FTIR和XPS对沸石合成特性及Cr(Ⅲ)去除机制的谱学表征

以粉煤灰为原料,采用优化的水热晶化法合成沸石,使用XRD,SEM和ζ电位分析沸石产品的组成特性,借助FTIR和XPS等揭示废水中Cr(Ⅲ)的去除机制。合成产品主要为NaP1型沸石,在pH值8～12区间内,ζ电位由-8.72mV降到-24.46mV。准二级方程和Langmuir等温线对试验的拟合效果更好,理论饱和吸附量为33.557 0mg.g-1。FTIR图谱表明—OH和Si—O类官能团在反应过程中有重要贡献。XPS全谱发现:结合能576.45eV为Cr(2p3/2)的特征峰,揭示了吸附过程的有效性。吸附Cr(Ⅲ)后,沸石中Si—Si和Si—O对应的结合能增加了0.25和0.60eV,含Si官能团可能与Cr(Ⅲ)发生了配位反应。O(1s)的结合能在反应后变得更低。这些证据表明:沸石对Cr(Ⅲ)的去除过程是物理吸附和化学吸附共同作用的结果。     

表面润湿法合成β沸石体系中晶种作用的研究

系统研究了表面润湿法合成β沸石的体系中,干晶种、润湿态晶种、异晶晶种(Y沸石、ZSM 5沸石)以及碱处理β沸石晶种在此晶化体系中的作用.采用β沸石产品及异晶作晶种时,可使产品的相对结晶度稍有提高,但对沸石微晶核的结构导向作用不明显.经浓碱液处理20min后的β沸石产品(碱处理晶种)作晶种引入晶化体系后,可以显著提高产品的相对结晶度,降低模板剂的用量,缩短晶化诱导期,成为表面润湿法合成β沸石体系的有效晶种形式.     

液氮比潜热的测定

每种物质在不同压力和温度下可以是以气体、液体或固体的形态存在,或者说可以是以气相、液相或固相存在.在一定的压力和温度条件下,物质从一相转变为另一相,这种物理现象统称为相变.一般地,由气相转变为液相称为凝结,其逆过程,即液相转变为气相称为汽化;由液相转变为固相称为凝固,而由固相转变为液相称为熔解;有时固     

KZnF3:Ce3+,Tb3+纳米粒子合成与发光

采用微乳液法合成了Ce3 ,Tb3 单掺和双掺KZnF3纳米晶。分析了样品的结构与形态,结果表明,所合成的样品均为单相,颗粒粒度分布均匀。讨论了光谱特性,并与高温固相法合成的产物作了对比。研究发现,KZnF3:Ce3 纳米晶的发射光谱与体相多晶相比,最强峰位置红移约35nm;在KZnF3纳米晶双掺体系中存在Ce3 →Tb3 能量传递,尤其是Tb3 的5D4→7F5跃迁发射显著增强,有望成为一种有发展前途的绿色荧光材料。     

Bi-Pb-Sr-Ca-Cu-O系反应过程研究

采用高温X射线和DTA技术研究了三步反应法合成Bi-Pb-Sr-Ca-Cu-O超导体的反应过程。实验结果表明样品在740℃能形成2212相,在825℃形成2223相.2212相在875℃左右异分熔化成2201相和液相,2223相在935℃左右同分熔化。2212相在晶化过程中容易形成强的c轴取向。 关键词：     

DTA和XRD用于(14-x)SrCO3-xCaCO3-24CuO系统合成spin-ladder化合物Sr14-xCaxCu24O41的研究

采用差热分析(DTA)技术和粉末X射线衍射(XRD)技术研究了(14-x)SrCO3xCaCO324CuO体系(x=0、0.4、2.8、5.6、8.4、11.2、13.6和14)的热分解和固相反应过程,第一次详细地分析了该体系的热行为与合成纯spin ladder化合物Sr14-xCaxCu24O41的关系.实验结果表明,x≤5.6时,DTA曲线在1000℃以下显示了两个吸热峰,DTA曲线可分成三个阶段,分别对应于合成单相Sr14-xCaxCu24O41的固相反应过程;x≥8.4时,DTA曲线在1000℃以下显示了三个吸热峰,800℃附近的第一个吸热峰反映系统中CaCO3的含量,第三个吸热峰的有无是能否合成单相化合物的决定性标志.     

