Table of Content

12 September 2022, Volume 53 Issue 9

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DEVELOPMENT AND APPLICATION OF CORE TECHNOLOGY AND TECHNICAL ROUTE SUPPORTING CONTINUOUS UPGRADING OF GASOLINE QUALITY IN CHINA 1.Theoretical Basis and Industrial Practice of Olefin Content Control in FCC Gasoline

2022, 53(9):  1-9. 

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Deep reduction of the olefins content in gasoline is the key to upgrading gasoline quality in China. Based on the in-depth study of the synergy and competition between bimolecular cracking reaction and hydrogen transfer reaction, the effects of these two kinds of reactions on the decrease of gasoline olefins content and the increase of coke production were divided into three regions, named “coke yield controllable region”, “coke yield transition region” and “coke uncontrollable region”, respectively. Based on this, the development ideal of FCC process for controlling olefins content in gasoline by zones was put forward. Furthermore, the variable-diameter fluidized bed catalytic cracking process suitable for “coke yield controllable zone”, the optimum reaction mode of catalytic cracking process suitable for “coke yield transition zone”, and the catalytic cracking technology suitable for ultra-low olefin gasoline in coke-controlled zone have been developed. Especially in the region where the coke content could not be controlled, the creative introduction of hydrogen negative ion releasing agent and the optimization of the introduction mode have fundamentally solved the key contradiction between deep reduction of olefins content in gasoline and rapid increase of coke yield. The increase rate of coke yield was controlled while the olefin content in gasoline was greatly reduced, which provided a reliable guarantee for upgrading gasoline quality.

OPERATION OPTIMIZATION OF RESID DCC UNIT FOR ETHYLENE AND PROPYLENE PRODUCTION

2022, 53(9):  10-16. 

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The 1.5 Mt/a resid DCC uint for ethylene and propylene production in Shaanxi Yanchang Coal Yulin Energy and Chemical Co., Ltd. adopts the design of DCC-plus reactor configuration. The design feedstock is atmospheric resid of Yanchang oilfield, and the main target products are ethylene and propylene. Since the unit was put into operation in 2014, the feedstock processing capacity and main operating conditions of the unit have been basically stable, and the iron content in the feed oil has fluctuated. Through technical breakthroughs such as operation optimization, unit revamping and catalyst improvement, the yield of ethylene and propylene has been steadily improved. During the calibration period, using the atmospheric resid of Yanchang oilfield as feedstock, the unit throughput was 100%, the ethylene yield was 13.82%, the propylene yield was 23.30%, the ethylene plus propylene yield reached 37.12%, and the unit operation could meet the design requirements.

COMMERCIAL APPLICATION OF JET FUEL HYDROTREATING TECHNOLOGY（JeFIT） WITH WIDE-DISTILLATION-RANGE FEED

Zhang Rui Wang Wei Kai XU

2022, 53(9):  17-21. 

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In order to increase jet fuel production, the No.2 kerosene hydrogenation unit of SINOPEC-SK (Wuhan) Petrochemical Company Limited was revamped by using the jet fuel hydrofining technology (JeFIT) developed by the SINOPEC Research Institute of Petroleum Processing. After retrofitting, the unit was successfully started, and the technical calibration and long-term operation test of industrial unit were carried out. The results of calibration showed that the final distillation point was about 263 ℃, the color of the refined kerosene was +30, the basic nitrogen content was less than 1 μg/g, thermal oxidation stability breaking point temperature was more than 320 ℃，static stability oxidation precipitation was less than 4.6 mg/(100 mL)，and other indexes all met the quality requirements of China No.3 jet fuel. The long-term operation of the industrial plant showed that the application of JeFIT technology could realize the safe and stable long-term operation of the plant and the goal of increasing the production of jet fuel by more than 30%.

IMPROVING OCTANE NUMBER AND REDUCING BENZENE CONTENT OF PRODUCT BY OPTIMIZING CATALYTIC REFORMING FEED

2022, 53(9):  22-26. 

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After adopting the SR-1000 semi-regeneration reforming catalyst developed by SINOPEC Research Institute of Petroleum Processing (RIPP), revamping the existing evaporator of the semi-regeneration catalytic reforming unit, reasonable controlling and optimizing the raw material properties, cutting out the precursor of benzene (including benzene and cyclohexane) before catalytic reforming, and using the combined process of isomerization of C₅/C₆ developed by RIPP,the RON of the product was increased to above 96, the blending component of gasoline whose benzene content was less than 1.0% could be produced, and the single benzene extraction unit could be shut down. The economic and social benefits were remarkable.

