Ru-La2O3/γ-Al2O3催化CO选择性氧化反应

采用浸渍法制备了Ru-La2O3/γ-Al2O3复合氧化物催化剂,在固定床微反装置中考察了催化剂中稀土La的掺杂量、氧气量、原料气中水和CO2含量以及空速等工艺条件对Ru-La2O3/γ-Al2O3催化剂在CO选择性氧化反应中催化性能的影响.结果表明,Ru/γ-Al2O3催化剂添加质量分数10%的La2O3后的催化性能较好,且具有较好到抗湿性和抗CO2能力.在原料气组成为65%H2,25%CO2,1%CO,9%He,氧气的分压与CO分压相等,气体流速为100 mL/min和气体空速为10 000 h-1的条件下,在110～170℃进行CO选择性氧化,CO转化率大于99%,CO的出口浓度小于100 μL/L,满足了质子交换膜燃料电池对富氢气体中CO浓度的要求.     

稀土助剂Pr改性Cu/Zn/ZrO2合成甲醇催化剂的催化性能

采用共沉淀法制备了Cu/Zn/ZrO2催化剂,并以稀土元素镨(Pr)为助剂添加不同含量对其进行改性。通过XRD、H2-TPR、CO2-TPD等表征手段考察了稀土助剂Pr2O3的含量对Cu/Zn/ZrO2催化剂结构的影响。在固定床连续流动反应装置上考察了5种助剂含量改性的Cu/Zn/ZrO2催化剂对CO2加氢合成甲醇反应的催化性能。结果表明:加入稀土助剂后,催化剂的表面碱性明显增强,有效地促进了活性组分的分散,稳定了催化剂的活性中心。当Pr2O3的含量为3%时,Cu/Zn/ZrO2催化剂催化活性最佳。     

稀土基汽车尾气催化剂的研究 Ⅱ:稀土助剂对催化活性的影响

利用浸渍法制备含Ce-La稀土助剂改性的Pt-Rh三效催化剂,采用多种表征手段和高温抗硫水热老化实验,考察Ce-La稀土对Al2O3载体的热稳定性和催化剂活性的影响。结果表明:稀土La2O3的添加主要改善载体Al2O3的高温高比表面性能;CeO2的引入明显提高了CO和NO的催化转化活性,但对HC的转化几乎无影响;CeO2的添加也促进了催化剂的抗硫水热老化性能,并显著拓宽催化剂的三效窗口。主要归因于CeO2的添加促进了催化剂上CO、HC和NO间的相互作用以及CeO2所特有的储氧功能。     

助剂对二氧化碳加氢合成甲醇催化剂性能的影响

采用并流共沉淀方法制备了CuO-ZnO-ZrO2催化剂,并以金属氧化物为助剂对其进行了改性,在固定窗连续流动反应装置上考察了Ag2O和La2O32种助剂对CuO-ZnO-ZrO2催化剂催化CO2加氢合成甲醇反应性能的影响,及不同La2O3含量的CuO-ZnO-ZrO2的催化性能,采用X射线衍射(XRD)、H2-程序升温还原(H2-TPR)等方法对催化剂进行了表征。实验结果表明Ag2O和La2O3都可以提高CuO-ZnO-ZrO2催化剂的活性,而且添加6%La2O3(文中均指质量分数)的催化剂催化效果最好。添加Ag2O的催化剂中Ag作为活性中心参与CO2加氢合成甲醇的反应;对于La2O3改性的CuO-ZnO-ZrO2催化剂,适量La2O3有利于提高催化剂中CuO和ZnO的分散度。     

Ru1LaxOδ/γ-Al2O3 催化剂上CO选择性氧化去除性能及焙烧温度的影响

采用共浸渍法制备了一系列Ru1LaxOδ/γ-Al2O3复合氧化物催化剂,考察了La2O3的加入量、焙烧温度对CO选择性氧化反应性能的影响.添加La2O3的Ru1La10Oδ/y-AI2O3催化剂在110～170℃时能达到99%以上的CO转化率,选择性相对较高;镧的加入提高了催化剂的热稳定性.在500℃以前焙烧钌的晶粒大小变化不大,但是焙烧温度达到了600℃后.晶粒明显长大.催化剂活性也随之下降.     

