Table of Content

12 September 2013, Volume 44 Issue 9

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EFFECT OF NOBLE METAL ON COBALT-BASED FISCHER-TROPSCH SYNTHESIS CATALYSTS SUPPORTED ON ALUMINA

2013, 44(9):  1-5. 

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The influence of noble metal promoter Pt, Pd and Re on F-T cobalt synthesis catalysts was investigated and the catalysts were characterized by XRD, TPR and H2-TPD. It is suggested that the influence of different promoters on the properties of catalyst varies greatly. The addition of 0.1%Pt or 0.1%Re obviously increases the activity and C5+ selectivity, but 0.1%Pd gives a high CO conversion with a relatively lower C5+ selectivity. The addition of small amount of noble metal additive can decrease the reduction temperature of the catalyst, proved by the characterization results. The reducibility and activation of the catalyst under the industrial reduction conditions as well as the dispersion of Co metal can be improved through the addition of noble metals.

INFLUENCE OF SULFUR ON CATALYST ACTIVITY AND CHEMICAL REACTION IN VEGETABLE-OIL HYDROTREATING

2013, 44(9):  6-10. 

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The effect of sulfur on catalyst activity and reaction route in bean oil hydrogenation was investigated. The activity of sulfided catalyst used in hydroprocessing vegetable oil will gradually decline due to the sulfur loss because of low content sulfur in feed. The experiments were carried out in a fixed bed reactor. The results indicate that continually adding sulfur agent (thiophene or H2S) can significantly slow down and partially restore the activity. Different sulfides have different role. However, the activity cannot be fully recovered as the degradation of active site is caused by loss of sulfur. The addition of moderate amount of thiophene as the sulfur resource is able to keep the catalyst activity; while the excess thiophene will has the opposite effect. On contrast, H2S enables to steadily promote hydroprocessing vegetable oil. In addition, both the thiophene and H2S can considerably lower hydrodeoxygenation/decarboxylation ratios.

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COMMERCIAL APPLICATION OF HEAVY OIL CATALYTIC CRACKING LOG-90 CATALYST FOR HIGH OCTANE GASOLINE

2013, 44(9):  11-14. 

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This paper introduced the characters and commercial application of LOG-90 high octane catalyst for residue catalytic cracking. The commercial application of LOG-90 results show that compared with the blank results, under the conditions of same coke and gas yield the total liquid yield can increase by 0.11% and the research octane number increase by 1.57 units. The analysis results of gas chromatography show that LOG-90 catalyst can significantly increase aromatic content and the ratio of iso/normal alkanes which is the main reason for the increase of ON of FCCG. The gasoline octane number loss is also reduced after hydrogenation.

COMMERCIAL APPLICATION OF LDO-70 EFFICIENT CONVERSION CATALYST FOR HEAVY OIL

2013, 44(9):  15-18. 

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The commercial application of LDO-70 catalyst for residue catalytic cracking in the 1.2 Mt?a-1 RFCC unit of PetroChina Wulumqi Petrochemical Company was introduced. Compared with base case, the slurry yield decreases by 0.35%, the yield of dry gas and coke reduces by 0.50% and 0.77%, respectively. The commercial results also show that the total liquid yield increases by 1.69%, the light oil yield increases by 1.45%. Especially the additional increment of propylene of 1.1%, and 1.7 units RON of gasoline are obtained. LDO-70 catalyst can significantly increase heavy oil conversion and propylene yield and improve the product distribution and the octane number of gasoline.

HYDROTHERMAL SYNTHESIS OF Ni-Mo UNSUPPORTED CATALYST AND THEIR CATALYTIC PERFORMANCE

2013, 44(9):  19-24. 

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The composite metal oxides with different Ni-Mo atomic ratio were synthetized by hydrothermal reaction and characterized by XRD、BET and SEM. The unsupported catalysts were prepared from the composite metal oxides and their activities of HDS, HDN and HYD were evaluated in a continuous flow high-pressure micro reactor. The results show that the composite metal oxides are mainly composed of ammonium nickel molybdate, while the phase of Ni3S2 and MoS2 are detected in the unsupported sulfided catalysts. N2 adsorption-desorption characterization indicate that the composite oxides exhibits the bimodal mesoporous structures, and the specific surface area and pore volume increase with increasing amount of basic nickel carbonate tetrahydrate. Catalytic results manifest that the unsupported Ni-Mo catalyst with the Ni-Mo ratio of 1:1 has better hydrogenation activity: HDS of DBT is 100%, while HDN of quinoline and HYD of naphthalene reach 62.3% and 27.3%, respectively.

