Oxidative Degradation of Athabasca Bitumen,Fuel Oil,and Used Transformer Oil

Abstract

Oxidative cracking of bitumen, waxy fuel oil, and used transformer oils were carried out individually in an autoclave with 0.6 wt% of hydroquinone as a catalyst. The cracking process is conducted at 410°C in an atmosphere of oxygen gas of 0.15 MPa, for 30 min. The identification and quantitative determination of both the liquids and gases obtained during the cracking process are achieved using packed and capillary gas chromatography (GC) connected with suitable detectors. It was found that the degraded liquid products obtained have a higher percentage of lower hydrocarbons compared to the original feed stocks. Several analytical parameters including API gravity, calorific value, viscosity, density, pour point, etc., were used to evaluate the liquid product obtained. Also, the calorific values of the liberated gases were calculated and compared with that of natural gas. The cracked oil products were distilled and compared to their corresponding petroleum fractions. The cracked fractions have the same characteristics as their corresponding petroleum fractions with the exception of some properties that depend on the aromatic, naphthenic, and waxy nature of the virgin oil.     

Catalytic Oxidative Cracking of Heavy Wax Distillates, Slack Wax, and Polyethylene Wastes to Yield Liquid and Gas Fuels

A petroleum waxy distillate, slack waxes, and plastic wastes were charged in an autoclave with 0.6 wt% of hydroquinone as a catalyst. Oxidative cracking process is conducted at 410°C, in oxygen atmosphere of 0.15 MPa for a time of reaction 30 min. Different analytical parameters are used to investigate the physicochemical properties of the products obtained and their corresponding virgin feed stocks. The obtained oily products were distilled to petroleum boiling range like fractions such as gasoline, kerosene, gas oil, and residue. These products have petroleum fuels like properties according to the ASTM test methods. Moreover, the composition of the obtained liquids and liberated gases during the cracked products were identified quantitatively using gas chromatographic technique. Results show that such oxidative cracking process can be used for upgrading petroleum heavy fractions.     

Catalytic Oxidative Cracking of Heavy Wax Distillates,Slack Wax,and Polyethylene Wastes to Yield Liquid and Gas Fuels

Abstract

A petroleum waxy distillate, slack waxes, and plastic wastes were charged in an autoclave with 0.6 wt% of hydroquinone as a catalyst. Oxidative cracking process is conducted at 410°C, in oxygen atmosphere of 0.15 MPa for a time of reaction 30 min. Different analytical parameters are used to investigate the physicochemical properties of the products obtained and their corresponding virgin feed stocks. The obtained oily products were distilled to petroleum boiling range like fractions such as gasoline, kerosene, gas oil, and residue. These products have petroleum fuels like properties according to the ASTM test methods. Moreover, the composition of the obtained liquids and liberated gases during the cracked products were identified quantitatively using gas chromatographic technique. Results show that such oxidative cracking process can be used for upgrading petroleum heavy fractions.     

A Kinetics Lumped Model for VGO Catalytic Cracking in a Fluidized Bed Reactor

Abstract

Fluid catalytic cracking (FCC) is a process used to converted heavy petroleum products to light products such as gasoline, light fuel oil, and petroleum gas. In the fluid catalytic cracking reactor heavy gas oil is cracked into more valuable lighter hydrocarbon products. The reactor input is a mixture of hydrocarbons that makes the reaction kinetics very complicated due to the involved reactions. In this article, a four-lump model is proposed to describe the kinetics of vacuum gas–oil (VGO) cracking in the FCC process. This model is different from other models mainly in that the deposition rate of coke on catalyst can be predicted from gas–oil conversion and isolated from the C1-C4 gas yield. By this lumped model for the kinetic of cracking VGO we can also conclude that the C1-C4 gas yield increases with increasing reactor temperature, whereas the production of gasoline and coke decreases. We can also conclude that with decreasing space velocity the product yield will increase.     

