Table of Content

12 August 2018, Volume 49 Issue 8

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RESEARCH OF ZEOLITE MODIFICATION FOR XYLENE ISOMERIZATION

2018, 49(8):  1-5. 

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The effect of liquid modification on the HZSM-5 zeolite for the xylene isomerization using alkaline reagents and fluorine-containing reagents (ammonium fluoride) was conducted; the modified samples were characterized by NH3-TPD, BET, XRD and XRF techniques. The isomerization performance was evaluated by de-ethyl type xylene isomerization reaction. The changes of morphology after modification by both reagents were observed. The alkali modification increases the surface roughness, lowers the Si/Al ratio due to removing the Si atoms selectively, resulting in more amount of acid; while for fluoride modified samples, some nano-scale microcrystalline clusters appear on the modified surface, ammonium fluoride modification has no selectivity for silicon removal, but the amount of acid is significantly reduced. The isomerization activity and xylene yield are improved by the alkali modification, indicating the better catalytic performance than the fluoride modification.

COMMERCIAL APPLICATION OF SGC-1 CATALYST FOR LTAG TECHNOLOGY

2018, 49(8):  6-10. 

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The commercial application of SLG-1 catalyst for LTAG technology in the 3rd MIP-CGP unit of SINOPEC Shijiazhuang Refinery & Chemical Company was presented. The results showed that the yield of gasoline increases 4.00 percentage points (from 46.79% to 50.79%), octane-barrel increases by 3.46, the yields of LCO and dry gas decrease, while total liquid yield increases by 2.17 percentage points. SLG-1 catalyst showed significant advances in increasing bottoms cracking and improving the conversion of hydrotreated LCO.

COMMERCIAL APPLICATION OF RDNOX-PC1 ADDITIVE IN INCOMPLETE REGENERATION FCCU

Haitao Song Tian Huiping

2018, 49(8):  11-14. 

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RDNOx-PC1 additive for reducing NOx emission was commercially applied in an incomplete regeneration MIP-CGP unit with 1.05 Mt/a in SINOPEC Baling Company. The results showed that RDNOx-PC1 can decrease NOx emission at lower CO concentration in outlet flue gas of boiler, which is beneficial for energy recovery and CO emission control. At similar CO concentration, NOx in flue gas is decreased by about 20% compared with the reference, and meets the requirement of≤200mg/m3. Furthermore, the application of RDNOx-PC1 has little negative influence on product distribution and composition.

STUDY ON SELECTIVE HDS CATALYST MODIFIED BY Ti FOR FCC GASOLINE

2018, 49(8):  15-20. 

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Ti modified alumina carriers were prepared with metatitanic acid and aluminium hydroxide dry powder. CoMo/Al2O3-TiO2 catalysts with different Ti content and different ligands were made by isometric immersion method respectively, and were characterized by XRD, BET, TPR and HRTEM techniques. The selective hydrodesulfurization activities of the catalysts were evaluated in a 10mL fixed-bed micro-reactor. The results showed that the catalyst having 10% TiO2 in carrier and using glycol modifier has higher HDS activity and selectivity.

EFFECTS OF PHOSPHORUS TEMPLATE AND SILICON SOURCES ON STRUCTURE AND CATALYTIC PERFORMANCE OF HIERARCHICAL ZSM-5 ZEOLITE

Li Peng Li Feng Liu Yujian Zheng Jiajun Li Wenlin Cui Xingyu Li Ruifeng

2018, 49(8):  21-27. 

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ZSM-5 molecular sieves with hierarchical porous structure were synthesized by using mixture of phosphorus-containing template TBPOH and TPAOH with different proportions, and characterized by XRD，BET，SEM，TEM，NH3-TPD and MAS NMR. The synergistic effect of TPAOH and TBPOH was investigated, by which the phosphorus-containing hier-ZSM-5 with fairly high degree of crystallinity can be obtained. The results showed that the morphology of ZSM-5 is regular and it shows higher specific surface area and pore volume when the molar ratio of TBPOH and TPAOH is 1∶1 with TEOS as the silicon source. The average pore size distributes at 4-10 nm and 50-70 nm. ZSM-5 zeolite rich in mesoporous structure was constituted by accumulation of small grains. Compared with conventional ZSM-5 molecular sieve，hier-ZSM-5 shows greater weak acidity and total amount of acidity. At same conversion of 1，3，5-triisopropylbenzene cracking reaction，the microporous ZSM-5 zeolite shows better selectivity for benzene and diisopropylbenzene，while the hier-ZSM-5 with mesopores shows more excellent selectivity for propylene and cumene.

COMMERCIAL APPLICATION OF SHB-01 CATALYST FOR C4 STREAM SELECTIVE HYDROGENATION

Huangfu Xieli Li Shiwei Zhao Duo

2018, 49(8):  28-31. 

