Table of Content

12 June 2014, Volume 45 Issue 6

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COMPARISON OF HENAN SHALE OIL, CONVENTIONAL CRUDE OIL AND KEROGEN SHALE OIL

2014, 45(6):  1-8. 

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The properties of Henan shale oil were analyzed and compared with Daqing crude oil and conventional kerogen shale oil. The molecular characterization of Henan shale oil was also determined. The results show that the properties of Henan shale oil are different from kerogen shale oil, but are almost the same as Daqing crude oil and can be processed by the method similar to conventional crude oils.

EFFECT OF ATMOSPHERE ON ZINC SILICATE FORMATION IN S ZORB SORBENTS

2014, 45(6):  9-14. 

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The commercial operation indicated that the formation of Zinc Silicate is one of the key reasons for the deactivation of S Zorb sorbent. The commercial used sorbents in different state are tested under simulated industrial conditions with different atmospheres to investigate the relations of Zn2SiO4 formation with atmospheric environment and the silicon source. The results show that it is difficult to form Zn2SiO4 in fresh sorbent in simply dry or water vapor atmosphere even at 550℃. While Zn2SiO4 appears when the spent sorbent or regenerated sorbent coexists with the fresh one under hydrothermal condition at this temperature. The collaboration generated between SO2 produced during calcination of ZnS and high temperature hydrothermal surrounding will promote the formation of Zn2SiO4. The results also show that in the atmosphere of hydrothermal and acid, the more S in the spent sorbent, the more Zn2SiO4 formed. The growth rate of Zn2SiO4 will increases if Zn2SiO4 already exists in the spent sorbent. Different Si source will cause a different trend in the formation of Zn2SiO4, where the structured Si sources possess stronger resistance to hydrothermal-acid environment. Key words：S Zorb sorbent；Zinc Silicate；acid atmosphere

THERMODYNAMICS OF 2-METHYLPHENANTHRENE HYDROGENATION REACTION

2014, 45(6):  15-19. 

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The hydrogenation of 2-methylphenanthrene was studied by group contributions and corresponding state methods to investigate the physicochemical properties of compounds involved. The Gibbs free energy change, equilibrium constants and enthalpy changes of each step of the reaction network at different temperatures were calculated based on the physicochemical properties obtained. The calculations of the product compositions and hydrogen consumptions under different pressures and temperatures according to the equilibrium constants were conducted. The calculation results show that all step reactions are exothermic, their equilibrium constants decrease as the reaction temperature increases. High temperature and low pressure are beneficial for the production of intermediate 2-methyl-9,10-dihydro-phenanthrene and for the reduction of total hydrogen consumption.

STUDY ON BASIC CHEMICAL STRUCTURE AND ASSOCIATION OF ASPHALTENE IN HEAVY OIL

2014, 45(6):  20-25. 

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Four kinds of asphaltenes were obtained from four different heavy oils with n-pentane solvent. Their functional structures were characterized by FTIR spectroscopy, and the basic structural parameters of the asphaltenes were determined by 1H-NMR, then the average molecular formula of the asphaltene were given by molecular weight and element content. The dipole moments were also measured to indicate the polarities of the asphaltene molecules. The results show that the presence of heteroatom in asphaltene makes the asphalt form the polar groups with high polarity, and the higher the content of impurity atoms, the greater the polarity, the stronger the association, the higher the association numbers. In addition, molecular diameters were measured by two methods: intrinsic viscosity method, and relative density and relative molecular mass method. With the increase of relative molecular mass, the molecular size of asphaltene becomes larger. However, the molecular diameter measured by viscosity method is related to the selected solvents and usually is larger than the size obtained by relative density and relative molecular mass method, and the latter method can well reflect the molecular size.

STUDY ON FACTORS OF FLUE GAS TURBINE FOULING IN FCCU

2014, 45(6):  26-31. 

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The metals on the catalyst particles，flue gas chemical composition and device operation conditions have a great relationship with the fouling of flue gas turbine. The influence of Ca, Fe, Na and other metals deposited on catalyst from feed and the content of SOx in flue gas is getting more and more attention. The simulation of the sintering process in the laboratory was conducted to test the influence of the quantity of metal elements, P oxides and SOx on adhesion and sintering of the catalyst particles, which is considered to be the reason for the flue gas turbine fouling. The results show that at SOx atmosphere, with the content of Ca, Fe, Na, and other metals in the catalyst particles increasing, the degree of adhesion and sintering increases, and more metals and sulfur exist in the sintering neck than in fresh catalyst. The influence of P oxides on the catalyst particle sintering is not obvious.

