宽筛分脱油油砂颗粒流化床中固含量轴向分布

引言 随着全球石油资源的日益短缺和石油需求的不断增加,开发非常规石油资源作为石油替代能源已引起广泛关注.油砂是非常规石油资源的主要来源之一,是一种含有沥青或焦油的砂或砂岩,其主要成分为沥青、砂、水、黏土及矿物质[1-2].目前,油砂制油工艺主要有热水碱洗[3-4]、溶剂萃取[5-6]和热解焦化[7-9]三种.     

油砂资源储量与开发分析

油砂作为一种重要的能源资源正在得到人们越来越多的关注,随着其市场开发和能源地位不断被挖掘,本文简要概述世界油砂资源、加拿大油砂资源及我国油砂资源情况。     

油砂资源现状及其开采分离方法浅谈

世界油砂矿藏主要沿环太平洋带和阿尔卑斯带展布,目前大约95%所探明的油砂矿藏分布于加拿大、委内瑞拉及美国。油砂的可采资源量约为6510亿桶,占世界石油可采总量的近三分之一。露天开采的油砂要经过油砂分离,沥青改质和废物处理三个环节。其中油砂分离包括热碱水法、溶剂萃取法以及干馏法等。     

加拿大油砂业 现实很骨感

随着世界常规石油储量的发现越来越难，全球对非常规油气资源寄予厚望。特别是美国页岩气产量快速增长之后，人们对加拿大油砂开发越来越有信心。然而，前不久笔者访问了加拿大油砂现场，对其近距离观察后却发现，由于油价下滑，不少已投入巨资的大项目不堪压力先后停工。加拿大油砂开发梦想虽丰满，现实却很骨感。     

全球非常规油气资源勘探开发前景

面对巨大的能源需求,非常规油气资源的战略地位日趋重要。本文概述了世界油砂、油页岩气、煤层气等非常规油气资源的储量与分布,探讨了非常规油气资源勘探开发所面临的机遇和挑战,指出了各大油公司在非常规油气资源勘探开发方面的应对策略。     

油砂及其分离方法的研究进展

油砂是一种重要的非常规油气资源,其分离技术的研究近些年来引起了国内外科研工作人员的重视。介绍了目前世界上主要采取的油砂分离技术,并对各分离技术的原理及影响因素进行了深入讨论,最后针对具体的油砂矿提出了行之有效的分离方法。     

水基提取技术用于油砂分离的研究进展

油砂作为一种重要的非常规油气资源,其分离技术的研究近些年来引起了国内科研工作人员的重视。介绍了目前世界上最重要的油砂分离技术--水基提取技术的基本原理及影响油砂分离的重要影响因素,阐述了油砂结构、特性与水基提取分离的重要关系及分离条件对沥青回收率的重要影响作用,同时探讨了原子力显微镜用于油砂水基分离过程中相关微观机理研究的重要应用,最后对水基提取技术用于油砂工业生产的流程进行了简单介绍。     

世界油砂勘探开发和综合利用

文章重点阐述了油砂作为一种非常规能源,全球资源量丰富,发展前景巨大。目前油砂开采技术上已取得突破,开采成本大幅度降低,通过对油砂的发展现状和全球几个主要油砂储最丰富的国家进行油砂地质分布等阐述,阐明其备自资源量和相关开采等政策,同时分析了油砂发展过程的不足和风险,说明油砂的未来发展趋势。     

非常规油气资源勘探开发的几点思考

概述了世界油砂、油页岩气、煤层气等非常规油气资源的储量与分布,探讨了非常规油气资源勘探开发所面临的机遇和挑战,分析了地球物理技术在非常规油气资源勘探中所起的作用,指出了各大油公司与服务商在非常规油气资源勘探开发方面所发挥的作用和应对策略,最后提出了中国物探公司应对非常规油气资源勘探开发业务发展的建议.     

世界油气资源未来供应潜力分析

分析了世界石油和天然气最终可采资源量、剩余可采储量、剩余储采比、待发现储量及储量增长潜力等反映油气资源供应能力的指标,预测了未来世界石油的生产能力及油气供需平衡能力,指出未来 20年内世界油气供应潜力丰富,但地区分布不均衡性将进一步增大。     

利用GC-MS与NMR技术研究干馏终温对桦甸页岩油组成性质的影响

通过控制桦甸油页岩干馏终温,得到5个不同终温下页岩油样品,对各页岩油样按沸点300℃进行切割,其中轻质油馏分(<300℃)进行GC-MS检测,对产物分类统计,分析页岩油组成成分随干馏终温变化规律;重质油馏分(>300℃)进行了¹H和¹³C核磁共振波谱分析,对谱图积分获得其氢、碳分布情况,研究了干馏终温对页岩油化学结构的影响。结果显示,轻质油组成中脂肪族化合物占绝大部分,其中正构烷烃、α-烯烃和正构醛、醇三者具有同源性,均由烷基自由基生成。随着干馏终温的升高,长链烷烃分解,支链烷烃侧链断裂,使轻质油脂肪烃碳链长度变短,重质油直链脂肪烃增多,页岩油发生更多的芳环缩合反应导致轻质油与重质油芳香环数量均增多,同时轻质油中芳环缩合程度加深。     

