稀土固体超强酸Gd3+-SO2-4/ZrO2催化合成乙酸正丁醋

采用乙酸、正丁醇为原料,以固体超强酸Gd3+-SO24-/ZrO2作为催化剂,催化合成乙酸正丁酯。用固体超强酸Gd3+-SO42-/ZrO2和SO24-/ZrO2进行催化活性对比试验,考察浸渍硫酸浓度、浸渍时间、焙烧温度对催化剂活性的影响以及原料酸醇比、反应时间、催化剂用量对酯化率的影响,从而确定固体超强酸的最佳制备条件。试验结果表明:在反应温度105～110℃,催化剂用量1.5g,n(正丁醇)∶n(乙酸)=2.5∶1,反应时间2.5h条件下,酯化率可达98.86%;催化剂重复使用效果明显;加Gd3+的固体超强酸的催化活性明显增强。     

Lewis酸型固体酸催化剂Ce-Ag-PW的制备、表征及催化酯化反应合成生物柴油性能研究

通过超声浸渍法，经Ce3+和Ag+协同改性磷钨杂多酸（HPW）制备了一种以Lewis酸性活性位为主的固体酸催化剂Ce-Ag-PW。采用X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、扫描电镜（SEM）、透射电镜（TEM）、热重（TG）、NH₃程序升温脱附（NH₃-TPD）、吡啶吸附红外光谱（Py-IR）和X射线光电子能谱（XPS）等表征手段对其物理化学性能进行了表征分析。并以Ce-Ag-PW为经甲醇和油酸酯化反应来合成生物柴油的催化剂，对其的催化活性和稳定性进行了研究。结果表明，Ce-Ag-PW具有高催化活性和稳定性，以其为催化剂，当甲醇与油酸的物质的量比为14: 1，催化剂用量为反应物总质量的2%，反应温度为65 ℃，反应6 h后，油酸的转化率即高达91%。固体酸催化剂在经过4次循环使用后，油酸的转化率仍可达到80.5%。Ce-Ag-PW的高催化活性和稳定性可归因于Ag+可置换HPW中的质子，以及Ce3+的强吸电子作用，使其由Br?nsted酸型催化剂转化为以Lewis酸型为主的催化剂。由于Br?nsted酸位易与酯化反应过程中生成的水发生水合反应而失活，因而Lewis酸位的形成有助于减少催化剂的失活现象发生。因此，当通过油酸与甲醇酯化反应合成生物柴油时，Ce-Ag-PW是一种具有高催化活性和稳定性的以Lewis酸性活性位为主的固体酸催化剂。      

钨钼混配型杂多酸盐催化剂上酯化反应条件的优化研究

以Na2WO4·2H2O和 Na2MoO4·2H2O为原料,通过硝酸酸化-乙醚萃取法制备了一种钨钼混配型杂多酸盐催化剂（Na4SiMoW12O40·xH2O）.应用X射线荧光光谱对合成的催化剂的元素组成进行了分析;通过红外光谱对其的官能团结构进行了分析;借助热重分析对其的热稳定性进行了研究.并以正丁醇和乙酸为反应物,研究了所制备的钨钼混配型杂多酸盐在催化酯化反应时的活性和稳定性.通过正交试验[L9（3）4]对影响乙酸正丁酯收率的关键影响参数进行了优化,包括催化剂与反应物的质量比、反应时间和温度、以及正丁醇与乙酸的摩尔比.结果表明：当反应时间为120 min,反应温度为90℃,催化剂用量为0.4 g,醇酸摩尔比为2∶1,酯化效果最好,达到93.24 wt%.     

