不同有机酸对矿物溶解的动力学实验研究

用石英、微斜长石和方解石混合颗粒模拟碎屑组分分别与不同有机酸水溶液进行溶蚀实验,以比较储集层内不同矿物在含低分子量有机酸地层水中溶解的速率,并试图探讨矿物溶蚀的微观机理。结果表明：①所有矿物颗粒都发生了不同程度的溶解,表现为颗粒失重,溶液中SiO2和金属阳离子含量增加,pH值上升。②优先溶解的是方解石,其次是硅酸盐矿物。③温度增加,硅酸盐矿物在水中的溶解度明显增加,而方解石的溶解度基本不变。④由于不同有机酸与二氧化硅和金属阳离子生成的络合物稳定性不同,因此,在不同有机酸水溶液中,矿物的溶蚀速率有较大差别。多官能团有机酸的水溶液中,不同矿物有更大的溶解;但在含有丰富Ca2＋的草酸水溶液中,由于矿物颗粒表面难溶草酸钙的沉淀,方解石的溶解变得更加困难。⑤多官能团有机酸与SiO2形成的多环螯合物由于完全取代了硅氧四面体的氧原子,在水中具有高度稳定性,可能有助于(铝)硅酸盐的溶蚀和硅元素的迁移     

黄龙嗜冷细菌胞外琥珀酸组分对碳酸钙矿化的影响

为探索黄龙钙华的生物成因,本研究以黄龙嗜冷细菌的胞外特征有机酸组分——琥珀酸为研究对象,通过模拟黄龙水体的低温沉积环境,利用X射线粉末衍射(XRD)和扫描电镜(SEM),考察了琥珀酸对钙化体系中的钙化动力学过程、碳酸钙晶型和形貌的影响。结果表明： ① 高浓度琥珀酸、低pH值,低温都会在一定程度上抑制碳酸钙沉积。② 高浓度琥珀酸可以诱导球霰石型碳酸钙的形成; ③ 高温促进了体系中碳酸钙微晶的聚合。综上可见,黄龙嗜冷细菌的胞外琥珀酸组分在一定程度上参与了碳酸钙的沉积过程,对晶体的晶型和形貌具有一定的调控作用。其结果可为黄龙钙华生物成因的探究提供理论基础。     

降尘矿物在柠檬酸中的溶出顺序研究

针对自然降尘进行的物相、成分分析表明该降尘的物相组成非常复杂,以石英、方解石、钠长石、白云石、云母为主要物相成分。为探讨降尘中矿物在有机酸中的溶解情况,进一步揭示其对人体的危害程度。本文以西宁降尘为研究对象,并选择柠檬酸为代表有机酸,分别用XRD、FTIR及ICP-AES等方法对柠檬酸处理前后降尘的残余固体及反应上清液进行分析。结果表明,降尘中方解石在经柠檬酸作用10 min后完全溶解,白云石在16 h内基本溶解完全,根据红外分析结果,Si—O、Al—O结构未发生明显破坏。然而,溶出元素结果显示,Al、Si的溶出量随着溶解时间的增长而缓慢增加,说明柠檬酸对Si—O四面体及Al—O八面体也造成了一定的破坏作用。通过分析降尘中3种难溶矿物在相同条件下的溶解速率可以得出,在整个溶解过程中,钠长石的溶解速率高于绢云母,而石英的溶解速率在不同的溶解时间有着较大的差异。根据3种纯矿的溶解速率推断三者的溶解顺序,钠长石明显先于云母溶解,石英的溶解先后顺序还有待进一步研究。通过降尘及纯矿在柠檬酸中溶解过程中不同时刻的元素溶出比例及矿物溶出速率可以得出除石英外4种主要矿物的溶解顺序为:方解石,白云石,钠长石,绢云母。     