PREPARATION AND CATALYTIC PERFORMANCE OF MICRO/MESOPORE COMPOSITE MOLECULAR SIEVES

2013, 44(9):  25-29. 

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AlSBA-15/HY composite molecular sieves were prepared by multi-hydrolysis and crystallization under high ratio of SiO2/H2O with recycling mother liquid. The preparation efficiency increases as twice as classic synthesis method, meanwhile the cost of raw material greatly drops and almost no wastes of acid and water are discharged. NiW/AlSBA-15/HY catalyst was then prepared by volume impregnation of AlSBA-15/HY with Ni-W solution and used in hydrocracking of Daqing vacuum gas oil in a 200ml one stage serial connection process. The results indicate that NiW /AlSBA-15/HY catalyst has high catalytic activity, good middle distillates selectivity and excellent object products. Under the test conditions: temperature of 383℃，pph of 12.5MPa, H2/oil of 1000, and Sv of 1.4h-1，the diesel yield is 52.85%, middle fraction selectivity 79.4%, potential aromatic of heavy naphtha 43.5% and BMCI of tail-oil 5.0.

RESEARCH ON COMPOSITION AND PROPERTIES OF BIO-JET FUEL

2013, 44(9):  30-33. 

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The chemical compositions of the bio-jet fuel from different resources were analyzed and the effect of resources on product properties was discussed, then a comparison between bio-jet fuel and petroleum-based jet fuel was made to find out the composition difference between them. After that, the bio-jet fuel was blended with petroleum-based jet fuel. The chemical compositions as well as the properties of the blends were determined to see the difference in aspect of properties for above two fuels. The comparison data show that the property of bio-jet fuel was fully in compliance with the requirements of ASTM D7566 appendix 2 and the blends was fully in compliance with the requirements of Jet-3.

CALCULATION OF CHARACTORIZATION FACTOR OF FCC FEEDSTOCKS

2013, 44(9):  34-37. 

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By nomograph, the average boiling point and the relationship between density and temperature of the feedstock can be established using a correlation formula developed when the complete distillation data of feedstock are available. The characterization factor is then able to be calculated based on the correlations of the average boiling points and density of feedstock. Using feedstock density and temperature at distillation volume of 10%, another correlation for calculating the average boiling points is also developed. This correlation can be used to evaluate the characterization factor with routine analysis data of FCC feed. The relative error of the correlation is less than 4%. Therefore, the correlation has good simulation accuracy.

STUDIES ON EXOTHERMIC MODES OF THE MIDDLE-CHANNEL MODEL IN COKE DRUM

2013, 44(9):  38-41. 

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Three exothermic modes: the given wall temperature mode, the boiling heat transfer mode and the adiabatic mode, were analyzed for calculating cooling water vaporization rate of coke layer with middle channel structure in coking tower by temperature field calculating program using Visual Basic, assuming the coke layer cooling heat being equal to the cooling water vaporization heat. And the results compared with the site operation data indicate that a large deviation is observed for adiabatic mode. While for other two modes, the analyzed results are close to the site operation data.

APPLICATION STUDY OF BACTERIUM FOR DIESEL OIL DENITROGEN

2013, 44(9):  42-46. 

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On the basis of previous work，further study on the influence of the addition of (NH4)2SO4 on quinoline denitrogen efficiency was conducted and under the best operation conditions for quinoline denitrogen, the denitrogen bacterium HY9 cultivated in nutrients was tested for nitrogen removal from diesel fuels. Experimental results show that inorganic nitrogen has no influence on the degradation of quinoline. The proportion of nutrients to diesel oil has little effect on diesel oil denitrogen and the best proportion is 1.5:1. The ratio of diesel oil denitrogen is increased from 12.9% to 16.7% when the surfactant tween80 is added at the optimal ratio of 0.175 g Tween80/25 mL diesel oil. Higher shaking speed improves the nitrogen removal efficiency as it can reduce the size of oil-water drop to dissolve more oxygen. The shaking speed tests show that the optimal conditions are 3 mL of suspension of HY9 cultivated and 250r/min with a denitrogen ratio of 19.5%. However，the times have no effect on efficiency of denitrogen.

