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期刊基本信息
主办单位：中国石油化工股份有限公司
　　　　　石油化工科学研究院
编辑出版：石油炼制与化工编辑部
主　　编：汪燮卿院士
执行主编：李才英教授
副 主 编：刘鸿洲 刘迎春
国际标准刊号：ISSN 1005-2399
国内统一刊号：CN 11-3399/TQ
邮发代号：2-332

Table of Content

    12 September 2019, Volume 50 Issue 9
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    DEVELOPMENT AND COMMERCIAL PRACTICE OF FCC GAS OIL HYDROGENATION
    Liu Tao Xu Youhao Yang Qinghe Dai Lishun Li Dadong
    2019, 50(9):  1-4. 
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    According to the characteristics of FCC gas oil（FGO）, a special catalyst RDA-1 for FGO hydrogenation was developed and the optimum selective hydrogenation process (HAR) for FGO was studied. The industrial test of HAR was conducted in a 20 kt/a hydrogenation unit in a company of SINOPEC. The calibration results showed that the hydrogen content increased by more than 1.65 percentage points after FGO hydrogenation and the saturation rate of polycyclic aromatic hydrocarbons （PAHs）was up to 67.7%, and the cracking performance of FGO was greatly improved.
    DISCUSSION ON FCC REPROCESSING OF HYDROTREATED CATALYTIC CRACKING DIESEL
    Zhou Jianhua
    2019, 50(9):  5-9. 
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    Using a mixture of hydrotreated LCO and HVGO as feed, the FCC reprocessing (MIP-LTG technology) was conducted in a small-scale unit. The results showed that compared with the comprehensive calculation results of the individual results of hydrotreated wax oil and diesel oil, the yields of low-value products such as dry gas，slurry and coke reduced，and the total liquid yield increased by 0.97 percentage points. The commercial application data in Company A showed that when the ratio of the hydrotreated LCO in the mixed materials increased by 7 percentage points，the total liquid yield increased by 1.55 percentage points，the dry gas yield decreased by 0.31 percentage points，and the RON of gasoline improved by 0.6 units. The results in Company B indicated that in the case of poorer feed and the ratio of hydrotreated LCO as high as 11 percentage points，the total liquid yield increased by 0.2 percentage points，the dry gas yield decreased by 0.69 percentage points，and the RON of gasoline increased by 1.1 units. The industrial results showed that the MIP-LTG technology is a simple route and has a good performance for hydrotreated LCO conversion.
    STUDY ON UTILIZATION OF NARROW FRACTIONS OF LCO HYDROCONVERSION PRODUCTS
    2019, 50(9):  10-14. 
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    new process technology (FD2G) was developed by SINOPEC Dalian(Fushun) Research Institute of Petroleum & Petrochemicals for producing high octane gasoline blending component using hydrotreated LCO as feed. Based on the composition analysis of LCO hydro-upgrading products, the solutions were raised for the best utilization of the products to strengthen the market competitiveness. The results showed that when processing LCO with high aromatic content, the obtained gasoline product possessed of high aromatic content and high octane number, its narrow fraction enriched in C6~C8 aromatics could be used as feed of aromatic extraction process. When processing hydrotreated LCO with low aromatic content, the gasoline product contained low content of aromatics and low octane number but its narrow fraction, rich in naphthenic hydrocarbons, could be used as feed for the reformer, and the remaining narrow fraction with high aromatic content could be used as a high octane gasoline blending component.
    MEASURES AND OPERATION ANALYSIS OF NATIONAL Ⅵ QUALITY UPGRADING OF DIESEL IN MHUG-II UNIT
    Yang Wen
    2019, 50(9):  15-20. 
