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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 December 2021, Volume 52 Issue 12
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    SYNTHESIS OF BOROSILICATE ZEOLITE AND THEIR CATALYTIC PERFORMANCE FOR REFORMING REACTION OF HEAVY FEED
    Wang Jiaxin Ma Aizeng Zang Gaoshan
    2021, 52(12):  1-6. 
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    The synthesis of borosilicate zeolite was studied in the system Na2O-TEAOH-B2O3-SiO2-H2O by hydrothermal crystallization with different synthesis conditions. Catalysts with borosilicate zeolite as support were prepared and their catalytic performances for reforming reaction were evaluated for heavy hydrocarbon feed. The results show that the template amount and SiO2/B2O3 ratio in synthesis mixture play a key role in the crystal form of the zeolite, and borosilicate β zeolite (Bβ) with high crystallinity can be synthesized under proper synthesis conditions. When n-tridecane is used as the model compound, the Pt/Bβcatalyst shows better aromatization performance. Compared with PR-D catalyst, Pt/Bβcatalyst shows higher BTX and naphthalene yields and lower C9+ aromatics yield. Treating heavy feed by Pt/Bβcatalyst, the reaction pressure should not be too low; moreover, higher reaction temperature and lower WHSV are beneficial for the formation of BTX.
    STUDY OF STRUCTURE-ACTIVITY RELATIONSHIP OF Pt/SZA CATALYST FOR n-HEXANE ISOMERIZATION
    2021, 52(12):  7-12. 
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    The solid super acid catalyst Pt/SZA was prepared by the equal volume impregnation method. The effects of calcination temperature on the crystal phase, pore structure and acidity of the catalyst were characterized by XRD, nitrogen adsorption and desorption, NH3-TPD and other methods. The effect of calcination temperature and sulfur loading of the super acid support on the isomerization performance of the catalyst were also investigated. The results showed that the optimum calcination temperature was 550 ℃ and the sulfur content of the catalyst was 3.15%. Under this condition, the prepared Pt/SZA catalyst exhibited little monoclinic zirconia, more active sites of acid centers and suitable pore structure properties. The catalyst had the highest catalytic activity for the isomerization of n-hexane and excellent distribution of isomerization product distribution in the same reaction condition.
    EFFECT OF DIFFERENT PRECIPITATING AGENTS ON PHYSIC-CHEMICAL PROPERTIES AND ACTIVITY OF BULK HYDROGENATION CATALYSTS
    2021, 52(12):  13-20. 
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    A series of bulk catalysts were synthesized by using NH3.H2O, NaOH, Na2CO3 and mixtures with different ratios of NaOH and  Na2CO3 as precipitating agents. Characterization methods such as XRD, BET, TEM, SEM and EPMA are used to analyze the microscopic morphology, pore structure, crushing strength and phase of the synthesized catalysts, and a series of bulk catalysts are evaluated for hydrodesulfurization activity on a small hydrogenation unit. The results show that when a single precipitating agent is used, the bulk catalyst synthesized with NaOH has the best crushing strength and pore structure, the active metal is evenly dispersed, and its hydrodesulfurization activity is the highest. The mixed precipitating agent of NaOH and Na2CO3 can expand the pores of the bulk catalyst, which can improve the performance of the catalyst. When the mixed precipitating agent is m( Na2CO3): m(NaOH)=2:3, the catalyst has the best physical and chemical properties and activity, the specific surface area of the catalyst is 213 m2/g, the pore volume is 0.308 cm3/g, the bulk density is 1.01 g/cm3, and the crushing strength is 14.9 N/mm. The relative desulfurization activity of the bulk catalyst at this ratio is 1.66 times that of the catalyst using NaOH as the precipitating agent.
    PREPARATION AND PERFORMANCE EVALUATION OF HYDROGENATION CATALYST FOR SELECTIVE ARSENIC REMOVAL FROM FCC HEAVY GASOLINE
    2021, 52(12):  21-26. 
