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Assessment of wheat straw pre-treatment for oils, dyes and heavy

metals adsorption

D. Sidiras (1), F. Batzias(1), Chryssa Chandrinou(2), Maria Bidikoudi(2), Nikos Boukos(2),


Polycarpos Falaras(2), Michael Fardis(2), George Apostolopoulos(3)
(1)
Lab. Simulation of Industrial Processes, Dep. Industrial Management and Technology, Sch.
Maritime and Industry, Univ. Piraeus, 80 Karaoli & Dimitriou, GR 18534 Piraeus, Greece
Phone Number +302104142360, e-mail sidiras@unipi.gr .
(2)
Inst. Nuclear & Radiological Sciences and Technology, Energy & Safety, National Centre for
Scientific Research Demokritos GR15310 Agia Paraskevi Attikis, Greece.
(3)
Inst. Nanoscience & Nanotechnology, National Centre for Scientific Research "Demokritos",
GR15310 Agia Paraskevi Attikis, Greece.

1. Introduction Waste lignocellulosic biomass is natural adsorbent for dyes, heavy metals and
hydrocarbons from wastewater, seawater, rivers and lakes. The thermochemical treatment of
lignocellulosic waste biomass can provide low-cost adsorbents with increased sorption capacity,
biodegradability and for removing dyes, heavy metals and oil spills [1-5]. The modification of
lignocellulosic wastes can provide adsorbents with relatively high sorption capacity, biodegradability, and
cost-effectiveness for the adsorption of dyes, heavy metals and oil products [6-9]. Straws are renewable
materials for production of cellulose, glucose, bioethanol and other chemicals. Moreover, they are often
used during containment and cleanup of oil spills while the surface properties of straws play a crucial
role. Straw adsorption capacity varies due to different apparent densities of straw and its structure. The
absorption of oil depends on both, the surface properties and the interior structure of straw [10]. Literature
data shows that walnut shell [1], biomass [11], raw bagasse [12], carbonized pith bagasse [13], acetylated
sugarcane bagasse [14], peat [15-16], fatty acid grafted straw [17], carbonized fir fibers [18], barley straw
[10, 19-22], wheat straw [23], rice straw [24], rice husk [25-26], sludge, garlic and onions peels [27],
banana trunk fiber [28], and groundnut husks [29], can be used as adsorbents for oil-spills.
This paper deals with the scaling-up of the pre-treatment process. Scaling-up uses the results from
physical simulators whereas the ability to solve large-scale problems through the reproduction of the
problem in small-scale physical simulators (scale down) is examined. Problem-solving will proceed to
minimize the economic and environmental impact. The Laboratory of Simulation of Industrial Processes
produced the novel materials in the scale-up conditions, whereas their surfaces were examined with
improved analytical methods by the two collaborative Institutes of National Centre for Scientific
Research Demokritos. The pollutants adsorption by untreated and modified wheat straw was studied on
real/simulated seawater, and real lake/stream water.

2. Experimental - The wheat straw was obtained from the Kapareli village, close to the city of Thiva
(Thebes) city at the Kopaida area (former lake Kopaida) in central Greece. The moisture content of the
material was 8% w/w. After screening, the particle sizes
isolated were (a) 20.5 cm and (b) 205 cm.
The wheat straw was pre-treated by dilute maleic or
sulfuric acid hydrolysis; the acid hydrolysis process was
performed in (a) a 0.5 L glass reactor, (b) a 3.75 L batch
reactor PARR 4843 and (c) in a 20 L CHEMGLASS reactor
for scaling up. In the first case, it was pretreated in a 3.75-L
batch reactor PARR 4843 by hydrolysis catalyzed with
maleic acid (C4H4O4). The acid hydrolysis time was 0-50
min isothermal acid hydrolysis time-periods not including
the preheating time; the reaction was catalyzed by maleic
acid 0.01-0.09 M during acid hydrolysis process at a liquid-
to-solid ratio of 20:1; the liquid phase volume was 2000 mL Image 1. Field-water sampling locations (two ports for
the solid material dose (wheat straw) was 100 g. The reaction seawater, one lake and one stream): = Piraeus Port,
= Skaramaga Port, = Koumoundourou Lake, and
ending temperature was 140 180 C, reached after the 35 - P6 = Pikrodafnis Stream. Sampling period: 2013-2015.
50 min preheating time-periods, respectively. Moreover, the
wheat straw sulfuric acid hydrolysis pretreatment was
performed in a 0.5 L glass reactor as regards the small
particles and in a 20 L CHEMGLASS glass reactor for the
big particles. In the case of the 0.5 L glass reactor, the acid
hydrolysis isothermal time was 0-4 h (not including the
preheating time); the reaction was catalyzed by sulfuric acid
0.06-1.8 M at a liquid-to-solid ratio of 10:1; the liquid phase
volume (water) was 400 mL and the solid material dose
(wheat straw) was 40 g. The reaction ending temperature was
100 C reached after the 40 min preheating period. In the
case of the 20 L CHEMGLASS reactor, the acid hydrolysis
isothermal time was 4 h (not including the preheating time);
the reaction was catalyzed by sulfuric acid 0.45 M at a
liquid-to-solid ratio of 20:1; the liquid phase volume (water)
was 10 L and the solid material dose (wheat straw) was 500
g. The reaction ending temperature was 100 C reached after
the 1 h and 50 min preheating period. The 20 L Image 2: SEM image of wheat straw interior
CHEMGLASS reactor experiments resulted in a solid pretreated at 140 C, 0.09 M C4H4O4, 50 min;
residue yield equal to 55.34% w/w on dry basis. magnification (a) x75, (b) x750, (c) x7500 and (d)
The study of untreated and pre-treated wheat straw x20000.
samples by scanning electron microscopy, SEM, was carried
out at the Institute of the Nanoscience & Nanotechnology of
the National Center for Scientific Research Demokritos
using an FEI INSPECT SEM equipped with an EDAX super
ultra-thin window analyzer for energy dispersive X-ray
spectroscopy (EDS). The magnification was X75, X750,
X7,500 and X20,000.
The concentration of Methylene Blue in the solution was
obtained by measuring O.D. at 663 nm, using a HACH DR
6000 UV VIS Spectrophotometer with RFID technology.
The water and oil adsorbency, defined as the ratio of
water or oil adsorbed to dry adsorbent weight, according to
the ASTM F726-06 method, 2006, test was performed,
following the procedure of this standard method, using diesel
10 PPM produced by Hellenic Petroleum SA and crude oil.
In a 2 L vessel we put 4 g untreated or pretreated wheat
straw and 300 ml water or diesel or crude oil. In the cases of
oil spills we put 250 mL and 50 ml diesel or crude oil to Image 3: SEM image of wheat straw cross section
produce a 3 mm thickness spill. After 17 min mild agitation pretreated at 140 C, 0.09 M C4H4O4, 50 min;
the wheat straw was separated by sieves and weighted. magnification (a) x75, (b) x750, (c) x7500 and (d)
x20000.