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    In order to produce national VI diesel and meet the requirement of long-term operation of the unit, SINOPEC Hainan Refining and Chemical Company, Limited. upgraded the 2.48Mt/a diesel hydroupgrading MHUG-II unit, added a new refining reactor, regenerated the first-cycle used catalyst, adopted RS-2100 hydrorefining catalyst, and optimized the gradation of RG series protective catalysts. The calibration results showed that the density of diesel products was 0.843 4 kg/m3, the cetane number was 51.6, the sulfur content was 2.3μg/g, the polycyclic aromatic hydrocarbons content was 3.4% （mass fraction）, and the total pollutant content was 5 μg/g, all of which met national VI diesel standards. From January 23, 2018 to April 30, 2019, the unit flexibly produced national V/VI diesel oils for 463 days. The average deactivation rates of refining and hydroupgrading catalysts were 0.029 ℃/d and 0.015 ℃/d, respectively. The average deactivation rates of refining reactor I and II catalysts were 0.027 ℃/d and 0.012 ℃/d, respectively. The total life cycle of each catalyst satisfied with the target of 4-5 years maintenance requirements.
    APPLICATION OF REGENERATION TECHNOLOGY FOR CATALYST OF COUNTERCURRENT CONTINUOUS CATALYTIC REFORMING
    Zhang Weiqi Chen Xiang Pan Long Li Yuanyuan
    2019, 50(9):  21-27. 
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    The characteristics of catalyst regeneration technology of countercurrent continuous catalytic reforming were introduced from the aspects of catalyst flow direction，loading ratio，catalyst circulation and process safety of regenerative system. And at the same time，the possible or existing problems in the catalyst regeneration process were discussed. The corresponding countermeasures and practical solutions were suggested. The PS-VI catalyst developed by SINOPEC Research Institute of Petroleum Process showed high activity，stability，chlorine holding ability as well as wear resistance in the industrial application.
    STUDY ON COMPOSITIONS AND VISCOSITY-TEMPERATURE PERFORMANCE OF OILS IN PRODUCING BASE OIL FROM HYDROGENATION OF VGO
    2019, 50(9):  28-32. 
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    To understand the effect of feedstock change on hydrotreated lube base oil, the physicochemical properties of vacuum gas oil (VGO), hydrocracking tail oil and hydrotreated base oil were analyzed to investigate the key factors that determine the viscosity-temperature performance of base oil. The results showed that the viscosity index(VI) and the sum of the mass fraction of paraffins, monocyclic naphthene and alkyl benzenes of VGO are positively correlated with the VI of base oil produced from VGO. The relations between VI and chemical compositions of the base oil indicated that the VI of the base oil was mainly affected by the content of paraffins and monocyclic naphthene, the distribution of carbon number and the degree of isomerization.
    EFFECT OF NITROGEN SUBSTITUTION ON ADSORPTION PROPERTIES OF CYCLIC HYDROCARBONS IN H-FAU ZEOLITE
    2019, 50(9):  33-39. 
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    Nitrogen-containing heterocyclic compounds in FCC feedstock, which have strong adsorption capacity and diffusion resistance, are important factors for the poisoning and deactivation of zeolite catalysts. In this paper, two nitrogen-containing heterocyclic compounds, pyridine and piperidine, and two cyclic hydrocarbons with similar structures, benzene and cyclohexane, were selected as model compounds, and the adsorption behaviors of the four compounds on H-FAU zeolite channels and acid sites were investigated by GCMC and DFT methods at 298K. The results showed that the four molecules were mainly distributed in the supercage, and the distribution of two of them was more concentrated. The order of adsorption energy was: piperidine > pyridine > benzene > cyclohexane, and the adsorption of nitrides was chemical adsorption, while benzene and cyclohexane was physically adsorpted. The results of charge density maps revealed that the charge transfer occurs in different degrees between two alkali nitrogen molecules and H protons. The results provide theoretical guidance for the study of nitrogen poisoning mechanism of zeolite catalyst.
    ANALYSIS OF CLUSTER EXISTENCE TIME IN COMBINED DIAMETER-CHANGING RISER
    Wu Guangheng Wang Dewu
    2019, 50(9):  40-46. 
