Mor 2016
Mor 2016
Mor 2016
PII: S0959-6526(16)32003-0
DOI: 10.1016/j.jclepro.2016.11.142
Reference: JCLP 8531
Please cite this article as: Mor S, Manchanda CK, Kansal SK, Ravindra K, Nanosilica extraction from
processed agricultural residue using green technology, Journal of Cleaner Production (2016), doi:
10.1016/j.jclepro.2016.11.142.
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Sol-gel
Rice Husk precipitation
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nanoparticles
Cement
Dental
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Fillers Rubber
Nano
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Medicine Adsorbent
Cosmetics
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Nanosilica Extraction from Processed Agricultural Residue using Green Technology
Suman Mora,b,*, Chhavi. K. Manchandaa, Sushil. K. Kansalc , Khaiwal Ravindrad
a, b
Department of Environment Studies, Panjab University, Chandigarh 160014, India
b
Centre for Public Health, Panjab University (PU), Chandigarh 160025, India
c
Dr. S.S. Bhatanagar Institute of Chemical Engineering and Technology, Panjab
University, Chandigarh 160014, India
d
School of Public Health, Postgraduate Institute of Medical Education and Research
(PGIMER), Chandigarh 160012, India
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Abstract
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Rice Husk Ash is a major voluminous and bulky by-product of rice-milling industries and its
disposal is a major environmental concern. Considering this, a green technology was applied
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to obtain silica nano particles from Rice husk ash using sol-gel method. The solution of
sodium silicate was prepared through hydrothermal activation of Rice husk ash instead of
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commercially available expensive and sometimes toxic raw materials. Further, the
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commercial production of silica requires high temperature up to 1300C, which makes the
process energy and cost intensive. Structure, composition, morphology and size of
synthesized silica powder were studied using by various techniques. X-ray Diffractometry
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analysis revealed broad peak of silica at diffraction angle of 22confirming its amorphous and
non-crystalline nature. Fourier transform infrared spectroscopy results indicated the presence
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of silica oxygen bonding (- Si-O-Si-) at 796 cm-1 and Si-OH bonds (300-3500 cm-1).
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Scanning electron microscopy revealed the surface morphology of spheroid particles with
little agglomeration and transmission electron microscopy gave a detailed view of internal
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morphology of particles interlinked with each other and of varying size in range of 10-30 nm.
EDX analysis revealed presence of silicon and oxygen elements together comprising 99% by
weight. Hence, proposed environmental- friendly method yielded nearly ultra-pure (98.9%)
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amorphous nano silica particles at lower temperature, which can be utilized in various
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industrial applications such as for the preparation of solar cells, nano medicine, cosmetics and
filler in plastics and rubber.
Keywords: Rice Husk Ash, Acid precipitation, Calcinations, Surfactant free and Industrial
grade nano silica, Economic analysis
1. Introduction
Recent development in the field of nanotechnology has led various researches targeting the
synthesis and use of nanomaterials. Nano structured materials have wide range of application
as they can be specifically tailored owing to their exceptional physical and chemical
properties. Nanomaterials have found applications in various industries such as electronics,
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textile, agriculture, food, medicine and cosmetic industries (Alshatwi et al., 2015). At present,
various methods are used for production of nano materials but energy intensive techniques
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and complicated methodologies are major constraints for their wider use and application
(Tolba et al., 2015). Extraction of useful nano materials from abundant agricultural waste
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could be used as sustainable approach solving twin problems of environmental degradation
and economic substitute for industrial raw material.
