Table of Content

12 April 2016, Volume 47 Issue 4

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THE SELECTION AND PROCESSING PERFORMANCE RESEARCH OF A RECIPE OF CRUDE OIL WHICH A REFINERY WILL PROCESS INSTEAD OF DAQING MIXED CRUDE OIL

2016, 47(4):  1-6. 

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An alternative crude oil selection method which combines with the refinery mathematical programming modeling method and the selection of recipe of crude oil method is developed. This method is used to solve the problem of a large fuel-lube based refinery of which supply of Daqing tube-mixed oil is about to stop. Two kinds of planning cases have been calculated in mathematical programming model to determine which recipe of import crude oil is the appropriate one to replacing the existing Daqing tube-mixed oil. One kind of planning cases is calculated under the condition of lubricant base oil production, the other is calculated under the condition of no lubricant base oil production. The article results show that the recipe of import crude oil which selected by the method described in this article is not only suitable for the refinery process characteristic and the constraints of crude oil transmission, the supply of crude oil resources is also guaranteed, and the price and implementation of the oil also has advantages. The appropriate alternative crude oil can significantly improve the economic benifits of the refinery for 25-137 yuan per ton.

CYCLE PREDICTION BASED ON ANALYSIS OF LONG-TERM OPERATION OF DIESEL HYDRO-UPGRADING PROCESS UNIT

2016, 47(4):  7-11. 

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In order to further understand the performance of running, analysis and forecast ofhainanrefining &chemical Co. Ltd. SINOPEC 2.48Mt / a diesel hydro-upgrading MHUG-Ⅱ,it products to meet the Ⅳand V clean diesel long-term operation. Go into operation to June 30,2015,product Ⅳ accumulated 479 days, V diesel accumulated 146 days. Operation analysis shows that the reactorof hydro-upgrading and reforming catalyst deactivation average rate was 0.015℃/d and 0.042℃/d, refining reactor catalyst deactivation average rate was 0.055℃/d, two reactors total pressure drop rise a rate of 6.4×10-4MPa/d. At the same time considering the nature of raw materials and processing changes in the proportion, the product Ⅳ&V rotation effect the catalyst life and reactor pressure drop. To predict the refining reactor catalyst then run 620 days to reach the regeneration cycle or exchange.

NUMERICAL SIMULATION OF NEW HYBRID ATOMIZATION PROCESS FOR COKE COOLING IN DELAYED COKER

2016, 47(4):  12-18. 

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A axisymmetric fluid solid coupled model of coke tower containing the equations of momentum and mass transfer of porous media, as well as the equivalent fluid model is developed in this paper, which is used to simulate both the traditional and a new cooling method by mixing spray with vapor in big flow unit of delayed coking. In the paper, the calculated transient temperature field of coke drum with shell model applied in pure vapor has been validated by the measured data. Meanwhile, it predicts transient temperature field of coke drum in new way of cooling, illustrates the impacts of the mass fraction of liquid water on the effects of coke drum cooling, and quantitative evaluated the vapor saving and economic cost of new process. The research results indicates that the cooling effect is first quickly improved then slow down and final restrained with the increase of content of liquid water, the optimum fraction is 0.8 to realize the best cooling effect. The article give the vapor saving percentage and annual saving cost at the liquid water fraction from 0.4 to 0.9in the condition that the pressure is 0.3MPa and the mass flow is 7.5t/h. The conclusions will be helpful for optimizing process parameters in delayed coking.

PREPARATION OF WARM-MIXED FLAME RETARDANT ASPHALT AND ITS PHYSICO-CHEMICAL PROPERTIES

2016, 47(4):  19-22. 

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Using stirring temperature, stirring speed, stirring time and the amount of warm mix additive to study the preparation technology of LKWO-Ⅱ warm mix flame retardant asphalt. Changing the amount of warm mix additive to study the influence of warm mix additive on the main technology indexes of flame retardant asphalt. The test results show that the best preparation technology of LKWO-Ⅱ warm mix flame retardant asphalt is that: stirring temperature 130℃, stirring speed 200r/min, stirring time 35min and the amount of warm mix additive is 8‰ by mass. LKWO-Ⅱ warm mix additive can reduce the softening point of flame retardant asphalt and increase the penetration and ductility of flame retardant asphalt. LKWO-Ⅱ warm mix additive can improve the low temperature performance of asphalt and remedy the disadvantage that can decrease the low temperature performance of asphalt of flame retarder.