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    Cluster existence time in an combined diameter adjustable riser of circulating fluidized bed was measured and analyzed within the Gs/（ρg.Ug） range of 2.13 — 47.95. It was found that the existence time of single cluster was 0.001 28 — 0.601 60 s. However，mean existence time of local cluster was 0.014 32 — 0.160 64s. The clusters with existence time higher than 0.064 00 s accounted for 12.31%，while clusters with existence time lower than 0.064 00 s was 87.69%. When the solid/gas ratio was relatively low, the average duration was dominated by low concentration aggregates. When the solid/gas ratio was high, the residence time of cluster in area close to the reactor wall was dominated by high concentration of aggregates. By multi-scale analysis of time，in low concentration cluster，the quantity of the clusters within the duration range of 0.001 28 — 0.038 40 s was primary, and in terms of the influence on the average duration, the aggregate with a duration of 0.012 80 — 0.038 40 s was the most important. While on the amount and the influence on the average duration, the aggregate with a duration of 0.064 00 — 0.128 00 s was in the first position.
    MODIFIED CHITOSAN FOR VANADIUM REMOVAL FROM SPENT FCC CATALYST
    2019, 50(9):  47-52. 
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    Fluid catalytic cracking (FCC) catalysts are poisoned and deactivated due to metal deposition during operation. Traditional landfill treatment not only causes ecological pollution, but also increases production costs. Therefore, finding an effective regeneration method has become a hot issue in the industry. Dithiocarbamates (DTC-CTS) was synthesized by modified chitosan made by nucleophilic addition reaction using chitosan and CS2 as raw materials. The DTC-CTS was used to remove vanadium from spent FCC catalyst to achieve the purpose of regeneration. The technological conditions of vanadium removal using DTC-CTS were further investigated. It was found that at 125℃ and the reaction time of 4.5h, the vanadium removal ratio reached the maximum (54.9%), which indicates that DTC-CTS has a good removal efficiency on vanadium from the equilibrium catalyst. The structure of FCC equilibrium catalyst before and after regeneration was determined by XRD、BET and SEM techniques. The results showed that the crystal structure of Y zeolite was retained in the regenerated catalyst, and the specific surface area and pore volume of the catalyst were increased. The MAT activity was increased by 5 percentage points.
    STUDY ON DEACTIVATION OF Zn/ZSM-5 CATALYST IN CO-AROMATIZATION REACTION OF n-PENTANE AND METHANOL
    2019, 50(9):  53-58. 
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    The deactivation factors for Zn/ZSM-5 catalyst in co-aromatization reaction of methanol and n-pentane were investigated by continuous reaction and regeneration experiments. The results were compared with the single compound aromatization. The fresh and the regenerated catalyst were characterized by XRD, NH3-TPD, Py-FTIR, BET techniques. The results showed that compared with methanol aromatization, the deactivation of the catalyst was slower, and the selectivity of aromatics was improved by co-aromatization compared with n-pentane aromatization. When methanol is present in the co-aromatization reaction system, the catalyst was deactivated not only by coke, but also by hydrothermal dealumination of molecular sieve, so that the regenerated catalyst cannot completely recover its original activity.
    COMMERCIAL APPLICATION OF GARDES-Ⅱ EX-SITU PRESULFIDED CATALYST IN FCC GASOLINE HYDRODESULFURATION UNIT
    2019, 50(9):  59-63. 
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    The GARDES-Ⅱtechnique for gasoline hydrodesulfurization with ex-situ presulfided catalysts were applied in a 1.2 Mt/a FCC gasoline HDS unit of PetroChina Hohhot Petrochemical Company and the results were introduced. Compared with the oxidized catalyst, the ex-situ presulfided catalyst has the superiorities of safe, environmental friendly, simple and less time-consuming in the start-up stage. The calibration data indicated that the gasoline produced by GARDES-Ⅱ ex-situ presulfided catalysts could completely meets the requirements of China VI（A）gasoline standard under the current conditions of Hohhot Petrochemical Company of PetroChina. The average sulfur content of the product by Doctor Test was 7.1 μg/g, the octane number loss was 1.1-1.3 units with the gasoline yield of 99.0% and energy consumption of 516.23 MJ/t. In addition, the average olefin reduction of heavy cracked naphtha（HCN）was 11.4 percentage point. It is concluded that the GARDES -Ⅱ with ex-situ presulfided catalysts reaches the HDS level of in-situ presulfurization process and have good desulfurization activity and octane number recovery.
