离子交换分子筛对NO吸附的研究

在273K条件下,考察了不同阳离子交换的ZSM-5型和Y型两种分子筛对NO的吸附性能,得出了在273K时的可逆及不可逆吸附量,并对不可逆吸附的NO进行了程序升温脱附(TPD)研究;对样品吸附NO的本质进行了讨论.

在Nd_(2-x)Sr_xNio_(4±λ)系催化剂上NO分解反应的研究

氮氧化物(NO_x)是严重的空气污染物,是产生酸雨的主要来源之一.消除NO_x已成为目前国际上环保化学中最为关键的问题之一.目前,世界各国都在大力开发新的消除NO_x的方法,其中最令人注意的有NO直接分解和寻找可取代NH_x的还原剂.根据已报道的文献看,最有希望的NO直接分解催化剂除了贵金属Pd,Pt之外有Cu-ZSM-5分子筛、含Cu的超导体Y-Ba-Cu-O和含Co的ABO_x复合氧化物.把A_2BO_4型复合氧化物应用于NO分解反应的报道很少,本文首次在NO分解反应中系统研究了Ln_(2-x)Sr_xMO_4(Ln=La,Pr,Nd,Sm,

沸石分子筛孔道中聚苯胺的选择性掺杂研究

用电化学方法聚合分子筛孔道内的苯胺,根据聚苯胺在无机质子酸中的掺杂反应研究了ZSM-5,Y型分子筛对磷钼杂多酸的形状选择作用.

Eastman-Kodak AQ膜修饰电极阴极溶出伏安法测定痕量铁

本文用热处理法成功地制备了性能稳定的Eastman-Kodak AQ/GC修饰电极,对Fe~(3+)/Fe~(2+)及其络合阳离子在该电极上的行为进行了研究。表明AQ膜对Fe~(3+)和Fe~(2+)具有相近的交换能力,可用于Fe~(3+)或Fe~(2+)及其总量的阴极溶出伏安法测定。线性范围分别为2.0×10~(-7)～2.2×10~(-5)mol/L(Fe~(3+))和5.0×10~(-7)～2.0×10~(-5)mol/L(Fe~(2+)),检出限为1.0×10~(-7)mol/L(Fe~(3+))。文中对电极反应和再生进行了探讨。

非碱性介质中全硅分子筛的合成与表征

在非碱性介质中,F-离子存在下,采用水热方法研究了全硅分子筛的合成。以三丙胺、胆碱、三亚乙基二胺和哌嗪为模板剂,合成出具有MFI结构(ZSM-5型)的全硅分子筛。全硅Theta-1和ZSM-39的模板剂分别为1,6-已二胺和四甲基溴化铵。~(29)Si MAS NMR研究结果表明,该体系得到的全硅分子筛具有结晶度高和缺陷少的特点。

东太平洋海隆13°N附近沉积物元素地球化学研究

对东太平洋海隆（EPR）13°N西侧2个沉积物岩芯进行了碳酸盐、常量和微量元素含量测定。E271站位沉积物中Fe含量在8.5~13.8%之间，Mn含量在1.7~3.17%之间；E272站位Fe 5.7~13%，Mn 0.12~3.31%，沉积物中高铁锰含量显示在热液柱颗粒物质在EPR13°N西翼沉降明显。E271站位CaCO3含量在5.9~27.6%之间，E272站位CaCO3含量在6.7~38.2%之间，在两个站位沉积物柱样中发现少量有孔虫化石。Cu、Pb和Zn因为热液柱颗粒物质沉降，在沉积物中富集。Cu/Fe，Pb/Fe和Zn/Fe比值比热液喷口处颗粒物中低，Pb表现出在海水中运移距离较短或者是只有少量Pb随热液柱扩散运移。热液柱沉降作用使Li，Mo和Ni在沉积物中富集。此外，铁锰氧化物颗粒在海水中吸附-共沉淀作用导致V在沉积物中富集。沉积物中Ti和Al有非常好的相关性，其Ti/Al比值为0.05左右。U在岩芯中含量与深海沉积相似。

