Table of Content

12 June 2018, Volume 49 Issue 6

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STUDY ON RHT TECHNOLOGY FOR DEEP DESULFURIZATION OF RESIDUE

2018, 49(6):  1-4. 

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Hainan RDS feedstock and the third generation RHT series catalysts were used for studying RHT process. The optimized catalyst grading and the calculated metal capacity of RHT graded catalysts were investigated. The process experiments were conducted using the best gradation of catalysts and the results indicated that to produce hydrotreated oil with sulfur content lower than 0.20%, the volume space velocity is at least reduced to 0.20 h-1. The stability test to produce hydrotreated oil with the sulfur content lower than 0.17% showed that using the optimized catalysts gradation and the appropriate process conditions (the partial pressure of hydrogen of 15.0 MPa, the standard state volume ratio of hydrogen to oil 700, the volume space velocity 0.20 h-1), the average deactivation rate of third generation RHT series catalysts is 0.082 ℃/d from 1 000 h to 2 000 h, which meets requirement for the long period operation.

EXPERIMENTAL STUDY OF LOW-RANK COAL PYROLYSIS AND CHAR GASIFICATION IN FIXED FLUIDIZED BED REACTOR

2018, 49(6):  5-10. 

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The pyrolysis characters of three kinds of low-rank coals and gasification performance of their char were studied in a fixed fluidized bed reactor. The effect of sample particle size, reaction temperature, time，and the content of O2 in fluidizing gas on test results were explored. The suitable reaction conditions for circulating fluidized bed pyrolysis coupled with gasification process were determined. The results showed that the sample particle size could hardly affect the pyrolysis process. The gas yield of coal pyrolysis increased and the char yield decreased with the increase of temperature in steam atmosphere. The highest tar yield was achieved at 600 ℃ and 20 min. The effective gas yield of circulating fluidized bed pyrolysis coupled with gasification process which can produce tar simultaneously was higher than that of coal gasification in fixed fluidized bed reactor. The higher the temperature of gasification was, the higher the effective gas yield and carbon conversion yield was. The O2 content had a little influence on syngas yield but could adjust the relative content of CO and H2 in the experimental range. It can be obtained an ideal syngas yield and effective carbon conversion yield at 900 ℃ and 15 min.

STUDY ON RHT TECHNOLOGY FOR DEEP DESULFURIZATION

2018, 49(6):  11-17. 

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In order to solve the problem of low load of hydrocracking unit and poor quality of secondary diesel, SINOPEC Beijing Yanshan Company adjusted the feedstock compositions of hydrocracking unit by blending a certain proportion of FCC diesel or coker diesel. The two solutions were compared. Blending coker diesel as feed, the outlet temperature of the second bed of refining reactor decreases by about 8.6 ℃, the total temperature drop of refining reactor declines by 19.4 ℃. The total pressure drop of refining and cracking reactors decreases. When the conversion is 68.0%, the hydrogen consumptions of blending FCC diesel and coker diesel are 3.48% and 3.10%, respectively. Aromatics content in aviation fuel is down from 15.7% to 6.1%, the smoke point increases 1.5 mm, the yield of diesel increases 7.26 percent points, the cetane number rises 3 points, and the BMCI value of tail oil reduces by 0.7, the overall energy consumption showed a slight increase of 1.6 MJ/t.

RVAMPING SEMI-REGENERATION REFORMING UNIT TO SCCCR PROCESS

Wang Ting Yuan Zhongxun

2018, 49(6):  18-22. 

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A semi-regeneration reforming unit was relocated and revamped to a counter-current continuous catalytic reforming configuration. The method and the effectiveness were discussed in terms of product quality, facility revamp, utility, energy consumption, investment, and technical economy. As a conclusion, SCCCR configuration is one of the best solutions for upgrading of semi-regeneration reforming process.

REVAMPING GASOLINE AND DIESEL HYDROTREATING UNIT USING MHUG TECHNOLOGY TO PRODUCE NATIONAL V DIESEL

Wu Zhenhua

2018, 49(6):  23-27. 

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The No.1 gasoline and diesel hybrid hydrotreating unit in Tahe Refining and Chemical Co. Ltd. was revamped according to MHUG technology developed by RIPP. The process configuration is composed of hydrogenation and then hydro-upgrading sectors. A new hydrofining reactor was added as the first reactor loaded with RN-410 refining catalyst. The original reactor is transformed into a hydrotreating reactor as a second reactor loaded with RIC-3 upgrading catalyst and post-refining catalyst RN-410. The China V diesel is successfully produced, the cetane number increases from 40 of feed to about 51.2 of the product，the sulfur content of less than 5 μg/g，and the PAHs is only 1.8%. The device is stable under full load conditions.

