Table of Content

12 January 2017, Volume 48 Issue 1

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CHARACTERISTICS DIFFERENCE IN HYDROTREATING REACTION OF DIFFERENT RESIDUE FEEDSTOCKS

2017, 48(1):  1-5. 

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In order to investigate the reaction characteristics of two typical residue feedstocks in hydrotreating process, the hydrotreating test was conducted in a pilot unit with the same catalyst grading under the same reaction conditions. The results indicate that HDS is easy while HDN and HDCCR are difficult for both feeds; it is difficult to remove S, N and CCR for residues with low sulfur content and high nitrogen content, compared with the feed with high sulfur content and low nitrogen content. The difference in reaction characteristics is related to heteroatom content, component composition as well as molecular structure. The results are in consistent with the results of two commercial VRDS unit operations

PROBLEM ANALYSIS OF TAHE CRUDE OIL DEMULSIFICATION AND COUNTERMEASURES

2017, 48(1):  6-10. 

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The properties of Tahe crude oil produced in 2008-2014 were analyzed to investigate the reasons for difficult demulsification. The analysis reveals a inferior trend in crude quality year by year due to increased asphaltene content and the mechanical impurities while decreased mass ratio of resin/asphaltene, which may be the reasons accounting for difficult demulsification of Tahe crude oil. The oil soluble demulsifier RP-04 was developed by mixing polyacrylate polyether, a main agent with alkyl phenolic polyether A, an aid agent. The water soluble demulsifier RP-05 was obtained by compositing the main agent 05-M with aid agent R30 which has the effect that makes the iron particles wetting. The RP-04 and RP-05 were used jointly in a 3.5 Mt/a desalting unit of a refinery. The results show that in the steady operation conditions of high water injection rate and high mixing intensity, the salt content of treated oil decreases from 10.5 mgNaCl/L to 5-6 mgNaCl/L without desalting current jump.

APPLICATION OF RSDS-III TECHNOLOGY FOR NATIONAL V STANDARD GASOLINE PRODUCTION

2017, 48(1):  11-13. 

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The commercial application of RSDS-Ⅲ technology, developed by SINOPEC Research Institute of Petroleum Processing, in a 600 kt/a HDS unit of FCC gasoline in Qingdao Petrochemical Co.Ltd., for the production of national V gasoline was introduced. It proves that the gasoline product in compliant with national V standard (w(S)<10μg/g) can be produced by the RSDS-Ⅲ technology from FCC gasoline with a sulfur content of 300-900μg/g. Compared with RSDS-II, the RSDS-Ⅲ technology possesses higher S removal selectivity and a longer cycle life.

APPLICATION OF LTAG TECHNOLOG IN WAX OIL HYDROTREATING UNIT

2017, 48(1):  14-18. 

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LTAG technology developed by SINOPEC Research Institute of Petroleum Processing was used in the wax oil hydrotreating unit and FCC unit in SINOPEC Luoyang Company. The results show that the amount of hydrotreated diesel as FCC feed, drawing from the optimized fractionator in hydrotreatment system, reaches 25 t/h, more than the design value of 4.4 t/h. The end point of naphtha can be controlled in 155-175 ℃ range and the energy consumption is kept at about 250 MJ/t. The yield of FCC gasoline increases by 5.86 percentage points and the yield of diesel decreases by 4.92 percentage points. The diesel-gasoline ratio reduces to 0.78, 0.3 lower than before using LTAG technology, indicating a significant effect of the technology on reduction of diesel-gasoline ratio.

INDUSTRIAL APPLICATION OF RICP TECHNOLOGY IN FCC UNIT

2017, 48(1):  19-21. 

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The RICP technology (Residue Integrated Combination Process) was adopted after revamping of FCC unit of PetroChina Sichuan Petrochemical Co. Ltd. The vacuum residue mixed with heavy cycle oil from FCC unit was used as hydrotreating feed and then the hydrotreated effluent was processed in FCCU. By this technology, the properties of FCC feed are significantly improved: the carbon residue reduces by 0.47 percentage point, the content of hydrogen increases by 0.3 percentage point, the content of saturated hydrocarbon increases by 4.26 percentage points, and the content of resin and asphaltene significantly declines. The improved properties of the FCC feed increase FCC conversion rate and the total liquid yield by 0.67 percentage point and 1.42 percentage points, respectively. While the coke and slurry yield reduced by 0.63 percentage point and 0.85 percentage point, respectively. The cetane number of diesel fraction also improved.

INDUSTRIAL APPLICATION OF SRCA BIODIESEL PROCESS

2017, 48(1):  22-25. 