Catalytic combustion study of soot on Ce0.7Zr0.3O2 solid solution

The Ce0.7Zr0.3O2 solid solution and CeO2 were prepared using the sol-gel method. The phase structure, crystallite sizes and the reducibility of the catalysts were characterized by XRD and H2-TPR techniques. XRD results indicated that Zr^4＋ had replaced part of Ce^4＋ to form a fluorite-like solid solution, which was favorable to obtain ultrafine nanoparticles. The ratio of main HE consumption for Ce0.7Zr0.3O2：CeO2 was 4.4：1.0, implying that the solid solution could improve the reducibility compared to the single CeO2. The Ce0.7Zr0.3O2 solid solution catalyst showed a sharp combustion peak at 397 ℃, which was 200 ℃ lower than that of the single soot. The good catalytic activity of the Ce0.7Zr0.3O2 was attributed to the formation of nano-CeO2-based solid solution, which enhanced the reducibility and then improved the combustion activity. As Ce0.7Zr0.3O2 could be easily reduced to Ce0.7Zr0.3O2-x meanwhile, after oxygenation, the Ce0.7Zr0.3O2.x was recovered to Ce0.7Zr0.3O2 completely. A catalytic combustion reaction mechanism was proposed： the Ce0.7Zr0.3O2 was reduced to Ce0.7Zr0.3O2-x by the reaction with carbon and then it was recovered to Ce0.7Zr0.3O2-x by the interaction with O2.     

固体超强酸S_2O_8~(2-)/TiO_2-WO_3的制备及其催化性能研究

用溶胶-凝胶法制备了固体超强酸S2O82-/TiO2-WO3,并对其进行了XRD与IR表征,用乙酸乙酯合成模型反应考察了其催化性能,系统研究了WO3的含量、焙烧温度等制备条件对S2O82-/TiO2-WO3性能的影响。实验表明:在(NH4)10W12O41.xH2O质量分数为5.0%、焙烧温度为500℃条件下通过溶胶-凝胶法制备的固体超强酸S2O82-/TiO2-WO3,其载体为微细且晶格不太完整的锐钛矿型TiO2,比表面积较大,具有比浸渍法制备的SO42-/TiO2更高的硫含量和更强酸性,并具有较高的催化酯化活性和稳定性,在反应条件为:醇酸摩尔比1.48∶1、催化剂用量为冰醋酸的6.0%、反应时间2.0h,乙酸转化率可达74.1%(不加分水器)。催化剂在无需任何再生的条件下重复使用,活性下降趋势平缓,显示良好的稳定性。     

钨源对碳化钨分散性及电催化性能的影响

碳化钨具有类铂催化性能、抗一氧化碳中毒和高导电性等特点,如能进一步改善其形貌、降低其尺寸及提高其比表面积,有望取代或部分取代贵金属催化剂.在以碳纳米管为载体,柠檬酸为络合剂的前提下,分别以偏钨酸铵、钨酸钠及仲钨酸铵为钨源,利用水热法制备了钨酸和碳纳米管复合物.采用温度控制程序,在空气气氛中于600℃对该复合物进行煅烧,得到氧化钨中间体,随之在氮气气氛中于950℃通入碳源进行碳化,得到碳化钨,发现以偏钨酸铵为钨源制备的碳化钨分散性最好,尺寸(约100 nm)最小,而以钨酸钠为钨源制备的碳化钨分散性和尺寸(约100~500 nm)次之,以仲钨酸铵为钨源制备的碳化钨分散性最差、尺寸(大于500 nm)最大.碳化钨载铂后的电催化测试结果表明,以偏钨酸铵为钨源制备的碳化钨作为载体担载铂颗粒,在硫酸体系中的峰电流密度(32.59 mA/cm2)优于钨酸钠(11.32 mA/cm2)和仲钨酸铵的(5.13 mA/cm2),在甲醇和硫酸体系中的峰电流密度(106.92 mA/cm2)优于钨酸钠(90.13 mA/cm2)和仲钨酸铵的(72.15 mA/cm2).      

稀土复合固体超强酸SO42-/ZrO2- 2% Gd2O3催化合成乙酸戊酯

制备了稀土复合固体超强酸SO₄2-/ZrO_2- 2%Gd₂O₃催化剂,并对以乙酸和戊醇为原料合成乙酸戊酯的反应条件进行了研究。研究表明:当戊醇与乙酸的摩尔比为1:1.5,反应时间为6h,反应温度为130℃,催化剂用量为6%戊醇的质量时,反应酯化率最高,酯化率可达98.93%,选择性高达100%。研究发现,该催化剂可重复使用,并能活化再生。      