EFFECT OF HYDROCARBON COMPOSITION OF CATALYTIC CRACKING FEEDSTOCK ON THE PRODUCTION OF LIGHT OLEFINS

2022, 53(9):  27-32. 

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A fixed fluidized bed reactor was used to study the effect of hydrocarbon components of catalytic cracking feedstock on the production of light olefins from the feedstock of HVGO-1, HVGO-2, HVGO-3, HVGO-3 light fraction and HVGO-3 heavy fraction. Compared with HVGO-1 with the similar density and hydrogen content, the higher cycloalkane content and lower aromatic content of HVGO-2 resulted in higher light olefins yield, and the same reaction rules were obtained for HVGO-3, HVGO-3 light fraction and HVGO-3 heavy fraction. Paraffins, naphthenes and monocyclic aromatics are the dominant components in the production of light olefins and gasoline. Among them, paraffins and naphthenes are the high value components in the production of light olefins, while alkylbenzenes are the high potential components in the production of gasoline and light aromatics (BTX). Under the same reaction conditions, the high content of cycloalkylbenzene in the HVGO-3 light fraction leads to the hydrogen transfer side reaction of light olefin precursors and light olefins, which affects the formation of light olefins. The hydrogenation pretreatment of FCC feedstock can improve the yield of light olefins by controlling the hydrogenation depth and realizing the conversion of polycyclic aromatic hydrocarbons to naphthenes, avoiding the formation of cycloalkylbenzene due to the lack of hydrogenation depth.

DEVELOPMENT OF DEHYDRATION PROCESS FOR TRANSFORMER OIL IN FIXED BED

2022, 53(9):  33-39. 

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In view of the many shortcomings of the vacuum filtering technology for transformer oil, the feasibility of applying the fixed bed adsorption process at room temperature and normal pressure to the dehydration of transformer oil was explored, the performance of different materials such as modified resin, 5A zeolite, activated carbon, and silica gel was investigated. The results showed that the performance of modified resin dehydrating agent was the best, followed by the anhydrous calcium chloride, the silica gel and 5A zeolite. When the water content of the feed oil was 33 μg/g, the initial water content at the outlet was less than 10 μg/g after fixed bed adsorption dehydration at WHSV of 30 h^-1. If taking the water content higher than 20 μg/g as the deactivation standard, the adsorption capacity of fresh modified resin was 96.03 mg/g. The modified resin could be used for many times, but the adsorption capacity would be lightly decreased after regeneration.

STUDY ON LOW TEMPERATURE PROPERTY OF API III BASE OIL PORDUCT FROM HYGROISOMERIZATION OF FISCHER-TROPSCH SYNTHETIC WAX

2022, 53(9):  40-43. 

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Based on the process and parameters of the hydroisomerization/hydrofining in industrial production of API Ⅱ base oil and catalysts suitable for the processing of Fischer-Tropsch synthetic wax, the influence of Fischer-Tropsch synthetic wax as raw material and process parameters on the cloud point and pour point of API Ⅲ 5cSt base oil were studied in the 200 mL hydrogenation pilot plant. The results showed that high hydroisomerization temperature, low hydroisomerization pressure and low carbon number of Fischer-Tropsch synthetic wax could reduce the cloud point and pour point of 5cSt base oil. When Fischer-Tropsch synthetic wax was used as raw material, the proportion of hydrocarbons with carbon number more than 40 did not exceed 0.5%, the isomerization pressure was 2.5 MPa, and the temperature was 348 ℃, the cloud point and pour point of 5cSt base oil were not higher than -15 ℃ and -30 ℃ respectively, the viscosity index was not lower than 135, and the yield was not lower than 30%.

DEVELOPMENT OF A HIGH-EFFICIENCY SLURRY REACTOR WITH FILTRATION-REACTION COUPLING

2022, 53(9):  44-49. 

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The slurry-bed reactor has been widely used because of its excellent mass transfer performance. High-efficiency solid-liquid separation is the key of technology to ensure its long-term stable operation due to the use of fine powder microsphere catalyst, which is particularly important for the development of hydrogen peroxide production technology by slurry-bed anthraquinone method with a very large treatment amount. Through a series of cold model tests, the effects of the average particle size of catalyst, the pore size of the filter material, the stirator leaf end linear velocity, the filter pressure difference on the filtration flux were studied in detail, and a high-efficiency slurry-bed reactor integrated reaction, filtration and gas-liquid separation was developed. The slurry-bed reactor was applied to the hydrogenation process of alkylanthraquinone. The experimental device used the new slurry-bed reactor could run continuously with high-throughput filtering for more than 1 000 hours without any backflushing, which verified the feasibility of the new slurry reactor.

