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1.
利用钾长石合成雪硅钙石纳米粉体的反应机理研究   总被引:2,自引:2,他引:0  
刘贺  马鸿文  聂轶苗  王蕾 《现代地质》2006,20(2):347-353
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+AlO1.5)、晶化温度和晶化时间等。在n(CaO)/n(SiO2+AlO1.5)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(SiO2·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。  相似文献   

2.
利用钾长石粉体合成雪硅钙石的实验研究   总被引:11,自引:1,他引:11       下载免费PDF全文
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。  相似文献   

3.
以合成雪硅钙石为晶种回收废水中的磷   总被引:2,自引:0,他引:2  
以合成雪硅钙石为晶种,探索了用结晶法以磷酸钙形式回收废水中磷的适宜条件。结果表明,在实验水质条件下,模拟废水pH=8、n(Ca)/n(P)=2、晶种用量大于1.6g/L、振荡24h后溶液中残留磷可达到国家污水综合排放标准一级(0.5mg/L)以下;在优化条件下证实了合成雪硅钙石的供碱能力,循环利用18次,回收磷的效果仍然很好。运用XRD、FTIR、SEM和EDS等测试手段对在实验条件下重复使用18次的雪硅钙石进行了表征,证明回收的磷主要以结晶度不高的羟基磷灰石形态存在。  相似文献   

4.
为处理钾长石水热制备钾霞石所产生的碱性滤液,本文采用水热法,考察了氢氧化铝溶解时间、晶化时间、晶化温度、水碱比对钾霞石产率和白度的影响,并对合成钾霞石物相进行了表征。结果表明,合成钾霞石的最佳条件为,氢氧化铝溶解时间为1.5 h,晶化时间为4 h,晶化温度280℃,水碱比为1.8。XRD结果表明,产物为钾霞石粉体。傅里叶变换红外光谱表明,Al(OH)3中的Al在水热条件下进入到Si—O骨架中形成了Si—O—Al官能团,从而印证了钾霞石的合成。差热分析结果表明,合成钾霞石具有良好的热稳定性。氮气吸附结果表明,合成钾霞石比表面积为5.18 m2/g,平均孔径为32.98 nm。实现了钾长石水热制备钾霞石所剩碱性滤液的资源化利用,并为钾长石水热制备钾霞石提供了一种母液循环的思路,使水热制备钾霞石工业化成为一种可能。  相似文献   

5.
通过具体实例,简要介绍了矿物材料学研究中有关反应动力学研究的基本原理,给出了对硅酸盐体系若干典型过程的反应动力学研究结果,包括:(1)高铝粉煤灰-Na2CO3体系的中温烧结反应和钾长石-石膏-碳酸钙体系钾长石的热分解反应;(2)KA lS i3O8-Ca(OH)2-H2O体系钾长石水热分解-雪硅钙石晶化反应;(3)S iO2-A l2O3-CaO体系微晶玻璃的β硅灰石晶化反应;(4)13X微孔分子筛和MCM-41介孔分子筛对Hg2+的吸附反应。反应动力学研究成果可望对矿物材料制备实验方案优化、工业生产过程的条件控制以及改进矿物材料性能提供理论指导。  相似文献   

6.
与均相水热反应相比,异相水热反应不仅可以提供一个骨架离子的适度过饱和环境,而且其新相成核所需逾越的能垒较低,更有利于晶体的形成和生长。本文采用异相水热法合成在皂石,即固定初始物料中氧化镁的添加量与硅、铝的添加量之和的摩尔比为一定值,n(Mg)/n(Si+Al)=3∶4],在不同的合成温度和时间条件下合成了一系列不同Si/Al比的样品。所有样品的XRD图均呈现层状硅酸盐矿物的特征衍射峰,且d(060)≥0.153 nm,说明合成的是皂石矿物。其中,当n(Si)/n(Al)=5.43~7.89时,皂石的结晶度较好。实验表明,延长时间、提高合成温度有利于皂石晶体生长。在较低温度(160℃)下,样品中的杂相主要为水镁石和方沸石。水镁石相的存在主要归因于氧化镁在碱性条件下的快速水合及水镁石的慢速溶解,而方沸石则是由于Mg2+释放缓慢,导致溶液中Si4+及Al3+相对过剩而形成。这两种杂相均会随着反应时间的延长而逐渐消失。在较高温度(300℃)下,皂石的结晶度明显升高,并由于Mg2+的快速释放导致Mg2+的局部过剩,因而形成了少量1∶1型的纤蛇纹石。  相似文献   