EFFECT OF CALCINATION TEMPERATURE ON METHANOL ADSORPTION PERFORMANCE OF BINDERLESS 5A SPHERICAL ADSORBENT

2016, 47(4):  23-29. 

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The NaApellets composed of kaolin and NaA molecular sieve were calcinated,and the small pellets were successivelytreated with alkali solutionand exchanged with Ca2+solution. Samples were characterized and evaluated by TG-DTA, XRD, 27Al-NMR, methanol adsorption, nitrogen physical adsorption and pulse test. The results showedthat kaolininNaApelletswas changedintometakaolinduring calcinations at 500-700 ℃, and the latter was converted to NaAmolecular sieve after alklitreatment.When calcinated at 750 ℃,NaA molecular sieve in pellets was changed in structure and lost adsorption capacity of methol, however,afteralkali treatment, not only kaolin in pellets was converted to NaA molecular sieve, but alsothe destroyedNaA molecular sieve was repairedandhad higher adsorption capacity than uncalcinedNaA. When calcination temperature was above 800 ℃, NaAwas transformed into more stable carnegeiteand nepheline. Physical analysis and mercury intrusion showed that, NaApelletscalcinatedat750 ℃ had larger apparent bulk density and crush strength compared to thatcalcinatedbelow 700 ℃。This was because particlesin pelletsbindsmore tightly during higher temperature.

SYNTHESIS AND ADSORPTION PROPERTY OF ZSM-5 ABSORBENT FOR SEPARATING MONOMETHYL ISOPARAFFIN FROM NAPHTHA

2016, 47(4):  30-35. 

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In order to improving the utilization efficiency of hydrocarbons in naphtha, zeolites ZSM-5 was synthesized by hydrothermal method to separate monomethyl isoparaffins from naphtha. The effects of preparation conditions on the properties of zeolites ZSM-5 were investigated using 2-methylpentane/cyclohexane as separation system. The optimum preparation conditions for zeolites ZSM-5 were using n-butylamine as the template, the SiO2/Al2O3 of 80, the aging time of 36h and the crystallizing time of 48 h. The static saturated adsorption capacity of zeolites ZSM-5 synthesized in this paper was 2.39 g 2-methylpentane/(100 g) zeolite at 25 ℃, which is 20% higher than the contrastive zeolites ZSM-5. The total content of normal paraffins and monomethyl isoparaffinsin naphtha was 97.47% after the adsorption separation by zeolites ZSM-5. The potential aromatic contents of naphtha was increased from 23.19% to 34.21%.The content of 30% of normal paraffins and 12% monomethyl isoparaffins was separated from naphtha with synthesized zeolites ZSM-5.

SYNTHESIS AND PERFORMANCE OF NEW OIL-SOLUBLE ASPHALTENE DISPERSANTS FOR XINJIANG HEAVY OIL

2016, 47(4):  36-41. 

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To solve the serious asphaltene deposition problem of Xinjiang heavy crude oil，two new oil-soluble asphaltene dispersants were designed and synthesized with polyisobutylene succinic anhydride, aniline, aminophenol. The inhibitory effect of the obtained dispersants on asphaltene deposition was evaluated by spectrophotometry and microscope methods. The results show that the asphaltene dispersant PA2 which has a phenolic hydroxyl head group performs better than PA1 which has a phenyl head group. The optimum reaction conditions of PA2 are obtained as follows: 1.2:1 of n(p-aminophenol): n(polyisobutylene succinic anhydride), 120 ℃ of reaction temperature and 6 hours of reaction time．When the dosage of PA2 dispersant is 200 mg/L, the asphaltenes flocculation onset of Xinjiang heavy crude oil can be increased from -19.87 to 8.63.

