Table of Content

12 October 2019, Volume 50 Issue 10

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EFFECT OF FLUORINE MODIFICATION ON DISPERSION OF DIFFERENT TUNGSTEN SPECIES ON SUPPORT AND HYDRODESULFURIZATION PERFORMANCE

2019, 50(10):  1-7. 

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To study the effect of support surface properties on the dispersion of metal species and hydrodesulfurization performance, ammonium metatungstate and tunstophosphoric acid were loaded on Al2O3 and F-Al2O3, respectively,to prepare corresponding catalysts. The samples were characterized by XRD, IR, N2 physisorption, XPS and TEM techniques. The characterization results showed that fluorine modification notably decreased the amounts of hydroxyl groups on alumina support and lowered the isoelectric point of support; compared with that of ammonium metatungstate solution, the pH value of tunstophosphoric acid solution was lower, which favors the adsorption of tunstophosphoric acid anions on the support. On the oxidic or sulfided catalysts, the presence of closely-bonded and well-dispersed tungsten species on support impeded the formation of (pseudo-) boehmite under hydrothermal conditions, but could not avoid the formation of aluminum fluoride by reaction of fluoride and alumina. The catalyst prepared by matching tunstophosphoric acid and F-Al2O3 exhibited better HDS activity for 4, 6-DMDBT than the other catalysts, due to higher degree of W sul?dation and more shorter WS2 slabs with proper stacking number.

STUDY ON STRUCTURAL PARAMETERS AFFECTING EVAPORATION LOSS OF ALKYL AROMATICS

2019, 50(10):  8-12. 

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Considering the close relationship between the evaporation loss and boiling point of base oil at lower pressure and the shortcomings of existing analysis methods, the structures of 106 kinds of alkylaromatics and their boiling points at 1 333.22 Pa were collected. Based on the data, the Eigenvalues of microstructures such as energies of frontier obitals and charge distributions and topological indexes were calculated by molecular simulation method. GFA method was selected to elucidate the relationship between the structures of alkyl aromatics and their boiling points at 1333.22Pa pressure, resulting in a quantitative equation with the square of correlation coefficient of 0.978 and the square of cross-validated coefficient of 0.962, which means that the equation has a strong predictability for boiling points of alkylaromatics at 1333.22Pa pressure, so as for its evaporation loss. The equation has clear physical meanings, which showed that LUMO-HOMO gap，molecular polarizability, and radius of gyration of alkyl aromatics were the three main structural parameters for prediction of boiling point at 1333.22Pa pressure. The narrower the LUMO-HOMO gap, the higher the molecular polarizability and the larger the radius of gyration, then the higher the boiling point at 1333.22Pa pressure, the greater the evaporation difficulty and the lower the evaporation loss. The established equation with these three structural parameters could be used to predict the boiling points of alkyl aromatics at 1333.22Pa pressure accurately.

SYNTHESIS OF ZSM-5 ZEOLITE BY A TWO-STEP CRYSTALLIZATION METHOD IN TEMPLATE-FREE SYSTEM

2019, 50(10):  13-17. 

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ZSM-5 with well-defined crystallinity was synthesized by a two-step crystallization method in a template-free system using sodium silicate as a silica source. The effects of the cystallization time at lower temperature and at higher temperature and the effect of introduction of NaCl on crystal morphology and the final crystal size of ZSM-5 were systematically studied. The synthesized samples were investigated using XRD, SEM and N2 adsorption and desorption techniques. The results showed that two-step crystallization method could control the crystal size and size distribution of ZSM-5. The optimum time duration for nucleation at lower temperature and higher temperature were 5 h and 4 h, respectively, under such conditions, the synthesized sample had the smallest grain size. The crystal size of ZSM-5 was decreased by introduction of NaCl. When the range of n（NaCl）/n（Al2O3）was 10-30, the synthesized ZSM-5 had the smaller crystal size and higher crystallinity.

EXPERIMENTAL STUDY AND DYNAMIC SIMULATION OF SURFACTANT ENHANCED OIL RECOVERY MECHANISM

2019, 50(10):  18-24. 