两相区中生长单晶的几个问题

在非同成分配比条件下.从熔态中生长单晶体的问题是十分重要的.这是由于目前正在广泛应用和探索的新型单晶材料,大都是多组元体系,往往不存在固液同成分点,或者即使存在固液同成分点,但由于配料误差,作同成分的挥发损失,容易造成体系组分偏离同成分点,单晶生长过程也将是在固-液两相区进行. 为了讨论在两相区生长单晶发生的分凝现象,Pfann[1]推导了组分分布公式;Hurle[2]推导了不产生组分过冷的条件.他们的推导是在分凝系数k为常数的假定下进行的,也就是对二元系,固相线与液相线为直线相交于某一组元熔点的情况. 本文的目的是对分凝系数不…     

表面活性剂辅助固相法合成碘化银纳米线束与光谱表征

卤化银具有光致变色特性,广泛应用于光致变色玻璃,照相感光乳剂等。作为一种光信息载体,具有记录和保存光信息的功能,它还是一类重要的半导体光催化剂,有着广泛的应用。以AgNO3与KI为原料,在非离子表面活性剂聚乙二醇(PEG-400)存在条件下,进行室温固相反应,合成了碘化银纳米线束。采用XRD,TEM和SEM等测试手段对产物结构和形貌进行表征,结果表明,产物为一维碘化银纳米线束,其直径在80～100nm之间,长度约为20μm,长径比>200。表面活性剂PEG-400在碘化银纳米线束的形成过程中起到了软模板剂的作用,诱导产物纳米晶沿着某一特定方向定向有序生长从而生成纳米线束。该方法消除了水对反应过程的影响,操作简单,成本较低,对碘化银纳米线束的制备技术研究具有重要意义。     

晶化时间及硅源对SAPO-5分子筛的结构及模板剂状态的影响

通过改变硅源和晶化时间的方法,采用水热法合成了系列SAPO-5分子筛材料,用X光衍射(XRD)和²⁷Al MAS NMR对产物的晶相结构进行表征,用¹³C CP MAS NMR研究了不同阶段的产物中模板剂的存在状态。结果可见:以SiO₂凝胶为硅源时;薄水铝石反应物有较高的活性,在48h的晶化时间内,延长晶化时间有助于SAPO-5分子筛的完整结晶,当晶化时间超过48h时,其中已形成的SAPO-5的结构部分被破坏,并转化为SAPO-34.且SAPO-34的量随晶化时间的延长而增多。当以Si(OEt)₄为硅源时,铝反应物的反应活性较低,在72h的晶化时间范围内,延长晶化时间有助于SAPO-5产物的形成,使其结构愈加完整,在SAPO-5分子筛的形成过程中,模板剂的状态随分子筛结构的变化而变化,由于三乙胺(Et₃N)模板剂中的甲基和亚甲基所处位置不同,其弛豫时间受分子筛结构的影响较大,可用其中甲基的¹³C MAS NMR诺线的强度及化学位移来表示分子筛结构的完整性。     

固-液-气三相环境下非均相苯加氢反应的原位核磁共振研究

本文使用原位核磁共振（NMR）方法成功实现了对固-液-气三相环境下加氢反应的在线监测.在反应过程中,无需分离产物.以Pd纳米颗粒粉末及不同晶面形貌的Pd催化剂作为研究对象,我们研究了反应压强、反应时间,以及催化剂表面性质对加氢反应的影响.结果表明,压强和反应时间都可以影响加氢反应产物的产率,使用暴露不同晶面的Pd共催化剂时,苯加氢产物不同.该原位NMR方法为研究固-液-气三相催化环境下的加氢反应机理提供了可能.     

In situ ultrasonic diagnostic of zeolite X crystallization with novel (hierarchical) morphology from coal fly ash

In this paper the applicability of an in situ ultrasonic diagnostic technique in understanding the formation process of zeolite X with a novel morphology was demonstrated. The complexity of the starting fly ash feedstock demands independent studies of the formation process for each type of zeolite since it is not known whether the crystallization mechanism will always follow the expected reaction pathway. The hierarchical zeolite X was noted to follow a solution phase-mediated crystallization mechanism which differs from earlier studies of the zeolite A formation process from unaged, clear solution extracted from fused fly ash. The use of the in situ ultrasonic monitoring system provided sufficient data points which enabled closer estimation of the time of transition from the nucleation to the crystal growth step. In order to evaluate the effect of temperature on the resulting in situ attenuation signal, synthesis at three higher temperatures (80, 90 and 94 °C) was investigated. It was shown, by the shift of the US-attenuation signal, that faster crystallization occurred when higher temperatures were applied. The novel hierarchical zeolite X was comprised of intergrown disc-like platelets. It was further observed that there was preferential growth of the disc-shaped platelets of zeolite X crystals in one dimension as the synthesis temperature was increased, allowing tailoring of the hierarchical morphology.     

