Table of Content

12 May 2013, Volume 44 Issue 5

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EFFECTS AND MECHANISM OF La OR Ce MODIFIED ZSM-5 ZEOLITE ON OLEFIN CRACKING FOR PROPYLENE

2013, 44(5):  1-5. 

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The catalytic cracking reaction of FCC naphtha was studied on La or Ce modified ZSM-5 zeolite under 550℃, atmospheric pressure and water vapor conditions. Experimental results suggest that the modification of rare earth La3+ and Ce4+ can increase the total acid amount of ZSM-5 molecular sieve, especially strong acid acidity, so FCC gasoline conversion rate and in particular the olefin cracking reactions obtain marked improvement. In addition, after the modification, the selectivity of the olefin cracking reaction and the yield of ethylene, propylene, butylene, especially propylene are also significantly increased. Molecular simulation results show that La3+ and Ce4+ locate at the corner in bent Z type channel of ZSM - 5 molecular sieve, 3~4? away from the hole center, making the volume of the bend decrease obviously. This leads to the increase of energy barrier for all reactions including cracking, cyclization, aromatization and polymerization, but the cracking barrier increases minimum which improves the selectivity of cracking reaction of olefins.

STUDY ON WATER SOLUBILITY OF BASIC COBALT CARBONATE FROM DIFFERENT SOURCES

2013, 44(5):  6-9. 

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The solubility of basic cobalt carbonates from different sources in acid and basic water solution was studied. The crystal structure, thermal properties and pore structure were characterized by XRD, TG and BET, respectively. The results show that the water solubility of different basic cobalt carbonates is very different, the solubility of basic cobalt carbonate in acid solution is better than in basic solution. The difference in physico-chemical property of different basic cobalt carbonates influences the water solubility obviously. It is concluded that the salts with high surface area, large pore volume and high purity will have better solubility and Co3O4 existing in the salt affects the water solubility of basic cobalt carbonate significantly.

INFLUENCE OF SOURCE OF SILICA AND ALUMINUM ON SYNTHESIS OF ZEOLITE L

2013, 44(5):  10-13. 

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To study the influence of raw materials on the synthesis of zeolite L, Al(OH)3 from different sources and fumed-silica of different grades were used. The samples were characterized by XRD and BET. The relative crystallinity was calculated. Results show that the carbonation Al(OH)3 is the best aluminum source for increasing relative crystallinity of L zeolite, and the high purity fumed-silica as a single silicon source has also higher crystallinity of L zeolite . Ultrafine fumed-silica can improve the filtering property of zeolite L，and the optimum ratio of ultrafine fumed-silica in hybrid silicon source is 50%, the highest overall efficiency may be achieved at this point.

DEHYDROGENATION CRACKING OF i-BUTANE TO PRODUCE LIGHT OLEFINS

2013, 44(5):  14-18. 

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The dehydrogenation cracking of i-butane was studied over mixed catalysts comprised of Cr2O3/Al2O3 dehydrogenation catalyst and HZSM-5 catalyst in a fixed-bed reactor. The results demonstrate that conversion and product distribution vary signi?cantly depending on different location of Cr2O3/Al2O3 and HZSM-5 catalyst and the amount of Cr2O3/Al2O3 catalyst in the reactor, and the reaction performance is the best when two kinds of catalysts are homogeneously mixed. On the mixed catalyst HZSM-5 with a 20% Cr2O3/Al2O3, the conversion of reaction is 81%, and the yield of ethylene, propylene and butylene is 12.4%, 24.1% and 13.4%, respectively. The conversion increases by 21% and the selectivity of total olefins (ethylene, propylene and butylene) increases by 2.57%, compared with the pure HZSM-5. Besides, i-butane mixed with N2 enters the reactor at a fixed residence time of i-butane, the reaction results become better, and the advantage are more obvious as dilution ratio increases.

STUDY ON CARBONYLZATION OF TOLUENE IN CHLOROALUMINATE IONIC LIQUID

2013, 44(5):  19-23. 

