Table of Content

12 November 2015, Volume 46 Issue 11

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SIMULATION STUDY OF MOLECULAR COMPOSITION OF RESIDUE

2015, 46(11):  1-6. 

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Based on the molecular type homologous series matrix, a structure oriented lumping (SOL) method was established to simulate molecular composition of residue, where 65 single cores and 12 multi-cores assumed structure were chosen as the seed molecules which were divided by carbon number of the side chain, resulting in 3 749 kinds of virtual molecules to represent the residue molecular compositions. Each molecule was composed of 15 kinds of basic structure vectors to represent the reaction process of molecules and to calculate the individual properties. With the structural attribute distributions of the residue, the mole fractions of each molecule can be confirmed, and the bulk properties were derived from the calculated mole fractions and the individual properties. Therefore, the mole fractions were determined based on the parameters of the attribute distributions by simulation annealing algorithm. As the results of 3 kinds of residual samples show that the calculated values of bulk properties of residue are in accordance with the measured ones, the distribution of the molecular weight reveals obvious gamma distribution for relative molecular mass of each residue aromatics. It is feasible to represent the residue with the 3 749 kinds virtual molecules, and the method based on the structural attribute distributions can well be used to calculate the mole fractions.

CATALYTIC CRACKING PERFORMANCE OF PENGLAI AND DALIYA VACUUM GAS OILS

2015, 46(11):  7-11. 

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The catalytic cracking performance of Penglai and Daliya vacuum gas oils (VGO) was investigated in a fixed fluidized bed. The influence of reaction temperature (T), catalyst to oil weight ratio (C/O), weight hourly space velocity (WHSV) and steam to oil weight ratio (S/O) on the distribution of the cracking products was studied. The yield of light oils increases with decreased reaction temperature and C/O and with increased WHSV and S/O. At the industrial operating conditions (T=500 ℃, C/O=6, WHSV=20 h-1, S/O=0.08), the conversion, light oil yield and total liquid yield of Penglai VGO reach 92.18%, 62.62% and 81.71%, respectively, and those of Daliya VGO are 94.14%, 64.14% and 82.63%, respectively. At the optimal operating conditions (T=490 °C, C/O=5, WHSV=25 h-1, S/O=0.10), the conversion, light oil yield and total liquid yield of Penglai VGO is up to 91.98%, 66.54% and 84.09%, respectively, and those of Daliya VGO are 93.59%, 70.98% and 84.86%, respectively. It is concluded that the cracking performance of Daliya VGO is better than that of Penglai VGO.

N-OCTANE HYDROCRACKING KINETIC MODELING BASED ON SINGLE EVENT METHOD

2015, 46(11):  12-19. 

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The n-octane hydrocracking kinetic modeling was studied over a Ni-W catalyst. The kinetic data were obtained in a tubular fixed-bed reactor. The condensed liquids and non-condensable gas components were analyzed by offline and online GCs, respectively. The reaction network was built based on the carbenium-ion mechanism. PCP isomerization and β-scission were assumed as rate determining steps. With the application of Single Event method, the number of independent parameters was reduced. The genetic algorithm and the Marquardt algorithm were used for 12 parameters estimation. The calculated rate values are in agreement with the experimental values. The parameters can be used in kinetic studies of FT wax hydrocracking and other materials with high carbon because of the intrinsic property of the Single Event based values.

STUDY ON STABILITY OF SULFURIC ACID/n-HEPTANE EMULSION

2015, 46(11):  20-24. 

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The stability of emulsion for sulfuric acid and hydrocarbon was evaluated by Turbiscan Lab dispersion stability analyzer. The effect of operating variables, including composition of the sulphuric acid, time of agitation, severity of agitation, volumetric ratio of acid to hydrocarbon, and various hydrocarbons on the dispersion system stability were investigated. The results show that the fresh concentrated sulfuric acid can only make a small amount of n-heptane dispersing into sulfuric acid, while the waste acid can make n-heptane fully spread in waste sulfuric acid to form emulsification. When acid-hydrocarbon emulsion reaches balance, little effect of increasing mixing time on emulsion is found. And the higher the stirring speed and the higher acid-hydrocarbon ratio, the more stable of the emulsion; Different hydrocarbons and concentrated sulfuric acid form the emulsions with different stability. The stability of the emulsion consisted of isooctane and concentrated sulfuric acid is best, petroleum ether is the next. The stability of the emulsion formed by n-heptane and concentrated sulfuric acid is the worst.

COMPLEXATION DENITROGENATION OF LIAOHUA COKER GAS OIL

2015, 46(11):  25-29. 