Sonochemical synthesis of zeolite NaP from clinoptilolite

In the present work, natural clinoptilolite was converted to zeolite NaP using ultrasonic energy, in which the transformation time shortened remarkably. The effect of post-synthesis treatment using conventional hydrothermal was also investigated. The synthesized powders were characterized by XRD, TGA/DTA, SEM, and PSD analysis. The results showed that, increasing the sonication time (energy) has no significant effect on the product’s morphology. The crystallinity of the synthesized samples increased slightly with increasing sonication time, but their yield remained relatively unchanged. Furthermore, post-synthesis hydrothermal treatment showed very little influence on properties of the final product. Because the ultrasonic irradiation creates acoustic cavitation cracks on the surface structure of clinoptilolite particulates and increases the concentration of soluble alumino-silicate species, which favors the prevailing super-saturation, crystallization and crystal growth of zeolite NaP happen faster. The particles of zeolite NaP synthesized by ultrasonic irradiation consist of small crystallites of uniform size.     

Synthesis of NaP zeolite at room temperature and short crystallization time by sonochemical method

NaP zeolite nano crystals were synthesized by sonochemical method at room temperature with crystallization time of 3 h. For comparison, to insure the effect of sonochemical method, the hydrothermal method at conventional synthesis condition, with same initial sol composition was studied. NaP zeolites are directly formed by ultrasonic treatment without the application of autogenous pressure and also hydrothermal treatment. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, the crystallinity of the powders decreased but phase purity remain unchanged. The synthesized powders were characterized by XRD, IR, DTA TGA, FESEM, and TEM analysis. FESEM images revealed that 50 nm zeolite crystals were formed at room temperature by using sonochemical method. However, agglomerated particles having cactus/cabbage like structure was obtained by sonochemical method followed by hydrothermal treatment. In sonochemical process, formation of cavitation and the collapsing of bubbles produced huge energy which is sufficient for crystallization of zeolite compared to that supplied by hydrothermal process for conventional synthesis. With increasing irradiation energy and time, the crystallinity of the synthesized zeolite samples increased slightly.     

Synthesis of zeolite A from coal fly ash using ultrasonic treatment – A replacement for fusion step

The synthesis of zeolites from fly ash has become an increasingly promising remedy to the crisis of coal fly ash production and disposal in South Africa. In recent studies, South African fly ash was proven to be a suitable feedstock for the synthesis of essential industrially used zeolite A. However, the process involves a costly energy intensive step whereby fly ash is fused at high temperatures, which may make the process economically unattractive on a large scale. The aim of this study is to investigate the possibility of replacing high temperature fusion with less energy intensive sonochemical treatment for the synthesis of zeolite A. Sonochemical treatment was first thought possible due to the violent cavitation caused by high intensity sonication. The results of the study showed that fusion can be replaced by 10 min of high intensity sonication. The incorporation of sonication also consequently reduced the crystallization temperature of the process making it possible to synthesize a pure phase zeolite A at lower temperatures and reduced times. This study effectively developed a novel process to replace the energy intensive fusion step with a short, easy and inexpensive treatment. Scale up of this synthesis approach may proffer a promising alternative option to the anticipated energy demand of the synthesis of fly ash-based zeolite with fusion method.     

Insight of arsenic transformation behavior during high-arsenic coal combustion

The release of arsenic vapors (As³⁺) during high-arsenic coal combustion not only raises serious environmental concerns, but also causes catalyst deactivation in selective catalytic reduction (SCR) systems. To illuminate the mechanisms involved in the transformation of arsenic vapors towards less troublesome arsenates (As⁵⁺) during coal combustion, the accessory minerals in the high-arsenic coal were identified and the association relationship of these compounds with arsenic in fly ash was estimated. The results showed that Si/Al were the main inorganic elements in high-arsenic coal while the content of Ca was quite low. Ca was mostly transformed into sulfates during coal combustion and the effect of Ca on the arsenic transformation was limited. Al/Fe played a more significant role in arsenic speciation transformation and arsenic in the fly ash was predominantly bound with Al/Fe-oxides as arsenates. It was further confirmed that Al in kaolin/metakaolin showed good capacity on arsenic capture. In addition, few arsenic vapors were captured through the physical adsorption mechanism and the large fraction of As³⁺ in some fine particles was mostly attributed to the chemical reactions between arsenic vapors and Al-compounds. Meanwhile, a certain amount of arsenic vapors were converted into As₂O₅(s) under the influence of SCR catalyst and then carried by flue gas to participate in fly ash. Besides, part of arsenic distributed in the fly ash was through the stabilization of ash matrix in high temperature conditions. The transformation of arsenic from vapors towards particulate arsenic favored arsenic emission control by particulate matter control devices.     

