Table of Content

12 September 2015, Volume 46 Issue 9

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INFLUENCE OF CITRIC ACID ON PROMOTER ROLE IN CoMo/Al2O3 CATALYST

2015, 46(9):  1-6. 

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A series of CoMo/Al2O3 catalysts with different metal ratio（Co/(Co+Mo)） were prepared using citric acid (CA) as a chelating agent by stepwise impregnation method. The effect of CA on the role of promoter was studied and the prepared CoMo/Al2O3 catalysts were characterized by BET，XRD，XPS and HRTEM techniques. The results show that CA can increase the dispersion of Co and Mo, and enhance the promotion role of the promoter，especially at higher metal ratio. The activity of 4, 6-dimethyldibenzothiophene hydrodesulfurization show a trend of increase first than decrease as increasing the metal ratio, and reaches its highest value at the ratio around 0.3. Meanwhile, it is apparent that the catalytic activity obtains an important enhancement when the catalysts are prepared in presence of CA，especially at higher metal ratio.

OLIGOMERIZATION OF 1-HEXENE OVER ZSM-5 ZEOLITE

2015, 46(9):  7-11. 

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ZSM-5 zeolite synthesized from amine-free system was dealuminated by acid treatment under different conditions. Four ZSM-5 zeolites with different aluminum content and pore structure were prepared. The samples were characterized by XRD, XRF, BET, and NH3-TPD techniques to analyze the crystallinity, element composition, morphology and size, pore structure as well as acidity distribution. The performance of 1-hexene oligomerization was evaluated over ZSM-5 zeolites at the conditions of 4.5 Pa，245 ℃ and mass hourly space velocity of 0.5 h-1. The results show that with increasing the Si/Al ratio，the conversion of 1-hexene decreases while the yield of dimers shows a tendency of firstly increase and then decrease. The maximum yield is obtained at the Si/Al ratio of 102. The ZSM-5 zeolite with lower Si /Al ratio has more by-products and more carbon deposition. From yield of dimers and raw material utility consideration, the ZSM-5 zeolite with Si/Al of 102 is the most suitable catalyst for the production of jet fuel component.

STUDY ON CATALYST SYSTEM FOR SBS RUBBER EXTENDER OIL PRODUCTION FROM SUIZHONG 361 VGO

2015, 46(9):  12-15. 

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Three catalyst systems: non-noble metal dewaxing-non-noble metal hydrofinishing, non-noble metal dewaxing-noble metal hydrofinishing, and noble metal dewaxing-noble metal hydrofinishing, were tested for production of SBS rubber extender oil from CNOOC Suizhong-361 VGO#2 & VGO#3. No much difference in product yield for the three catalyst systems was observed at similar product pour point; however, the noble metal dewaxing-noble hydrofinishing catalyst system indeed offers a higher yield, 1.4 percentage points and 2.3 percentage points higher than that of other two catalyst systems, respectively. Products from the two catalyst systems with noble metal have much better light and thermal stability than that of the non-noble metal catalysts. It is concluded that for industry unit, the selection of catalyst system depends on the consideration of the market needs and economic evaluation.

ANALYSIS AND SUGGESTION OF LONG-TERM OPERATION OF NNI-1 C5/C6 ALKANE ISOMERIZATION CATALYST

2015, 46(9):  16-19. 

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Topped oil of CCR unit has been used as feedstock and used the once through process，do not set up the isopentane and the stabilize column, has been adopted in the 0.2Mt/a C5/C6 alkanes isomerization unit.Through debutanizer stabilized in the CCR unit as the blending component of gasoline.Analysis of the parameters in the first two cycles showed that the NNI-1 catalyst has good performance, higher activity & stability and the requirements of production have been met. RON greater than 78，the rates of C5 andC6isomerization are over 60% and 80% respectively. C6 selectivity is about 15% ，reached the technical requirements.The third cycle running data indicated that increasing the reaction temperature has not been able to overcome the reduction of catalyst activity, RON of the feedstock has been increased by 2-3 units and the rates of C5 andC6isomerization are about 50% and 70% respectively. C6 selectivity is low10% .Therefore recommend propose of a long-term running.

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INDUSTRIAL PRACTICE OF LONG-TREM RUNNING OF HYDROPROCESSING RESIDUE WITH HIGH Fe AND Ca CONTENT

2015, 46(9):  20-23. 

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Residue with high Fe and Ca content were hydroprocessed in a 1.7 Mt/a VRDS unit of SINOPEC Changling Branch Co., The long-term cycle operation processing high Fe and Ca content residue was achieved in the second cycle operation through setting a new device in the electric desalting unit for injecting decalcification agent and adjusting the layered catalyst beds in the 1st reactor of VRDS unit. It is seen that the higher pressure drop (above the threshold value of 0.7 MPa) is the key point to the shutdown of the unit in the first cycle. The analysis of the operation data and the spent catalysts indicates that the reasons for excessive pressure drop of the 1st reactor in the first cycle are Fe and Ca depositions as well as coke formation.

