PETROLEUM PROCESSING AND PETROCHEMICALS

COMPARATIVE STUDY OF THERMAL CONVERSION REACTION PROPERTIES OF ASPHALTENES FROM DIFFERENT SOURCES

2019, 50(3): 1-5.

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A series of porous silica-alumina materials with different pore structure and acidity was prepared through co-gel，aging and post-treatment process，the structural properties was characterized by XRD，BET，FT-IR，NH3-TPD，and the cracking activities of the catalysts preparated by these materials were evaluated with the heavy oil micro-reactor. The results revealed that the materials with pore diameters of 7-14 nm，total acid contents of 0.617-1.046 mmol/g，and with both Br?nsted acid and Lewis acid are obtained by the adjustment of preparation conditions. Pore structure and acidic property as well as hydrothermal stability play important roles on cracking activity and product distribution，but pore size and acidity have different effects. When the pore size is between 11-14 nm after hydrothermal ageing treatment，the functions of pore structure and acidic property are complementary and promote the activity of cracking. As the pore sizes become larger，the effect of pore structure on cracking is much stronger than that of acidity. For acidity，the cracking activity is affected dramatically by the total acid content，but the product distribution mainly depends on the distribution of acid centers.

CFD MODELING OF SPRAY DRYING PROCESS FOR FCC CATALYST PREPARATION

2019, 50(3): 13-18.

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On the basis of gas-liquid two-phase flow theory (CFD) and properties of FCC spray drying process, a CFD model was developed to simulate the amount of two phases flow, heat and mass transfer process in the spray dryer, and the flow velocity patterns, temperature distribution, and solid particle trajectories in the spray dryer are then obtained and visualized. The simulation results are compared with the experimental data of spray drying tower in pilot plant, and the results showed that the two trends are consistent with the maximum deviation of less than 10%. The model can be used to simulate the FCC catalyst spray drying process.

STUDY OF THIOPHENE ADSORPTION ONTO Ni/Al2O3 BY FT-IR SPECTROSCOPY

2019, 50(3): 19-23.

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NiO/γ-Al2O3 catalyst was prepared into self-supporting wafers, and the adsorption patterns of thiophene molecules on Ni were investigated by FT-IR spectroscopy. Rare earth Ce was introduced to modify NiO/γ-Al2O3 catalyst, and it was found that Ce improves the reduction performance of NiO, and enhances the direct interaction of sulfur-metal on thiophene adsorption, thus improves the selectivity of thiophene desulfurization.

STUDY ON HYDROGEN SUPPLY PERFORMANCE OF PRE-HYDROTREATED COAL TAR HEAVY OIL

2019, 50(3): 24-28.

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The coal tar heavy oil was pre-hydrotreated and then characterized by means of infrared spectroscopy，nuclear magnetic resonance and elemental analysis. The physicochemical properties and the hydrogen supply ability of the pre-hydrotreated oil were investigated from the molecular structure point of view. The results showed that after the aromaticity of the hydrotreated heavy oil decreases from 0.89 of feed to 0.80, the degree of substitution of aromatic rings increases from 0.12 to 0.20 and the hydrogen supply index （PDQI） increases from 3.21 to 4.02. The hydrogen consumption of coal tar heavy oil in coal-oil co-processing from 4.03% to 3.74%，the conversion rate and the oil yield are improved，the asphaltene content in the product decreases significantly, the oil quality is greatly improved .

VISCOSITY PREDICTION MODEL FOR HEAVY MARINE OIL

2019, 50(3): 29-35.

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The feasibility to predict the viscosity of heavy marine fuel oil using the existing viscosity prediction models was studied. Several common viscosity physical models were compared and selected the best one based on the analysis of experimental data. The Cragoe model was modified based on the heavy marine fuel oil database and the viscosity reduction data by dilution, the impact of the blending mechanism on the relative error of the prediction model was analyzed. The results showed that for the heavy fuel oil blending components commonly used in the current market, the Cragoe viscosity model has minor prediction errors due to the fact that the Cragoe viscosity prediction model is not limited by the viscosity ratio of the component oils, and is the best model suited for heavy marine fuel oils. The proposed correction model can further reduce the error in predicting the viscosity of heavy marine fuel oil. The analysis of multi-component blending results showed that if the profile of the viscosities distribution of the components is in a gradient form, the prediction error can be reduced. In addition, when the residual oil and dilute components are blended, the complexing effect of asphaltenes affects the prediction accuracy of the model to some extent.

