AIR OXIDATION OF EASTERN OIL SHALES OF KENTUCKY. II. THE EFFECTS OF AMBIENT AUTOXIDATION

ABSTRACT

Ambient air oxidation leads to lower Fischer assay oil yields and often lower process yields from retorting of eastern oil shales. Slight changes in the kerogen and mineral matter of the oil shale and in its pyrolysis products, both liquid and gaseous, were evident following autoxidation. Experimental observations suggest that the hydrogen deficiency of eastern kerogen, as compared to western kerogen, makes its synfuel potential (by Fischer assay) a more sensitive function of the degree of oxidation.

A better yield of oil from oxidized eastern oil shale could be obtained by dissolving away sulfates and other water soluble oxidized materials prior to retorting. The air oxidation of pyrite was demonstrated by SEH, and addition of iron(II) sulfate was shown to reduce assay oil yields. Such observations suggest that combusted shale may not always be a suitable heat transfer agent for atmospheric pressure retorting applications.     

AIR OXIDATION OF EASTERN OIL SHALES OF KENTUCKY. I. OXYGEN UPTAKE

The Devonian oil shale of Kentucky (Cleveland Member of the Ohio Shale) proves to be more susceptible to air oxidation than a high sulfur coal such as Western Kentucky No. 9, and much more susceptible than the Eocene Green River Formation shale of Colorado. The Mississippian oil shale (Sunbury Shale) is also readily air oxidized. Oxygen uptake per 100-grams organic carbon content over 10 hours at 30*C taken from plots of oxygen uptake vs. time is as follows: Ohio Shale, 650 cc; Sunbury Shale, 200 cc; Green River Formation shale, 50 cc; Ky No. 9 coal, 40 cc.

Special care in protecting samples from autoxidaion is required if good assays and analyses are to be obtained. The aging chacacteristics of eastern oil shales could potentially affect mining, transportation, crushing, screening, and stockpiling of feedstocks, particularly fines, for a commercial oil shale operation in Kentucky.     

AIR OXIDATION OF EASTERN OIL SHALES OF KENTUCKY. I. OXYGEN UPTAKE

ABSTRACT

The Devonian oil shale of Kentucky (Cleveland Member of the Ohio Shale) proves to be more susceptible to air oxidation than a high sulfur coal such as Western Kentucky No. 9, and much more susceptible than the Eocene Green River Formation shale of Colorado. The Mississippian oil shale (Sunbury Shale) is also readily air oxidized. Oxygen uptake per 100-grams organic carbon content over 10 hours at 30?C taken from plots of oxygen uptake vs. time is as follows: Ohio Shale, 650 cc; Sunbury Shale, 200 cc; Green River Formation shale, 50 cc; Ky No. 9 coal, 40 cc.

Special care in protecting samples from autoxidaion is required if good assays and analyses are to be obtained. The aging chacacteristics of eastern oil shales could potentially affect mining, transportation, crushing, screening, and stockpiling of feedstocks, particularly fines, for a commercial oil shale operation in Kentucky.     

COMPARISON OF OILS PRODUCED FROM KENTUCKY OIL SHALES BY FLUID BED AND FISCHER ASSAY RETORTING

ABSTRACT

Physical properties and chemical composition of oils produced from a master sample of the Ohio Shale by bench scale fluid bed and Fischer Assay retorting are compared. The fluid bed oil was found to have a higher nitrogen content, lower H/C ratio, more heteroaromatic and heavy hydrocarbons, higher alkene/alkane ratios, a higher naphthalene/(C₁₁ + C₁₂) ratio and a higher aromatic carbon content than the Fischer Assay oil. Since vapor phase cracking is the major source of oil loss during fluid bed retorting with coking being near zero, these results are in agreement with correlations developed for western U.S. shales. Additionally, there is evidence to suggest that under fluid bed conditions, raw shale aromatic carbon is converted to oil.     

