Role of nickel on vanadium poisoned FCC catalyst: A study of physiochemical properties

Active sites of Fluid catalytic cracking (FCC) catalyst are poisoned during operation in the FCC reactor due to causes including feedstock contaminant metals deposition. This leads to activity, selectivity and increasing coking problems, thereby raising concern to the refiner. This work investigated effect of nickel coexisting with vanadium in the FCC feedstock on the standard FCC catalyst during cracking process, in which destruction of active sites occurs as a result of the metals deposition. Laboratory simulated equilibrium catalysts (E-cats) were studied by XRD, FTIR spectroscopy, N-2 adsorption, solid state MAS-NMR, SEM and H-2-TPR. Results revealed that vanadium, above a certain concentration in the catalyst, under hydrothermal conditions, is highly detrimental to the catalyst's structure and activity. Conversely, nickel hardly affects the catalyst structure, but its co-presence in the catalyst reduces destructive effects of vanadium. The mechanism of nickel inhibition of vanadium poisoning of the catalyst is discussed. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

A FCC Catalyst Prepared by in situ Technique Based on Application of Filter Residue and Kaolin

This paper has provided an effective method to utilize the filter residue. A Y zeolite-containing composite and a fluid catalytic cracking(FCC) catalyst had been successfully prepared by an in-situ crystallization technology using filter residue and kaolin as raw materials. The samples were characterized by XRD, FT-IR, SEM, and N_2 adsorption-desorption techniques and evaluated in a bench FCC unit. In comparison to the reference samples synthesized from single kaolin,the silica/alumina molar ratio, the external surface area, and the total pore volume of the composite increased by 16.2%,14.5%, and 16.2%, respectively. The catalyst possessed more meso-and macro-pores and more acid sites than the reference catalyst, and exhibited better coke selectivity. The prepared catalyst had the optimum isomerization and aromatization performance. The olefin content in the cracked gasoline obtained over this catalyst was reduced by 5.05 percentage points with the research octane number of gasoline increased by 0.5 units.

The Project “Study on Technology for Manufacture of High-Spheroidicity FCC Catalysts” Passed SINOPEC's Appraisal

On January 7, 2015 the project ＂Study on the technology formanufacture of high-spheroidicity FCC catalysts ＂undertakenby the SINOPEC Research Institute of Petroleum Processing（RIPP） has passed the technical appraisal organized by theScience and Technology Division of the Sinopec Corp.

Research on Catalytic Cracking Performance Improvement of Waste FCC Catalyst by Magnesium Modification

In this study,the deactivation mechanism caused by high accessibility of strong acid sites for the waste FCC catalyst was proposed and verified for the first time.Based on the proposed deactivation mechanism,magnesium modification through magnesium chloride impregnation was employed for the regeneration of waste FCC catalyst.The regenerated waste FCC catalyst was characterized,with its heavy oil catalytic cracking performance tested.The characterization results indicated that,in comparison with the unmodified waste FCC catalyst,the acid sites strength of the regenerated waste FCC catalyst was weakened,with no prominent alterations of the total acid sites quantity and textural properties.The heavy oil catalytic cracking results suggested that the catalytic cracking performance of the regenerated waste FCC catalyst was greatly improved due to the suitable surface acidity of the sample.In contrast with the unmodified waste FCC catalyst,the gasoline yield over the regenerated waste FCC catalyst significantly increased by 3.04 percentage points,meanwhile the yield of dry gas,LPG,coke and bottoms obviously decreased by 0.36,0.81,1.28 and 0.87 percentage points,respectively,making the regenerated waste FCC catalyst serve as a partial substitute for the fresh FCC catalyst.Finally,the acid property change mechanism was discussed.

THE DESIGN OF VANADIUM TRAPPING SYSTEM FOR FCC CATALYSTS

The addition of distillation residues to the FCC feedstock leads to increased vanadiumloading on catalyst and the problems in catalyst deactivation.The deactivation process is related tothe destructive attack on the zeolite crystallite by V2O5.Formation of low melting pointV2O5-USY-Na2O phases accelerates the diffusion of vanadium through the catalyst.A proposedmechanism,based on accelerated dealumination,is shown in the paper.Comparative vanadiumtrapping performances have been tested for FCC catalysts and the crystalline ABO3 as an effectivevanadium trap is demonstrated in laboratory tests.