ASSOCIATION STUDY OF PROPERTIES OF ASPHALT WITH FCC SLURRY AND ITS SBS MODIFIED ASPHALT

2019, 50(3): 36-40.

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By analyzing the properties and SARA of the raw materials and the asphalt blending with FCC slurry, the influence of the properties of the blending asphalt on the performance of its SBS modified asphalt was discussed. Meanwhile, the dispersion and microstructure of SBS in the blending asphalt were investigated by fluorescence micrograph. The results demonstrated that high content of aromatic contributes to the better performance of the asphalt blending with FCC slurry and compatibility between SBS and asphalt with FCC slurry, which enhance the performance of SBS modified asphalt with FCC slurry. Moreover, the properties of SBS modified asphalt with condensed FCC slurry was superior to those of SBS modified asphalt with FCC slurry and satisfy the requirement of I-D grand standard of SBS modified asphalt.

TPAOH TREATMENT OF HZSM-5 ZEOLITES AND THEIR PROPANE DEHYDROGENATION PERFORMANCE

2019, 50(3): 41-47.

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HZSM-5 zeolites were treated with different concentrations of TPAOH solutions. Pt/HZSM-5 catalysts were prepared for propane dehydrogenation by loading Pt on HZSM-5 zeolites before and after alkaline treatment. The HZSM-5 samples before and after alkaline treatment were characterized by XRD, SEM, BET, NH3-TPD, H2 chemisorption, FT-IR and TG techniques to investigate the effects of different concentrations of TPAOH solutions on the crystal structure, surface morphology, pore structure, surface acidity. The propane dehydrogenation on Pt/HZSM-5 catalysts was tested. The results showed that the treatment of HZSM-5 by TPAOH solution could effectively introduce mesoporous structure with less influence on the crystal structure and surface morphology of the zeolite, the formation of mesoporous structure is highly adjustable and could modulate the acidity of HZSM-5 zeolites. With the increase of TPAOH concentration, the activity of propane dehydrogenation increases first and then decreases. When the concentration of TPAOH solution is 0.2 mol/L, the initial propane conversion and propene selectivity are 32.7% and 98.6%, respectively.

STUDY ON EFFECTS OF SiO2/Al2O3 RATIO OF HZSM-5 ZEOLITES ON n-BUTANE CRACKING

Zhang Wenfang Wang Pengzhao Zhang Minxiu Yang Chaohe Li Chunyi

2019, 50(3): 48-53.

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The HZSM-5 zeolites with different mole ratio of SiO2/Al2O3 were characterized by in-situ FT-IR and their n-butane cracking activities were investigated in a continuous flow fixed-bed micro-reactor to reveal the relationship between Si/Al ratio, active sites and catalytic behavior. The results indicated that the kind，number， and strength of active sites of HZSM-5 zeolites with Si/Al ratio of 38 and 200 were significantly different. HZSM-5-38 zeolites have more acid bridging Si-O（H）-Al groups and non-skeleton aluminum hydroxyl with strong acidity, while，HZSM-5-200 zeolites only show several isolated hydroxyl groups with small amount of weakly acidic or non-acidic neighbouring silica hydroxyl groups in microporous. HZSM-5-200 zeolites result in higher yield of light olefins, indicating that lower acid density and strength is suitable for producing more olefins.

STUDY OF ISOMERIZATION OF n-HEPTANE OVER Pd/HZSM-5 CATALYSTS

2019, 50(3): 54-57.

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The isomerization reaction of n-heptane over Pd/HZSM-5 bifunctional catalyst was studied. The effect of Si/Al ratio, crystal size and Pd loading on the reaction were investigated by micro-reactor-chromatograph system. The results showed that as the Si/Al ratio increases, the number of acid sites and the conversion of n-heptane decrease, however the isomerization selectivity of the catalyst is improved. Being the little effect of grain size of ZSM-5 molecular sieve on external surface area and acidity of the carrier, it has little influence on the isomerization performance of Pd/HZSM-5 catalysts. Loading Pd leads the conversion of n-heptane and isomerization activity improved significantly. However, when the Pd loading exceeds 0.4%, the metal function and acid function of catalyst reaches equilibrium state, and the conversion of n-heptane and isomerization activity no longer change significantly.

MACROPOROUS FCC CATALYST PREPARED BY ORGANIC ADDITIVE AND IN-SITU CRYSTALLIZATION

2019, 50(3): 58-62.

