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。     

MIP催化裂化柴油与渣油联合加氢工艺研究

以长岭渣油作为原料油,在不同操作条件下,研究了中国石化石家庄炼化分公司MIP催化裂化重柴油的掺入对渣油加氢的影响。结果表明,MIP催化裂化重柴油的掺入使得脱硫率和脱(Ni+V)率均有提高,脱硫率最高提高了2.36百分点,脱(Ni+V)率最高提高了3.14百分点。收集渣油加氢生成油进行催化裂化试验,结果表明,按循环操作计算,MIP催化裂化汽油收率可增加8.69百分点。     

Study on Residual Oil HDS Process with Mechanism Model and ANN Model

Based on the Residual Oil Hydrodesulfurization Treatment Unit (S-RHT), the n-order reaction kinetic model for residual oil HDS reactions and artificial neural network (ANN) model were developed to determine the sulfur content of hydrogenated residual oil. The established ANN model covered 4 input variables, 1 output variable and 1 hidden layer with 15 neurons. The comparison between the results of two models was listed. The results showed that the predicted mean relative errors of the two models with three ...     

催化裂化柴油馏分加氢精制提高十六烷值研究

在中型加氢试验装置上,采用NiMoW/Al2O3加氢精制催化剂对催化裂化柴油进行加氢精制,以提高柴油的十六烷值,考察了反应温度、体积空速、氢油体积比等工艺参数对催化裂化柴油加氢精制产品十六烷值及其烃类反应规律的影响。结果表明：在6.4 MPa氢分压条件下,经过不同深度加氢精制后产品柴油的十六烷值有较大幅度的提高,十六烷值可以提高7~13个单位;催化裂化柴油中各烃类在具有高加氢活性的Ni-Mo-W/Al2O3加氢精制催化剂作用下,对提高产品十六烷值有利的反应主要是芳烃加氢饱和反应;反应温度、体积空速、氢油比等操作条件对提高催化裂化柴油十六烷值有较大的影响,在氢分压一定的条件下,适宜的反应温度和氢油体积比、较低的体积空速等有利于芳烃加氢饱和反应,从而提高催化裂化柴油的十六烷值。     

加氢精制深度对催化裂化柴油性质的影响

在固定床小型加氢实验装置上,以不同的催化裂化柴油为原料,模拟两段加氢处理技术生产低硫低芳烃柴油,考察加氢精制深度对柴油性质的影响。评价时第一反应器装填Ni-W催化剂,第二反应器装填Pt-Pd贵金属催化剂,通过调整空速和反应压力,得到不同加氢精制深度的柴油。结果表明：经过深度加氢精制,柴油的密度、折射率、硫含量、氮含量、总芳烃含量均减小,氢含量、十六烷值提高;加氢精制后的柴油芳烃含量与化学氢耗、折射率、密度、十六烷值成线性关系;不同催化裂化柴油加氢精制后的芳烃含量与十六烷值的线性拟合斜率和截距各不相同,与柴油的烃类组成和碳数分布密切相关,截距代表了芳烃完全饱和时的十六烷值,斜率反映了芳烃饱和对十六烷值的贡献;对总芳烃质量分数为88.2%的催化裂化柴油LCO-I,芳烃质量分数每降低1百分点,十六烷值可提高0.26个单位,芳烃完全饱和时十六烷值可达到42,对总芳烃质量分数为31.3%的混合柴油LCO-II,芳烃质量分数每降低1百分点,十六烷值可提高0.66个单位。     

催化裂化柴油及其加氢产物中芳烃类型 与分子结构的表征

基于气相色谱-质谱(GC-MS)测定催化裂化柴油(LCO)及其加氢产物中芳烃的组成。根据色谱保留时间和质谱断裂特征,分析了LCO及其加氢产物中芳烃的类型与结构,并对C₉~C₁₁的C_nH_2n-8类及C_nH_2n-12类芳烃进行了分子结构鉴别。结果表明：C_nH_2n-8类芳烃在LCO中为具有五元环结构的茚满类,在加氢产物中既有四氢萘类,也有茚满类,后者可由前者发生异构化反应生成;C_nH_2n-10类芳烃在LCO中是以含有双键的环烷芳烃为主,如茚类、二氢萘类,在加氢产物中则是以含有饱和环结构的芳烃,如二环烷基苯类为主;LCO及其加氢产物中的C_nH_2n-16类芳烃均为芴类;萘类侧链的碳数、个数与位置均会影响其加氢转化率。此研究可为芳烃的选择性加氢以及后续加工提供信息。     

