Spruce lignocellulosic biomass alternative

treatments in packed adsorption column for

dyes removal
Cite as: AIP Conference Proceedings 2611, 130003 (2022); https://doi.org/10.1063/5.0120340
Published Online: 23 November 2022

Stephanos D. V. Giakoumatos and Odysseas N. Kopsidas

AIP Conference Proceedings 2611, 130003 (2022); https://doi.org/10.1063/5.0120340 2611, 130003

© 2022 Author(s).
 Spruce Lignocellulosic Biomass Alternative Treatments in
Packed Adsorption Column for Dyes Removal
Stephanos D.V. Giakoumatosa), Odysseas N. Kopsidas b)

Laboratory of Simulation of Industrial Processes, Department of Industrial Management and Technology,

School of Maritime and Industrial Studies, University of Piraeus, 80 Karaoli and Dimitriou,
GR 18534, Piraeus, Greece

a)Corresponding Author: sgiakou@hotmail.com, sgiakoum@unipi.gr

b)odykopsi@yahoo.gr

Abstract. In the present study, low-cost byproducts derived from forest biomass i.e. spruce sawdust, were employed to pack in
two different sizes adsorption columns. Methylene Blue (basic dye) aqueous solution was tested in three lignocellulosic spruce
states, (i) untreated, (ii) hydrolysed with brine, and (iii) acid aided hydrolysis in constant flow rate and desirable contact time, once
through in up-flow direction. The operating capacity was calculated by regulating the linear velocity in the laboratory scale
columns. The objective target was the determination of the dye removal by means of the pre-weighted packed biomass. The results
indicated that spruce sawdust undergone brine pretreatment, achieved remarkable adsorption properties and therefore discoloration
of the column effluents. The same outcome was noticed for acid aided hydrolysis which was more or less expected. Considering
the abundance, low cost and mainly the easiness to get the acquired quantities of lignocellulosic material, it is concluded that spruce
low-cost treatment could serve satisfactorily as a cost-effective adsorbent for basic dyes removal.
Keywords: adsorption, spruce sawdust, column, methylene blue, packed column, autohydrolysis

INTRODUCTION

Industrial effluents are still a major concern in industrial ecology, since significant quantities of many chemical
agents when disposed to the soil surface are inadequately treated. Dyes and pigments as residue of numerous
industrial activities such as textiles, leather, pulp & paper industry, plastic, food & pharmaceutical industry,
chemical dye & print production, might incur potentially serious environmental degradation.
Dyes are basically synthetic chemical compounds that incorporate a “Chromophore” intramolecular part which,
when exposed to the visible light, is expected to absorb and reflect a certain color. Such a highly colored compound
contains at least one chromophore substructure. The most widely applied conventional treatment techniques are
mainly flocculation/coagulation [1-3], chemical oxidation [4], and membrane separation [2]. Other promising
techniques are photocatalytic degradation [5], ultrasonic-assisted adsorption [6], irradiation [7] etc.
Coagulation is the most commonly used method in the treatment of textile wastewater and especially organic
coagulants that are considered to be the more effective ones for color removal before discharge. Nonetheless, due
to high water solubility and biodegradability of many dyes, conventional treatment techniques such as
flocculation/coagulation, chemical oxidation, membrane separation, as well as biological treatment with biomass
utilization are not always easily appliable. Furthermore, the need to achieve cost treatment reduction turn scientists
to even more simple methods where the employment of raw materials in great abundance (dyes entrapments via
physical adsorption) easy to use and low-cost solutions.
Amid numerous low-cost materials to have been proposed, certain noteworthy are rice husk, straw, sawdust,
duckweeds, gram husk, bagasse (dry pulpy fibrous remnant after sugarcane or sorghum stalks crushing) and many
others [8].

