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91.
汞易挥发且通常以气态形式在大气环境中迁移转化,检测汞在气相中的含量可为汞的治理工作提供依据,但检测气相汞的技术并不成熟。该项工作需要准确地对气相元素汞量进行测定,而测定的前提是必须具备准确、可靠的标定方法。本研究提出以Hg~(2+)离子为前驱体标定煤热解气中气相元素汞量的方法。该方法是基于水溶液中Hg~(2+)可被还原剂定量还原成元素汞蒸汽的原理,实现对气相元素汞量的标定。与传统的基于饱和蒸汽原理的标定方法相比,该方法的优点是取样时不易受温度影响,易于精确控制汞量,且避免了实验室内储存汞蒸汽所造成的汞污染。以测定四种煤在热解过程中元素汞的释放量为例考察了本方法的准确性,结果表明本方法具有较好的重复性和适应性。与美国Ontario-Hydro方法分析的结果进行对比,两种方法的相对标准偏差均小于3.0%,说明本研究的标定方法的可靠性较高。 相似文献
92.
为了发展油页岩催化热解方法,本文对油页岩中干酪根在催化剂(SnCl2,MoCl5,ZnCl2)作用下的热解转化进行了研究。运用傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、热重(TG)分析等手段对样品在较低温度下(350℃)热解前后的半焦产物进行了分析,利用Coats-Redfern方法计算了热解后的残余半焦动力学参数。结果表明,催化剂可以使干酪根在350℃发生热解反应,同时也能够降低残余半焦的活化能,其中SnCl2、MoCl5和ZnCl2催化处理后残余半焦的活化能分别降低15.10、10.66和20.58 kJ/mol。 相似文献
93.
塔里木轮南地区原油沥青质的分子结构及其初步应用:热解、甲基化-热解和RICO研究 总被引:3,自引:3,他引:0
利用瞬间热解、甲基化-热解和钌离子催化氧化(RICO)降解技术研究了塔里木盆地轮南地区原油沥青质的分子结构,并对其在石油地球化学研究中的指示意义进行了讨论.轮南地区原油沥青质分子中的取代官能团以烷基侧链为主,烷基桥次之,另外还有少量的烷基-环己烷、支链烷烃和苯系物,这些化合物可能大都以C-C键结合到缩合芳环体系上;沥青质分子中的芳环体系大多数可能是萘或菲类型的芳香结构,高度缩合的芳香结构可能较少.轮南地区不同构造带原油沥青质热解产物的一致性指示它们可能来自沉积环境相同的母源.沥青质的分子结构表明,其母源可能主要来自浮游藻类的类脂物.热解产物中较高含量的1,2,3,4-四甲基-苯和2,6-二甲基、2,6,10-三甲基烷烃类化合物的检出表明其母质可能形成于较强的还原环境.沥青质热解产物中姥鲛-1-烯的相对含量较低,RICO产物中一元脂肪酸远高于二元脂肪酸,指示该区原油具有较高的成熟度.部分脂肪酸类化合物通过酯键连接在沥青质分子中,可能反映了原油在储层中经历了生物降解等后生作用. 相似文献
94.
以往对鄂尔多斯盆地南部地区长7油层组(简称长7)中烃源岩生烃潜力的研究主要是采用静态地球化学指标进行的,目前尚无对生烃动态特征的系统评价,因而制约了对长7烃源岩生烃潜力和页岩油资源分布有利岩性的客观认识。为此,选取长7不同类型的烃源岩样品,通过开放和封闭热模拟实验,对比分析了不同类型烃源岩的动力学参数、生烃产物、产率特征及生烃演化规律。结果表明:(1)黑色页岩活化能分布范围比暗色泥岩更为集中,且主频活化能和频率因子均低于暗色泥岩,体现了快速生烃的特性;(2)在外推到地质条件下,黑色页岩主要生烃期对应的Ro值(0.70%~0.87%)低于暗色泥岩(1.06%~1.72%),且以生油为主;(3)Ro在0.9%~1.3%范围内,黑色页岩的总烃产率高于暗色泥岩,生油量高于暗色泥岩。结合研究区两类烃源岩的地球化学资料综合分析表明,黑色页岩是研究区页岩油资源形成与分布的有利烃源岩。 相似文献
95.
96.
Vegetative remains of three coalified Lower Devonian vascular plants (Zosterophyllum, Psilophyton, Renalia) were analyzed using flash pyrolysis-gas chromatography-mass spectrometry. The distributions of pyrolysis products are compared with those from younger vascular plant fossil xylem (Cordaixylon, Callixylon) and cuticle (Pachypteris). The likelihood of the chemical preservation of characteristic higher plant macromolecules (e.g., lignin and cutan) in the Lower Devonian plant fossils is considered in light of this comparison and associated thermal maturity assessments. Reflectance values from vitrinite-like macerals, which may not be vitrinite sensu stricto in the Lower Devonian host rocks for the fossils selected for this study, are shown to provide a reasonable assessment of the thermal maturity of these early vascular plant fossils. Although lignin altered through burial maturation is the most likely source of the prominent alkylphenols and aromatic hydrocarbons in the Lower Devonian tracheophyte flash pyrolysates, a contribution from thermally modified tannins cannot be ruled out. Comparison of the highly aliphatic pyrolysates from the Zosterophyllum and Psilophyton axes with that of a thermally mature fossil gymnosperm leaf revealed that cutan was an important component in the Devonian plant remains. This is the earliest chemical evidence for the presence of cutan in vascular plants. 相似文献
97.
