PETROLEUM PROCESSING AND PETROCHEMICALS

SUSTAINABLE DEVELOPMENT OF CHINA’S REFINING SECTOR IN THE ERA OF LOW CARBON ECONOMY

2011, 42(1): 1-6. doi:

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The progress made in China’s refining industry over the past six decades is briefly reviewed and the current status is introduced. New challenges for this industry in the era of low carbon economy are evaluated, and recommendations for further growth are provided. To name a few, utilizing heavier and lower quality crudes, producing cleaner fuels and products at lower energy cost and lower emission, competing with fuel products from alternative source are the main challenges for today’s refining industry. To respond, the following recommendations are presented: 1) processing schemes of existing refineries should be upgraded to accommodate new changes; 2) integration of refining and chemical production should be upheld to improve the utilization of resource; 3) investment to technology innovation should be intensified to provide a solid support for sustainable growth in low carbon emission era; 4) providing clean and high quality fuel products for customers; 5) deployment and development of advanced technology for reducing emission and energy consumption should be encouraged; 6) development and application of information integration in refining and management should be enhanced; 7) conversion processes for alternative fuel should be incorporated into refinery to optimize the utilization of diversified resources and to produce diversified products.

EFFECT OF GASOLINE HYDROCARBON COMPOSITIONS ON DRY GAS FORMATION IN CATALYTIC CRACKING REACTION

Chao-Gang Xie

2011, 42(1): 7-10. doi:

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The effect of gasoline group compositions on the formation of dry gas in FCC process was investigated using a fixed-fluidized bed reaction unit and MMC-2 catalyst. Results show that in the FCC process dry gas is mainly produced by catalytic cracking reactions, the percentage of dry gas formed by thermal cracking is low. With the increase of olefin content in gasoline feedstock, the ethylene yield increases significantly, yet the yields of hydrogen, methane and ethane remain almost unchanged. The dry gas components, hydrogen, methane, ethane and ethylene, are produced during the scissions of penta-coordinated carbonium ions formed by the protonation of paraffin. Ethylene could also be produced by the β-scissions of tri-coordinated primary carbonium ions formed by the protonation of olefin. The ratio of theβ-scissions of the primary carbonium ions and theβ-scissions of the secondary carbonium ions formed by the isomerization of primary carbonium ions is fixed.

STUDY ON THE MACRO KINETIC MODEL OF VGO HYDRODESULFURIZATION

Zhihai Hu

2011, 42(1): 11-14. doi:

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Using vacuum gas oil (VGO) as feedstock, the effect of reaction temperature, hydrogen partial pressure, LHSV, hydrogen to oil ratio and feedstock properties on the sulfur content of hydro-fined oil was investigated. A macro kinetic model of VGO hydrodesulfurization was established, the kinetics parameters were correlated and the model was validated by a case study. Results showed that the proposed sulfur content of treated oil by this model was in good agreement with the actual experimental data.

ADSORPTION KINETICS OF n-HEPTANE AND n-OCTANE ON BINDER-FREE 5A MOLECULAR SIEVE

SUN Hui,Ben-xian Shen

2011, 42(1): 15-19. doi:

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Adsorption kinetics of n-heptane and n-octane on 5A molecular sieve pellets with/without binder was studied using gravimetric method. Diffusivities were derived from the simplified model and diffusion activation energies were evaluated. Results show that the diffusion time constants of n-paraffins on binder-free pellets are larger than those of adsorbates on pellets with binder. In the temperatures range of 300-480 K, the micropore diffusivities of n-pentane and n-hexane on binder-free pellets are (20.84~85.77)×10-14 and (3.80-23.44)×10-14 cm2/s, respectively; the macropore diffusivities of n-pentane and n-hexane on pellets with binder are (4.87-38.58)×10-7 and (4.28-14.65)×10-7 cm2/s, respectively. The diffusion activation energies of n-pentane and n-hexane are 10.74 and 12.71 kJ/mol on binder-free 5A molecular sieve respectively, 14.16 and 16.35 kJ/mol on 5A molecular sieve with binder respectively.

THE EFFECT OF ACIDITY AND SODIUM CONTENT OF SUPPORT ON THE HDS PERFORMACE OF Ni-Mo CATALYSTS

2011, 42(1): 20-27. doi:

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A series of Ni-Mo HDS catalysts were prepared by using various supports including MCM-41, NaMCM-41, HY, NaY and their mechanical mixtures. The supports and the catalysts were characterized by TPR, UV-Vis, ICP-AES and IR. The HDS activities of these prepared catalysts were evaluated using dibenzothiophene (DBT) as model compound to study the effect of support acidity and sodium content on the HDS activity of catalyst. It is found that the HDS activities of these catalysts are related to the Brønsted acidity and sodium contents of the supports: Brønsted acidity has a positive effect on the HDS activity of the supported Ni-Mo catalysts while Na+ has a negative effect. Furthermore, it seems that some synergetic effects exist between the acid sites of support and the active components linking by spillover hydrogen as shown from the results of TPR characterization and HDS evaluation.

