Table of Content

12 July 2018, Volume 49 Issue 7

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CATALYTIC CRACKING REACTION CHARACTERISTICS OF COKER GASOLINE

2018, 49(7):  1-6. 

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Based on the analysis on composition characteristics of coker gasoline, coker gasoline cracking experiments over zeolite catalyst were conducted in a laboratory fixed fluidized bed reactor. The main influence factors on reaction conversion, yields and selectivities of light olefins of coker gasoline cracking were studied. The results indicated that the conversion of coker gasoline is low under the cracking reaction conditions. Increasing reaction temperature is one of the effective ways to promote the yields of light olefins; however, the selectivity of the target products changes little. The yields and selectivities of ethylene and propylene can be enhanced simultaneously by employing a new high selectivity catalyst along with lower butylene yield. The conversion degree of alkanes in coker gasoline, especially for C5~C7, is lower due to the fact that β-scission is not easy to occur for cabonium ion with less than 7 carbon atoms.

STUDY ON CRACKING REACTION PRFORMANCE OF BIOLOGICAL HEAVY OIL

Yang Yinan

2018, 49(7):  7-13. 

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The cracking reaction performance was investigated for a typical FCC feedstock (TC-M，a hydrotreated vacuum gas oil) and a feed blending different proportions of bio-heavy oil (BHO) using the conventional RFCC catalyst MLC-500 with various catalyst/oil ratio in a fixed fluidized bed. The results showed that the degree of cracking reaction is weakened and the conversion rate is decreased with the increase of the proportions of BHO. For the product selectivity, the product selectivities are improved except LPG. The process condition test indicated that the appropriate catalyst to oil ratio can ensure the proper depth of heavy oil conversion and better product selectivity. Gasoline olefins increase by about 10 percentage points, aromatics decreases, and no obvious RON changes. The oxides in BHO that converted to CO and CO2 are 14.9% and 7.8%, respectively when the mass ratio of catalyst to oil is 6.0 and BHO blending is 15%, the rest of oxides are counted in water. Liquid products (including gasoline, diesel and heavy oil) are essentially free of oxygen.

EFFECT OF CARRIER GAS ON n-BUTANE ISOMERIZATION OVER SO42-/ZRO2-AL2O3

2018, 49(7):  14-18. 

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The alumina-promoted sulfated zirconia catalysts were prepared by precipitation-impregnation method. The effect of carrier gas on n-butane isomerization over SO42-/ZrO2-Al2O3 was investigated in a continuous flow fixed-bed micro-reactor at atmospheric pressure and 200 ℃ using hydrogen, nitrogen, and mixture of hydrogen and nitrogen as carrier gas. The results showed that the inert nitrogen only plays the role of diluent gas, which decreases the concentration of n-butane and intermediate species. However, the hydrogen adsorbed on the catalyst surface is active in reaction. In addition to dilution, the hydrogen accelerates the desorption of intermediate species and product molecules from the catalyst surface through competitive adsorption with n-butane and improves the stability of catalyst significantly due to interaction between H2 and catalyst active size, which is the determining factor for this improvement.

STUDY ON MICROEMULSION FORMULA FOR LOW PERMEABILITY RESERVOIR AND MICROSCOPIC RESIDUAL OIL FLOODING MECHANISM

2018, 49(7):  19-24. 

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According to the orthogonal design experiment, the best microemulsion system was selected. The natural rock core displacement tests were conducted to verify the improvement of oil recovery by microemulsion techniques. The lithographic glass model was used to conduct the visualization test of the remaining oil micro-displacement process and its mechanism. The results showed that compared with water flooding, when the permeability of rock core increases from 1.78×10-3μm2 to 29.11×10-3μm2, the enhanced oil recovery (EOR) by microemulsion is from 5.45 percentages to 12.14 percentages, which is consistent with the results of lithographic glass model tests. The five micro-residual oil types are observed: cluster type, column type, blind-end, droplets type, and oil film type. Among them, the flooding proportions of the cluster and droplet residual oil are the highest, the displacement effect is better, and the oil film residual oil is the lowest, and the displacement effect is poor.

STUDY OF HYDROGENATION PROCESS OF LOW VISCOSITY PAO

Wang Xinmiao Xu Weichi Liu Lijun Guo Jintao

2018, 49(7):  25-28. 

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The PAO4 crude product was hydrogenated using Ni-W/Al2O3 catalyst developed by PetroChina Petrochemical Research Institute. The optimal reaction conditions were determined. The results showed that at 240-260 ℃，4.0-8.0 MPa， LHSV 0.2-0.4 h-1 ,and the hydrogen/oil ratio of 300:1-600:1(v)，the hydrogenated PAO4 has a similar aromatic content with the PAO4 products abroad. No Saybolt color changes of the hydrogenated PAO4 are observed after light test for 90 days, indicating its good light stability.