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IMPACTS OF SODIUM NITRATE ADDITIVE ON ALUMINA SHAPE

2013, 44(9):  47-50. 

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Well-crystallised flat hexagonal nano alumina was prepared by hydrothermal synthesis method with addition of sodium nitrate additive. Changing the quantity of sodium nitrate to observe the transformation of alumina shape and its characters was conducted. The samples are characterized by BET, XRD, TEM, HRTEM and FT-IR techniques. The experimental results indicate that crystalline structure of alumina and boehmite are not changed by sodium nitrate addition and their quantities, but the profiles of alumina were larger than that without sodium nitrate additive, and the area of crystal planes (100) and (111) are increased. The larger quantity of sodium nitrate additive will make the area and pore volume of alumina decrease and the pore size increase.

IMPROVING LIGHT LIQUID YIELDS OF HEAVY OIL BY SOLVENT DEASPHALTING- COKING COMBINED PROCESS

2013, 44(9):  51-54. 

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Effectively improving light oil yield from heavy oil is very important for refinery. Decarburization process is an easy and important technology dealing with heavy oil. In this paper, the single coking process and the solvent deasphalting-coking combined process was compared using two different vacuum residue and de-oiled asphalt feeds. The results show that the solvent deasphalting-coking combined process could give a higher light liquid yield than that of the single coking process. When propane was used as the solvent for deasphalting, 9.6% more light liquid yields could be obtained by the combined process than the coking process; when butane was used as the solvent for deasphalting, the combined process improved the light liquid yields with 14.08%.

STUDY ON CATALYTIC CRACKING PERFORMANCE OF FCC TOP REFLUX

2013, 44(9):  55-60. 

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The study on catalytic cracking performance of FCC top reflux was conducted on a fixed fluidized bed reactor (FFB) with MLC-500 catalyst under the conditions of a weight hourly space velocity of 5h-1, a catalyst-to-oil mass ratio of 8 and a reaction temperature range of 460-540℃. Results show that 17.41% of FCC top reflux which is in diesel distillation range is cracked into gasoline fraction. Thus FCC gasoline yield can be improved. Besides, the contents of high octane number components, aromatics and C4 hydrocarbons in liquid products are increased. The aromatics in the product can be more than 50%. More than 75% aromatic hydrocarbons in the product come from alkyl-benzene cracking of FCC top reflux. Optimal reaction models for each component of hydrocarbons in FCC top reflux were also proposed.

SCALE FORMATION AND INHIBITION IN RFCC SLURRY

2013, 44(9):  61-65. 

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The scale formation mechanism in slurry system of RFCC unit was introduced and analyzed. It is found the slurry scale is composed of catalyst, coke and metal compound and originates from deposition of catalyst, coking in transfer line, coking at the bottom of fractionator and slurry cycling with the coking in transfer line as the main reason. Stabilizing the operation conditions of RFCC will inhibit scale in transfer line from entering slurry system. Adding anti-scale agent in slurry is also an effective way to slow down scale formation.

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DEVELOPMENT AND APPLICATION OF GARDES TECNOLOGY FOR FLUID CATALYTIC CRACKING GASOLINE HYDRO-UPGRADING

2013, 44(9):  66-72. 

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With the aim of producing clean gasoline from fluid catalytic cracking (FCC) naphtha with higher sulfur and olefin contents，a GARDES technology for hydro-upgrading FCC naphtha was developed by coupling the deep desulfurization and directed olefin conversion. This article introduced the process configuration, catalyst design, and industrial results of the GARDES technology and then presented some pilot-plant results for producing clean gasoline fraction that meets the China IV and V standards. The industrial results show that the hydro-upgraded naphtha can be used as a blend component for the China IV gasoline pool with olefin reduction of 16 v% and ON loss<1 unit. The pilot plant evaluation demonstrate that at HDS of 69%~89%, the product can be used as a blend component for the China IV gasoline pool with ON loss of 0.3~0.5；while at HDS of 88%~96%，the product can be used as a blend component for the China V gasoline pool with ON loss of 0.7~0.9.

