Preparation of a Zirconia-Based Ceramic Membrane and Its Application for Drinking Water Treatment

2 symmetry moPt A Article Preparation of a ZirconiaBased Ceramic Membrane and Its Application for Drinking Water Treatment Mohamed Boussemghoune Mustapha Chikhi Fouzia Balaska 1 Yasin Ozay 7 Nadir Dizge and Brahim Kebabi 1 Department of Environmental Engineering University Salah Boubnider Constantine 3 New City Ali Menjeli Constantine 25000 Algeria mustaphachikhiunivconstantine3dz MC fouziachikhiunivconstantine3dz EB 2 Department of Environmental Engineering Mersin University Mersin 33343 Turkey yozaymersinedutr YO ndizgemersinedutr ND 3 Chemical Department University Mentouri Constantine 1 Constantine 25000 Algeria brahimkebabiumcedudz Correspondence mohamedboussemghouneunivconstantine3dz Gg check for Received 20 April 2020 Accepted 6 May 2020 Published 3 June 2020 updates Abstract This work concerns the preparation of a mineral membrane by the slip casting method based on zirconium oxide ZrO2 and kaolin The membrane support is produced from a mixture of clay kaolin and calcium carbonate calcite powders using heat treatment sintering Membrane and support characterization were performed by Scanning Electron Microscopy SEM Xray Fluorescence XRF Fourier Transform Infrared Spectroscopy FTIR Xray Diffraction XRD and Raman Spectroscopy The prepared mineral membrane was tested to treat drinking water obtained from different zones of the El Athmania Algeria water station raw coagulated decanted and bio filtered water Experimental parameters such as permeate flux turbidity and total coliforms were monitored The results showed that the mineral membrane was mainly composed of SiOz and Al2O3 and the outer surface which represented the membrane support was much more porous than the inner surface where the membrane was deposited The permeate flux of the raw water decreased with filtration time due to a rejection of the organic matters contained in the raw water Moreover the absence of total coliforms in the filtrate and the increase in concentration in the concentrate indicate that the prepared mineral membrane can be used for drinking water treatment Keywords kaolin membrane ZrO flux turbidity total coliforms 1 Introduction Membrane processes are increasingly used in industrial areas covering a wide range of operating conditions and module designs Using membrane technology instead of a conventional separation or purification step that is part of an existing industrial process can reduce overall energy consumption and produce acceptable results under softer conditions In addition membrane processes generally permit continuous operation and can be combined easily with other separation processes 13 The significant development of membrane filtration processes has generated a great deal of interest in research on membrane materials Although polymeric membranes have been used in industrial areas for many years inorganic membranes also known as ceramic membranes are used for longer life considering their better chemical and mechanical stabilities compared to polymeric membranes 46 For this reason many studies have been performed in recent years to develop new types of inorganic membranes 78 The development of claybased inorganic membranes can lead to an important new technological application that will add economic value to the enormous natural deposits of clay minerals many of Symmetry 2020 12 933 doi103390sym12060933 wwwmdpicomjournalsymmetry Symmetry 2020 12 933 2 of 15 which are currently underutilized 9 Kaolins are white friable and refractory clays consisting mainly of kaolinite of the formula Al2Si2O5OH4 or aluminum silicates Al2SiO5 It was discovered in China and it is used on the basis of porcelain manufacturing and also in the ceramic industry 10 Clay kaolin is used extensively for the production of microporous tubular supports that can withstand high pressures and chemical attacks where zirconium oxide gels are deposited for the preparation of membranes 11 Ceramic membranes CM have been used in various industries such as food petrochemical chemical biotechnological pharmaceutical dairy etc 12 So far many materials such as zeolites α and γ alumina Al2O3 titania TiO2 zirconia ZrO2 silicon oxide SiO2 and microporous glasses are commonly used in the development of ceramic membranes 1314 To date various methods have been used to prepare inorganic ceramic membranes These methods include chemical extraction the solgel method solid state sintering phase separation chemical vapor deposition and synthesis methods 1517 Zirconium oxide ZrO2 was used to prepare a flexible and thermally stable porous ceramic membrane using PVdFHFP as a binder The membrane showed 60 porosity with good electrolyte uptake thermal stability of up to 400 C and substantial Liion transport number 18 Ceramic zirconium membranes were used in the separation of oilinwater emulsion 1920 Commercial alumina microfiltration membranes were coated by the nanosized ZrO2 to reduce the membrane fouling by oil droplets They reported that the modified membrane reached the steady flux in a very short