Evaluation of a delayed coking process by H and C n.m.r. spectroscopy: 1. Material balances

The use of ¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectroscopy to evaluate the performance of a delayed coking process is presented in a series of papers, of which this is the first. A meaningful analysis requires an accurate balance, which in turn requires analysis of the various types of atoms in the feed and in all products, including solid coke, as well as the amounts of each. Product yields were determined in a delayed coking pilot plant. Complete n.m.r. (¹H and ¹³C) characterization of feed and all delayed coking products, using a consistent classification, was combined with pilot plant data to obtain the total distribution of carbon and proton atoms in the delayed coking process. Changes in carbon and hydrogen distributions (products versus feedstock) reveal the nature of the thermal cracking reactions involved; the main change is a substantial increase in the number of aromatic and paraffinic carbons at the expense of naphthenic carbons.     

霍林河褐煤化学结构特性的13C NMR与FTIR对比分析

采用¹³C NMR及FTIR对霍林河褐煤的化学结构特性进行深入分析,通过¹³C NMR计算得到霍林河褐煤包含34.32%的脂肪族碳、61.25%的芳香族碳以及4.43%的羰基碳。平均每个芳环团簇包含1~2个芳香环,每个芳香环中平均碳原子取代数为3~4。平均亚甲基碳链数为1.4,烷链支化度为25.47%,说明脂肪族多以短链分支形式存在。通过对霍林河褐煤红外光谱进行分峰拟合,计算得到煤的FTIR结构参数（平均亚甲基碳链数、芳香环取代度、烷链支化度）与¹³C NMR计算结果相吻合。虽然芳碳率（f_ar-F=55.37%）与¹³C NMR计算结果存在一定的偏差,但是FTIR很大程度上仍然可以反映煤的碳骨架结构特性。     

固体核磁共振在膦酸基质子交换膜中的应用

综述了固体核磁共振(NMR)技术的特点及其在燃料电池用膦酸基质子交换膜分析研究中的应用,重点介绍了运用¹H、³¹P、²⁹Si固体NMR以及¹H、³¹P变温固体NMR技术表征膦酸基质子交换膜的化学结构、氢键网络和质子传导机理等方面的研究进展。该综述表明固体NMR技术是一种研究膦酸基质子交换膜中氢键网络以及局部质子移动性的有效手段,并能进一步探索其质子传导的机理,为固体NMR技术在其他类型质子交换膜研究中的应用给予借鉴,为质子交换膜结构的表征提供一种新的方法。     

Conversion of propylene into cyclohexane on PtGaZr/SiO2 catalyst

The light olefins present in Delay Coker and fluid catalytic cracker dry gas can be valorized into naphthenes using a new PtGaZr/SiO₂ catalyst. This catalyst was compared to a GaZrSiO₂ catalyst prepared with the same methodology. Both were characterized by XRD, and FTIR, XPS, ⁷¹Ga, ²⁹Si and ¹H NMR spectroscopies. Propylene is treated in the presence of CS₂, hydrogen, and benzene in a semi-batch type reactor and the product composition is analyzed by GC and MS techniques. The different operating variables were explored to study the effect of Pt on activity, selectivity and catalyst stability. The spent catalysts after 10 cycles in operation were analyzed using ¹³C NMR, ¹H NMR, IR, and XPS spectroscopies. The paper discusses the catalytic surface composition, the effect of temperature, contact time, hydrogen partial pressure and benzene in the feed. The study demonstrated that the effect of Pt, hydrogen and benzene is crucial to orient the reaction toward naphthenes production.     

桥联茂金属催化1-癸烯聚合及其产物结构与性能

采用桥联茂金属催化体系rac-Et(1-Ind)₂ZrCl₂/Al(ⁱBu)₃/[Me₂NHPh]⁺[B(C₆F₅)₄]^-催化1-癸烯聚合,考察了茂金属浓度、Al/Zr摩尔比、B/Zr摩尔比、温度、反应时间对反应转化率、黏度和摩尔质量的影响.当反应条件为1-癸烯20mL、甲苯20mL、Zr/烯摩尔比8×10^-5、Al/Zr摩尔比80、B/Zr摩尔比1.5、温度80℃、反应时间1h时,转化率达到96.2%.采用¹³C NMR和¹H NMR表征了产物的结构,优化条件下所得的聚合产物具有高黏度指数(259)和低分子量分布(2.088),可作为理想的润滑油基础油的原料.     

Hydrocarbon structural group analysis of Athabasca asphaltene and its g.p.c. fractions by C n.m.r.

