Crystal chemistry of titanite-structured compounds: the CaTi1-x Zr x OSiO4 (x≤0.5) series

Inhomogeneous aggregates of late-stage titanite enriched in Zr have been described recently from post-magmatic parageneses in silica-undersaturated rocks. In the natural samples, simple isovalent substitution of the large Zr (^[vi]R⁴⁺=0.72 Å) for Ti (^[vi]R⁴⁺=0.605 Å) is limited to an empirical maximum of 0.25 afu (15.3 wt.% ZrO₂). As the natural material is not suitable for crystallographic study, a series of CaTi_1-xZr_xOSiO₄ titanite samples have been synthesized by standard ceramic methods at ambient pressure in air, and their crystal structure determined by Rietveld refinement of laboratory powder X-ray diffraction patterns. All of the synthetic Zr-doped titanite varieties adopt space group A2/a and consist of distorted CaO₇ polyhedra together with less distorted (Ti_1-xZr_x)O₆ octahedra and SiO₄ tetrahedra. Cell dimensions and atomic coordinates together with volumes and distortion indices are given for all polyhedra. The empirical limit for Zr substitution in synthetic (F,OH)-free titanite is 0.5 afu (29.6 wt.% ZrO₂). The existence of a Zr analogue of titanite in nature is considered to be unlikely.     

磺化层柱状有机膦酸锆的合成及催化反应研究

在氢氟酸溶液中,混合亚磷酸、4,4’-联苯二膦酸和锆离子反应生成4,4’-联苯二膦酸锆／亚磷酸锆（简称MCZP）,改变有机酸和亚磷酸的比例,可以合成具有相同组分但结构不同的一系列化合物。通过磺化反应,在苯环上接上磺酸基团后,它具有类似强酸性阳离子交换树脂特性．该文首次对这类化合物催化酯化、醚化等典型的酸催化有机反应进行了研究,结果表明其催化转化率高、催化剂可重复使用和再生,是一种很有发展前途的新型固体酸催化剂．     

莫桑比克东部沿海锆钛砂矿矿石质量特征——以赞比西亚省5004C矿区为例

滨海砂矿是目前全球最大的潜在海洋矿产资源之一,仅次于石油与天然气。莫桑比克东部沿海滨海砂矿资源丰富,在世界上占有重要地位。该文结合莫桑比克赞比西亚省5004C矿区锆钛砂矿,分析矿石结构与构造、矿石物质组成、矿物含量及变化等矿石质量特征,为莫桑比克东部沿海锆钛砂矿的勘探和开发提供有利信息。     

Detrital and authigenic(?) baddeleyite (ZrO2) in ferromanganese nodules of Central Indian Ocean Basin

Occurrence of baddeleyite (ZrO2) which is a rare mineral has been recorded in ferromanganese nodules of Central Indian Ocean Basin (CIOB). The mineral occurs either as independent isolated sub-rounded to elliptical grains or in clusters forming fine subhedral crystals (<3 mm) within ferromanganese concretionary growth bands. The mode of occurrence, textural features and chemistry of the mineral suggest detrital and possibly an authigenic origin for baddeleyite. For authigenic origin it is proposed that zirconium might have got released either from the terrigenous sediments or the altered seafloor rocks forming halogen complexes and subsequently it has re-precipitated in the form of baddeleyite within manganese nodules under oxic to sub-oxic conditions.     

中国锆资源利用现状及其进出口形势分析

锆（Zirconium）的原子序数是40,是一种银白色过渡金属,因其制取工艺复杂,不易被提取,所以也常被称为“稀有金属”。锆在空气中表面易形成一层氧化膜,具有光泽,故外观与钢相似。锆耐腐蚀性很强,但是可溶于氢氟酸和王水;高温时,可与非金属元素和许多金属元素反应。锆作为一种相对稀缺性资源,被广泛地应用于电子、陶瓷、玻璃、石化、建材、医药、纺织以及日用品等领域。由于具有惊人的抗腐蚀性能、极高的熔点、超高的硬度和强度等特性,锆在航空航天、军工、核反应、原子能领域也有着不可或缺的地位。核级锆材作为核反应堆堆芯核燃料的包壳材料,与核工业的发展密切关联,在国家战略安全领域具有特殊意义。     

L'érosion chimique et l'érosion mécanique à long terme du substrat granitique (Vendée,France)

We calculate the chemical depletion fraction of the granitic bedrock by analysing the rock-soil enrichment of zirconium. In Vendée (France), chemical weathering rates account for 26% of the denudation rates. Such a chemical depletion fraction characterizes temperate regimes. It is three times lower than that of humid tropical regimes. To cite this article: J.-C. Maurin et al., C. R. Geoscience 337 (2005).     

