Table of Content

12 June 2022, Volume 53 Issue 6

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STUDY ON TECHNICAL ROUTE OF OIL REFINING TRANSFORMATION AND DEVELOPMENT

2022, 53(6):  1-5. 

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Due to the excess refining capacity and the slowdown of oil consumption, the utilization of crude oil resources has been changed from fuel oil production to oil-chemical integration, so as to enhance the competitiveness. Based on the market environment and the needs of survival and development, a detailed analysis and study on the integrated conversion scheme of oil and chemical was carried out, and an integrated model of decarbonization and full hydrogenation refining and chemical was designed. Through the comparison of investment, product distribution, technical and economic indexes, it can provide reference for the new refinery and the transformation of the existing enterprises.

STUDY ON THE PROCESS OF HIGH DENSITY JET FUEL PRODUCTION FROM FCC LCO

2022, 53(6):  6-11. 

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Based on the characteristics of high density and rich aromatics of FCC light cycle oil（LCO），the process technology of producing high-density jet fuel from the whole fraction of LCO was studied. The results show that the mass fraction of aromatics can be reduced to less than 5% by using NiMoW/Al₂O₃ hydrofining catalyst with high aromatics saturation activity through ultra-deep hydrogenation saturation under proper process conditions. Further detailed hydrocarbon analysis by gas chromatography-mass spectrometry (GC-MS) can clarify the distribution of hydrocarbons and investigate the fractions enriched with monocyclic，bicyclic and tricyclic cycloalkanes. The final boiling point of ideal fraction was 270 - 280 ℃ when the full fraction LCO was hydrogenated to produce high density jet fuel. Freezing point of high-density jet fuel component is lower than －47 ℃ and density（20 ℃）is greater than 0.835 g/cm³.

EFFECT OF THE RATIO OF HYDROGEN TO OIL ON DESULFURIZATION AND AROMATICS SATURATION SELECTIVITY IN DIESEL HYDROTREATING PROCESS

2022, 53(6):  12-17. 

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In order to better understand the influence of the ratio of hydrogen to oil on diesel hydrotreating process and improve the operation cycle and production benefit of the unit by optimizing the process parameter, the mixture oil of straight run diesel and catalytic cracking diesel from multiple refineries was used as feedstock. The hydrodesulfurization performance of diesel, the saturation performance of polycyclic aromatic hydrocarbons and monocyclic aromatic hydrocarbons and the effective utilization rate of hydrogen were investigated. By adding polycyclic aromatic phenanthrene to the feedstock, the reaction performance of the feedstock was investigated, and the reason of increasing the ratio of hydrogen to oil to improve the reaction performance was analyzed. The results show that increasing the ratio of hydrogen to oil can improve the atomization effect of feedstock, further promote the desulfurization and polycyclic aromatic hydrocarbon saturation reaction, and China Ⅵ diesel can be produced at lower reaction temperature, so as to prolong the operation cycle of the unit. At the same time, high ratio of hydrogen to oil can inhibit the saturation of monocyclic aromatic hydrocarbons to a certain extent, reduce hydrogen consumption, so as to improve the effective utilization rate of hydrogen.

IMPLEMENTATION PLAN AND EFFECT OF INCREASING PROPYLENE PRODUCTION BY RECYCLING LIGHT GASOLINE DISTILLATE INTO MIP UNIT

2022, 53(6):  18-22. 

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In order to reduce the fuel oil yield and increase the propylene yield, light gasoline distillates with high olefin content can be sent back to MIP unit for reprocessing. There are four ways of light gasoline refining methods: light gasoline is refined in a separate riser, light gasoline is used as quench oil into MIP reactor, light gasoline is recycled to the bottom of pre-lifting zone of the riser, and light gasoline is refined in a separate refining nozzle (below the heavy oil nozzle). After comparison and analysis, it was found that the reaction time and depth could be adjusted by adding a new light gasoline recycling nozzle under the heavy oil nozzle, the product distribution of light gasoline reaction was reasonable, the negative impact on MIP product properties was small, and the economic benefit was good.

RESOURCE UTILIZATION OF STYRENE TAR IN REFINERY

2022, 53(6):  23-27. 

