二水硫酸钙结晶动力学研究

主要研究了过饱和溶液中CaSO4 ·2H2 O晶体成核及生长现象 ,同时对垢的形成机理进行了探讨。实验表明 ,成核延迟时间随溶液过饱和度增大而减小 ;CaSO4 ·2H2 O晶体生长属于表面反应控制 ,且与粒径相关 ,当温度为 3 0℃ ,粒径为2 8～ 67μm ,Ca2 + 浓度为 0 .0 3 5mol/L时 ,晶体生长速度在 0 .5× 10 - 8～ 5 .8× 10 - 8m/s之间     

斧石晶体的微形貌特征,化学成分及形成条件

通过对个旧斧石晶体的微形貌、化学成分及生成条件的研究认为,个旧产出的斧石种类属于铁斧石,它是在fo_2=10~(-21)—10~(-31),中偏高温溶液中生成的.应用晶体人工生成的研完成果表明:斧石晶体表面台阶是溶液中的溶质通过体扩散形成的;而不同密度台阶的叠置则反映了晶体生长过程中的动力学参数的变化.     

四川仁寿牛角寨石窟盐风化作用机理与气候响应

盐风化作用是石质文物风化劣化的重要机制之一,但其作用机理及其与气候的响应过程仍需进一步的研究。笔者等以仁寿牛角寨石窟的岩芯样品和风化样品为对比研究对象,采用镜下鉴定、X射线荧光光谱（XRF）及X射线衍射（XRD）和电子探针（EPMA）对样品的化学组成和矿物组成进行对比研究,并重点研究了样品中可溶盐的组成及结晶状态。化学组成上,风化样品中SO3平均含量是岩芯样品的16倍以上;矿物组成上,岩芯样品仅在表层0~22 cm中发现微量的石膏,而风化样品中检出了至少17. 5倍高于岩芯的石膏以及微量的Na2SO4和NaCl,这指示石窟砂岩的风化劣化与可溶盐尤其是硫酸盐有关。通过对Na2SO4、NaCl及石膏性质的研究,发现Na2SO4可以响应气候条件发生反复的Na2SO4+10 H2O Na2SO4·10H2O结晶—脱水反应,结晶时体积膨胀416%,特别是在潮湿气候条件下Na2SO4的二次结晶作用可对岩石产生更强的破坏;NaCl的存在可以降低Na2SO4的脱水相变温度（最低可至17. 6℃）和溶解度,放大Na2SO4在岩石风化过程中的作用;CaSO4对岩石风化劣化的贡献较小,但其可作为在风化作用下岩石中可溶盐聚集的指示产物。结合对温度、湿度监测数据的研究,发现每日温度、湿度随时间的变化天然契合Na2SO4—NaCl体系的温度、湿度转变条件。气候条件耦合盐风化作用是牛角寨石窟表层砂岩的主要风化方式。     

小秦岭金矿含金石英脉中石英晶体微形貌研究

利用微分干涉显微镜等手段对小秦岭金矿含金石英脉中不同成矿阶段的石英晶体微形貌进行了研究。石英晶体{101^-1}、{011^-1}、{101^-0}单形晶面上不同特征的微形貌对了解石英晶体的生长机理、生长速率、生长环境的变化及成矿溶液的过饱和度具有重要意义，同时也可提供成矿阶段划分及晶体生长时热力学条件的信息。     

添加剂对KAlSi_3O_8-CaSO_4-CaCO_3体系反应表观活化能的影响

首先测定了KAlSi3O8-CaSO4-CaCO3体系在不同焙烧条件下钾长石转化成可溶性氧化钾的转化率,进而通过模拟计算表明:KAlSi3O8-CaSO4-CaCO3体系的固相扩散动力学过程符合金斯特林格动力学方程,反应表观活化能Ea为128.92kJ/mol。并着重考察了4种添加剂Na2SO4、Na2SO3、NaCl和NaF对KAlSi3O8-CaSO4-CaCO3体系的影响,结果表明:向体系中分别加入占反应物总质量3%的Na2SO4、Na2SO3、NaCl和1%的NaF后,体系的反应表观活化能Ea从原来的128.92kJ/mol依次下降至87.15、98.71、117.38和126.14kJ/mol,这表明4种添加剂中Na2SO4的效果最好,它能较大程度上降低反应表观活化能,从而降低反应温度和提高固相反应速率。     