滇东南都龙锡锌多金属矿床矿物学及年代学

都龙锡锌多金属矿床位于云南省马关县都龙镇，是我国最大的锡石硫化物矿床之一。在野外地质和岩矿鉴定基础上,本文对该矿床的绿泥石、鲕状黄铁矿、磁黄铁矿异构交生体、铁闪锌矿的“黄铜矿疾病”等矿物和特殊组构，开展了比较系统的电子探针、拉曼光谱和X光衍射等微束分析，结合对该矿床的黑云母Ar-Ar年代学、锡石TIMS法U-Pb年代学研究，基本明确了矿床各个成矿期次的具体成矿特点，丰富和完善了该矿床的成矿模式。论文取得的主要认识有： （1）绿泥石与锡矿化同为燕山期岩浆热液作用的产物。绿泥石的形成温度（231~304oC）和环境（还原环境）表明，岩浆热液叠加成矿环境为中、低温的还原环境。 （2）鲕状黄铁矿为热水沉积期的特征矿物，是Fe、Zn、S等成矿元素的主要物源。 （3）磁黄铁矿主要在区域变质晚期，由黄铁矿（主要为鲕状黄铁矿）变质脱硫而成。辣子寨矿段单斜磁黄铁矿的出现，说明燕山期岩浆热液叠加成矿温度在该矿段以中低温为主。 （4）铁闪锌矿的“黄铜矿疾病”主要是黄铜矿交代铁闪锌矿的结果，其中的Fe主要来自变质期形成的铁闪锌矿和磁黄铁矿，而Cu主要来自岩浆热液。 （5）自然铋、自然银、锡石、黄铜矿、方铅矿等矿物广泛共生，且交代、穿切其他矿物，表明岩浆热液期的成矿元素组合主要为Bi+Ag+Sn+Cu+Pb。在该矿床首次发现的自然铋和自然银，指示岩浆热液期为低硫、中低温的还原环境。 （6）利用远红外（IR-Laser）阶段加热技术，获得黑云母的低温段和高温段坪年龄，分别为179.0± 5 .0Ma和195.7± 6.6Ma。在黑云母组构显微分析的基础上，认为179.0± 5 .0Ma大致代表了变质成矿作用的年龄。 （7）都龙锡锌多金属矿床属于多成因复成矿床，其形成主要经历了热水沉积、变质改造和岩浆热液叠加三个过程。热水沉积成矿作用形成的鲕状黄铁矿，可能是后期成矿作用中Fe、Zn、S等成矿元素的主要物源。变质改造成矿作用与印支期晚期区域变形-变质作用有关，形成了大量铁闪锌矿、磁黄铁矿，可能对应于造山后伸展事件。岩浆热液叠加成矿作用与燕山晚期老君山花岗岩有关，发生大规模的锡、铜、银、铅、铋矿化。 另外，本次研究在该矿床中首次发现了自然铋、自然银等自然元素，其矿床成因意义有待进一步研究。

