水热法分解钾长石制备雪硅钙石的实验研究

采用CaO作为助剂,在低温、中压的水热条件下分解钾长石,继而合成一种水合硅酸钙--雪硅钙石,同时得到KOH稀溶液,可用于制备高纯碳酸钾。影响晶化反应的主要因素有n(Ca)/n(Al+Si)、晶化温度、晶化时间、水固比（质量比）、搅拌速度等。讨论了各因素对钾长石分解及雪硅钙石形成的影响,通过X射线粉末衍射、热重-差热分析、扫描电镜等手段对合成产物进行结构性能表征。实验结果表明,以CaO为助剂分解钾长石,同时合成雪硅钙石的工艺方法可行,资源利用率接近100%。实验得到的优化工艺条件为：晶化温度为220～250 ℃,n(Ca)/n(Al+Si)在0.8～1.0之间,晶化时间5～8 h,水固比为20～25,搅拌速度400 r/min。在此条件下,钾长石中K₂O的溶出率达80%以上,同时得到结晶良好的针状雪硅钙石晶体。     

利用钾长石合成雪硅钙石纳米粉体的反应机理研究

采用CaO为助剂,在水热条件下分解钾长石,进而合成雪硅钙石。影响反应的主要因素为：n(CaO)/n(SiO₂+AlO_1.5)、晶化温度和晶化时间等。在n(CaO)/n(SiO₂+AlO_1.5)为0.75～1.00、晶化温度为230～250 ℃、晶化时间为5～8 h的条件下,可以合成结晶良好的雪硅钙石晶体。反应机理分析表明：在钾长石-氧化钙的水热体系中,钾长石的分解并不是简单的离子交换作用或铝硅酸盐解聚作用,而是在碱金属离子与水作用的基础上,反应物中H⁺与矿物表面的碱金属离子K⁺、Na⁺、Ca²⁺作用,首先形成表面富硅贫铝的前驱聚合体（SiO_2·nH₂O）;然后这些前驱聚合体分解,与溶液中的Ca²⁺作用,生成C-S-H凝胶和水钙铝榴石;随着反应时间的延长,C-S-H凝胶和水钙铝榴石进一步转变为雪硅钙石。     

硅酸钙晶种法回收污水中磷的实验研究

实验研究了以钾长石水热分解的副产物沉淀硅酸钙为晶种,回收模拟污水中磷的效果。结果表明,晶种用量0.4 g/L、p H值为8、Ca/P(摩尔比)=2条件下反应2 h后,污水中剩余磷浓度为0.32 mg/L,低于我国污水综合排放一级A标准0.5 mg/L。沉淀硅酸钙重复使用60次后回收磷的效果仍然较好,回收率为79.5%以上。采用扫描电镜、红外光谱、粉晶X射线衍射等测试手段对回收产物进行的分析表明,回收磷产物以羟磷灰石形态存在,产物中P2O5含量在35%以上,达到了富磷矿的品位。沉淀硅酸钙有望成为回收磷的理想晶种材料。     

利用钾长石粉体合成雪硅钙石的实验研究

以氧化钙为反应物料,在200～250℃的水热反应条件下分解钾长石。实验研究了在不同的Ca/(Si Al)摩尔比、水固比、反应温度和反应时间条件下,钾长石中K2O的溶出率和固相的物相变化。结果表明,液相中K2O的溶出率为40%～87%,固相反应产物为结晶良好雪硅钙石晶体。采用化学分析、XRD、SEM、DSC_TG和BET等方法对合成的雪硅钙石粉体进行了表征,结果表明,合成的雪硅钙石粉体是由长5～10μm、宽100～200nm、厚度为49～50nm的薄片纤维晶体交织成的直径为30～40μm的空心球形团聚体,耐火温度高于650℃,是制备硅酸钙保温材料的良好原料。     

雪硅钙石的矿物学特征研究

研究发现,雪硅钙石是一种硅酸钙水化物.根据电子探针分析结果计算得到的化学式为（Ca_4.424K_0.021Mg_0.003）_4.448（Si_5.731Al_0.728）_6.465O₁₆（OH）₂·4H₂O,与经典化学式Ca₅Si₆O₁₆（OH）₂·4H₂O基本一致.通过X射线粉晶衍射结果分析认为,该雪硅钙石属于1.4 nm类型雪硅钙石.雪硅钙石矿物呈放射状纤维集合体,颗粒大小为0.2 mm×0.5 mm×0.3 mm,黄褐色,正低突起,最高干涉色为Ⅰ级黄,二轴晶正光性,光轴角为53°.     

