Polymer-Plastics Technology and Engineering

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Animation of Wood Sawdust for Removing Anionic

Dyes from Aqueous Solutions

N. A. Ibrahim , A. Hashem & M. H. Abou-Shosha

To cite this article: N. A. Ibrahim , A. Hashem & M. H. Abou-Shosha (1997) Animation of Wood
Sawdust for Removing Anionic Dyes from Aqueous Solutions, Polymer-Plastics Technology and
Engineering, 36:6, 963-971, DOI: 10.1080/03602559708000673

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 P0LYM.-PLAST. TECHNOL. ENG.,36(6),963-971 (1997)

AMINATION OF WOOD SAWDUST FOR REMOVING

ANIONIC DYES FROM AQUEOUS SOLUTIONS
N. A. IBRAHIM, A. HASHEM,
and M. H. ABOU-SHOSHA
Polymer-Plastics Technology and Engineering 1997.36:963-971.

National Research Centre

Textile Research Division
Dokki, Cairo, Egypt

Abstract

Inexpensive and efficient cellulose-based adsorbents were pre-

pared by the reaction of cross-linked polyethylenimine (CPEI)
with an agricultural waste (i.e., wood sawdust). Factors affecting
the extent of amination, such a CPEI concentration, pH, time,
and temperature of reaction as well as sawdust particle size range,
were studied. The obtained adsorbents were found to be highly
effective for removal of anionic dyestuffs (i.e., direct, reactive,
and acid dyes) from aqueous solutions. The presence of CPEI on
and/or within the purified sawdust provides cationic active sites
(i.e., amino groups) and enhances the substantivity of wood cellu-
lose for anionic dyes, thereby improving the percent color re-
moval.

K e y Words: Sawdust; Polyethyleneimine; Adsorption; Dye re-

moval.
INTRODUCTION

Dyeing and/or printing processes have faced increasing pressure re-

garding environmental and waste-related concerns as a result of the
quantity and toxicity of generated wastewaters (1-3). Dye wastewater
is high in volume (i.e., spent dye bath and wash water) and pollutant
963

Copyright 0 1997 by Marcel Dekker, Inc.

 964 IBRAHIM, HASHEM, AND ABOU-SHOSHA

load (e.g., some intact dye, hydrolyzed dye, acids or alkalies, auxilia-
ries, surfactants, salts, heavy metals, etc.) ( 4 3 ) . The removal of dyes
from the dyehouse effluent has been given a top priority due to aesthetic
and health concerns.
Recently, many treatment methods have been used to remove the
dye component from the textile effluent [e.g., membrane filtration (6),
coagulation (7), adsorption (8,9), oxidation (2, lo), ion exchange
(11-13), precipitation (7), etc. have been reported (6-13)], but few of
them were accepted due to cost, low efficiency, and inapplicability to
a wide variety of dyes.
Polymer-Plastics Technology and Engineering 1997.36:963-971.

Accordingly, the present work is undertaken with a view of (a) study-

ing factors affecting preparation of an effective and economically attrac-
tive adsorbent based on aminated wood sawdust and (b) using the ob-
tained adsorbents for removal of anionic dyestuffs (i.e., direct, reactive
and acid dyes) from aqueous solutions.

EXPERIMENTAL
Materials

Wood sawdust substrate was used. Cross-linked polyethylenimine

(CPEI) having a nitrogen content of 2.67%(14) (Solidgen@R) was kindly
supplied by Hoechst . Commercial anionic dyestuffs, namely Solophe-
nyP Red 3BL (direct, Ciba), RemazoP Brill. Red GD (reactive,
Hoechst), and Kiton@Scarlet 4 (acid, Ciba) were used without further
purification. A nonionic wetting agent (SunaptoP DB) was kindly sup-
plied by Francolor, France.

