海洋非成岩天然气水合物原位快速制备实验及评价

我国的海洋天然气水合物（以下简称水合物）资源主要分布在沿海大陆架水深介于300～3 000 m的深水区，具有弱胶结、非成岩的特征，为了测试和研究该类型水合物必须原位、大量、快速制备样品，而目前常用的搅拌法、喷淋法、鼓泡法等制备技术却存在着生成速度慢、储气密度低等问题。为此，自主设计、研制了1 062 L非成岩水合物快速制备釜，针对我国南海非成岩水合物的物性特征，开展了搅拌法、鼓泡法、喷淋法单一制备方法及“三合一”法（上述3种方法相结合）水合物制备实验，测试了实验过程中温度、压力、电阻率及反应时间等数据，分析比较了几种不同制备方法的水合物生成情况与制备效率。实验结果表明：①搅拌法、鼓泡法、喷淋法制备水合物过程中，生成的水合物均缓慢增加并逐渐铺满整个液面；②搅拌法制备过程中可以观测到明显的诱导期，而喷淋法、鼓泡法及“三合一”法却无明显的诱导期；③单一制备方法及“三合一”法制备水合物过程中，电阻率均随反应时间的增加而增加，其变化趋势亦与水合物制备速率基本一致；④“三合一”法的制备周期明显短于单一制备方法（搅拌法、喷淋法、鼓泡法单一方法的制备时间分别约为“三合一”法的5.14倍、3.59倍、3.16倍）。结论认为，所研制的1 062 L水合物快速制备釜能够实现海洋非成岩水合物样品的原位、快速制备；较之于单一制备方法，“三合一”法大大提高了水合物的制备效率。     

利用地震品质因子Q比例的分布特征预测南川页岩气藏保存条件

根据地震数据、地质资料和地震属性，开展了南川地区五峰组-龙马溪组下部页岩的地震品质因子Q平面上分布与页岩气保存条件评价研究。针对南川地区页岩气开发中的断裂破碎带，提出了一种获取稳定品质因子Q比例及界限的工作流程和相应的迭代算法。研究表明，地震品质因子Q比例的分布可以快速、直观识别出断裂破碎带的内幕特征与不同类型页岩分布区。其中，断裂破碎带页岩区的品质因子Q比例总体上偏小，大多低于0.2，局部超过0.5，平面上分布杂乱、碎斑状；页岩呈北东向展布的条带，被断裂所撕裂、破碎，保存条件较差。稳定分布的页岩区的品质因子Q比例是较高的，超过0.7，平面变化稳定，没有突变现象，保存条件好。微裂缝发育的页岩区的品质因子Q比例具有渐变的趋势性，品质因子Q比例的分布从该页岩区的边部0.7向中部有规律地减小至0.1，保存条件最佳。实践证明，高产气井大多位于稳定分布的页岩区或内部微裂隙发育的稳定页岩区，地震品质因子Q比例研究方法对页岩气保存评价与开发井优化部署是一个实用工具。     

瓦斯抽采集成旁通阀二位放水器研制

针对井下瓦斯抽采中原放水器配气阀安装不规范、双截止阀使用繁琐、工人劳动强度大等现状,研制了具有集成调控装置的放水器,能够实现一个阀门控制所有气路和水路,自主放水和负压排水,从源头上杜绝了瓦斯喷孔和水流溢出等情况,大大降低了职工的劳动强度,实现了井下抽采系统安全可靠运行。     

无烟煤制工业燃气项目原料煤价与经济性的关系分析

针对我国建材行业传统使用的常压固定床煤气发生炉及化肥行业固定床间歇气化炉面临淘汰,无烟煤市场萎缩的情况,提出以晋城无烟煤为原料,利用赛鼎碎煤加压气化技术,生产适合建材行业大规模使用的工业燃气。以无烟煤为原料的河北沙河年产26亿m^3工业清洁燃气项目为基础,对无烟煤与天然气价格、项目经济性的关系进行了分析,结果表明,以晋城无烟块煤运到河北沙河的到厂价935元/t计算,盈亏平衡天然气价约2.26元/m^3;以沙河工业天然气到户售价2.5元/m^3计算,盈亏平衡到厂煤价约1 077元/t,项目经济性较好。     

超临界二氧化碳干气密封相态分布规律与密封性能研究

以超临界二氧化碳干气密封为研究对象，分别以维里方程、Lucas方程描述二氧化碳真实气体效应、黏度的变化，在考虑阻塞流效应的同时，采用有限差分法对考虑离心惯性力效应的Reynolds方程与能量控制方程进行耦合求解，分析讨论了工况参数与槽形结构参数对其相态分布规律与密封性能的影响。研究表明：S-CO₂从密封端面进口至出口的流动过程中，如果工况参数设置合理，将由超临界态逐渐转变为气态，并不会出现液态；较低的进口压力、进口温度以及转速，均会容易导致潜在的凝结流动发生；相比于工况参数对相态分布的影响，槽形参数对相态分布的影响较小，近乎可以忽略；开启力除了随进口温度的升高而减小外，均随进口压力、转速、槽深、螺旋角的增大而增大；泄漏率随进口温度和转速的增大而减小，但其随进口压力、槽深、螺旋角的增大而增大。这些结果为进一步研究超临界二氧化碳干气密封提供了一定的支撑。     