润滑油基础油中含氮化合物对其氧化安定性的影响

将用四氯化钛和二氧化铜两步络合法得到的含氮化合物，即碱性含氮化合物和非碱性含氮化合物的浓缩物，分别以不同浓度回反入１５０ＳＮ、５００ＳＮ、１５０ＺＮ和６００ＺＮ四种润滑油基础油中，考察其对基础油氧化安定性的影响。     

极压添加剂和抗氧添加剂对菜籽油生物降解性能影响的研究

以精制菜籽油为基础油,考察了几种硫化脂肪添加剂和磷系添加剂P120的加入对其生物降解性能的影响。试验结果表明：菜籽油中加入添加剂后会对其生物降解性能产生影响。添加剂的种类不同,对菜籽油的生物降解性能的影响也不相同。在所添加的几种添加剂中,添加剂的加入都不同程度降地低了菜籽油的生物降解性能,但对菜籽油的生物降解率影响不大。极压添加剂和抗氧剂配伍对菜籽油生物降解性能有一定的影响,二者对菜籽油的生物降解性能影响没有加和性。     

提高基础油氧化安定性的补充精制工艺

大庆高粘度和专用基础油通过深度脱氮以满足新氧化安定性标准，但该过程仍缺乏有效的补充精制工艺。对比白土精制工络合脱氮，临氢降凝－加氢精制三种方法后，推荐改造白土精制为络合脱氮的方法。     

汽油清净剂对汽油氧化安定性的影响

 考察了汽油清净剂对汽油氧化安定性的影响。方差分析表明，加剂汽油洗后胶质和洗前胶质主要影响因素均为汽油清净剂，其次为汽油；而加剂汽油诱导期主要影响因素为汽油，汽油清净剂影响较小。加剂汽油诱导期与空白汽油诱导期之间呈线性关系。随着加剂浓度的增加，胶质和诱导期均呈线性关系变化。清净剂加入汽油中，洗前胶质显著增加，为8.3~39.7 mg/100 mL，为空白汽油的2.5~42倍；洗后胶质普遍下降，下降率为15.0%~83.3%；诱导期变化幅度为-9.0%~14.0%。在选用清净剂时，通常选用对诱导期影响小，洗后胶质下降率大的清净剂。     

提高变压器油氧化安定性方法研究

在实验室中比较了络合萃取－白土法、络合－白土法对我国新疆克拉玛仪石化厂（以下简称克石化）生产的变压器油氧化安；定性的改善情况，并将以上两种精制油与法国进口成品变压器油的部分性质进行了比较，讨论和研究。结果表明：两种方法均可使克石化的变压器油的氧化安定性满足出口标准。     

用红外光谱分析车用油的氧化情况

以红外光谱为分析手段，分析由不同配方的复合添加剂调合油在高温下不同时间的氧化性能。我们把新油与旧油进行差谱，根据各种氧化产物在不同谱带产生的峰，来判定初始氧化产物、中间氧化产物和后期氧化产物。然后通过对油品的初始氧化情况、氧化深度以及后期氧化情况的分析，来判断油品在使用过程中的氧化程度。通过对添加剂在油品使用过程中的降解情况的分析，来了解添加剂在油品使用过程中各阶段所起的作用。这对我们了解油品的氧化情况，配方的筛选都有很大的帮助。     

渤海 Ｋ油田空气驱对原油低温氧化影响研究

以渤海K油田为研究对象,利用氧化实验仪,模拟油藏温度(110℃)和压力(24MPa),系统研究了不 同氧含量(3%~12%)减氧空气对该油田原油的氧化可行性;并利用气相及液相色谱仪检测减氧空气及原油氧化 前、后组份构成与含量。实验结果表明,实验前、后原油和减氧空气组份含量明显不同,如原油中较高烃组成(≥ C14)含量下降、较低烃组成(C8~C10)含量增加;减氧空气中氧含量下降、二氧化碳有定量(<0.6%)增加;说明K油田原油在油藏温度压力下可与减氧空气发生低温氧化反应。反应过程中,原油以氧化降解为主,完全氧化生成 二氧化碳为辅;该氧化反应进行程度随减氧空气中含氧量增加而增大,表现为对应氧耗量增大、原油被氧化的“临 界碳数”下降(由 C22下降至 C14)、二氧化碳含量由 0.075%增加至 0.6%。实验减氧空气与K油田原油氧化 120 h后残余氧含量均低于 10%,表明渤海Ｋ油田实施减氧空气驱具有良好的安全可行性。     

