REVIEWS Chinese Journal of Chemical Engineering, 21(2) 205215 (2013) DOI: 10.

1016/S1004-9541(13)60460-7

Progress on Porous Ceramic Membrane Reactors for Heterogeneous Catalysis over Ultrafine and Nano-sized Catalysts*
JIANG Hong (), MENG Lie (), CHEN Rizhi (), JIN Wanqin ()**, XING Weihong ()** and XU Nanping ()
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China

Abstract Heterogeneous catalysts with ultrafine or nano particle size have currently attracted considerable attentions in the chemical and petrochemical production processes, but their large-scale applications remain challenging because of difficulties associated with their efficient separation from the reaction slurry. A porous ceramic membrane reactor has emerged as a promising method to solve the problem concerning catalysts separation in situ from the reaction mixture and make the production process continuous in heterogeneous catalysis. This article presents a review of the present progress on porous ceramic membrane reactors for heterogeneous catalysis, which covers classification of configurations of porous ceramic membrane reactor, major considerations and some important industrial applications. A special emphasis is paid to major considerations in term of application-oriented ceramic membrane design, optimization of ceramic membrane reactor performance and membrane fouling mechanism. Finally, brief concluding remarks on porous ceramic membrane reactors are given and possible future research interests are also outlined. Keywords porous ceramic membrane, membrane reactor, heterogeneous catalysis

INTRODUCTION

Heterogeneous catalysis plays an important role in chemical and petrochemical production processes. Heterogeneous catalysts with ultrafine or nano particle size exhibit very high activity and selectivity for a large set of reactions [1], but their large-scale applications are often complicated by difficulties associated with their efficient separation from the reaction slurry. Alternatively, ultrafine or nano-sized catalysts can be immobilized onto a suitable substrate with larger grain size, which allows easier catalyst separation but at the expense of a decrease in the effective catalyst surface area and mass transfer limitations of reactants to the catalyst surface. Catalysts in suspension have been reported with a better catalytic activity than the immobilized counterparts [2, 3]. Magnetic separation is another feasible approach to separate particles of about 50 nm, which requires these particles to have a sufficiently high saturation magnetization [4]. Membrane reactor, a process that combines the heterogeneous catalysis with membrane separation, has emerged as a reasonable alternative to solve the problem mentioned above [5, 6]. The most representative features of the membrane reactors are to retain the catalysts in situ and make the reaction process continuous. In addition, the membrane reactor systems are easy to operate, control and scale up. Due to the generally severe conditions of heterogeneous catalysis, most membrane reactors use inorganic membranes, which can be dense or porous and inert or catalytically active, and made from different

materials such as metals, carbon, glass or ceramic [7-9]. Ceramic membranes are unsurpassed in terms of chemical stability, thermal conductivity, and mechanical strength compared with other membranes. All these advantages make their potential applications in some important heterogeneous catalytic reactions, particularly under harsh operating environments, such as high temperature and organic solvent. The porous ceramic membranes currently in use usually have an asymmetric structure consisting of a support layer (generally -alumina) with large pores and a separation layer (-alumina, zirconia, etc.) with fine pores which controls the permeation flux. Nowadays, ceramic porous membrane reactors have been widely applied in the fields of bioengineering, environment engineering, chemical and petrochemical [10, 11]. The aim of this article is not to provide an exhaustive overview of all applications but to focus on the progress on porous ceramic membrane reactors used for heterogeneous catalysis in chemical and petrochemical production processes. Many new developments in the field of heterogeneous photocatalysis are not addressed within the scope of the present contribution. Hybrid photocatalysis-membrane processes have been an often-reviewed field in the last decade with examples such as the monography by Ollis in 2003 [12], Molinari and Palmisano in 2005 [13], Augugliaro in 2006 [14] and Mozia et al. in 2010 [15]. The development of porous ceramic membrane reactors on gas phase catalytic reactions consuming or generating H2 or O2 is also not the topic of the article. The purpose of this article is to present the progress of

Received 2012-02-28, accepted 2012-06-18. * Supported by the National Natural Science Foundation of China (20990222, 21106061), the National Basic Research Program of China (2009CB623406), the National Key Science and Technology Program of China (2011BAE07B05) and the Natural Science Foundation of Jiangsu Province, China (BK2010549, BK2009021). ** To whom correspondence should be addressed. E-mail: wqjin@njut.edu.cn; xingwh@njut.edu.cn

