柴油加氢脱硫绝热反应动力学模型

研究了NiMo型催化剂在柴油加氢反应过程中的动力学规律,综合考虑硫化氢、氮化物和芳烃的抑制作用,建立了三集总加氢脱硫反应动力学模型。通过对反应过程中放热和温升的估算,建立了柴油绝热加氢脱硫反应动力学模型。根据模型计算了等温和绝热环境中物流性质沿反应器轴向的变化规律。结果显示,二者的变化规律存在明显差异,达到相同脱硫深度时,绝热条件中硫化物和氮化物前期脱除速率慢于等温条件。另外,通过模型详细描述了绝热条件各集总硫化物、氮化物和芳烃含量沿反应器轴向的变化规律,获得了各集总在反应器不同位置硫化物、氮化物和芳烃含量的定量数据,结果显示,硫化物、氮化物和芳烃含量各集总的变化趋势均不相同。     

常压柴油催化加氢脱硫反应动力学研究

以炼油厂常压柴油为原料,在固定床加氢反应器上进行催化加氢脱硫反应动力学研究。在工业级钴钼催化剂作用下,考察反应温度、H2分压、氢油体积比和液态空速对常压柴油催化加氢脱硫反应活性影响的规律。建立常压柴油催化加氢脱硫反应的动力学模型,并运用Levenberg-Marquard复合算法优化计算反应动力学模型中的相关参数。实验结果表明,在一定条件下,适当地增加反应温度、氢油体积比、H2分压以及减小液态空速,可提高常压柴油的脱硫率;动力学研究得出反应级数为1.6,表观活化能为18 580.24 J/mol;在实验条件范围内,建立了常压柴油催化加氢脱硫反应动力学模型;对所建模型进行相关性检验,发现实验值与模型计算值基本吻合。     

色谱-三重四级杆质谱定量分析深度加氢脱硫柴油中的二苯并噻吩类化合物

利用选择反应监测模式（SRM）,建立了一种快速、灵敏的深度加氢脱硫柴油中二苯并噻吩类化合物（DBTs）的气相色谱-三重四级杆质谱(GC-QQQ-MS/MS)测定方法。以5种DBTs混合标样绘制标准曲线,对深度加氢柴油中的C0～C4烷基取代二苯并噻吩（C0～C4DBTs）进行定量。实验结果表明,该方法能够有效消除柴油中其他化合物的干扰,快速准确地测定深度加氢脱硫柴油中C0～C4DBTs的含量,而且重现性好,相对标准偏差低于10%,方法的线性相关系数R2>0.9996,检出限和定量限分别为0.0006～0.0017 mg/L和0.002～0.006 mg/L,回收率为98.23～114.59%。该方法适用于深度加氢脱硫柴油中DBTs的测定。     

柴油加氢与微生物脱硫过程中硫化物类型变化规律研究

采用气相色谱-原子发射光谱联用(GC-AED)技术,研究了柴油馏分加氢前后各种硫化物的变化。在加氢脱硫过程中,二苯并噻吩类化合物中的硫最难脱除,催化剂的类型及各操作参数的选择应以柴油中二苯并噻吩类化合物含量来确定。研究了某加氢柴油进行微生物脱硫处理后各种硫化物的变化,并研究了硫含量不同的柴油馏分进行微生物脱硫处理后各种硫化物的分布。可选取在加氢脱硫过程中将柴油中的硫含量降到多大时,再进行生物脱硫技术处理的最佳方案。     

柴油加氢脱硫、脱芳烃反应动力学模型的研究

依据柴油馏分加氢脱硫、脱芳烃的反应机理,提出了按一级反应处理的柴油加氢脱硫四集总反应模型和柴油加氢脱芳烃可逆反应模型.对不同原料在不同反应条件下验证模型的适应性有较好的精度,可以用于柴油深度加氢脱硫、脱芳烃生产清洁燃料的新工艺开发及工艺优化.     

全硅MCM-41担载的Ni-W催化剂上二苯并噻吩加氢脱硫反应动力学研究

以二苯并噻吩(DBT)的质量分数为0．2％～0．8％的十氢萘溶液为模型化合物，在中压固定床反应器上，研究了全硅MCM-41担载的Ni—W硫化物催化剂上的加氢脱硫反应(HDS)动力学。理论分析和实验结果都表明，常用的Langmiur—Hinshelwood方程不适用于气—液—固三相滴流床积分反应器。应用假1级平推流反应模型，分别得到了各催化剂作用下的该反应的速率常数和表观活化能。催化剂的Ni俐摩尔比(nNi／nW)为0．25、0．5、0．75和1．0时，该催化HDS反应的表观活化能分别为117．3、96．7、64．4和72．9kJ／mol。其中，nNi／nW=0．75的反应表观活化能最低。将催化剂的HDS活性与表观活化能相关联可以发现，表观活化能和催化剂活性之间有对应关系，表观活化能越低，催化剂活性越高。     