International Conference of Computational Methods in Sciences and Engineering ICCMSE 2021

AIP Conf. Proc. 2611, 130003-1–130003-16; https://doi.org/10.1063/5.0120340
Published by AIP Publishing. 978-0-7354-4247-4/$30.00

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Adsorption columns in laboratory scale, packed with physical adsorbents (Picea Abies), at a size and geometry
that correspond to the sawdust are potentially a reasonable effluent decoloring technique to aqueous solutions,
prior to physical deposits.
Numerous review papers, emphasize the importance of highly promising low-cost adsorbents to be employed in
the near future for commercial decoloring purposes. It is apparent that all these organic materials might be suitable
substitutes of commercial activated carbon in dyes removal installations [9-15].

METHODOLOGY

Material Pretreatment

The Spruce (Picea Abies) sawdust employed was obtained from a local furniture manufacturing company, as a suitable
packing material source for laboratory and full-scale/industrial applications. The moisture content was 9% (w/w).
After screening, a magnitude particle fraction within 0.2 - 0.9 mm was segregated.
Methylene Blue (CI No.52015), is a heterocyclic aromatic chemical compound with the molecular formula
C16H18N3SCl. It has many uses in a range of different fields, such as biology and chemistry. At room temperature it
appears as a solid, odorless, dark green powder, that yields a blue solution when dissolved in water. The hydrated
form comprises 3:1 molecule of water and methylene blue ratio respectively. Methylene blue should not be confused
with methyl blue, another histology stain, new methylene blue, nor with the methyl violets often used as pH indicators.
The methylene blue sulfide test is a convenient method often used in soil microbiology to quickly detect in water the
metabolic activity of sulfate reducing bacteria (SRB). Laboratory employed MB, (Merck, CI 52015),
(C16H18N3SClāH2O, molecular weight of 373.9×10-3 g mol-1) was diluted with distilled water by dissolving 5 g of
MB in 25L to give a final stock solution for the experimental doses. Further dilutions were tested under certain
experimental conditions. MB concentration in column effluent was measured by means of the absorbent values
estimated by using a HACH type DR4000U, UV-VIS spectrophotometer at wavelength Ȝ=664 nm.
Brine is a salt solution (usually sodium chloride) in water. In different context, brine may refer to salt solutions ranging
from about 3.5% (a typical concentration of seawater, or the lower solution level used for brining foods) up to about
26% (a typical saturated solution, depending on temperature). Addition of salt to water lowers the freezing temperature
of the resulted solution and the heat transport efficiency can be greatly enhanced for the comparatively low cost of the
material. The lowest freezing point is obtainable for NaCl brine at í21.1 C, (23.3wt% NaCl, H2O solution).
Dyes removal by means of activated carbon adsorption columns is the most well-established technology when colored
effluent is to be treated. Nonetheless, a hindrance is its relatively high cost [16]. Hence, it is of pivotal importance,
low-cost absorbents to be tested as alternatives to activated carbon. Various types of untreated biomass have been
reported in numerous publications to have been tested as proper material to achieve sufficient dye removal: inter alia
sawdust [16] and [17], wheat straw [18], cedar sawdust [19], rubberwood sawdust [20], kudzu [21], banana and orange
peels [22], palm kernel fiber [23], [24], peanut husk [25], graphene [26], defatted jojoba [27] and sugar beet pulp [28].
Furthermore, numerous pretreated lignocellulosic materials were used in the past to remove dyes in water and
wastewater. Pyrolyzed date seed biomass [29] and date stones [30] have proved to be effective adsorbents. Acid and
alkali-pretreated lignocellulosic materials (wheat straw, corncobs, barley husks, wood sawdust) were successfully
used as adsorbents for a variety of dyes [31], [32] and [33]. Pre-hydrolysed (with diluted sulphuric acid aquatic
solution at 100 °C) wheat straw [34] and chloride salts treated (at 100°C) beech sawdust [35], [36] have been proven
to be effective for basic dyes adsorption in batch and fixed-bed systems.
The brine treatment process was performed in a 3.75 L capacity batch reactor, type PARR 4843. The isothermal
autohydrolysis process was spruce (Picea Abies) pretreatment before the packing of the two laboratory columns. The
tested isothermal autohydrolysis time was ti = 0, 10, 20, 30, 40 and 50 min respectively (excluding non-isothermal
preheating and cooling time phases). The final temperature tested in the batch reactor, was T = 160 °C, 200 °C and
240 °C, after t = 40, 60 and 80 min preheating time values, respectively. Reactions were catalyzed by organic acids
self-released by the pine sawdust ongoing biochemical transformations during autohydrolysis at a liquid-to-solid ratio

