Table of Content

12 November 2011, Volume 42 Issue 11

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催化剂

AN ANALYSIS OF THE FORMATION RATE OF ZINC SILICATE IN S ZORB SORBENTS

2011, 42(11):  1-4.  doi:

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Various conditions influencing the formation rate of zinc silicate on an industrial S Zorb sorbent (FCAS-R09) were investigated. The results indicated that the formation temperature of zinc silicate reached as high as 800℃ without water. The presence of water vapor could significantly promote the formation of zinc silicate. At a water vapor partial pressure of 10 kPa, zinc silicate could be formed below 500 ℃, and the formation rate increased with the increase of water vapor partial pressure and/or reaction temperature. At constant water vapor partial pressure and reaction temperature, the formation rate of zinc silicate could be speeded up with the increase of overall pressure. Meanwhile, the ambient atmosphere had little effect on the formation rate of zinc silicate.

STUDY ON THE HYDRODESULFURIZATION OF HEAVY FCC NAPHTHA OVER Mo-Co/Al2O3 CATALYST

Zhao Le-Ping,Bai-Ling You,Hong Pang

2011, 42(11):  5-8.  doi:

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The effect of presulfurization temperature (230-400℃) of MoCo/Al2O3 catalyst on its selective hydrodesulfurization (HDS) performance, such as HDS rate, hydro-saturation (HDY) rate and gasoline octane (RON) loss, was studied on a pilot plant unit using full range FCC gasoline as feed. The test results indicated that under reaction temperature of 260 ℃, with the increase of presulfurization temperature, the HDS rates of these catalysts increased from 84.4% to 91.1%; under reaction temperature of 280 ℃, the HDS rates of these catalysts were all over 96.0%, presulfurization temperature had less influence. However, in these two cases, MoCo/Al2O3 catalyst sulfurized at 250 ℃ exhibited the minimum HDY rate and gasoline RON loss, which indicated said catalyst possessed the best HDS selectivity. It was found that MoCo/Al2O3 catalyst could be well sulfurized at 250 ℃ and with less coke deposit, which would be favorable to provide good HDS selectivity when treating FCC gasoline.

PREPARATION OF SUPPORTED IRON CATALYSTS AND ITS APPLICATION IN SYNTHESIS OF 2,4,6-METHYLBENZOIC ACID

2011, 42(11):  9-12.  doi:

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The preparation of supported iron catalysts for application in the synthesis of 2,4,6-methylbenzoic acid was studied including factors influencing the catalyst preparation on the yield of α-chlor-1-(2,4,6-trimethylphenyl)-1-ethanone, which was a synthetic intermediate of 2,4,6-methylbenzoic acid. Test results showed that the optimum catalyst preparation conditions were using alumina support with an iron loaded amount of 20% and activation at 400 ℃. The optimum acylation conditions for mesitylene over said catalyst were obtained by orthogonal experiments as follows: C9H12/ClCH2COCl molar ratio of 0.5, a reaction temperature of 80 ℃, a reaction time of 4 h and a catalyst dosage of 0.25% (based on the mass of mesitylene). Under such reaction conditions, the yield of α-chlor-1-(2,4,6-trimethylphenyl)-1-ethanone reached 81.8%.

EVALUATION AND COMMERCIAL APPLICATION OF LDR-100 CATALYST FOR HEAVY OIL CATALYTIC CRACKING

2011, 42(11):  13-16.  doi:

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The performance of LDR-100 FCC catalyst developed by Lanzhou Petrochemical Research Center of PetroChina was investigated on a riser pilot plant unit and applied in commercial FCC unit processing heavy feedstocks. The evaluation results of pilot plant riser unit showed that as compared with a commercial reference catalyst, its propylene yield increased 0.74 percentage points, the RON of its gasoline increased 0.70 units, slurry oil yield reduced 1.45 percentage points and olefin volume fraction of gasoline reduced 6.13 percentage points. Commercial application results showed that compared with based case, the total liquid yield increased 0.42 percentage points, RON of gasoline increased 3 units, the consumption of catalyst reduced from 2.24 kg/t to 1.76 kg/t, an economical benefit of 26.387 7 million RMB could be obtained annually.

APPLICATION OF DEOXIDATION CATALYST IN RECOVERING LIGHT HYDROCARBONS FROM REFINING DRY GAS AND SUGGESTIONS

2011, 42(11):  17-22.  doi:

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The application of deoxidation catalyst C36-2-02 in recovering light hydrocarbons from dry gas of a refining-petrochemical integrated complex was introduced. Operation results showed that both the activity and selectivity of the catalyst were good enough to remove harmful impurities from dry gas for satisfying the requirements of production, and the unit was running smoothly. Some suggestions for further improving the catalyst application were proposed.