原油裂解气的形成、鉴别与运移研究综述

在综合国内外原油裂解气研究成果的基础上,对原油裂解气的形成模式、形成机制及动 力学过程、原油裂解气的金属催化作用、天然气的运移分馏作用、原油裂解气的鉴别指标和 我国台盆区原油裂解气藏的成因进行了系统的总结,通过此总结并对当前原油裂解气理论研 究、勘探进展进行了一些探讨。     

原油裂解气在天然气勘探中的意义

从油气生成理论和古油藏演化过程的讨论中引申出原油裂解气的问题。一般所说的原油裂解气主要是指古油藏演化中的原油裂解气 ,油藏中的原油由于后期深埋 ,必然发生裂解而形成天然气和沥青。这种原油裂解气只有在特定的地质条件下才能形成 ,如塔里木盆地巴楚隆起的和田河气田的天然气 ,主要是由于构造运动使早期形成的油藏埋藏很深导致原油裂解的产物。塔北隆起东部桑塔木断垒带的天然气与和田河气田的天然气同是源自寒武系烃源岩 ,但桑塔木天然气主要为干酪根裂解气 ,而和田河天然气主要为原油裂解气 ,因此二者在天然气组成和天然气组分碳同位素特征上存在差异 ,如虽然二者成熟度一致 ,但和田河气田天然气的非烃气体含量高于桑塔木天然气 ,其甲烷碳同位素值则比桑塔木天然气的轻。对于古油藏而言 ,原油裂解既对油藏起破坏作用 ,同时又可形成天然气藏的特殊气源。图 6参 1 2     

珠江口盆地白云凹陷原油半开放条件下裂解成气模拟实验

为深入研究珠江口盆地白云凹陷原油裂解机制及产物变化特征,选取了白云凹陷渐新统珠海组原油样品,利用高温高压模拟实验,模拟了地下压力、地下流体介质及半开放条件下、不同升温速率的原油裂解过程,分析了气产率和气体组分特征.研究表明,原油样品在365℃开始裂解,裂解产率随温度增加而增加,在20℃/h的升温速率下,最终(550℃)...     

烃类与非烃综合判识干酪根与原油裂解气

在天然气成因类型研究中,如何有效识别干酪根与原油裂解气一直是一个难题。选取不同类型干酪根、不同性质原油开展半封闭—半开放体系的热压生排烃模拟实验及其产物的地球化学分析研究,并对典型的干酪根、原油裂解气（田）进行了地球化学统计和比对。研究表明,干酪根热解气与原油裂解气中烷烃组分及其碳同位素组成显示相似的演化特征,Ln(C₂/C₃)值均呈早期近似水平和晚期近似垂向变化特征,在高过成熟阶段Ln(C₂/C₃)值与δ¹³C₂-δ¹³C₃差值具有快速增大的趋势,二者趋同性变化特征指示了生气母质的高温裂解过程,但这些指标不是干酪根与原油裂解气的判识标志,提出天然气中烷烃分子及同位素组成的有机组合是判断有机质（干酪根、原油）高温裂解气的可靠指标,却并不能直接识别干酪根热解气或原油裂解气;非烃组分的演化特征具有明显的差异性,干酪根热解气以高含氮气(N₂)为主,原油裂解气往往高含硫化氢(H₂ S), N₂、H₂ S含量作为一项重要指标可以与烷烃气同位素组成相结合有效区别干酪根与原油裂解气,分析结果与四川盆地、塔里木盆地不同油气田的地质实际相吻合。天然气中烃类和非烃组成的综合分析为有效判断干酪根与原油裂解气提供了新的途径。     

减压渣油热转化集总动力学的建模研究

以洛阳减压渣油为例,研究了减压渣油热转化集总动力学模型.对洛阳减压渣油分别在410、420、430和440℃下进行的热转化反应,通过数学分析建立了6集总动力学反应模型.减压渣油热转化反应生成裂化气、汽油、轻瓦斯油、重瓦斯油与焦炭,其反应均为2级反应;轻、重瓦斯油将继续发生2次反应,生成焦炭;动力学参数中缩合反应的活化能大于裂化生成馏分油的活化能,表明缩合反应对反应温度的变化更为敏感.计算结果表明,所建模型可以用来预测减压渣油热转化反应产物分布,预测值与实验值吻合较好.     