Cu/Zn比对CuO/ZnO/ZrO_2催化CO_2加氢合成甲醇性能的影响

研究了不同Cu/Zn摩尔比对CO2加氢合成甲醇催化性能的影响。采用草酸凝胶共沉淀法制备了一系列不同Cu/Zn摩尔比的Cu O/Zn O/Zr O2催化剂,考察不同温度及Cu/Zn摩尔比对催化性能的影响,并结合X射线衍射(XRD)、N2物理吸附、程序升温还原(H2-TPR)和程序升温脱附(H2/CO2-TPD)技术对催化剂的结构和性质进行表征。结果表明:适宜的Cu/Zn摩尔比可以提高催化剂的反应性能。在513 K,2.0 MPa,n(H2)/n(CO2)=3/1和GHSV=4 800 h-1反应条件下,当R(Cu/Zn)=4时,Cu O/Zn O/Zr O2催化剂反应性能最好,CO2转化率高达17.8%,甲醇选择性高达67.8%。     

二氧化碳加氢直接合成二甲醚催化剂的研究进展

综述了CuO-ZnO-Al2O3/HZSM-5、CuO-ZnO-ZrO_2/HZSM-5、CuO-Fe2O3-ZrO_2/HZSM-5等催化剂、催化剂制备方法以及添加不同助剂对CO_2加氢直接合成二甲醚反应催化性能的影响,展望了CO_2加氢直接合成二甲醚催化剂未来的发展方向。     

添加氧化锆对二氧化碳加氢合成二甲醚催化剂Cu-ZnO-Al_2O_3/HZSM-5性能的影响

本文采用共沉淀沉积法及化学还原法制备了一系列的非晶态铜基催化剂,在常规固定床高压流动反应装置上对其CO2加氢合成二甲醚催化性能进行了研究。结果表明:添加ZrO2提高CO2转化率;经NH3-TPD表征可知,氧化锆能增强催化剂表面酸性。另外,催化剂中HZSM-5分子筛含量增大,能显著提高二甲醚的选择性。XRD分析表明,催化剂中各个组分分散均匀。     

非晶态催化剂Cu-ZnO-Al2O3MnO2/HZSM-5二氧化碳加氢制备二甲醚的研究

考察了MnO2对CO2加氢直接合成二甲醚催化剂Cu-ZnO-A12O3/HZSM-5的影响.采用固定床反应装置对CO2加氢直接合成二甲醚的活性进行考察,并运用XRD、HZ-TPR技术对催化剂结构及表面性质进行研究.实验结果表明,催化剂中加入MnO2能显著提高Cu-ZnO-Al2O3/HZM-5催化剂的稳定性,促进催化剂...     

均匀凝胶法制备CuO-ZnO-Al2O3-Cr2O3/HZSM-5催化二氧化碳加氢合成二甲醚

采用均匀凝胶法制备了CuO-ZnO-Al2O3-Cr2O3/HzSM-5催化剂,采用X射线衍射(XRD)、傅立叶红外光谱(FT-IR)和热重-差热分析(TG-DTA)进行了表征,并在固定床微型反应器中考察了反应温度、反应压力,CuO与ZnO质量比、Al2O3和Cr2O3的质量分数对CuO-ZnO-Al23-Cr2O3/HzSM-5催化剂在CO2加氢制备二甲醚反应中催化性能的影响.结果表明,在533 K,3MPa,H2与CO2体积比为3和反应混合气体积空速为1600 h-1的条件下,在CuO与ZnO质量比2,Al2O3和Cr2O3分别占催化剂质量的10.0%和1.5%的CuO-ZnO-Al2O3-Cr2 O3/HZSM-5催化剂作用下,CO2的单程转化率达到28.94%,二甲醚的选择性和收率分别为31.76%和8.76%,甲醇和二甲醚的总收率达到13.98%.     