几种添加剂对合成硬硅钙石二次粒子形貌的影响

在利用高纯度钙质、硅质原料合成硬硅钙石过程中分别加入少量的Sr(NO3)2,Mn(CH3COO)2·4H2O,ZrOCl2·8H2O3种添加剂对硬硅钙石二次粒子形貌的影响。实验结果表明,单纯使用高纯度原料生成硬硅钙石结晶不好,纤维不明显;在原料中加入Mn(CH3COO)2·4H2O添加剂后,对于生成的硬硅钙石晶体有一定的帮助,可以看到比较明显的硬硅钙石纤维;原料中加入Sr(NO3)2添加剂后有利于生成硬硅钙石晶体,硬硅钙石二次粒子球形明显,也可以看到明显的硬硅钙石纤维;加入适当少量ZrOCl2·8H2O的添加剂后进一步可以获得结构中空的大直径超轻硬硅钙石二次粒子及良好的硬硅钙石纤维。     

水滑石及其焙烧产物对磷酸根的吸附

用共沉淀法合成了n(Mg)/n(Al)为2∶1的水滑石,通过在500℃下焙烧得到了其焙烧产物。研究了反应时间、pH及磷酸根浓度对磷酸根在水滑石及其焙烧产物上吸附量的影响。结果表明,水滑石对磷的吸附容量小于其焙烧产物,其吸附等温线都可以用Freundlich等温方程描述。在磷酸根浓度较低时(<0.05mmol/L),水滑石及其焙烧产物都可作为磷的高效吸附剂;当磷的浓度大于0.05mmol/L时,水滑石不能作为磷的高效吸附剂,但当磷酸根浓度在0.05～2.5mmol/L时,其焙烧产物仍可作为磷的高效吸附剂。在酸性环境下,水滑石及其焙烧产物在对阴离子的吸附过程中都有中和酸性溶液的作用。水滑石及其焙烧产物对磷的吸附具有不同的机理,并得到了X射线衍射的证实。     

利用13X沸石分子筛净化含Pb~(2+)废水的实验研究

采用静态间歇法 ,实验研究了含Pb2 +废水的 pH值及吸附时间对 13X沸石分子筛吸附Pb2 +性能的影响 ,得出了最佳去除效果的优化条件为 :废水的 pH值接近中性 ,吸附时间 10min。通过吸附实验 ,确定了在Pb2 +初始浓度为 2 0mg/L的条件下 ,13X沸石对Pb2 +的吸附量为 2 1 4 2mg/g ,即每克沸石净化含Pb2 +废水的最大体积量约为 75 0mL。解析实验表明 ,加入沉淀剂 ,浓缩洗脱液中的Pb2 +即以PbS的形式生成沉淀 ,为回收金属铅提供了可能 ;13X沸石在循环使用 5次的条件下 ,对废水中Pb2 +的吸附率仍高达 98% ,重复使用性能良好。经处理后的净化水中Pb2 +的浓度小于 0 4mg/L ,显著低于国家废水排放标准GB8978 88的指标 ( 1 0mg/L)。 13X沸石对Pb2 +的主要吸附形式是离子交换和表面络合反应。     

炉渣处理含磷废水的实验研究

以炉渣作为吸附剂，用静态吸附实验方法研究了炉渣对模拟含磷废水脱磷的一般规律，结果表明，炉渣是一种有效的吸附剂，对废水中的磷有较强的吸附去除性能。影响炉渣除磷的主要因素有吸附时间、炉渣用量、pH值和原水含磷浓度。在含磷浓度2～13mg／L、炉渣用量5g／L、中性、吸附时间为2h的实验条件下，磷的去除率可高达99％以上。     

