PARTITIONING OF ALKYLPYRIDINES BETWEEN SHALE-DERIVED MIDDLE DISTILLATE FUEL AND WATER

A nitrogen-rich shale-derived middle distillate fuel was selected for the study of the partitioning of alkyl pyridines with water of pH 5. This particular middle distillate fuel, was found to contain acid extractable compounds composed mainly, about 90%, of alkyl substituted pyridines. The pyridine content of the extracts was determined by combined capillary column GC/HS. The partitioning was observed to be acid dependent.     

NITROGEN COMPOUND DISTRIBUTION AND FUEL INCOMPATIBILITY REACTIONS IN A TAR SAND DERIVED MIDDLE DISTILLATE FUEL

A high paraffin, high nitrogen, low sulfur jet fuel derived from Athabasca tar sands was studied. The organo-nitrogen compounds in the fuel were isolated by mild acid extraction followed by silica-gel adsorption. Three extracts were derived from this fuel: a basic nitrogen compounds extract, BNC, in methylene chloride, a non-basic nitrogen compounds extract, NBNC, in methyl alcohol and an NBNC extract in methylene chloride. The major constituents of each extract were identified and quantitated by combined capillary column GC/MS. Alkyl substituted pyrroles, pyridines, indoles, tetrahydro-quinolines, carbazoles, and quinolines were the prevalent organo-nitrogen compounds present. Incompatibility tests were conducted on this fuel using the oxygen overpressure method with both doped and undoped fuel systems. The dopant of choice was cumene hydroperoxide. Practically no sediment formation was observed for the undoped fuel (0.1 mg/100mL fuel). The doped fuel matrix induced incompatibility behavior in proportion to the quantity of dopant present.     

HYDROPROCESSING OF COAL-DERIVED MIDDLE DISTILLATE

Coal-derived middle distillate, boiling range 437 to 623^°K, was hydrotreated in a fixed bed reactor with a commercial N_iO-M_o0₃/ Al₂O₃ catalyst. The feedstock contained predominantly highly-substituted aromatics. The product heteroatom content and aromaticity decreased with increased process temperature or pressure. Aromaticity was proportional to liquid space velocity. Heteroatonms could be effectively reduced at hydroprocessing conditions of 653^°K, 10 MPa, and 2 WHSV. Experimentally-derived cetane number was found to be proportional to product aromaticity. Severe hydroprocessing conditions were required to produce diesel fuel of acceptable cetane number.     

BASE EXTRACTION TO REMOVE THE COMPONENTS CONTRIBUTING TO LUBRICITY IN A MIDDLE DISTILLATE FUEL

ABSTRACT

With increased environmental demands for cleaner burning fuels, the use of severe hydrotreating has become commonplace in many of the world's refineries. In order to reduce sulfur and aromatic levels, this hydrotreating has brought about the removal of surface-active species that afford a fuel its inherent lubricity. The result is excessive wear of engine component parts that rely of this lubricity. For over 10 years, the American Society for Testing and Materials (ASTM) has been working on establishing methods to adequately assess the lubricating properties of petroleum fuels. The currently accepted methods involve mechanical bench testing. In the present research, a chemical method, base extraction, followed by gc analysis has been investigated. This technique appears promising in correlating with the traditional methods used for assessing lubricity of middle distillate fuels.     

煤直接液化制取喷气燃料原料油的组成分析

以国产煤液化油为原料,通过实沸点蒸馏,切割同喷气燃料馏分范围一致的航空煤油馏分;对切得的航空煤油馏分进行了理化性能、烃类组成分布、碳数分布及部分单体烃含量检测.结果表明,煤液化航空煤油馏分的部分指标不符合喷气燃料规范要求,不能直接用作喷气燃料,但它又具有高密度、高闪点、低冰点等突出优点.煤液化航空煤油馏分含有大量的环烷烃、四氢萘和茚满衍生物以及烷基苯酚类化合物.煤直接液化合成煤油馏分所具有的高密度、高闪点、低冰点以及富含环烷烃和氢化芳烃的特点,使其凸显高性能喷气燃料的特征,因此作为未来开发高性能喷气燃料的原液具有良好的发展前景.     

