PETROLEUM PROCESSING AND PETROCHEMICALS

STUDY ON THE CATALYTIC CRACKING PERFORMANCE OF LIGHT DISTILLATE FROM FISCHER-TROPSCH SYNTHESIS

2011, 42(4): 1-5. doi:

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The effects of operation parameters, such as reaction temperature, weight hourly space velocity (WHSV) and catalyst to oil ratio (CTO) on the catalytic cracking of light distillate from Fischer-Tropsch synthesis were investigated using a laboratory fixed fluidized bed reactor. Test results indicated that with the increase of reaction temperature, CTO and the decrease of WHSV, the yields of dry gas, LPG and coke increased, and the yields of gasoline and diesel fuel decreased. The olefin content in gasoline fraction increased with the decrease of reaction temperature, CTO and WHSV. As the reaction temperature decreased, CTO and WHSV increased, the isoparaffin content in gasoline fraction increased. High reaction temperature and high CTO were in favor of the formation of aromatics in gasoline fraction, and the aromatics were mainly from the cyclization and dehydrogenation of small olefin molecules. When WHSV was low, the side chain cracking reactions of big alkyl aromatic molecules were promoted, yet without significant effect on hydrogen transfer reaction.

AN ANALYSIS OF THE ADVANCE ENERGY SAVING AND EMISSION REDUCTION OF MIP SERIES TECHNOLOGIES

Jun Long

2011, 42(4): 6-9. doi:

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Data related with energy consumption, gasoline quality and product distributions of 33 MIP units were collected and analyzed in this paper. Compared with FCC units, the energy consumption of MIP units decreased by 330~425 MJ/t, in which 215.47~ 336.14 MJ/t was directly attributed to the heat reductions of feed heating and reaction heat. The contents of olefin, sulfur and benzene in MIP gasoline were decreased significantly, thus pollutants emission was reduced. Up to now, the total processing capacity of MIP series units reached more than 70.00 Mt/a, an increment of 1.092 Mt/a liquid products and a diminution of 0.354 8 Mt/a coke are obtained as compared with FCC process, just as reducing 1.30 Mt CO2 emission annually.

OPERATION ANALYSIS AND OPTIMIZATION OF NAPHTHA NON-HYDROUPGRANDING UNIT

2011, 42(4): 10-13. doi:

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The operation status of the 350 kt/a naphtha non-hydroupgranding unit in SINOPEC Qingdao Refining & Chemical Company was introduced and analyzed with using various feedstocks. It was found that when the price of naphtha was cheaper than that of gasoline, the economic effect of the unit was significant. Optimization of the catalyst regeneration process was carried out to shorten the coke burning time of the catalyst. Results showed that the coke burning time of a single reactor could be shortened 96-120 h by revamping, resulting in a 7.1% increase of production capacity, and the energy consumption of the unit reduced 1 906~2 859 GJ/a.

OPTIMIZATION OF PROCESSING INFERIOR FEEDSTOCKS IN FCC UNIT

2011, 42(4): 14-18. doi:

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The FCC feedstock quality of Zhenhai Refinery & Chemical Company has been declined since 2005. In this paper problems occurred during processing inferior feedstocks, such as high nickel and high acid vacuum residue (VR), high vanadium VR, high sodium VR, high sulfur VR and high density VGO, are analyzed and optimization measures for a safety and stable long-term running are summarized.

THE ADVANTAGES AND IMPERFECTNESS OF FDFCC-Ⅲ TECHNOLOGY IN COMMERCIAL APPLICATION

2011, 42(4): 19-23. doi:

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The operation data of FCC unit in SINOPEC Luoyang Company prior and post to revamping by FDFCC-Ⅲ technology were compared. Results showed that the revamping was successful; FDFCC-Ⅲ technology exhibited the advantages of reducing sulfur and olefin contents of gasoline, enhancing LPG yield and providing cleaner production. However, shortcomings of higher energy consumption and less propylene yield during the operation were analyzed technically and some suggestions for further improvement were put forward.

PILOT PLANT TEST OF FURFURAL EXTRACTION DENITROGENATION WITH ASSISTANTS ADDED FOR THIRD VACUUM SIDE DEWAXED OIL

2011, 42(4): 24-26. doi:

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Using a third vacuum side dewaxed oil as feed, the pilot plant test of furfural extraction denitrogenation with assistant (metallic salt) added was introduced in this paper. Results showed that adding assistant in the furfural denitrogenation process could enhance the removal of basic nitrogen compounds in dewaxed oil significantly; the removal rate reached 97.6%. Under the optimum operation conditions of an extractor top temperature of 115 ℃, an extractor bottom temperature of 67 ℃, a solvent/oil volume ratio of 2.0 and an assistant adding amount of 8 g/kg(oil), the treated oil had a basic nitrogen content of 10.47 μg/g, its viscous index was 112 and its rotating bomb oxidation test time reached 211 min.

