ISOLATION AND CHARACTERIZATION OF NATURAL SURFACTANTS FROM CHINESE OIL SAND BITUMENS

Abstract

Natural surfactants(NS) have been isolated from four Chinese oil sand bitumens (NNY,NSY,SNE,SUG) using the method of solvent extraction. These compounds were analyzed by IR and their interfacial tension (γ) against pH were measured. The results were compared with these obtained for fractions separated from the bitumen by conventional methods. The factors of NS to the extraction of bitumen from oil sand by hot water were investigated.     

ANALYSIS AND PHYSICO-CHEMICAL CHARACTERIZATION ON CHINESE OIL SAND BITUMENS

The extraction of four Chinese oil sands from Sinjiang and Inner Mongolia Autonomous Regions with Dean-Stark extractor were investigated. The mineral composition and sand grain distribution were determined and the bitumens were separated into saturates, aromatics, resin-I and resin-II, asphaltenes. The structure parameters and molecular model were made for the bitumens. Elemental analysis, molecular weight, FTIR, 1H-NMR were made for the bitumen fractions. The results show that the molecular structure of Mongolia bitumens have more polycyclic aromatics than that of Sinjiang bitumen. It is believed that the extraction of Sinjiang oil sand bitumen by hot alkaline water is much easier than Mongolia oil sand due to the difference of the viscosity of bitumen, the molecular structure and other physico-chemical properties of the bitumens.     

内蒙古油砂抽提沥青的实验研究

进行了热碱水抽提内蒙古油砂中沥青的实验研究。结果表明,最佳抽提条件为：碱液浓度0．3％,抽提温度90℃,碱液／油砂质量比1．5～2．0,搅拌速度75～100r／min,抽提时间20min。在抽提得到的粗沥青中加入质量分数为20％的石油醚（馏程60—90℃）,于45℃下进行了进一步的脱砂处理。结果表明,砂粒与沥青基本分离,所得沥青中沥青质的质量分数达43．40％。     

ANALYSIS AND PHYSICO-CHEMICAL CHARACTERIZATION ON CHINESE OIL SAND BITUMENS

Abstract

The extraction of four Chinese oil sands from Sinjiang and Inner Mongolia Autonomous Regions with Dean-Stark extractor were investigated. The mineral composition and sand grain distribution were determined and the bitumens were separated into saturates, aromatics, resin-I and resin-II, asphaltenes. The structure parameters and molecular model were made for the bitumens. Elemental analysis, molecular weight, FTIR, 1H-NMR were made for the bitumen fractions. The results show that the molecular structure of Mongolia bitumens have more polycyclic aromatics than that of Sinjiang bitumen. It is believed that the extraction of Sinjiang oil sand bitumen by hot alkaline water is much easier than Mongolia oil sand due to the difference of the viscosity of bitumen, the molecular structure and other physico-chemical properties of the bitumens.     

两种油砂加工方法的对比研究

分别采用溶剂萃取法和流化热转化法对内蒙古图牧吉油砂的加工方法进行了研究。溶剂萃取法可以得到油砂中几乎所有油品,但其液体产品具有高密度、高黏度及高残炭等特点,后续加工难度大;流化热转化法可以得到油砂中82.3%的油品,与溶剂萃取法相比,其液体产品的性质得到了较大程度的改善。对流化热转化得到的液体产品进行分馏和分析,其中汽油、柴油收率之和达到了37.32%,但是需要进一步精制才能达到国家油品标准的质量要求;重油收率达到了62.68%,可以通过进一步掺炼实现其轻质化。     

The Use of Microscopic Bitumen Froth Morphology for the Identification of Problem Oil Sand Ores

Abstract

Oil sand, which is found in various deposits around the world, consists mostly of sand, surrounded by up to 18 wt% bitumen. The largest deposits known are situated in northern Alberta, Canada, where reserves of bitumen are estimated to be 1.7 trillion barrels. Bitumen is similar to heavy oil, but with much higher viscosity and density. The two main commercial oil sand operations in Alberta are surface mines and use aqueous flotation of the bitumen to separate it from the rest of the oil sand. Under optimal conditions up to 95% of the bitumen can be recovered, but occasionally ores are mined that create problems in extraction, and recovery can drop to 70% or less. This article discusses the microscopic morphologies of various bitumen and heavy oil streams and their relationship to processing problems. The results of extensive microscopic work have demonstrated that the bitumen in an oil sand ore is the phase most susceptible to oxidation and that the resulting changes manifest themselves in particular microscopic structures. The presence and type of these structures can be related to the processing behavior of oil sand ores. Morphological features found in froths from commercial operations are similar to those found in froths from laboratory-prepared samples. The morphological features found in froths of oxidized ores have been categorized and quantified for a variety of samples and are referred to as degraded bitumen structures. Experiments in which fresh oil sand ores were subjected to low-temperature oxidation showed that bitumen froth morphology changed dramatically compared to that of nonoxidized ores for identical bulk compositions and extraction water chemistries.     

