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Table of Content

    12 September 2016, Volume 47 Issue 9
    LTAG TECHNOLOGY FOR PRODUCING HIGH OCTANE NUMBER GASOLINE AND LIGHT AROMATICS
    2016, 47(9):  1-5. 
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    The studies and commercial trials of two modes of combined process of LCO hydrotreatment and FCC (LTAG technology: LCO to aromatics and gasoline) for production of higher RON gasoline and light aromatics were introduced. The commercial trials were conducted at SINOPEC Shijiazhuang Refining and Chemical Co. The commercial results show that with LTAG modeⅠ(the LCO is first hydrotreated and then the treated LCO is used as FCC feed), LCO can be all converted under the condition of full circulation, the yields of gasoline, C6-C8 aromatics are 55.87% and 16.89%, respectively, the gasoline RON reaches 96.4; while with LTAG modeⅡ(the hydrotreated LCO and heavy oil feed is pumped into FCC at different inlets separately), the once through conversion of LCO is above 70.19%, and the gasoline selectivity is up to 80.00% with increase of RON and the bottom oil cracking ability is improved, the LCO can be converted totally through recycling operation.

    SELECTION OF HEAVY OIL PROCESSING ROUTES AT VARIOUS PRICES OF CRUDE OILS
    2016, 47(9):  6-12. 
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    The economic benefit analysis was made for several processing routes of Oman crude oil, Arab medium oil, Iranian heavy oil and Tahe crude oil at international oil price of $35-$100/bbl. The processing routes included slurry-bed, ebullated-bed, and fixed-bed residual oil hydroprocesses, delayed coking, and combination process with solvent deasphalting (SDA). The results show that the economic benefit of the slurry-bed is superior to that of the ebullated-bed residual oil hydroprocesses based on the price system used in this article. When the price of crude oil is above $80/bbl, the economic benefit of the slurry-bed residual oil hydroprocess is better than that of the fixed-bed residual oil hydroprocess using conventional crude oil as feed. With the constant improvement of technology and reduction of processing cost, the slurry-bed residual oil hydroprocesses have good market prospects. When the price of crude oil is more than $35/bbl, the economic benefit of SDA combination process has an advantage over the delayed coking. For the refineries which are lack of hydrogen source and have preferential raw materials for delayed coking, the SDA combination process is a good choice when the price of crude oil is less than $55/bbl. The fixed-bed residual oil hydroprocess is recommended when the price of conventional crude oil is between $45/bbl and $80/bbl.

    INDUSTRIAL APPLICATIONS OF ETHERIFICATION TECHNOLOGIES FOR FCC LIGHT NAPHTHA
    2016, 47(9):  13-17. 
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    A series of technologies (LNE-1, LNE-2 and LNE-3) for FCC light naphtha etherification, jointly developed by Lanzhou Petrochemical Research Center of PetroChina and other institutes, were applied in refineries that produce ethanol gasoline or non-ethanol gasoline. The results show that the tertiary amylene conversions of the LNE-1 and LNE-2 technology are 72.10% and 91.41%, respectively and the expected tertiary amylene conversion of LNE-3 process is more than 93%. The research octane number (RON) of FCC light gasoline is improved by 2.2 units after etherification by LNE-2 technology and the product can be used as a non-ethanol gasoline blending component; while for ethanol gasoline blending component production, the RON of etherified product by LNE-3 technology reaches above 100.

    PROBLEMS IN PROCESSING PURCHASED C8A AND COUNTERMEASURES
    2016, 47(9):  18-22. 
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    The pipe blockage problems during operation of PX combination plant in Zhenhai Petrochemical Co. when processing purchased C8A were analyzed. It is concluded that the coke formation due to olefin polymerization induced by the small amount of oxygen dissolved in C8A during storage and transportation is the main cause. Coking rate is positively correlated with the temperature and bromine index of the purchased C8A. A simple and cheap coking adsorption method was suggested and proved to be effective for solving the blockage problems during processing purchased C8A. It can be used for similar equipment to solve or to prevent similar problems.

    APPLICATION OF SVQS AND MSCS TECHNOLOGIES IN RFCC UNIT
    2016, 47(9):  23-27. 
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    The serious coking in disengager in 1.4 Mt/a RFCC unit of Daqing Branch of CNPC limited the long-term operation. The analysis on the post-riser system and the stripper of the unit indicated that the open-type structure of the exit-tube of primary cyclone separator without pre-stripping device led to a long residence time of oil and gas in the disengager and coking; the structure defects and single stripping technology of stripping section were the another important reason for the coking in disengager. The technologies of SVQS (oil and gas quick separation system) and MSCS (high efficiency stripping combination technology) developed by China University of Petroleum (Beijing) were employed to revamp the disengager. The results show that the light oil yield increases 3.46 percentage points, and the liquid yield increases 1.44 percent points, while the coke yield decreases 1.43 percentage points, and the unit energy consumption reduces by 41.5 MJ/t.

