Table of Content

12 July 2019, Volume 50 Issue 7

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COMPUTATIONAL FLUID DYNAMICS SIMULATIONS OF IMPREGNATING AND DRYING EQUIPMENTS FOR PREPARATION OF CATALYSTS

2019, 50(7):  1-6. 

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The quality indexes of catalyst，like particle size distribution, strength and sphericity, have a great influence on the catalytic process, especially for the supported catalysts used in non-fixed beds. Drying is one of the keys to the preparation of catalysts and greatly affects the quality index of catalysts. A coupling equipment of impregnating and drying was developed to improve the catalyst quality. Based on the demands of the process，a three dimensional model for the coupling equipment was established and the two-phase CFD simulations was conducted with Euler-Euler model. According to the information of flow field and gas-solid two-phase distribution in the dryer, the optimal feeding tube length was obtained. It provides reliable guidance for the design and scale-up of catalyst impregnated dryer.

CHARARTERIZATION OF METAL DEPOSITION ON SPENT RESIDUE HYDROTREATING CATALYSTS FROM INDUSTRIAL PLANT

Diao Yuxia Yuan Hui Qiu Limei Sun Shuling Xu Guangtong

2019, 50(7):  7-12. 

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The spent residue hydroprocessing catalysts withdrawn from industrial plant were treated by Soxhlet extraction with n-heptane and toluene to remove soluble coke deposits and residual oil，respectively, to investigate the metal content, morphology and distribution. It was recognized that the metal deposition was gradually decreased along the reactor axial down. The low content of asphaltene on the surface of spent catalysts was revealed by Raman and XPS. The active phases of the catalyst were MoS2，NiMoS or CoMoS. The coke and metal depositions reduced the active phase on the external surface of the catalysts.

PHOTOOXIDATION OF STYRENE TO BENZALDEHYDE BY BIVO4/SBA-15 PHOTOCATALYST

2019, 50(7):  13-18. 

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In order to improve the photocatalytic activity of BiVO4， BiVO4/SBA-15 photocatalyst was prepared by impregnation method of BiVO4 loaded on SBA-15 mesoporous molecular sieve. The samples were characterized and analyzed by XRD，N2 adsorption-desorption and FT-TR techniques. Under the irradiation of 400 W metal halide lamps, the oxidation of styrene was conducted with BiVO4/ SBA-15 and BiVO4 as catalyst to investigate the influence of reaction conditions on the oxidation performance. The results showed that the load of BiVO4 did not destroy the mesoporous structure of SBA-15 and it uniformly dispersed on the surface and that BiVO4/SBA-15 photocatalytic activity was significantly improved compared with BiVO4. The conversion of styrene and the selectivity of benzaldehyde reached 90.31% and 70.65%, respectively when Styrene:Acetone:Hydrogen peroxide (molar ratio)= 1: 2: 3.5, reaction temperature 70℃ and reaction time 2.5 h.

SIMULATION CALCULATION OF ADSORPTION OF QUINOLINE AND INDOLE ON MODIFIED Y ZEOLITE

2019, 50(7):  19-24. 

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Adsorptive and denitrogenation performances of CuY, AgY, NiY, CeY zeolites prepared by cation exchange were studied by using Dense Function Theory (DFT). In the theoretical calculation, the relevant functional and DNP basis sets of BLYP exchange under GGA approximation were used; The strength of Lewis acid in Y zeolites was studied quantitatively using Fukui functional response description and layout analysis. The results showed that the relationship between the acidity of different cation exchanged Y zeolites studied by Mulikun and Hirshfeld was: CeY>NiY>CuY>AgY; by calculating the adsorption energy of the two adsorption configurations, η5 and η1N, it could be concluded that the adsorption energy of quinoline and indole at the substituted η5 configurations of the four modified Y zeolites was higher than that of the substituted η1N, which indicates that the main adsorption configuration of quinoline and indole is η5. and the adsorption configuration was mainly in η5 .The adsorption isotherm of quinoline and indole at different temperature over CeY molecular sieve showed that the adsorption temperature had less impact on the adsorption of quinoline and indole, the balance adsorption amount of indole at 298 K over CeY was greater than that of quinoline.

PYROLYSIS OF VACUUM RESIDUE AND ITS RESINS SUBFRACTIONS BY PY-GC/MS

2019, 50(7):  25-30. 

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The Changqing vacuum residue and resin subfractions were studied by using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to test the effect of reaction temperature and heating rate on VR pyrolysis. The results showed that as the pyrolysis temperature increased, the yields of light olefins in the pyrolysis product rose gradually, whereas the yields of gasoline and diesel fractions first increased and then decreased with a maximum value at 700oC; when the heating rate is 1℃/ms, the yield of gasoline and diesel reached maximum. The pyrolysis of resins subfractions showed that the higher the aromaticity and the higher the condensation degree, the worse the pyrolysis ability of the resins.