铁矿石烧结中碱性熔剂对燃料燃烧的影响

 通过热重法和红外气相分析,考察了铁矿石烧结中碱性熔剂对煤粉燃烧速率和产物的影响,研究了熔剂对煤粉燃烧的催化机理,并定量分析了催化效果。试验结果表明：熔剂以氧化物的形态存在时,对煤粉的燃烧具有催化作用,但以碳酸盐的形态存在时不具有催化性。碳与空气的燃烧反应中,熔剂在低温下通过降低CO2分子的稳定性促进碳溶损反应的发生,高温下通过降低C-C键强度促进碳氧界面反应和碳溶损反应的发生。最后得到熔剂对碳燃烧的催化因子f=0.42。     

新型固体酸SO4^2-／MnO2／γ-Al2O3催化合成草酸二异戊酯

通过浸渍-焙烧法制备了新型固体酸SO4^2-／MnO2／γ-Al2O3催化剂,以草酸和异戊醇为原料合成了草酸二异戊酯,考察了催化剂的焙烧温度、催化剂用量、原料配比、反应时间、带水剂甲苯用量对反应的影响。最佳的反应条件为：催化剂焙烧温度500℃、催化剂用量1．5g,n（草酸）：n（异戊醇）=1：3、带水剂甲苯30mL、回流时间1．5h;在最佳反应务件下,草酸二异戊酯的收率可达99．6％。新型固体酸SO4^2-／MnO2／γ-Al2O3的催化活性高、产品收率高,后处理简便,无“三废”污染,符合节能环保、绿色催化的发展趋势。     

锑-溴酸钾-偶氮胭脂红B催化动力学光度法测定痕量锑

锑及其化合物是全球性污染物,易造成环境污染。但是,锑的催化效果差,测定锑的动力学光度法相对较少。在磷酸介质中,痕量锑(III)对溴酸钾氧化偶氮胭脂红B褪色反应有催化作用,据此,建立了动力学光度法测定锑的新方法。在两只比色管中分别加入适量的锑(III)样品溶液(催化反应,吸光度A)和同量的水(非催化反应,吸光度A₀),再分别加入0.7mL 4.0×10^-3 mol/L溴酸钾溶液、1.8mL 1.0mol/L磷酸和2.2mL 0.5g/L偶氮胭脂红B溶液,然后在90℃水浴中加热15min,在波长515nm处测定体系的吸光度A和A₀。实验结果表明,表观活化能Ea=33.6kJ/mol,锑的质量浓度在0.02~0.26μg/mL范围内与lg(A₀ /A)呈良好的线性关系,检出限为8.79×10^-9 g/mL。对复杂样品河泥的测定,先采用萃取的方法,规避了共存离子的干扰,再采用实验方法测定锑,结果的相对标准偏差(RSD,n=6)为3.3%~3.5%;加标回收率为96%~98%;并与原子荧光光谱法测定结果相吻合。     

锑-溴酸钾-偶氮胭脂红B催化动力学光度法测定痕量锑

锑及其化合物是全球性污染物,易造成环境污染。但是,锑的催化效果差,测定锑的动力学光度法相对较少。在磷酸介质中,痕量锑(III)对溴酸钾氧化偶氮胭脂红B褪色反应有催化作用,据此,建立了动力学光度法测定锑的新方法。在两只比色管中分别加入适量的锑(III)样品溶液(催化反应,吸光度A)和同量的水(非催化反应,吸光度A₀),再分别加入0.7mL 4.0×10^-3 mol/L溴酸钾溶液、1.8mL 1.0mol/L磷酸和2.2mL 0.5g/L偶氮胭脂红B溶液,然后在90℃水浴中加热15min,在波长515nm处测定体系的吸光度A和A₀。实验结果表明,表观活化能Ea=33.6kJ/mol,锑的质量浓度在0.02~0.26μg/mL范围内与lg(A₀ /A)呈良好的线性关系,检出限为8.79×10^-9 g/mL。对复杂样品河泥的测定,先采用萃取的方法,规避了共存离子的干扰,再采用实验方法测定锑,结果的相对标准偏差(RSD,n=6)为3.3%~3.5%;加标回收率为96%~98%;并与原子荧光光谱法测定结果相吻合。     

Steam effects over Pd/Ce0.67Zr0.33O2-Al2O3 three-way catalyst

Ceria-zirconia-alumina (CZA) solid solution was prepared by sol-gel method in the present study. 0.5 wt.% Pd supported on CZA was prepared by incipient wetness impregnation. The steam effects for CO and C3H8 oxidation, three-way catalytic activity and stoichiometric window property were studied. The light-off temperature of the CO oxidation reaction shifted to a lower temperature due to the water-gas shift (WGS) reactions. The oxidation of C3H8 was enhanced due to the steam reforming (SR) reactions. The steam promoted the C3H8 oxidation and NO reduction in three-way catalytic reaction. The amplitude of stoichiometric window was amplified by the addition of water to the feed stream.     

