渣油加氢裂化反应的窄馏分集总动力学模型

在１００ｍｌ高压釜反应器内，用工业Ｎｉ－Ｍｏ／Ａｌ２Ｏ３催化剂，于氢初压８．５ＭＰａ，搅拌转速８５０ｒ／ｍｉｎ，反应温度６６３－６９３Ｋ和不同的反应时间下，进行了孤岛渣油的加氢裂化反应实验。将其应用于描述渣油加氢裂化反应动力学规律，模型计算结果与实验值一致。     

渣油悬浮床加氢裂化尾油化学结构 及其裂化性能评价

 采用改进的B-L(Brown-Ladner)法和密度法，分析了克拉玛依渣油悬浮床加氢裂化尾油及其饱和分、芳香分、胶质、沥青质的化学结构；利用芳香性不同的溶剂对该尾油进行处理，在高压反应釜中评价了尾油、渣油和处理后尾油的裂化性能。结果表明，尾油平均分子结构中烷基碳率小于渣油分子，芳香碳率、芳环数和缩合指数大于渣油分子；尾油的裂化转化率比渣油低，缩合转化率比渣油高，对催化剂的感受性下降；采用低芳香性溶剂处理可改善尾油的反应性能，达到悬浮床加氢裂化循环油的要求。     

渣油悬浮床加氢裂化与热裂化反应过程中胶体稳定性的比较

考察克拉玛依常压渣油热裂化和悬浮床加氢裂化在不同反应时间的生焦量与生焦诱导期以及反应后产物的六组分质量分数及其数均相对分子质量，并利用质量分数电导率法研究了热裂化和悬浮床加氢裂化不同反应时间的胶体稳定性。结果表明，渣油悬浮床加氢裂化和热裂化两种反应体系在生焦诱导期内的胶体稳定性下降迅速，在生焦诱导期后的胶体稳定性下降趋于缓慢。在氢与加氢催化剂的作用下，渣油悬浮床加氢裂化在相同反应条件下比热裂化的生焦诱导期长，胶体稳定性好。     

分散型钼系催化剂在孤岛渣油加氢裂化中的作用：Ⅱ.渣油反…

本文对孤岛渣油在分散型Ｍｏ系催化剂存在下的加氢裂化与临氢裂化进行了对比研究，通过裂化气体的气相色谱分析，残渣油的组成，分析初步揭示了在分散型钼系催化剂存在下渣油加氢裂化反应的机理和分散型催化剂抑制生焦的机理，结果表明，在分散型Ｍｏ系催化剂存在下，测量油加氢裂化以自由其热裂化反应为主；但加氢反应抑制了胶质－沥青质的综合反应，同时催化剂对沥青质缩聚物的吸附作用，延缓了焦炭的生成。     

渣油及其悬浮床加氢裂化尾油中氮化物的转化趋势

以孤岛减压渣油为原料，在高压釜反应器中进行悬浮床加氢裂化反应，反应温度为415℃及430℃，对反应后产物进行常减压蒸馏，并对原料及悬浮床加氢尾油进行六组分分离，将得到的各馏分及各组分用非水电位滴定法测定碱性氮含量，用化学发光定氮法测定总氮含量，进行悬浮床加氢裂化尾油中氮化物分布的研究。结果表明：在渣油的悬浮床加氢裂化过程中，既有裂解反应，又有缩合反应，产物中的碱性氮和总氮主要集中在蜡油和尾油中。悬浮床加氢裂化反应后，在尾油六组分中随组分变重，氮含量增加。碱性氮化物在加氢裂化过程中含氮杂环会发生部分饱和，使非碱性氮化合物转化为碱性氮化合物。     

重质油窄馏分的HDS和HDN反应动力学特性

用破碎的工业加氢裂化催化剂Ｎｉ－Ｍｏ／Ａｌ２Ｏ３,在１００ｍｌ的高压反应釜内,对３种不同渣的超临界流体萃取分馏的窄馏分进行氢处理,建立了釜式反应器内渣油催化加氢脱硫和加氢脱氮反应的扩散－反应动力学模型,讨论了渣油窄馏分的扩散和加氢转化反应动力学特性。     

分散型铁催化剂存在下孤岛渣油加氢裂化的七集总动力学模型

本文研究了孤岛渣油在分散型铁催化剂存在下加氢裂化反应的动力学规律，建立了孤岛渣油加氢裂化反应七集总（气体Ｃ１－Ｃ４、馏分油Ｃ５－４８０℃、饱和分、芳香分、胶质、沥青质及苯不溶物－焦）动力学反应模型。在此，提出了在处理动力学模型时虑到反应物结构的变化，并且构造出了结构变化的计算函数，结果表明，当考虑到结构变化时，理论计算的动力学模型与试验数据能较好地吻合。     