time and the steady flux retained 88 of the initial flux even when oil rejection was above 978 20 The oily wastewater produced from the posttreatment unit of the refinery processes was treated using flocculation and a zirconiabased microfiltration membrane 02 µm 21 The membrane was operated at a transmembrane pressure of 011 MPa and a crossflow velocity of 256 ms The membrane filtration results showed that the membrane fouling decreased and the permeate flux as well as the permeate quality increased with flocculation as pretreatment 21 In another study Kroll et al fabricated and characterized zirconia microtubes with 16 and 10 mm outer and inner diameters respectively for bacteria filtration and digestion 22 Tubular zirconia membranes sintered with a temperature of 1050 C had an open porosity of 513 with pore sizes of 02 µm and were suitable for bacteria filtration 22 Commercial tubular zirconia membranes supported on the alumina were used for modification with two different grafting procedures 23 Different kinds of hydrophobic ceramic membranes were prepared by grafting organosilane molecules FAS on the membrane surface The hydrophobic ceramic membranes with 200 and 50 nm pore diameters were used for water desalination by membrane distillation 24 The zirconia membrane was prepared using an in situ hydrothermal crystallization technique for the separation of methyl orange dye 25 The porosity average pore size and pure water permeability of the zirconia membrane were estimated to be 42 066 µm and 144 106 m3m2 s kPa respectively The prepared membrane showed a 61 rejection of methyl orange from the aqueous solution and a high permeation flux of 228 105 m3m2 s at 68 kPa operating pressure 25 The zirconiabased ceramic composite membranes were used for the separation of whey components 26 The prepared membrane enhanced relatively high protein content 80 and low lactose retention 7 with a 40 Lm2h permeate flux value A zirconia ultrafiltration UF membrane with a mean pore diameter of 40 nm was prepared in single step coating of zirconia nanopowder suspension by the slip casting method 27 The membrane was applied for treatment of industrial tannery and domestic kitchen sink wastewater They reported that 82 and 92 removal of chemical oxygen demand COD were obtained for tannery wastewater and kitchen sink wastewater respectively Turbidity was reduced below 1 NTU for both the effluents with complete removal of pathogenic organisms 27 In this study an inexpensive tubular zirconia membrane on a low cost porous ceramic support was synthesized and characterized Kaolin powders were used to prepare the membrane support CaCO3 and Methocel were used in the support preparation as inorganic and organic additives respectively The prepared ceramic membrane and support were characterized by SEM XRF FTIR Symmetry 2020 12 933 3 of 15 XRD and Raman Spectroscopy The membrane was used to remove organic matters from drinking water The developed ceramic membrane was also tested for removal of Escherichia coli E coli Variations in the permeate flux of distilled and raw drinking water versus filtration time were investigated Moreover the characterizations of raw drinking water permeate and concentrate quality were also illustrated 2 Material and Methods 21 Characterization of Raw Kaolin Powders Table 1 shows the chemical composition of the raw kaolin determined by Xray fluorescence XRF analysis A chemical composition of kaolin powders for the ceramic membrane support showed that SiO2 Al2O3 Fe2O3 were major elements However K2O Na2O MgO P2O5 TiO2 and MnO were detected as minor elements Table 1 Chemical analysis wt of the raw kaolin Oxide Weight SiO2 55080 Al2O3 29041 Fe2O3 2813 K2O 1422 Na2O 0320 MgO 0172 CaO 0010 P2O5 0082 TiO2 0066 MnO 0014 Loss on ignition 10980 22 The Methods of the Membrane Support and Ceramic Membrane Preparation In this part we describe the methods of the membrane support from the clay powders kaolin and zirconiabased ceramic membrane preparations The clay consisted mainly of aluminum silicate Al2SiO5 intended for the manufacture of the tubular microporous support The method of tubular support preparation can be summarized in the following steps 2829 Thermal treatment of the clay material at a temperature of 400600 C for 30 min for the removal of water contained in kaolin dehydration and the combustion of organic matters Grinding of the clay material to obtain small particles Sieving of the small particles to obtain particles smaller than 125 µm Addition of kaolin 75 and calcium carbonate CaCO3 22 for the appearance of pores with an acceptable number and size in the final support Addition of an organic additive Methocel 3 to improve the elastic properties of the dough and to facilitate the formation process Mixing of the abovementioned materials with the presence of the solvent distilled water by using the mixer until a paste of good elastic properties was obtained Then the mixture was placed in a tightly closed plastic bag for 12 h to properly spread the water in the ceramic paste Extrusion of ceramic paste in tubular form Drying of the tubular