Table of Content

12 October 2011, Volume 42 Issue 10

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加工工艺

REACTION- SEPARATION COUPLING PROCESS OF TRANSESTERIFICATION FOR BIODIESEL PREPARATION

cao zhiguang,Ze-Xue Du,En-Ze Min

2011, 42(10):  1-4.  doi:

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The preparation of biodiesel from soybean oil and methanol catalyzed by KOH was carried out on a 500 mL test device of coupling transesterification reaction and glycerol separation, and the reaction conditions were studied. Test results show that under the conditions of a reaction temperature of 60℃，the methanol/oil molar ratio of 4.5-5.0，feed rate in the range of 500-2 000 mL/h and a catalyst dosage of 0.5%-0.75% (based on oil), the molar fraction of fatty acid methyl ester in the obtained biodiesel is not less than 97%. This process possesses the advantages of fast reaction rate, high equilibrium conversion and good product selectivity. The qualities of obtained biodiesel and B5 blended product (-10# diesel fuel blended with 5% biodiesel) meet the relative specifications of National Standard for diesel fuels, GB/T 20828-2007 and GB/T 25199-2010, respectively.

DEVELOPMENT AND COMMERCIAL APPLICATION OF RSDS-Ⅱ TECHNOLOGY

2011, 42(10):  5-8.  doi:

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The 2nd generation of selective hydrodesulfurization technology (RSDS-Ⅱ) was developed based on an investigation of the distributions of sulfur compounds and hydrocarbons in FCC gasoline. Pilot plant test results show that RSDS-Ⅱ technology possesses good adoptability to various feedstocks. The results of commercial performance test show that processing feedstock with olefin volume fraction of 38.7%-43.3% and sulfur mass fraction of 250-470 g/g, the sulfur content of the treated gasoline is less than 50 g/g, which well meets the exhaust requirements of Europe IV and Shanghai IV, and the loss of RON is only 0.3-0.6 units. Due to the high HDS activity and good selectivity, RSDS-Ⅱ technology is effective for gasoline upgrading.

THE APPLICATION OF MIP TECHNOLOGY FOR ENHANCING PROPYLENE YIELD ON AN ARGG UNIT

Haizhong Ding,Wenbo Li

2011, 42(10):  9-12.  doi:

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The revamping of MIP technology was completed on a 1.8 Mt/a ARGG unit in October, 2009. The commercial application results showed that although processing feedstock with higher CCR and higher residue blending ratio, the yields of LPG and propylene increased significantly, a 13.48% increase of propylene was observed. The overall energy consumption of the unit post to revamping was 2 550.22 MJ/t, which was 221.12 MJ/t lowered than that of prior to revamping, a 7.98% reduction was obtained. Furthermore, the olefin content of MIP stabilized gasoline reduced 11.1 percentage points, i.e. a 22.6% reduction. Results indicated that the revamping goal of reducing olefin content of stabilized gasoline, lower energy consumption of the unit and better product slates were achieved.

ADVANCES IN PROPYLENEN PRODUCTION VIA FLUID CATALYTIC CRACKING TECHNOLOGY

2011, 42(10):  13-17.  doi:

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The state of arts of the worldwide fluid catalytic cracking technologies for propylene production processing heavy feedstocks is reviewed and analyzed, including the development ideas and technical features of these technologies. Moreover, the latest issued DCC-Plus technology developed by Research Institute of Petroleum Processing based on DCC process is introduced in detail.

THE APPLICATIONAL RESEARCH OF PREPARING LUBE BASE OIL BY COMPLEXATION-ADSORPTION TECHNOLOGY

2011, 42(10):  18-23.  doi:

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Using MVI and HVIH distillates from Dushanzi Petrochemical Company as feedstocks respectively, the experiments of clay refining and complexing-adsorption refining were carried out in the laboratory. The process conditions and the quality of refined oil from these two refining processes were compared. Results indicate that the qualities of refined oils by these two processes all meet the technical requirements of Q/SY 44-2009 standard for lube base oil. However, for MVI feedstock, the qualities of refined oils from complexing-adsorption refining are better; for HVIH feedstock (from hydrocracking tail oil), the qualities of refined oils from both processes are similar. By technical economical analysis of these two processes, it can be seen that using complexing-adsorption refining to substitute clay refining the benefits are as follows: solid waste can be reduced up to 95%, refined oil yield increases 1.62 percentage points, the loss of oil decreases by 80% and comprehensive energy consumption can be reduced 11%, on the whole, the production cost is lowered significantly.

