STUDY OF SERIAL REACTION KINETICS AND CHANGES OF GROUP COMPOSITIONS OF PETROLEUM ASPHALTS IN CONTINUOUS HEAT AND AIR AGING

The serial reaction kinetics and the changes of group compositions of Shengli petroleum asphalt(SPA) and Huansanlian petroleum asphalt(HPA) were studied during continuous heat and air aging(CHAA) at 120 ∼ 180°C. The test results show that at given temperature the contents of saturate constituents of two asphalts change very little, aromatic constituents decrease clearly and asphaltenes increase gradually during CHAA. At lower temperatures(120 ∼ 140 °C) the contents of resins increase slowly and no toluene insolubles form obviously, but at higher temperature(180°C) the resins increase at first and then decrease and the toluene insolubles increase much quickly with the CHAA time. The higher the CHAA temperature, the more evidently the change of asphalt group compositions would change. The apparent aging rate constants and the apparent aging activation     

INFRARED STUDY OF THE AGING OF ASPHALTS IN CONTACT WITH AGGREGATES

ABSTRACT

The purpose of this work was to identify chemical compound types produced at or near the asphalt/aggregate interface during oxidative aging. Diffuse reflectance infrared Fourier transform (DRIFT) spectrometry was used to analyse samples of asphalt that had been oxidatively aged in contact with aggregate for various periods of time. Aging products were studied as a function of time, distance from the aggregate surface, asphalt composition, and aggregate composition. Three compound types were observed to form upon aging—sulfoxides, ketones, and carboxylic acids. All three compounds types are thought to cause hardening and cracking of asphalts. The composition of the virgin asphalt was a key factor in determining the kind and amounts of aging products formed. The amount of products formed was also related to aging time. Evidence for the concentration of any one aging product on or near the asphalt/aggregate interface was not found     

风城稠油中石油酸组成结构分析

由氢氧化钾-乙醇水溶液分离风城稠油中的石油酸,结合元素分析、红外光谱(FT-IR)、核磁共振(NMR)、电喷雾质谱(ESI-MS)、紫外光谱(UV-Vis)和荧光色谱等方法分析其结构组成。结果表明:风城稠油所含石油酸主要是一元羧酸二聚体,平均相对分子质量为665,平均分子式为C43.51H78.47O3.78,氢碳原子比为1.80;各类酸分布范围较广,其中,环烷酸含量最高,占79.84%,脂肪酸次之,占20.16%;环烷酸中一环环烷酸、二环环烷酸、三环环烷酸、四环环烷酸/芳环羧酸、五环环烷酸/芳环并一环羧酸和六环环烷酸/芳环并二环羧酸的含量相当,均在11.00%~18.88%之间。此外,还检测到微量3~4环的芳香结构物质。     

道路沥青老化动力学的研究--以软化点为参数建立沥青老化动力学模型

研究了以辽河油田生产的稠油为基质沥青自制的两种沥青老化后软化点的变化，以软化点为参数建立了沥青一级老化动力学模型。并用该动力学模型对这两种沥青的抗老化性能进行了研究，求得了动力学参数。实验结果表明，这两种沥青老化后软化点均升高，AH-70沥青抗老化性能优于AH-90沥青，以软化点为参数建立的沥青老化动力学模型较好地表征了沥青老化过程，为研究沥青老化提供了一种简便可行的分析方法。     

A STUDY ON KINETICS OF AGING OF PAVING ASPHALT

In this paper the aging processes of two penetration-grade paving asphalt which conform to the standard of Esson Company have been studied by rotation thin film oven (RTFO). The first order aging kinetic model has been established and some kinetics parameters were calculated. The relationship between pavement properties of asphalt and aging course was revealed. The intervention of oxygen in high temperature caused oxidation reactions, which changed the composition and structure of asphalt, the aging resistant performance of asphalt was weak, and the service performance went to bad.     

A STUDY ON KINETICS OF AGING OF PAVING ASPHALT

In this paper the aging processes of two penetration-grade paving asphalt which conform to the standard of Esson Company have been studied by rotation thin film oven (RTFO). The first order aging kinetic model has been established and some kinetics parameters were calculated. The relationship between pavement properties of asphalt and aging course was revealed. The intervention of oxygen in high temperature caused oxidation reactions, which changed the composition and structure of asphalt, the aging resistant performance of asphalt was weak, and the service performance went to bad.     