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Three surfactants were selected: sodium dodecyl sulfate (SDS), cetrimonium bromide (CTMAB), and polyglycerol fatty acid ester (PGFE) for evaluation of oil rheology, interfacial tension and oil-displacement effect on Liaohe crude oil. The molecular simulation was used to explore the oil-displacement of surfactants in multi-systems. The results showed that: (1) The order in which surfactants improved the rheological properties of crude oil from high to low is SDS>PGFE>CTMAB; (2) When the mass fraction of surfactant added was 0.3%, SDS had the lowest interfacial tension of 1.03×〖10〗^(-2)mN/ m, and the oil-displacement efficiency was as high as 87.3%; (3) The order of density reduction ability in molecular simulation was: CTMAB<PGFE<SDS; (4)The radial distribution function (r)of each crude oil system showed that the highest peaks of the four crude oil systems were at r=0.12nm, compared with the peak of the blank crude oil system of 11.432 nm. The highest peaks of the CTMAB system, PGFE system and SDS system were 10.084, 9.902 and 8.047 nm, respectively. The lower the position of peak r, the weaker the interaction between crude oil and rock. SDS had the best oil-displacement performance. The simulation results were in agreement with the experimental results, explaining the mechanism of oil-displacement by surfactant.

STUDY OF HYDROTREATING OF FISCHER-TROPSCH WAX

Liu Dongyang Shi Weiwei Cao Zubin Qiao Haiyan Cao Chuanyang Lv Na

2019, 50(10):  25-30. 

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Fischer-Tropsch wax was divided into light wax oil and heavy wax oil fractions under vacuum distillation. The self-made W-Mo-Ni catalyst was used to hydrogenate the oxygenated compounds and the olefins in samples to prepare the Fischer-Tropsch waxes with low oil content and high drop melting point. The effects of reaction temperature and pressure on the oil content of refined wax were studied. The carbon number，molecular structure and crystal structure of samples were analyzed by high temperature gas chromatography，Fourier transform infrared spectroscopy and XRD. The results showed that under the hydrotreating reactions at 6.0 MPa，260 ℃ for the light wax oil，and at 320 ℃ for the heavy wax oil，the oxygen removals of the two Fischer-Tropsch wax fractions were 95.86 % and 94.90 %， the melting points of 72 ℃ and 112 ℃，oil content of 0.76 % and 0.09 %, and carbon number distributions of 19-29 and 26-120，respectively.The FT-IR analysis indicated that the hydrotreated wax mainly composed of long chain normal paraffins.

CATALYTIC CRACKING OF NAPHTHA OVER NOVEL ZEOLITES FOR MAXIMIZING LIGHT OLEFINS YIELD

Wu Yufan Wang Lixia Tian Huiping Chen Junwen

2019, 50(10):  31-37. 

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Catalytic cracking of naphtha（NCC） was carried out in a fixed bed micro-activity test unit. A series of zeolites with different pore structures was investigated，namely HZSM-5，HIM-5，HEU-1 and HAl-ITQ-13. The structural and acidic properties of these zeolites were characterized by XRD，SEM，N2 adsorption-desorption and Py-IR. The results showed that HAl-ITQ-13，HEU-1 and HIM-5 increased the naphtha conversion compared to HZSM-5. The light olefins（ethylene＋propylene＋butylene） yield of HAl-ITQ-13 and HEU-1 increased 13.3 and 8.6 percentage points respectively，compared with HZSM-5. High catalytic activities of HAl-ITQ-13 and HEU-1 were ascribed to smaller pore size and lower concentration of acid sites. HIM-5 can not stimulate the production of light olefins with the light olefins yield lower than HZSM-5 by 3.5 percentage points. Additionally，the reactivity of propylene under NCC reaction conditions was investigated. It was found that propylene was an active product under NCC reaction conditions. The main products of propylene catalytic transformation included ethylene，propane，butylene. The suppression of hydrogen transfer reactions was critical for maximizing light olefins yield. When developing NCC new materials，the structural and acidic properties of zeolites should be considered thoroughly due to their great effects on the secondary reactions.

Zn MODIFICATION OF HGaZSM-5 AND ITS CATALYTIC PEFORMANCE IN METHANOL TO AROMATICS REACTION

2019, 50(10):  38-45. 

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GaZSM-5 zeolite was prepared by hydrothermal synthesis method followed by acid exchange and pelletization. A series of zinc modified GaZSM-5 zeolites was prepared by wet impregnation, mechanical mixing and ion exchange, denoted by WI, PM and IE, respectively. The catalysts were characterized by XRD, SEM, FT-IR, XPS, ICP, low temperature N2 physical adsorption and desorption, NH3-TPD and Py-IR. The catalytic performance in the reaction of methanol to aromatics was evaluated in a fixed bed reactor. The results indicated that preparation method had no effect on the crystal structure but regulated the pore distribution. The zinc modification decreased the strong acid amount, weakened strong acid and enhanced the ratio of L acid to B acid. There were two kinds of zinc species, i. e. ZnO species on the crystal surface and non-framework Zn species with strong interaction with the framework, both of the two zinc species could increase the aromatic selectivity. The catalyst with zinc mass content exceeding 3.0% made by wet impregnation would deactivate quickly. The catalyst made of mechanical mixing method had the average aromatics selectivity of 44.39% at 216 h operation due to the best effective synergetic of B acid sites and zinc active sites.