Ultrasound-assisted rapid hydrothermal design of efficient nanostructured MFI-Type aluminosilicate catalyst for methanol to propylene reaction

The influence of ultrasound-assisted rapid hydrothermal synthesis of aluminosilicate ZSM-5 catalysts was examined in this work. A series of MFI-type nanostructured materials with sonochemical approach and conventional heating were synthesized and evaluated for conversion of methanol to propylene reaction. The prepared samples were tested by characterization analyses such as XRD, FESEM, BET-BJH, FTIR, TPD-NH₃ and TG/DTG. The obtained results confirmed that ultrasound treatment enhanced the nucleation process and crystal growth for ZSM-5 sample synthesized at moderate temperature of 250 °C. Therefore, it was found the formation of pure MFI zeolite with high crystallinity and improved textural, structural and acidic properties for ZSM-5(UH-250) sample compared with the other zeolites. This observation was attributed to the relationship between the perfect crystallization mechanism and catalytic properties, which led to producing an efficient MFI zeolite toward the optimal catalytic performance. In this manner, the methanol conversion and products selectivity of prepared materials were carried out in MTP reaction at 460 °C and atmospheric pressure. The ZSM-5(UH-250) zeolite with slower deactivation regime exhibited the constant level of methanol conversion (84%) and high propylene selectivity (78%) after 2100 min time on stream. Moreover, the synthesis pathway for MFI zeolite at moderate temperature and also deactivation mechanism of improved sample were proposed.     

Partitioning and transformation behavior of selenium during coal combustion

The partitioning of selenium in coal-fired flue gas and desulfurization wastewater is of great threat to the ecological environment and human health. However, the unclear understanding of interactions between selenium vapors and fly ash hinders the emission control of selenium from coal-fired power plants. To further illuminate the mechanism of selenium partitioning and transformation, this study carefully estimated selenium distribution characteristics in the coal combustion byproducts from several industrial power plants. The effective temperature range as well as the key ash components for selenium retention by fly ash was clarified by multiple-scale experiments and theoretical perspectives. The results showed that gaseous selenium tended to be captured by fly ash at a medium-to-low temperature range (i.e. below 650 °C). The limited residence time resulted in the incomplete capture of gaseous selenium by fly ash. Mullite, quartz, iron oxides, and anhydrite in fly ash were found to be the main trappers for gaseous selenium. Among these components, iron oxides showed excellent selenium adsorption performance at a wide temperature range of 150-700 °C, which was realized by the strong chemical adsorption. By contrast, as the dominant phases in fly ash for the physical adsorption of gaseous selenium, mullite and quartz mainly captured gaseous selenium below 300 °C. On the other hand, sulfur dioxides had priority over gaseous selenium to react with calcium-containing ash components by forming anhydrite in the high-temperature region. The formed anhydrite had a limited selenium adsorption capacity, which was confirmed to capture gaseous selenium through a combination of physical adsorption and weak chemical adsorption. For the in-depth control of selenium emitted into desulfurization system and atmosphere environment, these findings provided a comprehensive insight into the behavior of selenium partitioning and transformation into fly ash during coal combustion.     

飞灰-硅酸锂吸收剂捕获CO_2的实验研究

以飞灰,碳酸锂为反应原料,通过高温固相反应,添加不同比例的碳酸钾,合成出一系列可在高温下吸收CO_2的飞灰-硅酸锂新型吸收剂。用扫描电子显微镜(SEM)、X-射线粉末衍射仪(XRD)对材料的表面形貌和结构特征进行表征,并用热重分析仪(TG)研究了硅酸锂材料吸收CO_2的特性以及固定床来测试捕获CO_2的循环性能。实验结果表明,通过适量K元素的掺杂,飞灰-硅酸锂材料在吸收速率、容量和循环性能上都取得较好的效果,使综合利用飞灰合成硅酸锂材料捕获CO_2成为一种可行的方法。     

Conversion of silica by-product into zeolites by thermo-sonochemical treatment

The fine powdered silica by-product of processing of aluminum fluoride (fertilizer plant, Lithuania) was used for zeolite synthesis as silica and aluminum source. The effect of sonication time and the time of hydrothermal synthesis on crystallinity of the synthesized zeolite were studied. This allowed the transformation of the by-product to the mixture of Na–P zeolite and Na–X zeolite. It was determined that ultrasonic-assisted hydrothermal action effected the “diamond” shape formation of Na–P zeolite with clear crystal edges. Na–P zeolite had the morphology of pseudo-spherical forms constituted by small plates when hydrothermal treatment (without sonication) was use for the preparation of zeolites. Moreover, it was determined that ultrasonic-assisted hydrothermal method effected a reduction in the crystal size compared with the zeolites which were synthesized only by using hydrothermal synthesis. The total amount of zeolites as high as 88–93% was achieved after 24 h of hydrothermal treatment followed or unfollowed by sonication. By using longer duration (20 min) of ultrasound pretreatment it is possible to reduce the duration of hydrothermal synthesis: from 24 h to 12 h of hydrothermal treatment. In this case, similar results of total amount of zeolites were detected. In the present work, low-cost raw materials, such as silica by-product have been investigated for the production of zeolites.