柠檬酸对黄龙碳酸钙矿化影响的模拟实验研究

为探索生物因素在黄龙钙华沉积过程中的作用及参与程度,本研究以黄龙水体中2株嗜冷细菌胞外特征有机酸组分——柠檬酸为研究对象,通过模拟黄龙常年水温和p H值,结合碳酸钙晶体晶型和形貌,探讨柠檬酸钙化体系中的钙化过程及柠檬酸对碳酸钙晶型和形貌的影响。结果表明:1柠檬酸浓度高、p H值低和温度低都会一定程度地抑制碳酸钙沉积;2柠檬酸浓度(20、40、80、160mg/L)对碳酸钙晶型影响不大,主要合成方解石型碳酸钙,但随着浓度的增加,伴随有花瓣状形貌的生成;3随着p H值的增大,棱柱体形貌转变为边缘较为圆滑的椭球体。综上可见,柠檬酸对碳酸钙的钙化速率、晶型和形貌具有一定的影响和调控作用,其结果可为黄龙钙华生物成因的探究提供理论基础。     

基于热模拟实验的富有机质泥页岩成岩作用及演化特征

富有机质泥页岩蕴含丰富的油气资源,但成岩研究基础薄弱,已成为制约页岩油气勘探开发进程的重要因素。通过开展成岩热模拟实验,结合扫描电镜观察、流体成分测试及有机酸测试等实验测试手段,全面描述实验过程中所发生的水-岩化学反应,试图揭示泥页岩成岩过程及成岩演化规律。研究结果显示,有机质热演化过程中存在一个较宽的有机酸生成窗口,对孔隙流体性质具有重要影响;长石和方解石存在接力溶蚀现象,长石溶蚀高峰过后紧接着出现方解石溶蚀高峰,但方解石溶蚀窗较窄,此后出现方解石重新沉淀结晶;黏土矿物转化及长石的溶蚀过程中会产生大量自生微晶石英,成链状或簇状胶结泥页岩骨架。泥页岩地层作为一个相对封闭体系,各类成岩作用之间相互关联,相互影响,构成错综复杂的成岩体系,进一步增加其成岩作用研究难度。     

鲕粒灰岩的溶解动力学特征和微观形貌的发育演化

鲕粒灰岩是重要的碳酸盐岩油气储层。通过常温常压下,北京西山鲕粒灰岩的溶解动力学实验发现,鲕粒灰岩的溶解主要受岩石和矿物的结构和化学成分控制。结构上表现为构造裂缝、鲕粒结合纹、颗粒晶体结合带等结构薄弱带优先发生溶蚀。成分上表现为白云岩化组分不仅自身较易溶蚀,而且能促进鲕粒灰岩的整体溶解;粘土矿物、石英等杂质组分常与鲕粒和白云岩化颗粒伴生,其对两者的阻溶效应更大。溶解过程中,鲕粒灰岩的构造裂隙、鲕粒放射结合纹和同心圈层等首先发生溶蚀,产生溶隙、粒内溶孔和粒间溶孔;其次为白云质组分以及白云质组分与方解石结合处而产生晶间溶孔、粒内溶孔;随着溶蚀强度的加强,围绕鲕粒形成环状溶蚀沟,在鲕粒溶蚀脱落后而形成鲕模孔。     

黄龙嗜冷细菌两种胞外单糖对碳酸钙矿化影响

为了探究黄龙水体中嗜冷细菌的胞外代谢产物对钙华沉积速率及沉积产物的影响,本文从黄龙钙华水体中分离到优势土著嗜冷细菌,并以其标志性胞外代谢产物D-葡萄糖和D-核糖作为研究对象,研究了两种单糖组分在低温环境下对钙华沉积的影响,并通过X射线衍射(XRD)、扫描电子显微镜(SEM)、红外吸收光谱(FT-IR)等分析手段对碳酸钙晶型、形貌以及结构组成进行了表征。实验表明:D-葡萄糖在低温条件下能促进方解石型碳酸钙的沉积,并加快沉积速率。低浓度下(20 mg/L和40 mg/L)的沉积产物均为方解石型碳酸钙并对其形貌有一定的影响;高浓度下(80 mg/L和160 mg/L)能诱导少量的文石型碳酸钙的合成。D-核糖在低温条件下能促进碳酸钙的沉积,加快沉积速率。与D-葡萄糖不同,D-核糖仅能合成方解石型碳酸钙,但对方解石晶面的生长表现为抑制作用,且随浓度增大抑制作用益明显。此结果可为黄龙钙华生物成因的探究提供一定的理论研究基础。     

