Study and Evaluation of Aging Performance of Petroleum Asphalts and Their Constituents During Oxygen Absorption. I. Oxygen Absorption Behaviors and Kinetics

The oxygen absorption behaviors and kinetics of Shanjiasi, Shengli, and Renqiu petroleum asphalts and their constituents including saturates, aromatics, resins, and asphaltenes were successfully studied at 50°C, 0.133 MPa (O₂) and 1 mm sample film in darkness by means of precise measurement of oxygen pressure changes in reactor. The experimental results that the resin and the asphaltene can easily absorb oxygen and they are more active constituents in petroleum asphalt, while the saturate hardly absorbs oxygen, which is the most stable constituent of petroleum asphalt. The better the antiaging performance of straight run petroleum asphalt, the more stable its constituents and the less oxygen they absorb generally. The oxygen absorption rate of asphaltene diluted with the lower viscous saturate is obviously higher than that of pure asphaltene. The resin constituent of Shanjiasi asphalt could remarkably improve the antiaging ability of Shengli asphalt by the constituent substitution. The kinetic model of maximum combined oxygen presented in this paper could satisfactorily explain the oxygen absorption behaviors of petroleum asphalts and their constituents, and the oxygen absorption quantities calculated by the model are very identified with the test ones.     

Study and Evaluation of Aging Performance of Petroleum Asphalts and Their Constituents During Oxygen Absorption. II. Chemical Group Composition and Structure Changes

The changes of the chemical group compositions and the structures of Chinese Shanjiasi, Shengli, and Renqiu petroleum asphalts and their constituents during oxygen absorption were successfully studied based on the sample oxygen absorption behaviors. The research results show that every asphalt constituent after absorbing oxygen would change into the near heavier one with the exception of saturates, of which the greatest is the conversion rate of resin into asphaltene. The oxygen molecules absorbed by samples are mainly converted into the oxygen atoms in some oxygen-containing function groups, such as O-H, C=O, and S=O groups. The asphalt colloidal stabilities deteriorate clearly and the molecular weight distributions of asphalts and their constituents spread toward higher molecular weights. The molecular weights of all samples increase gradually after oxygen absorption. Resins and asphaltenes are the more unstable constituents in asphalts as shown by their evident changes after oxygen absorption. The changes of Shengli asphalt and its constituents absorbing more easily oxygen are clearly greater than those of Shanjiasi asphalt and its constituents.     

Study and Evaluation of Aging Performance of Petroleum Asphalts and Their Constituents During Oxygen Absorption. II. Chemical Group Composition and Structure Changes

Abstract

The changes of the chemical group compositions and the structures of Chinese Shanjiasi, Shengli, and Renqiu petroleum asphalts and their constituents during oxygen absorption were successfully studied based on the sample oxygen absorption behaviors. The research results show that every asphalt constituent after absorbing oxygen would change into the near heavier one with the exception of saturates, of which the greatest is the conversion rate of resin into asphaltene. The oxygen molecules absorbed by samples are mainly converted into the oxygen atoms in some oxygen-containing function groups, such as O-H, C=O, and S=O groups. The asphalt colloidal stabilities deteriorate clearly and the molecular weight distributions of asphalts and their constituents spread toward higher molecular weights. The molecular weights of all samples increase gradually after oxygen absorption. Resins and asphaltenes are the more unstable constituents in asphalts as shown by their evident changes after oxygen absorption. The changes of Shengli asphalt and its constituents absorbing more easily oxygen are clearly greater than those of Shanjiasi asphalt and its constituents.     

Study and Evaluation of Aging Performance of Petroleum Asphalts and Their Constituents During Oxygen Absorption. III. Average Molecular Structure Parameter Changes

The changes of the structural parameters of the average molecules of Chinese Shanjiasi and Shengli petroleum asphalts and their constituents during oxygen absorption were studied based on the oxygen absorption behaviors and the chemical group composition and structure changes. The results show that all the structural parameters of the average molecules of asphalts and their constituents increase clearly after oxygen absorption with the exceptions of the naphthene carbon rates and the paraffin carbon rates. The parameters include the total carbon numbers, the aromatic carbon numbers, the naphthene carbon numbers, the paraffin carbon numbers, the total ring numbers, the aromatic ring numbers, the naphthene ring numbers, the total hydrogen numbers, the aromaticities, and the concentration indexes. The most obvious are the structural parameter changes of the average molecules of the asphalt resin and asphaltene constituents. The structural parameter changes of the average molecules of Shengli asphalt and its constituents are remarkably greater than those of Shanjiasi asphalt and its constituents. The clearer changes of all the average molecular structure parameters of SHL asphalt resin and asphaltene, especially resin could possibly be one of the key factors leading to the much clearer deterioration of the colloidal stability and the serviceability than SJS asphalt in oxygen absorption.     

