241 resultados para strong fields
Resumo:
现场总线的发展与应用引起了传统控制系统结构的改变,CAN总线因其自身的特点被广泛应用于自动控制领域。本文介绍了一种基于CAN总线的粮情测控系统,给出了系统的总体结构,并对系统的硬件配置和软件功能作了详细的说明。实际应用表明本系统具有结构简单、可靠性高、灵活方便等优点,并且具有较好的性能价格比,有着广泛的应用前景。
Resumo:
With the development of petroleum exploration in Gaoyou Depression, both old and new areas have been the active exploration targets, so the study of petroleum accumulation is significant to the petroleum exploration in the study area and the integrated oil and gas accumulation theory. Based on hydrocarbon accumulation theory and systematical research methods and combined with the structural characteristics of Gaoyou Depression, Chenbao and East of Chenbao were selected as the study areas in this dissertation, oil and gas migration pathways, accumulation periods, as well as accumulation models were studied, and favorable exploration targets were proposed. There develop three sets source rocks, which are Tai-2 Member, Fu-2 Member and Fu-4 Member respectively. Tai-2 Member is the predominant source rock in the eastern part. Fu-2 Member mainly occurs in the northern slope, while Fu-4 Member develops in the deep depression. In the study area, oil mainly comes from Fu-2 Member of Liuwushe subsag. The lower limit of TOC is 0.4%, and active source rock mostly distributed in the south fault-step zone. The source rock in Liuwushe subsag began to generate hydrocarbon in the late of Dainan depositional stage and the threshold was 2300m. The macro and micro characteristics of reservoirs and the reservoir heterogeneity characteristics of the Fu-1 Member were studied systematicly. The results show that Fu-1 Member, which has better reservoir properties, are medium porosity-medium permeability reservoir. The reservoir permeability has good correlation with porosity connectivity. The reservoirs have strong dissolution, pores are mainly thin to medium throat, and throat radii are distributed concentratedly, the sorting is good and pore structures are homogeneous. Sandstone reservoirs whether in the plan view, interlayer or in layers have a certain degree of heterogeneity, in particular, the heterogeneity in layers directly affect and control the oil and gas migration and accumulation. By analyzing the lithology correlation of the fault walls, shale smear, cross section stress, the configuration of fracture active periods and hydrocarbon generation and expulsion periods and fuzzy comprehensive evaluation, the main faults sealing were evaluated. The results show that the faults in Chenbao and East of Chenbao had poor sealing properties in Sanduo period and could be used as the migration pathways at that time. After Sanduo period, the tectonic stress fields in the area changed largely, and, consequently, the fault properties converted from tensional shear to compressive shear, the faults changed progressively from close to open, so the faults sealing became better and were conducive to the preservation of oil and gas reservoirs. According to the seismic event suspension modes and profile configurations above and under the unconformities, combined with tectonic evolutions of the study areas, the unconformity types can be classified into truncation unconformity, overlapped unconformity and parallel unconformity and the distribution characteristics of unconformities in the plan view was also studied. The unconformity structure was divided into basal conglomerate, weathered clay and semi-weathered layer vertically in the study area and this kind of structure make unconformities to be effective oil and gas migration pathways and is significant to hydrocarbon accumulation in a parts of areas. With the analyses of typical oil and gas reservoirs in the study area, combined with the research results of pathway systems, hydrocarbon accumulation models were established and the oil and gas accumulation laws in Chenbao and East of Chenbao analyzed. The oil and gas came from Liuwushe subsag and Liuliushe subsag. The oil and gas from Liuwushe subsag mainly migrated from the structural high parts into the fault-step zone along strata in northeast direction, a part of them migrated upward into the fault-step zone and the Wubao low uplift along Wu-1 Fault in northeast direction. The oil and gas from Liuliushe subsag mainly migrated into the upper reservoirs through Wu-2 fault, and lesser oil and gas migrated into the fault-step zone because of the controls of cross-section orientation, depression center and the hydrocarbon formation tendency. The favorable exploration targets in Chenbao and East of Chenbao have been concluded: the southern fault-step zone is a favorable oil and gas accumulation zone of Liuwushe subsag, and they are fault block reservoirs where fault acted as the barriers, the main target intervals are Fu-1 Member and Fu-3 Member in palaeocene; Oil and gas in the middle and northern fault-step zone mainly laterally migrated from the south areas, and the main target interval is Fu-3 Member in palaeocene; Fu-1 Member and the reserviors above the Wubao subsag are still the focuses in future explorations. The results of this study have important guiding significance for the future oil and gas exploration.