塔河油田溶洞充填物的元素地球化学特征及环境意义

塔河油田位于塔里木盆地塔北隆起阿克库勒凸起的西南部,加里东-海西期强烈抬升导致的大气淡水岩溶作用、早石炭世发生的广泛海侵以及二叠纪大规模的火山活动,对奥陶系岩溶储层产生了不同程度的改造。对塔河地区的地质演化特征以及塔河油田地区溶洞砂泥质充填物镓、铷、锶、钡等微量元素和稀土元素的研究表明,大部分样品表现出淡水岩溶特征,仅T615井等4口井的溶洞充填物却表现出海水成因特征,充填物的元素地球化学特征表现出与早期大气淡水岩溶作用的叠加效应;此外,还有少量样品具有能反映热液作用特征的Eu正异常,说明该区碳酸盐岩地层也受热水溶蚀作用的影响。通过溶洞方解石和溶洞方解石胶结物碳、氧同位素值分布特征的分析也证实了塔河地区除了发育大气淡水岩溶作用外,还存在海水-淡水混合水溶蚀作用和热液溶蚀作用。     

鄂尔多斯盆地南部奥陶系马家沟组五段白云岩埋藏溶蚀作用研究

为了解鄂尔多斯盆地南部奥陶系马家沟组五段白云岩储集层不同类型埋藏溶蚀作用的作用过程及其对物性的影响,依据岩心和镜下观察,结合包裹体温度、微量元素和稀土元素数据分析,将马五段埋藏溶蚀作用分为有机酸流体埋藏溶蚀作用、热液埋藏溶蚀作用和TSR作用,其中有机酸流体溶蚀作用会导致层状溶孔、沥青薄膜和圆环的形成,而热液溶蚀作用会导致无组构无选择性溶孔、块状和脉状黄铁矿充填、热液矿物(组合)充填的出现。研究区马五段埋藏溶蚀作用发生模式为: (1)中侏罗世直罗期,低温热液埋藏溶蚀作用发生;(2)中侏罗世末期,伴随第1次烃类充注,有机酸流体埋藏溶蚀作用开始;(3)早白垩世东胜期,中—高温热液埋藏溶蚀作用发生;(4)早白垩世末期,伴随着第2次更大规模的烃类注入,TSR作用发生。对比发现,有机酸和热液溶蚀作用均对储集层有建设性作用,但热液比有机酸流体可以更有效地提高储集层物性。     

川东北飞仙关组鲕滩储层硫酸溶蚀的证据和模式探讨

川东北飞仙关组鲕滩储层的主要储集空间为溶蚀孔洞,主要由大气淡水溶蚀作用、有机酸溶蚀作用和硫酸溶蚀作用所形成。通过硫酸对灰岩和白云岩溶蚀实验、天然气中硫化氢含量与飞仙关组石膏厚度关系分析、天然气中硫同位素与地层中的硫同位素比较、方解石胶结物的阴离子分析等证据,首次提出了硫酸溶蚀在该储层形成中起很重要的作用。探讨了硫酸溶蚀形成储层的模式。     

Hydrometallurgical processing and recovery of molybdenum trioxide from spent catalyst

Hydrometallurgical processing of spent hydrodesulphurisation (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixtures was investigated. The results indicated that the recovery of molybdenum was largely dependent on the concentrations of Na₂CO₃ and H₂O₂ in the reaction medium, which controls the acidity of the leach liquor and carry over of impurities such as Al, Ni, P, Si and V. Leaching process was exothermic and leaching efficiency of molybdenum decreased with increasing solid to liquid ratio. Large scale leaching of spent catalyst, under optimum conditions: 20% pulp density, 85 g/L Na₂CO₃, 10 vol.% H₂O₂ and 1 h reaction, resulted a leaching efficiency of 84% Mo. The obtained leach liquor contained (g/L): Mo — 22.0, Ni — 0.015 and Al — 0.82, P — 1.1, Si — 0.094 and minor quantities of V — 8 mg/L, As and Co — < 1 mg/L. Recovery of Mo from leach solution as MoO₃ of 97.30% purity was achieved by ammonium molybdate precipitation method.     

