PETROLEUM PROCESSING AND PETROCHEMICALS

DEVELOPMENT AND COMMERCIAL APPLICATION OF AN EXTRACTION PROCESS FOR PRODUCING ENVIRONMENTAL FRIENDLY AROMATIC RUBBER EXTENDER OIL

2011, 42(7): 1-4. doi:

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An extraction process for producing aromatic rubber extender oil was developed and named as ARE process by using a screened out high selective solvent to extract polycyclic aromatic hydrocarbons from aromatic-rich extracts. On a pilot plant four aromatic-rich extracts were used as feedstocks and relative four aromatic rubber extender oil (ARE oil) samples were obtained. The qualities of these ARE oil samples satisfied the requirements of European Directive 2005/69/EC. Later, an ARE unit with 70 kt/a capacity was set up in SINOPEC Jinan Company based on the ARE extraction process package developed by Research Institute of Petroleum Processing, and the produced environmental friendly ARE oil well met the requirements of European Directive 2005/69/EC. Results of rubber extending oil test showed that the qualities of ARE oil-extended rubber met the super grade specifications of SBR 1723 Rubber Standard perfectly.

RESEARCH AND APPLICATION OF ANTI-COKING TECHNOLOGY IN NMP EXTRACTIVE DISTILLATION SYSTEM

2011, 42(7): 5-8. doi:

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In order to solve the problem existing in the N-methyl pyrrolidone (NMP) extractive distillation system, such as reducing processing capacity, blocking of reboiler inlet tube, unstable operation and product quality, investigation on NMP extractant was carried out. It was found that compared with fresh NMP extractant the properties of used NMP extractant were changed including boiling range, pH value, color and some black coke-like deposits were formed. Tests of heating NMP extractant under air and pure nitrogen were carried out respectively, and the results showed that keeping NMP extractant away from air was a good way to prevent its degradation. Therefore, an air leak into the vacuum operation system during unit shutdown was the main cause for the changing of NMP extractant. Field application was conducted using natural gas as a protective gas to prevent NMP extractant contact with air during unit shutdown, since then the processing capacity of the unit increased almost 50% and the product quality was stable, which indicated that this anti-coking technology, i.e. using natural gas as a protective gas during unit shutdown, is feasible.

A PILOT PLANT STUDY OF NMP SOLVENT REFINING OF HIGH VISCOSITY VGO

Chen Zhen

2011, 42(7): 9-12. doi:

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Bench scale tests of N-methyl pyrrolidone (NMP) solvent refining were carried out using high-viscosity 5th vacuum side cut of Daqing and Shenbei mixed crude as feedstock. Optimum operation conditions of single stage extraction and solvent dewaxing were obtained. Based on the above results pilot plant tests were conducted under four various operation conditions. Results showed that under the pilot plant operation conditions, the qualities of the obtained refined oil samples after solvent dewaxing could basically meet the requirements of lube base oil 500SN. With the increase of water content in NMP solvent, in order to obtain deep refining, the volume ratio of solvent to oil (S/O) should be increased, such as with a water content of 0 and 2.0% in NMP solvent, at a S/O volume ratio of 0.75 and 1.38 respectively, HVIS 500SN base oil could be obtained; with a NMP water content of 1.5%, at a S/O volume ratio of 1.40, HVIW 500SN base oil could be obtained; with a water content of 2.5%, at a S/O volume ratio of 1.51, the obtained product could meet the requirements of HVIW 500SN base oil except oxidation stability.

OPTIMIZING PROCESS CONDITIONS TO CONTROL THE ACIDITY OF METHANOL PRODUCT

2011, 42(7): 13-16. doi:

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By analyzing factors affecting the acidity of fine methanol in a methanol production unit, some measures to overcome the high acidity of methanol product were proposed, such as adjusting the adding amount of sodium hydroxide to predistillation column, optimizing the operating parameters of predistillation column, using optimum reflux ratios for pressured distillation column and atmospheric distillation column, keeping the methanol synthesis system under optimum reaction conditions and venting the non-condensable gas of predistillation column under proper conditions. Since process improvements and the optimization of operation parameters, the acidity of fine methanol could meet the requirement of super grade product standard.

