含Ce_xZr_(1-x)O_2固溶体三效催化剂的制备及性能研究

用共沉淀技术在室温、pH =10 0的条件下制备出了CexZr1-xO2 固溶体 ,将其用于Pd基三效催化剂的制备 ,对催化剂的性能进行了评价 ,结果表明 :和纯的CeO2 相比 ,含CexZr1-xO2 固溶体的催化剂具有较高的催化性能 ,其中Pd/Ce0 6Zr0 .4 O2 催化剂性能最佳 ,HC、CO、NO的转化率在A/F =14 6时分别为 97 33%、89 5 2 %、10 0 %;新鲜催化剂的起燃温度分别为 186、180、185℃ ,高温处理后起燃温度分别为 2 49、2 41、2 46℃。     

助剂Ba对Pd/Al_2O_3和Pt/Al_2O_3催化剂的C1-C3烷烃催化燃烧性能的影响

通过浸渍法制备了Al_2O_3负载的Pd和Pt催化剂,考察催化剂的甲烷、乙烷和丙烷催化燃烧活性,以及助剂Ba对催化性能的影响。对于Pd/Al_2O_3催化剂,加入Ba使活性物种PdO颗粒变大和还原温度升高,形成更稳定的PdO活性物种,是Pd-Ba/Al_2O_3催化剂活性提升的主要原因。对于Pt/Al_2O_3催化剂,加入Ba助剂使活性物种Pt0含量降低,PtO_x与Al_2O_3载体相互作用增强,使PtO_x物种更难被还原为Pt~0,导致Pt-Ba/Al_2O_3催化剂活性降低。Pd和Pt催化剂催化烷烃氧化反应活性规律一致:丙烷乙烷甲烷。Pd/Al_2O_3催化剂有利于C—H键活化,Pt/Al_2O_3催化剂有利于C—C键活化。Pt/Al_2O_3催化剂对C1-C3烷烃氧化活性的差别明显大于Pd/Al_2O_3催化剂。Pt/Al_2O_3催化剂对碳比例高的烷烃活性更高。     

CH_4/CO_2重整反应中NiO-Ce_xZr_(1-x)O_2/Al_2O_3催化剂的研究

通过共沉淀法制备了一系列CexZr1-xO2的介孔材料,采取浸渍法负载10 wt%Ni O/γ-Al2O3,得到不同组成的Ni O-CexZr1-xO2/Al2O3(x=0,0.25,0.5,0.75,1)催化剂。对所得催化剂进行BET、XRD表征分析,同时考察了在相同条件下CH4/CO2重整反应中的催化性能。结果表明:Ni O-Ce0.75Zr0.25O2/Al2O3催化剂有较好的稳定性和抗积炭性,CH4、CO2转化率和H2收率分别可达85.5%、86.4%和93.8%;碱金属助剂有大的比表面积,可使活性组分Ni O充分分散,且随着Ce O2含量增加分散度也提高,使得催化剂抗积炭性能增强,催化活性提高。     

甲烷在Cr改性Pd/Al2O3催化剂上的催化燃烧性能

研究了Cr改性Pd/Al2O3催化剂上低浓度甲烷的催化燃烧反应,考察了载体Cr Al的制备方法和活性组分Pd的负载方法对催化剂催化活性的影响以及添加Ce对催化剂高温稳定性的影响。采用X射线衍射、程序升温还原等表征手段分析了催化剂结构和氧化还原性。结果表明,与采用沉淀法制备的载体P-Cr Al相比,采用浸渍法制备的载体I-Cr Al具有较高的比表面积和反应活性;用Na BH3对Pd负载过程进行还原处理能明显提高催化剂活性,其原因是还原过程加强了催化剂上Pd与载体Cr Al之间的作用,通过H2-TPR证明了其还原能力得到了增加;添加Ce缓解了Al2O3高温条件下的烧结,增强了催化剂的高温稳定性。     