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Process for the synthesis of para-tolualdehyde (PTAL) via carbonylization of toluene with CO catalyzed by chloroaluminate (III) type of ionic liquids (ILs) was investigated. Carbonylization reaction of toluene in ILs was tested. The results indicate Al2Cl7- is the catalytic active species and the conversion of toluene increases with increasing the amount of IL used, raising reaction temperature, prolonging reaction time, or enhancing the partial pressure of CO. The ionic liquid modified by both metallic cation and Br?nsted acid can improve the activity for the reaction. Furthermore, trialkylaminium-contained ILs with B-L complex acid such as IL-T IL-E and IL-P were prepared and firstly used in the reaction. It is found that their activity are much higher than IL-I, and IL-T who has the highest activity is the best catalyst for the reaction. Under the conditions of IL/toluene(molar ratio)=2.8, PCO 3.0Mpa, 40℃, 1h, conversion of toluene can be up to 56.4%.

STUDY ON SYNTHESIS OFCYCLOPENTADIENE/α-OLEFIN COPOLYMER TYPE DRAG REDUCING AGENT

2013, 44(5):  24-27. 

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A high performance drag reduction agent was synthesized by bulk polymerization of cyclopentadiene/α-octene /α-dodecene using TiCl3/AlEt2Cl as trigger. The impact factors on polymerization were investigated, such as pretreatment of raw materials, raw material composition and temperature. After the polymerization conducted under the conditions: water content of raw materials less than 30ppm; mole ratio of n(cyclopentadiene): n(α- octane): n(α- dodecene )=1:1:1; TiCl3 3 mg/L; mole ratio of n(TiC13):n(AlEt2Cl)=1:25，reaction temperature 0-5 ℃, reaction time 72 h, the reaction product was placed at room temperature for 2 days , the polymer molecular weight can be up to 6.4×106. The results of loop drag-reduction test of the agent indicate that drag reduction rate for diesel reaches to 48.3% at 10mg/L the polymer concentration.

INFLUENCE OF POLYOLEFIN CATALYST AGING ON DRAG REDUCTION RATE OF OIL SOLUBLE DRAG REDUCER

2013, 44(5):  28-32. 

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To examine the performance of the drag reduction reagent produced by polyolefin catalyst, an aging process was used to treat the polyolefin catalyst TiCl4/MgCl2 and promoter Al(i-Bu)3. And then the drag reduction performance of polymers produced by aged catalyst (and non-aged) was tested in an indoor loop evaluation device at different concentrations of TiCl4/MgCl2 and promoter Al(i-Bu)3. The effect of aging temperature and aging time on the drag reduction performance of polymer by both catalysts was surveyed. IR and XRD were used to characterize the prepared polymer structure. The results show that the drag reduction rate of polymer using aging catalyst is greater than that of nonaging one when the TiCl4/MgCl2 dosage is in 5.97×10-4mol/L to 11.09×10-4mol/L and the Al(i-Bu)3 dosage is more than 4.29×10-2mol/L and that as the polyolefin catalyst dosage increase, the drag reduction rate increases first and then decreases. The polymer having maximum drag reduction rate is obtained at the aging temperature of - 2 ℃and 10 min. Drag reduction rate can reach to 50%. The IR and XRD results show that the aging process haven’t change the structure of polymer product but makes its crystallinity decrease. Key words：catalyst; aging; drag reduction rate; drag reduction agent; polyolefin

STUDY ON EXTRACTIVE DESULFURIZATION OF ALKYLIMIDAZOLIUM PERCHLORATE IONIC LIQUID

2013, 44(5):  33-37. 

