分子筛膜反应器的研究进展

分子筛膜具有规整的微孔结构(<1 nm), 耐高温高压、 抗有机溶剂, 在液相和气相小分子分离中受到广泛关注. 分子筛膜可以与催化反应耦合于一体构成膜反应器, 使反应过程与组分分离同时进行, 促进反应平衡移动, 达到反应强化的效果. 本文概述了近十年不同类型分子筛膜反应器在催化反应中的应用研究进展, 并对分子筛膜反应器未来的发展趋势进行了展望.     

Structural and mathematical models for pressure-dependent electrodiffusion of an electrolyte through heterogeneous ion-exchange membranes: Pressure-dependent electrodiffusion of NaOH through the MA-41 anion-exchange membrane

Structural and mathematical models are proposed for describing electrolyte transport through heterogeneous anion-exchange membranes under conditions of pressure-dependent electrodiffusion. The idea that mesopores and macropores are present in the membrane provides the basis for the structural model. The Nernst-Planck equations with a convective term are used to describe ion transport in the solution filling the pores. Results of the solution to the mathematical problem and the experimental investigations demonstrate the possibility of decreasing the transport numbers of sodium ions through an anion-exchange membrane by applying a pressure gradient in the same direction as the electrolyte diffusion flux in the membrane.     

The effect of gas surface diffusion on the asymmetric permeability of two-layer porous membranes

The permeability is calculated for two-layer membranes composed of porous layers with nano- and microsized pores. It is found that, in nanosized pores, the gas transfer occurs in the free-molecular regime in the pore volume and via diffusion along the adsorption layer. The degree of adsorption layer filling is determined from the Langmuir isotherm. The dependence of the diffusion coefficient in the adsorption layer on the degree of surface coverage is taken into account. The transfer in the microsized pored is described in a hydrodynamic regime. The values of the membrane permeability are determined at different orientations with respect to the direction of a gas flow. It is shown that the difference between the permeability values may be as large as 60%.     

Characterization of microporous membranes for use in membrane contactors

Methods of selecting applicable membranes for use in membrane contactors for flue gas desulfurization are proposed in this paper. The mass transfer mechanism for SO₂ diffusion through gas filled pores is explored by simple measurements in order to identify suitable membrane structures for use in contactors for flue gas cleaning. It is attempted to correlate the experimentally determined membrane mass transfer coefficient to intrinsic physical properties of the membrane by applying theoretical and empirical correlations for the porosity-tortuosity relationship of the porous structure. Thereby limiting fluxes can be predicted with good accuracy from data quoted in the manufactures catalogue.     

Ceramic membranes for ozonation in wastewater treatment

Ozone, due to its high oxidative capacity, is often used in water treatment for the degradation of organic pollutants. Unfortunately, the application of ozone in the form of gas bubbles causes foam problems. To avoid the development and accumulation of foam, the transfer of ozone into the water through gas permeable membranes was investigated. Ceramic membranes were used because of the chemical inertness of the material. The hydrophilic behaviour of ceramic membranes made of metal oxides causes the water to penetrate into the pores. This creates a diffusion resistance for the ozone which decreases the transfer rates. To keep the water out of the porous structure and maintain the gas/water interface at the membrane surface, the surface properties of the membrane were changed. The membrane was soaked in a solution of a fluorinated compound. Water drop measurements and transfer rates were investigated and confirmed the stability of the hydrophobic nature of the membrane surface. The ozone transfer rates thus achieved were in the range of 12 grams of ozone per square meter per hour.     

Non-equilibrium molecular dynamics simulation study on permeation phenomena of LJ particles in slit-shaped membranes with periodic belt-like heterogeneous surfaces

In order to make clear the relationship between the pore structure and the diffusivity, we have carried out permeation simulations of pure gases through simple model membranes by using the external-field non-equilibrium molecular dynamics method. As the membrane, we model slit-shaped pores with periodic belt-like heterogeneous pore surfaces which are caused by the upheaval of surface atoms. Applying simulation results for membranes with several upheaval interval distances to Maxwell–Stefan (MS) theory, we calculate the effects of the molecular loading of permeating molecules in the pores on MS diffusivity (D_MS). In addition, the permeation potential barrier is estimated as the difference between the maximum and minimum permeation potential energies. The effect of the molecular loading on the permeation potential barrier and the D_MS are in inverse proportion. It is noted that, when the width of the adsorption area in the permeation direction is not common multiples of the molecular diameter, the permeation potential barrier decreases with the increase in the molecular loading. This is because the positive force against the permeation direction is caused to the permeating molecules by interactions with permeating molecules in the adsorpton area between adjacent upheavals. Therefore, we could suggest that the key factor for controlling diffusion property is the structural relationship between the adsorption area and the permeating molecules.     

