Table of Content

12 August 2012, Volume 43 Issue 8

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THE CHOICE OF CHINA’S GASOLINE PRODUCTION PROCESS ROUTE FOR THE FUTURE

2012, 43(8):  1-6. 

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The current gasoline pool in domestic refineries is reviewed including dominant FCC blending component, lack of components from catalytic reforming, alkylation and others. Given the trend of future crude supply, consumption demand of gasoline, strengthening environmental regulations toward gasoline quality and emission/waste reduction during production, it would be critical for refineries to seek appropriate process routes for gasoline production based on the current conditions and challenges facing. Several recommendations to domestic refineries for future gasoline production scheme are proposed in this paper. Firstly, the combination of hydrocracking and catalytic reforming process should be incorporated into gasoline production more actively; secondly, the combined process of hydro-pretreating residue feed—FCC—hydro-fining FCC gasoline should be promoted; thirdly, more attention should be paid to high quality gasoline blending components from LPG resources through processes, such as LPG aromatization, butylene—iso-butane alkylation and iso-butylene polymerization; and finally, light naphtha isomerization can play a more important role as well.

CONTROL MEASURES OF MAINTAINING CONTINUOUS LIQUID-PHASE WITHIN UP-FLOW HYDROGENATION REACTOR

2012, 43(8):  7-12. 

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Based on the basic data of a gas oil hydrotreating unit under various process conditions, the changing rule of liquid phase volume fraction in up-flow reactor and the effect of operation parameters on the liquid phase volume fraction are investigated. It is found that in an up-flow reactor, the liquid phase volume fraction increases along the inlet to the outlet of the catalyst bed gradually; the composition of make-up hydrogen, operation pressure and temperature only affect the liquid phase volume fraction slightly, yet recycle oil ratio and the feeding mode of make-up hydrogen have significant influence: the liquid phase volume fraction increases with the increase of recycle oil ratio and adopting multi-point feeding of make-up hydrogen can improve the liquid phase volume fraction effectively. The liquid phase volume fraction at the reactor outlet can be predicted by calculation using mathematical correlation equations, thus automated process control is made possible through DCS system to maintain stable operation of the unit.

DEVELOPMENT STUDY OF OCT-ME PROCESS FOR ULTRA DEEP SELECTIVE DESULFURIZATION OF FCC GASOLINE

2012, 43(8):  13-16. 

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To produce "sulfur-free gasoline", OCT-ME technology for ultra deep selective desulfurization of FCC gasoline was developed by Fushun Research Institute of Petroleum and Petrochemicals, which consists of FCC naphtha fractionation, LCN (light catalytic naphtha) sodium–free sweetening and fractioning with FCC diesel cut, HCN (heavy catalytic naphtha) hydrodesulfurization over a newly developed ME-1 catalyst. Results of pilot plant research showed that sweetened LCN and FCC diesel cut was easy to be separated through absorption fractionation, the sulfur content of treated LCN was in the range of 4.0—6.0 μg/g; compared with reference catalyst, when using ME-1 catalyst at a reaction temperature of 10 ℃ lower than the base case, at the sulfur content of treated HCN in the range of 5.0—8.0 μg/g, the olefin saturation rate reduced 22.7%—32.1% and the RON loss was 1.3—1.6 units less, which indicated that OCT-ME technology could produce "sulfur-free gasoline" (sulfur content less than 10 μg/g) with less RON loss.

PROCESS DESIGN OF IMPORTED LIGHT NAPHTHA ISOMERIZATION UNIT

2012, 43(8):  17-21. 

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The process design of the first imported 600 kt/a light naphtha isomerization unit is presented. The performances of various catalysts are analyzed and compared, the advanced Pt/Cl-Al2O3 catalyst is selected for this project and one through process flow is adopted. In this process, the design values for liquid yield is 97.01—97.28%, RON of isomerization product is 83.1—83.5, RVP of isomerization product is 100—103 kPa and energy consumption of the unit is 684.06 MJ /t(feed), all these values show that this unit is the most advanced one of the same type units in China.

