Table of Content

12 November 2013, Volume 44 Issue 11

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CHALLENGES & OPPORTUNITIES FOR U.S REFINERIES-A REVIEW OF 2013 AFPM ANNUAL MEETING TECHNICAL SESSIONS

2013, 44(11):  1-9. 

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The increasing shale gas production of North American results in lower hydrogen price than that from naphtha as feed and makes hydroprocessing technology and petrochemical industry has a competitive advantage. The United States becomes a net exporter of petroleum product. The soared shale oil production together with insufficient export ability results in tight oil price declined, making the West and Mid-continent refineries in U.S benefit a lot. Just under such a background，The 2013AFPM annual meeting was held in U.S. This paper outlines the 2013 AFPM annual meeting technical sessions. The meeting discussed the challenge & opportunities for U.S refineries, focusing on the influence of increasing shale oil and shale gas. The progress in oil processing technology in term of FCC，hydro-processing, bio-fuel, as well as shale oil processing were also introduced. The meeting presented the great advances in catalyst R&D at molecular level for FCC and hydro-technology, having a guiding significance for the development of new functional catalyst. Several technologies have been successfully developed for coking and residues processing, like new coking additives and non-hydrodesulfurization. The meeting indicated that the biofuel technology development prospects, many technologies are expected to industrial application in the future.

STUDY ON CATALYTIC ACTIVITY OF PLATINUM-TIN CATALYST FOR THE DEHYDROISOMERIZATION OF METHYLCYCLOPENTANE

2013, 44(11):  10-14. 

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To know more about the reactions of methylcyclopentane in the catalytic reforming process, the dehydroisomerization process to benzene was studied over Pt-Sn/Al2O3 catalysts using methylcyclopentane as a probe. Different kinds of Pt-Sn/Al2O3 and Pt /Al2O3 catalysts were prepared, and the influence of content of Pt、Cl and Sn on the methylcyclopentane conversion and benzene selectivity was investigated. The results show that the methylcyclopentane conversion increases firstly and then decrease with Pt content increasing. The introduction of tin reduces the methylcyclopentane conversion, while benzene selectivity presents a similar variation trend to the conversion as Pt content changes. It is suggested that the addition of Sn generates two kinds of active centers and that tin apparently changes the catalytic activities of Pt/Al2O3 catalysts because of interaction between Pt and Sn.

EFFECT OF AGING TEMPERATURE ON PHYSIC-CHEMICAL PROPERTY AND CRACKING ACTIVITY OF FCC CATALYST

2013, 44(11):  15-18. 

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The FCC catalysts from Huaxing, Maoming, Jinan Co.were pretreated in 100% steam at the range of 791~800 oC in every 3 ℃ interval for 17 h. The physic-chemical features of aged catalysts were characterized by XRD, N2-adsorption. The catalytic cracking performance of the samples was investigated on MAT and fixed fluidized bed reactor (ACE-MODEL R+ MM). The results show that the structure of molecular sieve in the catalyst aged at 791 oC is kept well and very similar to that of its fresh catalyst, and the crystallinity of molecular sieve is decreased significantly with increasing the aging temperature. The physic-chemical properties and cracking conversion of Huaxing catalyst aged at 797 oC iss equivalent to its equilibrium catalyst. However, the ACE results indicate that yields of carbon deposition, dry gas and LPG are significantly lower than that of its balance agent, and yield of gasoline is opposite. The significant differences in crystallinity compared with equilibrium catalysts exist between the catalysts steam aged at 800℃ from different company. The results show that a relative small change of aged temperature in the range of 791 oC~800 oC can significantly influence on the structure and catalytic cracking activity of aged catalysts. In order to reach the activity the same as the equilibrium catalyst, careful selection and control of the aging temperature based on the properties of fresh catalyst and its application are necessary.

INITIAL APPLICATION OF LOCALIZED EBULLATING-BED HYDROGENATION CATALYST

2013, 44(11):  19-23. 