Resumo:
Neutral winds and electric fields in the ionospheric F layer play important roles in the variations of the ionosphere, and also affect the thermospheric circulation via the close coupling between the ionosphere and the thermosphere. By now, the neutral winds and electric drifts are generally observed with ground-based Fabry-Perot interferometers (FPI) and incoherent scatter radars (ISR), rockets, and satellite-borne instrument. Based on the servo theory, the ionospheric equivalent winds, which include the information of both the neutral winds and electric fields, can be derived from these characteristic parameters observed by ionosondes. This indirect derivation has potential values in climatological researches and space weather forecast. With the data set of the incoherent scatter radar observations at Millstone Hill, USA, from 1976 to 2006, we statistically analyzed the climatological variations of the vertical component of the equivalent winds (VEWs) over Millstone Hill, which are derived from the ionospheric key parameters (the peak electron number density and peak height of the F2 layer, NmF2 and hmF2) on the basis of the servo theory, Liu's method, and measurements from the ion line-of-sight velocity as well. The main results of this analysis are summarized as follows: (1) The values of VEWs over Millstone Hill during nighttime are stronger than in the daytime, and the upward drift dominates most of the day. In 1993, Hagan found that the component of the neutral winds in the magnetic meridion in daytime is weaker than during nighttime under both solar maximum and minimum conditions; he also found that the equatorward winds dominate most of the day. Both results suggest that the thermosphere in Millstone Hill is modulated by the aurorally driven high-latitude circulation cell; that is, during geomagnetic quiet periods, the average auroral activity is strong enough to drive thermospheric circulation equatorward for most of the day at Millstone Hill. Moreover, since ion drag is the strongest during daytime when F region densities are enhanced by photoionization, the wind speeds are smaller during the daytime than in the nighttime. (2) There is equinoctial symmetry in VEWs at Millstone Hill. The amplitudes and phases of VEWs in spring are quite similar to those in autumn. In contrast, the nighttime upward drift in winter is weaker than in summer and the difference becomes more significant with increasing solar activity. This solstice asymmetry indicates that, the aurorally driven circulation in the northern hemisphere at Millstone Hill latitude is weaker in winter due to arctic darkness, because the subsolar point is in the southern hemisphere. (3) The comparison of the VEWs derived from three methods, i.e., the servo theory, Liu's method, and the ISR ion line-of-sight velocity measurements, indicates that the amplitudes and main phase tendencies of these VEWs accord well with each other during nighttime hours. However, the case in the daytime is relatively worse. This daytime discrepancy can be explained in terms of the effects of photochemical processes and the choices of the servo constants. A larger servo constant gives a stronger plasma drift in daytime. Therefore, this study tells how important to choose a suitable constant for deriving VEWs at Millstone Hill.
