Table of Content

12 May 2019, Volume 50 Issue 5

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STUDY ON PREPARATION OF MILLIMETER-SIZED ALUMINA PELLETS BY HOT OIL-DROP METHOD WITH PSEUDO-BOEHMITE

2019, 50(5):  1-5. 

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The feasibility of alumina sphere formation through hot oil-drop method with high purity pseudo-boehmite was investigated. By optimizing the ratios of raw material, peptizer and gelling agent, the crushing strength of alumina pellets prepared was higher than 50 N/ pellet, the bulk density was 0.55-0.63 g/mL, and the specific surface area was maintained above 155 m2/g after 650 ℃ and 10% water vapor treatment for 50 h，meeting the demand of new continuous catalytic regeneration (CCR) catalyst. Compared with the existing industrial pelleting technology, the process of this scheme is simpler and is more environmentally friendly. The naphtha reforming performance of the Pt-Sn/γ-Al2O3 catalyst prepared by the new technique has reached the level of industrial catalyst.

RESEARCH AND DEVELOPMENT OF LUBE HYDROISOMERIZATION DEWAXING CATALYST RIW-2

2019, 50(5):  6-11. 

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Based on the mechanism of alkane hydroisomerization and lube hydroisomerization dewaxing, the influence of properties of molecular sieve on the performance of hydroisomerization catalyst was investigated, the ZIP sieve with high activity and hydroisomerization selectivity was selected as acidic component of the new developed dewaxing catalyst RIW-2. At the same pour point, the yield of base oil for RIW-2 is much higher than that of the first generation catalyst RIW-1. RIW-2 can be used in the dewaxing of many kinds of waxy feedstocks to produce high viscosity index base oils, and can produce API III+ base oils.

INDUSTRIAL APPLICATION OF FHUDS-5/FHUDS-6 IN DEEP HYDRODESULFURIZATION OF DIESEL OIL

2019, 50(5):  12-17. 

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FHUDS-5 and FHUDS-6 ultra-deep diesel hydrodesulfurization catalysts developed by SINOPEC Fushun Research Institute of Petroleum and Petrochemcials were applied in a new-built 3.0 Mt/a diesel hydrogenation unit of Zhenhai Petroleum Refining and Petrochemical Company. The calibration report of catalysts showed that the total sulfur content of refined diesel oil was 4.8 μg/g and the nitrogen content was lower than 0.5 μg/g. The average mass fraction of PAHs decreased by about 20 percent points, and the average cetane number increased by 4.1, indicating the high HDS, HDN and aromatic saturation activities, as well as good cetane number upgrading performance．In terms of the operation conditions in the first 15 months, the catalyst deactivation rate was 0.8 ℃ monthly, the bed pressure drop of the reactor was lower than 0.1 MPa and the highest temperature in reactor was lower than 370 ℃. The results showed that the catalyst combination of FHUDS-5 / FHUDS-6 has good stability and can meet the requirements for long operation period of the device.

EFFECT OF DIFFERENT Ni CONTENT ON RING OPENING OF DECALIN OF TUNGSTEN-BASED CARBIDE CATALYSTS

2019, 50(5):  18-23. 

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A series of Ni-W/USY-Al2O3 carbides with different Ni content was prepared by co-impregnation method and were characterized by N2 adsorption-desorption, element analysis, CO titration, X-ray diffraction (XRD), and temperature programmed reduction. Decalin was chosen as the model reactant for measuring the effect of Ni content on tungsten-based carbide catalysts. The results showed that an appropriate atomic ratio of Ni to W can increase the metal sites of the catalysts, thus improving the ring opening performance of the catalysts.

APPLICATION OF NEW CATALYST HAT-300 FOR TOLUENE DISPROPORTIONATION

Wang Yubing

2019, 50(5):  24-28. 