内蒙古图牧吉油砂流化热转化反应规律

 在小型流化热转化实验装置上,考察了内蒙古图牧吉油砂的流化热转化反应规律。得到最佳的反应条件为反应温度490℃、反应时间5 min、水/油质量比0.4、热载体/油砂质量比2。在此最优操作条件下,液体产品收率达到79.87%, 轻油收率达到26.59%。随着图牧吉油砂流化热转化反应温度的升高,干气、液化气及汽油产率增加,这主要来自于重油的二次裂化。热转化后的液体产品相对于油砂沥青,残炭、微量金属含量及黏度都有大幅度的降低,同时馏程得到很大改善,有助于后续的加工利用。     

加氢裂化尾油窄馏分的催化裂化转化规律研究

将中东减压蜡油的加氢裂化尾油分为4个沸程范围不同的窄馏分,在固定流化床装置上考察了其催化裂化反应性能,采用GC/MS等方法对原料和裂化产物的烃类组成进行了分析。结果表明,4个窄馏分中饱和烃的质量分数均高于98.0%,随着馏分变重,窄馏分中的链烷烃含量增大,环烷烃含量减小,并且链烷烃和各族环烷烃均向高碳数方向移动。4个窄馏分均易于裂化,干气和焦炭产率低,液化气和汽油收率高。在相同的催化裂化条件下,随着馏分变重,其可裂化性能增强,干气和焦炭产率降低,液化气收率增加,汽油收率增加但辛烷值略有降低,柴油和重油收率均降低。     

减压渣油及其组分热转化前后平均结构参数的变化

 以胜利减压渣油、孤岛减压渣油、大庆减压渣油为原料,在高压釜中进行热转化反应。反应温度为405 ℃,反应时间为1 h。将渣油及热转化残渣油分离成6个组分,对渣油及其组分的平均结构参数进行分析、计算。结果表明,热转化后残渣油六组分中的戊烷沥青质组分(n-C5At)的含量比原料减压渣油六组分中的戊烷沥青质组分含量明显增加,其他组分（F1~F5）的含量均比原料减压渣油中相应组分的含量有所降低。热转化残渣油中各组分的相对分子质量、H/C摩尔比及总碳原子数均比原料渣油中相应的组分降低。而热转化后残渣油各组分的缩合指数和芳碳率比原料渣油中的要高。     

Characterization of Basic Nitrogen Aromatic Species Obtained during Fluid Catalytic Cracking by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

The basic-nitrogen aromatic compounds in feedstocks and liquid products from the micro-reactor and soluble components of coke obtained during fluid catalytic cracking (FCC) process were analyzed by the micro-electrospray ionization (ESI) 9.4T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with an average mass resolving power of 300 000 at a mass range of 100-1 200. The analytical results revealed that the coker gas oil (CGO) contained a higher abundance of basic-nitrogen aromatic compounds with the type of -5N to -9N compared with those in deasphalted oil (DAO) and mixed FCC feedstock. After catalytic cracking, the abundance of lowly condensed basic-nitrogen aromatic compounds was much less than those of highly condensed aromatics in the liquid products, with the carbon number mainly ranging from 6 to 25 and the average carbon number of the side-chains equating to 1-5. On the contrary, with respect to the soluble components of coke, the abundance of lowly condensed basic-nitrogen aromatic compounds was more than those of highly condensed aromatics, and the carbon number ranged from 12 to 30, which was much smaller than that of the mixed FCC feedstock but slightly larger than that of the cracked liquid products. These results have provided some fundamental information on FCC process.     