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The text introduces the successful industrial application of the localized T-star ebullating-bed catalyst FFT-1B developed by Shenhua Ordos Coal Liquefaction Company and Sinopec Fushun Research Institute of Petroleum and Petrochemicals jointly. The catalyst performance was evaluated by analysis of reaction temperature rise, hydrogen consumption, hydrogen donor performance of hydrogen donor solvent, etc. The results after operation for half-year in an imported ebullating-bed prove the successful application of the catalyst. The performance of the catalyst is stable with high reaction temperature rise and high hydrogen consumption. And the hydrogen donor performance of hydrogen donor solvent is improved remarkably.

STUDY ON ZSM-5 SYNTHESIS BY SEEDED METHOD

2013, 44(11):  24-28. 

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ZSM-5 was synthesized by seeded method and compared with that by using template. The sodium silicate was used as a silica source and the products were characterized by XRD, SEM and N2 adsorption. To obtain detailed information on the rules of synthesis process, the effect of crystallization time, crystallization temperature, n（H2O/SiO2）and the initial gel pH on ZSM-5 crystallinity were systematically studied. The results show that the prepared ZSM-5 with relative high crystallinity can be obtained successfully by seeded method at the conditions of crystallization time of 10～13 h，crystallization temperature of 180 ℃，gel pH of 9 under the fixed [n(H2O)/n(SiO2)] of 18. No differences are found in physical and chemical properties of ZSM-5 prepared by seeded method and template n-butylamine. The zeolites were tested in a micro fixed-bed reactor using Daqing vacuum gasoline oil (VGO) as a feed. The similar results are observed for the two zeolites.

METHANE DEHYDROAROMATIZATION OVER COBALT MODIFIED MO/HZSM-5 CATALYSTS IN ABSENCE OF OXIDANTS

2013, 44(11):  29-34. 

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A series of bi-metal Me-Mo/ HZSM-5 (Si/Al mole ratio 38) catalysts (here Me refers to the second metals: Mg, Ni, Cr, Cu, Zn, Co) were made by co-impregnation method and the promotion effect in methane dehydroaromatization (MDA) in absence of oxidants was evaluated. The results show that the benzene formation rate can be increased by adding Co as the second active component. Then the catalytic performance of Co-Mo/HZSM-5 catalysts in the MDA without oxidant oxygen was further studied. NH3-TPD, x-ray diffraction and TG-DTA were applied to characterize the Co-Mo/HZSM-5 catalysts, and the results indicate that the addition of Co can improve significantly the acidic properties (acid strength, acid amount and their ratio) of the catalysts and depress the carbon deposition，and that Co and Mo compounds can be evenly dispersed on the molecular sieve surface. The performance test results show that the addition of 0.7wt% Co has a good synergy with Mo in promoting the activity and the stability of the catalysts, the benzene yield can increase by 2%-5% relative to Mo/ HZSM-5.

COMMERCIAL APPLICATION OF HYDROCRACKING CATALYST PHC-03

2013, 44(11):  35-40. 

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The main features and process flow of a 1.2Mt/a hydrocracking unit in Daqing Petrochemical Company are introduced. The hydrocracking catalyst PHC-03 developed by Petrochemical Research Institute, PetroChina has been applied in Daqing refinery. The whole start up process of the device is described in detail, including catalyst loading, drying, sulfidation and passivation. The main operation parameters, feedstocks and products properties, material balance, energy consumption and operation situation are introduced by the analysis of the calibration data. The application results show that the unit has run smoothly and the performance of PHC-03 catalyst is good and flexible to different feeds. Excellent product quality and rational distribution with good middle distillate selectivity are obtained and the catalyst can be used to produce 3#jet fuel.

CAUSE ANALYSIS ON POOR DEMULSIFICATION RESULTS FOR HIGH TAN CRUDE OILS

2013, 44(11):  41-44. 

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The efficient desalting process for high TAN (Total Acid Number) crude oil has become a key technique for refineries. The main components and emulsification characteristic of three high TAN crude oils, Roncador, Doba and Albacora were studied in the paper. The results show that high TAN crude oils contain a certain amount of naphthenates, in addition to naphthenic acids. It is found that the naphthenic acids and naphthenates, except the alkaline naphthenates, have a limited impact upon the demulsification of the high TAN crude oil. However, the alkaline naphthenates makes the crude poor demulsification because the alkaline naphthenates have comparatively strong surface activity and thus promote the stability of the emulsion formed by high TAN crude oil and water during the desalting process, resulting in emulsion hard being broken.