氟、氯对热液钨、铜成矿的制约-以江西德兴铜矿、大吉山钨矿为例

矿化剂在热液矿床成矿过程中的重要作用一直为人们所关注，矿化剂地球化学行为直接影响成矿元素的富集成矿，不同的矿化剂元素可能对金属成矿具有一定的专属性。本文以著名的江西德兴铜厂超大型斑岩铜矿床和大吉山钨矿床作为研究对象，研究F、Cl与W、Cu成矿的关系。主要的认识如下：（1）F在花岗质岩浆中，可以降低岩浆的粘度、密度、固液相线温度、改变熔体结构，而Cl对熔体结构没有多大的影响。F在流体一花岗质熔体相间，绝大多数配分系数小于1.0，趋向于熔体相中配分，DF随体系中F浓度的升高而增加。Cl在流体一花岗质熔体相间的配分系数均大于1.0，且Dc1 随体系中Cl浓度的升高而增大·Cl强烈地趋向富集于流体相中。（2）Cu在流体一花岗质熔体作用过程中，铜总趋向于流体相中分布（DCu都大于1）。特别是在富Cl流体中Cu浓度较高，说明在富含Cl的热液流体能够从共存的熔体中活化迁移出大量的 Cu，S的加入DCu有降低的趋势。钨趋向于熔体相中富集，其配分系数大多小于1.0。（3）德兴铜厂花岗闪长斑岩属钙碱性系列岩石属I型花岗岩类，具有埃达克岩的特征。岩浆来源于深部，在结晶演化过程中发生了围岩物质的混染，这种高铜含量围岩的混染使成矿物质在岩浆中得到富集，有利于铜的活化、迁移。在铜厂岩体不同的蚀变带中，SiO2、K2O、Cu、Mo等从新鲜斑岩甚至弱蚀变带中带出，而在强蚀变带强烈富集，Cl同样有在强蚀变岩石中富集的趋势；而Na2O、Fe从斑岩体中带出，进入流体相中，流体中大量Fe的存在，有利于铜的沉淀、富集成矿。（4）德兴铜厂斑岩体微量元素和稀土元素地球化学特征表明，该岩体发生了流体一熔体作用，分异出来的流体是一种相对富氯的流体，同时成矿流体的流向是从岩体中心向接触带方向流动。（5）大吉山花岗岩具有高SiO2、A/CNK值，显示过铝质特点。黑云母花岗岩是壳源花岗岩但又受到慢源岩浆或慢源流体的影响。随着花岗岩的演化（从I→II→III）SiO2、K2O＋Na2O逐渐增加，ΣFe、Al2O3、CaO、F含量降低，为成矿提供了大量的矿化剂（F）和沉淀剂（Fe、Ca）。Eu负异常从I至III阶段花岗岩逐渐加强，表明该岩浆经历了高度的分异演化。（6）大吉山花岗岩类稀土元素具有“四重效应”配分的特点以及微量元素对玲Rb、Y/Ho、Zr/Hf以及Nb／Ta发生明显分异，暗示在花岗岩岩浆的演化过程中，经历了充分的流体一熔体作用，同时分异出大量富含F、W等矿化剂元素和成矿元素的热液流体，致使钨矿的形成。大吉山石英脉型钨矿的成矿年龄大约在155 Ma。（7）通过对成矿流体和花岗质岩石黑云母、白云母中卤素相对逸度的研究（log(H2O/fHCl）fluid、log（fHF/fHCl）fluid）发现，铜厂斑岩型铜矿床的成矿体系是相对富氯体系，而大吉山石英脉型钨矿床成矿体系相对富氟，同时氟可能主要迁移W、Sn、Nb、Ta等金属元素。（8）结合斑岩型铜矿床成矿流体特征，铜主要以C1的络合物形式存在和迁移，迁移形式主要是CuCl0、CuCl2等。石英脉型钨矿床中，钨主要以钨酸、钨酸盐及其离解形式存在和迁移，如WO42-、HWO4-、NaHWO4、Naw伍．等；在高度富氟的成矿流体中，钨的氟氧络合物（如WO3F-，WO2F42-等）对钨迁移也具有重要的作用。因此，不同矿化剂类型具有一定的成矿专属性，热液铜矿床主要与Cl、S有 关，而热液钨矿床大多与F有关。

膏盐沉积环境浅成烃地球化学

以江汉盆地潜江组沉积物为主要研究对象，结合其他沉积环境样品，详细讨论了膏盐沉积环境浅成烃地球化学特片、高硫干酷根特征、有机质与无机质联系以及膏盐沉积环境浅成未成熟原油的原因。1、研究表明膏盐沉积环境浅层生油岩转化率达22.6%，明显高于其他湖相沉积环境。江汉盆地潜江组浅层生油岩(<2200M)的有机碳平均值为1.44%。浅层生油岩和未成熟原油具有很高的非烃、沥青质含量(>60%)，明显不同于正常原油的族组成。潜江组浅层生油岩和未成熟原油具有较高的含硫量，高的可达14%。浅层生油岩和原油具有特征性烷烃生物标志物组成。未成熟生油岩的定量-模拟实验表明，烷烃中高含量的藿烷 、甾烷、伽玛蜡烷以及植烷是未成熟的标志。浅层生油岩和未成熟油芳烃化合物分布变化较烷烃大，常以某一类型的化合物为主。浅层高硫原油和高硫生油岩含有丰富的有机含硫化合物。潜江凹陷某些中等含 硫量的生油岩和原油含有脱羟基维生素E类化合物。首欠发现膏盐沉积环境存在新的自由基卟啉和金属卟啉。2、研究表明烷烃、卟啉生物标志化合物均可用于古沉积环境的评价，并首次建立了卟啉古环境判识指标。3、热模拟实验研究表明高硫干酷根在低温下可以生油。高硫干酷根的裂解不能解释江汉盆地未成熟原油的原因。4、C-S-Fe关系研究表明高硫有机物的形成与潜江组沉积时底部水厌氧、沉积速度快、铁来源受到限制有关。X-衍射和全岩化学分析表明潜江组生油岩的矿物成份缺少酸性粘土矿物，并有较多的碳酸盐含量。矿物成份对有机质的生成、演化具有重要的作用。5、江汉盆地产出的中等硫含量未成熟油高含硫未成熟油是类脂物质在特殊条件下富集而形成的。指出应注意在膏盐沉积环境中寻找未成熟原油。建立了高温色谱、高温色谱-质谱、镍弹测硫法、有机硫同位素测定法。将其成功地应用于卟啉化合物、含硫化合物的研究。