OPERATION ANALYSIS OF BENZENE EXTRACTION DISTILLATION UNIT AND MEASURES FOR OPERATING UNDER HEAVY LOAD

2011, 42(7): 17-20. doi:

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Problems and solutions during the operation of the 200 kt/a benzene extractive distillation unit at Sinopec Qingdao Refining & Chemical Company since startup were summarized, such as leaking in reboilers of extractive distillation column and solvent recovery column, liquid flooding of extractive distillation column kettle, fluctuating of benzene content in feed, flooding of flash tank and acidification of lean solvent. In order to enhance the process capacity of the unit over design value, measures including increase the C6 components in feed, decrease the ratio of solvent to feed and keeping constant cosolvent content were proposed to ensure the unit running in good conditions, thus the yield and quality of benzene could be stable even operating under heavy load.

STUDY ON THE PREPARATION, CHARACTERIZATION AND PERFORMANCE OF RESIDUE HYDRODEMETALLIZATION CATALYST WITH NON-UNIFORM DISTRIBUTION OF ACTIVE METALS

Hong Nie

2011, 42(7): 21-27. doi:

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The effect of the pH value of impregnation solution, calcination temperature of support and adding competitive adsorbates on the distribution of active metals on Al2O3 support was investigated. Ni/Al2O3 and Mo/Al2O3 catalysts with various active metal distributions were prepared by adjusting the pH value of impregnation solution and selecting support calcined under suitable temperature. Furthermore, during preparation adding a competitive adsorbate, phosphoric acid, catalysts with single/dual active metals having yolk-like non-uniform distribution of active metals could be obtained. These samples of support and catalyst were characterized by BET, FT-IR and SEM-EDS. The catalytic performance of the prepared residue hydrodemetallization NiMo/Al2O3 catalyst was evaluated using a residue feedstock. Results showed that the prepared NiMo/Al2O3 catalyst with yolk-like non-uniform distribution of active metals exhibited better activity, improved distribution of metal deposits and enhanced metal tolerance capacity as compared with the conventional catalyst having uniform distribution of active metals.

CHARACTERIZATION AND CATALITIC PROPERTY OF EGGSHELL Co/Al2O3 CATALYST FOR F-T SYNTHESIS

wang qian

2011, 42(7): 28-32. doi:

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Co/Al2O3 F-T synthesis catalyst with eggshell distribution of active metal (eggshell catalyst) was prepared and characterized by SEM, XRF, TPR, BET, XRD and UV－vis techniques. Results showed that cobalt was mainly dispersed on the outer surface of alumina pellets in this prepared eggshell catalyst; the physical properties of eggshell catalyst were almost the same with those of the conventional catalyst having uniform distribution of cobalt, and the average crystal size of Co3O4 was similar in these two cases. The evaluation results of catalytic performance showed that under the same evaluation conditions compared with conventional catalyst, eggshell catalyst exhibited an obviously higher activity and C5+ selectivity, at the same time, its CH4 selectivity was lower. Furthermore, the shell thickness had no significant effect on the catalytic performance of the catalyst in a certain limited range.

STUDY ON THE HYDRODEAROMATIZATON PERFORMANCE OF Ni-W/P-SBA-15 CATALYST

2011, 42(7): 33-37. doi:

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A hydrodearomatization (HDA) catalyst was prepared using phosphoric acid modified SBA-15 molecular sieve as carrier and Ni-W as active metals. The characterization results of XRD and BET show that this catalyst possesses two-dimensional crystal structure and the characteristics of meso-porous material. The HDA reaction performance of the catalyst was investigated using dodecane containing 7% naphthalene as feed. Results showed that catalyst having a phosphor mass fraction of 2% exhibited the optimal HDA performance and under the optimum conditions of a reaction temperature of 320 ℃, a reaction pressure of 4.0 MPa, a H2/oil volume ratio of 600 and a space velocity of 2.0 h-1, the HDA rate of the model compound reached 88.4%.