7.
贵州威宁窑上组沉积物物源特征及沉积控制因素分析   总被引:2,自引:2,他引:0  
根据威宁草海第四纪窑上组沉积物主量元素和REE特征,探讨沉积物物源特征、气候演变情况、沉积物堆积控制因素。结果表明:Al、Mg、Ca、K、Na和Ti的含量变化在剖面上一致,它们的相关系数很高(0.522~0.985)。Fe含量和Mn含量呈正相关形式,与Al、Mg、Ca、K、Na和Ti呈负相关。Fe2O3含量在土黄色粘土的铁质层很高(42.86%~50.57%)。样品中REE球粒陨石标准化配分模式与贵州土壤、贵州碳酸盐岩风化壳配分模式很相似,与峨眉山玄武岩配分模式不一致,但其含量略低于贵州碳酸盐岩风化壳的含量;沉积物主要来源于碳酸盐岩,且碳酸盐岩强烈风化成土作用使REE超常富集,在剖面上呈现高ΣREE(平均219.38μg/g)。通过Mg/Ca、MgO/Al2O3、(CaO+K2O+Na2O)/Al2O3、(Fe2O3+Al2O3)/(MgO+CaO)、(K+Na+Ca+Mg)/(Fe+Mn)、(Al+Fe+Mn)/(K+Ca+Mg)和(MgO+Na2O+CaO)/Al2O3等气候指标研究,表明在草海窑上期为湖泊沉积时期,气候经历了由温暖湿润向冷干的转变。同时,认为物源性质、构造运动、气候等共同控制该区沉积物形成。  相似文献   

8.
华南不同成因花岗质岩石中钾长石的结构态   总被引:1,自引:0,他引:1  
自然界长石的Al/Si有序程度是岩石形成条件的客观反映,它引起岩石学者的广泛兴趣。用X射线粉晶衍射法研究花岗质岩石中钾长石的Al/Si有序程度是一种简便而又迅速的方法。本文采用Al在钾长石的四种四面体位置中的占位率,即t_1o、t_1m、t_2o和t_2m,指示钾长石的Al/Si有序度。这些数值比通常采用的三斜度△_(131)或δ指数更直接反映长石中Al、Si的  相似文献   

9.
辽宁赛马碱性岩体早年因产铀矿而闻名,该岩体主要由响岩、霞石正长岩和异霞正长岩组成,其中铀、锆和稀土等元素矿化主要集中于异霞正长岩岩浆阶段。异性石是异霞正长岩中特征的锆-稀土矿物,主要分为两期,晚期异性石表现出更加富集Nb、REE等高场强元素的特点。早期异性石经历了一系列的热液蚀变,根据蚀变强弱程度,蚀变矿物组合可分为:(1)异性石+钠锆石+霓石±钠沸石;(2)异性石+钠锆石+锆石+钠沸石±霓石;(3)异性石假晶,假晶主要由残余异性石+钠锆石+锆石+钠沸石+霓石+钾长石+铈硅磷灰石组成。相比于岩浆锆石,蚀变组合中次生锆石具有富Ca、Al、Fe的特点,与异性石本身化学成分和流体性质密切相关。通过对异性石及其蚀变组合的精细矿物学研究,我们得知假晶的形成可能是异性石"溶解-再沉淀"的结果,致使假晶形成的流体至少包括:(1)占主导的富Na(±K)、Al、F的自交代流体;(2)少量晚期富Ca流体。假晶中次生锆石和铈硅磷灰石的结晶说明了Zr和REE等高场强元素的热液活动性,自交代碱性流体和富Ca流体在此过程中起到"搬运"和"提纯"的作用,这对认识碱性岩稀有、稀土成矿机制具有重要的指示意义。  相似文献   

