Development and characterization of tubular composite ceramic membranes using natural alumino-silicates for microfiltration applications

https://doi.org/10.1016/j.matchar.2015.03.009Get rights and content

Highlights

  • A new and economic approach to fabricate MF membranes is proposed.

  • Clays were used instead of high purity oxides, for MF membrane fabrication.

  • The effect of sintering temperature on pore size distribution of membranes

  • The fabricated porous membrane supports were mechanically acceptable.

  • A good adhesion between fabricated supports and membranes

Abstract

The preparation and characterization of porous tubular ceramic composite microfiltration membranes, using kaolins and calcium carbonates, were reported. The porous gehlenite (2CaO·Al2O3·SiO2) and anorthite (CaO·Al2O3·2SiO2) based ceramics were obtained by a solid state reaction. A ceramic support, sintered at 1250 °C, within an average pore size of about 8 μm, a porosity of about 47% and a compression strength around 40 MPa, was prepared. The microfiltration active top layer was added on the support by a slip casting from clay powder suspensions. The novel microfiltration membrane layer has a thickness of 40 μm and an APS value of about 0.2 μm. This average pore size value was improved and considerably lower than those reported in the literature (0.5 μm). The performance of the novel microfiltration ceramic membrane was determined for evaluating both the water permeability and rejection. This proved the potentiality of the membrane produced in the microfiltration field. Moreover, the good adhesion, between the support and the active microfiltration layer membranes, was also proved. A correlation between microstructures of used powders and physicochemical properties was discussed. Finally, the origin of the unique two powder order membrane depositions was also proposed.

Introduction

The use of traditional ceramics, using raw materials instead of industrial chemicals is becoming of more and more interest mainly due to the lower price of the raw material available. Algeria is one of the countries in the world that have abundantly available raw materials, such as calcium carbonates (CaCO3)(CC), dolomite (CaCO3·MgCO3), bones (natural derived hydroxyapatite (HA): Ca10(PO4)6(OH)2), kaolin, feldspar and quartz. Many works have already been published for valorizing these native raw materials, for the production of advanced ceramics [1], [2], [3], [4], [5], [6], [7], ceramic membranes [8], [9], [10], [11], [12], [13], [14], [15], [16], [17], [18], [19] and bioceramics [20], [21], [22], [23], [24], [25], [26], [27]. In particular, in the membrane field the possibility of replacing the more expensive starting materials by cheaper raw materials to be used as a support (which constitutes about 99% of the filter mass) is significantly important from economic and energetic points of view. In fact, the price of alumina, usually employed as support, is at least 100 times greater than that of kaolin. The other important advantage is the possibility of reducing the sintering temperature from about 1600 to about 1250 °C, when alumina supports are replaced by the raw materials. Other advantages are the relatively lower theoretical density of the prepared supports (2.8 g/cm3) when compared to that of alumina (3.98 g/cm3) and the mechanical strength comparable to that of alumina [14]. Actually, a flexural strength of 87 ± 2 MPa was obtained for 100 wt.% Al2O3 samples sintered at 1620 °C for 2 h [28], while nearly the same flexural strength value (87 ± 6 MPa) was also measured for compacts sintered only at 1250 °C for 1 h, using the proposed process. In this work, novel microfiltration (MF) ceramic composite membranes, made of thinner active layer supported on a porous support, have been prepared. Inorganic membranes are gaining a lot of interest in the recent years, thanks to the development of new types of inorganic membranes [28], [29], [30], [31], [32], [33], [34], [35], [36], [37]. The inorganic membranes have excellent high thermal, chemical stability, mechanical resistance [8], [13], [38], [39], [40], [41], [42], [43], a longer life-time, ease of cleaning, a low thermal conductivity and a low dielectric constant [43], [44]. Furthermore, these membranes are found to be able to resist corrosive highly acids and alkali media as well as to withstand high pressure applications.

MF is a membrane process for concentration, purification, and fractionation in diverse fields such as food, textile, pharmacy, chemical, paper, and leather industries. MF is often used to remove particles, microorganisms, and colloidal materials from suspensions [45], [46], [47]. Consequently, preparing inorganic membranes, especially ceramic composite membranes [48], [49], [50], [51], [52], [53], [54], [55], [56], for these applications are of high interest. Several materials are usually employed for the preparation of ceramics membranes, such as alumina, zirconia and titania. However, natural raw materials, such as kaolin (chemical structure: Al2O3·2SiO2·2H2O) [57], [58] are more and more used for preparing porous ceramics membranes [9], [10], [11], [12], [59], [60], [61], [62], [63], [64], [65], [66], [67], [68] and it has been used in this work as a starting material.

This membrane is fabricated in different steps. The first step is the preparation of macro porous tubular ceramic support from the Texenna kaolin halloysite type (TKH) and 20 wt.% CC mixtures, using an extrusion method. The second step is the synthesis of intermediate membrane using a coating method. This layer is necessary to minimize the surface defects and improve the surface roughness of the membrane support for obtaining a small thickness of the top membrane layer. The thin membrane has the double advantage of reducing the cost of material needed and also of increasing the permeate flux. After sintering of the intermediate layer, a top membrane layer is subsequently deposited. The MF composite ceramic membranes were characterized for evaluating their morphology, mechanical and chemical properties. Besides, the water flux and rejection of the membranes were also determined for evaluating their potentiality in the water treatment. A correlation between microstructures of used powders and physicochemical properties was furthermore discussed. Finally, the origin of the unique 2 powder order membrane depositions was also discussed.

Section snippets

Raw materials

A natural Texenna kaolin halloysite type (TKH), a Tamazert kaolin (TK) and CC (99.6% purity) powder were used as starting materials. These raw materials were obtained from Jijel and Constantine regions (Algeria), respectively. CC powder was used as a pore former. The particle size distribution of TKH and CC material was determined by the Dynamic Laser Beam Scattering (DLBS) technique. The organic additives, Amijel and methocel (methylcellulose) were used in order to improve the rheological

Analysis of the raw materials

The SEM pictures of the powders used are shown in Fig. 2. Fig. 2a shows that this TKH crystallizes nicely in the form of naturally hallow nano-rode halloysite crystals. Furthermore, the TKH powder structure is confirmed by XRD spectrum as shown in Fig. 3. Additionally, the TK powder structure is also confirmed by XRD spectrum showed in Fig. 4. Fig. 4 illustrates the XRD pattern of the TK; it confirms that kaolinite (K), quartz (Q) and muscovite (M) are the main crystalline minerals existing in

Conclusions

In this work, ceramic multilayer membranes in a tubular configuration were prepared. It consisted of an alternative support, one intermediate layer and a top layer. Ceramic supports have been obtained by extrusion using kaolin and calcium carbonates as starting materials. The prepared supports sintered at 1250 °C offer a better mechanical strength (40 MPa compression strength), chemical stability (< 5% weight loss in acidic media and negligible weight loss in basic media) good porosity (47%),

Acknowledgments

The authors gratefully acknowledge the partial financial support received from the DGRSDT, Algeria, (Grant No 4/u250/822), and thank Prof. H. Ourag DGRSDT Director-General for equipment delivering facilities (Hg-Porosimeter, BET, FTIR, …) and his continuous encouraging on the subject.

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