EFFECT OF SUPPORT MODIFIED BY ALKALINE ADDITIVE ON THE PROPERTIES OF Pd/Al2O3-TiO2 CATALYST

Kong Tao

2011, 42(7): 38-42. doi:

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Catalyst support was modified by alkaline additive using impregnation and wet-kneading methods respectively, and the relative Pd/Al2O3-TiO2 catalysts were prepared by impregnation method. The samples of catalyst and support were characterized by BET, XRD, NH3-TPD and Py-IR techniques. The activities of the prepared catalysts for alkyne selective hydrogenation were evaluated using alkyne containing C4 fraction as feedstock. Results showed that the modification methods had little influence on the crystal phase structure of support. However, the pore volume, average pore size and most probable pore size of the support modified by wet-kneading method were all larger than those of support modified by impregnation, the total acid amount and the strong/medium acid amount of the former were less, which would be helpful to improve the selectivity and stability of the prepared hydrogenation catalyst. Catalyst prepared by using support from wet-kneading method exhibited a alkyne conversion of 73%, the selectivity to butadiene and the loss of butadiene were 85% and 2.5%, respectively, its selectivity was better than that of catalyst without modification.

SYNTHESIS OF NANOCRYSTAL ZEOLITE Y AND ITS APPLICATION IN THE CATALYST FOR HYDRODESULFURIZATION AND HYDRODENITROGENATION OF DIESEL FUEL

LIU Chen-Guang

2011, 42(7): 43-47. doi:

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Zeolite Y nanocrystals were synthesized with water glass and sodium aluminate as raw materials and cetyltrimethylammonium bromide as dispersant. The effect of crystallization temperature, crystallization mode, the amount of directing agent and its aging time on the crystal size of zeolite Y was investigated systematically, and these synthesized samples were characterized by XRD, TEM and N2 adsorption-desorption techniques. Results show that the aging time of directing agent is the main factor affecting the crystal size of zeolite Y. Zeolite Y nanocrystals (50-100 nm) can be obtained under the conditions of a crystallization temperature of 100 ℃, using a directing agent aged for 19 days and adding 20 % of said agent to the synthesis system. The obtained nano-zeolite Y samples possess high external specific surface area: its BET surface area is 658 m2/g, which is equivalent with that of the conventional commercial product; its external surface area is 53.4 m2/g, which is much higher than that of the latter (1.0 m2/g). NiMo hydrofining catalyst containing nano-zeolite Y exhibits higher hydrodesulfurization and hydrodenitrogenation activities as compared with reference catalyst containing conventional zeolite Y, which shows valuable size effect.

A STUDY OF USING MIXED FUEL OF GASOLINE/JET FUEL AS GASOLINE ENGINE FUEL

2011, 42(7): 48-53. doi:

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A feasibility study of using mixed fuel of gasoline/jet fuel as emergency gasoline engine fuel was conducted. The properties and performance of the mixed fuel were evaluated by comprehensive approach including laboratory analysis, engine bench test and road test. Results show that by mixing jet fuel into gasoline, the volatility and anti-knock property of the mixed fuel decrease; with the increase of jet fuel mixing proportion, the power of gasoline engine reduces and the fuel consumption increases gradually. When the volume fraction of jet fuel reaches 40% in the mixed fuel, the engine power drops by 5.3%-11.7% and the fuel consumption increases by an average of 3.8%, at the meantime engine oil dilution and exhaust emission become worse. Thus for gasoline engine, the mixed fuel of gasoline/jet fuel could only be used as an emergency alternative fuel and with a volume fraction of jet fuel less than 40%, since it may be harmful to the engine.

