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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 April 2021, Volume 52 Issue 4
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    DESIGN AND PREPARATION OF HIGH SELECTIVE HYDRODESULFURIZATION COMO/Al2O3 CATALYST BY MODIFYING SURFACE PROPERTIES OF SUPPORT
    2021, 52(4):  1-7. 
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    To study the effect of alumina surface properties on hydrodesulfurization selectivity of CoMo/Al2O3 catalysts, three alumina supports, Al2O3-1, Al2O3-2 and Al2O3-3, were used to prepare corresponding catalysts, respectively. The catalyst samples were characterized by Mo equilibrium adsorption test, XRD, SEM, N2 adsorption-desorption, IR, XPS and TEM techniques. The characterization results indicated the large difference in surface area, pore volume and pore size distribution of the supports, which coule be attributed to the difference in crystallite size, crystallite shape and crystallite stacking mode of alumina. The difference of alumina surface properties could be evaluated by Mo equilibrium adsorption capacity. The CoMo/Al2O3 catalyst prepared by using alumina support with lower Mo equilibrium adsorption capacity exhibited better HDS selectivity than others due to its weaker metal-support interaction, which promoted higher degree of Mo sulfidation and formed more Co-Mo-S active phase with longer slab length.
    EFFECT OF SUPPORT PROPERTIES ON PERFORMANCE OF HYDRODESULFURIZATION CATALYST
    Sun Jin Guo Rong Yao Yunhai Liu Li Li Yang
    2021, 52(4):  8-14. 
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    The macroporous alumina powder was synthesized by using CTAB as a template，and then used to prepare alumina support. Other two macroporous alumina supports was prepared using ordinary alumina powder with or without adding graphite as a template. Three CoMo catalysts were prepared by using these supports. The properties and activities of these catalysts were tested by BET adsorption，SEM，NH3-TPD techniques,and so on. The results showed that both the CTAB template and the graphite template can be used to prepare macroporous alumina supports. But the amounts of surface hydroxyl group and acid of the support prepared by the graphite template are lower than the supports prepared using CTAB template and ordinary alumina powder. The HDS performance test showed that the sulfidation degree of the catalyst made from the support prepared by CTAB template was the highest, meanwhile had the maximum layers of the active phase slab and the best HDS activity.
    DEVELOPMENT AND APPLICATION OF LUBRICATING OIL HYDROISOMERIZATION CATALYST PHI-01
    2021, 52(4):  15-20. 
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    VGO, which is rich in long chain n-alkanes, is a high-quality raw material for producing heavy and high-quality API III lubricating base oil. However, the high wax content not only increases the viscosity index of lubricating base oil, but also increases the cloud point of base oil products. In view of this problem, PetroChina Petrochemical Research Institute(PRI) developed a new kind of nano-scale zeolite with short axis morphology and very good performance in n-alkane hydroisomerization process. Base on this zeolite, a new generation of lubricating oil hydroisomerization catalyst PHI-01 was developed, which solves the problem of balance between cloud point and yield caused by the increase of viscosity index of heavy base oil. The commercial application of the catalyst in 200 kt/a lube oil hydroisomerization unit of Daqing Refining and Chemical Company of PetroChina showed that the liquid yield was 96%, the yield of 10 cSt base oil was 68.1%, and the cloud point was －7 ℃, which was lower thanthe requirement of －5 ℃.
    STUDY OF REMOVAL OF TRACE CHLORIDE IN ALKYLATE BY MOLECULAR SIEVE ADSORBENT
    2021, 52(4):  21-26. 
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    The dechlorination effects of various molecular sieves were compared and screened, and the results showed that NaY molecular sieves had good dechlorination performance. Molecular sieve adsorbent was prepared by kneading method with NaY molecular sieve powder as active component, and the effect of preparation conditions on the dachlorination performance of the adsorbent was investigated with ionic liquid alkylate as raw material. The experimental results showed that using the adsorbent prepared under the optimized conditions of the mass ratio of NaY powder to binder being 2.0，the calcination temperature of 400 ℃ for 3 h，and at the adsorption temperature of 25 ℃ and LHSV of 1.0h-1, the penetration chlorine capacity could reach 3.11% ,and the adsorbent indicated a good reusability.
    COMMERCIAL TEST OF FISCHER-TROPSCH SYNTHESIS CATALYST CNFT-1
    2021, 52(4):  27-32. 