MOLECULAR CHARACTERIZATION AND VISCOSITY PROPERTY PREDICTION OF LUBE BASE OIL

2022, 53(9):  50-55. 

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The molecular composition of lube base oil was characterized by gas chromatography/field ionization time-of-flight mass spectrometry (GC/FI TOF MS). The carbon number distribution of alkanes and 1-6 rings naphthenes in base oils could be obtained simply and quickly by qualitative analysis based on accurate relative molecular mass and mass spectrum quantitative analysis. Based on the molecular composition data of the base oil, the Kennard-Stone design method was used to divide the sample set into a calibration set and a verification set. A model for predicting viscosity and viscosity index was established based on the partial least squares method (PLS). The standard deviations of the model calibration value and prediction value based on molecular composition data were less than 2.0 mm²/s for viscosity and 2 for viscosity index,respectively,and the correlation coefficient(R) was greater than 0.99. The model has good applicability and high accuracy for the prediction of base oil viscosity and viscosity index, and it has certain practical value.

EFFECTS OF SEED CRYSTALS ON HYDROTHERMAL SYSTHESIS OF SAPO-34 WITH SMALL PARTICLE SIZE

2022, 53(9):  56-64. 

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The effects of seed type, additive environment, additive amount and particle size of seed crystals on hydrothermal synthesis of SAPO-34 molecular sieves and the mechanism of seed were investigated by using triethylamine（TEA）as template. The results showed that SAPO-5 molecular sieves with the same AFI structure crystals could be induced by the seeds containing SAPO-5 heterocrystalline, but the pure SAPO-34 could be prepared by pre-treating the impure seed crystals with phosphoric acid for 20 h. The silicon-aluminum ratio of seed crystal has obvious influence on the yield and particle size of the synthetic product, whether added in the acidic or the weakly alkaline gel. The seeds prepared with high SiO2/Al2O3 molar ratio can improve the yield and reduce the average particle size of the product, and the etching effect of acidic system on the seeds can provide bigger surface, so that the seed induction effect is stronger. When the content of crystal seed was 0-0.5%，the yield of product was increased and D(50) was decreased with the increase of the content of seed crystal with high SiO2/Al2O3 ratio . Especially when the content of seed crystal was more than 1%, the effect of seed addition on yield and D (50) of product tended to be gentle. In addition, the small-grain products prepared by seed-assisted synthesis could continue to be used as seed inducers. The yield, average particle size, elemental composition, morphology and pore structure of the product are similar to those of the product prepared with the help of large grain seed, it lays a foundation for the stable and continuous synthesis of small-grain molecular sieves with controllable particle size.

REACTION MECHANISM AND KINETICS OF CATALYTIC HYDROLYSIS CARBONYL SULFIDE

2022, 53(9):  65-71. 

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The reaction mechanism and kinetics of carbonyl sulfide (COS) hydrolysis on LS-05 catalyst were studied. The mass spectrum (MS) signal intensity changes of reactants and different products during the room-temperature adsorption, temperature programmed desorption and surface reaction of COS and H2S on the catalyst were investigated, and the mechanism of catalytic hydrolysis of COS was analyzed. By adjusting the reaction temperature and reactant concentration, a series of kinetic data were obtained, and then the corresponding reaction rate equation was established to analyze the reaction process of COS on the catalyst. The results showed that COS hydrolysis accorded with Langmuir- Hinshelwood (L-H) mechanism. The determination coefficient R² of the model regression equation was 0.998, and the error between the regression result and the experimental data was less than 10%，which indicated that the regression results of the model had a high correlation with the experimental data.

PREPARATION AND CATALYTIC PERFORMANCE OF FCC CATALYST FROM WASTE RESIDUE

2022, 53(9):  72-77. 

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The waste residue produced in the production of cracking catalysts was analyzed by XRF, N₂ adsorption-desorption, IR, pyridine adsorption and other methods, and the treatment process of removing impurities from the waste residue was studied. The FCC catalysts were prepared by spray drying using the treated catalyst waste or/and kaolin as a support, the zeolite as the active component. The results showed that the optimal process for treating catalyst waste residue was as followed: the solution pH was 3.0, the stirring time was 20 min, NH₄Cl feeding mass ratio was 20%, reaction temperature was 60 ℃, washing medium was NH₄Cl, the order of washing and calcination was washing,calcination and washing again. Compared with the catalyst using kaolin as the supports, the catalyst with mass fraction 10%-20% waste residue in the optimum carrier had better heavy oil conversion ability, higher liquid yield, higher gasoline selectivity, higher content of isoolefin and lower content of olefin in gasoline composition under the conditions of a reaction temperature of 480 ℃, a mass ratio of catalyst to oil of 7.5, a mass space velocity of 4 h^-1，using Daqing VGO as feedstock.