EXPERIMENTAL STUDY ON OLEIC ACID MODIFIED Fe2(MoO4)3 FOR CATALYTIC AQUATHERMOLYSIS OF HEAVY OIL

2019, 50(7):  31-37. 

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The oleic acid modified Fe2(MoO4)3 catalyst was prepared and used in catalytic visbreaking by aquathermolysis for Karamay heavy oil. The effects of catalyst dosage, reaction temperature and reaction time on viscosity reduction were investigated. The optimum process conditions were 240 ℃, reaction time of 36 h, and 0.4% of catalyst. At the optimal conditions, the viscosity reduction rate was 61.21%. The SARA analysis indicated that 13.2% of the large hydrocarbon molecules were significantly cracked to form light components, which was the main reason for the viscosity reduction of heavy oil. The compared results of FT-IR, 1H NMR analysis of the heavy components of heavy oil before and after the reaction indicated that desulfurization, denitrogenation, ring opening, branch chain breaking and other reactions occurred in heavy components.

HYDROGENATION TECHNOLOGY OF PRODUCING LIQUID PARAFFIN FEEDSTOCK FROM COKING KEROSENE DISTILLATE AND ITS INDUSTRIAL APPLICATION

2019, 50(7):  38-41. 

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The coking kerosene distillate was hydrotreated to produce the feedstock for the liquid paraffin production by Fushun Research Institute of Petroleum Processing (FRIPP) and its industrial application was introduced. The pilot test results showed that when typical coking kerosene fractions were hydrotreated at 5.5 MPa, 320 ℃, LHSV 1.5 h-1, the volume ratio of hydrogen/oil 400 or at 4.5 MPa, 320 C, LHSV 1.0 h-1 and the volume ratio of hydrogen/oil 400 , the content of sulfur and nitrogen in product can be reduced to less than 1.0 ?g/g, which meets the quality requirements of liquid paraffin feedstock. The industrial application proved the feasibility of producing liquid paraffin feedstock by hydrogenation of coking kerosene distillate. It is concluded that the hydrogenation technology can provide a new technical route to supply liquid paraffin feedstock with increasing the added value of coking distillate oil.

PRODUCTION OF LIGHT WHITE OIL AND TRANSFORMER OIL BLENDING COMPONENTS BY DIESEL HYDROTREATING

2019, 50(7):  42-46. 

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The light white oil and transformer oil blending components were produced by the process consisting of hydrodewaxing，hydrofinishing and rectification. The results showed that the light white oil with aromatic content less than 0.2% and color of 30, which meets the requirements of NB/SH/T 0913—2015 standards and the blending components with low aromatic content, which meets the requirements of GB 2536—2011 standards of T-40℃ (universal) transformer oil can be produced by diesel hydrotreating.

ANALYSIS OF CATALYST LOSS IN FCCU BASED ON PARTICLE SIZE DISTRIBUTION

2019, 50(7):  47-51. 

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In view of the catalyst lost fault in FCCU, the inlet catalyst of the three-stage cyclone separator was sampled on site, and the particle size distribution and the scanning electron microscopy of the lost catalyst were analyzed. The results showed that there were multi-peaks in the particle size distribution curve of the sample, and the particle size corresponding to the peak value was 0.8, 9 and 30 microns, respectively. The first two smaller particle size particles were formed due to serious frictional wear and breakage of particles. On the other hand, because the separation efficiency of the cyclone separator decreases, the higher median particle size of the lost catalyst resulted in the peak of larger particle size.

STUDY ON DESULFURIZATION OF PETROLEUM COKE FROM VACUUM RESIDUE DELAYED COKER

Li Kang Chen Hui Lei Jie Zhang Dexin Chen Jianmin Liu Xuedong Han Haibo

2019, 50(7):  52-57. 

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Based on the knowledge that the chemical bond energy of sulfone and sulfone is lower than that of thiophene, it was proposed that the vacuum residue was pre-oxidized to reduce the sulfur content of the coke from delayed coking with acetic acid/hydrogen peroxide oxidation system. The effect of viscosity reduction by oxidation and the oxidation-viscosity reduction process assisted with hydrodynamic cavitation technology on the desulfurization of the petroleum coke were investigated. The results showed that the desulfurization of petroleum coke reached the best at the reaction conditions: cavitation pressure of 8 MPa，400℃，reaction time 1 h, and treating only once. The sulfur content of petroleum coke was reduced from 4.12% to 3.21%，and the coke yield reduced by 2.35 percentage points，the liquid yield increased by 1.93 percentage points.

DISCUSSION AND PRACTICE OF CAUSTIC INJECTION IN CRUDE DISTILLATION UNITS

2019, 50(7):  58-62. 