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    The commercial test of Fischer-Tropsch (F-T) synthesis catalyst CNFT-1 was carried out in two reactors of a 4 Mt/a coal-to-liquids (CTL) commercial plant. The test was divided into two stages: Firstly, the original catalyst in reactor was gradually replaced by CNFT-1 up to 95%. The results showed that the performance of CNFT-1 could meet the production requirement. Secondly, based on the data of the first stage test, the process conditions with CNFT-1 catalyst 100% loading were simulated and optimized by the F-T slurry reactor simulation software to guide the new test. the optimal conditions were as follows: the fresh syngas load of 102.34%, the catalyst inventory of 69.3 t, the effective fresh syngas space velocity of 5112 m3/(h.t), the reaction temperature of 273 ℃, the pressure of 2.81 MPa, the recycle ratio of 2.4, the decarbonization ratio of 0.156 and the H2/CO volume ratio of 1.66. Under these conditions, the total CO conversion reached 97.4% with CO2 selectivity of 18.8%, the CH4 selectivity of 2.0%, and the effective gas consumption of 5630 m3 per ton of oil.
    STUDY OF COKE AND METALLIC IMPURITIES DEPOSITION ON SPENT RESIDUE HYDROTREATING CATALYSTS IN INDUSTRIAL PLANT
    2021, 52(4):  33-44. 
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    Residue hydrotreating spent catalysts after pretreatment with toluene were characterized by C and S content analysis, XRF, XRD, SEM and TG techniques. The results showed that the metallic impurity was mainly captured by layered catalysts system consisted of the guard catalyst, guard-demetallization catalysts, demetallization catalysts and demetallization-desulfurization catalysts in sequence. The captured metal ultimately deposited on the spent catalyst as NiV2S4, while coke was mostly observed on desulfurization catalysts and carbon removal catalyst. Along the flow direction, the coke deposited gradually transferred from soft coke to hard coke and the amount increased. The amount of metal deposition and decomposition temperature increased first and then decreased, and the amount of metal deposition was the maximum in demetallization catalysts, and the molecular structure of sediment was the most complex. The guard-demetallization catalyst and demetallization catalyst system was hardened badly and along the flow direction, V content firstly increased and then decreased, Fe content decreased, while Ni and Ca content was evenly distributed where Fe was mainly deposited on the outer surface, the distribution of Ni element was relatively uniform, V existed more at the edge of the catalyst with lower in center. The distributions of V along the cross section of demetallization catalyst and demetallization-desulfurization catalyst were V-shaped, while on the desulfurization catalyst and carbon residue removal catalyst were U-shaped and distributed on the surface of catalyst particles. Suggestions for catalyst design were proposed.
    COMMERCIAL APPLICATION OF CATALYSTS RS-2100 AND RHC-133B IN 1.0 Mt/a DIESEL HYDROUPGRADING UNIT
    2021, 52(4):  45-49. 
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    In order to adapt to the change of current market demand, reduce the ratio of diesel to gasoline and increase the output of naphtha, a diesel hydrofining unit with a capacity of 1.0 Mt/a of PetroChina Liaoyang Petrochemical Company was transformed into a 1.0 Mt/a diesel hydroupgrading unit. The pre-sulfurized refining catalyst RS-2100 and hydroupgrading catalyst RHC-133B developed by SINOPEC Research Institute of Petroleum Process and produced by the catalyst factory of PetroChina Fushun Petrochemical Company of were used to produce naphtha with a yield not less than 11% and the China VI diesel fuel from straight-run diesel. In the process of start-up, the drying and catalyst activation was combined for the device, which greatly shortened the start-up time and was successfully started up in July 20, 2019. The device was calibrated from September 23 to 26, 2019. The calibration results showed that the naphtha average yield was more than 11.5%, and the aromatic potential content of the naphtha reached 50%, which could be used as reformer feedstock. Meanwhile, the cetane number of the produced diesel fuel increased by 3.5 with the mass fraction of polycyclic aromatics less than 7% and the mass fraction of sulfur less than 5 μg/g, meeting the China VI diesel fuel standard.
    NOVEL RHT-DCC BI-DIRECTIONAL COMBINED PROCESS FOR PRODUCING CHEMICAL RAW MATERIALS FROM RESIDUAL OIL
    2021, 52(4):  50-53. 