New progress in R&D of lower olefin synthesis

This paper gives a brief review of R&D researches for light olefin synthesis directly and indirectly from synthesis gas in the Dalian Institute of Chemical Physics (DICP). The first pilot plant test was on methanol to olefin (MTO) reaction and was finished in 1993, which was based on ZSM-5-type catalyst and fixed bed reaction. In the meantime, a new indirect method designated as SDTO (syngas via dimethylether to olefin) was proposed. In this process, metal-acid bifunctional catalyst was applied for synthesis gas to dimethylether(DME) reaction, and modified SAPO-34 catalyst that was synthesized by a new low-cost method with optimal crystal size was used to convert DME to light olefin on a fluidized bed reactor. The pilot plant test on SDTO was performed and finished in 1995. Evaluation of the pilot plant data showed that 190-200 g of DME were yielded by single-pass for each standard cubic meter of synthesis gas. For the second reaction, 1.880 tons of DME or 2.615 tons of methanol produced 1 ton of light olefins, which constitutes of 0.533 ton of ethylene, 0.349 ton of propylene and 0.118 ton of butene. DICP also paid some attention on direct conversion of synthesis gas to light olefins. A semi-pilot plant test (catalyst 1.8 1) was finished in 1995 with a CO conversion > 70% and a C(2)(=)-C(4)(=) olefin selectivity 71-74% in 1000 h. (C) 2000 Published by Elsevier Science B.V. All rights reserved.

Effect of pore ring number of zeolites on catalytic performance of Mo/Zeolite in methane aromatization under non-oxygen condition

The catalytic behavior of Mo-based zeolite catalysts with different pore structure and size, particularly with 8 membered ring ( M R), 10 M R, coexisted 10 and 12 M R, and 12 M R, was studied in methane aromatization under the conditions of SV=1500 ml/(g.h), p=0.1 MPa and T = 973 K. It was found that the catalytic performance is correlated with the pore structure of the zeolite supports. The zeolites that possess 10 MR or 10 and 12 MR pore structure with a pore diameter equal to or slightly larger than the dynamic diameter of benzene molecule, such as ZSM-5, ZSM-11, ZRP-1 and MCM-22, are fine supports. Among the tested zeolite supports, MCM-22 exhibits the highest activity and selectivity for benzene. A methane conversion of 10.5% with benzene selectivity of 80% was achieved over Mo/MCM-22 catalyst. The Mo/ERS-7 catalyst with 8 MR (0.45 nm) does not show any activity in methane dehydro-aromatization, while Mo/JQX-1 and Mo/SBA-15 catalysts with 12 MR pore exhibit little activity in the reaction. It can be concluded that the zeolites with 10 MR pore or coexisted 10 and 12 MR, having pore size equal to or slightly larger than the dynamic diameter of benzene molecule, are fine supports for methane activation and aromatization.