低温余热驱动的合成氨吸收分离及其与冷凝分离的比较

合成氨分离普遍采用的冷凝分离法不仅能耗高,而且不利于氨合成压力大幅度降低。通过对吸收法分离合成氨过程的模拟,分析了驱动热温度、冷却水温度等条件的影响,并将其火用耗与冷凝分离法进行了比较。吸收分离法有利于利用低温余热,并且可在较大的冷却水温度范围内稳定操作;吸收法分离合成氨的火用耗低,不足冷凝法的三分之二;可利用低温余热代替冷凝法所需的昂贵的电能;虽然其冷却水耗量明显高于冷凝分离法,但其影响较小。在较低的合成压力下,吸收法的分离效果显著优于冷凝法,该过程应用于低压合成氨系统非常有利。     

分步氟化法合成3,4-二氟苯腈的研究

以3,4-二氯苯腈为起始原料,通过分步氟化,实现了高收率制备3,4-二氟苯腈的方法。相比于先前的报道,本工艺不仅收率提高,同时有效地控制了体系焦化、聚合、变黑等高温下不利因素的影响。     

Selective oxidation of lupeol by iodosylbenzene catalyzed by manganese porphyrins

Manganese porphyrin-catalyzed oxidation of lupeol by iodosylbenzene was achieved under mild conditions with low isolated yields but with remarkable selectivity, depending on the catalyst of choice. Mn(III) meso-tetraphenylporphyrin and Mn(III) meso-tetrakis(4-carbomethoxyphenyl)porphyrin provided an entry for the preparation of 3β,30-dihydroxylup-20(29)-ene (6–14% yields), whereas Mn(III) β-octabromo-meso-tetrakis(4-carbomethoxyphenyl)porphyrin led to 20-oxo-3β-hydroxy-29-norlupeol (6% yield), as single products. Unreacted lupeol was recovered in quantitative yield. The oxidative transformations at lupeol C20 or C30 take place with no need for protection of C3 hydroxyl moiety.     

Optimal removal of chlorolignin by ultrafiltration achieved by pH control

The ultrafiltration of chlorolignin fractionated from pine kraft pulp bleach effluent originating from the first caustic stage of the bleachery was studied at different chlorolignin concentrations and pH using polysulfone and sulfonated polysulfone membranes.

Retention of chlorolignin increased along with pH and increasing degree of dissociation of chlorolignin, which is a low molecular weight anionic polyelectrolyte. Retention stayed very high, about 99 %, at high pH values. This is remarkable as the chlorolignin molecule is considered to be much smaller than the pore size of the membranes used. The high electrostatic repulsion between the chlorolignin molecules and the membrane surface is obviously the reason for that. Flux reduction decreased remarkably along with pH increase as well.

The results confirm that sufficient chlorolignin removal can be achieved if its ultrafiltration is carried out at pH 10, which is approximately the pH of the first caustic stage in the bleach process.     

Desulphurization of coals by flash pyrolysis followed by magnetic separation

Removal of inorganic sulphur from a Turkish lignite (Tunçbilek) by flash pyrolysis and magnetic separation was investigated. Pyrite is slightly paramagnetic, however, its paramagnetism is not sufficient to affect the separation from coal. Depending on the pyrolysis temperature pyrite, FeS₂, converts to a variety of iron sulfides, among which the ferrimagnetic pyrrhotite, Fe₇S₈, forms at 973 K. In this study, the highest rate of sulphur removal was observed at 923 K. For the particle size of −0.1 mm, a 35% sulphur reduction was achieved by flash pyrolysis and this reduction was further enhanced to 48% by magnetic separation.     