PREPARATION OF MESOPOROUS Y ZEOLITE BY TEMPLATE METHOD AND ITS APPLICATION IN CATALYTIC CRACKING

Zhao Jun Wang Genggeng Hu Jie Liu Baijun Liu Dongfeng

2019, 50(10):  46-51. 

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The mesoporous Y zeolites were prepared by hydrothermal synthesis method with three block polymer（F127）or cationic surfactant cetyl trimethylammonium bromide（CTAB）as template. The samples were characterized by XRD，SEM，TEM，N2 adsorption and desorption，and NH3-TPD. The catalytic cracking properties of the catalysts synthesized were evaluated in a micro-activity test unit，and light diesel was used as feedstock. The results of XRD and SEM showed that the hierarchical Y zeolites prepared using template had no difference in the structure and morphology with conventional USY. The analysis of N2 adsorption and desorption isotherms and NH3-TPD demonstrated that the mesoporous volume and total acid sites increased with the addition of templates. Compared to conventional catalyst CAT，the catalyst F-MCAT preparaed by F-MUSY using F127 as templates exhibited a better catalytic cracking property，and the micro-activity was 3.89 percentage points higher than that without template. It is concluded that the abundant mesopores volume and appropriate acidity have a stimulating effect on catalytic activity.

RESEARCH ON PRO-HYDROTREATING OF MID-LOW TEMPERATURE COAL TAR IN SLURRY-BED

Zhu Yuanbao Xin Jing Hou Zhanggui Zhang Haihong

2019, 50(10):  52-56. 

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The pro-hydrotreating of mid-low temperature coal tar was conducted in a magnetic-stirred autoclave to simulate the reaction situation of the slurry-bed. Using the self-designed heterogeneous catalyst LN，the effect of reaction conditions on product distribution and the conversion of toluene insoluble was explored. The results showed that the yield of light oil was improved with the increase of the temperature and the initial hydrogen pressure. At a reaction tenperature of 460 ℃, a initial pressure of hydrogen of 16.0 MPa, a addition od catalyst of 3.0 %，and a reaction time of 10 h, the yield of light oil and the conversion of toluene insoluble reached 54.21 %，86.5 %，respectively. The product distribution was significantly improved.

APPLICATION OF HIGH PRESSURE HYDROGEN STRIPPING TECHNOLOGY IN FULL HYDROGENATION PRODUCTION PROCESS OF LUBE BASE OIL

2019, 50(10):  57-61. 

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Full hydrogenation lube base oil production unit usually include hydrotreating, hydrodewaxing and hydrofinishing. As noble metal catalysts are mostly used in hydrodewaxing and hrdrofinishing section, to avoid catalyst poisoning, sulfur and nitrogen content in recycle gas and feed is strictly restricted. As a result, hydrodewaxing and hydrofinishing sections are usually arranged in series downstream the hydrotreating sections. Normal full hydrogenation lube base oil production unit require two separated high pressure reaction systems and relative high pressure equipment. Two-stage technology requires longer process and more equipment. The traditional full hydrogenation lube base oil production unit consists of two reaction stages, 1st stage hydrotreating and 2nd stage hydrodewaxing-hydrofinishing. Using the high pressure hydrogen stripping technology, the two reaction stage was integrated into one-stage series system, which coude optimize the original process and reduce land occupation, with the investment saved by 8% and the total unit energy consumption reduced by 12%.

EFFECTS OF CO IN HYDROGEN ON CATALYST PERFORMANCE FOR TOLUENE DISPROPORTIONATION AND TRANSALKYLATION

Li Shiwei

2019, 50(10):  62-66. 

