仪长渣油加氢处理反应规律的研究 I.仪长渣油性质特点及加氢反应特性

以仪长管输原油渣油（简称仪长渣油）为原料、以沙特阿拉伯轻质原油渣油（简称沙轻渣油）作为对比油,采用傅里叶变换离子回旋共振质谱仪及核磁共振波谱仪对两类渣油的烃类组成及结构参数进行表征,对比考察两种渣油的加氢处理反应性能。结果表明,与沙轻渣油相比,仪长渣油具有硫含量低、氮含量高、胶质含量高、芳香分含量低、大量分子都含有氮原子、分子较大、支化程度高等特点,在相同的催化剂体系和工艺条件下,仪长渣油的残炭降低率显著低于沙轻渣油。     

仪长渣油加氢处理反应规律的研究 Ⅰ.仪长渣油性质特点及加氢反应特性

以仪长管输原油渣油(简称仪长渣油)为原料、以沙特阿拉伯轻质原油渣油(简称沙轻渣油)作为对比油,采用傅里叶变换离子回旋共振质谱仪及核磁共振波谱仪对两类渣油的烃类组成及结构参数进行表征,对比考察两种渣油的加氢处理反应性能。结果表明,与沙轻渣油相比,仪长渣油具有硫含量低、氮含量高、胶质含量高、芳香分含量低、大量分子都含有氮原子、分子较大、支化程度高等特点,在相同的催化剂体系和工艺条件下,仪长渣油的残炭降低率显著低于沙轻渣油。     

不同分子结构渣油加氢反应性能研究

分别以石蜡基青海原油渣油（简称青海渣油）和中间基沙特阿拉伯轻质原油渣油（简称沙轻渣油）为原料,采用RHT系列渣油加氢催化剂进行了1 500 h 稳定性试验,采用傅里叶变换离子回旋共振质谱仪和核磁共振波谱仪分析原料和加氢生成油的分子结构差异及试验后催化剂（简称试验旧剂）上积炭组成。结果表明：青海渣油分子芳烃侧链多且长,通过初期快速升温可使其侧链断裂,改善其内扩散性能,且生焦倾向降低;沙轻渣油分子芳烃含量高,侧链较短,低温时即可达到较高杂质脱除率,高温则易生成结焦前躯物,造成催化剂快速失活;与青海渣油相比,沙轻渣油加氢试验旧剂的积炭量更大,硬炭比例更高。对青海渣油加氢反应的温度分布进行优化,快速升高脱金属催化剂床层温度,降低脱硫剂反应温度,形成前高后低的温度分布,结果表明优化后方案的加氢生成油性质更优。     

仪长渣油加氢处理反应规律的研究Ⅱ.新型催化剂及工艺条件的影响

针对仪长管输原油渣油(简称仪长渣油)的性质特点,开发了新型渣油加氢降残炭催化剂,并考察了加氢工艺条件对仪长渣油加氢处理反应的影响。通过选用镍钼型活性金属体系,改进载体的制备方法、浸渍工艺过程及添加助剂等开发了新型渣油加氢降残炭催化剂,使用该催化剂的级配体系具有更强的加氢饱和活性及杂原子脱除活性。在相同的操作条件下,与现工业装置应用的催化剂级配体系相比,使用新型加氢降残炭催化剂的级配体系可以使仪长渣油的残炭降低率提高3.3百分点、加氢脱氮率提高7.9百分点,有效提升仪长渣油的加氢生成油品质。在渣油加氢常规操作范围内,通过提高反应温度和氢分压、降低体积空速可以提高仪长渣油残炭降低率,促进加氢脱硫、加氢脱氮等反应的进行,有利于加氢生成油品质的提高。     

渣油加氢反应过程中芳香性化合物转化规律

在中型试验装置上考察了仪长渣油和沙轻渣油加氢反应性能差异,采用傅里叶离子回旋共振质谱分析方法,深入分析了沿反应器物流方向渣油中芳香性化合物加氢转化规律。结果表明,仪长加氢生成油中含有较高含量N1类化合物（含有1个氮原子的烃类,以下类推）,其中存在较高比例DBE值（化合物分子等效双键数目）大于15的化合物,是其脱残炭率相对较低的主要原因。仪长渣油中CH类、S1类和N1类化合物的平均碳数和平均DBE值均略高于沙轻渣油,随加氢深度增加,两类渣油CH类和S1类化合物逐渐向低碳数和低DBE值方向移动,N1类化合物的变化并不明显。经过加氢脱残炭剂后,沙轻渣油S1类化合物中高碳数和高DBE值的化合物大部分转化,而仪长渣油N1类化合物中出现了少量原料中不存在的高碳数和高DBE值的化合物。     

