Table of Content

12 June 2010, Volume 41 Issue 6

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基础研究

STUDY ON THE SYNERGETIC EFFECT OF COMPOSITE MOLECULAR SIEVE CATALYSTS IN HEXADECANE HYDROISOMERIZATION

2010, 41(6):  1-6.  doi:

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Using medium pore molecular sieve SAPO-11 and large pore zeolite β having various Si/Al ratios as active components, a series of catalysts containing composite molecular sieve or single molecular sieve were prepared. The catalysts were characterized by BET, XRD, NH3-TPD and FT-IR techniques. The hydroisomerization activity and selectivity of the catalyst were studied and compared using hexadecane as model compound. Test results showed that catalyst containing β(700) and SAPO-11 composite molecular sieve exhibited good hydroisomerization performance, the yield of multi-branched chain isohydrocanbons increased significantly and the isohydrocanbon yield could keep relatively high with the increase of reaction temperature. The characterization results showed that not only the types of molecular sieve but also the relative acidities of the molecular sieves could have a synergetic effect on catalyst.

STUDY ON THE CHANGES OF ASPHALTENE PROPERTIES IN PROCESSING RESIDUE FEED BY FIXED-BED HYDROTREATING

2010, 41(6):  7-11.  doi:

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Hydrotreated oil samples from guard catalyst zone, HDM，HDS and HDN zones were collected respectively from a fixed-bed hydrotreating device. The properties of asphaltenes from residue feedstock and the obtained samples were analyzed, as well as the average molecular weight of asphaltenes and the stability parameter of residue colloidal was calculated. Results showed that with the increase of hydrotreating severity, the C，H，S，N，Ni，V and Fe contents in the asphaltenes of treated oil samples decreased significantly, the average molecular weight of asphaltenes and the stability parameter of residue colloidal decreased as well.

STUDY ON THE STABILITY OF ALKALINE SILICA SOL

2010, 41(6):  12-16.  doi:

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29Si-NMR and TEM techniques were used to analyze the gelation process of alkaline silica sol and the effects of system pH value, SiO2 concentration and temperature on the sol stability were investigated. It was indicated by 29Si-NMR results that the interior structure of silica sol micelle was consisted of（-Si-O-Si-）, and its surface was covered by –SiOH and -Si(OH)2 groups. Results showed that the stability of alkaline silica sol increased with the increase of system pH value and decreased with the increase of SiO2 concentration and temperature. However, when temperature was below 45℃, little influence of temperature on the stability of alkaline silica sol was observed.

STUDY ON THE CORRELATIONS OF THE EVALUATION INDEXES IN OXIDATION STABILITY TEST OF TURBINE ENGINE LUBRICANT

2010, 41(6):  17-20.  doi:

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The oxidation stability of turbine engine lubricant is evaluated by corrosion and oxidation stability test method. In this paper the correlations of some evaluation indexes including total acid number, viscosity varied rate and the amount of deposits formed are discussed. Test results showed that the variation trends of total acid number and viscosity varied rate could reflect and predict the changing trend of deposits in some extent, yet without positive or quantitative correlations could be used to predict one another. Besides, using DSC two-peak method to predict the formation trend of deposits in oxidation stability test is not mature right now.

催化剂

STUDY ON THE HYDROISOMERIZATION OF n-DODECANE OVER β-Mo2C/SAPO-11 CATALYST

2010, 41(6):  21-25.  doi:

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β-Mo2C(20%)/SAPO-11 catalyst was prepared by impregnation and temperature programming reduction using n-hexane as carbon source. The test results of XRD, BET and FT-IR showed that β-Mo2C was well crystallized and the catalyst possessed preferable pore diameter and pore volume. The hydroisomerization performance of n-dodecane over β-Mo2C/SAPO-11 catalyst was studied using a fixed-bed down-flow reactor system, and the effect of reaction parameters, such as temperature, pressure, LHSV and the H2/oil volume ratio was investigated. Results showed that under the optimum conditions of a reaction temperature of 400℃, a reaction pressure of 3MPa, a LHSV of 1.0 h-1, and a H2/oil volume ratio of 400, the conversion of n-dodecane reached 80.2%, the isomers selectivity and the isomers yield were about 70% and 57%, respectively.

RESEARCH OF A NEW BULK CATALYST FOR GAS OIL HYDROTREATING

2010, 41(6):  26-29.  doi:

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A high activity bulk catalyst for gas oil hydrotreating was prepared. BET, XRD, SEM, TPR and SEM techniques were applied to characterize this new catalyst, and its hydrotreating activity was evaluated and compared with that of conventional supported catalyst using FCC LCO as feedstock. Results showed that the active components of the prepared bulk catalyst were well distributed and having curve structure. Evaluation results exhibited that as compared with the conventional catalyst at a double LHSV, this new bulk catalyst still had higher hydrodesulfurization, hydrodenitrogenation and aromatics saturation activities.

