Table of Content

12 March 2015, Volume 46 Issue 3

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EFFECT OF HYDROGEN DONOR ON PRODUCT DISTRIBUTION OF RESIDUE OIL HYDROTREATING

2015, 46(3):  1-4. 

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Residue oil hydro-upgrading was studied in an autoclave with hydrogen donor and supported catalyst. The product distribution was analyzed to determine the effect of hydrogen donor. The results show that hydrogen donor has no effect on the conversion ratio, but reduces the gas and coke yield. And the methane content in the gas is also decreased. The hydrogen donor can improve the distribution of liquid product and convert 350?500 ℃ fraction to more 180-350℃ fraction.

FACTORS AFFECTING DEMULSION OF EMULSIFIED CRUDE OIL OF ACIDIZING WELLS IN TAHE OILFIELD

2015, 46(3):  5-9. 

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Demulsification of emulsified crude oil of acidizing wells is always a technical difficult problem in Tahe oilfield. This work investigated the demulsification of two kinds of Tahe emulsified crude oils by light scattering method and electrostatic field method, respectively, and then analyzed the main factors affecting the demulsification of emulsified oil from three aspects of residual chemicals, solid particles, resins and asphaltenes. The results show that the guar gum in fracturing fluid and the hydrochloric acid in acidizing fluid are harmful to demulsification; the existing solid particle composed of lipophilic compounds of iron and sulfur promotes the stabilization of W/O fluids; the asphaltene aggregate having worse solubility in acid oil is easy to form a stable asphaltene film. The synergistic effect of these three factors together increases the difficulty on demulsification of Tahe emulsified oils.

KINETICS OF HYDRODESULFURIZATION AND HYDRODENITROGENATION OF THE 4TH SIDE VACUUM STREAM

2015, 46(3):  10-14. 

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The hydrodesulfurization and hydrodenitrogenation kinetics of the 4th side stream of vacuum tower of Maoming Co. Sinopec were studied in a trickle bed hydrogenation unit using FF-46，a NiMo/Al2O3 hydrofining catalyst, at conditions of total pressure of 6~15 MPa，temperature of 608.15~638.15 K，liquid hourly space velocity of 0.75~2.00 h-1 and gas to liquid volume ratio of 600. A hydrodesulfurization and hydrodenitrogenation kinetic model of the 4th side stream was established. The experimental data were fitted by the Levenberg-Marquardt and the general global optimization method, and then the model was verified by the real data. The results indicate that the reaction orders of HDS and HDN are 1.4 and 1.7, respectively, and the activation energies are 74.60 kJ/mol and 72.90 kJ/mol, respectively. The established model can well predict the sulfur and nitrogen content in the product.

STUDY OF AROMATIZATION REACTIVITY OF POST-MTBE C4 ON ZSM-5 CATALYST

2015, 46(3):  15-17. 

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The catalytic activity and performance in long operation of ZSM-5 catalyst for post-MTBE C4 aromatization in a fixed bed were studied. The results indicate that at the optimal reaction conditions of 380℃，2.0MPa, WHSV of 2.0h-1 and H2/oil volume ratio of 300, the conversion of olefin exceeds 99%, the yield of dry gas is less than 2.0%, the yield of C5+ is 35%~41%, the yield of LPG is 57%～64%, the yield of aromatic is 10%～12%, and the catalyst shows a stable performance. After 984 h running, the coke deposition on the catalyst is 11.56% and no deactivation of the catalyst is observed. The gaseous product is an excellent material for ethylene production.

DEVELOPMENT OF HIGHLY ACTIVE WHITE OIL HYDROGENATION CATALYST RLF-20

2015, 46(3):  18-23. 

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A highly active catalyst RLF-20 for white oil production is developed by optimizing carrier, metal ratio, metal loading, and using metal dispersion technology. A pilot plant test was done using KN4010 rubber filling oil from Kelamay refinery of CNPC as the feed. The results reveal that the product meets the quality standard for food grade white oil at LHSV, 25% higher than the original catalyst RLF-10W. The sulfur resistance of RLF-20 is also improved. The aromatics removal rate in the early stage reaches 87%, then decreases to 85% after 7 days running, only 2.3% less. Under the same conditions, No. 68 rubber filling oil with more than 10% aromatics from HangZhou Refinery of SINOPEC was used to do the stability test. The 1 000 h stability test demonstrates that small changes in UV adsorption at 275 nm only from 0.4 in the initial stage to ~0.6 are observed, which indicate a good stability of RLF-20 for food grade white oil production.

