A comparison of rates of disproportionation and transalkylation of m-xylene

The relative rates of toluene transalkylation, disproportionation and benzene transalkylation of m-xylene over a catalyst consisting of 72% HY zeolite, 18% β-AlF₃ and 10% (all w/w) Cu have been studied at a temperature of 723K, reciprocal space velocity of 352 g h^?1 mol^?1 and at total pressures varying between 101 and 911.93 kPa. The catalysed disproportionation of m-xylene is fastest and this has been explained in terms of the greater basicity of m-xylene over either benzene or toluene, whereas the catalyst is acidic. Thus m-xylene would be expected to adsorb more strongly on the catalyst.     

正丁烷异构化催化剂的制备及其反应的研究

制备了一系列担载贵金属Pt的分子筛催化剂，评价了不同载Pt量对催化剂活性的影响。分子筛Pt含量的变化对反应结果影响很大，确定了载Pt量为催化剂总量的0．2％Pt/HZSM-5催化剂，能使正丁烷转化率＞40％，异丁烷选择性＞80％，同时考虑了反应温度，反应压力和H2／nC4^0对正丁烷异构化反应转化率及选择性的影响，结果表明：反应温度350－450℃，反应压力1．0－2．0MPa;H2/nC40－1．3等工艺条件较适合于正丁烷异构化反应，担载贵金属Pt的分子筛型催化剂对正丁烷异构化反应是一种很理想的催化剂。     

ZSM-35分子筛催化正丁烯骨架异构的反应性能及失活再生

采用高硅铝比ZSM-35分子筛催化剂,在固定床连续反应器中进行了正丁烯骨架异构化稳定性实验,并采用氧气烧炭再生,利用TPO、BET、NH3-TPD、Py-IR对新鲜催化剂、不同反应时间后及再生的催化剂进行表征,研究了积炭对催化剂活性的影响。结果表明,正丁烯转化率为45%时,异丁烯选择性为95%,经过390 h的运行,异丁烯的收率仍能达到32%,该催化剂具有良好的稳定性及选择性,且再生性能良好。催化剂上积炭主要在反应初期形成,沉积在微孔内,且优先发生在强酸中心上,主要为难以烧除的类石墨炭。     

ZSM-35分子筛催化剂用于正丁烯骨架异构的反应性能及失活再生研究

采用高硅铝比ZSM-35分子筛催化剂,在固定床连续反应器中进行了正丁烯骨架异构化稳定性试验,并采用氧气烧炭再生,利用TPO、BET、NH3-TPD、Py-IR等技术,对新鲜催化剂、不同反应时间后及再生的催化剂进行表征,研究了积炭对催化剂活性的影响。结果表明：正丁烯转化率为45%时,异丁烯选择性为95%,经过390 h的运行,异丁烯的收率仍能达到32%,该催化剂具有良好的稳定性及选择性,且再生性能良好。催化剂上积炭主要在反应初期形成,沉积在微孔内,且优先发生在强酸中心上,主要为难以烧除的类石墨炭。     

1-Hexene Isomerization Over Nano-crystalline Zeolite Beta: Effects of Metal and Carrier Gases on Catalytic Performance

Zeolite Beta crystals in nanometer size (about 44 nm) were hydrothermally synthesized and its catalytic activities with and without Pt impregnation were studied for 1-hexene isomerization in presence of different carrier gases, namely, hydrogen, nitrogen and carbon dioxide and also in the absence of carrier gas at reaction temperatures of 473–573 K and 0.1 MPa. General observation for all the cases was that with reaction temperature, hexene conversion increased, however, total isomer selectivity dropped. With temperature skeletal isomerization increased at the cost of double bond shift isomerization. Observed product distribution has been explained on the basis of zeolite structure and crystal size. Catalyst performed better in nitrogen than in hydrogen or carbon dioxide as carrier gas. Nevertheless, catalyst life was shorter with nitrogen as carrier gas than that with hydrogen.     