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The first industrial application of SRCA biodiesel production technology developed by SINOPEC Research Institute of Petroleum Processing in a 60 kt/a demonstration unit of CNOOC New Energy Company was introduced. The results indicate that with the acidified waste lipid as raw material, the device operates smoothly and the production capacity reaches the design value, the three wastes discharge (waste water, waste gas and residues) is less and easy to handle. The qualities of the biodiesel product meet the requirements of the national standard of biodiesel (BD100) (GB/T 20828-2007) and the energy consumption of the unit is 4 259.76 MJ/t, less than the national standard of 4 390.50 MJ/t.

SOLUTION OF MAXIMIZING GASOLINE IN EXISTING UNITS

2017, 48(1):  26-28. 

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The solutions of maximizing gasoline using the existing units in Dagang petrochemical company were discussed. The main methods, such as broadening gasoline distillation range, increasing reforming unit feedstock, optimizing FCC raw materials and load, were taken to low diesel/gasoline ratio and raise yield of gasoline. The practices prove that in existing units, through production optimization, gasoline increases by 306 t/d and diesel/gasoline ratio drops from 2.43 to 1.60, while the benefit increases 21.9×104 Yuan /d.

RESEARCH ON SOLVENT REFINING OF BAOMING SHALE OIL

2017, 48(1):  29-32. 

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The goal of this research was to develop and optimize solvent extraction techniques for processing Baoming shale oil. The influence of extraction solvent, extraction temperature, solvent/oil mass ratio, and settling time on shale oil refining was investigated and the optimized conditions were determined. The results show that among the tested solvents, N,N-dimethyl formamide (DMF) solvent has the best extraction effect. At the conditions of 60 ℃, solvent/oil mass ratio 0.5, reaction time 10 min and settling time 30 min, the yield of raffinate oil and the extract oil is 72% and 26%, respectively. The raffinate oil with very low content of olefins, sulfur, nitrogen, oxygen, and the carbon residue can be used as raw oil for hydrotreating process. The hydrogen consumption for the raffinate oil hydrotreating is 52.48% lower than that for shale oil hydrotreating directly. The light fraction of the extract oil by distillation meets the quality of No.4 fuel oil, and the heavy component of the extract oil can be used for No.90 heavy traffic road asphalt.

CALCULATION OF VAPOR PRESSURE OF PURE COMPOUNDS IN GASOLINE

2017, 48(1):  33-37. 

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The cubic equation of state was used to predict the vapor pressure of pure compounds at the specified temperature at which vapor-liquid equilibrium occurred. The equation of state was solved using the programs, in which the vapor pressure was reported when the critical properties as the critical pressure, critical temperature and acentric factor were specified. The vapor pressures of more than 400 compounds in gasoline were calculated by SRK or PR EOS. The predictions of vapor pressure of some hydrocarbon compounds at 37.8℃are in good agreement with the observations. The average relative error is lower than 1% for the light compounds, and lower than 4% for all the compounds in full range gasoline.

EFFECT OF NON-PETROLEUM BASED SOLVENT ON VISCOSITY REDUCTION OF RESIDUE OIL AND RELATIVE DILUTION MODEL

2017, 48(1):  38-42. 

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In this work, three kinds of non-petroleum solvents (coal tar light oil, shale oil, and coal tar diesel) were used as solvents for viscosity reduction of residue oil. The influence of temperature, solvent, and solvent/residue ratio on viscosity reduction of residue was tested. A theoretical equation for liquid viscosity derived from the differential equation for a model of argon gas is extended to describe the temperature-viscosity relationship of blending mixture of residue and solvent, and establish a residue dilution model. The test results show that three kinds of non-petroleum-based solvents can be used to reduce the viscosity of residue. The viscosity of the mixture is reduced more significantly as the blending ratio increases. At a solvent/residue ratio of 0.3, the shale oil and coal tar light oil exhibit a better viscosity reduction effect. It is believed that the asphaltene association by solvent may be the important factor for viscosity reduction of residue. The established model proves that the calculated values are in good agreement with observations and the model parameters reflect the average molecular composition and the relationship of temperature and viscosity of blending residue.

RESEARCH ON PYROLYSIS OF OILY SLUDGE AND PYROLYTIC OIL HYDROTREATING

2017, 48(1):  43-46. 

