PETROLEUM PROCESSING AND PETROCHEMICALS

REFINING TECHNOLOGY ADVANCES SHAPED BY LEGISLATION AND ECONOMIC ISSUE-Outlines of 2011 NPRA Annual Meeting

2011, 42(9): 1-8. doi:

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This article reviews the 2011 NPRA Annual Meeting where the impact of legislative and economic factors on US oil refining industry is thoroughly discussed with its potential effect on green house gases emission, fuel specification requirements and market demands. Selected advances in mainstream refining technologies presented in the conference are briefed in the paper as well, which includes developments in FCC technology and operation, hydroprocessing process, hydrogen production technology and management, renewable fuels production. It is noted that more and more stringent environmental regulations and continuous global economic recession are imposing new challenges for refining industry and shaping the development of future refining technologies.

STUDY ON THE KINETICS OF OLEFIN SATURATION DURING SELECTIVE HYDRODESULFURIZATION OF FCC NAPHTHA

Hong Nie

2011, 42(9): 9-12. doi:

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The kinetics of olefin saturation during selective hydrodesulfurization of FCC naphtha was studied by a pilot plant device. The results showed that the reaction rate constant of olefin hydro-saturation decreases with the increase of olefin's carbon number. Under the same reaction conditions, the saturation rate of olefin decreases with the carbon number firstly, then trends to increase. The hydro-saturation reactions of total olefin, linear olefin, branched olefin and cyclic olefin all belong to one order reaction. The hydro-saturation reaction rate constants of linear olefin and branched olefin are greater than that of cyclic olefin, besides, as compare with branched olefin the reaction rate constant of linear olefin is more sensitive to temperature.

RESEARCH ON THE RELATIONSHIP OF GASOLINE STORAGE STABILITY AND HYDROCARBON GROUP COMPOSITIONS

2011, 42(9): 13-18. doi:

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Gasoline is composed of various kinds of hydrocarbons, including n-alkane, isoparaffin, naphthenic hydrocarbon, aromatic hydrocarbon, isoolefine, normal olefin, cyclic olefin and diolefin. Correlation analysis method is adopted to investigate the interrelation of various kinds of hydrocarbons in gasoline blending components or gasoline products and the gasoline storage stability indexes. Furthermore, a regression model of storage stability indexes and hydrocarbon group compositions is established by stepwise linear regression method. According to the regression model the main hydrocarbon compounds affecting the indexes of gasoline storage stability are as follows: aromatic hydrocarbons greatly influence the octane number, 10% evaporating temperature, 50% evaporating temperature, density and colourity; olefins, especially isoolefine and normal olefin, influence 90% evaporating temperature, acidity, gum, induction period, iodine value and saturated vapor pressure most. The results of F inspection show that the regression model with high significant can be used to predict the storage stability of domestic gasoline product.

SYNTHESIS OF POLYPROPYLENE CATALYST INTERNAL DONOR 1,1-CYCLOPENTYL DIMETHANOLDIMETHYL ETHER

xu zhao-hui

2011, 42(9): 19-22. doi:

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1,1-Cyclopentyl dimethanoldimethyl ether was synthesized from diethyl malonate and 1,4-dibromo butane by alkylation, ester reduction and etherification. The key factors affecting reactions were studied and the optimal reaction conditions were found as follows: (1) for alkylation, using CsOH as catalyst, n(diethyl malonate):n(CsOH):n(1,4-dibromo butane)=1.0:2.2:1.4, the yield of cyclobutane-1,1-dicarboxylic acid diethyl ester was 93.0%; (2)for ester reduction, using anhydro-ZnCl2 as catalyst, n(cyclopentyl-1,1-dicarboxylic acid diethyl ester):n(KBH4)=2.0:1.0, the yield of 1,1- cyclopentyl dimethanol was 88.1%; (3)for etherification, using tetrabutyl ammonium bromide as catalyst, n(1,1-cyclopentyl dimethanol)∶n(NaOH)∶n(dimethyl carbonate)=1.0∶8.0∶2.4, the yield of 1,1- cyclopentyl dimethanoldimethyl ether was 61.2%. The total yield of the objective product was 50.1% based on diethyl malonate.

