Table of Content

12 October 2015, Volume 46 Issue 10

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INFLUENCE OF SYNTHESIS CONDITIONS ON STRUCTURE OF CeAPO-5 MOLECULAR SIEVES

2015, 46(10):  1-5. 

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CeAPO-5 molecular sieves were synthesized in the absent of HF using hydrothermal method. The effect of synthesis conditions including gel process, the kinds of Al resource and template, and the adding amounts of template, CeO2, and H2O on the structure of CeAPO-5 molecular sieves was investigated by X-ray fluorescence spectrometry, N2 adsorption-desorption, XRD, and NMR of 27Al. When the Al resource is added into phosphoric acid aqueous solution under the synthesis conditions of V250 powder as an Al resource, triethylamine (Et3N) as a template, and n(Al2O3)/n(P2O5)=0.98, n(Et3N)/n(P2O5)=2.0, n(CeO2)/n(P2O5)=0.06, n(H2O)/n(P2O5)=50, the relative crystallinity of CeAPO-5 molecular sieve reaches 99.4%

EFFECT OF MATERIAL PROPERTIES ON COKING PERFORMANCE

2015, 46(10):  6-11. 

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The coking performance of coal tar 1, coal tar 2, vacuum residue W2 and FCC slurry was studied. The results show that the liquid yield increases and coke yield decreased if the raw oils are characterized by larger molecule, rich in paraffin and less in aromatic. The kinetics equation and parameters was obtained by infinitely parallel reaction model based on the data of thermal analyzer. The coking reaction is a first-order reaction and the apparent activation energy(Ea) is 18.04- 77.29 kJ/mol in 350-510 ℃. The order of activation energy of four raw materials is coal tar 2 > vacuum residue W2 > coal tar 1 > slurry. The factors influencing activation energy Ea was divided into 4 classes by the fuzzy clustering analysis method. It is found that the higher density (ρ) and the total number of carbon (CT) of raw oils, the lower the activation energy is. However, the more the residue carbon (CR) and the number of aromatic carbon (CA), the higher the activation energy is.

REACTION KINETICS OF 1-DECENE OLIGOMERIZATION CATALYZED BY AlCl3-ETHANOL COMPLEX

2015, 46(10):  12-16. 

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The oligomerization of 1-decene was studied with AlCl3-ethanol complex as catalyst. The products were analyzed by GC-MS to investigate the effect of reaction temperature on the reaction rate. The simplified kinetic equation was established, and the apparent activation energy was obtained by calculating the conversion of 1-decene. The results show that 1-decene oligomerization catalyzed by AlCl3-ethanol complex is a cationic reaction process with apparent activation energy of 4.98 kJ/mol. At AlCl3 mole ratio of 2%, ethanol/AlCl3 molar ratio of 0.9, reaction temperature in the range of 0-100 ℃, reaction time of 3 h and stirring speed of 600 rpm, the products of oligomerization are mainly trimers and tetramers. As the reaction temperature increase, the yield of dimmers and trimers increases, and the yield of tetramers and pentamer decreases.

RELATIONSHIP BETWEEN SURFACE ACIDITY AND MICROSTRUCTURE OF INDUSTRIAL γ-ALUMINA

2015, 46(10):  17-21. 

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The relationship between the surface acidic and microstructure of gamma-alumina support were studied on three industrial alumina based on the characterizations by XRD，NMR，TEM and pyridine-FTIR. The results show that there are three crystal planes on the surface of alumina: (110)，(100) and (111) planes, and the ratio of the three main planes were different on the alumina supports. The ratios of crystal planes (110)，(100)，(111) on sample alumina-1 ，alumina-2 and alumina-3 are 68%，19%，26%，and 63%，19%，18%，and 59%，19%，22%，respectively. The sample alumina-1 with higher ratio of (110) plane possesses more medium-strong and strong acidity; while the samples alumina-2 and alumina-3 with higher ratio of (100) plane possess more weak acidity.

EFFECT OF NATURAL SURFACTANTS AND CALCIUM CATIONS ON SILICA-BITUMEN SURFACE INTERACTIONS

2015, 46(10):  22-27. 

