NaY沸石的酸脱铝

对ＮａＹ沸石直接用酸脱铝进行了系统研究。考察了草酸、柠檬酸、酒石酸、磺基水杨酸和硫酸等分别直接作用于ＮａＹ沸石的脱铝效果，从脱铝剂用量、脱铝剂的加入速度、反应时间、反应温度等几个方面考察了反应条件对沸石酸脱铝的影响，找到了几种酸的最佳脱铝条件。提出了ＮａＹ沸石酸络合脱铝的机理。

纳米ZSM-5分子筛的酸脱铝改性及其催化萘和甲醇的烷基化反应性能

分别采用盐酸、草酸、柠檬酸对晶种引导的无模板剂合成的纳米ZSM-5分子筛进行脱铝改性,利用XRD、N2吸附-脱附、27 Al NMR、XRF、NH3-TPD、Py-IR等方法对其进行表征,并考察了不同种类的酸脱铝对ZSM-5分子筛的结构、酸性及其催化萘与甲醇的烷基化反应性能的影响。结果表明,盐酸、柠檬酸与草酸均可脱除分子筛的骨架铝和非骨架铝,但3种酸对分子筛的脱铝程度不同。纳米ZSM-5分子筛经酸脱铝后,在脱除了部分强酸中心的同时产生了一定比例的二次介孔,有效地改善了反应物和产物的扩散性能,使催化萘与甲醇的烷基化反应的萘转化率、2,6-二甲基萘(2,6-DMN)选择性和产物中n(2,6-DMN)/n(2,7-DMN)均有不同程度的提高,并且表现出更强的抗失活能力。

酸脱铝改性的HZSM-12分子筛催化合成2,6-二甲基萘的研究

分别用盐酸和柠檬酸对HZSM-12分子筛进行脱铝改性。通过XRD、XRF、N2物理吸附、TP的方法对脱铝改性前后HZSM-12分子筛的结构及酸性进行表征,并研究了脱铝改性HZSM-12分子筛催化合成2,6-二甲基萘反应性能的影响规律。结果表明,盐酸脱铝的同时可以脱除分子筛的强酸中心和弱酸中心,10 mol/L的HCl脱铝还会伴有脱硅现象发生,导致微孔体积减少。而柠檬酸则优先脱出强酸中心,对于弱酸中心影响不显著。脱铝改性的HZSM-12分子筛强酸中心数量减少,对萘和甲醇烷基化反应的催化活性有所降低,但是烷基化产物中2,6-DMN/2,7-DMN比显著提高,而且改性后的HZSM-12分子筛表现出更强的抗失活能力。

丝光沸石酸脱铝及吸附性能研究

对丝光沸石直接酸脱铝进行了研究。考察了盐酸和草酸分别作用于丝光沸石的脱铝效果。通过N2 吸附等温线的测定 ,考察了脱铝丝光沸石的吸附性能。实验结果表明 ,酸处理可以明显提高丝光沸石的Si/Al比 ,草酸的脱铝效果更好 。

丝光沸石水蒸气/酸浸渍脱铝的多核固体核磁共振研究

采用 1 H,2 9Si,2 7Al魔角旋转固体核磁共振 ( MAS NMR)及 1 H-2 9Si交叉极化 ( CP)技术研究丝光沸石水蒸气 /酸浸渍脱铝过程中各种铝物质的结构与性质 .结果表明 ,丝光沸石上骨架铝原子在水分子作用下 ,生成非骨架四配位铝物质 [Al( OH) 3( H2 O) ],分别在 2 7Al谱 δ45和 1 H谱 δ3 .0处出现共振信号 ,这种铝物质不同于扭曲四配位铝 ,在高温下进一步水合生成 Al( OH) 3( H2 O) 2 和 Al( OH) 3( H2 O) 3,即非骨架五配位和六配位铝物质 .1 H-2 9Si CP和1 H谱证实 ,水蒸气脱铝使丝光沸石产生了大量的硅羟基和铝羟基 .