support with ambient air by placing it on the machine containing the rotating cylinders to dry it uniformly and maintain its shape for 24 h Symmetry 2020 12 933 4 of 15 Sintering the components of the ceramic paste that forms the support at a temperature equal to 1100 C which will convert it to anorthite according to a series of reactions during a specific thermal program The sintering of the support was realized in the following steps First the temperature of the chamber was increased from the ambient temperature to the temperature of 250 C with a rise speed of 3 Cmin and a plateau of 15 min During this step water could be eliminated quickly Second the temperature was increased from 250 to 1100 C with a rise speed of 3 Cmin and a plateau of 60 min During this step organic matters could be removed Figure 1 Symmetry 2019 11 x FOR PEER REVIEW 4 of 16 The sintering of the support was realized in the following steps First the temperature of the chamber was increased from the ambient temperature to the temperature of 250 C with a rise speed of 3 Cmin and a plateau of 15 min During this step water could be eliminated quickly Second the temperature was increased from 250 to 1100 C with a rise speed of 3 Cmin and a plateau of 60 min During this step organic matters could be removed Figure 1 Figure 1 Thermal program used for the sintering of the support 23 The Method of the Slip Casting Membrane Preparation The method consisted of suspending zirconia and polyvinyl alcohol in distilled water and pouring the produced slip inside the porous support Figure 2 The method results in the controlled diffusion process which amounts to a simple loss of water from the suspension in the mass of the support this causes the accumulation of zirconia particles on its surface The support sintered with thermal sequences ensures that the material can withstand high pressures and chemical attacks However zircon oxide ZrO2 accumulated in the inner part of the tubular support provides the formation of selective permeable membrane The method of zirconiabased ceramic membrane preparation can be summarized in the following steps Take 70 of the distilled water and add in 4 by weight of ZrO2 powder to mix the mixture until a good homogeneous mixture was obtained Place the mixture in an ultrasonic bath for 10 min to dispel the granules and dissolve the sediments Then add 26 polyvinyl alcohol PVA and mix for 12 h to obtain the suspension solution The solution is poured into the support for 10 min and dried for 5 min Figure 1 Thermal program used for the sintering of the support 23 The Method of the Slip Casting Membrane Preparation The method consisted of suspending zirconia and polyvinyl alcohol in distilled water and pouring the produced slip inside the porous support Figure 2 The method results in the controlled diffusion process which amounts to a simple loss of water from the suspension in the mass of the support this causes the accumulation of zirconia particles on its surface The support sintered with thermal sequences ensures that the material can withstand high pressures and chemical attacks However zircon oxide ZrO2 accumulated in the inner part of the tubular support provides the formation of selective permeable membrane The method of zirconiabased ceramic membrane preparation can be summarized in the following steps Take 70 of the distilled water and add in 4 by weight of ZrO2 powder to mix the mixture until a good homogeneous mixture was obtained Place the mixture in an ultrasonic bath for 10 min to dispel the granules and dissolve the sediments Then add 26 polyvinyl alcohol PVA and mix for 12 h to obtain the suspension solution The solution is poured into the support for 10 min and dried for 5 min Symmetry 2020 12 933 5 of 15 Symmetry 2019 11 x FOR PEER REVIEW 5 of 16 Figure 2 The method for preparing the slip casting membrane 24 Experimental Setup of Filtration The prepared zirconiabased ceramic membrane was used for the treatment of drinking water obtained from Oued El Athmania water treatment plant Mila Algeria The filtration experiments were carried out using a tangential filtration system Figure 3 The total volume of the reservoir was 5 L and 3 L of drinking water was used for each experiment The effective membrane area was 45 cm2 and crossflow velocity was 418 ms The concentrate was recycled back into the feed tank and the filtered water permeate was collected in an Erlenmeyer flask for analysis The volume of filtrate was monitored as a function of time to determine the permeate flux Jp Figure 3 Experimental setup of the tangential filtration system reservoir 1 tangential membrane 2 module 3 pressure gauge 4 flowmeter 5 valve 6 pump 7 permeate 8 Figure 2 The method for preparing the slip casting membrane 24 Experimental Setup of Filtration The prepared zirconiabased ceramic membrane was used for the treatment of drinking water obtained from Oued El Athmania water treatment plant Mila Algeria The filtration experiments were carried out using a tangential filtration system Figure 3 The total volume of the reservoir was 5 L and 3 L of drinking water was