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Table of Content

    12 June 2016, Volume 47 Issue 6
    DEVELOPMENT OF FULL-RANGE CATALYTIC CRACKING GASOLINE SELECTIVE HYDRODESULFURIZATION TECHNOLOGY
    2016, 47(6):  1-4. 
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    Full-Range catalytic cracking gasoline selective hydrodesulfurization technology was developed. The pilot plant test results of effect of reaction conditions on selective hydrodesulfurization showed that high LHSV and H2/Oil volume ratio are conductive to improvement of hydrodesulfurization selectivity. The pilot plant test results also showed that using the technology to hydrotreat the feedstocks with sulfur content of 206 μg/g, 357 μg/g and 69 μg/g respectively, the sulfur content of product is 10 μg/g, 10 μg/g and 7 μg/g, and the RON loss of the product is 0.7, 0.6, and 0.2 respectively.

    THE HYDROGENATION UPGRADING INDUSTRIAL TEST TO PRODUCE LUBE AND WAX FROM F-T WAXES
    2016, 47(6):  5-9. 
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    The hydrogenation upgrading industrial test of F-T wax was carried out in Nangyang wax fine chemical plant in order to manufacture high quality lube oil base stock and special wax. The industrial test uses F-T wax manufactured by Zhenhai Refining & Chemnical Company as raw materials. Practice shows that it can manufacture pour point less than -30 ℃, viscosity index more than 140 lube oil base stock and special wax with high melting point by reasonable start up method and operating parameters.

    CRUDE VACUUM DISTILLATION TO INCREASE HYDROCRACKING FEEDSTOCKS
    2016, 47(6):  10-14. 
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    Combined hydrocracking expansion of production capacity for aviation kerosene demand to the sources of the raw materials, vacuum distillation technology is researched for increasing yield of the quality VGO from vacuum distillation production quality hydrocracking of raw materials as a starting point. And the comparison is made between simulation study and actual production of vacuum distillation. The results showed that technological research on production of hydrocracking raw materials by crude oil vacuum distillation can increase high-quality light gas oil yield. It has certain reference value for the enterprises to increase the production of aviation kerosene and the economic benefit.

    SCHEME AND IMPLEMENTATION EFFECT OF HIGH PRESSURE HYDROGENATION CRACKING UNIT FOR INCREASING YIELD OF AVIATION KEROSENE TECHNOLOGY
    Huiyong Yu
    2016, 47(6):  15-19. 
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    High pressure hydrocracking unit of Sinopec Yanshan Beijing Co first production cycle by RN-32/RHC-1 composite catalyst, steam jet fuel collection filter.19.35%,to change the production of jet fuel cycle second as RN-32V/RHC-3 composite catalyst, steam jet fuel collection filter.29.71%, An increase of percentage points, with the yield of 31.97% differern design, Sinopec Yanshan Beijing branch through the catalyst performance and equipment calibration data analysis, Main reason for after replacement of high activity catalyst cracking depth conversion improved significantly, caused by lack of device for high and low pressure separation system and product separation system capacity, can not guarantee the device with high conversion operation depth and jet fuel are completely separated. In view of the above problems, through the preliminary design calculation and feasibility analysis to determine the high and low pressure separation system of supporting instrumentation and fractionation system tray in the corresponding transformation and through the maintenance of it will problems may be eliminated.after the transformation of jet fuel,the average yield was 30.67%,Close to the design requireements, the yield of jet fuel aim.

