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2021年 第23卷 第1期    刊出日期:2021-03-31
Simulation and Optimization
DIFFUSION AND ADSORPTION OF TETRALIN HYDROCRACKING REACTION ON DIFFERENT ZEOLITES BY MOLECULAR SIMULATION
孙立杰 樊亚明 董松涛 羡策 龙湘云 李大东
2021, 23(1):  1-9. 
摘要 ( 187 )   PDF (1573KB) ( 358 )  
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Three different zeolite catalysts with different pore sizes (MFI-type, BEA-type, and FAU-type zeolites) have been prepared. The influence of different zeolite catalysts on reactivity and product shape selectivity of tetralin is investigated. Clear differences are observed in the reactivity of tetralin and distribution of products produced by different catalysts. The diffusion and adsorption of the reactant tetralin and its intermediates, n-butylbenzene and 1-methyl indan, under the reaction conditions are calculated using molecular simulation methods. Combining simulation results and experimental observations, it is shown that the difference in diffusion coefficient and competitive adsorption capacity can explain the reactivity of tetralin and the selectivity of products. The steric hindrance of MFI-type zeolite mainly limits the key step of ring opening of tetralin, leading lower selectivity of ring-open products. N-butylbenzene molecules diffuse sufficiently fast in the large pores of FAU-type zeolite and the weak adsorption capacity of n-butylbenzene leads to its insufficient cracking. In addition, it also explains the reason that BEA-type zeolite has the best BTX selectivity, because it can satisfy both good ring-opening activity and sufficient butylbenzene cracking depth. Key words: hydrocracking; tetralin; molecular simulation; diffusion; competitive adsorption.
柴油深度加氢脱硫反应器内不同区域反应类型及环境研究
代萌 李士才 李扬 徐大海 丁贺 陈光 郭蓉
2021, 23(1):  10-20. 
摘要 ( 113 )   PDF (1696KB) ( 299 )  
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本文进行反应条件对柴油产品S、N含量及烃类分布影响试验,总结其随不同停留时间变化规律。建立加氢脱硫、加氢脱氮、加氢脱芳半经验半机理动力学模型,依据模拟结果,将深度加氢脱硫反应器划分为五个反应区域,前两个区域主要完成三环芳烃和双环芳烃的大部分饱和、90%氮化物完成转化、全部简单硫化物转化及部分4,6-DMDBT加氢反应。在后三个反应区域内,加氢脱硫和加氢脱氮反应速度放缓,而单环芳烃饱和反应速度增加。
Analysis and Prediction of Corrosion Risk in Atmospheric Distillation Tower Overhead System
牛鲁娜 韩磊 陈文武 潘隆 张艳玲 屈定荣
2021, 23(1):  21-30. 
摘要 ( 89 )   PDF (1476KB) ( 227 )  
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In order to optimize the atmospheric tower overhead low-temperature system, the physical parameters, multiphase
composition, aqueous dew point temperature, and ammonium salt crystallization temperature are simulated with process
simulation software. The temperature distribution in overhead heat exchanger is calculated by heat transfer calculation. The
special parts with elbows near the inlet and outlet of heat exchanger are studied by fluid field analysis. Results indicate that
under current operating conditions, the aqueous dew point temperature and initial crystallization temperature of NH4Cl are
91 °C and 128 °C, respectively. Ammonium salt appears in the distillation tower and liquid water occurs in heat exchanger
tubes, in which the dew point induced corrosion is the most direct factor for heat exchanger corrosion. In the heat exchanger,
condensate water appearing in the area 2.7 meters away from the bundle inlet can give rise to corrosion risk under the moist
NH4Cl and high concentration of acidic solution circumstance. For the pipes and elbows located near the inlet and the outlet
of heat exchanger, the flow field presents an unsymmetrical distribution. High risk areas are mainly concentrated on the
external bend of elbows where the liquid water concentration is higher. The coupling of simulation methods established
thereby is approved as an effective way to evaluate the corrosion risk in the atmospheric column overhead system and can
provide a scientific basis for corrosion control.
Heat Exchanger Network Retrofit for Optimization of Crude Distillation Unit Using Pinch Analysis
孙梦迎 付佃亮 孙兰义
2021, 23(1):  31-40. 
