Fe-ZSM-5分子筛催化降解染料废水的研究

传统的Fenton均相亚铁盐催化剂处理染料废水,具有难以避免的二次污染和亚铁离子流失问题。分子筛催化剂相比传统催化剂具有高效环保的特点,在催化氧化染料废水领域有着良好的前景。本文通过液相离子交换法制备了Fe-ZSM-5非均相分子筛催化剂,替代传统的亚铁盐催化剂,应用X射线衍射对制备的Fe-ZSM-5分子筛催化剂进行表征,表明随离子交换次数的增加,Fe-ZSM-5催化剂负载的铁量上升,且较好地保持了分子筛结构,有利于提高亚铁离子的催化能力。通过实验确定了Fe-ZSM-5催化剂催化反应的最佳温度、pH值、Fe-ZSM-5的用量、反应时间等工艺参数,比较了Fe-ZSM-5催化剂和传统Fenton均相催化剂降解染料废水的脱色率和废水中铁离子的残留量,结果表明Fe-ZSM-5的脱色率达到98.5%,相比于Fenton均相催化剂的脱色率提升约3%;两种催化剂的铁离子残留量差别显著,Fe-ZSM-5催化剂处理的废水中只产生微量的Fe离子,可以认为Fe-ZSM-5非均相分子筛催化剂有效地解决了催化剂损耗和二次污染问题。     

Experimental study of natrolite and scolecite saturation with ammonium, methane, and propane

The incorporation of the molecular species of C-H-N fluid (ammonium, methane, and propane) into the structural cavities of natrolite and scolecite was experimentally studied at t = 200°C, P = 20 MPa, and an experiment duration of 192 h. The zeolites were modified without ion exchange by the exposure of a preliminarily dehydrated mineral to the appropriate gas. The presence of ammonium and light hydrocarbons in the crystal matrix of zeolites was confirmed by IR and Raman spectroscopy and gas chromatography. The data of differential thermogravimetry revealed differences in the behavior of CH₄- and NH₃-zeolites during heating. The X-ray diffraction patterns and IR and Raman spectra of zeolites in the region of framework vibration indicate deformations in the matrix structure after the experiments. The interaction of dehydrated scolecite with “dry” propane resulted in amorphization under the experimental parameters. The maximum methane contents in the freshly synthesized zeolites determined by gas chromatography are 4.12 wt % for CH₄-scolecite and 8.96 wt % for CH₄-natrolite. The synthetic C₃H₈-natrolite contains 4.45 wt % C₃H₈. In the zeolites saturated with respect to dry ammonium, the highest NH₃ contents were observed in the 0.4–0.25 mm scolecite fraction (12.86 wt %), 0.25–0.05 mm scolecite fraction (11.43 wt %), and NH₃-natrolite (9.28 wt %).     

Distribution,genesis, and pollution risk of ammonium nitrogen in groundwater in an arid loess plain,northwestern China

Nitrogenous pollutants from intense human activities have become serious environmental and health problems worldwide, particularly in groundwater source areas used for public water supply. To investigate the genesis and pollution risks associated with elevated concentrations of ammonium nitrogen in a groundwater source area, investigations were undertaken in the Jinji groundwater source area, located in an arid loess plain in northwestern China where 16 groundwater samples were collected from an aquifer used for water supply. The investigation indicated that high concentrations of ammonium nitrogen originated mainly from: infiltration of water from the Yellow River; livestock; and the discharge of industrial wastes. Measured parameters including pH, the permanganate index and the oxidation reduction potential could be used as important indicators of the genesis of ammonium nitrogen. A modified DRTCLN model was applied to the observed distribution of ammonium nitrogen to assess pollution risk of regional groundwater. The model was optimized by rebuilding the index system, and the analytic hierarchy process was used to calculate the rating scale of each index. A Monte Carlo simulation was performed to analyze the uncertainty of results of the risk assessment. The result showed that the risk value is relatively low in most areas of the groundwater source area. Only an industrial area in the southwestern part of the groundwater source area was classified as high risk; it should be the key factor of pollution control.     