铁铝柱撑酸化蒙脱土催化剂的表征及催化性能

为改善柱撑蒙脱土的催化活性,对蒙脱土进行酸预处理,并采用离子交换法制备铁铝柱撑酸化蒙脱土(Fe-Al-酸化土)催化剂,通过XRD、BET、ICP和FI-IR对其进行表征。结果表明,蒙脱土经酸化预处理制备Fe-Al酸化土催化剂比表面积为157.3 m^2·g^(-1),层间距d001为1.787 nm,铁铝柱撑剂进入酸化蒙脱土层间域形成均一稳定的Si—O—Fe结构,在2 930 cm-1处出现尖锐的吸收峰,在协同过氧化氢降解废水实验中表现出较高的活性和稳定性。

脱铝超稳Y沸石催化合成缩醛(酮)

The acetalization and ketalization of various aldehydes and ketones with alcohols by using dealuminated USY(ultrastable Y-type zeolite) as catalyst were studied. The influences of silica/alumina ratio in the catalyst, catalyst amount and reaction time on the reaction were investigated. It is showed that the dealuminated USY is a high active catalyst for acetalization and ketaliz ation and its high activity can be readily returned to original by heating at 500 ℃ for 5 hours.

Removal of S^(2-) ion from sodium aluminate solutions with sodium ferrite

The synthesis of sodium ferrite and its desulfurization performance in S2 -bearing sodium aluminate solutions were investigated. The thermodynamic analysis shows that the lowest temperature is about 810 K for synthesizing sodium ferrite by roasting the mixture of ferric oxide and sodium carbonate. The results indicate that the formation process of sodium ferrite can be completed at 1173 K for 60 min, meanwhile raising temperature and reducing NazCO3 particle size are beneficial to accelerating the formation of sodium ferrite. Sodium ferrite is an efficient desulfurizer to remove the S2- in aluminate solution, and the desulfurization rate can reach approximately 70% at 373 K for 60 min with the molar ratio of iron to sulfur of 1：1-1.5：1. Furthermore, the desulfurization is achieved by NaFeS2·2H2O precipitation through the reaction of Fe（OH）4 and S^2- in aluminate solution, and the desulfurization efficiency relies on the Fe（OH）4^- generated by dissolving sodium ferrite.

Interaction of sulfur with iron compounds in sodium aluminate solutions

Reaction behaviors of sulfur and iron compounds in sodium aluminate solutions were investigated. The results show that iron compounds can remarkably remove the S2 but cannot get rid of S2Oc2-, SO^2- and SO4^-2 in sodium aluminate solutions. The removal efficiency of S^2- using ferrous compound and ferric compound can reach 86.10% and 92.70% respectively when the iron compounds were added with a molar ratio of 2：1 compared with the sulfur in liquors at 100℃. Moreover, several same compounds are formed in those two desulfurization processes with ferrous or ferric compounds, including erdite, hematite, amorphous ferrous sulfide, polymerized sulfur-iron compounds and ferric sulfate. The major difference between these two processes is that the erdite generated from ferrous compounds at the initial reaction stage will convert to a sodium-free product FeS2 at the subsequent stage.

以煤系高岭土为原料合成ZSM-5分子筛

在综述有关国内外煤系高岭土的开发应用及使用高岭土合成分子筛的研究、ZSM-5分子筛的合成方法基础上,运用XRD等现代分析测试技术对以高岭土为原料合成ZSM-5分子筛的工艺条件和产品进行探究,初步确定了晶化时间为72 h,晶化温度为160℃,模板剂的加入量与硅的比为0.3︰1,是合成ZSM-5分子筛的适宜条件。

Mineral transition of desilication products precipitated in synthetic sodium aluminate solution under atmospheric pressure

The liquor concentration, mineral proportion, crystal parameters and micro morphology of various desilication products（DSPs） precipitated in silica-supersaturated sodium aluminate solution at 95 ℃ under different reaction conditions were systematically researched. The DSPs formed under atmospheric pressure comprise amorphous phase, zeolite A, zeolite and sodalite, and the DSPs concentration and crystallinity increase with the increase of initial silica concentration, initial molar ratio of caustic Na2O to Al2O3（αK） and desilication duration. Decreasing the initial silica concentration, initial αK and increasing the desilication duration can reduce the proportion of zeolite A. The zeolite and sodalite are the stable DSPs, while the precipitation of zeolite A occurs at a high silica-supersaturated state in sodium aluminate solution. The DSPs are precipitated in the form of agglomerates, but the morphologies of various DSPs are quite different. Both the molar ratios of Na2O to Al2O3 and SiO-2 to Al2O3 in DSPs increase with the increasing desilication duration, resulting in the increase of the cell volumes of various DSPs. The precipitation sequence of DSPs under atmospheric pressure is： amorphous phase→zeolite A→zeolite→sodalite.