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porous ceramic membrane reactors for heterogeneous catalysis with suspended ultrafine or nano-sized catalysts. Different configurations of porous ceramic membrane reactors are described and characterized. Major considerations of the porous ceramic membrane reactors in terms of membrane design, optimization of ceramic membrane reactor performance and membrane fouling are discussed. Some important industrial applications of porous ceramic membrane reactors are also introduced. 2 CERAMIC MEMBRANE REACTOR CONFIGURATIONS Generally, there are two main options of integrating the membrane into the heterogeneous catalysis: the side-stream configuration and submerged configuration [16, 17], as shown in Fig. 1. The side-stream membrane reactor, in which the reaction occurs in a stirred reaction vessel and the separation of the products is performed in a separated cross-flow membrane filtration unit. The submerged membrane reactor, as the name implies, is a combination of membranes positioned in a flooded tank, in which the liquid to be filtered is fed to the tank and the permeate is removed under suction by either a pump or gravity effect. Both configurations have advantages and disadvantages. In the former configuration, the membrane modules are more flexible and easier to be replaced, cleaned and scaled up due to the segregation of reaction zone and separation zone, but the potential loss of catalysts could be greater in the pipeline, membrane and pumping system and the use of recirculation loop leads to the increasing energy costs. While in the later configuration, the catalyst loss and the energy consumption are much lesser than the former because of the absence of the

recirculation pipeline and the high-flow recirculation pump [18]. The layout is more compact due to the integration of reaction and separation zones into a single unit. Just because of this, the membrane area per reactor volume is limited. Zhong et al. [16] developed a pilot-scale plant of side-stream membrane reactor for the hydrogenation of p-nitrophenol to p-aminophenol over nickel nanoparticles, in which the nickel nanoparticles could be recovered completely using a ceramic membrane. They found that the hydrogenation rate decreased rapidly with recycling of catalysts in comparison with that in laboratory. The problem was considered to be due to the adhesion of nickel nanoparticles on the surface of the pipeline, the tank, and the membrane, which caused a decrease in catalyst concentration in the reaction slurry and led to a consequent decline in the reaction rate and the permeate flux of the membrane. Later, a submerged membrane reactor was proposed by Chen et al. [19, 20] for the production of p-aminophenol over nickel nanoparticles, where the ceramic membrane was submerged in the reactor. They stated that the decrease in reaction rate in the submerged membrane reactor was much lower than that in the side-stream membrane reactor during the continuous reaction cycles, because the latter provided more areas for the adsorption of nickel nanoparticles. Although an almost 100% catalysts retention has been achieved in the two configurations discussed above, the minimization of byproducts has been ignored. Membrane distributors have been reported to be an emerging technology, which has been used for a high selectivity in vapor phase reactions [21]. If the membrane reactor combines the advantages of a reactor with distributed reactant addition and a reactor with catalyst separation, the two objectives of the product

(a)

(b)

(c) Figure 1 Various ceramic membrane reactor configurations (a) side-stream membrane reactor; (b) submerged membrane reactor and (c) dual-membrane reactor

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selectivity enhancement and catalysts separation can be simultaneously realized. Recently, Jiang et al. [22] developed a dual-membrane reactor by employing one tubular porous ceramic membrane as a reactant distributor controlling the supply of reactant and a second tubular porous ceramic membrane as a membrane separator for in-situ separation of catalysts from the products [Fig. 1 (c)]. To evaluate the feasibility and the performance of the dual-membrane reactor, phenol hydroxylation with hydrogen peroxide (H2O2) over titanium silicalite-1 (TS-1) catalyst was selected as a model reaction. As compared to traditional H2O2 feeding modes, the use of the porous ceramic membrane distributor allowed a uniform injection of H2O2 into the reaction system, leading to promote the dihydroxybenzene selectivity significantly. The phenol conversion and the dihydroxybenzene (DHB) selectivity above 15% and about 95% could be achieved in a continuous operation of 30 hours, respectively. Catalysts could be retained almost completely in the reactor system by the membrane separator. Their study demonstrates the advantages of the dual-membrane reactor in enhancing selectivity and catalysts separation in a continuous heterogeneous catalytic reaction. 3 MAJOR CONSIDERATIONS OF THE CERAMIC MEMBRANE REACTOR With respect to the porous ceramic membrane reactor, the performance and long-term operation stability are mainly attributed to the synergistic effects between the membrane separation and the heterogeneous catalytic reaction. The efficiency of the membrane separation processes strongly depends on the microstructure of the used membrane in relation to the application systems. Consistently the control of the porous membrane structure is of especial importance in the development of stable operation of membrane reactors. Considerations of the optimization of ceramic membrane reactor performance are significant for enhancing the efficiency of the membrane reactors, i.e., synergistic control of separation and reaction, optimization of process parameters and establishment of mathematical model. Membrane fouling is another important consideration as it affects cleaning requirements and operating costs. 3.1 Membrane design

