催化超临界水氧化偏二甲肼

采用CuO/γ-Al_2O_3和MnO_2/γ-Al_2O_3为催化剂,H_2O_2为氧化剂,在固定床反应器中进行催化超临界水氧化偏二甲肼实验.结果表明,CuO和MnO_2对偏二甲肼的氧化降解具有显著的促进作用.偏二甲肼的去除率随反应温度和压力的升高、停留时间的延长而提高.在24—26MPa、400—450℃条件下,数秒钟内COD去除率可达到99%以上.显示出催化超临界水氧化技术的高效性.催化剂CuO/γ-Al_2O_3的催化效果优于MnO_2/γ-Al_2O_3.进一步研究表明,偏二甲肼催化超临界水氧化为·OH引发的自由基反应,最终氧化产物为CO_2,N_2和H_2O.     

A comparative investigation of NdSrCu_(1-x) Co_x O_(4-δ) and Sm_(1.8) Ce_(0.2) Cu_(1-x) Co_x O_(4-δ) (x:0–0.4) for NO decomposition

A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ (x: 0–0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 NdSrCu 0.8 Co 0.2 O 3.736 NdSrCu 0.6 Co 0.4 O 3.789 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3+ /Cu 2+ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.     

V2O5/CeO2催化剂用于低温NH3-SCR的性能研究

采用浸渍法制备了系列V2O5/CeO2催化剂,用于低温NH3选择性催化还原(NH3-SCR)NO.同时,考察了催化剂中V2O5负载量和煅烧温度对催化活性的影响,并运用SEM,BET和XRD物理化学技术对催化剂进行了表征.结果表明,V2O5/CeO2催化剂对模拟烟气中的NO转化呈现出较高的活性,但是V2O5负载量和催化剂的催化活性并不呈线性递增的关系.当V2O5负载量超过10%时,催化剂的催化活性开始下降.随着煅烧温度的升高,由于钒酸铈的生成,催化剂的催化活性下降.400℃为最佳煅烧温度.     

Regeneration of commercial selective catalyst reduction catalysts deactivated by Pb and other inorganic elements

The regeneration of commercial SCR(Selective Catalyst Reduction) catalysts deactivated by Pb and other elements was studied.The deactivated catalyst samples were prepared by chemical impregnation with mixed solution containing K_2SO_4,Na_2SO_4,CaSO_4,Pb(NO_3)_2and NH_4H_2PO_4.A novel method combining Ethylenediaminetetraacetic acid disodium salt(EDTA-2Na) and H_2SO_4solution(viz.catalysts treated by dilute EDTA-2Na and H_2SO_4 solution in sequence) was used to recover the activity of deactivated samples,and the effect was compared with single H_2SO_4,oxalic acid,acetic acid,EDTA or HNO_3 solutions.The surface structure,acidity and reducibility of samples were characterized by N_2adsorption–desorption,inductively coupled plasma optical emission spectrometer(ICP-OES),scanning electron microscopy(SEM),X-ray diffraction(XRD),X-ray fluorescence(XRF),H-2-temperature programmed section(H_2-TPR),NH3-temperature programmed desorption(NH3-TPD) and in situ DRIFTS.Impurities caused a decrease of specific surface area and surface reducibility,as well as Br?nsted acid sites,and therefore led to severe deactivation of the SCR catalyst.The use of an acid solution alone possibly eliminated the impurities on the deactivated catalyst to some extent,and also increased the specific surface area and Br?nsted acid sites and promoted the surface reducibility,thus recovered the activity partially.The combination of EDTA-2Na and H_2SO_4 could remove most of the impurities and improve the activity significantly.The removal of Pb should be an important factor for regeneration.Due to a high removal rate for Pb and other impurities,the combination of EDTA-2Na and H_2SO_4 solutions provided the best efficiency.     

废弃SCR脱硝催化剂无害化处理的研究进展

鉴于废弃SCR脱硝催化剂中含有多种痕量重金属以及可回收利用物质,从处理工艺包括重金属的去除、有价金属的回收等方面综述了废弃SCR脱硝催化剂无害化处理的现状,总结了现阶段的研究重点以及工业化应用的瓶颈。目前主要关注废弃SCR脱硝催化剂中钒、钨、钛的回收工艺,但工业化成本昂贵,难以实现效益均衡化。根据现行废弃SCR脱硝催化剂的处置规范,烟气飞灰中重金属的存在是废催化剂处置工艺复杂化的关键。研究重金属的去除以及有价金属的回收,方能最终实现针对废弃SCR脱硝催化剂无害化处理工艺的综合研发。     