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In this paper, the roles of Ca2+ and natural surfactants in the oil sands water-based separation process were analyzed by AFM through quantitative description of the interaction behavior between the asphalt and silica surface. The effect of calcium cations, natural surfactants, and their combination on the asphalt and silicon surface interaction in different solution environment was investigated. The results show that in acidic aqueous environment, silica surface adsorbed cationic natural surfactant becomes to be hydrophobicity, the long-range force between asphalt and silica becomes a weak repulsive force and a strong adhesive force. Addition of calcium divalent ions makes both the long range force and adhesive force decrease due to the adsorption of Ca2+ on the surface of SiO2 and compression of the surface electric double layer. At strong alkalis condition, the Ca2+ is dissociated to form hydrolyzate CaOH+, which compresses the surface electric double layer and reduces its electronegativity. The anionic surfactant is adsorbed on outer layer of CaOH + through electrostatic interaction. This enhances the hydrophobicity of the silica surface, therefore, the long-range force between asphalt and silicon becomes attractive force from repulsive force and the cohesive force increases with the increase of Ca2 + concentration. These force curves can be reasonably explained through the changes of Zeta potential value of asphalt droplets and silica particles.

STUDY OF EFFECT OF FEED DUST CONCENTRATION ON SEPARATION EFFICIENCY OF PV TYPE CYCLONE WITH DIFFERENT EXIT TUBES

2015, 46(10):  28-33. 

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The feed dust concentration has an important influence on the separation efficiency and pressure drop of cyclone. In the range of dust concentration of 5~550 g/m3, the separation efficiency of 500mm diameter PV cyclone with three different exit tubes was investigated using 325 mesh talcum powder. The exit tubes with small cylindrical (type A), cone (type B) and big cylindrical (type C) were used, respectively. The experimental results show that the separation efficiencies go up with increasing dust concentration in feed. However the separation efficiency increases smoothly when the feed concentration is above 150 g/m3. With increasing the feed concentration, the tangential velocity decreases and thereby the separation ability decreases. As the aggregation between particles increases, the inertia separation ability rises, resulting in improved separation efficiency but more particles escaped. The experimental results also show that the exit tube structure of cyclone separator, especially the diameter, has a considerable effect on separation efficiency. Finally, according to the experiment date and considering the influence of inlet feed velocity and exit tube diameter, an empirical equation for calculating separation efficiency of cyclone is given.

EFFECT OF FCC GASOLINE PRE-HYDROGENATION ON CUTTING SCHEME FOR PRODUCTION OF NATIONAL PHASE IV GASOLINE

2015, 46(10):  34-38. 

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The FCC gasolines in three domestic refineries were cut into narrow fractions to analyze the sulfur and olefin content of each fraction. The aim is to see the possibility if the fractions < 105 ℃ with more olefins can be put into LCN as much as possible on the premise of ensuring total sulfur of LCN≯50 μg/g and reducing the octane number loss due to olefins saturation in the process of HCN hydrodesulphurization. The octane number loss of the FCC gasoline after hydrodesulphurization process with or without pre-hydrogenation was compared. The results indicate that the cutting point of HCN can be greatly increased by process with pre-hydrogenation and the product gasoline is in compliance with national phase IV with less octane number loss.

INDUSTRIAL APPLICATION OF RFCC CATALYST (CRM - 200) CONTAINING MESOPOROUS SILICA-ALUMINA

2015, 46(10):  39-43. 

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A new RFCC catalyst CRM-200 with disordered mesoporous silica-alumina material (JSA), which possesses properties of high hydrothermal stability, macromolecular cracking ability, good coke selectivity, low cost and easy to industrialization, was used in a RFCC unit of Qingdao Anbang Company. The industrial application results reveal that CRM-200 shows much higher cracking activity, the total liquid yield increases about 1.86%, the yield of slurry and coke decreases 0.92 percentage point and 1.59 percentage points, respectively. The distribution and properties of cracking products are improved. The processing capacity and recycle oil increases. The resid-ratio increases from 69.92% to 83.34%. The operation condition is optimized, at the same time the catalyst consumption reduces about 1 kg/t.

APPLICATION OF RMMC-1(HENGYUAN) IN 300 kt/a FCCU

2015, 46(10):  44-49. 