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    It is known that after hydrogenation, the polycyclic aromatic hydrocarbons in DCC light cycle oil and heavy cycle oil can be saturated into naphthenic-aromatic ring structure, which has catalytic cracking performance again. A novel RHT-DCC combined cycle process was developed by SINOPEC Research Institute of Petroleum Processing to produce chemical raw materials from residual oil. In this process residual oil blended with DCC light cycle oil and heavy cycle oil rich in poly-aromatics is co-hydrotreated in RHT unit and then deeply cracked in DCC unit to produce ethylene, propylene, butene and light aromatics, the newly produced DCC light and heavy cycle oils come into the RHT-DCC process again and form an integrated cycle process. Therefore, the combined cycle process of RHT-DCC can greatly improve the yield of low carbon olefins and light aromatic hydrocarbons. The total yield of ethylene, propylene, butene and light aromatics reached 55.01% (based on fresh Kuwait AR feed), far higher than that of conventional non-combined process(42.57%).
    STUDY OF CONTINUOUS CROSS-FLOW MICROFILTRATION PROCESS IN AIRLIFT EXTERNAL-LOOP SLURRY REACTOR
    2021, 52(4):  54-61. 
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    Industrial application of slurry bed F-T synthesis technology is limited by separation of fine particles in high solid holdup slurry. An airlift external-loop slurry reactor coupling with membrane separation was created to develop cross-flow microfiltration technology based on special hydrodynamic properties and three phase distribution characteristics. Cross-flow microfiltration performance of nitrogen, diesel and Co catalyst model system in an airlift external-loop slurry reactor was studied, influence of gas superficial velocity ug, solid holdup rs and transmembrane pressure difference ΔP were investigated. It was found that when ΔP was 0.45 MPa, ug was 0.1 m/s and rs were 10% and 20%, the stable permeate flux were 60 L/(m2.h) and 17 L/(m2.h) , respectively, and the particle concentration of permeate was less than 5 mg/L, the filter could run stably at least 720 min. The influence on recovering membrane flux of plused backflushing technology and single continuous backflushing technology was compared. The results showed that the former was more suitable to recover membrane flux.
    COMMERCIAL APPLICATION OF THE TECHNOLOGY FOR PRODUCING HIGH-QUALITY HIGH-VISCOSITY WHITE OIL FROM INTERMEDIATE BASE OIL
    2021, 52(4):  62-65. 
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    White oil hydrogenation catalyst RLF-20 has great aromatic saturation performance. SINOPEC Jingmen Company used heavy VGO of intermediate-base crude pretreated by furfural refining, hydrotreating, and ketone-benzol dewaxing to produce white oil with RLF-20 catalyst in a 100 kt/a white oil hydrogenation unit. The results showed that under the conditions of a H2 partial pressure of 15.1 MPa, a temperature of 236 ℃, and a LHSV of 0.5 h-1, the obtained white oil with a kinematic viscosity (100 ℃) of 11.06 mm2/s could meet the requirement of food grade white oil by GB/T 1886.215—2016 standard, and the product yield was high.
    STUDY OF GAS CONTENT CHANGE IN REFINING PROCESS OF NAPHTHENIC TRANSFORMER OIL
    2021, 52(4):  66-69. 
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    The gas content changes in each stage of hydrodeacidification, furfural refining, liquid phase denitrification, and clay refining of naphthenic transformer oil were investigated with the atmospheric cut 2 of naphthenic base crude oil produced by CNOOC as raw material. The results showed that the gas contents of H2, CO2, CH4, C2H4, and C2H6 in transformer oil increased significantly in the electro-refining stage of liquid phase denitrification. By adjusting the process conditions of electro-refining and adding vacuum filtration device, the gas content could be reduced, and the product could met the technical requirements of the electric power industry standard.
    PREPARATION OF CHITOSAN/ POLYETHYLENE GLYCOL SODIUM AND ITS APPLICATION IN TRANSFORMER OIL DESULFURIZATION
    2021, 52(4):  70-76. 