COMMERCIAL APPLICATION OF VRCC-1 CATALYST AT RFCC UNIT

2010, 41(6):  30-34.  doi:

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This paper presents the commercial application of VRCC-1 residue catalytic cracking catalyst at the RFCC unit of Sinopec Beijing Yanshan Company. Performance test results indicate that this catalyst possesses excellent residue crackability, good resistance to heavy metals contamination and improved coke selectivity, thus it is suitable for the use of processing heavy and poor feedstocks. When processing heavy feedstocks, the light oil yield and total liquid yield were more than 66% and more than 80%, respectively.

COMBINED APPLICATION OF RS-1000 CATALYST AND FH-5A CATALYST FOR ULTRA LOW SULFUR DIESEL PRODUCTION

2010, 41(6):  35-38.  doi:

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RS-1000 catalyst for ultra low sulfur diesel production was applied in the 3.0 Mt/a diesel hydrogenation unit of SINOPEC Zhenhai Company along with the conventional FH-5A/FH-5 catalysts. The packing, drying and presulfiding of the series catalysts were introduced. Performance test results showed that using RS-1000/ FH-5A/FH-5 combined catalysts and a feed with a sulfur content of 1.36%, under the conditions of a LHSV of 1.97 h-1, a hydrogen to oil volume ratio of 298, a reactor inlet pressure of 5.79 MPa, a reactor inlet temperature of 336 ℃ and an average bed temperature of 360℃, the sulfur content of the treated diesel was 0.044%. The average HDS and HDN rates were 96.8% and 85.2%, respectively; the hydrogen consumption was 0.77%, the pressure drop of reactor was 0.17 MPa and radial temperature difference was 3℃, which indicated that the combined catalysts possessed excellent activity. Data of 3.5 years running further supported that the activity as well as the stability of the combined catalysts was excellent.

加工工艺

EXPERIMENTAL STUDY OF DCC-PLUS TECHNOLOGY

Zhi Gang Zhang,Chao-Gang Xie

2010, 41(6):  39-43.  doi:

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A series of experiments for DCC-PLUS technology was carried out on pilot plant unit. Results showed that as compared with DCC technology, the yields of LPG, propylene and butylenes in DCC-PLUS process were enhanced significantly, at the same time, the yields of dry gas and coke were reduced; the induction period of gasoline reached 529 min. The improvement in product slates and product selectivity was even more significant when processing residue blended feedstock with DCC-PLUS technology.

EFFECT OF PROCESSING HIGH VANADIUM FEED IN FCC UNIT AND COUNTERMEASURES

2010, 41(6):  44-47.  doi:

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The effect of processing high vanadium feed on the FCC unit operation, product yield, processing cost and product quality was discussed based on the mechanism of vanadium contamination on FCC catalyst. Countermeasures, such as using optimum process conditions, selecting proper catalyst and additive for anti-vanadium contamination and adopting magnetic separation system to increase the equilibrium catalyst activity, were applied.

INVESTIGATION ON THE EXTRATION AGENT FOR REMOVING SULFIDES FROM PENTANE

Liu Yan-xiu,SONG Hua

2010, 41(6):  48-50.  doi:

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The desulfurization performance of several extraction agents were studied using industrial pentane as feed under the conditions of an extraction temperature of 15℃, a settling time of 15 min and an agent to oil ratio of 1. Test results indicated that: (1) As to single extraction agent, furfural and NaOH solution are preferred, which can reduce the sulfur content of pentane from 40.3 mg/L to 1.0 mg/L; (2) 5%NaOH solution and 95% ethanol could be formed composite agent in rather wide volume ratios, which can reduce the sulfur content of pentane to 1.0 mg/L; (3) Composite agent of DMF and 5%NaOH mixing with a volume ratio of 1 can reduce the sulfur content of pentane to 1.0 mg/L, yet exceeded amount of DMF in composite agent might suppress the removal of sulfides from pentane.

STUDY ON THE SYNTHESIS OF 1,3,5-TRIISOPROPYLBENZENE

Bo Jiang,Yang Li

2010, 41(6):  51-55.  doi:

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1,3,5-triisopropylbenzene was synthesized by alkylation of benzene and propylene using ionic liquids as catalyst. The compositions of ionic liquids and the alkylation conditions were studied. Moderate post-alkylation was used to improve the ratio of 1,3,5-triisopropylbenzene to 1,2,4-triisopropylbenzene in products and pure 1,3,5-triisopropylbenzene was obtained by fractionation. Results showed that 2AlCl3/Et3NHCl ionic liquid catalyst was preferred and the optimum reaction conditions were an ionic liquid volume ratio of 0.1, a reaction temperature of 50 ℃ and a propylene flow rate of 3.50 ml/s.

