PETROLEUM PROCESSING AND PETROCHEMICALS

EXPLORATION ON CATALYTIC CRACKING OF STRAIGHT-RUN MIDDLE DISTILLATE

2016, 47(12): 1-6.

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Exploration on catalytic conversion of straight-run middle distillate was conducted in a fixed fluidized bed reactor. The results show that catalytic cracking process is a practical technology for the conversion of straight-run middle distillate into high value added products. The gasoline yield of 48% and the propylene yield of 8% are obtained in this process. While using direct catalytic pyrolysis at 620 ℃ the total yield of light olefins and BTX is above 39% and a yield of byproduct gasoline with RON 99 is approximately 22%. The higher blending ratio of straight-run with heavy oil feed for FCC improves the gasoline selectivity, but increases the aromatics content in gasoline.

ON LINE WATER WASHING TECHNOLOGY FOR SALT DEPOSITION IN RFCC FRACTIONATING TOWER　

2016, 47(12): 7-10.

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The online water washing technology is the technology for removing salt deposition in the top circulation system of fractionating tower running under the conditions of full load operation. The application results in an 800 kt/a fractionator show that the salt deposition in the upper part of fractionator is effectively controlled, leading to a stable and reliable operation in the top circulation system, and no salt deposition exists; the online water washing with different water content has no impact on the distillation range of gasoline and diesel on specification. However, the water content must be controlled more than 50% to ensure the stability of the top circulation during the process.

DUAL OIL INLETS & DUAL ELECTRIC FIELDS DESALTER/DEHYDRATOR TECHNOLOGY AND ITS APPLICATION IN DAGANG PETROCHEMICAL COMPANY

2016, 47(12): 11-16.

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A combined technologies of high speed electrical desalting technology and AC/DC electric desalting technology were originally used in Petrochina Dagang Petrochemical Company electrical desalting device with a capacity of 5 Mt/a. However, the salt and water content was unqualified. After revamping with dual oil inlets & dual electric fields technology, the salt and water content in crude oil treated is less than 3 mg/L and 0.2%, respectively with thequalified rate of 100%. The oil content in discharged sewage is less than 150 mg/L, the qualified rate is 95%-100%. The calcium content in oil treated is reduced to less than 10 μg/g when the dosage of decalcifing agent is 25-35 μg/g.

PREPARATION OF SBS MODIFIED ASPHALT FROM TAHE CRUDE OIL

2016, 47(12): 17-21.

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Using 70# asphalt of Tahe crude oil as basic material, the solution for preparation of SBS modified asphalt was determined by performance evaluation of modified asphalt with different modifier, stabilizer and compatilizer in laboratory screening tests. The industrial practice was conducted based on the laboratory solution. The qualities of the produced SBS modified asphalt meet the SBSⅠ-C requirement of JTG F40-2004 standard. The product has advantages of higher softening point and penetration index, and better anti-aging performance, being the PG78-28 grade. The rutting tests indicate that the SBS modified asphalt mixture has a better performance both at high temperature and low temperature, and good water stability, meeting JTG F40-2004 requirement.

EFFECT OF SULFUR ON DEHYDROCYCLIZATION OF n-HEPTANE OVER Pt-Re REFORMING CATALYSTS

2016, 47(12): 22-27.

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Three different platinum-rhenium reforming catalysts were prepared by conventional reduction and presulfurization, sulfur injection at low temperature during reduction and the sulfate impregnation method，respectively. The performance of dehydrocyclization of n-heptane over the three catalysts was investigated using n-heptanes as a model compound. The catalysts were characterized by TPR and pyridine adsorption Fourier-transform infrared to test the effect of sulfur introduced by different ways on the performance of dehydrocyclization of n-heptane. The results show that the catalysts prepared by sulfur injection at low temperature during reduction and the sulfate impregnation method exhibit better aromatics yields and selectivities compared to the catalyst prepared by conventional method. Especially the catalyst prepared by sulfate impregnation method reveals the highest aromatics yield and selectivity.

INVESTIGATION OF INFLUENCE FACTORS ON CRUSH STRENGTH OF DECHLORINATION AGENT

2016, 47(12): 28-32.