方解石(10(-1)4)晶面在含重金属溶液中的生长及新生长面的溶解

溶液中的金属离子对方解石的生长和溶解均有影响,但关于方解石中固有的杂质离子对其溶解的影响还了解甚少.本研究利用原位原子力显微镜(AFM)考察了室温下方解石(10(-1)4)晶面在含Mn2+及含Cd2+溶液中的生长过程,并对其新生长面直接进行原位溶解观察.实验表明,溶液中的Mn2+和Cd2+可参与方解石的生长,分别形成(Ca,Mn)CO3固溶体和(Ca,Cd)CO3固溶体.新生成的含Mn、Cd方解石的溶解速率仅为纯方解石的14.3％～60.3％,说明晶体中的Mn和Cd可抑制方解石的溶解.因此方解石生长阶段可通过在(10(-1)4)晶面形成含重金属固溶体从而固定Mn和Cd,由于新生长的固溶体溶解速率小于纯方解石,从而延缓Mn和Cd的迁移,并降低其环境污染的风险.     

方解石(10(-1)4)晶面在含重金属溶液中的生长及新生长面的溶解

溶液中的金属离子对方解石的生长和溶解均有影响,但关于方解石中固有的杂质离子对其溶解的影响还了解甚少.本研究利用原位原子力显微镜(AFM)考察了室温下方解石(10(-1)4)晶面在含Mn2+及含Cd2+溶液中的生长过程,并对其新生长面直接进行原位溶解观察.实验表明,溶液中的Mn2+和Cd2+可参与方解石的生长,分别形成(Ca,Mn)CO3固溶体和(Ca,Cd)CO3固溶体.新生成的含Mn、Cd方解石的溶解速率仅为纯方解石的14.3％～60.3％,说明晶体中的Mn和Cd可抑制方解石的溶解.因此方解石生长阶段可通过在(10(-1)4)晶面形成含重金属固溶体从而固定Mn和Cd,由于新生长的固溶体溶解速率小于纯方解石,从而延缓Mn和Cd的迁移,并降低其环境污染的风险.     

四元体系K_2SO_4-K_2B_4O_7-K_2CO_3-H_2O 273K时介稳相平衡研究

采用等温蒸发法研究K2SO4-K2B4O7-K2CO3-H2O四元体系在低温273K时的介稳固液相平衡关系,测定了介稳平衡液相的溶解度和密度。研究发现,该四元体系273K时的介稳平衡相图有3个固相结晶相区分别为K2SO4,K2B4O7.4H2O和K2CO3.3/2H2O;3条单变量曲线E1E,E2E和E3E;一个共饱点E,在共饱点E处的液相中各盐的溶解度分别为K2CO3(43.46%),K2SO4(2.52%)和K2B4O7(3.10%);研究结果表明K2CO3对K2B4O7和K2SO4有强烈的盐析作用。实验证明在富含硼钾的扎布耶盐湖卤水中,低温平衡条件下硫酸钾和硼酸钾极易从溶液中结晶析出,而碳酸钾则由于溶解度大,介稳性强,即使在低温条件下也难以从溶液中析出。     

