PHOTOCHEMICAL AND CHEMICAL TRANSFORMATION OF Calotropis procera LATEX TOWARDS OBTAINING VALUE ADDED CHEMICALS AND FUELS

ABSTRACT

Photothermal degradation of the latex obtained from Calotropis procera showed enhanced extraction in heptane up to 50%. Treatment of the latex with different concentrations of NaOH resulted in the reduction in heptane extraction of the latex. Treatment of latex with aqueous HC1 coagulated it and thus resulted in an increase in extraction yield. The ¹HNMR, ^l3CNMR and FTTR spectral analyses of treated latex showed an increase in the olefinic and carbonyl groups in the latex. Thus, this showed that photothermal treatments rendered the latex more amenable to hydrocracking for obtaining value added chemicals and fuels from the latex.     

HYDROZEN TRANSFER HYDROCRAKING OF C.PROCERA UNDER AMBIENT PRESSURE CONDITIONS TO GET VALUE ADDED CHEMICALS AND FUELS

Biomass is renewable source of energy while the reserves of petroleum arc being depleted. The latex of a potential petrocrop, Colotropis procera, a lalicifcr, arid-plant which is rich in hydrocarbon type triterpene compounds etc. was found lo be a better feed slock for thermal hydrocracking as compared to whole plant biomass inlcrms of liquid product yield. Studies of chemical reaction dynamics of the thermal cracking of latex at 200-400°C showed that the process should be termed as hydrogen-tranfer (H-T) hydrocracking of latex under ambient pressure conditions. The hydrogen rich cracked trilcrpenoids act as the H-donors in this process, where nascent hydrogen atoms and free radicals chemically plug the cracked moities to stabilise these. Latex was also coagulated and the H-T hydrocracking of the feedstock coagulum gave a higher yield of cracked oil in comparision lo that from the dried latex. A model triterpene compound, ursolic acid has been subjected to H-T hydrocracking to understand the process of hydrocracking of latex under similar conditions and it was found that triterpencs on H-T hydrocracking produced only liquid and gaseous products and no solid char. The temperature for hydrocracking of latex has been optimized to 350°C and molecular sieve was round to catalyse the H-T Hytrocraking process to yield more liquid product The distillation range of cracked latex on(CLO)Obtained from H.T Hytrocracking of C procera Latex indicated that it can be used as fuel. Moreover CLO resembled diesel fuels and was predominantly paraffinic in nature as characterised by NMR and FTIR spectral analysis. A process has been recommended for gelling value added fuels and chemicals from C. procera latex.     

HYDROZEN TRANSFER HYDROCRAKING OF C.PROCERA UNDER AMBIENT PRESSURE CONDITIONS TO GET VALUE ADDED CHEMICALS AND FUELS

ABSTRACT

Biomass is renewable source of energy while the reserves of petroleum arc being depleted. The latex of a potential petrocrop, Colotropis procera, a lalicifcr, arid-plant which is rich in hydrocarbon type triterpene compounds etc. was found lo be a better feed slock for thermal hydrocracking as compared to whole plant biomass inlcrms of liquid product yield. Studies of chemical reaction dynamics of the thermal cracking of latex at 200-400°C showed that the process should be termed as hydrogen-tranfer (H-T) hydrocracking of latex under ambient pressure conditions. The hydrogen rich cracked trilcrpenoids act as the H-donors in this process, where nascent hydrogen atoms and free radicals chemically plug the cracked moities to stabilise these. Latex was also coagulated and the H-T hydrocracking of the feedstock coagulum gave a higher yield of cracked oil in comparision lo that from the dried latex. A model triterpene compound, ursolic acid has been subjected to H-T hydrocracking to understand the process of hydrocracking of latex under similar conditions and it was found that triterpencs on H-T hydrocracking produced only liquid and gaseous products and no solid char. The temperature for hydrocracking of latex has been optimized to 350°C and molecular sieve was round to catalyse the H-T Hytrocraking process to yield more liquid product The distillation range of cracked latex on(CLO)Obtained from H.T Hytrocracking of C procera Latex indicated that it can be used as fuel. Moreover CLO resembled diesel fuels and was predominantly paraffinic in nature as characterised by NMR and FTIR spectral analysis. A process has been recommended for gelling value added fuels and chemicals from C. procera latex.     

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.     

