Table of Content

12 July 2016, Volume 47 Issue 7

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DEVELOPMENT AND COMMERCIAL APPLICATION OF IHCC TECHNOLOGY FOR MAXIMIZING LIQUID YIELD

2016, 47(7):  1-8. 

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From 2007 to 2015, IHCC process (Integration of FCC Gas Oil Hydrotreating and Highly Selective Catalytic Cracking for Maximizing Liquid Yield), after process development and industrial test, completed a series of technical consideration, pilot plant experiments, basic and engineering design, key equipment development, as well as construction and start-up of industrial unit, industrial test plan formulation and calibration work. The commercial tests of IHCC disclose that compared with conventional FCC process, the liquid yield can be increased by 10.04 percentage points and coke yield decreased by over 20% , respectively using hydrotreated residue as feedstock, while liquid yield can be increased by 6 percentage points using paraffinic AR feed. The successful development of IHCC technology shift the refining technology from pursuing high conversion to high selectivity, leading to efficient utilization of oil resources, and reduction of CO2 emission and energy saving for SINOPEC.

APPLICATION OF GARDES TECHNOLOGY FOR PRODUCTION OF GASOLINE MEETING NATIONAL EMISSION STANDARD PHASE V

2016, 47(7):  9-13. 

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The production of gasoline meeting the national emission standard phase V using GARDES HDS technology in Daqing Petrochemical Co. was introduced. By the GARDES technology, the sulfur content in the product can be reduced to 5 μg/g, mercaptan and olefin content (φ) can be reduced to 4 μg/g and 30.1%, respectively. The RON loss is 1.3. The product meets the requirements of the national emission standard phase V.

TECHNICAL TRANSFORMATION OF ETHYLENE ENRICHMENT UNIT FOR PROCESSING CATALYTIC REFORMING PSA DESORPTION GAS

2016, 47(7):  14-17. 

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The technical transformation of ethylene enrichment unit for dry gas with a capacity of 30,000 m3/h in PetroChina Sichuan Petrochemical Co., was conducted to process PSA desorption gas of catalytic reforming unit. The heavy component (≥C3) in the desorption gas is up to 13.52%, far more than the design value of 3%, that makes more condensate in the ethylene enrichment unit. The condensate is mainly composed of C3-C5 components and a small amount of water. An additional pipeline with heat tracer was set for delivering the condensate to the catalytic cracking unit for recycling. The results after revamping show that C2 and C2 above components in the gas can effectively be recovered, and at the same time the impurities of H2S，CO2 and O2 were removed. The ethylene enriched gas is a qualified feed for ethylene unit, and the net profit reaches 50.63 million Yuan/a after transformation.

APPLICATION OF COKE POWDER REMOVAL TECHNOLOGY FOR SOUR WATER IN DELAYED COKER

2016, 47(7):  18-20. 

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The delayed coker in Lanzhou Petrochemical Co. produces normally 5-8 t/h sour water with coke powder content (w) about an average of 0.2%. The powder is easy to be deposited on the trays of the acid water treatment device, resulting in sour water stripper tray jam and suspension of the unit. In order to solve the problem, the acid water treatment unit was revamped by adopting a powder removal technique. The coke powder removal rate reaches more than 91% after the revamping, leading to a long period running of downstream device.

EFFECT OF AMMONIA ON SELECTIVE HYDROGENATION PERFORMANCE OF POLY-AROMATICS ON Ni-Mo-W/ Al2O3 AND Co-Mo/ Al2O3 CATALYSTS

2016, 47(7):  21-26. 

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The effect of ammonia on poly-aromatic selective hydrogenation saturation was studied with Ni-Mo-W/γ-Al2O3 and Co-Mo/γ-Al2O3 catalysts using LCO as a feed. The results indicate that the introduction of NH3 reduces slightly the saturation rate of poly-aromatics, and affects the mono-aromatics selectivities on different types of catalysts. At the same saturation rate of poly-aromatics, the ammonia addition increases the mono-aromatic selectivity for Ni-Mo-W catalyst, but no effect on HDN reaction is found; while for Co-Mo/γ-Al2O3 catalyst, no influence on the mono-aromatic selectivity is observed but significant inhibition of HDN reaction when increasing NH3 concentration. It is concluded that adding NH3 can improve selectivity for mono-aromatic on Ni-Mo-W/γ-Al2O3 catalyst.