SYNTHESIS AND TRIBOLOGICAL BEHAVIOR STUDY OF BIODEGRADATIVE LUBRICANT ADDITIVES

2011, 42(7): 54-57. doi:

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Benzotriazole phosphate derivative was designed, synthesized and characterized by means of FT-IR spectroscopy. The tribological properties and biodegradability of benzotriazole phosphate derivative as additive in liquid paraffin base oil were investigated and their reaction mechanisms were briefly discussed. Results show that the load carrying capacity, anti-wear and friction reducing properties of the base oil are improved significantly by adding said additive, furthermore, the biodegradability of liquid paraffin is improved as well, which infers that benzotriazole phosphate could be a potential environmental friendly lubricating additive．

STUDY ON SILICONE-POLYETHER COPOLYMERS AS NEW TURBINE OIL DEMULSIFIERS

2011, 42(7): 54-57. doi:

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Silicone-polyether copolymers were synthesized and used as turbine oil demulsifiers. The demulsification performance of the prepared copolymers was evaluated by stirring and steaming test methods respectively. Steaming test results show that the emulsion breaking time of this new demulsifier is about 90 seconds, which is 80 seconds shorter than that of the other like products. The anti-foaming and air-release properties of said demulsifier are also able to meet the requirements of GB/T 12579－2002 Standard and SH/T 0308－1992 Standard, respectively.

SIMULATION ANALYSIS AND ENERGY USE IMPROVEMENT FOR A SOLVENT REGENERATION UNIT

2011, 42(7): 61-66. doi:

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A solvent regeneration unit for N-Methyldiethanolamine (MDEA) recovery is simulated using the AMINE package in PRO/II software based on a detailed analysis of solvent regeneration mechanism. The effect of the flash temperature of rich amine on the removal of H2S and dissolved hydrocarbons is focused, as well as the effect of temperature/position of rich amine fed to the regeneration column, the reflux temperature and the H2S content in rich/lean amine on the energy consumption of the unit is investigated. Finally, optimized operation parameters are proposed as follows: the feeding temperature of rich amine to the regeneration column should be in the range of 90-100 ℃ and the inlet should be located at the 1st tray, the temperature of the acid gas separator at the top of the column is supposed to be 45-50 ℃, and the H2S content in the lean amine should be controlled at about 0.15 % for energy saving. However, ensuring the temperature of rich amine fed to the regeneration column is not affected, reasonably increase the 2nd stage heat exchange load of lean-rich amine streams before the flash drum will be helpful for the removal of dissolved hydrocarbons in rich amine, yet the operating temperature of the flash drum should be kept in the range of 65-70 ℃.

SIMULATION OF LIGHT GASOLINE ETHERIFICATION BY CATALYTIC DISTILLATION

2011, 42(7): 67-72. doi:

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Aspen Plus software was applied to the simulation of etherification of reactive C5 alkene in light gasoline with methanol producing tert-amyl methyl ether (TAME) by catalytic distillation (CD) process in this work. Homogeneous and heterogeneous reaction kinetic models were applied in the fixed bed pre-reactor and CD column; both the equilibrium and non-equilibrium models were adopted in the CD column. After been validated by experimental data, this model was applied to the light gasoline etherification process analysis, including the influence of space velocity, reaction temperature, methanol appending, feeding position, as well as the catalyst packing properties on the etherification efficiency. The optimized operating parameters were obtained from the model analysis, such as space velocity of 2-3 h-1, reaction temperature of 70℃ and so forth，which will be helpful for the optimization of light gasoline etherification operation, facture of suitable catalyst packets and process design as well.

SIMULATIVE COMPARISON OF PROCESS FLOWS FOR THE SEPARATION OF REFORMATE INCLUDING DIVIDING WALL COLUMN AND CONVENTIONAL CONFIGURATIONS

2011, 42(7): 73-76. doi:

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On the basis of reformate data from a CCR-aromatics complex unit, two process flows including a dividing wall column (DWC) configuration and a conventional two-column configuration for the separation of reformate are simulated by PRO II software and compared under obtaining the same qualities of products. It is concluded that compared with the conventional two-column process flow for DWC process flow the reductions of energy consumption, equipment investment cost and area occupation are approximately 31.2%, 20.3% and 38.3%, respectively.

