REACTION OF PHOSPHORIC ACID WITH THERMAL RESIDUES AND BITUMENS

ABSTRACT

The purpose of the work was to study the effect of the addition of small quantities of phosphoric acid (or P₂O₅), on the physical and chemical behaviour of petroleum residues and bitumens.

Phosphoric acid (and P₂O₅) reacts only with thermal products such as visbreaker (VB) residues and bitumens, and do not react with straight run (SR) products.

The unstable constituents of VB residues, i.e. carbonaceous material and part of the asphaltenes, contain significant amounts of free radicals which easily share electrons with phosphorous.

The resulting condensed particles are higher molecular wighht, polar material no longher soluble in the bitumen, and flocculate.

This reaction confirms the presence of stable free radicals in thermal bitumens and residues, suggests a way to neutralize their destabilizing effect.     

REACTION OF PHOSPHORIC ACID WITH THERMAL RESIDUES AND BITUMENS

The purpose of the work was to study the effect of the addition of small quantities of phosphoric acid (or P₂O₅), on the physical and chemical behaviour of petroleum residues and bitumens.

Phosphoric acid (and P₂O₅) reacts only with thermal products such as visbreaker (VB) residues and bitumens, and do not react with straight run (SR) products.

The unstable constituents of VB residues, i.e. carbonaceous material and part of the asphaltenes, contain significant amounts of free radicals which easily share electrons with phosphorous.

The resulting condensed particles are higher molecular wighht, polar material no longher soluble in the bitumen, and flocculate.

This reaction confirms the presence of stable free radicals in thermal bitumens and residues, suggests a way to neutralize their destabilizing effect.     

CHARACTERIZATION STUDIES ON VISBREAKER RESIDUES AND BITUMENS

ABSTRACT

To better characterize the visbreaker (VB) residues and bitumens, and to study the differences between visbreaker and stright run (SR) products, four groups of samples (VB and SR residues and bitumens) were produced in some italian refineries. The samples were tested and analysed in order to know their viscosity at various temperatures, and their composition (chemical analysis and nmr). Adhesion, stability to oxidation, flow resistance of asphalt concrete were also evaluated for the bitumens. The study showed that nmr-aromaticity of the visbreaker residues and bitumens was increased by the visbreaking operation. Visbreaker bitumens were sensitive to oxidation and gave higher Marshall resistances. The susceptibility of penetration and viscosity to temperature changes was higer for visbreaker bitumens.     

CHARACTERIZATION STUDIES ON VISBREAKER RESIDUES AND BITUMENS

To better characterize the visbreaker (VB) residues and bitumens, and to study the differences between visbreaker and stright run (SR) products, four groups of samples (VB and SR residues and bitumens) were produced in some italian refineries. The samples were tested and analysed in order to know their viscosity at various temperatures, and their composition (chemical analysis and nmr). Adhesion, stability to oxidation, flow resistance of asphalt concrete were also evaluated for the bitumens. The study showed that nmr-aromaticity of the visbreaker residues and bitumens was increased by the visbreaking operation. Visbreaker bitumens were sensitive to oxidation and gave higher Marshall resistances. The susceptibility of penetration and viscosity to temperature changes was higer for visbreaker bitumens.     

针入度对室温的敏感性与PI或PVN的关系

选用国内最具代表性的８种沥青，按照国际（ＧＢ／Ｔ４９０５）对针入度进行测定，通过平行实验和重度性试验，探讨了针入度对室温的敏感性与ＰＩ或ＰＶＮ的关系。     

硫对植物油加氢处理过程催化剂活性及化学反应的影响

采用精制大豆油于固定床微反装置上考察硫对植物油加氢过程中催化剂活性和化学反应的影响规律。结果表明,硫流失是催化剂失活的主要原因,催化剂一旦失活,补硫仅能恢复其部分活性;进料中添加适量的硫可稳定催化剂活性。不同含硫化合物对催化剂的活性影响不同,H2S对植物油加氢反应的活性有促进作用,而少量噻吩可作为催化剂的硫源,稳定催化剂的活性,但添加量较大时,则会抑制催化剂的活性。此外,H2S和噻吩均可以促进植物油加氢过程中的脱羧基反应。     

IMPROVEMENT OF WORKING CHARACTERISTICS OF ROAD BITUMENS

This article deals with those characteristics of road asphalts/bitumens and methods for improving performance.     