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The crush strength of dechlorination agent was influenced by dosage and type of binder, peptizer, extrusion aid, H2O/powder ratio, and amount of active component during preparation. The influence of different binders (polyvinyl alcohol, kaolin, and alumina sol), peptizers (nitric acid, hydrochloric acid, and acetic acid), and the extrusion aids (sesbania powder, citric acid, and oxalic acid) was tested, respectively. The results indicate that alumina sol, nitric acid and sebania powder are the most effective materials in improving the strength of the agent, their dosages are 50%, 5%, and 2.5%，respectively. The optimum ratios of H2O/powder and active component/carrier are 0.2~0.4ml/g and 1.11, respectively. With above proportions, the prepared dechlorination agent has the best strength of 150 N/cm.

EFFECT OF SILICON ON PERFORMANCE OF HYDROFINISHING CATALYST IN LUBE ISODEWAXING PROCESS

2016, 47(12): 33-36.

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The silicon was added in preparation to influence the performance of the hydrofinishing catalyst in lube hydroisomerization process. The results show that when SiO2 content is 30%, SA-30 the catalyst has a higher surface area and pore volume as well as stronger acid properties，and the best activity for aromatic saturation as well. Using the isodewaxed oil of hydrocracking tail oil as the raw oil and SA-30 as the catalyst，the best operation conditions for aromatic saturation are 230 ℃, 15 MPa, hydrogen/oil ratio of 500 and LHSV 1.1 h-1.

EVALUATION AND INDUSTRIAL APPLICATION OF PRE-HYDROTREATING CATALYST FOR REFORMING UNIT

2016, 47(12): 37-40.

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A pre-hydrotreating catalyst, developed by Daqing Petrochemical Research Center of PetroChina Petrochemical Institute, was evaluated in laboratory and applied in a 500 kt/a continuous reforming unit in Dushanzi Petrochemical Company. The results in lab show that the sulfur and nitrogen contents of the treated oil both are reduced to less than 0.5 μg/g from the 175 μg/g and 1.31 μg/g in feed, respectively at conditions of 265 ℃，2.0 MPa，H2 / oil volume ratio of 110 and LHSV of 4.44 h-1, better than reference catalyst. The results of nearly one year industrial application exhibit that the pre-hydrotreating catalyst has a higher activity for desulfurization and denitrogenation, and a lower pressure drop. The properties of pre-hydrotreated oil meet the feed requirements for reforming reactor.

EFFECT OF VANADIUM ON FCC CATALYST AND APPLICATION OF NEW ANTI-VANADIUM CATALYST

2016, 47(12): 41-44.

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Based on the deactivation mechanism of FCC catalyst by vanadium, this paper analyzed the influence of V on catalyst performance and product distribution on processing the high vanadium feedstocks. The new anti-vanadium FCC catalyst CGP-1YZ, developed by SINOPEC Research Institute of Petroleum Processing, was used in the No.2 FCC unit with capacity of 2 Mt/a in Yangzi Petrochemical Company. The industrial application results show that compared with the original catalyst, the new catalyst shows a good anti-vanadium ability, the conversion and gasoline yield increase by 9.51 and 5.67 percentage points, respectively. The catalyst consumption lowers 0.15 kg/t. The coke selectivity is significantly improved.

EX-SITU REGENERATION OF DIESEL HYDROTREATING CATALYST AND START-UP OF HYDROTREATING UNIT

2016, 47(12): 45-48.

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The unloading and ex-situ regeneration of catalyst, and restarting for 2.0 Mt/a diesel hydrotreating unit and problems occurred during these stages were introduced. The solutions for solving above problems were suggested. The calibration results indicate that the activity of the regenerated catalysts recovers well, close to the fresh catalyst. The hydrodesulfurization rate reaches 98.5%, and the sulfur content in diesel product is 170 μg/g, when a mixed feedstock of straight-run diesel and FCC diesel is processed.

DISTRIBUTION OF SULFUR TYPES IN MIDDLE EAST VGO

2016, 47(12): 49-52.

