ELECTROCATALYTIC OXIDATION AND FLOW-INJECTION DETERMINATION OF REDUCED NICOTINAMIDE COENZYME AT A GLASSY-CARBON ELECTRODE MODIFIED BY A POLYMER THIN-FILM

G chemically modified electrode (CME) was prepared by electrochemical copolymerization of pyrrole and Methylene Blue. The resulting CME exhibits effective electrocatalytic activity towards the oxidation of reduced nicotinamide coenzymes (NADH and NADPH),

AMPEROMETRIC DETECTION OF AMINO-ACIDS IN A FLOW-INJECTION SYSTEM WITH A NICKEL(II)-MODIFIED ELECTRODE WITH AN EASTMAN-AQ POLYMER FILM

Amperometic flow measurements were made at +0.55 V (vs. Ag/AgCl) in 0.1 mol l-1 KOH electrolyte with an Ni(II) chemically modified electrode (CME) with an Eastman-AQ polymer film. The use and characteristics of a Ni(II)-containing crystalline and polymer-modified electrode obtained by a double coating step as a detector for amino acids in a flow-injection system using reversed-phase liquid chromatography are described. The detection of these analytes is based on the higher oxidation state of nickel (NiOOH) controlled by the applied potential. The electroanalytical parameters and the detection current for a series of amines and amino acids were investigated. The use of such a CME in the flow-injection technique was found to be suitable in a solution at low pH. The linear range for glycine is 5 X 10(-6)-0.1 mol 1-1 with a detection limit of 1.0 X 10(-6) mol l-1. A 1 X 10(-4) mol 1-1 mixture of serine and tyrosine was also detected after separation on an Nucleosil C18 column.

FLOW-INJECTION ANALYSIS OF GLUCOSE AT AN AMPEROMETRIC GLUCOSE SENSOR-BASED ON ELECTROCHEMICAL CODEPOSITION OF PALLADIUM AND GLUCOSE-OXIDASE ON A GLASSY-CARBON ELECTRODE

A glassy carbon electrode (GCE) modified with palladium provides excellent electrocatalytic oxidation of hydrogen peroxide. When the electrolyte contains palladium chloride and glucose oxidase, the GCE can be modified by electrochemical codeposition at a given potential. The resulting modified surface was coated with a thin film of Nation to form a glucose sensor. Such a glucose sensor was successfully used in the flow-injection analysis of glucose with high stability and anti-poisoning ability. It gave a detection limit of 1 X 10(-7) M injected glucose, with a linear concentration range of 0.001-8 mM. There is no obvious interference from substances such as ascorbate and saccharides.

FLOW-INJECTION AMPEROMETRIC DETECTION OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

A Prussian Blue-modified glassy carbon electrode prepared by simple adsorption exhibited excellent electrocatalytic activity in the oxidation of hydrazine in acidic media. A film of the perfluorosulphonic acid polymer Nafion coated on top of the Prussian Blue-modified glassy carbon electrode can improve the mechanical stability of the Prussian Blue layer in the flow stream. Hydrazine was detected by flow-injection analysis at the modified electrode with high sensitivity. The limit of detection was 0.6 ng.

AMPEROMETRIC FLOW-INJECTION ANALYSIS OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT COBALT TETRAPHENYLPORPHYRIN MODIFIED ELECTRODE WITH HEAT-TREATMENT

Chemically modified electrodes prepared by treating the cobalt tetraphenylporphyrin modified glassy-carbon electrode at 750-degrees (HCME) are shown to catalyze the electrooxidation of hydrazine. The oxidation occurred at +0.63 V vs. Ag/AgCl (saturated potassium chloride) in pH 2.5 media. The catalytic response is evaluated with respect to solution pH, potential scan-rate, concentration dependence and flow-rate. The catalytic stability of the HCME is compared with that of the cobalt tetraphenylporphyrin adsorbed glassy-carbon electrode. The stability of the HCME was excellent in acidic solution and even in solutions containing organic solvent (50% CH3OH). When used as the sensing electrode in amperometric detection in flow-injection analysis, the HCME permitted sensitive detection of hydrazine at 0.5 V. The limit of detection was 0.1 ng. The linear range was from 50 ng to 2.4-mu-g. The method is very sensitive and selective.