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The source of styrene tar, the properties of polymerization inhibitor 2-sec-butyl-4,6- dinitrophenol (DNBP) and the composition of styrene tar were introduced. The feasibility of recycling styrene tar into qualified oil products was theoretically analyzed. The design and implementation of the scheme for converting styrene tar into qualified oil products in SINOPEC Anqing company were described in detail. The results show that when the styrene tar is sent to the delayed coking unit, the product value can increase while meeting the environmental protection requirements, and the total economic benefit can reach 8.3 million Yuan/a.

ANALYSIS OF LONG-TERM OPERATION OF CONDENSATE HYDROTREATING UNIT FOR PRODUCING LOW-SULFUR DIESEL AND NAPHTHA

2022, 53(6):  28-33. 

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The 5.0 Mt/a condensate hydrogenation unit in Fujian Fuhaichuang Petrochemical Co., Ltd. has continuously and stably produced low-sulfur naphtha and low-sulfur diesel products by means of full distillate hydrodesulfurization, denitrification and physical separation. The results of long-term industrial application show that using the catalyst HR-608, through the production test of different kinds of condensate oil, the refined naphtha and the low sulfur diesel oil can be produced by hydrogenation of the whole fraction condensate oil, and the refined naphtha can be beneficial to the stable operation of the reforming unit. It could be seen that the content of sulfur and nitrogen in the condensate could be effectively reduced by optimizing the process conditions of the condensate hydrotreating unit, the refined condensate products with sulfur content less than 3.0 μg/g could be produced, and the desired technical results were achieved. The heat release of the condensate hydrogenation process is low, and the energy consumption of fuel gas and high-pressure steam are high in the total energy consumption of the unit. By optimizing the parameters such as heat capacity, flue gas temperature, oxygen content of heating furnace, temperature of stripper bottom and reflux rate in convection section of heating furnace, the efficiency of heating furnace is improved and the consumption of high-pressure steam is reduced, thus the energy consumption of the device is reduced.

ENGINEERING PRACTICE OF USING MIP-CGP TECHNOLOGY TO INCREASE LIQUEFIED PETROLEUM GAS AND PROPYLENE IN FCC UNIT

2022, 53(6):  34-39. 

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In order to increase the production of liquefied petroleum gas (LPG) and propylene to meet the market demand, the production process of the catalytic cracking unit(Ⅱ) was adjusted from MIP technology to MIP-CGP technology, and the adaptive capacity expansion transformation was carried out for a series of gas separation units. After revamping, the operation of each unit was smoothly, the output of LPG was increased from 85.85 t/h to 117.20 t/h, and the yield was increased by 3.00 percentage points; the yield of propylene was increased from 24.89 t/h to 36.04 t/h, and the yield was increased by 1.26 percentage points. The product quality fully meets the requirements, greatly improving the economic benefits of the company. The MIP-CGP technical transformation provides a demonstration for improving the production of LPG and propylene in oil refining enterprises.

DEVELOPMENT OF COST-EFFECTIVE RESIDUE HYDROTREATING CATALYST FOR CARBON RESIDUE REDUCTION AND HYDRODESULFURIZATION

2022, 53(6):  40-45. 

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The platform of NATURE preparation technology for the cost-effective residue hydrotreating catalysts has been newly founded by SINOPEC Research Institute of Petroleum Processing. Based on this platform, RCS-202 catalyst with high performance-price ratio was developed by designing the pore structure, surface properties and active phase structure according to the molecular structure and reaction characteristics of carbon residue precursors in residue. The evaluation results showed that compared with the previous generation of industrial catalysts, the bulk density of the newly developed RCS-202 series catalyst was reduced by 20%, while the activity and stability of carbon residue reduction and HDS activities were improved significantly. Meanwhile, the characterization results showed that compared with the previous generation catalysts RCS-202 catalyst had higher pore volume and specific surface area, larger proportion of NiMoS phase in sulfided form, and lower carbon deposition after reactions. All of these structural characteristics have resulted in the cost-effective feature of the new RCS-202 series catalysts.

PREPARATION OF Ni/(ZSM-5/MCM-41) CATALYSTS AND THEIR CATALYTIC PERFORMANCE FOR HEPTANE ISOMERIZATION

2022, 53(6):  46-54. 