NUMERICAL SIMULATION OF EFFECT OF WALL ROUGHNESS ON PARTICLE DEPOSITION IN FCC FLUE GAS TURBINE

2016, 47(4):  42-48. 

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The standard k-ε model and discrete particle model (DPM) were used to simulate the process of collision and deposition in FCC flue gas turbine. We mainly investigate the effects of surface roughness on particles deposition. The suction surface of blade has a significant deposition than pressure surface. The area near the inlet of blade on the suction surface deposit a lot, as well as the area near the casing and hub on the pressure surface. Compared with the coating surface without fouling, the wall roughness alleviates deposition of pressure surface when it is between 100 μm and 500 μm, but aggravates the deposition of suction surface.

SYNTHESIS OF ZEOLITE ZSM-22 USING PSEUDO BOEHMITE AS ALUMINUM SOURCE

2016, 47(4):  49-54. 

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In the proposed boehmite as aluminum source, synthesis conditions investigated alumina ratio, the amount of seed, inorganic bases, crystallization time, crystallization temperature, water and other by hydrothermal crystallization method for the synthesis of zeolite ZSM-22 affected. Using XRD (X-ray diffraction), SEM (scanning electron microscope) and other characterization methods for the synthesis of the samples were characterized. Experimental results show that the crystallization temperature of 413-433 K, the crystallization time is 48 h, the seed addition amount of 1 500 μg/g, SiO2/Al2O3 mole ratio of 70-130, (1,6-hexanediamine) DAH/SiO2 is 0.3, H2O/SiO2 from 35-50, no inorganic base crystallinity can be synthesized ZSM-22 zeolite good.

HYDROISOMERIZATION OF n-HEPTANE OVER Ni2P/SAPO-11 CATALYST

2016, 47(4):  55-59. 

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Ni2P/SAPO-11 catalysts were prepared by the decomposition of nickel hypophosphite impregnated on SAPO-11 supporter through excessive impregnation method. Their properties were characterized by means of N2 sorption-desorption, XRD, HRTEM. The effects of reaction conditions and the nickel phosphide content on hydroisomerization performance of n-heptane were investigated in a fixed-bed reactor. The results showed that Ni2P supported on SAPO-11 molecular sieve had quite highisomerization selectivity, however, the isomerization activity and aromatization selectivity were relatively loweras compared with the Pt-based catalystssupported on SAPO-11. The optimum load of Ni2P on SAPO-11 molecular sieve was 4%. Under the optimal conditions as follows: temperature of 400 ℃, pressure of 0.5 MPa, H2/CH(volume ratio) of 500 and LHSV of 1 h-1, the conversion of n-heptane and the isomerization selectivity reaches 73% and 90% respectively.

ALKYLATION OF TOLUENE WITH METHANOL OVER ZSM-5/SBA-15 CATALYST

2016, 47(4):  60-64. 

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The micro-mesoporous composite molecular sieves of ZSM-5/SBA-15 composite sieves were prepared by post-synthesis method and characterized by XRD and N2 adsorption-desorption. The results indicated that ZSM-5/SBA-15 has both ZSM-5 microporous and SBA-15 mesoporous structure. The ZSM-5/SBA-15 composite molecular sieves used in toluene alkylation reaction of methanol, As the reaction conditions of 120 ℃, WHSV of 2 h-1, the Toluene Methanol mole ratio of 2, Toluene conversion rate was 17.35%, the selectivity and the yield of the p-xylene is 62.78% and 10.89%,respectively.

PREPARATION OF HIERARCHICAL POROUS ZSM-5 ZEOLITE AND ITS CATALYTIC CRACKING PERFORMANCE

2016, 47(4):  65-70. 