碳硅钙石的矿物学特征和晶体化学讨论

本文碳硅钙石产于安徽濉溪邹楼铁矿床中。对该矿物进行了某些矿物学研究,修正了前人的碳硅钙石X射线粉晶衍射指标中的错误和不足。根据晶体结构测定结果,作者应用键价模型讨论了碳硅钙石结构中配位多面体的结构畸变等晶体化学问题。     

Uptake of Eu(III) by 11 Å tobermorite and xonotlite: A TRLFS and EXAFS study

The uptake of Eu(III) by crystalline calcium silicate hydrate (C-S-H) phases 11 Å tobermorite and xonotlite has been investigated by the combined use of time-resolved laser fluorescence spectroscopy (TRLFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Eu(III) doped tobermorite and xonotlite samples with varying metal loading (0.4, 7 and 35 μmol Eu/g solid phase) and reaction time (1-570 days) were investigated. The structural environment of Eu(III) taken up by tobermorite and xonotlite was found to depend on both parameters.At high Eu(III) loading (7 μmol Eu/g solid phase), TRLFS data indicated presence of three Eu(III) species with different fluorescence lifetimes after 1 day reaction time. The emission lifetimes deduced for the different species correspond to ∼4.7, ∼1 and 0 water molecules in the first coordination sphere, thus suggesting the presence of one surface species forming an inner-sphere surface complex and two species incorporated in the crystal structure. After longer contact times (90 days, 570 days), the surface species was not observed. At the lower Eu(III) loading (0.4 μmol Eu/g solid phase) and reaction times between 1 and 310 days only two Eu(III) species with ∼1-2 and 0 water molecules were detected, corresponding to Eu(III) being incorporated in the crystal structure. The results from EXAFS showed that the distances between Eu(III) and neighboring Ca and Si atoms in Eu(III) doped tobermorite increase after prolonged reaction time. Furthermore, the number of neighboring Ca and Si atoms was found to increase with time. This study demonstrates that binding into the structure of 11 Å tobermorite and xonotlite is the dominant mode of Eu(III) immobilization after long reaction time. This finding is essential for an overall assessment of the safe disposal of actinides in deep geological repositories for radioactive waste, as incorporation into the crystal structure suggests long-term immobilization in the repository environment.     

中国北方某湖泊底泥污染分析及重金属潜在生态风险评价

以中国北方某湖泊(以下称A湖)为例,开展了底泥中氮磷污染及重金属生态风险评价研究,探讨多种评价方法的相关性,并分析底泥中氮磷元素向上覆水迁移造成水体富营养化的风险.选取A湖中心区域的10个底泥监测点位数据,对其总氮、总磷及重金属(Pb、Cr、As、Cd、Ni)含量进行分析,并采用有机污染指数法评价总氮污染,单因子指数法...     

钾、钠离子对垃圾渗滤液RO浓缩液中鸟粪石结晶的影响

垃圾渗滤液RO浓缩液等高氨氮废水中钾钠离子浓度较高,而钾钠离子对鸟粪石结晶法回收氨的影响规律尚未了解。本文通过向人工配制不同钾钠浓度的模拟和实际RO浓缩液中投加镁盐、磷酸盐促使鸟粪石结晶,测定结晶前后溶液中氨氮、磷酸盐、钾钠离子浓度,并利用XRD、SEM分析结晶产物的结构和形貌,探讨钾钠离子对鸟粪石结晶及氨回收率的影响。结果表明,随着K~+浓度增加,氨氮回收率由96. 5%降至83. 0%,结晶产物中K~+质量分数由2. 4%升至6. 4%;鸟粪石特征衍射峰向高角度偏移,说明K~+进入鸟粪石晶格位置形成含钾鸟粪石;由于K~+与NH4+存在竞争,在相同镁、氨氮、磷配比条件下会降低氨的回收率,但K~+对鸟粪石粒径和形貌基本无影响。Na+对氨氮回收率影响不显著,但会影响鸟粪石晶体形貌。用实际垃圾渗滤液RO浓缩液实验表明,在鸟粪石结晶回收氨氮的水处理中考虑到K~+的竞争,提高镁盐、氨氮与磷酸盐的投加比例为1. 8∶1∶1. 5即可保证氨氮的回收率,同时还可部分回收其中的K~+成为缓释肥营养组分。     