氯化物对方解石和白云石矿物溶解度的影响

借助PHREEQC软件,文章对方解石、白云石分别在无CO2和大气PCO2条件下NaCl、KCl、CaCl2和MgCl2溶液中的溶解度进行了模拟计算,结果显示:方解石在NaCl、KCl、和MgCl2溶液中以及白云石在NaCl、KCl溶液中的溶解度比纯水中大得多,其原因主要是盐效应。由于同离子效应,在CaCl2溶液中可降低方解石溶解度,而白云石在较高浓度CaCl2或MgCl2溶液中,虽发生同离子效应,其溶解度仍较纯水中有不同程度提高。模拟还显示,方解石在MgCl2溶液中以及白云石在CaCl2溶液中溶解时将分别发生白云石化和去白云石化反应,从而促使不全等溶解继续发生。在常规离子中,按方解石、白云石溶解度提高发挥作用的重要性排序为:阴离子中都是SO24->Cl-;对于方解石溶解,阳离子中Mg2+>Na+>K+>Ca2+;对于白云石溶解,当PCO2=0或PCO2=10-3.5bar且CaCl2浓度大约在1.5mol/L以下时,Na+>K+>Ca2+>Mg2+;当PCO2=10-3.5bar且CaCl2浓度大约在1.5mol/L以上时,Ca2+>Na+>K+>Mg2+。     

FeS2晶须的微观形貌学研究及其生长动力学意义

众多的研究已经表明,矿物的形貌是其成分、结构和生长环境的综合反映,对其进行研究可以获得晶体生长的地质条件等有关信息.矿物晶面的表面微形貌,对于晶体内部缺陷和生长环境的变迁反映非常敏感,它记录了晶体生长过程中更有价值的信息--界面的特性.     

四川盆地三叠系杂卤石形成条件的实验研究

四川盆地三叠系杂卤石有很大一部分产于硬石膏层中,与硬石膏互层。在许多杂卤石产出层位,缺失钾镁盐甚至石盐等易溶盐类。上述现象用已有的研究资料难以解释。本文通过100多个实验点的平衡实验,研究了35℃ K—Na—Mg—Ca—SO_4—Cl—H_2O六元海水体系中,NaCl及K、Mg盐均不饱和条件下杂卤石形成的可能性。与饱和溶液相比,不饱和溶液中杂卤石稳定区收缩。但在饱和溶液被稀释将近1倍时,杂卤石仍有一定的稳定范围。 在实验研究的基础上分析了四川盆地三叠系含杂卤石剖面的成因。由于成盐期卤水频繁地被淡化,形成“石膏——石盐+钾镁盐——石膏”沉积韵律。成岩作用中盐层遭受来自石膏层的水的溶滤。在石膏层较厚,盐层较薄的层段,石盐和钾镁盐可被全部溶掉,形成对NaCl及K、Mg盐均不饱和的液体。当这种对易溶盐类不饱和的液体进入膏层,部分K、Mg组分就能与CaSO_4结合生成杂卤石被保留下来,形成现在所看到的“硬石膏一杂卤石——硬石膏”剖面。     

耿庄金矿含FeS2晶须环带重晶石巨晶的特征及成因意义

在山西耿庄金矿区含金隐爆角砾岩体的晶洞内,发现了含FeS2晶须环带重晶石巨晶,用扫描电镜、电子探针、Ｘ射线粉晶衍射等手段系统研究了重晶石及其所含FeS2晶须的矿物特征。结果表明,重晶石化学成分单一;晶体结构标准;发育完好;晶须为FeS2 Fe(Ni, Co)S2的类质同象系列。根据地质背景,结合包裹体研究成果,运用晶体生长和地球化学理论,讨论了重晶石巨晶及所含晶须的成因。认为重晶石巨晶是该区燕山期花岗岩浆活动的期后热液演化到后期阶段时,SO2-4与围岩中的钡反应而形成;所含的FeS2晶须是持续进行的火山隐爆作用所产生的大量H2S、SO2等与热液中分解出的Fe2+、Ni2+、Co2+反应而形成的;富碱、H2S溶解度增大,S2-增高有利于晶须的生长;重晶石和晶须生长的地质环境具有宏观上的一致性和具体条件的差异性。当pH值为1~8.5、lgfO2为-31~-38时,优先进入FeS2生长的优势场,形成FeS2晶须矿物。当pH值为5.5~10、lgfO2在-25~-36时形成重晶石;FeS2环带和重晶石的共生现象是两者共结晶交互生长的结果;重晶石的套叠生长和晶须环带特征,是耿庄地区隐爆作用脉动性和周期性作用的结果。耿庄含晶须重晶石巨晶,明确标示出所形成的地质条件和地质作用过程,为深入研究隐爆作用和理解该区成矿作用提供了矿物学证据。     