Enzymatic activity of pig heart mitochondrial malate dehydrogenase monomolecular films by surface exchange technique

A technique for studying the catalytic activity of enzymes spread as a film at an air-water interface, by exchanging the subphase under the film to remove unspread enzyme molecules, was developed, and its effectiveness was studied using surface-spread mitochondrial malate dehydrogenase. Mitochondrial malate dehydrogenase formed stable films which gave reproducible pi-A curves. The enzyme activity was measured by the oxidation rate of reduced nicotinamide adenine dinucleotide (NADH) in the presence of the substrate oxalacetic acid. Oxalacetic acid and NADH were injected into the subphase. The catalytic activity of the enzyme was dependent on the surface pressure of the film. The maximum catalytic activity was observed at a surface pressure of 4.4 dynes/cm. The activity was higher at intermediate surface pressures than at very low or very high surface pressures. A high bulk catalytic activity was observed in the unstable region, i.e., at a high degree of compression, of the film. The catalytic activity of the surface-spread enzyme was only a fraction of an equivalent amount of enzyme in solution.     

Ce-Zr-Tb Oxide Solid Solution as Key Material for Three-Way Catalyst

Ce-Zr-Tb oxide solid solution (CZT) was prepared using co-precipitation technique and characterized by means of X-ray diffraction( XRD), FT-Raman spectra, scanning electronic microscopy(SEM). Meanwhile, The palladium-only three-way catalyst(TWC) containing CZT was prepared by slurry coating and its catalytic activity was evaluated under the condition of simulated exhaust. The results show that CZT has cubic fluorite structure and the TWC containing CZT has higher catalytic activity including a wider operation window of air/fuel ratio and lower lighter-off temperature. CZT is suitable for the key material of a new generation of TWC.     

新型CeO2-Fe2O3联合催化剂用于催化CO还原NO

采用3种不同的方法合成新型的以Fe₂O₃颗粒为载体的Ce-Fe复合氧化物催化剂,探究不同制备方式的复合氧化物催化剂的催化CO还原NO性能,并通过X射线衍射(XRD)、拉曼光谱(Raman)、氢气-程序升温还原(H2-TPR)、X射线光电子能谱(XPS)表征来对催化剂进行探究。结果证明Ce-Fe复合氧化物具有较高的催化活性,硝酸水热法Ce-Fe复合氧化物在900℃时脱硝率可达到99%以上。XRD中显示硝酸水热样品中CeO₂峰向高角度偏移,并且晶格常数变小。Raman结果说明硝酸水热样品CeO₂的振动峰向左大幅度偏移,结合XRD说明硝酸水热法可以形成Ce-O-Fe固溶体。H2-TPR说明氧化还原性:硝酸水热法>硝酸浸渍法>普通浸渍法。XPS结果说明硝酸水热法形成的Ce-O-Fe固溶体可以促进Fe³⁺向Fe²⁺、晶格氧向吸附氧的转换,这体现出复合催化剂Ce、Fe之间的联合作用。在整个反应过程中Fe₂O₃作为载体可以提供大量晶格氧,Ce-O-Fe固溶体的存在决定了复合催化剂的高催化活性。     

Preparation and characterization of Ce_1-xNi_xO₂ as oxygen carrier for selective oxidation methane to syngas in absence of gaseous oxygen

