Table of Content

12 January 2012, Volume 43 Issue 1

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DEVELOPMENT AND COMMERCIAL APPLICATION OF KEY TECHNOLOGY FOR EFFICIENT CONVERSION OF HEAVY OIL

2012, 43(1):  1-6. 

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To make full use of oil resources and obtain more light oil products, RIPP (Research Institute of Petroleum Processing) has developped RHT (Residue Hydrotreating Technology) and RICP (Residue hydrotreating Integrated with Catalytic cracking Process) key technology, an organic integration of RHT and RFCC, which can promote the heavy oil conversion and raise the light oil yield significantly. With regrad to RHT, on a basis of inheriting the advantages of RIPP's existing technologies, a new generation of RHT series catalysts and technology has been developped, featuring with hydroconversion of more large molecular species (such as asphaltene and gum) and hydrosaturation of more cracked polyaromatics molecules along with enhanced capability of removing metals (Ni and V) and hetero atoms (S and N). Results from commercial application show that achievements including high removal rate of impurities, prolonged operation cycle, a highly efficient utilization of both the catalysts and the reactor, as well as providing high quanlity feedstock for FCC process are realized successfully.

INDUSTRIAL APPLICATION OF GL-1 DECHLORINATION ADSORBENT IN CCR UNIT

2012, 43(1):  7-10. 

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GL-1 dechlorination adsorbent developed by Research Institute of Petroleum Processing has been applied in the 0.7 Mt/a CCR unit of Luoyang Petroleum Chemical Corporation since May 2009. The results of more than two years stably operation show that GL-1 dechlorination adsorbent possesses good dechlorination performance, for treating regeneration flue gas, the HCl mass fraction of treated gas is less than 0.5 μg/g. It also exhibits excellent anti-carbonation, anti-caking and anti-argillitization properties, thus the pressure drop of the dechlorination adsorbent bed is less than 0.03 MPa and its service life is over 4 months, which well meets the requirements for the dechlorination of regeneration flue gas in CCR unit.

DEVELOPMENT AND APPLICATION OF FF-46 CATALYST FOR HYDROCRACKING FEEDSTOCKS PRETREATMENT

2012, 43(1):  11-15. 

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In order to meet the requirement of processing high nitrogen and sulfur feedstocks, a new generation of hydrocracking pretreatment catalyst, FF-46, was developed by Fushun Research Institute of Petroleum and Petrochemicals. FF-46 catalyst having Mo-Ni active metal components was prepared by complexation technology and the acidity of its support was well adjusted. Lab evaluation results showed that the catalytic activity of FF-46 catalyst was significantly better than those of other catalysts including an industrial reference catalyst. FF-46 catalyst was applied in several hydrocracking units successfully. The industrial application results showed that FF-46 catalyst exhibited high HDN and HDS activities，it can meet the requirement of long-term operation.

TECHNICAL REVAMPING FOR SHORTENING COKING CYCLE OF COKING UNIT

2012, 43(1):  16-19. 

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To increase the throughput of a coking unit, a series of technical revamping including heating furnace and process flow, was carried out to shorten the coking cycle. After revamping the coking cycle is shortened from 24 h to 18 h, the throughput is increased from 1.0 Mt/a to 1.25 Mt/a, recycle ratio reduces from 0.25 to 0.15 and operation of flexibly adjusting recycle ratio is realized. The unit is operating stably with slightly reducing dry gas yield and increasing light oil yield, and the total energy consumption of the unit is reduced, an energy saving of 2.66×108 MJ/a is achieved.

STUDY ON THE NAPHTHENIC RING OPENING REACTIONS OF TETRAHYDRONAPHTHALENE OVER ZEOLITE CATALYSTS

2012, 43(1):  20-25. 

