LONG TERM STORAGE STABILITY OF MIDDLE DISTILLATE FUELS FROM A CHEMICAL MECHANISTIC POINT OP VIEW. PART 1.

The objective of this review is to (i) articulate the current level of understanding of the types of “reactive molecules” intimately involved in the long term oxidative storage instability of middle distillates, (ii) review the types of chemical reaction mechanisms most likely involved in the “oxidative phase” of insoluble formation, (iii) review the postulated chemical mechanisms of stabilizer (additive) operation, and (iv) discuss future research areas that must be explored if a greater understanding and control of middle distillate instability is to be realized.     

MECHANISTIC CONSIDERATIONS CONCERNING THE STABILITY TOWARDS DIOXYGEN OF EVOLUTIVE FUELS.

The interaction of phenalenonc and 2-methylindole in presence of stoechiomctric amounts of paratoluenesulfonic acid in methanol under argon, yields twelve compounds which have been spectroscopically characterised. Seven compounds or sets of compounds could be scpareted by flash chromatography. Phenalene 4. and phenalanone 8 result from a disproportionalion reaction of a key intermediate 18. 2-Methylindolylphenalene 5 and bis(2-methyl)indolylphenalene 6 and 7 exist under the form of a complex mixture of lauiomers. 2-Methylindolylphenalanones 9 and 10. 2-methylindolylphenalenones 11. 12. 1 3. and bis(2-methylindolyl)phenalenones 14 and 15. could also be isolated from the reaction mixture. In presence of air and light compounds 5, 6, and 7. oxidize into 11, 12, 13, 14, and 15 via the corresponding phenalenyl radical. The mechanism of formation and interconversion of these products is discussed and experimentally supported. The peculiar reactivity of the phenalenic derivatives is analysed and it is suggested that such structures are present in asphaltenes. An hypothesis about their genesis is proposed.     

MECHANISTIC CONSIDERATIONS CONCERNING THE STABILITY TOWARDS DIOXYGEN OF EVOLUTIVE FUELS.

Abstract

The interaction of phenalenonc and 2-methylindole in presence of stoechiomctric amounts of paratoluenesulfonic acid in methanol under argon, yields twelve compounds which have been spectroscopically characterised. Seven compounds or sets of compounds could be scpareted by flash chromatography. Phenalene 4. and phenalanone 8 result from a disproportionalion reaction of a key intermediate 18. 2-Methylindolylphenalene 5 and bis(2-methyl)indolylphenalene 6 and 7 exist under the form of a complex mixture of lauiomers. 2-Methylindolylphenalanones 9 and 10. 2-methylindolylphenalenones 11. 12. 1 3. and bis(2-methylindolyl)phenalenones 14 and 15. could also be isolated from the reaction mixture. In presence of air and light compounds 5, 6, and 7. oxidize into 11, 12, 13, 14, and 15 via the corresponding phenalenyl radical. The mechanism of formation and interconversion of these products is discussed and experimentally supported. The peculiar reactivity of the phenalenic derivatives is analysed and it is suggested that such structures are present in asphaltenes. An hypothesis about their genesis is proposed.     

STUDIES ON SLUDGE FROM STORAGE TANK OF WAXY CRUDE OIL PART - I : STRUCTURE AND COMPOSITION OF DISTILLATE FRACTIONS

Tank bottom sludge from storage tanks of Bombay High crude oil deposited during ten years have been studied. The yield of the sludge is approximately 0.1% wt. of the crude oil through-put. The residue boiling above 500°C amounts to over 50%. The distillate fractions collected at 50°C intervals have been analysed extensively and compared to fractions from whole crude of same boiling range. The sludge distillate are distinctly more paraffinic in nature.     

STUDIES ON SLUDGE FROM STORAGE TANK OF WAXY CRUDE OIL PART - I : STRUCTURE AND COMPOSITION OF DISTILLATE FRACTIONS

ABSTRACT

Tank bottom sludge from storage tanks of Bombay High crude oil deposited during ten years have been studied. The yield of the sludge is approximately 0.1% wt. of the crude oil through-put. The residue boiling above 500°C amounts to over 50%. The distillate fractions collected at 50°C intervals have been analysed extensively and compared to fractions from whole crude of same boiling range. The sludge distillate are distinctly more paraffinic in nature.     

