空心钛硅分子筛在二甲基硫醚液相氧化反应中的催化性能

在以过氧化氢为氧化剂的二甲基硫醚液相氧化反应体系中,对空心钛硅分子筛（HTS）的催化性能进行了系统研究,详细考察了催化剂存在与否以及催化剂用量、反应时间、反应物料配比及溶剂用量等不同反应条件变化对二甲基硫醚温和液相氧化反应的影响。研究发现,在温和反应条件下,HTS催化二甲基硫醚氧化反应中主要产物是二甲基亚砜和二甲基砜。经优化后,能够获得较好的氧化二甲基硫醚制备二甲基亚砜的反应效果,在二甲基硫醚转化率超过99%的情况下,二甲基亚砜选择性可达95%以上。     

Investigation of directly suspended droplet micro extraction method for extraction of trihalomethane and halomethane in water samples

Simple and efficient directly suspended droplet micro extraction (DSDME) in conjunction with gas chromatography-electron capture detector (GC-ECD) has been developed for extraction and determination of Halomethane and Trihalomethane from water samples. In this technique a micro drop of n-hexane is delivered to the surface of an aqueous sample while being agitated by a stirring bar in the bulk of solution. Factors relevant to the extraction efficiency were studied and optimized. The optimized extraction conditions were extraction solvent: n- hexane; NaCl concentration: 1 M; solvent extraction volume: 50 μL; stirring rate: 720 rpm and the extraction time: 5 min. The detection limits of the method were in the range of 0.059–0.137 µg L^?1, relative standard deviation (n = 3) range were 0.019–0.048%. A good linearity (r² ≥ 0.997) and a relatively broad dynamic linear range (10–200 µg L^?1) were obtained and recoveries of method were in the range of 97.69–99.51%. Finally, the proposed method was successfully utilized for pre concentration and determination of halo methane in different real samples. Successfully DSDME technique combined with capillary GC-ECD for the analysis of THMs and HMs in the water investigated samples.     

Experimental investigation of propagation mechanisms and fracture morphology for coalbed methane reservoirs

Fracture propagation mechanisms in coalbed methane (CBM) reservoirs are very complex due to the development of the internal cleat system. In this paper, the characteristics of initiation and propagation of hydraulic fractures in coal specimens at different angles between the face cleat and the maximum horizontal principal stress were investigated with hydraulic fracturing tests. The results indicate that the interactions between the hydraulic fractures and the cleat system have a major effect on fracture networks. “Step-like” fractures were formed in most experiments due to the existence of discontinuous butt cleats. The hydraulic fractures were more likely to divert or propagate along the butt cleat with an increase in the angles and a decrease in the horizontal principal stress difference. An increase in the injection rate and a decrease in the fracturing fluid viscosity were more conducive to fracture networks. In addition, the influence on fracture propagation of the residual coal fines in the wellbore was also studied. The existence of coal fines was an obstacle in fracturing, and no effective connection can be formed between fractures. The experimental investigation revealed the fracture propagation mechanisms and can provide guidance for hydraulic fracturing design of CBM reservoirs.     

Variation of Coenzyme F420 Activity and Methane Yield in Landfill Simulation of Organic Waste

A simulated landfill anaerobic bioreactor was used to characterize the anaerobic biodegradation and biogas generation of organic waste which was mainly composed of residuals of vegetables and foods. We investigated the dynamics of the coenzyme F420 activity and determined correlations between biogas yields, methane yields, methane concentration and coenzyme F420 activity. The experiment was carded out under different conditions from control without any treatment, addition of Fe^3＋, microorganism inoculation to a combination of Fe3＋ addition and inoculation at a temperature of 36±2℃. The experiment was lasted 120 d and coenzyme F420 activity was analyzed using ultraviolet spectrophotornetry. Experimental results indicated that activity of the coenzyme F420 treated by Fe and microorganism inoculation increased substantially. The waste treated by inoculation had the greatest increase. When the waste was treated by Fe^3＋, inoculation and the combination of Fe^3＋ and inoculation, biogas yields increased by 46.9%, 132.6% and 153.1%, respectively; while the methane yields increased 4, 97 and 98 times. Methane concentration varied between 0 and 6% in the control reactor, from 0 to 14% for waste treated by the addition of Fe^3＋, from 0 to 59% for waste treated by inoculation and from 0 to 63% for waste treated by Fe^3＋ addition and inoculation. Correlations between coenzyme F420 activity and biogas production, methane production and methane concentration proved to be positively significant （p〈0.05）, except for the control. Consequently, coenzyme F420 activity could be used as an index for monitoring the activity of methanogens during anaerobic biodegradation of the organic fraction of municipal solid waste.     