3. Results and Discussion - As regards field-simulation of


oil spills cleaning, field-water sampling locations were selected (in cooperation with the Hellenic Center
for Marine Research - HCMR) as follows: two ports for seawater ( = Skaramagas Port and =
Piraeus Port), one lake ( = Koumoundourou Lake), and one stream (P6 = Pikrodafnis Stream). The
map of these locations is presented in Image 1. The water sampling dates covered from 2013 to 2015. The
wheat straw used herein for adsorbent was harvested during 2012 and modified during 2013-2015.
The superiority of adsorptive properties of the modified lignocellulosic biomass in comparison with
the corresponding properties of the unmodified biomass was proved experimentally by estimating the
respective methylene blue and hexavalent chromium adsorption parameters while interpretation of results
is given mainly by means of SEM spectroscopy. Some scanning electron microscopy results of acid pre-
treated wheat straw are presented in Images 2-6. More specifically, in Image 2 the SEM of wheat straw
interior pretreated by acid hydrolysis at 140 C with 0.09 M maleic acid for 50 min is shown for
magnifications x75, x750, x7500 and x20000. Similarly, in Image 3 the SEM of wheat straw cross section
pretreated at the same conditions is presented. Moreover, in Image 4 the SEM of wheat straw exterior
pretreated at 160 C with 0.09 M maleic acid for 50 min is
given. In addition, in Image 5 the SEM of wheat straw fibers
pretreated at 180 C with 0.09 M maleic acid for 25 min is
shown. Finally, in Image 6 the SEM of the untreated and
pretreated by acid hydrolysis at 100 oC with 0.45 M sulfuric
acid for 4 h wheat straw interior is presented. The straw
surface becomes rough by the intensification of the pre-
treatment conditions favoring the adsorptivity of the
material.
The rate constants and the capacity are higher for the
Methylene Blue adsorption on pretreated wheat straw as
compared to the untreated one depending also on the particle
size of the innovative adsorbent. These constants are lower
for the large particles in comparison with the small ones. On
the other hand, the large particles are more appropriate for in Image 4: SEM image of wheat straw exterior
situ applications since they need no size reduction and form pretreated at 160 C, 0.09 M C4H4O4, 50 min;
magnification (a) x75, (b) x750, (c) x7500 and (d)
easier booms and pillows for oil spill adsorption using a net x20000.
with big openings. More specifically, the oil adsorbencies on
modified wheat straw are significantly higher compared to
those on the original material. More specifically, in Images 7
and 8 the adsorbencies on untreated and sulfuric acid
modified wheat straw of diesel and crude oil spill on tap
water, lake water, stream water, seawater and substitute
seawater are given, respectively.
Acid hydrolyzed wheat straw could be made widely
available for use as an alternative to commercial adsorbents
for the removal of basic dyes, heavy metals and
hydrocarbons from water/wastewater effluents and oil spills.
Furthermore, as straw is an industrial waste and no addition
of chemicals is required, we argue that this process of
adsorbent modification may be considered to take place
within an 'Industrial Ecology' framework, since a solid waste
is used to treat another aquatic waste, contributing to
pollution abatement without entailing excessive cost [3].

4. Conclusions - The acid pre-treatment significantly


improves the wheat straw adsorptivity as regards diesel, Image 5. SEM image of wheat straw fibers
crude oil, methylene blue and hexavalent chromium. More pretreated at 180C, 0.09 M C4H4O4, 25 min;
magnification (a) x75, (b) x750, (c) x7500,and (d)
specifically, the adsorbencies on acid modified wheat straw x20000..
of diesel and crude oil spill on tap water, lake water, stream
water, seawater and substitute seawater were increased 115%
and 97%, respectively, compared to those of the untreated material.

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6. Acknowledgments - This research has been co-financed straw of crude oil spill on tap water, lake water, stream
by the European Union (European Social Fund ESF) and water, seawater and substitute seawater.
Greek national funds through the Operational Program
"Education and Lifelong Learning" of the National Strategic
Reference Framework (NSRF) - Research Funding Program: THALIS. Investing in knowledge society
through the European Social Fund. - Project: THALIS University Of Piraeus Development of New
Material from Waste Biomass for Hydrocarbons Adsorption in Aquatic Environments.