CO-PROCESSING TECHNOLOGY OF CATALYTIC CRACKING OF HEAVY BIO-OIL AND VGO FOR PRODUCING GASOLINE WITH HIGH OCTANE NUMBER

2016, 47(7):  27-31. 

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Heavy bio-oil, the by-product from synthesis of biodiesel using two-step process with solid acid and alkali catalysts, was characterized by infrared spectroscopy and high-resolution mass spectrometry. The heavy bio-oil is mainly composed of high boiling point alcohols, ketones, esters and ethers with oxygen atoms number ranging from 1 to 12. The oxygenated compounds in the heavy bio-oil are converted to hydrocarbon by dehydration, decarbonylation and decarboxylation reactions. Compared with the single VGO feed, more aromatics are obtained by co-processing the mixed raw material of bio-oil (20%) and VGO, resulting in higher octane number of gasoline, but a little more dry gas and coke yields. The experiments indicate that the heavy bio-oil can be a promising alternative supplemental raw material for catalytic cracking unit, and the co-processing technology can convert the by-product to hydrocarbon products with high value and expand the source of catalytic cracking feedstock with lower cost.

EFFECT OF ASPHALTENE ON VISCOSITY OF VISCOUS OILS

2016, 47(7):  32-37. 

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Six kinds of Xinjiang heavy oils were used as the main research objects. The basic compositions and properties of the heavy oils were determined. The homologous and heterologous blended heavy oils were prepared with different contents of asphaltenes to study the influence of content of asphaltene on viscosity of blended heavy oils by viscosity method. The results show that the viscosity of both of homologous and heterologous heavy oils increases as asphaltene content increases; the viscosity increases sharply when the asphaltene content reaches a certain value. At the same temperature and asphaltene content, the viscosity of heavy oil treated by tetrahydrofuran is higher than that by methylbenzene. The extent of viscosity increase of the oils treated by tetrahydrofuran is larger than that by methylbenzene.

PREDICTION MODEL FOR ENGLER DISTILLATION DATA OF BLENDED GASOLINE

2016, 47(7):  38-42. 

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The Engler distillation data (ASTM distillation) of single gasoline in some refinery were used to predict the ASTM distillation results of blended gasoline by single gasoline distillation model and components linear model. The parameters of the single gasoline model were solved by LM method and their correlations were analyzed. The ASTM distillation data of the blended gasoline were obtained by using golden section method and compared with the experimental data to verify the reliability of the predictive method. Most of the data errors are within ±3 ℃, indicating the feasibility of this method for prediction of ASTM distillation of blended gasoline.

EFFECTS OF THICKER AMOUNT ON RHEOLOGY OF LITHIUM GREASE

2016, 47(7):  43-47. 

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To study the influence of thicker amount on the rheological properties of lithium grease, the rheological parameters of lithium grease were tested under conditions of steady shear flow and slight oscillation shear flow. By analyzing rheological parameters such as the thixotropy, yield stress and apparent viscosity, storage modulus and strain amplitude, the influences of thicker amount on rheological property were discussed. The results indicate that with increasing thicker content, the viscoelasticity of lithium grease is more significant, the structure of lithium grease is more stable.

EFFECTS OF THERMAL STABILIZERS ON DETERIORATIVE SULFOLANE AND APPLICATION OF SPSS SOFTWARE

2016, 47(7):  48-52. 

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The effects of four different stabilizers (2,4-di-tert-butylphenol, triethanolamine, dilauryl thiodipropionate and copper stearate) on the thermal stability of deteriorative sulfolane were investigated. At the conditions of sulfolane 100 g, N2 flow rate of 95 mL/min，240 ℃ and reaction time of 2 h, the thermal stabilities of deteriorative sulfolane were evaluated based on the release amount of SO2. The results show that the descending order of the influence of the additives on the thermal stability of deteriorative sulfolane is: 2,4-di-tert-butylphenol > triethanolamine > dilauryl thiodipropionate > copper stearate. When 2,4-di-tert-butylphenol dosage is 0.12% of deteriorative sulfolane, the release amount of SO2 is 331.04 mg, indicating the best effect for inhibiting thermal decomposition of sulfolane. A relationship between 2,4-di-tert-butylphenol dosage and the release amount of SO2 was established using SPSS software, which can be used for predicting the effect of the additive dosage on the thermal decomposition of sulfolane in the experimental range.