EASTMAN-AQ/NIII MODIFIED ELECTRODE CHARACTERIZATION AND APPLICATION IN FLOW-INJECTION DETERMINATION OF CARBOHYDRATES AND AMINO-ACIDS

A novel Eastman-AQ/Ni(II) chemically modified electrode (CME) produced by "double coating step" deposition of a poly(ester sulphonic acid) polymer film and Ni2+-containing crystalline species onto glassy carbon instead of a metallic nickel electrode exhibited stable electrocatalytic oxidation of numerous alpha-hydrogen compounds including carbohydrates, amines and amino acids. In cyclic voltammetry, the electrocatalysis appeared with an irreversible anodic wave at +0.55 V (vs. Ag/AgCl). The CME was adapted for constant-potential amperometric detection of these compounds in flow injection analysis. Using the CME, the linear response concentration range was between 1.0 x 10(-5) and 5.0 x 10(-2) mol/l and the detection limit was 5.0 x 10(-6) mol/l for glucose. The stability of the CME was adequate for routine quantitative application.

POLYANILINE CHEMICALLY MODIFIED ELECTRODE FOR DETECTION OF ANIONS IN FLOW-INJECTION ANALYSIS AND ION CHROMATOGRAPHY

An electrochemical detector based on a polyaniline conducting polymer chemically modified electrode (PAn CME) was developed for use in flow-injection analysis and ion chromatography. Iodide, bromide, thiocyanate and thiosulphate are detected by using ion chromatography with a PAn CME electrochemical detector. The detection limits are 1, 5, 10 and 10 mgl-1, respectively. The CME response for electroinactive anions varies selectively with the mobile phase composition in flow-injection analysis. By this approach, perchlorate, sulphate, nitrate, iodide, acetate and oxalate can be detected conveniently and reproducibly over a linear concentration range of at least 3 orders of magnitude. The electrode is stable for over 2 weeks with no evidence of chemical or mechanical deterioration.

FLOW-INJECTION ANALYSIS OF MYOGLOBIN AND HEMOGLOBIN AT TOLUIDINE BLUE CHEMICALLY MODIFIED ELECTRODE

Electrodeposition of the phenothiazine mediator titrant toluidine blue onto a glassy carbon substrate at an appropriate potential was used to construct a toluidine blue chemically modified electrode (CME) exhibiting electrocatalytic reduction for myoglobin and hemoglobin. The CME catalyzed the hemoprotein electroreduction at the reduction potential of the mediator molecule. When the CME as used as a detector for flow injection analysis at a constant applied potential of -0.30 V vs. a saturated calomel electrode, it gave detection limits of 20 and 50 ng (1.2 and 0.78 pmol) injected myoglobin and hemoglobin, respectively, with a dynamic linear concentration range over 2 orders of magnitude. After a brief equilibration period, the CME retained nearly 90% of its initial myoglobin response over 8 hours of continuous exposure to the flow-through system.

THE USE OF CHEMICALLY MODIFIED ELECTRODES FOR LIQUID-CHROMATOGRAPHY AND FLOW-INJECTION ANALYSIS

The use of chemically modified electrodes (CMEs) for liquid chromatography and flow-injection analysis is reviewed. Electrochemical detection with CMEs based on electrocatalysis, permselectivity, ion flow in redox films, and ion transfer across the water-solidified nitrobenzene interface is discussed in terms of improving the stability, selectivity, and scope of electrochemical detectors, and the detection of electroinactive substances. More than 90 references are included.

