Table of Content

12 April 2013, Volume 44 Issue 4

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Development and commercial application of ultra-low pressure naphtha reforming technology with continuous catalyst regeneration

2013, 44(4):  1-7. 

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The development process and major technological innovation of the ultra-low pressure naphtha reforming technology with continuous catalyst regeneration developed by our country were introduced. The technology was adopted by the 1000kt/a CCR unit at Guangzhou Petrochemical Company. After the determination of unit capacity, feedstock and product target, the suitable catalyst was selected. The design parameters as reaction pressure, octane number of C5+ product, reaction temperature, space velocity, hydrogen to hydrocarbon ratio and catalyst circulating rate were chosen upon the study on process conditions and process parameters. The commercial results showed that the research octane number of C5+ product reached 104 when the capacity reached 100% and 115% of the design value. The other technical targets reached or exceeded the expected value.

COMMERCIAL TEST OF KILO-TON SCALE DIRECT EPOXIDATION EPROPYLENE

2013, 44(4):  8-12. 

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A direct propylene epoxidation demonstration unit with 1500t/a capacity with catalyst TS-1 has been stably running for 4 000 h. The results indicated that the hydrogen peroxide conversion and the propylene oxide selectivity is maintained at 90%~96% and 90%~92%, respectively, meeting the unit design requirement. The quality of the product PO purified by distillation is in line with the national superior grade standard. By the direct propylene epoxidation technology, the pollutions of waste materials can be solved and the energy consumption can be reduced. And the existing problems and applying prospects are also discussed.

TECHNICAL REFORM MEASURES FOR HEAVY OIL CATALYTIC CRACKING UNIT AND ITS EFFECT

2013, 44(4):  13-18. 

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In order to improve the economic benefits of the FCCU in Yanshan Petrochemical Company, several technical reform measures for No.2 FCC unit processing heavy oil have been adopted. The operation changes after the reforming are discussed in detail. The technical measures include revamping the waste heat boiler（WHB） for energy saving and anti-corrosion, applying an airlift loop hybrid stripper, installing the fourth cyclone separating device and a new type of critical flow velocity injector, and a mid-reboiler in desorption tower. These measures enable the unit to have a long-term stable running. The economic benefits can be increased by more than 37 million yuan per year.

REVAMPING SCHEMES FOR PRODUCTION OF HIGH FLASH JET FUEL FROM HYDROCACKING UNIT

2013, 44(4):  19-23. 

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Kerosene in accord with No.3 jet fuel standard can be produced from the existent hydrocracking unit. In order to produce high flash kerosene, the hydrocracking unit need revamping. We use simulation software to do research, and select simple and feasible revamping scheme finally, that is increasing the reboiler duty and draw off. In the mean time the EBP of heavy naphtha is less than 180℃.

ANALYSIS OF LOW RECYCLE RATIO OPERATION OF DELAYED COKING UNIT

2013, 44(4):  24-28. 

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The low recycle ratio operation has been adopted on delayed coking unit in SINOPEC Luoyang Company recently. The result shows that the liquid yield and unit throughput were increased by 3.57 and 30 percentage points respectively, and energy consumption was reduced by 41.03%. Meanwhile several measures have been provided to the problems resulted from the lower recycle ratio, such as the coking in furnace pipes and bottom of fractionator.

EFFECT OF GUM CONTENT ON SULFOLANE LEAN PURIFICATION BY ANION-EXCHANGE METHOD IN AROMATIC EXTRACTION PROCESS

2013, 44(4):  29-33. 

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The lean sulfolane resulted from liquid-liquid extraction and extract-distillation process must be purified for recycling. The purification efficiencies of lean solvent sulfolane by macroporous weak basic anion-exchange resin were investigated for both cases in this paper. After purification, gum and chloride ion in lean solvent are removed, the pH value of the solvent is above 6.0 and the acid value decreases. In the case of liquid-liquid extraction 85.5% of gum and 79.94% of chloride ion can be removed due to lower colloid content in solvent. However, only 28.7%—32.6% of gum and 54.98%-59.95% of chloride ions can be removed, respectively, because of higher gum content in extract-distillation lean solvent. It can be concluded that higher gum content has inversely influence on the purification efficiency of lean solvent sulfolane in extract-distillation case.