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IMPROVE BLENDING SCHEME OF 93# GASOLINE PRODUCT

2012, 43(8):  22-24. 

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Due to lack of alkylation and pyrolysis gasoline blending components, qualified 93# gasoline could not be produced in Huizhou Refinery. In order to solve this problem, the blending scheme should be adjusted. Measures, such as using low sulfur FCC feedstock to reduce the sulfur content of the main FCC gasoline blending component, declining the blending ratio of CCR reformate to limit benzene content, and adding raffinate from aromatics extraction as blending component to minish gasoline vapor pressure were adopted. Results showed that the quality of the gasoline product obtained by the improved blending scheme could well meet the demand of national standard for 93# gasoline product.

STUDY ON THE AROMATIZATION OF i-BUTANE

2012, 43(8):  25-28. 

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The aromatization of i-butane over light hydrocarbon aromatization catalyst was investigated using pure i-butane and LPG rich in i-butane from C4 aromatization unit as feed respectively. The effect of reaction temperature, reaction pressure and space velocity on the conversion of i-butane was studied. Results showed that with LPG rich in i-butane as feed, under the conditions of a WHSV of 0.5 h-1, a reaction temperature of 400℃and a reaction pressure of 1.0 MPa, the yield of propane, gasoline fraction and dry gas plus loss was 60.05％, 11.57％ and less than 3％, respectively. The propane can be used as feed of ethylene cracking, and the produced gasoline fraction is a high octane gasoline blending component.

STUDY ON THE REACTION CONDITIONS OF TAHE VACUUM RESIDUE HYDROCONVERSION IN SLURRY REACTOR

2012, 43(8):  29-32. 

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The hydroconversion of Tahe vacuum residue (THVR) was studied by using autoclave to simulate the reaction process in slurry-bed reactor. The effects of reaction conditions on coke formation rate, conversion and product distribution during THVR hydroconversion were investigated. Experimental results show that the conversion and coke yield increase with the reaction temperature; the increase of initial hydrogen pressure can suppress coke formation significantly, conversion decreases firstly, when the initial hydrogen pressure is more than 8 MPa, it increases slightly; prolonging reaction time, both conversion and coke yield increase. The presence of catalyst can inhibit the reactions of coke formation effectively, yet cracking reactions are affected as well, so the amount of catalyst added should be optimized. By comprehensive consideration, the suitable reaction conditions are selected as follows: reaction temperature should not be more than 430 ℃, initial hydrogen pressure between 7—8 MPa, reaction time between 40—60 min and catalyst added amount in the range of 2 000—6 000 mg/kg.

DEEP OXIDATION DESULFURIZATION CATALYZED BY Ag/γ-Al₂O₃ CATALYST AND KINETICS MODEL EXPLORATION

2012, 43(8):  33-37. 

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The deep catalytic oxidation desulfurization of model oil (thiophene/petroleum ether) was studied using Ag/γ-Al2O3 as catalyst and gaseous oxygen as oxidant. The catalyst was characterized by X-ray diffraction (XRD) and low temperature N₂-adsorption techniques. The effects of catalyst amount, reaction temperature and time, as well as extraction conditions on the oxidation desulfurization were investigated. Test results showed that using 20 mL of model oil, 0.12 g of catalyst, reacting at 70 ℃ for 50 min, the obtained material was extracted by methanol at 20 ℃ for 30 min with a solvent/oil volume ratio of 1, the rate of desulphurization reached 98.1 %. The kinetic study indicates that catalytic oxidation of thiophene is a pseudo first-order reaction, which could be expressed as k =0.049 45exp[－10 683.4/(RT)].

A RESEARCH OF CATALYTIC COKE FORMATION ON THE PRE-OXIDATION SURFACE OF HP40 ALLOY

2012, 43(8):  38-43. 

