Table of Content

12 April 2019, Volume 50 Issue 4

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OPTIONS OF MARKET-ORIENTED TECHNOLOGIES FOR REFINERY TRANSITION AND UPGRADING

2019, 50(4):  1-6. 

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China's refineries are in a critical period of structural adjustment. It is very urgent to upgrade product quality, reduce diesel to gasoline ratio and transform to petrochemical industry. Considering the characteristics of the existing refining process in China, the combined processes of refined product structure adjustment and quality upgrade, and the related technologies were proposed, which could meet the needs of technical upgrade for most refineries. At the same time the typical processes of petrochemical-type refinery and the key technologies to the transformation of refining to petrochemical were also introduced to supply an optional technological route for revitalizing the stock of refinery assets, achieving the integration of refining and petrochemical, and increasing the economic efficiency of refinery.

DEMONSTRATION TEST OF SULFURIC ACID ALKYLATION TECHNOLOGY WITH LOW ACID CONSUMPTION

2019, 50(4):  7-11. 

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To meet the demand of domestic refineries for alkylate, an authorized low acid consumption sulfuric acid alkylation technology was developed by RIPP through the development of new reactors, enhanced mass transfer and separation processes. The demonstration plant test was conducted in an 80 t/a sulfuric acid alkylation unit built in SINOPEC Shijiazhuang Refining & Chemical Company. The test showed that the RON of the product was 96.5~97.0, the final boiling point was less than 197.5 °C. It meets the requirements of alkylation product and is a high-quality gasoline blending component. The acid consumption was determined to be 46.4 kg/t of alkylation product during the stable operation period, lower than the conventional technology.

INDUSTRIAL PRACTICE OF BLENDING DEASPHALTENE OIL IN FEEDSTOCKS OF RHT UNIT

2019, 50(4):  12-15. 

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The industrial application of blending deasphaltene oil (DAO) in the feedstocks of 1.7 Mt/a RHT unit was introduced. The operation parameters, feedstocks and product properties, and impurity removal rates were compared before and after blending DAO. The results of application showed that the properties of feedstocks and the impurity removal rates were improved, while the reactor pressure drop was decreased after blending DAO. The addition of DAO plays an active role for long-term cycle length due to the improved FCC feedstocks properties. The overall economic benefits of the company are also increased.

EFFECT OF REDUCING OPERATING PRESSURE ON COKING PROCESS

2019, 50(4):  16-19. 

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The effect of reducing operating pressure on delayed coking process was studied. The pilot test results showed the yield of liquid and gas oil increased by 2.03 and 4.64 percentage points, respectively, while the yield of gas and coke decreased when the operating pressure of coker drum was reduced from 0.195MPa to 0.115MPa under the basically same conditions of the outlet temperature of delayed coking furnace, steam injection amount and recycle ratio. With the decrease of operating pressure, the properties of coker gasoline and coker diesel oil changed little, but coking gas oil properties became worse, mainly in increases of density, carbon residue asphaltene and nitrogen content, metal content, while the distillation range 95% point temperature increased by 14℃and the volatile component decreased.

PROBLEMS AND MEASURES OF DEEP HYDROTREATING OPERATION OF FCC DIESEL AFTER UNIT REVAMPING

2019, 50(4):  20-26. 

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The 2# gasoline and diesel hydrotreating unit in SINOPEC Shijiazhuang Refining & Chemical Company was revamped and upgraded by using the SSHT technology developed by SINOPEC Research Institute of Petroleum Processing. The upgraded unit with a new added hydrotreating reactor used FCC diesel and coker naphtha as feedstocks to produce diesel and gasoline with mass fraction of sulfur of less than 10 μg/g through deep hydrodesulfurization. However some problems occurred during the operation, including the temperature rise of the reaction system on the right side, interruption of the cold oil, large radial temperature difference of the reactor, fluctuation of the liquid level of the high-pressure separator, and the unqualified color of the diesel product. To solve these problems, the short-term and long-term solutions were proposed to ensure the stable production and quality of the products.

PRODUCTION AND INDUSTRIAL APPLICATION OF WHITE OIL HYDROGENATION CATALYST RLF-20

2019, 50(4):  27-31. 

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The industrial production and application of white oil hydrogenation catalyst RLF-20 was introduced. The industrial production showed that no special equipment was required in the production of catalyst RLF-20. The product quality met the catalyst specification and was equivalent to the performance of laboratory sample. The performance of RLF-20 during industrial application was stable. The high-grade white oil products can be produced stably by using the catalyst and the feed with low or high aromatics content under mild hydrogenation operating conditions.

