Dispersion copolymerization of acrylamide with quaternary ammonium cationic monomer in aqueous salts solution

Dispersion copolymerization of acrylamide (AM) with 2-methylacryloylxyethyl trimethyl ammonium chloride (DMC) has been carried out in aqueous salts solution containing ammonium sulfate and sodium chloride with poly(acryloylxyethyl trimethyl ammonium chloride) (PDAC) as the stabilizer and 2,2'-azobis[2-(2-inidazolin-2-yl)propane]-dihydro chloride (VA-044) as the initiator. A new particle formation mechanism of the dispersion polymerization for the present system has been proposed. The effects of inorganic salts and stabilizer concentration on dispersion polymerization have been investigated. The results show that varying the salt concentration could affect the morphology and molecular weight of the resultant copolymer particles significantly. With increasing the stabilizer concentration, the particle size decreased at first and then increased, meanwhile the effect on the copolymer molecular weight was the contrary. These results had been rationalized based on the proposed mechanism.

Nano-reactors for controlling the selectivity of the free radical grafting of maleic anhydride onto polypropylene in the melt

This paper reports on a successful application of the concept of nanoreactors to effectively controlling the selectivity of the free radical grafting of maleic anhydride (MAH) onto polypropylene (PP) in the melt, an industrially relevant process. More specifically, a free radical initiator of type ROOR was first confined into (or encapsulated by) the galleries of an organically modified montmorillonite (o-MMT) whose interdistance was 2.4 nm. Primary free radicals (RO center dot) formed inside the o-MMT galleries had to diffuse out before they could react with the PP backbone. The controlled release of the primary free radicals significantly increased the grafting degree of MAH onto PP and greatly reduced the level of the chain scission of the latter. Those results were better understood by electron spin resonance studies on model systems and by Monte Carlo simulations.

近临界条件下苯/丙烯烷基化反应的研究

中国科学院山西煤炭化学研究所

Determination of three beta-blockers by capillary electrophoresis with end-column electrochemical detection

Three beta -blockers (propranolol, timolol, acebutolol) were separated by capillary electrophoresis (CE) and detected by end-column electrochemical detection (EC). In the present work, a carbon fiber (33 mum) electrode was used as the working electrode. The effect of the buffer concentration, buffer pH, detection potential and separation voltage on the separation of analytes and behavior of electrochemical detection was systematically investigated. The optimum conditions determined were as following: 40 cm length, 25 mum i.d. capillary; 17.5 kV separation voltage; 2 s injection at 15 kV; 70mM phosphate buffer, pH 3.5; detection potential + 1.2V (vs. Ag/AgCl). Under these conditions, the linear ranges of beta -blockers were over three orders of magnititude and the low detection limit of 10(-8)M was obtained. This method was also applied to detect the simulated urine sample.

Application of inductively coupled plasma mass spectrometry in biological samples analysis

Recent important applications of inductively coupled plasma mass spectrometry in biological samples analysis are reviewed. The sample preparation, sample introduction techniques, interference correction and typical applications are introduced in detail with 154 references.