STUDY ON HIGH CONVERSION AND LOW CARBON EMISSION PROCESSING ROUTES OF HEAVY OIL

2015, 46(9):  24-30. 

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This paper mainly discusses the impact of heavy oil processing routes (hydrogenation solutions like VRDS, slurry bed and ebullated bed, coking solution as well as the solutions of coking + ebullated bed) on light oil yield and carbon emission, and analyzes their economic benefits in detail. Compared with decarbonization route, hydrogenation route not only has a high light oil yield and a high benefit whether or not carbon tax, but high carbon emissions. In three hydrogenation routes, slurry-bed case has the best economic benefit with the highest light oil yield, middle level carbon emission and the least investment. The ebullated bed case has the worst economic benefit with the least light oil yield and the highest investment. VRDS case has the highest carbon emission. Its investment and benefit are the second. Compared with the ebullated bed and coking case, the light oil yield and the economic benefit are improved significantly by their combination solution.

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OPERATION ANALYSIS OF DIESEL UPGRADING CATALYST AND COUNTERMEASURES

2015, 46(9):  31-37. 

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The running of a 4.1 Mt/a diesel hydrogenation unit with deep desulfurization catalyst for quality upgrading was introduced. In the diesel quality upgrading process, the deactivation speed of catalyst became faster and the Si in coker gasoline made catalyst poisoned. In the mean while, the balance of diesel cetane number was broken. To solve above problems, the following countermeasures could be taken. Firstly, the space velocity should be decreased. Secondly, the Si content in coker gasoline should be controlled. Thirdly, the diesel cetane balance of the refinery plant should be optimized.

PROCESS ANALYSIS AND REVAMPING OF RAFFINATE COLUMN OF PX UNIT

2015, 46(9):  38-42. 

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By analysis on the cause of abnormal operation of the raffinate column of PX unit of SINOPEC Jinling Co., technical measures were suggested and applied. The improving measures include repairing air/water coolers, enlarging the diameter of vapor stream pipline in top condenser system, strengthening the feed liquid/vapor distributer, using multiple ruffled downcomer, and moving up the side drawing outlet. By successful revamping, the bottleneck of fractionation process operation is eliminated and the raffinate oil overload operation of the column is realized.

DEVELOPMENT AND COMMERCIAL APPLICATION OF ALKALI-FREE LPG REFINING

2015, 46(9):  43-46. 

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A new technology with new COS hydrolysis catalyst and demercaptan solvent for liquefied petroleum gas refining without caustic alkali was developed by China petroleum university (Beijing) to solve problems of frequent change of caustic solution, large amount of waste alkaline and out-spec sulfur content of refined liquefied gas found in conventional LPG caustic fining process. Jointing with Sunway petrochemical engineering Co. Ltd., the technology was successfully applied in LPG sweetening unit of CNPC Harbin petrochemical company. The results show that the process has good effect in desulfurization. The total sulfur content in refined products is below 10 μg/g. Compared with the traditional alkaline cleaning method, the process discharge without waste alkaline and the washing water can be discharged directly into the sewage treatment plant. The process is simple and the operating conditions are ease. The COS hydrolysis catalyst has a high activity and a long service life. The sweetening agents can be recycled with lower loss.

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SYNTHESIS，CHARACTERIZATION AND CRACKING PROPERTIES OF DISORDERED MESOPOROUS SILICA-ALUMINA MATERIAL

2015, 46(9):  47-51. 

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A disordered mesoporous silica-alumina material (JSA) with pseudo-boehmite structures was successfully prepared through co-gel and aging process. It was studied in detail by XRD，BET，MPM，SEM，TEM，FT-IR and NH3-TPD. The results reveal that the material possesses large surface areas and pore volumes, and the average pore diameter is in the range of 8~12 nm. This material is formed by many spherical particles aggregated together and its micrograph looks like uniform wrinkles. It has both Lewis acid and Br?nsted acid centers as well as relatively high total acid content. The material shows pretty high hydrothermal stabilities. The FCC catalysts prepared with JSA display much higher cracking activities in the conversion of heavy oil and excellent selectivity of coke, and the distribution of cracking products is improved.

CATALYTIC CRACKING PERFORMANCE OF NARROW FRACTIONS OF HYDROCRACKING TAIL OIL

2015, 46(9):  52-57. 