Method
Purification of Sawdust

Wood sawdust was used after treating with NaOH (25 g/L) and non-
ionic wetting agent (2 g/L) in a stationary autoclave, under pressure
(1.7 kp/cm2) at 120-130°C for 2 h using a material-to-liquor ratio of
1: 15. The alkali-treated sawdust was purified from water-soluble con-
taminants using boiling water, neutralized with dilute hydrochloric acid
solution, thoroughly washed to remove residual acidity, dried at am-
bient conditions, and, finally, sieved into discrete particle size
ranges (15).
 AMINATION OF SAWDUST TO REMOVE DYES 965

Amination of Sawdust

Modification was carried out by treating the purified sawdust with

SoIidgenB R by the exhaust method in an aqueous medium of pH 6.0
at 50°C for 45 min using a material-to-liquor ratio of 1 : 10. At the end
of reaction, the aminated samples were then filtered, thoroughly
washed with distilled water to remove unreacted cross-linked polyeth-
ylenimine (16), dried at 95°C for 2 h, and then placed over PzOs for 24
h before nitrogen analysis using the Kjeldahl method (14).
Polymer-Plastics Technology and Engineering 1997.36:963-971.

Removal of Anionic Dyes

The modified sawdust of constant particle size range and 100 mg/L
dye solution of pH 3.0 (adjusted with HCI) were shaken (135 rpm) at
25°C for 30 min using a material-to-liquor ratio of 1 :250. The substrate
was then filtered on a sintered glass crucible, and the concentration of
residual dye in the filtrate was determined colorimetrically using Cal
Zeiss Jenas UV spectrophotometer, Germany, at a wavelength of,,,A
(corresponding to the maximum wavelength of absorbance).

RESULTS AND DISCUSSION

The results obtained from studying such factors affecting the extent of
modification (%N) of wood sawdust and the effect of the latter on the
percentage color removal along with appropriate discussions follow.

Cross-linked Polyethylenimine Concentration

Table 1 shows the effect of Solidgens R concentration on the extent

of modification, expressed as %N, of the used substrate. It is clear that
for a given set of modifying conditions, increasing the polyethylenimine
concentration in the treating bath up to 100% (based on weight of sub-
strate) brings about a significant improvement in the %N. This is a
direct consequence of (a) the high substantivity of the used CPEI to
cellulose and (b) the increased extent of CPEI retention in or on the
wood cellulose substrate via a great number of hydrogen-bonding be-
tween PEI molecules and cellulose, Van der Waal’s forces (18) and/or
chemically via reaction between amino groups in CPEI and carbonyl
or carboxyl groups present or formed in the purified sawdust (19).
 966 IBRAHIM, HASHEM, AND ABOU-SHOSHA

TABLE 1
Dependence of the Extent of Modification (%N)on the Concentration of the
CPEI and Its Effect on Percentage Color Removal
Color removal (%)
~

CPEI N Solophenyl@ RemazoP Kiton@

(% ows) (%I Red 3BL Brill. Red GD Scarlet 4R
0.00 0.00 14.3 2.1 0.00
20 0.115 72.5 65.2 59.5
40 0.241 90.4 88.5 81.9
Polymer-Plastics Technology and Engineering 1997.36:963-971.

60 0.375 94.3 93.3 90.5

80 0.510 94.9 93.8 92.1
100 0.660 95.4 94.5 93.9
Note: Amination: Particle size range (425-500 pm); temperature = 50°C; time = 45
min; pH = 6; liquor ratio (LR) = 1 : 10.
Decolonzation: Dye (100 mg/L); pH = 3; rate of shaking = 135 rpm; time = 30 min,
temperature = 25°C. ows: based on weight of substrate.