摘要 ( 148 )   PDF (1784KB) ( 287 )  
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Crude distillation unit (CDU) is regarded as the main energy consumer in the entire refinery process. In this paper, the process simulation software and the energy management software are used to simulate the flowsheet and analyze the energy consumption, respectively. Stream data obtained from an existing CDU are applicable in the pinch analysis. To reduce the amount of cross-pinch heat transfer, three approaches of resequencing, repiping, and adding heat exchangers are adopted. Compared with the existing CDU, the results demonstrate that the inlet temperature of the furnace can be increased by 25.4 ℃, the amount of hot and cold utilities can be reduced by 15.1% and 19.6%, respectively. The economic evaluation indicates that the operating cost is saved by 8×106 $/a, and the payback period is about 9 months.
New Refining Technology
Fluid catalytic cracking technology for maximum gasoline production
严加松 于善青 龚剑洪 龙军
2021, 23(1):  41-47. 
摘要 ( 130 )   PDF (549KB) ( 298 )  
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Increasing gasoline production in FCCU can improve the utilization efficiency of petroleum resources and gain economic benefit. This paper discusses the technical principles to increase FCC gasoline yield from the aspects of feedstock properties, operating conditions, LCO recycling, catalyst selection and reactor type, and illustrates the industrial application examples for maximizing gasoline production. The technical measures, such as optimizing the feedstock, properly increasing the catalyst activity and reaction temperature, recycling LCO or hydrotreated LCO, applying high gasoline yield catalyst, and adopting the two-zone riser reactor, are proposed to enhance the gasoline yield.
劣质重油接触裂化-焦炭原位气化技术
李延军 张书红 任磊 申海平 吴雷 汪燮卿
2021, 23(1):  48-52. 
摘要 ( 121 )   PDF (678KB) ( 258 )  
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为了高效、绿色利用石油资源,解决我国目前炼厂存在的延迟焦化焦炭产率高、高硫焦利用以及环保等问题,石科院开发了一种劣质渣油接触裂化-焦炭原位气化技术。该技术基于薄层裂化、部分氧化、快速裂化三大技术特点,不仅降低加工过程焦炭和干气产率,增加液收,而且采用原位低温制气技术解决了高硫石油焦的清洁利用问题,起到公用工程岛的作用,是一项绿色低碳的劣质重油加工技术。
Catalyst Research
Effect of LaPO4 introduction as a vanadium trap on USY zeolite destruction
杜晓辉 高雄厚 刘璞生
2021, 23(1):  53-57. 
摘要 ( 100 )   PDF (826KB) ( 216 )  
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The use of lanthanum phosphate as a vanadium trap for preventing destruction of USY zeolite was studied. The effect of deposited vanadium on the hydrothermal destruction of zeolite was investigated by the solid-state NMR technique. LaPO4 species can inhibit the zeolite framework structure from being collapsed by vanadium after steaming treatment. The EPR results show the oxidation-reduction reaction in LaPO4 and V2O5 system and inhibition of zeolite destruction by V5+. The catalysts prepared from USY and LaPO-USY zeolites were also tested in the catalytic reactions of heavy oil. The assessment results indicated that the USY modified with LaPO4 could bring about remarkably high dehydrogenation ability.
水杨醛席夫碱金属配合物对模型硫化物的催化氧化性能研究
贾超洋 梁书源 刘蕾 绍雪 张龙力 王芳珠 姜翠玉
2021, 23(1):  58-66. 
摘要 ( 113 )   PDF (1166KB) ( 237 )  
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Seven kinds of Schiff base metal complexes (C1—C7) were synthesized by the reaction of substituted salicylaldehyde Schiff base with cobalt nitrate, nickel nitrate, and copper nitrate, respectively. The oxygen carrying performance, and the catalytic property of complexes for the oxidation of model sulfdes 1-hexanethiol, dibutyl sulfde, and 2-methylthiophene along with their infuencing factors were explored, while the oxidized products of the model sulfdes were also analyzed and characterized. The results show that the catalytic oxidation property of the complexes is determined by their oxygen carrying performance and solubility in n-octane. The oxygen carrying performance of the complexes is mainly afected by the central ion species, the electronic efects, and the spatial efects of the substituents as well as the degree of conjugation. More specifcally, the oxygen carrying performance can be improved by enhancing the oxygenation capacity of the central metal ions, increasing the electron donating ability of the ligand substituent, and diminishing the steric hindrance as well as extending the conjugated chain. Complexes C7 were found to be with high oxygen carrying capacity and high solubility in n-octane, which shows the best catalytic oxidation property, and the oxidation conversion rates for 1-hexylthiol, dibutyl sulfde, and 2-methylthiophene are 74.2%, 65.1%, and 22.7%, respectively. Upon using the oxidation catalyst of Schif base metal complexes, three sulfdes can be oxidized by oxygen to form sulfones and sulfoxides. 1-Hexanethiol and dibutyl sulfde will continue to be oxidized to form sulfates and sulftes.
