Table of Content

12 April 2022, Volume 53 Issue 4

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STUDY ON ENERGY EFFICIENCY EVALUATION METHOD OF OIL REFINING UNIT UNDER “DOUBLE CARBON” BACKGROUND

2022, 53(4):  1-8. 

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The existing energy efficiency evaluation methods used in refineries at domestic and overseas are mainly applicable to the comparison of the overall energy consumption level between enterprises. Based on the energy-using mechanism, the energy-using analysis of the “Three-link” theory, and the process simulation technology, the energy-using parameters of the key links of the unit and system were used to evaluate the energy consumption level in the refinery, and a new energy efficiency evaluation method was also proposed. The results of evaluating the energy efficiency level of atmospheric and vacuum distillation units show that this method can guide the analysis of energy-saving potential and optimization of the energy-saving scheme in the refinery units, which can make the single unit realize better energy-saving, and assist the realization of “double carbon” goal.

PROGRESS IN THE STUDY OF VOLATILE ORGANIC COMPOUND COMPOSITION OF PETROCHEMICAL INDUSTRIAL IN CHINA

2022, 53(4):  9-16. 

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The emission of VOCs from the petrochemical industry is one of the major sources of VOCs in the atmospheric, and it is the basis of the regulation, control and tracing of VOCs in the petrochemical industry to clarify the characteristics of VOCs emission from the petrochemical industry and to construct a complete and detailed composition spectrum of VOCs source. This paper summarizes the research progress of VOCs emission from petrochemical industry in China from the sources, monitoring technology and source profile, which can provide a theoretical reference for the regulation and treatment of VOCs emission from petrochemical industry.

ADVANCES IN CATALYSTS AND PROCESSES FOR LUBRICATING OIL HYDROGENATION

2022, 53(4):  17-23. 

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With the upgrading of lube base oil quality and the increasing demand of high-grade base oil, hydrogenation technology is gradually replacing traditional methods for producing the API II and API III base oils. Poly alpha olefin (PAO) has been developed rapidly as API IV base oil. In recent years, the technology development of high-grade lubricant oil has been paid more attention at domestic and overseas. Hydrotreating-hydroisomerization-hydrofinishing supplement refining process and PAO hydrogenation process have become the main methods to produce high-grade lubricating oil. In addition, the development of hydrotreating catalysts and hydrotreating process for producing lubricant base oil is summarized. The present technology and prospect of hydrotreating process for producing high grade lubricant base oil are introduced.

STUDY ON CATALYST AND PROCESS OF BENZENE AND SYNGAS ALKYLATION REACTION

2022, 53(4):  24-29. 

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A series of monometallic and metal-acid dual-functional catalysts were prepared by impregnation method, and the effects of different metals, acid materials, metal loading, number of acid centers, and the distance between metal and acid center on the reaction of benzene and syngas were investigated. Stability of the catalyst was also evaluated. As a result, Zn is the most active metal component; the dual-function catalyst composed of Zn and HZSM-5 has higher activity than the single-function catalyst; the proper ratio of metal to acid center is beneficial to the better dispersion of active components on the carrier and promote the reaction; the catalyst prepared by the impregnation method has a closer distance between the metal and the acid center, and has the highest reaction activity. At the same time, the possible reaction path of the benzene and syngas alkylation reaction is verified. The 300 h stability experiment result show that the average conversion rate of benzene is 36%, the selectivity of toluene and xylene is greater than 90%, and the catalyst has good reactivity and stability.

STUDY ON CATALYTIC PERFORMANCE OF Fe₂O₃/Al₂O₃ IN BIOMASS PYROLYSIS COUPLED WITH HEAVY OIL UPGRADING PROCESS

2022, 53(4):  30-37. 