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ZSM-5/MCM-41 composite molecular sieves were prepared by hydrothermal method using ZSM-5 as silicon source, NaOH as alkali source and cetyltrimethylammonium bromide (CTAB) as template agent, and the metal-acid center bifunctional catalyst was prepared by impregnating the supported metal Ni. The effects of alkali dissolution conditions and Ni loading on the structure and properties of the catalyst were investigated by means of X-ray diffraction spectroscopy, N2 adsorption-desorption, ammonia temperature-programmed desorption, transmission electron microscopy and other characterization methods, then the catalytic performance of catalyst for n-heptane isomerization was evaluated. The results showed that the optimum NaOH concentration, the optimum alkali solution temperature and the optimum alkali solution time were 1.5 mol/L, 40 °C and 30 min respectively, and the obtained composite molecular sieve had a suitable acidity and a typical microporous/mesoporous composite structure. After Ni was loaded, Ni was dispersed uniformly on the surface of composite molecular sieve. Using 2%Ni/ZSM-5/MCM-41 as catalyst, the conversion of n-heptane was 65.44% and the selectivity of iso-heptane was 70.59% at 290 °C.

COMMERCIAL APPLICATION OF TRUE SULFURIZED PHK-101 CATALYST FOR JET FUEL HYDROGENATION UNIT

2022, 53(6):  55-60. 

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True sulfurized PHK-101 catalyst developed by PetroChina Petrochemical Research Institute was commercially used in a 0.40 Mt/a jet fuel hydrogenation unit of a refinery. The start-up and calibration results show that PHK-101 catalyst has the characteristics of high start-up efficiency and environmental protection, and is fully applicable to jet fuel hydrogenation unit with low reaction temperature. Under the condition of 108% production load, when the average bed temperature was 245 ℃, the product quality can not only meet the requirements of No.3 jet fuel National standard (GB 6537—2018)，but also meet the requirements of GB Ⅵ diesel blend components with sulfur content less than 10 μg/g.

CHARACTERIZATION AND EVALUATION OF MO-Ni-NH₃/r-Al₂O₃ DISPERSED CATALYST

2022, 53(6):  61-67. 

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Four kinds of macroporous Mo-Ni-NH₃/r-Al₂O₃ catalysts with large pore size were prepared by supersaturation impregnation method. The structure and species distribution of the catalysts were characterized by XRD, TEM, N₂ adsorption-desorption, H₂-TPR and XPS, and the activity of the catalysts was evaluated by hydrofining of inferior FCC diesel. The results showed that the active phase dispersion of A40 catalyst prepared by co-solvent TEA was the best. There are a lot of highly dispersed MoS₂ lamella lattices on the surface of the catalyst after pre-sulfiding, A40 catalyst has lower reduction temperature and higher sulfurization degree, and the proportion of Mo4+ and NiMoS was 86.46% and 56.3%, respectively. Among the four catalysts, the A40 catalyst had the highest activity of HDS, HDN, and HDAr, and the average conversion rats of HDS, HDN, and HDAr were 95.99%, 97.48% and 65.82%, respectively, indicating that the A40 catalyst was a good hydrogenation catalyst.

STUDY ON La MODIFIED Ni-BASED CATALYSTS FOR SELECTIVE HYDROGENATION OF REFORMATE TO REMOVE TRACE OLEFINS

2022, 53(6):  68-75. 

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The lanthanum modified NiO/Al₂O₃ catalyst was prepared by equal volume impregnation method using aluminum hydroxide dry glue as the raw material. The effects of the introduction sequence of La₂O₃ and the amount of La₂O₃ loading on the selective hydrodeolefin performance of NiO/Al₂O₃ catalyst were investigated in a 10 mL fixed bed microreactor using the reformate with the bromine index of 3 836 mgBr/(100g)as feedstock. The results show that under the conditions of a reaction pressure of 1.0 MPa,a volumetric space velocity of 8 h^-1, and a hydrogen-to-oil volume ratio of 25, the catalyst with 1.0% La₂O₃ loading, prepared by the lanthanum first and nickel later, has good selectivity for olefin hydrogenation, the loss of aromatics is less than 1.0%, and the bromine index is less than 200 mgBr/(100 g).

EFFECT OF POLYMERS MODIFICATION ON MICROSTRUCTURE OF MESOPHASE PITCHES AND MECHANICAL PROPERTIES OF CARBON FIBERS

2022, 53(6):  76-83. 