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The pyrolytic oils and gases were obtained from oil sludge pyrolysis process at different temperatures and then hydrotreated in pilot scale and scale-up test. The results of pyrolysis experiment show that the oil yield declines as the reaction temperature increases, the oil and gas yield reaches 38.61% and 6.52% at 600 ℃，respectively with small amount of S, N,CCR, metal and asphaltene in the oil. At the hydrotreating conditions of 420 ℃, 12.0 MPa, hydrogen to oil ratio of 800, and space velocity of 1.0 h-1 , the removal rate of sulfur and nitrogen reaches 94.5% and 89.4%, respectively, with high yield of light oil which can be used as a blending component for fuels, while the heavier fraction can be used as hydrocracking feedstocks.

THERMAL OXIDATION STABILITY OF JET FUEL FROM COAL DIRECT LIQUEFACTION PROCESS

2017, 48(1):  47-52. 

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In order to investigate the thermal oxidative stability of RP-3 jet fuel and coal direct liquefaction jet fuel, we used the color, acid number and solid deposits as comparison indexes for both jet fuels. The differences between the two jet fuels in thermal oxidative process then were analyzed by UV-Vis absorption and fluorescence spectroscopy. The coal direct liquefaction jet fuel shows a better thermal oxidation performance than RP-3 jet fuel in color, acid number and solid deposits. The spectra demonstrate that the thermal oxidative reaction in coal direct liquefaction jet fuel occurs continuously as the temperature increases from 160-300 ℃, and the oxidative products begin to form resin and asphltene at 200 ℃, while the thermal oxidative reactions in RP-3 already occurs to the stage of resin and asphaltene formation below 200 ℃.It is proved that the coal direct liquefaction jet fuel possesses excellent thermal oxidative stability.

STUDY OF NETWORK STRUCTURE OF MODIFIER IN SBS MODIFIED ASPHALT BASED ON VISCOELASTIC MECHANICS

2017, 48(1):  53-56. 

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In order to investigate the reaction time on cross-linking process of modifier in SBS modified asphalt, based on the share stress versus time curve observed by shear test, the network intensity, a new concept used as an index was introduced to evaluate the network structure of modifier. The results, combined with the softening point test were used to study the relationship of network structure with performance at high temperature and storage stability. The network structure of the modifier forms through two stages: partial crosslinking and entire crosslinking. The partial crosslinking is a reversible process in a metastable state and only has limited effect on the improvement of storage stability and softening point. While the stability of entire crosslinking structure is much better and is a key factor to improve softening point. The changes of the softening point present a trend as the reaction time of the modifier with asphalt prolongs: first reduces and then elevates. This trend is resulted from both the modifier morphology and structure changes.

COMMERCIAL APPLICATION OF NOVEL ANTI-VANADIUM CTALYST CGP-1YZ IN MIP UNIT

2017, 48(1):  57-60. 

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CGP-1YZ is a FCC catalyst with enhanced anti-vanadium ability. The commercial application of the catalyst in 2# FCC unit of Yangzi Petrochemical Co. Ltd. was introduced in this paper. CGP-1YZ catalyst integrated the zeolite with high activity and stability, and vanadium trapping component, which made the catalyst prevent the deactivation by vanadium in the feed effectively. Under full-regeneration conditions, when the vanadium content on the equilibrium catalyst reached 1%, CGP-1YZ catalyst still showed better overall performance. Compared with the case of blank calibration, better product distribution was obtained in mid calibration period, and the LPG and gasoline yield increased 3.93 and 5.64 percentage points, respectively.

POLYMERIZATION OF 1-DECENE CATALYZED BY SILICON-BRIDGED METALLOCENE

2017, 48(1):  61-66. 

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Polymerization of 1-decene catalyzed by silicon-bridged metallocene catalyst system rac-Me2Si(1-Ind)2ZrCl2/Al(i-Bu)3/[Me2NHPh]+[B(C6F5)4]- was studied. The effects of the concentration of metallocene catalyst, molar ratio of Al to Zr, molar ratio of boron (B) to Zr, reaction temperature and reaction time on polymer properties were investigated. The results show that at molar ratio of Zr to 1-decene 4×10-5, molar ratio of Al to Zr 80, molar ratio of B to Zr 1.2, reaction temperature 80 ℃and reaction time 1 h, the conversion of 1-decene reaches 97.6% and the kinematic viscosity (100 ℃) is 599.4 mm2/s, the viscosity index(VI) is 285, the number-average molecular weight (Mn) is 12 608, and the molecular weight distribution is 1.87. Meanwhile, we analyzed the different performances of ethenylidene-bridged metallocene catalyst system (rac-Et(1-Ind)2ZrCl2/Al(i-Bu)3/[Me2NHPh]+[B(C6F5)4]-) and rac-Me2Si(1-Ind)2ZrCl2/Al(i-Bu)3/[Me2NHPh]+[B(C6F5)4]- in terms of catalytic polymerization of 1-decene based on polymerization mechanism and catalyst micro configurations. The results both from the activity of catalyst and from the product molecular weight indicate that the silicon-bridged metallocene catalyst system is better. Finally, automatic reaction calorimeter was used to analyze the reaction under scale–up conditions, and found that the polymerization reaction heat is 61. 8 kJ/mol.

