Table of Content

12 December 2013, Volume 44 Issue 12

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SIMULATION AND ANALYSIS OF ENERGY CONSUMPTION FOR MTG PROCESS

2013, 44(12):  1-5. 

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A model for simulation of 200kt/a MTG plant was developed using the ASPEN PLUS software. In this model, C6+ mixture in hydrocarbon feed was represented as a pseudo component with distillation range from 68℃ to 201℃. The product distribution, gasoline yield and properties and the utility consumption of unit were investigated. Results show that RVP and the yield of C5-C10 are the most important factors which affect the yield of MTG gasoline, and the yield of MTG gasoline produced from various feedstocks is also proportional to the content of C4 fraction in the gasoline. It is showed from the analysis of energy consumption that a large proportion in the overall utility consumption is occupied by the electricity and steam, in which the consumption of electricity of gas-recycle compressor accounts for 40.2%. Reaction heat in MTG reactors could be used to generate medium pressure steam, by which the energy consumption of the plant can be reduced greatly.

STUDY ON CLASSIFICATION OF FCC CATALYST FINE POWDER GATHERED FROM CALCINER EXIT GAS

2013, 44(12):  6-10. 

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The operation parameters of the centrifugal air classifier were tested and optimized for FCC catalyst fine powder from a calciner exit gas. The optimized operation conditions are: total air rate is of 2620 m3/h, wheel speed of classifier of 930 r/min，primary air and secondary air are 92% and 8% of the total air flow, respectively. Under the optimal operation conditions, the fine powder was clearly classified to coarse and fine parts. The content of particle less than 20 μm in the coarse part is decreased to 15.2% from its original 64% in the powder from calciner exhaust gas. But it reaches to 92.5% in the fine part. The Newton classification efficiency is 78.2% and the calculated cut size is 26.5 μm.

OPTIMIZATION OF PYROLYSIS FEED AND HYDROGEN RESOURCE FOR REFINING-CHEMICAL INTEGRATION

2013, 44(12):  11-14. 

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This article summarized the resources optimization for refining-chemical integration of Sinopec Zhenhai Refining & Chemical Company. It gave the introduction in detail of optimal utilization of feedstocks, such as naphtha, tail oil of hydrocracker, dry gas of FCC, light hydrocarbon of refinery and raffinate of ethylene aromatics extraction, etc., as well as hydrogen resource. The introduction can be used as reference to those same kind domestic integrated petrochemical enterprises for their process configuration design and optimization.

UPDATING OF 300 kt/a ULSD UNIT

2013, 44(12):  15-19. 

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The mass balance of diesel fractions produced in the refinery was calculated, based on the analysis of compositions and properties of hydrotreating feedstocks, product quality and calibration results of diesel hydrotreating unit in Xi’an Petrochemical Company of Sinopec in order to fine out the ways to upgrading the quality of the diesel pool of the refinery. A series of feasible revamping measures to upgrade the quality of diesel pool had been adopted to meet the requirements of National Emission Standard Ⅲ, such as replacing hydrodesulfurization catalyst, using new type effective feedstock filter, adding water heat exchanger before air cooler, optimizing operation conditions and feed compositions and lubricity modifier adding in diesel pool. Thus good economic benefit is achieved at low cost.

COMMERCIAL APPLICATION OF DIESEL LIQUID PHASE RECYCLING HYDROGENATION TECHNOLOGY

2013, 44(12):  20-22. 

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Diesel liquid phase recycling hydrogenation technology with SINOPEC independent intellectual property rights achieves successfully industrial application for the first time in Shijiazhuang Refining & Chemical Company. Industrial application results show that diesel meeting national Ⅳ vehicle diesel emission standards can be produced by this technology; energy consumption is 298.87 MJ/t with feedstock being partially direct hot feed in the performance test, while energy consumption will be 242.02 MJ/t if all feedstock are direct hot feed according to the design, far lower than about 418 MJ/t with the traditional trickle bed process.

ANALYSIS OF OPERATION CONDITIONS FOR MAXIMUM LIQUID YIELD OF DELAYED COKING UNIT

2013, 44(12):  23-26. 