Technical and Economical Analysis of Hydrogen Sulfide Removal from the Recycled Hydrogen in a Diesel Hydrodesulfurization Plant

Hydrodesulfurization (HDS) is a catalytic process used to remove sulfur compounds, which leads to very low sulfur concentrations. HDS turns more complicated and severe according to the feedstock boiling range, since sulfur compounds present in light cuts, normally sulfides and mercaptanes, are easy to remove, and sulfoaromatic compounds, specially polycyclics, are the more refractive ones (Speight, J. G. (1981). The Desulfurization of Heavy Oils and Residua. 2nd ed. Marcel Dekker, Inc.: Chemical Industries 4.) The hydrogen sulfide (H₂S) produced in the HDS has an inhibiting effect on the same reaction, as it has been widely observed (McCulloch, D. C. (1983). Applied Ind Catal. I:69; National Petroleum Refining Association (NPRA). (1993). Questions & Answers, 99; Leglise, J., Van Gestel, J., Duchet, J. C. (1994). Symposium on Advances in Hydrotreating Catalysts Presented before the Division of Petroleum Chemistry Inc. In: 208th National Meeting American Chemical Society. Washington D.C. p. 533). This effect is well known even at relatively low H₂S concentrations (2 mol%) for commercial operation conditions (Leglise, J., Van Gestel, J., Duchet, J. C. (1994). Symposium on Advances in Hydrotreating Catalysts Presented before the Division of Petroleum Chemistry Inc. In: 208th National Meeting American Chemical Society. Washington D.C. p. 533). Due to this, the H₂S removal from the recycled hydrogen to the reactor is mandatory in order to increase the desulfurization levels or to increase the processing capacity of an HDS plant. There are many options to low the H₂S concentration in the H₂ loop (Cooper, A., Stanislaus, A., Hannerup, P. N. (June 1993). Hyd Process 84; Johnson, A. D. (1983). Oil and Gas J 10:78; Nash, R. M. (1989). Oil and Gas J 13:47; Suchanek, A. J., Dave, D., Gupta, A., Van Stralen, H., Karlsson, K. (1993). In: NPRA Annual Meeting AM-93-24; Tippett, T., Knudsen, K. G. (1999). In: NPRA Annual Meeting. San Antonio, TX. 1999 NPRA Annual Meeting, San Antonio, TX, AM-99-06.), which are from a simple purge adjustment for light naphtha HDS to a full treatment of the H₂ stream for middle distillate HDS, where the H₂S concentration can reach levels of 10 mol% (National Petroleum Refining Association (NPRA). (1993). Questions & Answers, 99). This work presents the economical analysis of the introduction of an Amine Treating Unit in an HDS plant in operation to remove H₂S from the H₂ stream recycled to the reactor.     

Technical and Economical Analysis of Hydrogen Sulfide Removal from the Recycled Hydrogen in a Diesel Hydrodesulfurization Plant