    PRE-QUALIFICATION API Ⅱ+ BASE OIL PRODUCTION FROM CNOOCXIJIANG VGOs BY CLG ALL-HYDROPROCESSING TECHNOLOGIES
    2016, 47(6):  20-24. 
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    Pre-qualification API II+ base oil was produced from CNOOC Xijiang VGO#3 and VGO#4 using CLG high pressure all-hydroprocessing technologies and catalysts. Test results indicate that the all- hydroprocessing technology can successfully produce base oil to meet the API Ⅱ+ 4 cSt and API Ⅱ+ 8 cSt specifications. The two products have viscosity index of more than 118, cloud point of lower than -10 ℃, and pour point of lower than -28 ℃. These two products are excellent base oil for engine oil and industrial oilformulation.Hydrocracking and dewaxing reaction temperatures are the most important factors on base oil yield, kinematic viscosity, viscosity index, pour point, cloud point and other significant performance. When reaction temperature exceeds a certain value, product yield decreases rapidly. Under an appropriate reaction temperature, 4cSt oil yield of VGO #3 is about 64%,8cSt oil yield of VGO #4 is about 54%.
    INFLUENCE OF Na+ IN AMINE SOLUTION ON DESULFURIZATION AND COUNTERMEASURE
    2016, 47(6):  25-27. 
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    The problems which hydrogen sulfide (H2S) content in lean amine and desulfurized gas is not on-standard was appeared in West Pacific Petrochemical Co., Ltd. Dalian sulfur recovery plant amine desulfurization system during process operation. It is found that the main reason of the above problem is there was large amount of sodium ions (up to 7800ppm) in amine solution. With many experiments in lab, the ion exchange method is used to remove sodium ion from the amine solution. The hydrogen sulfide content analyzed in the sodium-removed lean amine solution reduced from 4g/L to 1.5g/L in industrial application, and gas desulphurization depth is increased significantly. Meanwhile desulfurization system steam usage decreased by 8t/h.

    DIFFICULTIES AND COUNTERMEASURES OF THE DIESEL OIL HYDROGENATION UNIT TO CHANGE THE STATE IV DIESEL OIL
    2016, 47(6):  28-31. 
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    Introduced diesel hydrotreating unit of SINOPEC Qingdao Petrochemical company at the end of the operation of the catalyst, the product of the vehicle is modified by the national standards for the national standards, and the sulfur content in the diesel is performed under the condition of 50 μg/g, diesel hydrogenation unit according to the actual operation, through optimization of production plan, optimizing the ratio of raw materials and raw material properties, improve hydrogen partial pressure, stable operation, predict summary of efforts, before Catalyst replacement makes full use of the catalyst activity, The production task of the state Ⅳ diesel oil was completed.

    LOW VISCOSITY PAO PREPARATION BY OLIGOMERIZATION OF ALPHA-OLEFIN FROM COAL WITH METALLOCENE CATALYST
    2016, 47(6):  32-36. 
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    The low viscosity PAO was synthesized by the oligomerization of olefin from coal with metallocene catalyst systems by kettle type polymerization. The effect of reaction conditions, such as mass fractions of the catalyst and co-catalyst, reaction temperature and reaction time on the conversion of stock and component distribution of PAO were examined. It is found that the optimum conditions are metallocene mass fraction 0.01%, proportion of co-catalyst and catalyst 9, the quality of organic boride and metallocene 2, reaction temperature of 115 ℃, reaction time of 2.5 h for the reaction system, under the optimum conditions, a low viscosity, high flash point, low pour point, low evaporation loss of PAO synthetic basestock with the kinetic viscosity of 8.15 mm2/s at 100 ℃, the viscosity index 158, the pour point -54 ℃, the flash point 286 ℃, the evaporation loss by Noack method 3.74% are obtained. The chromatographic analysis indicates that the produced PAO consists of a large part of tetramer, pentamer and a small part of trimer and hexamer. The same results are well repeated.