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Aiming at the poor upgrading effect of heavy oil and easy coking, a new idea of biomass pyrolysis coupled with heavy oil upgrading was proposed, and the catalytic effect of the catalyst Fe₂O₃/Al₂O₃ on biomass (microcrystalline cellulose and waste paper) pyrolysis behavior was investigated. The results show that the yield of biomass pyrolysis bio-oil is increased and the viscosity of the modified heavy oil is further reduced by using Fe₂O₃/Al₂O₃ as a catalyst. Under the conditions of a catalyst mass fraction of 0.4%,a reaction temperature of 350 ℃ and a reaction time of 30 min, the yields of cellulose and waste paper pyrolysis bio-oil were 76.25% and 65.26%, respectively. For the two coupling systems of cellulose-heavy oil and waste paper scraps-heavy oil, the viscosity reduction rate of the upgraded heavy oil was reached 74.14% and 65.93%, respectively. The results of FT-IR and SARA analysis before and after upgrading showed that the heavy oil was deeply cracked, and the C—C bonds and C—S bonds were broken under the action of the active hydrogen and Fe₂O₃, to produce light components.

RESEARCH ON IRON MIGRATION IN FCC REACTOR BED AND INDUSTRIAL APPLICATION OF NEW ANTI-IRON CATALYST

2022, 53(4):  38-42. 

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In order to solve the problem of the high iron content of long-term catalysts in the heavy oil catalytic cracking unit of SINOPEC Hainan Refining and Chemical Co.,Ltd., the distribution and migration of iron in the high iron-containing equilibrium catalyst were studied by means of SEM-EDS and EPMA. It was found that the iron in the equilibrium catalyst could migrate between particles, which could provide a guidance for the design and development of iron-resistant catalysts. The typical iron poisoning phenomenon in FCC unit was summarized, which was mainly manifested in the increase of secondary dilute phase density, the increase of slurry yield, and the decrease of ABD and pore volume. The new anti-iron catalyst CMT-1HN designed and developed by SINOPEC Research Institute of Petroleum Processing was industrially applied in Hainan Refining and Chemical Co.,Ltd. The application results showed that the fluidization in the unit was normal under the condition that the iron content of the equilibrium catalyst maintained 8 000-10 000 μg/g for a long time, and the heavy oil conversion was good, which indicated that the CMT-1HN catalyst had excellent performance of anti-iron contamination.

STUDY ON THE EFFECT OF HYDROTREATING ON CATALYTIC CRACKING PERFORMANCE OF RUSSIAN RESIDUE

2022, 53(4):  43-46. 

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The effect of hydrotreating on the catalytic cracking performance of the mixed oil of Russian vacuum residue and VGO with high sulfur, nitrogen, metal content and high residual carbon value was investigated. The results showed that compared with non-hydrotreated feedstock, when the hydrotreated residue was over 350 °C, the total liquid yield of the product and the gasoline yield were increased by 4.41 percentage points and 5.74 percentage points, respectively, the light oil yield was increased by 5.12 percentage points, and the coke yield was decreased by 3.40 percentage points; the sulfur content of FCC gasoline was decreased from 660 μg/g to 53 μg/g, the mass fraction of olefins was decreased from 40.8% to 36.9%, the octane number of the research method was increased by 0.69. The properties of FCC gasoline were significantly improved.

OPTIMIZATION OF PROCESS CONDITIONS FOR PENTANE AND METHANOL CO-AROMATIZATION

2022, 53(4):  47-53. 

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The effects of the reaction temperature, hydrocarbon base mass space velocity, and the feed molar ratio of methanol to n-pentane on the co-aromatization performance were systematically investigated in a fixed bed micro-reactor with ZSM-5 molecular sieve modified by ZnO as the catalyst. The results showed that the co-aromatization of n-pentane and methanol significantly improved the selectivity of aromatics and inhibited the formation of dry gas, the conversion rate of n-pentane decreased with the increase of the molar ratio of methanol to n-pentane. The optimum reaction conditions for the co-aromatization of n-pentane and methanol on ZSM-5 molecular sieve covered a temperature of 475 ℃, a hydrocarbon base mass space velocity of 2 h^-1, and a molar ratio of methanol to n-pentane of 3:1. The selectivity of aromatics in the co-aromatization of n-pentane with methanol was 31.68% at the optimum reaction conditions.

STUDY ON PRODUCING AROMATIC RUBBER PLASTICIZER FROM HIGH-SULFUR NAPHTHENIC VACUUM DISTILLATE BY HYDROGENATION PROCESS

2022, 53(4):  54-57. 