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To study the effect of various HP40 alloy surface status on the catalytic coke formation, HP40 alloy samples were oxidized by steam and air respectively at different temperatures, followed by coking tests. The oxidized surfaces of the samples and the morphology of coke were characterized by SEM, EDS and XRD, furthermore, the C/H ratio and the structure of coke were analyzed by elemental analysis and Raman spectroscopy. Test results showed that when alloy sample was oxidized under steam, a layer of needle type Fe rich oxide was formed on the surface; oxidation under air, Cr rich oxide particles were well dispersed on the alloy surface, with the increase of oxidation temperature, spalling of oxide layer from the alloy surface might happen, in this case, the exposed porous surface could be an idea area for forming catalytic coke. The coke formed was mainly catalytic filamentous coke with a diameter of about 80 nm, minor thermal cracking coke might exist too. The coke having a very condensed structure consisted of both ordered and amorphous types, and with low graphitization degree. However, the atmosphere of pre-oxidation had more influence on the oxidized surface of alloy, yet just little on the followed coking process, coke morphology and structure.

SYNTHESIS OF OXO-VANADIUM COMPLEX AND ITS CATALYTIC PERFORMANCE IN ETHYLENE POLYMERIZATION

2012, 43(8):  44-47. 

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Four extraction agents, i.e. di-(2-ethylhexyl)-phosphoric acid (P204), 2-ethylhexyl phosphoric acid mono-(2-ethylhexyl) ester (P507), tributyl phosphate (TBP) and 1-octanol (NOOH), were used to synthesize oxo-vanadium complexes by extraction method, and the synthesized complexes were used as catalysts for ethylene polymerization. These four complexes were characterized by elemental analysis, FT-IR and the structures of the polymerization products were characterized by GPC, DSC and 13C NMR. Test results showed that under atmospheric pressure, activated by Et3Al2Cl3, the catalytic activities for ethylene homopolymerization of these catalysts were in the range of 23—57 kg/(mol?h)，and the obtained polymers were linear high density polyethylene, with Mν = 4.8—9.5 × 104，PDI = 4.5, Tm = 136—138 °C.

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INDUSTRIAL APPLICATION OF TWO NOVEL C8 AROMATICS ISOMERIZATION CATALYSTS

2012, 43(8):  48-52. 

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The industrial application of two C8 aromatics isomerization catalysts, RIC-200 developed by Research Institute of Petroleum Processing and an imported catalyst represented the advanced world level, was introduced. The start-up, performance test and long-term operation of these two catalysts were compared. Industrial application results show that these two catalysts all exhibit good isomerization activity and stability; the conversion of ethylbenzene, C8 hydrocarbons yield and selectivity of RIC-200 are slightly better than those of the imported catalyst. Besides, RIC-200 catalyst is in reduced state, thus its start-up procedure is simple and the start-up period is shorten; its operation risk is low and more stable due to without water injection to adjust catalyst activity during operation.

STUDY ON THE REACTION RULES FOR AROMATIZATION OF ALKANE OVER Zn-Pt-Re/ZSM-5 CATALYST

2012, 43(8):  53-58. 

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The reaction rules for aromatization of alkanes having various carbon number and structure over Zn-Pt-Re/ZSM-5 catalyst were studied on a continuous flow micro-reactor device and using n-hexane, n-heptane, n-octane, methylcyclohexane and cyclohexane as probe molecules. The aromatization performance of alkane over Zn-Pt-Re/ZSM-5 catalyst and conventional reforming catalyst CB-8 was compared. Test results show that when reaction temperature is less than 450℃, the sequence of generating aromatization reactions from hard to easy is n-hexane, cyclohexane, methylcyclohexane, n-heptane and n-octane; when the reaction temperature is over 450℃, the aromatics yields of alkanes tested are all more than 90％. It is also found that the aromatization mechanism of alkane over CB-8 catalyst and Zn-Pt-Re/ZSM-5 catalyst is different: over CB-8 catalyst, alkane is turned into cycloalkane by dehydrocyclization firstly, followed by further dehydrogenization to form aromatics; over Zn-Pt-Re/ZSM-5 catalyst, two possible reaction pathways may exist, one is the same as over CB-8 catalyst, the other is alkanes crack to form light olefins firstly, followed by reactions including polymerization, cyclization and dehydrogenization to form aromatics, and it seems that the latter is the main one.

