PETROLEUM PROCESSING AND PETROCHEMICALS

RESEARCH PROGRESS OF RUTHENIUM-BASED ACIDIC OXYGEN CATALYST EVOLUTION IN WATER ELECTROLYSIS

2023, 54(10): 1-10.

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Bimodal porous materials have attracted much attention in the field of catalysis because of their ability to construct macromolecule diffusion channels and high reactive surface on the same catalyst. In this paper, the structural characteristics and construction mechanism of bimodal porous materials were reviewed, the preparation principle and method of bimodal porous materials were summarized, and their application in electrocatalysis, photocatalysis, catalytic hydrotreatment of oil and the principle of catalyst performance improvement were summarized. On this basis, the research direction of bimodal porous materials in the future was discussed.

STUDY ON PREPARATION OF NEEDLE COKE RAW MATERIALS BY HYDROTREATING FCC SLURRY

2023, 54(10): 39-44.

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The slurry from No. 2 catalytic cracking unit of SINOPEC Maoming Company was used as the research object, the process of slurry-bed hydrogenation was simulated by autoclave reaction with dispersed Co-Mo catalyst, and the effects of initial hydrogen pressure, reaction time, catalyst addition amount and reaction temperature on the product were investigated. The results showed that under the conditions of initial hydrogen pressure of 3 MPa, reaction time of 120 min, catalyst mass fraction of 5 000 μg/g and reaction temperature of 400 ℃, the content of sulfur and nitrogen in the product was 0.44% and 0.14%, respectively, which could meet the requirement of needle coke raw materials; the yield of heavy fraction and aromatics (tricyclic + tetracyclic) were 73.8% and 48.9%, respectively, which were 3.8 percentage points and 12.9 percentage points higher than that of the existing industrial pretreatment technology, respectively, indicating that the slurry-bed hydropretreatment process of FCC slurry could produce the high-quality needle coke raw material. At the same time, it had the technical advantages of high yield of heavy fraction and low loss rate of tricyclic and tetracyclic aromatic hydrocarbons.

APPLICATION OF FORMULATED CRUDE OIL TECHNOLOGY IN REFINERY CRUDE OIL PROCESSING

2023, 54(10): 45-51.

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In order to reduce the fluctuation of crude oil properties and the over-dependence on certain kind of profitable crude oil, based on the database of crude oil evaluation and crude oil near-infrared spectroscopy，the formulated crude oil technology with the main goal of stabilizing properties of processed crude oil was developed by using advanced calculation methods. Based on the properties and characteristics of crude oil processed by a certain refinery, the formulated crude oil blending recipes were designed and selected with the processed Cabinda crude oil as the target crude oil. Thus the target crude oil and two kinds of formulated crude oils were processed and sampled to evaluate. The results showed that the similarity between two kinds of formulated crude oil and the target crude oil was more than 90%, and the yields and properties of side-line fractions were similar. The formulated crude oil not only could meet the processing requirements of the crude oil distillation unit, but also had better profit than the target crude oil.

COMMERCIAL APPILICATION OF SOLID SUPERACID C₅/C₆ ISOMERIZATION TECHNOLOGY

2023, 54(10): 52-57.

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The solid superacid C₅/C₆ isomerization technology developed by SINOPEC Research Institute of Petroleum Processing Co., Ltd. consists of Pt/SO₄^2--ZrO₂ catalyst RISO-C and its supporting unit technologies of start-up, reaction parameter optimization, feed pretreatment, catalyst regeneration, etc. The industrial applications showed that the whole set of technology had strong adaptability, which could be used in the revamped units or the newly constructed units, and also be combined with proper separation technologies to further improve the RON of isomerization product. The isomerate with RON ranging from 80 to 90 could be produced to meet the needs of different users, which was an important supporting technology for upgrading gasoline standard.

INDUSTRIAL PRACTICE OF REVAMPING SEMI-REGENERATIVE REFROMING UNIT TO SOLID SUPERACID C5/C6 ISOMERIZATION UNIT

2023, 54(10): 58-64.