EFFECT OF CALCINATION TEMPERATURE OF MnO_x ON CATALYTIC REDUCTION OF NO

2022, 53(9):  78-82. 

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A series of MnO_x catalysts were prepared by using metal organic framework as sacrificial template, and the effect of calcination temperature on the denitrification performance of the catalysts was investigated. The surface structure and physicochemical properties of the catalysts were analyzed by a variety of characterization methods. The results showed that with the increase of calcination temperature, the crystallinity of Mn₃O₄ was improved, but it was unfavorable to the dispersion of active components; the specific surface area and pore volume of MnO_x catalyst were decreased and the pore size was increased ; the weak acid sites of MnO_x were decreased, the oxidation-reduction performance and denitrification activity of the catalyst at low temperature became worse. The results of activity evaluation showed that the MnO_x catalyst calcined at 300 ℃ had the best activity at low temperature. The NO conversion was over 90% at the reaction temperature of 120-200 ℃ and the space velocity of 20 000 h^-1.

CAUSE ANALYSIS AND COUNTERMEASURES OF NITROGEN POISONING OF SEMI-REGENERATIVE REFORMING CATALYST

2022, 53(9):  83-88. 

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The activity of the reforming catalyst SR-1000 was rapidly decreased and the octane number of the reforming gasoline was reduced because of the nitrogen poisoning of the reforming catalyst SR-1000 caused by excessive nitrogen content of the refined oil in the 450 kt/a semi-regenerative reforming unit of a refinery in October 2021. Through the systematic analysis of the reasons for the excessive nitrogen content of refined oil, it was found that the excessive nitrogen content of the refined oil was mainly caused by both the improper use of anti-corrosion neutralizing inhibitor which increased nitrogen content in the pre-hydrogenation feedstock and the low denitrification activity of pre-hydrogenation catalyst. In the practice of industrial application, such measures as selecting suitable corrosion inhibitor and controlling the injection amount, adjusting pre-hydrogenation unit reaction and operating conditions of the evaporation column, and using high-activity denitrification and pre-hydrogenation catalysts, etc. could effectively solve the problem of excessive nitrogen content in refined oil. The activity of the reforming catalyst could be recovered even if the impurity content of the refined oil was qualified.

PERPARATION OF MONOGLYCERIDE FROM BIODIESEL AND ITS ANTI-WEAR PERFORMANCE IN DIESEL

2022, 53(9):  89-95. 

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The monoglycerides were prepared from biodiesel and monoglycerol by transesterification reaction, and the products of monoglycerides were used as anti-wear additive in low sulfur diesel fuels. The anti-wear properties of glycerides prepared under different reaction conditions, such as reaction molar ratio, reaction time, and reaction temperature were investigated, the effects of freezing crystallization of biodiesel and short path distillation purification of reaction products on the anti-wear properties were discussed as well, and the lubricating stability of purified monoglycerides was further investigated. The results showed that the optimum reaction conditions were as follows: the molar ratio of biodiesel to glycerol was 1∶1, the reaction time was 8 h, and the reaction temperature range was 160-180 ℃. In addition, the anti-wear performance of monoglycerides obtained by freezing crystallization and short path distillation purification was better than that of monoglycerides obtained by the unrefined treatment, observably. Furthermore, the refined monoglycerides had good lubricating stability.

SYNTHESIS AND PERFORMANCE EVALUATION OF ANTI-RUST ADDITIVE GEMINI IMIDAZOLINE DERIVATIVES

2022, 53(9):  96-101. 

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A gemini imidazoline derivative anti-rust additive was prepared from oil acid and triethylenetetramine, and the synthesis conditions were optimized by response surface method. The performance of synthetic anti-rust additive was investigated by liquid corrosion test (synthetic seawater), hygrothermal test, emulsion resistance test, sludge test and corrosion tendency test. The optimum synthesis conditions were as follows:a molar ratio of triethylenetetramine to oil acid of 0.63:1, a reaction temperature of 248 ℃, and a reaction time of 7.9 h. The yield of gemini imidazoline derivative was 90%. The results of performance evaluation showed that gemini imidazoline derivatives could significantly improve the anti-rust performance of API I lube base oil, but had poor sensitivity to API II and API III base oil. In API class I base oil, the antirust performance of gemini imidazoline derivatives was equivalent to T705A and better than T746, T703, RHY702 and other rust inhibitors. When gemini imidazoline derivatives were used in the formulation of steam turbine oil, the steam turbine oil with different viscosity grades and properties meeting the quality requirements of Q/SY RH2087-2012 standard could be obtained.