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    A hydrogenation catalyst for selective arsenic removal from FCC heavy gasoline was synthesized by equal volume impregnation method with macroporous γ-Al2O3 as carrier and Mo-Ni as active component. The effects of aluminum oxide powder, sol,active metal and metal atom ratio on the catalyst activity and selectivity were studied. The results showed that the pore diameter distribution of aluminum oxide had a great influence on arsenic removal activities of the catalysts, and the large pores were good for improving arsenic removal activity. The organic acid as a sol could significantly increase the proportion of large pore in the carrier, and the appropriate Ni/(Ni+Mo) ratio was beneficial to the high arsenic removal activity and selectivity of the catalysts. The catalysts exhibited a good long-term stability and arsenic capacity, and the performance was comparable to the commercial arsenic removal catalysts.
    EFFECT OF GUARD CATALYSTS GRADING DESIGN ON FIXED BED RESIDUE HYDROTREATING PERFORMANCE
    2021, 52(12):  27-31. 
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    Five kinds of guard catalysts were designed along the flow direction by using different special-shaped catalysts, such as filamentous foam, honeycomb cylinder and Raschig ring. The catalyst has a large bed voidage.Along the flow direction, the bed voidage and pore size are gradually reduced and the active metal content is gradually increased. Outstanding gradation in bed voidage, pore properties and activity can better relieve the impurity removal pressure of the catalyst in the bed of demetallization catalyst, avoid the catalyst hardening at the junction of the guard catalyst and the demetallization catalyst, and ensure the stable and long time operation of the device. The removal rates of Fe and Ca of the self-made guard catalysts are better than those of reference catalyst, and self-made guard catalysts show certain removal ability of Ni, V, CCR and S. There is no pressure drop in the whole process of long period experiment, and the temperature increase during the test process is low.
    STUDY OF COMBINED PROCESS OF RESIDUE HYDROTREATING AND DELAYED COKING FOR THE PRODUCTION OF LOW SULFUR PETROLEUM COKE
    2021, 52(12):  32-37. 
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    The hydrotreating process conditions of high sulfur residue were investigated. The results show that increasing the reaction temperature and reducing the LHSV are beneficial for increasing the hydrodesulfurization reaction effect; lowering the reaction temperature, reducing the hydrogen partial pressure and increasing the LHSV are beneficial for increasing the hydrodesulfurization selectivity. In the case of achieving the same desulfurization rate, increasing the reaction temperature can greatly increase the LHSV, thereby reducing the processing cost of residue hydrogenation. Research on the combined process of residue hydrogenation and delayed coking shows that as the depth of hydrodesulfurization increases, the remaining sulfur compounds in the hydrogenated residue are more likely to remain in petroleum coke. The combined process can greatly reduce the sulfur mass fraction of petroleum coke to below 3.0%, which can meet the index requirements of low-sulfur coke. Compared with delayed coking process, the combined process can produce more high-value products, and the properties of the coking products are also better.
    APPLICATION OF HIGH AND LOW TEMPERATURE DUAL REACTION ZONE PROCESS RTS IN PETROLEUM PROCESSING FIELD
    2021, 52(12):  38-42. 
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    In order to realize deep desulfurization, nitrogen removal and aromatics saturation, the high and low temperature dual reaction zone RTS（Remove Trace Sulfur）process was developed. The technology can be applied in diesel quality upgrading, LCO hydrogenation to promote polycyclic aromatic saturation, low pressure hydrogenation of jet fuel with high nitrogen content or high final boling point, reforming prehydrogenation of secondary process naphtha. Commercial application results of the process in clean diesel production show that the sulfur content is less than 10 μg/g and the polycyclic aromatic content is less than 5% when hydrotreating diesel feed is mixed with 25% of secondary process diesel fraction, and the product quality can meet the China National VI standard. The operation cycle of the unit can exceed 3 years.