CONTROLLABLE HYDROTHERMAL SYNTHESIS OF NICKEL PHOSPHIDE MICRO/NANO-MATERIALS

2016, 47(7):  53-56. 

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Ni12P5 and Ni2P were controllably prepared by thermal synthesis using non-toxic red phosphorus instead of white phosphorus, and nickel nitrate at initial mole ratio of Ni/P. The adsorption capacities for Pb2+ and Cd2+ of the phosphides obtained were tested. The results show that at synthesis conditions of 120 ℃ and 12 h, the phase structure of the phosphide is transformed from the tetragonal Ni12P5 to the hexagonal Ni2P with increasing the initial P/Ni mole ratio. The later has a higher heavy metal adsorption capacity. The removal rate of Ni12P5 for Pb2+ and Cd2+ in solution are 83.13% and 52.59%, respectively. While for Ni2P, the removal rate reaches 89.33% and 56.57%, respectively.

DEVELOPMENT OF TOR-1 CATALYST FOR REMOVING OLEFINS IN REFORMATE

Gao-shan ZANG Aizeng Ma

2016, 47(7):  57-60. 

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TOR-1 catalyst composed of special molecular sieve as a main active ingredient was developed for removing olefins from reformate or mixed aromatic hydrocarbons. The catalyst evaluation results show that the industrial scaled-up catalyst TOR-1 has a better performance in olefin removal, stability and regeneration，compared with clay and the contrast catalyst R.

INVESTIGATION OF S Zorb CATALYST WITH LOW NICKEL LOADING

2016, 47(7):  61-64. 

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A series of S Zorb catalysts with low nickel loading was prepared by impregnation method using nickel nitrate or nickel acetate as precursor, and the catalysts were evaluated in a small fixed fluidized bed reactor to investigate the effect of the Ni loading and the source of nickel on the desulfurization performance and the octane number retention ability. The results show that under the condition of the same nickel loading, the catalysts prepared with nickel acetate have a larger specific surface area, better metal dispersion，higher initial and stable activity, and much lower octane number loss.

CHARACTERIZATION OF NiMoP/γ-Al2O3 CATALYSTS WITH DIFFERENT LOADINGS AND ITS HYDROTREATING PERFORMANCE OF GAS OIL

2016, 47(7):  65-70. 

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The NiMoP/γ-Al2O3 catalysts with different metal loadings were prepared by vacuum incipient wetness impregnation method. The catalysts were characterized by BET, XRD, H2-TPR, TPS, and HRTEM, and evaluated in terms of their performance in hydrotreating of gas oil. The results show that the catalyst with metal loading of 30% has the maximum number of active sites, the best active phase structure, and pore structure, leading to the most outstanding gas oil hydrotreating performance.

EFFECT OF CALCINATION TEMPERATURE ON PERFORMANCE OF HZSM-5 CATALYSTS IN METHANOL TO GASOLINE

2016, 47(7):  71-75. 

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Using NaZSM-5 zeolite as raw material, the HZSM-5 catalysts were prepared by ion exchange method and characterized by XRD, FT-IR, and N2 adsorption-desorption. The effect of calcination temperature on the catalytic performance for methanol to gasoline (MTG) reaction was investigated in a micro-fixed bed reactor. The results show that the calcination temperature has an evident influence on the catalytic performance of the HZSM-5 catalysts. With increasing calcination temperature, the catalyst activity decreases as part of the channel in the HZSM-5 catalysts are blocked and the acid sites rapidly reduced. The HZSM-5 catalysts calcined at 550 ℃ exhibit a higher specific surface area of 351.1 m2/g, and higher pore volume of 0.311 cm3/g and pore diameter of 3.20 nm, leading to an optimal methanol conversion, gasoline yield and aromatics selectivity.

OXIDATION STABILITY AND TRIBOLOGICAL PROPERTIES OF LUBRICATING OIL WITH MoDDP ADDITIVE

2016, 47(7):  76-81. 

