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    The Progress of Desulfurization Technology for Crude Oil
    China Petrol Proc & Petrochem Techn   
    Abstract3444)      PDF(pc) (132KB)(13693)       Save
    The poor quality of crude oil obviously leads to high sulfur content of oil products, and the technology for desulfurization of crude oil is urgently needed so that the sulfur content in petroleum products could be reduced from the root. This paper describes the progress in technology for desulfurization of crude oil. The present technologies for desulfurization of crude oil include caustic washing, dry gas desulfurization, hydrodesulfurization (HDS), etc. The new combined technologies for desulfurization of crude oil being studied are: biodesulfurization (BDS), hydrogenation-bacterial catalysis, the microwave-catalytic hydrogenation, the BDS-OD-RA desulfurization and oxidative desulfurization in electrostatic fields, and the ultrasonic/microwave-catalytic oxidation applied in our lab, with their development trends being also discussed.
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    Preparation of Bi2WO6 Photocatalyst and Its Application in the Photocatalytic Oxidative Desulfurization
    China Petrol Proc & Petrochem Techn   
    Abstract3248)      PDF(pc) (375KB)(4399)       Save
    A type of visible light catalysis Bi2WO6 was prepared from Bi(NO3)3•5H2O and Na2WO4•2H2O,by hydrothermal method and was characterized by UV-vis DRS, XRD. Oxidation desulfurization via photocatalysis was investigated by using thiophene in octane as themodel compound, and hydrogen peroxide is used as the oxidant. The effects of hydrogen peroxide mass fraction, irradiation time, photocatalyst Bi2WO6 mass on the desulfurization efficiency were also investigated. Under suitable conditions, the desulfurization rate of the model compound reach 70%.
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    Molecular-Based Simulation of Feedstock Properties for Complex Reaction System
    Fu-Sheng OuYang ,WenJun Bao ,HongBo Jiang ,HuiXin Weng
    China Petrol Proc & Petrochem Techn   
    Abstract3205)      PDF(pc) (153KB)(3806)       Save
    The kinetics of complex reaction systems were studied on molecular level with the combined method of Monte Carlo simulation and Structural Oriented Lumping by focusing on deep catalytic cracking (DCC) process, the model parameters were optimized by means of routine analytic data of a DCC unit. A model was established to transform the feedstock of the complex reaction systems such as DCC to 1000?0000 pseudo-molecules with the Monte Carlo simulation and every molecule was expressed by 19 attributes. The results of model simulation showed that these pseudo-molecules reflected the characteristics of feedstock very well and their average properties gave a good agreement with the plant data.
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    Research of Modified Y Zeolite and Its Behavior On Desulfurization for Naphtha
    China Petrol Proc & Petrochem Techn    2011, 13 (4): 41-44.  
    Abstract3152)      PDF(pc) (384KB)(4742)       Save
    NaY zeolite was modified using the method of ammonium ion-exchange to prepare NH4Y zeolite. Then LaY zeolite was obtained by NH4Y zeolite a second ion-exchanging with rare earth salt solution and calcinations.Test of dynamic adsorptive desulfurization of naphtha was conducted using modified Y zeolite, the sulfur contents of the treated naphtha samples were analyzed by microcoulometry.The results show that under dynamic conditions, using 1mol/L ammonium salt solution secondary ion-exchange to prepare LaY zeolite has a good effect on desulfurization of naphtha.At the same time under the condition of adsorption temperature 45℃, volume ratio of adsorbent to oil 1:2, the adsorption desulfurization effect of zeolite is best.
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    Molecular Simulation Study on Intrinsic Order of Interaction between Single Slab of Active Phase and Al-Si Support in HDS Catalysts
    LI Hao-Guang ,Hong NIE
    China Petrol Proc & Petrochem Techn   
    Abstract3100)      PDF(pc) (807KB)(2542)       Save
    Molecular-mechanics and quantum-mechanics, as molecular simulation methods, were performed to investigate the effects of the different surfaces, the promoter Co/Ni, the active phase of MoS2 or WS2, the content of Si and other facts on the order of interaction between MoS2 (WS2) single slab and support surface. The influences of the Si content was studied by molecular-mechanics, and an advantageous Si content was founded; Various surfaces, promoters and active phases also play important roles in the interaction between supports surfaces and active phases, and some significant trends were found; Quantum mechanics simulation was performed to study the possible effect of electrostatic interaction between support and active phase, in which the calculations suggested that it is possible for the advantageous Si content to exist; The electronic effects of Co/Ni/ and the intensity of Co/Mo/Ni/W/Li/Al/Si bonded to alumina support were also investigated by quantum-mechanics, and it was found that the different electronic effects of Co and Ni may bring some obvious influences to the interaction between supports and active phase. And the results of comparing intensity of Co/Mo/Ni/W/Li/Al/Si bonded to support can also explain the different interaction intensity in different catalyst systems.
