Table of Content

12 November 2012, Volume 43 Issue 11

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STUDY ON THE HYDROCRACKING REACTION RULE OF FEED CONTAINING TETRALINS AND NAPHTHALENES MIXTURE

2012, 43(11):  1-5. 

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The hydrocracking reaction rules of tetralins and naphthalenes mixture on Ni-Mo catalyst containing HY zeolite were investigated using two series of feeds: feedⅠwith constant tetralin content and various alky-naphthalene contents, feedⅡwith similar total aromatic hydrocarbon content and various tetralins to naphthalenes ratios. The conversion and selectivity of hydrocarbons took part in reactions were calculated from the detailed product analyst. Results showed that for feedⅠthe conversion of naphthalenes decreased with the increase of naphthalene content, the selectivity of tetralins ring opening to form alky-benzene was not affected significantly in this case, yet it was suppressed obviously in feedⅡcase with the increase of methyl-naphthalene content. Due to the occupation of hydrogenation sites and acid sites by the adsorption of polycyclic aromatic hydrocarbons, the hydrogenation and isomerization of tetralins were suppressed, especially for isomerization ring opening reactions.

STUDY ON THE EFFECT OF TAHE CRUDE OIL DENSITY ON THE PROPERTIES OF ASPHALT PRODUCED

2012, 43(11):  6-9. 

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Four kinds of crude oil samples from Tahe oil field were selected and their properties were determined. These four feeds were distilled separately to prepare asphalt samples whose penetration could meet the scope of 80—110 (0.1mm), and the prepared asphalt samples were analyzed according to the items of 100# product in standard SH/T 0522. The results are listed as follows: ①The density of crude oil can be used to characterize the properties of asphalt from said crude oil.②The properties of asphalt are relevant to the properties of crude oil, such as with the increase of crude oil density, the ductility (at 25℃ and 15℃) of asphalt decreases and the softening point of asphalt increases. ③When the density of crude oil reaches a certain value (about 0.94 g/cm3), for the prepared asphalt having penetration near the upper bound of 100# product requirement, it is a qualified product; yet if the penetration of the prepared asphalt sample is near the lower bound of 100# product, its ductility mostly cannot meet the product requirement. ④When the density of the selected crude oil is higher than 0.95 g/cm3, it cannot be used to produce 100# paving asphalt by distillation process.

EFFECTS OF CATIONIC EMULSIFIERS ON THE TEMPERATURE SUSCEPTIBILITY OF ASPHALT

2012, 43(11):  10-15. 

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The effects of two cationic emulsifiers (CAP-3 and CAP-1) and their content on the temperature susceptibility performance of the evaporation residue of asphalt emulsion, such as penetration index (PI), equivalent breaking point (T1.2), equivalent softening point (T800) and viscosity index (VTS), were investigated, in which three asphalt samples (Zhonghai AH-90, Karamay AH-90 and Jiangyin AH-90) were involved. Test results show that for emulsions having emulsifier mass fraction in the range of 0—5.0 %, the PI of evaporation residues from Zhonghai AH-90 and Jiangyin AH-70 asphalt emulsions decrease with the increase of CAP-3 emulsifier content, which indicates that their temperature susceptibilities at the medium temperature range degrade, besides, the PI changing trend of evaporation residue from Karamay AH-90 asphalt emulsion goes up firstly followed by decline with the increase of CAP-3 content; however, CAP-1 emulsifier has little effect on the three asphalts in this case. The low temperature crack resistance of these three asphalt samples is improved by adding CAP-3 emulsifier as shown by the reduction of T1.2, while CAP-1 emulsifier has less impact. Adding CAP-3 emulsifier could decrease the T800 of evaporation residues from these three asphalt samples significantly, thus the plastic deformation resistance at mid-high temperature range of these three samples deteriorates, the reduction sequence is Jiangyin AH-70≈Zhonghai AH-90> Karamay AH-90; nevertheless, the effect of CAP-1 emulsifier in this case is also insignificant. For high temperature susceptibility, with the increase of CAP-3 emulsifier content, Jiangyin AH-70 trends to decrease, Zhonghai AH-90 and Karamay AH-90 trend to increase slightly; this time adding CAP-1 emulsifier shows somewhat raise trends for all the three asphalt samples.

