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Table of Content

    12 December 2015, Volume 46 Issue 12
    TECHNICAL AND ECONOMIC ANALYSIS ON WHOLE LIFE CYCLE CONTINUOUS REFORMING CATALYST
    2015, 46(12):  1-4. 
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    Based on the processing cost, noble metal cost, noble metals recovery and catalyst life, the technical and economic analysis for the whole life cycle continuous reforming catalyst (from fresh catalyst to catalyst replacement) is conducted. The results show that these factors have a direct impact on the technical and economic indexes of the catalysts. Among of these factors, the life of catalyst is the most critical factor. The initial specific surface area and hydrothermal stability are the decisive factors affecting the service life of catalyst.

    EFFECT OF CRYSTLLIZATION CONDITIONS ON PROPERTIES OF ZSM-34
    2015, 46(12):  5-9. 
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    ZSM-34 with different sizes was synthesized successfully employing choline chloride as a template under crystallization conditions of single-stage, two-stage, two-stage with the help of seed, respectively. The products were characterized by X-ray diffraction, scanning electron microscopy, N2 adsorption/desorption, NH3-temperature programmed desorption and NMR techniques. The results show that two-stage crystallization has advantages in shorter crystallization time from 96h to 72 h, while the two-stage crystallization with the help of seed appears much more outstanding, the crystallization process is finished after only 24 h. The crystallization curve analysis indicates that two-stage crystallization with the help of seed is helpful to rapidly synthesize ZSM–34 with having stable properties.

    COMMERCIAL APPLICATION OF HIGH EFFICIENT HEAVY OIL CONVERSION FCC CATALYST
    2015, 46(12):  10-13. 
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    A new high efficient heavy oil conversion catalyst B was developed and commercialized for a RFCC unit with a capacity of 2.8 Mt/a in Petrochina Hohhot Petrochemical Company. The commercial application results show that though the worse quality feed was used and the slurry was back recycled, the coke yield is 0.22% lower than the results of the original catalyst A, the light liquid yield increases by 0.41%, propylene yield increases by 0.49%, RON of FCC gasoline improves by 1.3, and the unit consumption of catalyst decreases by 0.26 kg/t.
    COMMERCIAL APPLICATION OF FH-40C CATALYST FOR COKER GASOLINE HYDROFINING
    2015, 46(12):  14-19. 
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    FH-40C catalyst developed by Fushun Research Institute of Petroleum and Petrochemicals is used in a 0.2 Mt/a coker gasoline hydrofining unit of SINOPEC Anqing Company. Hierarchical filling technology and wet presulfurization method were used. To enhance the quality of products, FH-98 catalyst was replaced by FH-40C catalyst. The performance of the new catalyst for producing qualified catalytic reforming feedstock was tested. The properties and energy consumption of different products were studied. The operation results over three years indicate that FH-40C has the excellent performance, such as high mechanical strength, high HDS and HDN activity and the flexibility to meet the processing scheme. The coker gasoline after hydrotreating with different depth can be stably converted into qualified feedstocks for steam cracking or catalytic reforming units.

    KEY REASONS FOR UNCRACKED ALKANE IN FCC SLURRY
    2015, 46(12):  20-24. 
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    N-dodecane, butyl-cyclohexane, tetralin, decalin, and their mixtures were used as the model compounds and the combined techniques of FCC test and molecular simulation were adopted to study the reasons for a lot of uncracked chain alkane existing in FCC slurry. It is found that alkanes have different cracking performance in their single state or in a mixed one. When the alkane is mixed with strong hydrogen-donating molecules, like tetralin or decalin, the conversion of alkane is significantly depressed. Based on the results of experiment and molecule simulation, and reaction chemistry, a conclusion can be drawn that the hydride transfer between hydrocarbon molecules is the main reason that results in a lot of saturated, uncracked chain alkane in FCC slurry.