high cost of the membranes application, which hinders the development of membrane industry and application of membrane technology. Application-oriented ceramic membrane design may be a promising method to solve the problem described above. A research frame work of applicationoriented ceramic membrane design has been proposed (Fig. 2) by Xu et al [23]. Its fundamental idea is to build a performance-microstructure model based on an application system and optimize membrane microstructure aimed at the actual situation, then prepare appropriate membranes based on membrane structure-material model, finally solve the problem of engineering applications.

Figure 2 Framework of application-oriented ceramic membranes design [23]

Actually, the separation efficiency of membrane and the membrane flux depend, to a large extent, on the microstructure features of the membrane such as pore size and its distribution, thickness and porosity. Currently, the porous ceramic membrane can only be chosen from existing membrane for a certain application system, which may not be able to meet the requirements of the application object. Even if the chosen membrane is suitable for application system, it may not be the best choice. This situation leads to

In heterogeneous catalysis, the size of the catalyst is of considerable importance in that the extent of reaction is often inversely proportional to the particle size of the catalyst [24]. Ultrafine catalysts or nanosized catalysts have much greater catalytic activity and selectivity than those of traditional catalysts due to their unique crystal structure and surface properties, and have been paid more attentions. Many kinds of catalysts such as metal powders, metal oxide, highly dispersed supported metal catalysts, zeolites, carbon nanotubes and related porous carbons have been described lately in the literature [25-28]. Transition metal substituted molecular sieves are among the most studied solid catalysts due to the variety of available structures and pore sizes, and the tunable redox properties. One of the most versatile catalysts is titanium silicalite (TS-1), suitable for the epoxidation of olefins [29], the hydroxylation of aromatic and aliphatic C H bonds [30], the ammoxidation of ketones [31] etc. Besides, nano-sized metal catalysts such as Au, Pt, Pd and Ni have attracted a great deal of attention as potentially advanced materials possessing unique electronic, optic, and magnetic properties as well as catalytic functions [32-35]. In this section, ultrafine TS-1 suspension and nano-sized Ni suspension are taken as model systems to illustrate the ceramic membrane

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design for a given application. 3.1.1 Design of ceramic membranes for ultrafine titanium silicalite-1 As a new kind of catalyst, titanium silicalites have attracted extensive interest for their high catalytic activity and selectivity [36, 37]. However, the separation of TS-1 catalysts creates another problem to be solved in practical applications of the process. A major difficulty in the separation of TS-1 particles from the reaction slurry arises because TS-1 particles (particle size, 0.1-0.3 m) are too fine to be removed by gravity settling and porous tube filtration. Porous ceramic membranes have emerged as useful approach for separation of fine particles. Mathematical modeling is an important technique for the chosen of appropriate ceramic membrane in a given application system. Many models have been published to predict permeate fluxes in membrane filtration. These models can be divided into two major groups: transient permeate flux model and quasi-steady-state permeate flux model. The former describes the relationship of permeate flux with time, such as index model, filter cake model [38, 39] and blocking model [40]. The latter represents the balance relationships under quasi steady state conditions, mainly including model of concentration polarization and relevant modified model [41]. Most of these models focused on the effect of operating parameters on the membrane permeability. As a fact, flux is a function of time, and depends strongly on operating parameters, nature of the membrane and composition of the feed solution [42]. Therefore, it is necessary to develop models considering the membrane microstructure and the feed solution composition. Xu et al. [23, 43] proposed a blocking factor (k) to describe membrane fouling and a crossflow microfiltration model of ultrafine particle suspensions was built. The model discovered the correlation between membrane permeability and membrane microstructure, by which the variation of permeate flux with filtration time would be obtained and the influences of membrane structure parameters on permeate flux such as pore size, thickness and porosity were theoretically predicted and discussed under the ideal conditions that membrane pore size and particle size distribution were normal. On the basis of the method of applicationoriented ceramic membrane design, the relations between the operation conditions and permeate flux has been simulated for the TS-1 suspension. The simulated results showed that there was an optimum pore size between 200-300 nm in the filtration of TS-1 suspension. The flux increased with increasing membrane pore size below 200 nm and decreased above 300 nm. By using the ceramic membrane with a pore size of 200 nm, the experimental data of flux variation with time agreed with the simulation results [44]. 3.1.2 Design of ceramic membranes for nano-sized nickel Nano-sized nickel has been widely used for catalytic hydrogenation of aromatics such as benzene and