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Mesophase pitches were synthesized by the co-carbonization of an aromatic-rich heavy oil（FCCDO）and polyethylene glycol（PEG） under certain conditions, and the carbon fibers with excellent mechanical properties were prepared. The effects of PEG addition on the structure and properties of mesophase pitch and carbon fiber were analyzed by means of elemental analysis, X-ray diffraction and hydrogen NMR analysis et al., and the reaction mechanism of co-carbonization was speculated. The results show that with the increase of PEG addition, the softening point of mesophase pitch is gradually decreased, while the pitch yield and the number of aliphatic groups in the pitch molecular are gradually increased. At the same time, the optical structure of pitch was changed from the wide flow domain bulk mesophase to coarse flow domain mesophase, and finally to the mixed pitch with the coexistence of two phases（isotropic and mesophase components）. The mechanical properties of carbon fiber were increased at first and then decreased with the increase of PEG content. Carbon fibers with diameter of 11.4 μm and tensile strength up to 2.4 GPa were prepared by adding 5% PEG.

THREE-DIMENSIONAL GAS-PHASE FLOW FIELD IN A COUPLED CYCLONE WITH BUILT-IN GRANULAR BED FILTER

2022, 53(6):  84-92. 

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The five-hole probe was used to investigate three-dimensional gas flow field in a new cyclone-granular bed coupling separation equipment. The results show that the distribution of dimensionless tangential velocity is similar to that of configurations axial velocity under different inlet gas velocities; the axial symmetry of tangential velocity distribution is good, and the center of swirl is coincident with the center of geometry; the tangential velocity is decreased along the axial direction, but the radial distribution is different from that of the conventional cyclone; in the entrance annular space, the tangential velocity is increased in the range of 0°- 180°, but is decreased in the range of 180°- 270°; in the swirl space, the local spiraling air is concentrated at the 270° direction of the cylinder-cone connection; the law of radial velocity distribution is not obvious, and the radial velocity is the same order as the axial velocity in the straight tube section and has an important influence on the direction of the air flow; at the inlet section of exhaust pipe, the direction of external swirl flow is closely related to the inlet gas velocity. Combined with the distribution of the dynamic pressure field, it can be concluded that the gas flow in the cylinder-cone connection section is obviously decreased, and some gas is spiraled up into the granular bed, which may lead to the accumulation of dust in the actual operation. Due to the influence of the built-in particle bed, the whole gas phase inside the device moves in a spiral downward swirl flow, and the inner and outer boundary of the swirl flow is not very obvious. Because of the phenomena of short-circuit flow, the top ash ring and the back mixing are disappeared at the outlet of exhaust pipe.

STUDY ON PREPARATION OF NEEDLE COKE RAW MATERIAL FROM FCC SLURRY BY VACUUM DISTILLATION

2022, 53(6):  93-97. 

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The wide and narrow fractions of FCC slurry from Shandong Chambroad Petrochemical Co., Ltd. were cut by a 6 L real boiling point distillation unit. It was found that the sulfur and nitrogen content was increased with the increase of fraction yield, while the aromatic content was increased firstly and then decreased. When the fraction yield was 60%, the content of aromatic was the highest. In the cutting of every 10% narrow fraction, with the fraction becoming heavier, the content of tricyclic aromatics was decreased, the content of tetracyclic aromatics was increased at first and then decreased, and the content of tetracyclic aromatics were obviously decreased after 50%-60% narrow fraction. The optimum fraction to meet the demand of acicular coke was from the initial fraction to 60%.

DEVELOPMENT AND APPLICATION OF ANALYTICAL METHOD FOR COCONUT OIL METHYL ESTER HYDROGENATION PRODUCTS BY GAS CHROMATOGRAPHY

2022, 53(6):  98-107. 

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The components of raw materials and products were qualitatively analyzed by GC-MS and quantitatively analyzed by GC-FID with correction normalization. The detailed composition of hydrogenation products of coconut oil methyl ester with different hydrogenation degrees was determined. The method could be extended to analyze the different vegetable oil methyl esters and its processing products natural fatty alcohols.