The Use of Microscopic Bitumen Froth Morphology for the Identification of Problem Oil Sand Ores

Oil sand, which is found in various deposits around the world, consists mostly of sand, surrounded by up to 18 wt% bitumen. The largest deposits known are situated in northern Alberta, Canada, where reserves of bitumen are estimated to be 1.7 trillion barrels. Bitumen is similar to heavy oil, but with much higher viscosity and density. The two main commercial oil sand operations in Alberta are surface mines and use aqueous flotation of the bitumen to separate it from the rest of the oil sand. Under optimal conditions up to 95% of the bitumen can be recovered, but occasionally ores are mined that create problems in extraction, and recovery can drop to 70% or less. This article discusses the microscopic morphologies of various bitumen and heavy oil streams and their relationship to processing problems. The results of extensive microscopic work have demonstrated that the bitumen in an oil sand ore is the phase most susceptible to oxidation and that the resulting changes manifest themselves in particular microscopic structures. The presence and type of these structures can be related to the processing behavior of oil sand ores. Morphological features found in froths from commercial operations are similar to those found in froths from laboratory-prepared samples. The morphological features found in froths of oxidized ores have been categorized and quantified for a variety of samples and are referred to as degraded bitumen structures. Experiments in which fresh oil sand ores were subjected to low-temperature oxidation showed that bitumen froth morphology changed dramatically compared to that of nonoxidized ores for identical bulk compositions and extraction water chemistries.     

油砂沥青油的加工利用

利用溶剂抽提分离油砂沥青,比较了油砂沥青油的沸腾床加氢实验和焦化实验,以及油砂的干馏实验。结果表明,以甲苯为溶剂抽提分离油砂沥青,可使沥青油回收超过90%。油砂沥青油具有密度大、灰分高、盐含量高的特点,胶质沥青质质量分数超过90%。采用沸腾床加氢处理脱盐沥青油,可使其硫、残炭、镍、钒的脱除率分别达到7283%、6685%、9616%和9824%,胶质和沥青质的转化率分别为7353%和9863%,加氢产物是优质的深加工原料。采用焦化处理非脱盐沥青油,总液收6164%,焦炭产率2895%,资源相对有效利用率低。油砂直接干馏,沥青油总回收率只有7856%。从油砂沥青油的有效回收和利用上看,沸腾床加氢是最有效的手段。     

Synthesis of comb bipolymers and their pour point depressing properties

A bipolymer maleic anhydride-methyl acrylate(MAMA) was synthesized from maleic anhydride and methyl acrylate based on molecular design. MAMA further reacted with oleylamine or octadecyl alcohol to generate two comb polymers called Oleamide-MAMA(NMAMA) and OctadecanolMAMA(OMAMA), respectively. The structure of both the polymers was confirmed by their infrared spectral analysis(IR), gel permeation chromatography analysis(GPC) and differential scanning calorimeter(DSC). Moreover, the pour point depressing(PPD) properties of these comb polymers were examined experimentally. Experimental results showed that besides the molecular weight and concentration of the polymers, the length of side chains and the number of functional groups also had great influence on the pour point depressing performance. The π bonds and hydrogen bonds between depressants were the key factors for improving the pour point depressing properties. These results suggest that both OMAMA and NMAMA are potential pour point depressants for industry.     

印尼油砂溶剂抽提工艺条件的研究

对印尼油砂的组分、结构和粒径特征进行分析。分析结果表明，从印尼油砂中分离稠油沥青适用的方法是溶剂抽提工艺。考察了三氯乙烯、甲苯、石油醚、石脑油、含极性组分的石脑油5种溶剂对抽提效果的影响，确定较佳的抽提溶剂为含极性组分的石脑油。考察了印尼油砂溶剂抽提的工艺条件，推荐的最佳工艺参数为：溶剂与油砂的体积比1.3：1，抽提温度50～60 ℃，抽提时间15～30 min，搅拌速率100～300 r/min。在该条件下，稠油沥青一级抽提率达85%，二级抽提率达93%。     

13NMR CHARACTERIZATION OF HUMIC MATTER PRESENT IN DIFFERENT OIL SANDS

Insoluble organic matter (humic matter) present in oil sands can alter the wettability of the inorganic matrix and thereby cause serious problems during bitumen recovery.