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Taking the high-sulfur naphthenic vacuum second-line distillate（high-sulfur naphthenic vacuum distillate）as feedstock, using the independently developed hydrotreating，hydrodewaxing and refining catalysts, the production of rubber plasticizer A1004 by high pressure hydrogenation process was studied. The results showed that the aromatic rubber plasticizer A1004 could meet the requirements of GB/T 33322—2016 with a production yield of about 82%, and the aromatic carbon ratio CA was 11.2%.

STUDY ON EXTRACTION TECHNOLOGY OF THE INDONESIAN OIL SANDS BITUMEN BY ACCELERATED SOLVENT EXTRACTION

2022, 53(4):  58-62. 

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Accelerated solvent extraction technology was used to extract oil sands bitumen, and the optimum technological parameters of pressurized solvent extraction technology were obtained by single factor test and orthogonal test. The results show that the accelerated solvent extraction method is superior to the traditional Soxhlet extraction and Fisher test in the pressure condition and the mixture of diatomite dispersant. The optimal process parameters of accelerated solvent extraction for the extraction of oil sands bitumen were obtained by orthogonal test as follows: a pressureof 10 MPa, a soil-sand volume ratio of 2:1, a extraction temperature of 160 ℃ , a times of cycles of 5 , solvent tetrahydrofuran, and a single static extraction time of 12 min.

STUDY ON LOW COST PROCESSING SCHEME OF LOW SULFUR MARINE FUEL OIL

2022, 53(4):  63-69. 

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Marine fuel oil is mainly produced by blending vacuum residue, hydrotreated residue, FCC slurry and FCC diesel oil, and its pour point and viscosity are reduced by thermal upgrading of high viscosity components, which can reduce the amount of light blending components, optimize the production formula and reduce the production cost of marine fuel oil. W refinery planned to use atmospheric residue as low sulfur marine fuel product. Through the application of atmospheric and vacuum distillation and thermal upgrading combination process, the lab-scale results showed that the kinematic viscosity（50 ℃） of vacuum residue with appropriate cutting point could be reduced to less than 380 mm²/s. Selecting low sulfur blending components can release the whole straight-run diesel and VGO fractions and reduce the production cost of marine fuel oil. The marine fuel through the application of thermal upgrading and blending combination process was directly produced by using blending vacuum residue, preferred heavy oil F and FCC diesel oil as raw materials in H refinery. The pilot test results showed that the viscosity and pour point of vacuum residue were greatly decreased, the amount of blended diesel could be reduced by 50%, and the economic benefits of the refinery could be greatly improved.

COMMERCIAL APPLICATION OF m-XYLENE PRODUCTION PROCESS FROM RAFFINATE OF AROMATICS UNIT

2022, 53(4):  70-74. 

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The industrial application of a 200 kt/a m-xylene adsorption separation unit in ZhongJin Petrochemical Co. Ltd. was introduced. The unit was completed and began to be put into operation in 2020, which was the largest m-xylene production unit in the world. The test results show that the capacity of the unit is 203.3 kt/a, the purity of the m-xylene product is 99.53%, and the single-pass yield is 95.1%. The appropriate range of water content in the adsorbent is beneficial for the selectivity, which can improve the product purity and yield. In addition, benzene is a temporary poison for the adsorbent, and increasing benzene content in the desorbent will reduce the yield.

STUDY ON MICROSTRUCTURE OF INDUSTRIAL SPENT Pt-Sn/γ-Al₂O₃ REFORMING CATALYST

2022, 53(4):  75-81. 

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The morphology and microstructure of support as well as the location, size and aggregation state of active metals in industrial spent catalysts Pt-Sn/γ-Al₂O₃ (PS-V) were comprehensively characterized by various characterization methods. The results of X-ray diffraction showed that the crystal structure and parameters of both spent and fresh catalysts had no obvious difference. The high-resolution transmission electron microscope (HRTEM) images showed that carrier part of the spent catalyst was transformed into α-Al₂O₃ from γ-Al₂O₃ with honeycomb or laminar microstructure. Meanwhile, massive Pt atoms reacted with Sn atoms to form Pt-Sn alloy aggregates with the dimension ranging from 20 nm to 150 nm, and the statistical average size of Pt-Sn alloy aggregates was about 50 nm. The results of aberration-corrected high-resolution scanning transmission electron microscopy (Cs-STEM) showed that the unaggregated Pt atoms were still dispersed at the atomic level on the surface of the carrier. The in-situ Fourier transform infrared spectrocopy of CO probe (CO-FTIR) showed that the Pt metals were aggregated in the spent catalyst, and the interaction with the carrier was basically disappeared. At the same time, the microstructure of industrial spent catalyst was analyzed from both support and metal, and the structure-activity relationship between the structure change and the performance decline of catalyst was given.