The annual rice husk production in Asia and India accounts to 770 million tonnes and 120
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million tonne respectively. Now-a-days rice husk (RH) is mainly utilized in rice mills as a
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fuel due to its high calorific value of 1316 MJ/kg (An et al., 2010). Due to increase in fuel
oil cost, rice husk served an alternate good source of fuel to produce steam for heating
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purpose and electricity generation (Estevez et al., 2009). However, rice husk is used as an
alternate biomass, but its combustion produces large amount of ash termed as Rice Husk Ash
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(RHA). It is estimated that if an approximate of 1000 kg of paddy is milled than 220 kg that
is (22%) of husk is obtained. Rice husk is burnt in rice mills as an alternative fuel, which
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produces 25% RHA of initial total weight (Bazargan et al., 2014). RHA when enters into the
ecosystem causes air pollution, land pollution and problems such as eutrophication,
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waste water treatment and other industrial applications (Shen et al., 2014). Thus, the
extraction of silica particles from RHA offers as a green approach and help to protect the
human health and environment. Commercially used method for the silica production in
industries employs fusion of sodium carbonate and quartz at high temperature for the
preparation of sodium silicate that is further precipitated with sulphuric acid to obtain silica.
As per estimates it has been reported that for producing a ton of silica around 0.23tons of
carbon dioxide is released which sums up the greenhouse effect (Ma et al., 2012).
Considering this, current study aims to extract nano-sized silica of good purity index from
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RHA using a green and cost-effective method of hydrothermal activation at lower
temperature as compared to current methods being used for the commercial production of
silica. Thus, proposed approach not only assess the feasibility of turning agricultural by-
product in to a valuable resource but also will solve the problem of its disposal in the
environment, which otherwise results in water, air and soil pollution.
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2.1 Raw materials
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Rice milling industry uses rice husk to produce electricity and waste ash generated is
generally dumped in low-lying areas. Hence, in the current work RHA was used which was
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obtained from industry situated in Panipat. Sodium hydroxide in pellet form and
Hydrochloric acid of strength (37% w/v) was procured from Fisher Scientific. Further, the
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thermal behaviour of rice husk was studied using thermal-gravimetric analysis.
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2.2 Preparation of silica nanoparticles
RHA was sieved with standardized sieve 22 mesh size of particle size less than .71mm. After
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sieving RHA was given heat treatment at 600C for 2 h. Rice husk obtained after heating at
this temperature was light gray in colour. RHA was weighted and was subjected to
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the ratio of sodium hydroxide and RHA was adjusted to 1.2 by weight. The resultant mixture
was subjected to autoclave at 100C for 2 hours. The double distilled water was added to
above obtained mixture and resultant slurry was kept at stirring for 72 h at 80C. After this
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slurry was allowed to settle and supernatant was used for extraction of silica nano particles.
The filtrate solution predominantly contains sodium silicate and the silica was precipitated by
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hydrochloric acid. The filtrate collected from hydrothermal activation of RHA was titrated
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with 1NHCl at a very slow rate at constant temperature of 80 C and was stirred
mechanically. The white cloudy precipitate formed was collected, washed multiple times to
have pure silica. The product obtained was oven dried at 50C. The white fine powder was
stored in air- tight container for further characterization of the product. The process of
preparation of silica nanoparticles is depicted in supplementary Fig. S1.
2.3 Characterization
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Thermo gravimetric analysis was done by heating the sample in aluminium plate in the
temperature range of 27-1000C at the interval of 20C/ min (SDT/Q600). The crystalline
index and peaks identification of silica nanoparticles were examined using X-ray
diffractometer equipped with Cu-k (1.5406 ), 0.02 per second, 40 kV, (Panalytical Model
D/Max-2500). The sample extracted was analysed in the range of 5-80 of 2 diffraction
angles. FTIR analysis was done to analyze the functional groups using NICOLET (I-S50-FT-
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IR) Spectrometer. Sample was placed on diamond plate and pressed upon for analysis in the
range of 500-4000 cm-1 using 8 scans. FESEM, Hitachi SU 8010, Japan equipment was used
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to study surface features, shape and size equipped with EDX analysis tool. The field emission
scan electron microscopic graphs were taken under FE-SEM make (HITACHI SU8010)
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equipped with EDX. The sample was dispersed in absolute ethanol and ultra sonicated for 40
minutes in UV sonicator. The suspension of the dispersed sample was mounted on stub and
platinum coating was done, and then dried under lamp. It was then further analysed by
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instrument for images. The morphology and internal structure of extracted silica product was
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studied at high resolution Transmission electron microscope (TEM, HITACHI, Japan).