10.
千家坪钒矿床产于南秦岭下寒武统水沟口组(缀1sh)黑色岩系中,该黑色岩系由黑色含炭硅质岩、含炭硅质岩夹泥岩和泥岩等组成。钒矿体呈层状产出,矿石以黑色硅质岩夹泥岩型为主,含钒矿物主要为钒云母。黑色岩系岩石主要成分为SiO2、Al2O3、K2O等,富集TFe、Ba、Zn、P、Cu、Ni、Cr、Sr、Zr、Ag、Ti、Mn、V等多种元素。黑色岩系n(V)/n(Cr)=5.92~30.64、n(V)/n(V+Ni)=0.88~0.99、δU1,判断其为缺氧沉积环境。黑色硅质岩n(SiO2)/n(Al2O3)=238.81,U/Th1以及δ30Si=-0.1‰~0.5‰、δ18O=20.2‰~25.8‰,判断其为半深海滞留沉积盆地热水沉积成因。泥岩n(SiO2)/n(Al2O3)=5.69,n(Al)/n(Al+Fe+Mn)=0.63,n(Si)/n(Si+Al+Fe)=0.74~0.76判断其物源为陆源,但受到热水作用影响。钒矿化受下寒武世古隆起边缘断陷滞留盆地中形成的黑色岩系层位所控制。钒明显趋向在炭硅质岩所夹的泥岩或硅质岩附近的泥岩中富集,在炭硅质岩夹泥岩段向泥岩段过渡层位,常常含结核,钒元素含量达到峰值,其他Cu、Pb、Zn、As、W、Mo等元素富集规律与V元素基本一致。该矿床成矿物质主要来源于深部热水,泥岩的吸附作用对钒的富集具有重要作用。综合地质、地球化学特征,认为该矿床为热水喷流沉积成因。  相似文献   

11.
Batch reactor experiments were conducted to assess perthitic alkali-feldspar dissolution and secondary mineral formation in an initially acidic fluid (pH = 3.1) at 200 °C and 300 bars. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. Solid reaction products were retrieved from two identical experiments terminated after 5 and 78 days. Scanning electron microscopy revealed dissolution features and significant secondary mineral coverage on feldspar surfaces. Boehmite and kaolinite were identified as secondary minerals by X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy analysis of alkali-feldspar surfaces before and after reaction showed a trend of increasing Al/Si ratios and decreasing K/Al ratios with reaction progress, consistent with the formation of boehmite and kaolinite.Saturation indices of feldspars and secondary minerals suggest that albite dissolution occurred throughout the experiments, while K-feldspar exceeded saturation after 216 h of reaction. Reactions proceeded slowly and full equilibrium was not achieved, the relatively high temperature of the experiments notwithstanding. Thus, time series observations indicate continuous supersaturation with respect to boehmite and kaolinite, although the extent of this decreased with reaction progress as the driving force for albite dissolution decreased. The first experimental evidence of metastable co-existence of boehmite, kaolinite and alkali feldspar in the feldspar hydrolysis system is consistent with theoretical models of mineral dissolution/precipitation kinetics where the ratio of the secondary mineral precipitation rate constant to the rate constant of feldspar dissolution is well below unity. This has important implications for modeling the time-dependent evolution of feldspar dissolution and secondary mineral formation in natural systems.  相似文献   

12.
以长白山天然钾长石矿为原料,采用水热合成法制备了X型沸石分子筛,对影响合成工艺和产物性能等因素进行了研究.试验表明,反应混合物的配比:水钠比、硅铝比,反应过程中的搅拌速度及凝胶混合物的陈化是合成分子筛的关键工艺参数;晶化12 h是合成反应的最佳结晶时间;产物的吸附量达到了国家化学工业产品标准.  相似文献   