含氯盐和硫酸盐类盐渍土膨胀特性的研究

对含氯盐和硫酸盐类盐渍土的盐胀规律及影响因素进行了较为系统的试验研究，得出了盐胀随温度变化的若干规律，即盐胀随温度变化的关系式，起胀温度与各影响因素之间的关系式，盐胀与降温速度的关系式，成型温度对盐胀规律的影响等。分析了Ｎａ２ＳＯ４含量，ＮａＣｌ含量，Ｃｌ＾－／ＳＯ４＾２－，含水量对盐胀的影响，给出了盐胀与各影响因素之间的关系式。     

Feasibility study of crystallization process for water softening in a pellet reactor

One of the undesirable characteristics of some groundwater sources is hardness, which has some adverse effects on water pipes, boilers and soap consumption. Therefore several treatment processes have been introduced to remove or reduce the hardness from hard waters. One of the new innovations in this regard is crystallization process. Hardness can be removed from hard waters by growth of calcium carbonate crystals in a fluidized bed reactor called pellet reactor. The design, setting up, starts up and reaching optimal condition for calcium carbonate crystallization process in a pellet reactor which has been initially seeded with sand as a crystal citation can be a successful solution for treatment of hard waters. The chemistry of pellet softening process is essentially the same as conventional softening process, instead of precipitation of calcium carbonate which does not have any useful consumption and must be removed once in a while some how, crystallization process in a fluidized bed reactor produces pure solid grain of calcite. These pellets can be used in some industries and are in fact an economic commodity. For this purpose a pilot was set up as a crystallization reactor and water with total hardness ranging from 150 up to 500 mg/l as CaCO₃ was fed to the system with a flow rate of 24 l/hr. To remove hardness, caustic and soda, lime milk was fed to the system separately at first stage at then together. The formation of CaCO₃ crystals on the surface of sands represented the reduction of hardness. An analysis is made for the characteristics of a softed water resulted from the use of caustic soda, lime milk or both as regent.     

Holocene stromatolites and microbial laminites associated with lenticular gypsum in a marine-dominated environment, Ras El Shetan area, Gulf of Aqaba, Egypt

Field and petrographic investigations of Holocene evaporites in the Ras El Shetan area, Gulf of Aqaba, Egypt, indicate the presence of microbial mats either in the form of laminites or stromatolites. The morphology of microbial mats and gypsum crystal size characterize the following lithofacies: (1) slump-stromatolitic gypsarenite, (2) random gypsrudite, (3) stromatolitic gypsarenite, and (4) microbially laminated gypsrudite. These evaporite lithofacies are formed above pre-evaporitic mudstones rich in disrupted cyanobacterial filaments, burrows and cerithid gastropods. The morphology of the gypsum crystals is mainly lenticular, indicating enrichment of dissolved organic compounds in the depositional environment. The difference in size of the lenticular gypsum crystals is related to minor changes in salinity and temperature of the parent brine. Fluid inclusions in gypsum crystals indicate their formation at low temperature (<50°C) in a seawater sourced brine that evaporated to gypsum saturation or higher. The brine salinities range from 10·62 to 12·99 equivalent wt% NaCl, and the brine densities range from 1·08 to 1·11 g/cm³. The change in morphology of the microbial mats (stromatolites and laminites) is related mainly to changes in water depth, from a very shallow salina to a coastal sabkha. Lenticular gypsum nucleated displacively in the microbial mats from saline, oxygenated groundwater that seeped from the sea through a barrier.     

