Table of Content

12 December 2019, Volume 50 Issue 12

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STUDY ON TAHE RESIDUE THERMAL-CRACKING IN HYDROGEN AT HIGH TEMPERATURE

2019, 50(12):  1-5. 

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Taking Tahe vacuum residue as a raw material, the operation conditions and upgrading effect of thermal-cracking in the presence of hydrogen at high temperature were tested in autoclave and pilot plant with highly dispersed oil-soluble catalyst. The effect of reaction temperature，pressure，reaction time, catalyst dosage，amount of solvent oil and additive on the residue cracking conversion rate and condensation rate were investigated. The pilot test results showed that under the optimized conditions，the cracking rate of the fraction > 524℃ of Tahe residue was more than 85.2%，the yield of distillate oil was 80%，and the metal （Ni+V） and the asphaltene removal rate were both greater than 90%.

THE FIRST COMMERCIAL APPLICATION OF VGO MEDIUM PRESSURE HYDROCRACKING TO PRODUCE JET FUEL

Huang Xiaobo Luo Wei Wang Zhiping

2019, 50(12):  6-11. 

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In order to improve the efficiency of the 1.5 Mt/a medium pressure hydrocracking unit, SINOPEC Shanghai Petrochemical Co. Ltd. optimized the product structure by reducing diesel fraction and producing more jet fuel in the production cycle through improving the catalyst grading option and reforming the fractionation system, and the commercial application of medium pressure hydrocracking technology for jet fuel production with VGO feed was carried out. The calibration results showed that using the new technology,with the intermediate base VGO with final distillation point of 517 ℃ and BMCI of 45 as feed,under the pressure of high-pressure separator of 10.7 MPa，the yield of jet fuel was 21% with the smoke point of 25 mm and the naphthalene hydrocarbons mass fraction of less than 0.5%，which could meet the guality requirements of No.3 jet fuel,and the yield of tail oil was 27% with the BMCI of 10 which could be used as superior feed of steam cracking unit to produce ethylene.

COMMERCIAL APPLICATION OF LIQUID PHASE DECHLORINATION AGENT DL-1 FOR REFORMATE IN CONTINUOUS CATALYTIC REFORMING UNIT

Tian Changmin Liu Zhe

2019, 50(12):  12-16. 

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Because of the combination of nitrogen compounds in raw materials and chlorides in reformate to form ammonium salts，the 2.2 Mt/a CCR of PetroChina Dalian Petrochemical Company had the clogging and corrosion problems in air cooler at the top of de-pentane column and in pipeline. The solvent degradation of aromatics extraction unit occurred because of the equipment corrosion caused by chlorine in reformate and affected the normal operation of the unit. In 2014, dechlorination agent M was used. However, the dechlorination effect was not satisfactory until 2016 and the problems of ammonium salt blockage and solvent deterioration still existed. In December 2016，the dechlorination agent DL-1 developed by SINOPEC Research Institute of Petroleum Processing was adopted. The results showed that the agent DL-1 was effective to remove chloride from reformate and solved the problems of blockage and corrosion of equipment. The pH of solvent in extraction unit and the service life of resin were significantly improved，which ensured the smooth operation of the unit.

SELECTION OF C3 CUTTING SCHEME FROM LPG FOR PRODUCING HIGH PURITY ISOBUTANE

Zhang Jianhua Geng Qiang

2019, 50(12):  17-20. 

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The influence of C3 content in the feed LPG on the process for producing high purity isobutane was analysed, and the depropanizer tower was simulated and optimized using Aspen Software to get the suitable feeding position and reflux ratio. The results showed that the C3 content in the feed LPG has an effect on the energy consumption of the unit,the pressure and reaction performance of the hydrogenation system. The post C3-cutting process was suitable for the feed with C3 content lower than 20%, and the prior C3-cutting process was suitable for the feed with higher C3 content.

CAUSE ANALYSIS OF TURBIDITY IN DIESEL FROM HYDROUPGRADING UNIT AND COUNTERMEASURES

Xin Dingye Feng Zhongwei Liang Shun An Xiaojie

2019, 50(12):  21-26. 

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Due to the presence of water in diesel from the 1.5 Mt/a diesel hydroupgrading unit of a petrochemical company, the increase of process load and the sales of diesel fuel product are seriously restricted. In order to solve this problem, the cause of turbidityin diesel was analyzed in detail, and the industrial salt dehydration system and high efficiency coalescence dehydration system were designed and installed. The application results showed that the water mass fraction in diesel was reduced to 58—311 μg/g after the industrial salt dehydration process and 96.5—109 μg/g after the high-efficiency coalescer dehydration process, with the water removal rates higher than 78% and 93%, respectively. Both processes showed good dehydration effect for diesel fraction, in which the coalescer dehydration process was better. According to the seasonal characteristics of diesel production, the combination of the two processes can be used to ensure the water content and appearance of diesel product.