STUDY ON THE THERMAL STABILITY OF X ZEOLITE

2022, 53(4):  82-88. 

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In order to study the thermal stability of X zeolite, X zeolite was synthesized by using hydrothermal crystallization method, and then was calcined at 500, 600, 700, 800 and 900 ℃ in nitrogen atmosphere. X zeolite and its calcination products were thoroughly characterized by X-ray diffraction, N₂ adsorption-desorption, scanning electron microscope, thermogravimetry, differential scanning calorimetry, magic angle spinning solid nuclear magnetic resonance and Fourier transform infrared spectroscopy. The results showed that when the calcination temperature was lower than 800 °C, the crystalline structure and micropores of X zeolite were not destroyed, the calcination products still maintained the same octahedral morphology as the original X zeolite, the Si-O-Al connection in the crystalline structure was stable, and no non-framework aluminum species were formed. When the calcination temperature reached 900 °C, the crystalline structure of X zeolite was completely destroyed after melting, leading to the formation of the amorphous species with smooth edge and the micropore volume of 0. There were still a lot of Si-O-Al and Si-O-Si connections, and no obvious independent amorphous aluminum species was observed in the calcination products.

STUDY ON OPTIMIZATION METHOD FOR CALCULATION OF GRAPHITIZATION DEGREE OF CALCINED PETROLEUM COKE

2022, 53(4):  89-94. 

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The petroleum coke produced by the delayed coking process serves as a typical raw material for the production of artificial graphite anode of lithium batteries. The amount of lithium intercalated in the petroleum cokes is strongly related to the graphitization degree of petroleum cokes. The Mering-Maire method is commonly used to calculate the graphitization degree, which is based on the prerequisite that the interplanar distance of crystal face (d₀₀₂) is lower than 0.344 0 nm. The calcined petroleum coke does not undergo the graphitization process, sod₀₀₂ is larger. If d₀₀₂＞0.344 0 nm, graphitization degree of calcined petroleum coke can not be estimated by this method. In this study, a B-value method was proposed based on three kinds of petroleum cokes A, B, C, whose d₀₀₂ values are all greater than 0.344 0 nm. The estimated graphitization degree for the petroleum cokes is 25.29%, 24.58% and 22.29%,respectively. The modification method of graphitization degree proposed in this study is in good agreement with Mering-Maire method.

HIGH TEMPERATURE PERFORMANCE AND SLUDGE TENDENCY OF COMMON AMINE ANTI-OXIDANTS

2022, 53(4):  95-100. 

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The oxidation life and sludge deposition trend of turbine oil with different anti-oxidants were investigated by Dry-TOST tests, and the composition of the sludge was analyzed by Fourier transform infrared spectrum (FT-IR), X-ray energy dispersive spectrometry (EDS) and pyrolysis gas chromatograph-mass spectra (PY-GC-MS) to explore the source of the sludge with different anti-oxidants. The results show that N-phenyl-α-naphthylamine has better anti-oxidating performance than alkylated diphenylamine at high temperatures, and the oil added with single anti-oxidant (alkylated diphenylamine or N-phenyl-α-naphthylamine) produces more sludge, but the source of sludge is different. The sludge of turbine oil with alkylated diphenylamine mainly comes from the oxidation product of base oil, while the sludge of turbine oil with N-phenyl-α-naphthylamine mainly comes from the reaction product of anti-oxidant.

INFLUENCE OF LUBE BASE OIL AND ADDITIVES ON CONDUCTIVITY OF ELECTRIC VEHICLE TRANSMISSION FLUID

2022, 53(4):  101-107. 

