HZSM-5型分子筛硅铝比对一步法合成二甲醚的影响

以Cu/Zn/Al(摩尔比为6∶3∶1)甲醇合成催化剂与HZSM-5型分子筛混合,制备了一步法二甲醚合成催化剂。通过改用三种不同Si/Al摩尔比（摩尔比为25、38和50）的HZSM-5型分子筛,考察了催化剂中脱水组分（HZSM-5分子筛）的酸性对二甲醚合成的影响。结果表明,随着催化剂Si/Al摩尔比的降低,分子筛的酸性增强,使得CO单程转化率提高。当催化剂Si/Al＝38时,CO对二甲醚的选择性最高,可达到68.13％,其次是催化剂Si/Al＝50,选择性最差的是Si/Al＝25的催化剂。在553 K、 3 MPa和4 000 h－1的条件下,Si/Al＝25和Si/Al＝38的催化剂CO单程转化率和DME的选择性接近一致。在此条件下,两者的时空产率达到试验的最大值,分别为0.38 gDME/(gcat·h)和0.36 gDME/(gcat·h),在试验范围内,一步法合成二甲醚催化剂最佳的Si/Al摩尔比为25。     

磷酸硅铝分子筛SAPO-17的合成与性能研究

磷酸硅铝系列分子筛SAPO-n是美国联合碳化物公司于1984年首先合成^[1,2],SAPO-17是其中的一种。作为一种新的分子筛,对其晶胞参数,吸附和催化性能及热稳定性等方面的研究,至今很少见有文献报道。本文考察了SAPO-17的合成条件、物化性能、热稳定性及裂解正十六烷和粗柴油的催化性能,并测定了它的晶胞参数。     

铌硅铝磷分子筛的合成及催化酯化性能研究

合成了铌硅铝磷分子筛NbSAPO-5催化剂,并对其进行了XRD、BET表面吸附、ICP、SEM、NH3-TPD吸附表征,结果表明所合成的分子筛具有AFI的晶体结构;考察了催化剂对合成丙酮酸甲酯反应的催化酯化活性,表明Nb的引入使双功能催化剂的氧化和酯化功能更趋平衡,在改善酯化能力的同时,也使得酸酯总收率大大提高．     

氟离子对钛硅分子筛合成的影响

将氟离子引入钛硅分子筛合成体系，系统研究了氟离子对钛硅分子筛合成的影响。结果表明，四丙基溴化铵－NH4F体系与四丙基溴化铵－有机铵体系有着类似的合成规律：加入晶种可以降低分子筛晶粒粒度；随着NH4F／SiO2降低，晶粒增居；四丙基溴化铵最低用量在TPABr/SiO2=0.025-0.05之间；随着SiO2/TiO2增大，分子筛相对结晶度增加。将氟离子引入钛硅分子筛合成体系能促进钛硅分子筛晶化，但氯离子不具有同样的效应。     

双功能钛硅分子筛的合成、表征及催化性能

以四丙基溴化铵为模板剂, 硅溶胶为硅源, 正丁胺为碱源, 采用水热合成的方法, 将三价离子(Al³⁺, B³⁺或Fe³⁺)和Ti⁴⁺同时引入到MFI型分子筛的骨架, 得到同时具有氧化和酸催化活性的双功能钛硅分子筛M-TS-1(M=Al, B或Fe). 通过X射线粉末衍射、傅里叶变换红外光谱、紫外-可见漫反射光谱、氨程序升温脱附、电感耦合等离子体原子发射光谱和N₂吸附-脱附等温线手段对样品进行了表征. 结果表明, 三价离子的引入, 提高了TS-1的酸强度和酸量. 采用乙烯选择氧化为探针反应考察了M-TS-1的催化性能. 结果表明, Al-TS-1和B-TS-1在乙烯环氧化及后续的开环溶剂解反应中表现出较高的催化性能, H₂O₂的转化率在95%以上, H₂O₂的利用率大于90%, 乙二醇和乙二醇单甲醚的总收率可达10%以上.     

硅源对ITQ-13分子筛水热合成的影响

通过三种硅源, 正硅酸已脂(TEOS)、胶体二氧化硅、气相法白炭黑, 成功地合成出ITQ-13分子筛, 并用X射线衍射(XRD)、扫描电子显微镜(SEM)、BET表面积测试和氘代乙腈吸附等方法对合成的材料进行表征. 结果表明, 用硅胶和白炭黑为硅源合成出的ITQ-13具有较好的晶化度和较大的晶体尺寸.     