Gas-Generating Porous Electrodes: The Nature of the Low-Polarizability Portion in the Polarization Curves

The phenomenon of a low-polarizability portion (LPP) is discussed in the paper. The phenomenon is responsible for the possible rapid increase in the current in polarization curves (PC) for the gas generation in gas-generating porous electrodes (GGPE). A fresh viewpoint on the nature of LPP is propounded. The inflection in PC, which follows the linear Tafel portion, owes its inception to the emergence, in the electrode pores, of a network of gas pores that are freed of electrolyte and are connected with each other. The effective diffusion coefficient for gas molecules in gas pores filled with water vapor is larger than the effective diffusion coefficient for the same gas molecules in liquid pores filled with an electrolyte solution by several orders of magnitude. The emergence of a gas phase in a GGPE leads to a rapid increase in the effective diffusion coefficient. This circumstance in turn is capable of rapidly intensifying processes of the formation and removal of gas, which leads to a considerable increase in the overall current. A method for obtaining an approximate solution of the problem (the notion on ideal porous electrode) is suggested. A system of equations is derived, which can sufficiently accurately, qualitatively and quantitatively describe the character of variations in a polarization curve in the initial part of a low-polarizability portion. Theoretical and experimental polarization curves for the chlorine evolution on a dimensionally stable anode are compared quantitatively.     

Physicochemical Properties of Profiled Heterogeneous Ion-Exchange Membranes

Optimum values of parameters of hot pressing of heterogeneous ion-exchange membranes MK-40 and MA-40 (temperature, pressure, exposure duration) with the aim of creating geometrical profiles on their surfaces are determined. A method of optical visualization of membrane profiles and a diffusion technique of diagnostics of through pores in the membranes are developed and substantiated. Most important physicochemical and physicomechanical characteristics of profiled membranes are investigated. It is shown that the major obstacle in the production of profiled cation-exchange heterogeneous membranes is encapsulation of grains of the ion-exchange resin by an inert polyethylene film, which leads to an increase in the surface resistance of the membranes and to a decrease in the fraction of their active surface areas. The profiling of heterogeneous anion-exchange membranes is accompanied by an increase in their microscopic porosity and diffusion penetrability.     

粘结剂聚四氟乙烯乳液经过乙醇预处理后对气体扩散电极性能的影响

在气体扩散电极的制作工艺中,加入乙醇对粘结剂聚四氟乙烯(PTFE)进行预处理.通过伞自动微孔物理化学吸附仪对气体扩散电极进行BET比表面积、Langmuir比表面积、孔分布等进行测试,并用扫描电子显微镜(SEM)检测观察电极表观形貌.以锌电极作为负极组装成锌空气电池,检测在不同的电流密度下气体扩散电极相对锌电极的电位变化,研究PTFE乳液经过乙醇预处理后对电极性能的影响.结果显示,PTFE乳液经过乙醇处理后,先膨胀后收缩,能够增加催化层和气体扩散层的孔隙结构和比表面积,从而使得电极有效电化学反应场所相应增多,减低电极在大电流密度条件下放电时的极化过电位.     

Micro-BLMs on highly ordered porous silicon substrates: rupture process and lateral mobility

In a recent paper, we hypothesized that the continuous increase in membrane conductance observed for nano-BLMs is the result of an independent rupturing of single membranes or membrane patches covering the pores of the porous material. To prove this hypothesis, we prepared micro-BLMs on porous silicon substrates with a pore size of 7 mum. The upper surface of the silicon substrate was coated with a gold layer, followed by the chemisorption of 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol (DPPTE) and subsequent addition of a droplet of 1,2-diphytanoyl-sn-glycero-3-phosphocholine (DPhPC) dissolved in n-decane. The lipid membranes were fluorescently labeled and investigated by means of fluorescence microscopy and impedance spectroscopy. Impedance spectroscopy revealed the formation of pore-suspending bilayers with high membrane resistance. Increases in membrane capacitance and membrane conductance were observed. This increase in membrane conductance could be unambiguously related to the individual rupturing of membranes suspending the pores of the porous material as visualized by means of fluorescence microscopy. Moreover, by fluorescence recovery after photobleaching experiments, we investigated the lateral mobility of the lipids within the micro-BLMs leading to a mean effective diffusion coefficient of Deff = (14 +/- 1) microm2/s.     