河流成因储层沉积微相与剩余油分布及形成机理研究

Based on the study of fluvial sandstone reservoir in upper of Guantao group in Gudao and Gudong oilfields, this paper first introduces A.D.Miall's(1996a) architectural-element analysis method that was summarized from ground outcrop scale into the reservoir formation research of the study area, more subtly divides sedimentary microfacies and establishes sedimentary model of research area.on this base, this paper summarizes the laws of residual oil distribution of fluvial formation and the control effect of sedimentary microfacies to residual oil distribution, and reveals residual oil formation mechanism. These results have been applied to residual oil production, and the economic effect is good. This paper will be useful for residual oil research and production and enhancement of oil recovery in similar reservoir. The major conclusions of this paper are as follows. 1. Using the architectural-element analysis method to the core data, a interfacial division scheme of the first to the dixth scale is established for the studied fluvial formation. 2.Seven architectural-elements are divided in upper of Guantao group of study area. The sandstone group 5～1+2 of Neogene upper Gutao group belongs to high sinuous fine grain meandering river, and the sandstone group 6 is sandy braided river. 3. Inter layer, the residual oil saturation of "non-main layer" is higher than "main layer", but the residual recoverable reserve of former is larger. Therefore, "main layer" is the main body of residual oil distribution. The upper and middle part of inner layer has lower permeability and strong seeping resistance. Addition to gravity effect in process of driving, its driving efficiency is low; residual oil saturation is high. Because of controlling of inside non-permeable interlayer or sedimentary construction, the residual oil saturation of non-driving or lower driving efficiency position also is high. On plane, the position of high residual oil saturation mostly is at element LV, CS, CH (FF), FF etc, Which has lower porosity and permeability, as well as lens sand-body and sand-body edge that is not controlled by well-net, non-perfect area of injection and production, lower press difference resort area of inter-well diffiuent-line and shelter from fault, local high position of small structure. 4.Microscopic residual oil mainly includes the non-moved oil in the structure of fine pore network, oil in fine pore and path, oil segment in pore and path vertical to flow direction, oil spot or oil film in big pore, residual oil in non-connective pore. 5.The most essential and internal controlling factor of fluvial formation residual oil distribution is sedimentary microfacies. Status of injection and production is the exterior controlling factor of residual oil distribution. 6. The controlling effect of formation sedimentary microfacies to residual oil distribution indicates inter-layer vertical sedimentary facies change in scale of injection and production layer-series, planar sedimentary face change and inner-layer vertical sedimentary rhythm and interbed in single layer to residual oil distribution. 7. It is difficult to clear up the inter-layer difference in scale of injection and production layer-series. The using status of minor layer is not good and its residual oil saturation is high relatively. It is obvious that inter-layer vertical sedimentary facies changes control inter-layer residual oil distribution at the same or similar conditions of injection and production. For fluvial formation, this vertical sedimentary facies change mainly is positive gyration. Namely, from down to top, channel sediment (element CHL, LA) changes into over-bank sediment (element LV, CR, CS). 8. In water-injection developing process of transverse connecting fluvial sandstone oil formation, injection water always comes into channel nearby, and breaks through along channel and orientation of high pressure gradient, does not expand into side of channel until pressure gradient of channel orientation changes into low. It brings about that water-driving status of over-bank sedimentary element formation (LV, CR, CS) is not good, residual oil saturation is high. In non-connective abandoned channel element (CH) formation with channel, because this reverse is difficult to control by injection and production well-series, its using status is not good, even terribly not good, residual oil is enrichment. 9. The rhythm and sedimentary structure, sedimentary facies change in single sand body brings about vertical changes of formation character, growth character of inner layer interbed. These are important factor of controlling and affecting vertical water spread volume and inner layer residual oil forming and distribution in single sand body. Positive rhythm, is the principal part of fluvial sandstone inner layer sedimentary rhythm. Namely, from down to upside, rock grain granularity changes from coarse to fine, seeping ability changes from strong to feebleness. It brings about that water-driving status of inner layer upside is not good, residual oil saturation is high. Inner layer interbed has different degree affecting and controlling effect to seeping of oil and water. Its affecting degree lies on interbed thickness, extending scale, position, and jeted segment of production or injection well. The effect of interbed at upside of oil formation to oil and water seeping is less; the effect of interbed at middle of oil formation to oil and water seeping is more. 10. Indoor experiment and research indicate that wettability, permeability step, vertical permeability, position of Kmax and ratio of oil viscousity and water viscousity all have great effect on the water-driving recovery ratio. 11. Microscopic residual oil distribution is affected and controlled by formation pore network structure, pressure field distribution, and oil characteristic. 12.The residual oil forming mechanism: the over-bank sedimentary element and upper part of a positive rhythm sandstone have fine pore and throat network, permeability is low, displacement pressure of pore and throat is high. The water-driving power usually falls short of displacement pressure that brings about injection water does not spread into these pore and throat network, thereby immovable oil area, namely residual oil, is formed. At underside of channel sedimentary element and positive rhythm sandstone, porosity and permeability is relatively high, connecting degree of pore and throat is high, displacement pressure of pore and throat is low. Thereby injection water is easy to enter into pore and throat, driving oil in them. Because the pore space is irregular, the surface of pore wall is coarse and non-flat. That the oil locate on concave hole of pore wall and the dead angle of pore, and the oil attaches on surface of pore wall by surface tension, are difficult to be peeled off, becoming water-driving residual oil (remaining oil). On the other hand, Because flowing section lessens, flowing resistance increase, action of capillary fore, or seeping speed decreases at process of transfer at pass narrow throat path in the course carried by driving water. The "oil drop", "oil bead", or "oil segment" peeled off by driving water is difficult to carry and to drive out by water at less pressure difference. Thereby they are enclosed in pore to form discontinuous residual oil. 13.This results described above have been applied in nine develop blocks of Gudao and Gudong oilfield. Its applying effect is marked through local injection production adjustment, deploying replacement well, repair hole, replacement envelop, block off water and profile control etc. Relative method and technology can be applied to other oil production area of Shengli oilfield, and obtain better economic and societal effect.