    RESEARCH ON POLYCYCLIC AROMATIC HYDROCARBONS IN THE CATALYTIC CRACKING CONVERSION
    2016, 47(6):  37-41. 
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    This research based on catalytic cracking pilot plants unit, the use of inferior straight-run gas oil as raw material, through change different conversion rate ,we can get the transfer coefficient of polycyclic aromatic hydrocarbons, test result may illustrate conversion rule of polycyclic aromatic hydrocarbons: under the condition of conversion rate below 48.22%, the transformation of polycyclic aromatic hydrocarbons, the main reaction as the branched chain rupture; when Conversion rate ranged from 48.22% to 62.71%, the three ring and the four ring aromatic hydrocarbons transfer coefficient changed little in the catalytic heavy oil, aromatic nucleus is relatively stable, polycyclic aromatic hydrocarbons transfer coefficient is about 0.3~0.4. the conversion rate is suitable for high selective catalytic cracking. When the conversion rate is higher than 62.71%, the polycyclic aromatic hydrocarbons will condensate rapidly, enhance the contributions to coke increases.
    RON PREDICTION BY IMPROVED MODEL FOR BLENDED GASOLINE
    2016, 47(6):  42-46. 
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    Motor gasoline blending, a critical step in refinery, is a processing of enormous benefit. Due to octane number is the important quality index, it is so significant for refinery to possess a precise octane number model. By the blending experiment, we established a developed blending octane number model and obtained the model parameters through developed LM. Furthermore we made a comparison between linear model、blending octane number model and developed blending octane number model. These predicting date derived from three models indicate that the developed blending octane model is advantageous. In order to verify the correctness of the model, this article randomly selected 31 An Qing refinery production data to verify the accuracy of the actual model, the result is that mean absolute error is 0.49, the average relative error is 0.5%, MSE is 0.74,R2 is 1.08.

    EFFECT OF BLENDING FCC SLURRY ON THE PROPERTIES OF VACUUM RESIDUE
    2016, 47(6):  47-51. 
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    The raw materials of vacuum residue and catalytic cracking oil slurry were supplied by SINOPEC Maoming Petrochemical Company. The properties of mixed raw material were analyzed when they were mixed by different blend ratio, applying the method of mathematical regression to carry out the law. The colloidal stability of mixed raw material was measured by the mass fraction normalized conductivity method and the SARA compositions. The results show that, the viscosity of mixed raw material obeys properties of exponential functions; density, carbon residue, element content and group compositions obey properties of linear functions, the colloidal stability of mixed raw material declined. The blend ratio of FCC oil slurry was discussed based on the properties and colloidal stability of the mixed raw material, the value within 30% is more appropriate.

    APPLICATION OF FRACTION CUTTING METHODS IN FCC GASOLINE ADSORPTION DESULFURIZATION
    2016, 47(6):  52-58. 
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    The performance of selective adsorption desulfurization of FCC gasoline fractions over modified Y zeolites (Cu(I)Y, CeY, NiY) was investigated by using methods based on cutting of light and heavy gasoline, temperature point and equivoluminal. At the same time, combining with the microcoulomb analysis and GC-SCD technique analysed the removal rate of sulfur compounds in FCC gasoline fractions cutting. Results indicate that the types and intensities of B acid and L acid in the NiY, Cu(I)Y and CeY zeolites determine the desulfurization performance for different cutting fractions. The weak B acid and the weak acid L center in the NiY have higher desulfurization performance for less aromatic hydrocarbon fractions, the strong B acid and the weak L acid center in the CeY have better desulfurization performance for less olefins fractions, however, the strong B acid and strong acid L in the Cu(I)Y is poorer desulfurization performance for various cutting fractions. In equivoluminal cutting method, the combination of using NiY for the front cutting fractions and CeY for the back will improve the adsorption desulfurization rate of FCC gasoline, comparing with a single adsorbent, which can be increased by 47.54 and 22.40 percentage points.

    STUDY OF ANTI-OXIDATION AND TRIBOLOGICAL PROPERTIES OF MoDTC
    2016, 47(6):  59-64. 
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    In this paper,the crankcase simulation test was carried out to investigate the antioxidation of MoDTC additive,and the oxidized oil and deposits on aluminum board were seperately characterized by FTIR and EDS. Tribological properties of unoxidized and oxidized oils were examined using four-ball machine,and SEM、EDS were employed to analyze micromor-phologies and element constitute of worn surfaces.Results show that: (1)MoDTC has good antioxidation under moderate and low temperature,which could increase the stability of oil;in high temperature,the antioxidation property of oil with MoDTC additive went down firstly, then up with increasing additive content.(2)The mass of depositsincreased firstly, and then decreased with the increase of additive content.Elemental analysis of deposits revealed that the decomposition products were significant comstituent parts of deposits.(3)Under test conditions,the friction-reducing and extreme-pressure properties were weakened by oxidation, while the antiwear property was strengthened.