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In order to make full use of toluene and heavy aromatics resources and increase C8 aromatics production, a new catalyst HAT-300 developed by SINOPEC Shanghai Research Institute of Petrochemical Technology(SRIPT) was adopted on the existing toluene disproportionation and transalkylation unit (TDT) in a petrochemical company of SINOPEC. Without the key equipment replaced, only the inner components of some towers, pumps and pipelines were modified, the capacity expansion of the TDT unit was realized. The application results show that the HAT-300 catalyst has higher activity and selectivity, can adapt to the conditions of higher space velocity and lower hydrogen-hydrocarbon ratio. Even though the content of low-value heavy aromatics in the feed increased considerably, the HAT-300 catalyst exhibited excellent conversion and selectivity.

SINOALKY TECHNOLOGY FOR SULFURIC ACID ALKYLATION AND ITS APPLICATION

2019, 50(5):  29-32. 

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Alkylate has become one of the indispensable premium blending components for national VI gasoline and ethanol gasoline. SINOPEC has independently developed the sulfuric acid alkylation technology (SINOALKY) to meet the needs of alkylate market. SINOALKY integrates N-type multi-stage static mixer, self-vaporizing acid-hydrocarbon separator and multi-feeding method in its process. The first 200kt/a industrial demonstration unit using the SINOALKY was completed and put into operation at SINOPEC Shijiazhuang Refining & Chemical Company, on June, 2018. Industrial operating results confirmed that under full load, the RON of alkylate is 96.5-97.0, and the acid consumption is 58.9 kg/t. SINOALKY has the advantages of simple process, easy reactor maintenance, low acid consumption and high product quality.

OPERATION ANALYSIS OF 1.2 Mt/a MaxEne UNIT

2019, 50(5):  33-38. 

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The 1.2 Mt/a MaxEne unit of SINOPEC Yangzi Company was successfully start-up and put into operation on January 23, 2013. The function of MaxEne is to isolate n-alkanes from naphtha by simulated moving bed (SMB) process. The extract oil is used as the feed of steam cracking unit to produce ethylene. The raffinate oil is used as the feed of catalytic reforming unit. The commercial results showed that the n-alkanes purity was 94.83％ in the extract oil, and the recovery rate of n-alkanes was 87.02％, based on mass fraction of n-alkanes of 26.25% in naphtha. With the use of the extract oil as the feed of ethylene cracking, the ethylene yield increased by 14.10 percentage points and the aromatic potential content of the raffinate oil increased by 11.20 percentage points compared with the results of naphtha fraction as feedstock. The reasons for the periodic fluctuation of the raffinate column, the high consumption of desorbent and the flooding of the extract column were analyzed.

OPTIMIZATION OF PRE-HYDROGENATION PROCESS FOR REFORMING FEED WITH COKER NAPHTHA

2019, 50(5):  39-44. 

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The blending of reformer feed with coker naphtha increases the difficulty of pre-hydrogenation operation. The main factors affecting the process were investigated in a 200mL pilot plant by response surface design. The results of response surface interaction indicated that the reaction temperature and pressure had a greater influence on the removal of impurities. The optimum process conditions for pre-hydrogenation were temperature of 287 ℃， pressure of 2.0 MPa，LHSV of 2.0 h－1，and hydrogen/oil volume ratio of 200 when the feed contained 15% coker naphtha. Using the Design expert software，the relative error between the predicted value and the experimental value of the model equation is less than 5%. The model equation can accurately simulate the sulfur and nitrogen content of the oil produced under different operating conditions and provide technical support for the optimization of industrial process conditions.

SELECTION AND OPTIMIZATION OF PROCESSING ROUTE FOR FCC LIGHT CYCLE OIL

2019, 50(5):  45-51. 

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With the decline of diesel/gasoline ratio，SINOPEC Anqing Company adopted new technologies and better processing routes for FCC light cycle oil. The RLG technology processing route was selected and optimized by comparing various processes such as hydrofining depth，hydrotreating VGO mixed with LCO，hydrocracking of VR mixed with LCO，LTAG and RLG. The RLG process can produce more gasoline and reduce the diesel yield. The combination of RLG with the LTAG technology can further reduce the ratio of diesel/gasoline and obtain better economic benefit.