Effects of Vanadium Oxidation Number on Light Olefins Selectivity of FCC Catalyst

Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers(hereinafter abbreviated as Oxnum).Molecular modeling studies showed that vanadium with low Oxnum could affect the chemical conversion of large-size hydrocarbon molecules.However,the vanadium deposited on equilibrium catalyst had high Oxnum because of the oxidation reaction taking place in the regenerator,so an activation method to reduce vanadium Oxnum named "selective activation" was introduced.It was proved by means of Electron Paramagnetic Resonance(EPR) and Temperature-Programmed Reduction(TPR) methods that the vanadium Oxnum was decreased,when the catalyst was activated.The molecular modeling studies are consistent well with the lab evaluation results.The light olefins selectivity of activated equilibrium catalysts was better than that achieved by the inactivated catalysts.Similar results were observed with the lab vanadium-contaminated catalyst.The light olefins selectivity of the catalyst was optimized when the vanadium Oxnum was close to 2(VO).

Synthesis and Application of a Zeolite-containing Composite Material Made from Spent FCC Catalyst

Novel composite material with a wide pore distribution was synthesized by an in situ technique using spent FCC catalyst as raw material. The characterization results indicated that the composite material contained 56.7% of zeolite Y and exhibited a much larger specific surface area and pore volume as well as strong hydrothermal stability. Fluid catalytic cracking(FCC) catalyst was prepared based on the composite material. The results indicated that the as-prepared catalyst possessed a unique pore structure that was advantageous to the diffusion-controlled reactions. In addition, the attrition resistance, activity and hydrothermal stability of the studied catalyst were superior to those of the reference catalyst. The catalyst also exhibited excellent nickel and vanadium passivation performance, strong bottoms upgrading selectivity, and better gasoline and coke selectivity. In comparison to the reference catalyst, the yields of the gasoline and light oil increased by 1.61 and 1.31 percentage points, respectively, and the coke yield decreased by 0.22 percentage points, and the olefin content in the produced gasoline reduced by 2.51 percentage points, with the research octane number increased by 0.7 unit.

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。

Photocatalytic Denitrogenation over Modified Waste FCC Catalyst

The strontium modified waste FCC catalyst was prepared by magnetic stirring method and characterized by Xray diffractometry(XRD),UV-Vis diffuse reflectance spectrometry(DRS),X-ray photoelectron spectroscopy(XPS)and scanning electron microscopy(SEM).Meanwhile,its photocatalytic denitrogenation performance was evaluated in terms of its ability to degrade the N-containing simulation oil under visible light.A mixture of strontium nitrate solution(with a concentration of 0.5 mol/L)and waste FCC catalyst was calcined at 400℃for 5 h prior to taking part in the photocatalytic denitrogenation reaction.The test results showed that the photocatalytic degradation rate of pyridine contained in simulation oil in the presence of the strontium modified FCC catalyst could reach 92.0% under visible light irradiation for 2.5 h.

Silica-Dominated Matrix Platform and Its Application in FCC Catalysts

An advanced silica-dominated matrix technology platform and its application were introduced in this paper. Through novel proprietary processing,the advanced silica-dominated matrix was prepared from the unique silica sol and pseudo-boehmite.The matrix pore size distribution and acidity can be tailored to provide optimal coke-selectivity and bottoms-cracking ability matched to feedstock characteristics.A novel FCC catalyst(RSC-2006) for reducing coke and slurry yields was developed based on the silica-dominated matrix technology platform.The results of commercial application of the said technology indicated that the RSC-2006 catalyst exhibited excellent performance on bottoms cracking,coke selectivity and high value products yields.

水泥窑协同处置废FCC催化剂的生产实践

研究了水泥窑协同处置废FCC催化剂对窑运行工况及水泥熟料质量的影响,开展了废FCC催化剂特性分析、重金属浸出率及配伍方案分析试验,介绍了生产实践中协同处置废FCC催化剂的不足以及废FCC催化剂对窑尾烟气排放、生产区域水质、熟料质量等方面的影响。研究结果表明,利用水泥窑协同处置废FCC催化剂时,需提前做好配伍计算、强化过程质量控制;废FCC催化剂应与水泥原料配比充分融合。对于氧化铝含量约35%、氧化硅含量约33%的废FCC催化剂,处置量宜<1.6t/h。

Analysis of the fluid-bed stability of FCC catalysts at high temperature in terms of bed elasticity

The effect of temperature on the fluid-bed stability of three FCC catalysts has been analyzed through considerations on fluid-bed elasticity. Experimental findings on the effect of temperature on the elasticity modulus at minimum bubbling conditions, （E）mb, were analyzed using the hydrodynamic fluid-bed stability model developed by Foscolo and Gibilaro （1984） and adopting the interparticle-forces-based stability criterion developed by Mutsers and Rietema （1977）. For both models, the parameters which control changes in （E）mb with temperature are discussed, in order to establish the origin of the fluid-bed elasticity and analyze the ability of these models to discriminate between the relative importance of the hydrodynamic and interoarticle forces on the stability of the fluidized catalysts.