Platinum‐Group Element Results for Two Cobalt‐Rich Seamount Crust Ultra‐Fine Reference Materials: MCPt‐1and MCPt‐2

Two Co‐rich seamount crust reference materials, MCPt‐1 and MCPt‐2, were prepared using ultra‐fine particle size milling technique and characterised for the platinum‐group elements (PGEs). The raw material for these two reference materials was collected separately from the Magellan seamounts of the western Pacific Ocean and the seamounts of the central Pacific Ocean by Russian and Chinese scientists. First, they were ground by ball mill to a ?200 mesh powder, then further processed by ultra‐fine jet mill and well‐mixed. The particle size distributions of the samples were tested by a laser particle analyser; the average particle size was 1.8 and 1.5 μm (equal to about 2000 mesh) respectively. The homogeneity of six major and minor elements in these two materials was tested at the milligram level of sampling mass by high‐precision wavelength dispersive X‐ray fluorescence (XRF) spectrometry and at the microgram level of sampling mass by electron probe microanalyser. The homogeneity of more than forty trace elements, including Pt, was tested at the microgram level of sampling mass by LA‐ICP‐MS. Except for Rh, all PGEs were determined by isotope dilution‐ICP‐MS. Platinum in MCPt‐1 and MCPt‐2 was characterised as certified values, whereas the other five PGEs in MCPt‐1 and MCPt‐2 were reported as reference values. In addition, the information values of sixty‐two major, minor and trace elements were obtained by XRF, ICP‐AES and ICP‐MS. The minimum sampling mass for the determination of PGEs was 1 g, while the minimum sampling mass for the determination of the other elements was 2–5 mg.     

四川德阳浅层地下水高含铁成因分析

四川德阳地下水含量丰富,是主要饮用水水源,但铁含量高。通过模拟试验考察了pH值、微生物、铵态氮、氧化还原条件和有机质等因素对土壤二价铁浸出的影响。试验结果表明:（1）酸性条件下土壤二价铁浸出浓度相对较高;（2）在土壤溶液中添加有机质的情况下,随着有机质浓度的增加,土壤溶液中二价铁浓度也增高;（3）在没有微生物参与的条件下,土壤溶液二价铁浓度较低;（4）还原环境土壤溶液二价铁浓度受铵态氮的浓度影响较小;（5）还原条件下,土壤二价铁易被溶出且相比氧化环境下溶出浓度高。结合当地的水文地质和环境地质条件分析得出：德阳浅层地下水的弱酸性、土壤丰富的有机质含量以及还原环境为影响其地下水铁含量的主要原因。     

Hydrothermally grown buddingtonite,an anhydrous ammonium feldspar (NH4AlSi3O8)

Ammonium feldspar was grown hydrothermally from a gel, having a stöchiometric Al₂O₃·6SiO₂ composition. As a source for NH ₄ ⁺ , a 25 percent NH₃ solution was used. Internal Cr/CrN and graphite/methane buffers fixed the fugacity of NH₃ during the experiments. Unit cell parameters of the synthetic ammonium feldspar are a: 0.8824 (5) nm, b: 1.3077 (8) nm, c: 0.7186 (4) nm, β: 116.068 (12)°, V: 0.7448 (34) nm₃. the X-ray power diffraction pattern is measured and indexed in accordance to the space group C2/m. Infrared and thermal gravimetric analyses provide no evidence for the presence of structurally bound water molecules in the crystal structure of synthetic ammonium feldspar. Hydrothermally grown anhydrous ammonium feldspar is shown to be identical to the mineral buddingtonite by the similarity of the data between the synthetic and natural materials. There may be justification for considering natural buddingtonite as an anhydrous feldspar with the ideal formula NH₄Si₃O₈. Reexamination of natural specimens is desirable.     

石墨炉原子吸收法测定生物样品中微量钒

生物样品用灼烧法,除去有机物,在浓度为5％的盐酸介质中,加入EDTA和铵盐作为基本改进剂,清除石墨炉原子吸收法测定钒时铜、铁离子的干扰,可直接测定钒．采用标准加入法回收率为96．4-106．8％,相对标准偏差3．95％。     

碱处理对河北围场天然沸石结构和性能的影响及其机理研究

采用NaOH对围场地区天然沸石进行处理,采用X射线衍射仪、红外光谱仪、N2吸附-脱附技术、扫描电子显微镜等对材料进行表征分析,采用水蒸气吸附法评价材料的亲水性,采用Cr3+和Mn2+评价材料的离子交换性能,探讨了碱处理对天然沸石的结构、亲水性和离子交换性能的影响及其机理.实验结果表明,围场地区天然沸石中主要含有斜发沸石...     