Asphaltene from the Athabasca oil sand bitumen separated according to molecular weight by gel permeation chromatography was examined by high resolution solution-state ¹³C and ¹H and solid state ¹³C n.m.r. Integration of the inverse gated decoupled solution state and CP/MAS ¹³C n.m.r. spectra gave the aromaticity of each fraction as well as the relative number of carbon atoms responsible for well resolved signals in the aliphatic portion of the spectra. A two-pulse spin-echo ¹³C n.m.r. sequence in the solution state, and dipolar dephasing in the solid state, permitted the assignment of each aliphatic carbon signal to a methyl, methylene, or methine carbon; no quaternary aliphatic carbons were observed. These signals show that the aromatic core of the asphaltene is surrounded by alkyl chains with a mean length of 7.7 for the lowest molecular weight fraction (MW 1200), increasing to 12 for the highest MW fraction (MW 16900). Aromaticity of the fractions obtained from solution spectra ranged from 34 to 48%, the highest aromaticity being associated with the lowest molecular weight asphaltenes. In the solid state, the aromaticity ranged from 31 to 42 %. The degree of branching ranged from 0.5 per chain for the low MW asphaltene to 1.0 for the high MW fraction. The highest naphthenic carbon content was found in the high MW fractions; the 1200 MW fraction appeared to be nearly devoid of such carbon, this fraction having a much higher aromaticity than the second-lowest MW fraction.     

Chemical nature of a supercritical-gas extract of coal at 350 °C

A novel supercritical-gas (toluene) extract, comprising 17.0% of a low-rank coal, was separated by a combination of solvent fractionation and both silica-gel and gel-permeation chromatography. The average structure of the soluble fractions, together amounting to 85% of the extract, was investigated by a variety of spectroscopic methods, including high-resolution ¹H nuclear magnetic resonance, proton-decoupled pulse Fourier transform ¹³C magnetic resonance, infrared and low-ionizing-voltage mass spectrometry. Analyses were also made by gas chromatography. The results for the low-oxygen fractions are consistent with a generally open-chain polynuclear aromatic average structure with about 33% of the available sites carrying alkyl substituents. The most common of these is methyl, but there are also substantial numbers of longer-chain alkyls, some branched, and naphthenic groups. The fractions rich in oxygen also have similar structure but for the presence of phenolic hydroxyl groups, and, as is demonstrated for the first time by ¹³C n.m.r., ether oxygen links. Aliphatic constituents are mainly straight-chain alkanes with some branched-chain and isoprenoid hydrocarbons. These conclusions are discussed in terms of the thermal history of the extract and are compared with other contemporary views on the low-molecular-weight constituents of coal.     

Determination of the apparent ratio of quaternary to tertiary aromatic carbon atoms in an anthracite coal by C-H dipolar dephasing n.m.r.

¹³C-¹H heteronuclear dipolar dephasing n.m.r. techniques allow discrimination between different chemical species contributing to the ¹³C n.m.r. spectra of complex hydrocarbons. Model compound studies show significantly different effective transverse relaxation constants for carboxyl and quaternary carbon atoms (≈200 μs), secondary and tertiary (≈20 μs), and primary carbon atoms (≈80 μs). Use of these effective relaxation data, together with appropriately timed windows in the continuous wave decoupling applied in standard cross-polarization-magic-angle spinning experiments on anthracite coal allow discrimination between aromatic tertiary and aromatic quaternary ring carbon atoms in this coal. Within the accuracy of experimental error, and of the structural modelling experiments herein reported, the use of the dipolar dephasing technique together with results of X-ray diffraction on coals allows a reasonable estimate to be made of the average number of condensed polynuclear rings in an ‘average molecule’ in the anthracite studied. Based on a model of pericondensed aromatic rings, this number lies between 33 and 45.     

Mechanism of high-pressure hydrogenolysis of Hokkaido coals (Japan) 3. Chemical structure changes in coal asphaltenes during hydrogenolysis

Asphaltenes produced by hydrogenolysis of coal were further hydrogenated in a batch autoclave at 400°C and 22 MPa hydrogen pressure. Red-mud was used as a catalyst and sulfur as promoter. The hydrogen content of the residual asphaltene increases and the fraction of aromatic carbon and the fraction of protons bound to aromatic carbons decrease as the reaction proceeds, indicating that hydrogenation of aromatic rings occurs. Aromatic ring systems of more than 2 rings are relatively easily hydrogenated to 2 rings. However, 2 ring systems are not easily hydrogenated. The heteroatoms-to-carbon ratios are similar for both the oil and the residual asphaltene, but less than that of the original asphaltene. The main differences in the chemical structure between the oil and the residual asphaltene are the hydrogen-to-carbon ratio, the fraction of aromatic carbon, the molecular weights and the average degrees of crosslinking. The residual asphaltene is composed of trimers and/or oligomers of unit structures of two or more condensed aromatic rings bound together by crosslinks. The size and composition of the condensed ring systems varies about the average properties measured in these experiments. Cleavage of the crosslinks by hydrogenation and heteroatom removal produces oil, composed for the most part of monomers of unit structures of two condensed aromatic rings. Coals of different rank show similar behavior although the magnitude of the changes depends on rank.