Table of Content

12 May 2011, Volume 42 Issue 5

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催化剂

EFFECT OF PHOSPHORUS ON THE PERFORMANCE AND ACTIVE COMPONENT STRUCTURE OF MoCoNi/Al2O3 CATALYST

Niu Chuanfeng

2011, 42(5):  1-4.  doi:

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MoCoNi/Al2O3 and MoCoNiP/Al2O3 hydrotreating catalysts were prepared by saturation impregnation method respectively. The effect of phosphorus on the catalytic performance and active component structure of the catalysts was studied using Kuwait atmospheric residue as feedstock and characterizing by DRS, TPR and other techniques. Results showed that as compared with MoCoNi/Al2O3 catalyst, MoCoNiP/Al2O3 catalyst exhibited improved hydrotreating activity, and furthermore, its higher hydrogenation activity led to obtain a totally improved quality product for FCC feedstock. For MoCoNiP/Al2O3 catalyst, due to the increase of Mo(O) species in octahedral structure, the reduction ability of active components at low temperature was enhanced and the catalyst activity was promoted. The pore volume and surface area of the phosphorus modified catalyst were reduced in some extent, which was unfavorable to the metal tolerance performance of catalyst. However, the coke deposits on the catalysts with or without phosphorus were the same, indicating that the two catalysts had similar ability to restrain coke formation.

CATALYTIC CRACKING CATALYSTS FOR OVERSEA MARKETS

2011, 42(5):  5-9.  doi:

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Base on the various feedstock properties and requirements from customers of oversea markets, SINOPEC develops a series of fluid catalytic cracking (FCC) catalysts such as heavy oil upgrading catalysts, enhancing clean gasoline production catalysts and maximizing propylene yield catalysts, which all have good heavy oil crackability, excellent product selectivities and suitable for flexible operations. Some application cases in oversea refineries indicate that the sodium and titanium contents in equilibrium catalysts decrease and the lanthanum to cerium ratio changes during the catalyst replacement. In similar contamination level of heavy metals, the product selectivities improve, coke and gas factors decrease after using SINOPEC's catalysts. The application results validated that FCC catalysts designed and developed by SINOPEC are suitable to be used in oversea refineries widely.

RESEARCH ON NICKEL CATALYST FOR SELECTIVE HYDROGENATION OF REFORMATE

2011, 42(5):  10-13.  doi:

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The selective hydrogenation of reformate over Ni/Al2O3 catalyst prepared by isopyknic impregnation was studied using a reformate having a bromine value of 2.67 gBr/(100g) as feed. The effect of reaction temperature, liquid hourly space velocity (LHSV) and H2/oil ratio on the selective hydrogenation activity of the catalyst was investigated. Test results showed that under the conditions of a reaction temperature range of 70～80℃, a reaction pressure of 2.0 MPa, LHSV in the range of 1.0~2.0 h-1 and H2/oil volume ratio not less than 200, the bromine value of the treated reformate was less than 0.1 gBr/100g, the aromatic hydrocarbons in the feed was almost unsaturated and the loss of octane number was less than 0.2 units.

COMMERCIAL TRIAL OF Ni/Al2O3-SiO2 CATALYST FOR HYDROGENATION OF C5 FRACTION

2011, 42(5):  14-17.  doi:

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The commercial trial for hydrogenation of crude isopentene using Ni/Al2O3-SiO2 catalyst was carried out on an 8 kt/a hydrogenation unit based on the experimental data in lab. Results showed that the commercial trial was successful and the stability of Ni/Al2O3-SiO2 catalyst was excellent. The unit run 7 392 h totally and 12.018 kt crude isopentene was treated from 28 October, 2009 to 29 September, 2010. The average hydrogenation conversion was 98.82% and the average alkane content in products was more than 99%. The effect of organic sulfur content in feed and the CO content in hydrogen on the hydrogenation reactions, as well as the reason of better catalyst stability in commercial trial than in lab test were discussed.

