TiO2/clay Based Ceramic Membrane for Nitrate Removal by Flow

Adsorption System (Times New Roman: 14)

Is Fatimah1,*, Hijrah Purnama Putra2, Thorikul Huda3, Imam Sahroni1(Times New Roman: 11)
1
Chemistry Department, Islamic University of Indonesia
Gedung Laboratorium Terpadu, (Times New Roman: 10)

Kampus Terpadu UII, Jl. Kaliurang Km 14, Sleman, Yogyakarta, *email: isfatimah@uii.ac.id
2
Environmental Engineering Department, Faculty of Civil Engineering and Planning, Islamic University of
Indonesia
3
Professional Program of Chemical Analyst, Islamic University of Indonesia

Abstract(Times New Roman: 11)

TiO2/clay based ceramic membrane has been developed (Times New Roman: 11)for nitrate removal
from water. Granular ceramic prepared from TiO 2/clay combined with biomass was varied at the TiO 2
in relation with the physical attributes (particle size, pore size and distribution, surface roughness) of
the ceramic. Nitrate adsorption characteristics were studied in a flow system using ceramic in granular
form (20mesh) with respect to changes in initial concentration of nitrate and pH of solution. Nitrate
ion before and after adsorption were analyzed using EPA approved brucine method.
The experimental data revealed that ceramic membrane is effectively adsorbed nitrate ion at the
nitrate concentration range of 0-20mg/L by the adsorption capacity of 30-69meq/g.

Keywords: ceramic membrane, clay, adsorption, flow adsorption, adsorption capacity(Times New
Roman: 11)

Introduction(Times New Roman: 12, Spacing 1.5)

Ceramic membrane filtration is an interesting and important technique in water purification
and drinking water preservation and purification in some food industries. In drinking water
preservation, ceramic membrane filtration gaining increasing popularity due to their many
inherent advantages such as the more economic procedure(Treccani et al., 2013).
Physicochemical character of material in (Times New Roman: 12, Spacing 1.5) preparation of
ceramic membran play an important role of the filtration process. In general, performance of
any ceramic membranes mainly depends on the porous support. An excellent membrane
support should possess higher mechanical strength, higher permeability, narrow pore size
distribution and low manufacturing cost (Khemakem and Amar, 2011). Porous structure
within the membrane is the most important character directing removal of some pollutants
and microorganisms in water. Clay based material such as boehmit, mullite and kaolinite
with and without combination using photocatalyst semiconductor is the interesting
investigation area for producing low cost ceramic membrane. Due to huge potency of
Indonesian clay mineral specially kaolinite mineral, this investigation aimed to develop new
ceramic membrane made from natural kaolinite.
Refer to some investigation on the TiO 2 addition to the ceramic membrane formulation, this
work is focused on the investigation of membrane support properties by the addition TiO 2 in
the form of TiO2-Kaolinite (designated as TiO2-KAO) and its relation with nitrate reduction
from water in a flow system. The composite were investigated for its porosity, pore size
distribution, mean pore size as well as the structure and morphology analysis. The prepared
membrane supports from the combination of Ti O 2-KAO composite with other materials was
then studied by investigating the kinetics of nitrate reduction.
Material and Method (Times New Roman: 12, Spacing 1.5)
Ti-KAO was prepared by impregnating titanium with titanium isopropoxide in isopropanol
solution into natural kaolinite suspension until the theoretical content of Ti as 5% followed by
calcination at 500oC. X-ray diffraction (XRD) patterns of raw kaolinite powder and Ti O 2-
KAO were collected using a Rigaku using the Cu K. The surface morphology of the
materials was evidenced by Electron Microscopy (Seiko). The porosity and pore size of
fired capillaries were measured by porosimetry (NOVA 1200). Porous membrane was
prepared with a mixture of kaolin, ball clay, wood (Times New Roman: 12, Spacing 1.5) sawdust
in combination with Ti O2-KAO composite with Ti O2-KAO percentage of 10% w/w. The
mixture was firstly compounding by homogeneously grinding and mix with water and aging
for 24 h before was then pressed to get ceramic granule, which were then sintered at 950 o
using a programmable furnace.
Water filtration experiment was conducted with a nitrate solution at varied initial
concentration by a flow adsorption system using a coloumn filled with ceramic granule. At
each adsorption simulation, flow rate was at around 3-5mL/min. The effluent samples were
taken from certain volume sequentially and the nitrate concentration in the samples were
determined by using colorimetric brucin method using a HITACHI U-2010
spectrophotometer.
Result and Discussion(Times New Roman: 12, Spacing 1.5)
The raw material used in this work was natural kaolinite with XRD pattern as shown in Fig.
1. The pattern of kaolin shows some characteristical peaks basal reflections at about 2θ =
12.4, 20.0, 21.0 and 25.0° (JCPDS card No. 89-6538). Overall observation conveys that the
majority of the particles dominated by kaolinite. (Times New Roman: 12, Spacing 1.5) The
addition of TiO2 in ceramic membrane preparation was efforted to improve membrane
characteristics; one of them is to enhance the antibacterial activity for cleaning drinking
water. Moreover, effect of TiO2 addition to the kaolinite in the form of Ti-KAO composite
was identified by some new peaks reflecting the presence of TiO2 in anatase phase.
 Fig. 1. XRD pattern of materials(Times New Roman: 12, Spacing 1.0)
After was modified in a ceramic membrane composite, there are some phase changes
found. Some reflections correspond to the formation of mullite as result of phase transition
during high temperature calcination and some reflections correspond to anatase
transformation into rutile phase .