p-nitrophenol [45] or dehydrogenation reactions such as dehydrogenation of 2-butanol [46]. The catalytic properties (activity, selectivity and stability) of nanosized nickel (average particle size, 60 nm) have been proven to be superior to those of commercial Raney nickel [47]. Porous ceramic membranes have been used to separate nano-sized nickel catalysts from reaction slurry in the preparation of p-aminophenol, which are capable of removing nickel catalysts completely [48, 49]. However, it was found that nano-sized nickel particles would easily adsorb on the membrane surface, which caused the decrease of catalyst concentration in reaction slurry and led to consequent decline in membrane permeate flux. Therefore, how to select membrane with appropriate pore size for nano-sized nickel catalyst has turn to be an important issue to be solved in the application. Many models have been established for prediction of permeate flux decline. However, the accuracy of theoretical models describing the filtration process of nano-sized particles has been hampered by insufficient knowledge regarding to the complexity of fouling occurring during the filtration process. A mathematical model was established based on the analysis of hydrodynamic forces acting on a single spherical particle near the cake surface to predict the filtrate flow and layer growth [49]. The consideration of the forces requires a distinction between two cases: forces on a suspended particle in the crossflow and on a deposited particle on the membrane surface [50]. At technically relevant conditions, the flow in the membrane channel is turbulent, but the size of filtrated particles is usually smaller than the thickness of the laminar boundary layer. Two normal forces act on the suspended particle in the immediate vicinity of the membrane, which are drag force of the filtrate flow and the lift force. After particles deposit on the membrane surface, the adhesive force of interacting particles is acting on the particle additionally to the hydrodynamic forces. The deposition of a suspended particle depends on the balance between the drag force of the filtrate flow and the lift force. After they deposit, the reversibility of them depends on the balance between adhesive force and lift force. For this reason, the membrane filtration process was divided into initial membrane pore blockage and following formation of cake layer. A modified pore blockage-cake filtration model was employed to predict the time-dependent flux decline. In the modified model, the cake constructed by aggregates had a self-similar structure based on the SEM image of the nickel catalysts. The inner porosity in nickel particle aggregates was taken into consideration by estimating the fractal dimension of the aggregate (Fig. 3). The model is shown to be in excellent agreement with experimental data obtained during the crossflow filtration of suspensions through ceramic membranes over the entire course of the filtration. A suitable membrane with optimized pore size which gives the highest steady flux was obtained via calculation instead of numerous experiments.

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Figure 3

Schematic diagram of cake layer structure [49]

3.2 Optimization of ceramic membrane reactor performance After the integration of the heterogeneous catalysis with membrane separation, the reaction rate and membrane separation efficiency are highly dependent on the synergistic control of the two processes and the operation parameters. The appropriate utilization of mathematical model and simulation for the interpretation of experimental data enable the design and optimization of porous ceramic membrane reactors with sufficient capacity. 3.2.1 Synergistic control of separation and reaction A membrane reactor is a combination of a chemical reaction with a membrane process, in which reaction and separation are integrally coupled for creating synergies. With respect to the membrane reactor, the catalytic properties of the catalysts and the separation efficiency of the ceramic membrane are the two main points when evaluating the performance of the ceramic membrane reactor system, which must be taken into account integrally. How to maintain a good match between catalytic performance and separation efficiency is a hot topic of porous ceramic membrane reactors. A submerged membrane reactor was developed for the liquid-phase hydrogenation of p-nitrophenol to p-aminophenol over nickel nanoparticles with various particle morphologies obtained by hydrogen annealing at different temperatures [19]. The nickel nanoparticles annealed at different temperature showed remarkably different catalytic activity because of their specific structural properties. There was an unexpected nonlinear relationship between the nickel particle size and the flux, which was due to the changed nature of the cake layer formed on the membrane surface and the effect of pore blocking. The results from both aspects of catalysis and separation performance indicated that the nickel nanoparticles annealed at 100 C displayed a best balanced catalytic performance and separation efficiency for the submerged membrane reactor. Microsized particles such as silica and alumina were attempted to inhibit the adhesion of ultrafine catalyst particles on the contact surfaces and improve the operation stability of the membrane reactor system significantly [16, 48, 51, 52]. It was resulted from the scouring effect and the attachment of TS-1 particles on the surfaces of larger silica particles. According to the estimation of hydrodynamic forces acting on