    DISCUSSION ON PROPERTIES OF DIFFERENT ULTRASTABLE Y ZEOLITES
    2016, 47(9):  28-33. 
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    The structural properties of four kinds of USY zeolites were investigated by catalyst characterization techniques. The activity was evaluated with FCC MAT method. The results indicate that increasing total Al2O3 amount or Si(1Al)ratio means larger lattice constant, less Al2O3 amount and extra-framework Al; higher ratio of Si(1Al) is needed for better thermal stability; larger crystal constant, larger micro-pore surface area and pore volume with unobstructed pore channel are required for better acidity and higher activity. The higher ratio of extra-framework Al and Si is favor of formation of L-acid.

    KINETIC MODEL FOR STEAM CRACKING OF LIQUID PARAFFIN BASED ON STRUCTURE ORIENTED LUMPING METHOD
    2016, 47(9):  34-40. 
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    A kinetic model of liquid paraffin steam cracking process based on structure oriented lumping is established. A new structure vectors DB is built to indicate olefin exactly. The reaction network is composed of 108 molecules and 546 reactions. The structure oriented lumping model can forecast the conversion and α-olefin yield successfully. The optimum cracking conditions of a kind of liquid paraffin are obtained by the structure oriented lumping model. The optimum conditions are 660℃, 3.5s and steam to paraffin ratio of 0.1. Under the optimal conditions, the relative errors of conversion, α-olefin yield and cracking gas yield of calculated value and experiment value are 2.36%, 1.29% and 6.47%, respectively.

    SYNTHESIS OF ZSM-5 MICROPARTICLES WITH SUPERIOR SEDIMENTATION PROPERTY AND APPLICATION IN HYDRATION OF CYCLOHEXENE
    2016, 47(9):  41-45. 
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    The size-controlled ZSM-5 microparticals (MPs) were synthesized using industrial grade silica sol and aluminum hydroxide without template. Compared with commercial H-ZSM-5 product (size < 1.0 um) , the synthesized ZSM-5 microparticals (1.0-10 um) have a higher relative crystallinity, larger surface area and pore volume, more strong acid size and amount of Br?nsted acid, and exhibit higher catalytic activity and selectivity for the hydration of cyclohexene. Due to large ZSM-5 particles with clear arc edges, high crystallinity and less viscous amorphous state, the aggregation is prevented, resulting in excellent sedimentation properties compared with commercial ZSM-5 SMPs, which makes it useful in industrial precipitation separation process to reduce the catalyst loss.

    ACID MODIFICATION OF ACTIVATED CARBON AND ITS EFFECTS ON ACETYLEENE HYDROCHLORINATION
    2016, 47(9):  46-50. 
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    The activated carbon (AC) was modified by different acidic reagents (H3PO4,C6H8O7,HNO3). The pore structures and surface chemistry of the samples were characterized by BET,FI-IR,and SEM techniques. The catalytic performance in acetylene hydrochlorination was investigated in a fixed bed reactor. The experimental results show that the pore structures and surface chemistry changes with different acidic reagents though catalytic activities are all increased at various degrees. When nitric acid is used as a modifier, the surface area and pore volume decrease compared to untreated AC, while the average pore diameter increases. The activity of the nitric acid modified catalyst is the best due to greatly improve the content of oxygen-containing acidic groups. The conversion of acetylene is up to 71.8%; When phosphoric acid is used as a modifier, the reduction of specific surface area is the largest, whoever, its activity increases because of the introduction of phosphate. The activity of the catalyst treated with citric acid does not increase. In addition, it is found that high concentration of nitric acid or too long time treating does not help to improve the activity of the catalyst due to a strong corrosion of nitric acid. The catalytic activity is the best at nitric acid concentration of 5 mol/L and 6h.