STUDY ON THE HDS PERFORMANCE OF CoMo/SBA-15-γ-Al2O3 CATALYST

2011, 42(5):  18-22.  doi:

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CoMo/SBA-15-γ-Al2O3 catalysts were prepared using mesoporous molecular sieve SBA-15 and γ-Al2O3 as mixed support, Co and Mo as active metal components. Test results showed that the prepared catalysts exhibited the characteristics of mesoporous material with slightly decrease surface area. Using catalyst with CoO and MoO3 contents of 5% and 20%, respectively, under the conditions of a reaction temperature of 360℃, a reaction pressure of 6 MPa, a hydrogen/oil volume ratio of 600 and a LHSV of 2 h-1, the sulfur content of treated diesel fuel could be reduced to 6 μg/g from the feed of 829 μg/g.

INDUSTRIAL APPLICATION OF RJW-3 PARAFFIN HYDROREFINING CATALYST

刘玉庆 Liu Yu Qing

2011, 42(5):  23-26.  doi:

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Industrial application of RJW-3 paraffin hydrorefining catalyst in SINOPEC Jingmen Company was introduced. The industry operation results show that RJW-3 catalyst possess high catalytic activity, good aromatic hydrocarbon saturation performance, low cracking activity and high crushing strength. It can be used at low reaction temperature and high LHSV. Compared with RJW-2 catalyst when RJW-3 catalyst is applied under the conditions of a LHSV more than 15.7% higher, a reaction temperature 8℃ lower and lower hydrogen partial pressure, the product qualities still well meet the standard of food-grade wax even with poor quality feedstock.

INFLUENCE OF CALCINATION TEMPERATURE ON THE CATALYTIC PERFORMANCE OF Fe/HZSM-5 CATALYSTS FOR CONVERTING ETHANOL INTO LIGHT OLEFINS

2011, 42(5):  27-30.  doi:

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A series of iron-modified HZSM-5 catalysts was prepared by impregnation method and calcined under various temperatures. The obtained samples were characterized using XRD, NH3-TPD and TPR methods. The catalytic properties of the prepared catalysts were investigated by the reactions of converting ethanol into light olefins using a fix-bed micro reactor. It was found that the acidity, acid strength and the dispersion of iron on the catalyst surface changed with the calcination temperature. Fe/HZSM-5 catalyst calcined under optimum temperature could significantly improve the selectivity to light olefins, the hydrogen transfer reactions and aromatization reactions were suppressed. Using catalyst calcined at 700 ℃, the selectivity of propylene and butenes in product was 30.94% and 18.01%, respectively.

基础研究

STUDY ON THE PROPERTIES OF ACID DISPERSED PSEUDOBOEHMITE SLURRY

Ma Aizeng

2011, 42(5):  31-35.  doi:

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The properties of pseudoboehmite slurry prepared by acid dispersion were studied. The effect of acid amount and dispersion time on the acid dispersion index and viscosity of the slurry was investigated. Results showed that under the testing conditions, both acid dispersion index and viscosity of the slurry increased with the increase of acid amount and dispersion time, besides, the viscosity also increased with the increase of alumina content in slurry. Since gelation happened during the acid dispersion process, the variation tendency for the acid dispersion index and viscosity was varied significantly. The effect of slurry properties on the properties of prepared catalyst support was also studied. It was found that the bulk density of the prepared support could be increased by improving the acid dispersion index of the slurry. Spherical support and catalyst prepared under the optimum conditions in lab exhibited similar physicochemical properties and catalytic performance as compared with the commercial support and catalyst.

RESEARCH ON THE ACIDIC PROPERTIES OF RARE EARTH MODIFIED ZEOLITE Y

Sun Min,HE Zhen-Fu

2011, 42(5):  36-39.  doi:

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The acidic properties and the coordination of aluminum in zeolite Y modified by rare earth exchange were studied. Results show that after rare earth exchange, the acidic properties of zeolite Y change significantly, the acid density, the total amount of Br?nsted (B) acid and the amount of strong B acid, as well as the total amount of Lewis (L) acid and the amount of strong L acid all increase. However, when the degree of rare earth exchange exceeds a certain amount, the acid density, the amount of B acid and L acid decrease, thus the acidic properties of zeolite Y could be adjusted by rare earth exchange. Results also show that the formation of B acid site is affected by the tetra-coordinated, penta-coordinated and hexa-coordinated aluminum, and L acid site is affected by the non-framework aluminum in lower coordination.

