Table of Content

12 August 2013, Volume 44 Issue 8

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ADVANCES IN LOW AND ZERO RARE EARTH FCC CATALYSTS ABROAD

2013, 44(8):  1-7. 

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Soaring rare earth price is forcing refiners with FCC unit to adopt alternative FCC catalysts to reduce their costs. The development in low / zero rare earth FCC catalysts with high activity and selectivity by Grace Davison, Albemarle and BASF is introduced in detail，respectively. The optimization and substitute technologies of such rare earth FCC catalysts are discussed according to our national conditions in this paper.

INFLUENCE OF LOADING METHOD ON DISTRIBUTION OF ACTIVE METAL ON RESIDUE HYDROGENATION CATALYST

2013, 44(8):  8-12. 

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Alumina carrier was prepared using secondary nano particle self-assembly method and the residue hydrotreating catalysts prepared by impregnation with different contents of active metal using two different dipping methods were investigated. It is found that the pore volume of catalysts prepared through conventional way without complexing agent reduces from 1.2 mL/g to 0.3 mL/g and the specific surface area decreases from 253 m2/g to 55 m2/g and the active metal distribution is not even, as contrast with the impregnation results with complexing agent. Meanwhile the results indicate that the active metal is not evenly distributed on carrier with increasing amount of active metal loading, mainly concentrated and piled-up in smaller pore and on the surface of portion of the large pore. The addition of complexing agent in impregnation step can make active metal evenly distribute.

INVESTIGATION OF ESTERIFICATION OF OLEIC ACID AND METHANOL OVER TPA/ SnO2 SOLID ACID

2013, 44(8):  13-18. 

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A series of solid acid catalysts were synthesized by incipient wetness impregnation method with varying 12-tungstophosphoricacid (TPA) loading on tin oxide. The prepared catalysts were characterized by Hammett indicator、XRD，BET and its catalytic performance of the esterification reaction of oleic acid and methanol. The effecting factors of the catalyst preparation were discussed in detail. The results show that loading amount and calcinations both can affect the metal distribution and surface area. The 30-TPA/SnO2(500) catalyst shows good catalytic activity on the esterification. Under the reaction conditions of m(catalyst)/m(oleic acid) 8%, reaction time 8h and methanol:oleic acid molar ratio 12, the yield of oleic acid methyl ester exceeds 90%. A pseudo second order model was applied to calculate the kinetic parameters from the experimental data. The activation energy of the catalysts is 69.06 kJ/mol, pre-exponential factor is 4.30×1010 mol/(L?h).

INFLUENCE OF ZrO2 LOADING ON PERFORMANCE OF CuO/Y2O3-ZrO2-Al2O3 FOR CATALYTIC METHANE COMBUSTION

2013, 44(8):  19-22. 

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In order to obtain the high active catalysts for methane combustion at low temperature and good stability at high temperature, CuO/YSZ-γ-Al2O3 catalysts were prepared by sol-gel method. The effects of ZrO2 amount in carrier on the performance of CuO/YSZ-γ-Al2O3 were investigated, and the catalysts were characterized by XRD, BET and TPR techniques. The results show that the catalyst with 32.5% ZrO2 in carrier exhibits the best stability and activity. After aging at 1000 ℃ for 5h, the catalyst still has high specific surface area and better stability.

PREPARATION AND CATALYTIC PERFORMANCE OF Ti (SO4)2-Zr (SO4)2/SiO2 SOLID ACID CATALYST

2013, 44(8):  23-28. 

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Silica-supported titanic sulfate and zirconium sulfate solid acid catalyst (Ti(SO4)2-Zr(SO4)2/SiO2) was prepared by impregnation method. The supported catalyst was characterized by TG, acidimetric analysis, FT-IR and XRD. The effects of calcination and loading amount on the catalyst activity were investigated. The results indicate that the catalyst prepared has a esterification rate of 95.6% at the conditions of m(catalyst)2.0g/0.1mol oleic acid, ratio of methanol to oleic acid 4, reaction temperature 85℃ and reaction time 5h. It is found after the catalyst was continuously used for 5 times, the esterification rate drops to below 80% because of coking，proved by infrared analysis of deactivated catalyst, but the activity of the catalyst can successfully recovered after activation by roasting and/or supplementing certain amount of active components needed.