硅酸盐玻璃中的Na和K含量电子探针分析条件设定探讨

含Ti硅酸盐玻璃在基础科学研究和应用技术开发上均有重要价值,亟需对其进行准确的成分分析,为进一步的科研工作提供重要的数据支撑.对玻璃进行电子探针分析时,由于样品的易损性和其中(Na和K)阳离子在电子束轰击下极易发生迁移和扩散,因此往往需要经过条件实验来确定合适的分析条件,确保样品在该条件下能够保持尽量稳定的状态,才能获...     

A computer simulation study of OH defects in Mg2SiO4 and Mg2GeO4 spinels

Classical atomistic simulation techniques have been used to investigate the energies of hydrogen defects in Mg₂SiO₄ and Mg₂GeO₄ spinels. Ringwoodite (γ-Mg₂SiO₄) is considered to be the most abundant mineral in the lower part of the transition zone and can incorporate large amounts of water in the form of hydroxyls, whereas the germanate spinel (γ-Mg₂GeO₄) corresponds to a low-pressure structural analogue for ringwoodite. The calculated defect energies indicate that the most favourable mechanisms for hydrogen incorporation are coupled either with the reduction of ferric iron or with the creation of tetrahedral vacancies. Hydrogen will go preferentially into tetrahedral vacancies, eventually leading to the formation of the hydrogarnet defect, before associating with other negatively charged point defects. The presence of isolated hydroxyls is not expected. The same trend is observed for germanate, and thus γ-Mg₂GeO₄ could be used as a low-pressure analogue for ringwoodite in studies of water-related defects and their effect on physical properties.     

Elastic and thermoelastic properties of synthetic Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript> (åkermanite) and Ca<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> (hardystonite)

Elastic and thermoelastic constants of large single crystals of Ca₂MgSi₂O₇ and Ca₂ZnSi₂O₇ have been derived from ultrasonic resonance frequencies of plane-parallel plates and their shift upon variation of temperature, respectively. In addition, coefficients of thermal expansion and dielectric constants were determined. Both species possess quite similar properties. As observed in other isotypic magnesium and zinc compounds, the mean elastic stiffness and the deviation from the Cauchy relations are significantly larger in the zinc compound, due to a covalent contribution of the Zn–O bond. Positive thermoelastic constants T₄₄ and T₆₆ in Ca₂MgSi₂O₇ allow temperature-independent ultrasonic generators and oscillators to be manufactured.     

中国北方典型中小盆地城市大气颗粒物污染特征及趋势对比

分析了2014~2018年北方5个典型中小盆地城市(兰州、银川、临汾、太原、南阳)PM10与PM2.5的浓度变化特征和大致来源类型。除2018年银川PM2.5浓度外,各市PM10和PM2.5年均浓度均超标;兰州、银川和南阳PM10与PM2.5呈逐年下降趋势,南阳下降最明显;临汾PM10与PM2.5呈逐年上升趋势;太原PM10与PM2.5稳定维持在一个高浓度状态。5个城市颗粒物浓度的季节变化特征一致:冬春高、夏秋低。对PM2.5/PM10值而言,冬季和夏季该比值较高,分别受取暖和降水的影响;春季和秋季该比值较低,分别受沙尘和秸秆焚烧及高强度建筑施工的影响。5市PM2.5和PM10浓度具有良好的线性关系,细颗粒占比大小顺序为临汾>南阳>太原>银川>兰州。     

Low-temperature heat capacities of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and spinels of the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution

We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl₂O₄ and MgCr₂O₄. The data also include new low-temperature heat capacity measurements for MgAl₂O₄ spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl₂O₄ spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)₂O₄ spinels. We suggest a standard entropy for MgAl₂O₄ of 80.9 ± 0.6 J mol⁻¹ K⁻¹. For the solid solution between MgAl₂O₄ and MgCr₂O₄, we observe a linear increase of the standard entropies from 80.9 J mol⁻¹ K⁻¹ for MgAl₂O₄ to 118.3 J mol⁻¹ K⁻¹ for MgCr₂O₄.     