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The PDSC, crankcase simulation test and four ball tests were employed to investigate the oxidation stability and triboligical properties of lubricating oil with MoDDP additive. The oil samples before and after the crank simulation test and the worn scar surfaces were characterized by FTIR, ICP, UV fluorescence sulfur determinator, SEM, and EDS techniques. The results show that MoDDP additive has a good anti-oxidation ability that effectively enhances oil initial oxidation temperature and lower the oxidation extent of oil in the crankcase simulation test. It is found that the addition of MoDDP cause obvious deposits at high temperature in crankcase simulation test and that the triboligical properties of oil samples decrease significantly after crankcase simulation test. The element analysis indicates that the characteristic elements of MoDDP (S, P, Mo) are important components of deposits. The results of element analysis of oils and worn scar surfaces characterization suggest that the loss of element S, P, Mo in oil samples during test is the main reason.

CHARACTERIZATION OF METHYL-BENZOTRIAZOLE AMINE SALT

2016, 47(7):  82-85. 

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The granular methyl-benzotriazole and liquid fatty amine were used as raw materials for synthesis of methyl-benzotriazole amine salts. The sample was characterized by FT-IR, gas chromatography, elemental analysis and VPO molecular weight techniques. The basic properties of the samples were investigated in terms of solubility, copper corrosion and four ball machine tests. The results show that the synthesized methyl-benzotriazole amine salt has higher purity, better performance in low temperature oil solubility, corrosion inhibition and wear resistance than benzotriazole amine.

TRIBOLOGICAL PROPERTIES OF LITHIUM GREASE WITH LAYERED ZIRCONIUM PHOSPHATES

2016, 47(7):  86-91. 

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The tribological properties of the lithium grease with layered α-zirconium phosphates (α-ZrP and Cu-α-ZrP) additives were evaluated on steel-steel friction pair with a four - ball tester. The worn surfaces were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) and 3D optical profiler to investigate the worn surface morphology, element composition and bulk worn loss. The results show that both of α-ZrP and Cu-α-ZrP can exhibit a good performance of the lithium grease in anti-wear and anti-friction and bearing load-carrying capacity under extreme pressure. The protective film formed on the worn surface during the friction process mainly contains α-ZrP or Cu-α-ZrP, leading to a good tribological performance.

CORROSION IN HIGH PRESSURE HEAT EXCHANGERS OF HYDROGENATION UNIT AND COUNTERMEASURES

2016, 47(7):  92-95. 

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To solve the ammonium salt deposition and corrosion problems caused by Cl- in high pressure heat exchanger of hydrogenation unit, the source of chloride and the causes of corrosion were investigated. Based on the analysis, a series of measures was adopted: (i) adding intermediate feed tank to reduce water content in feed, (ii) increasing system pressure, (iii) increasing circulating hydrogen flow, (iv) raising the outlet temperature of heat exchanger E2101B, (v) increasing the water injection amount before heat exchanger E2101A/B, and (vi) reducing the total amount of injection water to the design range. After the complementation of the measures, the problems were effectively controlled, and the energy consumption of hydrogenation unit reduces from 596.87 MJ/t to 451.44 MJ/t.

APPLICATION OF PIMS ON CRUDE SELECTION DURING OVERALL CONFIGURATION OPTIMIZATION OF REFINERY

2016, 47(7):  96-100. 

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The configuration optimization of a grassroots 10 Mt/a refinery is selected as a case study. Saudi Arabian heavy crude oil (hereinafter referred to as AHC) and Saudi Arabian medium crude oil (hereinafter referred to as AMC) are studied respectively through setting up PIMS model, assessing the influence of crude on overall configuration and economic benefit. The result shows that AMC, which has lower density and better properties, not only improves the feed properties of RDS unit, e.g. lower content of heavy metals and asphaltene，but also achieves higher light oil yield (91.80%) and general commodity rate (79.81%). However, the refining margin of AMC is 53.5 Yuan per ton crude lower than AHC due to higher purchase cost. Considering the development tendency of crude refining, AHC is recommended to be the design crude, which can achieve better economic benefit and compatibility with AMC.