CAUSES OF FOULING AT THE REACTION SYSTEM OF COKER GASOLINE HYDROFINING UNIT AND COUNTERMEASURES

2011, 42(4): 27-29. doi:

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Due to the excessive pressure drop of reaction system, unstable running of recycle hydrogen compressor and short processing period of the 500 kt/a coker gasoline hydrofining unit in Sinopec Maoming Company, an analysis of the pressure drop in heat exchanger and reactor was carried out. Results showed that fouling happened in the shell side of the high pressure heat exchanger and the top section of reactor was the main cause of the excessive pressure drop. By analyzing the fouling materials, it was found that coke formed by the condensation reactions of dienes and resin existed in the feed was the main component of the fouling materials. Measures, such as properly controlling the feed quality, using guard catalyst, increase the porosity of the reactor top section and optimizing operation conditions, could significantly decrease the coking rate of feed, and the operation period of the unit was prolonged.

EFFECT OF NITROGEN COMPOUNDS ON THE HYDRODESULFURIZATION OF DIBENZOTHIOPHENE AND 4,6-DIMETHYLDIBENZOTHIOPHENE OVER ALUMINA-SUPPORTED NiW CATALYST

wang qian,Hong Nie

2011, 42(4): 30-34. doi:

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Effect of basic nitrogen compound (quinoline) and non-basic nitrogen compound (indole) on the catalytic activity and product selectivity of the hydrodesulfurization (HDS) reactions of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) were investigated over sulfided NiW/Al2O3 catalyst. The results for DBT and 4,6-DMDBT were varied. With the existence of nitrogen compounds, the HDS reactions of DBT enhanced due to the improved DDS reaction activity, yet for 4,6-DMDBT, its HDS reaction activity decreased significantly. The adsorption of nitrogen compounds on the hydrogenation active sites of catalyst could inhibit the adsorption of sulfur compounds, resulting in the suppression of HYD reactions, and simultaneously, the accessible active sites on the catalyst surface seemed to be redistributed. In this case, the molecule size and stereo structure of the sulfur compounds become essential. Smaller size DBT molecules could access hydrogenolysis active sites via sulfur atom easily and its hydrogenolysis activity improved; large 4,6-DMDBT molecules were suffocated by overcrowding nitrogen compounds to access active sites, thus the hydrogenolysis activity of 4,6-DMDBT decreased with the increase of nitrogen content.

STUDY ON THE NIOBIUM MODIFIED SBA-15

2011, 42(4): 35-39. doi:

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Niobium modified mesoporous molecular sieve catalysts were prepared by three methods: direct synthesis, post-synthesis and direct synthesis-oxalic acid treatment, the prepared catalysts were named as (Z)-Nb-SBA-15, (H)-Nb-SBA-15 and oxalic acid modified (Z)-Nb-SBA-15, respectively. These samples were characterized by XRD, BET, FT-IR and DTA techniques, and the results showed that the structure of (Z)-Nb-SBA-15 was varied from that of (H)-Nb-SBA-15. The catalytic performance of these catalysts was evaluated using synthesis of isopropyl oleate from isopropanol and leic acid as probe reaction. Evaluation results showed that (H)-Nb-SBA-15 had more reactive hydroxyl than (Z)-Nb-SBA-15, thus the catalytic activity of the former was higher than the latter, yet the stability of the latter was better than the former; the catalytic activity and stability of oxalic acid modified (Z)-Nb-SBA-15 were both improved.

EFFECT OF RARE EARTH CONTENT ON THE CRYSTALLINITY OF ZEOLITE BY XRD ANALYSIS

2011, 42(4): 40-44. doi:

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The crystallinity of rare earth (RE) exchanged zeolite Y is determined by XRD method. Results show that with the increase of RE contents in zeolite, the zeolite crystallinities decrease significantly, and the changes of crystallinity are not reflecting vary from zeolite crystal structure, just because the determination of zeolite crystallinity by XRD is disturbed by the existence of rare earth cations. The distribution of RE in zeolite trends to be even during calcination, thus the effect of RE cations on the determination of crystallinity is less for calcined RE-exchanged zeolite Y. By mathematical fitting, a formula is established between the changes of zeolite crystallinity and the contents of rare earth oxide in zeolite.