高硫渣油加氢生产低硫重质船用燃料油组分技术开发与应用

高硫渣油深度加氢脱硫过程中,最难脱除的含硫化合物因有侧链取代、空间位阻效应强而最难转化,深度脱硫过程中,催化剂上金属(镍+钒)沉积及积炭均会加快。针对加氢脱金属剂及加氢脱硫降残炭剂分别开展级配比例的研究,结果表明：脱金属率随反应物流在脱金属催化剂上停留时间的增加而增加,脱硫率随反应物流在脱硫降残炭剂上停留时间的增加而增加,但在达到一定停留时间后的增加趋势均明显变缓;所开发的新型渣油加氢脱硫降残炭剂初始加氢脱硫活性不高,随着运行时间的延长活性有所提升并保持稳定。基于级配研究结果及加氢脱金属脱硫剂的特性,开发了新型高硫渣油深度加氢脱硫催化剂级配技术,并在高硫渣油固定床加氢装置上进行了工业应用。结果表明,新型级配催化剂具有良好的加氢脱硫活性及优异的稳定性,该固定床渣油加氢装置在确保催化裂化装置原料供应的前提下能够稳定生产低硫重质船用燃料油调合组分。     

我国含硫原油加工技术路线和技术进步

(1)渣油加氢处理／渣油催化裂化(RHT／RFCC)技术 中国加工进口含硫原油不断增多，使含硫渣油加工处理成为渣油加工的一大课题。将渣油加氢处理与RFCC相组合，可最大量提高轻质产品产率。这种联合技术的特点可使渣油脱金属、脱硫、脱氮，适用于加工高含金属、硫和残炭的中东渣油。高硫渣油加氢处理(RHT)可生产经加氢处理的常压渣油(或减压渣油)，     

适应炼油结构转型的固定床渣油加氢技术选择

开发了固定床渣油深度加氢技术,可利用重质原料为催化裂解提供原料而多产丙烯。高硫低氮类常压渣油加氢后的产物氢含量增加值更高,更适宜用作渣油深度加氢技术的原料来生产优质催化裂解原料。利用硫质量分数4.95%的中东减压渣油开展相关研究,开发了固定床渣油加氢-延迟焦化组合生产低硫石油焦的工艺,结果表明：当加氢渣油的硫质量分数降低至0.52%时,石油焦的硫质量分数降至2.8%;随着渣油加氢深度的提高,硫传递系数相应增加;渣油加氢深度对延迟焦化产物分布影响明显,随着脱硫深度的提高,石油焦产率逐渐降低,液体产品产率明显增加。开发的高硫渣油深度脱硫生产低硫重质船用燃料油技术,结合具有活性缓释功能的渣油加氢脱金属脱硫催化剂的开发,提出了相应的催化剂级配技术,使整体催化剂的脱硫活性稳定性大幅提高,A公司利用此技术实现了稳定生产低硫重质船用燃料油。     

高铁钙渣油沸腾床加氢技术研究

以仪长管输原油渣油为原料,用连续搅拌釜反应器模拟沸腾床考察了高铁钙渣油的裂化性能和杂质脱除性能,并研究了沸腾床加氢催化剂的初期失活情况。结果表明,反应温度是影响高铁钙渣油转化率和杂质脱除率的主要因素,积炭、金属硫化物的沉积造成的催化剂孔口堵塞失活是影响高铁钙渣油沸腾床加氢工艺经济性的主要因素,铁钙含量应该作为采用沸腾床加氢工艺还是固定床加氢工艺加工高铁钙渣油的判断标准。     

渣油加氢脱金属催化剂初期失活的研究

以孤岛常压渣油和伊朗常压渣油为原料，在固定床试验装置上研究了两种加氢脱金属催化剂的初期失活，测定了不同运转时间催化剂上的积炭量。得到了催化剂加氢脱金属反应活性系数与运转时间的关联式。发现运转过程的前200h为初期失活阶段，此后进入稳定失活阶段。     