STUDY ON THE CUT POINTS OF LIGHT AND HEAVY GASOLINE FRACTIONS FOR SELECTIVE HYDRODESULFURIZATION OF FCC GASOLINE

shi quan

2011, 42(5):  40-44.  doi:

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Using a laboratory-made distillation device, 4 FCC gasoline samples were cut into 11 fractions respectively. The total sulfur, monomer hydrocarbon, PONA and monomer sulfide of these fractions were analyzed by gas chromatography to study the distribution rules of olefins and sulfur containing compounds in FCC gasoline, and then to select the optimum cut points of light and heavy gasoline fractions for selective hydrodesulfurization. Results showed that the compositions of hydrocarbon in FCC gasoline from various sources were quite similar, mainly formed by alkanes, cycloalkanes, aromatics and olefins from C4-C10. The content of sulfur compounds in the four gasoline samples were varied significantly, but the types of compounds were also similar, mainly formed by C0-C4 alkyl substituted thiophene-based compounds, and tetrahydro-thiophene based compounds were another important class of sulfur compounds. Small molecule thiols were found in FCC gasoline samples, but their percentages in the total sulfur compounds were varied with the source of sample. In order to achieve an ideal effect of FCC gasoline selective hydrodesulfurization, the optimum cut points of the light and heavy FCC gasoline fractions should be in the range of 72-80℃.

ADSORPTION BEHAVIOUR OF n-PARAFFINS CONTAINED IN NAPHTHA ON THE BED WITH BINDERLESS 5A MOLECULAR SIEVE

SUN Hui,Benxian Shen

2011, 42(5):  45-49.  doi:

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Adsorption of n-paraffins contained in naphtha on 5A molecular sieve pellets with/without binder was studied on a fixed bed adsorption device. The results indicated that the adsorption breakthrough times of various n-paraffins increased with the increase of n-paraffins' carbon number. As compared with molecular sieve with binder, the adsorption bed of binderless 5A molecular sieve showed higher adsorption capacities for n-paraffins; at an adsorption temperature of 300 ℃ and a space velocity of 90 h-1, the dynamic adsorption capacity of binderless 5A molecular sieve was 34.5% higher than that of molecular sieve with binder, which indicated that more naphtha feed could be processed or less molecular sieve pellets should be packed. Furthermore, the mass-transfer zone of bed with binderless 5A molecular sieve was shorter, which suggested that the effective using rate of this adsorption bed was higher.

EFFECT OF DISTRIBUTOR TYPES ON HYDRODYNAMICS BEHAVIOR IN A COMPOUND GAS-SOLID AIRLIFT LOOP REACTOR

Wang De-Wu,Lu Chunxi

2011, 42(5):  50-56.  doi:

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A large scale cold model experimental setup of a compound gas-solid airlift loop reactor was established according to olefin reduction technology with auxiliary reactor for FCC naphtha upgrading. The effect of distributor types on hydrodynamics behavior in the airlift loop reactor was experimentally measured, and three types of distributor were involved including concave spherical perforated plate (concave SPP), plane perforated plate (PPP) and convex spherical perforated plate (convex SPP). The experimental results show that the effect of distributor types on the hydrodynamics behavior within 0.50 m height upon the distributor is significant. The action scopes of gas and particle through the distributor on the particles (or clusters) in the reactor mainly locate in the central region above the concave surface for concave SPP distributor, in the projection region above the distributor for PPP distributor, and in the upper region of convex surface and around neighboring region for convex SPP distributor. Furthermore, in these action scopes, the solid holdup is lower and the particle velocity is higher than that in the other scopes of the reactor. While adopting such three types of distributors, the descending order of particle circulating velocity is as follows: PPP > concave SPP > convex SPP; the descending order of radial uniformity of solid holdup is as follows: convex SPP> PPP > concave SPP. Therefore, combined the flow field uniformity with the adjustable range of circulating velocity, the adoption of plane perforated plate (PPP) distributor is more feasible than the other two distributors in the compound gas-solid airlift loop reactor.