Effects of Operating Conditions on the Catalytic Performance of HZSM-5 Zeolites in n-Pentane Cracking
侯旭 , Zhao Liu, Ma Zhenzhou, Chen Bochong, Feng Jingyuan, Cui Tingting
2021, 23(1):  67-75. 
摘要 ( 127 )   PDF (1191KB) ( 252 )  
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Design and optimization of operating conditions was of significant importance for naphtha catalytic cracking to produce light olefins. In order to reveal the effects of operating conditions on the catalytic performance of HZSM-5 zeolites, n-pentane catalytic cracking was employed as a model reaction and carried out at 650 °C under atmosphere in this work. A particular attention was paid to the measurement of n-pentane conversion, light olefins production, product distribution, coke deposit, etc. Several reaction indexes were defined to qualitatively and quantitatively evaluate the effects of operating conditions. It was found that decreasing weight hourly space velocity, increasing reactant partial pressure, and increasing carrier gas flow rate inhibited C-H bond breaking, enhanced C-C bond breaking and hydride transfer reactions, and thus reduced alkenes selectivity, suppressing the formation of external coke and alleviating the deactivation of HZSM-5 zeolites in n-pentane catalytic cracking. It was deduced that the catalytic stability of HZSM-5 zeolites was improved at a cost of alkenes selectivity. Compared with decreasing weight hourly space velocity and increasing reactant partial pressure, increasing carrier gas flow rate enhanced the diffusion process, protected alkenes from consumption by coke formation, and thus improved the catalytic stability of HZSM-5 zeolites with less cost of alkenes selectivity. Tailoring carrier gas can be a candidate method to improve naphtha catalytic cracking to produce light olefins.
Scientific Research
不同改性方法处理ZSM-5分子筛对甲苯吸附性能的比较和分析:吸附动力学和机理研究
张帅 李孟 李炜 李雨薇 刘芳 薛明 王永强 赵朝成
2021, 23(1):  76-87. 
摘要 ( 153 )   PDF (2234KB) ( 262 )  
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MFI molecular sieve with high specific surface area, adjustable pore size and low production cost have been recognized as an effective adsorbent for VOCs removal. In this paper, NaOH solution was used to etch ZSM-5 to increase specific surface area and micro-mesoporous content. Graphene oxide (GO) was loaded on ZSM-5 by ultrasonic-assisted heating immersion method, and large π-bond structure and oxygen-containing functional groups were added to ZSM-5 for improving the composite adsorption performance. In addition, the properties of OH-ZSM-5 and ZSM-5@GO composites for toluene adsorption under different factors were also studied. It was positively correlated with initial concentration and adsorbent mass, but was negatively correlated with temperature. Meanwhile, the results showed that the saturated adsorption capacity of OH-ZSM-5 (107.3 mg/g) was 1.34 times higher than that of ZG-15% (80.2 mg/g). The pseudo-first-order and pseudo-second-order kinetic model can well describe the adsorption behavior of toluene on the OH-ZSM-5 and ZG-15%,  respectively. The adsorption mechanism of OH-ZSM-5 was mainly pore-filled adsorption. However, the adsorption mechanisms of ZSM-5@GO composite were pore-filled adsorption, π-π interaction, and H-bond interaction. This study will help to design a new strategy for enhancing the performance of traditional adsorbent ZSM-5 in VOCs removal.
Flow characteristics of high water fraction crude oil during the non-heating gathering and transportation
吕宇玲 谭浩 李娇 杨东海 徐沛扬
2021, 23(1):  88-97. 