Using a cold water agitation test, solids rich in organic matter were isolated from various oil sands which were chosen to reflect different behavior in the hot water extraction process.¹³C NMR examination of these separated solids showed significant structural variations between samples isolated from different oil sands. Humic matter from Utah oil sand appeared to be more aliphatic than that derived from Athabasca oil sand.

Humic acids extracted from organic rich solids as a result of prolonged treatment with 2% NaOH show remarkable similarity in their ¹³C NMR spectra. Humins differ substantially in the relative contribution of the terrestrial and marine source material. There was apparent correspondence between poor bitumen separation and the presence of humin with highly paraffinic structures.     

Reaction behavior of oil sand in fluidized-bed pyrolysis

The reaction behavior of oil sand from Inner Mongolia（China） were studied in a fluidizedbed pyrolysis process,and a comparative study was conducted on the properties of the liquid products obtained through fluidized-bed pyrolysis of oil sand and the native bitumen obtained by solvent extraction.The results indicated that the fluidized-bed pyrolysis,a feasible carbon rejection process,can be used to upgrade oil sand.The reaction temperature and time were found to be the key operating parameters affecting the product distribution and yields in fluidized-bed pyrolysis of oil sand.The optimal temperature was 490℃ and the most suitable reaction time was 5 min.Under these operation conditions,the maximum yield of liquid product was 80wt%.In addition,the pyrolysis kinetics of oil sand at different heating rates of 5,10,20 and 30℃/min was investigated using a thermogravimetric analyzer（TGA）.     

PHYSICAL STRUCTURE OF THE PRIMARY FROTH FROM ATHABASCA OIL SAND EXTRACTION: CRYOGENIC SAMPLING AND MICROSCOPIC OBSERVATION OF PILOT PLANT FROTHS

Significant incentives remain for decreasing the mean solids and water content and their variability in combined extraction froth from Athabasaca oil sands, both in the hot water processes now commercially implemented, and in projected processes typically operating at lower temperatures. The oil sand can be conditioned in different ways to generate aerated bitumen droplets which can be recovered as a froth by flotation. The froth formation processes determine the quantities of entrained water and solids, and hence froth quality is related to the vertical progression of physical structures in the froth layer. A sampling method was developed to take frozen samples simultaneously from different depths in the froth layer, for the first time, and applied in pilot plant extractions of Athabasca oil sands, operating in either the commercial (Clark) or a development (OSLO) configuration at various temperatures. The patterns of froth structures were rather similar, with minor differences more related to the process temperature than to the oil sand conditioning procedure. The froth structure progressed from loosely packed aerated bitumen droplets at the bottom to bitumen-continuous at the top with an extensive water-continuous middle region containing distorted aerated bitumen droplets and comprising approximately 70% of the total froth depth. An abrupt phase inversion had been expected but was clearly absent. A key factor determining the froth quality appears to be the ability of the bitumen droplets to distort without coalescing, and so to pack more closely allowing continued drainage of the aqueous phase. Implications for froth quality improvement are discussed.     

13NMR CHARACTERIZATION OF HUMIC MATTER PRESENT IN DIFFERENT OIL SANDS

ABSTRACT

Insoluble organic matter (humic matter) present in oil sands can alter the wettability of the inorganic matrix and thereby cause serious problems during bitumen recovery.

Using a cold water agitation test, solids rich in organic matter were isolated from various oil sands which were chosen to reflect different behavior in the hot water extraction process.¹³C NMR examination of these separated solids showed significant structural variations between samples isolated from different oil sands. Humic matter from Utah oil sand appeared to be more aliphatic than that derived from Athabasca oil sand.

Humic acids extracted from organic rich solids as a result of prolonged treatment with 2% NaOH show remarkable similarity in their ¹³C NMR spectra. Humins differ substantially in the relative contribution of the terrestrial and marine source material. There was apparent correspondence between poor bitumen separation and the presence of humin with highly paraffinic structures.     