A citric acid complex method was employed to prepare Ce/Ni mixed oxides with various Ce/Ni ratios useful for selective oxidation methane to syngas in the absence of gaseous oxygen,and the catalytic activity measurement was investigated in a fixed bed reactor at 800 oC.The prepared oxygen carriers were characterized by various characterization techniques such as TG-DSC,XRD and TPR.The results of TG-DSC indicated that the Ce1-xNixO2 precursor generated a stable phase after the heat-treatment at temperatures above 800 oC.The XRD characterization suggested that some Ce-Ni solid solution was formed when Ni2+ ions was incorporated into the lattice of CeO2,and it led to the generation of O-vacancy which could improve the oxygen mobility in the lattice of oxygen carriers.It was found that Ce0.8Ni0.2O2 gave the highest activity in the selective oxidation methane to syngas reaction,and the average methane conversion,CO and H2 selectivity reached to 82.31%,82.41% and 87.64%,respectively.The reason could be not only attributed to the fitting amount of NiO dispersed on the CeO2 surface and bulk but also to actual lattice oxygen amount increased in oxygen carrier.     

La-Hexaaluminate Catalyst Preparation and Its Performance for Methane Catalytic Combustion

The La-hexaaluminate catalysts with high performance ration method with the buffer solution of NH4HCO3 and NH4OH were synthesized by the modified controllable co-precipimixture as the precipitation agent. The physicochemical properties of catalysts were characterized by the means of BET, XRD, and TPR techniques. With methane catalytic combustion as the probe reaction, the catalytic performances were also tested on a fixed bed, continual flow system. The resuits show that it is a good method to obtain chemical homogeneous hexaaluminate materials by the buffer solution as the precipitation agent. The La-hexaaluminate can be formed at low temperatures ranging from 1050 to 1200 ℃. The cerium introduction plays a great role in the methane catalytic combustion on La-Mn hexaaluminate because of its high oxygen storage capacity property and the well synergic effect between Ce and Mn. However, the CeO2 appears in hexaaluminate through the XRD pattern, which reveals that Ce can not enter the crystal lattice position. Mn introduction improves the methane catalytic activity to a large extent due to its high redox property. When Mn atomic substitution amount for A1 is 2, the hexaaluminate shows the highest activity, and the catalyst possesses good H2 consumption and redox performance. Mn can easily occupy the hexaaluminate crystal position, which reveals that the Mn substitute La-hexaaluminate is a promising high temperature methane combustion catalyst with high activity and good stability.     

Preparation and characterizations of Ce-Cu-O monolithic catalysts for ethyl acetate catalytic combustion

Ce-Cu-O monolithic catalysts were prepared by using Ce0.9Cu0.1O1.9 solid solution or nitrate as precursors,and their catalytic performance for the combustion of ethyl acetate were studied.The catalysts calcined at a low temperature showed high catalytic activities.When calcined at high temperatures,the catalyst with Ce0.9Cu0.1O1.9 solid solution as precursor remained a high activity,while the catalyst with metal nitrates as precursors exhibited a suppressed reactivity.Therefore,the catalyst prepared with th...     

锡青铜中痕量磷的测定─—钼蓝萃取光度法

在盐酸介质中，以正丁醇、氯仿对锡青铜中微量磷进行钼蓝萃取，用分光光度法测量磷含量。磷含量为０．００５５％时，绝对误差为０．０００３。     

钐对Ni-B/SiO_2非晶态合金催化剂的催化性能及表面性质的影响

本文采用脉冲技术以己二腈气固相常压加氢为探针反应，研究了化学还原法制备的非晶态合金催化剂Ｎｉ－Ｂ、Ｎｉ－Ｂ－Ｓｍ的加氢活性及抗硫性能。并用Ｘ射线衍射（ＸＲＤ）、差示扫描量热分析（ＤＳＣ）、电感耦合等离子发射光谱（ＩＣＰ）、Ｘ射线光电子能谱（ＸＰＳ）、程序升温还原（ＴＰＲ）和程序升温脱附（ＴＰＤ）等手段对催化剂的结构、组成与表面性质进行了表征。实验结果表明，在此催化剂上该反应符合Ｌａｎｇｍｕｉｒ－Ｈｉｎｓｈｗｏｏｄ机理，活性中心座数为２。钐的加入可提高Ｎｉ－Ｂ非晶态合晶的热稳定性、催化活性和抗硫性。其原因可能是钐的给电子效应使合金的组成及表面性质发生了变化。