A BRIEF ANALYSIS OF ABNORMITY PRESSURE DROP IN XYLENE ADSORPTION CHAMBER AND TREATING MEASURES

2011, 42(10):  24-30.  doi:

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The effect of abnormity pressure drop in xylene adsorption chamber on the recovery rate and purity of paraxylene at adsorption-separation unit is described. By analyzing the causes of abnormity pressure drop, countermeasures to prevent this happening were proposed. In the case study of a commercial unit having such trouble, backwashing measure was recommended to reduce the pressure drop in xylene adsorption chamber temporarily, an increase of flow rate and wash time would benefit the effect of backwashing in some ways.

催化剂

CHEMICAL STATES OF Ni-W IN NiW/AlPO4-5-Al2O3 CATALYST MODIFIED BY TiO2

MA Shou-Tao

2011, 42(10):  31-34.  doi:

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Titania modified AlPO4-5/Al2O3 composite support was prepared by adding metatitanic acid to AlPO4-5/Al2O3 and a series of catalysts with various TiO2 content were prepared using W-Ni metals as active components. UV diffusion reflectance spectroscopy (DRS) in conjunction with laser Raman spectroscopy (LRS) and temperature programmed reduction (TPR) technique were used to characterize TiO2 modified AlPO4-5/Al2O3 supports and catalysts. Test results show that the addition of TiO2 promotes the combination of Ni and W, which can effectively inhibit the migration of nickel cations into alumina lattice to reduce the formation of inert nickel-aluminum spinel, thus the co-catalytic performance of nickel is enhanced. The presence of TiO2 makes tungsten species tend to form multicore tungsten acid WO3. The tungsten and nickel species on TiO2 modified composite support are more likely to be reduced and be sulfurized.

COMMERCIAL APPLICATION OF LDO-75 FCC CATALYST PROCESSING HEAVY FEEDSTOCKS

2011, 42(10):  35-38.  doi:

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The commercial application of LDO-75 FCC catalyst for heavy feedstocks in the 1st FCCU of PetroChina Dushanzi Petrochemical Company was presented. The results of performance test showed that when LDO-75 catalyst occupied over 80 % of the catalyst inventory, in comparison with reference catalyst the yields of slurry oil and dry gas reduced 0.17 and 0.49 percentage points, respectively; the yields of total liquid products and light oils increased 0.54 and 1.37 percentage points, respectively; the RON and MON of FCC gasoline increased 1.9 and 1.6 units, respectively. LDO-75 catalyst possesses the characteristics of increase heavy oil conversion, good product slates, high gasoline octane number, enhanced yields of liquid products and light oils, which could meet the requirements of producing high octane gasoline.

THE FIRST REGENERATION AND APPLICATION OF PRT-C/PRT-D REFORMING CATALYSTS

2011, 42(10):  39-42.  doi:

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Catalysts PTR-C and PTR-D were regenerated first time in the semi-regeneration catalytic reforming unit of Kalamay Petrochemical Company. Through coke-burning, the coke removal rates of both catalysts exceeded 99.5%; the catalyst recovery rates of PTR-C and PTR-D catalysts were 98.7% and 99.5%, respectively. Industrial application results showed that compared with prior to catalyst regeneration, under the same processing capacity and the similar RON of stabilized gasoline, the activity of regenerated catalyst was significantly higher as shown by the 14℃ lower of reactor inlet temperature (WAIT value), which indicated that the performance of the regenerated catalyst could well meet the demands of reforming unit for next production period.

EFFECT OF Ni/Ru ON THE HYDRODESULFURIZATION PERFORMANCE OF CoP CATALYST

2011, 42(10):  43-47.  doi:

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CoP bulk catalysts containing Ru and Ni respectively were prepared by means of non-equilibrium hydrogen plasma reduction, with RuCl3·3H2O and Ni (NO3)2·6H2O as Ru source and Ni source, respectively. XRD characterization indicated that CoP catalysts could be obtained at a lower voltage by adding Ru promoter. The hydrodesulfurization (HDS) performance of CoP catalysts with various contents of Ru and Ni was evaluated in a fixed bed reactor using DBT as model compound. The results show that adding Ru and Ni can significantly improve the HDS activity of CoP catalyst, and the optimal adding rate for Ru and Ni is 0.10% and 5%, respectively. The optimal conversion of DBT over CoP catalyst with 0.10% Ru and CoP catalyst with 5% Ni was 92.0% and 79.8%, respectively, which were 33.2 and 21.0 percentage points higher than that of CoP catalyst without promoter. The incorporation of Ru enhances the hydrogenation function of CoP catalyst, and the role of Ni leads the reactions to favor direct-desulfurization (DDS) path.