盐场卤水成色原因分析及脱色方法研究

以天津汉沽盐场高镁卤水为研究对象,对其杂质形式、成色原因进行了系统分析。研究表明,卤水中的成色物质主要是大量的饱和脂类、羧酸类、醇醚类、胺类及不饱和的芳烃类、醛酮类、烯烃类等有机物质,经过氧化氢氧化-氢氧化锆吸附联合脱色工艺后,卤水色度及CODCr去除率分别可达99%和85%,镁离子的损失率可控制在1%以下,吸附剂氢氧化锆经脱附再生后可循环使用,大大降低了工艺运行成本。     

盐场卤水氧化-吸附联合脱色工艺的研究

以天津汉沽盐场高镁卤水为研究对象,分析其成色原因,建立了过氧化氢氧化-氢氧化锆吸附联合脱色工艺,分别考察了脱色剂用量、温度、pH值等因素对卤水色度、CODCr及镁离子损失率的影响,确定了最佳的脱色工艺条件:用卤水处理量1%(体积比)的过氧化氢于室温下将卤水氧化2 h后,在pH值为2～3的条件下经氢氧化锆吸附脱色40 min,氢氧化锆用量为60 g/L。在此条件下,卤水色度及CODCr去除率分别可达99%和85%,镁离子的损失率可控制在1%以下,均高于目前使用的工艺方法。吸附剂氢氧化锆经脱附后可循环使用,大大降低了工艺运行成本。     

Distribution of high field strength elements (Y, Zr, REE, Hf, Ta, Th, U) in adjacent magnetite and chert bands and in reference standards FeR-3 and FeR-4 from the Temagami iron-formation, Canada, and the redox level of the Neoarchean ocean

Adjacent magnetite and chert bands and reference standards FeR-3 and FeR-4 from the Neoarchean Temagami iron-formation (IF) show shale-normalized rare earth and yttrium (REY) patterns with low Nd/Yb ratios and positive Eu, Gd and Y anomalies, indicating that they formed as marine chemical sediments. In contrast to previous claims, none of the samples shows any Ce anomaly, indicating the absence of oxidative Ce-REY decoupling and arguing against oxic conditions in the wider vicinity of the Neoarchean “Temagami seabasin”. The distribution of Zr, Hf and Ta yields Zr/Hf and Hf/Ta ratios that differ from those of chondrites, average upper continental crust and local shales, suggesting that the Temagami IF is the only case observed so far in which a significant fraction of these elements is non-detrital but sourced from seawater. If Neoarchean seawater was characterized by Zr/Hf and Hf/Ta ratios similar to those of modern seawater these ratios point towards preferential scavenging of Hf over Zr and Ta, as is typical of the modern ocean. Similar to the 2.9 Ga old Mozaan IF in the Pongola Supergroup, South Africa, the Temagami IF shows low Th/U ratios that differ from those of the respective local shales and from that of average upper continental crust. Decoupling of U and Th results from U⁴⁺ oxidation in the Earth's surface system and fractionated Th/U ratios in these marine chemical sediments are, therefore, at odds with the lack of Ce anomalies. This suggests a different redox-sensitivity of the two paleo-redox-proxies Th–U and Ce-REY and demonstrates that the Temagami IF and the Mozaan IF warrant further study of other paleo-redox-proxies.     

10000吨氧氯化锆生产工艺的改进研究和经济效益分析

通过对晶安高科万吨氧氯化锆生产工艺的研究改进,在生产中取得较好的经济效益,(1)洗渣中二氧化锆回收率提高;(2)用于洗涤硅渣的工业盐酸的加入量减少,减少了酸雾对环境的污染;(3)水转料中二氧化硅含量降低了,氧氯化锆的使回收率提高了;(4)水转料中氧化钠含量降低了,产品质量得到提高;二次废酸的使用周期延长.