    EXTENDED RESEARCH AND COMMERCIAL APPLICATION OF RICP PROCESS
    2021, 52(12):  43-48. 
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    Hydrogenation pilot tests are carried out using the Middle East high sulfur residue mixed with FCC light cycle oil (LCO) as feedstock. The results show that LCO mixture with residue for hydrogenation has better hydrogenation performance and the amount of coke deposited on the residue hydrogenation catalyst is reduced. The commercial application results of RICP-Ⅱ process in three companies show that compared with RUN-2, both metal and carbon content on spent catalyst of RUN-4 are lower in the residue hydrotreating (RHT) unit in company A; the total pressure drop, radial temperature difference and temperature rise of reactors are significantly reduced after adding LCO in the RHT unit in company B; HDS, HDN and HDCCR are all promoted, but the effect on HDM is not obvious; high proportion of LCO is introduced in the RHT unit in company C; the mass fraction of LCO account is 26.33% of the total amount of processing, the highest mass ratio of LCO account is for more than 45% of the total reaction feed, the total pressure drop of the reaction system is lower than 2.0 MPa, the temperature rise is less than 70 ℃, and the maximum radial temperature difference is below 9 ℃ in the whole operation cycle for 1 261 days.
    DEEP CATALYTIC CRACKING MODEL OF HEAVY OIL BASED ON BP NEURAL NETWORK
    2021, 52(12):  49-53. 
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    A deep catalytic cracking model of heavy oil based on BP neural network with structure 11-12-3 and Bayesian algorithm as learning algorithm was constructed and verified by using the experiment data of the heavy oil catalytic cracking reaction process and selecting 11 parameters such as raw material properties, catalyst activity, operation technology as input variables, and the yield of ethylene, propylene and light aromatics (BTX) as output variables. The results showed that the average relative errors of the model for the forecasts of the yields of ethylene, propylene and BTX were 4.59%, 3.92% and 2.28%, respectively. The established model has a good prediction effect on the yield of heavy oil catalytic cracking reaction products.
    EFFECT OF FLUORINE TREATMENT ON THE STRUCTURE, ACIDITY AND CATALYTIC ACTIVITY OF BETA ZEOLITE
    2021, 52(12):  54-59. 
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    The Beta zeolite was modified with NH4F/NH3.H2O solution, and the effect of fluorine modification on the structure, acidity and catalytic alkylation activity of the Beta zeolite was investigated. The results show that after being treated with NH4F/NH3.H2O solution, the non-framework aluminum of Beta zeolite was removed and the ratio of n(SiO2)/n(Al2O3) was increased. The total acid, L acid and B acid of Beta zeolite were relatively reduced, but the ratio of B acid to total acid was increased. The mesoporous specific surface area and mesopore volume of Beta zeolite were increased, which improved its adsorption capacity for organic vapor molecules and was favorable for the contact of feed molecules with the acidic sites of zeolite. Therefore, the performance of Beta zeolite catalyst for the alkylation reaction was improved by fluorine modification.
    HYDROTREATING CONVERSION PERFORMANCE OF DIFFERENT ASPHALTENES IN DECALIN SYSTEM
    2021, 52(12):  60-63. 
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    The hydrotreating conversion performance of different asphaltenes separated by different solvent in decalin was investigated in an autoclave. The results show that the asphaltenes have better hydrotreating conversion performance in decalin with the conversion rate higher than 60%, and coke yield lower than that of corresponding residue. The conversion of pentane-asphaltenes is higher than that of heptane-asphaltenes from the same raw material because of the different structure and composition of asphaltenes separated by different solvents. The coke yield of asphaltenes from paraffin-based crude used in this study is higher, and the conversion and product distribution are slightly lower, which is different from the traditional understanding. It shows that the hydrogenation reactivity of asphaltenes is not only related to the base genus of residual oil raw materials, but also to the molecular structure of asphaltenes itself.