Resumo:
Rock mass is widely recognized as a kind of geologic body which consists of rock blocks and discontinuities. The deformation and failure of rock mass is not only determined by rock block,but also by discontinuity which is virtually more important. Mutual cutting and combination of discontinuities controlled mechanical property of rock mass. The complex cutting of discontinuities determine the intense anisotropy on mechanical property of rock mass,especially under the effect of ground stress. Engineering practice has show that the brittle failure of hard rock always occurs when its working stress is far lower than the yield strength and compressive strength,the failure always directly related to the fracture propagation of discontinuities. Fracture propagation of discontinuities is the virtue of hard rock’s failure. We can research the rock mass discontinuous mechanical properties precisely by the methods of statistical analysis of discontinuities and Fracture Mechanics. According to Superposition Principle in Fracture Mechanics,A Problem or C Problem could be chosen to research. Problem A mainly calculates the crack-tip stress field and displacement field on internal discontinuities by numerical method. Problem C calculate the crack-tip stress field and displacement field under the assumption of that the mainly rock mass stress field has been known. So the Problem C avoid the complex mutual interference of stress fields of discontinuities,which is called crack system problem in Fracture Mechanics. To solve Problem C, field test on stress field in the rock mass is needed. The linear Superposition of discontinuities strain energies are Scientific and Rational. The difference of Fracture Mechanics between rock mass and other materials can mostly expression as:other materials Fracture Mechanics mostly face the problem A,and can’t avoid multi-crack puzzle, while the Rock mass Fracture Mechanics answer to the Problem C. Problem C can avoid multi-discontinuities mutual interference puzzle via the ground stress test. On the basis of Problem C, Fracture Mechanics could be used conveniently in rock mass. The rock mass statistics fracture constitutive relations, which introduced in this article, are based on the Problem C and the Discontinuity Strain Energy linear superposition. This constitutive relation has several merits: first, it is physical constitutive relation rather than empirical; second, it is very fit to describe the rock mass anisotropy properties; third, it elaborates the exogenous factors such as ground stress. The rock mass statistics fracture constitutive relation is the available approach to answer to the physical, anisotropic and ground stress impacted rock mass problems. This article stand on the foundation of predecessor’s statistics fractures constitutive relation, and improved the discontinuity distributive function. This article had derived the limitation of negative exponential distribution in the course of regression analysis, and advocated to using the two parameter negative exponential distribution for instead. In order to solve the problems of two-dimension stability on engineering key cross-sectional view in rock mass, this article derived the rock mass planar flexibility tensor, and established rock mass two-dimension penetrate statistics fracture constitutive relation on the basis of penetrate fracture mechanics. Based on the crack tip plasticity research production of penetrate fracture, for example the Irwin plasticity equifinality crack, this article established the way to deal with the discontinuity stress singularity and plastic yielding problem at discontinuity tip. The research on deformation parameters is always the high light region of rock mass mechanics field. After the dam foundation excavation of XiaoWan hydroelectric power station, dam foundation rock mass upgrowthed a great deal of unload cracks, rock mass mechanical property gotten intricacy and strong anisotropy. The dam foundation rock mass mostly upgrowthed three group discontinuities: the decantation discontinuity, the steep pitch discontinuity, and the schistosity plane. Most of the discontinuities have got partial unload looseness. In accordance with ground stress field data, the dam foundation stress field greatly non-uniform, which felled under the great impaction of tectonic stress field, self-weight stress field, excavation geometric boundary condition, and excavation, unload. The discontinuity complexity and stress field heterogeneity, created the rock mass mechanical property of dam foundation intricacy and levity. The research on the rock mass mechanics, if not take every respected influencing factor into consideration as best as we can, major errors likely to be created. This article calculated the rock mass elastic modulus that after Xiao Wan hydroelectric power station dam foundation gutter excavation finished. The calculation region covered possession monolith of Xiao Wan concrete double-curvature arch dam. Different monolith were adopted the penetrate fracture statistics constitutive relation or bury fracture statistics constitutive relation selectively. Statistics fracture constitutive relation is fit for the intensity anisotropy and heterogeneity rock mass of Xiao Wan hydroelectric power station dam foundation. This article had contrastive analysis the statistics fracture constitutive relation result with the inclined plane load test actual measurement elastic modulus and RMR method estimated elastic modulus, and find that the three methods elastic modulus have got greatly comparability. So, the statistics fracture constitutive relations are qualified for trust. Generally speaking,this article had finished following works based on predecessors job: “Argumentation the C Problems of superposition principle in Fracture Mechanics, establish two-dimension penetrate statistics fracture constitutive relation of rock mass, argue the negative exponential distribution limitation and improve it, improve of the three-dimension berry statistics fracture constitutive relation of rock mass, discontinuity-tip plastic zone isoeffect calculation, calculate the rock mass elastic modulus on two-dimension cross-sectional view”. The whole research clue of this article inherited from the “statistics rock mass mechanics” of Wu Faquan(1992).