INFLUENCE OF OPERATING CONDITIONS ON THE PERFORMANCE OF PT-SN-K/AL2O3 CATALYST FOR PROPANE DEHYDROGENATION

2013, 44(4):  34-38. 

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Thermodynamic analysis was carried out for the reaction of propane dehydrogenation, and the standard equilibrium constants and the equilibrium conversion at different conditions were calculated. In addition, the influence of operating conditions on the performance of the catalyst was studied. The results showed that high temperature and low pressure were favorable to the dehydrogenation reaction. But at higher temperature, the side reactions such as cracking were increased, and the lower pressure could increase the precursor of coke, which resulted to the increase of coke on the catalyst and the decrease of the activity of the catalyst. At low space velocity, the residence time of reactants in the reactor was longer, resulting to the increase of cracking reactions and the decrease of the selectivity. The increase of hydrogen hydrocarbon ratio could decrease the coke rate of the catalyst and the conversion of propane.

MESOSCALE SIMULATION OF EFFECT OF TEMPERATURE AND SHEARIN GRATE ON COLLOIDAL STRUCTURES OF HEAVY OIL

2013, 44(4):  39-44. 

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Heavy oil is an extremely complex colloidal system. In order to research the colloidal structure of heavy oil and its structure variation by change of external conditions such as temperature and shearing rate. Ten kinds of model compounds were chosen to represent the composition of heavy oil. Dissipative particle dynamics (DPD) was applied to simulate the changes of colloidal structure of heavy oil at different temperature and different shearing rate. The simulation results show that heavy oil possesses a colloidal structure made of components and that the polarity of the colloidal structure becomes gradually weaken from inside to outside. The dispersed phase is colloidal particle and the continuous phase is saturates and mononuclear aromatic. The heavy oil colloidal activation is greatly influenced by temperature. At certain temperature the heavy oil colloidal will has a most suitable activation status. Shear viscosity of heavy oil reduces with the increase of the shearing rate. Heavy oil exhibits the characteristics of pseudoplastic fluid.

ADSORPTION OF NORMAL PARAFFINS FROM NAPHTHA USING 5A MOLECULAR SIEVES IN A DOUBLE-COLUMN FIXED-BED

2013, 44(4):  45-50. 

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In order to make a better use of different components in naphtha to produce ethylene and aromatics based on the strategy of molecular scale management, this article carried out the studies on the adsorption separation of normal paraffins from naphtha using 5A molecular sieves in a double-column fixed-bed. After 5 adsorption/desorption circles，the adsorption separation process reached dynamic balance. The optimal conditions for the adsorption/desorption process were an operation temperature of 270℃, a naphtha feed space velocity of 153.4h-1, a switch time of 30 minutes, using N2 as desorption gas and a space velocity of 127.5h-1, an intermediate oil cutting time of 2 minutes. The normal paraffin content in the raffinate oil was less than 3% and the potential aromatic content of the raffinate oil was 10% higher than that of the SGPC naphtha. The normal paraffin content of the desorption oil was over 95% and the ethylene yield was improved by 13%-14% using the desorption oil as stream cracking feed compared to the naphtha feed.

REMOVAL OF TRACE CHLORIDES IN NAPHTHA BY MEANS OF ADSORPTION METHOD

2013, 44(4):  51-54. 

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Based on the analysis on occurrence form of chlorides in naphtha, the removal of chlorides from naphtha was investigated by means of adsorption method. The results indicated that N type and P type of adsorbents made in the laboratory had higher adsorptive dechlorination performance, and the dechlorination performance for new adsorbent with m(N):m(P)=2:1 preferred than that of single N or P. Under proper operational conditions, such as the adsorptive time was 2h, the adsorptive temperature was 10℃, and the ratio of adsorbent to oil was 1:10, the content of chlorine element could be brought down from 17.026mg/L to 1.652mg/L and the dechlorination rate was high to 90.03% in the presence of the adsorbents with particle size of 20-40 mesh and m(N):m(P)=2:1. Moreover, regenerative adsorbents via repeated adsorption-regeneration treatment possessed always excellent dechlorination performance, it is conducive to commercial application in the future.

