Cu/TiO2催化湿式氧化甲醛废水

甲醛废水排放入水体后,破坏生态系统,影响人们的身体健康。考察了以自制的Cu/TiO2为催化剂,用催化湿式氧化的方法降解甲醛废水的情况。通过优化反应条件,在180℃、pH=5、0.5 MPa、催化剂量为6 g/L时反应2 h,TOC的去除率高达85%,且Cu2+和Ti4+基本没有流失。此外还检测了甲醛溶液中甲醇变化情况和经处理后甲醛废水的降解产物甲酸。结果表明,以Cu/TiO2为催化剂的催化湿式氧化能有效地降解甲醛废水。     

Pt-CeO2/TiO2催化剂催化湿式氧化苯酚废水的研究

以TiO2为载体,利用分步浸渍法制备了Pt-CeO2/TiO2、Pt-ZrO2/TiO2、Pt-La2O3/TiO2、Pt-Pr2O3/TiO2和Pt-SnO2/TiO2催化剂,并催化湿式氧化高浓度苯酚废水。Pt-CeO2/TiO2催化剂的活性最好,在反应温度为160℃、氧分压为2.25 MPa,反应时间为2 h的条件下,苯酚和COD的去除率分别为87.53%和72.06%。进一步研究助剂含量对催化剂性能的影响,当CeO2负载量为12.5%时,催化剂Pt-CeO2/TiO2的催化性能最佳。XRD和TEM结果表明,助剂CeO2的引入起到降低Pt的粒径,提高Pt在载体表面的分散度的作用。     

炭吸附La2O3/TiO2复合粉体的制备及其光催化性能研究

采用炭吸附共沉淀法制备了La₂O₃/Ti O₂催化剂,利用TG-DTG、XRD、TEM、UV-Vis等对催化剂进行表征,并考察了不同条件制备的La₂O₃/Ti O₂对可见光催化甲基橙降解效果的影响。结果表明,炭黑的加入可有效阻止粉体在制备、干燥及焙烧过程中的团聚和烧结;在600℃煅烧后得到的粉体结晶度高、颗粒分散均匀、颗粒粒径小。在可见光照射1 h后,炭吸附沉淀法制备的La2O3/Ti O₂对甲基橙的降解率高达92.25%,是普通沉淀法制得的La₂O₃/Ti O₂的3倍,光催化活性显著提高。     

锶掺杂的La2Ce2O7烧绿石催化甲烷氧化偶联性能研究

基于烧绿石类材料热稳定性高、晶格氧流动性可调控的特点,通过溶胶-凝胶法制备了La₂Ce₂O₇催化剂,向其中掺杂碱土金属Sr,研究了其在甲烷氧化偶联（OCM）反应中的催化性能。通过一系列表征确认了La₂Ce₂O₇样品的缺陷立方萤石结构;锶掺杂不仅显著提高了晶格氧的活动性,还提升了催化剂表面强碱位点的比例;与OCM反应活性关联发现,晶格氧流动性增强以及表面强碱位点的增加是提高OCM反应活性的关键因素;在优化的La_1.5Sr_0.5Ce₂O₇催化剂上,800℃下可以获得57%的C₂选择性和14%以上的C₂收率,连续反应30 h性能保持稳定。     

Fe2O3/Ni2O3/Al2O3催化剂制备及其催化氧化靛蓝废水研究

以三氧化二铝为载体,采用浸渍沉淀法制备系列Fe2O3/Ni2O3/Al2O3催化剂。采用TG-DTA,XRD及ESEM等技术对催化剂进行表征,确定催化剂的最佳焙烧温度为460℃。以次氯酸钠为氧化剂,同时考察m(三氧化二镍)/m(三氧化二铝)、m(三氧化二铁)/m(三氧化二镍)、m(次氯酸钠)∶m(靛蓝废水)、pH对印染靛蓝废水处理的影响。结果表明:m(三氧化二镍)/m(三氧化二铝)=0.3,m(三氧化二铁)/m(三氧化二镍)=0.04,m(次氯酸钠)∶m(靛蓝废水)=1∶11,pH=7,反应温度为20℃,常压反应时间为2 h时,COD的去除率为95.3%。     