used for each experiment The effective membrane area was 45 cm2 and crossflow velocity was 418 ms The concentrate was recycled back into the feed tank and the filtered water permeate was collected in an Erlenmeyer flask for analysis The volume of filtrate was monitored as a function of time to determine the permeate flux Jp Symmetry 2019 11 x FOR PEER REVIEW 5 of 16 Figure 2 The method for preparing the slip casting membrane 24 Experimental Setup of Filtration The prepared zirconiabased ceramic membrane was used for the treatment of drinking water obtained from Oued El Athmania water treatment plant Mila Algeria The filtration experiments were carried out using a tangential filtration system Figure 3 The total volume of the reservoir was 5 L and 3 L of drinking water was used for each experiment The effective membrane area was 45 cm2 and crossflow velocity was 418 ms The concentrate was recycled back into the feed tank and the filtered water permeate was collected in an Erlenmeyer flask for analysis The volume of filtrate was monitored as a function of time to determine the permeate flux Jp Figure 3 Experimental setup of the tangential filtration system reservoir 1 tangential membrane 2 module 3 pressure gauge 4 flowmeter 5 valve 6 pump 7 permeate 8 Figure 3 Experimental setup of the tangential filtration system reservoir 1 tangential membrane 2 module 3 pressure gauge 4 flowmeter 5 valve 6 pump 7 permeate 8 Symmetry 2020 12 933 6 of 15 25 Determination Method of Total Coliform Bacteria Coliform bacteria filtration experiments were also carried out by prepared ceramic membrane Coliform bacteria in water thermotolerant coliforms and E coli were investigated and counted using the most probable number MPN technique in liquid medium BCP Bromocresol Purple Lactose Broth Tubes were used for presumptive identification and enrichment of total coliforms including thermotolerant coliforms Water samples were collected in sterile glass bottles 1 L in order to detect and count the final concentration of bacteria after filtration The final reading was carried out according to the requirements of the MPN table taking into account that E Coli is a producer of gas and indole at 44 C 3 Results 31 Characterization of the Support and ZirconiaBased Ceramic Membrane The characterizations of the support and zirconiabased ceramic membrane are given in Tables 2 and 3 Table 2 The characteristics of the tubular kaolin support Properties Support Material Outside diameter 9 mm Inside diameter 46 mm Thickness 22 mm Length 190 mm Operating pH range 114 Washing pH range 114 Table 3 The characteristics of the tubular zirconiabased ceramic membrane Properties Ceramic Membrane Total area 448 103 m2 Average pore diameter 02 µm Operating pH range 114 Washing pH range 114 311 Scanning Electron Microscopy SEM Scanning Electron Microscopy allows for the observation of the morphology and cavities of the membranesupport inner and outer surfaces It should be remembered that the slip casting membrane was deposited inside the tubular support Figure 4AB show the outer surface of the support material It could be seen from the figures that there were large and irregular pores on the support layer Figure 4CD show the inner surface of the ceramic membrane The layered structure of zirconia and the asymmetric distribution of the pores can be seen from the figures Moreover crosssection images of the tubular membrane are seen in Figure 4EF The outer surface of the support had wider cavities compared to the inner surface These cavities can be considered to be an advantage for deposition or adhesion of the solution inside the module Symmetry 2020 12 933 7 of 15 Symmetry 2019 11 x FOR PEER REVIEW 7 of 16 Figure 4 SEM images of the support and ceramic membrane AB the outer surface of the support material CD the inner surface of the ceramic membrane EF crosssection of the tubular membrane 312 XRay Fluorescence XRF The XRay fluorescence analyses were carried out by a Panalytical Epsilon 3 spectrophotometer for the evaluation of the most present elements in the membrane support This energy dispersive X Ray spectrophotometer was connected to a computer using the Omnian analysis software The sample was placed under helium flow during the analysis Fluorescence Xray spectra were recorded under different excitation conditions The use of a particular filter with a potential difference and a particular current allows for the better exploration of a particular region of the spectrum For the support material the first spectrum was realized with a potential difference dp of 500 keV and a current of 1000 μA Figure 5A It allowed us to explore the region of energies up to about 4 keV For the zirconiabased ceramic membrane the second spectrum was realized with a silver filter with a thickness of 100 μ a dp of 3000 keV and a current of 300 μA Figure 5B It allows the peaks of high energy to be observed However in this case the peaks are strongly attenuated From the spectrograms of Figure 5AB excitation energy spectra in the range of 1486 to 1597 keV and 1739 to 1836 keV corresponding to atoms Al and Si respectively