海泡石-Al２Ｏ３混合载体对铂催化剂环己烷脱氢反应的影响

以三氧化二铝或海泡石(Sepiolite)-三氧化二铝混合物为载体,金属铂为活性组分,采用浸渍法分别制备了Pt／Ａl_２Ｏ_３、Pt／Ｓep-Ａl_２Ｏ_３催化剂,并考察了它们对环己烷脱氢反应的性能、抗硫性能及催化剂活性中心的影响。结果表明,Pt／Ｓep-Ａl_２Ｏ_３催化活性及抗硫性能均高于工业用Pt／Ａl_２Ｏ_３催化剂,同时增大了铂催化剂上的活性中心数及分散度。     

甲烷在Ｚ１１０y型催化剂上转化反应的宏观动力学及有效因子

在３.１２ＭＰａ（绝压）下,反应温度５５０～７５０℃,Ｈ_２Ｏ／ΣＣ＝２.０～４.０（摩尔比）,甲烷碳空速３０００～１００００ｈ^－１范围内,采用内循环无梯度反应器研究了Ｚ１１０y型催化剂上甲烷蒸汽转化反应的宏观动力学。以平行反应模型表示转化反应,用非线性参数估值法处理实验测得数据,得到ＣＯ和ＣＯ_２的生成速率方程为：r_ＣＯ＝７.８９６×１０^７exp（－４６８９６／ＲＴ）Ｐ^０.７_ＣＨ４Ｐ^０.５_Ｈ２Ｏ（１－β_ＣＯ）r_ＣＯ２＝１.９３７×１０^５exp（－３６２８１／ＲＴ）Ｐ^０.７_ＣＨ４Ｐ^0.９_Ｈ２ＯＰ^{－０.３５}_Ｈ２（１－β_ＣＯ２）建立了Ｚ１１０y五筋车轮型催化剂数学模型,推导出了计算其有效因子的解析计算式,由此得到该催化剂的有效因子为：０.１３～０.２１。     

ＴｉＯ２／ＳｉＯ２漂浮固定床多孔材料光催化氧化活性研究

以淀粉改性的聚甲基丙烯酸酯为多孔固定床,负载纳米ＴｉＯ_２／ＳｉＯ_２,对芳烃油、苯酚的光催化氧化活性进行测试,表明催化剂负载20%时最佳,光催化降解率达94%,重复使用有效活性达95%。     

ＣeＯ２对Cu-ＺnＯ催化剂性质和CO２加氢反应性能的影响

运用活性评价、ＸＲＤ、ＴＰＲ、ＣＯ_２-ＴＰＤ和积炭测定手段,探讨了CeＯ_２对Cu-ＺnＯ催化剂性质和CO_２加氢反应性能的影响。结果表明,催化剂经CeＯ_２改性后,CuＯ晶粒明显长大,致使催化剂还原难度增加;有利于CO歧化反应进行,使催化剂上积炭量增加;CO_２吸附量减少,CO_２加氢生成甲醇的活性增加。     

LB205低温变换催化剂的研制开发

介绍了新型CO低温变换催化剂的研制情况。研制的LB₂0₅型低温变换催化剂在≤5.0 MPa、温度185～250 ℃、V(汽)／V(气)=0.2～0.6、干气空速1 000～4 000 h^－1、干气中CO 体积分数2.5%～4.0％、CO₂体积分数16%～19％和余量为H₂+N₂条件下,催化剂CO变换率≥95％,400 ℃耐热2 h后CO变换率≥93％。满足工厂对低变催化剂的要求,尤其适合在节能型合成氨厂的低汽/气条件下使用。     

硫酸铵法中低品位锂瓷土矿提锂尾液铷铯提取技术

研究了硫酸铵法利用宜丰中低品位[w（氧化锂）<2.0%]锂瓷土矿制备碳酸锂后的提锂母液进一步提取铷铯等贵金属的技术路线。一次碳化提锂后的母液中还含有若干溶解的铷、铯等金属的硫酸盐类,采用分步结晶法,结晶母液降温析出过程中,在温度高的前段步骤析出的是铷铯等溶解度较低的矾盐,而温度低的后段步骤析出的是钾铵等溶解度高的矾盐,从而达到铷铯矾与铵钾矾等初步分离的目的。将成矾除铝阶段硫酸铝钾、硫酸铝铵等矾盐,以焙烧分解的形式继续分出硫酸钾和氧化铝。     

含水气氛下γ-Ａl２Ｏ３的物性变化

本文利用X-光衍射、吸附仪等手段研究了γ-Ａl_２Ｏ_３、Co-Ｍo-Ｋ／γ-Ａl_２Ｏ₃系耐硫变换催化剂和镁铝尖晶石样品在含水蒸汽气氛下，特别是水煤气变换气氛下γ-Ａl_２Ｏ₃的物性变化。给出了随温度和水／气比变化的γ-Ａl_２Ｏ_３晶相转化规律。     