    COMMERCIAL APPLICATION OF DECREASING NOx EMISSION ADDITIVES FOR FCC REGENERATED FLUE GAS
    2016, 47(9):  51-56. 
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    RDNOx additive for decreasing FCC NOx emission was applied in the MIP-CGP unit in SINOPEC Beihai Company. The results show that RDNOx additive is effective in controlling the regenerator dilute-phase temperature and reducing “after burn”. The range and frequency of dilute-phase temperature fluctuation are apparently decreased. Furthermore, the NOx content in the treated flue gas analyzed on line is 30-60 mg/m3, which is lower than that of the latest environmental regulation of 100 mg/m3. Compared with 295 mg/m3 when Pt based CO promoter was used, NOx emission is decreased by more than 70%. During the application of RDNOx additive, no negative influence on FCC product distribution and properties is observed.

    STUDY OF MICROWAVE-ASSISTED DUAL FUNCTIONAL RESIDUE HYDROGENATION CATALYST
    2016, 47(9):  57-61. 
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    Using the microwave heating possesses selective characteristics,two kinds of microwave-assisted dual functional residue hydrogenation catalysts C-Fe and C-Si was prepared by adding the microwave sensitizer during the preparation of catalysts. The crystal phase, pore structure, acidity, acid strength distribution, reducibility and micro-morphology of the catalysts were characterized by X-ray diffraction, nitrogen adsorption-desorption, infrared spectroscopy, hydrogen temperature programmed reduction and field emission TEM techniques. The microwave-assisted catalytic hydrogenation of residue was conducted under the same microwave conditions to compare with the commercial catalyst. It is found that Fe2O3 is formed in the burning stage of the catalyst C-Fe. However, no reactions of the support or active metals with formed Fe2O3 or SiC in C-Si catalyst is observed. The pore volume of the catalyst containing microwave sensitizer is decreased, while the content of Br?nsted acid at mid-low temperature is increased. The reduction peak area of C-Fe is increased and the peak moves to higher temperature. The TEM results indicate that the microwave sensitizer was wrapped by alumina in the prepared residue hydrogenation catalyst. The C-Si has the equivalent impurity removal activity under microwave-assisted conditions with the commercial catalyst, while the performance of the catalyst C-Fe is the best of the three.

    EFFECT OF Nb ADDITION ON DE-NOX ACTIVITY OF Pd/Al2O3
    2016, 47(9):  62-66. 
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    In order to improve the HC-SCR activity, selectivity and stability of Pd based catalyst, and reduce the cost of the catalyst, the non-noble metal Nb is used to modify the texture, structure and redox properties of Pd based catalyst. The high porous Al2O3 support was prepared by adding pore-forming agent EDTA and low-cost commercial Al2O3 powder. Then the Nb modified Pd/Al2O3 catalysts was sucessfully made by impregnation. The catalysts were characterized by XRD,BET,NH3-TPD,H2-TPR,XPS to study the effect of Nb addition on the performance of catalysts in HC-SCR reaction. The results show that the addition of Nb effectively improves the activity of catalysts. The Pd-Nb/Al2O3 catalyst with 5% Nb has the best catalytic activity and stability, the NO conversion is 90% at only 269 ℃.

    EFFECT OF PHOSPHORUS MODIFICATION SEQUENCE ON HYDRODESULFURIZATION OF COAL TAR OVER Mo-Co/γ-Al2O3
    2016, 47(9):  67-74. 
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    Three catalysts with fixed compositions of MoO3, CoO, P2O5 of 13.50%, 2.11% and 4.16%, respectively were prepared by substep impregnation method with different P modification orders and characterized by XRD, H2-TPR, HRTEM techniques. The effect of phosphorus modification sequence on hydrodesulfurization performance of the catalysts was studied with the gasification tar distillates as raw materials. The results show that the P modification orders have different effect on acid sites distribution, reduction and sulfurization of active components as well as the pore structure of the catalysts, leading to a different HDS performance. The catalyst prepared by phosphoric acid pre-impregnation has the highest hydrodesulfurization activity;the sulfur removal rate reaches 96.98%.

    REUSE OF REGENERATED HIGH-PRESSURE HYDROTREATING CATALYSTS FOR LUBRICATING OIL PRODUCTION
    2016, 47(9):  75-80. 
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    The hydrotreating catalyst used in lubricating oil production under high pressure was regenerated for its lower activity. The activity of the regenerated catalyst is found lower than that of the fresh one. The medium-pressure hydrotreating and hydrodeacidification performance of the regenerated catalyst were evaluated in the laboratory. The results show that the regenerated catalyst can achieve the product specifications of medium-pressure hydrotreating and hydrodeacidification processes. This recycling program improves the utilization of the regenerated catalyst and makes a better benefit for the refinery.