13.
Myrmekite, as defined here, is the microscopic intergrowth between vermicular quartz and modestly anorthitic plagioclase (calcic albite-oligoclase), intimately associated with potassium feldspar in plutonic rocks of granitic composition. Hypotheses previously invoked in explanation of myrmekite include: (1) direct crystallization; (2) replacement; (3) exsolution. The occurrence of myrmekite in paragneisses and its absence in rocks devold of discrete grains of potassium feldspar challenge those hypotheses based on direct crystallization or replacement. However, several lines of evidence indicate that myrmekite may in fact originate in response to kinetic effects associated with the exsolution of calcic alkali feldspar into discrete potassium feldspar and plagioclase phases. Exsolution of potassium feldspar system projected from [AlSi2O8] involves the exchange CaAlK-1Si-1, in which the AlSi-1 tetrahedral couple is resistant to intracrystalline diffusion. By contrast, diffusion of octahedral K proceeds relatively easily where it remains uncoupled to the tetrahedral exchange. We suggest here that where the ternary feldspar system is open to excess silica, the exchange reaction that produces potassium feldspar in the ternary plane is aided by the net-transfer reaction K+Si=Orthoclase, leaving behind indigenous Si that reports as modal quartz in the evolving plagioclase as the CaAl component is concomitantly incorporated in this same phase. Thus silica is pumped into the reaction volume from a silica reservoir, a process that enhances redistribution of both Si and Al through the exsolving ternary feldspar.  相似文献   

14.
非水溶性钾矿制取碳酸钾: 副产硅铝胶凝材料   总被引:1,自引:0,他引:1  
白云鄂博稀土-铌-铁矿床上部围岩产富钾板岩, 其K2O平均含量达13.0%, 钾资源储量巨大.矿石的物相组成以微斜长石、黑云母为主, 是一种重要的非水溶性钾矿资源.实验表明, 以碳酸钠为助剂, 经中温烧结, 矿石分解率达98.2%以上.烧结物料中K2O的浸出率约70%, 且在水浸酸化反应过程中, 大部分Fe3+、Ti4+、Mn2+、Mg2+、Ca2+等杂质离子与硅铝质胶体同时沉淀析出, 为制取电子级碳酸钾提供了可能.硅铝质胶体滤渣用于制备矿物聚合材料.采用本项技术开发利用此类非水溶性钾矿资源, 符合节能高效和“清洁生产”的要求, 兼有规模化经济效益和良好的环境效益.   相似文献   

15.
Understanding the integrity of well-bore systems that are lined with Portland-based cements is critical to the successful storage of sequestered CO2 in gas and oil reservoirs. As a first step, we investigate reaction rates and mechanistic pathways for cement mineral growth in the absence of CO2 by coupling water chemistry with XRD and NMR spectroscopic data. We find that semi-crystalline calcium (alumino-)silicate hydrate (Al-CSH) forms as a precursor solid to the cement mineral tobermorite. Rate constants for tobermorite growth were found to be k = 0.6 (± 0.1) × 10-5 s-1 for a solution:solid of 10:1 and 1.6 (± 0.8) × 10-4 s-1 for a solution:solid of 5:1 (batch mode; T = 150°C). This data indicates that reaction rates for tobermorite growth are faster when the solution volume is reduced by half, suggesting that rates are dependent on solution saturation and that the Gibbs free energy is the reaction driver. However, calculated solution saturation indexes for Al-CSH and tobermorite differ by less than one log unit, which is within the measured uncertainty. Based on this data, we consider both heterogeneous nucleation as the thermodynamic driver and internal restructuring as possible mechanistic pathways for growth. We also use NMR spectroscopy to characterize the site symmetry and bonding environment of Al and Si in a reacted tobermorite sample. We find two [4]Al coordination structures at δ iso = 59.9 ppm and 66.3 ppm with quadrupolar product parameters (PQ) of 0.21 MHz and 0.10 MHz (± 0.08) from 27Al 3Q-MAS NMR and speculate on the Al occupancy of framework sites by probing the protonation environment of Al metal centers using 27Al{1H}CP-MAS NMR.  相似文献   

