Table of Content

12 January 2014, Volume 45 Issue 1

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EXPLORING THE TRANSFORMATION OF ECONOMIC DEVELOPMENT BY INNOVATION & INVENTION

2014, 45(1):  1-5. 

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The pathway starts from innovation and invention, therefore their meaning are defined first, their ways & means of formation are explored. Thereafter, how to utilize innovation and invention to transform the economic development of present enterprise and the formation of new enterprise is discussed.

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EFFECT OF IRON DEPOSITION ON RESIDE CRACKING PERFORMANCE OF CONTACT CARRIRE

2014, 45(1):  6-10. 

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The iron deposited contact carriers were characterized by BET, NH3-TPD,SEM-EDX and their MAT and residue cracking performance were evaluated by micro-reactor and fixed-fluidized bed reactor, respectively, using Tahe AR as feedstock. The results show that the specific surface area, pore volume, total acid amount and micro activity of contaminated carriers are all reduced with contamination increasing. However, the pore size distribution has little change. The iron from iron naphthenate can deposit evenly in the bulk phase of the carriers with suitable larger pore structure, and the iron enrichment on the surface is not obvious. The iron contamination has a marked effect on the product distribution of Tahe AR cracking reaction.

STUDY OF SELECTIVE CATALYST FOR DEALKYLATION OF C8 AROMATICS

2014, 45(1):  11-14. 

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A catalyst using ZSM-5 zeolite as a component was developed to catalyze ethylbenzene dealkylation. Chemical liquid deposition (CLD) modification by silicon-containing compounds was performed to improve the catalyst pore dimensions in order to enhance the selectivity of dealkylation and reduce the disproportionation and transalkylation. The catalytic performance are tested in a fixed bed reactor under the reaction conditions of temperature 673-693K, hydrogen partial pressure of 1.8MPa, weight hourly space velocity of 10-15h-1, H2/feed molar ratio of 1-2, xylene yield could reach 98.81% and EB conversion is up to 90.19%.

EFFECT OF SUPPORT ON ISOBUTENE DEHYDROGENATION REACTION OF Mo BASED CATALYSTS

2014, 45(1):  15-19. 

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A series of Mo-based catalysts with 5 wt% Mo loading based on different support, including Al2O3, SiO2, ZrO2, MgO and MgAl2O4, were prepared by incipient wetness impregnation method and characterized by XRD，BET，NH3-TPD，H2-TPR. The isobutane dehydrogenation activity tests show that 5Mo/MgAl2O4 catalyst exhibits the maximum single pass yield of isobutene (up to 33 w %) at 560 ℃. The characterization results of XRD, BET, NH3-TPD and H2-TPR reveal that compared with the other supports，Mo/MgAl2O4 possesses relatively large specific surface area which facilitates uniform distribution of Mo species. Besides, appropriate acid and redox properties of the catalysts also contribute to effective activation of isobutane and easy desorption of isobutene. Consequently, relatively high isobutane conversion and isobutene selectivity are achieved.

EVALUATION OF OIL-SOLUBLE HYDROCRACKING CATALYST FOR VENEZUELA INFERIOR HEAVY OIL IN SLURRY-BED

2014, 45(1):  20-23. 

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An oil-soluble catalyst with 5.44w% Mo was synthesized. UV and IR analysis show that the synthetic products have the objective organic group. The experiments indicate that the catalyst is oil soluble and insoluble in water. Influence of reaction temperature, pressure and catalyst concentration on hydrogenation activity of Venezuela heavy oil in slurry bed reactor was simulated by autoclave. It is found that hydrogenation activity for slurry-bed hydrocracking of Venezuela inferior heavy oil is increased by adding oil-soluble catalyst. Under the conditions of catalyst concentration 200μg/g, temperature 430℃ and hydrogen pressure 8.0MPa, the maximum light oil yield per unit of coke could be up to 42.69%.

SYNTHESIS AND CHARACTERIZATION OF MESOPOROUS ZIRCONIA MOLECULAR SIEVE FOR n-PENTANE ISOMERIZATION

2014, 45(1):  24-27. 