COKE ANALYSIS AND COKE BURNING OF HIGH CARBON CONTENT HEEL CATALYST OF CCR

2014, 45(6):  32-35. 

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Coke burning of CCR heel catalyst with high carbon content was done in lab and the physical properties of the regenerated heel catalyst were characterized. The results show that the heel catalyst contains graphite carbon and the carbon on the dead zone catalyst can be ignited at 540℃ in low oxygen content (1.0v %) atmosphere, while the coke on the heel catalyst can be burned up at 480℃ in high oxygen content (21v %) atmosphere.

HYDROGENATION PERFORMANCE OF 1-METHYLNAPHTHALENE ON DIFFERENT CATALYSTS

2014, 45(6):  36-39. 

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Using 1-methylnaphthalene as a model compound and sulfided CoMo/γ-Al2O3，NiW/γ-Al2O3，NiMo/γ-Al2O3，NiMoW/γ-Al2O3 as catalysts，the hydrogenation saturation performance of 1-methylnaphthalene on the four different catalysts was studied using a high pressure hydrogenation micro-reactor. It is found that the NiMoW/γ-Al2O3 catalyst has the best saturation performance for 1- methylnaphthalene and the CoMo is the lowest. The higher the activity is, the easier the aromatic saturation of 1- methylnaphthalene is to reach the thermodynamic equilibrium and the less sensitive to the change of reaction pressure. In the products the amount of 5-methyl tetralin is as twice as 1-methyl tetralin.

STUDY AND COMMERCIAL APPLICATION OF FCC NAPHTHA HYDRODESULFURIZATION CATALYST ME-1

2014, 45(6):  40-43. 

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ME-1 hydrodesulfurization catalyst newly developed by FRIPP was sulfided and the MoS2 phase morphology of the sulfided catalyst was characterized by higher resolution transmission electron microscopy (TEM) and compared with a commercial reference catalyst MoCo/Al2O3 for selective desulfurization of gasoline. Their HDS activity and selectivity were evaluated by heavy gasoline HDS test. The TEM results show that the numbers of stacking layers of MoS2 particles of ME-1 catalyst are 3.0-6.0 and the reference catalyst is 5.0-10.0, which indicates the higher dispersion of active component of ME-1 catalyst than the compared one. The HDS evaluation results show that when the sulfur content reaches 10μg/g in the product, the reaction temperature of ME-1 catalyst is 10 ℃ lower than the compared catalyst, olefin saturated rate is reduced by 32.2%, the research octane number (RON) loss of the product is reduced by 1.6. The evaluation tests demonstrate that the ME-1 catalyst has a higher HDS activity and selectivity. The commercial application results of ME-1 catalyst show that the sulfur content of FCCN can be reduced from 466 μg/g to 9.7μg/g, RON loss of 1.75. It is showed that ME-1 catalyst can meet the need for production of "sulfur-free gasoline" with less octane number loss.

COMMERCIAL APPLICATION OF PHF-101 DIESEL HYDROTREATING CATALYST

2014, 45(6):  44-47. 

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The first commercial application of PHF-101 diesel hydrotreating catalyst in a diesel hydrotreating unit with 1.20Mt/a capacity of Daqing PetroChemical Company，PetroChina is introduced. The feed is a mixture of Daqing FCC diesel, coker diesel and coker gasoline. Under different operation conditions, the diesel products can meet the standard of national phases of III, IV and V. The results of 37 month commercial operation prove that the catalyst has a high activity and good stability.

HYDRODESULFURIZATION OF DIBENZOTHIOPHENE ON MOS2 AND NI-MO-S PREPARED FROM AMMONIUM TETRATHIOMOLYBDATE

2014, 45(6):  48-53. 

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Molybdenum disulfide was prepared from ammonium tetrathiomolybdate as a precursor. Ni-Mo-S catalyst was also synthesized from ammonium tetrathiomolybdate with nickel as a promoter. The hydrodesulfurization (HDS) performance of these two catalysts were studied using a model fuel of decalin solution containing 0.8% DBT with and without quinoline in it. The results indicate that the introduction of nickel increases the HDS activity of molybdenum disulfide. The existence of quinoline restrains the HDS activities of these two catalysts. Both the activities of the hydrogenation pathway (HYD) and direct desulfurization (DDS) are suppressed for the molybdenum disulfide catalyst in case of the presence of quinoline. When quinoline exists, the DDS activity is enhanced on Ni-Mo-S catalyst and the HYD activity is just the other way. The inhibiting effect on HYD activity for Ni-Mo-S catalyst is significantly weaker than molybdenum disulfide, indicating that the introduction of nickel increases the nitrogen resistance of molybdenum disulfide.