固定床渣油加氢催化剂表面积炭分析

利用扫描电镜、热重-质谱联用、红外光谱、X射线荧光光谱及碳硫元素分析等手段,对工业运行450天的固定床渣油加氢工业脱金属催化剂RDM-32和脱硫催化剂RMS-30表面积炭进行表征,以研究催化剂积炭的组成及类型。结果表明：两种催化剂积炭量均从催化剂表面向中心不断降低,且脱硫催化剂积炭量下降更快;与脱金属催化剂相比,脱硫催化剂含有较高的积炭和较低的金属沉积,在积炭组成上,脱金属催化剂含有较多的软炭,占总炭的56.68%,脱硫催化剂基本为硬炭,占总炭的97.04%,在结构上,两种催化剂积炭的结构也有较大差别,脱硫催化剂表面积炭芳环缩合度高于脱金属催化剂,因此其积炭更加难以转化。     

An Investigation of the Deactivation Behavior of Industrial Mo/Al2O3 and Ni-Mo/Al2O3 Catalysts in Hydrotreating Kuwait Atmospheric Residue

The catalyst system for fixed-bed residue hydrotreating processes usually consists of different types of catalysts designed to promote hydrodemetallation (HDM), hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) reactions to desired levels. Overall catalyst life is determined by the performance of the individual catalysts in the different reactors. Therefore, information about the activity, stability, selectivity, and deactivation behavior of the individual catalyst is highly desirable to design improved catalysts that can prolong catalyst life, increase stream efficiency, and improve process economics. In the present work, residue hydrotreating experiments were conducted on two types of industrial hydrotreating catalysts, namely Mo/Al₂O₃ and Ni-Mo/Al₂O₃, that have been used as HDM and HDS catalysts, respectively, in an industrial ARDS process. The primary objective of the study was to compare the deactivation behavior of both types of catalyst. The characterization of the used catalysts by elemental analysis, surface area, pore volume, and pore size measurements along with TPO-MS, ¹³C NMR, and electron microprobe analysis showed significant differences in the nature of the coke and metal deposits on the two types of catalysts. The role of initial coking, the relative importance of the coke, and metal depositions on the deactivation of the two types of catalyst are discussed.     

渣油加氢失活催化剂的积炭规律

以正庚烷为溶剂,采用索氏抽提法对渣油加氢工业失活催化剂进行预处理,以脱除表面吸附的烃类组分;采用碳硫元素分析仪、扫描电子显微镜 能谱分析仪(SEM EDS)分别测定了失活催化剂的碳、硫含量及碳含量沿颗粒的径向分布,并采用热重 质谱联用分析仪(TG MS)和BET低温物理吸附仪研究了失活催化剂的热解行为及其孔结构的变化。结果表明,沿着反应器物流方向,失活剂的积炭量呈上升趋势,硫含量呈下降趋势;脱金属失活剂的积炭沿颗粒径向分布比较均匀,而脱硫、脱残炭失活剂颗粒的碳含量呈现边缘部位较内部含量偏高;沿物流方向,积炭氧化温度逐渐升高;积炭影响催化剂的孔结构特性,对脱金属剂的孔结构影响相对较小,而对脱硫剂、脱残炭剂的孔结构影响比较大;脱硫、脱残炭失活剂高温脱炭后,比表面积和孔容可恢复率高,尤其是脱残炭剂。     

An Investigation of the Deactivation Behavior of Industrial Mo/Al2O3 and Ni-Mo/Al2O3 Catalysts in Hydrotreating Kuwait Atmospheric Residue

Abstract

The catalyst system for fixed-bed residue hydrotreating processes usually consists of different types of catalysts designed to promote hydrodemetallation (HDM), hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) reactions to desired levels. Overall catalyst life is determined by the performance of the individual catalysts in the different reactors. Therefore, information about the activity, stability, selectivity, and deactivation behavior of the individual catalyst is highly desirable to design improved catalysts that can prolong catalyst life, increase stream efficiency, and improve process economics. In the present work, residue hydrotreating experiments were conducted on two types of industrial hydrotreating catalysts, namely Mo/Al₂O₃ and Ni-Mo/Al₂O₃, that have been used as HDM and HDS catalysts, respectively, in an industrial ARDS process. The primary objective of the study was to compare the deactivation behavior of both types of catalyst. The characterization of the used catalysts by elemental analysis, surface area, pore volume, and pore size measurements along with TPO-MS, ¹³C NMR, and electron microprobe analysis showed significant differences in the nature of the coke and metal deposits on the two types of catalysts. The role of initial coking, the relative importance of the coke, and metal depositions on the deactivation of the two types of catalyst are discussed.     