APPLICATION OF CATALYTIC CRACKING ADDITIVE FLOS-III FOR MORE PROPYLENE AND ISOBUTENE

2015, 46(3):  24-28. 

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The application of catalytic cracking additive FLOS-III for more propylene and isobutene in a 1.05 Mt/a MIP-CGP FCC unit of Baling Refining and Chemical Company was described. The first application shows that when the inventory ratio of the additive reaches 6%, the yield of LPG, propylene and isobutene increases by 2.68 percentage points, 1.01 percentage points, and 0.54 percentage point, respectively, with improved product distribution. The yield of the poor quality and low added value LCO decreases by 2.09 percentage points, the coke yield decreases by 0.25 percentage point, while the total liquid yield increases by 0.17 percentage point. The yield of gasoline and its RON is similar to the blank test. It is concluded that the use of additive FLOS-Ⅲ is helpful to produce more propylene and isobutene with significant economic benefits.

INDUSTRIAL APPLICATION OF RFCC CATALYST ZCG-1 FOR INCREASING GASOLINE PRODUCTION

2015, 46(3):  29-33. 

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The industrial application of ZCG-1 catalyst in the RFCC unit of Beijing Yanshan Company，SINOPEC was introduced. The results of application indicate that ZCG-1 catalyst shows excellent residue cracking ability, resistance to heavy metal contamination and good coke selectivity, especially gasoline selectivity. When the feedstock contains 50 % (w) residue, the gasoline yield reaches 48%-50 % (w), increased by 6.0 percentage points than the former catalyst VRCC-1 and the liquid yield maintains at 82%-83% with a good product distribution and a remarkable economic benefit.

APPLICATION OF LS-951T HYDROGENATION CATALYST FOR SULFUR RECOVERY TAIL GAS TREATMENT

2015, 46(3):  34-38. 

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LS-951T catalyst developed by Research Institute of Qilu Petrochemical Company is a new hydrogenation catalyst for treating sulfur recovery tail gas. LS-951T catalyst, with the advantages of uniform distribution of active components, light bulk density and high hydrogenation activity, has a good applicability. The properties of the catalyst and the commercial processes of catalyst loading, presulfurization in a 380kt/a sulfur recovery tail gas unit in Sinochem Quanzhou Petrochemical Co.，Ltd were described. The performance of the catalyst was examined and compared in low and high load operation case．The loading pattern of LS-951T catalyst was modified because it’s easy to flow in the later case. The application results after modification of loading show that the catalyst presents good hydrogenation activity ever if in high load case. The SO2 content is less than 300mg/m3 in the treated gas, lower than the country’s emission standard of 960mg/m3.

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EFFECT OF HYDROISODEWAXING CATALYST AND REACTION TEMPERATURE ON VISCOSITY INDEX OF BASE OIL

2015, 46(3):  39-42. 

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Pre-hydrofined light dewaxed oil (200SN) and heavy furfural refined oil (650SN) from Daqing Refining and Chemical company were used as feedstocks to investigate the effect of new isohydrodewaxing catalyst PIC-812 with improved B acid and operation conditions of pre-hydrofining and hydroisomerization on viscosity index of base oils. The industrial data indicate that the improvement of B acid and the higher reaction temperature of pre-hydrofining and hydroisodewaxing can all increase the ring opening selectivity, resulting in higher viscosity index of base oil. Compared with the previous generation hydroisodewaxing catalyst PIC-802, PIC-812 shows a higher activity. The reaction temperatures of PIC-812 are 2 ℃ and 26 ℃ lower than PIC-802, respectively, with other reaction conditions being the same using PIC-802. Both the base oil yields increase by 4 % and the viscosity index can increase 4 to 9 points.

STUDY ON DIRECT DECOMPOSITION OF NO ON Cu-ZSM-5 CATALYST

2015, 46(3):  43-47. 

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A series of Cu-ZSM-5 catalysts were synthesized by hydrothermal synthesis method using silica sol as silica source and sodium aluminate as aluminum source under different synthesis conditions. The simulated flue gas was used to exams the catalyst activity for NO direct decomposition, de-NOx conditions as well as the activity stability. The results find that the best catalyst performance is achieved at the synthesis conditions of silica/alumina ratio of 60, silicon/copper ratio of 17 and pH of 10-12. The catalyst prepared shows the best thermal tolerance and feed flexibility. The optimum working conditions for de-NOx of simulated flue gas with 580 ~ 680 μg /g of NO are: gas space velocity of 18 000 h-1 with O2 volume fraction of 5% and reaction temperature of 325~425℃.Under the above conditions, the removal rate of NO reaches more than 50% and the highest removal rate can reach 61% within 40h operation. The activity stability of the catalyst is the best at 375 ℃.