APPLICATION OF VEGETABLE OIL, FATTY ACIDS AND VEGETABLE OIL METHYL ESTER IN VISCOSITY REDUCTION OF TAHE HEAVY OIL

2019, 50(12):  27-30. 

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Heavy oil has high viscosity because it is rich in heavy components such as asphaltene and resins, which bring great difficulties to the exploitation and transportation. It is very important to reduce the viscosity of heavy oil and improve its fluidity. Vegetable oil, fatty acid and vegetable oil methyl ester were chosen as dilute medium for Tahe heavy oil. The performance of these three different dilute media on Tahe heavy oil were investigated and compared. The results showed that all these three dilute media showed good diluting effect on heavy oil. At the same dilute ratio, vegetable oil methyl ester demonstrated the best viscosity reduction effect, followed by fatty acid, and finally vegetable oil. The compatibility and system stability of dilute medium and heavy oil were investigated by speckle test. Results showed that the compatibility and stability of vegetable oil methyl ester with heavy oil were the best, while the fatty acid and vegetable oil were relatively poor.

AQUEOUS-PHASE REFORMING OF METHANOL FOR HYDROGEN PRODUCTION OVER SUPPORTED METAL CATALYST

2019, 50(12):  31-37. 

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Aqueous-phase reforming (APR) of the water solution with methanol mass fraction of 5 % over catalysts with Pt, Ru, Ni as active metals was studied. Pt-based catalysts exhibited good reaction performance at suitable temperature and LHSV. The conversion rate of methanol reached 99%, the selectivity of hydrogen was over 98%, and CO volume fraction in the product was below 0.01%. The conversion rate of methanol over Ni/Al2O3 was > 98%, however, the hydrogen selectivity decreased with the increase of the conversion rate but it was still above 80%. The methanol conversion rate on Ru/Al2O3 was over 98%, but the hydrogen selectivity decreased rapidly from 68% to 20% with the increase of methanol conversion rate. The reaction mechanism was obviously different from that of Pt and Ni. According to the reaction conditions and the product composition, the reaction path of methanol APR was further discussed. When the ratio of H2 to methane (CH4) in the product was higher than 2/3, the main reaction path was mainly hydrogen production. When the ratio was lower than 2/3, the reaction path was dominated by methanation.

STUDY ON INDUSTRIAL CALCINATION TECHNIQUES OF HYDROGENATION CATALYST SUPPORT

2019, 50(12):  38-41. 

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The mechanical strength, bulk density, pore volume, specific surface, crystalline phase and acidity of hydrogenation catalyst support treated by heat radiation or hot air circulation calcination were characterized and compared using N2 adsorption-desorption,FT-IR,NH3-TPD and XRD. The results showed that the thermal radiation treated support had higher strength and lower density, and the crystal growth process was more stable. The support obtained by hot air circulating calcination technology possessed larger specific surface area, larger proportion of small pores, more suitable acidic center distribution and higher hydrogenation activity.

INFLUENCE OF STATUS OF Zn SPECIES IN Zn/ZSM-5 ON ITS CATALYTIC PERFORMANCE

2019, 50(12):  42-50. 

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Zn modified ZSM-5 zeolites with various Zn status were prepared by different methods （in situ hydrothermal synthesis，mechanical mixing，incipient wetness impregnation，solid-state ion exchange，and liquid phase ion exchange） and systematically investigated by X-ray diffraction（XRD），transmission electron microscope（TEM），27Al magic-angle spinning（MAS） NMR techniques. The results proved that both the in-situ hydrothermal synthesis and the liquid phase ion exchange methods could facilitate the migration of zinc species into cation site of zeolites in the form of Zn2+. The mechanical mixing and the solid-state ion exchange methods promoted the formation of extra-framework ZnO nanoparticles that were mainly located on the external surface of zeolites. While, the incipient wetness impregnation method promoted part of the Zn species into cation site of zeolites and part of the Zn species on the external surface of zeolites，simultaneously. The synergistic effect between Zn species and zeolites makes ZSM-5 zeolite modified by Zn have outstanding catalytic performance.

INFLUENCE OF SOLVENT AROMATICITY ON ASPHALTENE STABILITY

2019, 50(12):  51-55. 