黄骅坳陷高尘头地区储层非均质性及成藏研究

Gaochentou region is located in the southwest direction of Gaochentou village in Huanghua city of Hebei province. In regionally structural position, It lies in Qikou sag In the middle part of Huanghua depression, which belongs to the east part of the south Dagang structure zone in the middle part of Huanghua depression. Its' very beneficial at regional structure in Gaochentou , and It becomes the advantage area for oil and gas gathered and preserved, Sandstone reservoir of Dongying Formation is main bearing bed .Dongying Formation in Gaochentou region of Huanghua depression is consisted of set of mudstone and sandstone interbeds by deposited delta fades . Dongying Formation can be divided into 3 members from above to below: the first member of Dongying Formation (FMDF), the second member of Dongying Formation (SMDF), and third member of Dongying Formation (TMDF). The lithology of the upper part of FMDF was consisted of mostly middle-grained and fine-grained sandstone, and it is small for the oil-bearing area of the sand bodies .The lithology of the lower part is coarse-grained sandstone bodies which are well connected between sandstone bodies of wells, and the lower part was main bed of oil production in Dongying Formation; SMDF and TMDF are consisted of larger scale set of mudstone, in which the sandbodies are lenticular and pinch out quickly, and the lithology was mostly fine sandstone and silt stone, in which there are little oil and gas .Because the reservoirs in this area are largely influenced by the factors such as lithology, fault and others, and the reservoirs have the strong,heterogeneity , there exists the problem of oil-down and water-up for vertical distribution of oil and gas bearing. It is not very clearly for the three dimension distribution of sandstone , and the geology researchs is not enough. So, it can't satisfy the need of further development and production for Gaochentou oilfield.Having the key problem of oil-down and water-up and the mechanism of the reservoir for Gaochentou area, There are as follow study works, the first, is study of the high-resolution correlation of sequence stratigraphy and sedimentary microfacies. Dongying Formation was divided into three parasequence sets and each parasequence set was divided into different amount of parasequences. FMDF, as the main oil and gas producing bed, can be divided into seven parasequences. Oil and gas are discovered in six parasequences except the seventh. On the basis of study of sedimentary microfacies, the sediments of Dongying Formation are considered deposited mainly in delta front subfacies. The microfacies types of Dongying Formation are sub-water distirbutary channel, sub-water natural bank, inter distributary channel bay, distributary channel mouth dam, and delta front mat sand.Seismic facies analysis and logging-constrained inversion technique were applied by Author for transverse prediction of sandstone reservoir. Having 4 modes of interwell single sandbodies correlation technique, Author have described distribution characteristics of sandbodies, and established geological reservoir model of Gaochentou reservoir.Author presented that the reservoirs characteristic have very strong heterogeneity ,and In the section of sandstone interlayed with mudstone,the folium sandstone interlayed with each other, and the wedge shaped sandbodies pinched out in the mudstone. So the pinch-out up sandstone trap and lenticular sandstone trap are easily formed. They are most small scale overlying pinches out in the place of slope. This article applies the concept of deep basin oil to resolve reasonably the problem of which the oil is below the water in Gaochentou area. Combined with the study of sedimentary facies, reservoir and other aspects, the mechanism and patterns of deep basin oil are studied on the basis of characteristics in Gaochentou area.On the basis of the above study, the mechanism of the oil and gas' migration and accumulation in isotropic sandstone and heterogeneous sandstone are thoroughly analyzed through experiments on physical modeling. Experiments on physical modeling show that the discrepancy between sand layers with different permeability and thickness has important influence on the direction, path, and injection layer of oil's migration. At the beginning of the injection of oil and gas in high permeability sand layer, the pressure is low, the migration resistance is small, and the oil and gas are more easily displacing the water in sand. So it can act as good transformation layer or reservoir. But at the beginning of the injection of oil and gas in sand layer with low permeability, the pressure is high, the migration resistance is big, and the oil and gas are more difficultly displacing the water in sand. So it can only act as bad or worse transformation layer or reservoir. Even if it cannot act as transformation layer or reservoir, it can act as water layer or dry layer. The discrepancy between sand layers on permeability and thickness can make discrepancy in injection of oil and gas between different layers. Consequently it leads to small amount of oil and gas injection in sand layers with low permeability. Ultimately it affects the oil's accumulation and distribution in different sand layers.At Last, combining analysis of the structure and pool forming condition, The thesis has established models of reservoir formation to predict the advantage distribution of oil and gas bearing , and put forward the prospective target It is not only of theoretical signification for explosion and importance, but also has realistic value in guiding the progressive petroleum exploration and exploitation.