STUDY ON THE PERFORMANCE OF Co-SBA-15 CATALYST FOR CATALYTIC OXIDATION OF STYRENE TO BENZALDEHYDE

2011, 42(11):  23-27.  doi:

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Cobalt-containing mesoporous molecular sieves Co-SBA-15 were prepared using Co(NO3)2.6H2O as cobalt source and the obtained molecular sieves were characterized by XRD and BET. Test results showed that Co-SBA-15 possessed the characteristic structural features of mesoporous molecular sieve. The performance of Co-SBA-15 for catalytic oxidation of styrene was investigated using 30% H2O2 as oxidant and acetone as solvent. Under the conditions of using 5 mL of styrene, 10 mL of acetone, 100 mg Co(15%)-SBA-15 catalyst calcined at 500 ℃, H2O2/styrene molar ratio of 2, a reaction temperature of 100 ℃ and a reaction time of 4 h, the conversion of styrene reached 99.12%, the selectivity and yield of benzaldehyde was 77.62% and 76.94%, respectively.

基础研究

STUDY ON THE ACIDITY OF SHAPE SELECTIVE ZEOLITE IN FCC CATALYSTS

Sun Min

2011, 42(11):  28-31.  doi:

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The coordination status of Al atom in MFI type shape selective zeolites used in FCC catalysts and the relationship of Al atom coordination with the acidity of zeolite were investigated in this paper. Results showed that with the increase of Fe, P and RE contents in zeolite samples, the framework tetracoordinated Al atoms increase, as well as the non-framework pentacoordinated and hexacoordinated Al atoms increase, thus the acid density of the zeolite increases. However, the total amount of Br?nsted acid increases and the total amount of Lewis acid decreases, which indicates that the framework tetracoordinated Al atoms relate with the formation of weak Br?nsted acid sites, the non-framework pentacoordinated and hexacoordinated Al atoms associate with the formation of strong Br?nsted acid sites, and the non-framework low coordinated Al atoms effect the formation of Lewis acid sites.

BASIC RESEARCH ON THE ADSORPTIVE DENITROGENATION OF MODEL DIESEL FUEL WITH MODIFIED SILICA GEL

2011, 42(11):  32-35.  doi:

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Five denitrogenation adsorbents loaded with 1.4%, 2.6%, 3.8%, 5.0% and 6.2% of nickel respectively were prepared by volumetric impregnation method using chromatographic silica gel as carrier. The adsorptive denitrogenation performances of the prepared adsorbents were investigated on a laboratory batch device under the conditions of an adsorption temperature of 120 ℃ and oil to adsorbent mass ratio of 60, using model diesel samples with initial nitrogen content of 1 000 μg/g containing indole or quinoline respectively. Test results show that the adsorption of quinoline and indole on the nickel containing adsorbent is characterized by multi-molecular layer adsorption significantly, and the best equilibrium adsorption capacity for quinoline and indole is obtained with adsorbent having Ni content of 5.0% and 2.6%, respectively. By studying the effect of adsorption temperature, it can be seen that for quinoline and indole, the optimum adsorption temperature is 100℃/120℃ and 140℃, respectively.

MECHANISM STUDY ON THE DEACIDIFICATION OF NAPHTHENIC ACID OVER BR?NSTED ACID SITES

LI Chunyi Li

2011, 42(11):  36-40.  doi:

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In view of the experimental results that the main product of naphthenic acid deacidification on Br?nsted acid sites is CO, cyclohexylcarboxylic acid and cyclohexyl-butylcarboxylic acid are used for model compounds to investigate the deacidification mechanism of naphthenic acid. The simulation by DMol3 involves the changes of bond order and charge distribution prior and post to interact with Br?nsted acid sites, according to the relative positions between carboxyl group and cycloalkyl, various deacidification mechanisms were proposed. While carboxyl group connects with the cycloalkyl directly, the ring opening reactions proceed prior to deacidification, CO is produced mainly; in the indirect connection case, the deacidification of naphthenic acid happens directly and CO is the dominant product.

EFFECT OF CALCINATION TEMPERATURE ON THE MICROSTRUCTURE AND SURFACE ACIDITY OF ALUMINA

2011, 42(11):  41-45.  doi:

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Taking boehmite as precursor, alumina samples calcined under various temperatures were prepared, and their chemical properties and microstructures were characterized by XRD, FT-IR and HRTE to study the effect of calcination temperature on the microstructures and surface acidities of alumina samples. Results show that with the increase of calcination temperature (450-900 ℃), the acid amounts of alumina samples show a downward trend. When calcination temperature is in the range of 500-800 ℃, the obtained samples are γ-Al2O3 with microstructure of layer or lamellar fold; when calcination temperatures reach 700℃ and 800 ℃, the edges and corners of the laminar microstructure become obvious, yet the crystal sizes are basically unchanged; when calcination temperature reaches 900 ℃, partial δ-Al2O3 is observed, the sample morphology seems to be large flake structure. In these samples, Al2O3 (110) plane is the dominant crystal face, and a maximum exposure of Al2O3 (110) plane is observed with sample calcined at 700 ℃.