Sorption characteristics and mechanisms of ammonium by coal by-products: slag, honeycomb-cinder and coal gangue

The adsorption behaviors of ammonium from aqueous solutions were investigated for three solid coal wastes, slag, honeycomb-cinder and coal gangue. The ammonium sorption processes were well modeled by the pseudo second-order model (R ² > 0.99). The experimental data were fitted to both the Langmuir model and the Freundlich model, with the Langmuir model better representing the data. The maximum ammonium sorption capacities calculated from the Langmuir model were 3.1, 5.0 and 6.0 mg/g for the slag, honeycomb-cinder and coal gangue samples, respectively. The pH value of the solution affected the ammonium removal, and the higher uptakes found in either neutral or alkaline conditions for the three materials. The thermodynamic parameters, ΔH, were calculated to be 29.75, 25.21 and 17.91 kJ/mol for the SL, HC and CG samples, respectively, with the positive values indicating that the ammonium sorption processes were endothermic. Based on the results, it can be concluded that coal gangue may have more potential for being used as a sorbent for the ammonium removal from wastewater among the three coal by-products.     

Classical and New Procedures of Whole Rock Dissolution for Trace Element Determination by ICP‐MS

Sample digestion is a critical stage in the process of chemical analysis of geological materials by ICP‐MS. We present a new HF/HNO₃ procedure to dissolve silicate rock samples using a high pressure asher system. The formation of insoluble AlF₃ was the major obstacle in achieving full recoveries. This was overcome by setting an appropriate digestion temperature and adding Mg to the samples before digestion. Sodium peroxide sintering was also investigated and the inclusion of a heating step to the alkaline sinter solution improved the recoveries of thirteen elements other than the lanthanides. The results of these procedures were compared with data sets generated by common acid decomposition techniques. Forty‐one trace elements were determined using an ICP‐QMS equipped with a collision cell. Under optimum conditions of gas flow and kinetic energy discrimination, polyatomic interferences were eliminated or attenuated. The measurement bias obtained for eight reference materials (BCR‐2, BHVO‐2, BIR‐1, BRP‐1, OU‐6, GSP‐2, GSR‐1 and RGM‐1) and intermediate precision (RSD) were generally better than ± 5%. The expanded measurement uncertainties estimated for two certified reference materials were mostly between 7 and 15%. New data sets for the reference materials are provided, including constituents with previously unavailable values and also for the USGS candidate reference material G‐3.     

磁铁石英岩铁运输沉淀的pH值条件约束:以朝鲜半岛龙渊铁矿床为例

前寒武纪时期铁矿形成过程中铁物质如何迁移的研究,已取得了众多科研成果,但仍有些问题未得到很好的解决。尤其是对陆壳来源性铁矿床(非Algoma类型)的成因,仍然具有诸多争议,焦点主要集中在铁迁移问题。笔者以朝鲜半岛龙渊铁矿床为例研究了铁介质形成和运输的问题。首先通过铁矿石的地球化学研究和前人研究结果的考察,发现此铁矿床不属于Algoma类型,而是在强酸性介质条件下陆壳物质风化、移动和沉积而形成的。那么为什么会出现如此强大的酸性环境条件呢？为了揭示这一点,对在当时环境下把水的性质能够变成酸性的物质进行了热力学计算。研究结果表明,当硫化物如黄铁矿风化时,形成了能够使铁源物质风化和迁移的介质。这些结果也符合这样一个事实,即目前从富含硫化物地层淋沥的水的pH值小于3.5,并且铁含量远高于非硫化物类型的地层。本次研究结果表明,陆壳来源的铁矿床形成过程中,不能忽视硫化物的风化作用。     

Refinement of Phosphorus Determination in Quartz by LA‐ICP‐MS through Defining New Reference Material Values

The aim of this study was to improve the quality of laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) determination of phosphorus in crystalline quartz. Over the last decade, the Geological Survey of Norway has routinely performed trace element determinations on quartz from both operating and potential quartz deposits by LA‐ICP‐MS. The determined phosphorus concentrations were, with but few exceptions, consistently within the range of 10 to 30 μg g^?1, results that seemed to be both too high and too consistent. The multi‐material calibration curve obtained from a suite of reference materials (NIST SRM 610, 612, 614, 1830, BAM No. 1 amorphous SiO₂ glass) did not define a precise regression line. Published phosphorus concentrations for the reference materials are poorly constrained and the observed dispersions along the multi‐material calibration curve suggest that some of the reference values may be inaccurate. Furthermore, the calibration curve did not pass through the origin of the [(cps ³¹P/cps ³⁰Si) · cone. Si] vs. P concentration diagram; thus, in addition to the uncertainties of the literature values of phosphorus, it is difficult to define the calibration curve. Three reference materials (NIST SRM 614, 1830, synthetic quartz KORTH) were sent for phosphorus accelerator implantation, providing an independent and accurate (± 3%) approach for determining phosphorus concentrations in crystalline quartz. The intrinsic phosphorus concentrations of the three implanted samples plus those for NIST SRM 610 and 612 were determined by secondary ion mass spectrometry (SIMS), yielding new phosphorus values for NIST SRM 610, 612, 614 and 1830. Using these new values resulted in a better defined LA‐ICP‐MS calibration curve. However, the source of the ICP‐MS related background could not be defined, such that it must still be empirically corrected for.     