膜催化研究II. 多孔无要膜的制备与表征及其反应器对甲醇脱氢反应的促进作用

采用溶胶-凝胶法制备了多孔氧化铝膜, 并通过DSC、TGA、SEM、N~2吸附和气体透过率测定等手段, 对膜的性能进行了表征。结果表明, 用这种方法制备的多孔氧化铝膜是一种均匀无裂痕和具有较窄孔径分布(约4nm)的膜材料。将此多孔氧化铝膜制成膜反应器后, 用于甲醇催化脱氢制甲醛的反应, 发现甲醇转化率比常规反应器有较大幅度的提高。同时首次尝试采用溶胶-凝胶法将催化活性组分直接负载到多孔氧化铝膜上, 从而得到了一种具有催化活性的多孔膜, 并考察了它的反应活性。文中对由这两种多孔膜及钯/陶瓷复合膜制成的反应器的特点进行了比较。     

杂多化合物膜的制备及催化作用

Heteropoly compounds (HPC), a kind of polyoxometallates, with their strong acidity and oxidative ability, are good homogeneous and heterogeneous catalysts in both acid-catalyzed and selective oxidation reactions, and have been widely used in petroleum and fine chemical industries. Owing to the diversity in their composition and structure, the catalytic properties of HPC can be altered in a wide range. Among them, the heteropolyanions with Keggin structure have been studied by far the most,especially on their applications in heterogeneous catalysis. However, since they are thermally unstable at high temperatures, their utilization in this field has been restricted. In the last ten years, inorganic membranes have been proved to be beneficial to heterogeneous catalytic processes for their high selectivity and good heat-conductivity. And the sol-gel method, one of the most common approaches to prepare inorganic membranes, is becoming mature. Here a sol-gel method to prepare a porous HPC membrane is reported. The catalytic performance of the membrane was tested through a model reaction, the selective oxidation of t-BuOH.     

Nano/subnano-tuning of porous ceramic membranes for molecular separation

In sol–gel processing, porous ceramic membranes can be prepared by sol-coating porous substrates and drying for gelling, followed by a firing process. Ceramic membranes prepared by sol–gel processing can be categorized into amorphous materials such as silica, and crystalline materials such as alumina and titania. Amorphous silica networks, which can be prepared by the polymeric sol route, have ultra-microporous pores that allow small molecules such as helium and hydrogen to permeate. On the other hand, crystalline materials, which are mostly prepared by the colloidal sol route, have nano-sized pores in the range of one to several nanometers. In this article, sol–gel derived SiO₂ and TiO₂ membranes with controlled pore sizes in the range of sub-nano to nanometers will be reviewed with respect to membrane preparation and to their application in the separation of the gas and liquid phases. Ceramic membranes with high performance can be obtained by precise control of membrane structures (pore size, pore size distribution, thickness, pore shape, etc.) and membrane materials (SiO₂, TiO₂, composite oxide, hybrid materials, etc.). Nano/subnano-tuning of porous ceramic membranes is quite important for the improvement of membrane permeability and selectivity.     

Über die Aktivierung von Molekeln an oxidischen Halbleiteroberflächen

Assuming inelastic scattering of quasi-free charge carriers of solids by adsorbed gas molecules, a simple model for heterogeneous catalytic reactions is developed which allows to describe mathematically the increase of catalytic activation energy on increasing deviation of the energy of the impact partners from the resonance condition of energy transfer. The model is proved for simple decomposition reactions.     

Thermal effects in osmotic distillation

Osmotic distillation (OD) is a concentration technique for aqueous mixtures based on porous hydrophobic membranes in contact on both sides with liquid phases at pressure lower than the pressure needed to displace the gas phase in the pores. The driving force for the water vapour diffusion through the gas phase immobilised within the membrane pores is sustained by an activity difference by using a hypertonic solution, typically concentrated brines, downstream the membrane. The mass transfer causes a cooling down of the feed and a warm up of the brine, as a consequence a temperature difference is created which reduces the effective driving force for mass transfer. This ‘thermal effect’ is investigated both theoretically and experimentally, it is shown that the effect on the flux is substantial.     

金属-有机骨架材料中吸附气体的扩散速率

采用分子动力学方法,以甲烷为探针分子研究了不同压力条件下气体在具有不同孔道结构的金属-有机骨架材料(MOFs)中的扩散速率.通过计算气体在八种材料中的自扩散系数,并结合气体分子在材料中的质心分布图等,讨论了气体扩散速率与孔道结构之间的关系.研究结果表明:对于同时含有孔笼(pocket)和三维正交孔道(channel)结构的MOF材料(P-C材料),低压时甲烷气体吸附在孔笼结构中,随着压力的升高,气体分子开始进入正交孔道,同时其自扩散系数增加;而对于只含有三维立方孔道结构的IRMOF(isoreticular MOF)系列材料,在中低压范围内,气体分子在其中的自扩散系数随压力变化较小.当压力进一步升高时,气体分子在材料孔道中的吸附逐渐接近饱和,其自扩散系数均降低.因此,在不同MOF材料中气体分子扩散速率的差异主要取决于孔道结构的不同.对P-C材料,中低压下通过控制压力可以控制气体在其中的扩散速率,从而为MOF材料在气体存储、分离等方面的实际应用提供参考信息.     