环境保护

PREPARATION AND PROPERTIES OF A NEW SERIES CATALYST FOR TREATING ORGANIC WASTEWATER BY CATALYTIC WET AIR OXIDATION

Zhi-Lin Cheng

2010, 41(6):  56-59.  doi:

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Cu-Zn-Ce-Al precursors with hydrotalcite-like layered structure were prepared by cocurrent coprecipitation method. After calcining at 720oC for 8 h, the precursors transformed to a series of spinel structure catalyst. The compositions of the catalysts were analyzed; reaction conditions including temperature, space velocity and oxygen partial pressure, as well as life test were investigated. Results showed that when using a catalyst having metal compositions of Cu: Zn: Ce: Al = 2:0.8:0.2:1 to treat an acrylic acid wastewater (COD concentration of 26 000 mg/L) under the conditions of a reaction temperature of 150 ℃, an oxygen partial pressure of 1.0MPa and a reaction space velocity of 1h-1, the COD removal rate reached more than 90%. After running 100 h, the Cu dissolution loss was 0.23 mg/L (less than the requirement of National Standard for Water Qualities of 0.3 mg/L), which indicated that the catalyst possessed good catalytic oxidation performance and structure stability.

INITIAL RESEARCH ABOUT TREATMENT OF OILFIELD WASTEWATER WITH IONIC LIQUIDS

2010, 41(6):  60-63.  doi:

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Three imidazole-based hydrophobic ionic liquids ([bmim]PF6, [hmim]PF6 and [omim]PF6) were synthesized using oil bath. The effects of extraction time, the amount of ionic liquids, pH value and the length of alkyl chain of the imidazole hydrophobic ionic liquids on the extraction of oilfield wastewater were investigated using these three ionic liquids. Test results showed that the extraction equilibrium could be reached within 20 min, good treating performance could be obtained at a wastewater to ionic liquid volume ratio of 5 and a wastewater pH value of 3 by using [bmim]PF6 ionic liquid. The treating performance was enhanced with the increase of the hydrophobic of the ionic liquid. [bmim]PF6 ionic liquid could be regenerated and reused for several times, the average COD removal rate of the regenerated ionic liquid was about 80%.

控制与优化

ANALYSIS AND IMPROVEMENT FOR BOTTLENECKS OF CAPACITY EXPANSION AND ENERGY UTILIZATION IN DELAYED COKING UNIT

2010, 41(6):  64-67.  doi:

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Based on the three-link strategic method of energy integration and optimization, a domestic delayed coking unit is taken as research background. The influence of the three-link method on the capacity expansion and energy-use is discussed, thus the relative bottlenecks are found. Using simulation software the strategies for capacity enlargement and measures for debottlenecking energy-use are proposed. It is demonstrated that the capacity enlargement and energy integration can be achieved simultaneously through optimization of furnace, optimizing the operation of fractionator, flexible design of the heat exchange networks and proper adjusting the recycle ratio, etc. Finally, based on the original process flow and equipments, a 25% increase of processing capacity and a decrease in energy consumption are achieved, the economic benefit is significant.

PROCESS OPTIMIZATION OF HIGH PURITY ISOBUTANE PRODUCTION

2010, 41(6):  68-71.  doi:

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Based on the operation of 99.5% purity iso-butane production, a new process model was set up to calculate the process parameters for producing 99.9% purity iso-butane. Optimization of process parameters and production process was carried out. By updating the furnace and pressure-difference regulation system, the control of production process was more accurate and stable. Therefore, the n-butane content in the feed of iso-butane tower could be reduced to less than 0.085% from the original of less than 0.3%; the back flow of butane tower was increased to 20 m3/h; the temperature of both towers was controlled stably. Eventually the more than 99.9% high purity iso-butane product was obtained.

分析与评定

COMPARISON OF METHODS FOR DETERMINING WAX CONTENT IN CRUDE OIL

TIAN Songbai

2010, 41(6):  72-76.  doi:

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Four standard methods (SY/T 0537, SY/T 7550, ГОСТ 11851 and UOP 46) for determining wax content in crude oil are compared. Significant differences and certain regularities among the wax content results obtained by these methods are observed. The wax contents obtained from high to low are in the order of UOP 46> SY/T 0537> SY/T 7550> ГОСТ 11851. It can be seen that in these four methods, the dewaxing conditions, solvent compositions and the solubility of wax in solvent are varied, which leads to the differences of results obtained by each method. Furthermore, based on the analysis of wax compositions it is found that the differences are mainly caused by the various solubilities of ≤C25 n-paraffins and other hydrocarbons in the individual solvent under individual dewaxing conditions.