Cu/Fe3O4 catalyst for water gas shift reaction: Insight into the effect of Fe2+ and Fe3+ distribution in Fe3O4

Two precursors, namely, p-CFO-T (tetragonal) and p-CFO-C (cubic), were fabricated by a sol-gel method via citric acid and poly(vinyl alcohol) complexation, respectively. After H₂-reduction, the two were converted to Cu/Fe₃O₄ catalysts of different complexions, which are named as CFO-CA and CFO-PVA, respectively. The distribution of Fe²⁺ and Fe³⁺ in the Cu/Fe₃O₄ catalysts was studied by Raman and XPS techniques. It was disclosed that the distribution of Fe²⁺ and Fe³⁺ in Fe₃O₄ has an effect on Cu–Fe₃O₄ interaction and catalyst surface basicity. Compared to CFO-PVA, CFO-CA has a larger amount of Fe³⁺, which mostly sits at the octahedral sites, leading to stronger Cu–Fe₃O₄ interaction, and a larger amount of catalyst surface sites that are of weak basicity. As a result, the critical elementary steps of WGS reaction, viz. water dissociation, –COOH decomposition and CO₂ desorption are promoted as reflected in the lower E_a and higher catalytic activity of CFO-CA.     

Development of mobile miniature natural gas liquefiers

With increasing consumption of natural gas (NG), small NG reservoirs, such as coalbed methane and oil field associated gas, have recently drawn significant attention. Owing to their special characteristics (e.g., scattered distribution and small output), small-scale NG liquefiers are highly required. Similarly, the mixed refrigerant cycle (MRC) is suitable for small-scale liquefaction systems due to its moderate complexity and power consumption. In consideration of the above, this paper reviews the development of mobile miniature NG liquefiers in Technical Institute of Physics and Chemistry (TIPC), China. To effectively liquefy the scattered NG and overcome the drawbacks of existing technologies, three main improvements, i.e., low-pressure MRC process driven by oil-lubricated screw compressor, compact cold box with the new designed heat exchangers, and standardized equipment manufacturing and integrated process technology have been made. The development pattern of “rapid cluster application and flexible liquefaction center” has been eventually proposed. The small-scale NG liquefier developed by TIPC has reached a minimum liquefaction power consumption of about 0.35 kW·h/Nm³. It is suitable to exploit small remote gas reserves which can also be used in boil-off gas reliquefaction and distributed peak-shaving of pipe networks.     

Effects of phenylenediamines and alkoxysilanes on gas transport properties of polyimide - silica hybrid membranes

Gas transport properties of polyimides (PIs) and their silica hybrids were investigated. The PIs synthesized with several methyl-substituted phenylenediamines were hybridized with silica via a sol–gel process with different alkoxysilanes. The prepared hybrid membranes showed controlled gas permselectivity, depending on the selected phenylenediamines and alkoxysilanes. It was worth noting that the hybrids prepared with tetraethoxysilane possessed improved CO₂ permselectivity with increasing silica content, which tended to exceed the upper-bound trade-off line. This fact suggested the additional formation of free volume holes especially favorable for the CO₂/CH₄ separation around the polymer/silica interfacial area.     

Zeolite imidazolate framework (ZIF)-based mixed matrix membranes for CO2 separation: A review

Mixed matrix membranes (MMMs), which combine the good separation performance of inorganic materials with the low cost of polymers, have emerged as a research hotspot for gas separation membranes. Zeolite imidazolate frameworks (ZIFs) are widely used as fillers to prepare MMMs owing to their advantageous characteristics, such as adjustable pore channels, unsaturated sites, and easy functionalization. For MMMs, three directions can be employed as criteria for improvement compared with pristine polymeric membranes. In this article, the progress of ZIF-based MMMs is reviewed from the aspects of sole-ZIF-based MMMs and modified ZIF-based MMMs. Both strategies improve the separation performance through different improvement directions and mechanisms. Our analysis shows that the synergistic effect of the modified filler can change the structure of the membranes, such as by improving the filler–polymer interface voids, which provides a foundation to overcome the trade-off effect to a certain extent. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48968.     

Ni、Zn改性Cu/水泥催化剂及其甲醇高温裂解性能

以碱式碳酸镍、碱式碳酸锌、碱式碳酸铜和水泥为原料制备水泥负载的Cu-Ni，Cu-Zn，Cu-Ni-Zn催化剂，考察了合成催化剂的甲醇裂解反应性能。结果表明：在常压、质量空速为3.39 h-1、温度为380~420 ℃的条件下，Cu-Ni/水泥催化剂作用下的甲醇转化率均在96%以上；Cu-Zn/水泥催化剂作用下的甲醇转化率较低，但对H2和CO选择性较高；Cu-Ni-Zn/水泥催化剂经1 600 h运转，甲醇转化率和产物分布变化不大，甲醇转化率基本维持在81%以上，(H2+CO)摩尔分数大于98%，说明Cu-Ni-Zn/水泥催化剂具有良好的高温稳定性。