come from aluminum silicate Al2SiO5 the clay material Moreover in the spectrogram of Figure 5B the excitation energy spectrum of 15744 keV Figure 4 SEM images of the support and ceramic membrane AB the outer surface of the support material CD the inner surface of the ceramic membrane EF crosssection of the tubular membrane 312 Xray Fluorescence XRF The Xray fluorescence analyses were carried out by a Panalytical Epsilon 3 spectrophotometer for the evaluation of the most present elements in the membrane support This energy dispersive Xray spectrophotometer was connected to a computer using the Omnian analysis software The sample was placed under helium flow during the analysis Fluorescence Xray spectra were recorded under different excitation conditions The use of a particular filter with a potential difference and a particular current allows for the better exploration of a particular region of the spectrum For the support material the first spectrum was realized with a potential difference dp of 500 keV and a current of 1000 µA Figure 5A It allowed us to explore the region of energies up to about 4 keV For the zirconiabased ceramic membrane the second spectrum was realized with a silver filter with a thickness of 100 µ a dp of 3000 keV and a current of 300 µA Figure 5B It allows the peaks of high energy to be observed However in this case the peaks are strongly attenuated From the spectrograms of Figure 5AB excitation energy spectra in the range of 1486 to 1597 keV and 1739 to 1836 keV corresponding to atoms Al and Si respectively come from aluminum silicate Al2SiO5 the clay material Moreover in the spectrogram of Figure 5B Symmetry 2020 12 933 8 of 15 the excitation energy spectrum of 15744 keV corresponding to the zirconia atom Zr constituent of the zirconia oxide ZrO2 membrane was noted Zirconia detected in the ceramic membrane showed that zirconia had entered the structure of the support material Symmetry 2019 11 x FOR PEER REVIEW 8 of 16 excitation energy spectra in the range of 1486 to 1597 keV and 1739 to 1836 keV corresponding to atoms Al and Si respectively come from aluminum silicate Al2SiO5 the clay material Moreover in the spectrogram of Figure 5B the excitation energy spectrum of 15744 keV corresponding to the zirconia atom Zr constituent of the zirconia oxide ZrO2 membrane was noted Zirconia detected in the ceramic membrane showed that zirconia had entered the structure of the support material It was also found from the spectrograms of Figure 5CD that the clay used in the preparation of the support contained other constituents such as Mn and Fe We also noticed excitation energy spectra in the range of 35 to 4 keV which confirmed the presence of the calcium Ca It composed the calcium oxide CaO by addition of calcite CaCO3 transformed into CaO during the heat treatment of the support paste Figure 5 XRay Fluorescence XRF spectrum of the support A C D and ceramic membraneB 313 XRay Diffraction XRD The support was characterized by a Panalytical Empyrian brand diffractometer operating under the following conditions 40 mA 45 kV with monochromatic radiation Kα 154 A of copper equipped with a goniometer and an Xray detector Figure 6 represents XRD reflections of the support at a temperature of 1100 C for 1 h The main phase identified in the membrane support was the anorthite CaO Al2O3 2SiO2 which was a predominant phase This phase was very important because of its promising physical and mechanical properties 529 Figure 5 Xray Fluorescence XRF spectrum of the support ACD and ceramic membrane B It was also found from the spectrograms of Figure 5CD that the clay used in the preparation of the support contained other constituents such as Mn and Fe We also noticed excitation energy spectra in the range of 35 to 4 keV which confirmed the presence of the calcium Ca It composed the calcium oxide CaO by addition of calcite CaCO3 transformed into CaO during the heat treatment of the support paste 313 Xray Diffraction XRD The support was characterized by a Panalytical Empyrian brand diffractometer operating under the following conditions 40 mA 45 kV with monochromatic radiation Kα 154 A of copper equipped with a goniometer and an Xray detector Figure 6 represents XRD reflections of the support at a temperature of 1100 C for 1 h The main phase identified in the membrane support was the anorthite CaO Al2O3 2SiO2 which was a predominant phase This phase was very important because of its promising physical and mechanical properties 529 Symmetry 2020 12 933 9 of 15 Symmetry 2019 11 x FOR PEER REVIEW 9 of 16 Figure 6 Diffractogram of the clay support 314 FourierTransform Infrared Spectroscopy FTIR Infrared spectra were recorded on a spectrophotometer equipped with an ATR accessory Jasco FTIR4000 Infrared spectroscopy is a tool for mineralogists to characterize the crystallinity of materials by observing the relative intensities of the hydroxyl OH vibration bands and that of the SiO SiOSi AlOH and AlO in their structures 3031 The IR spectrogram of the clay support represented by Figure 7 was divided into two main zones The first peaks corresponded