从世界看我国油气勘探战略

根据大量数据及实例,总结出世界油气勘探的现状、趋势及特点,经过对比分析,提出中国油气勘探战略:(1)寻找大型油、气田应列为首要目标,以西部的塔里木、准噶尔两大盐地和东南海域希望最大,到“九五”和21世纪初将会做出巨大贡献;(2)“八五”期间欲保证年产量1.4～1.5亿吨,主要依靠东、中部老油气区,需大力寻找非背斜油气藏和相对新区;(3)迅速加强天然气勘探,寻找大、中型气田将是以气补油的重要途径,油型气与煤型气并重.     

环境友好燃料炼厂的技术要求Ⅱ环境友好燃料炼厂

这部分将简要介绍环境友好燃料炼厂的技术要求,并将这种“清洁”炼厂与传统技术基础上的新炼厂作经济分析比较。这种“清洁”炼厂借助附加的加工步骤消除了当前炼厂中生产的焦炭,这种产品的硫和重金属含量高。将原油的残油经流化床焦化和焦炭气化进行组合加工以生产Ｈ２,并将硫和金属作为有价值的副产品回收。此外,用清洁加工技术尽可能减少其它固体废物和空气／水毒物,该技术主要是用轻烯烃生产环境友好的高级运输燃料。尽管“     

CHEMICAL BASIS OF MIDDLE DISTILLATE FUEL INSTABILITY: Interactive Effects of Selected Nitrogen Heterocycles with Organic Bases in a Shale-Derived Diesel Fuel.

Fuel instability reactions are defined in terms of the formation of deleterious products such as filterable sediments and peroxides. Gravimetric stability tests have been carried out at 80^°C using two model nitrogen heterocycles: 2,5-dimethy1pyrrole, DMP, and 3-methylindole, 3-MI, in an otherwise stable shale derived middle distillate fuel. Potential interactive effects for these model nitrogen heterocycles have been described by the presence of organic base co-dopants. Organic bases employed included: tri-n-butylamine, N, N-dimethyl-aniline, and 4-dimethylaminopyridine. Simple organic amines exerted only minor interactive effects, usually an increase in filterable sediment in the range of 5-15%. However, the diamine species, 4-dimethylaminopyridine, interacted in a strong positive fashion to generate increased amounts, 22-44%, of sediment.     

CHEMICAL BASIS OF MIDDLE DISTILLATE FUEL INSTABILITY: Interactive Effects of Selected Nitrogen Heterocycles with Organic Bases in a Shale-Derived Diesel Fuel.

ABSTRACT

Fuel instability reactions are defined in terms of the formation of deleterious products such as filterable sediments and peroxides. Gravimetric stability tests have been carried out at 80^°C using two model nitrogen heterocycles: 2,5-dimethy1pyrrole, DMP, and 3-methylindole, 3-MI, in an otherwise stable shale derived middle distillate fuel. Potential interactive effects for these model nitrogen heterocycles have been described by the presence of organic base co-dopants. Organic bases employed included: tri-n-butylamine, N, N-dimethyl-aniline, and 4-dimethylaminopyridine. Simple organic amines exerted only minor interactive effects, usually an increase in filterable sediment in the range of 5–15%. However, the diamine species, 4-dimethylaminopyridine, interacted in a strong positive fashion to generate increased amounts, 22–44%, of sediment.     

对环境友好燃料炼厂的技术要求：I.美国现状概述

尽管目前对汽油组分影响各种环境条件的理解还有限,但已经认识到,现有燃料中的几种组分若以高浓度释放到大气中,对环境是有害的,如溢漏、挥发损耗或不完全燃烧。这些组分包括芳烃特别是苯、高蒸汽压烃如ｎ－丁烷、反应性烃如烯烃以及硫化合物,它们会促使烟和酸的形成,本文将阐述与当前炼油加工过程有关的这些环境问题     

SELECTIVE REMOVAL OF H2S FROM PETROLEUM REFINERY GASES. II. A NEW DESULFURIZER BEHAVIOR OF DESORPTION AND THERMAL STABILITY

Desulfurizer JPE-7, a sterically hindered amine, has higher selectivity and absorption capacities than MDEA. JPE-7 has fast and complete regenerability, which has constant and lower H₂S content in the reduplicate tail gas. Thermal stability of JPE-7 is favorable for industrial operation condition. With the concentration of JPE-7 increasing, the absorption of CO₂ rapidly increases, while that of H₂S is reluctant to increase thus the selectivity and absorptivity is reluctant to increase. The optimum concentration of JPE-7 is range from 30 wt% to 40 wt%. The dimethyl yellow-methenyl blue method is recommended to determine the concentration of JPE-7 with reasonable accuracy.     