SELECTIVE HYDRODESULFURIZATION TECHNOLOGY OF FCC GASOLINE WITH LONG AND STABLE OPERATION

2013, 44(8):  29-32. 

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The 2nd generation selective hydrodesulfurization technology（RSDS-Ⅱ）for FCCG has been developed and commercialized. The technology uses the stabilized gasoline as feed, sets a pre-reactor to remove diene and adopts a feed filter. These measures guarantee the HDS unit to run consecutively and stably for a long period. The commercial results show that RSDS-Ⅱ technology can produce clean gasoline with sulfur content less than 150 μg/g or 50 μg/g and the octane number loss of product is less. Due to high selectivity and good stability, RSDS-II technology can meet the requirement of refinery gasoline upgrading.

PRODUCTION OF ENVIRONMENTAL FRIENDLY RUBBER EXTENDER OIL FROM HIGH POUR POINT AROMATIC-RICH

2013, 44(8):  33-36. 

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According to the properties of extract oil featured by high pour point and high aromatic content, a solvent dewaxing method with dewaxing aid for the extract oil was developed to produce environmental friendly aromatic rubber extender oils. Filtration rate and wax cake thickness in extract oil dewaxing process can be improved and controlled for the addition of dewaxing aid so that the dewaxing process can be continuously conducted. The dewaxed oil can then be solvent extracted to obtain rubber extender oil. The contents of PCA, B(a)P and PAHs in produced extender oils satisfied with the requirement of Directive 2005/69/EC of the European Parliament and of the Council. Results of rubber filling oil test show that the performance of the oil extended rubber is good, no oil bead and can meet the superior grade specifications of SBR 1723.

APPLICATION OF DIESEL LOW TEMPERATURE CRITICAL ABSORPTION TECHNOLOGY IN OIL VAPOR RECOVERY

2013, 44(8):  37-40. 

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After analyzing the characters of diesel in oil vapor absorption process, a concept of low temperature critical absorption technology for oil vapor recovery using diesel as absorber is brought up in this article. A corresponding technology has been developed as well. The use of this technology on the vent gas from sour water tank in JLPEC has received significant results. The recovery rate of oil gas in the vent gas from sour water tank reaches to 95% and above. Currently the technology has been widely used.

DEVELOPMENT OF COMBINATION PROCESS OF HYDROCRACKING – HYDROTREATING FOR COKER FRACTIONS HYDROPROCESSING

2013, 44(8):  41-44. 

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Aiming at the technical and economic problems in hydroprocessing technologies for different coking fractions, FRIPP has developed a combination process of hydrocracking - hydrotreating, which is characterized by simple process, high integration and sharing of equipment, less units, good quality of products, and low cost of investment and operation. Feedstock adaptability test results show that this technology has very good feedstock adaptability and high operating flexibility. High quality naphtha and ultra-low sulfur diesel can be obtained when processing coker fractions with high content of nitrogen or high end boiling point under mild operating conditions.

PRODUCTION OF ULTRA-LOW SULFUR GASOLINE USING S Zorb TECHNOLOGY IN YANSHAN REFINERY

2013, 44(8):  45-50. 

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Sulfur content in gasoline is limited blow 10 μg/g by newly executive legislation in Beijing. The S Zorb technology has been used for desulfurization of FCC gasoline in Yanshan refinery. In this paper, measures such as controlling the load of the unit, sulfur content in feed and activities of sorbent are adopted to ensure the stable operation. Problems occurred in operation and countermeasures and improvement are also discussed in detail and the results indicate that these measures are useful for long and stable running of S Zorb unit.