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Complexation denitrogenation of the Liaohe coker gas oil from Liaoyang Petrochemical Company was investigated. Single factor test, orthogonal test, reaction kettle and static mixer test were carried out. The results of Single factor test and orthogonal test show that the optimal reaction temperature is 65 ℃, and the optimum volume ratio of solvent to oil (S/O) is 1%. At this conditions, the total refined nitrogen by the kettle is 1 945 μg/g and the yield is 98.36%. Besides, when the S/O ratio drops from 1% to 0.86%, the total nitrogen of refined oil increases from 1 778 μg/g to 1 998 μg/g and the yield climbs from 98.13% to 98.78% by the static mixer. The refined oil meets the quality specification of catalytic cracking blending feed.

APPLICATION OF MIP TECHNOLOGY IN 1.40 Mt/a FCCU OF JILIN PETROCHEMICAL CORPORATION

2015, 46(11):  30-34. 

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The MIP process for maximizing iso-paraffins developed by Research Institute of Petroleum Processing，SINOPEC is a proprietary technology to produce clean gasoline component. The FCC-Ⅲ unit with 1.40 Mt/a in Jilin Petrochemical Corporation was revamped for MIP operation, and put into running smoothly since Nov.6,2010. The industrial results show that the adopted MIP process, in comparison with the previous conventional FCC process, the product slate with lower yields of dry gas and slurry, and a higher yield of total liquid products are obtained. The product gasoline is characterized by lower contents of olefin and sulfur. The RON of the gasoline is 93.0. The cetane number of the diesel product reaches 24. The total liquid yield (LPG+Gasoline+Diesel) is 81.15%.

THERMAL CRACKING DEACID TECHNOLOGY FOR SUDAN HIGH ACID CRUDE OIL AND ITS INDUSTRIAL APPLICATION

2015, 46(11):  35-41. 

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Investigations on acid distribution of Sudan crude and on thermal cracking acid-removing technology were conducted in the lab-scale and pilot plant devices. The technology developed was commercialized in Sudan refinery. The results show that high temperature and high circulation ratio can improve deacid efficiency, the acid removal reaches above 98% at the temperature about 500 ℃ and circulation ratio of the feed to gas oil about 0.3. The technology developed and applied in Sudan refinery for processing high TAN heavy crude has crude atmospheric distillation and delayed coking functions besides acid–removing. The commercial results show that the deacid rate is about 91%, the liquid yield and light oil yield reaches 80% and 64.31% respectively, the total acid number(TAN) of products drops sharply.

ADDITION OF VAPOR PHASE SIDE-DRAW PIPE IN XYLENE TOWER TO REDUCE END POINT OF NAPHTHA FRACTION OF CONTINOUS CATALYTIC REFORMING

2015, 46(11):  42-45. 

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The end point of C9+ distillates at the xylene tower bottom of the1800k/a continuous catalytic reforming unit in SINOPEC Qingdao Petrochemical Company was about 250 ℃, resulting in overstandard end point of naphtha. To solve the problems, a vapor-phase stream side-draw pipe was added to the xylene tower. The vapor-phase stream was used as a fraction of gasoline blending component directly. The bottom fraction of the tower was used as a fraction of the diesel oil blending. The results indicate that the measures can effectively remove the heavy components in C9+ fraction and reduce the end point of the naphtha.

ANALYSIS OF LONG PERIOD OPERATION S Zorb UNIT

2015, 46(11):  46-51. 

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The 1.2 Mt/a S Zorb unit of SINOPEC Changling Petrochemical Company has been running for more than three years. The measures for optimizing the filter operation, improving the heat exchanger efficiency of raw material, processing and regenerating the adsorbent agglomerate, reducing the line wear of temporary transfer agent as well as lock hopper system maintenance were summarized during the long operation period. The key to optimization of reactor filter operation is strengthening counter blowing system maintenance, smoothing reaction pressure control, monitoring large flange seal protection and discharging intermittently the powder in the system; the thermal efficiency can be improved by maintaining the raw materials purity and reducing feed heat exchanger fouling; the effect of adsorbent agglomerate on adsorbent recycling can be reduced by using the original dust unloading process. In the case of the horizontal tube poor in unloading, using the bend pipe with little and big instead of many small bend pipe can effectively reduce the wear of temporary transfer agent line. A series of measures to protect the wear in lock hopper program-controlled valve and shorten the failure processing time of the lock hopper make the S Zorb device synchronize with catalytic cracking unit.

APPLICATION OF FEED PREFRACTIONATION TECHNOLOGY FOR REDUCING BENZENE IN REFORMING GASOLINE

2015, 46(11):  52-55. 