载体及活性组分对甲烷低温燃烧催化性能的影响

以一定浓度的Pd为活性组分,-γA l2O3为载体,用浸渍法制备了甲烷低温燃烧催化剂,运用固定床反应装置着重研究载体对甲烷低温燃烧反应的催化性能的影响。同时采用同一种载体条件下,重点考察不同浓度的单一活性组分Pd或Pt和(Pt-Pd)双活性组分催化剂对甲烷低温燃烧反应的催化性能的影响。结果表明,由不同载体,负载同一浓度活性组份制备出的催化剂活性有较大差异。(Pt-Pd)/A l2O3双组分燃烧催化剂,性能优于单一组分的Pd/A l2O3或Pt/A l2O3催化剂,(Pd-Pt)/A l2O3体系具有较高的甲烷催化燃烧活性,催化燃烧的起燃温度最低。相比当(Pd 0.2%-Pt 0.1%)/A l2O3时催化剂活性最高,CH4转化率50%的温度为345℃,完全转化温度为405℃。通过1 000 h稳定性试验,显示出甲烷完全氧化温度为405℃左右,具有较好的低温活性及热稳定性。     

添加ZrO2的Pd/Al2O3催化剂及其催化蒽醌加氢性能

以四氯合钯（II）酸（H2PdCl4）为前体,活性氧化铝（Al2O3）为载体,硝酸锆（Zr（NO3）4）为添加组分,采用不同方式的分步浸渍法制备了添加ZrO2的Pd/Al2O3催化剂。考察了制备方法和反应条件对催化剂蒽醌加氢催化性能的影响,发现催化剂活性与制备方法有关。当对添加锆的载体进行适当焙烧,控制Pd负载量为0.3%,还原温度低于300℃时,催化剂的蒽醌加氢活性较高,与未添加ZrO2的催化剂相比提高了约20%。X射线衍射（XRD）、氮气物理吸附（BET）、透射电镜（TEM）、X光电子能谱（XPS）和程序升温还原（TPR）等表征对催化剂物相结构、比表面积、表面形貌及组分间相互作用的分析表明,ZrO2的掺杂提高了载体Al2O3的高温稳定性,改善了催化剂中活性组分Pd与载体间的相互作用,促进了Pd在载体表面的分散,从而提高了催化活性。     

不同载体和金属助剂负载Pt催化剂对丙烷催化氧化活性研究

制备了不同载体、不同金属助剂及不同贵金属Pt含量的蜂窝催化氧化催化剂,并评价了催化剂催化氧化含丙烷有机废气的活性:通过表面结构表征和活性评价实验,发现r-氧化铝作为载体时催化剂活性比分子筛和二氧化钛好;随着Pt含量的增加,催化剂的活性先升高后降低,Pt质量分数为0.2%时催化剂的活性最高;分别制备Pt/MO_x/Al_2O_3(M为铜、锰、钨、铈、锆、镧中的一种),在催化剂表面发现Pt聚集的颗粒,CeO_x的加入可改善贵金属的分布,Pt/CeO_x/Al_2O_3活性最佳,在400℃条件下,丙烷转化率达到95%以上,此时CeO_x的质量分数为1.0%。     

载体对丙烷脱氢过程中氢气选择氧化催化剂Pt/Al_2O_3性能的影响

通过X射线衍射(XRD)、透射电镜(TEM)和物理吸附(N_2吸附)等手段测定了不同合成条件下制备的Al_2O_3物性参数如比表面积,孔容和孔径等,并以合成的Al_2O_3为载体制备了单Pt/Al_2O_3催化剂,在固定床微型催化反应装置上考察了其在丙烷脱氢过程中催化氢气选择氧化性能。由相同条件下催化剂对混合气中氢气选择性氧化催化结果可知,在铝和葡萄糖物质的量比为1和弱碱条件下制备的Al_2O_3为载体,负载Pt质量分率0.5%的催化剂对烃损耗较小。NH_3的程序升温脱附(NH_3-TPD)表明,该催化剂表面碱性较强,活性较好。     

Pd-Pt-Ce/Al_2O_3催化剂在VOC净化处理中的催化性能

采用浸渍法制备Pd-Pt-Ce/Al_2O_3催化剂,考察贵金属Pd和Pt负载量、助剂种类及负载量、空速对催化甲苯燃烧活性的影响。结果表明,适宜的贵金属负载量和助剂可极大提高Pd-Pt/Al_2O_3催化剂活性,当Pd和Pt质量分数分别为0.05%和0.005%、助剂Ce质量分数为1%时,Pd-Pt-Ce/Al_2O_3催化剂在低温条件下表现出较好的催化性能。空速对催化剂的催化活性影响较为明显,适宜的空速低于20 000 h-1。     