DEVELOPMENT AND INDUSTRIAL APPLICATION OF C4 HYDROCARBON AROMATIZATION FOR PRODUCTION OF MIXED AROMATICS

2019, 50(5):  52-56. 

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The technology of C4 hydrocarbon aromatization to produce mixed aromatics developed by PetroChina Lanzhou Chemical Research Center was put into operation in the 200 kt/a C4 aromatization unit in Hengrun Petrochemical Company. The results of industrial application showed that using C4 with olefin mass fraction of 41.91% as raw material, under the hydrogenation conditions of 400℃, 2.0 MPa and LHSV 1.0 h-1, the conversion rate of C4 olefins was 99.02%, with the dry gas yield was 1.94%. The yields of liquefied gas and gasoline component were 53.90% and 40.11%, respectively. The gasoline octane number was 94-96. The diesel yield was 4.05%. The mass fraction of aromatic hydrocarbons in liquid phase products was 56.48%, among which the mass fraction of benzene was 2.01%, toluene 11.58% and xylene 19.00%.

STUDY OF PROCESS OPTIMIZATION FOR NAPHTHENIC RUBBER PLASTICIZER PRODUCTION FROM FURFURAL RAFFINATE OIL

2019, 50(5):  57-60. 

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Furfural raffinate oil with low nitrogen and aromatics content is suitable to produce colorless and low aromatic rubber plasticizer. In this paper, we use raffinate oil from SZ36-1 No.3 vacuum cut as raw material to produce naphthenic rubber plasticizer by the combined process of hydrotreating (catalyst RL-1), hydrodewaxing (catalyst SDD-800) and hydrofinishing (catalyst LN-5). The LHSV of RL-1,SDD-800,LN-5 was 1.3,0.8,0.6 h-1,respectively. The reaction temperature of hydrotreating and hydrodewaxing were both 340℃ and the temperature of hydrofinishing was 240℃. The experimental results showed that naphthenic rubber plasticizer produced met the N4010 indexes of HG/T 5085-2016 “Rubber plasticizer-naphthene base mineral oil”, the yield of the product was over 90%. The net profit increases by 1, 370 RMB/t compared with the direct sale of the residual oil. The potential economic benefits are significant.

IMPACT FACTORS ON SELECTIVITIES OF PROPYLENE AND BUTENE IN FCC PROCESS

2019, 50(5):  61-65. 

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ACE (Advanced Catalyst Evaluation) was employed to investigate the factors impacting the selectivities of propylene and butene in the process of catalytic cracking of heavy oil. The results showed that with the increase of temperature, there were maximum values for the selectivities of propylene and butene. But the corresponding reaction temperature for maximum butene selectivity was lower than that of propylene; with the increase of cat-to-oil ratio, selectivities of both propylene and butene decreased. However, the selectivity for butene dropped more than that of propylene; the increase of ZSM-5 zeolite was in favor of propylene, while selectivity of butene decreased. Moreover, modification ways of ZSM-5 had an impact on the selectivities of the both light olefins; with the increase of the molecular sieve cell constant of Y zeolite, the selectivities of the two olefins were decreased and the selectivity of butene decreased more than that of propylene.

HIGH TEMPERATURE SIMULATED DISTILLATION AND THERMOGRAVIMETRIC-MASS SPECTROMETRY ANALYSIS OF DELAYED COKING FEED

2019, 50(5):  66-70. 

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Distillation range and carbon distribution of vacuum residue of CNOOC Huizhou refinery were studied by high temperature simulated distillation. The pyrolysis behavior of residual oil and the on-line exhalation characteristics of pyrolysis gas phase products were studied by thermogravimetric and mass spectrometry. The results showed that the initial boiling point and the final boiling point of Huizhou refinery vacuum residue were 319℃and 733℃, respectively, the carbon number distribution was C18 - C120. The TG-MS system can monitor the escaping behavior of vapor volatiles while obtaining the thermogravimetric information. The pyrolysis of residual oil was mainly divided into three stages. The maximum weight loss rate occurred at 455℃, the residual amount was 14% of the feed mass. The main products escaped were H2, CH4, C2H4, C3H6, C3H4, CO2, H2O, H2S, SO2 and light hydrocarbons.