Fe/Al_2O_3催化剂催化氧化兰炭废水

采用浸渍法制备Fe/Al_2O_3催化剂,采用BET、XRD和穆斯堡尔谱等进行结构和性能表征。以自制Fe/Al_2O_3为催化剂,应用催化湿式过氧化氢氧化技术处理COD为6 742 mg·L-1的兰炭废水,通过建立正交实验确定最佳实验条件,结果表明,在p H=4、过氧化氢添加量9.6 m L、反应时间150 min和反应温度80℃条件下,兰炭废水COD去除率达66.30%。对催化氧化后的废水进行GC-MS分析,确定最终氧化产物主要为乙酸。表明自制Fe/Al_2O_3催化剂具有优良的催化效果,并使大分子难降解有机污染物分解为易生化的小分子污染物,甚至被完全分解矿化。     

Nd2O3对(Zr0.8,Sn0.2)TiO4微波介质陶瓷结构和性能影响

以(Zr_0.8,Sn_0.2)TiO₄为基,通过研究Nd₂O₃(0～0.20 mol%)掺杂(Zr_0.8,Sn_0.2)TiO₄微波介质陶瓷对物相结构、形貌和介电性能的影响,发现随着Nd₂O₃掺杂量的增加,(Zr_0.8,Sn_0.2)TiO₄介质陶瓷的晶格参数、晶粒尺寸变化微弱,Nd3+几乎不影响(Zr_0.8,Sn_0.2)TiO₄陶瓷阳离子有序生长,而是在(Zr_0.8,Sn_0.2)TiO₄介质陶瓷的晶界形成钉扎,通过降低介质外在损耗,有效提高陶瓷材料的Q×f值至45000(@15 GHz),并提高容量温度稳定性。     

CuO-H2O2非均相催化氧化染料废水

以活性艳红X-3B为模拟底物,研究了低温常压条件下CuO-H2O2体系催化氧化染料废水的各种影响因素及反应机制。结果表明,CuO-H2O2体系能高效彻底地氧化活性艳红X-3B,氧化率可高达99%。CuO-H2O2体系降解染料废水的速率随温度、氧化剂和催化剂投加量以及X-3B废水初始浓度的升高而升高。酸性条件能促进X-3B废水的降解。与直接染料相比,CuO-H2O2体系降解活性染料废水更加有效。     

Fe2O3-CuO/高岭土催化湿式氧化甲基橙废水的研究

以Fe_2O_3、Cu O为活性组分,高岭土为载体,采取浸渍法制备了Fe_2O_3-Cu O/高岭土催化剂,研究了其催化湿式氧化甲基橙废水的活性。实验结果表明,在催化剂用量为0.8g、30%H_2O_2用量为8m L、反应时间为1.5h、反应温度为35℃的条件下,甲基橙废水的最高降解率达到83.73%。     

La2O3助剂对Ni/γ-Al2O3/堇青石结构化催化剂催化加氢合成间苯二胺性能的影响

研究助剂La2O3对Ni/γ-Al2O3/堇青石结构化催化剂结构与性能的影响。采用悬浮液涂层法、活性组分浸渍法制备不同La2O3助剂含量的Ni/γ-Al2O3/堇青石结构化催化剂。通过BET、XRD、TPR、XPS对催化剂进行表征,发现不添加La2O3助剂时活性组分以NiAl2O4形式存在,添加La2O3助剂后则以NiAl2O4和NiO两种形式存在,易还原NiO的生成提高了催化剂的活性。添加La2O3助剂还能使催化剂的比表面积降低和孔尺寸增大,活性评价表明助剂La2O3存在适宜添加量,即La含量为3%。同时发现助剂La2O3对选择性的影响大于活性,La2O3具有结构助剂的特点。     

催化湿式氧化山梨酸生产废水催化剂的研究

以过渡金属氧化物CuO为主活性组分通过对Cr2O3的复合和掺入电子助剂La2O3的考察,研制出适用于催化湿式氧化处理山梨酸生产废水的复合催化剂。考察了各组分浸渍液浓度、焙烧温度和焙烧时间等制备条件对催化剂的催化活性和稳定性的影响,确定了最佳制备条件。结果表明:优化制备的CuO-Cr2O3-La2O3/TiO2催化剂,用于处理山梨酸生产废水时具有良好的催化活性和稳定性,在θ=220℃,p(O2)=2.5 MPa,反应时间t=120 min,山梨酸生产废水初始CODCr=10 030 mg/L条件下CODCr去除率达到96.6%,而在相同条件下未加催化剂的湿式氧化CODCr去除率只有60.8%。     