采用液硫自流式与流程式相结合布置硫磺回收装置设备平竖面

介绍了新设计的硫磺回收装置采用液硫自流式与流程式相结合的设备平竖面的方法及特点,经过一年半生产实践检验,证明这种布置可以提高装置操作弹性,保证装置长周期稳定生产,也有利于提高转化率、降低能耗,同时节省占地、减少投资.     

程序升温测硫技术在研制钴钼耐硫变换催化剂中的应用

利用程序升温测硫技术对自制的和一些工业的钴钼耐硫变换催化剂中硫的存在状态,作用等进行了研究。结果表明：（１）负载在γ－Ａｌ２Ｏ３的Ｍｏ的硫化物较未负载Ｍｏ的硫化物或９８％ＭｏＳ２易与氧,氢和水蒸气反应,载休不仅可提供大的反应表面,而且活化了与Ｍｏ相联的硫原子;（２）负载在γ－Ａｌ２Ｏ３上的Ｃｏ不能被硫化,但是当Ｍｏ／γ－Ａｌ２Ｏ３中加入Ｃｏ后,与Ｍｏ相联的硫变得更加活泼,更易与氧,氢和水蒸气反应,     

IMPROVEMENT OF WORKING CHARACTERISTICS OF ROAD BITUMENS

ABSTRACT

This article deals with those characteristics of road asphalts/bitumens and methods for improving performance.     

高含硫气藏流体相态实验和硫沉积数值模拟

高含硫酸性气藏在四川盆地有着广泛的分布,酸性气藏的开发对“川气东送”工程有着重要意义。由于H₂S的剧毒性和强腐蚀性,该类气藏的钻完井工程、开采工艺、修井作业、地面输送以及室内实验研究均存在较大难度和危险性。同时由于酸性气藏在开采过程中,存在复杂的相态变化和硫沉积现象,导致渗流规律极其复杂。为此,采用物理实验测试了酸性气藏混合气体偏差因子,并引入空气动力学理论,建立了考虑微粒和气流速度差异的高含硫酸性气藏气固耦合综合数学模型,模拟研究了气流速度、气体初始H₂S含量和地层渗透率对硫沉积和气井生产动态的影响。研究结果表明：①酸性气体偏差因子首先随着压力的升高而降低,当压力超过20 MPa后随着压力的增加而增加,压力超过55 MPa时呈明显的线性关系;②气流速度越大,硫沉积速率越快;③H₂S浓度越高,硫沉积越严重;④气藏渗透率越低,硫沉积现象越明显。     

MATHEMATICAL MODELLING OF THE RHEOLOGICAL PROPERTIES OF PETROLEUM BITUMENS

Three main rheological properties of petroleum bitumens were investigated with the aim of developing a suitable model for the determination of a quality parameter. Two mathematical models have been proposed; one relates softening point to penetration while the other correlates softening point and viscosity. Comparison of the two models with another previously developed model shows that the softening point/viscosity model produces the best results. It also has a great advantage since viscosity can be more accurately measured than penetration and on-line quality control can be effected through viscosity within a few seconds The results of this investigation justify the objective of finding a system of parameters relating the rheological characteristics of bitumens with the generally accepted criteria.     

THE VARIATION OF SULFUR FORMS IN SUPERCRITICAL DESULFURIZATION OF COAL WITH ETHANOL

Using Mossbauer and X-ray Photoelectron Spectroscopy ( XPS) techniques the sulfur forms in solid products obtained at different reaction were analyzed. The results show that: during supercritical desulfurization the pyritic sulfur is removed as following process: FeS₂ -FeS+ Fe_1-x S, the transformation amounts and the value of x are dependent on reaction conditions, especially on temperature. The conversion of pyrite is very little at 275° C. Pyrrhotite ( Fe_1-xS) is Fes_1.101 at 275° C and Fe_1.085 at 450° C. Among the organic sulfur groups PhSH. Ph₂ S and thiolane are easily removed; Ph ₂ SO is more difficult to be removed, its removal may be realized by increasing temperature and adding some water into ethanol; thiophene is most difficult to be removed, its removal needs high reaction temperature     

硫磺回收装置热反应炉及燃烧器

分析了硫磺回收装置热反应炉的设计、结构特点,材料及衬里层选取时应注意的问题.对燃烧器的设计原理、选用型式及其点火程序和火焰监测器做了系统阐述.     

