PETROLEUM PROCESSING AND PETROCHEMICALS

OPTIONS OF TECHNOLOGIES FOR REDUCING BENZENE IN GASOLINE

Ma Aizeng

2009, 40(9): 1-7. doi:

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Based on analyzing the benzene content of blending components in gasoline pool it is concluded that reformate is the key benzene source of gasoline. Technologic approaches for reducing benzene content of reformate are reviewed. It is proposed that selecting the optimum catalytic reformer modes and operation conditions, adopting pre-fractionation to remove benzene and benzene precursors from feed and removing benzene from reformate are the three main approaches to reduce benzene content. Discussions of pre-fractionation and post processing of reformate are conducted in detail including the utilization of light naphtha, isomerazation, benzene saturation, benzene extraction and benzene alkylation. Finally, five processing schemes for reducing the benzene content of reformate from conventional naphtha feed are compared and put forward for refineries to select according to their own requirements.

ENGINEERING DESIGN AND PERFORMANCE TEST OF A 58 000 BPSD DIESEL HYDROFINING UNIT

liu li

2009, 40(9): 8-11. doi:

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The engineering design and performance test of a 58 000 BPSD hydrofining unit in SINOPEC Gaoqiao Company are summarized including an introduction of the process and technology features and a brief analysis of performance test results. The results show that the vapor and liquid are well distributed in the reactor; the desulfurization performance of novel FH-UDS catalyst is excellent, the energy consumption of the unit reaches the advanced domestic level and finally, the qualities of the treated diesel fuels well meet the requirements of diesel fuels for satisfying Europe III/IV exhaust standards.

A DISCUSSION OF THE KARAMAY HEAVY OIL COKING TECHNOLOGY

Zhen Xinping

2009, 40(9): 12-16. doi:

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Based on the operation data of the heavy oil coking unit in Karamay Petrochemical Company, a comparison of heavy oil direct coking process and distillation-coking combine process was carried out. It can be seen that as compared with the combine process, heavy oil direct coking technology exhibited less investment, more cracking of VGO fractions and higher diesel to gasoline ratio, yet higher yields of coke and gas were observed. Because atmospheric tower was omitted in the heavy oil coking unit, energy consumption of the unit and the operation cost in subsequent processes became higher. Since naphthenic acid could be decomposed at high temperature in coke tower, a new idea about anti-corrosion of naphthenic acid was presented and discussed in this paper as well. For reducing energy consumption and saving downstream processing fee, a suggestion of adding an atmospheric distillation tower in the coking unit, adopting indirect heat exchange for residue coking and using carbon steel instead of 316L steel in the distillation system was proposed based on the above analysis. Furthermore, adding a coker gatch stripper could significantly improve the separation of coker gas oil from coker gatch, resulting in less downstream processing fee, and this was realized in this existed unit.

STUDY ON THE PREPARATION OF m-TOLUIC ACID BY OXIDATION WITH OXYGEN UNDER ATMOSPHERIC PRESSURE

SONG Hua

2009, 40(9): 17-21. doi:

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Gas-liquid phase oxidation of m-xylene under atmospheric pressure to prepare m-toluic acid was studied using oxygen as oxidant, cobalt acetate as catalyst and acetic anhydride as solvent. The effect of reaction conditions on the conversion of m-xylene and the yield of m-toluic acid was investigated and optimum conditions were obtained. It was found that under the optimum conditions of a m-xylene amount of 0.5 mL, a catalyst dosage of 0.05 g, a NaBr promoter dosage of 0.02 g, a solvent amount of 20 mL, an oxygen flow rate of 100 mL/min, a reaction temperature of 90℃ and a reaction time of 8 h, the conversion of m-xylene and the yield of m-toluic acid reached 100% and 98.36%, respectively.

A COMPARISON STUDY OF PROCESSES BETWEEN TWO PROPANE DEASPHALTING UNITS

2009, 40(9): 22-26. doi:

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Due to the various properties and yields of deasphalted oil (DAO) produced by two propane deasphalting units (250 kt/a and 800 kt/a) of Karamay Petrochemical Company, a comparison study was carried out for analyzing the process conditions and products properties. It was found that containing excess﹤560℃ components in the DAO of 800 kt/a unit was the main cause of its low viscosity, high yield and poor viscosity index, which was resulted from the differences in processes and operation conditions of the two units. By analyzing the structure of extractors and extraction process, countermeasures for improving the quality of DAO of 800 kt/a unit were proposed, such as enhancing the severity of vacuum distillation to reduce﹤560℃components in vacuum residue feed, increasing the top temperature of extractor and reducing the solvent to oil ratio in extraction.