to high frequency bands wave numbers between 3700 and 2800 cm1 and the second peaks corresponded to the lower frequencies located in the 1500500 cm1 area The high frequency bands zone II concerned the vibration of OH hydroxyls while the low frequency bands zone I related to the SiO SiOSi AlOHAl AlOH and AlO bond networks 32 Figure 6 Diffractogram of the clay support 314 FourierTransform Infrared Spectroscopy FTIR Infrared spectra were recorded on a spectrophotometer equipped with an ATR accessory Jasco FTIR4000 Infrared spectroscopy is a tool for mineralogists to characterize the crystallinity of materials by observing the relative intensities of the hydroxyl OH vibration bands and that of the SiO SiOSi AlOH and AlO in their structures 3031 The IR spectrogram of the clay support represented by Figure 7 was divided into two main zones The first peaks corresponded to high frequency bands wave numbers between 3700 and 2800 cm1 and the second peaks corresponded to the lower frequencies located in the 1500500 cm1 area The high frequency bands zone II concerned the vibration of OH hydroxyls while the low frequency bands zone I related to the SiO SiOSi AlOHAl AlOH and AlO bond networks 32 Symmetry 2019 11 x FOR PEER REVIEW 10 of 16 Figure 7 IR spectrogram of the support The wave numbers υ of peaks and the functional groups corresponding to kaolin are summarized in Table 4 According to Table 2 in correlation with the literature it was found that the clay used as support contained the different chemical elements with different percentages such as Si Al Fe and bonds with hydroxyls which has been confirmed by several authors 3335 Table 4 Attribution of vibration bands of IR spectra of clay materials Wave Number υ in cm1 of the Clay Support Wave Number υ in cm1 Observed in Literature Kaolin Band Assignment 3670 3695 3670 ν OH interlayer ν OH grain surface 1070 1096 10101033 νSiO νSiOSi 897 875 937 912915 AlOHFe3 δAlOHAl intern with Feuillet δAlOHAl external with layer 780 760 800778 757700 SiO of Quartz AlOH 540 540 AlO 315 Raman Spectroscopy The Raman scattering spectra were collected by a Thermo Fisher DXR spectrometer equipped with an optical microscope a threegrating monochromator triple additive mode and a CCD camera Figure 7 IR spectrogram of the support Symmetry 2020 12 933 10 of 15 The wave numbers υ of peaks and the functional groups corresponding to kaolin are summarized in Table 4 According to Table 2 in correlation with the literature it was found that the clay used as support contained the different chemical elements with different percentages such as Si Al Fe and bonds with hydroxyls which has been confirmed by several authors 3335 Table 4 Attribution of vibration bands of IR spectra of clay materials Wave Number υ in cm1 of the Clay Support Wave Number υ in cm1 Observed in Literature Kaolin Band Assignment 3670 3695 ν OH interlayer 3670 ν OH grain surface 1070 1096 νSiO 10101033 νSiOSi 897 875 AlOHFe3 937 δAlOHAl intern with Feuillet 912915 δAlOHAl external with layer 780 800778 SiO of Quartz 760 757700 AlOH 540 540 AlO 315 Raman Spectroscopy The Raman scattering spectra were collected by a Thermo Fisher DXR spectrometer equipped with an optical microscope a threegrating monochromator triple additive mode and a CCD camera detector Charge Coupled Device The exciting radiation of a wavelength of 780 nm was delivered by the beam of a NIR diode laser The beam was focused with a long frontal lens 100 magnification numerical aperture of 09 over 50 µm of the sample surface The power irradiating the sample was about 10 mW The scattered retro Raman spectrum was collected in confocal mode to avoid optical artifacts particularly the signal from the glass slide above the sample cell The spectral resolution was 19 cm1 with a precision on the measurement of the best wave number only 1 cm1 Figure 8 represents the Raman spectrum of the clay support where several bands were observed We noticed the appearance of new spectra at 1694 2080 and 3372 cm1 which express the vibrations of ν CO SiH and OH respectively 36 Symmetry 2019 11 x FOR PEER REVIEW 11 of 16 detector Charge Coupled Device The exciting radiation of a wavelength of 780 nm was delivered by the beam of a NIR diode laser The beam was focused with a long frontal lens 100 magnification numerical aperture of 09 over 50 µm of the sample surface The power irradiating the sample was about 10 mW The scattered retro Raman spectrum was collected in confocal mode to avoid optical artifacts particularly the signal from the glass slide above the sample cell The spectral resolution was 19 cm1 with a precision on the measurement of the best wave number only 1 cm1 Figure 8 represents the Raman spectrum of the clay support where several bands were observed We noticed the appearance of new spectra at 1694 2080 and 3372 cm1 which express the vibrations of ν C O SiH and OH respectively 36 Figure 8 Raman spectrogram of the clay support 32 Filtration Experiments 321 Permeate Flux Variation Versus TMP and Time Figure 9A shows that the permeate flux Jp of distilled water increases with the increase in the