催化湿式氧化法处理吡虫啉农药废水的优化工艺条件

采用催化湿式氧化技术在2 L高压反应釜中处理吡虫啉农药废水,分别以复合金属氧化物Cu/Mn、Cu/Ce、Ce/Mn及Ce/Ag为催化剂来考察对废水COD去除率的影响.发现Cu/Ce、Ce/Mn、Cu/Mn催化剂有较高的催化活性;Ce/Mn催化剂最稳定;Ce/Ag催化剂的Ag溶出量很大.选用性能良好的Ce/Mn催化剂,考察了反应温度、反应压力和废水的初始pH对催化湿式氧化效果的影响.结果表明,催化剂的加入可使COD去除率提高37%左右,同时处理后废水的BOD5/COD从0.19提高到0.65以上;当反应温度为150～230 ℃时,处理效率随温度升高明显增加;总压4.8 MPa、氧分压1.2～2.4 MPa时,适当增加氧分压亦能提高氧化效率;废水初始pH对氧化效果影响不大,但对催化剂的稳定性有影响.优化工艺条件最终为:催化剂为Ce/Mn;温度190 ℃;氧分压1.6 MPa;进水pH为6.21;反应时间120 min.     

催化湿式氧化吡虫啉农药废水催化剂的研究

通过共沉淀法制备了用于湿式氧化吡虫啉农药废水的Cu/Mn复合氧化物催化剂,研究了沉淀剂种类、沉淀温度、焙烧温度和活性组分配比等因素等对Cu/Mn复合氧化物催化剂的活性及稳定性的影响,确定了最佳制备条件,利用BET比表面积测定和XRD对催化剂进行了表征.结果表明,优化条件制备的Cu/Mn复合氧化物催化剂催化湿式氧化处理吡虫啉农药废水时,具有较高的催化活性和稳定性.催化剂用量4 g/L,反应温度190℃,氧分压1.6 MPa,反应120 min,COD去除率为92.3%,活性组分溶出量较小.     

Mn2O3/γ-Al2O3在超临界水氧化中催化活性的研究

采用浸渍法制备了Mn2O3/γ-Al2O3催化剂,在超临界水中催化氧化降解1,5-萘二磺酸,探索了催化剂Mn2O3活性组分负载量、催化剂空速和反应溶液pH对Mn2O3/γ-Al2O3催化剂活性的影响。结果表明：Mn2O3/γ-Al2O3的催化活性在一定范围内随Mn2O3活性组分负载量的增加而提高;在一定范围内,Mn2O3/γ-Al2O3空速越小,模拟废水的COD去除率越高;Mn2O3/γ-Al2O3催化活性在反应溶液呈酸性情况下比碱性时高。     

氧化还原共沉淀法制备的二元锰氧化物催化剂催化氧化苯的效果

通过氧化还原共沉淀法和共沉淀法制备了锰铈复合氧化物催化剂,用于苯的催化氧化,并结合一系列表征手段研究了催化剂的构效关系。结果表明,相对于共沉淀法,通过氧化还原共沉淀法制备的锰铈复合氧化物催化剂具有较大的孔径和比表面积,较好的低温还原性,拥有更好的苯催化氧化性能。之后采用氧化还原共沉淀法制备了不同金属元素(Co、Cu和Sn)掺杂改性的锰氧化物催化剂,并对苯进行催化氧化评价,发现不同元素(Co、Cu、Ce和Sn)掺杂均能提高锰氧化物催化剂的催化氧化活性,其中Ce、Sn掺杂之后得到的催化剂的催化氧化性能最佳,而对于不同催化体系,催化剂的氧化还原性与催化活性能之间没有必然联系。     

钛基催化剂的制备及其催化氧化苯乙烯性能

采用溶胶凝胶法制备负载型催化剂MnOx/TiO2和V2O5/TiO2,对比选择MnOx/TiO2催化剂。考察了锰系催化剂的活性组分负载量、焙烧温度及Ce掺杂量对催化氧化苯乙烯的影响,并结合XRD、BET和SEM表征手段对催化剂进行微观分析。结果表明,MnOx/TiO2对苯乙烯有良好的催化活性,Mn与Ti的摩尔比为0.1,焙烧温度为500℃时,起燃温度T50仅为150℃,当反应温度为254℃时,苯乙烯去除率超过90%。当掺杂Ce后催化剂MnOx-CeO2/TiO2对苯乙烯催化燃烧的起燃温度和完全转化温度均有明显降低,催化剂表面燃烧物颗粒的粒径有所减小,分散均匀,更有利于苯乙烯的催化燃烧处理。     