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NaY/kaolin composite microspheres and the corresponding FCC catalysts were prepared via in-situ synthesis by adding organic additives, starch and polymer PDDA. XRD, N2-adsorption and ACE were used to study the crystallinity, pore structures, and the cracking performances of the NaY/kaolin composites and catalysts. The results showed that the crystallinity of the composites is increased from 18% (blank) to 24% by adding starch or PDDA. The mesopore volume of the composites adding starch are increased from 0.180 cm3/g to 0.355 cm3/g, and further increased to 0.431 cm3/g by using PDDA additive. ACE tests showed the as-made catalyst using starch or PDDA improves the catalytic performances, the slurry yields are 1.98 and 2.43 percentage points lower than the reference, respectively, while the liquid yields increase 2.55 and 3.07 percentage points , respectively, compared to the catalysts prepared without additive.

PERFORMANCE OF NICKEL RESISTANCE OF IN SITU CRYSTALLIZATION CATALYST MODIFIED BY MAGNESIUM

2019, 50(3): 63-67.

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The effects of magnesium on nickel resistance of the in-situ crystallization catalysts were investigated. The magnesium-modified samples were prepared by impregnation of Mg and characterized by N2 adsorption-desorption isotherm method, IR, XRD and MAT techniques. The nickel resistance tests were conducted in a fixed fluidized reactor. The results showed that under the condition of nickel pollution, when the magnesium loading on the catalyst is 1.0%, the micro-reaction activity of the catalyst is reduced by 19 percentage points compared with the catalyst sample without magnesium,the dry gas yield and coke yield decreased by 0.81 and 4.36 percentage points, respectively, and the heavy oil conversion rate and C5+ gasoline yield changed slightly,which indicated that the proper amount of magnesium supported on the in-situ crystallization catalyst can improve the nickel resistance of the catalyst to some extent.

ANALYSIS OF PRODUCTION STATUS OF LUBE OIL HYDROGENATION UNIT AT THE END OF RUN

2019, 50(3): 68-71.

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At the end of run of the hydrogenation unit of lubricating oil, due to the fact that the hydrocracking tail oil cannot be blended, the nitrogen content in the feed of isomerization was excessive, resulting in unqualified pour point of the base oil and hot spots in the catalyst bed of the hydrocracking reactor. The measures of increasing the temperature of hydrocracking and isodewaxing reactors and using the low nitrogen second-line oil of vacuum distillation tower were proposed. Those methods make the nitrogen content in isomerization unit feed less than 2μg/g, the pour point of base oil not higher than -15 °C，and there are no hot spots in cracking catalyst bed.

PREPARATION OF CRUDE WHITE OIL USING LIGHT FURFURAL EXTRACT OIL AS FEEDSTOCK FOR HYDROGENATION UNIT

2019, 50(3): 72-76.

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In order to realize the value increment of light furfural extract oil, the technical feasibility of preparation of crude white oil by hydrogenation process using naphthenic light furfural extraction oil as blending feedstock was studied in pilot plant. The results indicated that the qualified crude white oil product can be prepared by adjusting the blending ratio and optimizing the process conditions of hydrogenation unit, while the unit can run smoothly using the light furfural extract oil as blending feedstock

CHARACTERISTICS AND OPERATION OF LARGE-SCALE S ZORB INDUSTRIAL PLANT

Zhang Shuguang

2019, 50(3): 77-79.

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The properties and operating performance of the large-scale S Zorb industrial plant with a capacity of 2.4 Mt/a was introduced. The unit adopted a new design of external filter of reactor. The plant was in good condition after it started up. The calibration test showed that when the feed with the sulfur and olefin content is 180μg/g and 22.69%, respectively, was processed, the sulfur content of the product is reduced to 4μg/g, meeting the China V gasoline standard. The RON loss is 0.4; the energy consumption is 250.8MJ/t.

EFFECT OF POLAR GROUPS OF DIESEL ANTI-WEAR AGENT ON ANTI-WEAR PERFORMANCE

Yan Li Long Jun Zhao Yi Jianmin JianminLin Zhou Han

2019, 50(3): 80-86.