APPLICATION OF RTS ULTRA-DEEP DIESEL HYDRODESULFURIZATION TECHNOLOGY

2015, 46(3):  48-51. 

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Ultra-deep diesel desulfurization technology (RTS) developed by RIPP has been adopted in a newly built 2.6 Mt/a diesel hydrotreating unit in Yanshan company SINOPEC since Sept. 2013 using RS-2000 catalyst and guard catalyst RG-1 to produce diesel meeting phase V Beijing standard. The industrial application results show that the device operats smoothly and the sulfur content of diesel product is less than 10 ?g/g. RS - 2000 catalyst exhibits a good active stability and can produce ultra-low sulfur diesel for a long period at low pressure; The energy consumption of the unit is 344.17 MJ/t, 53.62 MJ/t less than the design value of 397.79 MJ/t.

ANALYSIS AND APPLICATION OF FCC FLUE GAS DESULFURIZATION AND DENITROGENIZATION TECHNOLOGY

2015, 46(3):  52-56. 

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Based on the comparison of several FCC flue gas desulfurization and denitrogenization technologies, Sichuan Petrochemical Limited Liability Co. CNPC introduced Belco Company`s EDV ? desulfurization and LoTOXTM wet washing denitration technology for its 2.5 Mt/a catalytic cracking unit. By the technologies, the concentration of SO2 is reduced from 2020 mg/m3 to 35 mg/m3, the nitrogen oxides are lowered from 300 mg/m3 to 26 mg/m3and the catalyst particles are reduced from 150 mg/m3 to 20 mg/m3. The reduced amount of SO2, NOX and particles in the discharged flue gas are reduced significantly by 4 625 t/a, 638 t/a and 303 t/a, respectively. The pH, COD and total suspended solids of the discharged waste water are much lower than the design emission standards.

ANALYSIS OF SCALING FORMATION IN HYDROCRACKER HEAT EXCHANGERS

2015, 46(3):  57-60. 

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Salt scaling frequently occurred in the hydrocracking unit in PetroChina Jinzhou Petrochemical Company. The scaling was faster especially after coker gas oil was added into the feed. The contents of heteroatoms in crude oil, vacuum gas oil, coker gas oil, and reformate hydrogen were determined. It is verified that the main component of the scale is ammonium chloride and the scaling is caused by the excess chlorine and nitrogen content in the hydrocracking feedstocks, and high nitrogen content in feed from coker gas oil accelerates the trend of scaling formation.

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STUDY ON TRIBOLOGICAL PROPERTIES OF La2O3 PARTICLES

2015, 46(3):  61-66. 

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The tribological properties of La2O3 particles prepared under the conditions of different calcination temperatures and times were investigated. La2O3 particles were modified by oleic acid before use. The point and surface contact antifriction and antiwear properties of modified La2O3 particles in 400SN base oil were investigated. The worn surfaces were analyzed by SEM and EDX techniques. Results indicate that La2O3 particles calcined at 700 ℃ have good comprehensive tribological properties. The longer the calcination time, the better the crystal structure of La2O3 particle. The modification of oleic acid improves the dispersion of La2O3 particle in the oil. Compared the 400SN base oil without modified La2O3 particles, the point contact antifriction of the oil with modified particles increases by 10.8%，antiwear increases by 27.8%, meanwhile, in the case of surface contact，the antifriction performance increases by 16.9%.

STUDY OF COMBUSTION CHARACTERISTICS OF OXYGENATED FUELS UNDER OXYGEN DEFICIENT CONDITION

2015, 46(3):  67-70. 

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Diglyme, diethyl adipate and biodiesel were selected as oxygenated additives to mix with diesel in different proportions, respectively，to investigate the combustion characteristics of fuels under the oxygen deficient conditions by low pressure oxygen bomb calorimeter. The efficiencies were evaluated by the combustion improvement factor Ψ. The results show that the three oxygenated additives can all improve the combustion of diesel fuel under the oxygen deficient condition. The combustion efficiency is concerned with the calorific value and the oxygen content of the oxygenated additive. At the altitude of 3000 meters, the best oxygenated additive is Diglyme, and the perfect dosage is 18%.

INFLUENCE OF IRON PARTICLES IN EMULSION ON WEAR OF COLD-ROLLED SILICON STEEL SURFACE

Li Yan Sun Jianlin Chen Jingyue

2015, 46(3):  71-74. 