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    PEG-Na reagents were prepared by polyethylene glycol (PEG) with different molecular weights and NaOH. Chitosan-PEG (Na) desulfurization materials (CS-PEG (Na)) were prepared by PEG-400Na reagent and chitosan. The test sample with dibenzyl disulfide (DBDS) in the fresh transformer oil was prepared. The effect of CS-PEG (Na) on desulfurization of the corrosive sulfur in the test oil was investigated to obtain the best reaction conditions: the mass fraction of CS-PEG (Na) of 20%, the treatment temperature of 60℃, and the treatment time of 2 h. Under the optimal conditions, the corrosive sulfur in the test oil was almost completely removed by CS-PEG (Na). The desulfurization effect of CS-PEG (Na) for waste transformer oil was comparable to that of PEG-400Na reagent, but better than other desulfurizers, the removal rate of corrosive sulfur reached 84.6%. However, the electrical performance of waste transformer oil after desulfurization treatment decreased slightly.
    COMMERCIAL APPLICATION OF IsoTherming TECHNOLOGY FOR VACUUM GAS OIL
    2021, 52(4):  77-81. 
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    The 2.6Mt/a gas oil full-liquid phase hydrogenation unit of the second phase of the CNOOC Huizhou Petrochemical Co. Ltd. project was completed and put into operation in 2017. The unit is the first gas oil hydrogenation unit adopting DuPont's full-liquid hydrogenation technology in China. During 2 years operation， the device experienced many start-ups and shutdowns, but it still showed good operation convenience and economy. After more than two years of operation, the calibration results showed that for Saudi Arabia vacuum gas oil raw materials with sulfur mass fraction greater than 2.7% and nitrogen mass fraction greater than 500 μg/g, the sulfur mass fraction and nitrogen mass fraction of hydrogenated gas oil products was less than 1 000 μg/g and 100 μg/g, respectively, which could meet the feed requirements of catalytic cracking unit. The comprehensive energy consumption was 274.63 MJ/t，lower than those in traditional trickle-bed unit and superior to the device design.
    SUMMARY OF TRIAL OPERATION OF JET FUEL HYDROGENATION UNIT
    2021, 52(4):  82-86. 
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    A 0.40 Mt/a jet fuel hydrogenation unit which was transformed from a 0.90 Mt/a catalytic cracking gasoline hydrodesulfurization unit, successfully started up in 2018. By adjusting the operating parameters, the suitable process conditions for jet fuel hydrogenation were obtained. The causes of corrosion and unstable flash point of jet fuel product were analyzed. The problems were effectively solved by reducing the feed temperature and top part temperature and pressure of stripper tower, and using nitrogen stripper at the bottom of tower.
    DESIGN AND OPERATION ANALYSIS OF STANDPIPE-SLIDE VALVE SYSTEM IN FCC UNIT
    2021, 52(4):  87-92. 
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    The standpipe-slide valve system is the key component of the downstream flow of the catalyst particles cycle in FCC unit.The complexity of conveying catalyst operation in standpipe lies in the diversity of catalyst flow patterns in standpipe.The calculation method of standpipe-slide valve system in commercial FCC unit and pressure drop equation was introduced. On a 1.0Mt /a FCC unit, the flow direction, catalyst density and velocity distribution of gas and catalyst particles in the standpipe were analyzed by measuring the axial pressure distribution of the standpipe and recording the processing parameters in different operating conditions. According to the flow characteristics of the gas and catalyst particles, the standpipe was divided into three sections, namely, the negative differential pressure degassing section, the negative differential pressure holding gas section and the positive differential pressure gas leakage section. The reasons causing the formation of half pipe flow and effect of gas leakage from slide valve on standpipe pressure distribution were summarized.The results provided theoretical support for the design and operating adjustment of the standpipe-valve system in FCC unit.
    DYNAMIC CHANGE OF ASPHALTENE MICROSTRUCTURE DURING RESIDUE SLURRY-BED HYDROCRACKING
    2021, 52(4):  93-98. 
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    In order to study the dynamic changes of asphaltene microstructure during residue hydrogenation, Karamay atmospheric residue was used as raw oil for slurry bed hydrocracking reaction with different reaction time. The asphaltenes in reaction products were separated, and their basic properties and coke yield were analyzed. The asphaltenes were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The results suggested that the residue hydrocracking in slurry-bed could be divided into two reaction stages according to the change of asphaltenes microstructure. During the reaction time less than 20 min, the asphaltene content gradually increased, the surface changed from smooth to rough, and three-dimensional accumulation of particles appeared. The accumulation of aromatic lamellae tended to ordering changes, the number of layers increased gradually, and the interlayer spacing and alkyl side chain spacing decreased continuously. After the reaction time of 20 min, the asphaltenes converted to coke fast and the content of asphaltenes decreased significantly. The stacking of aromatic layers changed disorderly and the number of aromatic layers decreased, the spacing between aromatic layers and the spacing between alkyl side chains increased gradually.