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Researchers have worked on various techniques for the synthesis of silica nanoparticles using
different templates to control the shape and size of the particles (Sarangi et al., 2011).
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However in this present study, a simple sol-gel technique via precipitation, template free
method was used to prepare silica nano particles using hydrochloric acid as precipitating
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agent. RHA which predominantly contains silica dissolves in sodium hydroxide solution
during treatment (Amin et al., 2016). Sodium silicate formed is used as precursor for silica
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Rice husk was subjected to thermal-gravimetric analysis to understand the thermal behaviour.
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Fig. 1 shows the curve obtained from thermal decomposition of rice husk from 27C to
1000C. The obtained curve depicts that rice husk undergoes decomposition in three different
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stages. The first stage is of dehydration that is due to loss of water (Sarangi et al., 2011). The
weight loss percentage observed was up to 2.56% up to temperature of 120C. The second
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stage shows further increase in weight loss percentage of 6.07% up to 600C. This stage
depicts relatively faster and considerable loss in weight in temperature ranging from 120C -
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600C. It is due to decomposition of hemicelluloses and cellulose which decomposes in the
range of 150C -350C (Bakar et al., 2016). The third stage of decomposition shows weight
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loss of 4.03% from 600C- 1000C. Remaining 88% residual ash is non-combustible silica
(Liou, 2004).
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As shown in Fig. 2, a wide and broad peak centred at 22 clearly indicates the presence of
silica (JCPDS 050492) and absence of other crystalline peaks confirms its amorphous nature
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(Kumar et al., 2015). Rafiee and Shahebrahimi, 2012 also found the single broad peak at 2
equals to 22. The non-appearance of sharp peak indicates the absence of any other well-
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ordered crystalline compound or structure (Liou and Yang, 2011). The diffraction peak
around 2 angles between 20 to 30 is characteristic peak of silica which is due to
disordered form of cristobalite (Liou, 2011). The results are in agreement with several other
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researchers (Adam et al., 2010; Liu et al., 2011; Sarangi et al., 2011).
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3.5 Analysis of field emission scanning electron microscopy
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The images obtained are shown in Fig. 4a and 4b. The internal morphology by micrographs
shows spheroid silica particles of nano scale. The silica particles seemed porous with an
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average diameter of 10-15 nm. FE-SEM analysis of EDX shows that the major peaks of
elements were found to be silicon and oxygen as depicted in Fig. 5. EDX analysis confirms
the purity of the silica product as silicon and oxygen constitutes 98.9%. Remaining 1.1% of
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other minor peaks may be due to carbon and platinum. Platinum peaks at energy level
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(M=2.050) is because of coating of platinum on sample while carbon peak at corresponding
energy level of K=0.277 is due to carbon adhesive tape used to mount sample on aluminium
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stub. The elemental composition of the sample as confirmed by EDX is displayed in Table 1.
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internal structure of the silica obtained. The silica particles were of spherical shape and little
agglomeration was also seen. Similar shape and morphology of silica particles with little
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average diameter of the particles was found to vary from 10-15 nanometers.
However, silica extracted from agricultural waste processed with alkali yields high purity
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silica at relatively low temperature as compared to industrially used methods. Sodium silicate
can be easily obtained from RHA by its dissolution with sodium hydroxide solution and
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silica can be easily precipitated from solution via sol-gel method (Bai et al., 2010). Many
investigations have developed techniques to extract nanosized amorphous silica from RHA
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using template (Adam et al., 2010; Le et al., 2013), however in this present investigation, no
template and surfactant is used, thus avoiding the need for calcinations. Further, nano silica
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was extracted at significantly lower temperature 80 C as compared to >1000 C, which
make the extraction process more environmental friendly.
