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Table of Content

    12 August 2016, Volume 47 Issue 8
    STUDY OF AROMATIZATION AND ISOMERIZATION OF 1-HEPTENE OVER DIFFERENT MODIFIED ZSM-5 ZEOLITE-SUPPORTED Ni CATALYSTS
    2016, 47(8):  1-6. 
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    The aromatization and isomerization performance of 1-heptene over Ni/SiO2, Ni/NaZSM-5, Ni/ZSM-5-P and Ni/ZSM-5-P-Fe was investigated at the conditions of catalytic hydrodesulfurization (T = 673 K, P = 1.5 MPa, WHSV = 5 h-1). The catalysts were prepared by loading nickel on the carriers by spraying method and were characterized by XRD, XRF, N2 adsorption-desorption and NH3-TPD, H2-TPR, and pyridine-FTIR techniques. The product distributions show that Ni/ZSM-5-P-Fe and Ni/ZSM-5-P exhibit a remarkable enhancement of aromatization and isomerization of 1-heptene compared with that of Ni/ZSM-5, resulting in increased yields of isomerized product, aromatics, and dry gas. The performance of Ni/ZSM-5-P-Fe is even better because it has more mid-strong acid center and Bronsted acid, indicating that the Bronsted acid promotes the aromatization and isomerization of 1-heptene. It is concluded that the synergetic effect of metallic active sites and appropriate acid sites on the bifunctional catalysts is in favor of the aromatization and isomerization of 1-heptene.

    RING OPENING PERFORMANCE OF MONOCYCLIC NAPHTHENE OVER PHOSPHORUS MODIFIED BETA ZEOLITE
    2016, 47(8):  7-12. 
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    Hβ zeolites were modified by immersion method with different phosphorus content solutions. The physicochemical properties of the samples were characterized by XRD, BET, NH3-TPD, MAS NMR techniques. The ethyl cyclohexane was used as a model compound to investigate the ring opening performance of the catalysts. The results show that modification with suitable amount of phosphorus can stabilize the framework aluminum of β zeolite, and improve the hydrothermal stability and activity. With the increase of the w(P2O5)/w(Al2O3), the relative crystallinity, specific surface area and retained acid amount were first increased and then decreased, and the reactivity and propylene yield as well. When the w(P2O5)/w(Al2O3) is 1.15, the hydrothermal stability and activity of molecular sieves achieve the optimal.

    EFFECT OF La ON SELECTIVE HYDRODESULFURIZATION PERFORMANCE OF CoMo/γ-Al2O3 CATALYST
    2016, 47(8):  13-19. 
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    The CoMo/La2O3-Al2O3 selective hydrodesulfurization catalysts were prepared and characterized by BET, XRD, H2-TPR, XPS and TEM. Then the HDS performance of the catalysts was evaluated in a continuous flow fixed-bed micro-reactor. The results show that the addition of suitable content La can weaken the interaction between support and active component, facilitate the reduction of active component and the sulfidation of Mo, and is beneficial to the formation of CoMoS phase. The catalyst with 1.0% La2O3 shows the optimal selective HDS activity. With an FCC gasoline as the feed, the sulfur content in the heavy fractions (>65 ℃) can be reduced to 11.2 μg/g from 120.8 μg/g and the research octane number (RON) loss is 1.1. After blending with caustic-treated light fraction, the sulfur content in product gasoline is 9.0 μg/g and the RON loss is 0.8.

    COMPARISON OF FH-98 AND FH-40C CATALYST IN COKER GASOLINE HYDROGENATION
    2016, 47(8):  20-24. 
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    The performance of FH-98 and FH-40C catalyst developed by FRIPP in a 450 kt/a coking gasoline hydrogenation unit of PetroChina Karamay Petrochemical Co. Ltd.was compared. The results indicate that both catalysts displayed excellent activity in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN). The qualities of the hydrogenated gasoline in both cases meet the feedstock requirements for reforming pre-hydrogenation unit. As FH-98 catalyst has certain cracking performance, it is easy to cause large temperature fluctuations or runaway of the bed temperature, resulting in higher operation risk. In contrast the FH-40C catalyst is found to be safer in terms of sustaining a moderate reaction temperature due to its weaker cracking capability.