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CURRENT PROMOTION EFFECT IN CO2-RICH BIO-SYNGAS REFORMING

2013, 44(11):  45-49. 

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Previous studies show that the CO2-rich syngas is harmful to Fischer Tropsch (FT) and alcohols synthesis in terms of conversion and yield. Therefore, the reduction of CO2 content in bio-syngas is essential before synthesis. A novel enhanced reforming process of the CO2-rich bio-syngas into CO-rich bio-syngas by adding electric current was investigated at atmospheric pressure using a mixture of rice husk char and NiO/Al2O3 catalyst. The current promotion effect was examined in temperature ranges from 400 to 800 ℃ and current ranges from 0 to 4 A. The results indicate that the promotion effect of current is remarkable. The CO2 in bio-syngas is almost completely converted (99.5%) into CO at 4 A and 800 ℃. The current promotion effect is attributed to the synergy of dissociation of CO2 on the surface of NiO/Al2O3 catalyst induced by the thermal electrons, proved by the measurement of TOF-MS (time of flight mass spectrometer) and local heat effect which is helpful to the conversion of CO2.

STUDY ON METHYLTHIOPEHEN ADSORPTION ON MoS2 CLUSTER BY DENSITY FUNCTIONAL THEORY

2013, 44(11):  50-55. 

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Adsorption properties of thiophene and methylthiophenes on the unsaturated Mo site of MoS2 cluster were investigated by the first-principle DFT calculations. The calculated results indicate that the thiophene compounds prefer to lie on the top two Mo atoms of Mo16S32 cluster. The adsorption ability of thiophene compounds on the Mo16S32 cluster is 2,3-DMT>3-MT>3,4-DMT>2,4-DMT>TP>2-MT>2,5-DMT. The results indicate that thiophene with one methyl substituent in 3- position is beneficial to adsorption, but methyl in 2- position is not conducive to adsorption. When two positions on thiophene are substituted, the adsorption energy decreases as the distance of the two methyl increases. According to the bond length, Mayer bond order and Mulliken population analysis, the C-S bond length and bond order of the adsorbed thiophene is up and down, respectively after adsorption. The electrons in the hybridized orbitals of adsorbed thiophene ring transfer to Mo atoms, and the electrons in the 4dx2-y24dxy4dz2 atomic orbitals of Mo atom transfer to antibonding orbital of thiophene ring. It benefits for the thiophene rings activation and subsequent electrophilic hydrodesulfurization reaction.

STUDY OF TREATMENT OF METHYLORANGE SIMULATED WASTEWATER BY ZEOLITE SUPPERTED BIMETALS WITH ZERO-VALENT IRON

2013, 44(11):  56-60. 

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13X zeolite loaded with Cu and Mn were prepared by incipient wetness method and characterized by XRD, BET and atomic absorption spectroscopy (AAS). The decoloration of methyl orange simulated wastewater with different initial pH was tested by the co-processing of the bimetallic 13X zeolite together with zero-valent iron. It is found that the decoloration of methyl orange simulated wastewater is improved by the co-processing and gets more than 81 % decoloration ratio when treating for 3h using the bimetallic zeolite prepared under the optimal conditions. The optimal preparation conditions are: the concentration of impregnation solution is 1.0mol/L，the mole ratio of copper and manganese is 1.0 and the calcination temperature is 300℃. The characterization results indicate that the metals are uniformly loaded on zeolite and the metal leaching is increased with the decreasing calcination temperature. The leaching metal ions can boost the effect of decoloration of methyl orange simulated wastewater in some extent.

INTEGRATION AND REGULATION OF VACUUM DEEP- CUT TECHNOLOGY II．REGULATION OF RAW MATERIAL AND PROCESS TECHNOLOGY FOR VACUUM DEEP-CUT

2013, 44(11):  61-65. 