Resumo:
Productivity prediction is a serious factor to oil reservoir management and working out economic plans so that it is paid great attention to all the time. Gudao Oil Field, which has been yielding more than 100 million tons of crude oil accumulatively since it was put into developing in 1970's as a complete set of oil field, now entering double extra high water-bearing period after productivity construction, stable production and depletion stage. It's main layer series of development is thought to be type of channel sand reservoir in east China. Form channel sand reservoir in upper Guantao Group of Shengli Oil Field, there are several large oil fields such as Gudao, Gudong and Chengdao etc. with almost one-third reserves of whole Shengli Oil Field. It is considered the common characteristics in this area would be that the layer is less developed, the sand distribution is sporadic, the connectivity is weak, the heterogeneity is strong in plane, the oil layer is unconsolidated with big porosity, high permeability and serious sanding, and the oil is heavy. Because of the restricted factors to productivity of this kind of reservoir, it is very significant to study the productivity prediction this kind of reservoir. By selecting the upstream fluvial reservoir in Guantao Group of Neogene system as researching object, the author studied the forecasting technology with heterogeneous reservoir. Firstly, the author constructed the 3D subtle geological model quantificationally through researching exploitation geology in the way of combination of dynamic and static methods. Secondly, by the aid of dynamic material obtained while producing, the author analyzed the oil distribution law and influencing factors, then finished dynamic oil reservoir description on the basis of static oil reservoir description. Thirdly, via comparing and analyzing all the forecasting methods of productivity existed, the author developed a set of method to forecast productivity of single well and oil field which fit to channel sand reservoir. At last, under the support of ORACLE database, with the advanced computer technology, the author programmed the software called 'Channel Sand Reservoir Prediction System'. Up to now, this system has been putting into use in Gudao Oil Field and very successful.
Resumo:
This paper is belonging to Chinese Petrochemical Corporation's key project. Although it is difficult and great workload, it has important theoretical and practical value. Its targets is to establish 4 dimension stress fields of complex fault block groups, and then to predict the forming mechanism and distribution rule of petroleum pools, by applying the most advanced theories, methods and technology and the most sophisticated software in highly explored zones. By means of multi-discipline theories, methods, technologies and multi-source information, using computer with maximum efforts, investigating the strata framework, structure framework, petroleum pool forming mechanism and forming mode of complex fault block groups, several results have been achieved as following: The fastigiated mode of Xianhe complex fault block groups was established, pointed out the control function of pool accumulate in Xianhe complex fault block groups Xianhe fastigiated complex fault block groups are the results of combining stress of extending, slipping and reversing, which formed in early Shahejie stage, changed and perplexed during Dongying stage and that control the forming and destruction of petroleum pools. By measuring the earth stress and rock mechanics parameters in the research region, the model of 4 dimension stress field and potential fields of migrating fluids was established from ES3 stage to current, with their space distribution and time evolve and petroleum accumulate. The fault-sealing model in Xianhe complex fault block groups was established, which reveal the sealing mechanism of petroleum about control-fault, made for petroleum pool prediction in complex fault block. The petroleum pool forming mode and mechanism in complex fault block was established. Petroleum distribution were predicted in three stress inverse zones, and remaining oil were point out in the high points of 2 micro-structures and the region with strong fault-sealing capabilities. (6). A set of theories, technology and methods of complex fault block petroleum pool have been developed, bring on an improvement of the development geology theory in continental fault depression lake basin, good economic benefits have been obtained by applying on both east and west areas of our country.
