"反应-吸附法"精制焦化柴油的研究

以物质A为反应物,白土为脱色物质,研究用反应-吸附的方法提高焦化柴油的质量。实验表明:精制油的色度、氧化安定性沉渣、实际胶质均可达到国标合格柴油的要求,焦化柴油中的硫、氮等杂原子化合物和不饱和烃类化合物等不安定组分得到有效脱除,柴油质量大大提高,精制柴油收率在98%以上。     

High quality diesel by hydrotreating of atmospheric gas oil/light cycle oil blends

An improved process for high-quality diesel fuel production by hydrotreating atmospheric gas oil (SRGO) and light cycle oil (LCO) blends is presented in this paper. For this purpose, a set of blends of 5, 10 and 15% by volume of LCO with final boiling points of 300, 325 and 350 °C with a full range gas oil (FBP 350 °C) was hydrotreated in a pilot plant at 340-380 °C, 5.4 MPa, 2.5 h⁻¹ LHSV using a commercial Co-Mo catalyst. A relationship between the concentration of refractory sulfur compounds (those boiling above 316 °C) and aromatics content in the feedstock with the hydrotreating temperature required for meeting a 0.05% sulfur specification was found.The experimental data obtained during the desulfurization was quantitatively represented by a 1.50 to 1.56 order rate equation, with activation energies between 18.9 and 34.1 kcal/mol, depending on the feedstock.     

焦化蜡油加氢处理催化剂的研制

本文阐述了用于劣质焦化蜡油加氢处理催化剂的研制,并利用LTOC、TPR、XRD及TEM技术对所研制的催化剂进行了表征,同时对所研制的催化剂进行了活性和稳定性试验,取得了良好结果。目前该催化剂己应用在长岭炼油厂300kt/a加氢装置上,经济效益明显。     

催化裂化吸附转化加工焦化蜡油工艺

分析了焦化蜡油（CGO）与直馏蜡油（VGO）的性质,焦化蜡油与直馏蜡油性质相差较大,主要表现在焦化蜡油残炭、碱氮化合物、胶质、沥青质及金属含量较直馏蜡油高,催化裂化（FCC）直接掺炼焦化蜡油,会造成转化率降低,产物分布恶化,运转周期缩短。通过常规催化裂化加工焦化蜡油工艺与FCC通过吸附转化工艺加工焦化蜡油比较,得出催化裂化吸附转化加工焦化蜡油工艺可以明显改善产物分布,提高转化率,降低碱氮化合物对催化剂的毒害作用,提高装置的整体经济效益。     

Hydrotreating of gas oil on SBA-15 supported NiMo catalysts

The siliceous and the metal substituted (B or Al)-SBA-15 molecular sieves were used as a support for NiMo hydrotreating catalysts (12 wt.% Mo and 2.4 wt.% Ni). The supports were characterized by X-ray diffraction (XRD), scanning electron microscopy and N₂ adsorption–desorption isotherms. The SBA-15 supported NiMo catalysts in oxide state were characterized by BET surface area analysis and XRD. The sulfided NiMo/SBA-15 catalysts were examined by DRIFT of CO adsorption and TPD of NH₃. The HDN and HDS activities with bitumen derived light gas oil at industrial conditions showed that Al substituted SBA-15 (Al-SBA-15) is the best among the supports studied for NiMo catalyst. A series of NiMo catalysts containing 7–22 wt.% Mo with Ni/Mo weight ratio of 0.2 was prepared using Al-SBA-15 support and characterized by BET surface area analysis, XRD and temperature programmed reduction and DRIFT spectroscopy of adsorbed CO. The DRIFT spectra of adsorbed CO showed the presence of both unpromoted and Ni promoted MoS₂ sites in all the catalysts, and maximum “NiMoS” sites concentration with 17 wt.% of Mo loading. The HDN and HDS activities of NiMo/Al-SBA-15 catalysts were studied using light gas oil at temperature, pressure and WHSV of 370 °C, 1300 psig and 4.5 h⁻¹, respectively. The NiMo/Al-SBA-15 catalyst with 17 wt.% Mo and 3.4 wt.% of Ni is found to be the best catalyst. The HDN and HDS activities of this catalyst are comparable with the conventional Al₂O₃ supported NiMo catalyst in real feed at industrial conditions.     