Fig. 2. SEM Profile of KAO and TiO2-KAO(Times New Roman: 12, Spacing 1.0)
Fig. 2. illustrates the SEM images of the membrane sintered 1050oC. The confirmation of the
phase transition is confirmed by DTA-TGA (Fig.3). (Times New Roman: 12, Spacing 1.5) An
exothermic peak attributed to the pre-dehydration process takes place at around 100-200oC,
as a result of the reorganization in the octahedral layer. Further heating until the temperature
range 450–650 °C, dehydroxylation of kaolinite and formation of metakaolinite takes place,
while at about 1000 °C, mullite was formed, as indicated by an exothermic peak(Fabbri et al.,
2013).
It is found that the morphology of the membrane was significantly changed in that it is
clearly visible that the pore size and pore structure changed after the compounding and
sintering. Effect of TiO2 addition to the composite formation to the porous structure was
identified by the presence of some granule-like form (Times New Roman: 12, Spacing 1.5) on
surface that is probably the titania particles dispersed. Surface parameters from the
adsorption-desorption analysis result was tabulated in Table 1. It can be found that the
specific surface area of porous structure in ceramic membrane composite is at around 45-
60m2/g.

Table 1. Specific surface area of porous structure in ceramic membrane composite compared
to raw material and TiO2-KAO(Times New Roman: 12, Spacing 1.0)

Sample Specific Surface Porous Structure

Area (m2/g)

KAO 9,98 Micropori

TiO2-KAO 50,98 Micropore-Mesopore

Ceramic Membrane 60,78 Micropore-Mesopore

Fig. 3. DTA profile of ceramic membran raw composite (Times New Roman: 12, Spacing 1.0)

The presence of pores in ceramic membran was utilized to reduce NO3- in a flow filtration
system. The pattern of NO3- reduction is depicted by Fig.4. Refer to that the operating
condition for membrane filtration was conducted in a stable flow rate and in atmospheric
pressure, the filtrated nitrate is (Times New Roman: 12, Spacing 1.5) strongly affected by the
formation of porous membrane structure. This is also proofen by the comparison of nitrate
uptake capacity (30-69.8mg/g) of ceramic prepared with TiO 2-KAO to that without TiO2-
KAO(11.5mg/g). Another reason is the presence of titania particles that attract nitrate anions
refer to similar preparation using metal in sintering process (Daub et al., 1999; Daub et al.,
2001).
 Fig. 4. The pattern of NO3- reduction by ceramic membrane(Times New Roman: 12, Spacing
1.0)

Conclusion(Times New Roman: 12, Spacing 1.5)

Ceramic membrane based on TiO2-Kaolinite Clay was successfully synthesized and the
membrane filtration performances were tested for nitrate reduction. From the
physicochemical characterization it was found that the membrane has the better porous
structure as well as specific surface area. From the kinetic data of flow adsorption, the present
study provides information that membrane will allow more efficient nitrate uptake from
water in association with the presence of titania particles in the surface.
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