    INFLUENCE OF PRODUCED LIQUID TEMPERATURE ON FLOW FIELD AND SEPARATION PERFORMANCE OF HYDROCYCLONE FOR OIL-WATER SEPARATION
    2021, 52(12):  64-71. 
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    In order to explore the influence of produced liquid temperature on the separation performance of hydrocyclone for oil-water separation(referred to as hydrocyclone), the parameters of the flow field, oil phase distribution and the separation efficiency of hydrocyclone were studied by the method of experiment and numerical simulation. The results showed that, in the research range, the tangential velocity, pressure and turbulent kinetic energy of the mixture in the separation flow field and the radial settling velocity of oil drop were positively correlated with temperature. The increase of the tangential velocity, pressure and the radial settling velocity improved the separation performance of hydrocyclone. Moreover, with the increase of produced liquid temperature, the volume fraction of oil in the axis was increased by 13.97 percentage points, the non-uniformity of oil phase volume distribution was decreased to less than 80%, the average diameter of the oil wick decreases by 0.16 mm, and the enrichment degree of oil phase at the axial was also increased. Ultimately, when the produced liquid temperature was higher than 70 ℃, the separation efficiency was more than 99%, and the separation performance of hydrocyclone was the best.
    EFFECT OF CHEMICAL STRUCTURE MODIFICATION OF AROMATICS-RICH HEAVY OIL ON MESOPHASE PITCH FORMATION
    2021, 52(12):  72-78. 
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    The thermal conversion behavior of aromatics-rich heavy oil to secondary asphalt and its hydrogenated asphalt were compared, and the influence of chemical structure on mesophase formation during thermal conversion was studied. The chemical structure and composition of the secondary asphalt and the hydrogenated secondary asphalt were analyzed by FTIR, the results were compared with those by polarized light microscopy and XRD, and the formation process of mesophase pitch in two systems was investigated. The results show that controlling the content of short alkyl side chain can effectively inhibit the occurrence of over carbonization and improve the microcosmic ordering degree of carbonized products, the short alkyl side chain can release small molecular free radicals stably, and the control of macromolecular radical significantly improves the homogeneity of the microstructure of carbonized products.
    SENSIBILITY OF GREASE ADDITIVES IN POLYUREA GREASE
    2021, 52(12):  79-86. 
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    Several kinds of grease additives were added to polyurea grease. The sensitivity of different additives to friction and wear of polyurea grease was studied by using MS-10 four-ball friction tester. The wear surface morphology, element content and chemical state of the steel balls were analyzed by scanning electron microscope (SEM), X-ray energy dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS), and the high temperature stability of the polyurea compound grease was analyzed by thermogravimetric analyzer (TGA). The results showed that the load-carrying capacity, anti-wear and friction reduction performance of polyurea grease could be improved obviously by the compound additives.
    NEW UTILIZATION OF RESIDUE FOR SYNTHESIS OF FLAME RETARDANT
    2021, 52(12):  87-91. 
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    Residue is rich in polycyclic aromatics with large carbon residue and high oxygen index, so it has stable thermal stability and flame retardancy. Aromatics are obtained by separating the residue, hydroxyl groups are introduced into their structures by chemical modification method, and flame retardant with aromatic phosphate ester is got by reacting with phosphorus oxychloride. The results of FTIR，TG/DTG, carbon residue and oxygen index show that a new type of residue flame retardant with flame retardancy is successfully synthesized. The flame-retardant PE is characterized by LOI and the UL-94 tests. The results show that the modified residue have great flame retardant. The synthesis of aromatic ester flame retardants modified by residuum and the compounding of them into new intumescent flame retardants can not only be used to prepare flame retardant polymers, but also provide a new source of raw materials for flame retardants synthesis and open up a new way for high value-added utilization of residue.
    APPLICABILITY STUDY OF FCC SLURRY AS RAW MATERIAL FOR PRODUCING NEEDLE COKE
    2021, 52(12):  92-95. 