基于价值工程的生物乙醇基醇醚燃料制备及分离纯化研究

根据高清洁汽油的发展趋势及其要求,结合中国汽油池催化裂化汽油高达70%以上的特点,在生物基醇醚燃料制备价值工程研究的基础上,提出了通过多重耦合制备醇醚燃料来破解汽油升级与乙醇汽油困局的发展思路,分别针对叔烷基（醇）醚及ETBE制备提出了复合精馏-萃取和精馏-萃取耦合分离纯化新工艺,并以ETBE为例进行了过程模拟与实验研究,分别可降低醇醚分离能耗约25%及33%以上,尤其是以ETBE/乙醇的耦合分离纯化技术为杠杆,来联产制备ETBE和脱水乙醇,甚至还可包括联合制备TAEE/THEE,可对醇醚燃料发展及炼油、汽油池价值提升产生积极的杠杆效应。     

危险化学品生产、储运和废弃中安全问题及对策

为加大对危险化学品的安全管理力度,国家安全生产监督管理局专门设立危险化学品安全监督管理司,综合监督管理危险化学品安全工作。我国对危险化学品的管理,已逐步建立了从法律、法规、条例到国家标准的多层次管理体系。2002年3月15日颁布实施的《危险化学品安全管理条例》提出了对危险化学品从生产、储存、经营、运输、使用到废弃的全过程监督管理体系。分别从这六个环节分析危险化学品的安全现状,指出问题的严重性,并提出了相关的解决对策,希望可以为解决危险化学品的安全问题作出贡献。     

硫磷硅毒物共存对甲醇催化剂失活的影响

本文采用电子能谱仅、x光衍射仪、BET吸附仅、原子吸收光语仪等分析仪器,对硫、磷、硅共存时对甲醇催化剂中毒失活情况进行研究和剖析。结果表明：硫、磷、硅共存时甲醇催化剂的中毒与硫或硫氯存在时甲醇催化剂的中毒明显不同,毒物完全破坏了催化剂原有的表面结构。     

OIL FAMILY TYPING,BIODEGRADATION AND SOURCE ROCK AFFINITY OF LIQUID PETROLEUM IN THE DANISH NORTH SEA

Variations in liquid petroleum compositions in the Danish Central Graben and Siri Fairway, North Sea, demonstrate the presence of several active source rock facies. To address this issue in detail, a total of 213 samples of liquid petroleum from the Danish Central Graben and the Siri Fairway were typed to eight main oil families and three sub‐families based on characteristic geochemical properties and principal component analysis (PCA). Comparison with source rock extract data made it possible to suggest correlative source rocks for each oil family together with the source rock depositional environments. The main oil families are: 1(B), 2(B), 3a(B), 3b(B), 4(B‐D/E), 5(D/E‐B), 6(D/E‐F) and 7(A), where the capital letters in brackets refer to the organofacies types of Pepper and Corvi (1995), thus directly linking the oil family type to the source rock facies. Oil families 1(B), 2(B), 3a(B) and 3b(B) were charged from marine shales (principally the Upper Jurassic Farsund Formation); oil families 4(B‐D/E) and 5(D/E‐B) are mixed petroleums with both terrigenous and marine components; oil family 6(D/E‐F) was charged from Middle Jurassic coaly units; whereas oil family 7(A) was charged from a carbonate source (Zechstein dolomites). Family 7(A) has only been documented in the form of oil stains. The most widespread oil family is 3a(B), sourced from Upper Jurassic marine shales. Charging from different organofacies is indicated by oil family 3b(B), which was derived from parts of the same shale succession which were more terrigenous‐influenced and possibly slightly more oxic; and families 2(B) and 1(B), which were sourced from more organic‐rich, anoxic parts of the shales. Mildly biodegraded oils (Level 1 to 2) appear mainly to occur in the central to southern parts of the Danish Central Graben.     

渤海湾盆地济阳坳陷气源岩和原油生物模拟实验研究

通过细菌检测实验,系统分析了渤海湾盆地济阳坳陷生物气源岩中细菌的赋存状况。实验表明,济阳坳陷浅层气源岩中产甲烷菌较为丰富,在2522m深处还有产甲烷菌存在,并且产甲烷菌赋存的源岩与源岩时代无相关关系,只要有适合生物气形成的环境条件,生化作用就可能发生。通过气源岩和原油在不同温度下的生物模拟实验,分析了济阳坳陷生物模拟气产率、组分及碳氢同位素特征,结果表明,无论是气源岩还是原油厌氧降解生成的生物气,都只生成甲烷和二氧化碳;45℃和65℃是生物气生成的高峰期,生物气产率分布范围为每吨TOC产气20~160m³和每吨原油产气10~15m³;生物模拟实验产物的碳同位素值随温度变化差异明显,变化范围为-80.2‰~-41.5‰;生成的二氧化碳的碳同位素值变化与甲烷碳同位素值变化规律相反;生物模拟气中氢同位素的值则比实际生物气的氢同位素值轻,模拟气中氢同位素值主要分布在-300‰~-350‰,而实际生物气的氢同位素值则分布于-240‰~-270‰。     