Study and Evaluation of Aging Performance of Petroleum Asphalts and Their Constituents During Oxygen Absorption. III. Average Molecular Structure Parameter Changes

Abstract

The changes of the structural parameters of the average molecules of Chinese Shanjiasi and Shengli petroleum asphalts and their constituents during oxygen absorption were studied based on the oxygen absorption behaviors and the chemical group composition and structure changes. The results show that all the structural parameters of the average molecules of asphalts and their constituents increase clearly after oxygen absorption with the exceptions of the naphthene carbon rates and the paraffin carbon rates. The parameters include the total carbon numbers, the aromatic carbon numbers, the naphthene carbon numbers, the paraffin carbon numbers, the total ring numbers, the aromatic ring numbers, the naphthene ring numbers, the total hydrogen numbers, the aromaticities, and the concentration indexes. The most obvious are the structural parameter changes of the average molecules of the asphalt resin and asphaltene constituents. The structural parameter changes of the average molecules of Shengli asphalt and its constituents are remarkably greater than those of Shanjiasi asphalt and its constituents. The clearer changes of all the average molecular structure parameters of SHL asphalt resin and asphaltene, especially resin could possibly be one of the key factors leading to the much clearer deterioration of the colloidal stability and the serviceability than SJS asphalt in oxygen absorption.     

紫外线吸收抗老化剂在沥青中的应用研究:老化动力学模型的建立

为了能够简捷、直观地评价加入紫外线吸收抗老化剂的沥青的抗老化性能，本研究建立了以正戊烷沥青质含量为参数的老化动力学模型。通过考察老化过程中正戊烷沥青质含量的变化，计算得到了有关动力学参数，建立了老化动力学模型，比较了加入抗老化剂的沥青以及原沥青的抗老化性能。     

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

ABSTRACT

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     

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     

热分析法研究渣油和沥青的热性能

采用热分析技术对２种渣油、４种沥青、３种吸氧老化沥青和经吸附柱色谱法分离得到的４种沥青组份的热性能进行了研究，获得厂各种试样的热重（ＴＧ）、微分热重（ＤＴＧ）和差热（ＤＴＡ）曲线，从热性能方面揭示了这些试样的差别、并对试样的族组成进行了探讨。     

Studies on Nigerian Crudes IV. Improvement of Asphaltic Properties of Residual Asphalts

Abstract

Residual asphalts obtained from 25 samples of Nigerian light, medium, and heavy crude oils were chemically treated by air-oxidation and sulfurization to improve their characteristic properties. The asphalt yield for light crudes varied from 27.7–33.7 wt% and 33.4–67.5 wt% for medium crudes. The chemical treatment brought about changes in chemical composition, increase in molecular mass and modification of consistency resulting in highly improved asphaltic properties. There were manifold increases in viscosity and softening points, which came as a result of the higher asphaltene content of the treated materials. The asphalts obtained meet quality specifications for typical commercial grade products thus confirming the suitability of Nigerian crude oils for the production of residual asphalts.     

STUDIES ON NIGERIAN CRUDES 3. ANALYSIS OF SULFURIZED ASPHALTS

ABSTRACT

The residual asphalts obtained from three Nigerian medium crudes were chemically treated with elemental sulfur at 210 to 250°C. The course of the reaction was followed by monitoring the growth of the asphaltene content of the products. The sulfurization reaction led to 5- to 10-fold increases in the asphaltene content of the products. The asphaltene content of one of the samples initially increased with temperature from 210 to 240°C and then dropped sharply. The results obtained revealed that the optimum temperature of the sulfurization reaction was 240°C. It was also observed that the lower the asphaltene content of the untreated asphalt, the higher the growth of the asphaltene content of the product at the same reaction temperature. The absolute viscosity of the sulfurized asphalts increased rapidly with increasing temperature of reaction.     