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In response to the new requirements for the electrical performance of the transmission fluid of electric vehicle motor, reducer, and controller "three-in-one" integrated drive system, the influence of lube base oil and additives on the conductivity of electric vehicle transmission fluid at different temperatures was systematically studied according to the conductivity measurement method of liquid hydrocarbons (ASTM D4308). The results show that with the temperature increases, the conductivity of all test samples increases due to the decrease of oil viscosity and the increase of carrier migration rate; and the influence of lube base oil, anti-wear, anti-oxygen and anti-corrosion additives on the conductivity of transmission fluid is negligible. Detergents play the dominate role on the conductivity of lubricants. Among them, detergents with high total base number (TBN) have significantly greater influence on conductivity than that of medium and low TBN detergents. The dispersant is another key ingredients influence factor on the oil conductivity, and the conductivity of the lubricating oil with dispersant treated by boron and phosphate is the highest than that of others.

DETECTION METHOD OF TRACE AMOUNTS OF CRUDE OIL LEAKAGE BASED ON RAMAN FLUORESCENCE BACKGROUND

2022, 53(4):  108-113. 

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In the process of heat exchange between crude oil and light oil on the side line of atmospheric distillation column, there is the problem of crude oil leakage in refining and chemical enterprises, which has an adverse effect on the safety production and subsequent processing. Based on the sensitivity of Raman fluorescence background to crude oil, the detection of trace amounts of crude oil in light oil was introduced. Raman spectra of 90 naphtha samples containing trace amounts of crude oil were scanned as experimental data, and the model was established using partial least squares regression (PLSR) combined with genetic algorithm (GA), random frog algorithm (RF) and competitive adaptive reweighting sampling algorithm (CARS). The best model is the combination of CARS and PLSR, in which RMSEP is 1.567 4 μg/g. The results show that the detection method using Raman spectral fluorescence background can be used to accurately detect trace crude oil of 1-100 μg/g after algorithm optimization, which can fully meet the requirements of refining and chemical enterprises.

THERMAL DESORPTION BEHAVIOR OF THE FRACTIONS OF PETROLEUM HYDROCARBONS IN SOIL

2022, 53(4):  114-118. 

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The effects of heating temperature, retention time and vacuum conditions on the thermal desorption process of the fractions of petroleum hydrocarbon in soil were investigated by simulating the thermal desorption process in a tubular furnace, which provided a theoretical basis for the actual petroleum hydrocarbon contaminated soil. The results showed that increasing the heating temperature, prolonging the retention time, and providing negative pressure conditions had positive effects on improving the removal rate of total petroleum hydrocarbons(TPH) in soil. Keeping the temperature at 250 °C for 2.0 h or at 300 °C for 1.0 h, the removal rate of petroleum hydrocarbons was over 97%, and the residue amount of TPH was lower than the risk screening value of the first type of land in “Soil environmental quality：Risk control standard for soil contamination of development land” GB 36600-12018. The removal rates of C₁₀-C₁₆，C₁₇-C₂₈ and C₂₉-C₄₀ fractions were lower than 40% at 150 ℃ for 1.0 h, and C₁₀-C₁₆，C₁₇-C₂₈  fractions in soil could be quickly and effectively removed at 250 ℃. The removal efficiency of C₂₉-C₄₀ fractions was the key to reach the goal of remediation, because C₂₉-C₄₀ fractions were obviously affected by heating temperature and retention time.

CORROSION INHIBITION EFFECT OF THIADIAZOLE DERIVATIVES ON COPPER PLATE IMMERSED IN O/W EMULSION

2022, 53(4):  119-124. 

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To solve the problem of oxidation and discoloration of copper surface during metal-forming process, the corrosion inhibition behaviors of methyl benzentriazole derivatives(MBD), 2,5-bis(n-octyldithiazole) thiadiazole(EDD) and 2,5-bis(dodecyldithiazole) thiadiazole (BDDT) as corrosion inhibitor in vacuum, oil, water and emulsions were studied by density functional theory (DFT), electrochemistry and surface characterization methods. The results show that the adsorption of MBD on Cu surface is dominated by physical adsorption, while the adsorption of EDD and BDDT on Cu surface is dominated by chemical adsorption. The inhibition efficiency of the three corrosion inhibitors on the copper surface is in the order of MBD(76.39%) <EDD(83.95%) <BDDT(89.01%). BDDT has the best inhibition effect on inhibiting the corrosion of copper immersed in emulsion.