    STUDY OF CATALYTIC OXIDATIVE DESULFURIZATION PERFORMANCE OF AMMONIUM MOLYBDATE IN LACTIC ACID BASED DEEP EUTECTIC SOLVENT
    2021, 52(4):  99-105. 
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    Using caprolactam as hydrogen bond acceptor and lactic acid as hydrogen bond donor, a lactic acid based deep eutectic solvent(DES) was synthesized. The hydrogen bond interaction between caprolactam and lactic acid was determined by FT-IR and 1H NMR. Using dibenzothiophene (DBT) and n-octane as simulated oil,the lactic acid based DES as extractant and cocatalyst, hydrogen peroxide as oxidant and ammonium molybdate as catalyst, the effects of reaction temperature, n(H2O2) /n(DBT), catalyst dosage and volume ratio of lactic acid based DES to oil and sulfide type on the desulfurization rate of the simulated oil were investigated. The optimum reaction conditions were determined as follows: q reaction temperature of 70 ℃, a reaction time of 100 min,a n(H2O2)/n(DBT) of 6∶1, an ammonium molybdate dosage of 4 g/L and a volume ratio of DES to oil equalling 1∶10. Under the optimal reaction conditions, the desulfurization rates of the simulated oil of DBT, 4,6-dimethyldibenzothiophene and benzothiophene were 100%, 98% and 78%, respectively. After using for 5 times, the desulfurization rate of simulated oil by lactic acid based DES can still reach 95%, indicating the good reusability of DES.
    STUDY OF ENERGY-SAVING WAYS OF HYDROGENATION UNITS
    2021, 52(4):  106-112. 
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    The energy-saving ways for hydrogenation unit were discussed from three aspects: process energy saving, equipment energy-saving and joint energy -saving among units. Among them, the selection of energy-saving process technology and optimization of process flow were discussed; for equipment energy -saving, setting up stepless regulation system of compressor gas volume and energy saving/recovery facilities such as hydraulic permeability were highlighted; while for joint energy-saving of devices, the joint scheme of hydrogen cascade utilization, energy transfer and heat inlet/outlet between devices were discussed.
    ENERGY-SAVING OPTIMIZATION OF GAS FRACTIONATOR BY IMPROVED MOGWO ALGORITHM
    2021, 52(4):  112-118. 
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    The energy-saving optimization for gas fractionation unit was discussed. A PRO/II process simulation model was established by using the actual working condition data of the device. The sensitivity analysis of operation parameters were carried out, and then a multi-objective optimization model of gas fractionator were built by using the multiple linear regression theory. The penalty function algorithm and the improved multi-objective grey wolf algorithm method were used to solve the optimization model．The results showed that the optimal collocation of multiple groups of operating parameters could increase the production and decrease the propylene emission and the energy consumption to realize the energy-saving optimization of gas fractionation unit. This method can provide a new theoretical basis for optimization design of gas separation plant and other distillation processes
    CHALLENGES AND COUNTERMEASURES OF GROUNDWATER REMEDIATION AND TREATMENT IN PETROCHEMICAL CONTAMINATED SITES
    2021, 52(4):  119-126. 
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    Groundwater contamination in petrochemical sites seriously restricts ecological civilization construction. Safe and efficient remediation of contaminated sites is a key problem to be discussed and solved urgently in the development of petrochemical industry. The challenges for groundwater remediation in petrochemical contaminated sites are analyzed from three aspects: particular contaminants，hydrogeology conditions and environmental effects. The promising groundwater remediation techniques including regional remediation strategies regarding to different pollution levels are discussed. As revealed by the analysis，the difficulties for accurate pollution positioning and in situ remediation in petrochemical contaminated sites have been increased due to the hydrophobicity of non-aqueous phase pollutants （NAPLs），different migration characteristics of compound pollutants，the heterogeneity of strata，as well as the frequent interactions between surface water and groundwater. Major breakthroughs of groundwater remediation technology in future petrochemical sites include the development of sustained-release and long-acting materials with improved mass transfer and transmission performance and of high efficiency remediation technologies for heterogeneous aquifers. The remediation effects can be significantly improved by combining subregional remediation and in situ multi- remediation technologies，which further ensures the safe production of petrochemical sites.