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The C4 selective hydrogenation Catalyst SHB-01 developed by SINOPEC Shanghai Research Institute of Petrochemical Technology was successfully applied in No.1 MTBE unit of SINOPEC Shanghai Petrochemical Co. Ltd. The results showed that catalyst SHB-01 exhibits high activity，good selectivity and flexible operability and high 1-butene yield with low butadiene remaining. During the period of running，the butadiene remaining is less than 10 μg/g and 1-butene yield higher than 95.2%，meeting the requirement of polymer grade 1-butene.

APPLICATION OF MOFs ADSORBENTS IN C8 AROMATICS ADSORPTION SEPARATION

Li Lunxi Long Jun Wu Wei Qiao Xiaofei

2018, 49(8):  32-37. 

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Metal Organic Framework MIL-53 was synthesized using aluminium nitrate and terephthalic acid as raw materials via hydrothermal synthesis method and analyzed by XRD and SEM. The adsorption performance of the sample obtained under the optimal preparation conditions was evaluated by adsorption isotherms, liquid phase static equilibrium adsorption and pulse adsorption experiment. The results showed that the material has a regular micro morphology, and the particle sizes are in the range of about 50～80 nm. When the mole ratio of aluminum nitrate and terephthalic acid is 1:1, and the solvent is N, N-dimethylformamide, the MIL-53 has the maximum capacity for methylbenzene adsorption. The adsorption performance of different components is different under the similar temperature and pressure. It is concluded that MIL-53 has preferential adsorption selectivity for o-xylene.

FORMATION OF METHONAL IN CRACKED GAS DURING CATALYTIC CRACKING PROCESS

Xue-Feng Chen

2018, 49(8):  38-42. 

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Due to the growing demands of light olefins, FCC is an important process for propylene production. However, methanol was found in cracking gas which affects the downstream polymerization. The source of oxygen during methanol formation, methanol formation discipline and influence factors were studied. The results indicated that the oxygen contained in methanol is from water, gas mixture of SOx and NOx. With the presence of SO2 and NOx, methanol is formed by reaction of SOx, NOx and H2O. Thermal cracking reaction occurs when catalyst activity is lower, leading to the generation of methanol which follows the free radical mechanism. To inhibit the methanol generation, measures be adopted in commercial operation: (i) reducing the content of SOx and NOx in the flue gas entrained by regenerated catalyst; (ii) maintaining catalyst activity high enough.

CLUSTER ANALYSIS FOR VACUUM RESIDUE BASED ON MOLECULAR COMPOSITON

2018, 49(8):  43-48. 

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Coke-forming is a serious problem in vacuum residue processing, and affected by its compound classes distribution. Deepening its understanding at the molecular level is important in guiding vacuum residue processing. The detailed carbon numbers and double bond equivalent (DBE) distributions of various compounds in vacuum residues were obtained by Fourier transform ion cyclotron resonance mass spectrometry (APPI FT-ICR MS) and were grouped into 10 categories according to the carbon number distribution of the aromatic hydrocarbons, S1 compounds (single S atom in molecule), S2 compounds (two S atoms in molecule), and N1 compounds (single N atom in molecule), respectively. The cluster analysis was applied for 71 kind of vacuum residues based on above molecular group compositions. Results showed that 71 vacuum residues were divided into type I, type II, and type III according to their molecular composition characteristics. To verify the accuracy of cluster analysis, carbon residue value of the vacuum residue was acted as the basis of rational judgment of the cluster analysis. The type I vacuum residues have the lowest carbon residue values, and is classified as less coking residue. The carbon residue value of type III vacuum residues is the highest, belonging to coking residue. The type II vaccum residue is in the middle. This work used cluster analysis to classify vacuum residue samples based on their molecular composition, the effective management of FT-ICR MS data could be realized, and the molecular composition of vacuum residue is closely linked to its processing performance is proved.

BED PRESSURE FLUCTUATION CHARACTERISTICS IN JET AREA OF PIPE GRID GAS DISTRIBUTOR IN FCC REGENERATOR

2018, 49(8):  49-55. 