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    Medium-Pressure Hydro-upgrading (MHUG) Technology for Producing Clean Diesel Fuel
    Jiang Donghong; Zhang Yuying; Hu Zhihai; Nie Hong
    China Petrol Proc & Petrochem Techn    2012, 14 (1): 1-7.  
    Abstract3084)      PDF(pc) (971KB)(4285)       Save
    This article introduces the development and application of the medium-pressure hydro-upgrading (MHUG) technology developed by the Research Institute of Petroleum Processing (RIPP). The MHUG technology based on the chemistry of diesel hydro-upgrading reactions has the advantages of flexible product slate and excellent product quality that can increase the cetane rating of diesel fuel up to more than 15 units. The hydrotreating and hydro-upgrading catalysts associated with the MHUG technology have outstanding performance to meet the demand of MHUG technology for hydro-saturation and selective ring-opening of aromatic rings. New MHUG process flow scheme can further increase the yield and selectivity of target products. Commercial application of multiple MHUG units has revealed that the MHUG technology designated for clean diesel production features good feedstock adaptability and operating stability.
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    Simulating the Effect of Propylene Promoter on Product Yield with FCC Mechanism Model
    China Petrol Proc & Petrochem Techn   
    Abstract3007)      PDF(pc) (112KB)(873)       Save
    A FCC mechanism model was used to predict the effects of propylene promoter in a 3.0 Mt/a FCCU. The FCC mechanism model was developed based on one set of commercial FCC data without using the promoter, and was modified by using another set of commercial FCC data with 3w % promoter in the catalyst inventory, and the calculations by means of this simulation model were performed to predict the data of the FCC unit containing 4 w% promoter in the catalyst inventory. The test results showed that the calculated values agreed well with the data obtained from the commercial FCC unit, in which the deviations of calculated product yields versus the actual product yields at the commercial FCC unit being equal to 1.74 percentage points for gasoline, 2.59 percentage points for diesel, 1.50 percentage points for dry gas and LPG, and 0.28 percentage points for coke. The proposed method regarding the development of a simulation model and modifications to the model for commercial FCC unit was feasible.
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    Study on industrial application of hydrogen sulfide removal by wet oxidation method withhigh gravity technology
    China Petrol Proc & Petrochem Techn    2011, 13 (4): 29-34.  
    Abstract3003)      PDF(pc) (451KB)(4853)       Save
    The removal of hydrogen sulfide from gas plays an important role in reasonable utilization of resources and environmental protection. In this paper, the process of hydrogen sulfide removal by wet oxidation method in a rotating pacded bed was investigated on the scale of 10000Nm3/h gas. On the basis of studying the influence of the species and concentration of alkali source, volume ratio of liquid-gas, high gravity fgctor and hydrogen sulfide content in feed gas on desulfurization effect, the suitable technological conditions were obtained. The removal efficiency of hydrogen sulfide could reach 98.0% under this conditions. The continuous operation results showed that high gravity method has many merits which includes higher desulfurization and stability, lower volume ratio of liquid-gas, small volume, large elasticity of operation and energy saving.
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    MIP TECHNOLOGY FOR PRUDUCTION OF EURO Ⅳ CLEAN GASOLINE Ⅱ:CORRELATION MODEL OF SULFUR CONTENT OF MIP NAPHTHA AND ITS APPLICATION
    TANG Jin-lian
    China Petrol Proc & Petrochem Techn   
    Abstract2957)      PDF(pc) (163KB)(4350)       Save
    On the basis of the reaction rules and its influencing factors of sulfur compounds of MIP naphtha, a correlation model for describing the relation of mass fraction of sulfur in MIP naphtha to mass fraction of sulfur in feedstock and volume fraction of olefin in naphtha was developed and the model’s parameters were estimated. The residual error distribution and statistical test showed that the developed model was reasonable and reliable and able to predict the mass fraction of naphtha sulfur compounds. The model can provide theoretical guidance and operation base for adjusting process parameters to produce EURO Ⅳ gasoline through MIP units. The model was validated by its application on MIP unit of Qingdao Refining & Chemical Corporation. For this unit, the tail oil with low sulfur content by hydrotreating gas oil was used as feedstock and the olefin content of naphtha was reduced by promoting hydrogen transfer reaction though adjustment of process parameters. Thus, EURO Ⅳ gasoline was achieved by this MIP unit.