16.
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.  相似文献   

17.
三元复合驱技术能够显著提高石油的采收率,但在生产过程中三元复合注入液易与储层矿物反应,破坏储层并结垢,造成井下堵塞、采收率降低等问题,因此研究三元复合驱液在储层中的溶、运、堵过程及反应机理成为当务之急。本文利用X射线衍射(XRD)、X射线光电子能谱(XPS)、场发射环境扫描电镜(ESEM)及X射线能谱仪(EDS)测试手段精细表征了大庆油田储层矿物钾长石、石英、高岭石与强碱三元复合驱液作用的反应过程及变化特征,并通过反应动力学计算得到了相应的Si、Al溶出动力学方程及矿物溶蚀再沉积规律,深入探讨了反应机理。结果显示,钾长石与强碱复合驱液作用60 d后Si溶出量约为Al的3倍,生成三水铝石和硅酸盐沉淀物;石英的Si溶出量呈线性增加,60 d后超过300×10-6,表面生成碳酸盐颗粒;高岭石60 d后Al溶出量约为Si的3倍,结晶度下降25.26%,生成水钙沸石;强碱对矿物的溶蚀破坏程度与其浓度呈正相关。  相似文献   

18.
Lunar plagioclase posed an enigma because optical properties indicate slow cooling while structural properties suggest rapid quenching when compared directly to terrestrial plagioclase. If, however, the An-content is inferred from the Al/Si ratio rather than from the Ca/Na ratio, lunar plagioclase corresponds more closely to normal volcanic plagioclase. The differences between An=4(Al/(Al+Si))-1 and An=Ca/(Ca+Na+K) is caused by substitutions which appear so far to be unique to lunar feldspars. A vector representation of chemical composition makes it possible to single out several substitutions which account for the chemical peculiarities of lunar plagioclase. It permits to assign sites in the structure to various minor elements simply from the chemical analysis without having to rely on sophisticated spectroscopic techniques or an X-ray structure determination. 1. The deficiency in Al+Si (up to 0.06 per formula unit) is compensated for by Fe, Mg, and small amounts of Na or Ca occupying tetrahedral sites. The Ca/Na ratio is increased accordingly to balance the electric charge. This substitution accounts for most of the differences. 2. The vacancycoupled substitution Ca+□ → 2 Na (Weill et al., 1970) is another cause for the increased Ca/Na ratio. 3. The amount of alkali evaporation from plagioclase, if it occurred, is probably small. These unusual substitutions are an expression of special conditions on the moon during the crystallization of plagioclase. Crystallization at high temperatures, rapid cooling, and peculiar magma composition seem to be important factors, but experimental work and detailed study of terrestrial volcanic plagioclase are necessary to interpret the chemical composition quantitatively.  相似文献   

19.
库车坳陷白垩系深层致密砂岩储层溶蚀作用实验模拟研究   总被引:1,自引:1,他引:0  
库车坳陷前陆区白垩系发育特低物性、强非均质性和高稳产砂岩储层,溶蚀作用显著,但成因机制尚不是很明确。利用高温高压热模拟实验还原了目的层在成岩演化过程中1种表生流体和2种埋藏流体环境下溶蚀作用差异,揭示了成岩矿物演化过程及储集空间结构变化特征。结果表明,表生成岩期大气淡水淋滤弱酸性流体环境(CO2饱和溶液,pCO2=1 MPa)溶蚀作用最为显著,长石类矿物发生明显溶蚀,石英和黏土矿物相对难溶,Na+、Ca2+和K+等离子析出明显,Si4+和Al3+析出较少,样品表面沉淀出较多的疑似多边形石英和铝硅酸类矿物;成岩晚期油气充注酸性流体环境(乙酸溶液,2 mL/L)溶蚀作用其次,易于溶解白云石、石膏和长石类矿物,Ca2+、Mg2+、Na+和Si4+等离子析出明显,样品表面无沉淀;成岩早-中期碱性流体环境(NaHCO3溶液,pH=7.46、HCO3-=0.6 mol/L)溶蚀作用相对较弱,石英、长石和部分黏土矿物均发生了不同程度的溶蚀,且随着温度、压力的增加,溶蚀作用程度增加。综合分析表明:表生流体是研究区砂岩储层溶蚀孔隙发育的关键因素,其次为有机酸和碱性埋藏流体。这一认识能够丰富致密砂岩储层孔隙成岩演化理论,为下一步寻找规模储层发育区和气田有效开发提供理论支撑。  相似文献   

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