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In the catalytic cracking unit, the bottom of the regenerator is equipped with a pipe grid gas distributor. The gas is distributed into the regenerator bed through the nozzles on the distributor. The pressure signals in the jet area can react well to the flow characteristics of the distributor, which provide a theoretical basis for the structural improvement to reduce wear. The experimental study on the distribution of pressure and pressure fluctuation in jet area was conducted in a two-dimensional bed experimental device. The experimental results showed that the pressure of bed between the branch pipes decreases along the axial height of the bed, decreases with the increase of the jet angle, increases with the increase of the nozzle gas velocity, and the static bed height, bed pressure is determined by the amount of particles above the measuring point, which could judge different operating conditions; When the jet angle is 0 ° and 22.5 °, the pressure fluctuation between branch pipes first increases and then decreases, which corresponds to the law of bubble generating, convergenting and crushing; when the jet angle is 45.0 ° and 67.5 °, the lean phase space is formed by the jet between the two branches, the pressure fluctuation is determined by the turbulence degree of the jet and higher than that of the dense phase, increases with the gas velocity and the height of the static bed, providing a basis for reducing the external wear of branch pipes. The co-work of adjacent nozzle jet impact and particles are the factor to influence the nozzle jet pressure fluctuation. Jet pressure fluctuation at a jet angle of 22.5 ° has a critical gas velocity depending on whether it is impacted by an adjacent jet, providing a basis for the stability of the jet and reducing internal and external erosion wear of gas distributor.

EFFECT OF MATRIX ASPHALT COMPONENTS ON VISCOELASTIC PROPERTIES OF SBS MODIFIED ASPHALTS USING DMA METHOD

2018, 49(8):  56-60. 

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SBS modified asphalts were prepared by using four kinds of matrix asphalts with different components, and the viscoelastic properties of the modified asphalts were analyzed by dynamic mechanical analysis (DMA). The results showed that the high temperature properties of modified asphalts obtained by temperature scanning, frequency scanning and steady flow test are consistent. The aromatic content of matrix asphalts is the main factor influencing the viscoelastic properties of modified asphalts. The viscoelastic performance of modified asphalts gets better with the rise of aromatic content, while the content of high saturated component would weaken the cohesion of modified asphalts, reducing the high-temperature viscosity. The bending beam rheometer tests showed that the resin and asphaltene mainly affect the low-temperature performance of the modified asphalts. The low-temperature extensibility of modified asphalts becomes poor when asphaltene content is too high.

INFLUENCE OFATMOSPHERIC RESIDUE FROM RUSSIAN CRUDE ON CATALYTIC CRACKING REACTION AND PRODUCTS OF FCC UNIT

2018, 49(8):  61-65. 

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The processiing of Russian atmospheric residue in FCC unit of Daqing Zhonglan Petrochemical Company was introduced. Catalytic cracking of the Russian AR is difficult because of its high sulfur content, high density, high content of gum and asphaltene, leading to high coke yield and more metal on the equilibrium catalyst. In view of this concern, the material upgrade of the key parts of the device was conducted and corresponding measures were taken to improve the gasoline octane number. A stable transition before and after raw material changes is guaranteed.

STUDY ON PRODUCTION OF JET FUEL BY FITS TECHNOLOGY OF THE FIRST ATMOSPHERIC SIDE-STREAM

Cui Xiaoqin Yang Qingpin Guo Zhaohui Qu Yeqing

2018, 49(8):  66-69. 

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The clean jet fuel production by FITS technology using No.1 side-stream of atmospheric distillation of Geermu refinery as feed was studied. The effects of reaction pressure, temperature, space velocity and H2/oil ratio on FITS results were investigated, The test showed that the clean jet fuel with total sulfur content less than 10μg/g can be produced at conditions of 4.0 MPa， 300 ℃，LHSV 8.0 h－1，and hydrogen to oil ratio 40(v). The1000 hours continuous test indicated the excellent stability of the catalyst activity, the desulfurization rate keeps about 85%，mercapten removal about 87% and deacidification rate about 80%. It shows that the FITS process can realize the long - cycle production of clean jet fuel. The technical and economic assessment demonstrates that the FITS device is lower in construction investment, floor area and energy consumption than that of the same size trickle bed reactor, and has a good prospect of industrial application.

MEASURES FOR SAVING ADSORBENT IN S-Zorb UNIT

Bai Yongtao Ma Jianwei song hongyan

2018, 49(8):  70-73. 

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According to the low sulfur property of the catalytic gasoline, the adsorbent desulfurization principle was analyzed. Measures were implemented, such as controlling the water content in FCC gasoline and process, carbon on adsorbents, sulfur content difference between adsorbent and unreduced adsorbent, optimizing process parameters, reforming heat removal system, to achieve the purpose of saving the consumption of adsorbent. The actual consumption of adsorbent of 1.8 Mt/a S-Zorb unit after optimizing the parameters is 12 tons/year, far lower than the design value（60 t/a）. The operation cost is effectively reduced and considerable economic benefits are achieved.

DISCRIMINATION OF ANTI-WEAR PROPERTY OF MARINE STEAM TURBINE OIL BY FOUR BALL METHOD

Wang Jianhua Zhang Bo

2018, 49(8):  74-78. 