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The critical operation technology for controlling shot coke formation in the delayed coker has been established in SINOPEC Luoyang Company. Based on the mechanism of shot coke and tests results, it is pointed out that the critical operation conditions, under which the shot coke will be occurred, can be strictly controlled by reducing recycle ratio and reaction pressure and increasing the reaction temperature to obtain the highest liquid yield. Meanwhile several measures, including monitoring neutron level indicator of point C on the coke drums, amount of quench, temperature of point C on coke drums, and optimal coker operation conditions, have been adopted to build a forecasting system for the shot coke formation, which would provide security and operational basis.

STUDY OF CONDITIONS OF OXIDATION AND CARBONIZATION IN SWEETENING RESIDUE TREATMENT ON EXTRACTION GASOLINE QUALITY

2013, 44(12):  27-30. 

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In order to treat the large number of harmful alkali residue produced in gasoline sweetening process, the three steps of oxidation, carbonization and phenol removal (gasoline extraction, LiFT-CR technique) were successively adopted. The optimal conditions for oxidation, carbonization were studied. The results indicate that by means of adjusting alkali residue oxidation time, oxidation temperature, carbon dioxide flow rate, and the dosage of Na2S and NaSR, the content of active sulfur compounds can be controlled to lower than 100μg/g after oxidation, and the pH value of carbonization waste water can be in between 8.5 and 9.5, resulting in qualified extraction gasoline. The waste water from the sweetening process reaches the requirement of sewage treatment plant.

STUDY ON APPLICATION OF PT/SBA-15 IN CATALYTIC REFORMING REACTION OF N-HEPTANE

2013, 44(12):  31-34. 

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Pt/SBA-15 catalysts with different Pt loading were prepared by wet incipient impregnation method and characterized by means of X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), N2 adsorption-desorption and TEM. The performance of Pt/SBA-15 and mixtures ofPt/SBA-15 and PR-D in catalytic reforming reaction of n-heptane was investigated. It is found that the mixture of Pt/SBA-15 and PR-D (1:9) show almost same n-heptane conversion, lower gas yield and higher liquid yield than when they are used alone. On 1.0%Pt/SBA-15 and PR-D mixture (1:9), the aromatics yield is increased by 3.2% than PR-D alone.

EFFECT OF ZSM-5 ACIDITY ON XYLENE ISOMERIZATION REACTION

2013, 44(12):  35-40. 

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A series of ZSM-5 zeolites were prepared by modification of thermal or inorganic acid treatment to investigate the effect of acidity on their catalytic performance. The meta-xylene (MX) transformation reaction was used as a probe reaction. The modified ZSM-5 zeolites were characterized by Py-FTIR, NH3-TPD and 27 Al NMR. It is found that a part of bronsted acid is converted to Lewis acid by thermal treatment, and a part of Al atom is removed from the framework of the zeolite by acid treatment. The catalytic test results show that at the similar conversion of MX isomerization reaction, the disproportionation reaction of MX increases as the Lewis acid proportion increases.

PREPARATION OF Ni2P/γ-Al2O3 CATALYST AND ITS DEHYDROGENATION PERFORMANCE

2013, 44(12):  41-45. 

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Alumina-supported Ni2P catalysts were prepared by the mixture of pseudo-boehmite and nickel hypophosphite. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction and transmission electron microscopy. The specific surface area of a Ni2P/γ-Al2O3 catalyst with 15wt% Ni2P is 166cm2/g. The active component Ni2P is well dispersed on the γ-Al2O3 support with a particle size of 5-7 nm shown by TEM analysis. The catalytic performance of the catalyst was evaluated in a fixed-bed reactor for cyclohexane dehydrogenation. Under the conditions of a reaction temperature of 420 oC, a reaction pressure of 0.5 MPa, a WHSV of 1 h-1, and a hydrogen-to-cyclohexane molar ratio of 0.24, the conversion of cyclohexane and selectivity of benzene reaches 99.5% and 99.8%, respectively.

EFFCT OF INCORPORATION WAYS OF PROMOTERS ON MoNi HYDROGENATION CATALYSTS

2013, 44(12):  46-50. 