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The evaluation data of various fatty acids and their ester derivatives showed that the key factor affecting the anti-wear was the structure of polar groups of the molecules. By molecular simulation method，the effects of polar group structure of anti-wear agent molecule on its physical and chemical adsorption energy, molecular-interaction energy and the anti-wear performance was explored. The results showed that enhancing the adsorption on the friction surface and intermolecular binding energy of the anti-wear agent molecules is beneficial to strengthen the adsorption stability and structural stability of the lubrication film, which helps improving the anti-wear performance of the agents. Introducing small polar groups，such as —OH，near the polar group of anti-wear agent molecule can heighten the adsorption ability and molecular interaction of the anti-wear agent molecules. The anti-wear performance tests proved that after introducing –OH, the anti-wear performance of the agent is significantly increased，which is consistent with the theoretical research results.

EFFECT OF WARM MIXTURE AGENT AND FLAME RETARDANT ON RHEOLOGICAL PROPERTIES OF SBS MODIFIED ASPHALT

2019, 50(3): 87-91.

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The SBS modified asphalt blended with the EC130 warm mixture agent and the FRMAXTM flame retardant was tested by the dynamic shear rheometer (DSR), the curved beam rheometer (BBR) and the Brookfield to investigate the effects of two modifiers on the rheological properties of SBS modified asphalt. The results showed that the cooling effect of the EC130 warm mixture agent is obvious, which can effectively reduce the construction temperature of 25℃, however, it has an adverse effect on the low temperature rheological properties of the SBS modified asphalt, the low temperature PG classification drops to -12℃from -18℃; the FRMAXTM flame retardant can improve the high temperature deformation resistance of the SBS modified asphalt, the high temperature PG grade rises to 88℃ from 82℃, but has certain adverse influence on the low temperature rheological properties and the viscosity temperature performance, the low temperature PG grade drops to -12℃ from -18℃, the asphalt mixture construction temperature rises by 5℃. When the two added to the SBS modified asphalt together, the high temperature performance and the viscosity temperature performance are improved. The high temperature PG grade rises to 88℃ from 82℃, the construction temperature drops by 20℃, and the low temperature PG grade drops to -12℃ from -18℃.

STUDY OF MODIFICATION OF KARAMAY ASPHALT BY CHEMICAL METHOD

2019, 50(3): 92-96.

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In view of the difficult modification of Karamay asphalts and the poor stability of the product, the physical and chemical modification methods were used to study the elemental composition, infrared spectra, group composition and molecular weight of four kinds of asphalts before and after modification as well as the differences from the properties of SBS-modified asphalts. The results showed that, compared with the physical modification, the chemical modification not only significantly reduced the reaction temperature of SBS modified asphalt, but also improved the high temperature performance of SBS modified asphalt.

STUDY ON TREATMENT OF OILY SLUDGE WITH IONIC LIQUID AND ORGANIC SOLVENT COMPOSITE TECHNOLOGY

2019, 50(3): 97-100.

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Ionic liquid assisted extraction method was selected to recover oil from oily sludge, of Shengli Oil Field. The effects of solvent systems, solvent-oil ratio, temperature, reaction time and stirring speed were investigated. Experimental results showed that the desorption efficiency of oil and asphaltenes were 90.5 % and 83.1 %, respectively under the following conditions: using n-heptane and ionic liquid [Emin][BF4] as solvent system, the solvent-oily sludge ratio of 50/3, ionic liquid 10 mL, temperature 50℃, reaction time 20 min, stirring speed 2000 r/min. In addition, n-heptane and ionic liquid can be recycled with high recovery efficiency. The primary and secondary recovery rates of n-heptane are 89.2% and 74.2%, respectively, the recovery of ionic liquid is more than 95.4 %. The recovery rates of oil and asphaltenes are more than 85 % and 75 %, respectively. The desorption mechanism of oil from sludge was studied. It is concluded that the oil recovery from oily sludge is improved significantly by ionic liquid and solvent composite technology.

APPLICATION OF NEURAL NETWORK TECHNOLOGY ON DIESEL HYDROFINING UNIT

2019, 50(3): 101-107.

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In view of the product quality was difficult to be predicted in diesel hydrofining process, the artificial neural network model was proposed. Based on the production operation data of 1.0 Mt/a diesel hydrofining unit in a petrochemical enterprise, the model for predicting sulfur content of diesel hydrogenation products were established by using momentum BP neural network, LMBP neural network and RBF neural network. The generalization ability of the RBF neural network model was also investigated. The results showed that, the average relative errors of the prediction of momentum BP neural network, LMBP neural network and RBF neural network are 3.50%, 2.30% and 2.18%, respectively. The RBF neural network model has the best prediction performance and good generalization ability. The RBF neural network could predict the sulfur content of the diesel product accurately when the process parameters changes. The work provides guidance for the better operation of the diesel hydrofining unit.

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