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With the increasing proportion of poor quality crudes with high acid, high sulfur processing, corrosion has become a common problem for the world's oil refiners. The corrosion of the distillation tower overhead system of the crude distillation unit (CDU) is the most prominent issue. The advantages and disadvantages of caustic injection into CDU were discussed, including the effects of caustic injection limits, alkali brittleness of pipeline and heater tube, heat exchanger scaling and secondary processing device. Measures were proposed, including caustic dosage, injection location, injection equipment and selection of building materials, as well as related corrosion monitoring and inspection. The results of the application in domestic refineries indicated that as a traditional and effective anti-corrosion measure, the crude oil caustic injection technology has a very good effect on controlling the corrosion of the top system of CUD unit under the condition of unfavorable factors as alkali brittleness, scale formation and catalyst poisoning.

STUDY ON HIGH QUALITY ROAD ASPHALT FROM CHUNFENG AND TAHE HEAVY OIL

2019, 50(7):  63-68. 

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By studying the properties of vacuum residues of Chunfeng crude in Southern Xinjiang and Tahe crude in Northern Xinjiang, it was found that two kinds of vacuum residues had distinct compositions and properties, the blending bitumen had good complementarity, and the matching of four components was more reasonable. According to the study of blending regulation, the penetration degree of blending asphalt increased first and then decreased with the increase of Tahe residual oil content. Selecting raw materials and blending ratio with suitable penetration could produce grade A road asphalts with excellent high and low temperature performance. The properties of the industrial product not only met the requirements of grade A asphalt specifications, and the softening point, dynamic viscosity(60℃), ductility(10℃), penetration ratio were all higher than the requirements. The road test showed that the blending bitumen prepared by two kinds of vacuum residues from Chunfeng and Tahe had a better performance than similar asphalt products.

EFFECT OF DIFFERENT TYPES OF FATTY ACIDS ON PERFORMANCE OF LITHIUM GREASE

2019, 50(7):  69-74. 

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Preparation of 12-hydroxystearic acid complex lithium grease and stearic acid complex lithium grease containing molybdenum disulfide were conducted through one step method using 12-hydroxystearic and stearic acid as thickener, respectively and 85W-40 heavy-duty vehicle gear oil as base oil. The effects of different types of fatty acids on the properties of lithium complex greases were investigated. The results showed that the lithium complex grease prepared by 12-hydroxystearic acid had higher sintering load, dropping point and thermal stability than the lithium complex grease prepared by stearic acid. Compared with the base grease, when the amount of molybdenum disulfide added to the lithium complex grease prepared from12-hydroxystearic acid was 10%, the load-bearing capacity increased by 96.8%; while for the complex lithium-based grease prepared by stearic acid, the load-bearing capacity increased 100% when the adding amount of disulfide was 15%.

PERFORMANCE OF C8 AROMATICS ISOMERIZATION CATALYST RIC-270 IN INDUSTRIAL APPLICATION

2019, 50(7):  75-79. 

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The C8 aromatics isomerization catalyst RIC-270 for ethylbenzene conversion, developed by SINOPEC Research Institute of Petroleum Processing, was applied in SINOPEC Yangzi Petrochemical Company's No. 2 para-xylene plant. The adaptability of RIC-270 catalyst to high ethylbenzene content feedstock was investigated. The application results showed that the isomerization activity of RIC-270 catalyst reached more than 23.3 %, ethylbenzene conversion rate reached 36.5 %, and C8 ring loss was 1.7 %. The average C8 aromatics loss was as low as 2.5 % under the harsh operating conditions of high load and high conversion rate, the temperature and pressure rising rate was low. The catalyst has high activity and selectivity, good stability, and remarkable economic benefits.

APPLICATION OF MESOPOROUS ALUMINA IN PREPARATION OF ANTI-IRON CONTAMINATION FCC CATALYST

2019, 50(7):  80-84. 

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Mesoporous alumina was prepared through sol-gel method using cellulose and pseudo boehmite as template and Al source, respectively, and further used as matrix material for the preparation of anti-iron contamination FCC catalyst, which were characterized by XRD, N2 adsorption-desorption, FT-IR, SEM and ACE techniques. Characterization results indicated that the prepared mesoporous alumina had much higher surface area, pore volume, pore size and acidity density in contrast with pseudo boehmite. Evaluation results illustrated that the negative effect caused by iron contamination on the catalytic cracking performance of the FCC catalyst containing mesoporous alumina was much lower, compared with traditional FCC catalyst, indicating that the anti-iron contamination performance of the catalyst was significantly improved.

EFFECT OF DIATOMACEOUS EARTH ON HYDROTHERMAL/MECHANICAL STABILITY OF BULK HYDRODEOXYGENATION CATALYST

2019, 50(7):  85-91. 