    EFFECT OF ADDITION OF LIQUID HYDROCARBONS ON PERFORMANCE OF COBALT-BASED CATALYST IN FIXED-BED FISCHER-TROPSCH SYNTHESIS
    2015, 46(12):  25-30. 
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    In order to avoid thermal instability in the catalytic bed during Fischer-Tropsch synthesis, the light synthetic oil and feed gas were co-fed into the reactor. The effect of light synthetic oil on the performance of cobalt-based catalyst was investigated in a fixed-bed reactor by changing space velocity and light oil compositions. The light synthetic oils are found to have a positive effect on decreasing the selectivity of CO2. Increase of liquid space velocity leads to an increase of methane selectivity and a decrease of C5+ selectivity. The content of olefin decreases significantly. The local hot spots in the bed are no longer present. The temperature distribution of the catalytic bed is improved. As the light oil fed into the bed becomes heavier, the selectivity of methane and C5+ are both decreased, while the temperature distribution of the catalyst bed is further improved. It is concluded that the addition of light synthetic oil can not only improve the temperature gradient and catalyst performance, but also can adjust the F-T product distributions by changing the composition of the light synthetic oils.

    STRUCTURE CHARACTERIZATION OF RESIN AND ASPHALTENE AND VISCOSITY REDUCTION OF SOUTH CHINA SEA CRUDE OIL
    2015, 46(12):  31-40. 
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    The South China Sea crude oil has rich reserves; its exploitation has important economic value and strategic significance. Resin and n-heptane asphaltene were separated from the crude oil and their structures were determined. In addition, a nitrogen-containing long-chain polymeric viscosity reducer was synthesized and its effect on viscosity of South China Sea crude oil was studied. The results indicate that South China Sea crude oil has high contents of resin and asphaltene. The high viscosity of South China Sea crude oil is mainly attributed to its associative structure of resin and asphaltene. Moreover, resin and asphaltene molecules contain aromatic sheet with side chain, connecting with alkyl chain and the polar groups which can form hydrogen bonds. Furthermore, the average molecular weights of resin and asphaltene are 760 and 1 129, respectively. The comparison results show that the parameters of average molecular structures of resin and asphaltene are consistent with the characterization values. With an addition of 1 000 of viscosity reducer, the viscosity of South China Sea crude oil at 15 ℃ and 40 ℃ decrease 44.2% and 40.2%, respectively. And the yield stress is reduced from 1 070 Pa to 563 Pa, indicating the remarkable viscosity reduction effect.

    EFFECT OF OUTLET DIAMETER OF TRICKLE VALVE ON DISCHARGE CHARACTERISTICS OF CYCLONE DIPLEG - TRICKLE VALVE
    2015, 46(12):  41-46. 
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    A cold model experiment was conducted in a cyclone dipleg with 150 mm inner diameter and 5000mm high fitted with trickle valve. FCC equilibrium catalyst was used as experimental materials. The effect of outlet inner diameter on the discharge characteristics of cyclone dipleg with trickle valve at the conditions of solid mass flux (Gs) between 0 to 50 kg/(m2?s) and negative pressure difference (ΔP) of 0 to 10 kPa was investigated. The experimental results show that there are two types of discharges, i.e. continuous discharge and intermittent discharge. The discharge forms, axial pressures and flapper plate opening angle were affected by changes of ID of trickle valve outlet, compared with conventional cyclone dipleg-trickle valve. Under the same operating conditions, the flapper plate opening angles of the cyclone dipleg- trickle valve with smaller ID of outlet pipe are all less than the case with larger ID of trickle valve outlet.

    TEN LUMPED KINETIC MODEL FOR TMP PROCESS
    2015, 46(12):  47-52. 
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    STUDY ON NON-ISOTHERMAL THERMOLYSIS OF TAHE ATMOSPHERE RESIDUE AND ITS SUB-FRACTIONS
    2015, 46(12):  53-58. 
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    The behavior of non-isothermal thermolysis properties of Tahe atmospheric residue and its sub-fractions (SARA components) were investigated by thermogravimetric analysis. Based on the Sharp differential method, the kinetic parameters, such as maximum rate and its corresponding reaction temperature, conversion and severe cracking temperature range of residue and SARA, as well as the coke formation tendency of SARA were obtained by piecewise fitting. It is found that the coking rate of SARA was in the order of saturates<aromatics<resins<asphaltenes, and the coke formation is mainly from asphaltenes. The weighted coke rate of the SARA component is 4.21 percentage points higher than that of the residue. This indicates that the mixing of SARA is conductive to suppress the coke formation and that saturates promote the coke formation from other groups, while aromatics and resins inhabit the coke formation from asphaltenes and aromatics is better. In the thermal cracking process, the thermal cracking activity is in the order of saturates>aromatics>resins>asphaltenes, and the activation energy of SARA components in low and high temperature range is in the order of saturates<aromatics<resins<asphaltenes, which shows that resins and asphaltenes need more energy during thermal cracking process.

