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.

Characterization of polyethylene glycol-modified proteins by semi-aqueous capillary electrophoresis

A new program to characterize polyethylene glycol-modified (PEGylated) proteins is outlined using capillary zone electrophoresis (CZE). PEGylated ribonuclease A and lysozyme were selected as examples. Five separation procedures were compared to select out the mixed buffer of acetonitrile-water (1:1, v/v) at pH 2.5 as the best to characterize the PEGylated proteins without sample pretreatment. Polyethylene oxide (PEO) with a high molecular mass of 8X10(6) was applied to rinse the capillary to form a dynamic coating which would decrease the undesirable proteins adsorbed to the inner wall of the silica. The electroosmotic flow (EOF) mobility of the five procedures was determined, respectively. It is found that acetonitrile is mainly responsible for the good resolution of PEGylated proteins with the help of PEO coating in the semi-aqueous system. The low EOF mobility and current in the semi-aqueous system might also have some responsibility for the high resolution. The semi-aqueous procedure described in this paper also demonstrates higher resolution of natural proteins than aqueous ones. (C) 2001 Elsevier Science B.V. All rights reserved.

Separation of acidic compounds by strong anion-exchange capillary electrochromatography

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.

Capillary electrochromatography using a strong cation-exchange column with a dynamically modified cationic surfactant

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.

Protein A tangential flow affinity membrane cartridge for extracorporeal immunoadsorption therapy

Tangential flow affinity membrane cartridge (TFAMC) fs a new model of immunoadsorption therapy for hemoperfusion. Recombinant Protein A was immobilized on the membrane cartridge through Schiff base formation for extracorporeal IgG and immune complex removal from blood. Flow characteristics, immunoadsorption capacity and biocompatibility of protein A TFAMC were studied. The results showed that the pressure drop increased with the increasing flow rate of water, plasma and blood, demonstrating reliable strength of membrane at high now rare. The adsorption capacities of protein A TFAMC for IgG from human plasma and blood were measured. The cartridge with 139 mg protein A immobilized on the matrix (6 mg protein A/g dry matrix) adsorbed 553 mg IgG (23.8 mg IgG/g dry matrix) from human plasma and 499.4 mg IgG (21.5 mg IgG/g dry matrix) from human blood, respectively. The circulation time had a major influence on IgG adsorption capacity, but the flow rate had little influence. Experiments in vitro and in vivo confirmed that protein A TFAMC mainly adsorbed Ige and Little of other plasma proteins, and that blood cell damage was negligible. The extracorporeal circulation system is safe and reliable. Copyright (C) 1999 John Wiley & Sons, Ltd.

Capillary electrochromatography with monolithic poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase

A new kind of monolithic capillary electrochromatography column with poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase has been developed. The stationary phase was found to be porous by scanning electron microscopy and the composition of the continuous bed was proved by IR spectroscopy to be the ternary polymer of styrene, divinylbenzene, and methacrylic acid. The effects of operating parameters, such as voltage, electrolyte, and organic modifier concentration in the mobile phase on electroosmotic flow were studied systematically, The retention mechanism of neutral solutes on such a column proved to be similar to that of reversed-phase high performance liquid chromatography. In addition, fast analyses of phenols, chlorobenzenes, anilines, isomeric compounds of phenylenediamine and alkylbenzenes within 4.5 min were achieved.

On-line concentration of peptides and proteins with the hyphenation of polymer monolithic immobilized metal affinity chromatography and capillary electrophoresis

An iminodiacetic acid (IDA)-type adsorbent is prepared at the one end of a capillary by covalently bonding IDA to the monolithic rods of macroporous poly(glycidyl methacrylate-co-ethylene dimethacrylate). Cu(II) is later introduced to the support via the interaction with IDA. By this means, polymer monolithic immobilized metal affinity chromatography (IMAC) materials are prepared. With such a column, IMAC for on-line concentration and capillary electrophoresis (CE) for the subsequent analysis are hyphenated for the analysis of peptides and proteins. The reproducibility of such a column has been proved good with relative standard deviations (RSDs) of dead time of less than 5% for injection-to-injection and 12% for column-to-column (n = 3). Through application on the analysis of standard peptides and real protein samples, such a technique has shown promising in proteome study.

Hybrid organic-inorganic phenyl monolithic column for capillary electrochromatography

A novel hybrid organic-inorganic silica-based monolithic column possessing phenyl ligands for reversed-phase (RP) capillary electrochromatography (CEC) is described. The monolithic stationary phase was prepared by in situ co-condensation of tetraethoxysilane (TEOS) with phenyltriethoxysilane (PTES) via a two-step catalytic sol-gel procedure to introduce phenyl groups distributed throughout the silica matrix for chromatographic interaction. The hydrolysis and condensation reactions of precursors were chemically controlled through pH variation by adding hydrochloric acid and dodecylamine, respectively. The structural property of the monolithic column can be easily tailored through adjusting the composition of starting sol solution. The effect of PTES/TEOS ratios on the morphology of the created stationary phases was investigated. A variety of neutral and basic analytes were used to evaluate the column performance. The CEC columns exhibited typical RP chromatographic retention mechanism for neutral compounds and had improved peak shape for basic solutes.