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Hierarchical porous ZSM-5 zolites were prepared by direct synthesis and post modification and characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption/desorption and temperture-programmed desorption of ammonia (NH3-TPD), respectively. The catalytic cracking performance of the samples was evaluated in a micro fixed-bed reactor. The results indicate that compared with conventional ZSM-5, the hierarchical porous ZSM-5 zeolites have the advantages in higher surface area, mesoporous volume and ratio of meso/micro. The propylene yield is increased because the mesopores are introduced in the modified sieve, which make the product more easily to diffuse and th effectively suppress the hydrogen transfer reaction. Over the nanolayered NZSM-5-300 with the highest ratio of meso/micro, the selectivity of ethylene and reaches 15.8% and 40.1%,respectively. The test results indicate that with increase of meso/micro ratio, the sample exhibits better stability and lower deactivation rate as well as longer.

STABILITY OF ADDITIVES IN DIESEL ENGINE OILS

2016, 47(4):  71-75. 

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The stability of diesel engine oil additives is investigated with several methods associated with sediment and particle. Study shows that overbased calcium alkylbenzene sulfonate is found to have the most sediment and the largest particle diameter. A lot of sediment is found when overbased calcium alkylbenzene sulfonate mixes with overbased sulfurized calcium alkylphenolate because forming larger particles through collision of the small particles,resulting in unstable colloid system, but no interaction is occurred. The addition of ashless dispersants makes the overbased calcium alkylbenzene sulfonate more stable becaused of the space steric effect of the dispersant.

ANTIOXIDANT EFFECT OF NEW TYPE DIBUTYL DITHIOCARBAMATE

2016, 47(4):  76-79. 

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The performances of novel dibutyl dithiocarbamate (ADMC) in mineral base oil are investigated comparing with the same type of additives. The results show that ADMC exhibits good oil solubility, tribological properties, and corrosion resistance. Meanwhile, the thermal oxidation stability of ADMC and p,p-dioctylphenylamine (DODPA) in Poly-a-olefin synthetic base oil is evaluated by pressure differential scanning calorimetry (PDSC). The results show that DODPA possess better antioxidant properties than ADMC, the initial oxidation temperature and extends oxidation induction time of PAO containing DODPA are improved obviously when ADMC was combined with DODPA. Accordingly, they exhibit good antioxidant synergistic effects.

PERFORMANCE OF SURFACE MODIFIED NANO SILICA LUBRICATING GREASE

2016, 47(4):  80-85. 

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Surface modification has a great influence on the preparation and performance of nano silica lubrication grease. This study examined nano silica lubrication grease made with four nano silica, with and without surface modification by KH570, 1-octanol, hexamethyldisilizane. Results show that nano silica lubrication grease with surface modification can overcome the shortage of excessive age-hardening, poor water resistance, poor mechanical stability, each modifier has a suitable modification condition, the nano silica lubrication grease modified with KH570 shows the best performance.

STUDY OF PERFORMANCE DEGRADATION OF SYNTHETIC SULFUR-PHOSPHORUS TYPE GEAR OIL BY FT-IR

2016, 47(4):  86-90. 

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This paper used FT-IR to analysisthe before and after oxidation of oil and the infrared absorption band of the gear oil was located in 1 724—1 684 cm-1. By analyzing the sulfur and phosphorus type additives，the wave number ranges of C—S groups were located in 1 130—1 100 cm-1 and 920—870 cm-1，P—O—C groups in 1 130—1 090 cm-1 and P=S groups in 920—870 cm-1. By using the IR spectrometer，the decay law of gear oil（GL-5 75w-90）which used in locomotive wasstudied。The results show that the changes of oxidation were rapidly increased within 100 000 km，and changed smoothly after 100 000 km. The degradation of extreme pressure-antiwear additives was mainly the degradation of phosphorus type additives，and the P=S groupsplayed a major role.

DEVELOPMENT AND APPLICATION OF QUALITATIVE AND QUANTITATIVE ANALYTICAL FOR NITROGEN COMPOUNDS IN GASOLINE

2016, 47(4):  91-95. 

