原料族组成对汽油馏分催化裂解反应性能的影响

利用多产低碳烯烃催化剂NHC-516,在小型固定流化床实验装置上对催化裂化汽油、焦化汽油和直馏汽油的催化裂解性能进行了实验研究,考察了不同原料族组成对催化裂解产物分布、低碳烯烃收率以及催化裂解液相产物族组成的影响.结果表明:乙烯的收率随着反应温度的升高呈抛物线增长;催化汽油和焦化汽油的丙烯收率远高于直馏汽油的丙烯收率;烯烃与链烷烃有协同作用,烯烃能够加速链烷烃的反应速率,这是焦化汽油干气收率高的主要原因;在有烯烃存在时,芳烃会生成大量的焦炭;烯烃和链烷烃是生成低碳烯烃的主要来源,是催化裂解的理想组分.     

Composition and structure of solid petroleum hydrocarbons which form urea complexes

Conclusions Analysis of the chemical composition of the solid petroleum hydrocarbons which form urea complexes shows that they compose a group of hydrocarbons of varied chemical structure (normal alkanes and isoalkanes, alkylcyclanes and alkylarenes) which have as a mandatory structural element a long unbranched alkyl chain. The chemical composition of solid hydrocarbon fractions isolated from petroleum with urea depends on the nature of the petroleum and the character of the feedstock fraction (low-boiling or high-boiling distillates or residues from distillation).A feature of the molecular structure of the solid saturated petroleum hydrocarbons which form urea complexes — the presence of a long unbranched alkyl chain in conjunction with general low branchedness of isoalkane or alkylcyclane molecules—determines the commonness of various properties and phase behavior of the fractions being studied, which makes this group of hydrocarbons close in many ways to normal alkanes. The principles given present interest in consideration of distillate paraffins composed predominantly of complex-forming hydrocarbons.Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 7, pp. 22–25, July, 1968.     

燕山FCC汽油C5窄馏分催化裂解反应特性

 采用重油催化裂解多产丙烯专用催化剂R0,考察了燕山FCC汽油C₅窄馏分的催化裂解反应特性。由于热裂解反应和催化裂解反应的反应机理不同,对于C₅窄馏分,其中的烷烃热裂解反应转化率高于烯烃热裂解反应转化率;而烯烃的催化裂解反应转化率高于烷烃的催化裂解反应转化率,且催化裂解反应的丙烯收率较高。C₅窄馏分的催化裂解反应中,C₅烯烃转化率随温度变化较小,C₅烷烃转化率随温度升高显著增加,且丙烯选择性随温度先增加后降低,表明烯烃更易于生成丙烯;C₅烷烃转化率和C₅烯烃转化率均随质量空速的增加而降低,且C₅烷烃转化率下降更显著;C₅烷烃转化率和C₅烯烃转化率均随催化剂积炭量的增加而降低,且C₅烷烃转化率降低更为显著。当催化剂积炭量达0.44%后,烷烃的催化裂解反应消失,烷烃转化率完全由热裂解反应所控制。     

Catalytic cracking of vegetable oils for production of high-octane gasoline and petrochemical feedstock

The routes of transformation of vegetable oils under catalytic cracking conditions have been investigated. The influence of the component composition of the catalyst on distribution of the desired cracking products and their chemical group composition has been revealed. It has been shown that introduction of H-ZSM-5 zeolite into the composition of the oil cracking catalyst promotes the formation of C₂-C₄ light olefins??the yield of propylene and butylene mainly increases. During cracking on bizeolites catalysts, high yields of both gasoline fractions and light olefins are observed. The relationship between the unsaturation index of the vegetable oils and the product distribution during their catalytic cracking has been established. Oils with a high index of unsaturation are cracked on the bizeolite catalyst yielding primarily mono- and polyaromatic hydrocarbons.     

汽油润滑性研究II.汽油化学组成的特点

化学组成是决定燃料润滑性的最重要的因素。研究汽油中存在哪些种类的化合物 ,包括烃和非烃 ,是研究汽油润滑性的关键。但是 ,汽油的组成在很大程度上取决于生产时进料的成分和加工的方法。近百年来 ,在汽车和汽油平行发展的过程中 ,汽油组成不断改变 ,而且各国情形也各不相同。直到 80年代末 ,完整的燃料组成数据还是很难得到。本研究中收集归纳了尽可能完整的系统的汽油组成数据 ,用于今后发展汽油润滑的模型及解释汽油润滑性的测定结果。这些数据包括烷烃、烯烃、芳烃、含硫化合物、含氮化合物、含氧化合物、染料和添加剂的结构和含量。     

Catalytic Oxidative Cracking of Heavy Wax Distillates,Slack Wax,and Polyethylene Wastes to Yield Liquid and Gas Fuels

