Selective hydrocracking of light cycle oil into high-octane gasoline over bi-functional catalysts

Light cycle oil(LCO) with high content of poly-aromatics was difficult to upgrade and convert,which had hindered upgrading fuel quality to meet with the standard of automotive diesel for the purpose of sustainable development.The hydrocracking behaviors of typical aromatics in LCO of naphthalene and tetralin were investigated over NiMo and CoMo catalysts.Several characterization methods including N2-adsoprtion and desorption,ammonia temperature-programmed desorption(NH3-TPD),Pyridine infrared spectroscopy(Py-IR),CO infrared spectroscopy(CO-IR),Raman and X-ray photoelectron spectroscopy(XPS) were applied to determine the properties of different catalysts.The results showed that CoMo catalyst with high concentration of S-edges could hydrosaturate more naphthalene to tetralin but exhibit lower yield of high-value light aromatics(carbon numbers less than 10) than NiMo catalyst.NiMo catalyst with high concentration of Mo-edges also presented a higher selectivity of converting naphthalene into cyclanes than CoMo catalyst.Subsequently,the naphthalene and LCO hydrocracking performances were also investigated over different catalysts systems.The activity evaluation and kinetic analysis results showed that the naphthalene hydrocracking conversion and the yield of light aromatics for CoMo-AY/NiMo-AY grading catalysts were higher than NiMo-AY/CoMo-AY grading catalysts at same condition.A stepwise reaction principle was proposed to explain the high efficiency of CoMo-AY/NiMoAY grading catalysts.Finally,the LCO hydrocracking evaluation results confirmed that CoMo-AY/NiMoAY catalysts grading system with low carbon deposition and high stability could remain high percentage of active phases,which was more efficient to convert LCO to high-octane gasoline.

Introduction of table sugar as a soft second template in ZSM-5 nanocatalyst and its effect on product distribution and catalyst lifetime in methanol to gasoline conversion

Methanol to gasoline reaction was investigated on two prepared ZSM-5 catalysts. The first one was a conventional catalyst denoted as ZSM-5（C） and the other was a hierarchical catalyst-ZSM-5（S） which was prepared by incorporation of table sugar in catalyst gel during the synthesis procedure. The catalysts were characterized by FTIR, XRD, FE-SEM, N2 adsorption-desorption, NH3-TPD and TGA analytical technics. The proposed material showed pore modification as well as acidity moderating properties in ZSM-5 catalyst. The methanol to gasoline reaction was conducted in a fixed bed reactor with a WHSV of 1.5 h-1.Methanol conversions, gasoline yield and selectivity in production for the synthesized catalysts were determined by gas chromatography method. The sugar modified catalyst converted more methanol than the conventional one and an enhancement in catalyst’s life time was observed. The selectivity to aromatics and durene were reduced compared to the conventional catalyst, so the gasoline quality was also further improved. The coking rate of catalysts was calculated employing TGA method. A reduction in coking rate and an increase in coke capacity of the modified catalyst were observed.

Study on Reaction Mechanism for Cracking FCC Gasoline on Acid Catalyst

This article is based on the experimental data on reaction of FCC naphtha in the presence of acid catalysts. The data published in the literature were reprocessed and compared with experimental data and the relationship of hydrogen and methane contained in the dry gas with the conversion rate was identified.The similarity between the route for cracking of olefin enriched FCC gasoline and the route for reaction of individual hydrocarbons was deduced, while the route for formation of ethylene in dry gas was also proposed to identify the relationship between the reaction path for formation of ethylene and the conversion rate.

Development and Commercial Application of RFCC Catalyst for Reducing Sulfur Content in Gasoline

减少硫的功能的部件 -- 吊楔酸硷的对化合物 -- 并且联系活跃沸石部件被开发为在汽油减少硫内容准备 RFCC 催化剂 DOS。催化剂评估的结果表明了酸硷的对化合物在此开发了的吊楔能提高分子的硫由催化剂加重支持 desulfurization 反应继续的宏的变换，并且酸硷的对化合物能毫无疑问减少的选择沸石和吊楔的合作行动在汽油的石蜡和硫内容。因此开发的催化剂 DOS 的重油变换能力更高结合了一个提高的电阻到重金属污染在超过 20% 在汽油减少硫内容。在西诺佩克·久贾恩格·布朗奇公司的这催化剂的商业应用程序表明了与 GRV-C 催化剂相比，催化剂 DOS 获得的油泥浆收益在汽油与一种改进 cok e 选择，增加的全部的液体收益，和一个减少的石蜡内容一起被减少。在汽油 / 硫在的硫的比率喂油能被 20.3 m% 减少。

