受载原煤中瓦斯的扩散规律

为研究受载原煤中瓦斯的扩散规律,以原煤煤样为实验对象,利用自主研发的含瓦斯煤热流固耦合实验系统,在恒温的三轴加载条件下,进行了加载-吸附-解吸-再加载直至煤样破坏过程中的瓦斯解吸实验。研究结果表明,受载原煤的解吸量随时间变化规律符合颗粒煤瓦斯解吸的数学模型;在恒温恒围压下,随轴压的增大,受载原煤瓦斯的解吸量呈下降趋势;当轴压大于峰值强度后,瓦斯解吸量随轴压迅速增大;受载原煤煤样压密、线弹性阶段瓦斯解吸-运移速度随应力增大而线性减小;当煤样处于屈服阶段和峰值破坏阶段瓦斯解吸-运移速度随应力增大呈指数式增长。研究成果对瓦斯抽采,瓦斯突出机理研究有一定的理论价值。     

A Quantitative Evaluation of Shale Gas Content in Different Occurrence States of the Longmaxi Formation: A New Insight from Well JY-A in the Fuling Shale Gas Field,Sichuan Basin

Comprehensive quantitative evaluation of shale gas content and the controlling factors in different occurrence states is of great significance for accurately assessing gas-bearing capacity and providing effective well-production strategies. A total of 122 core samples from well JY-A in the Fuling shale gas field were studied to reveal the characteristics of S_1 l shale,15 of which were selected to further predict the shale gas content in different occurrence states, which are dependent on geological factors in the thermal evolution process. Geological parameters were researched by a number of laboratory programs, and the factors influential in controlling shale gas content were extracted by both PCA and GRA methods and prediction models were confirmed by the BE method using SPSS software. Results reveal that the adsorbed gas content is mainly controlled by TOC, Ro, SSA, PD and pyrite content, and the free gas content is mainly controlled by S_2, quartz content, gas saturation and formation pressure for S_1 l in well JY-A. Three methods, including the on-site gas desorption method, the empirical formula method, and the multiple regression analysis method were used in combination to evaluate the shale gas capacity of well JY-A, all of which show that the overall shale gas content of well JY-A is in the range of 2.0–5.0 m~3/t and that the free gas ratio is about 50%, lower than that of well JY-1. Cause analysis further confirms the tectonics and preservation conditions of S_1 l in the geological processes, especially the influence of eastern boundary faults on well JY-A, as the fundamental reasons for the differences in shale gas enrichment in the Jiaoshiba area.     

Effects of low molecular weight organic acids on sorption and desorption behavior of p-chlorophenol by yellow earth

Low molecular weight organic acids （LMWOAs） are important components of root exudates. They play an important role in immobilizing and remobilizing contaminants in rhizospheric soil. Effects of four LMWOAs on the sorption and desorption behavior of p-chlorophenol by yellow earth was studied in batch mode. The results showed that the previous application of LMWOAs to enhanced adsorption capacity of p-chlorophenol of the soil in the order of maleic acid〉malic acid〉oxalic acid〉citric acid. However, when LMWOAs were applied to soil where p-chlorophenol had been previously adsorbed, substantial p-chlorophenol was desorbed from soil by oxalic acid, whereas citric acid, malic acid and maleic acid didn＇t desorb as much p-chlorophenol from soil as deionized water.     

自吸水分对煤中瓦斯解吸的综合影响

为研究自吸水分对煤中瓦斯解吸的影响,利用自主设计的实验装置,实现了水分在煤中的自发渗吸,单独研究了水分对瓦斯的置换效应,并对不同含水率条件下煤中瓦斯的置换解吸量、卸压解吸量以及残余瓦斯含量进行了测定。结果表明：水分能够促进煤中吸附态瓦斯发生置换解吸,且含水率越大,置换解吸量越大;卸压解吸过程中,相同时间内含水煤样瓦斯解吸量小于干燥煤,且随着含水率升高,解吸量逐渐减小;充分解吸后含水煤样的残余瓦斯含量小于干燥煤,在4%~10%含水率,随着含水率升高,残余瓦斯含量逐渐降低;针对晋城矿区永红煤矿的无烟煤,自吸水分对瓦斯解吸整体上表现为促进作用,水分对瓦斯解吸的影响是置换效应与水锁效应综合作用的结果。     