Abstract

A petroleum waxy distillate, slack waxes, and plastic wastes were charged in an autoclave with 0.6 wt% of hydroquinone as a catalyst. Oxidative cracking process is conducted at 410°C, in oxygen atmosphere of 0.15 MPa for a time of reaction 30 min. Different analytical parameters are used to investigate the physicochemical properties of the products obtained and their corresponding virgin feed stocks. The obtained oily products were distilled to petroleum boiling range like fractions such as gasoline, kerosene, gas oil, and residue. These products have petroleum fuels like properties according to the ASTM test methods. Moreover, the composition of the obtained liquids and liberated gases during the cracked products were identified quantitatively using gas chromatographic technique. Results show that such oxidative cracking process can be used for upgrading petroleum heavy fractions.     

Catalytic Oxidative Cracking of Heavy Wax Distillates, Slack Wax, and Polyethylene Wastes to Yield Liquid and Gas Fuels

A petroleum waxy distillate, slack waxes, and plastic wastes were charged in an autoclave with 0.6 wt% of hydroquinone as a catalyst. Oxidative cracking process is conducted at 410°C, in oxygen atmosphere of 0.15 MPa for a time of reaction 30 min. Different analytical parameters are used to investigate the physicochemical properties of the products obtained and their corresponding virgin feed stocks. The obtained oily products were distilled to petroleum boiling range like fractions such as gasoline, kerosene, gas oil, and residue. These products have petroleum fuels like properties according to the ASTM test methods. Moreover, the composition of the obtained liquids and liberated gases during the cracked products were identified quantitatively using gas chromatographic technique. Results show that such oxidative cracking process can be used for upgrading petroleum heavy fractions.     

A New Downstream Process Design for a Fluid Catalytic Cracking Unit to Raise Propylene Yield and Decrease Gasoline Olefin Content

Abstract

Based on the paraffins, olefins, naphthenes, aromatics (PONA) composition of crude light gasoline, crude heavy gasoline, stabilized gasoline, and wet gas of a pilot plant fluid catalytic cracking (FCC) unit, it was found that the root cause of high gasoline olefin content and low propylene yield was low C₅ and C₆ olefin content of crude light gasoline. A new design for the main fractionater and absorber–stripper–stabilizer was presented to obtain stabilized light gasoline that contains more C₅ and C₆ olefins recracked in the secondary riser. Industrial studies on the revamped unit showed that gasoline olefin content was decreased markedly, though research octane number (RON) was preserved. In addition, propylene yield was raised to a higher level and unit energy consumption (or operating cost) was not increased.     

Conversion of Mixed Lower Olefins and Paraffins on Galloaluminosilicate

At many oil refineries and gas processing plants, the C₂–C₅ fractions obtained as by–products do not have any qualified application. These hydrocarbons can be converted into valuable products on zeolite–based catalysts from the pentasil family. The characteristics of conversion of mixed C₂–C₄ olefins and paraffins into aliphatic and aromatic C₅₊ hydrocarbons in the presence of a galloaluminosilicate catalyst with the structure of pentasil were investigated. The temperature intervals of formation of isoparaffins from ethylene and propylene and aromatic hydrocarbons from mixed C₂–C₄ olefins and paraffins were found. Key words: C₂–C₄ olefins and paraffins, aliphatic and aromatic hydrocarbons, zeolites of the pentasil family, galloaluminosilicates.     

APPLICATION OF MULTICOLUMN VALVE SWITCHING GAS CHROMATOGRAPHY FOR THE ANALYSIS OF NAPHTHA AND KEROSENE FRACTIONS OF SAUDI ARABIAN LIGHT CRUDE OIL

Abstract

The straight run naphtha and kerosene fractions of Saudi Arabian Light crude oil were analyzed for paraffins, olefins, naphthenes and aromatics (PONA) using a gas chromatographic technique. This method is based upon group type separation according to carbon numbers using a programmed multiple valve switching sequence and employing multicolumn approach. The chromatographic operating conditions and carrier gas flow rates were selected to determine PONA contents of naphtha and kerosene fractions. These straight run fractions were produced by an automatic true boiling point (TBP) apparatus. Boiling range distributions of these fractions were determined using a standard ASTM method of simulated distillation. PONA results were compared with the literature. Total paraffins, naphthenes and aromatics agreed with each other.     