阴离子种类及浓度对RCT催化剂催化湿式氧化处理头孢废水的影响

采用催化湿式氧化法处理头孢类废水,以RCT为催化剂,考察了阴离子对污染物降解效果的影响。结果表明,不加阴离子时,RCT催化剂能有效催化污染物的降解,TOC和TN去除率分别为78.3%和85.9%;投加不同阴离子对反应的影响不同。RCT催化剂可将头孢氨苄废水中的有机N转化为$N_{2}$,少部分以$NO_{3}-N$形式存在;阴离子F^-、Cl^-、Br^-、I-及$S^{2-}_{4}$对TN的降解影响不大,而$N^{-}_{3}$、$P^{3-}_4$、$CO^{2-}_{3}$、$Si^{2-}_{3}$及$B_{4}O^{2-}_{7}$则明显抑制了对TN的去除。投加F^-、Cl^-、Br^-、I-及$NO^{-}_{3}$对TOC的降解有促进作用(I^-> F^-> Cl^-> Br^-> $NO^{-}_{3}$),TOC的降解率提高了3.1~18.6个百分点;而投加$S^{2-}_{4}$、P,$P^{3-}_4$、$CO^{2-}_{3}$、$SiO^{2-}_{3}$及$B_{4}O^{2-}_{7}$对TOC的降解有抑制作用($SiO^{2-}_{3}$> ,$P^{3-}_4$> $CO^{2-}_{3}$> $B_{4}O^{2-}_{7}$> $S^{2-}_{4}$),TOC的降解率降低了2.0~46.9个百分点。研究Cl-浓度对RCT催化剂降解效果的影响,当Cl-为0.1 mol·L-1时,对TOC的去除有抑制作用,而较高的Cl-浓度(≥0.3 mol·L-1)对TOC的去除却有促进作用,投加Cl-对TN的去除有促进作用,但随着Cl-浓度的增加[(0.1~0.8) mol·L-1],TN的去除率变化不明显(约为88%)。     

催化湿式氧化法和厌氧发酵法联用处理异佛尔酮废水

分别以沉淀法、共沸蒸馏法和高温老化法制备ZrO₂载体,采用等体积浸渍法制备Ru/ZrO₂催化剂,用于催化湿式氧化法处理异佛尔酮废水。研究了反应温度、催化剂用量及反应时间对异佛尔酮废水乙酸浓度、COD去除率、TOC去除率及废水可生化性的影响。废水经催化湿式氧化处理的中间产物主要为乙酸,可由产甲烷菌转化为甲烷。结果表明,提高反应温度、增加催化剂用量及延长反应时间均可提高异佛尔酮废水COD去除率、TOC去除率及废水可生化性。在270 ℃、氧分压2.5 MPa和催化剂用量9 g·L^－1条件下,超过180 min异佛尔酮废水COD及TOC去除率分别可达90.4%和84.9%。在270 ℃、氧分压2.5 MPa和催化剂用量1 g·L^－1反应条件下,120 min时异佛尔酮废水乙酸浓度最大,为5 582.98 mg·L^－1。催化湿式氧化处理后出水利用产甲烷菌进行厌氧发酵,反应9天产甲烷体积达到最大值820 mL。     

Ag-Fe_2O_3-V_2O_5/TiO_2催化剂制备及其甲基吡啶催化氧化脱甲基性能

针对甲基吡啶氧化脱甲基反应,以TiO_2为载体经浸渍法制备Ag-Fe_2O_3-V_2O_5/TiO_2催化剂,结合结构表征和催化剂性能评价,考察制备条件对其催化甲基吡啶氧化脱甲基性能的影响。结果表明,通过Fe_2O_3改性可以提高Ag-V_2O_5/TiO_2催化剂对3-甲基吡啶氧化脱甲基化反应的催化性能,其作用主要是抑制V_2O_5团聚,促进V物种的分散。同时,锐钛矿相TiO_2载体表面B酸中心有利于催化3-甲基吡啶脱甲基,提高产物吡啶选择性。经实验优化,Ag-Fe_2O_3-V_2O_5/TiO_2催化剂适宜制备条件为:焙烧温度450℃、焙烧时间4 h、V_2O_5和Ag的负载质量分数分别为15%和1.5%、Fe与V物质的量比1∶2。在优化条件下,吡啶收率与选择性最高可达到62.97%和78.75%。     

TiO2-SiO2 and V2O5/TiO2-SiO2 catalyst: Physico-chemical characteristics and catalytic behavior in selective catalytic reduction of NO by NH3

