Table of Content

12 October 2017, Volume 48 Issue 10

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DIFFUSION STUDY OF VGO IN FAU ZEOLITE SEIEVE

2017, 48(10):  1-6. 

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The dimensions of the rigid groups in the VGO model compounds and the dimensions of VGO molecules are calculated by using molecular simulation techniques. Dynamics methods were applied to investigate the diffusion process of VGO compounds at 800 K in FAU zeolite. The diffusibility difference of different VGO model compounds was studied by calculated penetration distance. The results indicated that the carbon chain length of VGO molecule and the dimensions of rigid group are the main factors that influence the diffusion ability of VGO in FAU zeolite. The increase in chain length leads to a lower diffusion ability due to the crimp of VGO molecules. The increase in ring number in naphthene and aromatics or the branched chain in the molecule increases the minimum crosssection size of the molecular rigid group of the hydrocarbon molecules， thus reducing the diffusion ability of the hydrocarbon molecules. When the hydrocarbon mixed with polycyclic aromatics as a model， the diffusion ability of the easy diffused molecules is lowered due to pore block by polycyclic aromatics.

COMMERCIAL APPLICATION OF RCGP-1 CATALYST FOR PRODUCING GASOLINE IN RESIDUE OIL MIP UNIT PROCESSING

2017, 48(10):  7-10. 

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The commercial application of RCGP-1 catalyst for improving gasoline yield in the 3rd MIP-CGP unit of SINOPEC Yanshan Company was presented. The result showed that the yield of gasoline increases by 2.01percent points, the RON and MON increases by 1.3 and 0.4 respectively; the yield of LPG and total liquid increases by 2.22 and 0.83 percent points, respectively; the yield of LCO decreases by 3.41 percent points, while the yield of dry gas is reduced and the coke selectivity is similar to the blank one. RCGP-1 catalyst showed significant advances in increasing bottoms cracking and anti-metal contamination ability along with improving the gasoline octane barrels significantly.

SYNTHESIS OF F127-MoO3/Al2O3 AND ITS PERFORMANCE OF OXIDATIVE REMOVAL OF DIBENZOTHIOPHENE

2017, 48(10):  11-16. 

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F127-MoO3/Al2O3 catalysts were prepared by precipitation method using poly ethylene oxide - propylene oxide - ethylene oxide (F127) as template agent， and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and field emission scanning electron microscope (FE-SEM). The influences of catalyst preparation and reaction conditions on oxidative desulfurization of model oil were investigated. The result showed that the addition of F127 as template agent promotes the high dispersion of MoO3 on the surface of Al2O3. For 10.0 ml model fuel (mass fraction of sulfur element is 400 ug/g)，DBT in the model oil can be almost totally removed under the conditions of m (catalyst)/m (model oil)=0.71%, V (H2O2)/V (model oil)=0.30%, reaction temperature 60 ℃ and 10 min, and converted into DBTO2. The desulfurization rate of DBT is 95.81% after the catalysts was used for eight times.

COMMERCIAL APPLICATION AND OPERATION ANALYSIS OF PS-Ⅵ CONTINUOUS REFORMING CATALYST

2017, 48(10):  17-21. 

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Based on the historical operation data，the performance of PS Ⅵ reforming catalyst was summarized.The analysis indicated that the PS Ⅵ reforming catalyst has good wear resistance，hydrothermal stability and chlorine holding capacity.The initial activity of the catalyst is high along with a long stable service life and good catalyst strength.Keeping moderate higher Cl content on the catalyst is helpful to get better product distribution.The sulfur，nitrogen and metal impurities in feed affect the performance of the catalyst and higher sulfur in feed has worse effect on the carbon deposition，thus the coke burning operation conditions in the regeneration sector must be adjusted； The nitrogen in the reforming feed reacts with chlorine to produce ammonium salt，which causes the blockage and corrosion in the separation equipment and the pipeline of the reforming device.