TRANSALKYLATION OF BENZENE AND 1,2,4- TRIMETHYLBENZENE OVER NANOSIZED HZSM-5

2011, 42(9): 23-26. doi:

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In this present study, nanosized HZSM-5 was treated by tetraethoxysilane and pyridine respectively to study the effect on the reactions in benzene and 1,2,4-trimethylbenzene (1,2,4-TMB) system. It was found that the primary reactions such as transalkylation of benzene and 1,2,4-TMB, dealkylation of 1,2,4-TMB and isomerization of 1,2,4-TMB occurred at the acid sites of the external surface and pore opening near by. Secondary reactions such as dealkylation of xylenes, transalkylation of benzene and xylenes occurred at acid sites of the internal surface. These reactions were catalyzed by Br?nsted acid sites.

APPLICATION OF MIP TECHNOLOGY IN FCC UNIT PROCESSING PARAFFINIC FEEDSTOCK

Zhiming Wan,Weiqing Wang,Kaiqi Li

2011, 42(9): 27-32. doi:

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MIP technology was successfully applied in the 2nd FCC unit of Daqing Petrochemical Company processing paraffinic feedstock. The properties of naphtha, LCO and slurry oil prior and post to revamping of MIP technology were compared by performance test and daily production data. Results showed that MIP technology could effectively control cracking reactions, enhance hydrogen transfer and aromatization reactions, thus the olefin content of naphtha was decreased significantly. Under gasoline production mode, the yield of total liquid products reached 83.44%, in which stabilized naphtha having volumetric olefin content of less than 30% and RON of over 90.

STRATEGIES FOR IMPROVING THE ECONOMIC EFFECT OF A REFINERY WITH FCC UNIT AS KEY UNIT

2011, 42(9): 33-36. doi:

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To improve the economic benefits of a 10 Mt/a refinery with FCC unit as one of the key units, various optimization measures were applied including deep vacuum distillation, using hydrotreated diesel as partial FCC feedstock and adopting less severe FCC reaction conditions. Since then a 273.03 million RMB economic effect was obtained annually, this case study could be a reference for other refineries to enhance refining economic benefit.

AQUATHERMOLYSIS OF SHENGLI EXTRA-HEAVY CRUDE OIL FOR VISCOSITY REDUCTION WITHOUT DESALINATION

2011, 42(9): 37-42. doi:

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Shengli extra-heavy crude oil was aquathermolysis treated under low temperature with the aim of reducing its viscosity for better gathering and transferring. Analyses of viscosity, elemental composition, SARA (saturates, aromatics, resins and asphaltines), fraction distribution and salt content of crude samples treated under various aquathermolysis conditions were carried out. It was found that the viscosity of Shengli extra-heavy crude could be significantly reduced by aquathermolysis treatment, and the viscosity of the treated crude was heavily depended on the cracking conversion. The cracking conversion of extra-heavy crude could be enhanced by adding catalyst, increase aquathermolysis temperature and time effectively. With the presence of suitable catalyst, the treated temperature was lower and treated time was shortened. Using a coke base porosity catalyst A, under the conditions of an aquathermolysis temperature of 330℃ and a treated time of 60 min, the cracking conversion reached 30.11%, the viscosity of Shengli extra-heavy crude was dropped to 1 536 mPa·s from the original of 52 410 mPa·s, a viscosity reduction rate of 97.07% was obtained. The fluidity of the treated crude was improved significantly and it can be gathered and transferred as conventional crude, which indicates that the application of aquathermolysis in the field of pipeline transporting heavy crude is promising.