SELECTIVE REMOVAL OF H2S FROM PETROLEUM REFINERY GASES. II. A NEW DESULFURIZER BEHAVIOR OF DESORPTION AND THERMAL STABILITY

Desulfurizer JPE-7, a sterically hindered amine, has higher selectivity and absorption capacities than MDEA. JPE-7 has fast and complete regenerability, which has constant and lower H₂S content in the reduplicate tail gas. Thermal stability of JPE-7 is favorable for industrial operation condition. With the concentration of JPE-7 increasing, the absorption of CO₂ rapidly increases, while that of H₂S is reluctant to increase thus the selectivity and absorptivity is reluctant to increase. The optimum concentration of JPE-7 is range from 30 wt% to 40 wt%. The dimethyl yellow-methenyl blue method is recommended to determine the concentration of JPE-7 with reasonable accuracy.     

CO2和CH4的转化与气田的关系之我见

长期以来，在石油地质研究领域对CO₂与CH₄的转化关系及其转化成因尚无统一的定论。一般只将CO₂作为生油还原环境的参数指标之一。因此在油气田勘探研究中，常将CO₂在储存空间的保存完好性作为判定生、储油气层保存完好性的指标，这样CO₂在油气田勘探阶段中仅作为寻找油气藏的一个线索。但在如下几种条件：①存在CO₂催化剂（触媒剂）；②存在H₂及H₂的化合物；③具备一定的温度和压力条件；④处于特定的保存条件下，则CO₂可以转化为CH₄及烃类，或者CH₄及烃类能够转化为CO₂。由此认为，CO₂可作为勘探开发大气田的指示气体，而且在发现有高含量和高产量的CO₂气井地区内，有可能勘探到丰富的天然气资源。     

SUPPRESSION AND RETARDATION OF VITRINITE REFLECTANCE, PART 2. DERIVATION AND TESTING OF A KINETIC MODEL FOR SUPPRESSION

The presence of suppressed and retarded vitrinite reflectance (VR) data introduces a number of dificulties into the prediction of hydrocarbon generation in sedimentary basins. Although the effects of suppression can be removed from measured VR values manually, a kinetic model for suppressed vitrinite maturation would enable both suppressed and unsuppressed VR values to be predicted using thermal histories derived from basin modelling. The evaluation of hydrocarbon generation fiom suppressed and unsuppressed vitrinite shows that both have similar reaction kinetics. While hydrocarbon generation involves the rupture of the bonds holding volatiles into the vitrinite structure, increases in VR are mainly produced by aromatisation and condensation reactions which take place after volatiles have been expelled. The reactions involved in hydrocarbon generation are diyerent from those responsible for increases in VR, and it is not therefore appropriate to derive kinetic models of vitrinite maturation from laboratory hydrocarbon generation experiments. During the maturation of normal (unsuppressed) vitrinite, the volatiles generated are expelled via the microporous network; the expulsion efficiency is not limited by the capacity of the microporous network. In hydrogen‐rich (suppressed) vitrinites, excess volatiles saturate the microporous network, restricting further aromatisation and condensation processes within the vitrinite, which results in suppression of VR. Kinetically, this has been modelled by using a variable pre‐exponential or “A” value. Two versions of a kinetic model of vitrinite maturation (SMod‐1 and SMod‐2) have been prepared, based on the amount of suppression predicted by HI‐VR calibration models published by Lo (1993) and Samuels son and Middleton (1998). Two case studies, involving wells Bunga Orkid‐1 (Malay Basin) and 2013–4 (Outer Moray Firth, North Sea), are discussed. Both wells contain suppressed VR values; well 20/3–4 is also overpressured and contains VR data that are both retarded and suppressed. The application of the SMod model to the wells enables heat flow histories derived from tectonic (rift) histories to be used for the prediction of VR data, although in the case of well 20/3–4, the use of a pressure retardation model was also required. Complementary evidence to support the use of the heat flow history applied to well 2013–4 is provided by palaeotemperature data obtained from diagenetic concretions.     

