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.     

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

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. 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.     

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.     

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。     

催化裂化柴油空气氧化脱硫工艺研究

实验以空气作氧化剂,甲酸作催化剂,甲醇作萃取剂,以催化氧化反应与溶剂萃取相结合法,对催化裂化柴油进行氧化萃取脱硫。经单因素实验考察了催化剂用量、催化氧化温度、时间、空气压力及萃取剂的用量等对催化裂化柴油硫含量的影响。适宜的脱硫条件为:反应温度80℃,反应时间60 min,空气压力0.6 MPa,催化剂用量10%(与柴油的体积比)。经催化氧化,柴油硫含量可由1 694.2μg/g降至347.3μg/g,脱硫率达79.5%。     

氧气直接催化氧化苯酚合成对苯醌

以乙醇为溶剂,铜锂复合金属离子为催化剂,用氧气直接催化氧化苯酚合成对苯醌。考察了催化剂配比、催化剂与苯酚质量比、反应压力、反应温度和反应时间对苯酚催化氧化反应的影响。确定了苯酚催化氧化制备对苯醌的最优工艺条件为:n(Cu~(2+)):n(Li~+)=1:3,m(催化剂):m(苯酚)=1:2,温度80℃,压力2.7 MPa,反应时间3 h。在此反应条件下,苯酚转化率达85.50%,对苯醌选择性可达83.15%。     

油页岩干酪根热降解的动力学性质及其地球化学意义

页岩油生产过程中的动力学研究,已有半个多世纪的历史了。近几年来,随着干酪根成油学说的发展,为了揭示成烃机理,关于油页岩和生油岩干酪根热降解反应动力学的研究,引起了许多石油地球化学工作者的极大兴趣。     

PETROGRAPHY AND GEOCHEMISTRY OF SOME JORDANIAN OIL SHALES FROM NORTH JORDAN

Twenty-two "oil shale" samples from north Jordan have been investigated. They are in fact all bituminous limestones, of ages ranging from Uppermost Cretaceous to Paleocene. Major elements, organic matter and trace elements, were determined, together with aspects of mineralogy and petrography. Although macrofossils are rare, trace fossils were encountered. These rocks are postulated to be normal limestones deposited in an oxygenated shallow marine environment. The H₂S/O₂ interface coincided or lay just below the water/sediment interface. The organic matter is indigenous and not related to migrating oil.     

润滑油基础油中硫,氮化合物的氧化性能研究：Ⅰ.硫,氮化 …

利用红外光谱和色谱－质谱对含硫、氮模型化合物－－甲基苄基硫醚、二苯并噻吩、喹啉和吲哚氧化前后的结构变化进行鉴定。结果表明,在氧化条件下,喹啉单独存在时具有较高生,部分氧化后的产物为酮亚胺,与在白油中喹啉的氧化产物一致;吲哚的氧化活性比喹啉强,除了自身氧化生成酰胺外,极易事反应。从所推测的氧化历程来看,喹啉和嘴哚在烃类化过程中起引发剂的作用,一个喹啉分子可以诱导产生３个烃自由基;而吲哚只能诱导产生２     

OXIDATION OF BITUMEN IN THE PRESENCE OF A CONSTANT CONCENTRATION OF OXYGEN

The rate of oxidation of bitumens oxidised in an approximately constant concentration of oxygen (300 psi air in a pressure vessel) can be accurately described by an equation derived assuming two concurrent simple first order reactions. The equation was successfully fitted to oxidation rate data obtained in terms of viscosity increase of neat bitumen under 300 psi of air at 60°C, 70°C and 80°C, and carbonyl group content in solution (6-15%) at 30°C. Bitumen oxidation can be generalised as consisting of a group of fast reactions obeying approximately first order kinetics, and involving carbonyl and sulphoxide formation and a much slower process involving carbonyl formation which is approximately constant over the experimental time frame. Parameters in the equation can be used as a simple means to compare the durability of bitumens oxidised at temperatures characteristic of field conditions.     

OXIDATION OF BITUMEN IN THE PRESENCE OF A CONSTANT CONCENTRATION OF OXYGEN

The rate of oxidation of bitumens oxidised in an approximately constant concentration of oxygen (300 psi air in a pressure vessel) can be accurately described by an equation derived assuming two concurrent simple first order reactions. The equation was successfully fitted to oxidation rate data obtained in terms of viscosity increase of neat bitumen under 300 psi of air at 60°C, 70°C and 80°C, and carbonyl group content in solution (6-15%) at 30°C. Bitumen oxidation can be generalised as consisting of a group of fast reactions obeying approximately first order kinetics, and involving carbonyl and sulphoxide formation and a much slower process involving carbonyl formation which is approximately constant over the experimental time frame. Parameters in the equation can be used as a simple means to compare the durability of bitumens oxidised at temperatures characteristic of field conditions.     