CATALYTIC OXIDATIVE DESULFURIZATION OF THIOPHENE OVER CATALYST OF PHOSPHOTUNGSTIC ACID SUPPORTED ON ZINC FERRITE

juan wang,qingguo yao

2011, 42(9): 43-46. doi:

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Using H2O2 as oxidation agent, oxidation/extraction desulfurization of thiophene containing model compound over catalyst of phosphotungstic acid supported on zinc ferrite was investigated including the effect of oxidation agent amount, oxidation temperature and time, the amount of phosphotungstic acid on catalyst and catalyst activation temperature on the desulfurization rate. Results showed that using catalyst activated at 250℃ and having an optimal phosphotungstic acid mass fraction of 13%, under the optimum conditions of a reaction temperature of 40℃, a reaction time of 210 min and H2O2/S molar ratio of 5, the sulfur removal rate of thiophene reached 90.1%.

INDUSTRIAL APPLICATION OF LCC-300 CATALYST FOR ENHANCING PROPYLENE YIELD IN TWO-STAGE RISER CATALYTIC PYROLYSIS OF HEAVY OIL

2011, 42(9): 47-50. doi:

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LCC-300 catalyst was developed for the two-stage riser catalytic pyrolysis of heavy oil based on analyzing the characteristics of said pyrolysis process. The evaluation tests of LCC-300 catalyst were carried out on a single riser reaction device to simulate the two-stage riser catalytic pyrolysis using atmospheric residue (AR) as feedstock. Test results showed that the total liquid yield reached 80.08%, in which propylene yield was 22.27%, and the obtained naphtha was high in aromatics and low in olefins, which could be a high octane gasoline blending component. The industrial application of LCC-300 catalyst was conducted on TMP industrial trial unit, mixed C4 and Daqing AR were used as combined feedstock for 1st stage riser, 2nd stage riser used a combined feedstock of recycle light naphtha, recycle oil and recycle slurry. The results of performance test showed that the total liquid yield reached 82.95%, in which propylene yield was 20.38%, and the yield of dry gas and coke was only 13.99%, which indicated that LCC-300 catalyst was good at increase propylene yield and decrease the formation of dry gas and coke.

EFFECT OF ORGANIC ACIDS ON THE PROPERTIES OF NiW/Al2O3 HYDRODESULFURIZATION CATALYSTS

2011, 42(9): 51-55. doi:

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NiW/Al2O3 catalysts without and with the addition of organic acids, such as butyric acid, succinic acid and citric acid, were prepared and characterized by TPR, XRD, HRTEM and SEM-EDS. The effect of various organic acids on the properties and the hydrodesulfurization performance of NiW/Al2O3 catalysts were investigated. The results showed that the addition of organic acids during catalyst preparation could weaken the interaction between metal species (Ni and W) and support, promote the sulfidation of metal species, increase the stacking layer number of WS2 particular, and reduce the agglomeration of metal species. Thus, the hydrodesulfurization activities of catalysts adding succinic acid and citric acid during preparation were higher than that of catalyst prepared without adding organic acid.

EXPERIMENTAL RESEARCH ON THE PERFORMANCE OF Cu-Zn-Ni/Al2O3 THREE-WAY DESULFURIZER TREATING NATURAL GAS

2011, 42(9): 56-59. doi:

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Cu-Zn-Ni/Al2O3 desulfurizers having Ni contents of 0, 5% and 10% were prepared by co-precipitation and impregnation methods, and their desulfurization performance was studied using natural gas as feed. Test results showed that suitable Ni content could enhance the fine desulfurization performance of desulfurizer, and the fine desulfurization performance enhanced with the reaction temperature to reach a stable stage. Cu-Zn-Ni/Al2O3 desulfurizer having Ni contents of 5% exhibited the best desulfurization performance, under the temperature of 285℃, space velocity of 400, 1 200 and 2 400 h-1, the sulfur content of treated natural gas reached 5, 5 and 6 L/m3, respectively. When the space velocities were 400, 1 200 h-1, the desulfurization performance of Cu-Zn/Al2O3 desulfurizer was better than that of Cu-Zn-Ni/Al2O3 desulfurizer with Ni content of 10%, yet under the space velocity of 2 400 h-1, the results were reversed.