松辽盆地南部大情字井地区CO2埋存体地质格架及储层建模

Increasing attentions have been paid to the subsurface geological storage for CO2 in view of the huge storage capacity of subsurface reservoirs. The basic requirement for subsurface CO2 storage is that the CO2 should be sequestrated as supercritical fluids (physical trapping), which may also interact with ambient reservoir rocks and formation waters, forming new minerals (chemical trapping). In order to the effective, durable and safe storage for CO2, enough storage space and stable sealing caprock with strong sealing capacity are necessitated, in an appropriate geological framework. Up till now, hydrocarbon reservoirs are to the most valid and appropriate CO2 storage container, which is well proven as the favorable compartment with huge storage capacity and sealing condition. The thesis focuses on two principal issues related to the storage and sealing capacity of storage compartment for the Qingshankou and Yaojia formations in the Daqingzijing block, Southern Songliao Basin, which was selected as the pilot well site for CO2-EOR storage. In the operation area, three facies, including deltaic plain, deltaic front and subdeep-deep lake facies associations, are recognized, in which 11 subfacies such as subaqueous distributary channel, river- mouth bar, interdistributary bay, sheet sandbody, crevasse splay and overflooding plain are further identified. These subfacies are the basic genetic units in the reservoir and sealing rocks. These facies further comprise the retrogradational and progradational depositional cycles, which were formed base- level rise and fall, respectively. During the regressive or lake lowstand stage, various sands including some turbidites and fans occurred mostly at the bottom of the hinged slope. During the progradation stage, these sands became smaller in size and episodically stepped backwards upon the slope, with greatly expanded and deeped lake. However, most of Cretaceous strata in the study area, localized in the basin centre under this stage, are mainly composed of grey or grizzly siltstones and grey or dark grey mudstones intercalated with minor fine sandstones and purple mudstones. On the base of borehole and core data, these siltstones are widespread, thin from 10 to 50 m thick, good grain sorting, and have relative mature sedimentary structures with graded bedding and cross- lamination or crossbeds such as ripples, which reflect strong hydrodynamic causes. Due to late diagenesis, pores are not widespread in the reservoirs, especially the first member of Qingshankou formation. There are two types of pores: primary pore and secondary cores. The primary pores include intergranular pores and micropores, and the secondary pores include emposieus and fracture pores. Throat channels related to pores is also small and the radius of throat in the first, second and third member of Qingshankou formation is only 0.757 μm, 0.802 μm and 0.631 μm respectively. In addition, based on analyzing the probability plot according to frequency of occurrence of porosity and permeability, they appear single- peaked distribution, which reflects strong hetero- geneity. All these facts indicate that the conditions of physical property of reservoirs are not better. One reason may be provided to interpret this question is that physical property of reservoirs in the study area is strong controlled by the depositional microfacies. From the statistics, the average porosity and permeability of microfacies such as subaqueous distributary channel, channel mouth bar, turbidites, is more than 9 percent and 1md respectively. On the contrary, the average porosity and permeability of microfacies including sand sheet, flagstone and crevasse splay are less than 9 percent and 0.2md respectively. Basically, different hydrodynamic environment under different microfacies can decide different physical property. According to the reservoir models of the first member of Qingshankou formation in the No. well Hei47 block, the character of sedimentary according to the facies models is accord to regional disposition evolution. Meantime, the parameter models of physical property of reservoir indicate that low porosity and low permeability reservoirs widespread widely in the study area, but the sand reservoirs located in the channels are better than other places and they are the main sand reservoirs. The distribution and sealing ability of fault- fractures and caprock are the key aspects to evaluate the stable conditions of compartments to store CO2 in the study area. Based on the core observation, the fractures widespread in the study area, especially around the wells, and most of them are located in the first and second member of Qingshankou formation, almost very few in the third member of Qingshankou formation and Yaojia formation instead. In addition, analyzing the sealing ability of eleven faults in the three-dimensional area in the study area demonstrates that most of faults have strong sealing ability, especially in the No. well Hei56 and Qing90-27. To some extent, the sealing ability of faults in the No. well Hei49, Qing4-6 and Qing84-29 are worse than others. Besides, the deposition environment of most of formations in the study area belongs to moderately deep and deep lake facies, which undoubtedly take advantage to caprocks composed of mudstones widespread and large scale under this deposition environment. In the study area, these mudstones distribute widely in the third member of Qingshankou formation, Yaojia and Nenjiang formation. The effective thickness of mudstone is nearly ~550m on an average with few or simple faults and fractures. In addition, there are many reservoir beds with widely- developed insulated interbeds consist of mudstones or silty mudstone, which can be the valid barrier to CO2 upper movement or leakage through diffusion, dispersion and convection. Above all, the closed thick mud caprock with underdeveloped fractures and reservoir beds can be taken regard as the favorable caprocks to provide stable conditions to avoid CO2 leakage.