Fully developed laminar flow and heat transfer in smooth trapezoidal microchannel

Numerical analysis of fully developed laminar slip flow and heat transfer in trapezoidal micro-channels has been studied with uniform wall heat flux boundary conditions. Through coordinate transformation, the governing equations are transformed from physical plane to computational domain, and the resulting equations are solved by a finite-difference scheme. The influences of velocity slip and temperature jump on friction coefficient and Nusselt number are investigated in detail. The calculation also shows that the aspect ratio and base angle have significant effect on flow and heat transfer in trapezoidal micro-channel. (c) 2005 Elsevier Ltd. All rights reserved.

Preparation of monolithic silica column with strong cation-exchange stationary phase for capillary electrochromatography

A monolithic silica based strong cation-exchange stationary phase was successfully prepared for capillary electrochromatography. The monolithic silica matrix from a sol-gel process was chemically modified by treatment with 3-mercaptopropyltrimethoxysilane followed by a chemical oxidation procedure to produce the desired function. The strong cation-exchange stationary phase was characterized by its substantial and stable electroosmotic flow (EOF), and it was observed that the EOF value of the prepared column remained almost unchanged at different buffer pH values and slowly decreased with increasing phosphate concentration in the mobile phase. The monolithic silica column with strong cation-exchange stationary phase has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). The column efficiencies for the tested beta-blockers varied from 210,000 to 340,000 plates/m. A peak compression effect was observed for atenolol with the mobile phase having a low phosphate concentration.

Electrochromatographic evaluation of a silica monolith capillary column for separation of basic pharmaceuticals

A silica-based monolithic capillary column was prepared via a sol-gel process. The continuous skeleton and large through-pore structure were characterized by scanning electron microscopy (SEM). The native silica monolith has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). Column efficiencies greater than 250000 plates/m for capillary electrochromatography (CEC) separation of basic compounds were obtained. It was observed that retention of basic pharmaceuticals on the silica monolith was mainly contributed by a cation-exchange mechanism. Other retention mechanisms including reversed-phase and normal-phase mechanisms and electrophoresis of basic compounds also played a role in separation. A comparison of the differences between CEC and capillary zone electrophoresis (CZE) separation was also discussed.

Rapid protein identification using monolithic enzymatic microreactor and LC-ESI-MS/MS

A monolithic enzymatic microreactor was prepared in a fused-silica capillary by in situ polymerization of acrylamide, glycidyl methacrylate (GMA) and ethylene dimethacrylate (EDMA) in the presence of a binary porogenic mixture of dodecanol and cyclohexanol, followed by ammonia solution treatment, glutaraldehyde activation and trypsin modification. The choice of acrylamide as co-monomer was found useful to improve the efficiency of trypsin modification, thus, to increase the enzyme activity. The optimized microreactor offered very low back pressure, enabling the fast digestion of proteins flowing through the reactor. The performance of the monolithic microreactor was demonstrated with the digestion of cytochrome c at high flow rate. The digests were then characterized by CE and HPLC-MS/MS with the sequence coverage of 57.7%. The digestion efficiency was found over 230 times as high as that of the conventional method. in addition, for the first time, protein digestion carried out in a mixture of water and ACN was compared with the conventional aqueous reaction using MS/MS detection, and the former solution was found more compatible and more efficient for protein digestion.

Interface of chip-based capillary electrophoresis-inductively coupled plasma-atomic emission spectrometry (CE-ICP-AES)

An interface of chip-based capillary electrophoresis (CE)-inductively coupled plasma-atomic emission spectrometry (ICP-AES) that is based on cross-flow nebulization has been developed. A polydimethylsiloxane (PDMS) CE-chip with conventional cross channel layout was used. A stainless steel tube was placed orthogonal to the exit of the CE separation channel for cross flow nebulization. A supplementary flow of buffer solution at the channel exit was used to improve nebulization efficiency. Two capillaries were inserted into the CE chip near the inlet of the separation channel for sample and buffer solution injection. Syringe pumps were used to manipulate the flow rate and flow direction of the sample, buffer, and supplementary buffer solution. Peak broadening due to the shape (bulb and tube-shaped) and size of the spray chambers was studied. The smaller tube-shaped spray chamber was used because of smaller peak broadening effect due to aerosol transport. The nebulization and transport efficiency of the CE-ICP interface was approximately 10%. Ba2+ and Mg2+ ions were eluted from the CE-chip within 30 s. Resolution of the Ba2+ and Mg2+ peaks was 0.7 using the chip-based CE-ICP-AES system.