UV AND THERMAL STABILITY IMPROVEMENT BY INCREASING POST-HYDROFINING TEMPERATURE OF NAPHTHENIC BASE OIL HYDROPROCESSING

2018, 49(7):  29-33. 

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Compared with solvent refining process, the UV and thermal stability of naphthenic base oil from high pressure hydroprocessing is poor. UV and thermal stabilizers are generally added to solve this problem. Taizhou Petrochemical Company was also used the same method for N4006 and N4010 base oils, and the cost is increased by 80 yuan/t. Therefore, tests of increasing post-hydrofining temperature are conducted to improve the oil stability. The results showed that higher temperature of post-hydrofining can improve the UV and thermal stability of N4006 effectively, while no obvious effect on N4010. The yield of either base oil is not affected.

PRODUCTION OF RUBBER PLASTICIZER A0709 FROM SECOND SIDE STREAM OF VACUUM DISTILLATION

2018, 49(7):  34-36. 

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The rubber plasticizer A0709 derived from the 2nd side stream of vacuum distillation of SZ36-1 naphthenic-base crude was prepared by a combined process of hydrodeacidification-solvent refining-clay refining. The process conditions were optimized. The results showed that by the combined technology, the rubber plasticizer A0709 can be produced and reach the GB/T 33322 standard. Under the optimized process conditions, the product yield is up to 74.1% and the CA% is 11.2%.

APPLICATION EVALUATION OF LOW-VOLATILE GREASE

qinghua Duan

2018, 49(7):  37-41. 

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A kind of low-volatile grease was prepared by adding a variety of additives in composite sodium soap thickened polyalkylcyclopentane and evaluated its physical and chemical properties. A series of application tests such as the saturated vapor pressure, the vacuum mass loss, the radiation resistance, compatibility, and vacuum thermal cycling bench test were conducted. The result showed that the grease not only has good performance in high and low temperature, colloid stability, oxidation stability, corrosion resistance, extreme pressure and abrasion resistance, lower saturated vapor pressure (3.4 × 10-6Pa), lower volatility (total loss rate of 0.95%, condensable volatile matter content of 0.088%), strong radiation resistance (which can withstand 1 × 105 Gy dose) and good compatibility with the vacuum equipment material. The grease passed the vacuum thermal cycling bench test.

SYNTHESIS OF PAO BASE OIL USING ALPHA OLEFIN FROM POLYETHYLENE WAX CRACKING

2018, 49(7):  42-45. 

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The α-olefin was prepared by pyrolysis of polyethylene wax, which was used as the raw material to synthesize poly-α-olefin (PAO) under the action of AlCl3. The effects of catalyst amount, reaction time and temperature on the properties and yield of polyalpha-olefins were investigated. The results showed that at AlCl3 amount of 3% (mass fraction, raw material quantity as the benchmark), reaction time of 3h and reaction temperature of 60 ℃, the yield of synthetic polyolefin oil is 63%, the viscosity is 29.71 mm2/s (40 ℃) and 5.74 mm2/s (100 ℃), and the viscosity index is 145 with a pour point of -43℃.

RESEARCH OF ANTICOKING AND LIQUID YIELD BOOSTER FOR DELAYED COKING

2018, 49(7):  46-49. 

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A high temperature dispersant was synthesized from polyisobutylsuccinimide 1H-benzotriazole and salicylaldehyde, and was characterized by IR and TG. The results showed that the synthesized product is the target product and has obvious high temperature resistance. According to the principle of anti-coke and increasing liquid, the anticoking and liquid yield booster was prepared, and was used in the delayed coking simulation test device. The results showed that the effect of anticoking and liquid yield booster containing high temperature dispersant was significantly better than that of polyisobutylsuccinimide. The addition of 200μg/g anticoking and liquid yield booster increases liquid yield by 4.5 percentage points, where the yield of gasoline, diesel and wax fraction increases by 1.24, 3.16 and 0.1 percentage points, respectively. The gas yield of gas and coke deceases by 1.58 and 2.92 percentage points, respectively. The analysis results showed that the addition of anticoking and liquid yield booster has no significant influence on group composition of the liquid fractions; therefore, the liquid product quality of delayed coking is not affected.

PREPARATION AND CATALYTIC PROPERTIES OF TiO2 HONEYCOMB DENITRATION CATALYST MIXED WITH MONTMORILLONITE

2018, 49(7):  50-53. 

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A honeycomb type denitration catalyst was prepared by titanium dioxide mixed with montmorillonite, ammonium vanadate and ammonium tungstate solutions and was characterized by XRD, BET and SEM, and the denitration activity evaluation. The results showed that the phase structure of the catalyst is anatase TiO2, and the diffraction peak of montmorillonite is not observed, indicating the good compatibility with titanium dioxide. The specific surface area and pore volume of the catalyst increase with the increase of the amount of montmorillonite. When the amount of doped montmorillonite is 10%, the denitration rate of the catalyst is up to 95.8%. The catalysts have good mechanical and wear strength.