COMMERCIAL APPLICATION OF FCC TECHNOLOGY FOR HIGH ACID CRUDE OIL

2014, 45(6):  54-58. 

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Conventional methods processing high acid crude cause serious corrosion problems on atmosphere and vacuum distillation unit. A new technology that the high acid crude is directly processed by FCC is developed to avoid these problems. Two kinds of commercial trial solutions were implemented: one is the blending feed of vacuum gas oil and acid crude; another is the only acid crude used as FCC feed directly. The commercial results show that the qualities for the two feeds after desalting and dewatering can meet the FCC feed requirements of sodium and water content. The perfect FCC product distribution can be obtained and deacidification is over 99% in both cases. The acidity or acid value of the product meet the standards or downstream process requirements. Processing the blending feed can obtain better benefits.

APPILICATION OF DENITRIFICATION ADDITIVE FOR REDUCTION OF NOX IN FCC REGENERATED FLUE GAS

2014, 45(6):  59-62. 

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In order to meet the strict environmental requirements, the denitrification additive D was used in a similar way as the CO combustion additive to reduce NOx content in FCC regenerated flue gas in a trial run in CNOOC Huizhou Refinery. Due to the existence of catalytic additive, NO can be translated to N2 in FCC regenerator. The results indicate that the effect of denitrification additive D on the activity of catalyst, product distribution and the nature of the gasoline, diesel is not obvious. It is concluded that NOx content in FCC regenerated flue gas can be controlled by addition of such kind of additive without any more process modification.

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OPERATION FLEXIBILITY AND PROFIT ANALYSIS OF 2.0 Mt/a HYDROCRACKING UNIT

2014, 45(6):  63-67. 

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Based on the industrial operation data and the design data of 2.0 Mt/a hydrocracking unit in Qingdao Refining & Chemical Co. Ltd, SINOPEC, the operation flexibility of the unit was defined. The feedstock (VGO) properties are limited in the ranges: boiling point of 233-570 ℃，density of 850-931 kg/m3(20 ℃)，and sulfur content of 0.8%-2.5% and the operation parameters are as follows: throughput of 150-318 t/h, hydrorefining temperature 330-414 ℃, and cracking temperature 340-429 ℃. Under those constraint conditions, the yields of kerosene, diesel and tail-oil can reach 46.01%, 60.49% and 54.88% for kerosene, diesel and tail-oil solutions, respectively. The economic profit analysis of the solutions indicates that under the current pricing system, the kerosene solution is the best one.

OPTIMIZATION ANALYSIS OF HYDROCRACKING OPERATION

2014, 45(6):  68-73. 

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A numerical model was established by spline curve interpolation method to study the relationship between physico-chemical properties of the cracking products and the operation parameters of throughput and temperature in hydrocracking process. This model was applied to the optimization analysis of a VGO hydrocracking process. The smoke point and freezing point of aviation jet fuel, diesel yield as well as middle distillate selectivity were used as the constraint objects in the optimization to investigate the feasible operation parameter ranges of throughput and reaction temperature. Under the constraint objects, the minimum conversion was calculated by the model to get the operation parameters for high tail oil yield and compared with the experimental data. The comparison shows that the method has a good effectiveness and the data calculated is close to the experimental results.

APPLICATION AND TRANSFORMATION OF CHLORSORB TECHNOLOGY IN 1.0MT/A CCR UNIT

2014, 45(6):  74-78. 

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The 3rd generation ultra-low pressure continous catalytic reforming technology introduced from abroad with a ChlorsorbTM system is adopted in the newly built unit in Tianjin branch, SINOPEC using the PS-VI catalyst developed by RIPP. The PS-VI catalyst has a good chlorine adsorptive capacity, by which the dechlorination rate of the regeneration flue gas is up to 98%, meeting the request of the chlorine adsorption technology. However, the chlorine adsorption technology makes the water content increases largely in the regeneration circulating gas. This speeds up the reduction of catalyst specific surface, and causes the catalyst lifetime shortened and corrosion of the equipment seriously. After the technical transformation by using the solid dechlorination technology and GL-1 regeneration flue gas dechlorination agent, both developed by RIPP, the chlorine mass fraction of regeneration flue gas is reduced to less than 2μg/g. The decline trend of the specific surface area of PS-VI is returned to normal. The PS-VI catalyst lifetime is extended greatly.