EFFECT OF ADDITIVES ON THE COMPATIBILITY BETWEEN AVIATION LUBRICANTS AND RUBBERS

2019, 50(5):  71-75. 

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The influence of three kinds of antioxidants and three kinds of extreme-pressure anti-wear additives on the compatibility between aviation lubricants and rubbers was studied by using pentaerythritol ester as base oil which meets MIL-PRF-23699F standard applied in aviation engine oil. The results showed that the most of additives had little effect on the volume change rate of acrylonitrile-butadiene rubbers, while phosphate additive exacerbated the volume change rate. Three kinds of extreme-pressure anti-wear additives had little effect on the volume change rate of fluoro rubber, while three antioxidants slightly reduced the volume change rate of it. Amine additives in ester lubricants had little effect on the tensile properties of fluoro rubber. Acidic phosphate reduced the volume change rate of silicone rubber and fluorosilicone rubber，even shrinked the volume of silicone rubber. Acidic phosphate can react with silicone rubber and fluorosilicone rubber, which caused the loss of the tensile properties.

STUDY ON RELATIONSHIP AMONG SULFUR-RELATED ITEMS IN GASOLINE QUALITY STANDARDS

2019, 50(5):  76-81. 

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Based on the renewal of items relating to sulfur and corrosion in motor gasoline quality standards, combined with sulfur distribution, processing and blending techniques of gasoline, the reason and the development direction of the test method changes for sulfur content in automobile gasoline and the relationship between sulfur content and mercaptan sulfur content were analyzed. Influence of the structure of -SH in mercaptan molecule and chemical environment such as composition, additives and other factors, on regularity of the detection limit in doctoral test was also discussed. It is pointed out that the chemical activity variances of -SH among different structures of mercaptan is the reason why doctor's test and copper sheet corrosion test are not unified and that the actual copper corrosion test can integrally and objectively reflect the corrosion performance of the sample gasoline. The effective control of sulfur content and copper corrosion can both reduce the emission of SOx and weaken corrosion extent.

GROWTH LAW OF Cladosporium AND ITS EFFECT ON PROPERTIES OF JET FUEL

2019, 50(5):  82-86. 

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To investigate the effect of characteristic fungi on jet fuel properties of jet fuel, a culture medium and a jet fuel culture system were constructed. The luminescence intensity in the aqueous phase was detected every 4 hours, and the physical and chemical indicators such as total acid number, surface tension, water separation grade, silver corrosion grade and pH value of jet fuel, was detected every 24 hours. The growth curves were plotted with time; luminescence intensity and the change of total acid number and surface tension of jet fuel were obtained. The results showed that the growth and reproduction of characteristic fungi increased the total acid value of jet fuel, while decreased the surface tension of jet fuel and lowered the pH value of dissolved water, and affected the corrosiveness and cleanliness of jet fuel. Cladosporium began to proliferate logarithmically and the bottom of the jet fuel was heavily contaminated when the luminescence intensity in the water phase reached 400 RLU/mL.

TWELVE-LUMP KINETIC MODEL FOR HEAVY OIL FLUID CATALYTIC CRACKING

2019, 50(5):  87-92. 

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Based on the catalytic cracking reaction mechanism and product distribution characteristics, a 12-lump reaction network for heavy oil catalytic cracking including 54 virtual reaction paths was established. The mathematical equations of the model are transformed into a programming language with the Python platform on the basis of experiment data in Davison Circulating Riser (DCR) apparatus. The kinetic parameters of the model were calculated by the fourth order Runge-Kutta algorithm applied to sovle the model differential equations and the BFGS algorithm applied to optimize the objective function. Validation of model parameters showed that the relative errors between the calculated and experimental values for the main products were all below 5%. This indicates that the kinetic parameters of the model are reliable, and can better reflect the reaction rules for heavy oil catalytic cracking. The model can be further used to simulate and optimize practical production processes.