particles, microsized particles were hard to deposit on the contact surfaces at the studied conditions and therefore a longer stable operation of the membrane reactor system was achieved. 3.2.2 Process optimization Process optimization is the discipline of adjusting a process so as to optimize some specified set of parameters without violating some constraint. The most common goals are maximizing throughput and/or efficiency and minimizing cost. This is one of the major quantitative tools in making industrial decision. The orthogonal array design or single factor optimization can be used to optimize the process parameters so as to obtain the highest reaction efficiency [17, 22, 53, 54]. For example, with respect to the phenol hydroxylation over TS-1 in a submerged ceramic membrane reactor, Lu et al. [17] investigated the effects of operation conditions including residence time, stirring rate, temperature, catalyst concentration, and molar ratio of phenol/H2O2 on the phenol conversion and the selectivity (including catechol and hydroquinone) by single factor experiments. The corresponding filtration resistances were also analyzed simultaneously. Experimental results showed that the performance of the membrane reactor depended obviously on the operation conditions. The long-term operation study under optimal operation conditions showed the membrane reactor could maintain a steady production of catechol and hydroquinone over 20 h, and was of a higher productivity than the batch reactor and the fixed-bed. 3.2.3 Mathematical model and simulation A mathematical model is a practical, reliable, and useful package for the analysis, design, scale-up, and optimization of the membrane process systems under given conditions. The important attributes of the model are its robustness and reliability in providing the best design features for a new or modernized system, besides determining optimal operating conditions and improving the efficiency of the exiting processes. The reactor performance can be modeled by formulating equations based on the reactant consumption or product formation [55, 56]. A simple design model of the submerged membrane reactor [Eq. (1)] was developed for phenol hydroxylation over TS-1 based on the material balance of the phenol under steady state and the reported kinetic studies [57].

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Y=

F E Cphenol(0) XS = A exp a VR RT
2 2

Cphenol(0) (1 X )

( CH O (0) Cphenol(0) X )

(1)

where Y is the yield, F is the feeding rate (mlmin1), VR is the reaction volume (ml), Cphenol(0) is the initial concentration of phenol in the feed (molL1), X is the phenol conversion, S is the dihydroxybenzene selectivity, A is the pre-exponential factor, Ea is the activation energy, R is the molar gas constant, T is the reaction temperature, CH2 O2 (0) is the concentration of H2O2 in the feed, and , is order of reaction with respect to phenol and H2O2. According to Eq. (1), the feeding flow rate and reactant concentration in the feed are considered as the main controlling parameters affecting the yield. Based on the developed model, the theoretical phenol conversions and yield at steady state could be calculated using the kinetic parameters obtained from the previous batch experiments. The theoretical conversions were in good agreement with the experimental data obtained in the submerged membrane reactor within relative error of 5%. The model can be used to determine the optimal experimental conditions to carry out the phenol hydroxylation over TS-1 in the submerged membrane reactor. 3.3 Membrane fouling

Membrane fouling is the main obstacle to the wide application of porous ceramic membrane reactors as it significantly affects the economic and commercial viability. The membrane flux decreases due to the membrane fouling. Thus, to make the membrane reactor operate stably, higher transmembrane pressure (TMP) and frequent membrane cleaning are needed to maintain the membrane flux, which can result in the decrease of productivity and the increases of operational costs. Fouling is inevitable but can be controlled to a certain extent based on the known fouling mechanisms. 3.3.1 Membrane fouling mechanism Many empirical and theoretical models have been proposed to describe the membrane fouling phenomena [58-64]. The simplest is the resistance-in-series model [58]. The resistances are conventionally measured through a series of filtration experiments comprising pure-water filtration, catalyst filtration, and pure-water filtration following filter cake removal, which are not always practical. Some modified models have been established to solve the problem. For example, Gander et al. [59] quoted a single resistance value, Rf, including all resistances offered other than that of the clean membrane. Some empirical models have also been proposed to describe the initial flux decline in constant pressure filtration, which imply a dependence of flux decline on the ratio of particle size to the pore diameter [60]. And some mass transport models based