DEVELOPMENT OF H2S SELECTIVE OXIDATION CATALYST LS-06

Jin-Shan XU

2017, 48(10):  22-27. 

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The selective oxidation catalyst LS-06 was prepared by impregnation method using chemical inertness fumed silica as a carrier and the composite oxide of modifier and iron oxide as active component.The results of laboratory evaluation showed that the selective oxidation conversion rate of hydrogen sulfide over the catalyst is more than 95% and the sulfur yield is more than 90% at reaction temperature of 200 ℃，the gas volume space velocity of 1 600 h-1 and the volume concentration of hydrogen sulfide of 1%—3%.The results of 1 000 h long cycle contrast experiment indicated that the LS-06 catalyst has a good activity and stability，and the comprehensive performance reaches the same level as foreign similar catalyst.

EFFECT OF BASIC NITROGEN COMPOUNDS ON FCC PROCESS AND RELATIVE REACTION CHEMISTRY

zhenyu dai

2017, 48(10):  28-34. 

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In order to study the influences and reaction chemistry of basic nitrogen compounds in FCC process，the model compounds of quinoline and 7，8-benzoquinoline were used to investigate the conversion rules of N-containing compounds and nitrogen distribution in FCC products by fixed fluidized bed（FFB）.The reaction chemistry of samples were studied by molecular simulation.The results showed that the addition of basic nitrogen compounds reduces the conversion and influences the product distribution.Quinoline and benzoquinoline are most susceptible to alkylation.In the process of hydrogen transfer，the nitrogen ring in the quinoline molecule is more easily saturated，and then the ring-opening cracking reaction generates aniline nitrides； while for 7，8-benzoquinoline，the benzene ring in the middle of the molecule is most probably to be saturated first by hydrogen transfer reaction，and then be converted to aliphatic amine or ammonia，but not generate aniline.Aniline and five element nitrogen heterocyclic compounds are generated by cyclic condensation reaction of ammonia with olefins.The macromolecular nitrogen compounds are produced from small nitrogen-containing molecules by alkylation or cyclization-condensation reactions.

STUDY ON STRAIGHT-RUN DIESEL OIL TO LIGHT AROMATICS

2017, 48(10):  35-40. 

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Catalytic cracking experiments of straight-run diesel were conducted in a fixed fluidized bed reactor to study the effect of operation parameters and catalysts containing three different zeolites on product slates.The results showed that the straight-run middle distillate rich in naphthenic hydrocarbons and monocyclic aromatics has a higher yield of light aromatics.The higher conversion rate and gasoline and light aromatics yields are obtained using Y type zeolite catalyst and the light aromatics yield is up to 13.32%.As the reaction temperature increases from 510 ℃ to 610 ℃，the conversion is increased by 12.95 percentage points and the yield of light aromatics is increased by 7.16 percentage points.The ratio of catalyst/oil has little effect on the yield of light aromatics，but the yield of gasoline decreases when the ratio is too high.The cracking products have 26.4 percentage points naphthene less than that of the SR diesel feed，indicating more than 80.94% naphthene hydrocarbons to participate in the reaction.The more ring number in the naphthene，the higher the proportion of the naphthene involved in the reaction.

INFLUENCE OF MIXING RATIO ON PERFORMANCE OF ISOBUTANOL-DIESEL FUEL

Yi Li Yang He

2017, 48(10):  41-45. 

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The influence of the isobutanol-diesel mixing ratios on the engine combustion process and performance was investigated by turbocharged and intercooled common rail diesel engine.The results showed that under the same load，the fuel heating value is reduced as the increase of mixing ratio，while the fuel consumption is increased； after blending isobutanol，the oxygen content is increased，which can inhibit soot emission effectively，but the cetane number is decreased.At the working conditions of ESC-13，the fuel with 10% isobutanol generates the lowest soot weighting specific emissions.Under the same speed and small load conditions，increasing the mixing ratio has a trend of increasing the latent heat of vaporization of the fuel，and with a lower octane number，causing the prolonged ignition delay of the fuels and lower cylinder temperature and more the CO，HC and particulate emissions.While the higher cycle heat in cylinder under large load working conditions can effectively restrain the trend，except for the NOx emission，the rest of the harmful specific emissions are lowered.