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Experiments of tetrahydronaphthalene cracking over Y and ZSM-5 zeolite catalysts under certain reaction temperature and catalyst/oil (C/O) ratio were conducted on a fixed fluidized bed (FFB) unit in laboratory. Test results show that the products of tetrahydronaphthalene cracking over these two zeolite catalysts by naphthenic ring opening reactions were non-aromatics (propane, propylene, butane, butylenes, methylpenptane, cyclopentane, cyclohexane) and monocyclic aromatics (benzene, C1～C4 alkyl benzene). Products of which by dehydrogenation condensation reactions were polycyclic aromatics (naphthalene, alkyl naphthalene, phenanthrenes, pyrenes and so on) and coke. Among them, the relative ratio of naphthenic ring opening reactions to dehydrogenation condensation reactions over Y and ZSM-5 zeolite catalysts was 1.22 and 0.95, respectively. Due to the diffusion and adsorption of naphthenic aromatics on catalysts, the selectivity of naphthenic ring opening reactions are higher over Y zeolite catalyst than those over ZSM-5 zeolite catalyst. Under the conditions of a WHSV of 10 h-1, reaction temperature in the range of 450-550℃, C/O mass ratio in the range of 3-9, the reactions of bimolecular hydrogen transfer and dehydrogenation condensation enhance with the increase of reaction temperature and/or C/O ratio, as a result, the selectivity to the products from naphthenic ring opening reactions decreases.

FORMATION MECHANISM OF POROUS MOLECULAR SIEVE Y COMPOSITE

2012, 43(1):  26-31. 

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Novel structure zeolite Y (NSY) composites were synthesized by hydrothermal synthesis method using sodium silicate and metakaolin as raw materials. The structure composition, distribution of pore size, pore volume, grain size, morphology of the synthesized samples and raw materials were obtained by X-ray diffraction, nitrogen sorption, mercury porosimetry and scanning electron microscope respectively. The results show that in NSY composites, micro-pores, meso-pores and macro-pores coexist, and the meso-pores and macro-pores of NSY composites are varied from those in metakaolin. Based on these results, a pore-forming mechanism of NSY composite is proposed including nucleation in solid phase and intergranular interaction in crystal growth.

RELATIONSHIP BETWEEN MOLECULAR TOPOLOGICAL STRUCTURE AND PROPERTY OF LINEAR MERCAPTAN

2012, 43(1):  32-35. 

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Based on the topological structure characteristics of linear mercaptan, topological indices WN and SG were proposed by distance matrix, and indices WN and SG of more than 10 mercaptans were calculated. Using linear-regression analysis method, a series of quantitative structure-property relationship (QSPR) models among topological indices and some properties of mercaptan including standard enthalpy, standard free energy, standard entropy, boiling point and chromatography retention index, were built and their multiple correlation coefficients were 0.999 0, 0.999 4, 0.999 7, 0.993 4 and 0.995 1, respectively. Results show that good correlations exist among these properties of mercaptan and topological indices WN and SG; QSPR models exhibit good stability to predict these physical properties of linear mercaptans.

EFFECT OF DRYING AND CALCINATION TEMPERATURE ON HYDROCRACKING CATALYST

2012, 43(1):  36-40. 

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A series of W/Ni-based hydrocracking catalysts dried and calcined under various temperatures was prepared by impregnation method. The prepared catalysts were characterized by means of N2-adsorption, NH3-TPD, XRD and TPR technique; the hydrocracking performance of these catalysts was investigated using dodecane as model compound. The results showed that with the increase of calcination temperature, the specific surface area of the catalyst decreased slightly, pore size increased and pore volume was basically unchanged. The acid amount and hydrocracking activity of the catalyst both showed a tendency to ascend firstly, followed to descend with the increase of calcination temperature, and the peak value for the former and the latter was at 400 ℃ and 500 ℃, respectively. When the calcination temperature reached 600 ℃, aggregation of the metal components happened on the surface of the carrier. On the whole, catalyst calcined under suitable temperature could improve its performance, yet high temperature calcination might suppress the activity of the catalyst. Reducing the catalyst drying temperature from 200 ℃ to 120 ℃, the specific surface area of the catalyst decreased, pore size and pore volume increased, acid amount was basically unchanged and the catalyst activity enhanced.