INDUSTRIAL APPLICATION OF CATALYTIC OXIDATION TECHNOLOGY FOR PO/SM WASTE GAS

2013, 44(9):  73-78. 

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Ningbo ZRCC Lyondell Chemical Co.,Ltd. uses catalytic oxidation device with WSH-2 catalyst to treat exhaust gas from PO/SM (propylene oxide/styrene). Under the reaction conditions of 85 000 m3/h exhaust gas, the total non-methane hydrocarbon (NMHC) concentration 2800 mg/m3, oxygen content 2%~4%, and the reactor inlet temperature 260~330 ℃, the purified gas after treatment conforms to the national standards (GB 16297—1996 and GB 14554—1993). This technology has a very good significance to spread.

INFLUENCE OF TRACE WATER ON PERFORMANCE OF HIGH VISCOSITY PAO

2013, 44(9):  79-81. 

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Trace water was uniformly dispersed into high viscosity Polymer Alpha Olefins (PAO) using high shear dispersing emulsifier. The influence of trace water on the properties of high viscosity PAO was studied by the methods of determination of foaming characteristics, kinematic viscosity and viscosity index, and flash point (Pensky-Martens closed cup method) and TGA. The results show that the trace water of 0.001% and 0.005% can effectively improve the foaming tendency and reduce the foaming stability, 100 ℃ kinematic viscosity and viscosity index. However, no influence on flash point (closed cup) and TGA of high viscosity PAO is observed.

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PROBLEMS AND TECHNICAL RETROFIT MEASURES FOR CLAY REFINING UNIT OF BASE OIL PRODUCTION

2013, 44(9):  82-86. 

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The problems in lubricating oil clay purification device were analyzed and the corresponding retrofit techniques were proposed and applied, including: adjusting feed oil flow, adding material degassing tower, adopting complexing denitrification process, solving the corrosion of the overhead vacuum evaporation system. The technical improvement in equipment include: replacing plate and frame filter press and clay feeder, retrofitting pump at the degassing tower bottom, solving the scaling problems of water ring vacuum pump. Some techniques based on the current situation were put forward. A good social and economic benefits are obtained followed the above retrofit measures.

ENERGY CONSUMPTION ANALYSIS AND APPLICATION OF MEASURES FOR ENERGY SAVING OF 2.9 Mt/a FCC UNIT

2013, 44(9):  87-92. 

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An energy consumption analysis of the 2.9 Mt/a fluid catalytic cracking unit in Qingdao Refining & Chemical Company was carried out based on the design value and the data of the first year operation. Some measures for energy saving were proposed based on the production status of the plant. Through maximizing process capacity of the existing unit, optimizing feed composition and operation conditions, implementing energy saving projects, like pump and impeller cutting and retrofit of waste heat boiler, etc, the energy consumption of the plant was reduced significantly. The energy consumption of the plant reached as low as 1 602.1 MJ/t, which is a new record of low energy consumption within the same type internal units. All kinds of these measures implemented by the plant can reduce process cost of 67.38 million RMB (over the design value) per year and be a reference for other plants to save energy.

SELECTION AND OPTIMIZATION FOR C5/C6 PARAFFINS ISOMERIZATION PROCESS FLOWSHEET

Yong-Ming ZHANG

2013, 44(9):  93-96. 

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The simulation and optimization were conducted for a 567kt/a light naphtha isomerization unit using Pt/Cl-Al2O3 low reaction temperature isomerization catalyst. Based on the once through mode (OT) for isomerization reaction, the best flowsheet of de-isopentane (DIP) + (OT)+de- isohexane (DIH)+de-pentane (DP) was finally selected. The design RON of product is 91.23/90.77 (SOR/EOR), the design RVP is 96.50/95.15kPa (SOR/EOR), and the design product yield is 97.22/97.50 (SOR/EOR) lv%. The ideas and analysis methods in this paper can be used as reference for similar units in China.