加工工艺

STUDY ON THE CATALYTIC PYROLYSIS OF COKER GAS OIL AND COKER NAPHTHA UPGRADING BASED ON TMP TECHNOLOGY

SUN Jin-Peng,Hong-hong SHAN,Chun-YI LI,Xiao-Bo CHEN

2011, 42(11):  46-51.  doi:

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The catalytic pyrolysis performance of coker gas oil (CGO) and coupling with coker naphtha (CN) upgrading was investigated on a pilot plant riser unit under the process conditions of two-stage riser maximizing propylene (TMP) technology. Results showed that TMP technology displayed good adaptability to process CGO feed. The conversion of total two stage reactions reached 87.80%, the yield and selectivity of propylene was 18.12% and 64.87%, respectively; the yields of light oil and dry gas were 37.19% and 4.27%, respectively. However, the enhanced octane number of CN could only be obtained with the coupling of CGO catalytic pyrolysis and CN upgrading, not for single CN upgrading, with a 25% CN in the combined feedstock of CGO and CN, the RON of obtained gasoline could be more than 90.

STUDY ON THE CAUSES OF ISOPRENE LOSS DURING THE SEPARATION OF CRACKED C5 FRACTIONS

2011, 42(11):  52-56.  doi:

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Under various reaction temperatures and reaction time, the behaviors of isoprene (IP), 1,3-pentadiene (PD) and cyclopentadiene (CPD) during thermal dimerization of steam cracking C5 were studied by seal-tube method. The produced codimers (CPD with IP and CPD with PD) and self-dimers were analyzed to investigate the causes of IP loss during thermal dimerization. Results showed that the co-dimerization between CPD and IP was the main cause of IP loss, besides, the self-dimerization of IP at high temperature range (110-130 ℃) was another cause for the increase of IP conversion under high temperature. Therefore, in the design of process and thermal dimerization reactor, to eliminate the contact of CPD and IP is essential, as well as processing under lower temperature (below 110 ℃) and relatively short resident time.

DEVELOPMENT OF T-STAR PROCESS AND ITS APPLICATION IN COAL LIQUEFACTION PROCESS

2011, 42(11):  57-61.  doi:

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The development, characteristics and application of T-STAR process are summarized in this paper focusing on its first application in the direct coal liquefaction project of Ordos Coal Liquefaction Branch of China Shenhua Coal to Liquid and Chemical Corporation Ltd. The process flow is introduced and the advantages of coupling T-STAR process with direct coal liquefaction project are discussed based on investigating the feedstocks, products and temperature field in the reactor, which displays a promising prospect for the application of T-STAR process in coal liquefaction field.

油品与添加剂

STUDY ON 1-DECENE OLIGOMERIZATION CATALYZED BY IONIC LIQUIDS TO PREPARE POLY-α-OLEFINS

li ling

2011, 42(11):  62-65.  doi:

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Oligomerization of 1-decene was carried out with ionic liquids as catalyst to obtain poly-α-olefins synthetic oil (PAO). The influences of AlCl3 molar fraction in ionic liquids, reaction temperature, reaction time and the amount of catalyst on the catalytic performance were studied. The experimental results showed that under the conditions of AlCl3 molar fraction more than 0.57 and reaction temperature less than 60 ℃, ionic liquids displayed good catalytic performance for the oligomerization of 1-decene, the kinematic viscosity of the prepared PAO was over 40 mm2/s (100 ℃). The kinematic viscosity of PAO was largely depended on the reaction temperature, which would influence the chain-transfer reactions. Side-reactions, such as isomerization, were observed and were enhanced significantly with the increase of ionic liquids. In addition, the produced PAO were insoluble in the ionic liquids, the separation was convenient and the catalyst could be used repeatedly without obvious deactivation.

STUDY ON THE PREPARATION AND PROPERTIES OF POLYETHYLENE WAX FROM PYROLYSIS OF HIGH DENSITY POLYETHYLENE

MEI Tao

2011, 42(11):  66-69.  doi:

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Polyethylene wax is prepared by pyrolysis of high density polyethylene in solvent. The effect of various solvents and reaction conditions on the product yield and properties was investigated. Test results show that mixed solvent with a mixing ratio of A/B=2:3 could be the optimal solvent for preparing polyethylene wax. By orthogonal experiments, it is shown that factors affecting the product yield are in the order of temperature > time > solvent/feed ratio. Under the optimum conditions of a reaction temperature of 320 ℃, a reaction time of 3 h and solvent/feed ratio of 1, the obtained product has a relative molecular weight of around 2 000 and melting range of 118-123 ℃.