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A Chromium-doped mesoporous zirconia molecular sieve was directly synthesized using zirconium nitrate hydrate and chromium chloride hexahydrate and then impregnated in H2SO4 solution to make a super acid solid catalyst. XRD and NH3-TPD were adopted to characterize the phase and superficial acidity of the as-synthesized sieve and catalyst. The influence of the addition of triethanolamine and chromium on synthesised products was studied in detail. The isomerization of n-pentane was used to evaluate the catalytic activities of the as-synthesized super acid samples. It is found that the addition of chromium is helpful to the thermal stability of mesoporous zirconia because the possibility that the quadratic crystal of the zirconia transforms to monoclinic phase reduces and that the addition of triethanolamine increases the order degree of the Cr mesoporous zirconia and the dispersion of chromium. The isomerisation results show that with chromium incorporation the acid sites and acid intensity of the mesoporus zirconia are increased, resulting in stable pentane conversion and isopentane selectivity. The selectivity and yield of i-pentane are 40 % and 10 %, respectively.

HYDROISOMERIZATION PERFORMANCE OF SMALL SIZE SAPO-11 MOLECULAR SIEVE SYNTHESIZED BY SILYLANIZATION OF SEED CRYSTAL

2014, 45(1):  28-34. 

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The SAPO-11 seed crystal was first silylanized using n-Propyltriethoxysilane (Pr-TES) in synthesis process and the SAPO-11 molecular sieve with small particle size (H-SAPO-11-S) was then synthesized by crystallization in cyclohexane-1-butanol system. Samples were analyzed by XRD，SEM，nitrogen adsorption-desorption and Py-IR. Characterization results show that pure phase SAPO-11 molecular sieve is obtained by silylanizing seed crystal. The mean particle size for H-SAPO-11-S molecular sieve is much smaller than normal SAPO-11 molecular sieve (H-SAPO-11-N) synthesized by conventional method, reducing from 8.0 μm of H-SAPO-11-N to 1.0 μm of H-SAPO-11-S. Compared with H-SAPO-11-N molecular sieve，H-SAPO-11-S molecular sieve possesses much more external specific surface area, larger pore volume and more suitable acid amount and acid strength. The results of n-hexadecane hydroisomerization show that the catalyst Pt/H-SAPO-11-S exhibits much better activity and higher isomers selectivity than that of the Pt/H-SAPO-11-N catalyst.

STUDY ON SIX-LUMPED KINETIC MODEL FOR VACUUM GAS OIL HYDROCRACKING

2014, 45(1):  35-41. 

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A six-lumped high pressure hydrocracking kinetic model based on VGO hydrocracking experiment data of catalyst A was established to predict product yields. Based on the actual hydrocracking product cutting scheme, the oils (feedstock and product oils) were divided into six lumps according to the fixed distillation range: vacuum gas oil and unconverted bottom oil (>360 ℃), diesel fraction (290-360 ℃), kerosene fraction (175-290 ℃), heavy naphtha fraction (65-175 ℃), light naphtha fraction (<65 ℃) and refinery gas (C4-). The parameters of the lumped kinetic model were regressed from the hydrocracking experiment data by nonlinear least squares algorithm in Matlab 2011b. Partial reaction pathways among six lumps were ignored after statistics analysis. The results show that the calculation is in good agreement with the experimental product yields with the largest deviation of 1.8% which meet the industrial demands.

SYNTHESIS AND SURFACE PROPERTIES OF NANOSTRUCTURE AlOOH(Al2O3)

2014, 45(1):  42-46. 

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The AlOOH nanorods and nanoflakes were prepared via hydrothermal synthesis using AlCl3?6H2O and NaOH. They were further converted into Al2O3 with same shape after calcination. Several techniques such as X-ray diffraction (XRD), Transmission electron microscopy (TEM) and Fourier-transform infrared (FTIR) measurements were used to characterize the products. The results show that the products are γ-AlOOH. They were converted into γ-Al2O3 after calcinations. All the nanocrystals are single crystal with high crystallinity. The ratio of n（OH-）/n（Al3+） has a great influence on the shape of AlOOH and Al2O3. With the n（OH-）/n（Al3+）increasing, the ratio of length to diameter decreases for AlOOH which finally become nanoflakes. There are two types of OH groups on γ-Al2O3 nanorod, i.e HO-μ2-AlⅥ of Al2O3 (110) crystal plane and HO-μ2-AlⅥ of Al2O3 (100) crystal plane, respectively; There are four types of OH groups on γ-Al2O3 nanoflake. They are HO-μ3-AlⅥ and HO-μ2-AlⅥ of Al2O3 (111) crystal plane and HO-μ2-AlⅥ and HO-μ3-AlⅥ of Al2O3 (110) crystal plane.