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5. Economic and environment assessment of the process
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There are several methods reported obtaining silica from rice husk and other commercial
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common silica Therefore extraction of nanosilica using agro waste is economic and
environmentally benign (Liu et al., 2016). Table 2 summarizes the different routes followed
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for extraction of silica from rice husk. As obvious from table-2 there are four major
different routes for silica extraction from rice husk and Soltani et al., (2014) also
highlighted them. Thermal method in which rice husk is subjected to heat treatment in the
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range of 400-700C is further classified into three different routes that is alkaline treatment,
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acid leaching and through NH4F. Hydrothermal baric method involves high pressure
treatment and can be done under high and low temperatures whereas chemical treatment
involves use of different acids, alkali and other alkaline reagents. In current study alkali
route is used after thermal treatment of rice husk followed by acid precipitation. In the light
of environment restoration the present method reduces the use of toxic chemicals and high
temperature as in chemical treatment. Further the proposed method does not involve use of
high pressure and temperature as in hydro thermo baric method. In view of environmental
aspect of carbon dioxide emissions during calcinations of rice husk for ash formation, net
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emissions from burning of biomass waste are considered zero as per IPCC guidelines, 2006
(Pipatti et al., 2006).
An overview of nanosized silica production by different thermal treatment methods is
provided in table 3. Bakar et al., 2016 synthesized silica of .5-7 m size from HCl leached
rice husk ash by heating in range of 500C-900C. Silica preparation of 100-200nm scale
was done by using acid precipitation method and husk was washed with HCl prior to
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extraction using polyethylene glycol (PEG) as template by An et al., (2011). Various studies
are reported for silica preparation with the use of costly templates and surfactants and use of
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acid washing under high temperature and atmospheric pressure. However very few studies
have reported silica extraction in which use of surfactants were avoided. It can be seen in
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the comparative account that under thermal treatment and alkalization of the rice husk,
present study has eliminated the step of acid leaching and use of templates and processing
temperature is also comparatively low in order to keep the process simple and green. Also,
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the purity and nanoscale size of the silica were not compromised and yielded good
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comparative results.
Comparison of cost estimate of silica production from agro waste and industrial process is
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presented in table 4. It could be observed that this process was comparatively cheaper and
also very energy intensive as compared to commercial and industrial methods being used
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5). Considering cost price of raw materials and energy used in production of nano silica
from RHA and market selling price of commercial nanosilica of 10-20 nm range and >
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98% purity net profit of 65.75$ was estimated. Owing to industrial importance of the
element, this study provides a simple and economic approach of waste utilization and waste
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benzoic acid. The heterogeneous catalyst made was successfully employed for the conversion
of cyclohexane to cyclohexanone by Adam et al., (2009). Synthesis of nano-sized zeolites
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was achieved by extracting silica from rice husk ash by Sari et al., 2015.The suitability of
silica extracted from RHA was also investigated as dental filler and reported by Zulkifli et
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al., 2013b. Tolba et al., 2015 assessed the silica derived from RHA as an adsorbent for the
removal of methylene blue. Studies from literature suggest applicability of this value based
product in diverse fields of industry and environment.
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7. Conclusions
Nano-sized nearly ultrapure (98.9%) amorphous silica particles were obtained through simple
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step. FTIR results confirmed the presence of siloxane bonding and presence of hydroxyl
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functional groups. SEM and TEM micrographs revealed porous spherically shaped silica
particles of an average 10-15 nm diameter. Energy dispersive X-ray analysis showed the
presence of silica (40.35%) and oxygen (58.65%) in their weight percentage. Estimate cost
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production of nanosilica per kg from rice husk and its market price as a commodity shows the
process to be economical and environmentally sound. Simplicity of method, template free
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synthesis route, low-cost raw material, use of biomass waste are key features, which makes
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Acknowledgement
Author would like to thank the UGC PURSE grant and Department of Health Research
(DHR), Indian Council of Medical Research (ICMR), Ministry of Health and Family
Welfare, for providing the Fellowship Training Programme in Environmental Health under
Human Resource Development Health Research Scheme. Author is also thankful to CIL
laboratory, Panjab University Chandigarh for their help in instrumentation.