    CRUDE FORMULATION TECHNOLOGY AND ITS APPLICATION IN OPTIMIZATION OF CRUDE RESOURCES
    2019, 50(9):  64-69. 
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    The relative stability of crude oil is important to ensure safe operation and profit improvement of refineries. By combining the crude oil spectral database, crude oil evaluation database, crude oil rapid assay and advanced calculation method,SINOPEC Research Institute of Petroleum Processing has combined several crude oils in a certain proportion to obtain a formulated crude oil that are very close to the properties of target crude oil, thus forming the crude formulation technology. Refinery can choose the appropriate crude formula according to the principles of crude oil price, availability of crude oil, processing performance of mixed crude oil and optimization target of refinery. Laboratory evaluation shows that the actual analysis results are similar to those calculated by the technology. If this technology can be popularized and used, it can play an important role in improving refinery profit.
    EXERGOECONOMIC ANALYSIS AND OPTIMIZATION OF MULTI-STAGE GAS COMPRESSION PROCESSES
    2019, 50(9):  70-74. 
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    Exergoeconomic analysis was conducted on an actual cracking gas multi-stage compression process based on simulation data from Aspen Plus. The impacts of number of compressing stages on the total economic performance at different prices of input exergy were studied to reveal the relationship between optimal stage number and price of input exergy. The results obtained showed that the higher the price of input exergy, the more the impact of the stage number on the total cost. The optimal stage number increased as the price of the input exergy increased. Among them,the optimal number of compressor stage was 3 When the price of input exergy was 0.31-0.0.58 Yuan/(kW.h),When price of input exergy was 0.59-0.94 Yuan/(kW.h), the optimal number of stage was 4, and as input exergy exceeded 0.94 Yuan/(kW.h), the optimal number of stages was 5 at least.
    MICROSTRUCTURE OF LITHIUM GREASE
    2019, 50(9):  75-80. 
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    Thickener is the main component of grease, whose structure and composition determine the important properties of the grease. The structural changes of thickener fiber in lithium grease during growth and destruction were studied by combination of structural simulation and experimental verification methods and MS, XRD, SEM characterization techniques. The results showed that the thickener fiber was the aggregates of thickener molecules, the growth process was a crystallization process in which the molecules of the thickener were arranged in order. The thickener fibers grow differently in three - dimensional direction: the width direction was preferred, and the length direction was followed and twisted. The destruction process of thickener fiber was opposite to its growth basically, which was more similar to the C model.
    PREPARATION OF HIGH VISCOSITY PAO FROM POLYMERIZATION OF 1-DECENE
    2019, 50(9):  81-85. 
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    Poly-alpha-olefin(PAO) synthetic oil was synthesized from 1-decene with AlCl3 catalyst at low temperature(<10 ℃) and high polymerization temperature. The effects of catalyst dosage, reaction time, high polymerization temperature on PAO properties were investigated. The optimum process conditions were determined, viz. a catalyst dosage of 3% (based on raw materials), a reaction time of 10 h at low temperature and a polymerization temperature of 80 ℃ for 2 h. At the optimum conditions, the PAO yield was 90.88% with the kinematic viscosity (100 ℃) of 62.66 mm2/s and the viscosity index of 163, the flash point of 295 ℃, and the pour point of 45 ℃. Under the hydrogenation conditions covering a temperature of 230 ℃, a pressure of 4.0 MPa, a LHSV of 0.2 h-1 and a hydrogen-oil ratio of 300, the hydrogenated PAO was obtained with the kinematic viscosity (100 ℃) of 60.07 mm 2 /s, the viscosity index of 161, the flash point of 290 ℃, and the pour point of －40 ℃.
    PREPARATION OF SERPENTINE ULTRAFINE POWDER AND ITS EFFECT ON TRIBOLOGICAL PROPERTIES OF WATER-GLYCOL HYDRAULIC FLUID
    2019, 50(9):  86-90. 