SiO2负载磷钨酸铯盐催化剂上香兰素与1，2-丙二醇的缩合反应

制备一系列硅胶(SiO2)负载的磷钨酸铯盐催化剂,将其用于香兰素与1,2-丙二醇的缩合反应,合成香兰素丙二醇缩醛,考察催化剂中Cs+取代数、磷钨酸铯盐负载量、催化剂用量、1,2-丙二醇与香兰素摩尔比及反应时间对缩合反应的影响.结果表明:磷钨酸铯盐的Cs+取代数为2.5、负载量为40%时催化剂活性最高;在反应温度368 K、n(1,2-丙二醇)/n(香兰素)=2.4、催化剂用量占反应体系质量分数1.5%、带水剂苯的用量30 mL、回流反应3 h的条件下,香兰素的转化率达到86.6%,香兰素丙二醇缩醛的选择性为100%.     

钛铝复合氧化物载体的制备及应用

本文评述了ＴiＯ_２-Ａl_２Ｏ_３复合氧化物的制备方法,介绍了ＴiＯ_２-Ａl_２Ｏ_３复合氧化物作为催化剂载体应用于工业生产的现状。     

稀土双膦酸酯配合物和稀土氯化物对Mannich反应的催化作用

研究了Dy(OTf)₃、DyCl₃和稀土双膦酸酯配合物{ ［Dy(OTf)₂L₂(H₂O)₂］(OTf)(CH₃CN)}［L=(iPrO)₂P(O)CH₂P(O)(iPrO)₂］ 等对Mannich 反应的催化作用,发现以Dy(OTf)₃为催化剂时,收率为54%,［Dy(OTf)₂L₂(H₂O)₂］(OTf)(CH₃CN)的收率仅为8%,DyCl₃收率达47%。研究了12种稀土金属氯化物对Mannich 反应的催化作用,其中,ErCl₃催化剂的收率最高,达到61%。     

Penetration of alkali atoms throughout a graphene membrane: theoretical modeling

Theoretical studies of penetration of various alkali atoms (Li, Na, Rb, Cs) throughout a graphene membrane grown on a silicon carbide substrate are reported and compared with recent experimental results. Results of first principles modeling demonstrate a rather low (about 0.8 eV) energy barrier for the formation of temporary defects in the carbon layer required for the penetration of Li at a high concentration of adatoms, a higher (about 2 eV) barrier for Na, and barriers above 4 eV for Rb and Cs. Experiments prove migration of lithium adatoms from the graphene surface to the buffer layer and SiC substrate at room temperature, sodium at 100 °C and impenetrability of the graphene membrane for Rb and Cs. Differences between epitaxial and free-standing graphene for the penetration of alkali ions are also discussed.     

常温常压催化氧化法处理炼油废碱液试验研究

废碱液是石油化工行业排放的含高浓度CODCr、硫化物和少量挥发酚的高毒碱性废水。通过添加FeSO4和NaOH对炼油废碱液进行空气氧化,可使大部分硫化物转化为硫代硫酸盐、亚硫酸盐和硫酸盐,并使CODCr和挥发酚浓度有一定程度的降低。试验结果表明:在反应温度为60℃时,FeSO4和NaOH的投加量均为30%(实际投药量占理论投药量的比例),反应32h,污染物的去除效果最好。此时,硫化物、CODCr和挥发酚的去除率分别为95.15%、17.05%和15.57%;废碱液由混浊变得清澈透明,颜色由棕褐色变成淡黄色,臭味完全消失。     

Electrochemical properties of alkali bis(trifluoromethylsulfonyl)amides and their eutectic mixtures

Densities, viscosities and ionic conductivities of single salts and the binary eutectic mixtures of alkali bis(trifluoromethylsulfonyl)amides, MTFSAs (M = Li, Na, K, Rb, Cs), were measured in the temperature range of 413-573 K. Cyclic voltammetry revealed that the binary eutectic melts have wide electrochemical windows of 5.0-6.0 V. It was found that alkali metals reversibly deposit on a nickel electrode at the cathode limit potentials. The order of the deposition potential was determined to be Na > Li > (K, Rb, Cs).     

果胶/AMP-Zn微球的制备及对Cs 的吸附性能

采用溶胶-凝胶法,以Zn2+为交联剂,将磷钼酸铵(AMP)通过静电注射装置包埋于果胶中,制备了果胶/AMP-Zn微球吸附剂,用于放射性废水中Cs~+的去除。系统探讨了不同pH、吸附剂质量、接触时间、Cs~+质量浓度、温度及共存离子对果胶/AMP-Zn去除Cs~+的影响,并利用SEM、FTIR和XPS分析了吸附机理。结果表明:果胶/AMP-Zn可在pH=3~11内使用,耐酸碱性能良好,且在25℃、pH=5、Cs~+质量浓度为120 mg/L、吸附剂质量为0.05 g、接触时间为330 min的条件下,吸附剂的吸附量为41.837 mg/g;共存离子K+、Na+、Li+、Ca2+和Mg2+对Cs~+的吸附影响不大,说明该吸附剂具有较好的吸附选择性;热力学和动力学研究结果表明:此吸附过程符合Freundlich等温吸附模型和准二级动力学模型,且是一个自发放热的过程。果胶/AMP-Zn吸附Cs~+的吸附机理可能是Cs~+与AMP上的NH4+发生离子交换作用。     

