Table of Content

12 April 2012, Volume 43 Issue 4

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EFFECT OF CATALYST TO OIL RATIO AND SPACE VELOCITY ON THE FORMATION OF LPG IN DEEP CATALYTIC CRACKING PROCESS

2012, 43(4):  1-4. 

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The effect of catalyst to oil (C/O) ratio and weight hourly space velocity (WHSV) on the yield and compositions of LPG was investigated using a laboratory fixed-fluidized bed (FFB) unit, VGO feedstock, a catalyst containing zeolite Y and shape-selective zeolite. Test results show that with the decrease of WHSV and the increase of C/O ratio, both the LPG yield and heavy oil conversion enhance, but their effects on the compositions of LPG are distinct. With the decrease of WHSV the propylene content of LPG increases; contrarily, with the increase of C/O ratio, the propylene content of LPG decreases, the reason of which is discussed as well. It is found that the decrease of WHSV favors chemical reactions happened in the shape-selective zeolite, and with the increase of C/O ratio, reactions took place in zeolite Y are benefited.

ANALYSIS AND APPLICATION OF MEASURES FOR OPTIMIZING PRODUCTION SCHEME TO INCREASE GASOLINE YIELD

2012, 43(4):  5-9. 

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A case study on the potential of enhancing gasoline production was carried out by analyzing the components of gasoline pool in this study and the specifications of gasoline products. It was obvious that gasoline blending components from FCC unit and CCR unit were the dominant components. Thus measures, such as providing more feedstocks for FCC and CCR units, maximizing the production load of these two units, and recycling heavy CCR gasoline fraction to FCC unit were adopted. Successful results showed that the production of gasoline increased 172.6 kt (over the design value) in 2010, which indicated an economic benefit of 86.13 million RMB was obtained.

RESEARCH ON THE SOLVENT EXTRACTION OF AROMATIC HYDROCARBON FROM FCC DIESEL FRACTIONS

2012, 43(4):  10-14. 

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The FCC diesel fraction of SINOPEC Changling Company was rich in aromatics and low in cetane number, thus, studies of extracting aromatic hydrocarbons from this diesel fraction with selected solvent to improve its cetane number were carried out. Test results showed that when solvent extractions were carried out under the conditions of extraction temperature in the range of 130—150℃, solvent to oil volume ratio in the range of 1.5—6.0, the aromatic mass fractions of these obtained raffinate oils could be decreased to 38.4—63.3% and their cetane number reached more than 45, the increments were over 20 units as compared with the feed. The aromatic extract from this process was rich in monocylic aromatic, which could be used as aromatic solvent.

DEVELOPMENT AND COMMERCIAL APPLICATION OF CCR REFORMING CATALYSTS HAVING LOW COKE DEPOSITION RATE

2012, 43(4):  15-20. 

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By means of adopting new promoters and preparation procedures to adjust the acidic and metallic active centers of CCR catalyst, a low coke deposition and high selective PS-VI catalyst was developed by Research Institute of Petroleum Processing. Compared with the previous PS-V catalyst, PS-VI catalyst showed a 21% decrease in coke deposition, yet its yields of reformate and aromatics increased. Based on these experiences, by optimizing the interaction between promoters and Pt centers to further adjust the microstructure and the ratio of two kinds of Pt centers, PS-VII catalyst was obtained and commercialized. The application results showed that the coke deposition of PS-VII catalyst decreased by 36% as compared with reference catalyst, at the same time, the yields of reformate, aromatics and hydrogen increased significantly.

AN ANALYSIS ON OPERATION STATUS OF FHUDS-3 DIESEL HYDROFINING CATALYST

2012, 43(4):  21-24. 