Formation of the V center on H-type zeolites with thermal treatment

The effect of thermal treatment on H-MCM-22 and H-ZSM-5 zeolites was investigated using the electron spin resonance technique. A six-line signal (denoted as A, g = 2.048, A = 22. 15 G) was detected on H-MCM-22 after He purging at high temperatures, whose intensities increased with the treating temperature. The same signal was also found on H-ZSM-5 zeolites with different crystal sizes. The paramagnetic center was identified as a V center, namely, a hole of an electron trapped on an oxygen atom bonding to a nearby aluminum atom. These signals appeared only on a dealuminated sample or a sample concomitantly with dealumination. The formation of the hole might involve an electron transferring from the lattice oxygen to a nonframework aluminum species, and the hyperfine splitting is caused by the interaction between the electron hole locating on the p orbit of oxygen and the framework aluminum bonding with the oxygen. The signal disappeared after the sample was exposed to air or oxygen at room temperature. However, the process was reversible. A new set of signals (denoted as B, g(1) = 2.008, g(2) = 2.003, g(3) = 1.9985) was observed after oxygen adsorption on the H-MCM-22 pretreated with He at 973 K or He purging at 973 K on the H-MCM-22 pretreated with oxygen at 813 K, which was attributed to the O- species.

The active sites in different TS-1 zeolites for propylene epoxidation studied by ultraviolet resonance Raman and ultraviolet visible absorption spectroscopies

The titanium species in four kinds of titanium-containing MFI zeolites have been studied by ultraviolet (UV)-Raman and ultraviolet visible (UV-Vis) absorption spectroscopies and by the epoxidation of propylene with diluted H2O2 solution (30%). UV-Raman spectroscopy is proved to be a suitable means to estimate qualitatively the framework titanium in TS-l zeolites. Based on the comparison of the relative intensity ratio I-1125/I-380 of UV-Raman spectra, the TS-1(conv.) sample synthesized hydrothermally by the conventional procedure shows the highest amount of framework titanium. UV-Vis spectroscopy reveals that besides minor anatase. titanium species are mainly tetrahydrally coordinated into the framework for TS-l(conv.) or the Ti-ZSM-5 sample prepared by gas-solid reaction between deboronated B-ZSM-5 and TiCl4 vapor at elevated temperatures. For the TS-1(org.) and TS-1(inorg.) samples synthesized hydrothermally using tetrapropylammonium bromide (TPABr) as template and tetrabutylorthotitanite (TBOT) and TiCl3 as titanium source, respectively, the presence of mononuclear and isolated TiOx species which are proposed to bond to the zeolite extraframework is observed. In addition to the framework titanium species, these isolated TiOx species are assumed to be also active for propylene epoxidation.

Coke formation during the methanol conversion to olefins in zeolites studied by UV Raman spectroscopy

Coke formation on/in ZSM-5, USY and SAPO-34 zeolites was investigated during the methanol conversion to olefins at temperatures from 298 to 773 K using ultraviolet (UV) Raman spectroscopy. The fluorescence interference that usually obscures the Raman spectra of zeolites in the conventional Raman spectroscopy, particularly for coked catalysts, can be successfully avoided in the UV Raman spectroscopy. Raman spectra are almost the same for adsorbed methanol on the three zeolites at room temperature. However, the Raman spectra of the surface species formed at elevated temperatures are quite different for the three zeolites. Coke species formed in/on SAPO-34 are mainly polyolefinic species, and in/on ZSM-5 are some aromatic species, but polyaromatic or substituted aromatic species are predominant in USY at high temperatures. Most of the coke species can be removed after a treatment with O-2 at 773 K, while some small amount of coke species always remains in these zeolites, particularly for USY. The main reason for the different behavior of coke formation in the three zeolites could be attributed to the different pore structures of the zeolites. (C) 2000 Elsevier Science B.V. All rights reserved.

Characterization of melanoidins from a glucose-glycine model system

The properties of melanoidins prepared from glucose and glycine (GG) were investigated by a three step purification protocol consisting of dialysis, gel filtration at high ionic strength and ion metal affinity chromatography. The high molecular weight fraction obtained in the GG system is responsible for 80% of the total brown colour and its antioxidative ability was about 1/4 of that of Trolox measured by the inhibition of linoleic acid oxidation. GG melanoidins have good affinity towards Cu (II) (32% bound to the resin) while it is much lower towards Pb (II) (10%) and Fe (II) (5%). Capillary zone electrophoresis analysis suggests that GG melanoidins are positively charged, although no signal was observed analysing melanoidins by matrix-assisted laser desorption-ionisation time-of-flight mass spectrometry (MALDI-TOF/MS).