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of 10:1; the liquid phase volume (aqueous) was 2,000 mL and the solid material dose (pine sawdust) was pre-weighted
at 200 g. A continuous stirring was taking place in the reactor with a steady speed at 150 rpm.
The autohydrolysis product was filtered by using a Büchner funnel upon which a Munktell filter paper sheet (grade
34/N) was placed to separate the two phases (liquid & solid). The solid residue was washed out with distillate water
until neutral pH to be measured. The initial filtrate pH was in between 2.90–4.76 depending on the autohydrolysis
degree. The solid residue was dried at 110 °C for 10 days and left over at room temperature until the humidity of the
untreated material to be gained gradually. At this point, it considered to be well prepared before packing.

Spruce dilute acid hydrolysis treatment was performed as well in the afore mentioned 3.75 L capacity batch reactor,
type PARR 4843. Acid aided (0.045N H2SO4) hydrolysis was tested at t = 30, 40, 50 & 60 min whereas the temperature
was at T = 160 °C. The dilute acid hydrolysis outcome was treated as described above in autohydrolysis process.

Columns Setup and experimental implementation

Stainless steel columns No 1 & 2 (FIGURE 4c & 4d) were feeding with MB (FIGURE 1) aqueous solution via a
plastic (PP) tank of 25 L capacity (FIGURE 4a). The interconnection was achieved by means of a flexible tube and
proper sealing, all made of polytetrafluoroethylene (PTFE) material. The mean packing density was 0.212 g.mL-1 and
0.277 g.mL-1 respectively. Inlet flow rate was kept steady for all series of experiments for each column i.e. an average
of 22.5 & 16.8 mL.min-1 by using a HPLC-type pump, model “LaPrep P110 - VWR - VWR International” (FIGURE
4b) so as continuous-flow experiments to be carried out. The column bed height was x = 15 and 25 cm, respectively.
Effluent samples were analyzed to yield output concentration breakthrough curves. In the case of the laboratory scale
stainless steel columns, the cross-section, both of them, was identical i.e. 4.9 cm2 (see TABLE 1) and the adsorbent
(spruce sawdust) was of an average concentration of 0.212 and 0.277 g.mL-1 respectively (TABLE 2).
Proper initial stock solution dilutions were carried out to yield the experimental inflow MB concentrations of 40, 80
& 160 mg L-1. The sampling frequency (effluent) was predetermined at a frequency of 100 mL discharge, as regards
columns No 1 & 2.

TABLE 1. Geometrical characteristics of the columns

Column Height Width Cross section Shell material Volume
No (cm) (cm) (cm2) (cm3)
1 15 2.5 4,9 Stainless steel 73.5
2 25 2.5 4,9 Stainless steel 122.5

TABLE 2. Operational characteristics of the columns

Column Inlet flow rate MB concentration Packing density Retention time Packing material -
No (mg.L-1) (mg.L-1) (g.mL-1) (min) average (g)
1 22.5 159.68 0.212 3.26 15.6
2 16.8 163.37 0.277 7.29 34.0

The effluent concentration of Methylene Blue was estimated by employing the Optical Density technique i.e. (OD)
which corresponds to the Absorbance reading at 663 nm (UV–visible spectrum), using a HACH model DR4000U
spectrophotometer (FIGURE 3).

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FIGURE 1. Methylene Blue (C16H18N3SCl) molecular
structure and molecular weight of 319.85 g.mol-1.