    1-DECENE OLIGOMERIZATION WITH PENTAERYTHROTOL-BF3
    2016, 47(8):  25-27. 
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    1-decene oligomerization was studied using pentaerythrotol as initiator and BF3 as catalyst. The effect of mass ratio of pentaerythrotol/1-decene, reaction time and temperature on the reaction as well as the best conditions for 1-decene oligomerization and the recyclability of pentaerythrotol were investigated. The oligomerization products were analyzed by gas chromatography. The results indicate that at the conditions of mass ratio of 1-decene/pentaerythrotol of 10, 20 ℃ and 2.5 h, the conversion of 1-decene oligomerization is up to 97.90%. The yield of trimer and tetramer together is 84.17%. The recycling effect of pentaerythritol is good. The product can be used to prepare high performance synthetic lubricant base oil.
    ANALYSIS AND APPLICATION OF MEASURES OF INCREASING BENEFITS FOR COKING ROUTE REFINERY
    2016, 47(8):  28-34. 
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    In order to increase economic benefits of a coking type refinery, the advantages and disadvantages of the technical rout are analyzed. It is found that the coking type refinery has advantages such as flexible crude oil procurement, lower construction investment and lower operating cost, but poor product distribution and product quality compared with products of hydrogenation route refinery. The refinery adopts measures to optimize crude oil procurement, reduce the petroleum coke, and produce more gasoline and jet fuels, raise energy efficiency, reduce consumption as well as keep long term operation of CFB boilers. As a result, compared with the design scheme, an annual benefit of 1.033 billion yuan are realized according to the product slate in 2015.

    FACTORS AFFECTING YIELD OF PROPYLENE IN GAS FRACTIONATION UNIT AND MEASURES
    2016, 47(8):  35-39. 
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    The reasons of lower yield of propylene in gas fractionation unit were analyzed. Revamping measures were adopted based on the analysis. After revamping, the handling capacity of the fractionator is raised to 90 t/h. The revamping measures include: (i) connecting the high pressure gas discharge line on the top of deethanizer to the feed line of absorption-desorption tower of diesel oil hydrogenation unit, which reduces the discharge of propylene furthest and recovers propylene about 2.88 t/d with an benefit about 7.68 million yuan annually; (ii) using an advanced control system for gas fractionation unit to optimize the operation of propylene rectification tower, which reduces the temperature difference at the bottoms of the propylene tower, improves the purity of propane, and increases the yield of propylene. Through the above three measures, waste of propylene emissions is reduced and the propylene yield of the gas fractionation unit is increased to a great extent.

    CAUSE ANALYSIS OF BLOCKAGE OF HEAT EXCHANGER FOR PROCESSING SUIZHONG 36-1 CRUDE AND ONLINE CLEANING STUDY
    2016, 47(8):  40-43. 
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    The problem of high pressure drop and low heat exchange efficiency of heater exchanger when processing Suizhong 36-1 oil is analyzed by element composition, FT-IR, and toluene dissolution test. Combined with the knowledge of crude oil production process and the additives used, the material with cage-like structures caused by polyacrylamide is found to be the reason for heater exchanger blockage. An online clean method, in which the No.1 side cut of atmosphere distillation tower is pumped into the inlet pipeline of crude, is proposed. The commercial application proves that the suggested method is effective and feasible, and has both cost efficiency and energy saving effect.

    APPLICATION OF DIRECTIONAL REFLECTION DEEP CRACKING TECHNOLOGY IN HEAVY OIL COKING FURNACE
    2016, 47(8):  44-46. 
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    The directional reflection deep cracking technology developed by the Chinese University of Petroleum was adopted for heater revamping of the 1.2 Mt/a coking plant during overhaul in PetroChina Karamay Petrochemical Co. Ltd. under the preconditions of the constant overall structure of the furnace. In this technology, the tube with oil was heated by fire directively reflected from the furnace wall and the oil in the tube was cracked deeply. After the transformation, the average surface temperature of the tube reduces by 30 ℃, the yield of gasoline and diesel increases 2 percentage points, the coke yield decreases by 1.15 percentage points, and the heat efficiency increases 2.23 percentage points. This means that the measures of changing the tube direction arrangement, increasing the tube number, extending the heavy oil residence time, improving the quantity and quality of heat are in favor of reducing coke yield and increasing gasoline and diesel yield.