加拿大重瓦斯油催化裂化研究--不同反应器的产品产率与质量对比

Several series of cracking tests in a comprehensive study were conducted on separate occasions involving all or parts of ten Canadian vacuum gas oils (VGOs) and two catalysts with bottoms-cracking or octane-barrel capability.VGOs were cracked in fixed- and/or fluid-bed microactivity test (MAT) units, in an Advanced Cracking Evaluation (ACE)unit, and in a modified ARCO riser reactor. Individual yields of gas, liquid, and coke from the MATs at 55, 65, 70, and 81 wt% conversion levels were compared with their respective pilot plant data. Good linear correlations could be established between MAT and riser yields except for liquefied petroleum gas (LPG) and light cycle oil (LCO). At a given conversion,correlations existed among the fixed- and fluid-bed MAT units and the ACE for each product yield. Liquid products from the fixed or fluid-bed MAT were analyzed for hydrocarbon types, sulfur, nitrogen and density, most of which showed good agreement with those obtained from the riser study. When cracking Canadian oil-sands-derived VGOs, the bottomscracking catalyst containing a large-pore active matrix was found to be more suitable than the octane-barrel catalyst with smaller pores to produce higher yields of valuable distillates, but with less superior qualities (in terms of sulfur and nitrogen contents). The advantages of hydrotreating some poor feeds to improve product yields and qualities were demonstrated and discussed.     

FCC Study of Canadian Heavy Gas Oils—Comparisons of Product Yields and Qualities between Reactors

1. Introduction Oil-sands bitumen is a mixture of immature andcomplex hydrocarbons with a relatively lowhydrogen-to-carbon ratio (i.e., very aromatic) and anabundance of chemical impurities. Because of its highviscosity, the bitumen can only be transported throughpipelines after being mixed with suitable diluents suchas natural gas condensates. Alternatively, the bitumencan be upgraded to a light and bottomless syntheticcrude oil (SCO) that is pipelineable. Syncrude Ca…     

Destructive Conversion of Gas Oil in the Presence of a Nickel-Based Nanosized Catalyst

The decomposition of nickel 2-ethylhexanoate by heating in a vacuum gas oil (VGO) medium at 355–365°С has been found to yield nickel and nickel sulfide nanoparticles. The size of the particles is 20–120 nm. The catalytic cracking of VGO in the presence of these nickel-containing particles provides a 70.15% yield of the distillate with a boiling point up to 220°C. The structural-group composition of the products of VGO cracking in the presence of nickel-based nanoscale catalysts has been studied using gas chromatography–mass spectrometry. The group composition of samples containing cracked products has been analyzed to cover eleven classes of organic compounds. The structural composition of the test samples has been considered with respect to eight groups of compounds, of which three include two to three classes of compounds. In the catalytic cracking of VGO, the concentration of alkanes increases by 3.11% and that of alkenes and alkylbenzenes decreases by 1.31 and 2.59%, respectively, as compared to their content in the products of VGO distillation without a catalyst.     

柯克亚地区原油裂解气的地质-地球化学特征

对柯克亚地区原油和天然气的地球化学特征分析表明：原油和天然气的成熟度相对较高，均处于裂解气的成熟阶段；原油中存在着丰富的金刚烷，缺少含氮化合物，与在国外发现的裂解气共生的原油有相似之处；随着油层深度的增加，天然气中甲烷的含量依次增多。认为柯克亚地区天然气主要为原油裂解气，原油裂解作用是该区天然气的主要成因之一。     