添加剂对渣油加氢脱金属性能的影响

以不同种类和不同含量高芳香性的催化裂化产物重循环油(HCO)和轻循环油(LCO)作为添加剂,考察了其对常压渣油加氢脱金属反应(HDM)性能的影响。结果表明,HCO和LCO添加剂的加入,可改善渣油在反应过程中的扩散性能,促进渣油中沥青质的溶解,从而提高渣油的HDM性能,其对加氢脱镍(HDNi)性能的提高更优于加氢脱钒(HDV)。同时发现,加入高芳香性添加剂后,渣油HDM过程中S、N和CCR的脱除率均有提高,反应产物的相对分子质量分布明显向低相对分子质量方向移动;随着LCO添加剂含量的增加,渣油的HDNi、HDV性能逐步提高,但当LCO质量分数增加到20%后,其提高渣油HDM性能的作用稍有下降。     

HYDROCRACKING OF ARABIAN MIX ASPHALTENES IN THE PRESENCE OF MODIFIED RED MUD

Asphaltenes precipitated from an Arabian Mix vacuum residue were hydro-cracked in a batch autoclave at 435 and 460°C for 5-90 min. Experiments without catalyst, with modified red mud and with an industrial Co Mo/Al₂0₃ catalyst were compared. The products were fractionated into gas, naphtha, oil, asphaltenes and coke. Feed asphaltenes and several product fractions were characterised by elemental analysis, by average molecular mass and by ¹H n.mr. Due to the hydrogenation activity, both catalysts caused - with similar efficiency - the decrease of coke formation and the increase of quantity and quality of oil.     

DEVELOPMENT OF HIGH-PERFORMANCE HEAVY OIL HYDROCRACK1NG CATALYSTS: CHARACTERIZATION OF ATMOSPHERIC RESIDUE FEED

ABSTRACT

The characterization results of the atmospheric residue obtained from Saudi Arabian Light crude oil show the complex nature and composition of this material. The distillation results showed that about 50 percent of Arab Light crude is the atmospheric residue. The elemental analysis of the residue showed that high amount of carbon, sulfur and nitrogen is present along with heavy metals such as nickel and vanadium. The determination of hydrocarbon types by HPLC exhibited that 12% polars and 27% aromatics are present along with 6% asphaltenes. Nuclear magnetic resonance study conducted on the residue and its fraction provides a detailed composition in terms of aliphatic and aromatic nature of the residue and its fractions. The results showed that the residue contains 21% aromatic and 79% aliphatic carbon. The aliphatic carbon is present in saturates and as side chains of aromatic and polar molecules whereas the aromatic carbons are those in the ring structure. Asphaltenes separated from the residue were characterized for their different properties to understand its complexity. The use of electron spin resonance spectroscopy provides determination of the free radicals present in the residue. Asphaltenes were analyzed using the state-of-the-art high temperature high pressure electron spin resonance (ESR) technique in the temperature range 20 to 625 °C and at 30 and 50 bar hydrogen pressure. The ESR determination at 30 bar shows that me pressure was not enough to prevent the boiling of the asphaltene and thus a decrease in the spin concentration was observed beyond 350 °C temperature. The data at 50 bar pressure showed the adequacy of this pressure for ESR measurement. The PMRTA analysis of asphaltene showed a decrease in residual hydrogen with increasing temperature.     

生产优质催化裂解原料的渣油深度加氢技术研究

以5种不同的渣油为原料,从催化剂开发、催化剂级配、工艺条件优化、原料适应性考察等角度深入研究并开发了渣油深度加氢技术。结果表明：新开发的渣油深度加氢系列催化剂活性显著高于常规催化剂;反应温度是影响加氢深度最关键的因素;在优化的催化剂级配方案和工艺条件下,渣油深度加氢技术不仅可以显著提高原料中杂原子的脱除率,提高生成油的氢含量,还可以实现多烃类定向转化产化学品;高硫、低氮常压渣油更适宜采用渣油深度加氢技术生产优质催化裂解原料。