STUDY ON THE EFFECT OF n-ALKANOL ON THE PHASE STABILITY OF METHANOL–STRAIGHT-RUN GASOLINE BLENDS

2012, 43(11):  16-20. 

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Effects of a series of n-alkanol additives on the phase stability of methanol–straight-run gasoline blends were studied by testing phase separate temperature of these blends and analyzing linear regression equation of curves related with n-alkanol amount–phase separate temperature. Results show that the positive effects of C4-C10 n-alkanol on the phase stability of methanol–straight-run gasoline blends are better than that of low carbon number alcohol. Those effects are relative to HLB values of n-alkanol and the volume fraction of methanol (MVF) in the system. The most effective additive to maintain a stable system for M15 and M85 blends (MVF of 15% and 85%, respectively, following the same) is n-hexanol, so does n-decanol for M30, M50 and M65 blends. Under medium MVFs, for blends with same MVF, its phase stability can be improved with the decrease of n-alkanol HLB value; for blends with high MVF or low MVF, there is always an optimum n-alkanol HLB value to maintain a stable system. For systems adding the same n-alkanol, with the increase of MVF in the blends, the phase stability of the system weakens gradually.

REACTION BEHAVIOR OF STRAIGHT-RUN NAPHTHA DURING CATALYTIC CRACKING AND THERMAL CRACKING

2012, 43(11):  21-26. 

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The behavior of catalytic cracking and thermal cracking of straight-run naphtha was investigated over ZRP catalyst and kaolin thermal medium respectively. The results indicated that compared with thermal cracking, catalytic cracking of naphtha occurred at lower temperature with higher conversion and higher yield of cracked gas, especially, the yields of ethylene and propylene increased 2—3 percentage point and 5—7 percentage point, respectively. The volume fractions of components in dry gas from catalytic cracking and thermal cracking reactions were different; it could be attributed to the cracking reaction pathway varied with temperature. The changing trends of the gasoline compositions in catalytic cracking and thermal cracking were similar based on the composition of feedstock, of which naphthenes were apt to take part in sorts of reactions and aromatics increased greatly at high temperature.

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APPLICATION OF PRIME-G+ TECHNOLOGY IN FCC NAPHTHA HYDRODESULFURIZATION UNIT

2012, 43(11):  27-30. 

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To meet the sulfur content of gasoline product satisfying national emission standard Ⅳ, a 1.8 Mt/a hydrodesulfurization unit processing FCC naphtha feed was built at Lanzhou Petrochemical Company adopting Prime-G+ technology. Performance test data of this unit show that when processing FCC naphtha with sulfur content of 195 μg/g, the obtained mixed gasoline product has total sulfur content and mercaptaneous sulfur content of 38.5 μg/g and 3.5 μg/g, respectively. The RON loss of the gasoline product is 1 unit, which is less than the design value (1.8 units). Furthermore, the yield of mixed gasoline product was 99.91% which is a bit higher than the design value (99.90%), and the energy consumption was 934.6 MJ/t which is lower than the design value (937.2 MJ/t). The unit is operated stably under full-capacity with significant economic efficiency, an increment of 690 MRMB annually.

EXPERIMENTAL STUDY ON VACUUM DEEP CUT TECHNOLOGY BASED ON MOLTEN SALT HEATING VACUUM RESIDUE

2012, 43(11):  31-35. 

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Factors affecting vacuum deep cut of residue oil were analyzed. A technology for vacuum deep cut based on heating vacuum residue (VR) by molten salt was introduced and put into practice on a newly built pilot plant device of a refinery. Results of pilot plant tests showed that by molten salt heating the temperature of VR could reach the required temperature for conducting vacuum deep cut, furthermore, the heating by molten salt was uniformed and the temperature difference between tube surface and VR was only a little. Under the conditions of a vacuum column feed inlet temperature of 415 ℃, column bottom temperature of 380 ℃, top temperature of 355 ℃, top absolute pressure of 0.90-0.92 kPa, the distillate yield of VR (from said refinery) by deep distillation reached 35%.