PREPARATION OF PHOSPHORUS MODIFIED ZEOLITE BETA AND ITS APPLICATION IN BENZENE-ETHYLENE ALKYLATION REACTION

2012, 43(1):  41-44. 

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Phosphorus modified β zeolite samples were prepared by using ammonium biphosphate solution under high temperature and pressure. The crystallinity, elemental composition, acidity and structure of the phosphorus modified β zeolite samples were characterized, and their catalytic activities during benzene-ethylene alkylation under high space velocities were investigated. Results showed that the total acid amount, B-acid sites and L-acid sites of the P-modified β zeolite samples increased significantly. Furthermore, structures of P(4Al) and Al(4P) were found existing in the framework of P-modified β zeolite as shown by 31P MASNMR and 27Al MASNMR spectrum, thus, the framework aluminum atoms were stabilized and the activity stability of the zeolite catalyst enhanced. P-modified β zeolite catalyst with 2% P2O5 exhibited the best activity stability during benzene-ethylene alkylation under high space velocity.

CHARACTERIZATION OF COKE ON SPENT CATALYSTS FROM FIXED-BED HYDROTREATING UNIT PROCESSING RESIDUE FEED

2012, 43(1):  45-48. 

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Coke on spent catalysts from various stages of a commercial fixed-bed hydrotreating unit processing residue feed was characterized by SEM, TPO-MS and CHO elemental analyzer. Test results show that following the feed flow direction, the coke contents of catalysts exhibit a trend of firstly decrease then increase, the H/C atomic ratios of coke show decrease trend and oxidation temperatures of coke increase gradually. It is shown that the formation of coke is related with the nitrogen containing compounds of feed in some ways, asphaltene containing nitrogen atom is easy to be adsorbed on the acid sites of catalyst and to form coke further.

STUDY ON THE DEACTIVATION AND REGENERATION OF HZSM-5 CATALYSTS IN HYDRATION OF CYCLOHEXENE

2012, 43(1):  49-53. 

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The deactivation and regeneration of HZSM-5 catalysts in hydration process of cyclohexene to prepare cyclohexanol were investigated, combining with characterization of various catalyst samples by FT-IR, XRD, ICP-AES and N2 adsorption-desorption techniques. Results indicated that the framework structure of deactivated HZSM-5 catalyst was basically unchanged, and a little dealumination of the catalyst could not cause the serious deactivation of catalyst, thus the deposition of coke species on catalyst surface and pore channel blockage should be the main causes of catalyst deactivation. The coke species was analyzed by FT-IR, TG-DTG and GC-MS. It was shown that the coke species was mainly consisted of dicyclohexyl ether and alkene oligomers. However, the deactivated HZSM-5 catalyst could be regenerated and reactivation by suitable methods to recover its catalytic activity for reuse.

PREPARATION OF γ-Al2O3 POWDER BY COMBUSTION SYNTHESIS METHOD AND CHARACTERIZATION

2012, 43(1):  54-57. 

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Nanometer γ-Al2O3 powder was prepared by combustion synthesis method using aluminum nitrate and glycine as raw materials. The prepared γ-Al2O3 powder was characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM) and thermogravimetric-differential thermal analysis (TG-DTA). The influence of solution pH value, raw materials molar ratio, calcination temperature on the particle size, purity and morphology of γ-Al2O3 powder were investigated. Under the optimal preparation conditions of aluminum nitrate/glycine molar ratio of 3:5, a solution pH value of 2 and a calcination temperature of 750℃, fluffy γ-Al2O3 powder with high purity could be obtained.

APPLICATION OF LixK2-xTi2O5 IN THE PURIFICATION OF SOOT FROM DIESEL EXHAUST

2012, 43(1):  58-61. 