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The tribological performance of emulsions with or without iron powder was tested by MRS-10A four-ball friction and wear testing machine and MM-W1A vertical universal friction-wear testing machine. The LMS-30 laser diffraction and scattering particle detection technology was applied in analyzing iron particle size in emulsions. The lubricating properties of the emulsions were conducted on a 4-high cold-rolling mill. The results show that the traces of steel ball grinding spot are deeper with a larger diameter using KD-1 emulsion containing iron powder. The average friction factor of KD-1 emulsion is 0.1007, 22.34% higher than that of KD-2 emulsion. The wear loss of the silicon steel surface is 35% higher than KD-2 emulsion. Obvious abrasion wear and plough wear on the silicon steel surface with the KD-1 emulsion are observed. The experimental results indicate that the content of iron powder in emulsion should be less than 150μg/g with the particle size less than 3μm in the high speed cold-rolled process. In addition, the content of iron can be reduced by magnetic filter or skimmers.

EFFECT OF STRUCTURE OF CALCIUM ALKYL SALICYLATES ON OIL-WATER SEPARATION PERFORMANCE OF MARINE ENGINE OIL

2015, 46(3):  75-78. 

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Four kinds of different calcium alkyl salicylate additives were mixed with base oil ，respectively，to test their water separation performance according to the method of SH/T 0619. The results find an obvious difference in water separation property of the four additives. The phenomena were discussed from average molecular weight and the alkyl chain structure. The analysis indicates that the alkyl carbon chain branching degree of calcium alkyl salicylates is the main reason for the difference. The less the branching degree is, the better the water separation performance is. There is little relationship between the average molecular weight and the water separation property.

DETERMINATION OF COMPATIBILITY OF CRUDE OIL AND CORRELATION WITH OIL PROPERTIES

2015, 46(3):  79-83. 

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The incompatibility of crude oils brings negative effect on refinery processing. To investigate the relationship between compatibility and properties of crude oil, the compatibility parameters were determined and correlation analysis was studied. The results show that initial flocculation point of crude oil can be determined by optical detection and then to calculate the compatibility parameters. It is found that the solubility blending number (SBN) is linear with the proportion of the blends. The higher the SBN, the better the compatibility. The density, K-factor, resin and asphaltene content of crude oil are related very well with compatibility parameters. A relationship between compatibility parameters and oil properties is established. The deviation between calculated results and the measured values is smaller.

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APPLICATION OF NEW COLUMN CHROMATOGRAPHY SEPARATION TECHNOLOGY IN SEPARATION OF TAHE VACUUM GAS OIL

2015, 46(3):  84-91. 

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A new column-chromatography separation method, which takes the packing loading silver ion as stationary phase, was developed to separate the various hydrocarbon components in heavy oils effectively. Tahe vacuum gas oil was separated into five components of saturates, light aromatics, middle aromatics, heavy aromatics and resin. Hydrocarbon types and carbon number distribution of components were characterized by GC-MS and GC-FI-TOFMS. Compared with the traditional two-adsorbent separation method, the new column-chromatography separation method improves the separation efficiency, and shortens the separation time to 4～5h. Contrasted with the patent separation method, the new column-chromatography separation method avoids the pollution of silver ion lost from stationary phase, and realizes the further separation and enrichment of aromatics. The content of mono-aromatics in light aromatic component, the content of di-aromatics in the middle aromatic component and the content of poly-aromatics in the heavy aromatic component are 74.3 %, 37.1 %, 65.9%, respectively.

FACTORS AFFECTING DETERMINATION OF SALT CONTENT OF CRUDE OIL

2015, 46(3):  92-96. 

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At present SY/T 0536 method is widely used to measure the salt content of crude oils at home. This work introduces the application of WC-200 microcomputer in this aspect and some factors influencing measuring results were discussed. The results show that bias voltage, conversion rate, integral resistor, and magnification gain has a great influence on the accuracy of the measurement. The optimal conditions using WC-200 microcomputer are bias voltage of 260 mv, conversion rate of 84%, integral resistor of 2 K and gain of 2 400. At optimal conditions, samples with salt content of 3，5，10，20，50，100 mg/L were measured to see the accuracy of the WC-200 microcomputer method. The results show that the relative errors are less than 2%, satisfied with the standard deviation of 5% of instrument in concentration range. The salt contents of thirteen kinds of crude oils from different sources were analyzed. The standard deviations are SD≤1.150 mg/L, less than the relative standard deviation of RSD≤2.63% of the instrument requirement.