STUDY ON THE STABILITY OF PSEUDO-BOEHMITE SOL BY USING TURBISCAN LAB DISPERSION STEADY INDICATOR

zhang jinfeng

2011, 42(1): 28-32. doi:

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The stability of pseudo-boehmite sol was studied by using TURBISCAN Lab Dispersion Steady Indicator. The effect of various acidic peptizing agents, peptizing temperature, sol solid content and peptizing time on the stability of pseudo-boehmite sol was investigated, and a stability parameter was introduced to characterize the stability of sol system. Test results show that the pseudo-boehmite sol sample obtained by using hydrochloric acid as peptizing agent is more stable than that of using nitric acid. With the increase of peptizing temperature and peptizing time, the stability parameters of pseudo-boehmite sol increase, indicating that the sol system becomes unstable. The peptizing of pseudo-boehmite is an endothermic reaction; peptizing reactions proceed with the increase of temperature, which could be seen from the changes of sol particle size, specific surface area and the space between sol particles with temperature. In some extent, the nano-scale pseudo-boehmite sol is a thermodynamically unstable system as shown by the increase of stability parameter with peptizing time.

COMMERCIAL APPLICATION OF RECYCLING LIGHT DIESEL FRACTION TO ENHANCE HIGH OCTANE GASOLINE YIELD IN MIP UNIT

2011, 42(1): 33-36. doi:

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MIP process for enhancing high octane gasoline production was commercially applied at SINOPEC Baling Petrochemical Company, in this process light diesel fraction was recycled and cracked. Application results showed that the yield of light diesel fraction decreased 1.41 percentage points, the yield of target products (gasoline and LPG) increased 1.16 percentage points, gasoline RON increased slightly and MON increased 0.5 units, which indicating that the yield of high octane gasoline could be increased by selectively cracking the low quality light diesel fraction.

PILOT PLANT TEST OF FCC GASOLINE DESULFURIZATION BY ALKYLATION

2011, 42(1): 37-40. doi:

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Since hydrodesulfurization (HDS) of FCC gasoline is a high investment and high operation cost process, a lower cost desulfurization process through alkylation was tested by Wuxi Bluestar Petrochemical Company and Southwest Petroleum University (SWPU). A pilot plant test using SW-1 catalyst developed by SWPU and FCC gasoline from Wuxi Bluestar Petrochemical Company was presented. Test results showed that under the optimum conditions of a reaction temperature of 60 ℃, a pressure range of 0.5~0.8 MPa, a LHSV of 3.77 h-1 and using 100 mL SW-1 catalyst to process 27.5 L gasoline feedstock, the sulfur content of treated gasoline was 191 μg/g and the yield was 87.90%. The treated gasoline was blended with straight-run gasoline, C9 aromatics and MTBE in the mass ratios of 67:15:10:8 to produce automobile gasoline. This gasoline product had a RON of 93.4, a density of 0.721 5 g/cm3 and a sulfur content of 142 μg/g, meeting the sulfur requirement of National Standard for Automobile Gasoline Ⅲ. As compared with HDS process, this process is simple, easy to operate, less octane loss, lower investment/operation cost and lower energy consumption.

STUDY ON THE ADSORPTION OF BASIC NITROGEN COMPOUNDS FROM OIL WITH HY MOLECULAR SIEVE

2011, 42(1): 41-44. doi:

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The adsorption of basic nitrogen compounds from oil was studied using self-made HY molecular sieve as adsorbent and dodecane containing quinoline as model oil. Test results showed that under the optimal adsorption temperature of 373 K and adsorbent/oil mass ratio of 0.03, using HY molecular sieve calcined at 773 K, the time to reach saturated adsorption was 30 min and a desulfurization rate of 50.4% was obtained. Yoon-Nelson equation and Boltzmann model equation of Origin8.0 were used to fit the adsorption breakthrough curve respectively, and the results showed that the simulated values by Boltzmann model equation agreed well with the experimental data.