基于分子筛模板的银/硅铝无定形结构复合材料的合成及光谱性质

利用硅铝无定形结构作为保护层的银纳米颗粒在杀菌和催化领域具有重要应用. 银纳米颗粒的形貌控制是其优异性能的重要保证, 尤其是具有规则结构的银纳米颗粒的合成一直是该领域的难点. 本文以亚稳态结构的硅铝分子筛作为模板, 在室温条件下采用离子交换方法, 通过调整银离子的含量和离子交换时间, 控制银在分子筛中的分布和含量, 在还原剂N(C₂H₅)₃存在下, 通过微波还原反应获得了不同银/硅铝无定形结构比例的复合材料. 透射电子显微镜测试结果表明, 不同比例的前驱体经微波法还原后, 小尺寸的银纳米颗粒可以分布在无定形的硅铝基质中; 当增大银的比例后, 银纳米颗粒则出现项链式结构, 并且由无定形硅铝薄层链接并包裹. 这类结构既具有银纳米颗粒的催化性能, 同时又在硅铝薄层的保护下表现出良好的稳定性, 在杀菌和催化领域具有广泛的应用前景.     

一种新型介孔磷酸硅铝(SAPO)分子筛的合成及表征

以Silicate-1晶种为硅源,水热合成了一种新型介孔磷酸硅铝(SAPO-1)分子筛,并且通过X射线粉末衍射、红外光谱、透射电镜、扫描电镜、热重分析、N2吸附/脱附和氨气程序升温脱附(NH₃-TPD)等多种手段对产物进行了表征.红外光谱表明,Silicate-1导向剂成功地引入了介孔骨架;氨气程序升温脱附(NH₃-TPD)结果表明,SAPO-1具有较强的酸性.催化结果表明,SAPO-1在大分子催化反应中有较高的活性.     

CuSAPO-5分子筛的合成、表征及对甲苯吸附性能

采用水热合成法,以三乙烯四胺(TETA)为模板剂,合成Cu SAPO-5分子筛。通过扫描电子显微镜(SEM)、粉末X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、热重(TG)、N2吸附及元素分析等手段对分子筛样品进行表征,考察了不同硅铝比对合成分子筛晶体的影响,并测定了分子筛样品对甲苯的吸附性能。结果表明,将合成液的p H值调节为4.8~5.0,于150~170℃晶化1d,可合成晶体形貌为球体的Cu SAPO-5分子筛,粒径约为30μm。分子筛样品具有较好的热稳定性,仍保持了SAPO-5分子筛的AFI骨架结构,属于微孔分子筛,孔径约为0.70nm,比表面积约为265 m2·g-1。元素分析结果表明分子筛中P、Si、Al和Cu的含量分别为12.56%、4.48%、7.17%和6.25%。样品对甲苯的吸附约在120 min时达到饱和,吸附量约为180 mg·g-1。     

CuSAPO-5分子筛的合成、表征及对甲苯吸附性能

采用水热合成法,以三乙烯四胺（TETA）为模板剂,合成CuSAPO-5分子筛。通过扫描电子显微镜（SEM）、粉末X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、热重（TG）、N₂吸附及元素分析等手段对分子筛样品进行表征,考察了不同硅铝比对合成分子筛晶体的影响,并测定了分子筛样品对甲苯的吸附性能。结果表明,将合成液的pH值调节为4.8～5.0,于150～170℃晶化1 d,可合成晶体形貌为球体的CuSAPO-5分子筛,粒径约为30 μm。分子筛样品具有较好的热稳定性,仍保持了SAPO-5分子筛的AFI骨架结构,属于微孔分子筛,孔径约为0.70nm,比表面积约为265 m²·g^-1。元素分析结果表明分子筛中P、Si、Al和Cu的含量分别为12.56%、4.48%、7.17%和6.25%。样品对甲苯的吸附约在120 min时达到饱和,吸附量约为180 mg·g^-1。     