STUDY ON THE HYDROAROMATIZATION OF FULL-RANGE FCC NAPHTHA OVER MoP/ZrO2/HZSM-5 CATALYST

zhaozhao,shi yan

2011, 42(9): 60-64. doi:

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Using HZSM-5 zeolite as support, ammonium molybdate, ammonium biphosphate and zirconium nitrate as the sources of molybdenum, phosphorus and zirconium respectively, an oxidized precursor was obtained by co-precipitation method, and followed by temperature-programming reduction (TPR) to form MoP/ZrO2/HZSM-5 catalyst. The prepared catalysts were characterized by XRD and BET methods. The aromatization tests of full-range FCC naphtha over MoP/ZrO2/HZSM-5 catalysts were conducted on a small-scale fixed bed reactor to investigate the effect of catalyst compositions on the catalytic performance of catalyst. Results showed that optimal aromatization performance was observed with a catalyst containing 25% molybdenum, 10% ZrO2 and having initial Mo/P molar ratio of 1:1.5, under the conditions of a reaction temperature of 360 ℃，a reaction pressure of 2.5 Mpa, a LHSV of 1.0 h-1 and H2/oil volume ratio of 400, the liquid product yield was 92.52 % and this liquid product having an aromatic mass fraction of 38.37 % and an olefin mass fraction of 18.11 %.

PRELIMINARY STUDY ON THE FEASIBILITY OF USING 1-ETHOXYCARBONYLMETHYL-3-METHYL IMIDAZOLIUM TETRAFLUOROBORATE IONIC LIQUID AS LUBRICANT

2011, 42(9): 65-69. doi:

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A new kind of ester-group functionalized ionic liquid, 1-ethoxycarbonylmethyl-3-methyl imidazolium tetrafluoroborate ([EAMIM]BF4), were synthesized. Its physicochemical properties, tribological behavior (at room temperature and 100℃), compatibility and susceptibility to some conventional lube additives were studied and compared with a conventional ionic liquid, 1-butyl-3-methy imidazolium tetrafluoroborate ([BMIM]BF4), which had the same alkyl as the functionalized one. It was found that both ionic liquids had good low-temperature fluidity, low evaporation loss and high thermal stability. Their solubility with most commonly oil-soluble lube additives was poor, except with some having strong polar compounds or with heterocyclic structures, and between these two, [BMIM]BF4 was better. The friction reducing performance of [EAMIM]BF4 was less significant than that of [BMIM]BF4 due to its high viscosity, yet its antiwear ability was better than that of [BMIM]BF4 at both room temperature and 100℃. The addition of antiwear additive di-n-butylphosphite could improve the antiwear performance of [BMIM]BF4, however, negative effect was observed with [EAMIM]BF4.

SYNTHESIS OF LONG CHAIN DIALKYLDITHIOCARBAMATE DERIVATIVES AND THEIR TRIBOLOGICAL PROPERTIES

JIAO Ye-Ye,hongbin zhao

2011, 42(9): 70-74. doi:

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Six environmentally friendly ashless and non-phosphorus long chain dialkyldithiocarbamate derivatives as lubricating oil Six long chain dialkyldithiocarbamate derivatives were synthesized and supposed to be used as environmental friendly ashless and non-phosphorus lube additives. Molecular structures of the prepared derivatives were confirmed by IR, UV-Vis, 1H NMR and 13C NMR. The thermal stabilities and antioxidation performances of theses derivatives were studied using a thermo-gravimetric analyzer (TGA), and their tribological performances as lube additives in liquid paraffin were evaluated with a four-ball testing machine. Results indicate that the synthesized lubricant additives exhibit excellent thermal stability, good load-carrying capacity and anti-wear property.

