云南煤层气资源与开发前景

煤层气的开发利用是集开发新的高效洁净能源、有利煤矿生产安全、有利大气环保于一身的崭新的绿色工程。本文概略介绍我省煤层气勘探及研究工作进展情况,强调云南丰富的煤层气资源,应是云南的资源优势。     

复合固体超强酸催化合成醋酸正丁酯的研究

研究了以复合型固体超强酸为催化剂率合成醋酸正丁酯,探讨了酯化反应条件和催化剂的制作工艺对酯产生率的影响,实验结果表明,复合型固体超强酸（ＳＯ＾２－４／ＺｒＯ２－Ａｌ２Ｏ３）具有较高的催化活性和选择性,在最佳工艺条件下醌产率可达９６％,产品质量符合国标要求,该工艺操作简便,条件易控制,对环境无污染。     

Response surface methodology (RSM) optimization approach for degradation of Direct Blue 71 dye using CuO–ZnO nanocomposite

The present study highlights the synthesis of CuO–ZnO nanocomposite via facile hydrothermal method at 150 °C and autogenous pressure. The structural and textural features of prepared composite material was characterized by several characterization techniques such as X-ray powder diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The optimized prepared nanocomposite was utilized for photocatalytic degradation of aromatic Direct Blue 71 dye (DB71) under natural sunlight conditions. The catalytic activity results by CuO–ZnO nanocomposite were observed to be higher than the reagent-grade zinc oxide under visible light conditions. The response surface methodology protocol (RSM) with central composite design was optimized by different photodegradation operational parameters such as pH, dye concentration, catalyst amount, and reaction time. The optimized RSM results demonstrated that a quadratic polynomial model was found suitable to define the relation between the photocatalytic activity and operational parameters. Moreover, the observed high R ² value (0.9786) confirms a strong evaluation of experimental data. To achieve maximum DB71 degradation, optimized condition was found at 177.13 min of contact time, 3.93 solution pH, and 24.34 mg/L of dye concentration with 1.85 g/L of catalyst dose The identical optimum conditions resulted maximum 89.58% DB71 degradation.     

Synthesis,characterization of CdS/rectorite nanocomposites and its photocatalytic activity

CdS/rectorite nanocomposite was synthesized via a cation-exchange reaction followed by a sulfurization process. The obtained samples were characterized by using X-ray diffraction (XRD), fourier transform infrared spectra (FTIR), transmission electron microscope (TEM), UV-Vis diffuse reflectance spectra (DRS), and thermal analysis. The measured results indicate that CdS species in the composites exist in the form of pillars and nanoparticles, the crystallized CdS particles are in the hexagonal symmetry. The photocatalytic activities of the pillared nanocomposite were enhanced significantly comparing with the bare rectorite and the pure CdS. Moreover, the photostabilities of the obtained nanocomposites are also better than that of the pure CdS due to the hosts retard the photocorrosion of the CdS.     

Green synthesis of magnetic mesoporous silica nanocomposite and its adsorptive performance against organochlorine pesticides

Green synthesis of nanomaterials has received increasing attention as an eco-friendly technology in materials science. Here, we have used two types of extractions from green tea leaf (i.e., total extraction and tannin extraction) as reducing agents for a rapid, simple and one-step synthesis method of mesoporous silica nanoparticles/iron oxide nanocomposite based on deposition of iron oxide onto mesoporous silica nanoparticles. Mesoporous silica nanoparticles/iron oxide nanocomposite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray, vibrating sample magnetometer, N₂ adsorption and high-resolution transmission electron microscopy. Mesoporous silica nanoparticles/iron oxide nanocomposite was used as a solid adsorbent for removal of lindane pesticide from aqueous solutions. The developed system possesses the advantages of silica as core that include large surface area and advantages of iron oxide (shell) that include the capability to interact with chlorinated compounds and ability to release by using external magnetic field. UV-Vis technique was used as a simple and easy method for monitoring the removal of lindane. Effects of pH and temperature on the removal efficiency of the developed mesoporous silica nanoparticles/iron oxide nanocomposite toward lindane pesticide were also investigated. Fourier transform infrared spectroscopy, high-performance liquid chromatography and gas chromatography techniques were used to confirm the high ability of mesoporous silica nanoparticles/iron oxide nanocomposite for sensing and the capture of lindane molecules with high sorption capacity (about 99%) that could develop a new eco-friendly strategy for detection and removal of pesticide and as a promising material for water treatment.     