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The commercial application of RMMC-1 (Hengyuan) in Shandong Hengyuan Petrochemical Company was introduced. Ltd. Considering the inferior feedstock such as CGO, the emphasis in design of RMMC-1 (Hengyuan) catalyst was put on the inhibition of aromatization and isomerization reactions as much as possible during the initial oil-catalyst contact to ensure long straight-chain hydrocarbon involved in cracking reaction and to increase the ring opening probability of naphthene and reduce the proportion of dehydrocyclization and condensation. The matrix of RMMC-1(Hengyuan) catalyst is characterized by large surface areas, which can effectively deal with the influence of basic nitrogen and other pollutants on the catalyst performance and improve the ability of heavy oil cracking and the yield of propylene. The running results show that the yield of total liquid and of light oil changes little, LPG and propylene yields increase. The conversion rate of feedstock and the gasoline yield increases 4.1 percentage points and 3.4 percentage points, respectively. While the yield of dry gas and diesel reduces 0.4 percentage point and 4.4 percentage points，respectively. The coke selectivity is significantly improved.

INFLUENCE OF POLYETHYLENEGLYCOL ON HPMO/SIO2 STRUCTURE AND ITS PERFORMACE OF OXIDATIVE REMOVAL OF DIBENZOTHIOPHENE

2015, 46(10):  50-55. 

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PEG-HPMo/SiO2 catalysts were prepared by precipitation method using PEG6000 as template and tetraethyl orthosilicate (TEOS) as silica source and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM) and 31P Superconducting nuclear magnetic resonance spectrometer (31P-NMR). The specific surface area, pore size distribution and mesoporous ratio were calculated via the NLDFT equilibrium model. The influence of various parameters including dosage of catalyst, dosage of H2O2, reaction temperature and reaction time on the conversion of DBT was investigated. The results show that PEG-HPMo/SiO2 contains the Keggin active structures. For 10 mL model fuel(mass fraction of sulfur element is 400 ?g/g), DBT in the model oil can be almost totally removed under the conditions of catalyst 0.05 g，H2O2 0.03 mL, reaction temperature 50 ℃ and reaction time 15 minutes. The catalytic activity of PEG-HPMo/SiO2 is not significantly reduced after the catalyst is reused for 6 times.

FACTORS OF INFLUENCING ULTRA-LOW SULFUR DIESEL PRODUCTION USING RS-2000 CATALYST

2015, 46(10):  56-60. 

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To meet the requirement of producing national standard V diesel, SINOPEC Guangzhou Co. tried to produce national V diesel in the 2.0 Mt/a diesel hydrotreating unit in January 2015. Trial production results show that compared with the production of phase IV diesel, the higher operation severity can meet the phase V diesel quality requirements by increasing the reaction temperature and decreasing space velocity. Reaction temperature, feedstock properties, processing throughput, recycle hydrogen purity and other factors all influence the sulfur content of diesel product. Under the same reaction conditions, the effect of the 95% distillate temperature on product sulfur content is more obvious than the sulfur content of feed.

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STUDY ON PREPARATION OF MICRO-MESOPOROUS ZSM-5 ZEOLITE BY ALKALI TREATMENT AND PROFORMANCE IN HYDRODESULFURIZATION OF FCC GASOLINE

2015, 46(10):  61-66. 

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ZSM-5 zeolites were treated by different concentrations of Na2CO3 and NaOH solution. The zeolites before and after alkali treatment were characterized by XRD, BET, SEM and NH3-TPD techniques. The hydrodesulfurization and aromatization performance of the catalysts loaded with Co-Mo based on zeolites before and after treated by different concentrations of alkali solution was investigated. The results show that ZSM-5 zeolite is apt to form micro-mesoporous structure after alkali-treatment. The alkali treatment could modulate the acidity and significantly improve the activity of desulfurization and olefins aromatization. The low concentration NaOH solution (0.5 mol/L) impacts on the crystal structure of ZSM-5 zeolite and the relative crystallization declines to 90.8%. When the concentration of NaOH solution is 1.0 mol/L, the crystallinity of ZSM-5 zeolite is only 78.3%, the BET surface area, pore size and pore volume are all reduced. However, the Na2CO3 solution treatment for desilication, micro- mesoporous ZSM-5 zeolite can be obtained with the crystal structure hardly affected. The Co-Mo catalyst based on the zeolite treated with Na2CO3 solution (4.0 mol/L) displays a higher FCCG hydrodesulfurization and aromatization activity. The desulfurization rate reaches 94.2% and the aromatics increase 20.7 percentage points.