PROPERTIES OF ROAD BIO-BINDER AND ITS MIXTURE

2017, 48(10):  46-51. 

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Bio-oil was prepared using wood powder，and then mixed with 50＃asphalt product and additives to obtain bio-binders with different bio-oil/asphalt ratios.The penetration，softening point，ductility（10 ℃）and other properties of the samples before and after RTFO aging were investigated.The bio-binder meeting the requirements of the specification was selected followed by preparation of bio-binder mixture.The rutting test，freeze-thaw splitting test，small beam bending test，low temperature bonding test were conducted for the mixture to investigate the effect of the amount of bio-oil blended into asphalt on the performance of the road bio-binder.The results showed that with increasing the bio-oil amount added，the penetration and ductility along with the low temperature crack resistance are improved；the softening point is reduced，indicating the negative effect for the high temperature performance.Compared with that of 50＃asphalt mixture，the maximum bending strain ratio of the bio-binder mixture with 10%w bio-oil is improved by 20.90%，the splitting tensile strain of freeze-thaw cycle samples increases by 12.56%，the water stability and low temperature performance are all improved； the bond ability is improved greatly while the high temperature performance is decreased in some extent.The properties of bio-binder mixture satisfies with the requirements of specification（JTG E20—2011）when the bio-oil content is 10%.

CO-REFINING OF PALM ACIDIC OIL AND WOOD POWDER

Jianbo Hu

2017, 48(10):  52-55. 

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The co-refining of acidic palm oil and poplar powder were conducted in supercritical methanol to investigate the effect of reaction temperature and time，stirring speed on the decomposition and gasification rate of wood powder as well as light and heavy oil yields.The optimized reaction conditions are：300—320 ℃ and 15—30 min； the maximum liquefaction ratio is 53.0% under the optimized conditions，and the conversion of the acidic oil is nearly 100%.It was found that the decomposition ratios of cellulose，hemicellulose and lignin are enhanced by 18.9%，11.2% and 25.0%，respectively due to the co-fining with palm acidic oil，compared with the results of direct conversion in supercritical methanol medium.

APPLICATION OF FCC FLUE GAS DESULFURIZATION AND DENITRATION TECHNOLOGY

2017, 48(10):  56-59. 

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The wet clean system for treating FCC regeneration flue gas in 2.5Mt/a FCCU of Sichuan Petrochemical Company was described. The system consists of EDV?5000 (Electro-DynamicVenturei) desulphurization and LoTOx (Low Temperature Oxidation) denitration process introduced from DuPont-Belco Corp. The application of the technology make the concentrations of pollutants in the flue gas reduce significantly. The concentration of SOx is reduced from 850.0mg/m3 to 5.0mg/m3, the nitrogen oxides is reduced from 205.0mg/m3 to 33.2mg/m3, and the catalyst particles is decreased from149.8mg/m3 to 24.3mg/m3. The quality of the treated flue gas is in consistence with the requirements of GB31570-2015 oil refining industrial pollutants emission standards.

COMPARISON OF TWO PROCESSES FOR HYDROGENATION OF LIGHT HYDROCARBONS TO LOW AROMATIC SOLVENT

2017, 48(10):  60-65. 

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Two kinds of combined hydrogenation processes (CoMo/Al2O3 desulfurization+mid temperature ZnO + Ni/Al2O3 dearomatization process I and Ni/ZnO adsorption + Ni/Al2O3 process II) were compared to investigate which one is suitable for producing vegetable oil extraction solvent. The test feeds were two light hydrocarbons with S content of 106μg/g and 25μg/g, respectively. The results showed that the bromine indexes and the contents of aromatics are very low in initial reaction stage of process-I for the two feeds. But 400 h and 550 h later, the content of aromatics rises up and all exceeds 0.1%. For process-Ⅱ, when the sulfur content in feed is 25 μg/g, the bromine index of the product maintains below 16 mg Br/（100g）, and the content of aromatics is less than 0.09%, indicating that processⅡis suitable for producing vegetable oil extraction solvent from the low s content feed.