涪陵页岩气田水平井组优快钻井技术

涪陵页岩气田是我国第一个投入商业化开发的国家级页岩气示范区,与北美相比,涪陵地区地表条件、地质条件和页岩气储层特征更加复杂、储层埋藏更深,开发初期钻井机械钻速低、钻井周期长、成本高。为此开展了涪陵页岩气田水平井组优快钻井技术研究,形成了集水平井组钻井工程优化设计、水平井优快钻井技术、国产低成本油基钻井液、满足大型压裂要求的长水平段水平井固井技术、山地特点“井工厂”钻井技术以及绿色环保钻井技术为核心的页岩气水平井组优快钻井技术体系。在涪陵页岩气田推广应用了290口井,完井256口,平均单井机械钻速提高了182%,平均单井钻井周期缩短了55%,平均单井钻井成本降低了34%。为涪陵页岩气田年50亿m3一期产能建设的顺利完成提供了强有力的技术支撑,对我国页岩气规模开发提供了重要的借鉴和引领作用。     

The presentation of an agro-environmental nanocomposite: the study of its acoustic,physical and mechanical properties

Nanocomposites can be used as an acoustic panel to adsorb noise. The aim of this study was to evaluate: (1) acoustic, (2) physical, and (3) mechanical properties of agro-environmental nanocomposites. To prepare the nanocomposites, wood flour, PVA glue, and aluminum nanoparticles (between 1 and 4 %) were hardly mixed and heated at near 220 °C for 120 min. In the next step, sound absorption coefficient, transmission loss, water absorption percentage, thickness swelling percentage, density, flexural strength, flexural modulus, tensile strength, and tensile modulus of nanocomposites were measured. This study showed that the increase in nanoparticle percentage led to the increase in flexural strength, flexural modulus, water absorption percentage, thickness swelling percentage, density, and sound absorption coefficient. But, the increase in nanoparticle percentage led to the decrease in tensile strength, tensile modulus, and transmission loss. The authors think that the nanocomposites are suitable as an agro-industrial nanocomposite to reduce noise.     

Adsorption Behavior and Mechanism of Environmental Pollutants on Graphene Oxide

Graphene oxide, as an emerging material for contaminants removal,possesses relatively large specific surface area, and it shows good dispersion in water phase due to the hydrophilicessence resulted from abundant oxygen-containing functional groups on the edge, thus leading to a potential excellent adsorbent. Current studies revealthat, because graphene oxide is negatively-charged in a wide range of pHs, the removal efficiency of heavy metals and cationic dyes by graphene oxide is significantly higher than by traditional adsorbents, like activated carbon. However, its applications are still limited due to its structural defects. For example, its π domain is destructed during fabrication process. Therefore, certain structural modifications need to be conducted on the purpose of improving its performance, achieving a better result in water purification. This paper presented the preparation and structure of graphene oxide, and reviewed the adsorption behaviors, adsorption mechanisms, adsorption models and influence factors of heavy metals and organic pollutants on graphene oxide and its composites, respectively. In view of unresolved issues, further research should focus on comprehensive adsorption mechanisms, more facile and effectivemethods for structural modifications and the treatment of graphene oxide after adsorption process.     