加工工艺

INDUSTRIALIZATION OF ISOMERIZATION AND ASYMMTRIC CRACKING TECHNOLOGY FOR THE DEWAXING OF LUBE BASE OIL

Hu sheng

2011, 42(5):  57-60.  doi:

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Hydrorefining-isomerization and asymmetric cracking-hydrofinishing technology developed by Petrochemical Research Institute and Dalian Institute of Chemical Physics has been successfully applied at the 200 kt/a lube base oil hydrodewaxing unit of Daqing Refining & Petrochemical Company for more than one year. Results show that using paraffin base 200N light dewaxed oil, 650N furfural refined oil and foots oil as feedstocks under mild operating conditions, high quality lube base oil including light cut, medium cut, and heavy cut of API Ⅱ, Ⅲ group could be produced with high yield. Compared with conventional isomerization dewaxing technology, using this new technology the yields of API Ⅱ medium cut and API Ⅲ heavy cut were about 9 and 20 percentage points higher, respectively.

THE RULE OF FLUID FLOW IN TRICKLE-BED REACTOR AND ITS EFFECT ON ISOPRENE SELECTIVE HYDROGENATION REACTION

Xing-Liang Huang,Wei Huan-Jin,Qian-Bao Liu,Jian-Jun Wang

2011, 42(5):  61-65.  doi:

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On a cold model device of trickle-bed reactor, the variations of gas holdup and pressure drop with gas velocity and liquid velocity were investigated. The effect of operating parameters, such as different catalyst positions, gas velocity and liquid velocity on isoprene hydrogenation was also studied under the conditions of hot model using isoprene containing cyclohexane as feed. The experimental results show that under the same liquid velocity, when gas velocity is less than 0.88 m/min and the gas/liquid volume ratio is less than 4.0, the gas holdups increase with the increase of gas velocities significantly, and pressure drops decrease. When the gas velocity exceeds a certain value, the increase of gas holdup becomes slowly, yet pressure drop increases. The isoprene hydrogenation performance of LNEH-1 catalyst was varied with the locations of catalyst in the trickle-bed reactor. The isoprene hydrogenation activity and isopentane selectivity of the catalyst in liquid-dominant region is obviously higher than that in gas-dominant region. The effect of gas velocity on the catalytic activity and selectivity of the catalyst is more significant than that of liquid velocity. When the liquid velocities increase from 0.07m/min to 0.29m/min under constant gas velocity, the activity and selectivity of the catalyst in the liquid-dominant region is basically unchanged. But if the gas velocity increases from 0.11m/min to 0.27m/min under constant liquid velocity, the isoprene conversion and isopentane selectivity change from 96.6% and 91.0% to 98.5% and 96.1%, respectively.

EFFECT OF REACTION CONDITIONS ON THE HDM PERFORMANCE OF RESIDUE HYDROGENATION CATALYST IN EBULLATED BED REACTOR

ZHENG Zhenwei,Hailong Ge

2011, 42(5):  66-70.  doi:

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The effect of reaction temperature, hydrogen to oil volume ratio and space velocity on the HDM rate of inferior high-sulfur residue feeds was studied in STRONG reactor, which is an ebullated bed mixed flow reactor, and a self-developed microspherical catalyst was involved. Results showed that under the test conditions, the HDM rate increased with the increase of reaction temperature, and the optimum reaction temperature was 380 ℃; the HDM rate decreased significantly with the increase of space velocity, and the optimum space velocity was 1.6 h-1; With the increase of hydrogen to oil volume ratio, the HDM rate increased firstly to reach a steady zone (H2/oil volume ratio in the range of 450-550) which was an optimum reaction zone, then decreased with the further increase of H2/oil ratio.