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LixK2-xTi2O5(x=0.125, 0.15, 0.2) samples were synthesized by solid-phase method using TiO2, KNO3 and LiOH·H2O as raw materials. The prepared catalysts were characterized by XRD, and their catalytic activities of soot oxidation were evaluated using TPR system under various conditions. Results showed that the structure of LixK2-xTi2O5 doped with a little Li+ was basically the same as K2Ti2O5; Li0.15K1.85Ti2O5 exhibited the highest catalytic activity among the three LixK2-xTi2O5 samples, its ignition temperature of soot was 210 ℃ and the peak temperature was 290 ℃. Furthermore, its catalytic activity of soot oxidation was significantly higher than some conventional noble metal catalyst (such as Pt-ZSM5), transition metal catalyst (such as Co,Ba,K/ZrO2) and others. Besides, its catalytic activity is higher under catalyst and soot in packed condition than in loose condition.

STUDY ON THE STABILITY OF EMULSIFIED ASPHALT FOR CA MORTAR

2012, 43(1):  62-67. 

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The effects of specific factors (including equipment, emulsifier, additives and asphalt content) on the stability of emulsified asphalt for cement and asphalt (CA) mortar were studied. Results showed that the emulsifying equipment, the amount of emulsifier, the type and amount of additives and asphalt content had great influences on the stability of emulsion, the optimum preparation conditions of emulsified asphalt were using SD-2 emulsifier with a dosage of 3.5%, an association thickening agent T of 0.4 %, a cellulose sodium (CMC) of 0.06 %, an asphalt mass fraction of 60% and applying colloid mill. The qualities of emulsified asphalt obtained under such conditions and CA mortar prepared by said emulsion could well meet the requirements of relative specifications issued by Ministry of Railways.

EFFECT OF OLEIC DIETHANOLAMIDE PHOSPHATE ON THE BIODEGRADABILITY AND LUBRICITY OF LUBRICATING OIL

2012, 43(1):  68-71. 

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Oleic diethanolamide phosphate (OEAP) was synthesized with oleic acid，diethanolamine and phosphorus pentoxide and its structure was characterized by means of IR spectroscopy. The impacts of OEAP as an additive on the biodegradability, corrosiveness, antiwear and friction-reducing ability of HVI350 mineral lube base oil were investigated. Test results indicated that OEAP additive could effectively enhance the biodegradability, load carrying capacity and friction-reducing ability of HVI350 mineral oil. Furthermore, the corrosion resistant of HVI350 lube oil was also improved by OEAP additive.

A STUDY OF CRUDE OIL RAPID ASSAY BY NEAR INFRARED SPECTROSCOPY

2012, 43(1):  72-77. 

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Near infrared (NIR) spectroscopy calibration models for determining the main physical and chemical properties of crude oil were built using partial least square method based on NIR spectral library consisting of data from 275 crude oils. A method for rapid identification of crude oil type, named moving window correlation coefficient, was proposed, which can distinguish spectra of highly similar crude oils.For blended crude oils, library spectra fitting method was used to obtain pseudo-blended crude oil types and their corresponding blending proportions. Combined with crude oil assay database, detailed crude oil data of unknown crude oils can be rapidly provided by the above methods.

SYNTHESIS AND CHARACTERIZATION OF 4-TERT-BUTYLCATECHOL

2012, 43(1):  78-83. 

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Para-tert-butylcatechol (4-TBC) is synthesized from catechol and MTBE using sulfuric acid catalyst. The methods of analysis and characterization on reaction process are investigated. 13C-NMR technique combined with gas chromatography (GC) is introduced to characterize the synthesized products. Adopting 13C-NMR technique to analyze the progress of reactions real timely, optimum process parameters can be obtained. The results show that characterizing the product by GC alone is much complex, and it is difficult to distinguish the peaks of impurities. By 13C-NMR method, the chemical shift of various carbon positions in the molecular structure can be determined, thus the reaction mechanism and carbon positions for reactions could be inferred, in a word, the components in product can be distinguished more clearly. Under the conditions of a mass ratio of catechol to MTBE of 1, a catalyst dosage of 6% (based on catechol), a reaction temperature of (120±2) ℃, MTBE adding time of 2.0-2.5 h, at 1.5 h after the completion of adding MTBE, the content of 4-TBC in the mixed product is 84.3%, and a 1.6% of 3,5-DTBC is detected.