STUDY ON SKELETAL ISOMERIZATION OF N-BUTENES INTO ISOBUTENE 10 MOLECCULAR SIEVE CATALYSTS

2013, 44(4):  55-58. 

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The AEL-, TON-, and FER-type molecular sieves with 10 MR pore structures were used as the catalysts, and their skeletal isomerization performance of n-butene into isobutene were studied. The effect of temperature and space velocity on the n-butenes conversion, isobutene selectivity and yield was discussed. The results show that the AEL- and FER-type molecular sieves are suitable for the industrial process of isobutene isomerized from n-butene. The AEL-type molecule sieve prefers to be operated at the high temperature and low space velocity mode, and the isobutene yield is 41.4% at a pressure of 0.25 MPa, a temperature of 450 oC and a space velocity of 4 h-1. Whereas the FER-type one prefers to be at the low temperature and high space velocity operation mode, and the maximum isobutene yield reaches 45.9% at a pressure of 0.25 MPa, a temperature of 350 oC and a space velocity of 6 h-1.

INDUSTRIAL SYNTHESIS AND CATALYTIC PROPERTIES OF Y-ZEOLITE-CONTAINING COMPOSITE MATERIAL WITH MICRO/MESOPOROUS STRUCTURE

2013, 44(4):  59-63. 

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An Y-zeolite-containing composite material(novel structure zeolite Y,NSY) with micro/mesoporous structure has been synthesized by industrial production. The industrial NSY have investigated by XRD, BET and SEM. Evaluation of catalytic activity of both the commercial Y-zeolite and the novel Y-zeolite-containing composite has carried out in the pulse micro-chromatography platform with probe molecule 1,3,5 tri-iso-propyl benzene. It is found that the Y-zeolite-containing composite is richer in external surface and meso-/macro-pore; The evaluation result of RU shows that catalyst NSC has good hydrothermal stability, selectivity to coke and heavy oil conversion ability than the commercial catalyst.

STUDY OF PROBE REACTION OF N-PENTANE CONVERSION CATALYZED BY Zn-MODIFIED KL ZEOLITE

2013, 44(4):  64-69. 

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A series of Zn/KL zeolite catalysts were obtained by impregnation. The synthesized samples were characterized by X-ray powder diffraction (XRD) and infrared spectroscope (FT-IR). The catalytic properties of Zn/KL with Zn content (mass fraction) of 0.5%, 1.0% and 3.0%, respectively, were tested on a fixed-bed microreactor using the n-pentane isomerization and aromatization as a probe reaction. The results show that at the reaction temperature of 460℃, the catalyst with Zn of 0.5% has the best catalytic performance. The isomerization rate reaches 86.72% and aromatization rate 12.19%. And compared with Pt/KL and Pt/Al2O3, the Zn/KL catalyst with Zn of 0.5% has the highest isomerization rate. However, its aromatization rate is lower than that of both Pt/L and Pt/Al2O3 catalysts.

EFFECT OF S-CONTAINING ADDITIVES IN LUBRICANT OIL ON COPPER CORROSION

2013, 44(4):  70-74. 

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The effect of various additives, such as xanthagenate,ZDDP,sulfurized calcium alkylphenate in formulated lubricant on copper corrosion was evaluated by corrosive bench test (CBT). The corrosion mechanism was also discussed from two aspects of the chemical structure of the additives and their manufacturing processes. It is found that active sulfur amount from homolytic fission of long chain S bridge（Sx，x≥4）and unreacted S element remained in the manufacturing process is the main factor for the Cu corrosion, especially in sulfurized calcium alkylphenates and that there are obvious differences in the structure of the sulfur bridge and the form of the molecule groups in the molecules between sulfurized calcium alkylphenates from different sources.

ANALYSIS OF FACTORS INFLUENCING SO2 EMISSION OF SULFUR PLANT

2013, 44(4):  75-79. 

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This paper describes the main sources of SO2 in the sulfur recovery unit flue gas and analyses the various factors that affect the flue gas SO2 emission concentration. Based on the existing status quo and requirement for the new emission standard, optimization of unit design, operation, standard process configuration, choice of solvent and catalyst grading were recommended to reduce SO2 emission concentration of the sulfur recovery unit flue gas.