STUDY ON THE COMPREHENSIVE UTILIZATION OF PRODUCTS FROM MIXED C4 AROMATIZATION

2011, 42(1): 45-48. doi:

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The comprehensive utilization of products from mixed C4 aromatization was studied on a 500 ml fixed-bed reaction system using mixed C4 from Daqing Petrochemical Company as feed. Test results showed that using catalyst containing nano-molecular sieve, under the conditions of a reaction temperature range of 360～400 ℃, a reaction pressure of 2.0 MPa, a H2/oil volume ratio of 500 and a LHSV of 1.0 h-1, the catalyst exhibited high activity and the product distributions were optimum, in which C3~C4 fraction could be used as ethylene feed and C5~C10 fraction could be used as the blending component of high octane gasoline.

EFFECTS OF FCC CATALYST PREPARATION PROCESS ON THE CATALYTIC CRACKING PERFORMANCE OF CATALYST

2011, 42(1): 49-52. doi:

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The physicochemical properties and catalytic cracking performance of four catalysts prepared by various processes were compared. Results showed that adding dispersant could significantly improve the catalyst performance, such as the heavy oil conversion of the catalyst could be increased more than 0.75 units as compared with that of catalyst prepared without dispersant. The performance of the catalyst could be adjusted in some ways by controlling the effective acid amount to acidify preudoboehmite, the attrition index of catalyst prepared by this method could be less than 2.0%.

AN INVESTIGATION IN THE REACTION CONDITIONS OF GASOLINE OLEFIN REDUCTION OVER ZSM-5/MCM-41 COMPOSITE MOLECULAR SIEVE

2011, 42(1): 53-59. doi:

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The effects of reaction conditions on the olefin reduction of gasoline over ZSM-5/MCM-41 composite molecular sieve prepared by nano-assembling method were investigated on a continuous micro-reactor unit with pressure using FCC gasoline as feed. By analyzing the influences of various reaction temperature, pressure and WHSV on the liquid yield, coke yield and the group compositions of product, the optimum conditions were obtained as follows: a reaction temperature of 673 K, a reaction pressure of 2 MPa and a WHSV of 3.0 h-1. The performance of ZSM-5/MCM-41 during various reaction times was also evaluated. Results indicated that the deactivation of composite molecular sieve was mainly due to the formation of coke, however, this composite molecular sieve exhibited good regeneration performance.

PREPARATION OF TITANIUM MODIFIED AlPO4-5/Al2O3 COMPOSITE CATALYST AND EVALUATION OF ITS HDS AND AROMATIC HYDROGENATION PERFORMANCE

MA Shou-Tao

2011, 42(1): 60-63. doi:

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TiO2 was incorporated into AlPO4-5/Al2O3 support by adding meta-titanic acid. A series of catalysts was prepared using W-Ni active component and Ti-AlPO4-5/Al2O3 composite supports with various TiO2 contents. The catalytic performance (HDS and aromatics saturation) of these catalyst samples were evaluated on a micro-reactor and using dibenzothiophene and tetralin as model compounds respectively. Results showed that as comparing the effect of TiO2 contents, under a reaction pressure of 4.0 MPa, a H2/oil volume ratio of 500 and a certain reaction temperature, the catalyst having a TiO2 content of 15.0% exhibited the best HDS activity and the highest conversion of tetralin.

PREPARATION OF Ni2P/SiO2 CATALYST AND ITS HYDRODESULFURIZATION PERFORMANCE

LIU Li-Hua,LIU Chen-Guang

2011, 42(1): 64-68. doi:

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Silica-supported Ni2P catalysts were prepared by the solid phase reaction of nickel hypophosphite under N2 atmosphere and low temperature. X-ray diffraction (XRD), N2 adsorption-desorption isotherms, and transmission electron microscopy (TEM) were used to analyze and obtain the structure parameters of the prepared catalysts. The speciﬁc surface area of a Ni2P/SiO2 catalyst having 20% Ni2P was 226.2 m2/g; the active components, Ni2P, were well dispersed on the SiO2 support with a particle size of 5~8 nm as shown by TEM analysis. The catalytic performance of this catalyst was evaluated in a fixed-bed reactor for hydrodesulfurization using a model feed containing 2% dibenzothiophene (DBT). Under the conditions of a reaction temperature of 340 ℃, a hydrogen partial pressure of 2.0 MPa, a LHSV of 2.0 h-1 and a H2/oil volume ratio of 300, the conversion of DBT reached 99.1%. Furthermore, the desulfurization reactions had a strong tendency of following direct desulfurization pathway.

OPTIMIZATION AND IMPROVEMENT OF ENERGY UTILIZATION IN A CCR UNIT

2011, 42(1): 69-74. doi:

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The revamping and optimization of energy conservation in the No.1 CCR unit of SINOPEC Jinling Company were introduced. By optimizing the reflux ratios of a series of aromatic fractionation columns and adjusting the solvent/oil ratio of the aromatic extraction system, as well as optimizing heat exchange network by adding an o-xylene/xylene heat exchanger and using low-temperature heat to heat up the demineralized water, the energy consumption of the whole unit was reduced significantly, a 419 MJ/t reduction of comprehensive energy consumption was achieved. Meanwhile, a revamping proposal for further energy conservation was put forward.