    INVESTIGATION ON REACTION BEHAVIOR OF COUNTERCURRENT CCR UNDER LOW SEVERITY
    2016, 47(8):  47-52. 
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    The behavior of coking on catalyst and catalytic reforming reaction in a countercurrent CCR unit with a capacity of 600 kt/a in SINOPEC Jinan Branch Co. was investigated. The coke combustion characteristics were studied with TPO. The experimental results show that the countercurrent CCR process is a commercially feasible technology; compared to concurrent CCR, the temperature drop of the 1st reactor descended most and the distribution of temperature drop in reactors becomes even, and the total amount of coke generated in the 3rd and 4th reactor of countercurrent CCR, especially in the 4th reactor, increases sharply while the proportion of the coke in the 1st reactor decreases apparently. Different from concurrent CCR, the conversion of naphthene partly shifts from the 1st and 2nd reactor to the 3rd and 4th reactor. The conversion rates of paraffin in the 3rd and 4th reactor are slightly higher than that in the 3rd and 4th reactor of concurrent CCR mode; The olefin content in liquid products of the 3rd reactor reaches a peak value but declines in the 4th reactor; Compared to that of concurrent CCR, the coke burn-up temperature of countercurrent CCR rises.

    FUNDAMENTAL STUDY ON THERMAL UPGRADING WITH HYDROGEN DONOR FOR CANADIAN OIL SANDS BITUMEN ATMOSPHERIC RESIDUE
    2016, 47(8):  53-57. 
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    The hydrogen donating abilities of three fractions of atmospheric residue (FA, FB, and FC) were evaluated and the FB fraction was chosen as the best hydrogen donor. The impacts of FB on atmospheric residue thermal upgrading process was studied under different reaction conditions. The results show that the relative hydrogen donating ability has the order of FB>FC>FA. Compared with conventional thermal cracking, the coke induction period extends 3-4.5 min, the spot test rate of upgrading oil reduces by 1-2 grades(420 ℃,20-40 min). The density of upgrading oil decreases significantly as time and temperature increase in hydrogen donor upgrading process. Besides, the total viscosity reduction rate of thermal upgrading oil with hydrogen donor is 1.14-1.40 times of net viscosity reduction rate with light fraction blending.

    OPTIMIZATION OF DIBENZOTHIOPHENE DESULFURIZATION CONDITIONS OF BACTERIUM RHODOPSEUDOMONAS SP. AS-21
    2016, 47(8):  58-63. 
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    The specific DBT desulfurization bacterium Rhodopseudomonas sp. AS-21 was selected. The effects of temperature, pH, carbon source, nitrogen source, and initial concentration of DBT on S removal rate and cell concentration were investigated by single-factor experiments. The best conditions for the growth and desulfurization of AS-21 is 30℃, initial pH 7.5, concentration of glycerin as carbon source 10g/L, concentration of NH4Cl as nitrogen source 2g/L and initial concentration of DBT 100mg/L. The significance analysis results with Design-Expert show that temperature, pH and initial concentration of DBT have higher effects on desulfurization. Box-Behnken Design (BBD) response surface methodology was used to design total 20 experiments with three factors and three levels to obtain quadratic regression model for desulfurization rate and cell mass concentration. The optimization solution of the maximum response values under the simulated conditions by Design-Expert software predicts that the best factors for the highest desulfurization rate and strain growth are 29.70℃,pH 7.43,initial concentration of DBT 105.47mg/L. The highest desulfurization rate and strain growth are 72.32% and 2.311g/L, respectively, which are proven to be right through experiments.
    COMPARATIVE STUDY OF SUITABILITY OF MANUAL TRANSMISSION OILS FOR SYNCHRONIZER BY SRV-IV TEST AND WS2001 BENCH TEST
    2016, 47(8):  64-69. 
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    To save the cost of screening the oil, the suitability of manual transmission oils for synchronizer were investigated by SRV-Ⅳ testing machine and WS2001 synchronizer bench test. The correlation of the two methods was also discussed. The experimental results indicate that (i) the friction coefficient and the change trend, the wear scar of SRV-Ⅳ were correspondence with WS2001 synchronizer bench test, but not obviously related with WS2001 service life; (ii) The running status and failure mode of manual transmission oils on WS2001 test can be preliminary anticipated by the performance of oil on SRV-Ⅳ testing machine. The oil with high SRV-Ⅳ friction coefficient (>0.131) and high stability in long-running, measured by ASTM D6425 and variable-frequency method, has a good running stability and a high stable friction coefficient on the WS2001 test as well. While the oils tested by WS2001 synchronizer was stable in the early stage with friction coefficient higher than 0.110 and then rapidly reduced to 0.090, the damaged gear occurs. The oils that the wear scar is larger than 1.394 mm2 and 4.43 μm in depth after SRV-Ⅳtest easily cause the wear failure of the WS2001 synchronizer.