X射线荧光光谱法同时测定钛精矿中主次量组分

采用铁矿标准样品和高纯二氧化钛混合配制钛精矿的校准样品,X射线荧光光谱法同时测定钛精矿中氧化镁、三氧化二铝、二氧化硅、磷、硫、氧化钙、二氧化钛、五氧化二钒、锰、铁等主次量成分,并对熔剂选择、熔融条件、钒Kα峰位确定及基体效应校正等进行了探讨。测定结果与标准样品标称值吻合,相对标准偏差(RSD,n=7)除低含量的磷、硫外均在5%以下,能满足钛精矿的检测需要。     

A review of the synthesis and characterisation of pillared clays and related porous materials for cracking of vegetable oils to produce biofuels

This paper presents an overview of the modification of clay minerals by propping apart the clay layers with an inorganic complex. This expanded material is converted into a permanent two-dimensional structure, known as pillared clay or shortly PILC, by thermal treatment. The resulting material exhibits a two-dimensional porous structure with acidic properties comparable to that of zeolites. Synthetic as well as natural smectites serve as precursors for the synthesis of Al, Zr, Ti, Fe, Cr, Ga, V, Si and other pillared clays as well as mixed Fe/Al, Ga/Al, Si/Al, Zr/Al and other mixed metal pillared clays. Biofuels form an interesting renewable energy source, where these porous, catalytically active materials can play an important role in the conversion of vegetable oils, such as canola oil, into biodiesel. Transesterification of vegetable oil is currently the method of choice for conversion to biofuel. The second part of this review focuses on the catalysts and cracking reaction conditions used for the production of biofuel. A distinction has been made in three different vegetable oils as starting materials: canola oil, palm oil and sunflower oil.     

红层软岩模型试验相似材料的配比试验研究

相似模型试验是研究红层软岩工程性质的重要手段之一,其试验结果的可靠性依赖于相似材料的正确选择与合理配比。针对红层软岩遇水极易软化的特性,在传统相似材料配比基础上添加生石灰,采用正交设计方法开展了相似材料配比试验,以骨料中铁粉与钡粉质量比例、铁粉与钡粉总质量中铁粉的质量比例、石膏质量、生石灰质量为4个因素,每个因素设置了5个取值水平,共制作25组、610个试样。每组试样均测试了其软化系数、密度、无侧限单轴抗压强度、抗拉强度及黏聚力与内摩擦角等物理力学参数,并研究了这些参数随上述4个因素取值水平的不同而变化的规律。最后,基于上述结果,配制了3种典型的软岩相似材料,并分别开展了真实软岩材料的饱水软化平行对比试验。研究结果表明：（1）根据配比方案所配相似材料物理力学参数可基本满足软岩相似模型试验的要求;（2）相似材料物理力学参数变化规律明显,便于通过调节其配比模拟不同软岩材料;（3）三组对比试验中相似材料饱水软化系数与真实软岩具有较高吻合度。     

自动电位滴定测定锰矿石中锰的方法研究

多批次的锰矿石锰含量滴定分析消耗大量人工,随着自动化电位滴定仪的普及,利用仪器完成容量滴定成为可能,而将手工滴定向自动电位滴定移植是当前需要解决的课题。本文建立了一套自动电位滴定仪测定锰矿石中锰含量的方法,确定了相关滴定参数和等当点识别标准。锰矿石样品采用盐酸、磷酸分解,硝酸去除碳和有机物,高氯酸氧化,形成样品溶液。自动电位滴定仪先用硫酸亚铁铵标准溶液对预先移取的重铬酸钾标准溶液和标定空白溶液分别进行氧化还原滴定,用铂复合电极指示,计算得到硫酸亚铁铵标准溶液浓度,再对样品空白溶液和样品溶液进行氧化还原滴定,得到样品锰含量,方法检测范围为5%～60%。采用本法分析国家一级标准物质,测定结果的准确度和精密度高;分析多个产地不同水平的锰矿石样品,测定结果与手工方法进行对照,经t检验无显著性差异。建立的滴定方法自动化程度高、方法稳健,适用于冶炼企业、港口商检等行业,具有推广价值。     