采用双氧水氧化-萃取耦合法生产超低硫戊烷

 以双氧水为氧化剂,研究混合戊烷催化氧化-萃取耦合脱硫技术,考察了催化剂及其用量、氧化剂用量、甲醇用量、反应温度和反应时间对混合戊烷脱硫效果的影响。结果表明,氧化和萃取过程可以相互促进达到更好的脱硫效果;在混合戊烷10 mL、双氧水0.1 mL、催化剂钨酸0.012 g、甲醇1.6 mL、温度70℃、时间50 min的条件下,混合戊烷中硫的质量浓度由187.3 mg/L降至7.9 mg/L,脱硫率可达95.8%。     

磷钼杂多酸钠盐脱硫制硫反应机理研究

磷钼杂多化合物是一种新开发的面向天然气净化的液相氧化脱硫剂。笔者综合运用离子选择电极分析、差示扫描量热分析与能谱等手段对磷钼杂多酸钠盐与硫化氢的反应机理进行了研究。结果表明,磷钼酸钠体系在脱硫过程中具有稳定的化学性能,脱硫产物中基本不含Ｍｏ、Ｐ的物相;磷钼酸钠吸收Ｈ２Ｓ过程的化学反应式为：Ｈ２Ｓ＋Ｎａ３ＰＭｏ（Ⅵ）１２Ｏ４０→Ｓ↓＋Ｎａ３Ｈ２ＰＭｏ（Ⅵ）１０Ｍｏ（Ⅴ）２Ｏ４０,即在磷钼酸钠分子中有     

MATHEMATICAL MODELLING OF THE RHEOLOGICAL PROPERTIES OF PETROLEUM BITUMENS

ABSTRACT

Three main rheological properties of petroleum bitumens were investigated with the aim of developing a suitable model for the determination of a quality parameter. Two mathematical models have been proposed; one relates softening point to penetration while the other correlates softening point and viscosity. Comparison of the two models with another previously developed model shows that the softening point/viscosity model produces the best results. It also has a great advantage since viscosity can be more accurately measured than penetration and on-line quality control can be effected through viscosity within a few seconds The results of this investigation justify the objective of finding a system of parameters relating the rheological characteristics of bitumens with the generally accepted criteria.     

THE VARIATION OF SULFUR FORMS IN SUPERCRITICAL DESULFURIZATION OF COAL WITH ETHANOL

ABSTRACT

Using Mossbauer and X-ray Photoelectron Spectroscopy ( XPS) techniques the sulfur forms in solid products obtained at different reaction were analyzed. The results show that: during supercritical desulfurization the pyritic sulfur is removed as following process: FeS₂ -FeS+ Fe_1-x S, the transformation amounts and the value of x are dependent on reaction conditions, especially on temperature. The conversion of pyrite is very little at 275° C. Pyrrhotite ( Fe_1-xS) is Fes_1.101 at 275° C and Fe_1.085 at 450° C. Among the organic sulfur groups PhSH. Ph₂ S and thiolane are easily removed; Ph ₂ SO is more difficult to be removed, its removal may be realized by increasing temperature and adding some water into ethanol; thiophene is most difficult to be removed, its removal needs high reaction temperature     

辽河渣油减粘裂化装置工艺设计特点及分析

辽河40×10     

未脱硫催化裂化干气用于加氢催化剂的补充预硫化

中国石油化工股份有限公司西安石化分公司在新建制氢装置原料加氢精制催化剂JT-4和JT-1G的预硫化过程中,先用常规方法未能实现完全硫化,后采用未脱硫催化裂化干气(硫化氢体积分数为0．8％)进行补充预硫化,取得了很好的效果。