Simulation and Optimization of Cracked Gasoline Hydrofining Process

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Study of Carbon Nanotube Supported Co-Mo Selective Hydrodesulphurization Catalysts for Fluid Catalytic Cracking Gasoline

In this paper, carbon nanotube supported Co-Mo catalysts for selective hydrodesulphurization （HDS） of fluid catalytic cracking （FCC） gasoline were studied, using di-isobutylene, cyclohexene, 1-octene and thiophene as model compounds to simulate FCC gasoline. The results show that the Co-Mo/CNT has very high HDS activity and HDS/hydrogenation selectivity comparing with the Co-Mo/γ-Al2O3 and Co-Mo/AC catalyst systems. The saturation ratio of cyclohexene was lower than 50%, and the saturation ratio of 1,3-di-isobutylene lower than 60% for the Co-Mo/CNT catalysts. Co/Mo atomic ratio was found to be one of the most important key factors in influencing the hydrogenation selectivity and HDS activity, and the most suitable Co/Mo atomic ratio was 0.4. Co/CNT and Mo/CNT mono-metallic catalysts showed lower HDS activity and selectivity than the Co-Mo/CNT bi-metallic catalysts.

Preliminary Study on Reducing Olefin Content of FCC Gasoline over Cracking Catalyst

Using fixed bed micro-reactor and cracking catalyst, re-cracking of fluid catalytic cracking (FCC) gasoline at lower temperature than conventional cracking condition has been studied. The results reveal that at lower temperature from 350℃-450℃ and catalyst to feed ratio of 3, the olefin content is reduced from 49% to 27%(by mass) over the catalyst whose micro-reacting activation index is 53, and the octane number is kept on high level.

Commercial Test of HGY-2000R FCC Catalyst for Maximizing Gasoline Yield

HGY-2000R catalyst developed by Research Institute of Petroleum Processing, SINOPEC wastested in the RFCC unit, Ulsan complex, SK Corporation, Korea from July to August 2002. The primaryresults of commercial test show that it has good performance of higher activity, good hydrothermal stability,higher residue cracking ability, good coke selectivity and good fluidization properties as well as maximizinggasoline yield with a lower olefin content.

Fischer-Tropsch Synthesis of the Promoted Co/ZSM-5 Hybrid Catalysts for the Production of Gasoline Range Hydrocarbons

Fischer-Tropsch synthesis (FTS) reaction for the direct production of gasoline range hydrocarbons (C5-C9) from syngas was investigated on Ru, Pt, and La promoted Co/ZSM-5 (Si/Al = 25) catalysts. The hybrid catalysts were characterized by BET surface area, XRD, H2-TPR, NH3-TPD and XPS analyses. These physico-chemical properties were correlated with activity and selectivity of the catalysts. The promoted Co/ZSM-5 hybrid catalysts were found to be superior to the unpromoted Co/ZSM-5 catalyst in terms of better C5-C9 selectivity. Pt-Co/ZSM-5 exhibited the highest catalytic activity because of the small cobalt particle size.

Development of a Novel Type Catalyst SY-2 for Two-Stage Hydrogenation of Pyrolysis Gasoline

By using the group ⅢB or groupⅦB metals and modulating the characteristics of electric charges on carrier surface, improving the catalyst preparation process and techniques for loading the active metal components, a novel type SY-2 catalyst earmarked for two-stage hydrogenation of pyrolysis gasoline has been developed. The catalyst evaluation results have indicated that the novel catalyst is characterized by a better hydrogenation reaction activity to give higher aromatic yield.