Further, Table 1 shows the percentage removal of the used anionic

dyes as a function of the extent of modification ( % N ) . It is clear that
within the range examined, increasing the %N of the modified sawdust
up to 0.241 brings about a sharp increase in the dye sorptivity, regard-
less of the used anionic dye (i.e., the higher the extent of modification,
the greater is the percentage removal of the dye anions). This indicates
that the presence of accessible sorptive sites (i.e., reactive amino
groups) onto the cellulose structure seems to (i) enhance the accessibil-
ity and reactivity of the used substrate thereby improving the dye up-
take, (ii) improve the swellability of the modified substrate thereby
assisting diffusion and penetration of dye anions and/or molecules
within the cellulose structure, and (iii) affording positive active sites
thereby allowing sorption of more anions from the dye solution (20-22).
The ultimate effect of the aforementioned factors along with other phys-
ical bonds would certainly cause greater dye removability.
Further increases in %N of the modified substrate up to 0.375 brings
about a slight increase in the percentage dye removal; then, the latter
tends to level off at a higher nitrogen content, regardless of the anionic
dye used. This is a direct consequence of the shortage in the accessible
 AMINATION OF SAWDUST TO REMOVE DYES 967

sorptive sites on the modified substrate along with a depletion in the

dye anions and/or molecules in aqueous solutions of the dyes used.
On the other hand, the differences in the percentage of dye remova-
bility upon using different anionic dyes (Table l ) are probably due to
differences in chemical nature, molecular size, functionality, and de-
gree of affinity and substantivity toward the substrate used (22-24).

pH of Treating Bath

Table 2 shows the extent of modification ( % N ) as a function of pH. It

Polymer-Plastics Technology and Engineering 1997.36:963-971.

is clear that lowering the pH from 8 down to 4.5 brings about a slight
increase in % N . This could be associated with increasing the extent of
interaction between the cellulose anion and cross-linked PEI as a weak
base via salt linkages, in addition to other physical bonds. On the other
hand, for a given set of conditions, increasing the %N of aminated
sawdust from 0.310 up to 0.449 has only a slight effect on the percentage
color removal, irrespective of the anionic dye used.

Effect of Time

Table 3 shows the effect of treating time on the extent of amination

(%N) of the modified wood sawdust. It is clear that, within the range

TABLE 2
Dependence of the Extent of Modification ( % N ) on the pH of Treating Bath,
and Its Effect on the Percentage Color Removal
Color removal (%)
~~

N SolophenyP RemazoP Kiton@

PH (%I Red 3BL Brill. Red GD Scarlet 4R
8 0.310 93.1 91.8 89.8
6 0.375 94.3 93.3 90.5
5 0.416 94.5 93.9 91 .O
4.5 0.439 94.8 94.3 91.5
N o f e : Amination: CPEI (60% owls), particle size range (425-500 pm); temperature
= 50°C; time = 45 min; LR = 1 : 10.
Decolorization: Dye (100 mg/L); pH = 3; rate of shaking = 135 rpm; time = 30 min;
temperature = 25°C. ows: based on weight of subtrate.
 968 IBRAHIM, HASHEM, AND ABOU-SHOSHA

TABLE 3
Dependence of the Extent of Modification ( % N ) on the Time of Amination,
and Its Effect on the Color Removal
Color removal (%)
Time N Solophenylg Remazola Kitong
(rnin) (%I Red 3BL Brill. Red GD Scarlet 4R
15 0.298 92.6 91 .O 88.6
30 0.329 93.8 93.0 89.9
45 0.375 94.3 93.3 90.5
Polymer-Plastics Technology and Engineering 1997.36:963-971.

60 0.390 94.7 93.8 90.9

Note: Amination: Particle size range (425-500 pm); temperature = 50°C; CPEI (60%
ows); pH = 6; LR = 1 : 10. Decolorization: Dye (100 mg/L); pH = 3; rate of shaking
= 135 rpm; time = 30 min, temperature = 25°C. ows: based on weight of substance.

examined (15-60 min), prolonging the treatment time is accompanied

by a slight increase in the %N. It is understandable that sufficient time
is needed for transformation, adsorption, diffusion, and penetration,
as well as retention of the cross-linked PEI on and/or within the wood
cellulose by hydrogen bonding, entanglement, and electrostatic bonds
between the cellulose anion [Cell*O- J and the protonated nitrogen atom
+
of the tertiary amino groups of the cross-linked PEI [P-Nm]
I
according to