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The qualitative analysis of the nitrogen compounds in gasoline was carried out by enrichment and identification of mass spectrometry，contrasting the retention times of the standard substances. And the quantitative analysis was conducted by GC-NCD. The detective limit of single nitrogen compound was 0.6 mg/L. The speciation and concentration of nitrogen compounds in the gasoline samples were studied. The nitriles，pyridyl，pyrrolic，aniline nitrogen compounds were identified in catalytic cracking gasoline fractions. Nitrogen compounds from motor gasoline samples were analyzed. The amounts of aniline nitrogen compounds were below 50 mg/L in conventional samples and the amounts of aniline nitrogen compounds were above 100 mg/L in some samples.

STUDY ON DRIVEABILITY INDEX FOR MOTOR GASOLINE

2016, 47(4):  96-100. 

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Driveability Index (DI) is a widely used index of overall driveability, especially in predicting cold-start and warm-up driveability. The research background, developments and applications of DI were stated. DI values of a large number of gasoline samples were determined and analyzed. The gasoline samples varied in regions, seasons and specifications. The results showed some regions have a large range of DI value. The DI level varies greatly among different regions. For the studied regions, the DI value is obviously lower as a whole in winter than summer. DI value in recent years changes very little according to the studied regions. Samples in some regions with high DI value need careful attention.

DETERMINATION OF CARBON NUMBER DISTRIBUTION OF FISCHER-TROPSCH WAX BY HIGH TEMPERATURE GAS CHROMATOGRAPHY

2016, 47(4):  101-104. 

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A rapid and efficient method was developed to determine the carbon number distribution of Fischer-Tropsch wax by high temperature gas chromatography coupled with cold-on-column inlet and flame ionization detector (FID). The experimental parameters, such as column flow, oven temperature program, injection volume and sample concentration, were studied in detailed by using a DB-HT-SimDis column. The optimized GC conditions were as follows: Column: DB-HT-SimDis 5 m×0.53 mm×0.15 μm. Carrier gas: hydrogen at flow-rate of 9.0 mL/min (constant flow); Flame ionization detector (FID) temperature 400 ℃. Combustion gases: hydrogen, 40 mL/min; air, 400 mL/min. Nitrogen as makeup gas, 30 mL/min; Oven temperature program: initial oven temperature 60 ℃, hold 1 min; ramp 1 rate, 10 ℃/min to 240 ℃, hold 1 min; ramp 2 rate, 5 ℃/min to 400 ℃, hold 10 min; Inlet temperature: track oven temperature; Injection volume, 0.5 μL; Sample concentration in heated n-heptane: 0.5%. Under above conditions, the carbon number distribution of Fischer-Tropsch wax between C21 and C101 was analyzed within 60 minutes accurately. The GC resolutions higher than 1.5 and 1.2 were obtained in the ranges of C21 to C74 and C74 to C101, respectively. The linear correlation coefficient value between Ln(W/n) and carbon number in the range of C57 and C101 was 0.999 3 and the chain growth probability (α value) of 0.928 was calculated.

SPECTRAL ANALYSIS OF CHEMICAL COMPOSITION AND STRUCTURE OF SARA IN TAHE ATMOSPHERIC RESIDUE

2016, 47(4):  105-110. 

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Taking residue oil from TaHe as the object of the research, n-hexane as solvent to obtain asphaltene which was mixed with the residue oil to prepare the feedstock with different asphaltene content for autoclave hydrothermal conversion experiments. The characteristic of the reaction was analyzed by thermogravimetric analyzer and the structural differences of the unsaturated products were investigated by 1H-NMR and 13C-NMR. The results showed that asphaltene was the component that had a low thermal reaction activity. With the asphaltene content increasing, the yield of coke and gas presented linear increase, Sa* got the maximum value of 55.04% with 30% asphaltene content. In addition, various types of hydrogen and carbon content of cleavage products showed that with the asphaltene content increased, the break off of alkyl side chains and opening of naphthenic rings of the unsaturated components, which increased the content of aromatic hydrogen (HA) and hydrogen in the α-position to aromatic ring (Hα), the saturated carbon fraction f(CS) in Ar*, Re* and As* showed a significant decreasing trend, while the aromatic carbon fraction f(CA), co-bicyclic aromatic carbon fraction f(CAA) and tricyclic aromatic carbon fraction f(CAAA) showed a significant increase.