隆页2HF页岩气水平井钻井技术研究与实践

四川盆地周缘蕴藏有大面积常压低丰度海相页岩气,依目前的开发成本,储量难以动用,亟需开展低成本钻井工程工艺技术攻关,盘活该类页岩气资源。中石化华东油气分公司在渝东南武隆地区从钻、测、录、固等方面开展了低成本钻井技术研究。通过分析导致钻井成本高的原因,重点从井身结构优化、井眼轨迹控制优化、钻井工具优选、防漏堵漏措施以及测井、录井、固井工艺优化等方面进行了技术研究与现场实践,试验井隆页2HF井由导眼井与侧钻水平井两部分构成,钻井成本较邻井降低了30%,为武隆地区常压页岩气开发奠定了基础。     

中国煤炭资源保障程度和绿色勘查开发途径

文中进一步厘定了煤炭资源/储量的概念,全面分析了我国煤炭资源勘查开发现状,深入阐述了我国煤炭资源保障程度,认为煤炭资源总体丰富,可采、预可采储量不足,服务年限少,区域煤炭资源保障不平衡,优质炼焦用煤稀缺,中东部地区煤炭资源压覆严重,中西部煤炭开发的生态环境问题突出。在分析煤炭资源保障程度基础上,根据煤炭安全高效绿色勘查开发的基本要求,提出了煤炭资源绿色勘查技术、煤矿高精度高效安全开采地质探测技术、煤矿水害探测与防治技术、煤矿绿色充填开采关键技术、采煤沉陷综合治理与生态环境恢复再造技术、煤矿瓦斯井上井下联合抽采技术、废弃矿山资源综合利用和环境恢复技术研究、煤矿高矿化度矿井水及固废处理技术、洁净煤技术的基础地质研究、煤系多能源矿产综合勘查开发和利用技术、煤炭地下气化与煤层气联合协调勘查开发技术、煤源雾霾研究和二氧化碳地质封存技术十二项煤炭绿色勘查开发的技术途径。     

Synthesis and Characterization of the Composites of Polyaniline and Graphene Oxide in Situ Polymerization

The novel high-performance nanocomposites of polyaniline (PANI) and graphene oxide sheets (GOs) was synthesized via in situ polymerization in the presence of Hexadecyl trimethyl ammonium Bromide intercalated graphite oxide (CGO), basing on PANI and GOs as a matrix respectively. The result showed that ANI monomer was intercalated into the spacing of CGO, and the CGO was well exfoliated into nanosheets while polymerization. Owing to π–π electron stacking effect between the PANI and the GOs, the electrical conductivity of GOs/PANI nanocomposites (0.47 S/cm), which basing on PANI as a matrix, improved in comparison with pure PANI nanowires (0.02 S/cm) and GO (2.5×10-5 S/cm), while the electrical conductivity of PANI/GOs nanocomposites, which basing on GOs as a matrix, was only 6.2×10-3 S/cm. And it also indicated that the mole ratio of APS, the concentration of HCl, other with the polymerization time, are also important influencing factors of the conductivity of nanocomposites.     

锆石中两种成分变化趋势及其成因标型意义

锆石从晶体中心至边缘的两种成分变化趋势与成因有内在联系。岩浆成因锆石从中心至边缘具有ＺｒＯ２含量及ＺｒＯ２／ＨｆＯ２值下降，ＨｆＯ２和（ＵＯ２＋ＴｈＯ２）含量上升的特征，而变质成因锆石则与此相反，本文论述了它们的成因及成因标型意义。     

Microstructure and Mechanical Properties of Mica Glass-Ceramics Prepared by Pressureless Sintering a Phlogopite and Various Additives

Mica glass-ceramics were prepared by pressureless sintering with a phlogopite and various additives as raw materials. The effects of CaF2 content, Li2O content, ZrO2 content, and sintering temperature on the microstructure and mechanical properties of the mica glass-ceramics were investigated by X-ray diffraction, scanning electron microscopy, and mechanical testing, respectively. The results show that the additive of ZrO2 has the best reinforcing effect on the flexural strength of the mica glass-ceramics. The smaller powder particles and the larger forming pressure result in the larger bulk density of the mica glass-ceramics samples. The main crystallite phases of samples with ZrO2 as additive were phlogopite and quartz with sintering temperature lower than 1120 ℃. The crystal phase of glass ceramics appeared fiberform and cross arranges with good lap. The highest value of flexural strength, 63.7 MPa, was shown on sample with 10wt% ZrO2 as additive and sintering temperature of 1120 ℃.     