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A series of alkylimidazolium perchlorate type of ionic liquids (ILs) with different length of alkyl chains were synthesized using N-methylimidazolum, n-alkyl bromide, sodium perchlorate as raw material. The desulfurization of the model or real oil using ILs was investigated under different conditions. The results show that the best desulfurization rate is obtained after 50 min under the condition of [C6mim]ClO4:oil=4:1(v/v), 60℃, using [C6mim]ClO4 as extracting reagent. The sulfur removal reaches 86.90 % for the model oil ([S]0=1164μg/g). When the volume ratio between IL and fuel oil is 1:1, the sulfur removal is 65.24% for the FCC gasoline ([S]0=117μg/g) and 58.05% for the FCC diesel ([S]0=1974μg/g). After the reaction, the fuel oil and ionic liquid can be separated simply by decantation. The ILs used can be purified by fractional distillation and recycled at least for 5 times without significant loss of activity.

PREPARATION AND CHARACTERIZATION OF CATIONIC MESOPOROUS SiO2 AND ITS ADSORPTION PERFORMANCE OF HPAM FROM WATER

2013, 44(5):  38-42. 

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The mesoporous SiO2 was synthesized by template P123 and modified with γ-aminopropyl triethoxysilane (APTES). The pore structures and degree of order of cationic mesoporous SiO2 were characterized by low-angle X-ray Diffraction (XRD), nitrogen adsorption-desorption (BET) and transmission electron microscopy (TEM). The functional group was analyzed with Fourier infrared spectrum (FT-IR). The adsorption of HPAM on cationic mesoporous SiO2 was studied. The results show that the cationic mesoporous SiO2 is successfully prepared and possesses ordered hexagonal structure. The BET surface area and pore size is 66.3m2.g-1 and 6.9nm, respectively. The optimum adsorption conditions for the solution with initial pH 6.5 are the adsorption time of 120min, 50℃, solid-liquid ratio of 4:1. Under these conditions, the adsorption capacity is up to 1340mg/g.

INDUSTRIAL APPLICATION OF DOMESTIC SORBENT ADSORPTION IN S ZORB GASOLINE DESULFURIZATION UNIT

2013, 44(5):  43-46. 

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The domestic S-Zorb sorbent developed by Research Institute of Petroleum Process (RIPP) and produced by Sinopec Catalyst Nanjing branch was used in the 1.2Mt/a FCC gasoline desulfurization unit in Yanshan refinery. The industrial results indicate that the start-up operation is stable when all domestic sorbent is used in the reaction - regeneration system. When the feedstock is FCC gasoline, the runaway of reactor temperature can be avoided effectively by fine operation and sorbent pre-sulfidation. The domestic sorbent used shows high desulfurization activity for FCC gasoline. The sulfur content of gasoline product can be controlled below 8 μg / g, meeting the standard of Beijing V gasoline.

CO-PRODUCTION TECHNOLOGY OF HIGH OCTANE NUMBER GASOLINE AND STEAM CRACKING FEED BY C4 AROMATIZATION AND ALKYLATION

2013, 44(5):  47-51. 

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To make use of C4 olefins is extensively concerned by domestic petro-chemicals enterprises. The aromatization performance of nano-sized zeolite catalyst SHY-DL is studied in the thesis. The effect of hydrogen pressure, alkadiene content, and reaction temperature and space velocity on aromatization is explored. The results indicate that with refinery C4 as feedstock, under the conditions of 360℃ to 450℃, 2.0MPa, LHSV 0.9h-1 to 1.2h-1, the conversion of C4 olefin can be up to 99% and that the yield of dry gas is less than 2 %, the yield of C5 and C5+ is 43% to 50% and the RON and MON of the gasoline are 98 and 87.9, respectively. The cracking performance of the by-product LPG obtained in the aromatization process was evaluated on a bench scale pyrolysis apparatus. The yield of ethylene is 30.98%, the yield of ethylene and propylene is 46.93% under the cracking conditions of 910℃ and water to oil mass ratio 0.45. This illustrates that the by-product LPG is a better feed for ethylene production.

STUDY OF LPG AND MTBE DESULFURIZATION TECHNOLOGY

2013, 44(5):  52-56. 