COMMERCIAL APPLICATION OF PHF CATALYST IN HIGH SULFUR STRAIGHT-RUN DIESEL HYDROTREATING

feng liankun

2018, 49(7):  54-57. 

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The commercial operation of 2.8 Mt/a diesel hydrotreating unit in Yunnan refinery using PHF catalyst was introduced. The results showed that at reactor inlet temperature of 324 ℃, space velocity 0.79 h-1, volume ratio of hydrogen to oil 625:1, the sulfur content of refined diesel is 4 μg/g from 12 700 μg/g in feed. The product meets the requirements of the state Ⅴ diesel specification.

STUDY OF LEAD CORROSION OF DIESEL ENGINE OIL IN MACK T-12 ENGINE TEST

Jie XU

2018, 49(7):  58-62. 

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The physical and chemical properties of diesel engine oil after Mack T-12 engine test were analyzed. The ZDDP degradation was investigated by 31P-NMR spectroscopy. The lead corrosion of diesel engine oil and its influence factors were studied. The results showed the lead corrosion is related to oil degradation levels, the earlier the total base number and total acid number cross point appears during the test, the more severe lead corrosion. The lead corrosion is also related with ZDDP degradation rate, the lower the molar concentration of basic ZDP plus neutral ZDP in used oil, the higher degree of lead corrosion.

RESEARCH ON THE CORROSION BEHAVIOR IN NITROGEN PROTECTION ATMOSPHERE FOR SHUTDOWN EQUIPMENT OF REFINING AND PETROCHEMICAL PROCESS UNITS

2018, 49(7):  63-68. 

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The corrosion behaviors of four typical materials in nitrogen protection atmosphere were studied in the simulated wet environment. The corrosion rate, corrosion appearance and the composition of corrosion products were investigated through weight-loss method profilometry and X-Ray diffraction (XRD), respectively. The results show that, in the gas phase, the trend of corrosion rate for two kinds of carbon steel decrease followed by a steady increase with the increasing of oxygen content; The Cr5Mo and 304 stainless steel both maintain stably at a low level. In the liquid phase, the corrosion rates of carbon steel and chromium-molybdenum steel increase obviously when oxygen content reaches to 1.0%. There is small difference of material corrosion rates when the oxygen content changes in the range of 0.5%~1.0% in both gas and liquid phase. The corrosion characteristics of carbon steel and chromium-molybdenum steel are basically the same. The corrosion products mainly consist of γ-FeOOH and Fe3O4, with metal ulcerated and etched. The 304 stainless steel still maintains the metallic luster and has no obvious corrosion.

SYNTHESIS AND BACTERICIDAL PERFORMANCE STUDY OF NEW BACTERICIDES FOR OILFIELDS

2018, 49(7):  69-72. 

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A new bactericide was synthesized using dodecylamine and 2, 3-epoxypropyltrimethyl ammonium chloride. The effects of the amount of raw materials, reaction time, reaction temperature, and dosage of solvent on bactericide yield were investigated. The structure of the product was characterized by IR，MS，NMR and Hydroxyl value. The results showed that the yield of bactericide can reach up to 93.8% under the following conditions: reaction time of 10h, reaction temperature 90℃ and 2:1 of 2, 3-epoxypropyltrimethylammonium chloride: dodecylamine. The comparative tests on sterilization ability of the synthesized bactericide and conventional fungicides were conducted. Results showed that the bactericidal effect of cationic biquaternary ammonium salt is the best.

DEEP PURIFICATION TECHNOLOGIES FOR VOCs WASTE GASES DURING LOADING OF GASOLINE, JET FUEL, STYRENE AND METHANOL

Liu Zhongsheng Wang Haibo Wang Xin Liao Changjian Liu Zhiyu Zhao Lei

2018, 49(7):  73-80. 

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The emission standards for volatile organic compounds（VOCs）waste gases such as gasoline, jet fuel, styrene, etc, and the collection and transportation technologies for oil product vapors were summarized, showing that domestic standards are comparable to or even slightly stricter than the foreign strictest standards. It is recommended to transport the VOCs out of top immersed crane pipe to the processing equipment by fans. A series of loading VOCs deep purification technologies developed by SINOPEC Dalian Research Institute of Petroleum and Petrochemicals （former Fushun Research Institute of Petroleum and Petrochemicals, FRIPP）were introduced, including "Low-Temperature Diesel Absorption" ，and "Low-Temperature Diesel Absorption-Total Hydrocarbon Homogenization - Catalytic Oxidation (AHCO-1) " technology, and "Low-Temperature Diesel Absorption - Incineration" technology for gasoline, jet fuel, styrene. The "Water Absorption - Total Hydrocarbon Homogenization-Catalytic Oxidation (AHCO-2)” technology for methanol, and acetic acid, the condensation generative thermal oxidation" technology for gasoline oil and gas treatment. After treated by "Low-Temperature Diesel Absorption" technology, the recovery of gasoline oil and gas can reach over 97%; similarly, for the loading VOCs, the total hydrocarbon concentration of purified gas is less than 20 mg/m3, while the total hydrocarbon removal rate is more than 99% by recycling, catalytic oxidation, incineration treatment.