EFFECT OF THE PREPARATION CONDITIONS OF TiO2-SiO2 COMPLEX SUPPORT ON HYDRODENITROGENATION PERFORMANCE

2011, 42(10):  48-51.  doi:

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TiO2-SiO2 complex support was prepared by sol-gel method and the effect of the preparation conditions on the hydrodenitrogenation (HDN) performance of Ni2P/TiO2-SiO2 catalyst was investigated．Test results showed that the optimum preparation conditions of TiO2-SiO2 complex support were obtained as follows: n(Ti):n(Si)=1:2，n(CTAB):n(TBOT)=1:5, a sol pH of 3.0 and a final calcination temperature of 550℃. The HDN performance of the prepared Ni2P/TiO2-SiO2 catalyst was evaluated on a small continuous fixed-bed reactor using quinoline as model compound under the conditions of a reaction temperature of 360℃, hydrogen partial pressure of 3 MPa，hydrogen/oil volume ratio of 500 and a LHSV of 3.0 h-1, the HDN rate of quinoline reached 93.2%.

加工工艺

STUDY ON THE PREPARATION AND SEPARATION OF BIO-ETHANOL BASED ALCOHOL ETHER FUELS BY VALUE ENGINEERING

2011, 42(10):  52-58.  doi:

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Meeting the needs and trend of clean gasoline development, combined with the characteristics of gasoline pool in China, and based on value engineering, the technique of multi-coupling preparation for bio-ethanol-based alcohol ether fuels is put forward to relieve the problems arising from gasoline upgrade and gasohol. New processes for preparing tertiary alkyl ether(s), especially ETBE by compositing distillation-extraction and coupling separation are proposed, and a case study of ETBE involving process simulation, experiment and value analysis is conducted. It can be seen that the energy consumptions of compositing distillation-extraction process and process coupling distillation-extraction with separation-purification are much lower than those of the conventional processes, a 25% reduction and a 52% reduction of energy consumption is observed, respectively. By applying the technique of coupling separation of ETBE/ethanol, the leverage of raising the value of TAEE/THEE preparation and/or even oil refining/gasoline pool will take effect.

基础研究

EXPERIMENTAL STUDY ON SEPARATION PERFORMANCE OF A CYCLONE SEPARATOR FOR OIL SHALE PROCESSES

2011, 42(10):  59-62.  doi:

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Cold model experiments were carried out to determine the separation efficiency of oil shale particles in a PV type cyclone separator. Effects of inlet velocity and vortex-finder diameter on the separation efficiency were examined, and the separation differences between oil shale particles and talcum powder were compared. It is shown that with the same cyclone separator, significant differences exist in the efficiency curves of these two materials; the inlet velocity of the highest separation efficiency for oil shale is much lower than that for talc; the change of vortex-finder diameter seems to have little effect on the inlet velocity for obtaining the highest separation efficiency. With the decrease of vortex-finder diameter, the separation efficiency increases and operation flexibility improves. These results indicate that the differences in particle types should be considered during the design and application of cyclone separators in oil shale processes.

STUDY ON THE CATALYTIC OXIDATIVE DESULFURIZATION OF MODEL GASOLINE OVER NIOBIC ACID CATALYST

SHEN Jian SHEN

2011, 42(10):  63-66.  doi:

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Using dibenzothiophene containing isooctane as model oil and hydrogen peroxide as oxidant, the effect of three niobic acid catalysts (treated by water, nitric acid and nitric acid/phosphoric acid respectively) on the catalytic performance of oxidative desulfurization was investigated by a steel bomb reactor. Test results showed that niobic acid treated by nitric acid and phosphoric acid exhibited the best catalytic activity and stability among the three catalysts. Under the conditions of a catalyst dosage of 5%, a reaction temperature of 60 ℃, a reaction time of 3 h, a H2O2/S molar ratio of 3 and solvent to oil volume ratio of 1, the desulfurization rate reached 96.34%.

油品与添加剂

SIMULATION EXPERIMENTS FOR STORAGE STABILITY OF DIESEL USING SUPER OXYGEN PRESSURE METHOD

2011, 42(10):  67-72.  doi:

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In this paper simulation experiments based on super oxygen pressure method (ASTM D5304) were carried out to investigate the storage stabilities of various diesel fuels focused on the indexes of total insolubles, existent gum and acid value. Quality indexes of diesel fuel for longtime storage, storable diesel and military use were proposed as follows: after 48 h simulation test, the content of total insolubles, existent gum and acid value for longtime storage should be not more than 2.5 mg/100mL, 50 mg/100mL and 7 mgKOH/100mL, respectively; for storable diesel should be not more than 10 mg/100mL, 100 mg/100mL and 7 mgKOH/100mL, respectively; for longtime military storage -- after 72 h simulation test, the content of total insolubles, existent gum and acid value should be not more than 1.5 mg/100mL, 10 mg/100mL and 5 mgKOH/100mL, respectively. These results could be used as scientific basis for reserve management work of domestic oil products.