分子筛复合膜的结构类型及结构模型设计

对沸石复合膜的结构类型作了综述,指出各类沸石膜的性能缺陷,设计了新型超微沸石粒子充填－分散型分子筛复合膜的结构,介绍了其工艺方法。     

碱处理对X沸石孔结构影响的研究

研究了X型沸石经碱溶液处理后介孔的形成,考察了碱溶液浓度、碱处理温度和时间对形成介孔的影响.并采用ICP、N2吸附-脱附、SEM、XRD等进行表征.结果表明:碱处理抽提沸石骨架上的硅使处理后样品硅铝比发生变化,从而改变了X型沸石的性能;浓度为0.05 mol·L-1的NaOH溶液70℃下处理30 min是形成介孔的最佳条件,在此条件下形成介孔孔容为0.24 cm3·g-1,孔径分布为2.3～8 nm的介孔,比表面积从处理前的352.69 m2·g-1升高到443.11 m2·g-1.而碱处理温度低于70 ℃,沸石骨架上硅不易抽提;碱溶液浓度高于0.05 mol·L-1或碱处理时间长于30 min,X型沸石则易形成大孔.样品经亚甲基蓝吸附测试,证实X型沸石碱处理后确实形成了一定量的介孔.     

络合-溶剂热法制备钯基催化剂及其催化氧化间二甲苯性能

通过采用络合-溶剂热法、水热法和浸渍法三种方法制备了负载量为0.6%（质量分数）的Pd/Al₂O₃催化剂，重点考察不同制备方法催化氧化间二甲苯作为典型的挥发性有机化合物的能力。结果表明：络合-溶剂热法制备的Pd/Al₂O₃-com催化剂催化氧化间二甲苯的能力最强，间二甲苯体积分数为0.002%时完全转化温度（T₁₀₀）为130℃，低于浸渍法制备催化剂的完全转化温度30℃。对Pd/Al₂O₃催化剂进行了比表面积（BET）、X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电镜（SEM）等表征分析，发现Pd/Al₂O₃-com中Pd主要以还原态Pd⁰高度分散于载体表面，而另两种方法制备的催化剂均有明显的Pd²⁺存在。结合性能测试及表征分析，表明络合-溶剂热法制备的Pd/Al₂O₃-com催化剂活性组分Pd的高度分散，增强了催化活性，可满足高浓度间二甲苯、宽气体体积空速条件下催化氧化脱除间二甲苯的工业应用要求。     

磷改性对Y型分子筛结构及催化性能的影响

采用原位晶化法制备含磷的PY型分子筛,并用X射线衍射(XRD)、程序升温氨脱附(NH3-TPD)等测试方法对磷改性的PY型分子筛进行了表征。结果表明,磷的引入不影响分子筛的晶形,分子筛的相对结晶度变化很小,晶胞收缩,晶胞常数减小;分子筛的硅铝摩尔比(简称硅铝比,下同)增大。适量磷(质量分数0.1%)的引入降低了催化剂的总酸量、弱酸量和强酸量,增加了催化剂的中强酸的酸量。因此,可以有效调变催化剂的酸量和酸强度。在小型固定流化床装置上对催化剂的反应性能进行评价,发现与Y型催化剂相比,PY型催化剂在总液收提高了2.35%的条件下,使重油产率降低了0.32%,焦炭产率降低了0.22%,同时汽油收率和轻油收率分别提高了1.75%和1.68%,表现出很强的重质油转化能力和良好的裂化产物选择性。     

硅源对纳米A型沸石结构及形貌的影响

分别以硅溶胶和正硅酸乙酯为硅源,采用水热法合成了纳米A型沸石.研究了不同硅源对纳米A型沸石结构和形貌的影响.应用X射线衍射仪(XRD)、能量色散X射线光谱仪(EDX)、激光粒度分布仪(DLS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱仪(FTIR)等测试手段对产物进行表征.结果表明:使用硅溶胶作为硅源的产物结晶度较高,Si/Al=1.37,颗粒粒径分布为140～ 460 nm;而使用正硅酸乙酯作为硅源的产物结晶度较低,Si/Al=1.15,颗粒粒径分布为60～150 nm.     