用于丙烷催化燃烧的Pd_xPt_y-ZSM-5/Cordierite整体式催化剂

以ZSM-5分子筛、铝溶胶、硝酸钯、硝酸铂和水为原料制备分子筛浆料,采用真空抽提-一次涂覆法在堇青石蜂窝陶瓷载体表面制备出Pd_(x )Pt_y-ZSM-5/Cordierite整体式催化剂,考察了Pd负载量、ZSM-5分子筛的硅铝比和Pd/Pt质量比对整体式催化剂的丙烷催化燃烧性能的影响,并用超声波振荡、SEM、XRD、H_2-TPR和C_3H_8-TPD等手段对整体式催化剂进行了表征。当球磨时间为60 min,分子筛浆料固含量为38%时,整体式催化剂的涂层上载量可达到178 g?L~(-1),涂层脱落率低于0.5%。Pd_2Pt_3-ZSM-5/Cordierite整体式催化剂(贵金属总负载量为1.2g?L~(-1))对于丙烷的催化燃烧具有较好的催化活性(T_(50)=259℃,T_(90)=323℃)和稳定性,具有良好的工业应用前景,其中较低的ZSM-5分子筛硅铝比以及Pd和Pt之间的相互作用增加了对丙烷的吸附能力和表面活性氧物种的数量,从而提高了整体式催化剂的催化活性。     

The System Na2O-CaO-SiO2-H2O

A portion of the quaternary phase diagram for Na₂O-CaO-SiO₂-H₂O has been constructed. Plotting concentrations as their 10th roots allows compounds having solubilities which differ by several orders of magnitude to be represented on a single diagram. The compositional relationships among sodium-substituted calcium silicate hydrate, calcium-substituted sodium silicate hydrate, calcium bydroxide, a quaternary compound of approximate composition 0.25Na₂O · CaO · SiO₂· 3H₂O, sodium hydroxide monohydrate, and miscellaneous sodium silicate hydrates are presented. The quaternary diagram constructed shows the quaternary compound to exist in equilibrium with sodium-substituted calcium silicate hydrate and calcium hydroxide. Conditions in concrete pore solutions which favor the formation of this quaternary compound may also favor the occurrence of the alkali-silica reaction.     

Self-organized nano-crystallisation of BaF2 from Na2O/K2O/BaF2/Al2O3/SiO2 glasses

In glasses with the compositions (100 ? x)(2Na₂O·16K₂O·8Al₂O₃·74SiO₂)xBaF₂ (with x = 0 to 6), the glass transition temperature decreases with increasing BaF₂-concentration. Samples with x = 6 were thermally treated at temperatures in the range from 500 to 600 °C for 5–160 h. This leads to the crystallisation of BaF₂. The quantity of crystalline BaF₂ increases with increasing time of thermal treatment, while the mean crystallite size remains constant within the limits of error. The glass transformation temperature of partially crystallised samples increases with increasing crystallisation time and approaches a value equal to the temperature, at which the samples were treated. This is explained by the formation of a highly viscous layer enriched in SiO₂ which is formed during crystallisation. This layer acts as a diffusion barrier and hinders further crystal growth.     

复合固体超强酸SO42-/ZrO2-Al2O3催化合成乳酸正丁酯的研究

合成了几种不同Zr、Al原子比的SO42-/ZrO2-Al2O3复合固体超强酸,将其用于催化乳酸与正丁醇的酯化反应,均有较好的催化活性,尤以ZrAl=12的催化效果最好,经济性优于ZrO2超强酸催化剂.其最佳反应条件为酸醇摩尔比为13,催化剂用量为乳酸质量的10%,反应时间2～2.5h,酯化率达96.9%.该催化剂具有制备容易、催化活性高、不污染环境、可重复使用的优点.     