Effects of Reaction Temperature on Distribution of Aromatization Reaction Products of Lanlian FCC Gasoline

Abstract

By using Lanlian FCC gasoline as a feedstock, the effects of temperature on the product distribution, light oil compound (gasoline and diesel), off-gas, and liquefied gas were researched in a confined fluidized bed reactor. The experimental results showed the off-gas, liquefied gas, and coke conversion were slowly increased with increasing temperature; the gasoline conversion had a maximum with increasing temperature; the diesel conversion showed no change; the olefins conversion was increased with increasing temperature; the aromatics yield was increased from 390°C to 430°C and from 430°C to 490°C, respectively; and the FCC gasoline Research Octane Number (RON) increased value was increased almost linearly with increasing the temperature. Aromatization index (AI) was put up in order to judge the aromatization degree of the FCC gasoline. The method obtained provided technical instruction for the petroleum chemical plant.     

APPLICATION OF MULTICOLUMN VALVE SWITCHING GAS CHROMATOGRAPHY FOR THE ANALYSIS OF NAPHTHA AND KEROSENE FRACTIONS OF SAUDI ARABIAN LIGHT CRUDE OIL

The straight run naphtha and kerosene fractions of Saudi Arabian Light crude oil were analyzed for paraffins, olefins, naphthenes and aromatics (PONA) using a gas chromatographic technique. This method is based upon group type separation according to carbon numbers using a programmed multiple valve switching sequence and employing multicolumn approach. The chromatographic operating conditions and carrier gas flow rates were selected to determine PONA contents of naphtha and kerosene fractions. These straight run fractions were produced by an automatic true boiling point (TBP) apparatus. Boiling range distributions of these fractions were determined using a standard ASTM method of simulated distillation. PONA results were compared with the literature. Total paraffins, naphthenes and aromatics agreed with each other.     

Migration and occurrence of high wax oils in the Damintun Depression, Northeast, China: Implication for primary controls of petroleum migration pathways in heterogeneous carrier beds

This paper discusses migration styles and primary controls of petroleum migration pathways in heterogeneous carrier beds in the Damintun Depression, Bohai Bay Basin. There are two types of crude oils in the Damintun Depression: a high wax oil (wax hydrocarbon content between 8 and 60%) and a normal oil (wax hydrocarbon content lower than 8%). The high wax oil and normal oil are distinctly different both in biomarker compositions and in distribution patterns of carbon isotopic ratios for individual alkanes, and were confirmed to have been generated from different source rocks. Modeling of secondary migration pathways of both the high wax oil and the normal oil was conducted using a simple three-dimensional model, which assumes that the positions of petroleum migration pathways are controlled by the morphology of the sealing surfaces without taking into consideration the influence of permeability heterogeneity (the morphology-controlled migration model). The modeling results have reasonably well predicted the occurrences of both the high wax oil and the normal oil. All commercial petroleum accumulations are along the predicted preferential petroleum migration pathways (PPMP) formed by focusing of numerous “small petroleum streams” close to the kitchens. The focusing of oils originating from a large area of the generative kitchens is essential for the formation of large oilfields. The strong porosity and permeability heterogeneities of the carrier beds, and the relatively high prediction accuracy of the modeling, suggest that the preferential petroleum migration pathways, although influenced by permeability contrast at local scales, can be effectively predicted at a basin or depression scale under certain circumstances using a model that does not take into consideration the effect of heterogeneity. Most dry holes are not on the predicted petroleum migration pathways, suggesting that the three-dimensional migration pathway modeling may provide a useful tool to reduce exploration risk.     

基于多产化工品的重油原料烃类结构导向研究

石油炼制的化工转型及中间基原油供给比例持续增大的趋势均愈发明显。但中间基劣质渣油中硫、氮、重金属等杂原子含量高,稠环芳烃、胶质、沥青质等难裂化重组分多,对多产化工品途径带来挑战,需通过加氢等前处理工艺进行改质。基于重油分子水平组成、烃分子结构结合催化裂解反应化学研究,提出多产化工品的优势原料烃类组成结构为链烷烃、一环～四环环烷烃及烷基苯,需要渣油加氢与催化裂解两个单元很好地耦合。中间基渣油加氢改质的方向为稠环芳烃超深度加氢饱和并适度裂化。从分子水平表征中间基渣油加氢前后烃组成结构的变化显示,中国石化石油化工科学研究院以烃类结构为导向,采用加氢过程实现了多环芳烃、噻吩型含硫芳烃、胶质、沥青质的深度加氢饱和,定向转化为链烷烃和环烷烃尤其是一环～三环环烷烃等可多产化工品的优势烃类结构,进而与高选择性催化裂解技术耦合可实现劣质中间基渣油多产低碳烯烃和BTX（苯、甲苯、二甲苯）等化工品的目标。     