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A batch of Mo-Ni catalysts with different contents of promoters was prepared via two different adding methods, i.e. ①Si was introduced during the formation of dry alumina powder and P2O5 in the preparation of catalyst support; ②Si and P2O5 were added together during the carrier preparation procedure. The catalysts were characterized by BET, H2-TPR, Raman, and XPS. The effect of the adding methods of promoters on the microstructure properties of the catalysts, active metal coordination structure and reducibility of the catalysts, interaction between metal and carrier were investigated. The catalytic performance was evaluated using liquid wax feed containing thiophene, piperidine and naphthalene. It is shown that under the same conditions，the HDS activity of Mo-Ni-P catalysts prepared by the second method is higher than the first one, while the HDN activity is just on the contrary. When the ratio of SiO2/P2O5 is 2.5, the hydrogenation activity of the catalysts, the proportion of octahedral coordinated molybdenum species in the catalysts and the hydrogen consumption during H2-TPR reach to the maximum, meanwhile the interaction between active metal molybdenum and aluminum oxide is the weakest.

STUDY ON PD/ZSM-5 HYDROCRACKING CATALYST

2013, 44(12):  51-55. 

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In this paper, the effect of silicon/aluminum ratio and grain size on pore structure and acidity of ZSM-5 molecular sieve was investigated by N2 adsorption-desorption and NH3-TPD methods, and the hydrogenation performance of modified ZSM-5 molecular sieves and Pd/ZSM-5 catalysts were evaluated using heptane and cyclohexane as feeds. Results indicate that increasing the ratio of silicon and aluminum will reduce the acid sites of the catalyst and relatively increase the amount of hydrogenation active center. Due to reduction of secondary cracking, the selectivity of isomerization is improved; the nano-size ZSM-5 greatly improves the activity of the catalyst. The Pd loading changes the reaction pathway and lowers dawn the alkanes activation energy, resulting in improvement of hydrogenation activity. When the Pd loading is larger than 0.4%, the hydrogenation activity of the catalyst will level off.

APPLICATION OF IN ADVANCE SULFIDATION TECHNOLOGY OF HYDROGENATION CATALYST IN SULFUR RECOVERY UNIT

2013, 44(12):  56-60. 

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Long start-up period and more SO2 emission are the two problems existing in Claus tail gas hydrogenation process. To solve the problems, a sulfidation technology in advance of hydrogenation catalyst is applied for the first time in the No.2 100kt/a sulfur recovery plant of Zhenhai Refining & Chemical Company. The advantages and difficulties of the sulfidation technology in advance and the procedures were analyzed and introduced in detail. The application results show that the technology can satisfy the working need of the unit and cut the start-up time, save fuel and electricity consumption, and reduce the SO2 emissions.

STUDY ON DEMULSIFICATION OF PRODUCED LIQUID BY BINARY COMBINATION FLOODING

2013, 44(12):  61-65. 

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Demulsification of produced liquid by surfactant-polymer flooding from an oilfield was very difficulty, and the existing demulsification technology can’t satisfy the demand of oilfield. This paper analyzed the physicochemical properties and micro morphology of this produced liquid and compared the results with polymer flooding produced liquid by means of bottle test method and light-scatter method. A high efficiency demulsifier named DS had been developed based on the analysis. The experiments results show that a high oil-water separating velocity of the sample can be reached with 50mg/L DS added, and the oil in water phase can be decreased to 224.2mg/L in 1h. Moreover, the stability index of the sample is 14.95(compared with 6.31 of the existing demulsifier). It can be concluded that the DS can meet the demand for demulsification of the produced liquid for its higher efficiency compared with the existing demulsifier.

STUDY ON COLLOID STABILITY OF RESIDUE DURING EBULLATED HYDROCRACKING

2013, 44(12):  66-70. 

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The vacuum residue that consists of SARA is usually considered as a stable colloid system. The changes of SARA of vacuum residue from Saudi and Iran light crude under different conditions in STRONG ebullated processing were investigated. The relations of the conversion and the stability of the systems during processing were analyzed by Spot test, Separability Number test and Colloid Stability Index test. The results indicate that Spot test can directly reflect the trend of the stability of the system. The inner spot begins to emerge in spot imaging figure when the conversion reaches to 43%, indicating the system turns into unstable. Colloid Stability Index (CSI) can quantitatively predict the stability variation.The system becomes unstable if CSI is smaller than 0.7, in accord well with the Spot test results; Based on the ability to resist dilution of the overall system, Separability Number has more accurate results than the other two methods, and when the Separability Number is larger than 33, the system becomes unstable obviously.

STUDY OF DESULFURIZATION MECHANISM FOR HIGH SULFUR CRUDE OIL AND REGENERATION OF SnSb INTERATALLIC

2013, 44(12):  71-76. 