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    Aiming at the high-value application of FCC slurry, the slurry properties of 40 sets of FCC units in SINOPEC were evaluated. The sulfur content, nitrogen content, ash content, resins content, asphaltenes content and aromatics content were analyzed and their influence on the production of needle coke were discussed. The properties of ideal raw materials suitable for the production of needle coke were put forward. In SINOPEC,FCC slurry which is suitable for the production of needle coke exceeds 2.0 Mt/a.
    AFFECTING FACTORS OF ACID NUMBER DETERMINATION OF PETROLEUM AND PETROLEUM PRODUCTS BY CATALYTIC THERMOMETRIC TITRATION
    2021, 52(12):  96-101. 
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    Acid number of petroleum and petroleum products was determined by catalytic thermometric titration, and various factors that might affect the test results were investigated, including particle size of paraformaldehyde, amount of paraformaldehyde, titration rate, filter factor, ambient temperature, solvent blank and so on. The results show that when particle size of paraformaldehyde is less than 75 μm, titration rate is 2 mL/min, filter factor is 45, the data precision is better when the blank value of solvent is taken into account. The environmental temperature and amount of paraformaldehyde have little influence on the results of titration analysis. In addition, a simple and feasible method for determine solvent blank value was developed.
    DETERMINATION OF CARBAZOLE COMPOUNDS IN DEEP HYDROGENATED DIESEL
    2021, 52(12):  102-108. 
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    A gas chromatography quadrupole time-of-flight mass spectrometry method was developed for the qualitative and quantitative measurement of carbazole compounds in deeply hydrogenated diesel. This method could be used for qualitative analysis of five carbazole compounds with mass fraction in ng/g level，the linear correlation coefficient of the quantitative standard curve was above 0.998 0, and the recovery range was 81.86%-89.27%. The relative standard deviation range was 2.36%-4.14%，showing that the quantitative accuracy of the method was good. The minimum detection limits were 0.000 4-0.001 6 mg/L and the quantitation limits were 0.001 2-0.005 4 mg/L，illustrating that the sensitivity of the method was high. The carbazole compounds in hydrogenated diesel with different hydrofining depths were analyzed by this method. The results showed that carbazole and methyl carbazole was easily removed in the hydrofining process, and the 1- or 8-methyl-substituted dimethylcarbazole and trimethylcarbazole compounds had large steric hindrance and were difficult to be removed by hydrogenation.
    CORROSION CAUSES AND CONTROL OF COPPER HEAT EXCHANGER IN CIRCULATING WATER SYSTEM
    Zhang Xiangnong
    2021, 52(12):  109-112. 
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    Corrosion of copper heat exchanger is a serious threat to the stable operation of production equipment. In view of the over-standard corrosion of copper strip in the circulating water system of a petrochemical enterprise in north China, the corrosion characteristics, ammonia, organic phosphine, microorganism and other factors of the circulating water quality were comprehensively analyzed. Among these factors, low alkalinity, over-standard ammonia content and high concentration of chloride ion were the main reasons for the corrosion of copper strip. Measures such as increasing the M alkalinity and the concentration of corrosion inhibitor were taken, which could effectively reduce the corrosion rate of copper equipment and avoid the safety risk of copper heat exchanger corrosion to the production unit.
    QUALITY UPGRADE OF DIESEL PRODUCTS AND APPLICATION PROGRESS OF CLEAN DIESEL PRODUCTION TECHNOLOGY
    2021, 52(12):  113-118. 
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    The process of diesel product quality upgrading and the change of diesel product specifications in China are introduced.The development progress of diesel hydrofining catalyst and process technology at home and abroad, as well as the industrial application of typical catalysts and process technology in response to the rapid quality upgrading of diesel products are introduced in detail.The purpose of this paper is to introduce and analyze various catalysts and process technologies to help users make reasonable technical choices when dealing with the quality upgrade of diesel products.