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The selective oxidation method with tetrabutylammonium periodate, separation - X ray fluorescence spectrometry, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) techniques were used to elucidate the types and distributions of sulfur compounds (thioether, thiophene, DBT, and more complex benzothiophene compounds) in Middle East vacuum gas oil (VGO) and in its 9 fractions before and after hydrotreatment. The results show that sulfidic sulfur accounts for 13.6% of the total sulfur in the VGO, the others are all thiophenic compounds. With increasing boiling point of the fractions，the contents of total sulfur, sulfidic sulfur, thiophenic sulfur and more complex compounds sulfur increase gradually, while the proportion of sulfidic sulfur in the total sulfur of the fractions increases. The alkylthiophenic sulfur, concentrated in lower boiling fractions and the alkylbenzothiophene sulfur decrease as the fraction becomes heavier. Total sulfur content in the VGO is greatly reduced after hydrotreating, the proportions of sulfidic sulfur and benzothiophenic sulfur decrease，while the proportion of more complex sulfur compounds increases. With the increase of hydrotreating depth，the proportions of sulfidic sulfur and alkylthiophenic sulfur decrease gradually and the sulfur content in complex sulfur compounds increases gradually.

DEVELOPMENT AND PERFORMANCE OF OIL SOLUBLE DEMULSIFIER FOR TAHE HEAVY CRUDE OIL

2016, 47(12): 53-58.

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Tahe heavy oil has the characters of high asphaltene content and mechanical mixture. An oil soluble demulsifier by graft copolymerization of polyether and polyacrylic acid was synthesized aiming at the properties of the crude oil. The effect of synthesis conditions, such as synthesis routes, amount of acrylic acid and initiator, and dropping temperature of acrylic acid, on the performance of product was investigated. A complex demulsifier RP-04 was then prepared by combination of the oil soluble demulsifier and an aid agent. The laboratory continuous evaluation test shows that the water content in 3 level desalting and dewatering crude treated by the RP-04 and the reference demulsifier on-the-spot is 0.09% and 0.70%, respectively，and the salt (NaCl）content is 7 mg/L and 9 mg/L, respectively. When the demulsifier RP-04 was used together with desalting aid agent, the total chloride of treated oil is reduced from16 μg/g to4.9 μg/g.

OXIDATION DETERIORATION CHARACTERISTICS OF UNSATURATED FATTY ACID METHYL ESTERS BASED ON COMPUTATIONAL CHEMISTRY AND SPECTROSCOPIC ANALYSIS

2016, 47(12): 59-63.

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The computational chemistry (Hartree-Fock, 3-21G basis) method was employed to obtain theoretical parameters of C-H bond dissociation energies and C-H bond lengths of unsaturated fatty acid methyl esters (UFAME), and then the relationship between molecular structures of unsaturated FAME and its oxidation deterioration characteristics were elucidated. Methyl oleate and methyl linoleate were used as models. The results show that the allylichydrogens(α-CH2), close to the double bond of the mode molecule, especially the α-CH2 with bis-allylichydrogens are the easy position for dehydrogenation, and the dehydrogenation at double bond (-CH=CH-) are the most difficult to occur. By analysis of the structure and composition changes of UFAME molecules in the oxidation process through FTIR and UV analysis, it is suggested that the oxidation deterioration of UFAME follows the principles of resonance effect of the radical, i.e. oxidation→resonance→double bond shift→isomerization.

CFD SIMULATION OF GAS FLOW FIELD IN GAS PIPE DISTRIBUTOR IN REGENERATOR OF FCCU

2016, 47(12): 64-69.

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A gas pipe distributor is widely used in regenerator of FCCU. However, there are problems of gas maldistribution and nozzle erosion in the pipe distributor. Therefore, the gas flow field in pipe distributor was simulated by using the CFD commercial software. The result shows that the gas velocity in each branch tube is different, depending on the length of the tube. The gas flow rate through each nozzle is also different which leads to a big inhomogeneity of gas distribution. In addition, there exists an obvious deflective flow at the inlet side of nozzle tube and non-uniform of pressure distribution, which may cause low pressure drop of nozzle, leading to catalyst entrainment into banching pipe and erosion.

STUDY ON STORAGE STABILITY OF UPGRADED OIL-SAND BITUMEN BY HYDROGEN DONOR THERMAL CRACKING

2016, 47(12): 70-75.