高等级道路沥青老化动力学研究

在实验室研究了AH－70和AH－90两种高等级道路沥青在老化过程中,正戊烷沥青质及针入度、软化点、延度等指标的变化,并根据老化过程中,正戊烷沥青质的变化,进行了沥青老化动力学研究,计算得出了有关动力学参数,得到了沥青老化动力学方程,其计算值与试验数据相吻合。表明高等级道路沥青老化属于一级动力学反应。实际老化过程中针入度、软化点及延度的变化进一步证明了所得动力学模型是可靠的。     

炼油过程能量优化和低温余热回收利用

通过分析炼油过程能量传递和低温余热热源及热阱特征,运用热力学试探法和数学规划法建立了炼油过程系统能量优化方法和低温余热大系统优化回收利用方法。系统能量优化涵盖炼油过程总能规划、直接热联合和热供料、装置内部能量优化、低温余热利用等方面;低温余热利用包括热源热阱分类评价、热水子网络建立、大系统柔性分析。在中国石化洛阳分公司的应用结果表明,该方法能有效地应用于炼油厂节能改造和运行优化,实施后全厂能耗降低97.8 MJ/t,年节能效益为4 111.62万元。     

A STUDY ON AGING KINETICS OF ANSHAN PAVING ASPHALT

ABSTRACT

The aging processes of two Anshan paving asphalts conforming to GB/T15180-94 standard have been studied by Rotation Thin Film Oven Test (RTFOT) and the aging kinetic models of two paving asphalts have been determined. The results show that the aging of the prepared paving asphalt is a first order reaction. The viscosity of the asphalt increases gradually with the aging time. The greater the aging index is, the more easily the asphalt is aged. Because the chains break down to form free radicals, oxidation reactions occur. The aging resistance of the asphalt with lower aromaticity and with less aromatic cycle numbers is weak.     

A STUDY ON AGING KINETICS OF ANSHAN PAVING ASPHALT

The aging processes of two Anshan paving asphalts conforming to GB/T15180-94 standard have been studied by Rotation Thin Film Oven Test (RTFOT) and the aging kinetic models of two paving asphalts have been determined. The results show that the aging of the prepared paving asphalt is a first order reaction. The viscosity of the asphalt increases gradually with the aging time. The greater the aging index is, the more easily the asphalt is aged. Because the chains break down to form free radicals, oxidation reactions occur. The aging resistance of the asphalt with lower aromaticity and with less aromatic cycle numbers is weak.     

石油渣油空气氧化和氮气热缩聚的比较研究

以石油渣油为原料，通过在220℃空气氧化300－720min和在310℃氮气热缩聚130－370min制备了一系列具有相近软化点的石油沥青。通过NMR、FT－IR、元素分析、软化点测定、偏光光学分析、热重和族组成分析等进行原料与石油沥青的化学结构分析。在1．6MPa、480℃下将石油沥青进行焦化，考察了焦产率和光学组织结构变化情况。结果表明，空气氧化和氮气热缩聚可提高石油沥青的软化点、焦产率和正庚烷不溶物含量。与氮气热缩聚沥青相比，相近软化点的空气氧化沥青具有较高的H／C原子比和O／C原子比。空气氧化石油渣油在提高焦产率方面更有效。空气氧化和氮气热缩聚方法得到的沥青成焦后均生成各向异性广域光学结构。     

连续反应装置合成二丙酮醇研究

介绍采用连续反应装置,由丙酮非均相催化缩合,合成二丙酮醇的新方法。它便于控制反应条件并能生产不同规格要求的产品,而且无“三废”污染。在该装置上采用强碱性阴离子交换树脂催化剂,由均匀设计实验法得到最佳工艺条件：反应床温度 ５０～５５℃,蒸馏釜沸腾温度 ６５～７５℃,进料速度 ０． ５０ Ｌ／ｈ,二丙酮醇单产可达０．０９５ ｋｇ／［ｋｇ（ｃａｔ．）· ｈ］,釜液含二丙酮醇 ２５％～６０％之间。     

NaNO2与NH4Cl反应动力学及其在油田的应用研究

通过对亚硝酸钠(NaNO2)与氯化铵(NH4Cl)反应的化学动力学的研究,得到其动力学方程,阐述了NaNO2与NH4Cl放热反应所产生的"热峰"位置的计算方法,介绍了利用NaNO2水溶液与NH4Cl水溶液在井下发生放热反应所产生的热量和氮气来处理井下沉积石蜡的有效方法。     