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    Serpentine ultrafine powders were prepared by hydrothermal method, and the structure and morphology of the powder were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. The effects of powders prepared at different reaction temperatures and their dosages on tribological properties of 68# water-glycol hydraulic fluid were studied by using four-ball tester, and the mechanism of anti-wear and friction reduction was discussed. The results showed that the microstructure, chemical composition and crystal form of the hydrothermally synthesized serpentine powder at different temperatures were different. The hydrothermal synthesis product below 200°C was a mixture of serpentine, brucite, etc., and the serpentine powder synthesized by hydrothermal method at 200°C or above 200°C was a hollow tubular nanofiber serpentine. When using the nano-fiber serpentine powders prepared at 200°C and the adding amount was 0.06 % of the mass of water-glycol hydraulic fluid, the comprehensive tribological performance of water-glycol hydraulic fluid was the best. The friction coefficient and the wear spot diameter were 0.0562 and 0.39 mm, respectively, which were 18.07% and 33.90% lower than those of the basic hydraulic fluid, respectively. The morphology and energy spectrum analysis showed that serpentine powder added to hydraulic fluid can fill furrowing and repair the surface of wear marks, so as to achieve anti-wear and anti-friction.
    NMR CHARACTERIZATION OF LUBE BASE OIL STRUCTURE
    2019, 50(9):  91-96. 
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    The structures and properties of six lube base oils produced by Fischer-Tropsch synthesis and fourteen hydroisomeric lube base oils were studied and analyzed by nuclear magnetic resonance(NMR) technology. The correlations of viscosity index(VI) and contents of 8 kinds of isomers were established. The influences of hydrocarbon composition and structure of lube base oils on their VI were investigated. The specific structures played an important role in controlling the viscosity-temperature performance of lube base oils. The presence of the molecules with methyl-substituted at position 2, 3 and 4 in lube base oils reduced the VI of lube base oils, while normal paraffins and the methyl substituted at position 6 or 7 structures contribute positively to the VI. For lube base oils produced by Fischer-Tropsch synthesis, the larger the branched degree and branched number of lube base oils were, the higher the branching degree of lube base oils were. For lube base oils with different average carbon numbers of molecules, the branching degree decreased with the reduction of relative branched number. VI corresponded linearly to the relative branched number with correlation coefficient of 0.95.
    RESEARCH ON DETERMINATION METHOD OF NET HEAT OF COMBUSTION OF JET FUEL PRODUCED FROM COAL DIRECT LIQUEFACTION
    2019, 50(9):  97-101. 
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    The estimation method, such as GB/T 2429, ASTM D3338, ASTM D4529, and the precision methods (oxygen bomb method), such as GB/T 384 and ASTM D4809, are the commonly used methods for determination of net heat of combustion of jet fuel. The results indicated that because of the very different composition of coal direct liquefaction jet fuel from prtroleum-based jet fuels, the net heat of combustion by estimation methods were lower in varying degrees, especially the aniline point estimation methods including GB/T 2429 and ASTM D4529, which were obviously lower than other methods with the maximum difference of 0.3 MJ/kg, because the coal direct liquefaction jet fuel contains a mass fraction of 90% cycloalkane and almost no aromatic hydrocarbon, which are markedly different from the composition of petroleum-based jet fuel. Systematic errors exist in the GB/T 384 method, resulting in a result about 0.2 MJ/kg lower. As a consequence, ASTM D4809 method was recommended as the net heat of combustion test method for coal direct liquefaction jet fuel when high accuracy of data was required, while ASTM D3338 method was recommended under the conditions of no special requirement.
    ADVANCES IN ISOBUTYLENE SELECTIVE OLIGOMERIZATION PROCESS
    2019, 50(9):  108-115. 
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    The latest research progresses in isobutylene selective oligomerization and the successful experience in revamping MTBE unit abroad to produce isooctane or isooctene are introduced, focusing on the technology developed by SINOPEC Research Institute of Petroleum Processing (RIPP) for isobutene selective oligomerization by revamping existing MTBE device. The industrial test results show that by RIPP` technology, the conversion rate of isobutylene is 90%-92%, the selectivity of C8 is more than 90%, and the RON of product is 102-110, indicating that it can be commercialized.