EFFECT OF MEDIUM LEAKING ON WATER QUALITY OF CIRCULATING COOLING WATER AND BIOFOULING CHARACTERISTICS

2013, 44(4):  80-85. 

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The biological slime was developed with adding different concentration oil into the circulating cooling water to simulate medium leaking phenomenon in oil refining enterprise. The water quality of the circulating cooling water and biofouling characteristics were investigated under the influence of medium leaking, and microstructure of biological slime was observed by using scanning electron microscope (SEM). The results show that the content of turbidity, COD, petroleum hydrocarbon, total iron and zinc ion are widely changed with variation of diesel dosage, but the total hardness and total phosphorus has little change. The content of biomass, polysaccharide, protein content, EPS and fat phosphorus have obvious volcanic type change trends as with the diesel dosage increasing. Combined with the results of the SEM, it can be drawn that medium leaking has positive effect on the biological slime at the diesel dosage of 0.1，0.2，0.3，0.5 g/L, but negative effect on the biological slime will occur at the diesel dosage of 0.7, 0.9 g/L. These results can be very help to select biocides for oil refining enterprise.

SOURCE AND REMOVAL OF ORGANIC CHLORIDE IN TAHE CRUDE OIL

2013, 44(4):  86-90. 

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The existing forms of chloride salt in Tahe crude oil and their sources were analyzed and an assistant agent H for organic chloride removal was developed and tested. It is found that there are two forms of chloride salts in Tahe crude oil: inorganic and organic chloride and that the content of organic chloride is above 50％. The organic chloride cannot be completely removed by traditional method and mainly goes into residual oil fraction during distillation. The test results show that the agent H with demulsifier together can decrease the chloride content in treated oil to less than 10 ?g/g and salt content to less than 3 mg NaCl/L. Meanwhile it has little disadvantageous effect on demulsification.

DETERMINATION OF PURITY AND IMPURITIES IN CHEMICAL GRADE MTBE BY HEART-CUT GAS CHROMATOGRAPHY

2013, 44(4):  91-96. 

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Chemical grade MTBE is mainly used for the production of polymerization grade isobutene, all types of impurities in MTBE should be controlled strictly. However, the detection limit of the existing method SH/T 1550-2000 is 0.02% (mass fraction) which cannot meet the analysis requirements. In this study, the advanced heart cutting technology is used, in which the components difficult to separate in nonpolar capillary chromatographic column are cut out and sent to the second polarity capillary column for separation. Double hydrogen flame ionization detector (FID) is used, and the calibration areas are normalized. The main components difficult to separate, such as methanol and isobutene, t-butanol and 2- pentene, methyl butyl ether and 2-butyl alcohol can be separated better and detected by heart cutting method, and the detection limit is improved to 0.002% (mass fraction).

RESEARCH ON SIMULATING EVALUATION METHOD FOR AXLETREE CORROSION PROPERTY OF SYNTHETIC AIRCRAFT LUBRICANTS

2013, 44(4):  97-99. 

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Based on the experimental methods abroad, a simulating evaluation method for axletree corrosion property of synthetic aircraft lubricants was established with two kinds of synthetic aircraft lubricants as standard. The axletree corrosion properties of the two standard lubricants and seven kinds of synthetic aircraft lubricant samples at home and abroad were evaluated. The results show that the method has favorable repeatability and distinguishability and those two kinds of standard lubricants can simply and unfailingly ensure the efficiency of the experiment. Through the evaluating method, the axletree corrosion property of synthetic aircraft lubricants can be distinguished.

DETERMINATION OF METAL ELEMENTS IN PIPELINE TRANSPORTATION CRUDE OIL BY CRUCIBLE ASHING AND ICP-AES

2013, 44(4):  100-104. 

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The determination method for 14 kinds of metal elements in pipeline transportation crude oil was established using crucible and ICP-AES. The test results show that quartz crucible is a good choice for ashing crude oil and the suitable ashing conditions for pipeline transportation crude oil are 550 ℃，3hr. And a variety of elements can be detected accurately at the same time with sampling once. The element detection limit of the method is between 0.0006-0.7230 mg/L, RSD <7.0% (except cadmium 28.75%), and the standard recovery rate of 91%-115%.