Abstract

Hydrodesulfurization (HDS) is a catalytic process used to remove sulfur compounds, which leads to very low sulfur concentrations. HDS turns more complicated and severe according to the feedstock boiling range, since sulfur compounds present in light cuts, normally sulfides and mercaptanes, are easy to remove, and sulfoaromatic compounds, specially polycyclics, are the more refractive ones (Speight, J. G. (1981 Speight, J. G. 1981. The Desulfurization of Heavy Oils and Residua Chemical Industries 4. , 2nd ed. Marcel Dekker Inc.  [Google Scholar]). The Desulfurization of Heavy Oils and Residua. 2nd ed. Marcel Dekker, Inc.: Chemical Industries 4.) The hydrogen sulfide (H₂S) produced in the HDS has an inhibiting effect on the same reaction, as it has been widely observed (McCulloch, D. C. (1983 McCulloch, D. C. 1983. Applied Ind. Catal., I: 69 [Google Scholar]). Applied Ind Catal. I:69; National Petroleum Refining Association (NPRA). (1993 National Petroleum Refining Association, NPRA. 1993. Questions & Answers 99 [Google Scholar]). Questions & Answers, 99; Leglise, J., Van Gestel, J., Duchet, J. C. (1994 Leglise, J., Van Gestel, J. and Duchet, J. C. Symposium on advances in hydrotreating catalysts presented before the division of petroleum chemistry Inc. 208th National Meeting. pp.pp. 533Washington, D.C.: American Chemical Society.  [Google Scholar]). Symposium on Advances in Hydrotreating Catalysts Presented before the Division of Petroleum Chemistry Inc. In: 208th National Meeting American Chemical Society. Washington D.C. p. 533). This effect is well known even at relatively low H₂S concentrations (2 mol%) for commercial operation conditions (Leglise, J., Van Gestel, J., Duchet, J. C. (1994 Leglise, J., Van Gestel, J. and Duchet, J. C. Symposium on advances in hydrotreating catalysts presented before the division of petroleum chemistry Inc. 208th National Meeting. pp.pp. 533Washington, D.C.: American Chemical Society.  [Google Scholar]). Symposium on Advances in Hydrotreating Catalysts Presented before the Division of Petroleum Chemistry Inc. In: 208th National Meeting American Chemical Society. Washington D.C. p. 533). Due to this, the H₂S removal from the recycled hydrogen to the reactor is mandatory in order to increase the desulfurization levels or to increase the processing capacity of an HDS plant. There are many options to low the H₂S concentration in the H₂ loop (Cooper, A., Stanislaus, A., Hannerup, P. N. (June 1993 Cooper, A., Stanislaus, A. and Hannerup, P. N. 1993. Hyd. Process., June: 84 June [Google Scholar]). Hyd Process 84; Johnson, A. D. (1983 Johnson, A. D. 1983. Oil and Gas J., 10: 78 [Google Scholar]). Oil and Gas J 10:78; Nash, R. M. (1989 Nash, R. M. 1989. Oil and Gas J., 13: 47 [Google Scholar]). Oil and Gas J 13:47; Suchanek, A. J., Dave, D., Gupta, A., Van Stralen, H., Karlsson, K. (1993 Suchanek, A. J., Dave, D., Gupta, A., Van Stralen, H. and Karlsson, K. NPRA Annual Meeting. AM-93-24 [Google Scholar]). In: NPRA Annual Meeting AM-93-24; Tippett, T., Knudsen, K. G. (1999 Tippett, T. and Knudsen, K. G. NPRA Annual Meeting. San Antonio, TX. AM-99-06 [Google Scholar]). In: NPRA Annual Meeting. San Antonio, TX. 1999 NPRA Annual Meeting, San Antonio, TX, AM-99-06.), which are from a simple purge adjustment for light naphtha HDS to a full treatment of the H₂ stream for middle distillate HDS, where the H₂S concentration can reach levels of 10 mol% (National Petroleum Refining Association (NPRA). (1993 National Petroleum Refining Association, NPRA. 1993. Questions & Answers 99 [Google Scholar]). Questions & Answers, 99). This work presents the economical analysis of the introduction of an Amine Treating Unit in an HDS plant in operation to remove H₂S from the H₂ stream recycled to the reactor.     

储油罐挥发性有机物的回收与利用

针对储油罐挥发气排放到大气中造成的能源浪费和环境污染,为满足排放指标要求,降低能耗和污染,从影响排放的原因及损耗类型出发,采用瓦廖夫斯基-契尔尼金公式对储罐自然通风损耗、"大呼吸"损耗和"小呼吸"损耗的损耗量进行计算,并应用挥发气回收技术对储油罐挥发性有机物进行回收利用,将回收的油田伴生气进行燃烧或发电,截止目前38座储油罐的挥发气全部回收利用,总回收气量达到21 513 m^3/d,年创经济效益1 095万元,解决了环境污染的同时,提高了原油商品率。     

A Study on the Effect of Hydrogenated Residual Oil Four-Component Properties on Sulfur Distribution of Light Oil in the FCC Process

Abstract

Based on the data of a hydrogenated residual oil fluid catalytic cracking (FCC) process in a petrochemical company, the effect of hydrogenated residual oil four-component (saturates, aromatics, resins, and asphaltenes; SARA) property on sulfur distribution of light oil in an FCC process was reviewed and a conjunction formula between sulfur distribution of light oil and SARA property was established. The associated results indicated that sulfur distribution of light oil in the FCC process was reduced as the saturate, aromatic, and resin component of hydrogenated residual oil increased, and the effect factor decreased in the order, saturate > aromatic > resin. On the other hand, the enhancement of the asphaltene component made the sulfur distribution of light oil increase slightly. In addition, the conjunction formula was used to predict sulfur distribution of light oil by the other hydrogenated residual oil feedstock and the calculated sulfur distribution of light oil was in good agreement with the actual data; all the predicted relative errors were less than 5% and the mean relative error was 2.98%. The results showed that the established conjunction formula possessed good predictive features and reliability.     