A novel method for enhancing the stability of ZSM-5 zeolites used for catalytic cracking of LPG: Catalyst modification by dealumination and subsequent silicon loading

Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic acid, which could only diffuse into the mesopores and not the mi‐cropores owing to the size of the trichloroacetic acid molecules. Empty spaces are created in the catalyst as a result of removal of the Al atoms from the zeolite structure. If Si atoms fill the empty space, then the structure of the mesopores becomes similar to silicates, which do not have any cata‐lytic properties. Silicon containing solution was used to fill the empty spaces, and in doing so, a unique method was developed, by which silicon atoms can directly replace the extracted Al atoms from the mesopore structure. Therefore, by changing the geometry and properties of the mesopores and micropores, the amount of coke reduced from 14%for HZSM‐5 to 3%for the modified zeolite.

Influence of silicate anions structure on desilication in silicate-bearing sodium aluminate solution

The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivative spectra. The results show that the desilication ratio in the solution prepared by the addition of sodium silicate(solution-SS) is much greater than that in the solution by the addition of green liquor(solution-GL), and low alumina concentration in the sodium aluminate solutions facilitates the desilication process. It is also shown that alumino-silicate anions in the solution-GL, and Q^3 polymeric silicate anions in solution-SS are predominant, respectively. In addition, increasing the concentration of silica favors respectively the formation of the alumino-silicate or the Q^3 silicate anions in the solution-GL or the solution-SS. Therefore, it can be inferred that the low desilication ratio in the silicate-bearing aluminate solution is mainly attributed to the existence of alumino-silicate anions.

Comparison of deep desulfurization methods in alumina production process

Several methods of deep desulfurization in alumina production process were studied, and the costs of these methods were compared. It is found that most of the S2- in sodium aluminate solution can be removed by adding sodium nitrate or hydrogen peroxide in digestion process, and in this way the effect of S2- on alumina product quality is eliminated. However, the removal efficiency of 2?32OS in sodium aluminate solution is very low by this method. Both S2- and 2?32OS in sodium aluminate solution can be removed completely by wet oxidation method in digestion process. The cost of desulfurization by wet oxidation is lower than by adding sodium nitrate or hydrogen peroxide. The results of this research reveal that wet oxidation is an economical and feasible method for the removal of sulfur in alumina production process to improve alumina quality, and provide valuable guidelines for alumina production by high-sulfur bauxite.

Tert-butylation of Toluene with Tert-butyl Alcohol over Realuminated H-mordenite Zeolite

The realuminated H-mordenite catalysts （HM1-4） treated with different concentrations of NaOH and NaAlO2 aqueous solutions were prepared, and characterized by inductively coupled plasma （ICP）, X-ray diffraction （XRD）, Fourier transform-infrared spectroscopy （FT-IR） and temperature-programmed desorption of ammonia, They are of lower Si/AI ratio and higher acid amount while keeping a high relative crystallinity. Their catalytic performances were evaluated with the liquid-phase tert-butylation of toluene with tert-butyl alcohol in a 100 ml stainless steel batch reactor equipped with a stirrer. HM2 zeolite catalyst, obtained by treating HM in 0.1 mol.L-1 NaOH followed by 0.05 mol·L^-1 NaAlO2 aqueous solution, shows a higher catalytic activity because of its highest acid amount. For HM2 catalyst the influences of reaction conditions on catalytic performance were investigated. The conversion of toluene is 50.3% and the selectivity ofp-tert-butyltoluene is 74.7% at a temperature of 180℃, 2 of molar ratio of tert-butyl alcohol to toluene, 4h of reaction time and 0.2 of M（catalyst）/M（toluene）.