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In order to produce high octane gasoline in accordance with the national VIB gasoline standard, the solid superacid C₅/C₆ isomerization catalyst developed by SINOPEC Research Institute of Petroleum Processing was used in a refinery and its supporting process technology was also adopted. The idle 190 kt/a semi-regeneration catalytic reforming unit was converted into a C₅/C₆ isomerization unit for the processing of reformer topping oil rich in benzene and heptane. The industrial practice results showed that it was feasible to transform the semi-regeneration reforming unit into the isomerization unit of solid superacid C₅/C₆. Under the condition of qualified water content, catalyst RISO-C had excellent isomerization activity and stability even when the benzene and C₇ mass fraction of C₅/C₆ isomerization feedstock were 4%-8% and 10%-18%, respectively. At the same time, it had good benzene hydrogenation activity, which increased the research octane number (RON) of isomerized products by 4-8 units, reaching 82 or above, and the benzene content was below 0.8%. Combining the C₅/C₆ isomerization unit of solid superacid with C₇+ reforming unit, the benzene content of reformer gasoline could be reduced, and the high octane number gasoline conforming to the national VIB gasoline standard could be produced, which had remarkable economic and social benefits.

STUDY ON FORMATION OF ZINC SILICATE IN S Zorb CATALYST DURING DESULFURIZATION

2023, 54(10): 65-72.

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The formation mechanism of zinc silicate in S Zorb catalyst was studied in view of deactivation and breakage of the catalyst in different degrees during the operation of the S Zorb unit. A series of catalysts with fixed zinc source, different silicon sources and different zinc source were prepared, and the aging tests were carried out in a well type aging furnace under different temperature and atmosphere conditions. The formation of zinc silicate in the catalyst was investigated by the Rietveld method, and the impact of silicon source morphology, SiO₂ content, and ZnO particle size on the formation of zinc silicate in S Zorb catalyst was simulated. The results showed that amorphous SiO₂ reacted with ZnO more easily than the crystalline SiO₂ to form zinc silicate. At 800 ℃, the yield (w) of zinc silicate reached 68.7% when amorphous SiO₂ was used as the silicon source, while the yield (w) of zinc silicate was 10.3% when pure SiO₂with crystal structure reacted with ZnO. The larger particle size of ZnO, the less zinc silicate was formed. By comparing the formation of zinc silicate in different atmospheres, it was found that the formation of zinc silicate was promoted by the presence of water vapor and SO₂, and the formation of zinc silicate was further accelerated by the co-existence of SO₂ and water vapor.

REGENERATION OF USED TRANSFORMER INSULATING OIL BY HYDROGENATION

2023, 54(10): 73-77.

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Aiming at the problems of high acid number, deep color, bad oxidation stability and electric properties, and increasing power consumption of transformer insulating oil caused by high temperature oxidation and high voltage electric field, the direct hydrogenation regeneration of used transformer insulating oil(UTIO) was studied by using a self-made Ni-Mo-W regeneration catalyst, and the effects of the hydrogenation conditions on the properties and composition of UTIO were investigated. The results indicated that after the regeneration of UTIO by direct hydrogenation, the color became lighter, the anti-oxidation stability increased, and electricity properties improved, the metal, polychlorinated biphenyls and antioxidant content could not be detected, and the content of polycyclic aromatic hydrocarbons decreased. The optimum hydrogenation conditions were as follows: reaction pressure 4.0 MPa, space velocity 2-3 h^-1, reaction temperature 220-260 ℃, and the hydrogen/oil volume ratio 300-500. The hydrogenated oil could meet the requirements of transformer insulating oils, which revealed that the catalyst had high selectivity and catalytic performance.

STUDY ON S-1 ZEOLITE CATALYST FOR THE VAPOR PHASE BECKMANN REARRANGEMENT OF CYCLOHEXANONE OXIME

2023, 54(10): 78-84.

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S-1 zeolites were synthesized by hydrothermal method, Fe was introduced to adjust the proportion of different silicon hydroxyl groups in the S-1 zeolites, and S-1 catalysts were obtained after post-treatment of the S-1 zeolites with N-containing buffer solution. The S-1 zeolites were characterized by XRD, N2 adsorption-desorption isotherm, FT-IR, ICP-AES, and SEM. The influences of Fe content and post-treatment of N-containing buffer solution on the physicochemical properties of the S-1 zeolites and their catalytic performances for the vapor phase Beckmann rearrangement of cyclohexanone oxime to produce ε-caprolactam were investigated. The results showed the optimum Fe content of S-1 zeolites was 254 μg/g, relative total amount of siloxane hydroxyl and the ratio of nested siloxane hydroxyl groups increased obviously after the post-treatment of N-containing buffer solution, and the conversion of cyclohexanone oxime to gas phase Beckmann rearrangement and the selectivity of cyclohexanone oxime to epsilon-caprolactam were to 99.9% and 95.0%, respectively.