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MTBE is an impotent additive of gasoline product and manufactured from refined LPG. The sulfur remained in the refined LPG influence the sulfur content of MTBE. It is found that the sulfur in refined LPG mainly comes from oxidized sulfonated cobalt phthalocyanine where the sulfide is in the form of disulfide and/or polysulfide. Based on these findings, the sulfur removal technologies from LPG and MTBE are tentatively proposed, respectively. Sulfur can be effectively removed from oxidized sulfonated cobalt phthalocyanine by organic solvent extraction to decrease the sulfur content in refined LPG and the MTBE with less than 10 ?g/g sulfur can be produced by distillation.

STUDY ON TECHNIQUE OF REMOVING TRACE BENZENE AND HEXANE FROM CYCLOPENTANE AND ITS APPLICATION

2013, 44(5):  57-60. 

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The industrial cyclopentane satisfied with national standard can be produced by the distillation technique, but it cannot yet meet the European Union standard of the cyclopentane solvent (benzene mass fraction ≤0.00005%, hexane mass fraction ≤0.0008%). In order to remove trace benzene and hexane from cyclopentane, a distillation-adsorption complex technique was exploited. Both active carbon fiber and zeolite molecular sieve purchased from the market are used as composite adsorbents, and both dehydration tower and debenzolization-dehexane tower are set in industrial process. The results of commercial experiments show that cyclopentane solvent met with the European Union standard can be produced by means of both distillation-adsorption complex technique and adsorbents composed of active carbon fiber and zeolite molecular sieve. Both active carbon fiber and zeolite molecular sieve are innocuous and unpoisonous, recyclable, and easy to obtain. The distillation-adsorption complex technique is worthy of being popularized because of its simple, convenient and safty.

TRIBOLOGICAL PROPERTIES OF NANO-ZnO IN WATER BASED ROLLING LIQUID

2013, 44(5):  61-66. 

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The nano-ZnO was dispersed into water-based rolling fluid by dispersant, extreme pressure agent, rust inhibitor. And the best recipe and the best working conditions were selected by orthogonal experiment. The results show that under the conditions of nano-ZnO 0.4% (mass fraction), heating 60 °C, stirring 10min, the tribological properties is of optimum. The tribology analysis and cold rolling experimental results further indicate that excellent lubrication properties can be obtained using the best formula rolling fluid. Nanoparticles lubrication mechanism was analyzed by strip surface morphology and elemental analysis. It is argued that due to the extreme pressure film formed through combination of nanoparticles with additives and the filled defects on the strip surface by the nanoparticles, the surface roughness is lowered and thus the surface quality is improved.

DEVELOPMENT AND PERFORMANCE OF COMPOSITE ADDITIVES FOR SPECIAL CYLINDER OIL IN BLENDER-ON-BOARD SYSTEM

2013, 44(5):  67-70. 

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The performance of the BOB (Blender-on-Board system) composite additives developed by Dalian lubricating Oil R&D Institute for special cylinder oil blending was tested. Some simulation methods of differential scanning calorimetry, Caterpillar Micro Oxidation Test, hot tube tester, panel coker tester, spread-ability tester, SRV, SEM，were carried out to evaluate the anti-oxidation performance, deposit control, spread-ability and friction resistance under the conditions of low dosage of BOB additives. The results reveal that the optimal BOB additives show better overall performance but less anti-oxidation, comparing with foreign reference.

STUDy ON NEURAL NETWORK MODEL FOR GASOLINE BLENDING OPTIMIZATION

2013, 44(5):  71-75. 

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Back-Propagation Neural Network was used to develop the gasoline blending mathematical model for a specific petroleum refinery. Based on the characteristics of its gasoline production units, the topological structure of the neural network was decided. By using real gasoline production data of the refinery, the learning function of the network and the number of neurons in the hidden layers were selected, the model was trained, and a gasoline blending model with reasonable fitting and predicting ability was established. Compared with other blending models, the model established in this paper is much more adaptive because it does not require knowing blending mechanism. Application results showed that the neural network model could precisely predict those nonlinear parameters like octane number, induction period, etc., and also provide optimized gasoline blending schemes according to real production data.