REGENERATION AND REACTION PERFORMANCE OF CATALYSTS IN MHUG PROCESS

2017, 48(1):  67-71. 

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MHUG hydro-upgrading technology with hydrorefining catalyst RN-10B and hydrocracking catalyst RT-5 was applied in a 3.6Mt/a hydrocracking unit in CNOOC Huizhou Refining & Petrochemicals Company using the mixture of naphthenic straight-run gasoline/diesel and MIP diesel as feedstock, the main products are naphtha, 3# jet fuel and national V diesel. The ex-situ regeneration of the catalysts was conducted after continuous operation for 5 years and 6 months. The regenerated catalysts still show good activities for HDS, HDN, and cetane number improvement, equals to that of fresh one, indicating the good activity stability and regeneration performance of both the catalysts. The product distribution reaches or even better than the design value, showing the better long term operation ability of the catalysts, and lower activity declines after regeneration.

ANALYSIS OF PHYSICOCHEMICAL PROPERTY CHANGES OF ENGINE OIL IN MACK T-9 BENCH TEST

2017, 48(1):  72-77. 

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The changes in soot content, viscosity, mental content, total acid value, total alkali value, nitrification and phosphorus chemical state of eight kinds of engine oils in 500-hours Mack T-9 bench test were analyzed to investigate the effects on the cylinder liner wear. The results indicate that the diesel engine oil with steady viscosity, strong anti-oxidization ability and high total alkali value is useful to improve the anti-wear performance. The knowledge from the results is helpful to develop high-grade diesel engine oils.

INFLUENCE OF NITROGEN AND SULFUR COMPOUNDS ON LIGHT STABILITY OF LUBE BASE OIL

2017, 48(1):  78-84. 

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The sediments deposited from lube base oil were analyzed by means of elemental analysis and FT-ICR MS, and the model system was constructed to study the influence of nitrogen and sulfur compounds on the light stability of lube base oil by the addition of quinoline, indole and dibenzothiophene in blank sample. The results showed that the content of sulfur and nitrogen in sediments was 2 000 times more than that in the lube base oil, and the sediment was mainly composed of high condensated nitrogen and oxygen compounds. Nitrogen compounds on the light stability of lube base oil was very significant, and the influence of non-basic nitrogen compounds was far greater than the influence of basic nitrogen compounds. Thiophene sulfur compounds had small influence on the light stability of lube base oil, and low content of thiophenic sulfur compounds made the light stability of lube base oil worse, while high content of thiophenic sulfur compounds could inhibit the light stability of lube base oil deterioration.

TEST OF REGENERATION PROCESSES OF WASTE GASOLINE ENGINE OIL

2017, 48(1):  85-88. 

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Regeneration processes of used gasoline engine oil were investigated. The results show that the methods of electric desalting and clay adsorption for waste oil decalcification are not suitable. While the base oil on specification can be obtained by distillation-hydrotreating process. The regenerated oil meets the lubricating base oil standard of VHVI 5 with a yield (>360 ℃ fraction) of 77.09%. When the addition of the distillation residue is 3% in 90# asphalt product, the load asphalt in compliant with 90# JIG F40-2004 standard can be produced. Increasing the dope of residue to 5%, 110 load asphalt, meeting 110# JTG F40-2004 standard, can also obtained. It is concluded that the distillation-hydrotreating process is suitable for regeneration of waste lube oil with high recovery of base oil and utilization of distillation residue.

DETERMINATION OF TRACE METALS IN EMULSIFIED LUBRICATING OIL BY ICP-MS

2017, 48(1):  89-93. 

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An analytical method using ICP-MS for the determination of trace metals in lubricating oils emulsified by TritonX-100 is established. After the experimental conditions and instrumental parameters were optimized and the internal standard solutions are added, the emulsified samples were then introduced directly into the plasma. The addition of internal standard is to eliminate the matrix effect caused by samples emulsified and standard solutions. The inorganic-metallic standard solution is used for calibration instead of expensive organic-metallic standards. The established method shows the advantages of easy-handle, good precision and accuracy. The recoveries are 90-110%. The RSD of all elements is less than 7.0%. The results of this method are in good agreement with those obtained by organic-metallic standard solution.