四川盆地陆相天然气地球化学特征及对比

为了系统认识四川盆地陆相天然气地球化学特征及差异,利用天然气组分、碳同位素与轻烃等地球化学资料,对四川盆地不同地区不同层位陆相天然气地球化学特征进行分析及对比,探讨其差异成因。结果表明,四川盆地陆相天然气地球化学特征在横向与纵向均存在较大差异。横向上,川西地区天然气甲烷含量与干燥系数均高于川中地区,川西地区天然气以干气为主,川中地区天然气以湿气为主,地层厚度、埋深及气源岩的不同是造成上述差异的主要原因。不同地区的天然气组分特征参数纵向变化规律也明显不同,川西地区该变化规律主要受烃源岩成熟度与天然气运移分馏影响,而川中地区则主要受烃源岩成熟度及类型的影响。四川盆地陆相天然气以成熟气与高成熟气为主,仅川中地区侏罗系天然气以成熟气为主,川西地区天然气成熟度最高,川中地区与川南地区上三叠统次之,川中地区侏罗系最低,烃源岩埋深与厚度的差异造就了上述成熟度差异。四川盆地陆相天然气以煤型气为主,同时存在一定的油型气,不同地区油型气的含量、分布、成因与来源均存在较大的差异：川西地区仅须二段存在少量油型气,来自马鞍塘组—小塘子组生成的石油裂解;川中地区侏罗系以油型气为主,来自侏罗系干酪根裂解;川南地区须家河组有一定的石油裂解成因油型气,主要来自下伏气藏。四川盆地上三叠统天然气以水溶相与游离相运移,而侏罗系天然气则主要以游离相运移。[JP]     

THE EFFECTS OF HIGH PRESSURE ON OIL‐TO‐GAS CRACKING DURING LABORATORY SIMULATION EXPERIMENTS

The effects of high pressures on the yield and kinetics of gas generated by the cracking of crude oil were investigated in laboratory simulation experiments. Samples of a low‐maturity non‐marine oil were recovered from the Paleogene Shahejie Formation in the Dongying depression, Bohai Bay Basin, eastern China. The oils were cracked to gas under different pressure and temperature conditions in an autoclave. Initial temperatures of 300 °C were increased to 650 °C at rates of either 30 or 100 °C/h. Reaction products were analysed at the end of each 50 °C temperature increase. Pressure conditions were either 0.1 MPa (i.e. atmospheric) or 20 MPa. Results show that high pressures inhibit or delay oil‐to‐gas cracking and retard the initiation of the cracking process. The temperature at which oil was cracked and the activation energy of the formation of C_1–5 hydrocarbons increased under high pressure conditions, demonstrating the effects of pressure on the kinetics of the oil‐to‐gas cracking process. High pressures and high temperatures inhibited the conversion of C_2–5 hydrocarbons to methane during secondary cracking. In addition, high pressures retarded the generation of N₂, H₂ and CO during cracking of oil. The presence of water increased the yields of total cracked gas, C_2–5 hydrocarbons and CO₂ in high‐pressure conditions. The simulation results show that CO₂ and C_2–5 hydrocarbons have similar yields during oil‐to‐gas cracking. Using the kinetic parameters determined from the laboratory experiments, the yield and production rate of gas generated during the cracking of oil from Member 4 of the Paleogene Shahejie Formation in the Minfeng‐Lijin sag (Dongying depression) were calculated. The results indicate that only limited volumes of natural gas in this area were derived from the cracking of oil, and that most of the gas was derived from the thermal decomposition of kerogen.     

松辽盆地白垩系湖相Ⅰ型有机质生烃动力学

针对松辽盆地白垩系湖相Ⅰ型有机质的生烃特征和动力学,利用黄金管模拟装置开展了升温热解实验。液态产物和气体产物的定量分析结果表明,该Ⅰ型有机质在热演化过程中以生油为主,干酪根初次裂解气产量仅为100 mg/g左右。轻质油的色谱演化和烃类气体生成的活化能分布共同证实,封闭体系的烃类气体来源于多种反应途径,其中早期生成液态产物的二次裂解作出了很重要的贡献。同时,动力学计算的结果表明,不同液态产物生成反应的动力学参数存在差异,轻质组分生成的活化能明显要高于重质组分;源内残留油二次裂解的平均活化能为57.3 kcal/mol,要低于油藏内正常原油裂解的活化能;Ⅰ型有机质初次裂解气形成于生油初期到源内残留烃裂解早期阶段。