Hydrodesulfurization, Hydrodenitrogenation, Hydrodemetallization, and Hydrodeasphaltenization of Maya Crude over NiMo/Al2O3 Modified with Ti and P

The effect of adding Ti (4.5 wt%) and P (∼1.0 wt%) by several routes to a NiMo/ab Al₂O₃ catalyst on the hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM), and hydrodeasphaltenization (HDAs) of heavy Maya crude was investigated. The results show that not all the catalyst functionalities respond equally well to the addition of Ti and P to the catalyst formulation. There is not a single catalyst formulation that can achieve optimum performance in all the catalyst functionalities. For HDS, Ti incorporation increases activity but the route by which P is added afterwards can improve or be detrimental to HDS activity. For HDN, the incorporation of P to the catalyst can lead to significant improvements in catalytic activity and catalyst stability. Ti increases HDM activity but the addition of P to the catalyst is detrimental to this functionality. For the elimination of asphaltenes, the catalyst supported on pure alumina is the best. So for HDAs, no benefit is obtained by the addition of Ti or P to the catalyst. Textural properties are important and HDM and HDAs increase with catalyst average pore diameter. Hydrodemetallization activity increases with the acidity of the catalyst.     

氮化物对柴油深度和超深度加氢脱硫的影响Ⅰ.氮化物含量的影响

氮化物和硫化物同时存在于柴油之中。采用硅胶脱除原料中氮化物，得到硫含量相同而氮含量不同的4种柴油原料。为了考察氮化物对加氢脱硫（HDS）的影响，在反应温度350℃、氢分压4．8MPa、液时空速2．0h^-1和氢／油体积比300的条件下，采用工业化的NiW／Al2O3催化剂在小型固定床实验装置上对该4种柴油原料进行加氢脱硫实验。结果表明，在真实油品的复杂体系中，氮化物对加氢脱硫反应有明显的抑制作用，加氢脱硫反应速率随着原料中氮含量的增加而降低。分子模拟计算结果表明，氮化物与硫化物在催化剂活性位上发生竞争吸附，氮化物的吸附能力较强，抑制了加氢脱硫反应。     

Characterization of Nitrogen Compounds in Vacuum Residue and Their Structure Comparison with Coker Gas Oil

In this study, the heteroatom classes and molecular structures of nitrogen compounds in vacuum residue are characterized by the electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) combined with the Fourier transform infrared(FT-IR) spectroscopy. The results demonstrate that three basic nitrogen compounds, N1(in which a molecule contains one nitrogen atom, similarly hereinafter), N1O1 and N2, are identified by their positive-ion mass spectra, and three non-basic nitrogen compounds, N1, N1O1, and N1S1, are characterized by their negative-ion mass spectra. Among these nitrogen compounds, the N1 class species are the most predominant. Combined with the data of ESI FT-ICR MS and FT-IR, the basic N1 class species are likely alkyl quinolines, naphthenic quinolines, acridines, benzonacridines, while the abundant non-basic N1 class species are derivatives of benzocarbazole. In comparison with CGO, the N1 basic nitrogen compounds in VR exhibit a higher average degree of condensation and have much longer alkyl side chains.     

轻油泵房无真空系统辅助卸油单元的实验和分析

对轻油泵房无真空系统辅助同单元运行了实验测试和理论分析。实验测试和理论分析表明,辅助卸油单元与现有的真空系统工作原理不同;辅助卸油单元可以完全取代现有轻油泵房中的真空系统,具有十分重要的使用价值。     

煤系低熟油形成机制及其意义

从煤系有机质组成的复杂性和“显微组分分期生油”的角度,讨论了煤系中低熟油生成的可能性,结合实例阐述了树脂体早期生烃和木栓质体早期生烃两种煤系低熟油形成机制根据对煤的物理性质与煤层排液过程关系的分析指出,低熟油生成时期恰好是煤层释放液态烃类的最佳时期。因此,煤系存在低熟油形成机制是煤成油有效聚集的先决条件之一。     