on shear-induced diffusion, surface transport, and inertial migration, which is the implication of the influence of particle size and recirculation rate, or cross-flow velocity (CFV) on flux, have been developed to predict flux behavior [61, 62]. In recent years, several studies on the precise diagnosis and prediction of the membrane fouling have been carried out to obtain an efficient operation of membrane reactors. For heterogeneous catalysis, membrane fouling in porous ceramic membrane reactors is attributed to the physicochemical interactions between the reaction suspension and ceramic membrane. To date, few researches were carried out to develop membrane fouling models with respect to membrane reactors [65, 66], because the nature and extent of fouling in membrane reactors is strongly influenced by many factors: (1) reaction suspension characteristics including dissolved matter, particle size and particle size distribution; (2) membrane characteristics such as pore size, porosity, roughness, hydrophilicity/hydrophobicity, etc.; and (3) operating conditions related to cross-flow velocity, transmembrane pressure, etc [67, 68]. Here, we give two examples to explain the fouling mechanisms of porous ceramic membrane reactors for heterogeneous catalysis, involving in ultrafine TS-1 catalysts and nano-sized nickel catalysts. For the system of recovering TS-1 catalysts, fouling material are probably composed of organic matter, fine particles, unknown purities and silica sol additive which was added to the reaction slurry to inhibit the dissolution erosion of silica from the TS-1 caused by ammonia leading to deactivation of the catalyst. Adsorption of organic matter and silica additive, plugging of membrane pores, and deposition of TS-1 particles and formation of filter cakes on the membrane surface are suggested as causes for fouling. However, the dominant fouling cause and the physical or chemical interactions between these foulants are not clear, which are critical for membrane permeability and cleaning strategies. Work on the exploration of membrane fouling mechanism for recovering TS-1 catalysts was pioneered by Zhong et al [50]. They investigated the fouling mechanisms by the combination of experiment design and model analysis, which has been discussed in Section 3.1.2. They stated that organic matters involved in this reaction system were monomers, which had little effect on the permeate flux of the membrane. Membrane flux for different combinations of feed solutions such as TS-1 slurry alone, silica sol solution alone, and a mixture of TS-1 and silica sol were compared (Fig. 4). During filtration of silica sol solution alone, silica was adsorbed into membrane pores and coupled with the concentration polarization effect occurring next to the membrane surface, resulting in accumulation of silica polymers on membrane surface. When filtration of TS-1 solution alone was performed, a porous cake layer was formed. When silica sol was added to TS-1 solution, it would be adsorbed onto the surfaces of particles either in suspension or in the cake layer. Moreover, the silica additive can occupy the vacancies

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Figure 4 Membrane flux vs. operating time with different combinations of TS-1 and silica sol [50] silica sol only; TS-1 only; TS-1 + silica sol; silica sol; TS-1

between the TS-1 particles, thus a dense cake layer was formed and a noticeable flux declined. That is to say the interaction between the silica additive and TS-1 catalysts in the system played a significant role in the membrane fouling. In addition, the iron ions formed insoluble iron hydroxide precipitates on the membrane surface and enhanced the deposition of silica onto the membrane surface. Following this, they further reported what and how silica acts in porous membrane reactors [69]. The effects of different silica sources and solution environment on the membrane fouling were investigated in detail. Three main silica sources (residual silica on the catalyst particles surface during preparation, silica dissolved from TS-1 catalyst particles by ammonia solvent and silica sol) were added into the reaction slurry to inhibit the dissolution erosion of the TS-1 catalyst. The silica dissolved by ammonia has been proved to influence membrane fouling most among the three silica sources. This was because the amount of silica dissolved by ammonia was the largest, and the polymerization of silica monomers at high concentration caused colloid particles formation, leading to a dense cake layer depositing on the membrane surface. Meanwhile, the size reduction of catalyst particles caused by alkaline dissolution also increased specific resistances of cake layers. For the system of recovering nano-sized nickel catalysts, experimental results demonstrated that the adhesion of nickel particles to contact surfaces caused a rapid decline in the hydrogenation rate and membrane flux [16]. A particle in contact with a flat surface comprises two processes: first, the adhesion of particle on the surface that is kept by the physicochemical interactions; and second, the detachment of particle from the surface that is controlled by hydrodynamic interactions due to the flowing fluid [70]. In both processes, materials properties and operating parameters play an important role. Surface roughness is one of the important surface properties governing the adhesion of particles to different substrates. Rougher surfaces have more adhesion than smooth ones, so the membrane should be polished as smooth as possible. Surface