EFFECT OF POUR-POINT DEPRESSANT ON THE RHEOLOGICAL PROPERTY OF WAXY CRUDE FROM ALASHANKO PORT OF SINO-KAZAKHSTAN OIL PIPELINE

2011, 42(11):  70-75.  doi:

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Suitable pour point depressant (PPD) for improving the rheological property of waxy crude from Alashanko port of Sino-Kazakhstan oil pipeline was screened. The changes in viscosity-temperature curves prior and post to adding PPD, the influence of heating repetitively, high-speed shearing on the viscosity and setting point of crude oil, as well as standing stability were investigated. Results showed that using the grafted copolymer of ethylene vinyl acetate/acrylic acid as PPD with an adding dosage of 50 μg/g and adding at 60 ℃, the setting points of crude oil samples were lowered 10-20 ℃，furthermore, the viscosity, abnormal point and yield value were decreased significantly as well. Heating repetitively below 60 ℃ could cause degradation of the effect of PPD, and the degradation became worse with the lowering of heating temperature. The influence of high-speed shearing on the effect of PPD depended on the shearing temperature, serious negative effect was observed at temperature near the maximum wax precipitation zone. However, the standing stability of crude with PPD was good.

分析与评定

CHARACTERIZATION OF ALKENE TYPES AND DISTRIBUTIONS IN FCC DIESEL AND COKER DIESEL FUEL

Ze-Long LIU

2011, 42(11):  76-80.  doi:

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An Ag-SiO2 stationary phase was prepared and applied in solid phase extraction (SPE) technique to separate alkenes from FCC diesel fractions and coker diesel fractions. GC/MS and 1H NMR were used to characterize the types and carbon number distributions of the separated alkenes. Test results showed that normal α-olefin, internal monoolefin, diolefin and cycloolefin were the main types of alkenes in FCC diesel fractions and coker diesel fractions. The mole fraction of internal ene hydrogen in FCC diesel fractions was 80.41%, and the mole fraction of normal α-ene hydrogen in coker diesel fractions was 53.32%. The distributions of alkenes in FCC diesel fractions and coker diesel fractions were focused on C11 C15 and C12 C22, respectively.

DETERMINATION OF IRON，COPPER，NICKEL AND MAGNESIUM IN LUBRICATING OIL BY ATOMIC ABSORPTION SPECTROMETRY

2011, 42(11):  81-84.  doi:

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To determine the contents of iron, copper, nickel and magnesium in lubricating oil, lube oil samples were treated by dry ashing method and then dissolved in water to be tested by atomic absorption spectrometry. The interference of coexisting elements, silicon and etc., was investigated. Results showed that in certain concentration range the interference of silicon to the determination of iron and magnesium happened, yet it could be eliminated by the addition of lanthanum-based inhibitor. Test results for precision and accuracy showed that the relative standard deviations for these four tested elements were all less than 5%, and the recovery rates of individual elements were in the range of 96%-105%.

设备及防腐

EXPERIMENTAL STUDY ON THE SPONTANEOUS OXIDATION OF CORROSION PRODUCTS IN REFINING UNITS

Jun-cheng JIANG

2011, 42(11):  85-88.  doi:

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Corrosion products from various locations of refining units were collected and natural oxidation experiments were arranged to study the oxidation and spontaneous combustion behaviors of these corrosion products. Results show that the existence of elemental sulfur could promote the oxidation of corrosion products and even speeds up the process of spontaneous combustion, which threatens the refinery security, thus sulfur recovery units should be the main object to be concerned. Water could inhibit the spontaneous combustion of corrosion products by absorbing heat, reducing temperature and isolating oxygen in some ways. But if the content of ferrous sulfide in the corrosion products is high enough, spontaneous combustion may happen as well. Corrosion products collected from the top of refining units are more dangerous than those from the bottom since containing less water.

优化与控制

OPTIMIZATION OF PROCESS AND OPERATION IN ABSORPTION-STABILIZATION SYSTEM

2011, 42(11):  89-94.  doi:

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Most of the absorption-stabilization systems of FCCUs are troubled by serious C3+ components entrained in dry gas and high energy consumption, in this paper, analysis of process and operation is carried out to find out the causes, and based on integrating new techniques an optimized process and operation scheme is proposed, including desorption tower is equipped with a re-boiler at the middle and feeding full cold feed, adding a side cut line at the lower part of the stabilization column to draw out light gasoline for the replacement of stabilized gasoline as supplement absorbent, increase the operation temperature of condensed oil tank and decrease the operation temperature of absorption tower appropriately. Results of a case study applying said proposal showed that the volume fraction of entrained C3+ components in dry gas decreased by 42.09% and the energy consumption of the system reduced 17% as compared with prior to optimization.