transmembrane pressure TMP according to the Darcy law 37 The variations of the permeate flux Jp versus time using distilled and raw drinking water are presented in Figure 9B According to the obtained results it can be seen that the permeate flux for the distilled and the raw water were not of the same order This behavior can be explained by the retention of certain matters by the ceramic membrane causing a blockage of the pores which leads to the reduction of the amount of water passing through the membrane permeate The straight line for distilled water explains that the flow of water was constant over the filtration time On the other hand the permeate flux of raw drinking water decreased during the first 20 min and then became constant It could be explained by there being a certain amount of suspended matter which had deposited on the surface of the membrane Figure 8 Raman spectrogram of the clay support Symmetry 2020 12 933 11 of 15 32 Filtration Experiments 321 Permeate Flux Variation versus TMP and Time Figure 9A shows that the permeate flux Jp of distilled water increases with the increase in the transmembrane pressure TMP according to the Darcy law 37 The variations of the permeate flux Jp versus time using distilled and raw drinking water are presented in Figure 9B According to the obtained results it can be seen that the permeate flux for the distilled and the raw water were not of the same order This behavior can be explained by the retention of certain matters by the ceramic membrane causing a blockage of the pores which leads to the reduction of the amount of water passing through the membrane permeate The straight line for distilled water explains that the flow of water was constant over the filtration time On the other hand the permeate flux of raw drinking water decreased during the first 20 min and then became constant It could be explained by there being a certain amount of suspended matter which had deposited on the surface of the membrane Symmetry 2019 11 x FOR PEER REVIEW 12 of 16 Figure 9 A Variation of permeate flux Jp of distilled water versus transmembrane pressure TMP B Variation of permeate flux of distilled and raw drinking water versus filtration time at TPM 08 bar 322 Turbidity Variation Versus Time Turbidity was determined using a 2100Q portable turbidimeter proposed by Hach with a tungsten filament lamp equipped with a twodetector ratio optical system for accurate results during routine analyses It brings greater measurement sensitivity over a wider range of 0 to 1000 NTU The suspended solid in water causes turbidity The membrane filtration experiments were carried out for raw drinking water obtained from Oued El Athmania water treatment plant The turbidity of raw drinking water increased in the concentrate versus filtration time because the water was completely recycled into the feed tank Figure 10 Figure 10 Turbidity variation of the permeate and concentrate versus filtration time at TMP 08 bar The characterizations of raw drinking water permeate and concentrate quality are presented in Table 5 Figure 9 A Variation of permeate flux Jp of distilled water versus transmembrane pressure TMP B Variation of permeate flux of distilled and raw drinking water versus filtration time at TPM 08 bar 322 Turbidity Variation Versus Time Turbidity was determined using a 2100Q portable turbidimeter proposed by Hach with a tungsten filament lamp equipped with a twodetector ratio optical system for accurate results during routine analyses It brings greater measurement sensitivity over a wider range of 0 to 1000 NTU The suspended solid in water causes turbidity The membrane filtration experiments were carried out for raw drinking water obtained from Oued El Athmania water treatment plant The turbidity of raw drinking water increased in the concentrate versus filtration time because the water was completely recycled into the feed tank Figure 10 Symmetry 2019 11 x FOR PEER REVIEW 12 of 16 Figure 9 A Variation of permeate flux Jp of distilled water versus transmembrane pressure TMP B Variation of permeate flux of distilled and raw drinking water versus filtration time at TPM 08 bar 322 Turbidity Variation Versus Time Turbidity was determined using a 2100Q portable turbidimeter proposed by Hach with a tungsten filament lamp equipped with a twodetector ratio optical system for accurate results during routine analyses It brings greater measurement sensitivity over a wider range of 0 to 1000 NTU The suspended solid in water causes turbidity The membrane filtration experiments were carried out for raw drinking water obtained from Oued El Athmania water treatment plant The turbidity of raw drinking water increased in the concentrate versus filtration time because the water was completely recycled into the feed tank Figure 10 Figure 10 Turbidity variation of the permeate and concentrate versus filtration time at TMP 08 bar The characterizations of raw drinking water permeate and concentrate quality are presented in Table 5 Figure 10 Turbidity variation of the permeate and concentrate versus filtration time at TMP 08 bar Symmetry 2020 12 