H2O2在α-Fe2O3表面非均相氧化SO2机理的模拟研究

通过密度泛函理论模拟了H_2O_2和SO_2气体在矿物氧化物(α-Fe_2O_3)表面上的非均相反应,研究了H_2O_2和SO_2在α-Fe_2O_3(001)表面的吸附机制和氧化机制。研究结果表明,SO_2、H_2O_2均在α-Fe_2O_3(001)表面通过Fe原子进行吸附,H_2O_2相比于SO_2优先吸附在α-Fe_2O_3(001)表面,且H_2O_2在表面的赋存形式趋向于两个·OH形式吸附。通过二者共吸附的局域态密度、差分电荷密度、Mulliken电荷布局分析结果发现,SO_2和H_2O_2的共吸附形式是通过H_2O_2产生的·OH吸附在α-Fe_2O_3(001)表面,同时SO_2被H_2O_2产生的·OH氧化[S(SO_2)-电荷布局:0. 79 e→1. 32 e; O(H_2O_2)-电荷布局:-0. 77 e→-1. 11 e]形成·OH+SO_2团簇。模拟结果表明大气微量气体H_2O_2能够在矿物氧化物表面介导SO_2吸附并促进SO_2的转化,为理解H_2O_2在大气中非均相氧化SO_2的反应过程提供了理论依据。     

HONO在γ-Al2O3(110)表面非均相氧化SO2机理的第一性原理研究

为研究亚硝酸(HONO)在γ-Al_2O_3(110)表面非均相氧化SO_2的机理,基于密度泛函理论(density functional theory,DFT)的第一性原理计算了SO_2和HONO在γ-Al_2O_3(110)表面的吸附机制和氧化机制。结果表明,SO_2以分子的形式吸附在完整或缺陷的γ-Al_2O_3(110)表面,而HONO仅在完整表面上以分子的形式存在。表面氧缺陷的存在不仅会增强SO_2和HONO的吸附强度,而且能诱导HONO在含氧缺陷表面的分解(HONO→NO+·OH)。通过局域态密度(partial density of states,PDOS)和Mulliken电荷布局分析表明,HONO的分解遵循Haber-Weiss机制。当SO_2和HONO共同吸附在氧缺陷表面时,HONO分解产生·OH,氧化SO_2形成HOSO_2团簇分子。该研究不仅有助于理解HONO在矿物氧化物表面氧化SO_2的作用,而且为解释大气硫酸盐气溶胶的形成提供了理论依据。     

CO2全球循环及其同位素示踪研究

极地冰盖气泡研究表明,工业革命前大气圈天然ＣＯ₂浓度约为２８０×１０－６,天然ＣＯ₂浓度变化反映了冰期－间冰期循环这一长期气候变化固有特征。工业革命后,大量人为ＣＯ₂进人大气圈,人为ＣＯ₂收支明显不平衡,一个大于２．６ＧＴＣ／ａ的未知陆地生态汇很可能存在于北半球中纬度地带。土壤、岩溶作用、河流作用、地球化学作用、干旱－半干旱环境等系统以及海洋内部ＣＯ₂循环的同位素示踪研究,可为人为ＣＯ₂未知汇即“ＭｉｓｓｉｎｇＳｉｎｋ”的探求提供线索。     

云贵高原湖泊CO2的地球化学变化及其大气CO2源汇效应

湖泊是大气CO₂的源还是汇,长期以来一直都存有争议。云贵高原地区的湖泊由于受流域碳酸盐岩风化作用的影响,使这一问题就显得更特殊,也更复杂。本次研究通过化学平衡计算和气相色谱测定两种方法得到了比较一致的湖水CO₂浓度结果。研究发现,在夏季强烈的光合作用消耗了湖水CO₂,致使湖水中CO₂浓度降低。在贵州草海、百花湖以及云南的泸沽湖、杞麓湖,表层湖水CO₂分压(为便于与大气CO₂比较,文中湖水CO2用分压单位表示)小于200μatm,远低于大气CO₂分压,湖泊正不断地从大气中吸收CO₂,从而构成大气CO₂的汇。     

BrF5法氧同位素实验系统中CO2转换器的改进及意义

硅酸盐、氧化物的氧同位素测定分析,是成岩成矿物质 源区鉴定、矿物岩石形成温度确定、成岩成矿地球化学机理 推测的重要手段之一^[1]。在固体地球科学的诸多学科^{[2]以 及环境科学、水文、古气候、天体化学等其他学科均有着广泛 的应用。因此,随着样品量的增加,提高实验室的BrF5法氧 同位素实验系统的工作效率颇有意义。 图1为BrF₅法氧同位素实验系统装置。当系统真空抽 至3×10-3Pa时,充入氩气。分别将已称好的200目干燥样 品12mg加入各反应器,经2小时200℃去气抽真空后,将化 学计算量}     