SYNTHESIS AND CHARACTERIZATION OF ZEOLITE ZSM-11 USING ZEOLITE EU-1 AS HETEROGENOUS CRYSTAL SEED

2011, 42(7): 77-80. doi:

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Abstract: With zeolite EU-1 as heterogenous crystal seed, two ZSM-11 zeolite samples having various crystal sizes were synthesized by using different synthesis methods, templates and silicon sources. The prepared ZSM-11 samples were characterized by XRD, FT-IR, SEM, N2 adsorption-desorption and so on. The influence of the adding amount of heterogenous crystal seed was studied. Results showed that zeolite ZSM-11 with high crystallinity could be obtained when using 1%-10% heterogenous crystal seed and crystallization under a certain temperature for 1-10 days. The characterization results showed that the morphologies and crystal size of ZSM-11 samples synthesized by different methods were varied: one exhibited as spherical nanometer crystals with particle size under 100 nm, and another was elliptic globosity micron crystals (200 nm×700 nm) having large mesoporous structure, which was agglomerated by panel particles. Furthermore, the SiO2/Al2O3 ratios of these two samples were varied significantly as well, the nanometer sample was lower and the micron one was higher.

A RESEARCH OF ALUMINA CARRIER WITH PENETRATING PORE STRUCTURE FOR ASPHALTENE MICELLES TO DIFFUSE

wangdingcong,Gang Wang

2011, 42(7): 81-84. doi:

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An alumina carrier was synthesized by the method of secondary self-assembly technique. This prepared alumina carrier holds penetrating pore structure with pore size distribution concentrated at 32~95 nm, which is favourable for asphaltene micelles to diffuse. The characterization results show that said alumina carrier possesses a pore volume of 0.852 mL/g, a specific surface area of 195 m2/g, an average pore size of 41.9 nm, a most probable pore diameter of 62.5 nm, a pore-throat ratio of 2.7 and the pore volume of pores in the range of 32~95 nm occupied 52.33% of the total pore volume.

A THEORETICAL STUDY OF DIRECT HYDRODESULFURIZATION OF DIBENZOTHIOPHENE

2011, 42(7): 85-90. doi:

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The direct hydrodesulfurization (DDS) of dibenzothiophene (DBT) is theoretically studied using density functional theory method with 6-31G* basis set. The energy and main geometry parameters of the intermediates and transition states of DBT molecules during reaction process are calculated by means of quantum chemistry. Consequently, it is validated that the cleavage of C-S bond in DBT can be happened to achieve ring opening over acidic catalyst. From the results of energy-analysis, it is shown that the cleavage of C-S bond needs high energy, it is the key step, as well as the most difficult step, in the DDS reaction pathway, once it happens sulfur removal in the following steps becomes easy. The active hydrogen atoms existing in the system play an important role in reaction process.

PROGRESS IN ALTERNATIVE FUELS FOR AVIATION AND SUGGESTIONS OF ITS DEVELOPMENT IN CHINA

Tao Zhiping

2011, 42(7): 91-96. doi:

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With the rapid development of world economy, the demand of jet fuel is increasing heavily. However, the global aviation industry is facing the challenges of declining in crude oil resources and forcing to reduce greenhouse gas emissions. Thus, the development of alternative fuels for aviation is urged since it could increase jet fuel resources and reduce greenhouse gas emissions in some ways. In this paper three types of current international alternative fuels for aviation, including coal to liquids (CTL) jet fuel, gas to liquids (GTL) jet fuel and bio-jet fuel (BTL) are reviewed from the aspects of material sources, process technologies, standard specifications and latest developments. Some suggestions for the strategies of developing alternative jet fuel in China are proposed based on considering the progress in domestic aviation industry, the increasing demands of jet fuel and environmental protection.

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