Adsorption of REEs from Aqueous Solution by EDTA-Chitosan Modified with Zeolite Imidazole Framework (ZIF-8)

Chitosan (CS) modified with ethylenediamine tetraacetic acid (EDTA) was further modified with the zeolite imidazole framework (ZIF-8) by in situ growth method and was employed as adsorbent for the removal of rare-earth elements (REEs). The material (EDTA–CS@ZIF-8) and ZIF-8 and CS were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), and nitrogen adsorption/desorption experiments (N₂- Brunauer–Emmet–Teller (BET)). The effects of adsorbent dosage, temperature, the pH of the aqueous solution, contact time on the adsorption of REEs (La(III), Eu(III), and Yb(III)) by EDTA–CS@ZIF-8 were studied. Typical adsorption isotherms (Langmuir, Freundlich, and Dubinin–Radushkevich (D-R)) were determined for the adsorption process, and the maximal adsorption capacity was estimated as 256.4 mg g⁻¹ for La(III), 270.3 mg g⁻¹ for Eu(III), and 294.1 mg g⁻¹ for Yb(III). The adsorption kinetics results were consistent with the pseudo-second-order equation, indicating that the adsorption process was mainly chemical adsorption. The influence of competing ions on REE adsorption was also investigated. After multiple cycles of adsorption/desorption behavior, EDTA–CS@ZIF-8 still maintained high adsorption capacity for REEs. As a result, EDTA–CS@ZIF-8 possessed good adsorption properties such as stability and reusability, which have potential application in wastewater treatment.     

Infrared Multiphoton Induced Isomerization of cis-3,4-Dichlorocyclobutene. III. Pressure Dependence of the Yield

The multiphoton induced isomerization of cis-3,4-dichlorocyclobutene (DCCB) was studied as a function of pressure. Three experiments indicated the existence of a nonthermal mechanism at neat pressures below 60 mtorr. These were: (i) the leveling off of the fractional yield of isomerization products at low pressures; (ii) the absence of dissociation products from 2-iodo-2-methyl propane, which served as a chemical thermometer in the presence of a large excess of DCCB; and (iii) a break in the power-law dependence of the optoacoustic signal produced by neat DCCB. The increased yield at higher DCCB pressures is believed to be due partly to a thermal reaction and partly to increased absorption caused by rotational or vibrational hole filling. Optoacoustic measurements also showed that at constant fluence the absorbed energy was greater for long, low intensity pulses, as might be expected for inhomogeneous excitation. However, the present experiments did not reveal an intensity dependence of the reaction yield. Addition of argon as a buffer gas monotonically decreased the yield, indicating that vibrational quenching more than offsets any hole-filling effects.     

沸石的结构特征及在给水处理中的应用

在论述沸石结构的基础上,讨论了利用沸石的吸附和离子交换性质去除水中有机物、氨氮、氟离子及硬水软化技术,并提出生物沸石法将使沸石的应用更加广泛。沸石将为过滤和生物过滤提供一种新的材料。     

Diethoxysilane formation by the disproportionation of triethoxysilane over heat-treated calcium hydroxide

The disproportionation of triethoxysilane was carried out in a fixed-bed flow reactor over the solids obtained by heat-treating calcium hydroxide at various temperatures. In the disproportionation, the reaction proceeding to completeness to afford silane and tetraethoxysilane occurs to far lesser extent: predominantly diethoxysilane is obtained together with tetraethoxysilane. Dimethoxysilane is obtained by the disproportionation of trimethoxysilane also over the heat- treated calcium hydroxide. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and Properties of Carbon/Zeolite Composites with Corrugated Structure