CO-EXTRACTION PROCESS OF OIL SLUDGE AND TAILINGS TO RECOVER OIL

Kuan-Yong LUO yun donghan

2017, 48(10):  66-70. 

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The mineral composition, morphology and particle size distribution of Liaohe scum oil sludge and Yumen tailing oil sands were characterized by XRD, SEM and standard size sieve. A new co-extraction process for mixture of oil sludge and tailings was proposed for oil recovery efficiently base on the different properties of sludge and tailings. The results indicated that the tailings are mainly composed of quartz and calcium carbonate with high crystallinity and the size of more than 95% particle is larger than 75 μm, while oil sludge mainly contains clay minerals with soft texture and 89.7% of particles with size less than 75 μm. The effects of tailings/oil sludge mass ratio, solvent/(oil sludge+tailings sample) mass ratio, extraction temperature and time on the oil recovery were investigated. The results showed that under the optimal operation conditions: 60℃ and contact time 20 min, tailings/oil sludge=0.5, solvent/sample=2, the oil recovery by one stage co-extraction is 81.8% and the total oil recovery by two stage co-extraction can be as high as 89.4%. It is concluded that the oil recovery from oil sludge can be improved by co-extraction of tailings and oil sludge.

ANALYSIS OF COKE MORPHOLOGY IN FILTERS DOWNSTREAM OF COKING FRACTIONATOR AND COUNTERMEASURE

Xiaoqiang Wang yang youwen

2017, 48(10):  71-74. 

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There are two forms of coke（flake and powder）found in filters downstream of coker fractionator in 1.2 Mt/a delayed coking unit in PetroChina Dushanzi Petrochemical Company.It is found that the flake coke is from the spalling of the coke layer in large oil and gas pipeline due to a small blow after the coke drum switching； while the powdered coke is from the foam entering the fractionator at the EOR of coking drum and after drum changing.Therefore，preventing the coke powder from entering the fractionator and reducing the wall temperature of large oil and gas pipeline to promote the coke spalling on the tube wall is the key to solve the problem.Adjusting coking drum switching operation is an effective measure to promote further the spalling of coke in large oil and gas lines.The filter SR-109B downstream of the coking drum is switched to a larger filter and the filter SR-109A is changed to a new horizontal-back flush filter，respectively，and the coking drum operation conditions are adjusted as well.The results indicate that the SR-109B can run for 32 days and the SR-109A reaches 4 years long.By adjusting the defoamer injection at different stages of coking drum operation，the coke powder entering the fractionator can be reduced further，resulting in much longer operation period of the filters.

STUDY OF DISPERSION STABILITY OF NANO-MOLYBDENUM DISULFIDE IN GREASE

wang jia

2017, 48(10):  75-78. 

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As a solid lubricant, nano-molybdenum disulfide has an excellent tribological performance, and is applied widely in grease. However, besides its small amount, the larger specific surface area and the higher specific surface energy leads nanoparticle to reunite, then forming a larger particles and precipitation, losing the lubrication effect. This paper studied the dispersion stability of lauramidopropylamine modified nano-MoS2 in grease. The structure and state of the modified nano-MoS2 in grease was characterized by IR and SEM techniques. The results showed that the modification of wrapping MoS2 by lauramidopropylamine makes the centrifugal oil separation rate of MoS2 reduce from 64% in blank grease to 25% in modified grease, proving that the surface properties are changed by lauramidopropylamine modification, resulting in better dispersion stability in modified grease.

EFFECT OF HYDROCARBON TYPE STRUCTURE ON BASE OIL THERMAL STABILITY

2017, 48(10):  79-93. 