STUDY OF THE TEMPERATURE AND ENTHALPY OF WAX CRYSTALLIZATION FROM MIDDLE DISTILLATE BY DSC

ABSTRACT

The temperature and enthalpy of the wax crystallization as well as of melting have been studied in the middle distillate (boiling range: 250–375°C) obtained from the indigenous Bombay-High (Off-Shore) crude oil by using a differential scanning calorimeter (DSC). In order to have better understanding of the gel formation processes the broad distillate fraction was fractionated into five narrow fractions of 25°C interval each. From these narrow subfractions the saturates were separated from aromatics by column chromatography, and from saturates the n-paraffins were separated from iso-and cyclo-paraffins by urea adduction, to obtain the n-paraffins concentrates (urea adductables)–-the wax- and the saturated solvent portion–-the UNA. The thermal behaviour of narrow subfractions alongwith their urea adductables and the solvent portions have been studied and the wax appearance temperature (WAT) thus measured has been compared with those obtained by optical microscopy and with the ASTM cloud point, wherever possible. To obtain a clearer picture of the solidification process, further study has been done by preparing synthetic blends of urea adductables in different concentrations in the respective aromatic and iso- and cyclo-paraffinic solvents (UNA) and studying the thermal behaviour of each blend. It is found that the variation in WAT with wax concentration as measured by DSC is identical with that measured by optical microscopy and the ASTM cloud point. However, DSC values are lower than microscopic values and higher than ASTM cloud point. The enthalpy of the blends with the same amount of wax in the aromatic and iso- and cyclo-parffinic solvents indicated that it is higher in the saturated solvent in comparison to aromatic solvent. This confirms the fact that in an aromatic solvent the solubility of the wax is greater, and hence a comparatively lower WAT. The results are further discussed.     

STUDY OF THE TEMPERATURE AND ENTHALPY OF WAX CRYSTALLIZATION FROM MIDDLE DISTILLATE BY DSC

The temperature and enthalpy of the wax crystallization as well as of melting have been studied in the middle distillate (boiling range: 250-375°C) obtained from the indigenous Bombay-High (Off-Shore) crude oil by using a differential scanning calorimeter (DSC). In order to have better understanding of the gel formation processes the broad distillate fraction was fractionated into five narrow fractions of 25°C interval each. From these narrow subfractions the saturates were separated from aromatics by column chromatography, and from saturates the n-paraffins were separated from iso-and cyclo-paraffins by urea adduction, to obtain the n-paraffins concentrates (urea adductables)--the wax- and the saturated solvent portion--the UNA. The thermal behaviour of narrow subfractions alongwith their urea adductables and the solvent portions have been studied and the wax appearance temperature (WAT) thus measured has been compared with those obtained by optical microscopy and with the ASTM cloud point, wherever possible. To obtain a clearer picture of the solidification process, further study has been done by preparing synthetic blends of urea adductables in different concentrations in the respective aromatic and iso- and cyclo-paraffinic solvents (UNA) and studying the thermal behaviour of each blend. It is found that the variation in WAT with wax concentration as measured by DSC is identical with that measured by optical microscopy and the ASTM cloud point. However, DSC values are lower than microscopic values and higher than ASTM cloud point. The enthalpy of the blends with the same amount of wax in the aromatic and iso- and cyclo-parffinic solvents indicated that it is higher in the saturated solvent in comparison to aromatic solvent. This confirms the fact that in an aromatic solvent the solubility of the wax is greater, and hence a comparatively lower WAT. The results are further discussed.     

直馏柴油催化裂化加工技术探索

采用小型固定流化床实验装置,探索研究了直馏柴油催化裂化加工技术路线的可行性。结果表明：催化裂化是将直馏柴油转化为高附加值产物的切实可行的工艺技术;采用催化裂化技术路线时,直馏柴油直接催化裂化反应具有较高的汽油和丙烯收率,分别可达48%和8%左右;采用催化裂解技术路线时,直馏柴油直接催化裂解反应具有较高的低碳烯烃和BTX（苯、甲苯和二甲苯）收率,在反应温度为620℃时乙烯、丙烯和BTX总收率可达39%以上,并可副产22％以上的高辛烷值汽油,其 RON在99以上;重油原料掺炼直馏柴油时,直馏柴油掺入比例较高时催化裂化反应性能较好,但会导致汽油产物中芳烃含量增加。     

馏分油降凝在增产柴油中的作用

馏分油临氢和非临氢降凝工艺技术均已工业化。以直馏轻蜡油、催化裂化重柴油和加氢裂化尾油为原料，经降凝可大幅度增产柴油，并可提高炼油厂轻质油收率、提高柴汽比、满足市场需求。     

催化裂化增产柴油的研究

催化裂化增产柴油是炼油厂多产柴油的重要途径，简要阐述了进料特性和催化化操作条件对柴油产率的影响，增产柴油的裂化催化剂和工艺的初步技术构思与研究试验结果。     

ACID BASE PHENOMENA IN DISTILLATE FUEL STABILITY

Carboxylic and organic sulfonic acids, added to distillate fuel blends containing catalytically cracked stock, Increase deposit formation, sometimes very dramatically. The carboxylic acids data fitted into a unified treatment in relationship to hydrogen ion concentration calculated from pK_a values for aqueous solutions. These acids enhance deposit formation by catalytic action and are not Incorporated into the deposit. Organic sulfonic acids may fit into the unified acid catalysis pattern but await resolution of ionization phenomena in non-aqueous solution.

A tertiary aliphatic amine stabilizer was effective for reducing deposit amounts from fuel blends containing acids. This amine acts on a stoichiometric basis to counteract strong acids in the fuels. For weak acids, the amine stabilizer exhibited an effect slightly more than that for a 1:1 basis with the amount of acid in the fuel. Other amines exerted favorable behavior only if they were strong organic bases.     