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SnSb intermetallic compounds were prepared by chemical precipitation using NaBH4 as a reductive agent and SnCl2、SbCl3 as precursors and were tested to investigate the mechanism of electro-desulfurization of crude oil. The intermetallics were characterized by SEM-EDS for the morphology and element distribution on the surface of the SnSb before and after desulfurization. Gas chromatography-pulsed flame photometric detector（GC-PFPD）was used to analyze sulfur compounds in gasoline and diesel fractions separated from the crude oil before and after the test. The results indicate that the destructive adsorption of sulfur compounds occurred on the surface of the intermetallic and that desulfurization efficiency for sulfur compound with simple structure is high but relatively lower for larger sulfur species like dibenzothiophene. The used SnSb intermetallics can be regenerated by calcination、NaOH washing or toluene washing method with the toluene washing of the best.

STUDY ON DESULFURIZATION OF FCC LIGHT GASOLINE

2013, 44(12):  77-80. 

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Desulfurization tests of FCC light gasoline by extractive distillation were carried out. Optimum desulfurization solvent and the process conditions were selected. Results show that self-made TSJ is the optimum desulfurization solvent. Under the conditions of 2-stages distillation, a TSJ/FCC light gasoline volume ratio of 0.4 and a FCC light gasoline space velocity of 1.5h-1, the sulfur content of treated FCC light gasoline A is dropped from 114μg/g to 48.2μg/g, the desulfurization rate is 57.72% and the yield reaches 99.20%, meeting the sulfur content of National Ⅳ emission standard for gasoline（≯50μg/g）. The sulfur–rich solvent TSJ can be regenerated by N2 tripping. After 5 times of regeneration and desulfurization, the desulfurization rate of FCC light gasoline A is nearly unchanged. Desulfurization of several FCC light gasolines by extractive distillation using TSJ was investigated and high desulfurization rate and high yield can be obtained.

EXPLORATION AND PRACTICE IN STABLE PRODUCTION OF 120BS BRIGHT OIL

2013, 44(12):  81-85. 

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The floccules in 120BS bright stock produced in SINOPEC Jingmen Company occurred during storage in an environment below 5 ℃. To solve this problem, the analysis of floccules structure and dewaxing test of the hydrotreated bright stock were made in lab and industrial trial practice was conducted. The results indicate that the floccules consist of high solidification point hydrocarbons, like long chain paraffin, less branched alkanes and long side chain naphthene and that the good and stable qualified feed for acetone-benzol dewaxing can be obtained by optimization of crude oil composition, operation conditions of propane deasphalting, furfural extraction and hydrotreating, and the 120BS bright oil without the floccules can then be produced by carefully controlling the operation conditions of each step in acetone-benzol dewaxing process. The 120BS complies with the standard of API II and SINOPEC.

PRELIMINARY EXPLORATION OF MANUAL TRANSMISSION FLUID FRICTION CHARACTERISTICS AND SYNCHRONOUS DURABILITY

2013, 44(12):  86-90. 

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A manual transmission fluid was developed using self-prepared additives. Its antiwear and friction performance were investigated by SRV testing machine. The wear scar surface was analyzed by three-dimensional topography. The results were compared with reference oil. Finally the synchronous durability of reference oil and developed oil was verified by SSP180 bench test. The results show that the friction behaviour of the developed oil under selected SRV test conditions is correspondence with synchronous durability. The oil with high and stable friction coefficient（>0.115）, small and smooth wear scar (average wear scar diameter below 0.45mm) can pass SSP180 synchronous durability bench test(cycle 100000 times).

STUDY ON THERMAL OXIDATION STABILITY OF PAO BASE-OIL

2013, 44(12):  91-94. 

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By combining thin micro oxidation test and infrared spectrum analysis, the relations of the sediment content，mass reduction under the setting oxidation conditions with oxidation time were simulated and analyzed. It can be seen that the deposit appears after 90 minutes oxidation and increases with the extension of time. It is discovered that the ratio of carbonyl and methyl group infrared spectrum areas of PAO (CSI) can well reflect the depth of oil oxidation. The ratio first increases and then decreases as the oxidation time is extended. The results show that the good thermal oxidation stability of PAO lubricating base-oil can keep about 90 minutes at 230 ℃.