NEW PROCESS FOR RECOVERING C2+ FROM REFINERY DRY GAS

Bai Yuchen Gao Song

2018, 49(6):  28-32. 

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The basic principle and process of cold oil absorption method and PSA method in dry gas recovery plant was compared. A coupled process technology of PSA and cold oil absorption for recovering C2+ was introduced. Taking a dry gas unit as an example，the technical characteristics of this new method was discussed in terms of process configuration，energy consumption and area. Compared with the traditional dry gas recovery method，the coupled process technology of PSA and cold oil absorption has advantages in low energy consumption，greatly reduced amount of absorbent，and low plant installation cost.

HYDROISOMERIZATION OF PARAFFINIC BASED DIESEL FRACTION

2018, 49(6):  33-36. 

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Hydroisomerization of paraffinic base diesel fraction over a hydroisomerization catalyst was conducted in a fixed-bed reactor of pilot plant under different conditions. Results indicated that within a certain temperature range the hydroisomerization reaction and hydrocracking reaction are increased with increasing reaction temperature. While the hydroisomerization reaction and hydrocracking reaction is suppressed as the reaction pressure or space velocity increases. Although the hydroisomerization activity decreases with increasing reaction pressure, the same solidification point reduction can be reached by raising reaction temperature. While the yield of diesel fraction changes a little. Compared with catalytic dewaxing, the yields and cetane index of diesel are significantly higher in the case of hydrodewaxing when the solidification point of diesel is close.

TWO STAGE FURFURAL EXTRACTION PROCESS FOR PRODUCING HIGH AROMATIC RUBBER PLASTICIZER

2018, 49(6):  37-41. 

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CNOOC SZ36-1 vacuum 3rd line fraction was used as raw material to produce rubber plasticizer by using two stage furfural extractions in laboratory. The results showed that the reverse order process could produce the rubber plasticizer meeting the specification of A1820 according to the national standard GB/T 33322-2016 and the yield is 26.8%. The actual operation of the industrial unit verified the laboratory results. The properties and yield of industrial product are both slightly better than laboratory.

APPLICATION OF CERAMIC MEMBRANE FILTRATION AND PURIFICATION TECHNOLOGY IN COAL TAR

2018, 49(6):  42-45. 

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In order to meet the requirements of domestic coal tar hydrogenation process, 50nm ceramic membrane was used to filter the coal tar in this study. The results showed that the optimum filtration temperature is 140℃ and the optimum operating pressure is 0.3 MPa. The removal rate of heavy metal, ash and water can reach 90%. After cleaning the membrane the flux recovered to 90%.

HYDROTHERMAL STABILITY AND CATALYTIC CRACKING PERFORMANCE OF Y ZEOLITES MODIFIED BY ZIRCONIUM

2018, 49(6):  46-50. 

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Zirconium modified Y zeolites were prepared by impregnation with anhydrous-ethanol and aqueous ion exchange method, respectively. The samples were characterized by X-ray diffraction (XRD), nitrogen adsorption desorption, solid-state nuclear magnetic resonance(27Al MAS NMR) spectroscopy and Fourier transform infrared(FT-IR). The results indicated that zirconium modified Y zeolites have better microporous structure and higher thermal stability, and it is difficult for zirconium to replace framework Al of zeolites. The anhydrous ethanol impregnation method is more favorable for zirconium to enter into the cages of the zeolites and interact with the framework tetrahedral, so the prepared zirconium modified Y zeolite shows high crystallinity, specific surface area, and hydrothermal stability. The catalyst contained zirconium modified Y zeolite has high heavy oil conversion ability and gasoline yield, and has stronger resistance to heavy metal pollution.

FACTORS AFFECTING PERFORMANCE OF ETHYLBENZENE ISOMERIZATION CATALYST

2018, 49(6):  51-55. 

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The conversion of ethylbenzene to xylene was studied. The effects of metal dispersion, physical and chemical properties of the carrier，and the strength of B acid on the isomerization of ethylbenzene were investigated. The results showed that the conversion ability of ethylbenzene reaches the best level when the dispersion of platinum is 7.1 %. The size of carrier particles has a great influence on the dispersion of metal, and the conversion of ethylbenzene increases with the decreases of carrier particles and increases of metal dispersion. The ethylbenzene conversion capacity is different with structures of molecular sieves. When the ammonia desorption temperature is 350 ~ 450 ℃, the ethylbenzene conversion rate increases due to increase of B acid amount. Based on the above studies, a new type of catalyst RIC-270 for isomerization of C8 aromatics was developed by Research Institute of Petroleum Processing of SINOPEC. The industrial results showed that compared with RIC-200 catalyst, the ethylbenzene conversion capacity of RIC-270 is obviously improved, and ethylbenzene conversion reaches 81.7 % at equilibrium. The lower content of C8 non-aromatics effectively improves para-xylene content in the reaction product.