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    Selective Adsorption of Sulfur Compounds in Model Gasoline Containing Olefins by Modified Zeolites
    Lijuan Song ,Piyong Liang ,linhai Duan ,xiufang Ju ,zhaolin Sun
    China Petrol Proc & Petrochem Techn   
    Abstract2949)      PDF(pc) (315KB)(2797)       Save
    The effects of olefins were quantified by measuring the decreased amount of thiophenes removed by modified zeolites with an increasing olefin concentration in model fuels (300 wppm) via fixed-bed adsorption technique at room temperature and atmosphere pressure. The influence of olefins on adsorptive desulfurization of model fuel had been investigated by FT-IR techniques, which revealed that the protons in the zeolites were the sites responsible for the adsorption of olefins. On the CeY zeolite, in the presence of strong hydroxyl species in the zeolites, the adsorbed olefin compounds can attach to the protons molecularly via electrophilic interaction and undergo the opening of the C=C bonds depending on the acidity of the zeolites. The reduced desulfurization performance of CeY zeolite was attributed to the direct occupation of the absorbent's active sites by olefins. In contrast to the CeY zeolite, the NiY zeolites were unable to react directly with pure olefins. However the sulfur compounds and olefins adsorbed on the protons may subsequently undergo olefin alkylation reactions, which can block the zeolite pores and then prevent sulfide molecules from having access to super-cages to contact with the metal cations. This work demonstrates also that the NiY zeolites exhibit excellent performance for selective adsorption desulfurization of model fuel containing olefin compounds.
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    Hydrothermal Synthesis and Properties of Y-zeolite-containing Composite Material with Micro/mesoporous Structure
    Jihong Zhou ,Enze Min ,Xingtian Shu ,Baoning Zong ,Haiying Yang ,Yibin Luo
    China Petrol Proc & Petrochem Techn    2010, 12 (1): 0-.  
    Abstract2912)      PDF(pc) (162KB)(5439)       Save
    A Y-zeolite-containing composite material with micro/mesoporous structure had been synthesized from kaolin by means of the in-situ crystallization method. The obtained samples were investigated by XRD and BET methods. Evaluation of catalytic activity of both the commercial Y-zeolite and the novel Y-zeolite-containing composite material was carried out in the pulse micro-chromatography platform with two probe molecules of different molecular sizes: VGO feedstock and 1,3,5 tri-isopropyl benzene. It was found that the Y-zeolite-containing composite material was richer in external surface and meso-/macro-pores; the Y-zeolite-containing composite material demonstrated a smaller rate of deactivation compared to the commercial Y-zeolite.
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    Study toward the Mechanisms of Cyclohexanone Baeyer-Villiger Oxidation with hydrogen peroxide under Various Reaction Systems
    China Petrol Proc & Petrochem Techn    2012, 14 (2): 7-17.  
    Abstract2876)      PDF(pc) (724KB)(8598)       Save
    The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone to prepare ε-Caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of cyclohexanone Baeyer-Villiger oxidation with H2O2 in different reaction systems. Five main types have been addressed. 1) Noncatalyzed reaction type, the C=O of ketones is activated by H+, which is electrolytic dissociated from H2O2 and H2O, to improve the capability of C=O group to accept the electron pairs;2)Thermally activated radical reaction type, where the Criegee interminate is produced via two-steps of radical reaction with ·OH attack, with many more hydroxy radicals are excited in the presence of TS-1 zeolite ;3) Br?nsted acid catalysis reaction type, both O-O moiety and C=O group could be activated by Br?nsted acid; 4) Solid Lewis acid catalyzed C=O of the substrate activation reaction type, by enhancing the donor-acceptor interaction between the antibonding π*C=O orbital of cyclohexanone and HOMO of Sn-β zeolite; 5) Solid Lewis acid catalyzed H2O2 to form Me-OOH oxidative species, by employing the highest occupied molecular orbital (HOMO) of Ti-OOH becoming a singly occupied molecular orbital(SOMO), with the O-O group highly electrophilic to attack the C=O of cyclohexanone in Baeyer-Villiger oxidation. In the end, we also compare the different mechanisms and give our opinions on the development direction of catalytic materials for eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.