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Two pathways (the dehexanizer and the feed prefractionation) for reducing the benzene content in stabilized reforming gasoline were compared. It is found that the comprehensive energy consumption of the reformer unit decreases by 147.97 MJ/t through feed prefractionation, the reforming gasoline yield increases 7.36 percentage points, and the total liquid yield increases by 0.69 percentage point, gas and the loss reduce by 0.36 percentage point. The economic benefit increases by 5.783 4 million Yuan per month. And suggestions for further optimization of the prefractionation system are put forward.

PREPARATION AND COAL TAR HYDROCRACKING PERFORMANCE OF Co-Mo/USY CATALYSTS

2015, 46(11):  56-61. 

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CoMo/ USY hydrocracking catalysts were prepared using USY molecular sieve as support by using impregnation method and characterized by XRD, NH3-TPD, H2-TPR. (NH4)2S2O3 was used as a presulfidation agent. The performance of coal tar hydrocracking of catalysts prepared with different Mo loading was investigated by orthogonal test in a continuous flow fixed-bed reactor. The results indicate that the catalyst with 12% Mo is the best. The yield of fuel oil reached 86% under the reaction conditions of a temperature of 385 ℃, a pressure of 9 MPa, a WHSV of 0.6 h-1, and a H2/oil ratio of 1 000.

STUDY ON SILICON DEPOSITION ON COKER NAPHTHA AND DIESEL HYDROFINING CATALYSTS

2015, 46(11):  62-64. 

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This paper briefly described the deposition regularity of silicon on catalyst during coker naphtha and/or diesel hydrofining. The silicon content at different positions of catalysts bed during hydrofining of coker naphtha, coker naphtha and diesel and liquid phase diesel were analyzed. The results show that the silicon deposition in catalyst bed of coker naphtha hydrofining reactor is evenly distributed, while the silicon deposition in catalyst bed of liquid phase diesel hydrofining reactor is decreased layer by layer sharply. Moreover the deposition situation in coker gas and diesel mixture hydrofining is between the two before.

INDUSTRIAL APPLICATION OF CATALYST COMBINATION OF FH-40C/FHUDS-6 IN PRODUCING ULTRA LOW SULFUR DIESEL

2015, 46(11):  65-69. 

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In order to meet the requirements of producing phase V national standard diesel, part of FH-40C hydrotreating catalyst in Huizhou Refining & Petrochemicals Co. coker gasoline/diesel hydrotreating unit was replaced with a new generation of diesel deep hydrodesulphurization catalyst FHUDS-6 developed by SINOPEC Fushun Research Institute of Petroleum and Petrochemicals. The calibration was carried out at 110% load (269 t/h), and the results show that the catalyst combination of FH-40C/FHUDS-6 can produce refined diesel (the average sulfur content of 5.2 μg/g, the cetane number of 54.57 with a mixed feed of coker gasoline/diesel and straight run diesel (the average sulfur content of 1 923 μg/g at reaction conditions of 7.7 MPa in cold high pressure separator, average temperature of 365 ℃, LHSV of 1.931 h-1 and the ratio of hydrogen to oil of 523. The desulfurization rate reaches 99.786%, indicating the excellent performance in deep hydrodesulphurization and cetane number improvement of FHUDS-6 catalyst. The quality of refined diesel can meet the requirements of national phase V standard for diesel product.

STUDY ON PREPARATION AND REACTIVE ADSORPTION DESULFURIZATION PERFORMANCE OF RODLIKE Ni/CuO-ZnO

2015, 46(11):  70-73. 

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The rodlike CuO-ZnO complex oxides were prepared by hydrothermal synthesis method. The adsorbents of Ni/CuO-ZnO were prepared by incipient-wetness impregnation method. The complex oxides and the adsorbents were characterized by TG，XRD, SEM and BET techniques. The performance of reactive adsorption desulfurization for thiophene was evaluated in a fixed bed reactor. The results indicate that the suitable calcination temperature for composite oxides and Ni/CuO-ZnO is 500 ℃. The doping of Cu effectively improves the reactive adsorption desulfurization performance, and the adsorbent with 10% CuO shows the best desulfurization activity, 17.4 percentage points higher than the reference Ni/ZnO. And the adsorbent with Cu doping is more stable, the adsorbent still remain high desulfurization activity in 45 hour.

FORMATION MECHANISM OF SUSPENDED MATTERS IN JET FUEL

2015, 46(11):  74-77. 

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The microscope, energy dispersive X-ray spectroscope (EDX) and ICP were used to analyze the composition of suspended matters in jet fuel. Combined with Amorphotheca resina`s （typical fungus）growth in jet fuel, the formation mechanism of suspended matters was proposed. It is concluded that the flocculent suspended matter in jet fuel is the outcome of multiple factors. The fungus, fibre and particulate impurities all participate in the formation of suspended matters.

TRIBOLOGICAL PERFORMANCE OF OVERBASED CALCIUM ALKYL SALICYLATE AND SULFURIZED ISOBUTYLENE IN RAPESEED OIL

2015, 46(11):  78-82. 