重油加氢装置高压空冷器管束的腐蚀与防护

通过对重油加氢装置VRDS两台高压空冷器腐蚀泄漏原因进行分析 ,指出工艺条件的变化是造成管束穿孔的主要原因。由于NH4 Cl和NH4 HS的沉积 ,造成管内流速和温度的变化 ,从而使腐蚀加剧。并提出了在高压、临氢、含湿硫化氢、富氯的苛刻条件下空冷器的修复处理办法及采取的防护措施 ,增加注水设施 ,空冷器出口端安装钛保护套管和注多硫化钠缓蚀剂可有效延长空冷器寿命。     

稠油掺稀降粘举升环空摩阻分析

稠油掺稀降粘可显著降低沿程摩阻,改善稠油流动性。为正确进行举升工艺设计和优化掺稀比,文章分析稠油环空流动态规律,得到了沿程摩阻梯度方程,利用龙格-库塔方法对方程进行了数值求解。计算结果表明,稠油环空流的沿程摩阻损失主要由稠油的粘度引起的,流速起次要作用。     

Hydrotreating of Maya Crude Oil: I. Effect of Support Composition and Its Pore-diameter on Asphaltene Conversion

Abstract

A systematic study for a concept governing support effect in heavy oil hydrotreating (HDT) catalysts is performed. Different Al₂O₃ and its mixed oxides supports were prepared and CoMo supported catalysts were tested for Maya heavy crude oil hydrotreating. Fresh and spent catalysts are characterized with N₂ adsorption-desorption, element analysis, and scanning electron microscopy-energy dispersion analysis by x-ray (SEM-EDAX), which confirms that coke and metals deposition on the surface of catalyst is most probably near the pore mouth. It is also demonstrated from these results that asphaltene conversion depends on the pore diameter of the catalyst, while other hydrotreating conversions (hydrodesulfurization (HDS), hydrodenitogenation (HDN), and in some extent hydrodemetallization (HDM)) are more likely affected by the nature of active metal distribution. The evaluation of alumina mixed oxide (TiO₂, ZrO₂, B₂O₃, and MgO) supported catalysts indicates that supports with basic nature have better stability than the acid ones.     

Hydrotreating of Maya Crude Oil: I. Effect of Support Composition and Its Pore-diameter on Asphaltene Conversion

A systematic study for a concept governing support effect in heavy oil hydrotreating (HDT) catalysts is performed. Different Al₂O₃ and its mixed oxides supports were prepared and CoMo supported catalysts were tested for Maya heavy crude oil hydrotreating. Fresh and spent catalysts are characterized with N₂ adsorption-desorption, element analysis, and scanning electron microscopy-energy dispersion analysis by x-ray (SEM-EDAX), which confirms that coke and metals deposition on the surface of catalyst is most probably near the pore mouth. It is also demonstrated from these results that asphaltene conversion depends on the pore diameter of the catalyst, while other hydrotreating conversions (hydrodesulfurization (HDS), hydrodenitogenation (HDN), and in some extent hydrodemetallization (HDM)) are more likely affected by the nature of active metal distribution. The evaluation of alumina mixed oxide (TiO₂, ZrO₂, B₂O₃, and MgO) supported catalysts indicates that supports with basic nature have better stability than the acid ones.     

全二维气相色谱-高分辨飞行时间质谱分析LCO中芳烃化合物

采用全二维气相色谱 高分辨飞行时间质谱(GC×GC/HR-TOF MS)对催化裂化轻循环油(LCO)中的芳烃化合物进行详细表征。通过质谱图解析、沸点信息和标准物质保留时间对比,结合仪器高分辨率的优势,确定LCO中的主要芳烃类型及结构。对相同Z值、但类型不同的芳烃在总离子流色谱图中的峰面积进行归一化计算,结合SH/T 0606-2005法测定结果,得到不同类型芳烃在LCO中的含量。结果表明：LCO中除含有Z值为-6的烷基苯类、Z值为-12的萘类和Z值为-18的菲类和蒽类化合物外,还含有Z值为-8的芳烃包含茚满类和四氢萘类化合物,以茚满类为主;Z值为-10的芳烃主要为茚类,含有少量的二环烷基苯类;Z值为-14的芳烃包含联苯类、苊类和二苯并呋喃类化合物,以苊类为主;Z值为-16的芳烃主要为芴类,不含苊烯类化合物。该方法可以提供更为详细的芳烃类型和单体化合物的分子组成信息。