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    Review and comprehensive analysis of composition and origin of high acidity crude oils
    Cai Xin-heng ,Song-Bai Tian
    China Petrol Proc & Petrochem Techn   
    Abstract2866)      PDF(pc) (440KB)(5305)       Save
    High acidity crude oils have an advantage over normal oils in price, but can cause corrosion and refinery problems. They are so called opportunity crudes and likely to be important reserved resources in 21st century. Researches on high acidity crude oils are becoming more and more profound. Based on the existing research achievements, this article has given an overview of the chemical composition and acid distribution of high acidity oils, also analyzed their origin types and potential influence factors.
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    In-situ synthesis of ZSM-5 zeolite from metakaolin/spinel and its catalytic performance on methanol conversion
    Xianbo Yu ,Lei Qin ,Jingdai Wang ,Yongrong Yang
    China Petrol Proc & Petrochem Techn   
    Abstract2857)      PDF(pc) (221KB)(5632)       Save
    ZSM-5 zeolite was in-situ synthesized from metakaolin or spinel by incorporating additional silica and alumina sources, respectively. The ZSM-5 zeolite was characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and N2 adsorption measurement. This supported zeolite was tested on the methanol to propylene (MTP) processes. Experimental results showed that the ZSM-5 zeolite exhibited high selectivity for propylene. The yield of propylene on ZSM-5 zeolite made from metakaolin was increased by 17.73%, while that on ZSM-5 zeolite made from spinel was raised by 9.90%, compared to that achieved with the commercial ZSM-5 zeolite. The significant increase in propylene production is probably due to the distinctive morphology of the ZSM-5 zeolite, which possessed a rough external surface covered with sphere-like particles and distribution of small crystals sized at around 400-500 nm. This morphology could help to generate more crystal defects so that more active centers could be exposed to the reaction mixture. In addition, the zeolite product had a gradient pore distribution and many medium Br?nsted acid sites, both of which might also contribute to increased propylene production.
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    Deep Desulfurization of model oil products by silver ion modified bentonite
    Tang Xiao-lin ,Zheting Le ,Li Shi
    China Petrol Proc & Petrochem Techn   
    Abstract2851)      PDF(pc) (618KB)(3188)       Save
    In order to further reduce the sulfur content in liquid hydrocarbon fuels, we investigated a desulfurization process by adsorption for removing alkyl dibenzothiophenes. The desulfurization of model gasoline by bentonite adsorbents loaded with Silver Nitrate was studied. The results indicate that the bentonite adsorbents loaded with Ag+ in this work was effective for adsorbing the alkyl dibenzothiophenes. The bentonite adsorbents’ crystal structure characterized by X-ray diffraction (XRD) and their acidity characterization was tested by Fourier transform infrared (FT-IR). Several factors which influence the desulfurization capability, including Ag+ loading, baking temperature, as well as the reaction temperature were investigated. The desulfurization was enhance by increasing the Ag+ loading and the best result was obtained at the Ag+ loading of 7wt.%. It was found that the adsorption capacity of the alkyl dibenzothiophenes on bentonite loaded with Ag+ increased with the temperature drop. Baking of the sorbent could also improve the desulfurization capacity, and the optimum baking temperature was 423K.
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    The Influence of Paraffinic Base Oil on Low-temperature Viscosity of Naphthenic Base Oil
    China Petrol Proc & Petrochem Techn   
    Abstract2826)      PDF(pc) (143KB)(6155)       Save
    Low-temperature viscosity of lube oils mixed with paraffinic base oil and naphthenic base oil at different mass ratios has been tested by experiments. The influence of paraffinic base oil on the performance of naphthenic base oil was investigated by studying the low-temperature viscosity of tested oils. The viscosity of lube oils increased with an increasing content of high-viscosity paraffinic base oil in the oil mixture. And the low-temperature viscosity was less influenced when the content of paraffinic base oil in the mixture was insignificant. In order to reduce the cost for formulating lubricating oil, a small fraction of paraffinic base oil can be added into naphthenic base oil as far as the property of lubricating oil can meet the specification. According to the study on low-temperature viscosity of the oil mixed with paraffinic base oil and naphthenic base oil, a basic rule was worked out for the preparation of qualified lubricating oils.