Technology Relating to Catalyst for Boosting Gasoline Yield Developed by RIPP Passed Appraisal

Currently the project'Development and commercia application of FCC catalyst for boosting gasoline yield'jointly undertaken by the SINOPEC Research Institute of Petroleum Processing(RIPP),the SINOPEC Yanshan Branch Co.and the Branch of SINOPEC Catalyst Company has passed the appraisal.The catalyst aimed at boosting

Catalyst Innovation for Reducing Olefin Content in MGG Gasoline

为了在汽油减少石蜡内容，当保留 LPG 收益时，由 MGG (最大化的液化气体和汽油) 生产了过程， RIPP 开发了由一个更打开毛孔的矩阵和修改 Y 沸石和与金属氧化物修改的 ZRP 沸石组成的新奇催化剂。测试结果在反应变换率和产品分发由新奇催化剂提供了的可比较的反应条件下面与商业催化剂破布相比揭示了那是类似的，但是在汽油的石蜡内容获得了它在 LPG 部分与与石蜡内容的细微减小一起未改变的辛烷等级被减少。新奇催化剂的热水的稳定性比商业催化剂破布好。

Commercial Application of X-62 Catalyst for Reducing Olefins in Gasoline

In order to reduce the coke yield and increase the economic benefits of FCC unit under the prerequisites of securing the olefin content of gasoline in compliance with the requirement, SINOPEC Luoyang Branch Company applied in the period from July through October 2004 the new generation X-62 catalyst (FlexTec-LOL1) developed by the Engelhard Corporation of USA to improve the heavy oil conversion and to reduce coke make. The result of tests has shown that indicators on reducing the unit catalyst consumption,amplitude on reduction of non-ideal products (coke+oil slurry+dry gas) yield, and amplitude on reduction of coke yield were comparatively satisfactory.

Study on Disproportionation Reaction of FCC Gasoline on Acid Catalyst

Based on the experimental data relating to the reaction of FCC gasoline on acid catalyst the analysis of product distribution, and composition of gasoline and diesel fractions have been analyzed. The occurrence of disproportionation reaction of FCC gasoline on acid catalyst and the network of disproportionation reaction have been identified. Study has also shown that different reaction temperatures can result in different pathways of disproportionation reactions on acid catalyst.

Fischer-Tropsch wax catalytic cracking for the production of low olefin and high octane number gasoline: Process optimization and heat effect calculation

To produce low olefin gasoline with high octane number by Fischer-Tropsch (F-T) wax fluid catalytic cracking (FCC) process, operating conditions optimization were carried out in the pilot-scale riser and turbulent fluidized bed (TFB) FCC unit. The experimental results in the riser indicated that under the condition of low reaction temperature and regenerated catalyst temperature, large catalyst-to-oil weight ratio (C/O) and long reaction time, the gasoline olefin content could be reduced to 20.28 wt%, but there is large octane number loss owing to a great loss in high octane number olefin. Therefore, a novel FCC process using the TFB reactor was proposed to strengthen the aromatization reaction. The reaction performance of TFB reactor were investigated. The result demonstrated that the TFB reactor has more significant effect in reducing olefins and improving aromatics. At the expense of certain gasoline yield, the gasoline olefin content reduced to 23.70 wt%, aromatics content could increase to 26.79 wt% and the RON was up to 91.0. The comparison of reactor structure and fluidization demonstrated that the TFB reactor has higher catalyst bed density. The reaction heat and coke combustion heat was calculated indicating the feasibility of its industrial application of the TFB process.

Study on the in situ desulfurization and viscosity reduction of heavy oil over MoO_(3)–ZrO_(2)/HZSM-5 catalyst

Heavy oil is characterized by high viscosity.High viscosity makes it challenging to recover and transport.HZSM-5,MoO_(3)/HZSM-5,ZrO_(2)/HZSM-5 and MoO_(3)–ZrO_(2)/HZSM-5 catalysts were developed to promote in situ desulfurization and viscosity reduction of heavy oil.The physical and chemical properties of catalysts were characterized by XPS,XRD,TEM,NH3-TPD,etc.The effects of temperature,catalyst type and addition amount on viscosity and composition of heavy oil were evaluated.The results showed that the presence of MoO_(3)–ZrO_(2)/HZSM-5 nanoparticles during aquathermolysis could improve the oil quality by reducing the heavy fractions.It reduced viscosity by 82.56%after the reaction at 280℃ and catalyst addition of 1 wt%.The contents of resins and asphaltic in the oil samples were 5.69%lower than that in the crude oil.Sulfur content decreased from 1.45%to 1.03%.The concentration of H2S produced by the reaction was 2225 ppm.The contents of sulfur-containing functional groups sulfoxide and sulfone sulfur in the oil samples decreased by 19.92%after the catalytic reaction.The content of stable thiophene sulfur increased by 5.71%.This study provided a basis for understanding the mechanism of heavy oil desulfurization and viscosity reduction.