APPLICATION OF STEAM PIPE NETWORK OPTIMIZATION FOR CONDENSED WATER RECOVERY IN REFINERY

2011, 42(9): 75-77. doi:

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Due to the imperfect steam trap system, serious leakage of steam, less recovery of condensed water happened in Yulin refinery, and the poor quality condensed water could not be used as boiler make-up water as well. By adopting energy saving technology of steam pipe network, which included a combination of back pressure return and pressurized backwater, the condensed water was fully recovered and after fine treatment, it could be used as boiler make-up water. Since then, steam and water resource were saved, the utilization of low temperature heat was improved, operations were stable and production cost was reduced in some extent.

STUDY ON THE DEHYDRATION-DRYING OF OILY SLUDGE FROM SETTLING TANK

2011, 42(9): 78-82. doi:

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A dehydration-drying treatment for oily sludge was proposed using oily sludge from the settling tank of an oilfield sewage plant as research object. The effects of dehydration agents and amount, cationic polyacrylamide (CPAM) dosage, curing agents and amount on the treatment were investigated. It was found that using 2% of an optimal dehydration agent A, under the conditions of adding 200 mg/L CPAM prior to high speed stirring and 400 mg/L CPAM prior to low speed stirring, the water content of dehydrated oily sludge was reduced to 65% from the original of 85%. During the drying tests, adding 5% CaO or mixing with breeze (with a mass ratio of sludge/breeze=1/1.5), drying under sunlight for 3-4 h and calcination at 800 ℃ for 10-15 min, the obtained granules were combustible, thus the oily component in sludge was fully reused.

MEASURES FOR IMPROVING SOUR WATER TREATMENT OF DELAYED COKING UNIT AND SUGGESTIONS

2011, 42(9): 83-86. doi:

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The sour water from fractionating tower of delayed coking unit was seriously emulsified and entraining high amount of coke breeze. To solve the problem, cause analysis was carried out and countermeasures were proposed. By optimization adjusting the amount of injection steam for furnace tubes and ball valves, the total amount of sour water was reduced about 30%. A cationic demulsifier was applied to enhance the demulsification of sour water and an automatic backwashing filter was installed to remove some of the coke breeze. The application results showed that the removal rates of oil and coke breeze were 99.6% and 40%, respectively. The quality of sour water was improved significantly, which was helpful to ensure the stable operation of sewage stripping tower, thus its running cycle was prolonged. Furthermore, the yield of coker gasoline was increased and the environmental pollution was reduced.

THE DESIGN AND APPLICATION OF PROCESS SIMULATION AND OPTIMIZATION SYSTEM IN REFINING PLANT

Xiao-jian Yang,Sun Zhong-Xiao

2011, 42(9): 87-91. doi:

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A simulation and optimization system is designed which integrates multi-software platforms and interfaces. The system collects data from LIMS and PHD then builds models with a block that transfers lump of molecular structure to lump of NBP to realize total process simulation. The quality indexes of products are predicted by intelligent algorithm. User is guided with friendly GUI to make optimization schemes by simple operation. The system ensures the accuracy of simulation while packaging the complex process of data collecting and data processing, simplifying the operation of model with GUI. This process simulation and optimization system is successfully applied in a case study of hydrocracking unit, which validates the convenience and effectiveness of its operatio

CAUSE ANALYSIS OF SCALING-CORROSION IN WATER INJECTION LINE OF LIAOHE OILFIELD AND INHIBITOR APPLICATION TRIAL

2011, 42(9): 92-96. doi:

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Serious scaling and corrosion occurred in the water injection line of Liaohe oil field. Local water and on site scale samples were analyzed. It was found that the water of Liaohe oil field was slightly alkaline, and its saltness, alkalinity, mineralization degree, chloride ion were relatively high, especially the content of calcium cation was much higher than that of other cations. The XRD results of scale samples showed that calcium carbonate was the most, with a little of sulfates, carbonates, silicates and rust. Based on simulation experiments, TH607B scale and corrosion inhibitor was selected for field application trial． When the concentration of TH607B was 45 mg/L, the anti-scaling rate was 90.93%-95.96%, anti-corrosive rate was 90.97%-95.33% and corrosion rate was only 0.04-0.07 mm/a.

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