Resumo:
This paper is belonging to Chinese Petrochemical Corporation's science and technology project. Although it is difficult, it has important theoretical and practical value. The study was aimed to reveal inhomogeneity of two kinds of reservoirs of fan-shaped delta and braided river by using new theories, new methods and new technology about 3-D model building and reservoir knowledge repository throughout the world, and to build reservoir knowledge repository and 3-D geological model which would predict the type of sand body forming reason and distribution rule in order to improve exploration result in Qiuling oil fields. Multi-discipline theories such as petroleum structure geology, reservoir geology, petroleum geology, sequence geology, logging geology, geomathematics and so on are used as guide. The information of geology, seism, logging and production test is combined. Outcrop area and overlap area are combined. By making full use of computer, stable structure, reservoir geometric shape, spatial distribution and inhomogeneity of bed of interest are investigated, described and characterized. Petroleum pool 3-D static geological model of reservoir knowledge repository was built. Sand body distribution was predicted. It has guided oil development, lowed the investment and improved development benefits. Several results are achieved as follows: (1) Strata framework of Sanjianfang group in Qiuling oil field has been established. (2) Geometric shape, spatial distribution and evolve rule of two different forming reason's reservoir of fan-shaped delta and braided river of Sanjianfang group in Qiuling oil field are discussed. (3) The two kinds of reservoirs have lower pore and permeability and very strong inhomogeneity. (4) Reservoir knowledge repository of two different forming reasons has been built of Sanjianfang group, which includes 5 geological knowledge sublibrary. (5) 3-D geological model of two kinds of forming reason's reservoirs has been built. (6) That same sequence instruction a simulation and probability field were used to predict sand body of Sanjianfang group was put forward. Coincidence rate is high after production test. It shows this method has great popularity value. (7) A set of theories, methods and technologies of knowledge repository of two kinds of reservoir of braided river and fan-shaped delta and 3-D geological model building were finished. (8) A set of theories, methods and technologies of investigating, describing, characterizing and predicting two kinds of oil pool were developed. It gets noticeable economic benefit after exploration. Theory and method about extrusion basin are developed.
Resumo:
The Stack Spontaneous Potential (SSP) is a direct hydrocarbon location technology and a new hydrocarbon detection method with independent intellectual property. A subsurface hydrocarbon accumulation associated with the upward hydrocarbon micro seepage induces a relatively strong negative potential abnormal zone, of which the anomaly can be measured on the surface with specially designed instruments through careful field measuring procedures. With special software programmed according to a unique geochemical and geophysical model, the original data are analyzed, processed and interpreted on the computer, and then on a series of resulting anomaly distribution maps and/or profiles, the favorable surface locations of the hydrocarbon accumulations can be easily identified. The study of the SSP has been started since 1989, and especially from 1996 to 1997, both profile and area tests were conducted in the Daqing Oilfield. On the testing line of 15kms, there are 6 wells in total, among which some are oil-producing wells, and some are water-producing wells. The final matching ratio of the favorable oil well locations and the possible water well locations predicted by the SSP to those of known wells was up to 83 percent. In the area test, of which the acreage is 800 km2, the matching ratio compared with the existing wells was 87 percent; furthermore, regarding to wells subsequently drilled after the test, the matching ratio was 85 percent. The matching ratio in the development area is more about 10 percent than those of in exploration area. The reason is that, comparing the exploration area, the development area acreage is less and the container rocks are more simplex. In development area there is not so much interference of SSP also. Since 1997 the SSP has been tested and applied all over China to a number of hydrocarbon bearing basins and known oil fields, including the Daqing, Jiangsu, Changqing, Shengli, Nanyang, Jianghan and Zhongyuan Oilfields, only to name a few. The SSP surveys in total areas of over 10,000km2 in more than 30 regions in China so far have been completed in various exploration and development stages, the satisfactory outcomes of which have further evidenced that the dependence between the SP anomaly and abundance of hydrocarbon. Up to date, a substantial amount of successful tests