Separation and characterization of foulant material in coker gas oils from Athabasca bitumen

Gas oil streams from the upgrading of oilsands bitumen contain toluene insoluble, gummy, solid foulants that cause process problems by plugging hydrotreater feed filters and catalyst beds. From a process optimization standpoint, it is of considerable interest to determine the exact origin and nature of this material in order to design remedial measures. We selected coker heavy gas oil (KHGO) from bitumen upgrading as the primary test material for this work but also include samples from other parts of the process.Typically, solids content of gas oils are determined by a filtration method. For the KHGO sample used here, this approach yielded a value of 45 ppm. We also compared solids content using ultra- and low-speed centrifugation techniques. With toluene as the diluent, both of these centrifugation methods gave virtually the same toluene insolubles (TI) value, i.e. 24 and 23 ppm, respectively. For paraffinic diluents the measured TI contents ranged from about 50 to 200 ppm. Our results demonstrate that KHGO may contain significant amounts of TI not measured by conventional filtration.Characterization of gas oil TI from different sampling points in the bitumen upgrading circuit showed that it is a nitrogen and oxygen rich organic material, associated with minor amounts of inorganic elements representative of ash-forming iron minerals and alumino-silicate clay. The most likely source for this intractable toluene insoluble fraction appears to be a low molecular weight pyrrollic species present in heavy gas oil. Such compounds are easily oxidized to produce insoluble polymers that can interact with inorganic minerals and metals, producing gummy material capable of blinding filters.     

A novel composite support for hydrotreating catalyst aimed at ultra-clean fuels

To produce ultra-clean fuel, a well-designed composite support, the unique combination of titanosilicate ETS-10 and aluminophosphate AlPO₄-5 with alumina, was firstly developed. Compared with pure alumina, it owns a certain amount of B type acid sites of moderate acid strength, contributing to the removal of refractory 4,6-DMDBT effectively. Moreover, it can impede inactive nickel spinel formation, improve metal–support interactions and favor more polymeric tungsten species formation, which facilitates the promotion effect of nickel on tungsten. With FCC diesel (sulfur: 960.0 μg g⁻¹ and aromatics: 51.0 vol.%) as feed, the clean diesel product (sulfur: 2.7 μg g⁻¹ and aromatics: 15.0 vol.%) without much over-cracking fractions, can be obtained over the composite support based catalyst, at 8.0 MPa, 633 K, LHSV of 1 h⁻¹, H₂/oil ratio of 500 (v/v).     

Rey-zeolite and silica-alumina mixed support for hydrotreating heavy gas oil

Rare earth exchanged Y-type zeolite (REY-zeolite) was dispersed in a silica-alumina gel to prepare catalyst supports with better hydrogenolysis activity. Such support material showed improved hydrotreating properties compared to commercial catalysts, especially for heavy gas oils. Statistical experimental designs used to optimize the composition of such mixed supports suggested a composition of 10 wt.% silica, 25 wt.% zeolite and 65 wt.% alumina as optimum for hydrotreating a heavy gas oil (343°C to 525°C fraction) obtained from hydrocracking of Athabasca bitumen. The kinetic parameters were then evolved for the optimum catalyst.     

负载型杂多酸脱除焦化蜡油中碱性氮化物

以硅胶为载体,利用等体积浸渍法负载杂多酸制备3种不同负载型杂多酸吸附剂,采用傅里叶红外光谱和氮气吸附-脱附法对吸附剂负载状态进行了表征。将制备的负载型吸附剂用于焦化蜡油中碱性氮化物的脱除,考察了负载量、反应时间、反应温度和剂油质量比对焦化蜡油脱氮率的影响。结果表明,磷钨酸负载质量分数为40%、反应温度为50℃、反应时间为50min、剂油质量比为1:4的条件下,负载型杂多酸吸附剂能有效脱除焦化蜡油中的碱性氮化物,脱氮率达到89.07%,脱氮油收率达95.54%.     