化学修饰啤酒酵母菌对铀的吸附特性

以甲醛为交联剂, 将胱氨酸修饰到啤酒酵母菌(SC)上, 并采用海藻酸钠和明胶固定化, 得到一种新型的生物吸附剂--修饰啤酒酵母菌(MSC)。通过红外光谱(IR)分别表征了两种吸附剂的结构, 考察了其吸附铀的主要影响因素即溶液pH值、吸附时间等。结果表明: MSC细胞表面具有大量吸附铀的基团, MSC和SC吸附铀的最佳条件是: pH值为6.0, 相似文献   

Preparation of membranes by electropolymerization of pyrrole functionalized by a ferrocene group

The preparation of dense membranes by the electropolymerization of functionalized pyrrole (Py) by ferrocene units was carried out. The synthesis of N‐[3‐(pyrrol‐1‐yl)propyl]ferrocene‐1‐carboxamide (or [(ferrocenyl)amidopropyl] pyrrole, FAPP) is described. The electropolymerization of the monomer on platinum electrode and on stainless‐steel meshes was studied. The electroactivity of the grafted ferrocenyl group of the FAPP monomer was confirmed and the electrochemical properties of the electrogenerated FAPP film were investigated. The stability in potentiostatic and potentiodynamic modes of FAPP films was low and, to improve the latter, the electrochemical preparation of the copolymer between the pyrrole and the FAPP was performed. The electrochemical characterization of the copolymer showed that it was possible to control the oxidation state of both electroactive compounds of the film. The FAPP/Py copolymer was then prepared on stainless‐steel meshes to produce membranes, whose transport properties were electrochemically controllable. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3947–3958, 2004     

负载型双金属催化剂催化间苯二甲腈加氢制备间苯二甲胺

采用浸渍法制备活性炭负载Ni、Ru、Rh单金属及Ni-Ru、Ru-Rh双金属催化剂,考察反应温度、反应压力和m(催化剂)∶m(间苯二甲腈)对间苯二甲腈加氢制备间苯二甲胺的影响。结果表明,Ni-Ru/C催化活性高于Ru/C和Ni/C,通过分步浸渍法制备的Ni-Ru/C催化活性优于一步浸渍法。以甲醇和甲苯为混合溶剂,在m(催化剂)∶m(间苯二甲腈)=1∶20、反应温度120℃、反应压力4.0 MPa和1 000 r·min-1条件下,无需加入碱性抑制剂,间苯二甲胺收率最高可达97.78%。     

Comparison of the properties of clay polymer nanocomposites prepared by montmorillonite modified by silane and by quaternary ammonium salts

In this work, the silylation of sodium montmorillonite (Na⁺-Mt, Nanofil 757®) was performed using (3-aminopropyl)triethoxy silane (APTES). Different reaction conditions were used varying the reaction time and the amount of the aminosilane. Epoxy-based nanocomposites were prepared with different amounts of silylated Mt or commercial organically modified Mt intercalated with stearylbenzyldimethyl ammonium chloride (Nanofil 2®) and distearyldimethyl ammonium chloride (Nanofil 8®), respectively. The grafting/intercalation of the aminosilane inside the Mt interlayer spaces was studied by means of Fourier transform infrared (FTIR), X-ray diffraction (XRD), nuclear magnetic resonance (NMR) and thermogravimetric analysis (TGA). After isothermal curing at 90 °C the Mt epoxy nanocomposites were analyzed by means of XRD and dynamic mechanical analysis (DMA). The glass transition temperature of all prepared nanocomposites containing silylated Mt, is slightly higher than that of the neat epoxy (2 to 5 °C). In the presence of 1 to 5 m% of silylated Mt in epoxy matrix the storage modulus increases from about 5 to 15% at 25 °C, respectively, compared to the pristine epoxy matrix, while only 0–4% increase was observed for epoxy nanocomposites with commercial modified Mt.