双组分甲苯、氯苯的微波辅助催化氧化及机理

通过微波辅助氧化典型挥发性有机化合物甲苯与氯苯的实验,探讨了TiO2-5A分子筛复合载体负载铜、锰、铈催化剂活性组分的存在形式及其与催化氧化活性的关联,研究采用SEM、EDS、BET、XRD、XPS以及FTIR等方法对催化剂进行了表征。研究表明,双组分中甲苯的完全转化温度(T95)比单组分的要高出31℃,而单组分氯苯在双组分氯苯的T90温度下可被完全转化,催化剂上目标物的竞争吸附降低了其催化氧化效果。XRD和XPS分析表明,催化剂中的活性物质以多价态氧化物CuO/Cu2O、MnO2/MnO以及Cu1.5Mn1.5O4和CuMn2O4尖晶石形式均匀分散于载体表面,Cu2+/Cu+、Mn4+/Mn2+的相互转化促进了电子转移增强了甲苯氯苯被氧化的性能,以及有更高催化活性的CuMn2O4尖晶石的形成有利于催化剂活性的提高。CeO2/Ce2O3相互转化加强了催化剂表面储氧、输氧的能力并加快了氧化反应速率。FTIR与粉红色尾气吸收液检测结果推测:甲苯首先氧化成苯甲醛、苯甲酸类物质,而氯苯氧化成苯酚,210℃下可最终氧化成二氧化碳和水。     

乳化液废水的均相催化湿式氧化

在2L的高温高压反应釜中,以非贵的过渡金属盐作均相催化剂,研究了高浓度难降解的乳化液废水的催化湿式氧化.试验发现,单一金属盐催化活性为Cu2 ＞Mn2 ＞Co2 ,其中Cu2 在200℃时催化效果良好,可使TOC去除率提高13.3%;Cu2 受投量影响较明显,以200mg/L为宜;混合盐催化活性为Cu2 Mn2 ≈Mn2 Co2 (＞Cu2 )＞Cu2 Co2 .     

Mn203/γ-Al2O3在超临界水氧化中催化活性的研究

采用浸渍法制备了Mn2O3/γ-Al2O3催化剂,在超临界水中催化氯化降解1,5-萘二磺酸,探索了催化剂Mn2O3活性组分负载量、催化剂空速和反应溶液pH对Mn2O3/γ-Al2O3催化剂活性的影响.结果表明:Mn2O3/γ-Al2O3的催化活性在一定范围内随Mn2O3活性组分负载量的增加而提高;在一定范围内,Mn2O3/γ-Al2O3空速越小,模拟废水的COD去除率越高;Mn2O3/γ-Al2O3催化活性在反应溶液呈酸性情况下比碱性时高.     

煤化工高盐废水臭氧催化氧化脱除COD

针对煤化工高盐废水中有机物难降解问题,采用浸渍-煅烧法制备了负载有活性金属氧化物的活性氧化铝型催化剂,探索催化剂的制备工艺和反应操作条件对废水COD去除率的影响。结果表明:活性氧化铝载体催化性能优于陶粒,活性氧化铝负载Cu、Mn、Ni的催化活性较高,将2种活性组分进行组合制得的MnO_xNiO_x/γ-Al_2O_3催化剂,在经过60 min的臭氧催化氧化后,COD的去除率可达51.3%;利用BET、SEM-EDS、XRD对催化剂进行了表征和分析,Mn、Ni成功负载到活性氧化铝表面和孔隙内,2种元素负载量摩尔比约为2:1,且主要以氧化物形式存在;通过计算臭氧利用效率,发现MnO_x-NiO_x/γ-Al_2O_3臭氧催化氧化的_η值低于单独的臭氧氧化,这意味着通过MnO_x-NiO_x/γ-Ak_2O_3催化剂可以有效地将臭氧分解成活性氧;通过优化臭氧和催化剂投加量后发现,在臭氧为350 mg·(L·h)~(-1)、催化剂投加量为100 g·L~(-1)废水中,反应180 min后,COD去除率可达到72.3%;在连续进行4 h的臭氧催化氧化实验后,MnO_x-NiO_x/γ-Al_2O_3稳定性和重复利用性均较好,COD去除率能维持在约42%,锰、镍离子的溶出量均小于0.5 mg·L~(-1)。以上研究结果可为高效的臭氧催化体系在煤化工高盐废水处理领域的应用提供参考。     