and actual surveys finished in exploration and development practices have evidenced that the SSP is significantly more reliable in comparison with any other similar direct hydrocarbon indication technique generally known to the oil industry, such as the Redox. The SSP can be applied to search for almost all kinds of hydrocarbon accumulations, regardless of the type of traps, such as structural, stratigraphic, buried hill traps, and so on; however, it is interesting to be noted that the SSP seems to be particularly effective in detecting the stratigraphic oil traps according to our practices. On the other hand, there is virtually no surface geographical constrains in terms of field data acquisition, except for those water covered areas, because of the inherent characteristics of the technology itself. Furthermore, utilizing the SSP requires no special considerations to subsurface geological conditions in regard to formation resistivity, since the SSP measurements will not be influenced by either overly high or overly low resistivity of formations lying above the hydrocarbon accumulations. There are two kind of theory, of which, as we know one is called hypbyssal theory such as "Redox"[61 the other is call plutonic theory such as cracking of hydrocarbon [8][9] and natural polarization [3], to describe the mechanism of SP anomaly of oil reservoir and to indicate that the dependence between the SP abnormality and abundance of hydrocarbon has be existed theoretically/The quantitative dependence, which has not been founded due to the complicity of container rocks, be discovered during the exploration and development practices is the crux to the quantitative analysis of SP Anomaly processing. Based on the thorough study of the complex of collector rocks, every kind of thickness of collector rock can be conversed to be a standard effective thickness; the thickness is called apparent effective thickness (AET). The conversation coefficient (ai, 1=1,2,3) could be determined by the variety of every collector rock storability (CRS). The discoveration of quantitative: dependence between AET and the amplitude of SSP, in the practices of exploration and development, is a promotion for the SSP supplied in the oil exploration, and make the data analysis forward to the quantitative stage.
Resumo:
Separation of the acidic compounds in the ion-exchange capillary electrochromatograph (IE-CEC) with strong anion-exchange packing as the stationary phase was studied. It was observed that the electroosmotic flow (EOF) in strong anion-exchange CEC moderately changed with increase of the eluent ionic strength and decrease of the eluent pH, but the acetonitrile concentration in the eluent had almost no effect on the EOF. The EOF in Strong anion-exchange CEC with eluent of low pH value was much larger than that in RP-CEC with Spherisorb-ODS as the stationary phase. The retention of acidic compounds on the strong anion-exchange packing was relatively weak due to only partial ionization of them, and both chromatographic and electrophoretic processes contributed to separation. It was observed that the retention values of acidic compounds decreased with the increase of phosphate buffer and acetonitrile concentration in the eluent as well as the decrease of the applied voltage, and even the acidic compounds could elute before the void time. These factors also made an important contribution to the separation selectivity for tested acidic compounds, which could be separated rapidly with high column efficiency of more than 220 000 plates/m under the optimized separation conditions. (C) 2000 Elsevier Science BN. All rights reserved.
Resumo:
Separation of small peptides on ion-exchange capillary electrochromatography (IE-CEC) with strong cation-exchange packing (SCX) as stationary phase was investigated. It was observed that the number of theoretical plates for small peptides varied from 240 000 to 460 000/m, and the relative standard deviation for t(0) and the migration time of peptides were less than 0.57% and 0.27%, respectively for ten consecutive runs. Unusually high column efficiency has been explained by the capillary electrophoretic stacking and chromatofocusing phenomena during the injection and separation of positively charged peptides. The sample buffer concentration had a marked effect on the column efficiency and peak area of the retained peptides. The influences of the buffer concentration and pH value as well as the applied voltage on the separation were investigated. It has been shown that the electrostatic interaction between the positively charged peptides and the SCX stationary phase played a very important role in IE-CEC, which provided the different separation selectivity from those in the capillary electrophoresis and reversed-phase liquid chromatography. A fast separation of ten peptides in less than 3.5 min on IE-CEC by adoption of the highly applied voltage was demonstrated. (C) 2000 Elsevier Science B.V. All rights reserved.