沉积岩中无机CO2热模拟实验研究

结合三水盆地的地质特点，分析了无机CO₂热模拟实验研究的可能性，进行了不同条件下的模拟试验和相关的分析测试，提出了无机CO₂生成量和转化率的概念和计算方法。从实验结果来看：含有一定量碳酸盐矿物的沉积岩，在一定温度下可转化形成相当数量的无机CO₂，无机CO₂转化率越高，岩石中碳酸盐矿物越容易转化生成无机CO₂；相同热成熟度条件下，Ⅱ型干酪根生成有机CO₂的量较Ⅲ型的少；CO₂中碳同位素与CO₂的成因密切相关，随有机质热成熟度的增加，同种类型有机质生成的有机CO₂相对富集¹³C；无机CO₂较有机CO₂的碳同位素明显富集¹³C，随水介质的pH值降低，无机CO₂气含量、模拟温度及时间的增加，无机CO₂相对富集¹³C。实验研究结果为CO₂成因研究及其资源评价提供了实验依据。     

水射流破碎联合CO2置换开采天然气水合物新工艺及实验研究

本文对目前开采天然气水合物的5种方法进行了归纳总结,重点分析了CO₂置换开采以及固体开采法,并通过分析这2种开采方法的优劣势,提出了水射流冲蚀、破碎海洋天然气水合物储层联合CO₂置换开采天然气水合物的新思路。水射流冲蚀、破坏水合物储层后形成的采空区能为CO₂提供更好的储藏空间并提高其与储层的作用面积,提高置换效率;封存的CO₂水合物也可以提高水合物储层的稳定性,具有良好的互补效应。实验结果表明,在整个置换过程中,含采空区储层CH₄置换率为24.3%,CO₂封存率为22.1%;完整储层CH₄置换率为15.3%,CO₂封存率为20.9%,置换率提升约59%,封存率提升约5.7%。采空区的作用主要体现在提升水合物置换介质的注入量上。     

四川冕宁木落稀土矿床稀土矿物中富CO2和H2流体包裹体研究

木落稀土矿床位于四川省冕宁县境内，其成矿与喜山期岩浆碳酸岩有关。通过对矿床中主要稀土矿物氟碳铈矿中流体包裹体的岩相学、包裹体显微测温分析和包裹体成分的LRM分析等，对成矿流体的特征、演化及稀土矿化过程进行了讨论，结果表明与稀土成矿有关的流体为富CO₂和SO₂ 的中高温、高压超临界流体。温度、压力降低和流体不混溶是造成稀土矿物沉淀的主要机制。     

中国东部CO2气地球化学特征及其气藏分布

中国东部CO₂气田(藏)发育广泛,分布复杂。本文对中国东部松辽、渤海湾、苏北、三水、东海、珠江口、莺琼、北部湾等盆地和内蒙古商都地区以及部分现代构造岩浆活动区CO₂气田(藏)和气苗中CO₂的地球化学特征进行了分析和研究,探讨了中国东部CO₂气的成因、来源及分布。中国东部CO₂气的含量主要分布区间为0~10%,其次为90%~100%,呈现典型的U字型。δ¹³C_CO2值则呈现典型的单峰式分布,峰值区间为-6‰~-4‰。CO₂含量、δ¹³C_CO2值和R/Ra值综合表明,中国东部高含CO₂气以幔源无机成因为主,混有部分有机成因气和(或)壳源无机气。中国东部已发现的36个无机成因CO₂气田(藏)在空间分布上与新近纪及第四纪北西西向玄武岩活动带展布一致,深大断裂和岩浆活动是无机成因CO₂富集、运移和分布最重要、最直接的两大主控因素。     

用树轮δ13C重建1685年以来的大气CO2浓度变化趋势

对采自浙江西天目山地区的3株柳杉树盘,交叉定年后,测定了3株树轮^δ13C的年序列,分析了3株树轮^δ13C序列中所含的共同环境变化信息。用二项式拟合法去除气候因素引起的3个^δ13C序列的高频变化,得到3个低频变化序列。分析了theLowDome冰芯记录的大气CO₂浓度与树轮^δ13C序列低频变化趋势的关系,建立了相应的转移函数,重建了天目山地区1685年以来大气CO₂浓度变化。结果表明:用3株树轮^δ13C序列重建的结果有较好的一致性,并与南极冰芯的记录及前人研究结果有很好的吻合。这一结果表明用同一地区不同树木个体的树轮^δ13C序列的低频变化序列可以重建出基本一致的大气CO₂浓度变化历史。     