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The first commercial application of FHUDS-3 hydrofining catalyst newly developed by Fushun Research Institute of Petroleum and Petrochemicals was carried out at the 3.0 Mt/a diesel hydrofining unit of SINOPEC Shanghai Gaoqiao Petrochemical Corporation. The operations of nearly three years showed that FHUDS-3 catalyst possessed high activity, good selectivity and adaptability to various feedstocks, thus, it processed various mixed diesel feedstocks to produce low-sulfur clean diesel meeting the requirements of National Exhaust Emission Standard III and Shanghai Exhaust Emission Standard IV. Nevertheless, after running 26 months, the catalyst activity showed a significant decline trend. By analyzing the spent catalyst, it was found that the serious deactivation of catalyst was caused by the deposition of silicon on the catalyst surface, which reduced the pore volume and specific surface area of the catalyst, covered some active sites and led to catalyst deactivation finally. However, the silicon deposits came from coker distillate in the mixed feedstock due to the use of defoaming agent containing organic silicon at the upstream delayed coking unit.

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STUDY ON THE DEACTIVATION OF Pt/HZSM-5 ZEOLITIC REFORMING CATALYST BY COKE DEPOSITION

2012, 43(4):  25-29. 

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Experiments for coke deposition and deactivation of Pt/HZSM-5 reforming catalyst were carried out on a continuous fixed-bed micro-reactor by using n-octane as model compound. TG-DSC, N2 adsorption, XRD, NH3-TPD，FT-IR and TEM were used to characterize the fresh and deactivated catalyst samples for studying the effect of coke deposition on the physical properties of catalyst. Results showed that the coke deposits on the deactivated catalysts were mainly nano-tubular type and most of them were in the less than 4 nm microspores, which caused the reduction of specific surface area and pore volume, as well as the increase of average pore diameter. In addition, the crystal structure of coked ZSM-5 zeolite changed from monoclinic to orthorhombic system. The coking reactions preferred to happen on the strong acid sites, with the increase of coke deposits, the number of Bronsted acid sites and Lewis acid sites decreased significantly, in which the reduction of the former was more obvious.

EFFECT OF PREPARATION CONDITIONS BY MICROEMULSION METHOD ON THE ACTIVITY OF Pt/TiO2 CATALYST DURING SELECTIVE HYDROGENATION OF o-CHLORONITROBENZENE

2012, 43(4):  30-33. 

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Pt/TiO2 catalyst was prepared by microemulsion system of CTAB/butarol/cyclohexane/H2PtCl6 using hydrazine as reductant and TiO2 as support. The effect of microemulsion compositions and the crystalline state of TiO2 on the activities of Pt/TiO2 catalysts for selective hydrogenation was studied using o-chloronitrobenzene (o-CNB) selective hydrogenation as a probe reaction. The results showed that Pt/TiO2 catalyst having the highest activity in selective hydrogenation of o-CNB was prepared from a microemulsion system with mCTAB:mbutarol=3:7, (mCTAB+mbutarol):mcyclohexane=3:7 and the amount of H2PtCl6 solution occupied 3.6% of the total system mass. Furthermore, the study of crystalline states revealed that anatase type TiO2 was helpful to enhance the catalytic activity of Pt/TiO2 catalyst.

PRELIMINARY STUDY ON DEHYDROGENATION OF LUBE FRACTION TO FORM AROMATIC HYDROCARBONS

2012, 43(4):  34-37. 

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The aromatics formation trend of lube fraction under various reaction temperatures and hydrogen partial pressures was investigated over a supported noble metal catalyst. Test results show that with a reaction pressure of 6 MPa, the dehydrogenation reaction rate of lube fraction changes with the reaction temperature, and there is a thermodynamic equilibrium point, when the temperature exceeds this point, the reactions of aromatics formation are favored; the same to reaction pressure, under a reaction temperature of 360℃, when the reaction pressure is below the thermodynamic equilibrium point of 10 MPa, the reaction rates of aromatics formation speed up. Under high temperature and low pressure, some brown substances are adsorbed on the catalyst, and it is not easy to be cleaned or to be desorbed.