THE STUDY OF PRODUCING SBS MODIFIED ASPHALT BY USING LIAOSHU HIGH VISCOUS CRUDE OIL

The high viscous crude from Shuguang No.1 zone of Liaohe oilfield has the characteristics of high contents of resin, asphaltene and low wax content, which belongs to low sulfur naphthene-base crude oil and is ideal material for producing high grade paving asphalt. Waste oil used as blender and stabilizer that is rich in aromatics and poor in wax and styrene butadiene styrene (SBS) were added into vacuum residue of the said crude oil. By reasonable process, various brand SBS modified asphalts meeting JTJ036-98 specification were developed. The modified mechanism and road properties were studied. The laboratory test showed these modified paving asphalts had good low-temperature properties and antiaging feature.     

THE STUDY OF PRODUCING SBS MODIFIED ASPHALT BY USING LIAOSHU HIGH VISCOUS CRUDE OIL

The high viscous crude from Shuguang No.1 zone of Liaohe oilfield has the characteristics of high contents of resin, asphaltene and low wax content, which belongs to low sulfur naphthene-base crude oil and is ideal material for producing high grade paving asphalt. Waste oil used as blender and stabilizer that is rich in aromatics and poor in wax and styrene butadiene styrene (SBS) were added into vacuum residue of the said crude oil. By reasonable process, various brand SBS modified asphalts meeting JTJ036-98 specification were developed. The modified mechanism and road properties were studied. The laboratory test showed these modified paving asphalts had good low-temperature properties and antiaging feature.     

Study on Composition and Structure of Liaoshu Asphalt

Abstract

In this article, the structure characteristics of Liaoshu paving asphalts have been studied by the methods of element analysis, SARA and E-D-M. At same time, the relation between composition and structure and using performance of Liaoshu paving asphalt were established. The experimental results show that carbon and hydrogen contents were more than 95%, the hydrogen/carbon atom ratio was about 1.5 in the Liaoshu paving asphalts. The content of saturates is between 20 and 25% in the Liaoshu paving asphalt, aromatics 35 and 40%, resin 25 and 30%, and asphaltene 8 and 10%. There are 45 carbon atoms in the average asphalt molecule, which contain 16–17 aromatic carbon atoms. The number of total ring in the average asphalt molecule is 5–6, the aromatic ring is 3–4, and the naphthene ring is 1–2.     

反相气液色谱法研究沥青的吸氧老化性能

采用反相气液色谱技术,用甲苯将沥青溶解后均匀涂渍在担体上,作为固定相,在色谱吸氧老化条件下研究了沥青的吸氧老化性能。结果表明,沥青吸氧后相对极性增加,与沥青极性基团相似的分析物质的保留系数增加。氧化中各种沥青的老化综合指标存在较大的差别,可用来评价沥青的抗老化性能。     

CHARACTERIZATION OF HEAVY RESIDUA BY AAPPLICATION OF A MODIFIED D 2007 SEPARATION AND ELECTRON PARAMAGNETIC RESONANCE

ABSTRACT

Seven atmospheric residua (343^°C + [ 65O^°F + ]) were separated into saturate, aromatic, resin, and asphaltene fractions for detailled assessment of feed structure. The weight percent distribution of the fractions revealed two groupings of the residua. One grouping exhibited 20 wt % saturate composition, while the other only 10 wt %. The residua also exhibited high polar content (resin and asphaltene fractions) consisting of over 40% of the total residua. These results are related to the sulfur composition of the residua, and Indicate a fundamental relationship between the aromatic content and sulfur content. Discussion of the accuracy of the separation technique Is also Included.

The vanadium binding sites In the separated fractions were investigated by EPR spectroscopy. The resin and asphaltene fractions all appear to be dominated by 4N and N 0 2S coordination spheres. Discussion of this technique is also included.     