COMPOSITION OF DIAMONDOIDS IN OIL SAMPLES FROM THE ALPINE FORELAND BASIN,AUSTRIA: POTENTIAL AS INDICES OF SOURCE ROCK FACIES,MATURITY AND BIODEGRADATION

Twenty‐seven oil samples from Cretaceous, Eocene and Rupelian reservoir rocks in the Alpine Foreland Basin (Austria) were analysed to evaluate the composition of diamondoid hydrocarbons using gas chromatography – triple quadrupole mass spectrometry. The oils were generated from marly and shaly Oligocene source rocks buried beneath the nappes of the Alpine foldbelt to the south of the study area. Diamondoid hydrocarbons were detected in the saturated fraction of all the analysed oils. A biodegraded oil sample from a shallow reservoir in the NE part of the study area showed an enrichment in diamondoids due to the molecule's high resistance to microbial degradation. Variations in the organic matter type of the source rock facies and differences in maturity are known to influence the composition of diamondoids. However in this study, biomarker‐derived maturity parameters do not show a convincing correlation with diamondoid maturity parameters. Moreover, no cracking trend based on biomarkers and diamondoid concentrations was observed. The results indicate that the composition of diamondoids in oils from the Austrian part of the Alpine Foreland Basin is mainly controlled by heterogeneities in the Lower Oligocene source rocks, including the occurrence of a redeposited source rock succession in the western part of the study area. By contrast, EAI‐1 (the ethyladamantane index) shows a good correlation with various maturity parameters and seems to be independent of source rock facies.     

ELECTRON TRANSFER MECHANISMS IN OXIDATIVE SEDIMENT FORMATION IN FUELS. II. AN ELECTROCHEMICAL INVESTIGATION OF THE COUPLING BETWEEN PERINAPHTHENE AND INDOLE.

Cyclic voltammetry and electrolyses in acetonitrile and toluene have indicated the formation of coupling products between perinaphthene and indole similar to those found in the oxidized sediments of fuels. The formation of these coupling products involves intermediates which are one electron oxidized species. This paper discusses the possible mechanisms by which these products are formed.| Photochemical experiments were performed by irradiating the pyrex electrochemical cell with a 300 W tungsten lamp.     

NUCLEAR MAGNETIC RESONANCE STUDIES OF ASPHALTENES AND COALS. A NEW APPROACH TO OBTAINING ASPHALTENE STRUCTURAL PARAMETERS WITH DIPOLAR DEPHASING

ABSTRACT

Apparent carbon aromaticities, fa, of some asphaltenes have been measured by n.m.r. in solution and compared with those obtained by the CP/MAS technique on solid samples. The aromaticities were also measured for several Alberta plains coals. From the 1H solution spectra and 13C solid nmr spectra of asphaltenes, some of their skeletal features, not obtainable from solution spectra only, have been suggested.     

INTEGRATION OF BIODEGRADATION AND MIGRATION OF HYDROCARBONS IN A 2D PETROLEUM SYSTEMS MODEL: APPLICATION TO THE POTIGUAR BASIN,NE BRAZIL

Biodegradation is probably the most important in‐reservoir alteration process and is responsible for the majority of the known heavy oil accumulations. In the present study, biodegradation processes were integrated within a forward basin and petroleum systems model applied to the Potiguar Basin, NE Brazil. This basin was chosen because it has been studied in detail and data from previous investigations are publically available. In order to account for processes occurring during the biodegradation of hydrocarbons, the evolution of fluid properties was simulated through time. In the model, a new approach was developed in order to determine the intensity of microbial activity and the evolution of the oil‐water contact, the zone within which biodegradation is confined. The numerical results obtained by applying the forward simulator to a 2D model of the Potiguar Basin fit the observed data concerning the composition and quality of the oil in a series of oilfields. These accumulations are located along the NE‐SW oriented “Carnaubais trend” and show progressive biodegradation along the migration path from the offshore kitchen area. Our results show that the biodegradation trend observed along the cross‐section can in general be explained by the fact that reservoirs are successively filled as a result of spilling from previous reservoirs, with continuous hydrocarbon degradation occurring within the reservoirs. This charge history resulted in differences in the composition of oils transported from upstream to downstream reservoirs, and in the evolution over time of the ratio between biodegradation and reservoir filling rates. Thus, in addition to residence time in the biodegradation temperature window, the rate of reservoir infill, the rate of oil degradation and the migration pathways are key factors controlling biodegradation. This study also demonstrates how the approach developed within our petroleum system simulator, which integrates both migration and biodegradation, may improve the assessment of oil quantity, quality and migration timing.     