ORGANIC GEOCHEMISTRY OF THE GÖYNÜK AND SEYITOMER OIL SHALES OF TURKEY

The GCöynük and Seyitomer oil shales overlie coal seams. An investigation of their geochemistry by solid-state and high-resolution nuclear magnetic resonance, infra-red spectroscopy and gas chromatography/mass spectrometry of the extracted bitumen suggests a classification as immature Type I kerogens. However. the n-alkane distribution is consistent with a substantial input from terrestrial plants .     

THE INTERACTIONS OF THIOLS WITH OLEFINS AND THEIR EFFECTS ON AUTOXIDATION DURING JFTOT TESTING

ABSTRACT

Previous research has shown that low concentrations of thiols will act as radical traps to inhibit autoxidation. When added to a fuel, thiols accelerated the rate of oxygen reaction without a commensurate increase in peroxidation. Evidence for the oxidative addition of thiols to olefins has been found to occur by studying the addition of thiophenol to indene in a model fuel during stressing in the JFTOT apparatus. Two different thiol-indene adducts were found in the effluent, with the product distribution being temperature dependent. This process could account, in part, for the differences in thiol influences on autoxidation observed in model systems and in fuels.     

三种润滑油后精制工艺对油品质量的影响

分析了大庆石化公司炼油厂三种润滑油后精制工艺 (即白土补充精制、WSQ 2脱氮 -白土组合精制及加氢补充精制 )的特点及对润滑油基础油质量的影响 ,结果表明 ,WSQ 2脱氮 -白土组合精制工艺适合在润滑油生产中推广、使用。     

EFFECT OF OXIDATION ON THE RATE OF AGGLOMERATION OF COAL WITH OIL

A promising method for cleaning coal involves suspending the finely ground material in water and selectively agglomerating the more hydrophobic and oleophilic components with oil or a hydrocarbon such as heptane. In order to study the effect of coal surface properties and other parameters on the rate of agglomeration, a number of agglomeration tests were conducted in which a batch of coal was agglomerated with either heptane or hexadecane, and the rate of change in the turbidity of the suspension was determined. Two types of bituminous coal were utilized, and the surface properties of each type were varied by exposing the ground materials to air at 150^°C for periods ranging from a few hours to 84 hr. Measurements made by means of FT-IR photoacoustic spectroscopy showed that the concentration of oxygen functional groups increased with increasing oxidation time. Furthermore, the apparent rate of agglomeration of either type of coal decreased with increasing oxidation time. Therefore, the rate of agglomeration depended on both the rank of the coal and the extent of oxidation of the coal. The rate was also found to depend on the type of agglomerant and its dosage. While the rate tended to increase in direct proportion to agglomerant dosage, the rate of increase with respect to the dosage fell as the coal became more heavily oxidized.     

EFFECT OF OXIDATION ON THE RATE OF AGGLOMERATION OF COAL WITH OIL

ABSTRACT

A promising method for cleaning coal involves suspending the finely ground material in water and selectively agglomerating the more hydrophobic and oleophilic components with oil or a hydrocarbon such as heptane. In order to study the effect of coal surface properties and other parameters on the rate of agglomeration, a number of agglomeration tests were conducted in which a batch of coal was agglomerated with either heptane or hexadecane, and the rate of change in the turbidity of the suspension was determined. Two types of bituminous coal were utilized, and the surface properties of each type were varied by exposing the ground materials to air at 150^°C for periods ranging from a few hours to 84 hr. Measurements made by means of FT-IR photoacoustic spectroscopy showed that the concentration of oxygen functional groups increased with increasing oxidation time. Furthermore, the apparent rate of agglomeration of either type of coal decreased with increasing oxidation time. Therefore, the rate of agglomeration depended on both the rank of the coal and the extent of oxidation of the coal. The rate was also found to depend on the type of agglomerant and its dosage. While the rate tended to increase in direct proportion to agglomerant dosage, the rate of increase with respect to the dosage fell as the coal became more heavily oxidized.     