    STUDY OF THERMAL CONVERSION OF TAHE ATMOSPHERIC RESIDUE AND ITS DEASPHALTED OIL IN PRESENCE OF HYDROGEN
    2016, 47(6):  65-71. 
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    Using the atmosphere residue from TaHe (THAR) as the raw material, n-hexane as solvent to obtain C6-asphaltene and the deasphalted oil which was the feedstock for autoclave hydrothermal cracking evaluating experiments. The reaction characteristics of THAR and DAO were analyzed by thermogravimetric analyzer and the molecular structure parameters were systematically investigated by elemental analysis, FT-IR, 1H and 13C-NMR and GPC. The results showed that the carbon residues in 700 ℃of THAR and DAO were 15.77% and 3.70% respectively. Compared with THAR, DAO had a higher weight loss in the given temperature, which indicated that DAO had a higher thermal cracking activity, so that the light components were more easily released in the presence of heat. By solvent deasphalting, the molecular weight reduced dramatically and the aromacity, total rings, aromatic rings and Naphthenic rings decreased from 0.27 to 0.22,8.45 to 5.08, 5.94 to 3.16 and 2.51 to 1.92 respectively. The ratio of Aromatic rings to Naphthenic rings in THAR was 1.44 times that of DAO. The hydrothermal cracking results showed that the yield of gasoline and diesel for DAO were 22.57% and 42.26%, which were increased by 4.48 and 9.05 percentage points respectively, and the yield of coke was only 5.02, which was reduce by 18.64 Which was associated with high aromaticity, association number, and carbon residue, containing high levels of highly condensed aromatic hydrocarbon.

    DEVELOPMENT AND ACTIVITY EVALUATION OF THDS-I HYDROFINING CATALYST
    2016, 47(6):  72-77. 
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    According to the marine distillate’s characteristics of low sulfur, high nitrogen, and high acid cyclic alkyl, CNOOC Tianjin Chemical Research & Design Institute, has proposed using silicon modified pseudo-boehmite as the carrier material. During the preparation process of the catalyst, adding organic complexing agent develops the first generation of penta-dentate spherical THDS-I hydrofining catalyst at China National Offshore Oil Corporation. The result of the pilot evaluation indicates that THDS-I hydrofining catalyst has an outstanding hydrogenation performance and activity ability. Furthermore, the evaluation result of industrial amplification and industrial catalyst production states that THDS-I hydrogenation catalyst production is a reasonable and feasible program flow. Under appropriate proceess conditions, refinery could use THDS-I hydrofining catalyst to produce diesel which meets the national V sulfur content and quality standards.

    STUDY OF PHOTOCATALYTIC OXIDATION DESULFURIZATION OF DIESEL WITH WO3-TiO2/SBA-15
    2016, 47(6):  78-83. 
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    SBA-15 was modified by bimetal using the innel-pore hydrolysis method and characterized by means of XRD,N2 adsorption-desorption, the results showed that WO3-TiO2/SBA-15 retained the hexagonal mesoporous structure. The Photocatalytic oxidation desulfurization performance of WO3-TiO2/SBA-15 catalyst was investigated using dibenzothiophene and dodecane solution as the simulation diesel and the mass fraction of 30% H2O2 as oxidant under UV light irradiation. The process conditions of the reaction were determined by static experiments, and the optimum reaction condictions were as follows: the catalyst dosage was 4 g/L, O/S molar ratio was 8, reaction temperature was 50 ℃, reaction time was 2 h. Under the condition, the desulfurization rate of simulation diesel was up to 87.9%. After the catalyst was reused for five times, the desulfurization rate could still reach 64.9%, indicating that WO3-TiO2/SBA-15 had good performances of photocatalytic oxidation desulfurization and recyclable.