KINETIC MODEL OF THIOPHENE HYDRODESULFURIZATION OVER MoP/SiO2-TiO2-ZrO2 CATALYST

2011, 42(4): 45-49. doi:

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SiO2-TiO2-ZrO2 complex support was prepared by coprecipitation method. The kinetics of thiophene hydrodesulfurization (HDS) over MoP/ SiO2-TiO2-ZrO2 catalyst were investigated by a fixed micro-reactor under the conditions of hydrogen partial pressure of 2~5 MPa, reaction temperature of 320~340℃, hydrogen/oil volume ratio of 500~800 and LHSV of 2~8 h-1. The results showed that the conversion of thiophene increased with the increase of reaction temperature and hydrogen partial pressure; it decreased with the increase of hydrogen/oil volume ratio and LHSV. Experimental data were fitted by pseudo-first-order and pseudo-second-order kinetic models respectively, and using Levenberg-Marquardt (LM) method the parameters of the kinetic models were developed. A comparison of the HDS conversion of thiophene between experimental data and values calculated by kinetic models was carried out. It was shown that the calculated values by pseudo-first-order kinetic model were in better agreement with the experimental data.

NUMERICAL ANALYSIS OF LAMINAR FLOW FIELD IN A STIRRED TANK WITH A RUSHTON IMPELLER AND PITCH 4-BLADED TURBINES

2011, 42(4): 50-56. doi:

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Computational fluid dynamics (CFD) method was applied to the study of flow field in stirred tank with a Rushton impeller and pitch 4-bladed turbines．The laminar model was employed to simulate the flow field of stirred tank with glycerin fluid，and the flow structure in a stirred tank with four different impellers rotating at constant speed of 200 r/min was obtained．By comparing the velocity vector plots, velocity contours and velocity distribution curves in the directions of axial，radial and tangent, it was found that the stirring effect of Rushton impeller was better than that of pitch 4-bladed turbines, however, high power consumption was accompanied according to the calculated values of required power. The flow characteristics of the pitch 4-bladed turbines with various blade pitch angles were similar．

RESEARCH ONTO THE MECHANISM AND CHARACTERISTIC OF ELECTROSTATIC COALESCING FOR WATER-IN-OIL EMULSIONS IN ANNULAR FLOW CHANNEL

zhangbaosheng zhang

2011, 42(4): 57-61. doi:

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Based on the self-designed continuous-flow electro-coalescence experimental apparatus with vertical annular flow channel and high-voltage/high frequency AC power supply, the effects of electric field parameters including voltage, frequency, pulse width ratio and residence time in electric field, on the electrostatic coalescing characteristics of dispersed water droplets in water-in-oil emulsions were studied systematically. The experimental results showed that residence time and voltage were the major factors affecting the coalescing process of water droplets. Frequency and pulse width ratio play an important role for power consumption rather than coalescing process. Therefore, optimum operation conditions for a certain emulsion should be selected by considering the coalescing process, treating efficiency and power consumption comprehensively.

STUDY ON THE SYNTHESIS AND PERFORMANCE OF OVERBASED CALCIUM NAPHTHENATE

li ling

2011, 42(4): 62-66. doi:

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A synthesis technology of overbased calcium naphthenate is presented. The effect of process conditions including promoters, water and CO2 on the synthesis reactions is investigated. A co-promoter having antioxiding group is introduced and the optimal process conditions are obtained. In consequence, an overbased calcium naphthenate sample is synthesized by adding 100%~110% CO2 into a system containing 40% CaOH, 20% methanol, 15% promoter B3, 20% co-promoter C and 5% water. The obtained sample having calcium content over 10% and total base number more than 300 mgKOH/g, as compared with a conventional overbased calcium naphthenate product, said synthesized sample exhibits better antioxidation performance.

STUDY ON THE 1-DECENE OLIGOMERICATION CATALYZED BY ALUMINUM CHLORIDE- ISOPROPANOL COMPLEX

liu-pingping

2011, 42(4): 67-69. doi:

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The oligomerization of 1-decenes was studied using aluminum chloride-isopropanol complex as catalyst, and high viscosity poly-alpha-olefins (PAO) were synthesized. The effects of reaction conditions, such as catalyst amount, molar ratio of isopropanol/AlCl3, reaction temperature, reaction time and various olefin feeds on the yield and property of PAO were investigated. The experimental results showed that under the conditions of an AlCl3 mole fraction of 4%, an isopropanol/AlCl3 molar ratio in the range of 0.3~0.7, reaction temperature in the range of 20~60℃ and a reaction time of 4 h, the yield of high viscosity PAO could be more than 90%, and the product having low condensation point and high viscosity index.