川西矿山梁下寒武统沥青脉油气生成时间的厘定——来自于固体沥青Re—Os同位素等时线年龄的证据

川西龙门山北段沥青脉与油苗广泛分布,尤其是下寒武统沥青脉,说明在龙门山褶皱带北段东缘具有寻找震旦系—寒武系油藏的良好前景。尽管有关该区下寒武统沥青脉的来源研究取得了一些进展,但具体来源于那套烃源岩还存在较大的分歧,同时对固体沥青脉的油气生成时间还缺乏系统研究。铼_锇(Re—Os)同位素测年法作为一种创新性的油气成藏定年方法,可对川西龙门山北段矿山梁下寒武统沥青矿的油气生成时间及其来源进行探索研究。通过系统的条件实验,建立了固体沥青、原油中沥青质提取、溶样、Re—Os纯化富集及分离等前处理技术及Re—Os同位素测年方法,主要步骤依次为样品制备、样品酸化学消解、Re和Os纯化富集与化学分离、Re和Os含量与同位素比值分析、Isoplot软件处理等。川西广元地区下寒武统沥青脉Re_Os同位素年代学及其油源分析研究表明,下寒武统固体沥青热成熟度低,油气生成时间早,约在572～559Ma之间,对应于新元古代晚震旦世,反映其来源于时代古老的烃源岩;从固体沥青Re—Os等时线年龄、初始¹⁸⁷Os/¹⁸⁸Os比值、碳同位素组成以及生物标志物等综合研究表明下寒武统沥青脉来源于震旦系陡山沱组优质烃源岩,该烃源岩于572～599Ma期间在低成熟阶段生成的稠油,进入灯影组地层中形成古稠油藏,后期由于构造抬升,震旦系灯影组古油藏破坏形成了现今的沥青脉。     

油砂沥青改质产品中甲苯不溶物的表征

油砂沥青及其衍生产品中含有悬浮的甲苯不溶物如粘土和碳质固体颗粒，会导致后续加工过程中的结垢、催化剂失活和床层堵塞。笔者从油砂沥青衍生产品中分离出甲苯不溶物并进行了分析表征。研究发现，油砂沥青渣油中的甲苯不溶物主要是超细的硅铝酸盐粘土颗粒，结合了部分干酪根成分；焦化渣油和焦化瓦斯油储罐中沉积的甲苯不溶物类似焦炭；焦化瓦斯油中的甲苯不溶物主要是碳质有机物颗粒，但氮、氧含量相对丰富，并含少量矿物质和粘土颗粒，含氮的杂环化合物如吡咯类物质的存在可能是导致焦化瓦斯油中甲苯不溶物生成的主要因素。     

A PHYSICAL CHEMICAL EXPLANATION FOR DETERIORATION IN THE HOT WATER PROCESSABILITY OF ATHABASCA OIL SAND DUE TO AGING

The oxidation of sulphide minerals during storage of Athabasca oil sands causes solubilization of inorganic salts which affect recovery of bitumen during hot water extraction. DLVO and Ionizable Surface Group Model theories accurately predict that the level of soluble salts produced is sufficient to cause coagulation of the fine particles during the process which leads to a deterioration in froth quality and loss of bitumen recovery. The rate of aging is specific to each oil sand but storage of oil sands under an inert atmosphere in air-tight container at sub-zero temperatures will minimize oxidation.     

CATALYTIC TREATMENT OF HAMMAM AL-ALIL BITUMEN USING NICKEL HEXANOATE

Ham mam Al-Alil bitumen (HAB) is found in the Hammam Al-Alil area. The bitumen obtained from this area was found to be mixed with sand, sulfur and sedimentation. Purification of the sample from foreign materials was fulfilled. Asphaltenes were removed by treatment with heptane and the petrolenes obtained were eatalytically cracked using nickel hexanoate and ethanol. The study revealed the heavy nature of such bitumen and supported the idea of the geological and chemical information that deals with Mishraq sulfur deposit and the Qaiyarah crude oil; i.e., Hammam Al-Alil bitumen is Qaiyarah crude oil, which was reduced by Mishraq sulfur. The study of the carbon distributions was carried out using pmr spectroscopy and employing various equations with modification used by previous workers.     

沸石基油砂沥青改质催化剂的性能研究

研究和开发高效减黏、抗硫氮和重金属的水热催化裂化改质催化剂是油砂沥青资源利用技术的关键,以天然斜发沸石为基质制备氢型沸石载体和微孔镍基沸石催化剂,考察其应用于模型化合物水热裂化的性能和对加拿大麦肯河SAGD油砂沥青减黏改质的效果。结果表明：在正十六烷为模型化合物的水热裂化过程中,微孔镍基沸石催化剂表现出良好的催化裂化性能和优良的水热稳定性;在油砂沥青改质试验中,微孔镍基沸石催化剂能够显著降低油砂的黏度,增产中间馏分油,并在一定程度上降低硫、氮含量,可用于中低温和非临氢条件下的油砂沥青减黏改质。