Table of Content

12 February 2009, Volume 40 Issue 2

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加工工艺

Study on hydro-upgrading of highly acidic crude oils

liu tao lishun dai Niu Chuanfeng

2009, 40(2):  1-4.  doi:

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The hydro-upgrading of highly acidic crude oils was studied using two types of typical crude oils. The results indicated that Penglai crude could be processed as ordinary crude after hydro-upgrading under low pressure and high LHSV. The acid value, contents of sulfur, CCR and heavy metals of Shengli commingled crude decreased significantly after hydro-upgrading under high pressure and low LHSV, and its API gravity increased as well. The atmospheric residue of hydro-upgraded Shengli commingled crude could be used as RFCC feedstock directly. The relationships between operating conditions and hydro-deacidification were investigated. It was found that under low pressure and high LHSV, the acid removal rate increased with the increase of reaction temperature and decreased with the increase of LHSV; the decrease of hydrogen partial pressure could cause the reduction of acid removal rate significantly.

ANALYSIS OF THE APPLICATION OF RDS-RFCC COMBINED PROCESS

Mingyang Peng hongtao zhao

2009, 40(2):  5-8.  doi:

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The commercial operation was presented from a recently commissioned refinery featuring the combination of residue feed hydrotreating and resid fluid catalytic cracking (RDS-RFCC) process. For a refinery building around the combined RDS-RFCC process, it has overall advantages such as short processing flow scheme, deep residue conversion and long operation cycle. On the production side, this combination also exhibits superiority than conventional refinery design in terms of high light oil yield, high comprehasive products yield, excellent product quality and less waste streams. Meanwhile, it is worth to point out that this combination has limited flexibility to feedstocks and needs to resolve the issue with respect of catalysts loading. Suggestions which could help mitigate these problems are also proposed, including reducing the space velocity of RDS reactor, revamping the feed distributor of RDS reactor, optimizing catalysts graded loading and enlarging the heat release capacity of RFCC regenerator.

THE CAUSE OF FLUE GAS OVERHEATING OF REFORMER IN HYDROGEN PLANT AND COUNTERMEASURES

2009, 40(2):  9-12.  doi:

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Since the flue gas outlet temperature of reformer in the 50 000 m3/h hydrogen plant of SINOPEC Beijing Yanshan Company was much higher than the design temperature, cause analysis was carried out. It was found that a “flue gas aisle” existed between the walls of reformer and the heat-exchanged tubes, which affected the heat transfer efficiency of flue gas and also damage some heat-exchanged tubes. Measures including adding baffle boards and thickened part of the reformer walls were adopted. Since then the temperature of the outlet flue gas reduced and the heat utilization rate of flue gas increased, resulting in an 8.58 million RMB economic benefit per year and the investment recovery period was only 122 days.

STUDY ON ALKYLATION OF COKER GAS OIL

2009, 40(2):  13-16.  doi:

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The alkylation of coker gas oil over a combined catalyst, aluminum trichloride-trichloromethane, was studied using coker gas oil from the No.1 Refinery of PetroChina Fushun Petrochemical Company with a boiling range of 210~270℃. The effects of catalyst dosage, the ratio of benzene to olefin, reaction temperature and reaction time on the yield of alky-benzene and the quality of alkylate were investigated. Results showed that using aluminum trichloride combined catalyst under the conditions of a catalyst dosage of 5%, a benzene/olefin molar ratio of 8, a reaction temperature of 60℃ and a reaction time of 6 h, the yield of alky-benzene reached 19.6% and the quality of the obtained alkylate was significantly improved as compared with coker gas oil.