REACTION CHEMISTRY CONTROL IN DEEP CATALYTIC CRACKING PROCESS FOR MAXIMIZING PROPYLENE YIELD

Chao-Gang Xie

2009, 40(9): 27-31. doi:

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Based on analyzing the reaction chemistry of deep catalytic cracking, a basic idea for producing more propylene while reducing dry gas yield was proposed. The effect of monomolecular reactions and bimolecular reactions on the yields of propylene and dry gas was investigated in a fixed-bed micro-activity test unit using n-hexadecane and Daqing VGO as feedstocks respectively, under various reaction conditions and catalyst types. The results showed that enhancing monomolecular reactions could be favorable for increasing the propylene content in LPG, but the dry gas yield increased significantly. Promoting bimolecular reactions, mainly hydride transfer reactions, to some extent, would be helpful to inhibit the formation of dry gas; however, the high ratio of bimolecular reactions could cause the decrease of propylene yield. Hence, proper adjusting the ratio and/or the sequence of monomolecular reactions and bimolecular reactions might be an effective way for maximizing propylene yield and reducing dry gas yield simultaneously in deep catalytic cracking process.

STUDY ON THE KINETICS OF METHANOL DEHYDRATION TO DIMETHYL ETHER ON ZEOLITE Y

2009, 40(9): 32-36. doi:

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The kinetics of methanol dehydration to dimethyl ether (DME) over zeolite Y was studied in an integral reactor under atmospheric pressure. Based on the reaction mechanism of DME produced from methanol dehydration, four kinetic equations are obtained according to the Langmuir–Rideal (Rideal–Eley) mechanism and Langmuir-Hinshelwood mechanism. A six-parameter kinetic model of methanol dehydration to dimethyl ether over zeolite Y is obtained by data processing, and the calculated values are in good agreement with the test data.

STUDY ON THE SELECTIVE ADSORPTIVE DESULFURIZATION OF FCC NAPHTHA BY MODIFIED ZEOLITE Y

Li-juan Song

2009, 40(9): 37-41. doi:

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NaY zeolite was dealuminated by oxalic acid and ion-exchanged with NH4Cl to form NH4Y. Then HY was obtained by calcining NH4Y, and Ce(IV)Y was prepared by ion-exchanging NH4Y with cerium nitrate solution and calcination. Selective adsorptive desulfurization of FCC naphtha over various zeolite Y samples was conducted and the sulfur contents of naphtha samples were analyzed by microcoulometry. Static adsorption results showed that the sulfur removal rates of zeolite Y samples from high to low were in the order of Ce(IV)Y＞HY＞NaY; sulfur removal rates of Ce(IV)Y and HY were 79.0% and 77.8%, respectively. Kinetic adsorption results showed that dimethylthiophene (DMT) type sulfur containing compounds could be removed by Ce(IV)Y, but could not be removed by HY. The adsorption capacity of the regenerated Ce(IV)Y zeolite reached 95.5% of the fresh one.

STARTUP PERFORMANCE COMPARISON OF SULFURIZED STATE AND OXIDATION STATE RS-1 HYDROFINING CATALYSTS

2009, 40(9): 42-46. doi:

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Two hydrofining catalysts, oxidation state RS-1(O) and sulfurized state RS-1(S), developed by Research Institute of Petroleum Processing were applied in the pre-hydrofining of 1.20 Mt/a CCR unit of SINOPEC Zhenhai Company, and the startups of using these two catalysts were reviewed. The commercial results showed that the hydrofining performances of both catalysts were excellent, the startups were successful and the properties of treated feeds well met the requirements of CCR process. As a comparison, when using RS-1(S) catalyst the startup was less pollutive, less time consuming, more cost saving, more reliable and with simple startup procedure.