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HYDROCRACKING PERFORMANCE OF SMALL CRYSTAL SIZE ZEOLITE Y CATALYST

2012, 43(8):  59-62. 

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Hydrocracking catalyst containing small crystal size zeolite Y was prepared and its hydrocracking performance processing heavy oil was studied using a single stage device with two fixed-bed reactors in series. The effects of reaction temperature, liquid hourly space velocity (LHSV) and nitrogen content of hydrotreated feed on the cracking performance of catalyst were investigated, as well as the stability of catalyst was examined. Results showed that under the same reaction conditions, compared with conventional zeolite Y catalyst, using small crystal size zeolite catalyst the conversion of feed could be higher 3.5 percentage points. Results also showed that with the increase of reaction temperature, the conversion of feed increased; under constant conversion, the effect of LHSV on product distribution and product quality was little; the increase of nitrogen content in hydrotreated feed had negative effect on product yield and quality. During the long-term stability test, from 360 h to 2 160 h, the reaction temperature only increased 2 oC, and the distributions of products basically unchanged, which indicated that the operation stability of small crystal size zeolite Y catalyst was excellent.

STUDY ON THE ALKYLATION OF THIOPHENIC SULFUR CONTAINING COMPOUNDS IN FCC GASOLINE WITH HY CATALYST

2012, 43(8):  63-67. 

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The alkylation of olefins with thiophenic sulfur containing compounds in FCC gasoline using HY zeolite catalyst was studied. The effect of reaction temperature and reaction time on the alkylation reactions, the changing of sulfur existing forms and hydrocarbon compositions prior and post to reactions was investigated. Test results showed that with HY zeolite catalyst, under a reaction temperature of 130℃ and a reaction time of 60 min, about 90.98% of the sulfur containing compounds in the light fraction (＜120 ℃) were transferred to the heavy fraction (＞120 ℃). Combined process of this alkylation technique with hydrofining process was compared with the selective hydrodesulfurization (RSDS) process, it was found that this combined process could release the load of heavy fraction hydrofining due to higher cut point, the sulfur content of light fraction reduced and the octane loss of gasoline was less.

PREPARATION AND CHARACTERIZATION OF SO42-/SnO2-Nb2O5 SOLID SUPERACID CATALYST

2012, 43(8):  68-72. 

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SO42-/SnO2-Nb2O5 solid superacid catalyst was prepared by azeotropic dechlorination method, using n-butanol and anhydrous alcohol as solvents, a filtration step could be omitted, and thus the catalyst preparation time was much shortened. The prepared catalyst was characterized by XRD, FT-IR, TG-DTA and its catalytic performance was evaluated using isomerization of α-pinene as probe reaction. Test results showed that the optimum preparation conditions of SO42-/SnO2-Nb2O5 solid superacid catalyst were as follows: a Nb2O5/SnO2 mass ratio of 0.25, the concentration of impregnating sulfuric acid solution was 0.50 mol/L and calcined at 500 ℃ for 2.0 h; catalyst prepared under such conditions exhibited good catalytic performance in isomerization of α-pinene, the conversion of α-pinene and selectivity of camphene was 100% and 66.49%, respectively. Compared with other preparation methods, such as precipitation and sol-gel methods, catalyst prepared by azeotropic dechlorination method was better.

OPTIMIZATION OF ENERGY UTILIZATION FOR CONVERSION SYSTEM OF HYDROGEN PRODUCTION UNIT

2012, 43(8):  73-76. 

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The optimization and application of energy saving and consumption reduction measures for the conversion system of the 2nd hydrogen production unit in Karamay Petrochemical Company were introduced. By reducing the natural gas consumption in fuel gas, enhancing the recovery efficiency and utilization rate of residual heat from flue gas and reforming gas, as well as increase the amount of byproduct steam, the energy consumption of the unit was improved significantly, a 48 445.64 MJ/h reduction was obtained. The long-term running showed that the unit was operated smoothly and economically with all the qualities indexes in well control.

EFFECT OF SURFACTANTS ON PETROLEUM DEGRADATION BY WHITE ROT FUNGI

2012, 43(8):  77-81. 