汽油的化学组成与理化性质的定量关系研究

利用GC／MS分析了37个汽油调和组分和成品油的烃族化学组成,将其分为正构烷烃、异构烷烃、环烷烃、芳香烃、异构烯烃、正构烯烃、环状烯烃、双烯烃,测定了辛烷值、馏程、胶质、酸度、色度、诱导期、碘值、密度、饱和蒸汽压等理化性质,考察了我国各种烃类物质间的相互关系以及烃类物质与汽油理化性质的相关性;采用逐步线性回归方法,建立了理化性质与烃类组成关系的回归模型。F检验结果表明,回归模型显著,可为汽油生产工艺的选取、配方优化及产品质量预测提供参考。     

石油加工物料中硫化物的形态分析

用气相色谱-原子发射光谱联用技术对多套石油加工装置的98个进出口的物料中硫化物的形态分布进行了研究。分别建立了汽油类、柴油类、水样和气体试样的色谱分离条件,以多种方法对物料中的硫化物进行定性;分别以噻吩和H2S为标准试样,用外标法进行了定量。实验结果表明,当硫的质量浓度小于120mg/L时,硫的质量浓度与峰面积呈良好的线性关系,相关系数达0.998,汽油试样中5个主要硫化物测定的相对标准偏差均小于4%,噻吩标准试样的测定回收率为96.2%～101.6%,检出限为0.1mg/L。基本掌握了有关进出口物料中硫化物的形态和含量。该方法可用于分析石油加工过程中的各物料中硫的形态和含量。     

反应温度对LCC-2催化剂催化裂解制低碳烯烃性能的影响

以中国石油大庆炼化公司重油催化裂化装置所用原料油为原料,在固定流化床催化裂化试验装置上评价了LCC-2型催化剂的反应性能。结果表明,反应温度升高时,汽油、柴油和重油收率逐渐下降,干气和焦炭收率逐渐增加;液化气收率先升高后降低,590℃时达到最大值;乙烯收率逐渐增加,但丙烯和丁烯收率先升高后降低,均在620℃达到最大值。当反应温度为560~590℃时,低碳烯烃总收率最高可达到23.93%,液化气、汽油和柴油总收率最高为81.35%,干气、重油和焦炭的产率相对较低,产物分布较好。     

STUDY OF SATURATED COMPONENTS IN ASPHALT

ABSTRACT

The saturated fractions separated from blown and straight run asphalts of the same penetration grade have been investigated by using GC, MS and ¹³ The saturated components in asphalt represent complex mixture of polyalkyl structures in which straight chain paraffins prevail. The content of saturates in asphalt and their molecular composition were found to be affected by the chemical nature of crude oil as well as by the method of its processing into asphalt. Saturated fractions from blown asphalt are richer in long chain paraffins than those from straight run asphalts. The structural examination of saturated components separated from the products of asphalt pyrolysis has confirmed die presence of long straight-chain units in the asphalt-forming micelles. The structural differences between the saturated fractions obtained from asphalts of different origin (Uralian and Brent-blend) suggest, that the distribution of straigh-chain hydrocarbons in asphalts is dependent on the aliphatic network already existing in the raw material.     

加氢裂化尾油窄馏分的催化裂化转化规律研究

将中东减压蜡油的加氢裂化尾油分为4个沸程范围不同的窄馏分,在固定流化床装置上考察了其催化裂化反应性能,采用GC/MS等方法对原料和裂化产物的烃类组成进行了分析。结果表明,4个窄馏分中饱和烃的质量分数均高于98.0%,随着馏分变重,窄馏分中的链烷烃含量增大,环烷烃含量减小,并且链烷烃和各族环烷烃均向高碳数方向移动。4个窄馏分均易于裂化,干气和焦炭产率低,液化气和汽油收率高。在相同的催化裂化条件下,随着馏分变重,其可裂化性能增强,干气和焦炭产率降低,液化气收率增加,汽油收率增加但辛烷值略有降低,柴油和重油收率均降低。     

An integrated physicochemical and microbiological method for enhanced recovery of viscous oils from low temperature reservoirs of Mongolia

Reservoir fluids from the Tamsagbulag oilfield (Mongolia) have been studied to develop an integrated physicochemical method for intensification of oil production and enhanced oil recovery using micro-organisms. The reservoir conditions of the oilfield facilitate the formation of a diverse biotic community represented by microorganisms of the Arthrobacter, Pseudomonas, Bacillus, Micrococcus, and Flavobacterium genera. The microflora responds positively to the introduction of an oil-displacing composition at a concentration of 5% as a source of nitrogen nutrition. The reservoir microflora exhibits a hydrocarbon biodegradation activity with the degree of degradation of viscous oil of 8.15 and buildup of metabolic products, which reduce the surface tension from 70 to 42 mN/m. Chromatographic and IR analyses have confirmed the fact of severe destructive changes in viscous-oil hydrocarbons. In this case, the oxidation factor (C=O) has increased by a factor of 16. In modeling the displacement of viscous oil using the integrated method, a relative growth in the oil displacement efficiency by 14.4% has been obtained.