渣油加氢裂化反应中催化剂与表面活性剂的协同作用

 在高压釜中，以克拉玛依常压渣油(KLAR)为原料，考察了添加表面活性剂对悬浮床加氢裂化反应生焦的影响。结果表明，在渣油加氢裂化反应过程中，表面活性剂与加氢裂化水溶性分散型催化剂之间存在协同作用。表面活性剂SA1，SA4和SA5的加入能更有效地抑制渣油加氢裂化反应过程的生焦，其中添加SA4的抑焦效果最好，反应总生焦率由添加表面活性剂前的2.34%降至添加后的0.79%。表面活性剂与催化剂协同抑焦效果与表面活性剂的添加量有关，当表面活性剂的添加量较少时, 抑制生焦的效果较好；但当添加量超过一定值时, 甚至会促进生焦。红外光谱分析表明，SA4可以在沥青质表面吸附，从而起到稳定沥青质、降低生焦的作用。     

渣油加氢脱硫反应集总动力学模型的事前模拟

 通过渣油加氢脱硫(HDS)中试装置实测数据，对渣油HDS反应集总动力学进行事前模拟。根据渣油中硫化物加氢反应速率的快慢，将其分别划分为2~6个集总，建立了5种渣油HDS反应集总动力学模型。通过对该5种模型拟合误差的比较分析，得到三、四集总模型的拟合平均相对误差最小。然后分别针对三、四集总渣油HDS反应动力学模型，求取了其动力学参数，并采用实测数据对模型的稳定性和外推性进行了验证。结果表明，模型参数中，温度、空速和氢分压等因素对HDS反应的影响符合硫化物加氢反应规律，对三、四集总模型验证的平均相对误差分别为2.32%和1.98%，说明模型的拟合性和预测性良好。所建模型可为渣油HDS反应集总动力学的深入研究提供参考。     

中东渣油悬浮床加氢裂化反应产物及总硫分布的研究

以中东含硫渣油为原料，在高压釜中进行不同反应类型和不同分散型催化剂的悬浮床加氢裂化反应，分析产物分布及其中总硫分布。加氢活性高的催化剂具有较强的抑制反应产物二次裂解的能力，并且有较强的硫元素脱除能力。反应添加硫化剂对于含硫渣油的裂化产物及总硫分布没有明显的影响；加入供氢剂抑制了缩合反应及裂化反应，同时促进了硫的脱除。     

CHARACTERIZATION OF PETROLEUM RESIDUA THROUGH REDUCTIVE CHEMISTRY

Distillation residua from petroleum, containing 26 — 32% aromatic carbon (f_a), are reduced by K⁰ in tetrahydrofuran to form anions which are then alkylated by alkyl iodides. Consumption of potassium in 24 hours at room temperature is in the range 4 to 5 mmol K per gram resid, of which 19—23% goes to the formation of “K₂S” from the removal of sulfur from the resid. The anions of the resid are characterized by alkylation of the resid with ¹³C enriched methyl iodide followed by examination by heteronuclear correlated two—dimensional nuclear magnetic resonance of ¹H and ¹³C spins. Analysis of proton and carbon shifts of individual methyls demonstrates that attachment of methyls to carbon atoms of the resid is the principal chemistry of the reductive methylation.     

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

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.     

CHARACTERIZATION OF PETROLEUM RESIDUA THROUGH REDUCTIVE CHEMISTRY

ABSTRACT

Distillation residua from petroleum, containing 26 — 32% aromatic carbon (f_a), are reduced by K⁰ in tetrahydrofuran to form anions which are then alkylated by alkyl iodides. Consumption of potassium in 24 hours at room temperature is in the range 4 to 5 mmol K per gram resid, of which 19—23% goes to the formation of “K₂S” from the removal of sulfur from the resid. The anions of the resid are characterized by alkylation of the resid with ¹³C enriched methyl iodide followed by examination by heteronuclear correlated two—dimensional nuclear magnetic resonance of ¹H and ¹³C spins. Analysis of proton and carbon shifts of individual methyls demonstrates that attachment of methyls to carbon atoms of the resid is the principal chemistry of the reductive methylation.     

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.     