化学发光分析法测定锰的进展

对近20年来化学发光分析法测定锰的进展作了评述，内容包括发光体系、操作条件、检出限及线性范围、离子干扰与消除以及实际应用。引用文献24篇。     

Photocatalytic reduction of hexavalent chromium with commercial Fe/Ti oxide catalyst under UV and visible light irradiation

The photoreduction efficiency of toxic hexavalent chromium into non-toxic trivalent chromium was studied using local low-cost material and modern technology. The materials involved different iron–titanium oxide nanopowders synthesized via simple hydrothermal–hydrolysis process. X-ray diffraction and high-resolution transmission electron microscope were employed to study the structural properties of the as-prepared samples. The effects of molar ratio (Fe/Ti) and hydrothermal temperature on spectroscopic properties have been investigated using Fourier transform infrared FT-IR spectroscopy. The photocatalytic performance of hexavalent chromium was systematically studied at various conditions including initial concentration of Cr(VI), hydrothermal temperature and Fe/Ti ratios of mixed iron–titanium oxide powders. It has been found that the highest photoreduction efficiencies of Cr(VI) were 95.7 and 86.2% at initial concentrations 10 and 60 ppm of Cr(VI), respectively. The synthesized mixed Fe₂O₃–TiO₂ photocatalyst exhibited higher efficiency of about 88% under visible light irradiation. The as-prepared mixed oxide catalyst exhibited high photocatalytic conversion efficiency and recycling stability in comparison with different commercial catalysts.     

突出煤层CO2气相压裂高效抽采防突掘进技术

我国煤矿煤与瓦斯突出灾害严重影响煤矿安全生产。尽管近10年来这一灾害事故大幅度减少,但恶性事故依然发生,给矿工生命和煤矿安全生产造成严重损失。国内外现阶段的防治瓦斯突出技术,如水力压裂、水力割缝、水力冲孔、深孔爆破、密集钻孔等,不同程度地解决了防突安全掘进,但对于一些高瓦斯低渗透突出煤层,上述技术还难以从根本上解决消突安全快速掘进。所以,防突技术仍然是我国煤炭领域亟待攻关的重大科技难题。选取山西寿阳县新元煤矿31002工作面为试验案例,介绍CO₂气相压裂技术方法,并探讨其防突掘进效果。新元煤矿开采的山西组3号煤层为低渗透突出煤层,前期主要采用密集钻孔预抽瓦斯防突措施,抽采达标时间长,掘进速度慢。高效抽采瓦斯,防止煤与瓦斯突出,保障煤巷安全快速掘进,是新元煤矿安全高效生产的重大技术难题。在新元矿采取的气相压裂措施概况如下:在掘进工作面前方实施双钻孔气相压裂;完成9个瓦斯抽采钻孔以覆盖巷道两侧各15 m安全范围;全部11个钻孔联网抽采3~5 d,防突参数K₁值达标后恢复掘进。试验数据表明,气相压裂抽采防突技术措施的强化抽采效果显著,抽采效率大幅度提高,煤炮等动力现象减少,K₁值降低,掘进割煤时巷道瓦斯浓度得以降低和均化,保障了连续安全掘进。实践证明,CO₂气相压裂技术能够实现连续安全快速掘进理技术,在全国类似瓦斯地质条件煤矿中具有推广应用意义。      

Biogenic silver nanoparticles on carbonaceous material from sewage sludge for degradation of methylene blue in aqueous solution

Silver nanoparticles (Ag NPs) were synthesized in situ, using a one-step green methodology with Camellia sinensis (green tea) aqueous extract as reducing agent, and supported on a carbonaceous material (Ag-CM), originated from the pyrolysis of sewage sludge. UV–Vis spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Brunauer–Emmet–Teller were used to characterize the nanocomposite. Ag-CM composite exhibited very good catalytic activity in the degradation process of methylene blue (MB) dye in aqueous solution without using sunlight or UV radiation. Batch kinetic and isothermal experiments, using 30 mg/L MB solution, showed that Ag-CM composite removed near to 91 % of MB in 9 h, whereas the carbonaceous material alone removed only 60 % in 30 h. Experimental data were adjusted to different kinetic and isotherms models, where both materials fit the second-order and Langmuir–Freundlich models, respectively; therefore, a chemisorption mechanism probably occurs in these heterogeneous materials.     