    APPLICATION OF IMIDAZOLIUM DITHIOPHOSPHATES AS ANTI-WEAR ADDITIVES IN SEMI-SYNTHETIC ESTERS OIL
    2016, 47(8):  70-74. 
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    Ionic liquids have excellent tribological properties, but they can't dissolve in mineral oils and other nonpolar base oil, which limits their practical application. Two kinds of ionic liquids were synthesized and dissolved in esters semi-synthetic base oil as anti-wear additives and the tribological properties were evaluated by SRV IV oscillating friction and wear tester. The surface maps and wear volume of lower discs were measured by micro-3D surface mapping microscope. The chemical composition on the surface of wear scars were analyzed by X-ray photoelectron spectroscopes. The results indicate that the application of imidazolium dithiophosphates acid makes the semi-synthetic base oil decrease the friction coefficient from 0.085 to 0.034 and the wear volume from 84.2 x 10-5 mm3 to 20.6 x 10-5 mm3. This work provides an effective method for the practical application of ionic liquids.

    TRIBOLOGICAL PROPERTIES OF METALLOCENE POLY ALPHA-OLEFINS LITHIUM COMPLEX GREASE
    2016, 47(8):  75-80. 
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    Using metallocene poly alpha-olefins (mPAO) and poly α-olefin (PAO40) as base oils, and complex lithium soap as thickener, a kind of lithium complex greases were prepared. The high-speed reciprocating friction and wear testing machine was used to investigate the effect of molybdenum disulfide, molybdenum dithiocarbamates, zinc silicate additives and their mixtures on the friction and wear properties of complex lithium grease on steel - steel friction pair. Scanning electron microscopy (SEM) and energy spectrum analysis (EDS) were employed to analyze the worn surfaces. The tribological properties of the composites are significantly improved with addition of 5% molybdenum dithiocarbamate, 2% molybdenum disulfide or 4% zinc silicate in the lithium grease. The lithium grease using mPAO as base oil has better tribological properties compared to poly α-olefin as base oil.

    PERFORMANCE EVALUATION OF FRICTION REDUCERS IN POLYETHER (PAG) OIL
    2016, 47(8):  81-84. 
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    The compatibility and tribological properties of friction reducers(epoxy oleate, benzotriazole aliphatic amine, inactive sulfurized fatty acid ester, and boride oleic acid ester amides)in polyether (PAG) oil were investigated by four-ball test and MTM2 test machine. The results indicate that three kinds of friction reducers have a good compatibility and tribological properties with PAG, except benzotriazole aliphatic amine and inactive sulfurized fatty acid ester. The addition of amine phosphate has good effects on bearing capacity and the friction reduction for polyether. Great improvement in bearing capacity and friction reduction, friction factor, and traction coefficient of the PAG are observed after addition of amine phosphate.
    ESTABLISHMENT OF NEW VICKERS104C TEST BENCH AND METHOD
    2016, 47(8):  85-92. 
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    The conventional Vickers104C test bench in China cannot satisfy the demand of the ASTM D7043 standard in scope of application, test conditions or bench test parameters. A new Vickers104C test bench was established according to the ASTM D7043 standard strictly in this work. By comparison of the test data of this work and data abroad using the same oils and liquids, the repeatability and differentiability of the new test bench is proven to meet the demand of the ASTM D7043 and consistent with the data from abroad. It can be used for the evaluation of petroleum based and non-petroleum based hydraulic oil, water-glycol, emulsion and other water-base fluids.