STUDY ON PROCESS FOR PRODUCTION OF RUBBER EXTENDER OIL FROM NAPHTHENIC VGO

2013, 44(8):  51-53. 

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A combined process of solvent extraction and hydrotreating has been developed for producing environment-friendly tire rubber oil and SBS extender oil from naphthenic suizhong 36-1 VGO. The product qualities could reach or exceed the same overseas products and satisfy with EU (European Union) standard and domestic market requirement. Comparing with all hydrotreating process, the combined process has advantages of higher yield and low hydrogen consumption.

STUDY ON FLUID HYDRODYNAMIC BEHAVIOR IN AIRLIFT EXTERNAL-LOOP SLURRY REACTOR

2013, 44(8):  54-58. 

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The liquid hydrodynamic behavior of slurry reactor was studied in a system of nitrogen-diesel-solid particles. The influence of operating conditions and physical properties of the system on the hydrodynamic parameters was investigated. The experimental results show that this column was operated in the heterogeneous regime. The slip velocity increased with the increase of average gas holdup. The average gas holdup and slurry velocity increased with the increase of pressure and gas superficial velocity, but decreased with the increase of solid holdup. Correlations were developed to predict slip velocity, average gas holdup and slurry velocity. Calculated results by the correlations agreed with the experiment values very well with the relative error less than 10%.

NUMERICAL SIMULATION OF EFFECT OF PHYSICAL PROPERTIES ON LOOP REACTOR OF SLURRY BED

2013, 44(8):  59-62. 

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The numerical simulation of slurry bed hydrocracking loop reactor was carried out. The standard k-ε turbulence model and the Euler multiphase flow model were used for the simulation of gas-liquid two phase turbulence flow. The effect of difference in physical properties of fluid, like liquid density, gas density and liquid viscosity on gas holdup and flow field was tested and compared. The results show that the gas density has little effect but the liquid viscosity has a significant effect on flow field and gas holdup. The liquid density affects the gas holdup, but it has a little effect on the flow field.

STUDY ON PROCESS OF FCC SLURRY SOLVENT EXTRACTION

2013, 44(8):  63-66. 

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The solvent extraction method can effectively separate the light alkane and the condensed nucleus aromatic in FCC slurry. Furfural and PA (combined solvent) were used as extraction solvent and were compared for separation efficiency. The influence of extraction temperature, mass ratio of solvent to oil was investigated to find the best operation conditions of the multi-stage countercurrent extraction process. The results show that FCC slurry can be separated well at the extraction temperature 60℃, ratio of solvent to oil 2～3. The raffinate oil can be used as the blending component of RME (F) 180 series marine residual fuel oil. The extract oil can be used as the blending component of the KA8520 rubber filling oil.

COUPLING TECHNOLOGY OF NAPHTHA AROMATICS REMOVAL AND FCC GASOLINE DESULFURIZATION

2013, 44(8):  67-70. 

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Based on the principle of acid-base reaction, aromatics in naphtha can complex with some metals, and the replacement of aromatics in complexes by sulfur can also occur. Thus the aromatics in naphtha and sulfur in FCCG can be removed by complexing way. When AlCl3 consumption was 0.06 g/g, complexing agent L consumption 0.011g/g, complexing temperature 70 ℃ and complexing time 60 min, naphtha aromatics content can be reduced from 8.15% to 0.46%, the aromatics removal rate was up to 94.36%. Complexes MTS-1 produced from naphtha complextion dearomatization is used as FCC gasoline complexing desulfurization agent. When complexing desulfurization temperature was 35 ℃, complexing desulfurization time 3 min and mass ratio of MTS-1 to FCC gasoline 0.05, the aromatics in MTS-1 is displaced by the sulfur compounds, and the content of sulfide in FCC gasoline is dropped from 526μg/g to146 μg/g. The desulfurization rate was 72.24% and the yield was 99.81%. The FCCG qualities meet the state Ⅲ gasoline sulfur content standard (< 150 μ g/g). The FCC gasoline yield and octane number are improved.