液相空气氧化法制备氟代苯甲酸工艺研究

从氟代甲苯出发,以醋酸为溶剂,采用液相空气氧化法,在钴锰盐和1,1,2,2-四溴乙烷催化体系存在下,合成了氟代苯甲酸,采用升华方法进行精制。探讨了反应压力、催化剂配比及用量、溶剂比及溶剂浓度对氧化反应的影响,当反应压力为0.8～1.0 MPa、反应温度160～220℃、溶剂比4:1,钴锰催化剂质量比为2:1时,反应转化率接近100％;在真空度98 kPa下升华,总质量收率大于97％。     

OXIDATION OF BITUMEN IN THE PRESENCE OF A CONSTANT CONCENTRATION OF OXYGEN

ABSTRACT

The rate of oxidation of bitumens oxidised in an approximately constant concentration of oxygen (300 psi air in a pressure vessel) can be accurately described by an equation derived assuming two concurrent simple first order reactions. The equation was successfully fitted to oxidation rate data obtained in terms of viscosity increase of neat bitumen under 300 psi of air at 60°C, 70°C and 80°C, and carbonyl group content in solution (6-15%) at 30°C. Bitumen oxidation can be generalised as consisting of a group of fast reactions obeying approximately first order kinetics, and involving carbonyl and sulphoxide formation and a much slower process involving carbonyl formation which is approximately constant over the experimental time frame. Parameters in the equation can be used as a simple means to compare the durability of bitumens oxidised at temperatures characteristic of field conditions.     

OXYGEN AND NITROGEN COMPOUNDS OF ISRAELI SHALE OIL

Abstract

Israeli shale oil was separated into different components, and their composition was studied by means of IR, NMR, and GLC-MS. The yield of the components extracted from the 210-320^°C fraction of the oil was: components soluble in water 0.59, organic acids 0.32, phenols 8.5, and pyridine bases 3.5 wt. %. The phenols content in the total shale oil was found to be 5.4%, that of pyridine bases 3.2%. More than 20 individual compounds were identified in the products of separation, including phenol, methyl phenols, dimethyl phenols, methyl-ethyl phenols, and methyl naphtalenols, 4-propyl pyridine, 2,3,5-trimethyI pyrrol, 2-, and 3-ethyl-3,5-dimelhyi pyrroles, 2-ethyl-4,6-dimethyl pyridine, dimethyl indoles, dimethyl quinolines, uimethyl indoles. Aldehydes, alcohols, ethers Ar-O-R and R-O-R, and esters Ar-COO-R and R-COO-R are not present in the shale oil. NMR spectroscopy resulted in establishing the quantitative distribution of the oil fraction compounds among the principal structures.     

稳定东部的潜力分析

本对我国石油要稳定东部地区的潜力给予了科学分析，并且提出了具体的稳定步骤和措施。     

OXYGEN AND NITROGEN COMPOUNDS OF ISRAELI SHALE OIL

Israeli shale oil was separated into different components, and their composition was studied by means of IR, NMR, and GLC-MS. The yield of the components extracted from the 210-320^°C fraction of the oil was: components soluble in water 0.59, organic acids 0.32, phenols 8.5, and pyridine bases 3.5 wt. %. The phenols content in the total shale oil was found to be 5.4%, that of pyridine bases 3.2%. More than 20 individual compounds were identified in the products of separation, including phenol, methyl phenols, dimethyl phenols, methyl-ethyl phenols, and methyl naphtalenols, 4-propyl pyridine, 2,3,5-trimethyI pyrrol, 2-, and 3-ethyl-3,5-dimelhyi pyrroles, 2-ethyl-4,6-dimethyl pyridine, dimethyl indoles, dimethyl quinolines, uimethyl indoles. Aldehydes, alcohols, ethers Ar-O-R and R-O-R, and esters Ar-COO-R and R-COO-R are not present in the shale oil. NMR spectroscopy resulted in establishing the quantitative distribution of the oil fraction compounds among the principal structures.     

负载钴催化剂催化分子氧氧化环己烷

选用具有不同结构的分子筛Y、Beta、ZSM-5、MOR和MCM-22为载体,采用离子交换法制备了一系列负载Co分子筛催化剂,并采用XRD、UV-vis和元素分析对它们进行了表征。以O2为氧化剂,考察了所制催化剂在液相环己烷氧化反应中的催化性能。结果表明,分子筛载体的性质对所制备的负载Co催化剂在液相环己烷氧化反应中的催化性能有很大影响。在相同反应条件下,所制备的5种负载Co分子筛催化剂中,Co/Y催化环己烷氧化反应的环己醇和环己酮混合物(KA油)的选择性最高。在130℃、1.2MPa O2分压下反应3h,Co/Y催化环己烷氧化反应的转化率为15.9%,KA油的选择性为79.0%。Co/Y催化剂在所考察的反应条件下具有良好的稳定性,经重复使用5次,仍保持良好的催化性能。     

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。     

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。