Carbon isotopic fractionation by desorption of shale gases

Geochemical studies of shale gas and conventional reservoirs within the Triassic Yanchang Formation of Xiasiwan and Yongning Field, Ordos Basin show that methane is isotopically depleted in ¹³C as compared to δ¹³C₁ calculated by the Ro based on the relationship between δ¹³C₁ and Ro. Geochemical fractionation during the adsorption/desorption process of shale system may play a significant part in influencing δ¹³C₁ values of shale gas. Two shale core samples from confined coring of the Yanchang Formation were adopted segmented desorption experiments to examine this phenomenon. The results show that the δ¹³C₁ of desorbed gas changes little in the first few phases of the experiments at low desorption levels, but become less negative rapidly when the fraction of desorbed methane exceeds 85%. The desorption process for the last 15% fraction of the methane from the shale samples shows a wide variation in δ¹³C₁ from −49‰ to −33.9‰. Moreover, δ¹³C₁ of all desorbed methane from the shale samples is substantially depleted in ¹³C than that calculated by Ro, according to Stahl and Carey's δ¹³C₁–Ro equation for natural gas generated from sapropelic organic matter. This shows some gases with isotopically enriched in ¹³C cannot be desorbed under the temperature and pressure conditions of the desorption experiments. This observation may be the real reason for the δ¹³C₁ of shale gases and conventional reservoirs becomes more negative in Xiasiwan and Yongning Fields, Ordos Basin. The magnitude of the deviation between the δ¹³C₁ of shale gas and that calculated by Ro may be related to the adsorption capacity of shale or the proportion of absorbed gases. In this way, we may be able to evaluate the relative adsorption capacity of shale in geological conditions by δ¹³C₁ of the shale gas, or by δ¹³C₁ of conventional gas which generated by the shale with certainty. The δ¹³C₁ of conventional gas in Dingbian and Yingwang Fields have no deviation because the TOC value of the hydrocarbon source rock is relatively low.     

13X分子筛活化及其对氧气转移时吸附/解吸过程中氧同位素分馏效应的研究

在激光BrF5法分析硅酸盐和氧化物矿物的真空提取流程中,通常采用氧气作为工作气体来测定样品的氧同位素组成。这需要使用分子筛吸附并转移氧气到质谱进样系统,而分子筛的活化对于有效吸附和解吸氧气至关重要,否则会引起分析过程中的氧同位素分馏。通过采用13X分子筛进行多组实验分析,笔者发现用不同活化程度或中毒失活分子筛沸石转移时可能存在氧同位素分馏。在低温下分子筛是不能够活化的(或活化不完全),吸附能力很低,所测定的δ18O值是波动的。在200℃马弗炉中预加热24h,然后迅速转移到温度为100℃、真空度为10-3Pa系统中加热12h的分子筛,对氧气吸附能力很强,氧同位素分析的绝对误差为±0.05‰(1σ),能够满足地球化学氧同位素分析的要求。如果分子筛受BrF5污染,其吸附能力大为降低,测定的δ18O值呈下降趋势,氧同位素分馏高达0.7‰。如果分子筛受水汽污染,质谱接受电压不断地降低,存在解吸温度下的再吸附过程,测定δ18O值呈上升趋势。因此,分子筛在使用前要在适当条件下的活化,在发现污染或测量值发生波动变化时要及时更换,否则难以保证氧同位素分析数据的可靠性。     