EXPERIMENTAL STUDY ON CATALYTIC OXIDATION-EXTRACTION DESULPHURIZATION OF STRIGHT-RUN DIESEL

2012, 43(4):  38-40. 

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The desulphurization of straight-run diesel fraction was studied in laboratory by catalytic oxidation-extraction method, including the selection of catalyst and extractant, the effect of catalytic oxidation conditions on the sulfur removal rate. Test results showed that using cobalt acetate as catalyst, air as oxidant and furfural as extractant, when treating 30 mL straight-run diesel under the conditions of a catalyst dosage of 0.4 g, a reaction temperature of 50℃, a reaction time of 60 min, a stirring speed of 600 r/min, an extractant to oxidized diesel volume ratio of 0.2 and using 3-stage extraction, the sulfur content of the refined diesel dropped from 215 μg/g to about 30 μg/g (a sulfur removal rate of 86%), which well met the requirement of Europe IV Emission Standard.

INFLUENCES OF OPERATING CONDITIONS ON THE SELECTIVE HYDROGENATION OF FCC GASOLINE FOR DIOLEFINS REMOVAL BY CATALYTIC DISTILLATION

2012, 43(4):  41-45. 

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Experiments for the selective hydrogenation of FCC gasoline were carried out in a lab catalytic distillation unit using a NiMo/Al2O3 catalyst for selective hydrogenation and diene thioetherfication. The effects of H2/oil volume ratio, LHSV, reaction pressure and reflux ratio on the properties of light fraction obtained from the tower top were investigated. Under the optimum conditions of a reaction pressure of 0.70 MPa, a reaction temperature of about 140 ℃, a reflux ratio of 2, LHSV of 3 h-1 and H2/oil volume ratio of 10, the obtained light fraction had a total sulfur content of less than 20 μg/g, a mercaptan sulfur content of less than 2 μg/g and the removal rate of diolefins was more than 60%.

DEVELOPMENT OF OVERBASED CALCIUM SULFONATE FOR SYNTHETIC GREASE

Yinong Liu

2012, 43(4):  46-50. 

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5 types of alkyl benzene sulfonic acids (A,B,C,D,E) were used to synthesize overbased calcium sulfonates which were further to be used to prepare sulfonate grease. Test results indicated that sulfonate grease samples prepared by calcium sulfonates Ca-C and Ca-D (from sulfonic acids C and D, respectively) exhibited better performance as compared with the others. Orthogonal experiments were designed to investigate the influence of promoter amount, co-promoter, water and carbon dioxide on the properties of sulfonate, and to obtain the optimum preparation conditions. Based on these results, overbased calcium sulfonates Ca-C and Ca-D were prepared in 50 L pilot plant reactor, the TBN of prepared Ca-C and Ca-D was 396.1 mgKOH/g and 391.6 mgKOH/g, respectively; their 100 ℃ kinetic viscosities were 134.28 mm2/s and 92.27 mm2/s, respectively, and both having amorphous carbonate. Finally, two sulfonate grease products were prepared by calcium sulfonates Ca-C and Ca-D in pilot plant scale, it was observed that the conversion of calcium sulfonates Ca-C/Ca-D to synthetic grease could be completed in short time. The qualities of these two products met the requirements of relative product specifications, and they exhibited good performance at high temperature, as well as resistant to water.

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RECYCLE OF LUBE BASE OIL BY SUBCRITICAL CARBON DIOXIDE EXTRACTION OF TOPPED WASTE OIL

2012, 43(4):  51-54. 