Prediction of Immiscibility Boundaries of the Systems K2O-SiO2, K2O-Li20-SiO2, K20-Na2O-Si02, and K2O-BaO-SiO2

In earlier work, a prediction method of the immiscibility boundary of a ternary silicate glass system was developed involving two known binary immiscibility boundaries and a measured immiscibility temperature of one ternary glass composition. In the present work, the method is extended to the case where one of the two binary immiscibility boundaries is not known and is applied as an example to ternary silicate systems containing K₂O. First, the immiscibility boundary of the system K₂O-SiO₂ is estimated by measuring the immiscibility temperatures of three glasses in the system K₂O-Li₂O (or Na₂O)-SiO₂. Using this result the immiscibility boundaries of the systems K₂O-Li₂O-SiO₂, K₂O-Na₂O-SiO₂, and K₂O-BaO-SiO₂ are estimated. The results agree reasonably well with the experimentally determined immiscibility temperatures at selected compositions.     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

Some Properties of the System Na2O-NaF-B2O2-H2O

It was first shown that the enamel slips which have the best suspnding characteristics contain equal amounts of Na₂O and B₂O₃ and at least a moderate amount of NaF. The solubilities of mixtures of Na₂O, NaF, and B₂O₃ were then investigated. The pH of these solutions and the primary crystalline phases separating on evaporation also were determined. The solubility data obtained at room temperature were summarized. When the solutions were evaporated, NaF was the first crystalline phase to separate from a large proportion of the mixtures investigated. It was concluded that the desirable handling characteristics of enamels whose mill liquors contain the proper proportion of Na₂O, NaF, and B₂O₃ are not due to the formation of complex salts but to the following combination of properties: (1) the presence of salts with a moderate solubility which changes very slightly with temperature, (2) a moderate pH of about 10 in a probably well-buffered solution, (3) a relatively stable crystalline material, NaF, as a primary phase, and (4) a secondary phase which crystallizes slowly with relatively little shrinkage.     

固体超强酸SO^2—4／TiO2催化合成尿囊素的研究

用固体超强酸SO42/TiO2为催化剂,以尿素和乙醛酸为原料合成了尿囊素。得到最佳条件为TiO2在1mo1·L-1H2SO4溶液中浸渍12h,再在600℃焙烧3h;尿素与乙醛酸摩尔比3.51,催化剂9％,时间3h,温度72℃～75℃,产率达57.4％。     

SELECTIVE CARBON MONOXIDE OXIDATION IN H2-RICH GAS STREAM OVER Co3O4/CeO2/ZrO2, Ag/CeO2/ZrO2, AND MnO2/CeO2/ZrO2 CATALYSTS

Activity and selectivity of selective CO oxidation in an H₂-rich gas stream over Co₃O₄/CeO₂/ZrO₂, Ag/CeO₂/ZrO₂, and MnO₂/CeO₂/ZrO₂ catalysts were studied. Effects of the metaloxide types and metaloxide molar ratios were investigated. XRD, SEM, and N₂ physisorption techniques were used to characterize the catalysts. All catalysts showed mesoporous structure. The best activity was obtained from 80/10/10 Co₃O₄/CeO₂/ZrO₂ catalyst, which resulted in 90% CO conversion at 200°C and selectivity greater than 80% at 125°C. Activity of the Co₃O₄/CeO₂/ZrO₂ catalyst increased with increase in Co₃O₄ molar ratio.     

Crystallization of zeolite L from Na2O-K2O-Al2O3-SiO2-H2O system

Zeolite L powder was prepared from the substrate mixture of Na₂O-K₂O-Al₂O₃-SiO₂-H₂O system at temperatures of 373-443 K. In order to investigate the factors which influence the synthesis outcome, a reference system which yields zeolite L in a reproducible manner was chosen and subjected to controlled changes in synthesis parameters. The crystalline zeolite L samples obtained were characterized by elemental chemical analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). It was established that phase purity, morphology, and the size of crystals of crystalline product were affected by molar ratios of the substrate, such as SiO₂/Al₂O₃, (K₂O+Na₂O)/SiO₂, Na₂O/(K₂O+Na₂O), and H₂O/(K₂O+Na₂O). Amorphous silica powder (Zeosil) was the preferred silica source, and the crystallization rate was promoted by introducing gel aging, seeding, and rapid heating rate.