TiO₂-SiO₂ with various compositions prepared by the coprecipitation method and vanadia loaded on TiO₂-SiO₂ were investigated with respect to their physico-chemical characteristics and catalytic behavior in SCR of NO by NH₃ and in the undesired oxidation of SO₂ to SO₃, using BET, XRD, XPS, NH₃-TPD, acidity measurement by the titration method and activity test. TiO₂-SiO₂, compared with pure TiO₂, exhibits a remarkably stronger acidity, a higher BET surface area, a lower crystallinity of anatase titania and results in allowing a good thermal stability and a higher vanadia dispersion on the support up to high loadings of 15 wt% V₂O₅. The SCR activity and N₂ selectivity are found to be more excellent over vanadia loaded on TiO₂-SiO₂ with 10–20 mol% of SiO₂ than over that on pure TiO₂, and this is considered to be associated with highly dispersed vanadia on the supports and large amounts of NH₃ adsorbed on the catalysts. With increasing SiO₂ content, the remarkable activity decrease in the oxidation of SO₂ to SO₃, favorable for industrial SCR catalysts, was also observed, strongly depending on the existence of vanadium species of the oxidation state close to V⁴⁺ on TiO₂-SiO₂, while V⁵⁺ exists on TiO₂, according to XPS. It is concluded that vanadia loaded on Ti-rich TiO₂-SiO₂ with low SiO₂ content is suitable as SCR catalysts for sulfur-containing exhaust gases due to showing not only the excellent de-NO_x activity but also the low SO₂ oxidation performance.     

柠檬醛在La2O3/γ-Al2O3催化剂上的等温吸附

对柠檬醛-乙酸乙酯溶液中柠檬醛在La₂O₃/γ-Al₂O₃催化剂上等温吸附行为进行了研究。结果表明,30 ℃柠檬醛在La₂O₃/γ-Al₂O₃催化剂上的吸附动力学符合准二阶吸附动力学模型,吸附动力学方程为：1/q_t=2.350/t+0.063 3(R²=0.998 5)。（30~65） ℃柠檬醛在La₂O₃/γ-Al₂O₃催化剂上的等温吸附符合Langmuir方程,温度升高使柠檬醛的饱和吸附量增加,吸附热为32.19 kJ·mol^-1。     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

Development of Fe2O3-CeO2-TiO2/γ-Al2O3 as catalyst for catalytic wet air oxidation of methyl orange azo dye under room condition

In order to develop a catalyst with high activity and stability for catalytic wet air oxidation (CWAO) process at room temperature and atmospheric pressure, we prepared Fe₂O₃-CeO₂-TiO₂/γ-Al₂O₃ by consecutive impregnation, and determined its properties using BET, SEM, XRF, XPS and chemical analysis techniques. The degradation of an azo dye, methyl orange, in CWAO process with Fe₂O₃-CeO₂-TiO₂/γ-Al₂O₃ used as catalyst at room temperature and atmospheric pressure was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 500 mg/L methyl orange, and 98.09% of color and 96.08% of total organic carbon (TOC) can be removed in 2.5 h. The degradation pathway of methyl orange was analyzed by UV–vis and FT-IR spectra. The result of leaching tests shows the catalyst has an excellent stability with negligible leaching ions, and the leaching of Ce is effectively controlled by adding Ti, because Ce and Ti in the catalyst take the form of compound oxides, and the deactivation of the catalyst in successive runs is caused by the adsorption of intermediates on the surface and coverage of the active sites. The catalytic activity of the deactivated catalyst can be generally restored by rinsing it in hydrochloric acid followed by calcination.     

Wet oxidation of bleach plant effluent: Effects of pH on the oxidation with or without a Pd/Al2O3 catalyst

Wet oxidation of acidic bleach plant effluent was carried out at 423K and 1.5 MPa in a slurry reactor. The influence of pH of the bleach plant effluent was evaluated for both catalytic and non-catalytic oxidation in the liquid phase. The stability of the heterogeneous catalysts was investigated by measuring the extent of metal leaching into the solution. The pH of wastewater solution was found to influence significantly both the rate of total organic carbon (TOC) removal and the stability of the Pd/Al₂O₃ catalyst. Leaching of palladium and alumina occurred mostly at pH 2 and pH 11 under experimental conditions. With Pd/Al₂O₃, comparable rates of TOC removal were obtained in the pH range of 5 to 9 without significant leaching of both palladium and alumina. No metal leaching was observed using the Pd-Pt/Al₂O₃ catalyst at an initial pH value of 7. Implications of these experimental results for designing a catalytic wet oxidation process are discussed. A novel approach has been proposed for the treatment of effluents from softwood Kraft pulp mills.