Composites of carbon/zeolite with corrugated structures were prepared by carbonization, steam activation and/or hydrothermal treatment of corrugated paper. No zeolite formation resulted from conventional hydrothermal treatment of the carbonized and activated samples in NaOH solution but zeolite Na P1 was formed by addition of silica to the solution. By contrast, zeolites Na P1 and Na A were formed by the in-situ crystallization method (hydrothermal treatment of solid samples impregnated with NaOH solution). With higher impregnating NaOH concentrations, longer reaction times and higher reaction temperatures, the products changed to sodalite- and cancrinite-type compounds. Hydrothermal treatment was effective in increasing the specific surface area of the products by the formation of zeolite from amorphous calcium aluminosilicate, and also increased the mechanical strength by gluing together the carbon fibers in the samples. The resulting samples showed enhanced adsorption for polar molecules such as ammonia, water vapor and methanol due to the formation of composites of activated carbon with hydrophilic zeolites.     

Synthesis of Open Zeolite Structures from Mixtures of Tetramethylammonium and Benzylmethylalkylammonium Cations: A Step Towards Driving Aluminium Location in the Framework

Three bulky organic cations, benzylmethylpyrrolidinium (BMP), (S,S)-2-hydroxymethyl-1-benzyl-1-methylpyrrolidinium (BML) and benzylmethylhexamethyleniminium (BMH), were used in combination with the small cation tetramethylammonium (TMA) in the synthesis of zeolite materials. Two of them are distinguished by the number of carbon atoms forming the cyclic amine, which varies from 4 in BMP to 6 in BMH. In addition, a –CH₂–OH group has been introduced in the carbon atom belonging to the amine ring next to the nitrogen atom, to originate a chiral molecule, BML, the third SDA used in this work. It has been found that the combination of the small TMA with those three bulkier SDAs, promotes the crystallization of zeolite structures that contain cages and channels. BMP leads to the crystallization of the 10-ring zeolite ferrierite, where TMA is located inside the ferrierite cage. If the size of the N-cyclic amine moiety increases, the resulting cation cannot be accommodated in the relatively narrow 10-ring channels of ferrierite, and in these cases the zeolite MCM-22 crystallizes. This zeolite contains large cages whose cross section is delimited by a 12-ring, where both BMH and BML can be easily accommodated. In this system, cage-like, chlatrasil type structures often co-crystallize with the open structures, evidencing that an appropriate balance between TMA and the bulky SDA is required to achieve the crystallization of open-frameworks. When BMP is used, mixtures of structurally related ferrierite and cage-like RUB-10 are obtained if an excess of TMA is present in the synthesis gel, while MCM-22 crystallizes together with the structurally related cage-like MTN phase.     

紫外照射下聚丙烯结晶结构和力学性能变化的研究

研究了添加α成核剂聚丙烯(α-PP)、β成核剂聚丙烯(β-PP)和纯聚丙烯3种材料在紫外辐射下的聚集态结构变化、力学性能和表观变化的情况.结果表明:与其他两种聚丙烯相比,β-PP具有较高的抗降解能力;3种聚丙烯在紫外光辐射初期结晶度都有所提高,但随着辐射时间的增加,总结晶度都呈下降趋势;β-PP中的β相的结晶度先增后减,而α相的结晶度先减后增,312 h后基本保持不变.     

不同晶化温度对ZSM-5分子筛结构和形貌的影响

以四丙基溴化铵（TPABr）为结构导向剂,采用水热法制备了ZSM-5分子筛。利用XRD、FT-IR及SEM等表征手段研究了不同晶化温度对样品结构、形貌和粒径大小的影响规律。当晶化温度由95℃升高至175℃,结晶度由48．3％提高到95．1％,产物粒径分布更为均匀。晶化温度为195℃时,结晶度减至79．7％,部分粒径增大且不规则。由此可见,通过升高晶化温度可以提高ZSM-5分子筛的结晶度和粒径的均匀性,但是过高温度会使分子筛发生溶解-再结晶过程,部分转化成SiO2。