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IMPROVEMENTS IN PRETREATING PROCESS OF FENGCHENG SUPER HEAVY CRUDE OIL

2012, 43(11):  36-39. 

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When pretreating mixed Fengcheng super heavy crude oil (containing 60—70% Fengcheng super heavy crude), overload of electric current often happened at the electric desalting device of delayed coking unit. It was found that processing crude with high water content from the bottom of crude tank was the main reason. In order to keep electric desalting unit running safely and smoothly, some improvements were conducted, such as increase the dewater frequency and temperature of crude tank, mixed processing the high water bottom crude in small amount with conventional crude, shifting the demulsifier injection spot forward, decrease the mixing force of mixing valve, as well as the transformer voltage. Since then the water and salt contents of purified crude dropped to less than 0.5% and 7.5 mgNaCl/g, respectively. Some other measures to further reduce the water and salt contents of Fengcheng crude for meeting the required targets (less than 0.3% and 3.0 mgNaCl/g, respectively) were proposed as well.

AN ANALYSIS OF THE DEACTIVATION OF CLAY FOR REFINING MIXED XYLENES IN CCR UNIT AND COUNTERMEASURES

2012, 43(11):  40-43. 

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CCR reformate is rich in mixed xylenes and usually contains some trace olefins, which could be removed by active clay. The application status of clay at the xylene refining tower of CCR unit and the principle of clay refining were summarized, the deactivation of clay was analyzed from the quality of clay, operation conditions and reaction severity of CCR process as well. To prolong the service life of clay, measures including optimizing the process flow of clay refining, optimizing reforming feed and reaction conditions, as well as optimizing the operation conditions of clay refining tower, were put into practice. Since then, the service life of clay prolonged from 30 d to 60 d and the loss of xylene cut down due to less clay substitutions.

OPTIMAL UTILIZATION OF LIGHT FRACTIONS FROM AN ISODEWAXING UNIT

2012, 43(11):  44-46. 

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The properties of light fractions（including naphtha, kerosene and diesel）from the 400 kt/a lube isodewaxing unit of CNOOC Huizhou Company were reviewed and a proposal for optimizing the utilization of these fractions was presented, such as producing AR petroleum ether from naphtha; odorless kerosene and base oil for rolling aluminum foil from kerosene fraction; various types of solvent oil for all sorts of applications from diesel fraction.

HYDROTHERMAL SYNTHESIS OF WO3 NANORODS AND ITS CATALYTIC PERFORMANCE OF REMOVING DIBENZOTHIOPHENE

xiu-ping LI

2012, 43(11):  47-50. 

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WO3 nanorods were prepared under hydrothermal conditions using sodium tungstate and ammonium nitrate as raw materials. Oxidative desulfurization reactions of model oil containing dibenzothiophene (DBT) were studied over WO3 nanorods catalyst and using H2O2 as oxidant. The effect of experimental conditions on desulfurization rate was investigated and the optimum reaction conditions were determined. Test results show that H2O2/WO3/CTAB system is effective to remove DBT. Using 5 mL of model oil with DBT mass fraction of 500 μg/g, under the conditions of WO3 nanorods amount of 0.01 g, H2O2/DBT molar ratio of 8, a reaction temperature of 70℃, a reaction time of 1.5 h, using N-N-dimethylformamide as extractant with an amount of 8 mL and an extraction time of 5 min, the removal rate of DBT reaches 100 %. The catalyst is recycled five times and without significant decrease in DBT removal rate.

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INVESTIGATION ON THE PRODUCTION PROCESS OF CATALYST FOR OXIDIZING PROPYLENE TO ACRYLIC ACID

2012, 43(11):  51-54. 