柴油中各种硫化物的加氢脱硫反应活性

柴油的加氢脱硫反应是在一个间歇式高压反应器中进行的，温度范围为２８０￣４２０℃，反６应总压力为２．９ＭＰａ，反应时间为０￣９０分钟。反应分两个方案进行，即一步反应和两步反应，在每个方案里都使用了钴钼催化剂和镍钼催化剂。通过相应的定量分析，可详细地考查到柴油中苯并噻吩、二苯并噻吩、及其烷基化同系物的加氢脱硫反应活性。各种硫化物的拟一级反应速率常数代表它们的加氢脱硫反应活性，据此可以把这些硫化物分成四     

抚顺页岩油柴油馏分加氢脱硫动力学

针对抚顺页岩油柴油馏分加氢脱硫(HDS)反应的特点,采用集总的方法建立了抚顺页岩油柴油馏分加氢脱硫三集总动力学模型,并对相应的动力学参数进行了计算。结果表明,利用该模型计算得到的产物硫剩余率与实测值吻合较好,误差较小。该模型能够预测抚顺页岩油柴油馏分 HDS 过程中的硫化物脱除情况,所求取的动力学参数可靠,且模型具有一定的外推性。     

喹啉对Co-Mo/Al_2O_3催化二苯并噻吩加氢脱硫的反应动力学研究

在柴油加氢脱硫(HDS)催化剂FHUDS-5(Co-Mo/Al2O3)上,模拟工业高压搅拌反应釜生产工艺,考察了喹啉对二苯并噻吩(DBT)HDS反应活性的影响,并对其反应动力学进行了研究。结果表明,DBT的HDS反应主要通过加氢路径(HYD)和氢解路径(DDS)进行,符合一级反应动力学模型;当喹啉浓度很低时,其对DBT加氢脱硫反应的抑制作用强烈,但随着喹啉浓度的增加,这种抑制作用不再明显;当n为0.25时,喹啉对DBT加氢脱硫反应活性的影响符合于rDBT=kDBTCDBT/(1+Kn NCn N)动力学模型。     

柴油含硫化合物在FH-UDS催化剂上的加氢脱硫研究

在小试装置上采用气相色谱-原子发射光谱（GC-AED）方法,考察了催化裂化（FCC）柴油中的含硫化合物在FH-UDS催化剂上的催化转化性能。结果表明,反应温度对柴油加氢脱硫率的影响最为敏感。在反应温度375℃,氢分压6.0MPa,液时空速2.0h-1和氢/油体积比350的条件,FCC柴油含硫化合物总转化率为99.6%,其中,噻吩类硫化物和苯并噻吩类硫化物的转化率都达到100%,难脱除的4-甲基二苯并噻吩和4,6-二甲基二苯并噻吩转化率分别为99.2%和94.4%。可以在反应温度360℃,氢分压8.0MPa,液时空速1.5h-1～1.0h-1和氢/油体积比350的条件下,生产硫含量低于60μg/g和10μg/g的低硫和超低硫柴油产品。     

柴油加氢脱硫三集总动力学

采用固定床反应器,对加氢精制催化剂上的深度加氢脱硫(HDS)动力学进行研究,考察了反应温度、氢分压和空速对柴油脱硫效果的影响。根据柴油中各种硫化物的脱除行为,按被脱除的难易程度将柴油中的硫化物分为3类,构成三集总HDS模型,获得不同温度下的表观活化能(E)、指前因子(A)和对氢分压的分级数值。假定3类硫化物的活化能不变,将其指前因子与柴油的密度和馏程相关联,建立3个指前因子与中平均沸点的关系曲线,结合按温度切割的柴油窄馏分个数,建立三集总一级反应动力学模型,对方程进行了相关系数(R2)和残差检验。结果表明,所得动力学模型与实验数据吻合良好,在实际应用中可为开发新型超深度HDS催化剂及工艺提供理论指导。     

Non-Hydro Refining of Coker Diesel Oil

Abstract

Coker diesel oil is refined by extraction of furfural adding assistant in this study. The influences of different operating conditions, such as the amount of assistant, the solvent/oil ratio, the refining temperature, the refining time, and the settlement time, on the quality of refined oil were investigated in batch experiments, and suitable operating conditions under which coker diesel oil refined can meet product qualify specifications of 0# diesel oil were given out. These had been verified in continuous experiments, i.e., the amount of additive was 8 g/kg, the refining temperature was 70°C, the solvent/oil ratio (v) was 1.0, the settlement time was 30 min, and refining time was 30 min. The experimental results show that the influence of basic nitride on the stability of coker diesel oil is predominant.     