单斜相纳米氧化锆基低温SCR催化剂脱硝机制研究

以纳米m-ZrO2为载体,用浸渍法制备出MnOx-CeO2/m-ZrO2催化剂,考察反应温度、活性组分负载量对催化剂NH3-SCR脱硝活性影响,探讨催化剂表面织构特征,分析催化剂脱硝活性机制.结果表明,在低温脱硝温度范围,提高反应温度、增加活性组分负载量,有利于催化剂脱硝效率的增加.110℃时,2.5%MnOx-CeO2/m-ZrO2脱硝效率为55.5%,15%MnOxCeO2/m-ZrO2脱硝效率达93.5%.XRD、BET、XPS、H2-TPR表征结果表明,催化剂表面具有良好的氧化还原能力,表面织构对脱硝反应有利.NH3-TPD测试显示,MnOx-CeO2/m-ZrO2催化剂的脱硝反应机制为:NH3吸附在催化剂表面的Lewis酸性位和Brnsted酸性位上,通过反应生成相应中间产物NH2NO或NH4NO2,中间产物进一步分解最终转变为N2和H2O;催化剂总脱硝反应效率中,在Lewis酸性位上的脱硝反应占比较大.     

CuO对贵金属/CeO2/Al2O3催化剂的作用

制备含少量贵金属Ｐｔ、Ｐｄ的不同Ｃｕ和Ｃｅ摩尔含量比（０：１０,１：９,２：８）的催化剂,实验条件十加入ＣｕＯ可以提高Ｐｔ催化剂的二效活性;加入Ｃｕ：Ｃｅ＝２：８的ＣｕＯ降低了Ｐｄ催化剂的顾效性能,然而Ｃｕ：Ｃｅ＝１：９时可以改善Ｐｄ催化剂的三效催化性能。通过结构分析,认为ＣｕＯ的存在可以提高ｄ催化剂的比表面积,ＰｄＯ的分散度。     

Response of bioaerosol cells to photocatalytic inactivation with ZnO and TiO2 impregnated onto Perlite and Poraver carriers

•ZnO/Perlite inactivated 72% of bioaerosols in continuous gas phase. •TiO₂ triggered the highest level of cytotoxicity with 95% dead cells onto Poraver. •Inactivation mechanism occurred by membrane damage, morphological changes and lysis. •ZnO/Poraver showed null inactivation of bioaerosols. •Catalysts losses at the outlet of the photoreactor for all systems were negligible. Bioaerosols are airborne microorganisms that cause infectious sickness, respiratory and chronic health issues. They have become a latent threat, particularly in indoor environment. Photocatalysis is a promising process to inactivate completely bioaerosols from air. However, in systems treating a continuous air flow, catalysts can be partially lost in the gaseous effluent. To avoid such phenomenon, supporting materials can be used to fix catalysts. In the present work, four photocatalytic systems using Perlite or Poraver glass beads impregnated with ZnO or TiO₂ were tested. The inactivation mechanism of bioaerosols and the cytotoxic effect of the catalysts to bioaerosols were studied. The plug flow photocatalytic reactor treated a bioaerosol flow of 460×1 0⁶ cells/m³_air with a residence time of 5.7 s. Flow Cytometry (FC) was used to quantify and characterize bioaerosols in terms of dead, injured and live cells. The most efficient system was ZnO/Perlite with 72% inactivation of bioaerosols, maintaining such inactivation during 7.5 h due to the higher water retention capacity of Perlite (2.8 mL/g_Perlite) in comparison with Poraver (1.5 mL/g_Perlite). However, a global balance showed that TiO₂/Poraver system triggered the highest level of cytotoxicity to bioaerosols retained on the support after 96 h with 95% of dead cells. SEM and FC analyses showed that the mechanism of inactivation with ZnO was based on membrane damage, morphological cell changes and cell lysis; whereas only membrane damage and cell lysis were involved with TiO₂. Overall, results highlighted that photocatalytic technologies can completely inactivate bioaerosols in indoor environments.     

La-M-Co-O/堇青石催化剂的制备及催化氧化氯苯

采用柠檬酸络合法制备La-M-Co-O（M=Mn,Cr,Fe,Ni和Cu）/堇青石催化剂,运用BET,XRD,SEM,H₂-TPR和XPS技术对催化剂性能及微观结构进行表征分析,研究考察过渡金属掺杂,掺杂量以及焙烧温度等对催化剂催化氧化性能的影响.结果表明,随着催化剂焙烧温度升高至650℃时,催化剂表面所负载的活性氧化物颗粒最为分散,其氧化活性最佳,且当反应温度为350℃时,催化剂催化氧化氯苯转化率可达96.4%,究其原因是高温焙烧致使催化剂形成LaCoO₃钙钛矿型复合氧化物,其复合氧化物的晶体结构有利于催化剂催化氧化氯苯性能的提高.     

非均相高效催化剂在餐厨废油转化生物柴油中的应用

近年来,非均相催化剂在酯化和转酯化催化制备生物柴油中备受关注。综述了固体碱、固体酸、固定化酶等非均相高效催化剂在生物柴油制备中的研究进展,并展望了新型非均相催化剂在餐厨废油转化制备生物柴油的应用前景。