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Ni-Mo oxide powders were prepared by sol-gel method using carbon black as pore-enlarging agent. Ni-Mo composite oxide bulk catalysts were prepared by using a mixture of diatomaceous earth and alumina gel as binder. The catalysts were characterized by XRD, BET, Py-IR, NH3-TPD. The effect of diatomaceous earth addition on hydrothermal/mechanical stability of bulk hydrodeoxygenation catalyst was examined. The hydrodeoxygenation performance was evaluated using n-octane solution containing 20% jatropha oil as the raw material. The results showed that the addition of diatomaceous earth during the preparation of the catalyst did not significantly affect the crystal phase of the catalyst, but significantly increased the pore size of the catalyst; the added diatomaceous earth covered part of the Al3+ exposed on the surface of the catalyst and in the pores, which can effectively inhibits the collapse of the pore structure of the catalyst and the aggregation of the metal particles caused by the hydration reaction of the Al2O3. As a result, the hydrothermal/ mechanical stability of the catalyst are significantly improved.

ANALYSIS OF METAL SPECIATION IN AGED OIL

2019, 50(7):  92-96. 

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Pure water and hydrochloric acid solution were used to extract the aged oils of different depths in the oil tank, respectively. The metal contents in extracted oils were determined by inductively coupled plasma emission spectrometry (ICP-OES). Meanwhile, sodium benzoate, calcium naphthenate, nickel meso-tetraphenylporphine, nickel octaethylporphine, vanadyl meso-tetraphenylporphine, and vanadyl octaethylporphine were employed as model chemicals to study the metal species in the aged oils. The results showed that the contents of iron, sodium, calcium, and other metal elements in each phase were high and followed the rule of additivity after extraction and separation, respectively. The composition of the aged oil was complicated, and the iron in aged oil should be +2 valences according to the color of acid extract. It is expected that the aged oil can be recovered by means of washing and centrifugation to remove most of the metals in it. If further removal is required, acid reagent treatment should be considered.

DETERMINATION OF PHENOLS IN COAL TAR BY GC-OFID

Shi Junge Mei Wu

2019, 50(7):  97-102. 

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A method for the determination of phenols in coal tar was established by gas chromatography-oxygen selective flame ionization detector (GC-OFID). The method has good repeatability and can identify the content of lower phenol monomers (phenol, methylphenol, C2 phenol) and the total content of higher phenols. The RSD was less than 5%, the standard recovery was between 97% and 104%, and the linear correlation coefficient R2 was 0.99.The lower limit of oxygen mass fraction of a single substance was 10 μg/g, which met the general requirements of chromatographic analysis. Phenolic substances exist in the coal tar distillate less than 300 ℃. Low phenol content was higher, in which phenol, methyl phenol, phenol and 2, 5 - dimethyl ethyl phenol was principal, while senior phenolic substances had more variety but lower content.

UPGRADING SALINE WASTERWATER TREATMENT PLANT IN AN URBAN PETROLEUM REFINERY

2019, 50(7):  103-108. 

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The increasing pressure of environmental protection and residents' awareness of rights protection have exerted a huge impact on the survival and development of urban refineries. Moreover, the range of land use is difficult to expand anymore. Great attentions have been paid on seeking the solution to upgrade or reconstruct wastewater treatment plant (WTP) on precious land. This paper introduces such a case at SINOPEC Zhanjiang Dongxing petrochemical company. The reconstruction scheme was proposed based on the systematic diagnosis on problems existed in the original WTP. In order to deal with these key problems, specialized technologies were studied. After reconstruction, the capacity of WTP has been increased from 60 m3/h to 100 m3/h. One year commercial operation proved that the annual average of chemical oxygen demand (COD), NH3-N and total nitrogen (TN) was as low as 25.88 mg/L, 0.48 mg/L and 10.79 mg/L, respectively, far lower than the standard. The successful experience indicates that the revamping process can be used in similar urban petroleum refineries, which would be beneficial to the sustainable development of the enterprise.

γ-Al2O3 PREPARATION WITH DIFFERENT MORPHOLOGIES AND ITS EFFECT ON Pt STABILITY

Peng YanYang Min Jia Ma Aizeng Ji Nie Jian ZhiDa

2019, 50(7):  109-118. 

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γ-Al2O3 is one of the most widely used heterogeneous catalyst carriers. In recent years，researchers have found that γ-Al2O3 crystallite morphologies have a great influence on the surface properties and the stability of the active metals such as Pt. The preparation and characterization techniques of boehmite with different crystallite morphologies and the effects of exposed facets of γ-Al2O3 crystallite on the surface properties of the support and the stability of Pt atoms are reviewed. The problems existing in the present research results are discussed，and the future research directions are prospected.