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The hydrocracking tail oil of vacuum gas oil from Middle Eastern crude was cut into four narrow fractions. The catalytic cracking performance of fractions was tested in an advanced catalyst evaluation device (ACE). The hydrocarbon compositions of fractions and cracked products were analyzed by GC-MS. The results show that the content of saturates in the four fractions are all above 98.0%, and the content of paraffins increases while the content of naphthenes decreases with the cuts getting heavier, simultaneously, the paraffin and naphthene compounds shift toward the direction of high carbon numbers. The four fractions are prone to be cracked with high yields of LPG and gasoline and low yields of dry gas and coke. Under the same reaction conditions, as the fractions moving in the direction of high boiling point, the cracking ability increases, the yield of dry gas and coke decreases, the yield of LPG increases, the yield of gasoline increases with a slight loss in octane number, and the yield of diesel and heavy oil decreases.

MOLECULAR SIMULATION AND THERMODYNAMIC ANALYSIS OF FCC DRY GAS ADSORPTION IN ZSM-5 ZEOLITE

2015, 46(9):  58-64. 

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Adsorption and distribution of dry gas components: hydrogen, nitrogen, methane, ethane and ethylene in ZSM-5 zeolite were studied, respectively, by Grant Canonical Monte Carlo (GCMC) simulations at 298 k and 823 K and 0-1 000 kPa. Simulation results show that among all adsorbents, ethylene exhibits the most adsorption amounts, which reaches 3.05 mol/kg at 298 K under 10 kPa. Linear channels were prior adsorption space. The thermodynamic parameters, such as Gibbs free energy change, enthalpy change and entropy change were analyzed based on adsorption equilibrium constant. The results indicate that the adsorption of various components in ZSM-5 were spontaneous exothermic process with decrease of chaotic degree, low temperature favors this adsorption, and it is more favorable for ethylene to be adsorbed in ZSM-5. The simulation results of dry gas mixture adsorption in ZSM-5 show that there exist competing adsorption phenomena, the components competitiveness were affected by temperature. Under the total pressure of 500 kPa and 298 K and 823 K, methane and ethane in these mixtures rather than ethylene show the best adsorption performance, the adsorption amount ratios to ethylene were 1.5:1 and 2.3:1, respectively.

NUMERICAL SIMULATION OF EFFECT OF NOZZLE DIAMETER AND POSITION ON HYDRODYNAMICS IN AIRLIFT LOOP REACTOR

2015, 46(9):  65-70. 

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Euler-euler two flow model was applied to simulate the effect of nozzle diameter and nozzle position on the hydrodynamics in airlift loop reactor in the oil-hydrogen system to provide theoretical guidance for suspension bed industrial equipment. The simulation results show that related to the nozzle diameters of 40 mm and 80 mm, the circulation power is larger when nozzle diameter is 20 mm; the liquid circulation velocity in the rising and dropping is larger, but the gas holdups change small. The gas holdup when the nozzle was set at higher location is obviously higher than that of the gas holdup at the horizontal and low location, while there is not much difference of gas holdup between the horizontal and low location. The liquid circulation velocity magnitudes at three nozzle locations are: low>flat>high location. It is concluded by comprehensive consideration that the flow characteristics is better when the nozzle diameter is 20 mm at low location.

PREPARATION AND EVALUATION OF NEWASPHALTENE DISPERSANT

2015, 46(9):  71-74. 

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A new asphaltene dispersant was synthesized Using polyisobutylene keating diimide, methyl benzene, and three azole nitrogen and salicylaldehyde as raw materials and characterized by Fourier Transform Infrared Spectroscopy (FT-IR). The temperature resistance, dispersion and scale inhibition of the synthesized sample were studied by thermogravimetric analysis method, dispersion stability analysis method and dynamic anti-fouling performance evaluation method. The results show that under 400 ℃，no thermal weight loss rate of the synthesized sample is found, while at 450 ℃ and 500 ℃, the rates are 12.0% and 35.5%, respectively. The transmittance of asphaltene solution with the synthetic sample is 0, indicating the effective inhibition of the asphaltenes flocculation. For one of refinery sludge, the scale inhibition rate of the synthetic sample reaches 75.6% when it is added in an amount of 150 mg/L.

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INVESTIGATION ON EFFECT OF GREASE ON ROLLING BEARING LIFE UNDER LIGHT LOAD

2015, 46(9):  75-79. 

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The rolling bearing life of the greases composed of different thickeners and base oils were tested under light load condition. It is found that the maximum life is closely related to the properties of the antioxidant used, which is the main factor influencing the rolling bearing life, and has a linear relationship with amount of antioxidant. With the increase of added antioxidant, the bearing life is prolonged. But if the test temperature increases, due to the increase of the oxidation rate，the increasing trend of the bearing life with antioxidant amount declines.

TRIBOLOGICAL PROPERTIES OF CALCIUM SULFONATE COMPLEX GREASE WITH ULTRAFINE NICKLE/BISMUTH POWDERDS

2015, 46(9):  80-84. 