苯和噻吩在重油流化催化裂化催化剂及其活性组分上的吸附

利用智能重量分析仪测试了在30℃与400℃下苯和噻吩在重油流化催化裂化(RFCC)催化剂及其主活性分子筛组分上的吸附-脱附曲线和程序升温脱附曲线,并将其与催化裂化过程中的原位降硫性能进行了关联。结果表明,噻吩在RFCC催化剂上不仅存在着物理吸附和化学吸附,还会发生低聚反应;苯与RFCC催化剂间的作用力较弱,只存在1种吸附位,400℃下苯在RFCC催化剂上以扩散过程为主,这样可减少汽油因深度裂化而造成的辛烷值损失,提高RFCC催化剂对目标产物的选择性和耐结焦性能;噻吩在RFCC催化剂上的饱和吸附量远大于苯,说明RFCC催化剂对噻吩类硫化物的吸附选择性较好。     

含硫劣质原料对催化裂化汽油质量的影响及对策

运用实验分析数据及工业生产数据讨论了含硫劣质原料对重油催化裂化汽油质量的影响。结果表明,催化裂化原料中的硫、镍、钒含量及残炭对催化裂化的反应产物有不同的影响,其中硫含量是影响催化裂化精制汽油腐蚀性、安定性的主要因素。针对经常造成重油催化裂化汽油硫醇硫含量偏高、诱导期偏短的问题,结合重油催化裂化生产的具体特点及经验,提出了改善汽油质量的对策,并取得了满意效果。     

采用全二维气相色谱-飞行时间质谱表征渣油接触裂化液体产物中含硫化合物

采用全二维气相色谱-飞行时间质谱(GC×GC-TOFMS)方法对渣油接触裂化液体产物中的含硫化合物进行分子水平表征,鉴定出苯硫醚、苯硫酚、噻吩类、苯并噻吩类、二氢苯并噻吩类、二苯并噻吩类、萘噻吩类、四氢二苯并噻吩类、苯并萘噻吩类、菲噻吩类、苯并二噻吩类及噻喃类等含硫分子。通过GC×GC-TOFMS的族分离和瓦片效应重点研究了渣油接触裂化液体产物中的噻吩类、苯并噻吩类及二苯并噻吩类化合物的碳数分布,并对油品加工过程中较关注的C_2烷基取代二苯并噻吩类化合物进行了单体分子识别。结合渣油接触裂化工艺考察了接触剂活性对渣油接触裂化液体产物中的含硫化合物的分子类型分布及碳数分布的影响,结果表明,同种渣油在不同接触剂作用下接触裂化的液体产物中含硫化合物的分子类型分布基本相似,但含量分布存在明显差异。对于碳数分布,以苯并噻吩类为例,采用强微反活性的接触剂时,液体产物中的低碳数烷基(C_1~C_3)取代苯并噻吩的分布占优势,而采用弱活性接触剂时,产物中较高碳数烷基(C_4~+)取代苯并噻吩的分布占优势。     

VARIATION OF FREE RADICAL CONCENTRATION WITH MOLECULAR WEIGHT IN PETROLEUM FEEDSTOCKS

Two petroleum residua were studied, one of Mid-Eastern original and the other of Chinese origin. These residua were separated into fractions using preparative size-exclusion chromatography (SEC). Room temperature electron spin resonance (ESR) experiments of SEC separated petroleum-derived fractions are described. A variation of free radical concentration with different molecular weight fractions was observed. Significant increase in free radical concentration was observed in the 1000-2500 amu range. This is in the molecular weight range postulated to be necessary for formation of the mesophase state observed in carbonaceous pitches during conversion to coke and carbon by thermal treatment.     

原油减压渣油馏分的油-水界面性质Ⅺ.伊朗轻质减压渣油和大庆减压渣油乳状液的粒度特征

采用动态光散射法研究了伊朗轻质减压渣油和大庆减压渣油模拟乳状液的粒度特征。研究表明，伊朗轻质减压渣油和大庆减压渣油模拟乳状液的初始粒径较小，粒度分布较窄；随着时间的延长，其粒径逐渐增大，粒度分布变宽；随着馏分增重或体相质量浓度的增加，模拟乳状液的初始粒径增大。随着油相中芳烃含量增加，伊朗轻质减压渣油和大庆减压渣油中重馏分模拟乳状液的初始粒径增大，而大庆减压渣油轻馏分模拟乳状液的初始粒径减小。随着水相中碱或盐的加入，伊朗轻质减压渣油和大庆减压渣油模拟乳状液的初始粒径均增大。     

Suitability of Sour Crude Processing and Resid Hydrotreating Technologies

This article has analyzed the environment and tasks confronting China＇s petroleum refining industry, and has referred to principles for selecting the resid processing technologies and viability of various combination technologies for resid processing. Taking into account the actual commercial practice of resid hydrogenation units, this article has also discussed methods for processing high-sulfur inferior crudes as well as the suitability of resid hydrogenation technology.