    FUNDAMENTAL STUDY ON INCREASING CONVERSION OF VENEZUELAN ATMOSPHERIC RESIDUE
    2015, 46(12):  59-63. 
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    The product distributions of simulative slurry-bed hydrocracking and coking with Venezuelan atmospheric residue (VAR) were studied in an autoclave and a coking still pilot plant, respectively. The physical and chemical properties and average structural parameters of hydrocracking bottom oil were investigated. The results of single coking process and slurry-bed hydrocracking-coking combined process were compared. The results show that though the quality of the unconverted bottom oil is poor and the residue carbon is high, the alkyl carbon rate and content of saturates and aromatics can reach 39%-50% and 0.14-0.24, respectively, indicating a certain cracking ability of hydrocracking bottom oil. Compared with the single coking process, the slurry-bed hydrocracking-coking combined process has much higher liquid yield and diesel/gasoline ratio, and lower coke. It is concluded that the slurry-bed hydrocracking-coking combined process for processing Venezuela atmospheric residue is feasible.

    APPLICATION OF SINGLE HEATING CHAMBER FURNACE IN DELAYED COKER
    2015, 46(12):  64-67. 
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    The heating furnace of delayed coker in SINOPEC Luoyang Co. consisted of two heating chamber with four feeding inlet. To meet the fuel and petrochemical market volatility, according to the benefit of priority, the original structure of the furnace was first changed to a single heating chamber furnace. This change caused some problems: coking at the outlet of the heating furnace was occurred, more compressor surge was happened, the pump was damaged, the operation difficulty of the fractionation tower was increased and the quality of gasoline and diesel was adversely impacted. Several measures were adopted: injecting steam into furnace tube, extending the coking cycle, controlling the oil flow rate and recycling light hydrocarbon fractions, to ensure the safe and stable operation of the device. At the same time, the raw material was fed into the catalytic cracking unit. The benefit of about 5.4 million Yuan per month was obtained.

    TRIBOLOGICAL BEHAVIOR OF FLUORIDE BASE OILS IN ATMOSPHERE AND VACUUM ENVIRONMENT
    2015, 46(12):  68-72. 
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    By use of vacuum four-ball tribometer, the tribological behaviors of a series of base oils with fluorine were evaluated in air and vacuum environment, respectively. The worn surface was analyzed by scanning electron microscopy, X-ray photoelectron spectroscopy. The results show that relative to the atmospheric pressure condition, the anti-wear and friction reduction properties of perfluoropolyether oils (PFPE) are all degraded in vacuum, while the anti-wear properties of the fluorosilicone oils is improved and the friction reduction ability becomes poor in the same environment. This is due to the formation of new substance with Fe-Si bond during the friction process.

    INFLUENCE OF DIFFERENCE TYPE CARBON COMPOSITION ON OXIDATION STABILITY OF NAPHTHENIC BASE TRANSFORMER OILS
    2015, 46(12):  73-76. 
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    The effect of aromatic content on the oxidation stability of naphthenic base transformer oils with different carbon type compositions were detected using high pressure differential calorimeter scans (PDSC) and NB/SH/0811 method. The experimental results show that for transformer oils with anti-oxidant, the deeper the refining depth and the lower the aromatic content, the better the anti-oxidant sensitivity, also the better the oxidation stability. But in order to balance the dissolved performance and oxidation resistance after hydrotreatment, and to have a better anti-oxidation after the consumption of anti-oxidant, it is necessary to keep a certain refining depth and contain a certain amount of aromatic hydrocarbons for hydrotreated oils.

    PREPARATION OF 180# MARINE FUEL OIL WITH LOW SOLIDIFICATION POINT
    2015, 46(12):  77-80. 
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    The efficient ways for preparing low-cost and industry-standard 180# bunker oil using coal tar light oil, coal diesel and asphalt were investigated. The effect of depressants EVA, T602, and BEM on the reduction of solidification point of the blended marine fuel oil was tested. The results show that no significantly reduction in solidification point of the blending fuel oil is found by additing depressants. The C9 and C10 components can be used as depressants for their low solidification point and high aromaticity. When adding 10.7% of C9, the pour point of blended marine fuel oil drops to 15 ℃, which ensures the flow of marine fuel oil at normal temperature. The investigations of spot test and microscopic photos indicate that the addition of C9 can enhance the stability and compatibility of the blending marine fuel oil.