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CO2 was chosen as extractant in subcritical extraction of topped waste oil (1st, 2nd, 3rd and 4th side cuts), under the operation parameters of a CO2 flow rate of 30 L/h, an extracting temperature of 25 ℃ and an extracting time of 3 h, the effect of extracting pressure on the yield of recycled oil was investigated. In addition, main physical and chemical characteristics of recycled oil and the content of phosphorus and main metals were determined. Test results showed that the optimum extracting pressure for 1st side cut topped oil was 10 MPa, yet for 2nd, 3rd and 4th side cuts was 12 MPa. Operating under such extracting pressures, the recycled oil yields of these four side cuts reached 88.12 %，74.96 %，77.36 % and 73.19%, respectively. The physical and chemical properties of recycled oil came up to the quality standard of lube base oil basically; besides, the contents of phosphorus and main metals in recycle oil reduced significantly.

PERFORMANCE STUDY OF A HETEROCYCLIC DERIVATIVE USED AS GREASE ADDITIVE

2012, 43(4):  55-58. 

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In order to meet the requirements of high quality grease product for wind power system, a new heterocyclic derivative additive containing Sulfur (named as RHY317) was synthesized in laboratory. The tribological and anticorrosion properties of RHY317 used in 2# lithium complex grease were evaluated and compared with three other additives containing Sulfur. In addition, the application study of wind power grease containing RHY317 was carried out. Test results indicate that RHY317 exhibits excellent extreme pressure performance, good antiwear property and corrosion resistance in base grease; when it is used as main EP/AW additive for wind power grease, the quality of the product can fully satisfy the specifications.

INDUSTRIAL APPLYCATION OF RPD-JM CALCIUM REMOVAL AGENT FOR CRUDE OIL

2012, 43(4):  59-63. 

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RPD-JM, a calcium removal agent developed by Research Institute of Petroleum Processing, has been applied at the crude distillation unit of Jingmen Petrochemical Corporation since 2007, processing high calcium crude oils, such as Nanyang crude oil and Jianghan crude oil. The application results show that using RPD-JM calcium removal agent and demulsifier simultaneously, the average removal rates of calcium and iron reach more than 80% and 27.03%, respectively; the electric current of the desalting tank reduces, providing a 109.4 MWh electricity saving annually; by using calcium removal agent, the FCC catalyst consumption decreases by 4.44%, the activity of E-cat increases 2 units and the vacuum residue blending ratio of FCC unit increases 1.95 percentage points.

A DISCUSSION ON OPTIMIZING PRODUCTION SCHEME OF SOUR WATER STRIPPING UNIT

2012, 43(4):  64-67. 

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In order to improve the stripping efficiency of sour water stripping unit at SINOPEC Jinling Company, measures, such as refining according to storage, injecting more alkali and prolonging the sedimentation time of sour water, were adopted to optimize the process for treating sour water, enhance the stripping efficiency and improve the quality of water entering sewage disposal plant. After process optimization, the concentration reductions of CODcr and NH3-N2 for inlet water of sewage disposal plant were about 30% and 50%, respectively; the increase of BOD5 concentration was about 50%. The biological effect of sewage treatment was improved significantly, the average CODcr concentration of outlet water dropped from 90 mg/L to 70 mg/L.

BIODEGRADATION CHARACTERISTICS AND METABOLIC PATHWAY OF A STRAIN FOR QUINOLINE DEGRADATION

2012, 43(4):  68-73. 

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A bacterial strain (Q2), which could utilize quinoline as the sole sources of carbon, nitrogen and energy, was isolated from the soil contaminated by petroleum at the wastewater treating plant of a petrochemical refinery. Biodegradation experiments showed that this strain could degrade 500 mg/L of quinoline in growth medium completely within 32 h. The optimum degradation temperature, initial pH of growth medium and rotary speed of shaker for Q2 utilizing quinoline was 30 ℃, pH 8—10 and 100—200 r/min, respectively. The initial concentration of quinoline had great impact on the degradation by Q2, and this degradation process agreed with zero order kinetics equation when the initial concentration of quinoline in the range of 195—796 mg/L. During the biodegradation, the color of the medium changed from yellow to pink, and brown finally. FT-IR analysis exhibited that the degradation of quinoline was probably followed 8-hydroxycoumarin metabolic pathway, and that the nitrogen atom of heterocyclic compound was released as ammonium into the growth medium.