EFFECT OF REACTION CONDITIONS ON SELECTIVE HYDRODESULFURIZATION OVER CoMo/Al2O3 CATALYST

2009, 40(9): 47-50. doi:

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Effect of reaction conditions on the selective hydrodesulfurization over an industrial CoMo/Al2O3 catalyst was studied in a fixed-bed flow reactor with model feeds containing sulfur and olefin compounds. The experimental results showed that the olefin hydro-saturation could be reduced by the increase of space velocity, H2/oil molar ratio and the sulfiding temperature of catalyst, as well as by the decrease of hydrogen partial pressure, respectively, which resulted in the improvement of hydrodesulfurization selectivity. In addition, with the increase of olefin content in model feeds, the competitive adsorption of olefin molecules and thiophene molecules on the active sites enhanced, which led to the increase of olefin saturation and the decrease of hydrodesulfurization selectivity.

TRIBOLOGICAL INVESTIGATION OF ORGANIC/INORGANIC COMPOUND COATED NANO-COPPER AS LUBRICATING OIL ADDITIVE

2009, 40(9): 51-54. doi:

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An organic compound coated copper nanoparticles with diameter about 1~7 nm were prepared and suppose to use as lube additive to reduce friction and wear as well as to increase load-carrying capacity. The tribological performance of this additive in HVIWH150 base oil and SJ 5W/30 gasoline engine oil was investigated by four-ball testing machine, respectively. Results showed that said nano-Cu additive could reduce wear and increase load-carrying capacity. When 0.1% nano-Cu additive was added into HVIWH150 base oil, the PB value of the formulated base oil was increased about 30%, and its wear scar diameter was decreased about 50%; SJ 5W/30 gasoline engine oil added 0.1% said additive, its friction coefficient was reduced about 28%. The analysis of the friction surface boundary film revealed that the improvement of antiwear and extreme-pressure properties of the formulated oil was due to the formation of a deposited film by copper nanoparticles having superior ductility.

SYNTHESIS AND CHARACTERIZATION OF DRAG REDUCING COPOLYMER

Chen Wen-Sheng

2009, 40(9): 55-59. doi:

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High efficient drag reducing agent was synthesized by bulk polymerization using TiCl4/MgCl2-Al(i-Bu)3 as catalyst and mixed 1-octene/1-dodecene long chain α-olefins as monomers．The effect of reaction conditions on the drag reducing efficiency of copolymer was investigated and optimum process parameters were obtained. The prepared copolymer was characterized by GPC, 1H-NMR, IR and its drag reducing performance was evaluated by a loop testing system. Test results showed that a polymer obtained at a 1-octene volume ratio of 33% having high molecular weight (Mw=6.58×106, Mn=2.41×106, Mw/Mn=2.73) was well polymerized, and its drag reduction rate at an added dosage of 0.01 Kg/m3 with diesel fuel was up to 52.3%, which indicated that the obtained polymer could be used as drag reducing agent for crude oil.

A STUDY OF RECOVERING GASOLINE VAPOR ON ACTIVATED CARBON

2009, 40(9): 60-65. doi:

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Using activated carbon (AC) to recover gasoline vapor from the mixture of oil vapor and nitrogen was studied. Three AC adsorbents were involved and their pore structures were characterized by nitrogen adsorption measurement. The effect of AC pore structure, the inlet concentration of oil vapor and the size of the fixed bed on the adsorption capacity, as well as the vacuum degree and desorbing time on the desorption capacity were investigated. Results showed that the adsorption capacity of oil vapor on AC was depended on the volume of pores having diameter in the range of 1～2nm. The adsorption capacity of oil vapor could be increased with the increase of inlet oil concentration, yet the breakthrough time was shortened and the temperature rise of the adsorption bed could be extremely high. Large bed size was helpful for the increase of adsorption capacity as well as the extension of breakthrough time and keeping a moderate temperature rise of the bed. Gasoline vapor could be fully desorbed under a lower vacuum degree and a longer time while considering the operation cost simultaneously.

An ANALYSIS OF BIOMARKERS IN CRUDE OIL BY BACKFLUSH CUTTING AND MICROFLUIDIC CHROMATOGRAPHY

Jian Zhou TIAN Songbai

2009, 40(9): 66-70. doi:

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A novel method was proposed for the direct determination of biomarkers, such as n-alkanes, terpanes and steranes in crude oil by GC/MS coupling with backflush cutting technique and micro-fluidic splitter. The variability of 23 n-alkanes, 20 terpanes and 11 steranes was examined and the relative standard deviation (RSD) of retention time were less than 0.02%, while the RSD of peak area of n-alkanes by flame ion detector were in the range of 3.1~6.0%. This method can simultaneously detect mass and flame ion signals with the same retention time, it provides a fast and effective way for the determination of biomarkers in crude oils.

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