A RESEARCH OF HEAT INTEGRATION AMONG REFINING UNITS BY TAKING HOT FEED AS THE MAIN CHANCE

Ben Hua

2011, 42(1): 75-79. doi:

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Based on the three-link energy model of process system energy optimization, energy and exergy balance of heat exchange network were analyzed. Results showed that increase the temperature of intermediate streams between units could reduce the exergy loss during cooling and heating of these streams repeatedly. By taking hot feed from upstream to downstream directly might offer a chance to re-optimize the heat exchange network of individual unit, as well as promoting the further optimum integration of heat exchange in a much larger scope, finally, to reach the goal of utilizing energy comprehensively and then the energy consumption of the whole refinery could be reduced.

IMPACT OF REFRIGERATOR OIL ON THE REFRIGERATION EFFECT OF COMPRESSOR USING R600a REFRIGERANT

yanqiu li

2011, 42(1): 80-83. doi:

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The correlation between various types of refrigerator oil and the refrigeration effect of compressor with R600a refrigerant was investigated by using refrigeration test procedure for refrigerator compressor (GB 9098-1996). Results showed that suitable low-viscosity type of refrigerator oil could be helpful to enhance the refrigeration effect of compressor with R600a refrigerant. Refrigerator oil having viscosity corresponded to the cross point of refrigerating capacity curve and refrigerating coefficient curve was the optimum product to obtain optimal refrigeration effect. The effect of refrigerator oil on the refrigeration performance of compressor having various ratings was also tested, and results did not showed the existence of relationship.

PREPARATION OF VISCOSITY INDEX IMPROVER FOR 75W/90 AUTOMOTIVE GEAR OIL

2011, 42(1): 84-87. doi:

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Using esterification products of methacrylic acid and high-carbon alcohols as polymeric monomer, viscosity index improvers for 75W/90 automotive gear oil were obtained by free radical polymerization. FT-IR technique was used to analyze the structure of the esterified products and the copolymers. The service performance of the prepared copolymer was investigated and an import product was used as reference. FT-IR results showed that acid or alcohol was not detected in the esterified product, so it could be used as monomer in the further polymerization reaction. Residue methacrylic acid esters were not found in the prepared copolymers, indicating the polymerization reaction was successful. Results showed that compared with import product, the prepared copolymers exhibited enhanced viscosity improved performance and good shear stability, besides, superior low temperature performance and good adaptability with various hydrogenated base oils of this product were also observed.

EFFECTS OF THE HYDROCARBON COMPOSITIONS OF GASOLINE ON AUTOMOBILE EXHAUST EMISSIONS

2011, 42(1): 88-92. doi:

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Effects of the olefin and aromatic content of gasoline on the automobile exhaust emission during normal/low temperature cold start and evaporative emission were studied using six gasoline samples with various hydrocarbon compositions and vehicles meeting China National Standard for automobile emission III (E III) and emission standard IV (E IV). Results show that the effect of gasoline compositions on emission is significantly related with the types of vehicles, E IV vehicles exhibit the lowest emissions of HC, CO and NOx when using gasoline with an aromatic volume content of 35% and an olefin volume content of 25%, indicating that the olefin content in gasoline is not the lower the better. The effect of aromatic content is also related to the engine technology, however, on the whole exhaust emissions decrease with the decrease of aromatic content. The total evaporative emission increases with the increase of gasoline olefin content. The HC and CO emissions during cold start at low temperature increase with the increase of the total content of olefin and aromatics.

STUDY ON A METHOD FOR EVALUATING THE AMOUNT OF DETERGENT ADDITIVE IN AUTOMOBILE GASOLINE

siyuan li,zhao yan,yongsheng zhou,xiyu chen

2011, 42(1): 93-96. doi:

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The feasibility of evaluating the amount of detergent additives in automobile gasoline based on the difference value (D-value) between the amount of unwashed gum and existent gum was studied. By adding various amounts of given detergent additives to gasoline samples from various refineries and determining the D-values of these samples, the relationship of detergent types and added dosages on D-values was analyzed. In the analysis, a statistics software MINITAB was involved and finally a delimitative D-value was obtained, which could be used to evaluate the added amount of detergent in gasoline enough or not. Application results showed that this method is feasible and it could be used to supervise the addition of detergent in gasoline.

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