Hydrocracking of petroleum gas oil over NiW/MCM-48-USY composite catalyst

MCM-48-USY composite materials were prepared by coating USY zeolite by a layer of MCM-48 mesoporous material at different meso/microporous ratios (SiO₂/USY ratios of 0.1, 0.2, 0.3, 0.4, 0.5) and used as support for nickel and tungsten. The NiW/MCM-48-USY catalysts were prepared using the incipient wetness method. The prepared catalysts were characterized by TPD-TGA acidity, TGA thermal stability, BET surface area, pore volume, pore size, XRD, SEM and TEM and then tested for hydrocracking of petroleum gas oil at reaction temperature of 450 °C, contact time of 90 min and catalyst to gas oil ratio of 0.04. In all prepared samples, the catalyst activity and properties were improved with increasing SiO₂/USY ratio and found that maximum values of a total conversion and liquid product (total distillate fuels) were obtained at SiO₂/USY ratio of 0.5. Finally, the obtained results from hydrocracking of gas oil over composite MCM-48-USY catalysts were compared with those obtained over physically mixed USY and MCM-48 catalysts.     

Structural changes in catalytic hydroprocessing of syncrude coker gas oil

A method of Structural Group Analysis (SGA) was used to characterize feed and liquid products from catalytic hydroprocessing using a commercial Ni-Mo catalyst. Comparison of the structural profiles revealed significant changes in the concentration of various structural groups. SGA is a promising tool for investigating chemical changes in complex reacting systems.     

劣质蜡油加氢处理催化剂上金属杂质沉积规律研究

在缓和加氢条件下,采用新研制的FCC原料预处理催化剂处理含渣劣质蜡油,研究反应规律和杂质沉积规律。结果表明,研制的催化剂孔容和平均孔径较大,金属杂质在整个床层均匀沉积,在每个颗粒中由边缘到中心也均匀分布,这种沉积特点提高了催化剂活性稳定性。在2 500 h连续实验运转过程中,脱硫率无明显下降。     

辽河焦化蜡油脱芳烃实验研究

以辽河石化焦化蜡油(CGO)为研究对象,采用糠醛将其中的芳香组分和碱性氮化物选择性地脱除,并确定最适的反应条件为温度50℃、剂油体积比1.5.在此条件下,抽余油收率为67.55％,碱性氮含量为712.72 mg/kg,饱和分由61.00％提高到77.83％,芳香分由34.94％降至18.76％.碱性氮和四组分数据表明抽出油性质优于直馏蜡油,完全可以作为催化裂化的原料,而抽出油则可作为原料生产高附加值的化工产品.     

Hydrotreating of straight run gas oil–light cycle oil blends

A pilot plant study was conducted to evaluate the effect of up to 50 vol% light cycle oil (LCO) on product quality when it is used together with straight run gas oil (SRGO) as a hydrotreating feedstock. Experiments were carried out at reaction pressures of 54, 70 and 90 kg/cm²; reaction temperatures of 350, 360, 370 and 380°C, liquid hourly space velocity (LHSV) of 1.0, 1.5 and 2.0 h⁻¹, and constant hydrogen-to-oil ratio of 2000 ft³/bbl, over a commercial Co–Mo/γ-Al₂O₃ catalyst. The experimental results were used to determine apparent reaction orders and activation energies, which agree with those reported in the literature.     