Cell-0- + P-N + -AM---, Cell-0-N

I -P (1)
I I
rather than by covalent linkage (18,26).
On the other hand, the higher percentage dye removal observed with
higher %N, regardless of the anionic dye used, could be explained in
terms of higher availability of sorptive cationic sites as well as substan-
tivity of aminated wood cellulose for anionic dye [D*S03-J according
to the following equations (21,23):

Cell-OWN
I
I
-P +H + - pH3
Cell.0 N
-
I +
I
m P (2)
 AMINATION OF SAWDUST TO REMOVE DYES 969

I f I
Cell-0-N-P + D*S03- -+CelbO-N-P (3)
I I
DSO3

Effect of Temperature

It is clear (Table 4) that within the range examined (25-75"C), raising the
treating temperature from 25°C to 50°C brings about an enhancement in
the extent of modification (%A'). This is a direct consequence of (i)
Polymer-Plastics Technology and Engineering 1997.36:963-971.

opening up the cellulose structure, (ii) enhancing the mobility and ex-
tent of penetration of cross-linked PEI within the sawdust structure,
and (iii) overcoming the activation energy barrier of the amination pro-
cess, thereby enhancing and increasing the extent of retention of cross-
linked PEI on and/or in the treated sawdust (26). Further increases in
the treating temperature have no significant effect on the %N. This is
probably attributed to the encapsulation of sawdust particles by PEI
film, thereby hindering the extent of picking up and/or retention of
additional PET [i.e., minimizing the extent of modification (%N)].
Based on the percentage color removal as a function of the extent
of modification, it is evident (Table 4) that the ability of the aminated
sawdust to pick up, entrap, as well as to remove dye anions from aque-
ous solutions enhances by increasing the %N from 0.209 up to 0.375,
then leveling off.

TABLE 4
Dependence of the Extent of Modification (%N)on the Treating Temperature,
and Its Effect on the Percentage Color Removal
Color removal (%)
Temp. N SolophenyP RemazoP Kiton@
("C) Red 3BL Brill. Red GD Scarlet 4R
25 0.209 90.1 88.0 86.1
50 0.375 94.3 93.3 90.5
75 0.398 95.1 94.3 91.9
Note: Amination: Particle size range (425-500 Wm); CPEI (60% ows); time = 45 min;
pH = 6; LR = 1 : 10. Decolorization: Dye (100 mg/L); pH = 3; rate of shaking = 135
rpm; time = 30 min, temperature = 25°C. ows: based on weight of substance.
 970 IBRAHIM, HASHEM, AND ABOU-SHOSHA

TABLE 5
Dependence of the Extent of Modification ( % N ) on the Particle Size Range,
and Its Effect on Percentage Color Removal
Color removal (%)
Particle size
range N Solopheny P RemazoP Kiton@
(w-d Red 3BL Brill. Red GD Scarlet 4R
180-2 12 0.460 96.1 95.5 94.6
212-355 0.428 95.7 94.6 93.6
355-425 0.406 94.9 93.8 92.7
Polymer-Plastics Technology and Engineering 1997.36:963-971.

425-500 0.375 94.3 93.3 90.5

Note: Amination: CPEI (60% ows); temperature = 50°C; time = 45 min; pH = 6;
LR = 1: 10. Decolorization: Dye (100 mg/L); pH = 3; rate of shaking = 135 rpm;time
= 30 min, temperature = 25°C. ows: based on weight of substance.

Effect of Particle Size

The influence of sawdust particle size on the extent of modification

(%N) and, subsequently, on the percentage removal is given in Table
5 . It is clear that within the range examined (180-500 pn), the smaller
the wood sawdust particle size range, the greater is the %N of the
aminated substrate, which consequently results in producing modified
structure with higher dye receptivity, thereby enhancing the extent of
removing dye anions from aqueous solutions, regardless of the anionic
dye used. On the other hand, this enhancement in both %Nand percent-
age color removal could be interpreted in terms of the larger exter-
nal surface areas of the smaller particle size available for mass
transfer (27).

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