STRUCTURE OPTIMIZATION OF POLYETHER DEMULSIFIER FOR OIL SLURRY DESOLIDATION

2022, 53(9):  102-108. 

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In order to optimize the structure of polyether demulsifiers in slurry settling agents，carboxyl-terminated polypropylene glycol (PPG) was synthesized by means of carboxyl chain extension. Carboxyl-terminated polypropylene glycol reacts with polyethylene glycol (PEG) in the presence of a catalyst to form block polyether. The optimal conditions for the synthesis of carboxyl-terminated polypropanediol were determined by acid value, 1H NMR,FT-IR,GPC and other characterization methods. Polyether demulsifiers with different block structure, block proportion and average relative molecular weight were prepared by PEG and PPG with different average relative molecular weight, and the performance of different demulsifiers in the course of slurry de-solidifying was compared by slurry sedimentation test. The results showed that the PEG-PPG-PEG block polyether with molecular weight of 10 000 and mass ratio of PPG/PEG of 4:1 had the best performance, and the de-solidifying rate of slurry reached 92.4%, which could effectively reduce the ash content in the slurry and improved the slurry utilization rate, and had good market application prospect.

EFFECT OF HYDROCARBON COMPOSITION OF BASE OIL ON DIELECTRIC DISSIPATION FACTOR OF OIL-PAPER COMPOSITE SYSTEM

2022, 53(9):  109-114. 

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Dielectric dissipation factor is a very effective key parameter to judge the insulation condition of electrical equipment and the quality of insulating materials. In order to better guide the development of new transformer oil products and provide more exact fault diagnosis of operating equipment, the influence of hydrocarbon composition of base oil on dielectric dissipation factor of oil-paper composite system was studied at different temperatures. The results showed that the change of the content of saturated hydrocarbon and aromatic hydrocarbon in base oil had no obvious effect on the dielectric dissipation factor of oil immersed paperboard at low temperature, and the higher the content of alkane and aromatic hydrocarbon in base oil was, the greater the dielectric dissipation factor of oil immersed paperboard was. At the same time, the higher the sulfur content in base oil was, the greater the dielectric loss of the oil-paper composite system was, but the effect of sulfur content on dielectric loss at different temperatures was not significant. The ideal base oil for oil-paper composite system transformer oil is naphthenic base oil containing proper amount of aromatic hydrocarbons.

RESEARCH ADVANCENMENT OF IRIDIUM OXIDE CATALYSTS FOR THE OXYGEN EVOLUTION REACTION OF PROTON EXCHANG MEMBRANE WATER ELECTROLYSIS

2022, 53(9):  115-122. 

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High-performance and low-cost iridium oxide oxygen evolution reaction (OER) catalyst is the key for the large-scale application of proton exchange membrane (PEM) water electrolysis technology. The factors affecting the performance of iridium oxide catalyst were analyzed, and main preparation methods of iridium oxide catalyst were described, including Adams Fusion method, liquid phase reduction method, soft-hard template method, and other advanced preparation methods. Two evaluation methods [rotating disk electrode (RDE) and membrane electrode assembly (MEA)] for iridium oxide catalysts were compared in order to provide some references for the development of iridium catalysts with high activity and high stability.

RESEARCH PROGRESS OF HIGH-GRADE DIESEL ENGINE OIL ADDITIVES AND FORMULATION TECHNOLOGY

2022, 53(9):  123-130. 

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The quality standard of diesel engine oil has been upgraded due to the requirement of environmental protection and energy conservation. The quality of API CH-4 and above high-grade diesel engine oils has been greatly improved in many aspects. The progress of high grade diesel engine oil additives and formulation technology in recent years was reviewed. The technical improvement routes and its development trend to meet the specific performance of oil soot dispersion, wear resistance, anti-oxidative performance and exhaust after-treatment compatibility of diesel engine oil were investigated. The analysis results showed that the development of additives and formulation technology for high-grade diesel engine oil was mainly embodied in the development of new structural additives, the optimization of compatibility and synergy among additives, and the optimization of formulation for thickened base oil of lubricating oil. On this basis, some guiding suggestions were put forward for the research and development of domestic high-grade diesel engine oil products.