Resumo:
A novel mode of capillary electrochromatography (CEC), called dynamically modified strong cation-exchange CEC (DMSCX-CEC), is described in this paper. A column packed with a strong cation-exchange (SCX) packing material was dynamically modified with a long-chain quaternary ammonium salt, cetyltrimethylammonium bromide (CTAB), which was added to the mobile phase. CTAB ions were adsorbed onto the surface of the SCX packing material, and the resulting hydrophobic layer on this packing was used as the stationary phase. Using the dynamically modified SCX column, neutral solutes were separated with the CEC mode. The highest number of theoretical plates obtained was about 190 000/m, and the relative standard deviations (RSD's) for migration times and capacity factors of alkylbenzenes were less than 1.0% and 2.0% for five consecutive runs, respectively. The effects of CTAB and methanol concentrations and the pH value of the mobile phase on the electroosmotic flow and the separation mechanism were investigated. Excellent simultaneous separation of the basic and neutral solutes in DMSCX-CEC with a high-pH mobile phase was obtained, A mixture containing the acidic, basic, and neutral compounds was well separated in this mode with a low-pH mobile phase; however, peak tailing for basic compounds was observed in this mobile phase.
Resumo:
We combine theories of optimal pump-dump control and the related transient probe absorption spectroscopy in order to elucidate the relation between these two optical processes and the possibility of experimental realization. In the weak response regime, we identify the globally optimal pair of pump-dump control fields, and further propose a second-order difference detection scheme to monitor the wave packets dynamics that is jointly controlled by both the pump and dump fields. The globally optimal solution serves also as the initial input for the iterative search for the optimal control fields in the strong response regime. We use a model I-2 molecule to demonstrate numerically the pump-dump control and the detection of a highly vibrationally excited wave packet focusing dynamics on the ground X surface in both the weak and strong response regimes. The I2B surface serves as the intermediate to assist the pump-dump control and the optical detection processes. Demonstrated in the strong response regime are the optimal pair of pump-dump molecular-pi pulses that invert nearly total population onto the predefined target region within a half period of vibration motion. (C) 1999 American Institute of Physics. [S0021-9606(99)00115-4].
Resumo:
In order to improve the sulfur resistance of noble metal catalysts in the aromatic hydrogenation of diesel fuel, the alloying effect of non-noble metals with Pd was studied. Toluene hydrogenation over Pd and Pd-M bimetallic catalysts (M = Cr, W,La, Mn, Mo, Ag) on a mixed HY-Al2O3 support was investigated in the presence of 3000 ppm sulfur as thiophene in the feedstock. The results showed that the addition of the second metals strongly affected the activity of toluene hydrogenation, which suggests that the sulfur resistibility of Pd-M bimetallic catalysts is much different from single Pd. La, Mn, Mo and Ag decreased the sulfur resistance of the palladium catalysts. For example, the toluene conversion at 553 K was observed to decrease sharply from 39.4 wt.% on Pd to 1.6 wt.% on Pd-Ag, which is by a factor of 25. One of the important findings in this article is that Cr and W increase hydrogenation activity of Pd catalysts. The reactions occurring on these catalysts include hydrogenation, isomerization and hydrocracking, The addition of the second metals has no noticeable effects on the hydrogenation and isomerization selectivity, but it slightly suppresses hydrocracking reactions. The four typical catalysts, Pd-Cr, Pd-W, Pd-Ag and Pd were characterized by infrared (IR) spectroscopy of pyridine and CO. LR spectra of CO revealed the strong interaction between Pd and the second metal as Cr, W and Ag (or their oxide), indicating that the improvement in sulfur resistance originates from electron-deficient Pd with the addition of second metals. (C) 2001 Elsevier Science B.V. All rights reserved.