    STUDY ON PIECEWISE LINEAR RELAXATION FOR CRUDE SCHEDULING OPTIMIZATION
    2016, 47(8):  93-97. 
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    The efficiency of solving crude scheduling optimization models is seriously affected by nonlinear constraints, which are produced by the property calculations of mixed crudes. In order to empower the model to cope with multiple crude pooling situations, a piecewise linear relaxation approach was employed to convert the nonlinear constraints into linear ones. Crude scheduling optimization of a real refinery was used as an example and the sulfur content calculations of mixed crudes were converted into linear forms. The effect of the piecewise linear relaxation approach was compared with another two frequently-used approaches. The results indicated that by use of the piecewise linear relaxation approach, the efficiency of solving the converted model met industrial application demand; while the sulfur contents of the processed crudes lied between 0.50% and 3.00%, the piecewise linear relaxation approach was more conducive to acquire optimal scheduling schemes; as the sulfur content difference of the processed crudes increased from 0.50% to 2.50%, the calculated sulfur contents of mixed crudes in charging tanks remained close to the actual value with the piecewise linear relaxation approach, the relative deviations were under 5% and therefore the industrial demand for model accuracy was satisfied.

    APPLICATION OF OPTIMAL CONTROL SYSTEM IN CATALYTIC REFORMING UNIT OF QINGDAO PETROCHEMICALS AND EFFECT ANALYSIS
    2016, 47(8):  98-101. 
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    The optimal control system developed by Beijing optimipro control technology Co. Ltd. was used in reforming unit of Qingdao Petrochemicals. The operation of the control system was safe, stable and no abnormal situations. The use of this software ensured that the process constraint conditions were set within the scope of operation. By optimizing the inlet temperatures of four reactors, the octane number yield (the product of multiplying liquid yield by RON) and the economic benefit can be maximized. The octane yield of C5+ stabilized gasoline enhances 0.65 percentage point higher than the blank reference and the economic benefit increases nearly ¥19.63/t.
    DETERMINATION OF TRACE LEVEL LIGHT OXYGENATES IN GASOLINE BY GAS CHROMATOGRAPHY
    2016, 47(8):  102-108. 
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    A gas chromatographic system equipped with back-flush and heart-cutting (microfluidic deans switch) parts and three connected columns is established for determination of trace level light oxygenates in gasoline products. The oxygenate in gasoline comprising heavy hydrocarbons can directly be analyzed by pressure changes of carrier gas, and the hydrocarbon components in the sample do not interfere with the determination results. Through the pressure changes of carrier gas, the components with the boiling points lower than n-undecane can be eluted from a 2 meters long pre-column into a 30 meters long non-polar column, meanwhile the heavy fractions are back-flushed to the vent port to leave the system. The components coming into the 30 m long column are separated by switching solenoid valve of heart-cutting parts, only the separated components with boiling point lower than 2-hexanone can be eluted from the non-polar column and enter into a 10 meters long polar OxyPLOT column to separate the light oxygenates and hydrocarbons, and then the effluents are detected by flame ionization detector and quantitatively determined with external standard method. Light oxygenate contents such as C1-C4 alcohols, C2-C5 aldehydes, C3-C6 ketones, methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether in gasoline can be analyzed. The detection limit for single component is between 0.5-2.0 μg/g, the adding standard recovery rate for different components is 80%-120%, and the RSD (relative standard deviation ) is in the range of 2%-5%. The results of analysis of products from catalytic cracking and catalytic pyrolysis process show that the main oxygenates in these products are ketones with little amount of alcohols, aldehydes, and ethers.