摘要 ( 109 )   PDF (1278KB) ( 222 )  
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In order to ensure the safety of the non-heating gathering and transportation processes for high water fraction crude oil, the effect of temperature, water fraction, and flow rate on the flow characteristics of crude oil with high water fraction was studied in a flow experimental system of the X Oilfield. Four distinct flow patterns were identified by the photographic and local sampling techniques. Especially, three new flow patterns were found to occur below the pour point of crude oil, including EW/O&W stratified flow with gel deposition, EW/O&W intermittent flow with gel deposition, and water single-phase flow with gel deposition. Moreover, two characteristic temperatures, at which the change rate of pressure drop had changed obviously, were found during the change of pressure drop. The characteristic temperature of the first congestion of gel deposition in the pipeline was determined to be the safe temperature for the non-heating gathering and transportation of high water cut crude oil, while the pressure drop reached the peak at this temperature. An empirical formula for the safe temperature was established for oil-water flow with high water fraction/low fluid production rate. The results can serve as a guide for the safe operation of the non-heating gathering and transportation of crude oil in high water fraction oilfields.
配位离子液体NMP-0.5ZnCl2脱除柴油中的碱性氮化物
李文深 任永琪 李建祥 赵志军 刘洁
2021, 23(1):  98-104. 
摘要 ( 121 )   PDF (503KB) ( 259 )  
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以NMP和ZnCl2为原料合成一种配位离子液体,并用红外光谱进行结构表征。分别以喹啉模型油和焦化柴油为原料考察该离子液体的碱氮脱除性能。结果表明NMP-0.5ZnCl2离子液体具有良好的脱氮性能,在萃取温度50 ℃、剂油质量比1:2、萃取时间30min的条件下,喹啉脱除率可达99.68%;焦化柴油经过5级萃取脱氮后,碱氮脱除率可达91%以上,碱氮含量由536μg/g降至47μg/g。此外,配位离子液体NMP-0.5ZnCl2在回收利用4次后,喹啉脱除率仍可达到96.73%,具有较好的重复使用性能。
Enviromental Protection
Advanced nitrogen removal of denitrifying ammonium oxidation system for sulfamethoxazole-laden secondary effluent
刘春爽 李伟 段伟超 钟慧云 于海彤 李妍喆 刘芳 赵朝成
2021, 23(1):  105-110. 
摘要 ( 98 )   PDF (655KB) ( 242 )  
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Nitrogen removal is usually achieved in nitrification and denitrification system for antibiotics wastewater. However, high level of nitrate usually presents in the secondary effluent, which needs to be further treated, along with several milligrams per liter of sulfamethoxazole (SMX). The denitrifying ammonium oxidation (DAO) process was for the first time studied for advanced nitrogen removal from SMX-laden second effluent. The SMX stress has a little adverse effect on removal rates of nitrate; however, it moderately deteriorated ammonium removal rates when the concentration is higher than 2 mg L-1 SMX. The unclassified_f__Rhodobacteraceae sp. presented the heterotrophic denitrifier while Candidatus_Brocadia sp. and Candidatus_Kuenenia sp. presented the anammox bacteria for the present DAO reactions.
Effects of different plant hormones for microbial degradation of PASHs and diesel under aerobic conditions
尚秀芳 李琳 肖新峰 薛建良 高宇 高洪阁
2021, 23(1):  111-119. 
摘要 ( 109 )   PDF (921KB) ( 225 )  
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The effects of plant hormones for biodegradation of polycyclic aromatic sulfur heterocycles (PASHs) and diesel fuel were studied. Indole butyric acid (IBA) and gibberellin were found to promote biodegradation of DBT and diesel, respectively. Concentrations of plant hormones, pH, temperature, soil moisture and substrate concentrations were optimized in microbial metabolic processes. Two main factors including temperature and IBA concentration were determined by factor analysis in DBT biodegradation. And soil moisture and diesel concentration were important factors in diesel biodegradation. Binding sites between cell surface and DBT or diesel components were performed by molecular operating environment (MOE). This study suggested that plant hormones could be applied to effectively remove pollutants in environment. 
Lubrication Research
PREPARATION AND RHEOLOGICAL PROPERTIES OF VACUUM GREASE
何懿峰 孙洪伟 刘欣阳
2021, 23(1):  120-126. 
摘要 ( 122 )   PDF (880KB) ( 263 )  
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A kind of vacuum lubricating grease was prepared by using perfluoropolyether as base oil, perfluorinated polymer as thickener, and self-made additives. The colloidal stability of the grease was greatly improved by introducing a colloidal structure modifier. The rheological properties of the self-made grease (SMG), such as viscosity versus time, thixotropy, etc., were studied by a rheometer at different temperatures and were compared with those of foreign brand grease (FBG). The results show that the performance of SMG reached the level of similar FBG, and some properties such as mechanical stability, colloidal stability, extreme pressure and antiwear properties were better. It can be used for long life lubrication of moving parts in a vacuum environment.