DETERMINATION OF HYDROCARBON COMPOSITION AND CARBON NUMBER DISTRIBUTION IN THE MIDDLE FRACTION OF FISCHER-TROPSCH SYNTHETIC OIL BY SOLID PHASE EXTRACTION AND GAS CHROMATOGRAPHY-MASS SPECTROMETRY

2022, 53(6):  108-115. 

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SiO₂/Ag-Al₂O₃ double column solid phase extraction was used to separate the middle fraction of Fischer-Tropsch synthetic oil（F-T oil） into saturated hydrocarbons, olefins, aromatics and oxides etc. , and gas chromatography-mass spectrometry/hydrogen flame ionzation detector (GC-MS/FID) and gas chromatography field ionization time of flight mass spectrometry (GC-FI TOF MS) were used to characterize the type and carbon number distribution of each component. The results show that the middle fraction of low temperature F-T oil is mainly composed of n-alkanes, α-olefins and normal alcohols, whose contents are 41.0%, 30.3% and 8.8%, respectively, and other compounds are basically isomeric compounds. The middle fraction of high temperature F-T oil is complex, and the normal compounds are reduced while the proportions of isomeric compounds are significantly increased. Cycloalkanes were found in saturated hydrocarbons, dienes, trienes or cycloalkenes were found in olefins, and monocyclic aromatics were main aromatics.

SYNTHESIS AND PROPERTIES OF ANTIOXIDANT NONYLDIPHENYLAMINE

2022, 53(6):  116-119. 

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Antioxidant nonyldiphenylamine was synthesized from nonene and diphenylamine in the presence of catalyst. The thermal stability was analyzed by differential thermal analysis (DSC) and thermogravimetric analysis (TGA), and the oxidation resistance was evaluated by rotary oxygen bomb test (RBOT), pressure differential scanning calorimetry (PDSC), thin-film oxygen uptake test (TFOUT), thermo-oxidation engine oil simulation test (TEOST) and other methods. The results show that the synthesized nonyldiphenylamine has good thermal stability and antioxidant performance, and can meet the requirements of high-grade internal combustion engine oil.

CHARACTERISTICS OF VOCs EMISSION FROM A PETROCHEMICAL INDUSTRY AREA AND ASSOCIATED CONTRIBUTIONS TO SECONDARY POLLUTION

2022, 53(6):  120-127. 

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Atmospheric volatile organic compounds (VOCs) were continuously monitored using on-line gas chromatography mass spectrometer/flame ionization detector system（GC-MS/FID） in a petrochemical industry area from January 2020 to June 2020 to analyze the emission characteristics, ozone formation potential, and potential sources of VOCs. During the sampling period, alkanes were the most predominant VOCs, followed by aromatic compounds and oxygenated VOCs. Four potential sources of VOCs were quantified by the positive matrix factorization model, including chemical companies on the southeast side, chemical companies on the southwest side, refinery production areas, sewage treatment area. According to the secondary pollution assessment method, the contribution of chemical companies and refinery emission sources to the zone formation potential is 50% each, while the contribution of chemical companies to the secondary organic aerosol is significantly higher than that of refineries. Therefore, priority control strategies should be formulated based on the selected major pollution sources and key active components in the petrochemical industrial park.

PREPARATION OF BIOMASS COKE AND ADSORPTION PROPERTIES FOR VOCs

2022, 53(6):  128-131. 

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Biomass coke adsorbent was prepared from biomass waste (rice husk, orange peel and walnut shell), and the biomass coke was modified by steam, H₃PO₄ or H₂O₂ to enhance its adsorption performance of benzene. The factors affecting coke yield and adsorption performance of biomass coke were studied. The results showed that the coke yield of three kinds of biomass was gradually decreased with the increase of pyrolysis temperature, and the coke yield of rice husk was significantly higher than that of walnut shell and orange pee. There are C—H bonds on the surface of the three biomass coke, a large number of C—O bonds on the surface of rice husk coke, and aromatic cyanogens containing C≡N bonds on the surface of orange peel coke. Among the three kinds of original biomass coke, walnut shell coke had higher benzene adsorption efficiency, and rice shell coke was relatively poor. After steam activation and pore expansion, the benzene removal rate of rice shell coke could be still maintained at about 85% for 60 min, and the benzene removal efficiency of H₃PO₄ modified rice shell coke also reached above 80%, while the benzene adsorption performance of H₂O₂ modified rice shell coke had not changed significantly.