SYNTHESIS OF POLYAMINE AND ANTI-STATIC PROPERTY IN DIESEL

2013, 44(8):  71-75. 

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Polyamines were synthesized with different primary amines and epichlorohydrin. The total amine value and the tertiary amine value of the products were determined by the methods of perchloric acid nonaqueous titration. In addition, the vapour pressure osmometry (VPO) was used to determine the molecular weight of the products, and the structures of the products were characterized by infrared spectroscopy. Then, polyamines together with poly (1-decene sulfone) were added to commercial diesel fuel to evaluate its antistatic properties. The results show that the polyamines with different structures can improve the conductivity of the commercial diesel significantly, and the performance of the polyamine synthesized by chain fatty amines is perfect. When the dosage of the n-butylamine polyamine and the poly (1-decene sulfone) are both 2 mg/L, the conductivity of the 0# diesel can increase from 3 pS/m to 487 pS/m. After 9 days stored, the conductivity of the 0# diesel increased to more than 2000 pS/m, and did not decrease even stored in 25 days.

INFLUENCE OF ADDITIVES ON LIGHT STABILITY OF INSULATING OILS

2013, 44(8):  76-79. 

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Effect of additives on light stability of insulating oils with different aromatic contents was studied. The results show that light stability of high-pressure hydrorefining oil containing no aromatics is better than that of solvent refined oil with certain aromatics. The degree of impact of hindered phenolic antioxidants on light stability of insulating oils varies with different antioxidants. The more the antioxidant added in insulting oil, the sooner the color changes. Only when the antioxidant runs out, does the color of insulating oil return to that of oil with no antioxidants. The more the antioxidant content, the longer it takes to recover to normal. Adding some metal deactivator to insulating oil will produce sediment.

STUDY ON THERMAL OXIDATION STABILITY OF HIGH FLASH POINT JET FUEL

2013, 44(8):  80-84. 

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The thermal oxidization stabilities of high flash point jet fuel at 150~315℃ and 370~400℃ were examined by JFTOT test. The results show that the thermal oxidization stabilities of jet fuel tested are very good at these two temperature ranges. It is discovered that Cu ion and Fe involve in the thermal oxidization reactions of high flash point jet fuel and that Cu ion catalyzed and participated in oxidation, while Fe ion only acted as a catalyst to promote the oxidation and accelerate the deposition of the unstable compounds in the fuel.

QUALITATIVE AND QUANTITATIVE ANALYSIS FOR ORGANIC CHLORIDES IN NAPHTHA

2013, 44(8):  85-89. 

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The qualitative and quantitative analysis method (GC-ECD) for organic chlorides in naphtha is proposed. Through analysis of different naphtha from different crude oils, it is known that the main organic chlorides in naphtha of domestic crude oils are 1, 2-dichloro propane, methylene chloride, chloroform, carbon tetrachloride, etc. from assistant chemicals used in crude oil production The amount of other kinds of organic chloride is very low. The relative standard deviation of GC-ECD was less than 3.0% and the standard recovery was between 92.9%-103.5%. The results indicate that this method could meet the demand of conventional chromatograph analysis .

RESEARCH OF REFERENCE FUEL FOR AVIATION TURBINE TEST

2013, 44(8):  90-94. 

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Research of national reference fuel for aviation turbine engine performance test is introduced from the technical requirement, production, homogeneity, certificate traceability, stability and engine bench test et.al. The results show that the reference fuel for aviation turbine engine performance test is featured by uniformity, stability and traceable certificate information and can meet the requirements of engine test. The successful development of products can unify the reference fuel for aviation turbine engine performance test, fill the domestic blank, regulate the engine testing market and raise the level of technical arbitration.