方解石负载羟基磷灰石复合材料去除水中铀离子的PRB活性介质研究

铀污染地下水分布于世界多国,其危害备受关注。本文基于溶胶-凝胶法制备方解石负载羟基磷灰石复合材料(CLHC),通过静态与动态对比试验,探讨了PRB活性介质对水中铀离子的吸附机理和去除效果。试验结果表明,制备的CLHC表面被羟基磷灰石覆盖,对铀离子具有较强的吸附能力。当U的初浓度为5.0 mg/L、试验周期为2 h、溶液pH值为4、CLHC用量为0.5 g/L时,CLHC可以吸附水中所有的铀离子。CLHC对铀离子的吸附过程可以用Langmuir等温吸附模型、粒子内扩散吸附动力学模型和准二级吸附动力学模型较好地进行描述。石英砂负载羟基磷灰石与CLHC相比,后者具有更强的吸附能力,而且具有更长的使用寿命。CLHC在吸附铀的过程中没有价态变化,其对铀离子的吸附主要为离子交换的化学吸附。本研究的成果可为可渗透反应墙被应用于铀污染地下水修复提供试验依据。     

Behavior and effects of phosphorus in the system Na2O−K2O−Al2O3−SiO2−P2O5−H2O at 200 MPa(H2O)

The addition of phosphorus to H₂O-saturated and initially subaluminous haplogranitic (Qz–Ab–Or) compositions at 200 MPa(H₂O) promotes expansion of the liquidus field of quartz, a marked decrease of the solidus temperature, increased solubility limits of H₂O in melt at low phosphorus concentrations, and fractionation of melt out of the haplogranite plane (projected along an Or₂₈ isopleth) toward a peralkaline, silica-poor but quartz-saturated minimum composition. The partition coefficient for P₂O₅ between aqueous vapor and melt with an ASI (aluminum saturation index, mol Al/[mol Na+K])=1 is negligible (0.06), and consequently so are the effects of phosphorus on other melt-vapor relations involving major components. Phosphorus becomes more soluble in vapor, however, as the concentration of a NaPO₃ component increases via the fractionation of melt by crystallization of quartz and feldspar. The experimental results here corroborate existing concepts regarding the interaction of phosphorus with alkali aluminosilicate melt: phosphorus has an affinity for alkalis and Al, but not Si. Phosphorus is incorporated into alkali feldspars by the exchange component AlPSi_-2. For subaluminous compositions (ASI=1), the distribution coefficient of phosphorus between alkali feldspar and melt, D[P]Af/m, is 0.3. This value increases to D[P]Af/m=1.0 at a melt ASI value of 1.3. The increase in D[P]Af/m with ASI is expected from the fact that excess Al promotes the AlPSi_-2 exchange. With this experimental data, the P₂O₅ content of feldspars and whole rocks can reveal important facets of crystallization and phosphorus geochemistry in subaluminous to peraluminous granitic systems.     