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The maximized vacuum deep-cut benefits can only be achieved when the eligible reprocessed raw material is produced. We must take atmospheric and vacuum devices with reprocessing plant as a whole to consider, and based on the nature of raw materials and quality requirements, the right operation conditions for varies system can be determined, like the reasonable vacuum cutting temperature, the stripping of atmospheric tower bottom, flow rate and outlet temperature of vacuum furnace, liquid level of washing oil sump tank, segmentation of each side cuts in vacuum tower and micro-wet stripping of vacuum tower bottom, to reduce the energy consumption of vacuum deep-cut. Besides, the atmospheric distillation can be strengthened by the addition of FCC slurry oil together with the process optimization and regulation to produce qualified distillates, so as to realize the large system optimization and maximize the benefit of the whole refinery.

RESEARCH ON HIGH GRAVITY TECHNOLOGY FOR PURIFYING SOUR NATURAL GAS

SHANG Jian-feng

2013, 44(11):  66-70. 

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Based on the static measurement results of H2S absorption capacities of MDEA and different ratio sterically hindered amine solutions, the desulfurization performance of MDEA and sterically hindered amine solution with optimized ratio for high sulfur natural gas was investigated in a high gravity desulfurization side-stream apparatus under the conditions of operation pressure of 8.3 MPa and different gas/liquid ratio. The influence of rotating speed of high gravity apparatus on the selective desulfurization was also studied. The results indicate that No.8 solvent exhibits the largest H2S absorption capacity. The absorption capacities of No.8 solvent at 40 ℃ and 50 ℃ are 79.67g/L and 59.20g/L, respectively. The high gravity desulfurization technology can reduce the H2S content from 2.0×105 mg/m3 in raw gas to less than 100 mg/m3 in purified natural gas. At the ratio of gas to liquid of 95, purified gas has the H2S contents of 19.8 mg/m3 and total sulfur contents of 32.27 mg/m3 and CO2 contents of 0.38%, which meets the second category natural gas quality standard.

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ANALYSIS OF OPERATION MODE FOR FCC GASOLINE HYDRODESULFURIZATION SYSTEM

2013, 44(11):  71-74. 

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The effect of FCC gasoline selective hydrodesulfurization and the operation cost at different reaction temperature were analyzed. It is concluded that the lower reaction temperature is better for reducing RON loss and that the process of FCC gaosoline hydrodesulfulization followed by sweetening unit is good for lowering sulfur content of the final product to less than 10 ?g/g and at the same time for reducing the operation cost and prolonging the catalyst service life.

MEASURES AND SUGGESTIONS FOR ELECTRIC DESALTING SYSTEM DEALING WITH HIGH-WATER CRUDE OIL

2013, 44(11):  75-80. 

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The troubles of over current tripping, flooding and serious oil carrying in the discharged water from the first stage desalting unit often appear when processing the crude oil with high water content in the 1.6 Mt/a desalting unit in Sinopec Jingmen Company. To solve these problems, the improved pulse and desalting techniques were adopted. Then the flooding phenomenon is disappeared, desalination rate is up to 96.90 % and desalination pass rate is over 93.21%. Furthermore, several proposals were suggested in order to improve the electric desalination, such as optimizing demulsifier, using crude oil pretreatment agent in crude oil tank, and adding the new flow-path of electric desalination sewage discharge.

EFFECT OF BASE OIL ON TRIBOLOGICAL PROPERTIES OF CALCIUM SULFONATE COMPLEX & TITANIUM-BASED COMPOSITE GREASE

2013, 44(11):  81-85. 

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The processes of preparation of calcium sulfonate complex & titanium-based composite grease with different base oils are studied, and the effect of base oil on physic-chemical properties and tribological properties of the composite grease is analyzed. The results show that the base oils of synthetic ester and polyol ester have high flash point and high viscosity, but they can’t be converted into grease; however high temperature chain mineral oil, poly α-olefin and methyl silicone oils can all be smoothly thickened into grease, but the performances are not satisfied. Based on the test of comprehensive properties of the greases and bearing bench testing, it is found that the calcium sulfonate complex & titanium-based composite grease made from the mixture of KP6030 high viscosity mineral oil and methyl silicone oil has high dropping point, high oil film strength, high sintering load and excellent mechanical shear performance, less evaporation, good high temperature stability, long bench working life, so the mixture is a better base oil for the manufacture of calcium sulfonate & titanium-based composite grease.