甲乙苯脱氢制甲基苯乙烯反应工艺及动力学研究

使用工业脱氢催化剂,在温度580~635℃、水与甲乙苯质量比2.0~4.0、体积空速0.5~1.5h~(-1)、压力(a)30~101kPa的实验条件范围内,研究了工艺参数对甲乙苯脱氢制甲基苯乙烯反应的影响规律。结果表明:随着温度的升高,甲乙苯转化率提高,甲基苯乙烯选择性下降;随着水与甲乙苯配比的增加,转化率和选择性均上升;体积空速降低时,虽能提高转化率,但会使选择性降低;压力降低时,既可提高转化率,又有利于选择性的升高;适宜的工艺条件为压力(a)50kPa、温度620℃、水与甲乙苯质量比2.0、体积空速0.5h~(-1)。利用实验数据,对甲乙苯脱氢反应进行了动力学研究。假设并简化反应网络,根据不同反应机理提出3种可能的甲乙苯脱氢反应动力学模型,对模型进行统计学检验筛选后,确定双位吸附模型为最佳反应动力学模型,并估算了该模型的参数,可为反应器的设计和最佳操作条件的选择提供依据。     

石油炼制过程碳氢组成的变化及其合理利用

本文从石油中主要的两种元素——碳和氢的组成出发,研究其在脱碳和加氢等典型炼制过程中的变化规律,分析了采用不同过程生产所需要的石油产品时碳和氢的有效利用程度.为了在重质油品轻质化过程中取得更高的轻质油收率,指出了脱碳和加氢过程互相结合,发挥各自特点,以较小的代价实现氢碳比值合理调整的技术途径.     

石油焦与油页岩混合燃烧特性及其燃烧动力学

采用ZRY-2P综合热分析仪对不同质量比的石油焦/油页岩的混合燃料进行了热重分析,得到了它们的热重(Thermogravimetric, TG)及微商热重(Differential thermogravimetric,DTG)曲线和混合燃烧特性,并计算出燃烧动力学参数。结果表明,随着石油焦/油页岩的质量比逐渐降低,石油焦/油页岩混合燃料的TG曲线变化逐渐缓慢,DTG曲线逐渐呈现3个峰,其中有2个峰明显;当石油焦/油页岩的质量比为3/2时,综合燃烧性能最好,体现出混合燃烧所具有的优势。除石油焦/油页岩质量比为4/1的样品外的其他混合样品,在低温段和高温段活化能按大小排列的顺序与频率因子大小排列的顺序均相同,这体现了活化能和频率因子变化的一致性.石油焦与油页岩混合燃料在低温段的燃烧反应级数为1.30左右,所需活化能较低;在高温段的燃烧反应级数为1.00左右,所需活化能较高。石油焦与油页岩的混合燃料具有很大的实际工程应用价值。     

TLC/FID GROUP COMPOSITIONAL ANALYTICAL METHOD OF MICRO-AMOUNTS OF ASPHALTS AND ITS APPLICATION

Column-chiromatography has some limitations in group compositional analysis of heavy petroleum (asphalt). However, the new method of Thin Layer Chromatography (TLC) combined with Hydrogen Flame Ionized Detector (FID) is used. This method has advantages of rapidity and correctness, particularly fits to low-containing asphalts sample.     

渣油加氢反应动力学及失活模型

采用固定床连续操作装置进行渣油加氢中试研究.中试采集的大量数据作为建模基础,运用非线性拟合方法,拟合了渣油加氢动力学参数,建立了包括催化剂失活校正和操作条件校正的渣油加氢动力学模型.结果表明,该模型可以比较准确地预测渣油加氢处理过程.该动力学模型不仅可以预测不同操作条件下各反应的杂质脱除率,而且可以计算在保证杂质脱除率不变的条件下,各工艺参数之间的相互影响规律.     

连续流微通道反应器中二氯丙醇合成环氧氯丙烷的浓度分布及动力学分析

为简化反应系统的连续控制,提高装备利用率,采用一种具有脉冲混合结构的微通道反应器,考察了连续流反应器内二氯丙醇(DCH)合成环氧氯丙烷(ECH)的反应动力学,研究了反应温度、停留时间对反应产物组分的影响。建立了二氯丙醇环化与环氧氯丙烷水解的动力学方程,并进行了验证。环化反应动力学方程为:r_1=7.57×10~(14)·e~(-11146.3/T)·C_(DCH)·C_(NaOH),环氧氯丙烷的水解反应动力学方程为:r_2=5.43×10~(10)·e~(-8 263.2/T)·C_(ECH)·C_(NaOH)。利用得出的动力学数据,分析了连续流微通道反应器的优势,为反应器设计与连续流工艺的改进提供了依据。     

TLC/FID GROUP COMPOSITIONAL ANALYTICAL METHOD OF MICRO-AMOUNTS OF ASPHALTS AND ITS APPLICATION

ABSTRACT

Column-chiromatography has some limitations in group compositional analysis of heavy petroleum (asphalt). However, the new method of Thin Layer Chromatography (TLC) combined with Hydrogen Flame Ionized Detector (FID) is used. This method has advantages of rapidity and correctness, particularly fits to low-containing asphalts sample.