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Four-ball tests were performed for rapeseed oil (RSO) containing the sulfurized butylene (T321) and the overbased calcium alkyl sulfonate (T109) to investigate the tribological properties of T321, T109, and their synergistic effect. The results show that the addition of T109 can retain the extreme pressure properties of rapeseed oil containing T321, improve its anti-wear performance and prolong its working life. The element compositions on the worm surface of the tested steel balls were detected by EDS technique and the synergistic effect of T109 and T321 was analyzed. It is found that in comparison with 10s of extreme pressure test, except of obvious carbon, calcium deposition, no large difference was found for other elements in 30 min test. Thus the improved anti-wear ability of the lubricant with two additives seems to be caused by the formation of inorganic boundary film containg calcium and carbon on the friction surface. While the extreme pressure performance fails to ascend is due to the extreme pressure testing time is too short to make CaCO3 participate in the friction reaction.

SIMULATION ANALYSIS FOR ENERGY SAVING PROCESS OF ABSORPTION AND STABILIZATION SYSTEM OF INTENSIFIED ABSORPTION PROCESS

2015, 46(11):  83-87. 

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A novel and energy saving flowsheet is proposed in which a side draw line was added in the absorber. The bottom stream of the absorber flows into the stabilization column, and the liquid stream from the side line at the lower part of the tower enters the flash tank through cooling. The comparison of new flowsheet and conventional “four tower process” are made in view of energy efficiency. The study shows that the reboiling duty, cooling duty in front of the flash tank and energy consumption are reduced by 12.2%, 10.4% and 5.2%, respectively, compared with the conventional flowsheet.

STUDY OF METHYL ORANGE SIMULATED WASTEWATER TREATMENT BY ZEOLITE WITH Fe-Ce BIMETALS

2015, 46(11):  88-91. 

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A series of Fe-Ce/ZSM-5 catalysts were synthesized via equivalent-volume co-impregnation of ferric nitrate and cerium nitrate on micro-meso pore ZSM-5. The pore volume impregnation is thought the one with simple operation without complex equipment, and high efficiency. The optimal catalyst preparation condition was evaluated by catalytic oxidation of hydrogen peroxide (H2O2) technology (CWPO) to degrade the methyl orange solution. The results indicate that the best preparation conditions are: co-impregnation solution concentration 2.0 mol/L with the mole ratio of Fe/Ce of 3:1 and the calcination temperature 400 °C. In the presence of H2O2 and reaction time 100 min, more than 85% methyl orange is removed. TEM and XRD results show that Fe-Ce/ZSM-5 remains the ZSM-5 pore structure and the catalytic properties of iron oxides and cerium oxides.

DIRECT DETERMINATION OF SILICON CONTENT IN COKER DISTILLATES BY ICP-OES

2015, 46(11):  92-96. 

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The on-line internal standard with direct introduction of organic solvent method was established for the determination of silicon in coker distillates by inductively coupled plasma optical emission spectrometry (ICP-OES). The effect of twelve different silicon organic compounds on the response sensibility was tested. Among of them, the trimethylsilanol, triethylsilane, dimethoxydimethylsilane and hexamethyldisiloxane show higher sensibility than other eight compounds, and the ratios of measured and theoretical value (about 2 ?g/g) are 5.0, 3.4, 4.2 and 4.1, respectively. However, these four compounds have little effect on the determination of silicon in real coker distillates due to very low concentrations. The ring siloxanes are the main organic silicons in real coker distillates, the response sensitivity of these compounds are close to each other. The adding standard recoveries of Si in coker gasoline and coker diesel are 101% and 98.4%, respectively. The limit of detection of the method is 0.03 ?g/g. and therefore, the ICP-OES can be used for quantitative analysis of silicon content in the coker distillates.

STUDY ON STABILITY OF HEAVY MARINE FUEL OIL BY GRADIENT VISCOSITY METHOD

2015, 46(11):  97-100. 

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To reduce the production cost of marine fuel oil, the light oil from mid-temperature coal tar (coal-light oil) was used as a low-cost blending component, and therefore the blending method was studied. The gradient viscosity method, which simulates the property changes of heavy marine fuel oil in the process of storage after rapid aging, was established. Four factors of gradient density difference, viscosity, acid number, total deposits after rapid aging were used as stability indices. Among of them, the viscosity difference was taken as the major indicator to determine the stability of the blending system. The results show that the highest proportion of coal-light oil which can mix with asphalt, diesel from coal tar and shale oil is no more than 17% to ensure the stability of fuel oil. It is found that the properties of the samples after rapid aging for 10 h at 120 ℃ are similar to that of samples aged for15 days at room temperature.