THERMODYNAMIC ANALYSIS AND IMPROVEMENT FOR FEED PREHEATING PROCESS OF DELAYED COKING UNIT

2013, 44(5):  76-81. 

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Taking a delayed coking unit (DCU) in a domestic refinery as the research object, the feed preheating process was simulated by PRO/Ⅱ，the process simulation software. Considering the trait of the heat exchange network for DCU, the strategy of pinch analysis was introduced to calculate the highest theoretical heat exchange temperature for the feed, taken as the target temperature for the retrofit of the feed preheating process. In a case study, the quantitative energy grade and heat duty (ε-Q) diagram was constructed. By calculating the exergy destructions, it is found that the “bottleneck” of the preheating process is exergy destructions from mixing and heat exchange processes with large temperature differences. According to the principle of “counterpart temperature, cascade using”, the feed preheating process was retrofitted. The case study results show that the exergy destruction of mixing process is decreased by 80% and the exergy destruction of heat exchange process for preheating the feeds per 1℃ increase is decreased by 24.1% after the retrofit. Meanwhile, the final heat exchange temperature of feed is increased by 43℃. The heat duty of the coking furnace is decreased by 4.2MW, which indicates that the effect for energy saving is obvious.

DEVELOPMENT AND APPLICATION OF MANAGEMENT SYSTEM ON REFINING BENCHMARK PROCESSING LOSS

2013, 44(5):  82-86. 

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Using advanced software technology, an integrated management system was developed based on hydrocarbon loss theory and mathematical models. The system can calculate and forecast the benchmark loss of crude oil transportation, storage, processing, semi-finished products transit and products outgoing. It also provides many kinds of charts to help engineers analyze and evaluate the status of loss by comparing benchmark loss with statistical loss. The system has been applied in several refineries. The results show that it is helpful to decrease refinery loss.

CHARACTERIZATION OF NITROGEN COMPOUNDS IN FCC DIESEL FRACTION

2013, 44(5):  87-91. 

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The basic and non-basic N compounds in catalytic diesel were directly separated in this paper by acid-modified silica column and then quantified by gas chromatography-nitrogen chemiluminescence detection (GC-NCD) based on the established database obtained by following steps: firstly nitrogen compounds were extracted by neutral silica adsorption column, then the nitrogen compounds were concentrated and separated into basic and non-basic types using acid-modified silica column, and these two kinds of N compounds were finally analyzed by gas chromatography-mass spectrometer (GC-MS) to identify N compounds. Four kinds of catalytic diesels were tested. The results showed that the neutral nitrogen compounds including indole and carbazole in catalytic diesels oil occupied more than 90% (mass fraction) of the total nitrogen compounds. Catalytic diesel oils from different sources have different types and distributions of the neutral nitrogen compound. Basic nitrogen compounds, mainly including aniline, quinoline and benzoquinoline, occupied about 10% (mass fraction).

REVISION AND STANDARD METHOD FOR TESTING THERMAL STABILITY OF ORGANIC HEAT TRANSFER FLUID

2013, 44(5):  92-97. 

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Organic heat transfer fluid has been applied for heating system in various industries. Thermal stability is an important performance, which is an indication of decomposition and polymerization of oil at high temperature. SH/T 0680-1999《Heat Transfer Fluids-Determination of thermal Stability》was revised, taking standard DIN 51528-1998《Unused Heat Transfer Fluids-Determination of thermal Stability》as a reference. The differences are that the revised method requires to use capillary chromatographic column in gas chromatograph analysis, report the boiling range of sample before end point of 538℃, uniform the temperature distribution in whole equipment, and change the test time. The standard revised can reflect better thermal stability of different kinds of organic heat transfer fluids at different temperature and different heating time.