Biomimetic Mineralizated and Nano-Ag Loadedgraphene Oxide/Chitosan Hybrid Scaffold for Osteoinduction and Antibacterium

Graphene oxide (GO) is a graphene derivatives that has oxygen-containing functional groups on the graphene basal plane, such as hydroxyl, carbonyl, epoxy and carboxyl groups. GO is considered as a promising material for biological applications owing to its excellent surface functionalizability, high specific suface area and good biocompatibility. In this study, GO/chitosan hybrid scaffolds were prepared for tissue engineering. Nano silver was loaded into the scaffold to improve its antibacterial ability and biomimetic Ca-P coatings were deposited on the scaffold surface to enhance its osteoconductivity. First, GO was prepared by the chemical oxidization of graphite. Secondly, nano-Ag loaded GO was prepared by chemical reducing Ag ions in GO solutions. Then, nano-Ag loaded GO solution was mixed with CS solution to form GO-CS gel. Chitosan (CS) and GO were crosslinked by electrostatic interactions between oxygen-containing functional groups of GO and NH2 groups of CS. The gel were freeze dried to produce nano-Ag loaded GO/CS hybrid porous scaffolds. Finally, the as-prepared scaffolds were immersed the into a supersaturated calcium phosphate solution (SCPS) for 7 days to deposite CaP coatings on the surface of the micropores. SEM images showed that nano-Ag uniformly distributed in the scaffold and the CaP covered most of the scaffold surfaces. In vitro cell culture and antimicrobial test indicated the biomimetic mineralized Ag-CS-GO scaffolds have good osteoconductivity and bactericidal ability.     

基于不同排放情景的洞庭湖流域水资源演化研究

流域水资源演化与气候变化和人类活动紧密相关,气候变化与人类活动的加剧极大地改变了流域水文循环。通过相似性和独立性分析,从CMIP5公开发布的47个气候模式中筛选出5个代表性气候模式,然后计算未来高、中、低3种不同排放情景下的气温和降水,构造符合研究区产汇流特性的水文模型,计算洞庭湖流域水资源量并分析其演化规律。结果表明:不论温室气体排放水平如何,洞庭湖流域水资源量在未来60a呈现增加态势,汛期水量增加概率加大,而在高排放情景下枯季水资源量表现为减少趋势;未来洞庭湖流域水资源的时程分配将更趋不均匀化,而温室气体的持续排放将使其变化加剧。     

Low-temperature gas from marine shales: wet gas to dry gas over experimental time

Marine shales exhibit unusual behavior at low temperatures under anoxic gas flow. They generate catalytic gas 300° below thermal cracking temperatures, discontinuously in aperiodic episodes, and lose these properties on exposure to trace amounts of oxygen. Here we report a surprising reversal in hydrocarbon generation. Heavy hydrocarbons are formed before light hydrocarbons resulting in wet gas at the onset of generation grading to dryer gas over time. The effect is moderate under gas flow and substantial in closed reactions. In sequential closed reactions at 100°C, gas from a Cretaceous Mowry shale progresses from predominately heavy hydrocarbons (66% C₅, 2% C₁) to predominantly light hydrocarbons (56% C₁, 8% C₅), the opposite of that expected from desorption of preexisting hydrocarbons. Differences in catalyst substrate composition explain these dynamics. Gas flow should carry heavier hydrocarbons to catalytic sites, in contrast to static conditions where catalytic sites are limited to in-place hydrocarbons. In-place hydrocarbons and their products should become lighter with conversion thus generating lighter hydrocarbon over time, consistent with our experimental results.