THE INTERACTIONS OF THIOLS WITH OLEFINS AND THEIR EFFECTS ON AUTOXIDATION DURING JFTOT TESTING

Previous research has shown that low concentrations of thiols will act as radical traps to inhibit autoxidation. When added to a fuel, thiols accelerated the rate of oxygen reaction without a commensurate increase in peroxidation. Evidence for the oxidative addition of thiols to olefins has been found to occur by studying the addition of thiophenol to indene in a model fuel during stressing in the JFTOT apparatus. Two different thiol-indene adducts were found in the effluent, with the product distribution being temperature dependent. This process could account, in part, for the differences in thiol influences on autoxidation observed in model systems and in fuels.     

改性大豆油配方的氧化安定性研究

选用碱炼大豆油和三种基因改性大豆油作为基础油,采用加压差示扫描量热（PDSC）和旋转氧弹（RBOT）试验考察了四种改性大豆油中的起始氧化温度、不同添加剂配方对改性大豆基础油氧化安定性的影响以及基础油和降凝剂对改性大豆油低温流动性能的影响。结果表明,改性大豆油的不饱和脂肪酸含量越高,其氧化安定性越差;抗氧剂二戊基二硫代氨基甲酸锌和抗磨剂二烷基二硫代氨基甲酸锑在改性大豆油中均表现出了良好的抗氧协同性能,尤其在基因改性大豆油中,聚-α-烯烃和添加剂的复配使其起始氧化温度和氧化诱导时间均超过了相同配方的聚-α-烯烃油样。倾点试验结果表明,聚-α-烯烃和降凝剂的加入还可以明显提高改性大豆油的低温流动性能。     

GEOLOGICAL SYNTHESIS OF THE ORINOCO OIL BELT, EASTERN VENEZUELA

The Orinoco Oil Belt, considered to be the largest hydrocarbon accumulation in the world, is located on the southern border of the Eastern Venezuela basin. The stratigraphic column of the area includes rocks of Pre-Cambrian to Recent ages, but more than 90% of the crude oils are found in Miocene sediments.
Three transgressive-regressive cycles with wide regional distributions are recognised in the Tertiary system: Cycle 1 includes the La Pascua, Roblecito and Chaguaramas formations of Oligocene age; and Cycles 2 and 3 include the Officina, Upper Chaguaramas and Freites formations of Miocene age. Within the cycles, five lithostratigraphic units are defined, and a sedimento logical model for Units I and III is consequently established, recognizing north-orientated, wave and tide-influenced, prograding deltas.
Tensional tectonics characterize the area as having two structural provinces, separated by the Hato Viejo fault system: the Eastern Province, characterized by a transgressive sequence overlying the Pre-Cambrian basement; and the Western Province, where the Tertiary unconformably overlies Cretaceous and Paleozoic sediments. Hydrocarbon accumulations in the Orinoco Oil Belt predominantly occur in stratigraphic traps, but are controlled by regional structures.
Four types of crude oils are identified, with density values between 8.5 and 13° API. The volume of oil in-place in the Orinoco Oil Belt totals 187,897 MM † cu. m(1,181 B brl). The largest accumulations are found in the sands of Unit I .     

硫化物及氮化物在润滑油氧化进程中的作用

采用旋转氧弹法考察了硫化物在润滑油氧化进程中的作用，发现硫化物的加入不仅改变了润滑油的氧化安定性，而且改变了润滑油的氧化类型，证实了硫化物分解过氧化物的作用。采用顺磁共振（ＥＳＲ）法分析了不同氧化浓度时，高氮油及低氮油的氧化自由基浓度的变化，从而发现了氮化物促进自由基形成扩抗氧剂消耗的作用。