Development and Performance Evaluation of Catalyst for Productive Ethylene Cracking Feedstock in Selective Hydrocracking of Straight Run Diesel Oil

The upgrading of diesel oil to produce ethylene rich cracking feedstock is an important and promising technical route to reduce the ratio of diesel to gasoline. In the present work, a hydrocracking catalyst suitable for selective hydrocracking of straight run diesel oil to produce high-quality ethylene cracking feedstock at low cost was developed, by optimizing the composition of catalyst support materials, using amorphous silicon aluminum and aluminum oxide with high mesopore content as the main support, and modified Y zeolite with excellent aromatic ring opening selectivity as the acidic component. The catalyst has in-depth characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, N2-low temperature adsorption-desorption, NH3-temperature-programmed desorption, and IR techniques. And its catalytic cracking straight run diesel oil performance was evaluated. The results show that the prepared catalyst has high polycyclic aromatic hydrocarbon ring opening cracking selectivity. However, alkanes retained in diesel distillates can achieve the goal of producing more ethylene cracking feedstocks with low BMCI value under low and moderate pressure conditions. This work may shed significant technical insight for oil refining transformation.

半再生重整装置催化剂硅中毒现象及分析

某炼油企业的半再生重整装置因重整催化剂活性下降而停工,更换了第一反应器和第二反应器的催化剂。对旧催化剂进行分析后发现,第一反应器催化剂二氧化硅质量分数高达20.40%,因此判断重整催化剂发生了硅中毒。在硅中毒期间:第一反应器的温降由初期的73.70℃下降到末期的20.12℃,重整反应后移到第二反应器;循环氢的氢气纯度上升到90%,纯氢产率下降到2.17%;稳定汽油RON(研究法辛烷值)下降到83.7。重整催化剂硅中毒较为罕见,其表现与氮中毒相似,容易误判为催化剂氮中毒。对硅进行溯源,确认是原油携带。分析认为:重整预加氢捕硅剂无法完全捕获所有硅,导致部分硅穿透预加氢系统;硅对预加氢催化剂的影响小于对重整催化剂的影响;硅中毒会导致催化剂的氯流失,需要加大注氯量。

C_(4)烯烃转化制丙烯工艺及催化剂研究

目的开发C_(4)烯烃催化裂解制丙烯工艺和催化剂制备工艺技术,完成小试和工业侧线试验。方法采用固定床评价装置考查了催化剂配方、改性及工业条件对催化剂活性、选择性、稳定性能的影响。结果以ZSM-5分子筛为活性组分的催化剂在C_(4)烯烃转化制丙烯反应中具有较好的活性、选择性、稳定性和再生性,磷的引入未改变催化剂的晶型结构,但降低了催化剂酸性位点数量,并调节了催化剂的n(B酸)/n(L酸),随着磷负载量增加到5%(w),分子筛中磷与铝的相互作用逐渐增强,磷可以和骨架铝和非骨架铝相互作用。结论C_(4)烯烃的转化率达到80%以上,丙烯的选择性达到35%~45%,催化剂的单程寿命达到一个月以上,且经再生后,再生恢复率达95%。

ZSM-5/Ni Foam催化剂对生物质气化焦油裂解行为及机制研究

为了克服生物质气化过程中的焦油产生问题,以泡沫镍(Ni Foam)为镍源和载体、ZSM-5分子筛为活性添加物质,采用浸渍法制得ZSM-5/Ni Foam催化剂并在两段式固定床反应系统进行生物质焦油催化裂解实验。结果表明:三维骨架结构的Ni Foam上负载具有酸性活性位点的ZSM-5,不仅可增加焦油与催化剂活性位点的接触面积,还可减缓催化过程中积碳的形成,从而获得更高的催化性能,800℃下焦油转化率达到90.2%,使得ZSM-5/Ni Foam具有良好的催化活性及循环稳定性。同时,也揭示出ZSM-5/Ni Foam的催化机制。