933 12 of 15 The characterizations of raw drinking water permeate and concentrate quality are presented in Table 5 Table 5 The properties of raw drinking water permeate and concentrate PhysicoChemical Parameters Units Raw Water Permeate Concentrate pH 835 817 839 Conductivity µScm 1120 1100 1133 Dissolved Salt Rate DSR mgL 617 610 631 Turbidity NTU 810 069 2110 Total hardness mgL 400 380 410 Phosphate PO43 mgL 007 000 016 Ammonium NH4 mgL 003 002 006 Nitrite NO2 mgL 00 00 00 Nitrate NO3 mgL 700 618 740 Ferrous iron Fe2 mgL 017 003 033 Manganese Mn2 mgL 01 00 07 Aluminum Al3 mgL 00 00 00 Zinc Zn2 mgL 043 030 060 Chloride Cl mgL 17727 17372 18081 Calcium Ca2 mgL 8417 8016 9218 323 Total Coliform Bacteria Variation versus Time Biological tests of total coliform bacteria were also performed in this work to test the retention capacity of the ceramic membrane E coli are considered as indicators of the microbial quality of drinking water 38 In the filtered water permeate the number of coliforms was equal to zero during 60 min filtration which depicted that all of the total coliforms were rejected by the zirconiabased ceramic membrane Figure 11 On the other hand in the concentrated water an increase in the number of total coliforms from 15 to 35 in 100 mL was obtained after 60 min of filtration Symmetry 2019 11 x FOR PEER REVIEW 13 of 16 Table 5 The properties of raw drinking water permeate and concentrate Physicochemical Parameters Units Raw Water Permeate Concentrate pH 835 817 839 Conductivity µScm 1120 1100 1133 Dissolved Salt Rate DSR mgL 617 610 631 Turbidity NTU 810 069 2110 Total hardness mgL 400 380 410 Phosphate PO43 mgL 007 000 016 Ammonium NH4 mgL 003 002 006 Nitrite NO2 mgL 00 00 00 Nitrate NO3 mgL 700 618 740 Ferrous iron Fe2 mgL 017 003 033 Manganese Mn2 mgL 01 00 07 Aluminum Al3 mgL 00 00 00 Zinc Zn2 mgL 043 030 060 Chloride Cl mgL 17727 17372 18081 Calcium Ca2 mgL 8417 8016 9218 323 Total Coliform Bacteria Variation Versus Time Biological tests of total coliform bacteria were also performed in this work to test the retention capacity of the ceramic membrane E coli are considered as indicators of the microbial quality of drinking water 38 In the filtered water permeate the number of coliforms was equal to zero during 60 min filtration which depicted that all of the total coliforms were rejected by the zirconia based ceramic membrane Figure 11 On the other hand in the concentrated water an increase in the number of total coliforms from 15 to 35 in 100 mL was obtained after 60 min of filtration Figure 11 Evolution of the number of total coliforms in the permeate and concentrate and versus time 4 Conclusions In this work a zirconiabased ceramic membrane with a tubular configuration was prepared by the casting method The anorthite support which had favorable physical and mechanical properties Figure 11 Evolution of the number of total coliforms in the permeate and concentrate and versus time Symmetry 2020 12 933 13 of 15 4 Conclusions In this work a zirconiabased ceramic membrane with a tubular configuration was prepared by the casting method The anorthite support which had favorable physical and mechanical properties was prepared by the extrusion method The inner layer containing smaller pores compared to the support reduced the size of the pores and eliminated defects of the support The membrane filtration results showed that there was an improvement in the physicochemical and bacteriological quality of raw drinking water The prepared membrane retained all of the total coliforms Using a ceramic membrane can help to obtain a good clarification and can reduce the addition of chemical agents such as aluminum and chlorine used for coagulation and disinfection These agents form an additional pollution such as the presence of aluminum in the sludge from the settling basin and an acceptable taste of water after the addition of a smaller amount of chlorine Author Contributions This work was carried out by the contribution of all the authors cited in this paper the author MB was interested to the experimental preparation of a Zirconiabased ceramic membrane The other authors focused on the characterization of the membrane support Xray fluorescence XRF was devoted to BK Xray diffraction and FTIR were carried out by FB Raman Spectroscopy by YO the SEM and the experimental part of filtration as well as the discussion of all the results were carried out by ND MC and MB All authors have read and agreed to the published version of the manuscript Funding This research received no external funding Acknowledgments We would like to thank Farhat Bouzerara Lecturer at the University of Jijel for his help to realize the ceramic membrane Conflicts of Interest The authors declare no conflict of interest References 1 Lee SH Chung KC Shin MC Dong JI Lee HS Auh KH Preparation of ceramic membrane and application to the crossflow microfiltration of soluble waste oil Mater Lett 2002 52 266271 CrossRef 2 Oh HK Takizawa S Ohgaki S Katayama H Oguma K Yu MJ Removal of organics and viruses using hybrid ceramic MF 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