INFLUENCE OF CITRIC ACID ON QUINOLINE HYDRODENITROGENATION OF NiMoP/Al2O3 CATALYSTS

2019, 50(4):  32-38. 

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A series of NiMoP-C(x) catalysts was prepared with alumina support by adding different amounts of citric acids in NiMoP impregnating solutions. These catalysts exhibited high catalytic activity in hydrodenitrogenation reaction of quinolone and were analyzed with XRD, TPR and HRTEM techniques. XRD and TPR results showed that the active component dispersions on the surface of carrier were not affected by citric acid but their low temperature reduction peak moved to the lower temperature. HRTEM analysis indicated that citric acid increased the accumulation degree of MoS2 particles, reduced the proportion of active components entering the carrier phase, and further optimized the surface interaction between the active component and the carrier. XPS analysis showed that the interaction between Ni and carrier was reduced, resulting in improvement of the sulfidation degree of Ni and its effective utilization, the sulfidation of Ni was delayed, which promotes the formation of MoS2 particles with Ni atoms embedded in the edge. The addition of citric acid increased the number of active site on the surface of the catalyst, and further improved the activity of the catalyst.

PREPARATION OF HYDRODEWAXING CATALYST AND PERFORMANCE EVALUATION FOR HYDROCRACKING TAIL OIL

2019, 50(4):  39-43. 

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A Ni/Ca /ZSM-5 catalyst which used ZSM-5 molecular sieve as support was prepared. The performance of Ni and Ca modified ZSM-5 as hydrodewaxing catalyst in the melting point, yield and viscosity index of lube base oil was studied using hydrocracking tail oil as feedstock. The results showed that the cracking activity of the hydrodewaxing catalyst decreased and the yield and viscosity index of the lube base oil increased. For hydrocracking tail oil, the optimal reaction conditions were reaction temperature of 310 ℃, LHSV of 3.0 h-1, hydrogen pressure of 15 MPa and hydrogen to oil ratio of 500. Under the optimal conditions, the melting point of the produced lube base oil was －17 ℃, the viscosity index and the yield were 93 and 72%, respectively

EFFECT OF SUPPORT ON DENITRIFICATION PERFORMANCE OF Mn-Ce CATALYSTS AT LOW TEMPERATURE

2019, 50(4):  44-48. 

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Using three different kinds of titanium dioxide compositions as carriers, Mn-Ce/TiO2, Mn-Ce/TiO2-SiO2, Mn-Ce/TiO2-WO3 catalysts were prepared by impregnation and characterized by XRD, BET and SEM techniques. The effects of SiO2 and WO3 on denitration activity and sulfur resistance of the catalyst were investigated. The results showed that the addition of SiO2 and WO3 increased the specific surface area of the supports and the number of the surface active acidic sites of the catalyst, and the denitration efficiency and the sulfur resistance of the catalyst were improved. At the conditions of the space velocity of 10000h-1 and 100℃, the NO removal rate on Mn-Ce/TiO2 catalysts was only about 30%, and the NO removal rate on Mn-Ce/TiO2-SiO2 and Mn-Ce/TiO2-WO3 catalyst was 45% and 50%, respectively. Within 270 min reaction, the NO removal rate on Mn-Ce/TiO2 catalysts were reduced from 80% to 40% at 150℃ in presence of 150 μL/L SO2, and Mn-Ce/TiO2-SiO2 and Mn-Ce/TiO2-WO3 catalyst decreased from 84% to 55% and 70%,respectively.

PILOT STUDY ON INFLUENCE OF HYDROGENATED FEEDSTOCKS ON SOX EMISSION OF FCC FLUE GAS

2019, 50(4):  49-52. 

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In a pilot riser catalytic cracking unit, conventional heavy oil cracking catalyst VRCC was selected to investigate the cracking reaction performance and the SO2 content of regenerated flue gas of heavy oil feeds with different hydrogenation depths under the same experimental conditions. The results showed that with the increase of hydrogenation depth of raw materials, the concentration of SO2 of regenerated flue gas decreased from 526 mg/m3 of mild hydrogenated feed to 232 mg/m3 of deep hydrogenated feed. Compared to mild hydrogenated feedstock, using moderate hydrogenated feedstock,the LPG yield increased by 1.40 percentage points, the gasoline yield increased by 0.89 percentage points, the slurry yield decreased by 2.05 percentage points, and the total liquid product yields increased by 1.54 percentage points. Considering both the difficulty of hydrogenation of raw materials and the influence range on SOx emission of regenerated flue gas, selecting moderate hydrogenated feed for FCC can not only reduce the cost of hydrogenation process, but also meet the dual requirements of FCC on product distribution optimization and reduction of SOx emission of regenerated flue gas.