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The production process of catalyst for propylene oxidation to produce acrylic acid was studied in detail including the reaction process, spray drying and compression molding. Test results show that during the reaction stage, proper controlling the reaction time of ammonium molybdate, ammonium metavanadate and ammonium paratungstate is the key factor to ensure good repeatability of catalyst preparation and the optimum reaction time is 1.5 h. The optimum process parameters of spray drying are an inlet air temperature of 180—190 ℃, motor frequency for material feeding of 10 Hz and motor frequency for spray of 49 Hz. And the optimum process parameters of compression molding are water/silica sol volume ratio of 1.5 and mould rotational speed of 22 r/min.

STUDY ON THE XYLENE ISOMERIZATION PERFORMANCE OF SEVERAL MOLECULAR SIEVE CATALYSTS

2012, 43(11):  55-58. 

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Several molecular sieves with various pore structures were synthesized. The pore structure and acidity of these molecular sieves were characterized by BET and NH3-TPD, their catalytic performance in xylene isomerization was investigated as well. Test results indicate that both the pore structure and acidity of catalyst have significant effect on xylene isomerization. The types of reactions happened are mostly depended on the pore structure, overlarge pores are favored for transalkylation reactions take place to form heavy aromatics, which leads to increase the loss of C8 aromatics; on the other hand, extreme small pores could also increase the loss of C8 aromatics by cracking or dealkylation reactions. The catalyst activity and selectivity are closely related with the catalyst acidity, unsuitable acidity leads to increase the loss of C8 aromatics as well. Therefore, catalyst having good reaction performance in xylene isomerization should have appropriate pore structure and acidity simultaneously.

MODIFICATION OF NaY/β COMPOSITE MOLECULAR SIEVE AND ITS ADSORPTION PERFORMANCE OF REMOVING NITROGEN CONTAINING COMPOUNDS IN MODEL OIL

2012, 43(11):  59-62. 

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Using the method of ion-exchange followed calcination twice to prepare CeY/β and BaY/β composite molecular sieve samples from sodium type Y-β composite molecular sieve, the composite samples prior and post to modification were characterized by XRD and ICP-MS. The adsorption denitrogenation effects of these samples were investigated using model diesel oil with nitrogen content of 600 μg/g, and the process conditions were optimized. Test results show that the structure of molecular sieve samples prior and post to modification were basically unchanged, yet the nitrogen removal rates of the modified samples increased significantly and CeY/β sample showed the best. The optimum adsorption conditions of denitrogenation were obtained as follows: for CeY/β sample, an adsorbent/oil mass ratio of 1:20, a reaction temperature of 40 ℃ and an adsorption time of 3 h; for BaY/β sample, an adsorbent/oil mass ratio of 1:40, a reaction temperature of 40 ℃ and an adsorption time of 4 h.

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RECENT DEVELOPMENTS IN BIOMASS CARBON-BASED SOLID ACID CATALYST

2012, 43(11):  63-68. 

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The research progress in the preparation and application of biomass carbon-based solid acid catalyst was reviewed including a detail introduction of major preparation methods and catalyst performance in various application cases, a comparison of preparation methods and catalyst properties, and finally, a discussion about future research.

STUDY ON THE INHIBITION OF COPPER CORROSION WITH METAL PASSIVATOR T551 IN TRANSFORMER OIL

2012, 43(11):  69-72. 

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The corrosion inhibition function of benzotriazole (BTA) type metal passivator T551 in transformer oil was investigated based on corrosive sulfur test (ASTM D1275B), the related properties of transformer oil were tested and the copper strip samples were analyzed by SEM and TOF-SIMS. Test results showed that T551 metal passivator exhibited good inhibition function of copper corrosion and aging of transformer oil. Adding T551 metal passivator in transformer oil, the dielectric loss of transformer oil could be reduced from 0.21% to 0.08% and the volume resistivity improved from 5.97×1012Ω?cm to 7.05×1012 Ω?cm. The test results of copper strip surface indicated that chelation happened between T551 passivator and copper, the branch chain was broken from the nitrogen atom of BTA ring to form coordination compounds containing BTA and Cu on the copper surface.