EVALUATION OF THE INHIBITING POLYMERIZATION OF ISOPRENE USING TERT-BUTYL CATECHOL INHIBITOR

2009, 40(2):  17-21.  doi:

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Comparison of inhibitors for anti-polymerization of isoprene (IP), such as NaNO2, p-tert-butylcatechol (TBC), N-methyl pyrrolidone (NMP) and paradioxybenzene (HQ), was carried out using polymer segregation process and the results showed that TBC was the best one. Using TBC as inhibitor, the effects of reaction temperature, reaction time and TBC dosage on the IP loss were investigated by tube sealing test. Test results showed that when reaction temperature was less than 95℃, the temperature impact on IP loss was little, indicating low temperature was in favor of inhibiting IP polymerization; the best inhibition performance was obtained with a TBC mass fraction of 0.15%, higher TBC dosage could cause negative effect; the IP loss increased with the increase of reaction time.

催化剂

STUDY ON CATALYTIC PYROLYSIS OF 1-OCTENE OVER VARIOUS ZEOLITES USING MOLECULAR SIMULATION

2009, 40(2):  21-25.  doi:

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Catalytic pyrolysis of 1-octene over HY, Hβ and HZSM-5 zeolites was investigated. Results showed that HZSM-5 zeolite having medium pore structure and certain amount of strong and medium acid sites exhibited good 1-octene conversion and high light olefins selectivity. Molecular simulation technique was used to study the types of reactions involved in the catalytic pyrolysis of 1-octene. It was found that as compared with HY and Hβ zeolites, the characteristic pore structure of HZSM-5 zeolite, such as smaller pore size and lack of cages, restricted the reactions of cyclization and hydrogen transfer to take place during the catalytic pyrolysis of 1-octene, thus the conversion of 1-octene and the selectivity to light olefins of HZSM-5 zeolite were high.

SCALE UP OF PREPARING SOx TRANSFER ADDITIVES FOR REDUCING SOx EMISSION FROM FCC UNIT

2009, 40(2):  26-30.  doi:

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SOx transfer additive samples containing magnesium rich spinel and active components (Ce/Fe/V) were prepared in pilot plant scale using a spray drying device with pressure nozzle. The preparation conditions, esp. spray drying conditions, were investigated. Test results showed that microspheric samples having similar particle size distributions as FCC catalyst could be obtained using slurry with a solid content of 15% and a temperature of 80℃, under the spray drying conditions of hot air inlet temperature of 740～760℃，outlet temperature of 345～360℃ and atomizing pressure in the range of 5.0～5.5 MPa. The SOx transfer performance of the obtained samples was evaluated by micro-reactor and FFB simulating commercial FCC unit conditions. Results showed that the prepared SOx transfer additive samples could effectively reduce the SOx content in flue gas；hydrothermal treatment could reduce the SOx transfer activity of additive in some way.

PREPARATION OF Au/SiO2 CATALYSTS BY SELF-ASSEMBLY TECHNIQUE AND ITS CATALYTIC PERFORMANCE OF OXIDATING CYCLOHEXANE WITH AIR

2009, 40(2):  31-36.  doi:

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Nanocomposite catalysts of Au/SiO2 were prepared by self-assembly method. X-ray diffraction (XRD), transmission election microscopy (TEM), atom absorption spectrometry (AAS), ultraviolet-visible spectroscopy (UV-Vis) and nitrogen adsorption/desorption technique were used to characterize these samples. The oxidation of cyclohexane with air to produce cyclohexanol and cyclohexanone without using any organic solvent or co-catalyst was investigated over the as-prepared Au/SiO2 catalysts. The influences of gold content, reaction temperature, reaction pressure, reaction time and calcination temperature on the catalytic performance of catalysts prepared were studied. It was found that catalyst prepared with a gold loading of 1% and calcined at 500℃ exhibited good catalytic performance, when it was continuous reacted under an air pressure of 3.0 MPa for 4 h ,the conversion of cyclohexane and the total selectivity to cyclohexanol and cyclohexanone were about 10% and 92%, respectively.