INDUSTRIAL APPLICATION OF NCMA SOLVENT FOR CARBON DIOXIDE REMOVAL IN DRY GAS ENRICHMENT UNIT

2014, 45(6):  79-81. 

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The industrial application of NCMA solvent for CO2 removal in dry gas enrichment unit in Wuhan Co. Sinopec was reviewed. The results show that the NCMA solvent can improve CO2 absorption performance compared with MDEA. At the same throughput of the unit, the recycling amine solution rate to the dry gas absorption tower is dropped from 33t/h of MDEA to 14t/h of NCMA solvent and the concentration of CO2 in the treated gas also decreased from 400μL/L to less than 50μL/L. Meanwhile, the H2S loading of NCMA solvent and ability to remove mercaptan are higher than MDEA. Finally, the alkali consumption, electricity consumption and emissions of alkali waste of the process are all reduced by using NCMA solvent in stead of MDEA.

APPLICATION OF OXYGEN-ENRICHED PUSHING COMBUSTION IN FURNACE OF VACUUM DISTILLATION UNIT

2014, 45(6):  82-85. 

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An oxygen-enriched pushing combustion technique is newly used in the furnace of a vacuum distillation unit with 5 Mt/a capacity for the first time in Dagang Company, CNPC. A special program is designed for the technique. Using this technique, the fuel consumption of the furnace is reduced by 5.95%; the oxygen content of exhaust gas is reduced from 4.54% to 2.14%. This is a high efficiency technology with less investment. The income from energy saving is 2.156 million Yuan/a. The payback period is less than 10 months.

PREARATION AND ANTIOXIDANT CHARACTERISTICS OF OIL-SOLUBLE POLYETHER

2014, 45(6):  86-89. 

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Oil-soluble polyether (OSP) was prepared by the copolymerization of propylene oxide and butylene oxide using KOH as a catalyst. The viscosity grades of the prepared oil-soluble polyether are OSP-18，OSP-46，OSP-150, respectively. The structures of the products were defined by means of infrared spectroscopy (IR), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The anti-oxidation performance of OSPs were investigated by rotary oxygen bomb test method (ROBT). The results indicate that the oil-soluble polyether is poor in anti-oxidation with short induction period. However, the performance of the oil-soluble polyether is greatly improved by addition of the composite antioxidant, composed of α-aniline (AOA-4) and carbamate (AOL-1). The ROBT can reach to 1200 minutes. The performance of this composite antioxidant makes OSP the best application in different formulations.

STUDY ON RHEOLOGY OF LITHIUM LUBRICATING GREASE PREPARED FROM PARAFFIN-BASE MINERAL LUBE BASE OIL

2014, 45(6):  90-95. 

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In order to study the rheological properties of lithium lubricating grease systematically, the lithium lubricating greases were prepared using 12-hydroxy stearic acid lithium soap thickener and mineral lubricating base oil. The influence of base oil viscosity, thickening agent dosage and temperature on the thixotropy of lithium base grease, storage modulus, strain amplitude, the apparent viscosity, and the corresponding mechanisms were examined. The results show that with increase of soap content in lithium lubricating grease, the apparent viscosity and elastic potential energy increase while the yield stress shows the tendency of lowered after first increase. The 400SN lithium grease is the slowest one to restore its original structure, and that the yield stress and apparent viscosity increase with the soap dosage increasing, while the structure recovery rate decreases. Lithium grease possesses a linear sticky play area. Beyond the yield stress, the shear thinning appears. At the flow pour point, the grease shows its viscous flow properties.

RESEARCH AND APPLICATION OF IMIDAZOLINE CORROSION INHIBITIOR-A REVIEW

2014, 45(6):  96-102. 

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Imidazoline corrosion inhibitor is widely employed in oil industry to protect metal equipments from corrosion. The properties, synthesis and protective mechanism of imidazoline corrosion inhibitor were reviewed. The advances and various applications of imidazoline corrosion inhibitor were summarized. Some development directions of imidazoline corrosion inhibitor were discussed.