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The storage stability and mechanism of hydrogen donor thermal cracking (HDTC) of oil-sand bitumen was studied under different reaction conditions by investigating the changes in density，kinematic viscosity，stability，asphaltene content and toluene insoluble material content with the prolonging storage time and comparing with the results of visbreaking. The results show that the density，kinematic viscosity, content of asphaltene and toluene insoluble material increase greatly after visbreaking and hydrogen donor thermal cracking as the storage time increases, indicating the stability deterioration of the upgraded oils. Compared to the thermal visbreaking results, the increasing range of above parameters using HDTC is smaller. The spot test level of HDTC upgraded oil is not greater than No.2，which meets the stability requirements of transportation, demonstrating that the storage stability is superior to the conventional visbreaking upgrading oil after long-time storage. The main reasons for stability improvement are hydrogen donor effect and improved stability of resin system.

TRIBOLOGICAL PROPERTIES OF BASE OIL AND LUBRICANTS WITH AMMONIUM THIOPHOSPHATE IN MAGNETIC FIELD

2016, 47(12): 76-79.

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Friction and wear characteristics of 150SN base oil and oils containing ammonium thiophosphate (T307) were evaluated by an improved four-ball tester with or without magnetic fields. The morphologies of worn surfaces lubricated with tested oils were observed by scanning electron microscope (SEM), and the effect of the magnetic field, loading and T307 dosage on tribological properties of the oils was analyzed. The results indicate that the wear scar diameters in the magnetic field lubricated with the blank oil are smaller than those in non-magnetic field, the friction coefficients in magnetic field are larger than those without magnetic impact. Furthermore, the wear scar diameters and friction coefficients lubricated with T307-doped oils under the magnetic conditions are larger, indicating the negative effect of magnetic field on tribological performance of formulated oils. The magnetic field has an unfavorable effect for the formation of lubrication film on the metal surface through tribochemical reactions between T307 and metal surface.

LUBRICATING EFFECT OF SULFUR-AND PHOSPHORUS-FREE ORGANIC MOLYBDENUM ON DIFFERENT MATRIX MATERIALS

2016, 47(12): 80-86.

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Different amounts of sulfur- and phosphorus-free organic molybdenum (SPFOM) additive were added into diesel engine oil to measure the friction reduction and anti-wear properties of SPFOM on No.45 steel and GCr15 steel using SRV friction wear machine. Scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were employed to analyze the worn surface morphologies, elements with various valences. The test results show that the friction reduction property of SPFOM on No. 45 steel is improved with increasing additive amount, but the anti-wear property declines, and the wear volume is even larger than that of diesel engine oil without SPFOM when the additive amount is above 0.6%; the lubricating effect of SPFOM is much better on GCr15 steel than that on No. 45 steel, and both friction coefficient and wear volume decrease with the increasing of additive amount. Boundary lubricating film containing molybdenum and ferrous oxide is formed on the matrix surface during friction process with SPFOM in the oils, but too much SPFOM forms MoO3 particles, which increase wear volume of No. 45 steel, serious oxidation of the matrix surface, and wear trend. While the hardness of GCr15 steel is high enough to avoid the increase of wear volume, resulting in effective anti-wear for lubricating oil with SPFOM.

INFLUENCE FACTORS ON CORROSIVE SULFUR TESTING FOR ELECTRICAL INSULATING OILS AND CORROSION MECHANISM ANALYSIS

2016, 47(12): 87-90.

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Influences of temperature, time and base oil types on corrosion sulfur determined for transformer oil were tested according to ASTM D1275B standard test method for corrosive sulfur in electrical insulating oils and the corrosion mechanism of sulfide was studied. It is found that the irregular operations are reasons for differences of corrosive sulfur test results between different analyzers. It was suggested for user to use lower sulfur transformer oil, to avoid local overheating as a result of transformer overloaded, and to keep the base oil unchanged when selecting sulfur-containing additives.

OPTIMIZATION STUDY FOR ENERGY CONSUMPTION OF DISTILLATION COLUMN BASED ON ABSORPTION HEAT PUMP

2016, 47(12): 91-96.

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