PREPARATION OF EMULSIFIER FOR ETHANOL-DIESEL FUEL FROM TANNERY WASTE OIL

Jian zhong Ma,bin lv,mingjun yan

2011, 42(10):  73-77.  doi:

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Ethanol-diesel mixed fuel is an energy saving and environmental friendly fuel. In this paper using the waste oil from tannery, fatty acid methyl esters (FAME) were obtained firstly, and then emulsifiers for ethanol-diesel were prepared. Results of single factor experiments showed that under the conditions of FAME/DEA molar ratio of 1, KOH catalyst dosage of 1% (based on methyl ester), a reaction temperature of 130℃ and a reaction time of 5 h, the prepared emulsifier exhibited the best emulsifying properties. Stability test results of ethanol-diesel fuel showed that ethanol-diesel mixed fuel with the presence of said prepared emulsifier was stable in the temperature range of 0-70℃ as shown by the TEM photo: fine ethanol droplets were well dispersed in the diesel fuel. The burning rate of ethanol-diesel fuel was slightly slower than that of 0# diesel fuel, yet the smog release rate of the former was much lower than the latter (a 55.16% reduction). Besides, the mixed fuel containing the prepared emulsifier was not corrosive to engine.

分析与评定

STUDY ON THE DETERMINATION OF SOLID CONCENTRATIONS IN SUSPENSIONS BY TURBIDIMETRY

xiaojin Tang,xuefeng Li

2011, 42(10):  78-81.  doi:

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The concentrations of nine kinds of suspensions with various particles were examined by turbidimetry respectively. Results show that the relationship between the turbidity (T) of suspension and the mass concentration of particles (C) is linear in the test range. The correlation parameter (τ) depends on particle density (ρs) and not average particle diameter (d32). By these obtained correlations, the concentrations of various suspensions can be calculated with a relative error of less than 25%.

设备及防腐

SYNTHESIS OF CORROSION INHIBITOR CY-1 AND ITS CORROSION INHIBITION PERFORMANCE STUDY

2011, 42(10):  82-84.  doi:

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A new kind of oleic acid imidazoline corrosion inhibitor named CY-1 was synthesized from oleic acid/diethylene triamine and modified by zephirol. Its inhibition performance was investigated by weight loss test method using 20# steel as testing material and corrosive water collected on-site. Furthermore, its synergetic effects with other inhibitors which are commonly used in oilfield (e.g. GW1 and etc.) were tested as well. Test results show that under the conditions of an optimal CY-1 dosage of 200 μg/g, a testing temperature of 80 ℃ and a testing time of 168 h, the inhibiting rate is 74.31%; an optimum synergetic effect is obtained using a compounded inhibitor of CY-1 mixed with GW1 at the same dosage of 100 μg/g, the combined inhibiting rate is up to 79.86%.

节能减排

REVAMPING FOR ENERGY SAVING AND OPERATION ANALYSIS OF A FCC UNIT

Zhi Liang Zhang,Kun Zhen

2011, 42(10):  85-89.  doi:

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By analyzing the energy consumption status of the 0.8 million tons per year FCC unit of Yumen Oilfield Refining and Chemical Complex, it was found that the energy consumption of the unit was mainly depended on the coke-burning, steam and electricity three sections. Measures for reducing energy consumption, such as technical transformation of process, maintenance of key equipments and setting up integrated heat-exchange network with other units were proposed and realized during revamping. Since then the energy consumption in the above three sections reduced significantly, the comprehensive energy consumption reduced 421.85 MJ/t, i.e. a 12.13% reduction of energy consumption.

AN ANALYSIS OF ENERGY-SAVING PROCESS FLOWS FOR DUAL-TOWER ABSORPTION-STABILIZATION SYSTEM OF REFINING UNITS

2011, 42(10):  90-96.  doi:

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The research status and progress of dual-tower absorption-stabilization system flows of refining units were briefed in this paper. In order to solve the existing problems in current absorption-stabilization system, such as dry gas wetting, high energy consumption and poor product quality, some new energy-saving process flows of dual-tower absorption-stabilization system were discussed including improvements of the feed-in mode of desorption tower/absorption tower and selection of absorbents, focusing on analyzing the process applicability and energy-saving efficiency. These discussions are helpful for making further process improvement of absorption-stabilization system.