二氧化碳在孔隙咸水层中多相流动数值模拟研究

There has been a growing concern about the use of fossil fuels and its adverse effects on the atmospheric greenhouse and ecological environment. A reduction in the release rate of CO2 into the atmosphere poses a major challenge to the land ecology of China. The most promising way of achieving CO2 reduction is to dispose of CO2 in deep saline aquifers. Deep aquifers have a large potential for CO2 sequestration in geological medium in terms of volume and duration. Through the numerical simulation of multiphase flow in a porous media, the transformation and motion of CO2 in saline aquifers has been implemented under various temperature and hydrostatic pressure conditions, which plays an important role to the assessment of the reliability and safety of CO2 geological storage. As expected, the calculated results can provide meaningful and scientific information for management purposes. The key problem to the numerical simulation of multiphase flow in a porous media is to accurately capture the mass interface and to deal with the geological heterogeneity. In this study, the updated CE/SE (Space and time conservation element and solution element) method has been proposed, and the Hybrid Particle Level Set method (HPLS) has extended for multiphase flows in porous medium, which can accurately trace the transformation of the mass interface. The benchmark problems have been applied to evaluate and validate the proposed method. In this study, the reliability of CO2 storage in saline aquifers in Daqingzi oil field in Sunlong basin has been discussed. The simulation code developed in this study takes into account the state for CO2 covering the triple point temperature and pressure to the supercritical region. The geological heterogeneity has been implemented, using the well known geostatistical model (GSLIB) on the base of the hard data. The 2D and 3D model have been set up to simulate the CO2 multiphase flow in the porous saline aquifer, applying the CE/SE method and the HPLS method .The main contents and results are summarized as followings. (1) The 2D CE/SE method with first and second –order accuracy has been extended to simulate the multiphase flow in porous medium, which takes into account the contribution of source and sink in the momentum equation. The 3D CE/SE method with the first accuracy has been deduced. The accuracy and efficiency of the proposed CE/SE method have been investigated, using the benchmark problems. (2) The hybrid particle level set method has been made appropriate and extended for capturing the mass interface of multiphase flows in porous media, and the numerical method for level set function calculated has been formulated. (3) The closed equations for multiphase flow in porous medium has been developed, adept to both the Darcy flow and non-Darcy flow, getting over the limitation of Reynolds number to the calculation. It is found that Darcy number has a decisive influence on pressure as well as velocity given the Darcy number. (4) The new Euler scheme for numerical simulations of multiphase flows in porous medium has been proposed, which is efficient and can accurately capture the mass interface. The artificial compressibility method has been used to couple the velocities and pressure. It is found that the Darcy number has determinant effects on the numerical convergence and stability. In terms of the different Darcy numbers, the coefficient of artificial compressibility and the time step have been obtained. (5) The time scale of the critical instability for critical CO2 in the saline aquifer has been found, which is comparable with that of completely CO2 dissolved saline aquifer. (6) The concept model for CO2 multiphase flows in the saline aquifer has been configured, based on the temperature, pressure, porosity as well as permeability of the field site .Numerical simulation of CO2 hydrodynamic trapping in saline aquifers has been performed, applying the proposed CE/SE method. The state for CO2 has been employed to take into account realistic reservoir conditions for CO2 geological sequestration. The geological heterogeneity has been sufficiently treated , using the geostatistical model. (7) It is found that the Rayleigh-Taylor instability phenomenon, which is associated with the penetration of saline fluid into CO2 fluid in the direction of gravity, has been observed in CO2 multiphase flows in the saline aquifer. Development of a mushroom-type spike is a strong indication of the formation of Kelvin-Helmholtz instability due to the developed short wavelength perturbations present along the interface and parallel to the bulk flow. Additional key findings: the geological heterogeneity can distort the flow convection. The ascending of CO2 can induce the persistent flow cycling effects. The results show that boundary conditions of the field site have determinant effects on the transformation and motion of CO2 in saline aquifers. It is confirmed that the proposed method and numerical model has the reliability to simulate the process of the hydrodynamic trapping, which is the controlling mechanism for the initial period of CO2 storage at time scale of 100 years.

超临界溶液快速膨胀技术制备药物微细颗粒研究

本文主要研究了超临界溶液快速膨胀法（Rapid Expansi Qnofsu Percritical of Solution，RESs）制备微细颗粒装置的建立，并在此装置上考查了实现、布洛芬、黄体酮微细化处理的RESS过程工艺参数。RESS技术是超临界流体领域的一项新兴技术。其特点是借助于超．临界流体（Supercritial Fluids，SCF）的溶解性随其密度变化的关系，利用压力的改变，迅速地减小scF中溶质的溶解度，在极短的时间内在体系中造成极大的过饱和度和巨大扰动，形成微细而均一的溶质颗粒。在操作中可避免高温分解，还可有效避免副反应及有机物污染等问题。因此RESS法是一种安全、卫生的制备微细颗粒技术。我们根据RESS技术原理，查阅大量有关RESS过程的文献报道，利用原有超临界萃取装置的溶剂供应系统和萃取釜，又自行建立了包括预膨胀段、喷头、膨胀室、流量计以及附属于它们的控制、调节元件在内的膨胀收集单元：，构成了一套完整的RESS装置。许多药物的药效与其药物颗粒大小关系密切，随着颗粒尺寸的减小，它在体内的溶解和吸收速率提高。因此我们在本研究中选择两种药物-布洛芬、黄体酮进行微细化处理。布洛芬是一种重要的消炎镇痛药，我们首先在此装置上进行布洛芬的RESS过程研究，考察了操作条件对布洛芬微细颗粒粒径、比表面积、颗粒形态的影响。实验结果表明，利用此装置完全可以实现布洛芬的微细化处理。实验中还发现用多孔金属烧结板做喷嘴时，喷出产率特别大，这一特点为RESS法的工业化提供了重要可能性。黄体酮是一种重要的昌体类激素药物，它同时又是合成其它激素类药物的关键中间体。本研究也研究了黄体酮在此装置上实现RESS过程得到微细颗粒的可行性。研究结果表明：此装置同样适用于黄体酮的微细化处理。

Morphology transcription process from CMC micelles to inorganogel and its effect on the properties of alumina particle

In this study, a carboxymethyl cellulose (CMC)-mediated sol-gel process was developed to synthesize the alumina hydoxide whiskers. During the process, inexpensive inorganic salts were used as precursors and supercritical drying method was used to extract the water in hydrogel. The influences of CMC on the gel formation and the particle morphology were investigated. The results show that the formation of CMC-aluminium hydroxide organic-inorganic hybridgels led to a morphology transcription process from CMC micelles to aluminium hydroxide gel, as a result, the precursor with whiskerious morphology was obtained.