EFFECT OF Ni/Mo RATIO ON STRUCTURE OF Ni-Mo NITRIDE AND PROPANE AMMOXIDATION REACTION

2018, 49(6):  56-60. 

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Ni-Mo oxide was prepared by co-precipitation of nickel nitrate and ammonium heptamolybdate. Ni-Mo nitride catalysts were synthesized by temperature-programmed nitridation reaction of Ni-Mo oxide in a mixture of H2/N2. The structure and redox properties of the Ni-Mo oxide and corresponding nitride catalysts were characterized by XRD, visible-Raman, FT-IR, and H2-TPR. The catalytic performance for propane ammoxidation was tested. The experimental results showed that Ni2Mo3N or the mixture of g-Mo2N and Ni2Mo3N can be synthesized by controlling Ni/Mo atomic ratio. These results suggested that the synergetic effect between g-Mo2N and Ni2Mo3N in the mixed Ni-Mo nitrides plays an important role in the process of propane ammoxidation. The mixed Ni-Mo nitride catalyst shows much higher catalytic activity and selectivity for ACN than g-Mo2N or Ni2Mo3N alone. The mixed NiMo nitride catalyst with 3/2 of Ni/Mo atomic ratio showed the best catalytic performance for propane ammoxidation. At 773 K, the conversion of propane is 75.0%, the selectivity and the yield of ACN are 38.6% and 28.95%, respectively.

ANALYSIS OF USED DIESEL ENGINE OIL FROM RFWT ENGINE TEST

2018, 49(6):  61-65. 

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Six used diesel engine oils from RFWT engine test were studied on changes in physical and chemical properties and were characterized by 31P-NMR. The ZDDP degradation was investigated by NMR spectroscopy and the depth etchings on the surface of RFWT test pieces was analyzed by X - ray photoelectron spectroscopy (XPS). The results showed that the available phosphorus from ZDDP, nZDDP, and dithiophosphates, the decomposition product, in early stage is the key effective anti-wear component. The lower the ratio of effective phosphorus to intermediate phosphorus, the lower the wear is. XPS surface analysis revealed a thicker anti-wear film on surface of lower wear test part by ZDDP and its degradation products serves as anti-wear protection. The film contains phosphate, sulfide and sulphate.

PREPARATION AND TRIBOLOGICAL PROPERTIES OF LUBRICATING GREASE FOR WIND POWER BEARING

Xia Yanqiu Liu Luhuan

2018, 49(6):  66-71. 

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A kind of complex lithium-based grease for wind power was synthesized using poly-α olefin (PAO40）as base oil and complex lithium soap as thickener. The effects of additives including dibutyl dithiocarbamate（T351） and amino-sulfide（T323）on the friction reduction and anti-wear abilities for steel/steel pairs were investigated by MFT-R4000 high-speed reciprocating friction and wear tester. The morphologies and typical chemical composition of the worn surfaces were characterized by scanning electron microscopy （SEM） and energy-dispersive X-ray spectroscopy （EDS）. The results showed that the prepared wind power grease exhibits preferable tribological properties compared with the imported wind power grease.

EFFECT OF AROMATIC HYDROCARBONS ON TRANSFORMER OIL PERFORMANCE

2018, 49(6):  72-76. 

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Effects of different aromatics on electrical performance, anti-oxidation, solubility, gas tendency and thermal performance of transformer oil were studied. The results showed that in certain content range, aromatics has an negative effect on electrical performance of the oil with the order of heavy aromatics>medial aromatics > light aromatics, but has little influences on oxidation stability and thermal property, while medial and heavy aromatics are less susceptible to antioxidants; the solubility of base oil is mainly affected by aromatic hydrocarbon content, independent of the type of aromatics, the higher the content, the better solubility; aromatics, especially medial aromatics shows much better gassing tendency than light and heavy aromatics. Therefore, under the premise of good electrical performance and oxidation stability, the solubility and gassing tendency of transformer oil can be improved by addition of appropriate amount of aromatics.

COMPARATIVE STUDY OF LOW TEMPERATURE SWITCHING OIL AND TRANSFORMER OIL

2018, 49(6):  77-80. 