Effect of the sulfidation process on the mechanical properties of a CoMoP/Al2O3 hydrotreating catalyst

Mathematical models for the mechanical properties of a CoMoP/Al₂O₃ hydrotreating catalyst in the sulfidation process are developed with response surface methodology. A Doehlert design is performed to collectively study the effects of sulfidation temperature, time and heating rate on the mean strength, Weibull modulus and pellet density. Analysis of variance reveals that the models developed for the mean strength and Weibull modulus are adequate. The validity of the models is also verified by experimental data. Analyses of response surfaces show that in the great part of the experimental domain examined, as the sulfidation temperature increases the mean strength decreases, while the Weibull modulus increases at first and then decreases. The middle level of the sulfidation time results in smaller mean strength and higher Weibull modulus. The Weibull modulus decreases with increasing heating rate; however, the effect of the heating rate on the mean strength is statistically less pronounced. It is concluded that there is a great potential for improving the catalyst mechanical reliability in the sulfidation process, while the pellet density does not vary significantly.     

A comparative activity study of a new ultra-dispersed catalyst system for a hydrocracking/hydrotreating technology using vacuum residue oil: Merey/Mesa

Ultra-dispersed catalysts give an improvement over the main reactions activity by having a low deactivation rate. They provide as well other advantages like a diminution in the catalysts metal concentration, a reduction in contaminants and also these catalysts can be used in almost every area where heterogeneous catalysts are used. Catalysts synthesis optimization is important to improve process recovery, especially in hydrocracking/hydrotreating processes, where feedstock is vacuum residue. Here, we have evaluated the catalytic performance of two molybdenum–nickel catalysts prepared using different emulsion formulation, named E-T (base catalyst) and AT-48 (new catalyst). Our results showed that, the percentage of converted products for VR 500 °C⁺, asphaltenes and microcarbon are comparable for both E-T and AT-48 catalysts, despite the fact that for the latter a lower molybdenum concentration was used. In addition, post-catalytic particles analyses using SEM and TEM techniques demonstrated that AT-48 catalyst showed a non-aggregated and homogeneous narrower distribution of metallic particles than E-T one. The lower average particle size distribution is related to the improvement of the liquid product yields for the hydroconversion of Mery/Mesa VR using the AT-48 catalyst.     

负载型催化剂Al/SiO2催化制备环氧大豆油的研究

制备了含铝5%的负载型Al/SiO2多相催化剂,以其为催化剂,采用改进型无溶剂法工艺合成环氧大豆油。优化工艺条件为:反应时间4 h,大豆油∶甲酸(85%)∶H2O2(30%)=1∶0.2∶0.92(体积比),催化剂用量为2.0 g,反应温度40～60℃,所得产品色泽浅,环氧值高(>6.5%),产品质量优于国家标准,催化剂可重复使用,再生容易,无腐蚀,对环境友好。     

负载型催化剂AI／Si02催化制备环氧大豆油的研究

制备了含铝5％的负载型AI／SiO2多相催化剂,以其为催化剂,采用改进型无溶剂法工艺合成环氧大豆油。优化工艺条件为：反应时间4h,大豆油：甲酸（85％）：H202（30％）=1：0．2：0．92（体积比）．催化剂用量为2．0g,反应温度40。60℃,所得产品色泽浅,环氧值高（〉6．5％）,产品质量优于国家标准,催化剂可重复使用,再生容易,无腐蚀,对环境友好。     

磷改性拟薄水铝石性能及在蜡油加氢催化剂中的应用

在碳化法拟薄水铝石生产过程中加入磷改性剂制备磷改性拟薄水铝石。考察了磷含量对拟薄水铝石和模式载体的物理性能和酸性能的影响。结果表明,随着磷含量的增加,拟薄水铝石和载体的孔容和比表面积增大,但到一定程度后,孔容和比表面积下降,磷存在最佳加入量。磷改性后的拟薄水铝石和模式载体随着磷含量的增加,弱酸量增加,中强酸量降低,总酸量减少。以磷改性拟薄水铝石和不合磷碳化法拟薄水铝石为原料,制备了不同磷含量的氧化铝载体及催化剂,采用中国石油胜利炼油厂生产的减压蜡油在100mL小型加氢装置上进行评价实验,优化制备出适宜的蜡油加氢处理催化剂。