High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)Mg₅Si₈O₂₂(OH)₂ was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P2₁ /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm⁻¹, respectively, and two minor bands at 3,667 and 3,687 cm⁻¹. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (^A□_0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T _c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P2₁ /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ^ANa_0.8^B(Na_0.8Mg_1.2)^CMg₅Si₈O₂₂(OH)₂ indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T _c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.     

流体包裹体盐度低温拉曼光谱测定方法研究

氯盐溶液作为流体包裹体中最普遍和最重要的盐水化合物,是测定包裹体盐水溶液含盐度的主要溶质,但由于其强离子键化合物的分子特性在常温、常压下没有拉曼效应,拉曼光谱测试无法获取氯盐的有效特征信息,使得利用拉曼光谱研究流体包裹体分子组分及含盐度的方法存在严重缺陷。本文联合利用激光拉曼光谱探针和冷热台,原位采集了不同盐度的NaCl-H₂O和CaCl₂-H₂O标准盐水溶液在低温下(-185℃)形成的冰、NaCl水合物和CaCl₂水合物的拉曼光谱,分析了不同盐度标准盐水溶液形成的水合物拉曼特征峰的变化规律,尝试建立流体包裹体盐度低温拉曼光谱测定方法。分析表明,NaCl水合物约3425 cm^-1拉曼特征峰与冰约3120 cm^-1拉曼特征峰峰面积比值和配制的NaCl-H₂O标准溶液盐度呈良好的正相关(r²=0.9995),CaCl₂水合物约3431 cm^-1拉曼特征峰与冰约3120 cm^-1拉曼特征峰峰面积比值也和配制的CaCl₂-H₂O标准溶液盐度呈较好的正相关(r²=0.9458)。利用愈合人工水晶法合成的NaCl-H₂O和CaCl₂-H₂O包裹体标样检验了用上述方法低温测定流体包裹体盐度的可靠性,结果表明该技术用于盐度大于0.5 mol/L的NaCl-H₂O体系流体包裹体时,数据精度好于20%;用于盐度大于0.5 mol/L的CaCl₂-H₂O体系流体包裹体时,数据精度最高可达5%,完全可达到半定量-定量测定的要求。研究还发现,包裹体内压可能对低温拉曼光谱测定流体包裹体盐度影响不大,分析中获得的冰拉曼特征峰的拉曼位移(约3120 cm^-1)与前人略有差异,可能与实验条件下获得的冰的多型不同有关。与国内外同行的研究结果比较,本研究更加注重该项实验技术的实际应用,通过对不同体系盐水溶液系列进行拉曼光谱实验分析,对实验条件和方法进行不断优化,在确定流体体系的同时实现了包裹体盐水溶液盐度半定量-定量测定,准确度优于传统方法,并且该方法具有很强的实用性。     

Interpretation of carbon dioxide diffusion behavior in coals

Storage of carbon dioxide in geological formations is for many countries one of the options to reduce greenhouse gas emissions and thus to satisfy the Kyoto agreements. The CO₂ storage in unminable coal seams has the advantage that it stores CO₂ emissions from industrial processes and can be used to enhance coalbed methane recovery (CO₂-ECBM). For this purpose, the storage capacity of coal is an important reservoir parameter. While the amount of CO₂ sorption data on various natural coals has increased in recent years, only few measurements have been performed to estimate the rate of CO₂ sorption under reservoir conditions. An understanding of gas transport is crucial for processes associated with CO₂ injection, storage and enhanced coalbed methane (ECBM) production.A volumetric experimental set-up has been used to determine the rate of sorption of carbon dioxide in coal particles at various pressures and various grain size fractions. The pressure history during each pressure step was measured. The measurements are interpreted in terms of temperature relaxation and transport/sorption processes within the coal particles. The characteristic times of sorption increase with increasing pressure. No clear dependence of the characteristic time with respect to the particle size was found. At low pressures (below 1 MPa) fast gas diffusion is the prevailing mechanism for sorption, whereas at higher pressures, the slow diffusion process controls the gas uptake by the coal.