PREPARATION OF POLYANILINE-Mn3O4 COMPOSITE AND STUDY ON ITS CORROSION PROTECTION PERFORMANCE

2012, 43(1):  84-88. 

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Composite of polyaniline (PANI)-Mn3O4 (PMC) was prepared by chemical oxidative method using aniline as raw material and ammonium persulfate as oxidant in the presence of Mn3O4 nano-particles. Undoped PMC and undoped PANI were prepared by mixing with ammonia solution to remove impurities. The prepared polymers were characterized by XRD and IR techniques. To study the corrosion protection performance of the prepared polymers, PANI and PMC was coated on steel strip respectively, and the coated strips were immersed in 3.5% NaCl solution and 1.0 mol/L HCl solution respectively. Then open circuit potential and polarization curve measurements of the coatings were carried out to compare their corrosion protection performance. Results indicate that strong interactions of Mn3O4 particles and PANI exist, and the crystallization of PANI molecular chain is affected by Mn3O4 particles as well. The corrosion protection properties of coatings containing PANI and PMC are better than that of varnish, the corrosion current (icorr) of coating containing PMC is the smallest, and thus its corrosion protection performance is the best.

APPLIED RESEARCH ON THE INORGANIC ZINK-RICH COATING FOR CORROSION PROTECTION

2012, 43(1):  89-93. 

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A series of inorganic zinc-rich coating samples with various zinc contents was prepared by brush and spray methods to investigate the corrosion resistant performance of zinc-rich coating in oilfield produced water system, sour oilfield produced water system (pH value of 4) and marine atmosphere. Results showed that the acid resistant property of zinc-rich coating was not good enough, coating having a mass ratio of inorganic resin/zinc powder equaled 1:2.6, exhibited the best corrosion resistant property. By analyzing the morphology of sample prior and post to corrosion, comparing the XRD pattern of corrosion product, the phase and structure of the corrosion product was determined. It was found that Zn5(OH)8Cl2·H2O was the main corrosion product, under high chlorine conditions, insoluble Zn5(OH)8Cl2·H2O could inhibit further corrosion, soluble zinc acted as sacrificial anode for the cathodic protection of steel.

SYSTEM ANALYSIS AND OPERATION OPTIMIZATION FOR THE ABSORPTION AND STABILIZATION SYSTEM IN A FCC UNIT BASED ON PROCESS SIMULATION

2012, 43(1):  94-100. 

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Taking a typical absorption and stabilization system with four towers as research object, by comparing the calculation results from PRO/Ⅱsimulation software and the calibration data of the practical unit, parameters in the simulation are determined and SRK method is adopted to optimize simulation. In the premise of the specific qualities of dry gas, LPG and gasoline, the effect of operation parameters on the energy consumption and absorption results is studied, and the optimized operation parameters are obtained as follows: a complementary absorbent flow rate of 29 t/h, a system operation pressure of 1.4 MPa, the flow rate ratio of hot and cold feeds for the desorption tower is 7 to 3, and the feed inlet location and temperature of the stabilization tower is at 12th theory tray and 138 ℃, respectively. The simulation results demonstrate that by optimizing operation parameters, the cooling duty and heating duty of the unit is reduced about 4% and 5%, respectively.

PRESENT STATUS AND DEVELOPMENT OF TECHNOLOGY FOR REMOVING OLEFINS FROM REFORMATE

2012, 43(1):  101-106. 

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The present status and developing trend of processes and catalysts for removing olefins from reformate were introduced focusing on the evolvement of the processes and R & D of the catalysts in a few large Petrochemical Corporations worldwide. The distributions of olefins in reformate and factors affecting the formation of olefins were discussed. It was found that C6 and C7 olefins were the main olefins in reformate, and their contents increased with the reaction severity. Finally, suggestions for domestic research thinking in these aspects were proposed, such as developing catalyst having high activity and stability, can be regeneration for times to replace clay treatment substantially and so on.