, implying that accelerating the decomposition of these species could prevent the accumulation of urea deposit. CuWTi, Cuβ and CuZSM catalysts could lead to increased yield of CYA during pure urea thermolysis. Cuβ, CuWTi and VWTi catalysts tend to promote the thermolysis of CYA while VWTi has the most significant catalytic effects on the thermal decomposition of ammelide and ammeline.     

Investigating differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans in soil and soil components using selective supercritical fluid extraction

Supercritical fluid extraction (SFE) with pure carbon dioxide was performed at increasingly strong conditions to investigate differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in two impacted soils, in their sieved size fractions, and in small (a few mg) samples of industry-related waste products separated from impacted soil. The binding strengths of PCDD/Fs were shown to be different in the two soils, and in their different soil particle size fractions. As might be expected based on surface area considerations, one soil showed the strongest binding in the smallest (<5 μm) sieved fraction. However, the other soil showed the strongest binding in the larger sized fractions, possibly indicating that process-related particles could be controlling PCDD/F binding. Selective SFE of various types of particles including black carbon and charcoal (separated from soil), and from a suspected process anode residue did show different PCDD/F binding behavior ranging from quite weak binding (charcoal) to very strong binding (anode particles). Shifts to the stronger SFE fractions in the soils after activated carbon treatment agreed well with the decreases previously found in the uptake of PCDD/Fs by earthworms, as well as decreases in their freely-dissolved aqueous concentrations in soil/water slurries. These results show that, as previously demonstrated for PAHs and PCBs, selective SFE can be a useful tool to investigate differences in PCDD/F binding behaviors in impacted soils and sediments and their component parts, as well as a rapid tool for estimating the effectiveness of activated carbon treatments on decreasing the bioavailability of PCDD/Fs in soils and sediments.     

选择性非催化还原烟气脱硝技术在流化床锅炉上应用的探讨

对选择性非催化还原（SNCR）烟气脱硝技术与选择性催化还原（SCR）烟气脱硝技术在流化床锅炉上应用的适应性进行了对比分析。分析结果显示,相对于SCR技术,SNCR技术更适于流化床锅炉,指出了SNCR技术在流化床锅炉上应用存在的问题,N2O难以去除。     

SCR反应器短直进口段混氨技术研究

摘要：OI^2-SCR技术根据流场适应型设计理论设计了喷氨装置；以“主动利用不均”代替传统的“单—尺度的平均化”理念进行喷氨操作，在SCR反应器短直进口段内实现了良好的NH3／NOx混合效果，进而解决了改造工程中常见的空间制约问题。同时，充分发挥了有限体积的催化剂的效能，在较低氨逃逸率的前提下，实现了较高的脱硝效率。     

车用柴油机选择性催化还原技术研究进展

选择性催化还原技术(SCR)是目前唯一可以同时改善柴油机排放和燃油经济性的氮氧化物(NOX)净化技术,而以NH3作为还原剂的SCR技术(NH3-SCR)又是目前最成熟,最具推广前景的SCR技术。文章详细阐述了用于车用柴油机的NH3-SCR技术的反应机理,介绍了温度对SCR反应的影响;列举了典型SCR系统的主要部件并介绍了各部分的功能,以及法规中对车用尿素水溶液(AdBlue)主要指标的规定;总结了目前应用较多的开环、闭环两种控制策略的工作流程及特点,并且分析了各自的优缺点;在柴油机后处理系统集成的角度对SCR与颗粒捕集器(DPF)的两种整合方案进行了分析,对比了两种方案的优缺点;最后分析了SCR技术目前存在的几个问题。     

Transformation and removal of ammonium sulfate aerosols and ammonia slip from selective catalytic reduction in wet flue gas desulfurization system

Selective catalytic reduction (SCR) denitration may increase the emission of NH₄⁺ and NH₃. The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurization (WFGD) process, as well as the effect of desulfurization parameters, were investigated in an experimental system equipped with a simulated SCR flue gas generation system and a limestone-based WFGD system. The results indicate that the ammonium sulfate aerosols and ammonia slip in the flue gas from SCR can be partly removed by slurry scrubbing, while the entrainment and evaporation of desulfurization slurry with accumulated NH₄⁺ will generate new ammonium-containing particles and gaseous ammonia. The ammonium-containing particles formed by desulfurization are not only derived from the entrainment of slurry droplets, but also from the re-condensation of gaseous ammonia generated by slurry evaporation. Therefore, even if the concentration of NH₄⁺ in the desulfurization slurry is quite low, a high level of NH₄⁺ was still contained in the fine particles at the outlet of the scrubber. When the accumulated NH₄⁺ in the desulfurization slurry was high enough, the WFGD system promoted the conversion of NH₃ to NH₄⁺ and increased the additional emission of primary NH₄⁺ aerosols. With the decline of the liquid/gas ratio and flue gas temperature, the removal efficiency of ammonia sulfate aerosols increased, and the NH₄⁺ emitted from entrainment and evaporation of the desulfurization slurry decreased. In addition, the volatile ammonia concentration after the WFGD system was reduced with the decrease of the NH₄⁺ concentration and pH values of the slurry.