Mn、Ce掺杂改性γ-Al_2O_3催化剂对燃煤烟气Hg~0去除性能研究

以γ-Al_2O_3为掺杂,通过掺杂Mn、Ce活性物质制备复合催化剂去除模拟烟气中的Hg0,考察了Mn和Ce负载量、催化剂制备煅烧温度、反应温度以及模拟烟气中O_2和SO_2体积分数对于Hg0去除率的影响。结果表明,负载Mn、Ce活性组分后,复合催化剂对燃煤烟气Hg~0的去除率明显高于γ-Al_2O_3。当Mn、Ce负载量分别为0.10、0.02时(以Mn、Ce与Al的摩尔比计)时,制得的催化剂Mn0.10-Ce0.02/γ-Al_2O_3活性最好,催化剂最佳煅烧温度为400℃,最佳反应温度为150℃。常规燃煤烟气条件下的O_2体积分数能够满足Hg~0的有效氧化,烟气中的SO_2会严重抑制Hg~0的氧化。     

双氧水催化氧化中Cu/γ-Al_2O_3催化剂的稳定性研究

针对废水湿式双氧水催化氧化,采用浸渍法制备Cu催化剂,研究非均相Cu催化剂在常温常压湿式双氧水催化氧化中的稳定性与失活问题。研究表明,催化剂制备条件及催化氧化反应条件对催化剂中Cu2＋溶出均有影响。研究同时表明,催化剂失活与活性组分流失和活性组分被有机中间产物覆盖有关,高温焙烧可对催化剂再生。     

Removal of ammonia solutions used in catalytic wet oxidation processes

Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.     

废水催化湿式氧化稀土金属氧化物催化剂的研制

采用共沉淀法制得锰铈复合氧化物催化剂,催化湿式氧化处理高浓度苯酚废水。通过正交实验筛选催化剂制备条件,单因素实验优化制得催化剂。研究了CWAO处理废水条件下的金属离子溶出和催化剂的表征。结果表明,该催化剂在低温低压条件下具有优良的湿式氧化催化活性,且金属离子溶出量低,是一种CWAO处理高浓度有机废水中极具应用前景的新型高效催化剂。     

负载型Mn-Ce／TiO2催化剂的制备及其低温脱硝活性

以成型TiO2作为载体,通过浸渍法制备了Mn-Ce／TiO2低温SCR催化剂,并系统研究了制备方法、煅烧条件、活性组分担载量、Mn含量等参数对催化剂催化还原NO性能的影响。结果表明,煅烧温度的升高会促使活性组分结晶度的提高,从而引起催化活性的降低,在500℃和600℃下所得Mn-Ce／TiO2催化剂活性组分为无定型态,表现出较高的脱硝活性。活性组分担载量的增加有利于催化活性的提高。Mn含量对Mn-Ce／TiO2催化剂的活性有较大影响,当Mn／（Mn＋Ce）摩尔比为40％和85％时,催化剂活性最高。     

Mn的氧化价态对Mn／γ-Al2O3催化剂催化臭氧氧化气相低浓度甲苯的影响

采用共沉淀法,以Al2O3为载体制备Mn／γ-Al2O3和Mn—Ce／Mn／γ-Al2O3催化剂,并分别在N2气氛和O2气氛下焙烧。采用固定床连续流动反应器,研究所制备催化剂在室温条件下催化臭氧氧化甲苯的性能。通过XRD、XPS和FTIR等手段对催化剂的结构和组成进行表征。结果表明,Mn／Mn／γ-Al2O3催化剂具有良好的催化臭氧氧化甲苯和催化臭氧自身分解的性能,共沉淀法制备催化剂的最佳Mn负载量为20％。O2气氛焙烧和Ce的加入,可以有效提高催化剂的活性和寿命。原因是O2气氛焙烧和Ce的加入可以提高Mn的氧化价态。催化剂失活的主要原因是有机副产物在催化剂表面吸附堆积,失活催化剂在550℃、空气气氛下焙烧可恢复催化性能。     

La1-x Cex Cuy Mn1-yO3／HZSM-5催化剂低温去除柴油机碳烟和NOx

为实现对柴油机碳烟和NOx的低温同步去除,采用柠檬酸络合法制备分子筛负载钙钛矿型金属复合氧化物催化剂,应用x衍射分析仪（XRD）和电镜扫描仪（SEM）对催化剂性能进行表征,并在微型固定床反应器中对催化剂低温去除碳烟和NOx进行活性评价。利用程序升温反应（TPR）技术,进行催化剂活性评价、柴油机负荷和排放等特性实验。结果表明,A位用适量Ce部分取代La,B位用适量cu部分取代Mn,可使碳颗粒燃烧温度降低,CO2选择性好,NOx转化率升高。La0.4 Ce0.6 Cu0.2 Mn0.8O3／HZSM-5催化剂的最大NOx转化率为81．0％,Ti、Tm和Tf分别为250、350和475℃,表明该催化剂具有较好的催化活性,能在低温条件下去除碳烟和NOx。     