Modeling of pore formation in phase inversion processes: analysis of pore formation mechanism

The phase inversion process is the most important preparation process of porous polymer membranes. Recently, a numerical model based on first principles to predict pore structures has been proposed (Hopp-Hirschler and Nieken in J Membr Sci 564:820–831, 2018). This model enables a detailed investigation of the mechanism of pore formation in porous polymer membranes. This follow-up presents investigations of the mechanism of nucleation of pores during the phase inversion process in 1D. Pores originate due to accumulation of over-saturated mixtures inside a diffuse interface between homogeneous and demixed polymer solutions behind the precipitation front. This is caused by an expansion of the width of the diffuse interface and time-dependent concentration profiles which finally lead to a change of sign of total diffusive mass flux inside of the diffuse interface. As a result, oscillating compositions behind the precipitation front lead to formation of pores. It is concluded that large surface tension leads to initially small pore sizes. In the second part, a detailed discussion of directional diffusion behind the precipitation front is presented in 2D, which is responsible for different pore structures, e.g., finger or sponge pores. Depending on the dominant direction of diffusion finger pores, lamella structures or sponge pores are formed. This picture can straightforwardly be extended to 3D structures.

     

A new method of modification of inorganic membranes with pyrocarbon nano-sized crystallites

Gas-separating membranes were obtained according to an original method of directed modification of ultra filtration membranes having 50 nm pores by means of pyrocarbon nano-sized crystallites (PNCs). For the first time, the size of the pores was reduced not along the entire depth of the selective layer but only at the pore orifice, increasing their productivity by several orders of magnitude. PNC deposition was done at 800 and 650°C using methane and propane as a pyrolyzed gas at 90–100 kPa, respectively. The depth of PNC deposition was determined by scanning electron microscopy and energy dispersive spectrometry. It was demonstrated that at the used pressure, the depth of deposition was 1.5 μm, i.e., PNCs were deposited in the pore orifices. Gas permeability analysis for a membrane with r _pore ～ 0.8 nm allowed us to estimate the Knudsen ratio and surface diffusion. The Knudsen and surface diffusion fluxes were estimated. The advantages and challenges of the proposed approach are discussed; these are mainly related to the thermal stability of the porous structure and the compatibility of the thermal expansion coefficients of the porous substrate and deposited PNCs. An analysis of the obtained results is presented, along with an outline for further studies.     

Testing predictions of macroscopic binary diffusion coefficients using lattice models with site heterogeneity

Quantitatively predicting mass transport rates for chemical mixtures in porous materials is important in applications of materials such as adsorbents, membranes, and catalysts. Because directly assessing mixture transport experimentally is challenging, theoretical models that can predict mixture diffusion coefficients using only single-component information would have many uses. One such model was proposed by Skoulidas, Sholl, and Krishna (Langmuir, 2003, 19, 7977), and applications of this model to a variety of chemical mixtures in nanoporous materials have yielded promising results. In this paper, the accuracy of this model for predicting mixture diffusion coefficients in materials that exhibit a heterogeneous distribution of local binding energies is examined. To examine this issue, single-component and binary mixture diffusion coefficients are computed using kinetic Monte Carlo for a two-dimensional lattice model over a wide range of lattice occupancies and compositions. The approach suggested by Skoulidas, Sholl, and Krishna is found to be accurate in situations where the spatial distribution of binding site energies is relatively homogeneous, but is considerably less accurate for strongly heterogeneous energy distributions.     

Calculating Electrochemical Activity of Porous Electrodes of a Filled-up Type with an Immobilized Enzyme and Regular Gas Pores

A model for a porous electrode of a filled-up type with an immobilized enzyme, in which a system of regular gas pores is formed, is studied. The system of regular gas pores is in fact a collection of equidistant cylinders whose thicknesses are equal to one grain of the hydrophobizing agent. Usually, the gas reactant passes into a porous electrode via a number of chains that comprise porous grains of the hydrophobizing agent. The latter is distributed in the electrode bulk in a random fashion. In this case, channels for supplying gas are formed at high concentrations of the hydrophobizing agent. As a result, the number of molecules of a catalyst in a porous electrode, and along with it the current, are not great. Should we pass to electrodes with regular gas pores, the required amount of a hydrophobizing agent would decrease. As a result, the number of molecules of the enzyme in the electrode and the current would increase. The calculation of the last quantity is the subject matter to which the paper pays a major attention. The calculation is performed for two versions of distribution of a hydrophobizing agent over the electrode bulk, specifically, a random distribution and a regular distribution. Concrete calculations are carried out for an oxygen porous electrode with an enzyme whose electrochemical characteristics are close to those obtained on laccase. It was assumed in the calculations that the enzyme operates without mediators. It is established that a porous electrode with a quasi-regular structure has a considerable advantage. With an electrode thickness of 13 m one can manage to obtain currents of nearly 0.74 A cm^–2 as early as at an overvoltage of about 30 mV.