APPLICATION OF COMPLEXING IRON LIQUID PHASE OXIDATION DESULFURIZATION TECHNOLOGY FOR SULFUR RECOVERY FROM TAIL GAS TREATMENT

2018, 49(7):  81-84. 

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In order to meet the national emission standards for desulfurization unit, the upgrading of the equipment of PetroChina Sichuan Petrochemical Co., Ltd. was implemented, adopting complexing iron liquid phase oxidation desulfurization technology. After the transformation, the SO2 concentration in sulfur recovery unit exhaust gas is reduced from 400 mg/m3 to 15 mg/m3, in compliant with the requirement of SO2 concentration less than 100 mg/m3 in ‘Petroleum industry pollutant discharge standards’（GB 31570—2015）.

STUDY ON LOW TEMPERATURE HEAT RECOVERY PROCESS OF AROMATIC COMPLEX

Xuan Genhai Zhang Ying Li Yong Xing Bing

2018, 49(7):  85-89. 

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Through the statistics analysis，the technical difficulties in recovery of low temperature heat in domestic aromatic complexes were summarized. Using C6 or C7 hydrocarbons as a internal heat transfer medium，the In/Out double heat exchange system was designed for an aromatics unit through detailed analysis of its current situation of low temperature heat. The low temperature heat of the unit could be fully recovered by the new system which could achieve the amount of 41MW/h，this will further reduce the energy consumption by 10%～15%．This technique has made a breakthrough in technical difficulties for recovery of low temperature heat in aromatic unit and provided a new way to recover the low temperature heat of the column top stream of raffinate oil column，extraction column and p-xylene column in the aromatics unit.

DETERMINATION OF SALT CONTENT IN CRUDE OIL BY COLUMN-SWITCHING ION CHROMATOGRAPHY

HE PEI

2018, 49(7):  90-94. 

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A fast determination method for salt content in crude oil by ion chromatography was developed. The samples were extracted by high frequency oscillation extraction using mixture of water, ethanol, and xylene. The column-switching technique was then used on line to eliminate the interference of ethanol in extraction solution in chromatography analysis. Then the chloride was detected by ion chromatography. The results show a great linear relationship in the concentration range from 0.1 to 100 mgNaCl/L, the correlation coefficient is greater than 0.999. The detection limit for ion chromatography is 0.01 mgNaCl/L based on S/N of 3. The difference between this method and the coulometry method is not significant. The column-switching ion chromatography can meet the analysis requirement of salt content in crude oil but much fast and simple.

APPLICATION IN MULTY-ASPECT PREDICTION IN HYDROCRACKING UNIT BY BP NEURAL NETWORK

2018, 49(7):  95-99. 

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Three-layers BP neural network was established using MATLAB to predict the hydrocracking conversion, kerosene product endpoint and pressure drop of high pressure heat exchanger shell of middle pressure hydrocracking plant. The results revealed that the sample data quality and number of network hidden layer nodes affect the BP network accuracy evidently, while the network could predict the process parameters, product properties, and heat exchanger state primely. The prediction accuracy for hydrocracking conversion is the lowest, the relative error is ±(5%—10%); the accuracy of the prediction of jet fuel endpoint is high with a relative error of ± (0.15%—2.0%); The absolute error of the pressure drop prediction of the shell side of the heat exchanger is within ±0.03 MPa, indicating that the network established satisfies the requirements for heat exchanger condition monitoring.

PROPERTY CALCULATION METHOD AND MODEL STRUCTURE FOR CRUDE DISTILLATION UNIT SIMULATION

2018, 49(7):  100-106. 

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Property calculation method has great effect on the accuracy of the CDU simulation results, especially for the vacuum column. It is often observed that the simulated flow rate of vacuum residue is lower than the test-run data. This paper introduces a relatively more convinced methodology to simulate CDU using Aspen Plus. Based on a set of CDU test-run data, an Equation-Oriented model is built and solved in reconciliation mode on the Aspen Plus V10 Platform. Comparing the different results among the different property methods, the most accurate property method for CDU is presented. Finally the influence of different property methods on the analog computation results of CDU is explained theoretically.