STUDY ON THE ISOMERIZATION REACTION OF n-HEXANE OVER Mo2C/SAPO-11 CATALYST

Meng Yu Feng Gu

2009, 40(2):  37-40.  doi:

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A Mo2C/SAPO-11 catalyst was prepared by temperature programming reduction method using n-hexane as the source of carburization. It was shown from the XRD patterns that through hydrogen reduction the molybdenum phase in catalyst was changed to β-Mo2C, which possessed good isomerization activity. The influences of reaction temperature, reaction pressure, space velocity and hydrogen to hydrocarbon ratio on the catalytic isomerization performance of β-Mo2C/SAPO-11 catalyst in the presence of hydrogen were investigated by a continuous fixed-bed reactor system using n-hexane as model feed. Results showed that under the optimum conditions of a reaction temperature of 380℃, a reaction pressure of 1.5 MPa, a LHSV of 1.0 h-1 and hydrogen to hydrocarbon volume ratio of 200, the conversion of n-hexane reached 82.19%; the selectivity and yield of isomers were 73.57% and 60.47%, respectively.

STUDY ON THE ADSORPTIVE REMOVAL OF THIOPHENE OVER IN-SITU CRYSTALLIZED NaY ZOLITE MODIFIED BY VARIOUS METAL IONS

Shu-qin Zheng Ya-li Dai Dong Qian Jian-hui Yan

2009, 40(2):  41-44.  doi:

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Three adsorbents (CrNaY, MnNaY, CoNaY) were prepared by ion-exchange technique to introduce various transition metal ions (Cr3+, Mn2+ and Co2+) into in-situ synthesized NaY zeolite. The desulfurization behaviors of these adsorbents were investigated using model gasoline containing thiophene or 2-methyl thiophene. The results showed that CrNaY exhibited the best sulfur removal performance, and the removal rate of 2-methyl thiophene was higher than that of thiophene. Under the condition of 93℃, an adsorption time of 1 h and a mass ratio of adsorbent to oil of 0.5, the removal rate of thiophene over CrNaY reached 70.03%. The surface acidities of adsorbents were determined by nonaqueous solution back titration method, and the results showed that the total acidity of CrNaY was the highest, which indicated that the sulfur removal rate increased with the increase of adsorbent acidity.

环保

COMMERCIAL APPLICATION OF WSH-1 CATALYTIC COMBUSTION CATALYST FOR TREATING WASTE GASES FROM WASTE WATER TREATMENT SYSTEM IN REFINERY

2009, 40(2):  45-48.  doi:

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A catalytic combustion catalyst WSH-1 was developed by Fushun Research Institute of Petroleum and Petrochemical for treating organic waste gases, and it was applied in the catalytic oxidation reactor of waste water treatment system at SINOPEC Guangzhou Company. The more than 2-year running results showed that the activity and stability of WSH-1 catalyst were same as the imported one used with similar conditions. Under a waste gases throughput of 3 000~4 000 m3/h, a space velocity of 18 000～24 000 h-1, a reactor inlet temperature of 250～280 ℃, when the content of non-methane total hydrocarbons at the reactor inlet gas was in the range of 1 350～4 900 μL/L and the total sulfur content of the inlet gas was less than 10 mg/m3, the average removal rate of non-methane total hydrocarbons reached 96.9%, benzene, toluene and xylene were non-detectable. The contents of benzene, toluene, xylene and non-methane total hydrocarbons in the purified gases well met the targets of National Emission Standard.

控制与优化

OPTIMIZATION OF PROCUREMENT AND PROCESSING LOW QUALITY SOUR AND ACIDIC HEAVY CRUDES

LONG Wei-Can

2009, 40(2):  49-53.  doi:

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As the cost of high sulfur and highly acidic heavy crude oils are much lower than the light crude oils in the open oil market, SINOPEC Changling Company purchased some low quality sour and acidic heavy crudes for cost reduction and successfully processed these crudes with crude oil mixing technology and based on Changling’s own PIMS model. By optimizing processing scheme, naphtha flow, crude oil transportation plan and the proper selection of mix-processing crudes, the low quality crude oils were processed smoothly and the qualities of products well met the requirements. The cost of crude oil reduced significantly, thus great economic benefit was obtained.