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The effect of six surfactants (Tween80, Triton X-100, LAS, SDS, SAS, complex of SDS and dodecanol) on petroleum degradation by Phanerochaete chrysosporium in solution and soil-water system was studied. Results show that the type and concentration of surfactants, biodegradability and the existing state of petroleum contaminant all have impact on the degradation of petroleum. The degradation of petroleum by white rot fungi in both solution and soil system could be promoted by non-ionic surfactant and anionic surfactant in certain extent. In the solution system, the degradation rate of petroleum reduces with the increase of initial surfactant concentration, Tween80 surfactant at a concentration of 0.2 CMC shows the best performance, a degradation rate of 62.2%. Whereas TRITON X-100 surfactant at a concentration of 5 CMC exhibits the best performance in soil system, the degradation rate of petroleum reaches 60.17%.

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SELECTION AND APPLICATION OF ANALYTICAL METHODS FOR BOILING RANGE DISTRIBUTION OF PETROLEUM FRACTIONS BY GAS CHROMATOGRAPHY

2012, 43(8):  82-87. 

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Four standard test methods for determining the boiling range distribution of petroleum fractions by gas chromatography were compared, and data correlations of these standard test methods were studied as well. The test results of these four standard methods were basically in good agreement. ASTM D2887 method is simple, fast and with good precision for analyzing petroleum fractions in the boiling range of 55.5℃—538℃. ASTM D7500 method having wide measurement range is preferred to determine petroleum fractions, such as various lubricating oils, VGO and other heavy petroleum fractions. The effect of film thickness of capillary column on the determination result was also discussed. When testing heavy oil sample containing over n-C100 hydrocarbons, capillary column with film thickness of 0.1 μm is suggested to be used for better determination results.

STUDY ON THE FAST EVALUATION METHOD FOR SELECTING FCC SLURRY ANTIFOULANT IN LABORATORY

2012, 43(8):  88-91. 

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A method for fast evaluating the performance of FCC slurry antifoulant in laboratory is introduced. Using an autoclave with stirring, the suitable test conditions are obtained by orthogonal tests as follows：an antifoulant added amount of 100 mg/L, heat to 500 ℃and hold for 4 h. The test results obtained by this modified static evaluation method are compared with those from the dynamic simulation method, and their trends of ranging antifoulants by fouling inhibited rates are in good agreement, which indicates that this method could be used to fast evaluate slurry antifoulant in laboratory.

ADVANCES IN RESEARCHES ON AQUATHERMOLYSIS CATALYSTS FOR HEAVY CRUDE OILS

2012, 43(8):  92-97. 

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Catalytic aquathermolysis is one of the most potential recovery technologies for heavy crude oils. Advances in researches on aquathermolysis catalysts for heavy crude were summarized based on the importance and necessity of catalytic aquathermolysis for heavy crude recovery. Various catalysts were introduced in accordance with the development of techniques, and the develop tendency of catalyst and process was discussed as well. It seems that developing high activity catalyst system to conduct aquathermolysis of heavy crude under moderate reaction conditions is still the main research target; besides, combining aquathermolysis catalysts with other viscosity reduction methods and developing integrated complex viscosity reducing technologies to exploit synergetic effect should also be focused.

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RESEARCH HEADWAY OF SULFUR RECOVERY AND TAIL GAS HYDROGENATION CATALYSTS

2012, 43(8):  98-104. 

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The reaction mechanism, preparation, classification and characteristics of catalysts for sulfur recovery and tail gas hydrogenation are reviewed. Some application results of main commercial catalysts worldwide are compared. It can be briefly summarized that multi-functional sulfur recovery catalyst having leakage O2 protection function and organic sulfur hydrolysis function, also exhibits good Claus reaction activity and high resistance to sulfation; novel low temperature Claus tail gas hydrogenation catalyst due to having high activity could reduce reaction temperature and energy consumption, thus, less investment, good environmental and economic benefit could be provided. To optimize sulfur recovery production, from the economic point of view, the most effective solution is to develop series of all-purpose catalysts.