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SYNTHESIS AND CHARACTERIZATION OF ANTIOXIDANT WITH VISCOSITY MODIFIER FUNCTION FROM POLYISOBUTYLENE

2012, 43(11):  73-76. 

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A polyisobutylene base antioxidant having viscosity modifier function was synthesized using highly reactive polyisobutylene and 3-(3, 5-di-tert-butyl-4-hydroxy-phenyl) methyl acrylate as raw materials. The FT-IR analysis results showed that the structure of this synthesized antioxidant was consistent with that of the designed product. Results of TG analysis suggested that this antioxidant had excellent thermal oxidation stability and its incipient oxidative decomposition temperature was 40 oC higher than that of polyisobutylene. Rotary bomb oxidation test results showed this antioxidant exhibited good antioxidation properties, the oxidation induction time of mineral oil could be prolonged to 84 min (from 27 min) when this antioxidant was added with a mass fraction of 0.5%. The oxidation stability was improved evidently. When it was added with a mass fraction of 5.0%, testing kinematic viscosity of oil samples at 40 oC and 100 oC showed that the viscosity index of oil increased from 114 to 132, which indicated that this antioxidant also possessed the function of viscosity modifier.

STUDY ON THE ADDITIVE PACKAGE FOR 70TBN MARINE CYLINDER OIL BASE ON T114 METAL DETERGENT

2012, 43(11):  77-81. 

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An additive package for 70TBN marine cylinder oil was developed using high base number calcium naphthenate T114 as main metal detergent, then 70TBN marine cylinder oil was produced with said additive package. The physical and chemical properties of the prepared cylinder oil were tested and simulating performance evaluation was carried out using similar imported product as reference oil. Test results showed that the qualities of prepared cylinder oil and reference oil were at the same level, indicating that the prepared additive package could meet the demand of blending 70TBN marine cylinder oil. Moreover, this additive package exhibited good adaptability to various type I and type II base oil products (domestic and abroad) for blending qualified 70TBN marine cylinder oil. The commercial trial of producing said additive package showed that the reproducibility was excellent, and the prepared cylinder oil product having stable quality.

NEW PROGRESS OF CHEMICAL ANTICORROSIVE TECHNOLOGY FOR UNITS PROCESSING HIGH ACID CRUDE

2012, 43(11):  82-86. 

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By studying the characteristics of high acid crude, it is found that naphthenates not only promote naphthenic acid corrosion, but also increase the difficulty of water/oil system demulsification. The corrosion of unit processing high acid crude could be solved by technologies, such as evaluating the corrosiveness of crude, adopting demulsifier, neutralizing corrosion inhibitor and high temperature corrosion inhibiter comprehensively. Test results show that a new corrosion evaluation method based on copper strip weight loss developed by Research Institute of Petroleum Processing can simulate the corrosion of carbon steel by crude oil veritably. Some tailored demulsifier and metal removing agent packages exhibit excellent demulsification, demetallization, desalting and dehydration effect for processing high acid crude. Neutralizing corrosion inhibitors could effectively suppress "dew point" corrosion in condensing and cooling system; high temperature corrosion inhibiters reduce the corrosion rate at high temperature sites significantly.

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CORROSION ANALYSIS AND COUNTERMEASURES FOR LONG TERM OPERATION OF HIGH PRESSURE HYDROGENATION UNITS

2012, 43(11):  87-91. 

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The corrosion types of high pressure hydrogenation equipment and related effective protecting measures are introduced. Main equipment corrosion issues happened during the operation of two sets of high pressure hydrogenation units (residue hydrotreating and hydrocracking) in Hainan Petrochemical Company since startup, as well as the countermeasures are summarized, and some suggestions for operation and further improvement are proposed. From the years of production experiences, it can be seen that based on a proper design, optimum material selection and equipment manufacture, during the daily work, strengthening managements of process operation, equipment inspection and corrosion protection, a long-term safety and stable running of high pressure hydrogenation unit is truly possible.