Genesis of a low-grade apatite-ilmenite-magnetite deposit in the Kauhajärvi gabbro, western Finland

The Paleoproterozoic Kauhajärvi gabbro is one of several Fe-, Ti-, and P-rich mafic intrusions associated with granitoids in the Fennoscandian shield in western Finland. The gabbro is cut by the late-orogenic Lauhanvuori granite (ca.1870?Ma), whereas the surrounding area is composed of synorogenic, collision-related granitoids and calc-alkaline volcanic rocks (ca. 1890?Ma) belonging to the Mid Finland Granitoid Complex. The mafic intrusions were probably emplaced into a Svecofennian rift zone. They are characterized by a high phosphorus content; the common occurrence of ilmenite as separate grains; and the coeval crystallization of apatite, Fe-Ti oxides, and Fe-Mg silicates. The Kauhajärvi gabbro is composed of two geochemically and structurally distinct zones. The basal zone is composed of poorly-layered, fine- to medium-grained gabbro, which represents an early intrusion of tholeiitic magma, and has rather high concentrations of chromium, magnesium and silica. Typically, the concentrations of iron, titanium and phosphorus are low, except for the top that is enriched in apatite and ilmenite. During most of the crystal-liquid fractionation of the basal zone magma, low f _O2 limited the crystallization of Fe-Ti-oxides. Instead, titanium became enriched in the uppermost layer of the basal zone. The main zone represents a later injection of more evolved tholeiitic magma and makes up 80 to 90%of the total intrusion volume. Peridotite is common, along with gabbro and gabbronorite, in the lower and middle parts of the main zone, and anorthosite is common near the top of the main zone. The Mg:Fe ratio in mafic minerals and vanadium concentrations in magnetite decrease upwards. The variation within the main zone can be explained by crystal-liquid fractionation of a single batch of a parental magma under conditions of relatively high f _O2. Titanium is not progressively enriched. The ratio of titanium to iron (TiO₂/Fe₂O₃ = 0.16 to 0.20; Fe total as Fe₂O₃) is constant in the main zone and normal for mafic intrusions. Titanium is sited in separate ilmenite grains and in lamella within ilmenomagnetite (Ti-bearing magnetite). The high phosphorus content in the main zone is interpreted to result in crystallization of ilmenite and ilmenomagnetite instead of Ti-rich magnetite under relatively high f _O2 conditions. High concentrations of titanium, iron and phosphorus in rocks of the main zone can be explained by pre-emplacement crystal-melt fractionation in a deep magma reservoir and/or contamination of mantle-derived mafic magmas by granitic magmas from partial melting of crustal rocks. A low-grade Fe-Ti-P resource at Kauhajärvi consists of layers with as much as 20 wt. % combined ilmenite (usually 8 to 11 wt. %), apatite (1 to 8 wt. %) and magnetite (1 to 9 wt. %). Mineralized layers are of variable thickness (2?m to 30?m) and occur in variable host rocks (peridotite or gabbro). The Fe-Ti oxides are most abundant in peridotite and pyroxene- or olivine-rich gabbronorite within the main zone. The contact between mineralized rocks (4%TiO₂) and non- or slightly-mineralized rocks is gradual. The deposit as a whole consists of three to five mineralized layers with maximum combined thickness of 70?m. Apatite is most abundant in the oxide-rich layers, but is locally also concentrated in anorthosite with low Fe-Ti oxide contents. The weight ratio of ilmenite to magnetite is 3:2. The ratio of total Ti-Fe-oxides to apatite averages 4.0, with the range of 1.5 to >15.     

Effects of Sintering Temperature on Crystallization Behavior and Performance of Glass-Ceramics From Coal Fly Ash

The glass-ceramics was prepared from coal fly ash, limestone and Na2CO3 by sintering processes. Effects of the crystallization temperature (850–1100 ℃) on crystallization behavior, microstructure, sintering character and chemical stability of the glass-ceramics samples were analyzed by means of DTA, XRD, SEM and other analytical methods. The results show that the main crystalline phase of as-prepared glass-ceramics after crystallization treatment is gehlenite (Ca2Al2SiO7). The species of crystalline phases keep the same, however, the main crystalline intensity, line shrinkage rate and bulk density increase first then decrease with the increasing of heat treatment temperature. Water absorption of the samples was reduced as the heat treatment temperature rising. The glass-ceramics display high performance crystallization properties and chemical stability. The optimized glass-ceramics with desired sintering character and chemical stability was obtained by crystallized at 1050 ℃.