吸附法精制加氢焦化馏出油试制3号喷气燃料

为扩大喷气燃料资源，满足民航对喷气燃料的需求，对焦化全馏分油加氢后的喷气燃料馏分性质进行了分析，发现碱性氮的存在是影响焦化全馏分加氢后喷气燃料馏分颜色安定性的主要因素。在实验室里采用RA-01和RB-01特种吸附剂的非加氢组合工艺对焦化全馏分加氢后喷气燃料进行精制试验，结果表明，喷气燃料馏分经过非加氢精制后，颜色提高到 29，其它性质未见明显改变，所有性质均符合GB6537-94 3号喷气燃料标准。使用性能评定试验结果表明，焦化全馏分加氢后喷气燃料经过非加氢精制后其组成、橡胶相溶性、动态氧化热安定性、润滑性均可达到使用要求。     

高氮馏分油加氢精制催化剂的研制

以含SiO2和/或TiO2的γ-A12O3为复合载体、以W-Mo-Ni为活性金属组分,采用分步等体积浸渍法制备了一系列三叶草形加氢精制催化剂.采用X荧光射线、N2吸附比表面积、X射线衍射、扫描电镜等对催化剂结构进行了表征.在反应压力8.0 MPa、反应温度340℃、氢油体积比600∶1、体积空速1.5h-1条件下,测定...     

MINIMIZATION OF THE RATE OF AMBIENT DIOXYGEN CONSUMPTION BY A COAL-DERIVED MIDDLE DISTILLATE

ABSTRACT

Rates of molecular oxygen consumption at 23°C and 1 atm O₂ by a coal-derived middle distillate containing cyclohexanol and other additives are reported. Significant inhibition of fuel oxidation was observed in the presence of 0.15% w/w benzylidene benzoylhydrazine, HBBz, but was not observed if the fuel had first been treated with pentane to precipitate gum and the predominant metals. Gum precipitated in the presence of HBBz had a higher S content than in its absence. Equilibria between HBBz, metals in the fuel and catalyst X (which may contain sulfur) are suggested to account for inhibition of fuel oxidation by HBBz.     

MINIMIZATION OF THE RATE OF AMBIENT DIOXYGEN CONSUMPTION BY A COAL-DERIVED MIDDLE DISTILLATE

Rates of molecular oxygen consumption at 23°C and 1 atm O₂ by a coal-derived middle distillate containing cyclohexanol and other additives are reported. Significant inhibition of fuel oxidation was observed in the presence of 0.15% w/w benzylidene benzoylhydrazine, HBBz, but was not observed if the fuel had first been treated with pentane to precipitate gum and the predominant metals. Gum precipitated in the presence of HBBz had a higher S content than in its absence. Equilibria between HBBz, metals in the fuel and catalyst X (which may contain sulfur) are suggested to account for inhibition of fuel oxidation by HBBz.     

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.     

高抗氮多产中间馏分油型加氢裂化催化剂3976的研制

新一代高抗氮并能多产中间馏分油型加氢裂化催化剂（商品牌号为３９７６），经实验室研制、工业放大、性能评价及应用研究，结果表明，３９７６催化剂活性和中间馏分油选择性与３９０３催化剂相当，而抗氮能力明显高于后者。在裂化段进料氮含量为２０～５０μｇ／ｇ的条件下，不仅能保持高活性，而且稳定性好，甚至在进料中氮含量高达８０～１００μｇ／ｇ的条件下，仍能稳定运转，各种性能指标可满足现有加氢裂化装置扩能改造需要     

新一代最大量生产中间馏分油的加氢裂化催化剂的工业应用

介绍了抚顺石油化工研究院开发的新一代最大量生产中间馏分油 (高中油型 )的 3974加氢裂化催化剂在镇海炼油化工股份有限公司和茂名石油化工公司两套大型加氢裂化装置上的工业应用情况。在不同工艺操作方案或操作条件下所获得的工业运转结果证明 :3974催化剂是一种多产中间馏分油的加氢裂化催化剂。该剂不仅活性好、中油选择性高 ,而且具有产气量小、耗氢低的特点 ;改善了炼油厂产品分布 ,也有助于降低企业的生产成本。     

双组分硬沥青水浆燃料的研制

用二连脱油沥青和尤利卡沥青混合物作原料,按双指标控制的自然粒度分布粉碎,分段加入水和结构相似、相对分子质量接近的分散剂,可以制备一种清洁化的液体代用燃料。该燃料具有高沥青含量(大于65%),低粘度(小于100 mPa·s,100 r/s),泵送性能和流动性好,稳定性满足工业要求,燃烧效率高,便于组织燃烧,燃烧烟气有害物含量低等优点。采用不同软化点的硬沥青复合制成水浆,对解决高软化点沥青的出路问题、增强溶剂脱沥青和尤利卡热裂化工艺的竞争力以及解决沥青水浆工业化的难题都具有重要意义。