EFFECT OF CALCINATION TEMPERATURE ON STRUCTURE AND HYDRODESULFURIZATION ACTIVITY OF MoO3-ZrO2 COMPOSITE OXIDE

2015, 46(10):  67-71. 

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Mesoporous MoO3-ZrO2 composite oxides were prepared by sol-gel method and were characterized by XRD, BET, SEM and IR to study the effect of calcination temperature on crystal phase structure, specific surface area, pore size and morphology. The FCC gasoline hydrodesulfurization activity of the sulfided composite oxides was evaluated. The results show that at the calcination temperature of 550 ℃, the worm structure is appeared on the surface of ZrO2; At 650 ℃, Zr(MoO4)2 characteristic peaks begin to produce and at 700 ℃, ZrO2 is transformed from tetragonal phase to the monoclinic phase. It is concluded that the appropriate increase of the calcination temperature is beneficial to increase the average pore size and get the proper specific surface area, but too high calcination temperature can make composite oxide sintering and fracture. The MoO3-ZrO2 composite oxide calcined at 650 ℃has the highest HDS rate of 70.3%.

APPLICATION OF MIP TECHNOLOGY and PROPRIETARY CATALYSTS IN RFCC PROCESSING HYDROTREATED HEAVY OIL

2015, 46(10):  72-76. 

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The industrial application and calibration of MIP technology and its special catalyst CRMI-2 in 3.5Mt/a FCCU of SINOPEC Shanghai Petrochemical Company were introduced. The calibration results show that using MIP technology and special catalyst CRMI-2 and hydrotreated heavy oil feedstock, the process capacity of the unit exceeds its design value, and product yield distribution is better than design. Under the calibration conditions of maximum working load of 105.72% and 110.11%, the gasoline yields reach 45.16% and 46.89%, respectively, about 2.66 and 4.39 percentage points, higher than its design. The liquid product yields are 81.36% and 81.85%, respectively, about 0.56 percentage point and 1.05 percentage points, higher than the design value. The coke yield is significantly reduced. The olefin of stabilized gasoline is 24.4% and 23.2%, respectively, lower than its design value. The quality of the stabilized gasoline meets the design objective.

PRODUCTION OF HEAVY BASE OIL BY COMBINATION PROCESS OF HYDROTREATING AND TRADITIONAL TECHNOLOGIES

2015, 46(10):  77-82. 

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Base on separate refining and transportation technologies for crude oil, SINOPEC Jinan Co. applied the RIPP`s combination process of high pressure hydrotreating and traditional technologies of solvent refining-dewaxing-clay refining to produce high quality base oils, including HVIⅡ6 and HVIⅡ10 and HVIⅡ150BS short in market. In order to make full use of paraffin in feed, wax deoiling technology was adopted to produce wax products with high quality and high additional value，such as 62# to 68# waxes and 80# soft microwax. The plan by which the base oils and waxes are produced at the same time maximizes the yield of high value-added products.

COMPARATIVE ANALYSIS OF DELAYED COKEING PILOT PLANT WITH INDUSTRIAL APPARATUS

2015, 46(10):  83-87. 

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On the premise of the same raw material properties, process and main operation parameters, the comparison of the pilot plant results of delayed coking experiment with that of the typical industrial device are conducted. Although the inner diameter of the pilot plant coking furnace tube is 6 mm, significantly smaller than that of the industrial device (id=107 mm), the length/ diameter ratio of 3 833 is close to the industrial device 3 759, the pilot plant can operate normally like industrial unit, the furnace outlet temperature of pilot can reach 500 ℃. Feed conversion and gasification rate at the outlet of the coking furnace of the pilot are 6.1% and 22.4%, respectively, slightly less than the industrial unit 7.8% and 26.33%. The height/diameter ratio of pilot plant coking tower reaches 6(oil gas flow rate of 0.009 46 m/s in coking tower), more than the industrial device 4.12(oil and gas flow rate of 0.098 20 m/s in industrial device), but it is still in the recommended range of industrial design requirements (≯0.15 m/s). The test results which 3 kinds of different materials and 3 different circulation ratios show that the pilot plant product distribution and their main properties are very close to the industrial device results.