    STUDY OF HIHG TEMPERATURE ANTIOXIDANT FOR AVIATION LUBRICANTS
    2016, 47(9):  81-87. 
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    Oligomer antioxidants were synthesized using N-alkyl phenyl-1-naphthylamine and alkylated diphenylamine as raw materials at conditions of 130-180 ℃,5-10 h and characterized by IR, HPLC-MS techniques. After oxidation and anti-corrosion at 204 ℃, the total acid number of polyol ester lubricant containing the synthesized oligomer antioxidant changes 0.945 mgKOH/g, the 40 ℃ viscosity change rate is 10.025%, and the sludge is 2.537 mg/100 mL. Compared with conventional antioxidant, the synthetic antioxidant significantly improves the high temperature oxidation and corrosion resistances of polyol ester lubricant, which can meet the requirements of AS-5780A and MIL-PRF-23699F.

    STUDY OF PRODUCTION OF HIGH VISCOSITY INDEX LUBRICATING BASE OIL FROM XIJIANG CRUDE HVGO
    2016, 47(9):  88-92. 
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    The Xijang crude HVGO was tested in a pilot plant to produce high VI base oil by simulated Chevron's all hydrotreating processes. The operation conditions for hydrocracking, hydroiso-dewaxing and hydrofining processes were investigated respectively. It is concluded that APIⅡ+ 8cSt lube base oil can be produced by hydrocracking-hydroiso-dewaing-hydrofining processes. The product yield is high.

    PERFORMANCE COMPARISON OF INSULATING OILS IN TRACTION TRANSFORMERS FOR PASSENGER TRANSPORT EMU
    2016, 47(9):  93-97. 
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    The comparative analyses of silicone oil and ester insulating oil in general performance, insulation performance, heat transfer properties, tray gassing performance and oxidation stability was conducted. The results show that compared with silicone oil, ester insulating oil has lower ignition point, larger acid value, higher the dielectric loss factor, larger ECT and lower volume resistivity. As the temperature increases, insulation performance of ester insulating oil drops rapidly, while the silicone oils and ester oils have similar heat transfer performance. The silicone insulating oil has strong anti-lightning breakdown capability, excellent thermal and oxidation stabilities. Tray gassing production of silicone insulating oil is much less than the ester oil.

    DEVELOPMENT AND APPLICATION OF NEW BUILT-IN SCALE COLLECTOR
    2016, 47(9):  98-101. 
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    This paper introduces a new kind of built-in scale collector. The structure and working principle of the collector are introduced in detail. Compared with the prior art, the built-in scale collector has advantages of simple structure, and larger dirt holding capacity,good scaling effect. It does not occupy the catalyst bed space and can effectively delay the increase rate of reactor bed pressure drop, and prolong the operation cycle of the reactor. The built-in scale collector were applied successfully in wax hydrofining unit of Yanshan Petrochemical Branch, the pressure drop of the reactor is less than 0.1 MPa and the life cycle of the reactor are prolonged

    TREATMENT OF S Zorb REGENERATED FLUE GAS WITH ORGANIC CATALYST
    2016, 47(9):  102-105. 
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    According to the characteristics of high sulfur dioxide content and small gas volume of regenerator flue gas from S Zorb desulfurization device in Yongping Refinery of Shaanxi Yanchang Petroleum (Group) Co. Ltd., the organic catalytic treatment technology is employed. With this treatment method, the regenerator flue gas is introduced into a desulfurization unit, and then the sulfur dioxide is converted into ammonium sulfate after a series of reactions in absorption tower. After treatment the concentration of sulfur dioxide in the flue gas is reduced to below 100mg/m3, which is in line with the national emission standard. In addition, the appearance of ammonium sulfate product is white powder, no visible mechanical impurities, and the content of nitrogen, moisture and free acid are all in line with the by-product ammonium sulfate standard DL / T 808-2002.

    DETERMINATION OF SULFUR-CONTAINING COMPOUNDS IN DIESEL BY COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY
    2016, 47(9):  106-110. 
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    Sulfur-containing compound types in diesel oil were characterized by comprehensive two-dimensional gas chromatography coupled with a sulfur chemiluminescence detector. Based on the retention values, orthogonal separation characteristics as well as the identification results of two-dimensional mass spectrum, the sulfur compounds were qualitatively identified. The mole response characteristics and linear response range of sulfur chemiluminescence detector were investigated. Using 4,6-dimethyl dibenzothiophene solution as external standard sample,the quantitative analysis on major sulfur compounds was established.