    INFLUENCES OF DIFFERENT TRANSMISSION OILS ON PERFORMANCE OF WS2001 SYNCHRONIZER
    2016, 47(6):  84-89. 
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    Based on the custom-built WS2001 synchronous test bench, the influences of synchronizer oils on the WS2001 synchronizer performance was researched with six kinds of oils, such as GL-5 75W/90, heavy load and multifunctional gear oil 75W/90, 80W/90, 80W/140, CF-4 15W/40 and SJ/CD 15W/40. The experimental results indicated that the different lubricating oils had different service life and failure mode when they were used as the synchronizer oils for WS2001 synchronizer. The engine oils, such as CF-4 15W/40 and SJ/CD 15W/40 could ensure a good running stability, but the synchronizer test parts were easy to fail for wear and tear. Heavy load multifunctional gear oils had a good running stability in the early, but a rough stability in late running for oil oxidation. So the synchronizer test parts were easy to impact failure for oil oxidation. The viscosity, shear resistance and oxidation stability of transmission oils also had a certain influence on the performance of the synchronizer, and these influences should be considered when selecting and developing new type gearbox oils.

    STUDY ON PERFORMANCE OF CARBODIIMIDE AS ANTI-HYDROLYSIS ADDICTIVE FOR ESTER HYDRAULIC OIL
    2016, 47(6):  90-93. 
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    The method of ASTM D2619-09(Beverage Bottle Method) was used to analyze the ability of anti-hydrolysis of hydraulic base oil pentaerythritolester(PE) containing carbodiimide at different addition and hydrolysis time. Other properties of PE containing carbodiimide were examined. The results show that the hydrolysis of PE tends to decrease with the increase of carbodiimide, and the proper accretion of carbodiimide is 0.5%(mass fraction) . Carbodiimide has better ability of anti-hydrolysis than other amine antioxidants with the increase of hydrolysis time. The carbodiimide will not worsen other properties of PE, and the tribologicalcharacteristics of PE increase with carbodiimide has been improved.

    NUMERICAL SIMULATIONS OF FLUID DYNAMICS INSIDE SLURRY REACTORS FOR THERMAL CRACKING OF RESIDUE OIL IN PRESENCE OF HYDROGEN
    2016, 47(6):  94-98. 
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    Residue hydrotreating process is an important technical route in the area of heavy oil processing. There are four types of reactors can be applied for a thermal cracking process of residue, fixed bed, boiling bed, slurry bed and moving bed. Among them slurry bed is more proper for treating the residue with high concentration of the impurities for the advantages of less use level of catalysts, low investment, regular flow inside the reactor and high heat transfer performance. There are also four types of slurry bed reactors can be satisfied with the demand of residue hydrotreating process, including bubble column, inner loop reactor, forced recycling reactor and outer loop reactor. In accordance with the development of a 50kt/a slurry bed residue hydrotreating unit, the comparisons of the flowing behaviors of both gas phase and slurry phase inside the four slurry bed reactors were carried out with CFD simulations by using Euler-Euler multiphase model. According to the flowing informations, like velocity, hold up and volume fraction of slurry phase, an optimal reactor was obtained to fit for a large residue hydrotreating unit.

    NEW EFFICIENT INTERNALS FOR HYDROTREATING OF INFERIOR RAW MATERIALS
    2016, 47(6):  99-102. 
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    The technology of novel and high efficient hydrogenation reactor was introduced in this paper, with the related industrial application on the heavy oil hydrogenation units, which were developed by Research Institute of Petroleum Processing. Compared with existing technology, the overall logistics mixing and distribution performance are excellent with the new type hydrogenation reactor internals. The liquid phase distribution of the uneven factor is only 0.08 and the overall utilization rate of the catalyst was 95%. The flat structure can make the larger space for the 300mm ~ 500mm height of the bed catalyst. The Industrial application results showed that, the difficulty problems about the poor distribution effect of logistics and hot point in reaction bed, existed in the use of the deterioration of the heavy oil hydrogenation units. These could be solved through the new type of high efficient hydrogenation reactor internals. Also the average radial temperature difference of the catalyst bed is only 5.3 ℃, and it allows greater axial temperature rise. This could provide a reliable technical support the long period and high efficient operation for the units.