Alternative valorization of red mud waste as functional materials with catalytic activity for sulfide oxidation in wastewater

This work investigates the catalytic properties toward sulfide oxidation in wastewater for three composites which are functional materials obtained from red mud waste following its neutralization, chemical activation and functionalization of the iron by treatment with disodium salt of ethylenediaminetetraacetic acid, trisodium citrate or a combination of these two organic ligands. X-ray diffraction and diffuse reflectance Fourier transformed infrared spectroscopy characterizations indicated the coexistence of the corresponding iron chelates phases along with hematite the main crystallographic phase from red mud. The most active catalyst was the red mud-derived material obtained by functionalization with the mixture of ethylenediaminetetraacetate and citrate ligands. The results obtained after its testing in multiple reaction cycles showed that the decrease in conversion after 10 reaction cycles was less than 5%. Considering the results of diffuse reflectance ultraviolet visible narrow infrared spectroscopical analysis which revealed that this solid contains species with lower bond strength, it has been inferred that both the higher catalytic activity, as well as the enhanced stability, is directly related to the versatility of the active species.     

Transport and fate of ammonium and its impact on uranium and other trace elements at a former uranium mill tailing site

The remediation of ammonium-containing groundwater discharged from uranium mill tailing sites is a difficult problem facing the mining industry. The Monument Valley site is a former uranium mining site in the southwest US with both ammonium and nitrate contamination of groundwater. In this study, samples collected from 14 selected wells were analyzed for major cations and anions, trace elements, and isotopic composition of ammonium and nitrate. In addition, geochemical data from the U.S. Department of Energy (DOE) database were analyzed. Results showing oxic redox conditions and correspondence of isotopic compositions of ammonium and nitrate confirmed the natural attenuation of ammonium via nitrification. Moreover, it was observed that ammonium concentration within the plume area is closely related to concentrations of uranium and a series of other trace elements including chromium, selenium, vanadium, iron, and manganese. It is hypothesized that ammonium–nitrate transformation processes influence the disposition of the trace elements through mediation of redox potential, pH, and possibly aqueous complexation and solid-phase sorption. Despite the generally relatively low concentrations of trace elements present in groundwater, their transport and fate may be influenced by remediation of ammonium or nitrate at the site.     

Accurate Determination of Sr Isotopic Compositions in Clinopyroxene and Silicate Glasses by LA‐MC‐ICP‐MS

The low‐Sr content (generally < 100 μg g^?1) in clinopyroxene from peridotite makes accurate Sr isotopic determination by LA‐MC‐ICP‐MS a challenge. The effects of adding N₂ to the sample gas and using a guard electrode (GE) on instrumental sensitivity for Sr isotopic determination by LA‐MC‐ICP‐MS were investigated. Results revealed no significant sensitivity enhancement of Sr by adding N₂ to the ICP. Although using a GE led to a two‐fold sensitivity enhancement, it significantly increased the yield of polyatomic ion interferences of Ca‐related ions and TiAr⁺ on Sr isotopes. Applying the method established in this work, ⁸⁷Sr/⁸⁶Sr ratios (Rb/Sr < 0.14) of natural clinopyroxene from mantle and silicate glasses were accurately measured with similar measurement repeatability (0.0009–0.00006, 2SE) to previous studies but using a smaller spot size of 120 μm and low‐to‐moderate Sr content (30–518 μg g^?1). The measurement reproducibility was 0.0004 (2s, n = 33) for a sample with 100 μg g^?1 Sr. Destruction of the crystal structure by sample fusion showed no effect on Sr isotopic determination. Synthesised glasses with major element compositions similar to natural clinopyroxene have the potential to be adopted as reference materials for Sr isotopic determination by LA‐MC‐ICP‐MS.     

电感耦合等离子体原子发射光谱法测定小麦中的微量元素

小麦是中国北方人的主要粮食作物,小麦中含有大量的对人体有益的微量元素,查明这些微量元素的含量对于人体健康具有非常重要的意义。电感耦合等离子体（ICP）测试微量元素具有灵敏度高的特点。该文利用ICP的特点,将小麦硝化分解后,测试小麦中的微量元素,使用美国生产Optima 2100 DV型电感耦合等离子体发射光谱仪,对小麦中人体有益的微量元素硼、铁、钙、镁及重金属污染指标铜、铅、锌进行测试,该方法具有样品的加标回收率和RSD较好,分析速度快、分析结果准确可靠的特点。