PREPARATION OF 180# MARINE FUEL OIL BY EBULLATED-BED HYDROTREATMENT OF MEDIUM TEMPERATURE COAL TAR

2015, 46(10):  88-92. 

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The ebullated-bed hydrotreated products of medium temperature coal tar were distilled to get fractions of >355 ℃ and > 400 ℃, which then were analyzed for their compositions and properties. The compatibility and storage stability of the blended fuel oils, which were prepared by blending of > 400 fraction, the floating oil on the water, coal diesel and shale oil, were studied. The results show that the > 355 ℃ fraction can directly be used as 180# marine fuel oil; > 400 ℃ fraction has a good compatibility with floating oil, coal diesel and shale oil and can be used as a high quality blending component of 180 # marine fuel oil. The 180# marine fuel oil can be prepared by blending > 400 fractions, floating oil, shale oil and coal diesel with a ratio of 67%, 12%，10% and 11%, respectively. The product meets the national standard GB/T 17411 of marine fuel oil.

POUR POINT REDUCTION PHENOMENON OF NAPHTHENIC BASE OIL AND PARAFFINIC BASE OIL MIXTURE

2015, 46(10):  93-97. 

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The paper reveals a phenomenon that the pour point of mixed base oil is below the pour point of each component of the mixture. The phenomenon is obvious when naphthenic base oil is mixed with paraffinic base oil. Pour point and other physicochemical properties of mixtures with different naphthenic base oil and paraffinic base oil ratios and component were all analyzed. A hypothesis for the phenomenon was proposed based on the carbon structures of base oils and mechanism of pour point depressant, combined with the analysis of oil properties. The obvious degree of the phenomenon depends on the types, the pour point difference and the viscosity (100 ℃) difference of the two components. Tests show that the influence of three factors on the low temperature performance is in turn. The greater the solidification mode difference, the closer the pour point and viscosity (100 ℃) of two components, the more obvious of the phenomenon is. KN4010 is naphthenic base oil and HVIP8 is paraffinic base oil. The pour points of the two component are both -24 ℃, their viscosities of 100 ℃ are close, the pour point of the mixed oil of two component can be -42 ℃.

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PINCH TECHNOLOGY APPLICATION IN DELAYED COKING HEAT EXCHANGE NETWORK

2015, 46(10):  98-106. 

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There was a considerable energy saving potential in the delayed coking unit with a capacity of 1.20 Mt/a in a petrochemical plant. The heat exchanger network (HEN) of the delayed coking unit is analyzed and optimized by pinch technology. After obtaining the pinch point and energy targets, the pinch technology was applied to eliminate the heat exchange which violates the pinch rules. The optimized HEN was further optimized to cancel the problematic heat exchanger loop and raise the inlet temperature of the vacuum residue (VR) before entering the heating furnace, resulting in a final optimized HEN. Consequently, the modified HEN has achieved remarkable economic benefits by decreasing energy consumption of 11.89×104 GJ, which indicates that energy saving of this proposal can bring additional benefits of 4.577 0 million Yuan/a. The payback period of investment is 2 months with a total reconstructive investment of 0.778 2 million Yuan. The pinch technology for energy saving of delayed coking unit and the improvement of economic benefits has very important theoretical and practical significance.

CATALYSTS AND PROCESS TECHNOLOGY FOR SULFUR RECOVERY

2015, 46(10):  107-112. 

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Progresses in catalyst and process technology for sulfur recovery since the 1970s are reviewed. The development of the LS series catalysts for sulfur recovery and off-gas hydrogenation, and the performance and industrial applications are summarized, and the localization of the imported catalyst of sulfur recovery for large scale plant is described in detail. The process technologies developed by SINOPEC with complete self-owned intellectual property is summarized based on digestion and absorption of the imported plant and relevant advanced technologies and experiences. The design principles and advices for newly built large scale sulfur recovery plant are proposed.