锌水绿矾在自然界发现和研究

锌水绿矾产于陕西省南部红土石黄铁矿矿床氧化带。集合体呈钟乳状或皮壳状，单晶为短柱状和不规则粒状，极易溶于水。颜色为黄绿色或翠绿色。主要化学成分：ZnO16．35％，FeO8．86％，SO328．30％，H2O44．33％。分子式为（Zn，Fe）SO4·7H2O。主要X射线粉晶谱线是：0．4880（100），0．2739（80），0．5439（30），0．3225（30）和0．2476（30）um。它的化学成分和粉晶数据均与水绿矾（FeSO47H2O）或人工合成的锌水绿矾相似。     

流化床混凝装置中多级速度梯度的建立及其对混凝反应的影响

利用不同性质颗粒在流化状态下可实现自然水力分级的特征,在流化床反应器中沿水流方向实现了多级速度梯度的建立。在研究流化床混凝反应器的混凝动力学特征基础上,探讨了以800 μm和1 200 μm树脂颗粒为固相的多级速度梯度流化床（MGF）的速度梯度分布特征、混凝效率和絮体形态特征,并与以1 200 μm树脂颗粒为固相的单级速度梯度流化床（SGF）进行了对比研究。结果表明：与单级速度梯度相比,多级速度梯度可为胶体或微颗粒的高效碰撞和絮体再增长创造更适宜的环境,有助于形成尺寸更大、密度更大的絮体,提高了絮体的可沉降性;MGF在处理人工配置的高岭土悬浊液和分散红染料废水时,混凝效率比SGF分别提高了2%～4%和7%～20%。     

Kinetics and Equilibrium Sorption Studies of 4-Nitrophenol on pyrolyzed and activated oil shale residue

Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO₂ at 830 °C, while chemical activation was achieved by using KOH and ZnCl₂ as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl₂, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl₂-oil shale sorbents.     

Cyclic development of large,complex, calcite dendrite crystals in the Clinton travertine,Interior British Columbia,Canada

Bands of large (up to 4 cm long) three-dimensional crystallographic dendrites form the terrace fronts in an old travertine mound exposed near Clinton, British Columbia. The dendrites, with their long axes perpendicular to the terrace front, are characterized by numerous levels of branching. Each branch is formed of multitudes of skeletal rhombs, four- and six(?)-sided bipyramidal crystals, or prismatic hexagonal crystals that are precisely aligned along crystallographic precepts. Although individual branches are formed of one type of subcrystal, neighbouring branches may be formed of different subcrystal types.Highly supersaturated waters that were generated by rapid CO₂ degassing of the spring water during its turbulent flow over the steep terrace fronts probably drove dendrite precipitation. The presence of growth lines indicates that growth was episodic. Type I growth lines probably formed annually in response to seasonal climate changes whereas Type II growth lines, which formed less frequently, may reflect changes in the flow velocity and/or flow patterns of the spring waters.Early diagenetic modification of the dendrites involved crystal face enlargement, cements formed of trigonal prisms or needle-fiber crystals, microbial infestation that mediated substrate dissolution, and/or deposition of detrital calcite crystals that formed in the water column. Much of the diagenetic modification may have taken place during the periods when the dendrites had temporarily stopped growing.The dendrites in the Clinton travertine are an excellent example of complex, episodic calcite crystal growth that was extensively modified by early diagenetic processes in a surface environment. The same spring waters from which the dendrites were precipitated mediated much of the early diagenesis.     

流态化多级速度梯度混凝反应对絮体的保护作用

多级速度梯度的建立理论上可为絮体的成长创造更理想的环境。目前对流化床混凝工艺的研究多是基于单级速度梯度开展的。以粒径为800 μm 和1 200 μm的树脂颗粒为固相,建立多级速度梯度流化床混凝装置,探讨絮体的成长与形态特征。研究结果表明：在单级速度梯度流化床混凝装置中,当以1 200 μm树脂颗粒为固相颗粒、混凝时间为50.3 s时,絮体发生破碎,混凝效率较混凝时间为41.8 s时降低3%;相同初始填充高度的多级速度梯度条件下,絮体尺寸随着混凝时间的延长而逐渐增加,由5.7 μm成长至70.0~75.0 μm,同时混凝效率也较单级速度梯度下提高了5%~10%。絮体之间的碰撞为絮体成长的主要模式。