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。     

Effect of vacuum gas oil hydrotreating reactor on multiple reactors and hydrogen network

The inlet temperature of the Vacuum Gas Oil (VGO) hydrotreating reactor of a refinery is analyzed with the integration of multiple series reactors and hydrogen network considered. The effect of the inlet temperature (T₁) on hydrogen sinks/sources and the product output is analyzed systematically based on the simulation of the series reactors, including VGO hydrotreating reactor, hydrocracking reactor, fluid catalytic cracking reactor and visbreaking reactor. The general relation between the Hydrogen Utility Adjustment (HUA) and multiple pairs of varying sinks and sources is deduced, and correlations between varying streams and T₁ are linearly fitted. Based on this, the quantitative equation between HUA and T₁ is derived, and corresponding diagram is constructed. The T₁ corresponding the minimum hydrogen consumption is identified to be 345℃.     

沥青质在渣油加氢催化剂中的扩散行为

以甲苯为溶剂,在自制的扩散实验装置中,研究了不同初始质量分数下沥青质在渣油加氢催化剂中的扩散行为。结果表明:当沥青质初始质量分数由0.002%增加到0.030%时,随着前者的增加,沥青质聚集体的体积、单元体积分数和动力学直径增加,平移扩散系数减小,聚集效应明显,阻碍了沥青质在催化剂微孔中的扩散,有效扩散系数降低。另外,随着初始质量分数增加,沥青质聚集体的Langmuir动力学系数及其在催化剂中的饱和浓度增加,即聚集效应增强了沥青质的吸附能力。聚集效应对扩散和吸附的影响具有互补性,使扩散系数随沥青质初始质量分数增加的变化幅度减小。     

LTAG加氢单元原料和产品烃类组成中红外光谱快速分析技术

LTAG工艺在工况调整过程中需要对加氢单元LCO加氢原料和产物烃类组成的进行监控,本研究采集大量催化和加氢柴油样品的中红外光谱结合偏最小二乘方法建立LCO加氢原料和产物烃类组成的中红外分析模型。利用该方法可快速得到LCO加氢原料和产物的详细烃类组成,分析结果和质谱方法分析结果具有良好的一致性,与近红外光谱快速分析方法相比较具有更高的准确性。该方法操作简单、重复性好,能满足现场快速分析的需求。     

催化裂化柴油加氢转化馏分利用方案研究

中国石化大连(抚顺)石油化工研究院开发了以催化裂化柴油为原料生产高辛烷值汽油调合组分新工艺技术（FD2G技术）。针对催化裂化柴油加氢改质产品,通过分析其组分的烃类组成,分别加工利用,对于改善产品结构和提高市场竞争力十分有益。研究结果表明：加工高芳烃催化裂化柴油时,汽油产品芳烃含量高,辛烷值高,其中C6~C8芳烃富集的窄馏分可以作为芳烃抽提装置原料生产化工产品;加工低芳烃含量的催化裂化柴油时,汽油产品中芳烃含量低,辛烷值偏低,可将富集大量环烷烃的窄馏分作为重整装置原料,富含芳烃的窄馏分作为高辛烷值汽油调合组分。     

高压氢气汽提在全加氢型润滑油生产流程中的应用研究

全加氢型润滑油装置通常由加氢处理、加氢脱蜡、补充精制3部分组成。由于加氢脱蜡、补充精制多采用贵金属催化剂,为防止贵金属催化剂中毒,对循环氢及反应进料中的硫、氮含量要求高。因此在流程设置上,多数情况下将加氢脱蜡、补充精制作为一段串联布置在加氢处理单元的下游。常规全加氢型润滑油装置需要两套独立的高压反应系统及相关高压设备,即采用两段技术,流程相对较长,且设备较多。通过在全加氢型润滑油生产装置中引入高压氢气汽提技术,将传统的一段加氢处理和二段加氢脱蜡-补充精制两个反应系统整合为一段串联系统,既能缩短原有的加工流程、减少装置占地,又能节省装置投资8%左右,同时使全装置能耗减少12%左右。     

工业装置渣油加氢失活催化剂上的金属赋存状态研究

以工业固定床渣油加氢失活催化剂（失活剂）为研究对象,依次采用正庚烷、甲苯对其进行索氏抽提,通过对失活催化剂上金属含量、形态及分布进行分析表征,发现金属沉积量沿着物流方向呈现降低趋势。通过Raman光谱、XPS分析表征发现,渣油加氢失活剂表面沥青质类物质含量很低。渣油加氢处理催化剂的活性相主要有3种：MoS2相、NiMoS相或CoMoS相。沉积的焦炭和金属使得催化剂暴露在外表面的活性相数量非常少。     

Sulphidation of an oxidic CoMo/Al2O3 catalyst under practical conditions: different kinds of sulphur species

The sulphidation of a CoMo/Al₂O₃ hydrotreating catalyst was studied under pressure and flow conditions close to industrial practice. The sulphiding mixture contained equal amounts of H₂S and CH₄ diluted in hydrogen under 3.9 MPa total pressure. The oxidic precursor was flushed by the reagent gas at 40°C for 10 h, then the temperature was raised to 400°C within 2 h. Mass variation was continuously recorded by means of a suspension magnetic balance, and the gas phase was analysed by mass spectrometry. Sulphur contents were also determined at intermediate temperatures by chemical analyses. Thus, mass variations due to the presence of adsorbed species or to the formation of CoMo sulphides could be distinguished. The rapid gain in mass noted at 40°C was mostly due to adsorption of H₂S over the oxidic solid, since it increased with H₂S partial pressure. At this stage, however, a small amount of the reactive oxygen was already exchanged for sulphur. Upon raising the temperature, the mass decreased due to a combination of desorption and sulphiding steps. Above 140°C, H₂S consumption was evidenced, together with water production, and the rate of sulphiding increased with the H₂S partial pressure. At 300°C, the mass variation was close to that expected for complete transformation into Co₉S₈ and MoS₂. Above 350°C, the mass further increased due to the replacement of adsorbed water by H₂S. At 400°C, an important excess mass was observed at all H₂S partial pressures. Thus, the adsorption sites on the metal sulphides are essentially saturated by H₂S species under practical conditions.     

EDTA/CA对加氢处理催化剂性能的影响

以碱式碳酸镍、三氧化钼、磷酸为原料制备钼镍磷浸渍液，并在浸渍液中分别添加乙二胺四乙酸、柠檬酸、柠檬酸和乙二胺四乙酸，制备出含单一络合剂及双络合剂的加氢处理催化剂。通过XRD、HRTEM、H2-TPR、NH3-TPD等对其进行表征，发现双络合剂催化剂与单络合剂催化剂相比，降低了活性金属与载体的相互作用力，有利于形成更多的II类活性相，且片晶长度更长，片晶层数更多；同时又具有较大的比表面积和孔容，酸量及中强酸也得到增加。因此，双络合剂催化剂具有更高的加氢脱硫、脱氮活性。     

润滑油加氢工艺

随着对高规格润滑油需求量的不断增加,常规溶剂抽提工艺已无法满足APIⅡ类和APIⅢ类润滑油基础油的生产,而加氢工艺越来越广泛地用于生产高规格润滑油。为了提升中国的润滑油品质,提高产品的市场竞争力,炼化企业正加大对加氢工艺在高规格润滑油基础油生产上的推广和应用。简述了几种润滑油加氢工艺及其特点。