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The relationship of solvent aromaticity and asphaltene stability of Saudi light AR in RICP technology was studied by Flory-Huggins model and the aromaticity of the solvent was correlated with the solubility parameter. The results proved the availability of Flory-Huggins model for measuring asphaltene stability in residue. The aspaltene stability increased with the increase of solvent/AR ratio. The aromaticity could be evaluated by solubility parameter. The solvent with higher density and lower molar ratio of H/C possessed higher solubility parameter and is beneficial to asphaltene stability.

DEVELOPMENT OF POLYETHER SYNTHETIC INDUSTRIAL GEAR OIL

2019, 50(12):  56-60. 

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KGW polyether industrial gear oil with additives such as anti-wear agent, antioxidant and anti-rust agent based on polyether was synthesized. The synthesized gear oil had excellent viscosity-temperature property, low temperature performance, excellent extreme pressure and anti-wear performance and very low friction coefficient, which can meet the lubrication requirements of various gear transmission devices under harsh conditions such as high load and strong impact. This series of products has reached the same quality level of the abroad products.

RESEARCH ON SUPPORTING WHEEL BUSHING LUBRICANT FOR ROTARY KILN

2019, 50(12):  61-64. 

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In order to solve the lubrication problem of supporting wheel bushing of rotary kiln under harsh working conditions, a special lubricant was developed. In this study, polyalphaolefin was selected as the base oil, and the formula of supporting wheel bushing lubricant was obtained through the selection and compounding of viscosity index improver, extreme pressure antiwear agent, oiliness agent, antioxidant and solid additive. The developed products have excellent adhesion and viscosity temperature performance, good extreme pressure performance and oxidation resistance. Compared with the competitive products sold abroad, they have more excellent low-temperature performance and bearing capacity. After two years of practical use, the developed product can meet the lubrication requirements of the supporting wheel bushing of rotary kiln in cement plant, and solve the problem of the temperature rise of the bearing bush of the original oil under the low speed and heavy load conditions.

STUDY ON ANTI-WEAR PERFORMANCE OF ZDDP AND MoDTC IN PAO BASE OIL CONTAINING ESTER

2019, 50(12):  65-69. 

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The additives of zinc dialkyldithiophosphate (ZDDP) and molybdenum dialkyldithiocarbamate (MoDTC) was respectively added into samples of poly alpha olefin (PAO), PAO with dispersant and PAO with ester. The sensitivities of ZDDP and MoDTC in different samples were investigated by the grinding test of four-ball machine. In other test, the two additives were mixed and added into the samples and tested by scanning electron microscopy to observe the wear scar on the surface. The results indicated that the ester oil with a mass fraction of 5%-10% improved well the anti-wear performance of PAO base oil. For the PAO with dispersant T154B，the increase of ZDDP could not effectively reduce the diameter of the wear scar, while the increase of MoDTC could. In the ester-containing PAO base oil sample，the diameter of the wear scar was decreased when the ZDDP increased, indicating that the anti-wear effect of ZDDP was better than the MoDTC. No obvious synergistic effect was found for the composite additives compared with the single one. The analysis of wear scar morphology showed that the surface was flat, showing that the MoDTC had better effect on the repair of the worn surface. When ZDDP and MoDTC coexisted in the sample, the surface of the wear scar was irregular, indicating a competitive relationship between the two additives.

EFFECTS OF LONG DISTANCE PIPELINE TRANSPORT ON CONDUCTIVITY AND DETERGENCY OF NO.3 JET FUEL

2019, 50(12):  70-73. 

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The reason of serious decline in the conductivity of No. 3 jet fuel after long-distance pipeline transportation and the effect of adding antistatic agent on the conductivity and water reaction of the jet fuel were analyzed. The effects of long-distance pipeline transportation on the electrical conductivity and water reaction of refined jet fuel and distillate fraction were compared to see the advantages and disadvantages of the two pipeline transportation modes. For the long-distance pipeline transportation of No. 3 jet fuel, it was suggested that the preferred way to inject antistatic agent at the end of the pipeline transportation of jet fuel distillate. When the pipeline transport and car transport were needed at the same time, it was advisable to adopt the method of product pipeline transportation and to add the least amount of antistatic agent at the end of pipeline according to the electrical conductivity attenuation.

CATALYTIC OZONATION OF WASTEWATER CONTAINING PHENOLS BY WASTE FCC CATALYST

2019, 50(12):  74-78. 

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The solution of waste FCC catalyst has become a very important issue for refineries. It has great significance to modify it for catalytic ozonation of waste water containing phenols. Modified waste FCC catalyst through loading catalytic active component was used for catalytic ozonation in this work. The results showed that the effect of modified waste FCC catalyst was much better than the waste catalyst itself on degradation of waste water containing phenols. When MgO was loaded, the removal rate of TOC reached 46.50%, significantly higher than the removal rate of 28.19% without catalyst, indicating great catalytic activity of modified FCC waste catalyst.