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The hydrocarbon structures of seven kinds of base oils of heat transfer oils were characterized by mass spectrometry. The effect of the structures on the thermal stability of the base oils was tested. The results show that the thermal stability of the base oil of high temperature mineral type heat transfer oil is related to its hydrocarbon compositions. The thermal stability of naphthene is good, while that of paraffin and aromatics is poor. Moreover the deterioration rate of the base oil has a quantitative relationship with hydrocarbon compositions, which can better guide the selection of base oil for high temperature heat transfer oil.

COMPARATIVE STUDY OF TWO PRE-LIFTING STRUCTURES

2017, 48(10):  84-90. 

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Effects of two different pre-lifting structures on solid circulation rate in an experimental circulating fluidized bed with a riser of 10.6 m high and inner diameter of 0.1 m and the gas-solid flow behavior were compared macroscopically and microscopically.The results showed that there is a remarkable difference in solids circulation rate between standpipe-type riser and showerhead-type riser.Due to the increased particles flow areas and the reduced entrance resistance，solid circulation rate in standpipe-type riser as a whole is higher than showerhead-type riser，especially in high particle feed rate from storage vessel.Under the same operating conditions，the solid concentration at the bottom in showerhead-type riser is higher than standpipe-type riser because of the strong restraining effect from the showerhead structure-The higher radial non-uniformity index and intermittency index in showerhead-type riser indicates that while showerhead distributor causes a local intense particle turbulence，the interaction distributions between gas and particle as well as particles are even more uneven.The instantaneous solid concentration and probability density distribution reflect that although showerhead distributor at the bottom can partly relieve gas-solid segregations in transition region，no fundamental changes occur in general non-uniform flow structure as a whole.

TECHNOLOGY FOR TREATING TOP GAS OF ACIDIC WATER TANK

chuan-lei ZHANG

2017, 48(10):  91-94. 

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This paper introduced several conventional control and treatment methods for top gas of acidic water tanks. A new gas treatment technology was proposed and applied commercially, where the pressure of acidic gas was boosted by water ring vacuum pump followed by water washing to remove ammonia, the treated gas then entered into the amine tower to wipe out H2S, the cleaned gas was then discharged to flare system. The H2S concentration in the cleaned gas is reduced to 1.40μL/L. The classified process of gas components is realized in this way, and the effect is remarkable.

PREPARATION OF TITANIUM DIOXIDE NANOTUBE MODIFIED BY ZINC IRON OXIDES AND ITS APPLICATION IN PHOTOELECTROCATALYTIC REDUCTION OF CO2

XinYu Zhu

2017, 48(10):  95-100. 

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The upright and orderly TiO2 nanotubes, ATiO2NTs were prepared by anodic oxidation method on the base matrix TiO2. The ZnFe2O4/TiO2NTs were obtained by impregnation of ZnCl2 and FeCl3 solution and applied to the photoelectrocatalytic reduction of CO2. The TiO2NTs and ZnFe2O4/TiO2NTs were characterized by SEM, XRD and UV-vis. The effects of the preparation conditions on the morphology of TiO2NTs were discussed. The results showed that the zinc and iron oxide are on the surface of TiO2NTs, and the band gap of the catalyst is 2.48 eV. It was found that the catalyst has excellent photoelectrocatalytic reduction performance for CO2. The larger alcohol compounds, like isoamyl alcohol, alien alcohol, are obtained.

APPLICATION OF NEW GENERATION NMR ONLINE ANALYZER IN RAPID EVALUATION OF RAW OIL

2017, 48(10):  101-106. 

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A new generation of nuclear magnetic resonance online analyzer was introduced by SINOPEC Jiujiang Company for the analysis of physical properties of crude oil and its distillates.Through the understanding and analysis of the new generation NMR online analyzer，a corresponding mathematical model，which associates the nuclear magnetic spectrum with the oil property data，was established to analyze the physical properties of crude oil and its distillates.Compared with that of the conventional method，it showed that the data reproducibility is within the allowable error range of the analysis method.