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On the basis of the comparative study of the anti-wear property specification for the United States and Russian military turbine oil products by four ball method, the internal laws and discrimination of the anti-wear property of marine steam turbine oil were studied through SH/T 0189-1992 Lubricating oils determination of anti-wear by four ball method and GB/T 3142-1982 Lubricants-determination of load-carrying capacity by four ball method. The correlation of four ball method and FZG was analyzed based on the FZG results. The results showed that the larger the load, the lower the rotational speed, and the more stringent the friction environment is, the more obvious distinguish for the anti-wear properties of different oils; SH/T 0189-1992（147 N 1 200 r/min）can reasonably evaluate the anti-wear property of marine steam turbine oil. The maximum nonseizure load PB value has obvious distinction between marine steam turbine oils and can represent the anti-wear properties of oil products.

RESEARCH ON PROPERTIES OF SYNTHETIC AVIATION LUBRICANT AFTER HIGH TEMPERATURE OXIDATION CATALYZED BY METALS

2018, 49(8):  79-83. 

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Synthetic hydrocarbon aviation lubricating oil was oxidized at different temperatures (180 ° C, 200 ° C, 230 ° C, 250 ° C, and 300 ° C) with metals Cu and Fe as catalysts in a high temperature oxidation accelerator. The kinematic viscosity, acid value and pour point of the oil after reaction were measured, and the correlation coefficient between the three was calculated by the binary correlation method. The compositions of oxygenated oils were analyzed by GC/MS. Three rules are found: (i) highly negative correlations between kinematic viscosity and acid value, kinematic viscosity and pour point; highly positive correlation between acid value and pour point; (ii) highly positive correlation between relative contents of n-alkanes, iso-paraffins, olefins and other compounds and changes of the acid value and pour point after oxidation, but highly negatively correlated with the change of kinematic viscosity; and (iii) highly negative correlation between the relative contents of DIOA and antioxidants and the changes of the acid value and pour point of the oil after oxidation, but highly positively correlated with the change of kinematic viscosity.

DETERMINATION OF NAPHTHALENE IN HIGH TEMPREATURE COAL TAR BY CHROMATOGRAPHY USING BACK-FLUSH TECHNIQUE

2018, 49(8):  83-86. 

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A test method for determination of naphthalene was established by gas chromatography using back-flush technique. The effects of back flushing pressure, back flushing time, chromatographic column temperature, solvent, internal standard were explored, and the internal standard curve were established for quantification. The linear correlation coefficient of quantitative standard curve is 0.999 9, the recovery of naphthalene content is between 98.5%~101.1% with relative standard of deviation less than 0.34%. The method has good accuracy and repeatability and meets the requirement of the determination of naphthalene in high temperature coal tar.

STUDY ON RAPID EVALUATION METHOD OF LOW TEMPERATURE POTENTIAL IN REFINERY BASED ON RECIRCULATING WATER CORRECTION

2018, 49(8):  87-93. 

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Shortcomings and deficiencies existed in conventional rapid evaluation method for thermal potential in traditional refinery. A rapid evaluation method for refinery low-temperature heat potential based on modified circulating water was established by introducing the factors of the circulating water, energy efficiency. Data from 12 refineries were calculated. The deviations of the method were deternined. The results prove the superiority of the method for evaluation of refinery low-temperature heat potential. The rapid method is further verified when the low temperature heat potential coefficient of a typical refinery was calculated.

COMMERCIAL APPLICATION OF SGC-1 CATALYST FOR LTAG TECHNOLOGY

2018, 49(8):  94-97. 

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The commercial application of SLG-1 catalyst for LTAG technology in the 3rd MIP-CGP unit of SINOPEC Shijiazhuang Refinery & Chemical Company was presented. The results showed that the yield of gasoline increases 4.00 percentage points (from 46.79% to 50.79%), octane-barrel increases by 3.46, the yields of LCO and dry gas decrease, while total liquid yield increases by 2.17 percentage points. SLG-1 catalyst showed significant advances in increasing bottoms cracking and improving the conversion of hydrotreated LCO.

OPTIMIZING PRODUCT DISTRIBUTION OF FCC MIP PROCESS BY BP NEURAL NETWORK COMBINED WITH GENETIC ALGORITHM

Ouyang Fusheng You Junfeng Fang Weigang

2018, 49(8):  98-104. 

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Based on the commercial data from a FCC MIP unit, two variables, aromatics content and outlet temperature, are deleted from the 18 variables including properties of feedstocks, properties of regenerated catalysts and operating conditions by using Pearson correlation coefficient method. Using 16 variables as input variable and 4 main product yields as output variables, a 16-20-4 type of BP neural network model was established. The BP neural network model and genetic algorithm model were combined to optimize the operating conditions for the maximum gasoline yield and the maximum gasoline yield plus the lowest coke yield. The verification results indicated that the calculated values are good consistent with FCC actual values. The multi-objective optimizations can also be obtained by the combined model. Compared with the optimization results for only getting the maximum gasoline yield，though the gasoline yield drops slightly，the coke yield decreases substantially.