Mechanochemical activation of minerals on the cordierite synthesis

The cordierite is commonly prepared by reaction of talc, clay and gibbsite within the range of 1200-1350 °C. This study deals with the effect of the amorphization by grinding of that mixture and its influence on the cordierite formation.The mixture previously mentioned underwent six different treatments: mixing without grinding (A) (only mixing); non-amorphizing grinding (A_M) and amorphizing grinding in oscillating mill at four different times (H samples). The phases formed by thermal treatment were studied using differential thermal analysis (DTA)-thermogravimetric analysis (TG)-DTG, dilatometries and X-ray diffraction (XRD) techniques in certain combinations.The thermal analysis of the A and A_M series were compared and they do not show significant differences, whereas the H samples present remarkable alterations in the DTA peaks as well as in the weight losses (TG). Thus, a great number of DTA peaks tend to decrease the temperature of the maximum and to lower the intensity as the amorphization time increases.Calcination tests performed within the range 900-1200 °C show important differences in the diffractograms obtained from the intermediate products. While at 1350 °C the A and H samples reach the same final phases, within the range 1200-1360 °C they present important differences in the DTA indicating that the sequence and direction of reaction are different. The same behavior can be observed by dilatometric analysis.     

Three model-free methods for calculation of activation energy in TG

Two well-known isoconversion methods, the first one developed by Ozawa-Flynn-Wall and the second one developed by Friedman, are confronted with calculations made using modulated thermogravimetry (MTG). The latter variant is free from a number of assumptions and restrictions made in the isoconversion computations. In particular, it allows the use of a single decomposition curve and it remains in force even in the case of multistage decomposition with conjugated processes.To obtain the model-fitting methods from the model-free methods one should replace some functions averaged over isoconversion levels by the functions calculated on the basis of kinetic models. In the Ozawa-Flynn-Wall method it is the averaged reduced time (integral of Arrhenius exponential over time). In the method of Friedman it is the averaged differential conversion function.In MTG, the perturbations caused by the sinusoidal temperature modulation are connected with derivatives of mass loss by simple scaling, where activation energy plays a role of a scaling parameter. The ratio of the experimentally measured perturbations to the experimental derivative is used for the model-free computation of activation energy. If a theoretical derivative replaces the experimental one, this procedure leads to the model-fitting method. Even a rough approximation of the experimental derivative should not lead to an excessive error in activation energy. If in a vicinity of peaks maxima in derivatives of mass loss the decomposition is controlled by single rate-limiting processes, modulated thermogravimetry should give realistic activation energies for these processes. Inasmuch as the results of MTG are weakly sensitive to selection of kinetic models, this method should have a high predictive force.     

Thermal analysis study of imidazolinium and some benzimid azolium salts by TG

The imidazolinium and benzimidazolium bromide salts with pentafluor substituents on N atom were synthesized. The structures of imidazolinium and benzimidazolium bromide salts obtained were conformed by ¹H and ¹³C NMR, ¹⁹F NMR and elemental analysis. It was found that pyrolytic decomposition occurs with melting in salts. The imidazolinium and benzimidazolium bromide salts were studied by TG-DTG and DTA from ambient temperature to 1000°C in nitrogen atmosphere. The decomposition occurred mainly in one stage and the values of activation energy E, frequency factor A, reaction order n, enthalpy change ΔH ^#, entropy change ΔS ^# and Gibbs free energy ΔG ^#, of the thermal decomposition were calculated by means of Coats-Redfern (CR), MacCallum-Tanner (MC) and van Krevelen (vK) methods. The activation energy value obtained by CR and MC methods were in good agreement with each other while those obtained by vK were found to be 10–12 kJ mol⁻¹ larger.     

Aluminium‐27 NMR investigation of the influence of cation type on aluminosilicate solutions

The effects of tetraalkylammonium (TAA) and alkali metal cations on the equilibrium distribution of aluminosilicate oligomers in aqueous alkaline aluminosilicate solutions were investigated using ²⁷Al NMR spectra and their evolution with time. The results indicate that there are no differences in the initial equilibria involving solutions containing both TAA and alkali metal cations on the one hand and those containing alkali metal cations only. However, re‐equilibration of the aluminosilicate species for TAA/Na aluminosilicates is slow (usually not detectable on the time‐scale of the experiments), whereas when purely alkali metal cations are used, the spectra alter over a period of ～1 h, such that resolution is degraded substantially. In the latter case, it is suggested that the anions aggregate into larger systems, although the solutions are still clear. ²⁹Si NMR evidence for slow equilibration of silicate and aluminosilicate solutions at higher concentrations is also discussed. Copyright © 2002 John Wiley & Sons, Ltd.     