铯-铷-钒系低温硫酸催化剂上SO_2氧化反应速率的机理解释

以碱金属盐为助催化剂的铯 -铷 -钒系硫酸催化剂 ,在 380～ 5 2 0℃下 SO2 氧化反应机理为三步催化反应 ,并推导出其动力学机理模型 :r=k1P1/ 2O2k2 +k3 PSO3 +PSO3 PSO2(1- PSO3 PSO2 P1/ 2O2 KP)。采用内循环无梯度反应器测定了SO2 氧化反应动力学数据 ,并利用 Powell法对动力学模型进行参数估值 ,得到 :k1=0 .15 2 exp(- 6 2 0 73/ RT) ,k2 =8.18exp(- 2 384/ RT) ,k3 =0 .2 2 1exp(- 18949/ RT)。方差分析表明 ,在显著性水平 0 .0 1下 ,三步反应机理模型对反应速率实验值拟合较好 ,标准偏差为 0 .2 42     

甲醇钠催化地沟油制备生物柴油研究

以浓硫酸为催化剂,高酸值地沟油与甲醇酯化反应降酸的最优工艺条件为:n(甲醇):n(地沟油)=9:1,m(浓硫酸):m(地沟油)=1.1％,反应温度60℃,反应时间5h.制备生物柴油的最优工艺条件为:以甲醇钠为催化剂,反应时间2h,反应温度65℃,n(甲醇):n(地沟油)=7:1,m(甲醇钠):m(地沟油)=0.8％.制...     

Methanol adsorption and dehydration on alkali metal exchanged NaY zeolites

FT-IR spectroscopy has been applied in a study of methanol adsorption on M^INaY zeolites (M=Li, K, Rb, Cs). Coordinatively and/or hydrogen bonded methanol was registered in the temperature range 300–473 K. Dehydration of methanol to dimethyl ether occurred at 573 and 623 K. It was found that the activity of the catalyst for methanol dehydration strongly depends on the kind of alkali metal cation, and well correlates the IR data relative to methanol adsorption.     

The possible use of alkali metal modified NbMCM-41 in the synthesis of 1,4-dihydropyridine intermediates

In this work we have prepared the catalysts containing all alkali metals (from Li to Cs) supported on mesoporous niobosilicate molecular sieve, NbMCM-41, and for comparison also loaded on silicate MCM-41. The materials were characterised by N₂ adsorption, XRD, and test reactions (acetonylacetone cyclisation and Knoevenagel condensation). It has been found that niobium located in the mesoporous material plays a role of structural promoter which prevents the solid from the disordering caused by the treatment with alkali metal solution. Moreover, it changes the catalytic properties of basic centres generated by alkali metal loading in relation to those observed for alkali metals supported on silicate MCM-41. Rb/NbMCM-41 has been proposed as active and selective catalyst in the condensation of benzaldehyde and different substituted benzaldehydes with ethyl acetoacetate towards the synthesis of intermediates in the preparation of some dihydropyridines.     

Alkali metal modified nano-silicalite-1: an efficient catalyst for transesterification of triacetin

Nanocrystalline Silicalite-1 was synthesized by conventional hydrothermal method and transformed into efficient solid base catalyst by modification with alkali metals like lithium, potassium and cesium. The synthesized and modified catalyst was characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption/desorption, Infra-red spectroscopy, thermogravimetry and basicity determination. The catalysts were tested for transesterification reaction of short triglyceride triacetin with methanol. 1–3 wt% alkali metal ions have been loaded on nano Silicalite-1 and used for transesterification reaction. Among the tested catalyst, 3 % potassium loaded Silicalite-1 (KS-3) showed highest reactivity giving 94 % triacetin conversion, and 98 mol% selectivity for methyl acetate. Reaction parameters such as triglyceride/alcohol molar ratio, catalyst amount, time and temperature were optimized with KS-3 catalyst. Kinetic studies were also done and found that transesterification of triacetin follows first order dependence.     

Cs-Sb_2O_5/SiO_2催化剂用于合成丙烯酸甲酯

以SiO2为载体,在其上负载碱金属Cs和Sb2O5作为活性组分制备出Cs-Sb2O5/SiO2型固体碱催化剂,经扫描电镜分析能谱分析(SEM/EDS)负载量Sb质量分数为10.06%,Cs质量分数为8.84%。使用该催化剂在固定床微反色谱装置上进行了催化醋酸甲酯一步法合成丙烯酸甲酯的工艺研究,通过色质联用仪确定其产物为丙烯酸甲酯。研究结果表明:当醋酸甲酯与甲醛的摩尔比为3∶1,空速在4—5h-1,反应温度在390℃时合成效果较好,丙烯酸甲酯的收率可达47.6%。