SELECTIVE REMOVAL OF H2S FROM PETROLEUM REFINERY GASES. I. A NEW DESULFURIZER BEHAVIOR OF ABSORPTION

In order to improve the selective absorption behavior of desulfurizer, a new sterically hindered amine desulfurizer, JPE-7, was developed. The performance of the desulfurizer was evaluated in laboratory. The effects of raw gas flow rate, absorption temperature and time, meanwhile JPE-7 and MDEA compound concentration on selective absorption capacity for H₂S were investigated. Results showed that the desulfurizer JPE-7 had more excellent selectivity and absorption capacities than MDEA. The commercial availability of JPE-7 was discussed.     

SELECTIVE REMOVAL OF H2S FROM PETROLEUM REFINERY GASES. I. A NEW DESULFURIZER BEHAVIOR OF ABSORPTION

In order to improve the selective absorption behavior of desulfurizer, a new sterically hindered amine desulfurizer, JPE-7, was developed. The performance of the desulfurizer was evaluated in laboratory. The effects of raw gas flow rate, absorption temperature and time, meanwhile JPE-7 and MDEA compound concentration on selective absorption capacity for H₂S were investigated. Results showed that the desulfurizer JPE-7 had more excellent selectivity and absorption capacities than MDEA. The commercial availability of JPE-7 was discussed.     

应用生态地层学观点改善地层对比——以辽河断陷东营组一、二段分界为例

以辽河断陷东二段与东一段分界为例,阐明了处在湖水退缩的盆地中,湖盆边缘地区分布的化石组合特征,不一定与湖盆中心地区一致.适应性较强的广布种类比窄布种类有较长的延续时限.要正确对比地层必须把化石组合分解成标志化石带,结合古生态、沉积环境,尤其要把标志化石带与电测、岩性标准层、地震界面的追索,综合起来进行研究.     

综合多学科信息建模——以港东开发区二区六区块储层微相三维分布模型为例

遵循从点（单井）到面（二维平面分布）再到体（三维空间分布）的研究流程，提出了利用岩心、测井、地震以及动态资料等多学科信息对储层微相分布进行预测的思路，即：通过区域地质背景分析和井点岩心资料细分沉积微相来建立岩电模型；在此基础上，通过单井相分析并结合砂体二维等值线图和地震资料识别的河道（带）来建立储层微相平面分布模型；利用动态资料，确定砂体连通及延展情况，精细解剖砂体，获得不同微相储层的结构特征参数；利用随机模拟方法，预测储层微相三维展布特征。根据以上思路，建立了大港油田港东开发区河流相储层三维分布模型，为油田生产提供了地质依据，也为随后的储层物性预测乃至数值模拟研究提供了必要的支持。     

A DETAILED CHEMICAL ANALYSIS OF CHANGES TO BITUMEN PRODUCED BY THE IN SITU COMBUSTION PROCESS AT THE OXYGEN WOLF LAKE PROJECT,ALBERTA PART 2: DISTILLATION CUTS AND CHROMATOGRAPHIC FRACTIONS

ABSTRACT

The detailed chemical changes in bitumen brought about over a one year period by an in situ combustion process in an oil sands reservoir have been investigated. The analytical data for the distillation cuts and chromatographic fractions from a core sample and a number of produced oil samples revealed significant changes as a result of the recovery process, particularly for the naphtha and middle distillate cuts. The residue cut did not exhibit any increase in heteroatom or asphaltene content. None of the changes to the produced oil samples would be expected to negatively impact on the subsequent upgrading process. The relationship between the observed changes to the fractionated oil samples and the dynamics of the in situ combustion process are discussed.     

A DETAILED CHEMICAL ANALYSIS OF CHANGES TO BITUMEN PRODUCED BY THE IN SITU COMBUSTION PROCESS AT THE OXYGEN WOLF LAKE PROJECT, ALBERTA PART 2: DISTILLATION CUTS AND CHROMATOGRAPHIC FRACTIONS

The detailed chemical changes in bitumen brought about over a one year period by an in situ combustion process in an oil sands reservoir have been investigated. The analytical data for the distillation cuts and chromatographic fractions from a core sample and a number of produced oil samples revealed significant changes as a result of the recovery process, particularly for the naphtha and middle distillate cuts. The residue cut did not exhibit any increase in heteroatom or asphaltene content. None of the changes to the produced oil samples would be expected to negatively impact on the subsequent upgrading process. The relationship between the observed changes to the fractionated oil samples and the dynamics of the in situ combustion process are discussed.