油品与添加剂

STUDY ON THE TRIBOLOGICAL PROPERTIES OF LITHIUM BASE GREASE WITH ULTRA-FINE TIN POWDER

2011, 42(5):  71-74.  doi:

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In view of improving the tribological properties of lithium base grease ultra-fine tin powder was added, and the influence of adding methods, average particle size of the powder, adding amount and load on the tribological properties of lithium base grease was discussed. Scanning Electron Microscope (SEM) and Energy Disperse Spectroscopy (EDS) were employed to measure the surface of wear scar. Test results showed that when directly adding 2% of an ultra-fine tin powder having an average particle size of 90 nm, said lithium base grease exhibited an optimum anti-wear property. The mechanism of the improved tribological properties of lithium base grease with tin powder could be attributed to the self-repair function of ultra-fine tin particles on the surface of steel-ball. The research also found that the lithium base grease was more suitable for working under high load conditions when ultra-fine tin powder was added.

设备及防腐

RESEARCH ON THE COKING INHIBITION PERFORMANCE OF SiO2/S COATING AND SULFUR/PHOSPHORUS CONTAINING COKING INHIBITOR

2011, 42(5):  75-80.  doi:

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SiO2/S coating was prepared by atmospheric pressure chemical vapor deposition （APCVD）method on the inner surface of an off service 25Cr35Ni cracking tube in ethylene furnace. The anti-coking performance of the coating, adding sulfur/phosphorus containing coking inhibitor in feed and their combination was investigated respectively. The feature, chemical compositions and microstructure of the coating were characterized with scanning electron microscopy（SEM）, X-ray energy dispersion spectrometry（EDS）and Raman spectroscopy, so were the morphologies of coke deposits formed in various conditions. The results showed that the coating film was packed with 6~10 μm SiO2/S particles perfectly with a thickness of about 7 μm, and it was composed of three-member ring Si-O-Si structure and amorphous Si-O-S structure. The coking inhibition rates for coating and adding 200 μg/g coking inhibitor in feed were 65.07% and 69.20%, respectively. However, for the combination of coating and coking inhibitor with an adding dosage of 50 μg/g, the rate of combined coking inhibition reached 98.5%.

DISTRIBUTION PERFORMANCE OF LPT-1 LIQUID DISTRIBUTOR AND ITS INDUSTRY APPLICATION

GAO You-Fei

2011, 42(5):  81-85.  doi:

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The distribution performance of LPT-1 type liquid distributor was studied on a test device. Results showed that this distributor exhibited excellent distribution performance; its non-uniformity coefficient had a more than 40% reduction as compared with conventional trough liquid distributor and the heat transfer effect could be improved significantly. The industry application of LPT-1 type liquid distributor was carried out at the distillation unit of SINOPEC Cangzhou Company, and the results showed that the vacuum tower could be operated more flexibly with less fuel consumption, less pressure drop of the tower and higher distillate yield.

节能

OPTIMIZATION OF GAS OIL SYSTEM OPERATION AND ENERGY CONSERVATION IN A REFINERY

2011, 42(5):  85-88.  doi:

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Base on analyzing the operation status, problems and potential energy conservation of vacuum gas oil and coker gas oil (VGO & CGO) system in SINOPEC Zhenhai Company, some countermeasures for energy conservation were realized with low investment, such as optimizing the processing flow of VGO & CGO system, improving the feed supply modes for hydrocracking unit and FCC unit, enhancing the storing temperature of oil tanks, reducing the number of heat tracing piping and optimizing the allocation of gas oil pumps. Since then 9 557 kW of energy was saved and energy consumption was reduced 302 173 GJ annually. Suggestions for further optimization were proposed.

REVAMPING OF WASTE HEAT BOILER FOR ENERGY CONSERVATION IN RFCC UNIT

2011, 42(5):  89-92.  doi:

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To recover waste heat from flue gas, revamping of the flue gas energy recovery system in the RFCC unit of Karamay Petrochemical Company was carried out including removing the existing low pressure and medium pressure waste heat boilers, set up a new waste heat boiler and adopting novel energy conservation technology. The energy conservation effect was significant, the temperature of exhaust gas reduced to 164 ℃ from 190 ℃, the pressure drop of flue gas reduced by 9.6 KPa and the yield of medium pressure steam increased 17.9 t/h.