REDUCTION OF CO₂ BY Cu₂O/MnCo₂O₄ HETEROJUNCTION NANO-PHOTOCATALYST

2023, 54(10): 85-91.

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Z-type heterojunction photocatalyst is favored by researchers because of strong charge separation ability of conduction band and valence band, and strong oxidation- reduction ability. Z-type Cu₂O/MnCo₂O₄ heterojunction nano-photocatalysts were prepared by hydrothermal method, their physical and chemical properties were characterized in detail, and their photocatalytic CO₂ reduction performance was evaluated. The characteristic results of XRD, HRTEM, UV vis, PL and EIS showed that compared with MnCo₂O₄ nano-particles,Cu₂O/MnCo₂O₄eterojunction nano-photocatalyst could improve the visible light absorption performance, reduce the band gap, delay the recombination of electron-hole pairs effectively, and reduce the transfer resistance of electron-hole pairs, which confirmed that heterojunction nano-structures could effectively improve the photocatalytic activity for CO₂. The evaluation results of photocatalytic reduction of CO₂ showed that heterojunction nano-photocatalyst with 15%（w) Cu₂O content had the best photocatalytic activity for CO₂ reduction, and the CO yield was 98.6 μmol/g, the yield of CH₄ was 68.4 μmol/g, and its catalytic activity remained unchanged after 6 times of recycling uses.

PREPARATION OF MESO-MICROPOROUS COMPOSITE BETA-MCM-41 AND ITS CATALYTIC PERFORMANCE FOR n-HEPTANE HYDROISOMERIZATION

2023, 54(10): 92-101.

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The meso-microporous composite Beta-MCM-41 (denoted as BM-41) was prepared by nano-assembly of cationic surfactant cetyltrimethylammonium bromide (CTAB) with Beta zeolite treated with NaOH solution，and hydrogen-based composite HBeta-MCM-41(denoted as HBM-41) was prepared by ion-exchange between BM-41 and NH4Cl. The catalyst Pt/HBM-41 with 0.4% Pt loading (w) was prepared with HBM-41 as support, and applied to the hydroisomerization of n-heptane. The samples were characterized by X-ray diffraction, N₂ adsorption-desorption, and Fourier transform infrared spectroscopy. The catalysts were evaluated at 240 ℃, atmospheric pressure and mass space velocity of 2.46 h^-1. The results showed that Pt/HBM-41 exhibited higher isomerization selectivity (87.01%) and higher n-heptane conversion rate (78.75%) in three catalysts with the same Pt loading: Pt/HBeta, Pt/MCM-41, Pt/HBM-41, the yield of isoheptane was the highest (68.52%). This can be attributed to Beta-MCM-41 combining the excellent diffusion properties of the two-dimensional hexagonal mesoporous MCM-41 with the superior acid properties of Beta zeolite.

CATALYTIC PERFORMANCE OF THE CERIUM-BASED CATALYSTS IN THE LOW-TEMPERATURE COMBUSTION OF POLYETHYLENE

2023, 54(10): 102-109.

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In order to improve the combustion process of polymer wastes, six kinds of the cerium-based catalysts (Ce-Al₂O₃，Ce-SiO₂，Ce-Fe₂O₃，Ce-NiO，Ce-ZrO₂ and Ce-La₂O₃) were prepared by the impregnation method, the physical chemistry properties were analyzed by XRD, SEM, N₂ adsorption-desorption and O₂-TPD, and the catalytic performance was evaluated by using the low-temperature combustion of polyethylene. The results showed that CeO₂ particles were formed on the surface of Ce-Al₂O₃, which exhibited stronger oxygen adsorption and activation ability than that of polyethylene combustion without catalyst. Compared with polyethylene combustion without catalyst, Ce-Al₂O₃-catalyzed polyethylene combustion could increased both the combustion rate and the combustion efficiency, and thus increased the heat release in polyethylene low-temperature combustion, the selectivity of CO and CO₂ increased by 2.6 times. Ce-Al₂O₃ was reused for 6 times, and still maintained good catalytic performance. The combustion rate and the selectivity of CO and CO₂ in the catalytic polyethylene combustion reaction were higher than that of polyethylene combustion without catalyst.

EVALUATION OF BIOMASS JET FUEL SUSTAINABILITY AND LIFE-CYCLE CARBON FOOTPRINT

2023, 54(10): 110-116.