The rise of trees and their effects on Paleozoic atmospheric CO2 and O2

The rise of large vascular plants during the mid-Paleozoic brought about a major increase in the rates of weathering of silicate minerals that induced a drop in the level of atmospheric CO₂ and contributed, via the atmospheric greenhouse effect, to global cooling and the initiation of the most long lived and a really extensive glaciation of the past 550 million years. Sedimentary burial of the microbiologically resistant remains of the plants resulted during the Permo-Carboniferous in both further lowering of CO₂ and in elevation of atmospheric O₂. Evidence of changes in CO₂ and O₂ are provided by mathematical models, studies of paleosols, fossil plants, fossil insects, and the effects of modern plants on silicate weathering, and by laboratory studies of the effects of changes in O₂ on plants and insects. To cite this article: R.A. Berner, C. R. Geoscience 335 (2003).     

Laboratory study of self-potential signals during releasing of CO2 and N2 plumes

Carbon Capture Sequestration (CCS) projects require, for safety reasons, monitoring programmes focused on surveying gas leakage on the surface. Generally, these programmes include detection of chemical tracers that, once on the surface, could be associated with CO₂ degassing. We take a different approach by analysing feasibility of applying electrical surface techniques, specifically Self-Potential. A laboratory-scale model, using water-sand, was built for simulating a leakage scenario being monitored with non-polarisable electrodes. Electrical potentials were measured before, during and after gas injection (CO₂ and N₂) to determine if gas leakage is detectable. Variations of settings were done for assessing how the electrical potentials changed according to size of electrodes, distance from electrodes to the gas source, and type of gas. Results indicated that a degassing event is indeed detectable on electrodes located above injection source. Although the amount of gas could not be quantified from signals, injection timespan and increasing of injection rate were identified. Even though conditions of experiments were highly controlled contrasting to those usually found at field scale, we project that Self-Potential is a promising tool for detecting CO₂ leakage if electrodes are properly placed.     

低硅埃达克岩和高硅埃达克岩问题

低硅埃达克岩(low-SiO2adakites,LSA,SiO2<60%)和高硅埃达克岩(high-SiO2adakites,HSA,SiO2>60%)的术语是Martin等(2005)提出来的。本文不赞同上述分类,因为,他们的低硅埃达克岩是赞岐岩而不是埃达克岩。赞岐岩是幔源的,埃达克岩是壳源的,虽然埃达克岩可以与地幔混合形成高镁的埃达克岩,但仍然是壳源的。不应当把壳源的岩浆和幔源的岩浆混淆起来。     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

地下水中高锰酸盐指数和硝酸根铵根稳定性研究

高锰酸盐指数(CODMn)、硝酸根(NO-3)、铵根(NH+4)是判断水体是否受到三氮污染的重要指标。对于测定这三个指标的水样保存方式和时间,地质行业标准和国内外主要国家标准间存在明显差异。地质行业标准规定地下水样品原水室温保存,CODMn和NH+4在3天内测定;NO-3在20天内测定;国家标准和美国标准推荐样品硫酸酸化,避光或冷藏保存,在2~7天内完成CODMn和NO-3和1~7天内完成NH+4测试。为了分析各类标准在样品保存要求上的差异对检测结果的影响,确保检测数据能真实地反映水体污染状况,找寻简便的保存方式,本文在广州地区采集地下水,按照地质行业标准与国家标准进行处理和保存,并在不同时间段对三个指标进行测试。分析验证结果表明:地质行业标准与国家和美国标准关于水样的保存方法均非常可靠。地质行业标准主要针对静态地下水,保存方法相对宽松;国家标准和美国标准适用范围除了地下水,还包括动态的地表水和废水,采样对象成分更为复杂,更不稳定,更容易受外界影响发生变化,故保存条件高于地质标准。在广州地区,采用原水室温避光保存水样,CODMn、NH+4保存时间可为5天,NO-3保存时间可为30天;采用酸化水室温保存水样,CODMn、NO-3和NH+4保存时间可长达30天。这两种方式均比地质行业标准和国家标准推荐的有效时间长,且原水和酸化水室温保存方式相对于冷藏保存方式更为方便。本文提出,如果采集的水样能方便、快速送达实验室,可采用原水保存;如果不能在短时间内送达实验室检测,可采用硫酸酸化保存。     