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Table1. EDX spectrum of the silica extracted from RHA
Element Atomic number Weight % Atomic %
O K 8 58.65 71.18
Si K 14 40.35 27.82
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Table 2: Summary of silica extraction routes from RHA
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Different treatment methods of rice husk for silica extraction
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Thermal treatment Hydro thermal treatment Biological Chemical treatment
treatment
CO3
With Without Addition of Addition of Greater than Less than Calcinations Heated above Heated below
pressure pressure Na2CO3 NH3:H2O 240 C 240 C at 500-700 1100 C 900 C
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Ash used Size Acid Method of Template used Temperature Purity Reference
of washing extraction Index
silica
Rice husk 100- HCl Acid PEG Room 99.6% An et al.,
ash 200 washed precipitation temperature 2011
nm prior to method
extraction
Rice husk 0.5- HCl Thermal NA 500C-900C 99.582% Bakar et
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ash .7m leached method al., 2016
Rice husk NA Acid Acid- NA 90C NA Kumar et
washing precipitation al., 2015
with 1N method
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HCl
Rice husk 60- Boiled in Calcination NA Calcined at NA Li et al.,
ash 70 HCl method 700C 2015
SC
nm solution
Rice 40- Boiled NA 70-95C NA Liu et al.,
50 and Carbonization 2011
husk Ash nm refluxed method
with
U
dilute
HCl
AN
solution
Rice husk 75- Treated Acid- No template 90C NA Zulkifli et
ash 252 with precipitation al., 2013
nm dilute method
M
HCl
Rice Husk 100- Pre- Acid 5% by weight poly Room 98.2% An et al.,
ash 200 treated precipitation ethylene glycol temperature 2010
nm with HCl method (PEG)
D
PT
Comparative Current Unit Price Commercial Unit Price
Unit Method Method
RI
Raw Rice husk ash Zero cost Sodium meta 238.13 $ per kg
materials silicate,
SC
Tetra ethyl
silicate 61.79 $ per L
U
Processing 600C - 1300-2000C -
AN
temperature
Chemicals NaOH pellets 7.42 $ per kg CO2 114.45$ per L
used 1N HCl 7.3 $ per L
M
cost/power
TE
Na OH pellet 89.04 $
Hydro choleric Acid 0.0073 $
Energy cost 0.21$
Total cost of nano silica per kg 89.257$
Market price of nano silica * 155$
*http://www.us-nano.com/inc/sdetail/411
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0.12
100
0.10
98
PT
% (TGA)
0.08
% (DTG)
96
Weight (%)
RI
0.06
94
0.04
SC
92
0.02
90
U
0.00
0 200 400 600 800 1000
AN
o
Temperature C
PT
RI
SC
Fig.2: XRD spectrum of nano silica prepared using Rice Husk Ash
U
AN
O-H bonding
M
D
TE
EP
Si-O-Si bonding
C
Fig. 3: FTIR spectrum of nano silica prepared using Rice Husk Ash
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
Fig.4: Field emission scanning electron micrographs of nano silica prepared using Rice Husk
AN
Ash [(a:400nm), (b:200nm)]
M
D
TE
C EP
C
AC
Pt
Fig. 5: EDX spectrum of the silica particles prepared using Rice Husk Ash
ACCEPTED MANUSCRIPT
(a) (b)
PT
RI
SC
Fig. 6: TEM micrographs of extracted nano silica prepared using Rice Husk Ash [(a:100nm),
(b:20nm)]
U
AN
M
D
TE
C EP
AC
ACCEPTED MANUSCRIPT
Highlights
Utilization of the agro-industry waste for the extraction of nano silica particles
Extraction method is simple, achievable at 80C and at normal atmospheric pressure
FTIR revealed presence Si-O-Si and Si-OH functional groups
PT
Green approach, as it eliminate use of template/surfactant for silica extraction also acid
washing prior to processing was also avoided.
RI
Synthesized pure amorphous silica (99%) has good industrial and commercial value
U SC
AN
M
D
TE
C EP
AC