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The effects of  hydrogen from PSA, ethylene units and reforming unit on the performance of HLD-001 and HAT-099 catalyst for toluene disproportionate and transalkylation were analyzed. The results indicated that the reaction temperatures for catalyst HLD-001 increased from 362 ℃ to 378 ℃ after using hydrogen from reforming unit, replacing hydrogen from ethylene unit ,the total conversion ratio reduced by 0.23 percentage point, and the conversion ratio of C10 aromatics reduced by 6.83 percentage points; after using hydrogen from reforming unit, the reaction temperature for catalyst HAT-099 increased from 356 ℃ to 378 ℃, the total conversion ratio reduced by 1.58 percentage points and the conversion ratio of C10 aromatics reduced by 4.3 percentage points. It is concluded that the CO in the hydrogen from reforming unit has a great influence on the catalyst activity.

OPERATION PROBLEMS OF S Zorb UNIT AND COUNTERMEASURES

2019, 50(10):  67-72. 

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The S Zorb unit of SINOPEC Zhenhai Refining & Chemical Company is a 0.90 Mt/a FCC gasoline desulfurization unit. After the start-up in June 2018, it was found that the desulfurization activity was insufficient, the fine powder content of the adsorbent was greatly increased, and the zinc silicate content in the system was abnormal, even up to 15%. The pressure difference of the regenerative flue gas filter increased rapidly, close to the interlocking value of 65 kPa, which seriously affects the normal operation of the unit. The analysis and verification indicated that the main reason for the deactivation was the quality of the adsorbent decreased due to more hydrocarbons on the adsorbent. On the other hand, the fluidization state in the reactor was not good. By measures of replacing adsorbent, reducing the amount of hydrocarbons in the adsorbent, improving the fluidization state of the reactor, adjusting the circulation rate and regeneration temperature, the desulfurization activity, amount of fine powder, zinc silicate content and regenerative flue gas filter pressure difference were gradually improved.

STUDY ON DEWAXING TECHNOLOGY FOR RUBBER EXTENDER OIL PRODUCTION FROM NAPHTHENIC OILS

Quan Hui Yao Chunlei Zhang Zhiyin Sun Guoquan

2019, 50(10):  73-76. 

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Hydrodewaxing and hydroisomerization for rubber extender oil production were compared using two kinds of typical naphthenic VGOs. The test results proved that the hydroisomerization process was better than hydrodewaxing process in aspect of product yield and quality, and is the preferred technology for rubber extender oil production from naphthenic oils.

DEVELOPMENT OF SM/GF-4 GASOLINE ENGINE OIL

2019, 50(10):  77-82. 

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SM/GF-4 additive package and SM/GF-4 5W-30 gasoline engine oil formulation technology were developed by SINOPEC Research Institute of Petroleum Processing. The simulation tests and physical and chemical properties of the oil met all requirements of SM/GF-4 specifications. The dosage of the SM/GF-4 additive package was 7.5% (w). Through MTM and HFRR friction and wear tests, the anti-friction and low temperature anti-wear properties of the newly developed SM/GF-4 5W-30 oil were evaluated. Glycerol monoolete additive still had good friction reducing performance after aging. The piston deposit after sequence IIIG engine test, which evaluate the high temperature oxidation property of engine oil, was studied by X-ray photoelectron spectroscopy. The results showed that the piston deposits mainly contained sulphated ash of engine oil besides carbon deposit.

INFLUENCE OF SYNTHETIC ESTERS MOLECULAR STRUCTURE ON MUTUAL SOLUBILITY OF ESTERS AND REFRIGERANTS

2019, 50(10):  83-87. 

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The critical intersolubility temperatures of trimethylolpropane complex esters, pentaerythritol complex esters and dipentaerythritol esters with refrigerants (R22, R134a and R410A) were measured. Then the influences of polyhydric alcohol, binary acid and monoacid in complex esters on intersolubility of refrigerants were analyzed. Meanwhile, the effects of straight chain fatty acids and branched chain fatty acids in dipentaerythritol esters on solubility of refrigerants were also studied. Results showed that the intersolubilityof complex esters with refrigerants were mainly influenced by the basic molecular structure of the esters. The structural changes of polyhydric alcohols, binary acids and monoacids had no significant influence on solubility with R22, R134a and R410A. The basic molecular structure of dipentaerythritol ester is the decisive factor for excellent solubility with refrigerants. The dipentaerythritol ester containing more and longer straight chain fatty acids showed worse solubility with R134a. The more and the shorter branched chain fatty acids in dipentaerythritol ester, the lower the critical intersolubility temperature, and the stronger intersolubility with R134a.

INFLUENCE OF SYNTHETIC ESTER ON WET FILTERABILITY OF TURBINE OIL

2019, 50(10):  88-92. 