Pd/Co_3O_4催化剂上低浓度甲烷催化燃烧

采用沉淀法制备了Co3O4载体、浸渍法制备了Pd/Co3O4催化剂,对Pd/Co3O4催化剂上的低浓度甲烷燃烧反应进行了研究,考察了焙烧温度、Pd负载量及预处理条件等对其催化性能的影响。结果表明,随着焙烧温度的升高(从550℃到700℃),Co3O4结晶度提高,PdO颗粒增大,催化剂的比表面积和甲烷催化燃烧活性降低。随着钯负载量的增加,Pd/Co3O4催化剂的活性有所提高,但Pd含量高的催化剂,甲烷催化燃烧稳定性较差。550℃下焙烧Pd质量分数为1.0%的Pd/Co3O4催化剂对低浓度甲烷燃烧具有较好的低温催化活性和稳定性,甲烷转化率达到50%时的反应温度为416℃,500℃下运行96 h后,甲烷转化率仍然维持在90%以上。     

DIPA改性SBA-15介孔分子筛用于CO_2/CH_4分离的性能研究

CH4和CO2的大量排放是造成温室效应的主要因素,在全世界范围内对排放的CH4和CO2进行回收和利用是非常必要的。变压吸附是有效的气体分离技术,而高选择性吸附剂是变压吸附技术的关键。将DIPA(二异丙醇胺)负载在介孔分子筛上,使介孔分子筛的介孔和胺作用结合起来,合成了高选择性CO2/CH4分离吸附剂。首先以水热法合成SBA-15介孔分子筛,通过表征分析,其具有高度有序的六方结构,而DIPA改性后的SBA-15仍然保持介孔分子筛的有序结构,且DIPA基本都进入孔道内。SBA-15经DIPA改性后,CO2/CH4选择分离性能大大提高,分离因子达46.75,吸附的CH4可完全再生,吸附的CO2只能部分再生。负载DIPA对CH4的吸附容量没有明显影响,但大大提高CO2的吸附容量。在6次稳定性实验后,对CH4、CO2的吸附量保持稳定,CH4/CO2的分离因子在15.5左右。随操作温度的升高,DIPA改性SBA-15对CO2吸附容量增大,通过单塔吸附再生的性能比较,45℃时CO2吸附再生的综合性能最好。     

NiO-ZrO_2-Al_2O_3催化剂的制备方法对其催化性能的影响

以共沉淀法、柠檬酸络合法、水热合成法及浸渍-沉淀法分别制备NiO-ZrO_2-Al_2O_3催化剂,并以XRD,BET,TPR,TPD等对催化剂的晶相结构、表面积、表面性能等进行了表征。实验结果表明,以水热法制备的催化剂其比表面积较大,NiO的分散度大于其他方法所制备的催化剂。各种催化剂在CO_2重整CH_4反应中均有较好的催化活性,以浸渍沉-淀法所制备的催化剂稳定性较好,于800℃反应150 h后,CH_4和CO_2的转化率保持在88%和90%。     

煤层气井井底流压分析及计算

煤层气井井底流压的大小直接决定煤层气产量的大小,为了获得高产,必须清楚认识井底流压并精确计算其数值。根据垂直气液两相环空管流理论,首先描述了煤层气的环空流动特征及井底流压的组成部分;结合现场生产测试资料,采用Hasan-Kabir解析法和陈家琅实验回归两种方法计算了井底流压值,并分析了其与气体流量的关系。结论认为：①油套环空中流体由上而下分为纯气体段、混气液柱段（高含气泡沫段和普通液柱段）,井底流压为套压、纯气柱压力及混气液柱压力三者之和;②两种方法计算的井底流压值大体相同,与实测值误差小,精度高;③井底流压与气体流量呈负相关关系,而且随着井底流压下降,压降漏斗不断扩大,井底流压下降相同的数值能产出更多的煤层气。     

考虑煤自调节效应的煤层气藏物质平衡方程

在研究煤层气藏的物质平衡时,必须考虑裂缝孔隙度的动态变化问题。在考虑自调节效应(即气体吸附到基质表面时,基质膨胀;气体从基质表面解吸时,基质收缩)对孔隙度变化影响的前提下,推导了煤层气藏的物质平衡方程,并通过实例分析发现,若忽略或忽视自调节效应,则运用物质平衡法预测的煤层气地质储量将比真实值偏小。     

煤层气化工利用技术进展

介绍了国内外煤层气资源的利用现状,重点对煤层气化工利用的几种主要技术途径进行了分析和展望,认为我国煤层气在满足国内燃料市场需求的同时,其化工利用也具有广阔前景;今后应重点发展煤层气制合成气、甲醇下游产品(低碳烯烃、二甲醚等)、煤层气制氢等新型技术,实现煤层气资源合理有效利用。