hydrophilicity is another important surface property. The hydrophilic glass was found to absorb less nickel than hydrophobic PTFE. Therefore, to decrease the adhesion of nickel, the membrane surface can be modified for more hydrophilic. During ultrafiltration, the adhesion can be inhibited by increasing crossflow velocity and adding microsized particles in nano-sized nickel suspensions [16]. 3.3.2 Membrane fouling control and membrane regeneration Even though membrane fouling is an inevitable phenomenon during membrane filtration, it can be minimized by strategies such as cleaning and choice of operating conditions. The membranes require regular cleaning to remove membrane fouling and keep the permeability loss within a given range. As the reaction suspension composition varies greatly, different membrane fouling requires different cleaning strategies. Overall, two main cleaning methods can be distinguished: chemical cleaning and mechanical cleaning. The system is treated with an appropriate acid or alkali washing, depending on the nature of the fouling layer. For severely fouled membranes, sequential use of strongly acidic and basic solutions may be necessary, including addition of bleaching agents such as sodium hypochlorite. Other aspects of chemical cleaning concern mainly temperature, chemical concentration, pH, pressure, flow and time [71]. In addition to regular cleaning with chemical solutions, mechanical cleaning of the membrane may be used, particularly if chemical cleaning does not restore the membrane flux. Increasing shear stress and cross-flow velocity on the membrane surface and backflushing are conventional physical methods used to reduce fouling and restore flux, but their effectiveness often varies with the characteristics of solutions to be filtered [72]. Tubular membrane modules could be effectively cleaned by forcing sponge balls with a slightly larger diameter than the tube to gently scrape the membrane surface, removing deposited material [73]. Sponge-ball cleaning is an effective but relatively time-consuming process,

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and thus it is performed rather infrequently. However, automatic equipment for sponge-ball cleaning has been devised and has found a limited use [74]. So far, there is no standard cleaning strategy. As discussed above, for the ammoxidation of cyclohexanone over TS-1, the main foulants are TS-1 particles, organic matter, silica polymers and iron precipitates. The cleaning of a fouled membrane can be achieved by sequential use of strongly basic and acidic solutions [50]. For the hydrogenation of p-nitrophenol over nickel, the membrane fouling is mainly caused by adhension of nickel particles. The cleaning of a fouled membrane can be achieved by use of strong acidic solutions [49]. If the restoration of flux is less than expected, the particle cleaning combined with acid cleaning is effective to fully restore membrane flux. This method can save large amount of chemical agents, and what is more, the micro-sized particles can be used repeatedly. Particularly in the case that increasing CFV and backflushing are not effective in removing cake layer, the particle-cleaning method would be a good chose. 4 INDUSTRIAL APPLICATIONS

important, because it could be an efficient and greener route [75]. Ceramic microfiltration membrane provided by Jiangsu Jiuwu High-Tech Co. Ltd. was successfully employed to remove nano-sized catalysts from the reaction slurry and the product of p-aminophenol could thus meet its purity requirement. Initially, the ceramic membrane was just used to separate the catalysts from the slurry after hydrogenation. Later, a technology of tanks-in-series reactor with membrane assisted continuous reactor was proposed. Based on the researches on many aspects of the system such as membrane reactor design, membrane fouling control and membrane regeneration, we cooperated with the company to construct a project of 5000 ta1 for p-aminophenol production in Jiangsu province of China. The technology can greatly increase the yield of p-aminophenol in unit reactor volume, decrease the product cost per unit, and so as to effectively increase the market competitive. 5 CONCLUTIONS AND OUTLOOK

Porous ceramic membrane reactor shows promise for catalysts separation and recycling process with high efficiency. It is convenient to operation and management, easy to realize automatic control, and easy to reconstruct from the traditional craft. Recently, some industrial applications have already been realized. Here, two industrial applications examples for heterogeneous catalysis are introduced as follows. One is cyclohexanone oxime production from ammoxidation of cyclohexanone over ultrafine TS-1 catalyst. The other is p-aminophenol production from p-nitrophenol hydrogenation over nano-sized nickel. Cyclohexanone oxime is the intermediate to produce caprolactam, and 90% of caprolactam is produced by the rearrangement of cyclohexanone oxime. A new method of catalytic direct ammoxidation of cyclohexanone with NH3/H2O2 to the oxime over TS-1 was recently developed. However, the separation of ultrafine catalyst became another problem to be solved in practical applications of the process. A side-stream membrane reactor was developed for the ammoxidation of cyclohexanone over TS-1 to produce cyclohexanone oxime in Hunan province of China. The recovered catalysts were recycled continuously back to the reactor and reused in the next reaction. The cleaning of a fouled membrane can be achieved by sequential use of strongly basic and acidic solutions. The conversion and selectivity of the reaction were all higher than 99.5%. The catalyst in the permeation was very low as 1 mgL1. p-Aminophenol is an important intermediate, which is mainly used in rubber industry, photosensitive material industry and so on. In view of the growing demand for p-aminophenol, direct catalytic hydrogenation of p-nitrophenol to p-aminophenol becomes