STUDY ON DEEP PURIFICATION TECHNOLOGY OF LOADING EXHAUST GAS

2019, 50(4):  53-58. 

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The technology consisting of low-temperature diesel absorption-total hydrocarbon homogenization–catalytic oxidation was determined to treat the loading exhaust gas in a petrochemical enterprise of Shandong base on the analysis of control technologies of loading exhaust gas. The results indicated that at the operating conditions of the absorption oil flow rate of 15~20 m3/h，the absorption temperature 8~15 ℃，the absorption pressure 0.2 MPa， the catalytic oxidation temperature 250~350 ℃，and gas space velocity of catalytic oxidation 5 000~20 000 h-1, the concentration of non methane total hydrocarbon in the purified gas was less than 20 mg/m3，the emission concentration of benzene, toluene and xylene was lower than the limit of detection，and the purified gas meets the national and local discharge standards. The period of investment recovery was 5 years. The combined technology has a economic benefits and obvious environmental friendly.

NUMERICAL SIMULATION AND PARAMETER OPTIMIZATION OF LARGE FCC CATALYST SPRAY DRYING TOWER

2019, 50(4):  59-63. 

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In order to investigate the influence of the internal flow field of a large FCC catalyst preparation spray dryer on the performance of the catalyst, a 50-kt /a two-phase flow CFD model was established using the Euler-Lagrange model. The flow field information of the large spray drying tower was obtained through the preliminary simulation of the large spray drying tower and the simulation calculation of the modified model. The velocity field distribution data showed that the gas phase flows faster in the center of the tower, and vortices are generated on the left and right sides, but they were not completely symmetrical. The optimum number of spray guns and spray angle can be obtained from the study of parameter optimization process of spray drying tower.

STUDY ON OPTIMIZATION SCHEME OF ENERGY SAVING AND CAPACITY EXPANSION OF PROPYLENE DISTILLATION COLUMN

2019, 50(4):  64-68. 

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The influence of the feeding position and the number of trays on the energy consumption of the propylene fractionator was explored. Based on the control of the optimal feeding position variables，ProII process simulation and Origin data fitting were applied to obtain a certain feed composition and the expression of the reboiler load and the number of trays. The results showed that the thermal load of the propylene fractionator decreased with the increase of the number of trays，and the decreasing amplitude gradually decreased and finally reached a extreme value. Combined with the cost of utility and equipment，the work can provide certain theoretical support for the specific plan for the new-built or reformed propylene fractionator. When the old factory is reconstructed，the purpose of capacity expanding or reducing energy consumption can be achieved by optimizing the feeding position or increasing the number of trays.

EXERGY ANALYSIS OF MULTI-STAGE GAS COMPRESSION PROCESS BASED ON ASPEN PLUS SIMULATION

2019, 50(4):  69-74. 

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Different models for a polytropic compression process were analyzed by using Aspen Plus, with the multi-stage compression process of an actual cracking gas plant taken as background. According to the principle of thermodynamics, exergy analysis were conducted for the compression process of raw cracking gas under conditions of adiabatic, isothermal and multi-stage compression. The results showed that during the compression process, exergy increased as pressure increased, while the corresponding total exergy droped in the inter-stage cooling process. The compression exergy efficiency increased as the number of stages increased, and flattened gradually. The analysis for the practical five-stage compression process showed the exergy increase was 2 350 kW, and the exergy efficiency was 62.67%, potential for exergy recovery was 476 kW.

SEPARATION AND IDENTIFICATION OF CONTAMINANTS IN TANKER DIESEL

2019, 50(4):  75-77. 

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The contaminants of tanker diesel were separated and analyzed, and characterized by various analytical methods. The results showed that the contaminants were sodium carboxylate containing alcohol and ester. Contaminants can be removed by filtration or distillation without affecting diesel composition.

DETERMINATION OF NOBLE METAL CONTENTS IN CARBON MONOXIDE COMBUSTION PROMOTER BY ICP-AES AFTER MICROWAVE DIGESTION

2019, 50(4):  78-82. 