Photochemistry of N2O4 Adsorbed on Ice Surfaces at 193 nm

A multi-layer deposited ice film was prepared through water vapor deposition on a Ni plate in a vacuum chamber at 90 K, and was used as it was or after annealing at 140 K. NO₂ was adsorbed as N₂O₄ approximately 90 K on the ice film prepared as above, and irradiated by 193 nm excimer laser light. The time-of-flight (TOF) spectra of the desorbed species, i.e., NO₂, NO, O₂ and O, were measured by a quadrupole mass spectrometer. The photochemical process obeyed an one-photon process. The relative yields of the products and their TOF spectra were dependent on the preparation condition of the ice film and also varied with the continuation of the laser irradiation. From the ice film annealed at 140 K, NO₂, NO and O₂ were desorbed with an approximate ratio of 1:1:0.01. From the non-annealed film, the relative yield of NO₂ was much smaller than that of NO. The TOF spectrum of NO from the non-annealed ice film consisted of distinctly different two components corresponding to the 1700 and 100 K translational temperature, respectively. The fast component was lost when additional ice was deposited on the adsorbed N₂O₄. NO was supposed to be a predissociation product from the electronically excited NO₂ prepared through the photodissociation of N₂O₄.     

Effects of nitrate on phosphorus release: comparison of two Berlin lakes

After installation of phosphorus elimination plants at the inflows of the eutrophic Lake Tegel and Schlachtensee, phosphorus (P) loading declined by a factor of 40 and 100, respectively. This resulted in a pronounced reduction of phosphorus concentrations in the lake water, followed by a decline of chlorophyll‐a concentrations. However, for many years P release from sediments due to mineralization and desorption of sedimentary P continued. In Schlachtensee, the presence of nitrate above the sediment suppresses P release, because the Fe/P ratio is sufficient to provide enough aerobic sorption capacity. In Lake Tegel, some P release occurs even under aerobic conditions because of the low aerobic P sorption capacity of the sediments. There, nitrate could moderate the P release peaks which occur when the Fe‐P cycle at the sediment water interface is disturbed by precipitation of iron sulfide after reduction of sulfate during times of high mineralization intensity. The potentially mobile P pool in the sediments of both lakes is rather small, indicating that the P release could subside after sufficient reduction of the external P load in Lake Tegel and the disruption of the internal P cycle in Schlachtensee.     

Suspended sediment and phosphorus in proglacial rivers: bioavailability and potential impacts upon the P status of ice‐marginal receiving waters

This paper adopts standard tests developed in temperate catchment research to determine the total phosphorus (TP) and the algal available (base‐extractable) phosphorus (NaOH–P) content of a wide range of glaciofluvial sediments from the Northern Hemisphere. We find that the TP content of these sediments is broadly similar to the P content of major rock types in Earth's crust (230–670 µgP/g) and so the TP yields of glacier basins may be high owing to the efficacy of suspended sediment evacuation by glacial meltwaters. We show that this is best achieved where subglacial drainage systems are present. The NaOH–P pool of the sediments is found to be low (1–23 µgP/g) relative to the TP pool and also to the NaOH–P pool of suspended sediments in temperate, non‐glacierized catchments. This most probably reflects the restricted duration of intimate contact between dilute meltwaters and glacial suspended sediments during the ablation season. Thus, despite the high surface‐area:volume ratio of glacial suspended sediments, the potential for P adsorption to mineral surfaces following release by dissolution is also low. Further, sorption experiments and sequential extraction tests conducted using glacial suspended sediments from two Svalbard catchments indicate that the generation of reactive secondary minerals (e.g. Fe‐ and other hydroxides) with a strong capacity to scavenge P from solution (and thereby promote the continued dissolution of P) may also be limited by the short residence times. Most P is therefore associated with poorly weathered, calcite/apatite‐rich mineral phases. However, we use examples from the Svalbard glacier basins (Austre Brøggerbreen and Midre Lovénbreen) to show that the high sediment yields of glaciers may result in appreciable NaOH–P loading of ice‐marginal receiving waters. Again, the importance of subglacial drainage is highlighted, as it produces a major, episodic release of NaOH–P at Midre Lovénbreen that results in a yield (8·2 kg NaOH–P/km²/year) more than one order of magnitude greater than that at Austre Brøggerbreen (where subglacial drainage is absent and the yield is 0·48 kg NaOH‐P/km²/year). Therefore, as since both detrimental and beneficial effects of sediment‐bound P loading in ice marginal receiving waters are possible (i.e. either reduced primary productivity owing to increased turbidity or P fertilization following desorption) there is a pressing need to assess the ambient P status of such environments and also the capacity for ice‐marginal ecosystems to adapt to such inputs. Copyright © 2004 John Wiley & Sons, Ltd.