EFFECT OF RING-FEEDER FORM OF FCC RISER ON GAS-SOLIDS FLOW STRUCTURE

2014, 45(1):  47-50. 

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The gas-solid flow structure in FCC riser was studied in detail in a CFB cold model unit using ring-feeders with different form. Based on the gas and solids distributions, relative gas-solid contact efficiency (RCE) and cross-sectional gas-solid contact efficiency (CCE) were calculated and compared. Experimental results indicate that solid concentration and gas-solid contact efficiency could be different in riser with different form of feeder. However, the effect of the feeder form on the gas-solid flow structure is diminished along with the increase of riser height.

STUDY ON OZONATION–PHOTOELECTROCATALYSIS COMBINATION TECHNIQUE FOR REVERSE OSMOSIS CONCENTRATED WASTEWATER TREATMENT

2014, 45(1):  51-54. 

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The reverse osmosis concentrated water from double-membrane process of petrochemical plant is hard to treat for its high COD, poor biodegradability and high salinity. The test found that good results can be obtained by ozonation – photoelectrocatalysis combined technique. In this paper, three factors, namely O3 concentration, pH and temperature, which influence the treatment efficiency of the concentrated water, were examined. The results show that COD and oil concentration in the effluent are less than 50 mg?L-1 and 0.5 mg?L-1, respectively, when the wastewater with COD of 200-250 mg/L, oil concentration of 15-18 mg/L is treated under the conditions of the optimal pH value of 9, the O3 dosage of 16 mg/L, preaeration 90 min in O3 and reside time of 60min in photoelectrocatalysis unit. The qualities of the treated water meet the requirements of the enterprise.

STUDY OF IMPROVING FLASH POINT OF ASPHALT PRODUCED FROM TAHE CRUDE

2014, 45(1):  55-58. 

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The low flash point of Tahe vacuum residue affects its derivative asphalt product quality. Thus improving the Tahe vacuum residue flash point is beneficial to the asphalt product quality and to the capacity of the plant. Based on the analysis and comparison of Tahe crude with Kuwait crude, a conclusion could be drawn that the reason for low flash point of Tahe vacuum residue is due to high content of asphaltene in the crude. By blending FCC slurry in atmospheric residue and intensifying vacuum distillation, the Tahe vacuum residue flash point can be significantly improved. Blending 1% FCC slurry make the vacuum residue flash point increase by 1.6 ℃. A high quality road asphalt product can be manufactured using such residue with SBR.

OPERATION ANALYSIS FOR THE FIRST VRDS UNIT IN REFINARIES ALONG YANGTZE RIVER

2014, 45(1):  59-63. 

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The second generation catalysts of RHT residue hydrotreating technology have been successfully applied in the 1.7Mt/a VRDS unit of Changling Company SINOPEC, taking vacuum residue of Yichang crude oil with moderate acid content as main feed. The results showed that the first run cycle of the unit had been kept for 426 days with perfect activity and stability. The product quality met the design requirements.

PROBLEMS AND SOLUTIONS OF DELAYED COKING UNIT PROCESSING ULTRA-HEAVY OILS BLENDED WITH DIESEL OIL

2014, 45(1):  64-67. 

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The experience of processing ultra-heavy oils blending large proportion of diesel fraction in the delayed coking unit of Karamay Petrochemical Company was summarized. The problems of over-current in electrostatic desalting unit, exceptional running of equipments, entraining fine coke powder in oil vapor and lower diesel yield were caused by the blending of diesel. After controlling throughput, optimizing the heat exchanger system and revamping the side-cut of distillation unit, the CGO yield is reduced and the gasoline and diesel yield exceed the analog value. Furthermore, product distributions are optimized and the operation cycle of the unit is prolonged.

TECHNOLOGY TRANSFORMATION FOR COKE CONDENSATE OF DELAYED COKING UNIT

2014, 45(1):  68-71. 

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The effect of technical transformation for process direction of delayed coking condensate in Sinopec Luoyang Company was introduced. Considering the present process flow, a transfer line from condensate drum to VGO outlet of fractionation tower was added in order to withdraw the high temperature condensate (greater than 200 ℃) and VGO together from the fractionation tower, instead of recycling process of the heavy condensate. This ensures the operation stability of fractionation tower during coking tower preheating.

APPLICATION OF SULFUR REDUCTION SCHEME IN C4 FEEDSTOCK FOR MTBE

2014, 45(1):  72-76. 