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The effects of three different ester cosolvents on the filtrability of two different viscosity grades base oils were investigated. The results showed that the wet filtration of the two base oils was improved by the addition of synthetic ester cosolvent, and the content of synthetic ester had no influence on the wet filtration of the two base oils.

DEVELOPMENT AND APPLICATION OF ENVIRONMENT-FRIENDLY RUBBER PLASTICIZER A1220

2019, 50(10):  93-97. 

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The environment-friendly rubber plasticizer A1220 derived from vacuum distillates of naphthenic base was prepared through hydrodeacidification -furfural refining combined process, and its application performance in SBR and radial tire tread rubber was evaluated. The results showed that the rubber plasticizer A1220 prepared met the requirements of national specification GB/T 33322-2016, and the index of SBR1763 filled with rubber plasticizer A1220 was similar to that of traditional SBR1712, which met the quality requirements of SBR superior grade. The rubber plasticizer A1220 was applied well in radial tire tread rubber and the indexes were similar to foreign TDAE products. The application performance of rubber plasticizerA1220 met the requirements of radial tire tread rubber.

ANALYSIS AND SOLUTION OF CORROSION PROBLEM IN AROMATICS EXTRACTION UNIT

2019, 50(10):  98-102. 

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Aiming at the corrosion problem of sulfolane-solvent-based aromatics extraction unit, the conditions and characteristics of corrosion were analyzed from three aspects: process conditions, raw material properties and solvents through field investigation. The composition of corrosion samples was analyzed and the aromatics extraction process was simulated. Simulation of adsorption, chloride ion distribution, corrosion and solvent regeneration were conducted to find the solutions. The results showed that the sulfolane decomposition products and the chlorine in raw materials were the main causes for corrosion; anionic resin could effectively improve the pH value of solvents and reduce corrosion; chloride ions were mainly concentrated at the bottom of regeneration tower. Regular cleaning of the residual liquid at the bottom of regeneration tower could effectively reduce the chlorine content of solvents, which is conducive to solving the corrosion problem. It is concluded that using stainless steel can prevent corrosion effectively.

APPLICATION OF SCR IN RFCC FLUE GAS DENITRIFICATION

Zhou Ziyang Guan Yongheng

2019, 50(10):  103-107. 

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In order to meet the new requirements of environmental protection standards, SINOPEC Guangzhou Petrochemcal Company installed an selective catalytic reduction (SCR) system in the coal-saving section of the CO boiler to improve the denitration efficiency of the flue gas of RFCC unit in 2017. The application status of the project showed that the denitration efficiency was obviously improved after the SCR system was installed, and it would not lead a high pollutant concentration to the subsequent flue gas desulfurization waste water. The content of NOx components dropped from 162.9 mg/m3 to 58.4 mg/m3, which could reach the special limit emission standards for sensitive areas in the Petroleum Refining Industry Pollutant Emission Standard GB 31570-2015.

PROGRESS OF TREATMENT TECHNOLOGY OF CAUSTIC SLUDGE FROM REFINERY OR ETHYLENE PLANT

2019, 50(10):  108-114. 

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Caustic sludge generated from refinery and ethylene plant is considered as waste which contains excessive amount of alkaline, COD, sulfide, salt and nonbiodegradable organic compounds. It is suitable to be pretreated first and then into the sewage treatment field. Sulfuric acid neutralization-acidification is a a simple and traditional pretreatment method with low investment and operating cost, which can remove sulfide and several organic matters. However COD is still high and a large amount of malodorous gases is produced in the neutralization process. Increasing the extraction or biological aeration pretreatment on the basis of neutralization acidification can improve the COD removal rate, but still does not solve the problem of odor pollution. Wet air oxidation-SBR (sequencing batch reactor activated sludge process) pretreatment method has solved the odor pollution problem in caustic sludge neutralization process. All the pretreated caustic sludge can be treated in the sewage treatment field, but the oxidized tail gas has a small amount of odor and VOCs emissions, and its investment and operating cost is higher. Caustic sludge neutralization-acidification sulfur recovery and gas water purification technology is depended on the existing sewage treatment field in the factory, MDEA hydrogen sulfide recovery system, and VOCs exhaust gas treatment device. Through the newly established caustic sludge neutralization-acidification and nitrogen blowing reaction precipitator and blowing off hydrogen sulfide absorption tower, several goals can be achieved with relatively lower investment and operating cost, such as treated neutralized wastewater to meet discharge standards, hydrogen sulfide and VOCs recovery, high level purification of exhaust gas to meet the standard emissions.