THE APPLICATION OF ADVANCED PROCESS CONTROL TECHNOLOGY ON ONE CONTINUOUS CATALYTIC REFORMING UNIT

2009, 40(2):  54-58.  doi:

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The application of the advanced process control (APC) technology on the 1.2 Mt/a CCR unit of SINOPEC Zhenhai Company was introduced. After performed a detailed analysis of the status of equipment in the CCR unit, the control objectives were laid out and the strategy was determined. Controllers and soft instrumentation were then designed and developed to meet these requirements. After commissioning said APC system, the fluctuation of the standard deviation of key control parameters in the CCR unit reduced more then 30%. The APC technology also contributed to high unit stability and maximized unit capacity with qualified product. The goal of improving product yield while saving energy consumption was achieved with the commissioning of APC technology. It was found that the average fuel gas consumption rate decreased 4.44 Nm3/t, indicating a cost-saving worth up to 11.47 million RMB.

油品与添加剂

EFFECTS OF HYDROCARBON COMPOSITIONS ON THE EMISSIONS OF GASOLINE ENGINE

2009, 40(2):  59-62.  doi:

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Fuel compositions have great impact on gasoline engine emission. The effects of alkanes, olefins and aromatics on the emissions are summarized. Unburned alkanes are the main part of hydrocarbons (HC) emission for alkane fuels; for olefin fuels, propylene, isobutene and pentene are the main components, further more, the 1,3-butadiene content in HC emission increases with the increase of olefin content in gasoline. The content of benzene, toluene and ethylbenzene in HC emission increases with the increase of aromatics content in fuel. The operating conditions, such as air fuel ratio, spark timing and etc, affect the constitution of HC emission significantly. Therefore, it is important not only to investigate how to reduce the contents of olefins and aromatics in fuel, but also to reduce the negative effect caused from high olefins and aromatics fuel by optimizing engine combustion process.

A STUDY OF COLD FLOW IMPROVERS FOR SOYBEAN BIODIESEL FUEL

2009, 40(2):  63-66.  doi:

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The influences of three cold flow improvers, polymer of vinyl acetate-ethylene (VAE), polymethacrylate (PMA) and polymer of ethylene-vinylacetate (PEV), on the cold flow properties and viscosity-temperature characteristics of a soybean bio-diesel fuel were studied using a low-temperature flow tester and a rotatory viscometer. The crystal features of the bio-diesel fuel prior and post to adding improver at low temperature were investigated by a polarized microscope. Test results indicated that the cold flow improving performance of these three improvers was varied; VAE was the best one among them, which could reduce the cold filter plugging point and freezing point of soybean bio-diesel fuel significantly. At low temperature the apparent viscosity of bio-diesel fuel increased sharply and the formation of 3-dimensional wax crystal network made the fuel even lose fluidity. Adding VAE could suppress the formation of wax crystal network and prolong the increase of apparent viscosity, thus the cold flow properties of bio-diesel fuel was improved.

PREPARATION OF A MICRO-EMULSIFIED FUEL ADDITIVE AND ITS MICROSTRUCTURE STUDY

2009, 40(2):  67-72.  doi:

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A micro-emulsified additive (FAD) for gasoline and diesel fuel was prepared by micro-emulsification technique. Factors affected the preparation of FAD, the viscosity and stability of FAD was investigated. The microstructure of FAD was studied by freezing etch-scanning electron microscope, nano-silver chloride particles were prepared based on FAD system and characterized by scanning electron microscope and nano-particle size analysis. All these test results showed that the prepared FAD additive was a micro-emulsified system. When FAD was added to gasoline or diesel fuel, good phase solubility was observed and the electrical conductivity of the fuel increased significantly.