汶川M_s 8.0地震破裂带CO_2、CH_4、Rn和Hg脱气强度

地震活动断裂带能够向大气释放大量的温室气体、放射性气体和有毒气体(CO_2、CH_4、Rn和Hg),并对大气环境的影响产生复杂的影响。利用静态暗箱法,对汶川M_s8.0地震破裂带CO_2、Rn和Hg脱气强度进行实地测量,并计算了CO_2和Hg脱气对大气的年贡献量。结果表明:(1)破裂带土壤气中CO_2、CH_4、Rn和Hg异常浓度最大值分别可以达到7.98%、2.38%、524.30k Bq/m~3和161.00ng/m~3;破裂带CO_2、Rn和Hg脱气平均通量是34.95g·m~(-2)d~(-1)、36.11m Bq·m~(-2)s~(-1)和26.56ng·m~(-2)h~(-1),最大值分别达到259.23g·m~(-2)d~(-1)、580.35m Bq·m~(-2)s~(-1)和387.67ng·m~(-2)h~(-1);(2)汶川Ms8.0地震破裂带向大气脱气的CO_2年贡献量是0.95Mt,Hg的年贡献量是15.94kg。汶川Ms8.0地震破裂带破裂CO_2、CH_4、Rn和Hg等的脱气强度,不仅与破裂带渗透率有关,还与断裂带浅部存在的气藏、煤层以及磷矿层等气体源有重要的联系。     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

高温下TiO2的相转变动力学及后期颗粒生长研究

利用原位高温XRD方法测量了锐钛矿相TiO2在不同温度下(850、863、875、888、900℃)时间与转化率之间的关系,证实锐钛矿-金红石相转变为一级反应。计算的相转变活化能为432.788±25.657 kJ/mol,指前因子为4.847 454×1015 s-1。利用ESEM观察了样品在相转变完成后,经历不同温度(888、900、930、960、1 000℃)相同烧结时间(10 h),和相同温度(1 000℃)不同烧结时间(0、5、10、15、20 h)下颗粒晶型变化和颗粒长大情况。在1 000℃以下时,温度对颗粒粒度的影响并不明显,并且不出现完好的晶型。1 000℃时,随着时间的延长,颗粒粒度不断增大,并在10 h以后出现完好晶型。根据lnDt(Dt为t时间下颗粒的平均粒度)和lnt的关系图,认为颗粒生长应经过两个不同时期。     

Flue gas and pure CO2 sorption properties of coal: A comparative study

Presently many research projects focus on the reduction of anthropogenic CO₂ emissions. It is intended to apply underground storage techniques such as flue gas injection in unminable coal seams. In this context, an experimental study has been performed on the adsorption of pure CO₂ and preferential sorption behavior of flue gas. A coal sample from the Silesian Basin in Poland (0.68% V Rr), measured in the dry and wet state at 353 K has been chosen for this approach. The flue gas used was a custom class industrial flue gas with 10.9% of CO₂, 0.01% of CO, 9% of H₂, 3.01% of CH₄, 3.0% of O₂, 0.106% of SO₂ and nitrogen as balance.Adsorption isotherms of CO₂ and flue gas were measured upto a maximum of 11 MPa using a volumetric method. Total excess sorption capacities for CO₂ on dry and wet Silesia coal ranged between 1.9 and 1.3 mmol/g, respectively. Flue gas sorption capacities on dry and wet Silesia coal were much lower and ranged between 0.45 and 0.2 mmol/g, respectively, at pressures of 8 MPa. The low sorption capacity of wet coal has resulted from water occupying some of the more active adsorption sites and hence reducing the heterogeneity of adsorption sites relative to that of dry coal. Desorption tests with flue gas were conducted to study the degree of preferential sorption of the individual components. These experiments indicate that CO₂ is by far the prefered sorbing component under both wet and dry conditions. This is followed by CH₄. N₂ adsorbs very little on the coal in the presence of CO₂ and CH₄. It is also observed that the adsorption of CO₂ onto coal is not significantly hindered by the addition of other gases, other than dilution effect of the pressure.In addition to the sorption experiments, the density of the flue gas mixture has been determined up to 18 MPa at 318 K. A very good precision of these measurements were documented by volumetric methods.     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。