Preparation of B_(2)O_(3)/SBA-15 and Application as Matrix Component in Nickel-Tolerant Fluid Catalytic Cracking Catalyst

Fluid catalytic cracking(FCC)is still a key process in the modern refining industry,in which nickel contamination of the FCC catalyst can significantly increase the dry gas and coke yields and thus seriously affect the stability of the FCC unit.Therefore,in this work,B_(2)O_(3)-modified SBA-15 molecular sieves(B_(2)O_(3)/SBA-15)with different B_(2)O_(3) contents were prepared,characterized,and further used as matrix component in the preparation of Ni-tolerant FCC catalyst.The characterization results indicated that the B_(2)O_(3)/SBA-15 samples possessed excellent Ni passivation ability and kept the characteristic structure of the parent SBA-15 such as highly ordered mesopores,large surface area,and high pore volume,which enabled the B_(2)O_(3)/SBA-15 sample to greatly improve the Ni tolerance of the prepared FCC catalyst.The heavy oil catalytic cracking tests indicated that,under the same Ni contamination conditions,the dry gas,coke,and heavy oil yields of the FCC catalyst containing B_(2)O_(3)/SBA-15 decreased by 0.92%,1.65%,and 1.26%,respectively,compared with those of conventional FCC catalyst,while the total liquid yield increased by 3.83%.

共沉淀法FCC再生烟气脱硝催化剂的制备

针对FCC装置再生烟气脱硝,采用共沉淀法将过渡金属掺杂于TiO_(2)载体上制备V_(2)O_(5)-WO_(3)/TiO_(2)脱销催化剂,考察过渡金属对V_(2)O_(5)-WO_(3)/TiO_(2)催化剂脱硝性能的影响。结果表明,载体掺杂Ce制备的催化剂催化活性最好,NO最高转化率达99%。

Preparation of Alumina Abrasion-Resistant Ceramic Grinding Ball with Spent FCC Equilibrium Catalyst

化学作文，结构和从一个炼油厂的花的 FCC 平衡催化剂的热稳定性被 XRD，英尺红外， DTA-TG，赌注，完全的化学分析， SEM，和 XRF 描绘。花的 FCC 平衡催化剂，泥土，钡碳酸盐，和滑石被用作主要原料准备氧化铝在为建筑学瓦的制造磨工厂的粉末要过去常的磨损抵抗的陶器的球。结果证明在合适的明确的表达学习以后，花的 FCC 平衡催化剂能代替工业氧化铝准备磨球的高效。同时，磨擦的球的各种各样的表演索引能为类似的产品满足优秀标准，并且另外，节省效果的精力在磨擦的节的操作被完成，导致稳固的浪费的成功的全面利用。

Development of New Generation Catalysts for Selective Hydrodesulfurization of FCC Naphtha

The influence of active metal components of catalyst, additives and catalyst preparation method on the reactivity of catalyst for selective hydrodesulfurization (HDS) of FCC naphtha was investigated, and the RSDS-21 catalyst with high HDS performance and the RSDS-22 catalyst with high selectivity were developed by RIPP. The composite loading of a new series of catalysts for selective HDS of FCC gasoline has demonstrated excellent desulfurization activity and selectivity and can under conventional hydrotreating conditions manufacture clean gasoline product meeting the national IV emission standard and the Euro V emission standard with less loss in antiknock index. The finalized new series of FCC catalysts upon being adopted for selective HDS of FCC naphtha have good adaptability to different feedstocks along with good stability.