PROCESS SIMULATION AND OPTIMIZATION OF AROMATIC EXTRACTION DISTILLATION WITH N-FORMYLMORPHOLINE

2012, 43(4):  74-79. 

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Using Aspen Plus software, a process model of separating aromatics from non-aromatics by extractive distillation with N-formylmorpholine (NFM) is set up based on vapor-liquid equilibrium data of NFM and hydrocarbons system. Simulation results show that the calculations agree well with the actual operation data. The effect of solvent/oil ratio, inlet temperature of lean solvent and benzene content in lean solvent on the separation is investigated. Optimum operation parameters are obtained as follows: solvent/oil mass ratio of 4.66, lean solvent inlet temperature of 112 ℃ and mass fraction of benzene in lean solvent of about 1%. Calculations under optimization conditions show that the yield and purity of benzene enhance significantly, they increase 0.6 and 0.06 percentage points, respectively.

SIMULATION, ANALYSIS AND ENERGY-USE IMPROVEMENT OF A TWO-TOWER SOUR WATER STRIPPING UNIT

2012, 43(4):  80-86. 

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A two-tower sour water stripping unit is studied in this paper. Based on a detailed analysis for the mechanism of sour water stripping process, the process is simulated by sour water package in PRO/II software, focusing on the factors affecting the energy consumption of the unit, such as for H2S stripping tower, the ratio of cold feed, inlet temperature of hot feed and feeding position; for NH3 stripping tower, the ratio of recycle condensed wastewater, feed temperature and inlet position. The optimal operation parameters are proposed as follows: for H2S stripping tower, the ratio of the cold feed is 0.02, the hot feed temperature is 408 K; for NH3 stripping tower, the feed temperature is 435 K, the optimal feed inlet position is at 2nd plate and without recycle of condensed wastewater. Options for saving energy-use are also obtained: canceling the heat exchange between hot feed water of H2S stripping tower and NH3 containing water; adding heat exchange among top gas of NH3 stripping tower, steam condensate of reboilers and the hot feed water of H2S stripping tower. Simulation results show that after adopting these measures, the energy consumption of this unit reduces by 22.3%.

PROGRESS IN RESEARCH OF REACTION MECHANISM CONCERNING HYDROTHERMAL LIQUEFACTION OF BIOMASS

2012, 43(4):  87-92. 

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In this paper, the reaction mechanism concerning hydrothermal liquefaction of biomass is introduced, as well as the recent research progress in this area worldwide. Based on elaborating the reaction mechanism of monomers, such as monosaccharides, glucose, xylose and amino acids, the reaction mechanism of polymers including lignin, cellulose and protein etc. was analyzed. Finally, the liquefaction mechanism of lipid and its derivatives under hydrothermal condition is reviewed as well.

RECENT RESEARCH AND DEVELOPMENT OF HYDROCRACKING CATALYSTS OUTSIDE CHINA

2012, 43(4):  93-98. 

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With the strengthening of environmental regulations and motor fuel specifications, large refining companies and research institutes outside China pay more attention and provide more fund on the innovation of hydrocracking technology, thus, great progress in catalyst development is achieved. The performances of new series hydrocracking catalysts have been greatly improved since adopting new catalytic materials and preparation technologies. Through modifying the support pore structure and surface acidity distribution, adjusting the interaction between support and metals, incorporating more typeⅡactive sites (which is easy to be activated), the HDN/aromatics saturation activities and stability of new hydro-pretreating catalysts improve significantly. In addition, with the progress in technologies of zeolite synthesis and modification, the improved performances of new generation hydrocracking catalysts not only exhibit at the enhancement of activity, selectivity and stability, but also at the others including operation flexibility, feedstock adaptability, less hydrogen consumption and better product quality.