    PREPARATION OF BLENDING MARINE OIL WITH MICRO-EMULSIFIED VISCOSITY REDUCTION AGENTS
    2015, 46(12):  81-85. 
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    The mixture of vacuum residue, heavy vacuum gas oil (heavy VGO) and ethylene tar from Liaoyang Petrochemical Co.was used as marine fuel. The kinematic viscosity of the prepared marine fuel meets the standard of RMG380 and RME180, respectively when the ratio of vacuum residue:heavy VGO:ethylene tar is 5:2:3 and 3:4:3. To make full use of high viscosity vacuum residue and to improve its stability, the blending marine fuel with ratio of 5:3:2 was chosen to test the effect of micro-emulsified viscosity reduction agents. The experiments show that the complex viscosity reducer consisted of mixed JM agent and propylene glycol block polyether L61 can reduce the viscosity of the blending fuel from 520.5 mm2/s to 334.1 mm2/s. Meanwhile, no layered structure is observed in 90 days when the antioxidant 264 is added in the blending fuel and the viscosity of the final fuel is 348.9 mm2/s, meet the standard of RMG380. The cost of the method is 21.28% lower than that with other oil-soluble viscosity reducing methods.

    NEW SUBTRACTION METHOD FOR DETERMINING ORGANIC CHLORINE CONTENT IN CRUDE OILS
    2015, 46(12):  86-89. 
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    A new subtraction method for determination of the organic chlorine content in crude oils was proposed. The spiked recovery test was conducted under the optimized extraction conditions for inorganic chlorides in crude oils. The experiment results indicate that the given method is feasible for determination of organic chlorine content in crude oils. It not only avoids the limitations of GB/T 18612, but also better solves the problem of poor reliability in the existing subtraction method.

    DETERMINATION OF HYDROGEN SULFIDE CONTENT IN CRUDE OIL BY METHYLENE BLUE METHOD
    2015, 46(12):  90-93. 
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    Hydrogen sulfide is stripped out from a known mass of the crude oil with oxygen-free nitrogen into zinc acetate solution. The adsorbed hydrogen sulfide is subsequently reacted with N,N-dimethyl-1,4-phenylenediamine dihydrochloride in a strongly acidic solution with ferric chloride to form methylene blue. The amount of methylene blue is then determined by spectrophotometry to calculate the content of H2S. The determination limit of H2S is 0.042 ug/g,the RSD is 1.3%,and the spiked recoveries are ranged from 90% to 110%. This method can be applied to the determination of H2S in crude oil and its distillates.

    DETERMINATION OF CHLORINE CONTENT IN GASOLINE BY X-RAY FLUORESCENCE SPECTROMETRY
    2015, 46(12):  94-97. 
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    A method for determining chlorine content in gasoline by X-ray fluorescence analysis is introduced. At the best conditions of 25 kV and 1.0 mA, the chloride concentration in the range of 10-1 000 ug/g is linear with the fluorescence intensity. The influence of different substrates (mixture of petroleum ether and toluene (a valume ratio of 6:4 v/v), isooctane and commercially available chlorine standard sample)on the results of determination is studied, and their standard curves were established, respectively. It is found that the isooctane is the best substrate for the method. Precision and repeatability of the method were investigated. The effect of different gasoline and samples with different chlorine forms was invested. The results show that the recovery rate is between 95% and 105%, and the relative standard deviation is less than 4.2%.
    KEY TECHNIQUES OF DETERMINING DIENE VALUE BY MALEIC ANHYDRIDE ADDITION REACTION
    2015, 46(12):  98-101. 
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    The process of determining diene value of petroleum products by maleic anhydride addition reaction was studied. The results show that the boiling point of the solvent, sealing quality and the length of the stand-by time after the addition reaction are important factors for measuring diene value of petroleum products. Several key technical issues during the process of diene value determination based on the Diels-Alder reaction principle are indicated. The improvement for the national or industrial standard method is suggested.