NUCLEAR MAGNETIC RESONANCE STUDIES OF ASPHALTENES AND COALS. A NEW APPROACH TO OBTAINING ASPHALTENE STRUCTURAL PARAMETERS WITH DIPOLAR DEPHASING

Apparent carbon aromaticities, fa, of some asphaltenes have been measured by n.m.r. in solution and compared with those obtained by the CP/MAS technique on solid samples. The aromaticities were also measured for several Alberta plains coals. From the 1H solution spectra and 13C solid nmr spectra of asphaltenes, some of their skeletal features, not obtainable from solution spectra only, have been suggested.     

X-RAY DIFFRACTION USED TO MEASURE LEVELS OF SP2 AND SP3 CARBON IN FOSSIL FUELS: A MICROCOSM OF THE 1990'S,WORKING HARDER AND GETTING LESS

ABSTRACT

The proposition that a diffraction peak can be “far too intense to be caused by amorphous scattering and far too broad to be caused by conventional diffraction” is analyzed and found to be in error. Theoretically, Debye peaks arising from intermolecular interference in liquids and conventional Bragg peaks are part of a continuum. Experimentally, with respect to the “(002)” peak in benzenoid materials, not all aromatic carbons need contribute to an intermolecular interference peak, so that determinations of sp² or sp³ carbon abundance based on analysis of only the “(002)” peak are necessarily flawed. As a separate but related matter, journal citation trends of relevance to the court case Gordon and Breach v. AIP are analyzed     

X-RAY DIFFRACTION USED TO MEASURE LEVELS OF SP2 AND SP3 CARBON IN FOSSIL FUELS: A MICROCOSM OF THE 1990'S, WORKING HARDER AND GETTING LESS

The proposition that a diffraction peak can be “far too intense to be caused by amorphous scattering and far too broad to be caused by conventional diffraction” is analyzed and found to be in error. Theoretically, Debye peaks arising from intermolecular interference in liquids and conventional Bragg peaks are part of a continuum. Experimentally, with respect to the “(002)” peak in benzenoid materials, not all aromatic carbons need contribute to an intermolecular interference peak, so that determinations of sp² or sp³ carbon abundance based on analysis of only the “(002)” peak are necessarily flawed. As a separate but related matter, journal citation trends of relevance to the court case Gordon and Breach v. AIP are analyzed     

Weng 旋回与Poisson 、Gamma 分布的对比与分析

通过对Weng 旋回与Poisson、Gamma(亦记为Γ)分布模型的对比和分析表明, Weng旋回模型原式的自变量为特定的时间变量, 即其时间为实际发生时间的1/B.故模型原式在自变量从0~+∞积分, 其结果并非是真正的可采储量, 而是对应于特定时间的积分值, 这一数值等于可采储量的1/B;Weng 氏模型原式与Poisson分布尽管具有相似的表现形式,但却是两个完全不同的模型, 因为二者的自变量不具有同一数学意义;Weng旋回模型的本质符合连续型Gamma 随机分布的数学原理,以往对模型参数n规定取正整数的假设是不妥和多余的。在上述研究的基础上, 给出了Weng旋回模型的简明式和结构式, 使其上升到了一定的理论高度, 更加具有实际意义和Weng 氏特色, 同时给应用者带来了方便。     

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.     

克拉玛依油田六—七区石炭系测井研究与增产潜力

本文利用测井资料对克拉玛依油田六—七区石炭系储集层的构造、岩性、裂缝、物性参数和油层标准研究后,作出判别凝灰岩、安山岩、安山岩—火山角砾岩、蚀变火山角砾岩—安山岩、砂砾岩的△GR—△NR和△t—△NR图版;利用26口井数字处理结果作出油层孔隙度图和油层厚度图,结合构造图和初产量成果图总结出该区的油气分布与不整合面深度的密切关系。二次解释结果各井油层共1783.9m,发现其中未射开的油层有1230m,为增产提供了依据。     

SUPPRESSION AND RETARDATION OF VITRINITE REFLECTANCE, PART 1. FORMATION AND SIGNIFICANCE FOR HYDROCARBON GENERATION

Vitrinite consists of a number of macerals with varying morphology and reflectance. Although vitrinite reflectance (VR) generally increases with increasing depth of burial, a spread of values often occurs due to the presence of the different macerals. However, reports of suppressed and/or retarded VR values introduce a potential problem for the geologist attempting to assess the thermal maturity of a sedimentary basin. Suppression is defined as the reduction in reflectance resulting from:

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