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The application of sulfur reduction scheme in raw C4 materials for MTBE was introduced. The measures include adopting fiber film contactor to remove H2S and mercaptans from LPG, adding a separator for separation of the light C4 and heavy C4 fractions to enhance the content of the isobutylene in MTBE feed and optimizing the FCC operation. Low sulfur content in MTBE is then obtained by these measurements. The sulfur content in MTBE could be reduced from 457?g/g to 13 ?g/g.

ANALYSIS OF OFF-SPECIFICATION OF GASOLINE COPPER CORROSION AND COUNTERMEASURES

2014, 45(1):  77-80. 

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The copper corrosion test of refined FCC gasoline and gasoline product in pool is often not qualified in SINOPEC Jinan Company. The cause of off-specification of gasoline copper corrosion was analyzed and countermeasures were put forward. It is found that the element sulfur in refined FCC gasoline from straight run gasoline（SRG） is the main reason for that phenomenon. The problem of off-specification of gasoline copper corrosion has now been solved completely by means of changing process scheme where the SRG containing elemental sulfur，the stabilized gasoline from the No.1 catalytic cracking unit and part of the stabilized gasoline from the No.2 catalytic cracking unit are processed in S Zorb unit and the remaining stabilized gasoline from the No.2 catalytic cracking unit is sent to gasoline desulfurization and deodorization unit.

IMPACT OF DIESEL LEAK ON PERFORMANCE OF CORROSION AND SCALE INHIBITORS IN CIRCULATING COOLING WATER SYSTEM

2014, 45(1):  81-85. 

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Oil leak causes quality changes of circulating cooling water, which affect the performance of the corrosion and scale inhibitors in circulating water system. In this study, the results of ATMP, HEDP and other corrosion and scale inhibitors in the case of diesel leaking was observed. And by using ATMP and biological enzyme together, a good corrosion inhibition in the circulating cooling water is obtained. A conclusion can be drawn that diesel oil leak will diminish the effect of ATMP, HEDP and other corrosion inhibitor. The ATMP, lysozyme and laccase pharmaceutical compound can achieve good inhibition results in the circulating cooling water at diesel dosage of 80mg/L. When the concentration of ATMP, lysozyme and laccase is 10,30,40mg/L, respectively, good inhibition effect can be achieved. The corrosion rate of carbon steel can be controlled below 0.008 mm/a. The corrosion inhibition rate is up to 95%.

SIMULATION AND INDUSTRIAL VALIDATION OF EFFECT OF DESULFURIZATION SOLVENT CONCENTRATION ON ENERGY SAVING IN REFINERY GAS DESULFURIZATION SYSTEM

2014, 45(1):  86-91. 

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The constituent of energy consumption in the stripper for efficient desulfurization solvent (XDS) was analyzed by energy balance. Results suggested that the energy required to heat amine solution accounted for the major part of the reboiler heat duty and had the most significant impact on the energy consumption of the whole desulfurization system. The effect on reducing energy consumption with increasing the mass fraction of XDS solvent for refinery gas desulfurization system was simulated and analyzed by the process simulation software Aspen HYSYS, and then industrial validated in a refinery was conducted. Simulation results showed that the steam consumption for the stripper could be reduced by increasing mass fraction of XDS in lean solution and reducing solution circulation flow rate under the premise of ensuring the quality of purified gas. Industrial test results matched well with the simulated ones. In the petrochemical enterprise, if the mass fraction of XDS in lean solution was increased from 23.82% to 44.40%, the rich solution flow rate and corresponding steam consumption for the stripper could be reduced by 20.4% and 20.6%, respectively, which displayed the positive energy saving effect. Prior and post to increase mass fraction of XDS in lean solution, the foaming tendency and corrosive nature of XDS solution kept lower levels, and the desulfurization efficiency of the units remained stable.

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DEVELOPMENT AND APPLICATION OF FEEDFORWARD SYSTEM IN ATMOSPHERIC AND VACUUM DISTILLATION UNIT FOR MAXIMIZING JET FUEL YIELDAT ATMOSPHERIC VACUUM DISTILLATION PLANT

2014, 45(1):  92-96. 

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A feedforward system for maximizing jet fuel yield in 8 Mt/a atmospheric and vacuum distillation unit has been developed based on integration application of on-line analytic instruments and advanced process control system. The application indicates that the system has solved the lag issue brought by routine operation control mode which is in pursuit of target product yield of the unit. The original conventional single loop operation is upgraded to a multivariable system operation with a real time feedforward and the efficient creating capacity of the unit is thus increased.