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Aiming at the two-stage hydrogenation technology(SRJET) developed by SINOPEC to produce biomass jet fuel (bio jet fuel for short) from waste catering oil, basing on the life cycle assessment analysis, the accounting boundary was determined, and the carbon footprint of the life cycle of bio jet fuel (total direct and indirect CO₂emissions per unit of product lifecycle) was analyzed. The carbon emission reduction of bio-jet fuel replacing petroleum-based jet fuel was evaluated by comparing of the life-cycle carbon emissions. The results showed that the total carbon emission during the life cycle of producing 1 kg bio-jet fuel was 0.55 kg, and within the 90% confidence interval of the prediction result, the CO₂ emission of bio-jet fuel was 80.9%-93.2% lower than that of petroleum-based jet fuel. The promotion of bio-jet fuel is of great significance to achieve the strategic goal of emission peak and carbon neutrality.

OPTIMIZATION AND IMPLEMENTATION OF FLARE EMISSION REDUCTION IN AROMATIC COMBINED PLANT BASED ON HIPS AND PINCHED APPROACH

2023, 54(10): 117-121.

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An example is the newly built 1.5 Mt/a p-xylene aromatic unit, which uses adsorption simulate moving bed technology, and its utilities rely on the existing facilities of enterprise. The receiving capacity of original flare system is only 500 t/h, which can not meet the demand in case of general power failure（GPF）happened. HIPS was applied to xylene column, extract column and reformate splitter column, and the pinch point design was optimized to reduce the flare emission. The results showed that the application of HIPS and pinch technology could reduce the torch emission from 3 790 t/h to 438 t/h, which met the requirements of the whole plant GPF accident.

COMPUTER-AIDED SIMULATION OF CATALYST EFFICIENCY FACTOR

2023, 54(10): 122-131.

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The shape of catalyst has a great influence on the efficiency factor, and the distance between the active center and the boundary in the catalyst has a great influence on the efficiency factor. The geometrical distribution of the distance from the catalyst active centers to the boundary was plotted based on the value of the distance, which could be simulated by computer-aided techniques to calculate the distance from any point on the cross-sectional graph of the catalyst to the boundary. Based on the counting of isometric points and efficiency factors, the overall efficiency factor of the catalyst is obtained, and the simulation of the efficiency factor of complex morphological catalysts is realized.

NUMERICAL SIMULATION OF COMBUSTION CHARACTERISTICS OF STRONG EJECTOR FLARE ON OFFSHORE PLATFORM

2023, 54(10): 132-137.

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In order to solve the problem of black smoke from release flare during oil and gas production on offshore platform, a three-stage ejector structure was used to optimize the structural of the basic flare burner, and the combustion and black smoke generation of the new flare were simulated by Fluent software. The results showed that when the expansion angle of the flare head was 7°, the clearance of the draft shield was 207 mm, the number of Venturi ejectors was 8, the depth of the main discharge pipe of the flare gas was 242 mm, the peak value of the soot mass fraction decreased from 2.2 mg/g to 1.5 mg/g, and no black smoke phenomenon was observed outside the flame surface. The new structure of flare burner has obvious effect on reducing soot. The research results can provide a reference for the technical improvement of the release flare on offshore platforms.

INFLUENCE OF INCREASING MIXING AMOUNT OF RUSSIAN OIL ON THE CORROSION OF DISTILLATION UNITS AND COUNTERMEASURES

2023, 54(10): 138-142.

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As the price of Russian crude oil on the international market has fallen, some refining companies have increased the processing amount of Russian crude oil in atmospheric and vacuum distillation units in order to achieve their efficiency goals, resulting in the blending ratio of Russian crude oil exceeding the design conditions, and the corrosion problem of equipment in the units needs to be solved urgently. The potential corrosion of sulfur, chlorine, salt and other harmful substances in crude oil to atmospheric and vacuum distillation units was analyzed by comparing the change data of harmful components in crude oil before and after adjusting the blending ratio of Russian crude oil in an atmospheric and vacuum distillation unit. Combined with the equipment corrosion problems occurred in the plant in recent years, the anti-corrosion control measures for increasing the amount of Russian crude oil blending under super-design conditions were established from the aspects of technology, equipment and management, and the corrosion problem of atmospheric and vacuum distillation equipment caused by corrosive substances in Russian crude oil was solved. At the same time, corrosion analysis methods and control measures for atmospheric and vacuum distillation units with low blending ratio of Russian crude oil were provided.

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