废FCC催化剂提钒及制备无危害地聚合物工艺研究

采用草酸作为浸出剂提取废FCC催化剂中的钒,主要考察了浸出条件对钒、硅和铝浸出率的影响,在浸出时间240 min,浸出温度95℃,草酸浓度2 mol/L条件下,钒浸出率大于70%。将浸出后的废FCC催化剂渣和钢渣混合作为原料制备地聚合物,并测试其钒毒性浸出浓度。结果表明,将废FCC催化剂渣制备为地聚合物后,钒毒性浸出浓度升高,且固定率下降。通过XPS对废FCC催化剂中钒的存在形式和反应过程的变化进行分析,在制备地聚合物过程中废FCC催化剂中的V_(2)O_(5)转变为NaVO_(3),使地聚合物中的钒主要以VO_(3)^(-)-阴离子形式存在。因此,废FCC催化剂中的钒只能通过物理封装被地聚合物固定,且固定率与地聚合物的抗压强度呈正相关。在浸出过程中应同时控制减少硅、铝的浸出,使制备的地聚合物产品具有较好的机械性能,从而提高地聚合物对钒的物理封装效果,使毒性浸出达标。

有机酸在超声作用下对废FCC催化剂中有害金属脱除的影响

有害金属Fe、V、Ni是石油流化催化裂化(FCC)催化剂中毒的根源,导致FCC催化剂的活性降低。针对现有废FCC催化剂再生工艺存在有害金属脱除率低、废剂颗粒的微观形貌和分子筛骨架易被破坏、废剂无法回用等问题,以有机酸为浸出剂,提出超声协同有机酸脱除废催化剂中有害金属的强化处理工艺。本研究以保留废FCC催化剂的球状颗粒结构和Y型分子筛骨架结构为前提,研究在超声作用下氧化预处理、有机酸种类、反应温度、时间以及超声功率对废FCC催化剂中有害金属脱除的影响。实验结果表明,在超声作用下,不同有机酸对有害金属的脱除效果从弱到强的顺序为乙酸、EDTA、草酸+乙酸、草酸,而废剂微观结构被破坏的程度也增加。在草酸和乙酸的混合液为浸出剂、超声功率为250 W、浸出温度为70℃、浸出时间为30 min的条件下,V、Fe、Ni脱除率分别高达40.7%、27.5%和17.2%,且浸出后的FCC催化剂球状结构和分子筛骨架结构完整。与常规浸出相比,超声浸出对有害金属的脱除起到强化作用,V、Fe、Ni的浸出率分别提高了19.9%、13.1%和7.7%。

Preparation and Cracking Performance of FCC Co-Catalyst for Enhancing Light Oil Production

在这篇论文，为提高轻采油的 FCC 合作催化剂被大音阶的第五音胶化方法准备，并且它击碎催化剂的残余的表演上的效果在结果显示了的 CCFFB reactor.The 测试被评估液体产品收益显然增加了，在 FCC 平衡催化剂的表面与干燥气体的 co-catalyst.The 收益被使妊娠以后，泥浆和焦炭减少了，当柴油机收益改变了 slightly.And 时残余的 crackability 被增加；催化剂表面上的焦炭免职的率被减少，与这些结果显示出的热裂开反应 inhibited.All 合作催化剂能改进酸地点的密度并且改变催化剂酸味，它能支持由在 FCC 平衡催化剂的表面上扔合作催化剂延长催化剂活动。

废FCC催化剂中稀土元素的浸出及动力学分析

针对FCC废催化剂中所含的稀土元素,本研究以废FCC催化剂为原料,与无水碳酸钠混合焙烧活化,以盐酸为浸出剂,探究了盐酸浓度、浸出温度、浸出时间、浸出固液比以及焙烧时间等因素对FCC废催化剂中稀土元素镧(La)、铈(Ce)的浸出率的影响,并进行了浸出过程动力学分析和表观活化能计算。实验结果表明:废FCC催化剂在750℃条件下和碳酸钠以质量比为1:1混合焙烧300 min后,在70℃的条件下,用6 mol/L的盐酸溶液且固液比为1:25浸出120 min时,La、Ce最佳浸出率可达到88.06%、90.07%;FCC废催化剂浸出前后SEM和XRD测试分析表明废FCC在酸浸后衍射特征峰基本消失,晶格结构被破坏,浸出渣主要为SiO_(2);缩芯模型浸出过程动力学分析和Avrami表观活化能计算结果均表明:La和Ce的浸出活化能的测定值分别为27.1、21.2 KJ/mol,该浸出过程受扩散控制。该研究对固废资源中稀土元素的高效回收具有一定的指导意义。