柴油在硅藻土分散 NiMoW硫化催化剂上深度加氢脱硫研究

Diatomite-dispersed NiMoW catalyst was prepared and characterized, and the activity of catalyst samples was tested during the HDS reaction of FCC diesel. Sulfur compounds in the feedstock and the hydrogenated products obtained over different catalysts were determined by GC-PFPD. The test results showed that the diatomite-dispersed NiMoW catalyst had high hydrodesulfurization activity for FCC diesel, which could be contributed to the excellent hydrogenation perfor- mance of the said catalyst. Characterization of catalyst by TEM and XRD indicated that the diatomite-dispersed NiMoW catalyst possessed higher layer stacking, larger curvature of MoS2 or WS2, and segregated Ni3S2 crystals relative to the sup- ported catalyst. This kind of structure leads to high hydrogenation activity of the diatomite-dispersed NiMoW catalyst.     

加速氧化法精制焦化柴油的研究

采用加速氧化法对辽河炼油厂焦化柴油进行精制,考察了影响精制柴油色度的各种因素,确定最佳精制工艺条件为:氧化剂用量1.5%～2.5%,反应温度40～70℃,反应时间15～30min,沉降时间不低于30min,搅拌速度不低于600r/min,洗脱剂用量不低于1.0%.在此最佳条件下,产品收率为97.6%,各项指标均符合国家柴油质量标准.     

气相色谱-飞行时间质谱分析焦化柴油中氮化物组成

采用固相萃取法分离富集焦化柴油中的含氮化合物组分,然后通过气相色谱/场电离-飞行时间质谱(GC/FITOFMS)及气相色谱/四级杆-飞行时间质谱(GC/QTOFMS)对含氮化合物类型进行定性分析.结果表明,焦化柴油中除了常见的苯胺类、吲哚类、喹啉类、苯并喹啉类、咔唑类、苯并咔唑类氮化物外,还发现了四氢异喹啉类、苯基吡啶...     

Ni-Mo/TiO_2-Al_2O_3催化剂上柴油加氢脱硫反应动力学

采用高压滴流床反应器,在反应温度280～360℃、H2分压5～7 MPa、氢与油体积比300～900、液态空速1～6 h-1的条件下,考察了柴油在Ni-Mo/TiO2-Al2O3催化剂上的加氢脱硫反应规律,并建立了柴油加氢脱硫反应动力学模型。采用Levenberg-Marquard优化方法对实验数据进行回归,确定了反应动力学模型中的有关参数。实验结果表明,Ni-Mo/TiO2-Al2O3催化剂上柴油加氢脱硫反应为1.5级,表观活化能为78 002 J/mol。模型计算结果与实验数据吻合良好,平均相对偏差仅为2.7%。     

Kinetics of Oxidative Desulfurization of Sulfur Compounds in Diesel Fuel

Abstract

The oxidation of diesel fuel sample was carried out using tertiary butyl hydroperoxide oxidant in the presence of two commercially available Ni-Mo catalysts. The studies were carried out by changing reaction conditions such as treat ratios (oxidant/sulfur molar ratio), WHSV, temperature, etc., to achieve product diesel with sulfur content of <20 ppm. The results of the study on diesel were compared by carrying out similar experiments on model compound, namely, dibenzothiophene dissolved in sulfur-free liquid paraffin oil. GC-PFPD instrument was used to identify and group different sulfur compounds present in diesel and the kinetics of desulfurization was studied.     

A Comparative Study of the HDS Kinetics of Straight Run and Coker Gas Oils Under Deep Desulfurization Conditions

Abstract

Deep desulfurization of diesel blending streams has gained considerable importance in the petroleum refining industry in recent years due to environmental regulations which limit the sulfur content of diesel fuel to very low levels. Among the various factors influencing deep desulfurization of diesel to lower and lower sulfur levels, the quality of the feedstock plays an important role. In the present work, the degree of desulfurization of two different feedstocks, namely, coker gas oil (CGO) and straight run gas oil (SRGO) and their blends was investigated under different operating severities. The distributions of different types of sulfur compounds in both feeds were examined by GC-SCD. Kinetics of desulfurization of both feeds under deep desulfurization conditions was also studied. The results revealed that SRGO, in spite of having a significantly larger amount of total sulfur, desulfurized more easily and produced diesel fuel with low sulfur levels in the desired range (< 350 ppm) at lower temperatures compared with CGO. More severe operating conditions (higher temperature, lower LHSV etc.) were found necessary to bring about deep desulfurization of CGO and its blends with SRGO to the same sulfur level. Kinetic experiments showed a reaction order of 1.5 for the overall HDS of both types of feeds, but the activation energy was higher for CGO (30 kcal/mole) than SRGO (24 kcal/mole). The results are explained on the basis of the differences in the concentrations of nitrogen and refractory sulfur compounds present in the two feeds.