REVAMPING OF ENERGY SAVING AND EMISSION REDUCTION PROCESS OF CATALYTIC CRACKING LPG DESULFURIZATION SYSTEM AND EFFECT ANALYSIS

Ni Qianyin

2019, 50(12):  79-83. 

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Merox caustic washing extraction and caustic liquor air oxidation recycling process are widely used in the Merox mercaptan removal system for liquefied petroleum gas（LPG) at present. By analyzing the waste residue，waste water，waste gas emission and energy saving and emission reduction of the NO.3 FCC unit in SINOPEC Beijing Yanshan Company，a series of technological innovations was adopted to optimize the production. The measures for technical transformation of two-stage high-efficiency extraction, the tail gas desulfurization，control of the discharge of alkali residue of the catalytic cracking unit were adopted and realized the treatment of alkali residue in plant，reduced use of washing water for LPG，and processed the tail gas in regenerator. Through the above measures，the alkali residue，waste water and VOC emissions of the device were effectively reduced.

CAUSE OF SCALING OF FCC FLUE GAS EXPANDER AND PRECAUTION ANALYSIS

2019, 50(12):  84-89. 

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The composition and crystal phase of the scaling sample of FCC expander was characterized. Based on the results, the formation condition of scaling was analyzed and checked by calculating. The cause and precaution measures were thus proposed. The scaling procedure is as follows: Very few drops of raw oil was not fully vaporized but deposited on the catalyst to become coke；few coke solids entered the flue,the combustion continues to reach the melting temperature of fine coke powder, which was converted into liquid viscous substance; the smoke with trace high-temperature molten dust is subjected to high-speed centrifugation at the three-screw feeding mouth, the blade of the smoke expander and other parts, and adheres to the parts that are easy to form scale, forming unshaped scale. Scaling of expander could be reduced by improving atomization effect of feed oil nozzle, adjusting appropriate ratio of catalyst to oil and fine powder content in the reaction-regeneration system.

APPLICATION OF CATALYTIC COMBUSTION PROCESS FOR VOCs FROM REFINERY WASTEWATER

2019, 50(12):  90-95. 

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The volatile organic componds(VOCs) treatment unit of the wastewater treating plant of PetroChina Yunnan Petrochemical Co. Ltd. adopted the technology route of enhanced desulfurization - concentration homogenization - catalytic combustion. The process fluctuated greatly in the initial stage of operation, and there was a risk of excessive gas output from the reactor. The influence factors of sulfur content and water vapor were analyzed, and the optimum operating conditions including VOCs composition, reaction temperature and air speed were determined, which ensured the stable operation of the process and the stable discharge of gas from the reactor.

STUDY ON COMPOSITIONS OF CATALYTIC CRACKING PRODUCTS OF WASTE COOKING OIL

2019, 50(12):  96-101. 

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The catalytic cracking reaction of waste cooking oil was studied on self-made DY catalyst. The structure and composition of raw material and liquid products were characterized by 1H-NMR, 13C-NMR, gas chromatograph and gas chromatograph-mass spectrometer techniques. The results showed that the catalytic cracking reaction produced 24.88% of gas, 41.03% of gasoline, 21.73% of diesel, 2.53% of heavy oil, 1.03% of coke and 8.80% of water. Unlike the NMR spectra of raw material, 1H-NMR spectra of liquid products displayed weak peaks of alkene hydrogen, but strong peaks of aromatic hydrogen. Meanwhile, 13C-NMR spectra of liquid products observed no obvious peaks of carbonyl carbon or glycerol-based carbon. The results of hydrocarbon group composition analysis showed that gasoline product contained 53.4% of saturation and 34.8% of aromatics; 87.4% of diesel components were aromatic hydrocarbons, and 43.4% were alkylbenzenes. The mass fraction of aromatic hydrocarbons in heavy oil reached 98.5%, in which the mass fraction of four ring aromatic hydrocarbons was about 49.5%.

ADVANCES OF Pt CATALYSTS FOR PROPANE CATALYTIC DEHYDROGENATION TO PROPYLENE

2019, 50(12):  102-108. 

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The main technologies of propane dehydrogenation at home and abroad, the reaction mechanism of propane dehydrogenation on Pt catalyst, the support and the promoter of Pt catalyst were reviewed. The problems of other catalysts for propane dehydrogenation and the advantages of chemical looping dehydrogenation technology were briefly introduced. Pt catalyst was optimized continuously to reduce cost. The main research direction in the future is to improve the stability of catalyst while reducing Pt content and develop non-Platinum and non-Chromium environment-friendly dehydrogenation catalyst.