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    Adsorption and desorption of Thiophene Vapour on NaY/NiY
    Daosheng Liu
    China Petrol Proc & Petrochem Techn   
    Abstract2820)      PDF(pc) (323KB)(2843)       Save
    FT-IR, TPD and adsorption isotherms of thiophene on NaY/NiY were carried out and the diffusion coefficient was obtained by its dynamics of real time. Adsorption quantity of thiophene on NaY decreased with temperature increaesd, which due to physical adsorption. Both physical and chemical adsoption involved for the other, and complexation and interaction exsited in chemical adsoption. Adsorption quantity of thiophene on NiY at 302 k and 335 k was equivalent, but it decreased at 373 k. The diffusion coefficient of thiophene on NaY decreased when the loading increased more than 0.02 mmol/g, and on the contrary which on NiY was not obviously with the adsorption quantity.
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    Hydrothermal Synthesis and Mechanism for Formation of Novel Micro-Micro-Mesoporous Aluminosilicate Composite Zeolite
    Qi Jian ,Tianbo Zhao ,Xin Xu ,Fengyan Li ,Guida Sun
    China Petrol Proc & Petrochem Techn   
    Abstract2819)      PDF(pc) (479KB)(3005)       Save
    A novel micro-micro-mesoporous aluminosilicate LS-BFMZ (low-silica-BEA(beta)-faujasite (Y)-mesoporous) composite zeolite with the MCM-41 type structure was synthesized through a novel process involving the self-assembly of CTAB surfactant micellae with silica-alumina source originated from alkaline treatment of the beta zeolite. The physical properties of the LS-BFMZ composite zeolite were characterized using various techniques, including XRD, IR and SEM techniques. Meanwhile, a possible mechanism regarding the formation of the LS-BFMZ composite zeolite was proposed.
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    Kinetics and Selectivity of Asphaltene Thermal Hydrocracking and Catalytic Hydrocracking
    ZHAO Ying-Xian ,Da Li
    China Petrol Proc & Petrochem Techn   
    Abstract2795)      PDF(pc) (495KB)(5010)       Save
    A pentane-insoluble asphaltene was processed by thermal hydrocracking and catalytic hydrocracking over Ni-Mo/γ-Al2O3 in a microbatch reactor at 430ºC. The experimental data of asphaltene conversion fit second-order kinetics adequately, to give the apparent rate constants of 2.435 x10-2 and 9.360 x10-2 wt frac-1min-1for the two processes respectively. A three-lump kinetic model is proposed to evaluate rate constants of parallel reactions of asphaltenes to produce liquid oil (k1) and gas + coke (k3), and consecutive reaction from liquid to gas + coke (k2). The evaluated k1 is 2.430Х10-2 and 9.355Х10-2 wt frac-1min-1, k2 is 2.426Х10-2 and 6.347Х10-3 min-1 , and k3 is 5.416Х10-5 and 4.803Х10-5 wt frac-1min-1 for asphaltenes hydrocracking in the presence or absence of the catalyst, respectively. Analysis of selectivity shows that the catalytic hydrocracking process promotes liquid production and inhibits coke formation effectively.
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    Study on the Stability of Ion-exchange Resin Catalysts: ? TGA as a Rapid Evaluating Method
    Tan Song-Wei
    China Petrol Proc & Petrochem Techn   
    Abstract2786)      PDF(pc) (358KB)(2720)       Save
    The thermal stability of five commercial ion-exchange resin catalysts was studied by thermal gravimetric analysis (TGA) at elevated temperature up to 600°C and isotherm temperatures of 150°C and 200°C. Resins with different initial water contents were also investigated. The study indicated that TGA, as a complementary evaluating method to the plug flow reactor system approach, could be used as a fast analyzing method for the study of the thermal stability of ion-exchange resin catalysts. The stoichiometric calculation of the isotherm treated resin catalysts based on the FTIR analysis and acid capacity confirmed that the weight loss of the resins at 150℃ and 200℃ was caused by the desulfonation process and that desulfonation occurred mainly at the para-position of the benzene ring in the resins. H+ and moisture played an important role in the desulfonation process.
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