煤中矿物质对燃煤污染物排放特性的影响

利用热分析和X射线光电子能谱（XPS）研究了煤中矿物质在燃烧过程中对煤中氮与硫的排放特性的影响。结果表明,铜川煤中的可溶性矿物质如硫酸盐、碳酸盐等对NO排放有促进作用,当将这类可溶性矿物质从煤体中除去后,煤的NO排放量下降;铜川煤中的矿物质对SO2的排放有抑制作用,当这类碱性成分被脱除后,单位质量可燃硫的SO2排放量升高。     

Reactivity of C1 surface species formed in methane activation on Zn-modified H-ZSM-5 zeolite

Solid-state (13)C magic angle spinning (MAS) NMR spectroscopy investigations identified zinc methyl species, formate species, and methoxy species as C(1) surface species formed in methane activation on the zeolite Zn/H-ZSM-5 catalyst at T≤573 K. These C(1) surface species, which are possible intermediates in further transformations of methane, were prepared separately by adsorption of (13)C-enriched methane, carbon monoxide, and methanol onto zinc-containing catalysts, respectively. Successful isolation of each surface species allowed convenient investigations into their chemical nature on the working catalyst by solid-state (13)C MAS NMR spectroscopy. The reactivity of zinc methyl species with diverse probe molecules (i.e., water, methanol, hydrochloride, oxygen, or carbon dioxide) is correlated with that of organozinc compounds in organometallic chemistry. Moreover, surface formate and surface methoxy species possess distinct reactivity towards water, hydrochloride, ammonia, or hydrogen as probe molecules. To explain these and other observations, we propose that the C(1) surface species interconvert on zeolite Zn/H-ZSM-5. As implied by the reactivity information, potential applications of methane co-conversion on zinc-containing zeolites might, therefore, be possible by further transformation of these C(1) surface species with rationally designed co-reactants (i.e., probe molecules) under optimized reaction conditions.     

浆态床合成二甲醚复合催化剂失活原因探索

在反应温度260℃、压力5.0MPa的条件下,对浆态床反应器中二甲醚合成复合催化剂的失活规律进行了研究。结果表明, Cu基催化剂失活较快是导致浆态床二甲醚合成催化剂不稳定的主要原因。通过分析Cu基催化剂在浆态床反应器和固定床反应器中的活性变化规律,发现在浆态床反应器中不能及时导出反应体系的H2O对催化剂的毒副作用导致了浆态床Cu基催化剂快速失活。对失活催化剂进行的TPR、XRD和SEM EDS表征结果可以看出,Cu粒子的长大和积炭是Cu基催化剂失活的重要原因,与已有文献报道不同的是并未发现明显的Cu元素流失。     

On evaluate of the integral methods for the determination of the activation energy

Recently, Órfão obtained two simple equations for the estimation of the relative error in the activation energy calculated by the integral methods [2]. In this short communication, the validity of the equations has been evaluated by comparing the results calculated by the equations with the results calculated by the equation from theoretical derivation without introducing any assumption.     

Effects of thermal activation conditions on the microstructure regulation of corncob-derived activated carbon for hydrogen storage

Activated carbons derived from corncob （CACs） were prepared by pyrolysis carbonization and KOH activation. Through modifying activation conditions, samples with large pore volume and ultrahigh BET specific surface area could be obtained. The sample achieved the highest hydrogen uptake capacity of 5.80 wt% at 40 bar and -196℃ The as-obtained samples were characterized by N2-sorption, transmission electron microscopy （TEM） and scanning electron microscopy （SEM）. Besides, thermogravimetric analysis was also employed to investigate the activation behavior of CACs. Detailed investigation on the activation parameters reveals that moderate activation temperature and heating rate are favorable for preparing CACs with high surface area, large pore volume and optimal pore size distribution. Meanwhile, the micropore volume between 0.65 nm and 0.85 nm along with BET surface area and total pore volume has great effects on hydrogen uptake capacities. The present results indicate that CACs are the most promising materials for hydrogen storage application.