A RESEARCH OF PREPARING ENVIRONMENTAL FRIENDLY RUBBER PROCESSING OIL BY EXTRACTION

Shi Wei,Ji-He Yang

2011, 42(4): 70-73. doi:

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Environmental friendly rubber processing oil was prepared from naphthenic base crude feed using extraction or adsorption methods to remove polynuclear aromatic hydrocarbons (PAHs). The comparable experiments between preparation methods were carried out and the results showed that the removal of PAHs by extraction was much better than that by adsorption, thus extraction method was adopted. The effect of various solvents including complex solvent and extracting conditions on the removal of PAHs was investigated, as well as the properties of solvent raffinate. Results indicated that the complex solvent exhibited improved separation effect, its maximum separation coefficient reached up to 220.0 under the following process conditions: a solvent/oil ratio of 2, extracting at 60℃ for 15 min and using stirring speed of 150 r/min. After secondary extraction, the PAHs content in solvent raffinate was reduced to 1.7% from 14.0%. The yield of solvent raffinate was more than 82%, and its hydrocarbon group compositions were improved. By adding certain viscosity improver the quality of the final product could meet the product standard for VIVATEC500 rubber processing oil, which is an environmental friendly product.

EXPERIMENTAL STUDY ON DRAG REDUCTION OF OIL-PIPELINE WITH EPOXY COATINGS

2011, 42(4): 74-77. doi:

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Pipeline wall with resin coating can significantly reduce the resistance of its delivery. Epoxy coatings with various surface properties were prepared by adding different amounts of low surface energy filler. The drag reduction effect of epoxy varnish and epoxy color paints was evaluated in a circulation pipeline testing equipment in the laboratory using three oil samples having various viscosities. Results show that all the prepared coatings exhibit drag reduction function on the samples tested, and coatings containing low surface energy filler have better drag reduction effect, in which epoxy color paint with 3% PTFE shows the maximum drag reduction rate of 23.1% at a Reynolds number of 3 475. However, the drag reduction effect of epoxy coatings on oil samples is related to the oil viscosity and the surface property of coating, with the increase of oil viscosity and the decrease of coating surface tension, the drag reduction rate of coating increases.

SYNTHESIS OF SULPHONATE DETERGENTS USING QUANTITATIVE CARBON DIOXIDE METHOD

2011, 42(4): 78-82. doi:

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In order to improve the reproducibility of using conventional process to synthesize sulphonate detergents and to reduce the consumption of carbon dioxide during synthesis, a new quantitative carbon dioxide method was introduced to synthesize calcium sulphonate detergent and magnesium sulphonate detergent in laboratory. Experimental results showed the new method was not suitable for the synthesis of calcium sulphonate, but it was feasible to synthesize magnesium sulphonate. Under the conditions of an alkyl benzene sulphonate amount of 3.5 g, a xylene amount of 50 mL, a methanol amount of 3 mL, an ammonia solution amount of 1.5 mL, a carbon dioxide partial pressure of 3 MPa and a carbonation reaction time of 1 h, when the amount of active-60 magnesium oxide was 2.5 g and 3.5 g, medium alkaline magnesium sulphonate detergent with total base number (TBN) of 283 mgKOH/g and high alkaline magnesium sulphonate detergent with TBN of 339 mgKOH/g was obtained, respectively. Some amorphous magnesium carbonate existed in the detergent product as shown by FT-IR analysis.

RESEARCH AND APPLICATION OF RECYCLING WASTEWATER TO CIRCULATING WATER SYSTEM IN ETHYLENE PLANT

FU Xiao-Ping,Ben-Gao LI,Zheng-Qi YU,Ya-Hong LI

2011, 42(4): 83-87. doi:

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The recycle of wastewater is an effective way to reduce fresh water consumption and wastewater discharge. According to the characteristics of wastewater and working conditions of circulating water systems in ethylene plant, a wastewater pretreatment and water quality stabilizing technology for recycling pretreated wastewater to circulating water systems was developed and applied in the ethylene plant of SINOPEC Maoming Company successfully. The application results show that the quality of treated wastewater can meet the make-up water standard for industrial circulating water system by using the pretreatment procedure composed of BAF, oxidation and filtration. The water quality stabilizing technology well keeps the circulating water system contained recycle wastewater for a long-term and stable running. This combined technology possesses the advantages of short processing scheme, less investment, reliable and low operation cost, thus providing good economic effect.

APPLICATION OF PIMS MODEL IN OPTIMIZING PROCUREMENT PROCESS OF CRUDE OIL

maohui,zhencai zhu

2011, 42(4): 88-91. doi:

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The application of Processes Industry Modeling System (PIMS) model in procurement of crude oil is introduced in this paper. The model is used to calculate prices of various crude oil at their breakeven points and to simulate the spreads between equilibrium price lines when comparing light crude from heavy crude or between low sulfur crude and high sulfur crude, which is very helpful to the setting up of purchasing plan. This model can be used to find the optimum crude oil allocation in terms of light and heavy during various distillation processing capacities. The optimized cases of spot crude oil procurement are also investigated and compared through PIMS model. Various real case simulations are presented briefly. The results show that PIMS model has played a sound role in optimizing procurement process of crude oil in SINOPEC Qingdao Refining & Chemical Company.

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