INVESTIGATION AND EVALUATION OF PETROLEUM ASPHALT AGING PROPERTY ON OXYGEN ABSORPTION BY INVERSE GAS LIQUID CHROMATOGRAPHY

ABSTRACT

The aging mechanisms and performances on oxygen absorption of ten petroleum asphalts were studied and evaluated by the inverse gas liquid chromatography with the Aging Comprehensive Index, the Aging Subtraction Number, the Aging Total Area and the Aging Character Factor methods based on the changes of the retention coefficients of analytical compounds in the petroleum asphalt chromatographic column during continuous aging caused by oxygen absorption under an oxygen flow rate of 15～30 ml/min at 140°C, after the inert support was evenly coated with toluene-dissolved petroleum asphalt and packed into the chromatographic column. The relative polarity of petroleum asphalt and the retention coefficients of analytical compounds increase after absorbing oxygen and the changes of the retention coefficients of the oxygen-containing analytical compounds, especially phenol are evidently greater than those of the nitrogen and sulfur-containing and aromatic analytical compounds. There are obvious differences between the retention coefficients of analytical compounds in the petroleum asphalt columns from different sources and between their changes with the aging on oxygen absorption. The repeated determinations of these evaluation methods show that the standard deviations are less than 1.63 and the variable coefficients under 0.2. The test data are found.to be reliable by Grubhs examination at 95% confidence level. Of the four evaluation methods the Aging Subtraction Number method is the most simple and convenient in operation and takes least time in evaluation.     

胜利原油活性组分对其与烷基苯磺酸盐溶液组成的体系油-水界面张力的影响

 采用柱色谱四组分分离方法(SARA)对胜利原油进行分离,依次得到沥青质、饱和分、芳香分和胶质;采用碱醇液法萃取胜利原油得到其酸性组分,测定了各原油活性组分模拟油与烷基苯磺酸盐配制的系列标准溶液组成体系的油-水界面张力。结果表明,原油的酸性组分在低质量分数时通过改变油相的等效烷烃碳数（EACN）影响体系的油-水界面张力;高质量分数时则与表面活性剂混合吸附,使得体系油-水界面张力大幅度升高。胶质对其模拟油-表面活性剂标准溶液体系的油-水界面张力的影响与酸性组分的规律一致;沥青质的界面活性弱于酸性组分,混合吸附能力较弱,高质量分数时使体系油-水界面张力小幅度升高;饱和分和芳香分只影响油相的性质。     

网络结构理论在沥青改性研究中的应用

利用了网络结构理论解释了LDPE以及GMA-g-LDPE分别改性秦皇岛基质沥青、中海36-1基质沥青的软化点、低温延度、针入度指数以及高温稳定性随着改性剂含量变化而变化的规律。红外光谱研究表明，LDPE改性沥青体系中LDPE与沥青二者属于溶涨没有发生任何反应，GMA-g-LDPE改性沥青体系中GMA所含的C=O 的特征吸收峰仍然存在，但907.69cm - 1有环氧基吸收峰消失了，说明GMA-g-LDPE的侧链环氧环与沥青中的官能团发生了反应而形成网络结构。     

INVESTIGATION AND EVALUATION OF PETROLEUM ASPHALT AGING PROPERTY ON OXYGEN ABSORPTION BY INVERSE GAS LIQUID CHROMATOGRAPHY

The aging mechanisms and performances on oxygen absorption of ten petroleum asphalts were studied and evaluated by the inverse gas liquid chromatography with the Aging Comprehensive Index, the Aging Subtraction Number, the Aging Total Area and the Aging Character Factor methods based on the changes of the retention coefficients of analytical compounds in the petroleum asphalt chromatographic column during continuous aging caused by oxygen absorption under an oxygen flow rate of 15∼30 ml/min at 140°C, after the inert support was evenly coated with toluene-dissolved petroleum asphalt and packed into the chromatographic column. The relative polarity of petroleum asphalt and the retention coefficients of analytical compounds increase after absorbing oxygen and the changes of the retention coefficients of the oxygen-containing analytical compounds, especially phenol are evidently greater than those of the nitrogen and sulfur-containing and aromatic analytical compounds. There are obvious differences between the retention coefficients of analytical compounds in the petroleum asphalt columns from different sources and between their changes with the aging on oxygen absorption. The repeated determinations of these evaluation methods show that the standard deviations are less than 1.63 and the variable coefficients under 0.2. The test data are found.to be reliable by Grubhs examination at 95% confidence level. Of the four evaluation methods the Aging Subtraction Number method is the most simple and convenient in operation and takes least time in evaluation.