STUDY ON SYNERGISTIC PROPERTIES OF SULFUR- AND PHOSPHORUS-FREE ORGANIC MOLYBDENUM COMPOUNDS

2013, 44(11):  86-90. 

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The antiwear, friction reducing, antioxidation and corrosive properties of additives and their formulation were evaluated by four ball test, rotary bomb oxidation test, hot oil oxidation test and copper corrosion test. The results show that ME exhibits better synergistic antiwear and friction reducing properties with T 202 and T 203，respectively and has good synergistic antioxidation properties with DODPA. During oxidative degradation, lubricants containing ME possess good durability of antiwear and friction reducing capabilities, and have not produced corrosive tendency towards copper, compared with MoDDP and MoDTC in copper corrosion test. Consequently, Sulfur- and phosphorus-free organic molybdenum compounds can provide novel technical route to reduce contents of sulfur and phosphorus in engine oils, and improve effectively lubrication of oils.

EFFECT OF SOLID MATERIAL ON CHARACTERISTICS OF GAS PRODUCTION FROM TRANSFORMER OIL BASE OIL

2013, 44(11):  91-95. 

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Effect of solid material used in transformer manufacture on content of gases produced and dissolved in transformer oil base oil at low and high temperature was investigated. The results show that for base oil degassed, solid material bring no effect on gas content dissolved in oil at the normal（low）operation temperature, but negative influence is observed by solid material at local overheating temperature. For base oil without degassing, serious oxidation of oil can be observed by solid material, resulting in key gas content dissolved in base oil more than attention value required for the GB/T7252 standard both at the normal operation temperature and at local overheating temperature.

STUDY ON SYNTHESIS OF ALKYL NAPHTHALENE BASE OILS AND THEIR LUBRICATING PROPERTIES

2013, 44(11):  96-99. 

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The Friedel-Crafts alkylation of naphthalene with 1-octene was completed using methanesulfonic acid (MSA) as catalyst and 2,6-di-t-butylphenol as polymerization inhibitor. Single factor experiments were carried out to investigate the influence of the molar ratio of naphthalene to 1-octene, the amount of MSA, reaction temperature and reaction time on the olefin conversion and the yield of product in order to obtain the optimal reaction conditions. The experimental results show that after the reaction conduct for 3h at 353K, the olefin conversion of 95.2% and the yield of product of 78.4% are obtained with the molar ratio of naphthalene to 1-octene of 1.3 and the molar ratio of MSA to 1-octene of 1.0. Under the optimum conditions, the lubricating base oil is synthesized and its physical, chemical and electrical properties are determined. The results suggest that the synthetic base oil could be used as a component for transformer oil.

RESEARCH OF LOW VISCOSITY PAO PREPARATION BY OLIGOMERIZATION OF 1-DODECENE AT HIGH TEMPERATURE

2013, 44(11):  100-104. 

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the low viscosity PAO was synthesized through the oligomerization of 1-dodecene with aluminum trichloride as catalyst by high temperature solvent reflux and solution polymerization. The effect of reaction conditions, such as mass fractions of the catalyst, reaction temperature and reaction time on the conversion rate of raw material, yields, quality and component distribution of PAO were examined. It is found that the optimum conditions are AlCl3 mass fraction 1％, reaction temperature of 110℃ and reaction time of 2h for the reaction system. Under the optimum conditions, the conversion rate is 93％, the yield 83％, the solvent loss 15％ and a low pour point and high flash point of poly-alpha-olefin synthetic lubricant with the kinetic viscosity of 6.80mm2/s at 100℃, the viscosity index 151, the pour point -43℃, the flash point 240℃ are obtained. The chromatographic analysis indicate that the produced PAO consists of a large part of dimer, trimer，tetramer and a small part of pentamer. The same results are repeatedly obtained for 3 times experiments.