Catalytic hydrothermal treatment of pulping effluent using a mixture of Cu and Mn metals supported on activated carbon as catalyst

The present study was performed to investigate the performance of activated carbon-supported copper and manganese base catalyst for catalytic wet oxidation (CWO) of pulping effluent. CWO reaction was performed in a high pressure reactor (capacity?=?0.7 l) at temperatures ranging from 120 to 190 °C and oxygen partial pressures of 0.5 to 0.9 MPa with the catalyst concentration of 3 g/l for 3 h duration. With Cu/Mn/AC catalyst at 190 °C temperature and 0.9 MPa oxygen partial pressures, the maximum chemical oxygen demand (COD), total organic carbon (TOC), lignin, and color removals of 73, 71, 86, and 85 %, respectively, were achieved compared to only 52, 51, 53, and 54 % removals during the non-catalytic process. Biodegradability (in terms of 5-day biochemical oxygen demand (BOD₅) to COD ratio) of the pulping effluent was improved to 0.38 from an initial value of 0.16 after the catalytic reaction. The adsorbed carbonaceous fraction on the used catalyst was also determined which contributed meager TOC reduction of 3–4 %. The leaching test showed dissolution of the metals (i.e., Cu and Mn) from the catalysts in the wastewater during CWO reaction at 190 °C temperature and 0.9 MPa oxygen partial pressures. In the future, the investigations should focus on the catalyst reusability.     

CWAO of phenol using CeO2/gamma-Al2O3 with promoter--effectiveness of promoter addition and catalyst regeneration

The effect of promoter addition on activity of CeO(2)/gamma-Al(2)O(3) was assessed via the CWAO of phenol. Adding Cu as the promoter rendered the most effective performance, followed by Mn, although the performance of Mn-promoted catalyst was inferior to CeO(2)/gamma-Al(2)O(3). Mineralization of phenol was effectively implemented at 160 degrees C using Cu-promoted catalyst (Ce15Cu5). Furthermore, at 180 degrees C this catalyst produced about 100% conversion of phenol (1h) and 95% removal of chemical oxygen demand (4h), higher than that of CeO(2)/gamma-Al(2)O(3). In contrast, Mn-promoted catalyst (Ce15Mn5) required a temperature above 220 degrees C for acceptable performance. Activity of re-used catalyst declined noticeably, due to deposits of carbonaceous compounds and leaching of metal ions. Regeneration with acetone rinsing after the first run was effective in recovering activity of Ce15Cu5, although after a second run further regeneration with acetone rinsing had only a moderate effect, due to residual carbonaceous deposits and the additive effect of leached metal species in each run. As an alternative to acetone, HCl or HNO(3) solution (0.01 M) was less effective at regenerating activity. In promoted catalysts, leached metal ions accounted for the majority of mineralization of phenol, while the solid catalyst played a dual role of initiator and terminator of free radicals. Despite a superior catalytic performance, leaching of Cu(2+) from the promoted catalyst caused a severe decline in activity and poses the problem of secondary pollution of treated wastewater. Therefore, addition of Cu, as well as other metal species, is unfavorable in promoting the CeO(2)/gamma-Al(2)O(3) catalyst.     

Preparation of the Mn/Co mixed oxide catalysts for low-temperature CO oxidation reaction

The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m²g⁻¹ with a small mean pore size of 6.44 nm. The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co = 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst exhibited a CO conversion of 100% at 80 ^°C.

     

Fe (III) supported on resin as effective catalyst for the heterogeneous oxidation of phenol in aqueous solution

FeIII supported on resin as an effective catalyst for oxidation was prepared and applied for the degradation of aqueous phenol. Phenol was selected as a model pollutant and the catalytic oxidation was carried out in a batch reactor using hydrogen peroxide as the oxidant. The influent factors on oxidation, such as catalyst dosage, H2O2 concentration, pH, and phenol concentration were examined by considering both phenol conversion and chemical oxygen demand (COD) removal. The FeIII-resin catalyst possesses a high oxidation activity for phenol degradation in aqueous solution. The experimental results of this study show that almost 100% phenol conversion and over 80% COD removal can be achieved with the FeIII-resin catalyst catalytic oxidation system. A series of prepared resin were investigated for improving the oxidation efficiency. It was found that the reaction temperature and initial pH in solution significantly affected both of phenol conversion and COD removal efficiency. The activity of the catalyst significantly decreased at high pH, which was similar to the Fenton-like reaction mechanism. Results in this study indicate that the FeIII-resin catalytic oxidation process is an efficient method for the treatment of phenolic wastewater.