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Low temperature switching oil and transformer oil were compared in terms of standard and product properties. The results show that the paraffin content in low temperature switching oil is higher than transformer oil, dehydrogenation is easy to occur for the switching oil in a strong electric field, generating small molecules and hydrogen, this feature is extremely advantageous to the arc extinguishing; Switching oil has excellent thermal conductivity, therefore, the cooling of oil is more effective. Switching oil has low viscosity, resulting in faster flow, so it's good for the on-off and off. Switching oil has low flash point, so it has higher gas rate and evaporation rate, which improves the arc extinguishing ability.

ADSORPTION BEHAVIOR OF QUINOLINE OR PYRIDIINE IN MODEL DIESEL OVER ALLOCHROIC SILICA GEL

Hong Xin Li Yunhe Yuan Jiacheng Zhang Dan Tang Ke

2018, 49(6):  81-86. 

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The silica gel and allochroic silica gel were c characterized by X-ray diffraction （XRD），Fourier transform infrared spectrum （FT-IR），nitrogen adsorption and NH3-TPD. The results of XRD and FT-IR indicated that the two samples are amorphous structure. The average pore diameter of silica gel and allochroic silica gel are 18.46 nm and 1.80 nm，the surface areas are 437.86 and 623.39 m2/g，the pore volumes are 0.972 4 and 0.344 2 m3/g, respectively. The results of TPD showed that the acidity of allochroic silica gel is far stronger than that of silica gel. The adsorption removals of quinoline in model diesel over alumina，diatomite，silica gel and allochroic silica gel were investigated. The experiment results indicated that the adsorption denitrification performance of allochroic silica gel is much superior to that of other three adsorbents. The stronger acidity of allochroic silica gel is helpful to enhance its removal quinoline by adsorption. Moreover，the adsorption thermodynamics for removal of quinoline or pyridine over the allochroic silica gel from model diesel were further investigated. The adsorption isotherms of quinoline and pyridine belong to S type. Experiment data was fitted Langmuir and Freundlich equations with the R of two regression equations is much the same. But the adsorption of pyridine over allochroic silica gel belongs to Freundlich adsorption model; the R of Freundlich regression equation is far more than that of Langmuir.

APPLICABILITY OF DETERMINATION OF AROMATIC HYDROCARBON TYPES IN DIESELS BY LIQUID CHROMATOGRAPHY AND MASS SPECTROMETRY TECHNIQUES

2018, 49(6):  87-92. 

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A comparison between high performance liquid chromatography coupling with refractive index detector (HPLC-RID) method and gas chromatography coupling with mass spectrometry (GC-MS) method in terms of determination of aromatics content in diesel, standard recovery rate and blending accuracy were conducted. Eight automobile diesel fuels (VI) samples were tested by the two methods. The results indicated that the blending accuracies of two methods are reliable. The standard recovery rate produces a deviation using HLPC method due to the large amount of components with different structure in real diesel fuels from the model compounds and the difference of response characteristics of the refractive index detector. Somewhat deviations also exist in the content of polycyclic aromatic hydrocarbons and total aromatic hydrocarbons obtained by HPLC.

ANALYSIS OF ORGANIC MATTERS IN REVERSE OSMOSIS CONCENTRATE OF RECYCLING WASTE WATER IN REFINERY

2018, 49(6):  93-95. 

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To study the composition of reverse osmosis concentrate is of great significance to develop waste water processing technique. The organic matters were enriched by using solid phase extraction and solid phase micro-extraction respectively,and then analyzed by GC-MS. The results showed that organic matters in the reverse osmosis concentrate mainly consists of aromatic compounds. Combined with the MS spectrum database and external standard method, several kinds of organic matters are determined. The content of benzene and methyl substituted naphthalenes are higher.

STUDY ON MICROWAVE-ASSISTED DIGESTION OF BIODIESEL FOR DETERMINATION OF TRACE ELEMENTS BY ICP-MS

2018, 49(6):  96-100. 

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A microwave-assisted digestion using diluted nitric acid and hydrogen peroxide as auxiliary agent was explored to determine trace elements in biodiesel by inductively coupled plasma mass spectrometry (ICP-MS). The effect of nitric acid concentration and volume of hydrogen peroxide on biodiesel digestion was investigated, using residual carbon content and residual acidity in final solutions as evaluation index. Results showed that 0.6 g of biodiesel was almost completely digested under the optimal conditions: 6 mL nitric acid (6 mol/L) and 2.5 mL hydrogen peroxide. The residual carbon content and the residual acidity in digests were lower than 5.3% and 6.4%, respectively. After sample digested, Ba, Cr, Cu, Mn, Mo, Ni, Pb, Sr, V and Zn were determined by ICP-MS and the recovery rate was in the range of 94.2% to 107.4%. All RSDs were less than 4.33%.