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The CO combustion promoter was treated using HCl，HNO3 and HF mixed acid by microwave digestion technique to prepare sample water solution. Pt 265.945 nm and Pd 340.458 nm were selected as the analytical lines, using the determination method of inductively coupled plasma atom emission spectrometry. According to the results, the linear correlation coefficient of the calibration curve of each element was not less than 0.999 0. The detection limits of Pt and Pd were 0.030 mg/L and 0.014 mg/L, respectively. The presence of coexisting elements, Si and Al, had little effect on the determination results of Pt and Pd. According to the method of this experiment, the relative standard deviations（RSD，n=6）of results were less than 3%. The recoveries were between 97.00% and 104.0%.

INFLUENCE OF ADDITIVES ON FILTERABILITY OF TURBINE OIL

2019, 50(4):  83-87. 

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The influence of additives X and Y on the filter property of 8 kinds of base oils, the influence of the content of each single agent and cosolvent in additives on the wet filter properties of base oils, and the relationship between wet filter properties and average particle size of emulsion were studied. The results showed that the dry filter properties of the 8 base oils decreased slightly, while the wet filter decreased significantly. The main component that makes the wet filter property of base oil process worse was the cosolvent of additive, tetraethylene glycol monomethyl ether. After adding additives, the bigger the average particle size of the emulsion formed by the base oil, the worse its wet filtering property. The higher the content of ether cosolvent, the worse the wet filter properties.

INFLUENCE OF BORON AND NITROGEN MODIFIED SOYBEAN OIL ON BIODEGRADABILITY AND LUBRICITY OF RAPESEED OIL

2019, 50(4):  88-93. 

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To synthesize two Boron and Nitrogen-containing soybean oil additive (abbreviated as BNS-1 and BNS-2), boron and nitrogen were introduced into the soybean oil molecules through chemical modification. The influence of BNS-1 and BNS-2 on biodegradability and lubricity of rapeseed oils were studied. The morphologies and chemical species of the worn surfaces were investigated by scanning electron microscope (SEM) with an energy dispersive spectrometer (EDS). The results showed that BNS-1 and BNS-2 had little influence on the biodegradability of rapeseed oil. They possessed good anti-wear and friction-reducing properties, as well as extreme pressure properties. The friction-reducing properties of BNS-2 were better than those of BNS-1, however, its anti-wear properties were worse than BNS-1. The mechanism is that the electron-deficiency boron reacts with high reaction active nitrogen element at high temperature from friction, forming tribo chemical films, resulting in improved tribological properties.

STUDY ON REMOVAL OF CHLORIDE BY MAGNESIUM ALUMINUM SILICATE

2019, 50(4):  94-100. 

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Porous silicate materials possess excellent adsorption characteristics. Three kinds of adsorbents of magnesium silicate，aluminum silicate and magnesium silicate were synthesized by high temperature hydrothermal method at different treating time and characterized by BET, XRD and SEM techniques, and the chloride removal efficiencies from simulated oil were tested. The magnesium aluminum silicate was selected as the best adsorbent. The experimental results showed that the best adsorbents is obtained by reacting at 120 ℃ for 18 h. When the ratio of magnesium to aluminum was 3∶2， the adsorption time 12 h，the ratio of adsorbent to oil 1∶20 and the adsorption temperature 30 ℃，and the initial concentration of model oil 60 mg/L，the adsorption dechlorination rate reached 65.17%. This indicates that when the magnesium and aluminum oxides in the system co-exist and reach a certain proportion, the adsorbent particles accumulate more uniformly, the specific surface area and the pore volume increase obviously, and the adsorption capacity of the adsorbent increases effectively.

INDUSTRIAL APPLICATION OF PCL-100 LIQUID DECHLORINATION AGENT IN CONTINUOUS REFORMING UNIT

2019, 50(4):  101-104. 

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The problem of the corrosion of air cooler was happened in the depentanizer of the continuous reformer of Liaohe Petrochemical Company. The effect was not good by upgrading the material of air cooler, adding washing line and using common liquid dechlorination agent. The application of PCL-100 liquid dechlorination agent showed that the chloride content of reformate at the outlet of the dechlorinated device reduced to less than 0.5 μg/g. The service life was 10-months, and met the dechlorination requirements of reformate. The corrosion and salt deposition in the depentanizer were basically solved.