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To improve the tribological behavior of calcium sulfonate complex grease, the anti-wear and anti-friction performance of grease with ultrafine Ni powder or Ni/Bi composite powders with different load were investigated by four-ball tribological tester. The morphology and component of wear spot were characterized by Scanning Electron Microscope (SEM) and Electronic Differential System (EDS), and the anti-wear and anti-friction mechanism were discussed. The results show that the friction coefficient (μ) and wear scar diameter (WSD) all decrease first and then increase with the increase of the amount of Ni powders. The μ value of composite grease first decrease then increase with the increase of ratio and total amount of Ni/Bi composite powders, while the WSD value has no change. The composite grease achieves the best tribological performance when the Ni amount reaches 2.0% and the ratio of Ni/Bi is 1:2. The value of μ and WSD decrease 34.2% and 4.2%, respectively, compared with basic grease. The test results indicate that anti-friction performance of the calcium sulfonate complex grease with composite powders is improved significantly, while the anti-wear properties change little.

APPLICATION OF NEW COMBINED TRAPEZOID SPRAY TRAY IN ABSORBER, DESORBER AND STABILIZER

2015, 46(9):  85-88. 

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The combined trapezoid spray trays (CTST) are successfully applied in absorbers, desorbers and stabilizers in the FCCU of SINOPEC Zhanjiang Dongxing Petrochemical Co. Ltd. The revamping scheme was proposed based on computer simulation and the calculation of fluid dynamic performance. Switching the floating value trays to CTST without changing the supporting parts of the absorbers, desorbers and stabilizers in 1# FCCU and 2# FCCU were adopted. After revamping, the capacity of 1# and 2# FCCU is increased by 67% and 25%, respectively. In 1# FCCU stabilizer, the contents of C2 and C5 in LPG are less than 0.03%(v) and 0.02%(v), respectively. No C3 and C4 in the stabilized gasoline exist, and the saturated vapor pressure of stabilized gasoline is 63.65 kPa. In 2# FCCU stabilizer, the content of C2 is 0.03%(v) and C5 is 0.08%(v) in LPG, the stabilized gasoline has no C3 and C4, and the saturated vapor pressure of stabilized gasoline is less than 65 kPa. The contents of C3 in lean gas of 1# and 2# FCCU absorbers are 1.46%(v) and 0.95%(v), respectively. The contents of C2 in deethanized gasoline of 1# and 2# FCCU desorbers are 0.12%(v) and 0.03%(v), respectively.

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STUDY ON UTILIZATION OF WASTE FROM OVERBASED CALCIUM SULFONATE PRODUCTION

2015, 46(9):  89-93. 

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The effective ways of waste from the production of overbased calcium sulfonate were suggested based on the analysis of the characteristics of the waste and pilot plant test. The results show that the low molecular weight alcohols can be obtained by distillation separation of spent liquor from overbased calcium petroleum sulfonate production and used as the raw materials in the production of demulsifier, its performance is equal to that of one using new alcohol; the "low quality" additive by solvent extraction from centrifugal slag of overbased calcium petroleum sulfonate production can directly be sold as a product or used as a high alkali value additive blending component, resulting in higher economic benefits of additives products. The remaining calcium carbonate after drying can be used as a phase transfer agent for the production of calcium sulfonate complex grease, which can further reduce the cost of calcium sulfonate grease production.

STUDY ON CHANGE RULE OF DISSOLVED WATER CONTENT IN JET FUELS

2015, 46(9):  94-96. 

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Moisture content is an important performance index of the jet fuel quality inspection. Considering the effect of environmental temperature, humidity, storage time and anti-icing agent concentration on dissolved water content in jet fuel, this project determined the change rule of the dissolved water content under different conditions using trace moisture analyzer. The change rule model and the database of the desolved water were established. It provides an effective reference for accurate and efficient determination of jet fuel moisture content.

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DISTRIBUTION OF BASIC NITROGEN, MERCAPTAN SULFUR AND ACID VALUE IN FRACTIONS OF COKING DIESEL

2015, 46(9):  97-100. 

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A coker diesel was distillated on the base of equal volume way to obtain fractions, which was analyzed to investigate the basic nitrogen content, mercaptan sulfur content and acid number of each fraction. The results show that the basic nitrogen content increases with the increase of boiling point, but the mercaptan sulfur is just opposite. The qualitative analysis of the coking diesel by GC-MS finds that the acidic substances are all phenolic compounds, and the boiling points of majority of phenol substances are less than 257 ℃. It is concluded that the majority of basic nitrogen compounds are concentrated in the higher boiling fraction, while the phenols and mercaptan sulfur compounds are in the low boiling point fractions.