EFFECT OF MID-PUMPAROUND HEAT ON PRODUCT YIELD OF ATMOSPHERIC DISTILLATION COLUMN AND ANALYSIS OF OPTIMIZATION PRINCIPLE

2019, 50(5):  93-99. 

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Reasonable proportion of the mid-pumparound heat is one of the effective measures for energy saving and consumption reduction for the atmospheric and vacuum distillation unit. The deep analysis of the mid-pumparound heat theory was performed and the process simulation software（Pro/II） was used to simulate a 3.6 Mt/a atmospheric column of a refinery，revealing the effect of mid-pumparound heat on product yield of the distillation column. The theoretical explanation was given for the cause of this impact. Based on the research results of predecessors and comprehensive consideration of various factors，the relevant principles of the optimization of the mid-pumparound heat were proposed，which provided a basis for the stable operation，the regulation of production schemes and energy saving of the unit.

OPTIMIZATION OF SELF-OWNED POWER STATION ADJUSTMENT IN PETROCHEMICAL PLANT UNDER CARBON EMISSION TRADING MARKET

2019, 50(5):  100-105. 

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With the establishment of China's carbon emission trading market，the self-owned power stations of refinery and petrochemical enterprises are included as key emission units，and the allocation method of carbon quota is calculated by the benchmark method. As the requirements of refineries demand for steam and power produced by the self-owned power stations need to meet firstly，it is necessary to adjust their operation regularly，which has an important impact on the carbon emission performance of the self-owned power stations. In this paper，the steam-electric conversion model of steam turbine was established to predict the operation data with different heating extraction capacity. Based on this data，the influence of heating extraction on carbon emission，emission allowance and the allowance gap were studied. Based on the production data of a petrochemical enterprise，the influence of constant inlet adjust mode and constant condensation adjust mode on the quota was analyzed. When the heat supply increased from 1.792×103 TJ to 2.875×103 TJ，the total quota increased from 376.76 kt to 434.68 kt under constant intake mode，and the total quota increased from 355.98 kt to 502.76 kt under constant condensation mode. It is of great significance to guide the production and operation of enterprises.

INDUSTRIAL APPLICATION OF LZ-5G DENITRATION AGENT IN FCC UNIT

2019, 50(5):  106-109. 

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The industrial application of LZ-5G denitration agent on 1.2 Mt/a FCC unit of PetroChina Fushun Petrochemical Company was introduced. The results showed that at the similar nature of the raw materials and the main operation conditions, adding LZ-5G type denitration agent reduced the nitrogen oxides in the regenerated flue gas from 350 mg/m3 of blank calibration to 125 mg/m3, meeting national standard for NOx emission requirement of less than 200 mg/m3. During the trial period of LZ-5G denitration agent, the FCC unit was operated smoothly, the micro-reaction activity of the equilibrium catalyst increased by 0.2 percentage points, the yield of light oil (gasoline + diesel) increased by 0.16 percentage points, and there was no bad effects on equilibrium catalyst activity, product distribution, product quality and product properties.

STATUS AND PROGRESS OF METHODS FOR ANALYSIS OF VOLATILE ORGANIC COMPOUNDS IN SOIL

2019, 50(5):  110-118. 

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For the development of detection technologies for volatile organic compounds （VOCs） in soils in petrochemical industry, analytical standards, pretreatment technologies and detection methods at home and abroad were investigated, and several proposals were proposed. Seven analytical standards about VOCs in soils were developed in our country, but the types of VOCs were mainly about halogenated and aromatic hydrocarbons. Solvent extraction, headspace sampling, purge and trap, and solid-phase microextraction were included in the pretreatment technologies, and detection methods mainly contained GC-FID, GC-MS and GC-PID. However, not only halogenated hydrocarbons and aromatic hydrocarbons, but also ketones, aldehydes, alkanes, naphthenic hydrocarbons, olefins might be included in petrochemical industry, therefore, it is necessary to establish corresponding analysis standards according to different types of pollutants, and explore VOCs pre-treatment technology and detection methods suitable for the petrochemical industry.