S. Derenne P. Metzger C. Largeau P.F. Van Bergen J.P. Gatellier J.S. Sinninghe Damst J.W. de Leeuw C. Berkaloff 《Organic Geochemistry》1992,19(4-6)
Most Ordovician source rocks consist of accumulation of a colonial marine microorganism, Gloeocapsomorpha prisca (G. prisca) whose nature, ecology and affinity with extant organisms have been in dispute for years. Furthermore, recent studies have shown major differences in phenol moieties between two G. prisca-rich samples. Examination of five G. prisca-rich kerogens by electron microscopy and pyrolysis studies revealed (i) the occurrence of two markedly distinct “morpho/chemical” types: a “closed/phenol-rich” type (Baltic samples) and an “open/phenol-poor” one (North American samples) and (ii) the selective preservation of the resistant micromolecular material building up the thick cell walls in the original organism. Comparison with extant Botryococcus braunii (a widespread green microalga) grown on media of increasing salinity suggests that G. prisca is likely to be a planktonic green microalga related to B. braunii, which can adapt to large salinity variations which, in turn, control its polymorphism. The large differences in colony morphology and in the content of phenol moieties observed in fossil G. prisca and the resulting occurrence of two “morpho/chemical” types, should therefore reflect depositional environments with different salinities. The presence of thick, highly aliphatic, resistant walls in G. prisca selectively preserved during fossilization, accounts for the major contribution of this organism to Ordovician organic-rich sediments and for the resulting typical signature of Ordovician oils. 相似文献
98.
应用碳同位素动力学方法探讨阿克 1气藏天然气的来源 总被引:5,自引:1,他引:5
阿克 1气藏是塔西南前陆区喀什凹陷油气勘探上获得重大突破的工业性气藏.采用金管封闭体系热模拟实验和 GC-IRMS碳同位素测定,结合运用 GOR-ISOTOPE KINETICS专用软件,推导出了塔西南前陆区烃源岩 (煤和泥岩 )热解生成甲烷的碳同位素动力学参数.该区侏罗系煤、侏罗系泥岩和二叠系泥岩的平均活化能分别为 225.86 kJ/mol、 194.03 kJ/mol和 223.45 kJ/mol,甲烷 (12CH4)的指前因子各为 1.00× 1014 s-1、 1.00× 1013 s-1、 1.00× 1014 s-1.在此基础上,利用碳同位素动力学计算结果,并结合地质背景,进一步探讨了阿克 1气藏天然气的来源,为天然气定量评价提供了新思路.阿克 1气藏天然气为烃源岩过成熟阶段的烃产物,属于混源气,主要捕获了 Ro 为 2.0%~ 3.6%阶段的天然气;其气源区包括喀什凹陷中心和阿克 1井推覆体下盘,主力气源岩是石炭系烃源岩. 相似文献
99.
Kevin G. Knauss Sally A. Copenhaver Robert L. Braun Alan K. Burnham 《Organic Geochemistry》1997,27(7-8)
Hydrous pyrolysis in flexible gold-bag autoclaves was used to study the production of carboxylic acids and light hydrocarbons from two marine type IIb source rocks (New Albany and Phosphoria Shales). Kerogen pyrolysis produced significant amounts of the monocarboxylic acids (acetic > propionic > butyric). The gases were dominated by CO2 and methane, in that order, and progressively smaller amounts of the alkanes (ethane > propane > butane > pentane). Kinetic analyses of production rates for the New Albany Shale suggest mean activation energies (E) of 51-54 kcal/mol for both the light hydrocarbons and acids. Pressure had little effect on measured production rates for either shale over the pressure range investigated. Chemical thermodynamic speciation modeling suggests that in these experiments metal-organic acid anion complexation had little impact on aluminum speciation/solubility, but was important with respect to the alkaline earths. 相似文献
100.
Franois Gelin Ilco Boogers Anna A. M. Noordeloos Jaap S. Sinninghe Damste Roel Riegman Jan W. De Leeuw 《Organic Geochemistry》1997,26(11-12)
Non-hydrolysable macromolecular constituents (i.e. algaenans) were isolated from two out of seven marine microalgae investigated. Nannochloropsis salina and Nannochloropsis sp. from the class of Eustigmatophyceae produce highly aliphatic algaenans. Flash pyrolysis and chemical degradations with HI and RuO4 allowed for the identification of their chemical structure, which is mainly composed of polyether-linked long-chain (up to C36) n-alkyl units. The building blocks of this polymer were also recognized in lipid fractions. The green microalgae (Chlorophyceae) Chlorella spaerckii, Chlorococcum sp. and Nannochloris sp. were earlier thought to biosynthesize algaenans comprising aliphatic and/or aromatic moieties. However, a new isolation method utilizing trifluoroacetic acid (TFA) prior to the other hydrolyses revealed that the macromolecular material isolated from these three chlorophytes was either hydrolysable with TFA or artefacts from the former method. Similar to algaenans from fresh water green microalgae, the aliphatic eustigmatophyte algaenans are likely to be selectively preserved in depositional environments and might ultimately serve as source rock organic matter of marine crude oils. Furthermore, they may play an important role in the cycling of carbon. 相似文献