Porous ceramic membrane reactor as a developing technology has exhibited numerous advantages in heterogeneous catalysis over the conventional reactors. Significant progress has been made in terms of development of new reactor configurations, membrane design oriented process-engineering, optimization of the reactor performance, development of effective methods for controlling membrane fouling, and some industrial applications. However, further investigations are still needed to pave the way for large-scale industrial applications of porous ceramic membrane reactors. Three key issues are desired to consider: (i) mass transfer mechanism from the feed side to across the boundary layer and membrane, and then to the permeate side; (ii) synergy between membrane separation and heterogeneous catalytic reaction; and (iii) membrane fouling mechanism and fouling control. The mass transfer mechanism of substance separated through membrane is the basis of design and optimization of ceramic membranes. Currently, the significant progress has been made in membrane design and preparation. Many models have been established to apply to the optimization of process parameters and membrane microstructure. Quantitative preparation technology of ceramic membrane has already been initially established. However, there are still many problems to be solved, such as research on the interaction characteristics between ceramic membrane and the substance which transfer through a membrane, and the relationship between this interaction characteristics and macro-environment. Mass transfer models based on the synergistic effect of multiple effects on membrane surface and membrane pore, such as brownian diffusion, radial migration, shear-induced diffusion and scouring action, are desired. More studies on the cost of the membranes, their production in quantity and their reliability oriented application systems are needed. The performance and long-term operation stability are mainly attributed to the synergy between membrane

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separation and heterogeneous catalytic reaction. It is not enough to just put membrane tubes into the usual reactors. It is necessary to take into account the interaction between the catalytic reaction and membrane separation. Dual-membrane reactor, which combines the advantages of a reactor with distributed reactant addition and a reactor with catalyst separation, is expected to be a growing research area. From the industrial point of view, there are still many issues that have yet to be resolved. When the reactor is magnified from laboratory to industrial scale, the multiphase flow, the synergy between reaction and transfer in membrane reactor are complex because of the multi-scale characteristic of membrane reactor. It is difficult for choosing experimental means to realize real-time measurement of multi-scale dynamic behavior. Computational fluid dynamics (CFD) simulations is a promising approach to solve the problem discussed above. In the present CFD models, catalytic reaction and membrane separation process are considered separately. Establishment of CFD models of the coupling process are crucial. Computational simulation of micro-, meso-, macro-scale mass transfer and reaction in membrane reactors by means of CFD simulations combined with multiphase hydrodynamics and kinetic model will be another strong research area of porous ceramic membrane reactors. In recent literatures covering membrane applications to porous ceramic membrane reactors with suspended catalysts, membrane fouling is the most serious problem affecting system performance. Traditional studies on membrane fouling have been generally examined by the experimental evaluation of the flux decline behavior combined with conventional characterization means such as scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDX) and fourier transform infrared spectroscopy (FTIR). These methods are simple but can not give information on internal fouling structure or morphology or the sequential events of the fouling development. Non- invasive techniques that enable the membrane fouling or fouled membrane to be directly visualized are strongly required. Some new characterization techniques, such as 3D ultrasonic imaging technique, ultrasonic time domain reflectometry (UTDR), and Zeta potential technique can be used to directly distinguish the membrane fouling under different filtration conditions. For the large-scale applications of porous ceramic membrane reactors, real-time prediction and control of the membrane fouling is also very important for the stability of long-term operation. Therefore, fouling models that can evaluate the respective fouling contribution by the catalysts, the organics, membrane microstructure and the interactions among them are needed. In addition, fouling development can be simulated under different operation conditions, and thus the influence of various process variables on membrane fouling can be investigated. Certainly, simple and effective cleaning strategies for the membrane fouling are the urgent engineering requirement. More industrial applications for heterogeneous

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