FIGURE 3. Packed bed effluent absorbance measurement

by using spectrophotometer HACH model DR4000U

FIGURE 2. High pressure, type PARR 4843 reactor, of FIGURE 4. (a) MB solution in 25 L feed tank (left side) (b)
3,75L capacity feeding HPLC-type pump (c) laboratory scale packed
column 15 cm (in the middle) (d) laboratory scale packed
column 25 cm (right side)

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 Continuous Fixed-Bed Adsorption Column Calculation

Theory – Adsorption Column

In fixed bed adsorption column, Ergun equation [37] could be adopted to predict the pressure drop along the length of
a packed bed given the fluid velocity, the packing size, the viscosity and density of the fluid. The assumption made,
is that the rate of adsorption is controlled by the surface binding i.e. chemical reaction or physical interaction between
adsorbate and the intact part of the column. Therefore:

adsorption rate ൌ K ‫ כ‬C ‫ כ‬C୲ ሺ1ሻ

By setting up adsorbate material balance by means of a partial differential equation and the corresponding partial
differential equation for the C୲ decrease and by incorporating the superficial velocity speed u and taking into
consideration the insignificant diffusion and accumulation, which is legitimate in chemical engineering practice, a
differential equation can be integrated over the total length of the bed x, thus:

C୲ K‫כ‬N‫כ‬x
ln ൬ െ 1൰ ൌ ln ൬exp ൬ ൰ െ 1൰ െ K ‫ כ‬C୲ ‫ כ‬t ሺ2ሻ
C u

Bohart and Adams, (B-A) model, Eq. (2), is widely used in continuous fixed-bed-column model, for breakthrough
curve depiction in environmental sorption as well as in biosorption research and is proposed to be adopted to
correspond to the adsorption experimental curve [38].

Nomenclature

K is the adsorption rate coefficient (L.mg-1.min-1) K ୘୦ Thomas kinetic coefficient (mL.min-1.mg-1)

C is the adsorbate concentration at the solid phase at C୲ intact surface adsorptive capacity at time t, mass
column distance x or the effluent conc. (mg.L-1) per bed volume or the inflow conc. (mg.L-1)
t time (min) ݉ the packed adsorbent material (g)
qୣ the adsorption capacity (mg.g-1) ܳ the volumetric flow rate (mL.min-1)
u linear velocity (cm.min-1) V volume of the untreated solution (mL)
x bed length (cm) K ୆୅ Bohart Adams kinetic coefficient (mL.min-1.mg-1)
N the initial or total adsorpt. capacity coeff. (mg.L-1) R linear correlation coefficient

୏‫୶כ୒כ‬
Considering that exp ቀ ቁ ‫ ب‬1, Eq. (2) can be simplified to the new one Eq. (3) i.e.
୳

C୲ K‫כ‬N‫כ‬x
ln ൬ െ 1൰ ൌ െ K ‫ כ‬C୲ ‫ כ‬t ሺ3ሻ
C u

which is a much easier to handle formula in estimating ‫ ܭ‬and ܰ operational parameters by implementing linear
regression (y ൌ a ൅ b ‫ כ‬tሻ analysis.
େ
That it could be implemented by depicting either a ቀln ቀ ౪ െ 1ቁ vs t ቁ graph or even a ሺt vs x ሻ, on the ground that the
େ
following reformation is adopted as regards the second graph:

1 C୲ N
t ൌ െቈ ‫ כ‬ቆln ൬ െ 1൰ቇ቉ ൅ ൬ ൰‫כ‬x ሺ4ሻ
K ‫ כ‬C୲ C u ‫ כ‬C୲

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According to Eq. (4) rearrangement, t is the time to breakthrough, i.e., the time period required for concentration to
reach a predetermined value after passing through the column. The afore mentioned equation employment, entails C୲
and u to be kept constant when wastewater is passing through beds of varied length. The scope at the present work
was numerical results to be obtained comparable with corresponding data found for other fixed bed adsorption studies
in literature, the estimation of certain parameters K, N and B-A curve testing upon the experimental data. The simplified
(B-A) formula is given as follows:
۱‫ܜ‬ ۹ ۰‫ܢ כ ۼ כ ۯ‬
‫ ܖܔ‬൬ െ ૚൰ ൌ െ ۹ ۰‫ כ ۯ‬۱‫ܜ כ ܜ‬ ሺ૞ሻ
۱ ‫ܝ‬
Where ۱‫ ܜ‬, ۱, ‫ܜ‬, ‫ܝ‬, ‫ۼ‬, ۹ ۰‫ ۯ‬were all properly defined above, Eq. (5) was transformed in (Eq. 5a).

۱‫ܜ‬
‫ ܖܔ‬൬ െ ૚൰
۱
ൌ ‫ܖܔ‬ሺ‫ۯ‬ሻ െ ‫ܜ כ ܚ‬ ሺ૞‫܉‬ሻ
Where:
r ൌ K ୆୅ ‫ כ‬C୲ ሺ6ሻ

KBA ‫୸כ୒כ‬
Aൌe ୳ ሺ7ሻ

Considering the linear formula (5a), by applying the linear regression, A can be estimated for the best fitting of
experimental values upon the theoretical curve. Finally, Eq. (5a) can be rewritten in the intermediate formula that is:

C୲
Cൌ ሺ5bሻ
1 ൅ A ‫ כ‬eି୰‫୲כ‬

Clark’s model (Eq. 9), is an advanced Bohart and Adams’ formula by incorporating the parameter n (inverse of the
slope of the Freundlich isotherm) of the Freundlich adsorption isotherm which is given below (Eq. 8) [39] [40]. Hence:
భ
q ൌ K ୊ ‫ כ‬C౤ ሺ8ሻ

Where q the weight adsorbed per unit weight of adsorbent, thus:

ଵ
C୲ ୬ିଵ ୬ିଵ
Cൌቈ ቉ ሺ9ሻ
1 ൅ A ‫ כ‬eି୰‫୲כ‬

When n ൌ 2, Eq. (9) is reduced to Eq. (5b).

2.3.2 Experimental results

Through Eq. (9), an evaluation could be made regarding the sufficient model simulation upon experimental data.
Additionally, K ୆୅ , N coefficients are also estimated for a certain packed column scale. Thus:
ଵ
C ൌ C୲ ‫ כ‬ሺ1 ൅ A ‫ כ‬eି୰‫ ୲ڄ‬ሻି ୬ିଵ ሺ10ሻ

As shown in (FIGURE 5 & 7 & 9), (FIGURE 11-14), the theoretical model expressed by Eq. (10)
sufficiently simulates the experimental data. In addition, the adsorption rate coefficient (K) and the adsorption
capacity coefficient (N), were estimated from the A and r values obtained using Eq. (5a), (6) and (7) for sawdust
pretreated with brine (auto-hydrolyzed) (TABLE 3), acid hydrolyzed (TABLE 4) and spruce untreated (TABLE
5).

For the evaluation of breakthrough results Thomas model is applied to the experimental data of the column
studies [41]. The linearized form of the Thomas model is expressed as:

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 Ct
ln ቆ െ 1ቇ ൌ K ୘୦ ‫ כ‬q ୣ ‫ כ‬m ‫ כ‬Q െ K ୘୦ ‫ כ‬C୲ ‫ כ‬t ሺ11ሻ
C

The adsorption column capacity ሺq ୣ ሻ is given below:

ሺC୲ െ Cሻ ‫ כ‬V
qୣ ൌ ሺ12ሻ
m
TABLE 3. Experimental results of Fixed Bed Adsorption Column packed with brine pretreated spruce (columns No 1 & 2)
Repetitions T t (treat.) C୲ ܳ x ݉ N ۹ ۰‫ۯ‬ R qୣ
(× Times) (treatm) (min) (mg.L-1) (mL.min-1) (cm) (g) (mg.L-1) (L.mg-1.min-1) (mg.g-1)
(oC)
1 180 50 153 18 15 20 4948 0.000353 -0.9481 18.21
2 180 50 145 21 15 20 6975 0.000242 -0.9683 25.67
4 140 0 210 21 15 12.11 8461 0.000153 -0.9616 51.42
4 160 0 156 21 15 11.7 4304 0.000694 -0.9946 27.07
4 160 50 163 21 15 20 5834 0.000300 -0.9662 21.47
4 180 0 162 21 15 11.6 6054 0.000257 -0.9744 38.41
4 180 50 151 21 15 20 5666 0.000444 -0.9479 20.85
4 200 0 155 22 15 12.3 4682 0.000866 -0.9667 28.01
4 200 50 162 21 15 14.6 9259 0.000132 -0.9390 46.67
4 200 50 148 21 15 20 7713 0.000157 -0.9232 28.38
4 220 50 157 21 15 12 5840 0.000235 -0.9863 35.82
4 200 50 160 21 15 20 9233 0.000181 -0.9466 33.97
4 240 50 162 19 15 13 1358 0.000899 -0.9237 7.69
4 240 50 153 21 15 12 451 0.000369 -0.7918 2.76
4 240 50 153 21 15 12 451 0.000369 -0.7918 2.76
8 180 0 169 21 15 12 4715 0.000212 -0.9565 28.92
8 180 50 159 17 15 17.3 7089 0.000351 -0.9211 30.16
8 180 50 141 21 15 20 5695 0.000259 -0.9799 20.96

TABLE 4. Experimental results of Fixed Bed Adsorption Column packed with acid pretreated (hydrolyzed) spruce (‫=ݔ‬15cm)
T t ܳ ݉ N ۹ ۰‫ۯ‬ R qୣ
(oC) (min) (mL.min-1) (g) (mg.L-1) (L.mg-1.min-1) (mg.g-1)
160 0 20 16.5 9643 0.000146 -0.9313 43.01
160 0 20 16.5 6492 0.000541 -0.9651 28.96
160 20 20 16.5 6362 0.000449 -0.9573 28.38
160 30 20 16.5 7176 0.000381 -0.9325 32.01
160 40 20 16.5 6092 0.000596 -0.9779 27.17
160 50 20 16.5 10412 0.000193 -0.8966 46.44
180 10 20 16.5 6926 0.000371 -0.9740 30.89
240 30 20 13.81 7355 0.000229 -0.9551 41.06
240 50 20 14.16 5389 0.000275 -0.9813 28.38

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 TABLE 5. Experimental results of Fixed Bed Adsorption Column adsorption columns (‫ ݔ‬ൌ15 & 25cm) packed with spruce
(untreated)
C୲ ܳ x ݉ N K ୆୅ R qୣ
(mg.L-1) (mL.min-1) (cm) (g) (mg.L-1) (L.mg-1.min-1) (mg.g-1)
160 20 15 12 6683 0.000318 -0.9506 40.99
160 20 15 12 7400 0.000100 -0.9367 45.38
160 20 15 13 6507 0.000356 -0.9992 36.84
160 20 15 13 6387 0.000518 -0.9539 36.16
160 20 15 13 6387 0.000518 -0.9539 36.16
160 20 15 15 5329 0.000416 -0.9153 26.14
160 20 15 19 5274 0.000415 -0.9457 20.16
160 20 15 19 5274 0.000415 -0.9457 20.16
160 20 15 20 9248 0.000110 -0.9530 19.19
160 20 15 20 8738 0.000216 -0.9765 32.15
160 40 15 20 4459 0.000515 -0.9903 16.41
160 40 25 34 5320 0.000347 -0.9892 19.19
160 20 25 34 6154 0.000243 -0.9870 22.20
80 40 25 34 4480 0.000689 -0.9911 16.16

FIGURE 5. Effluent concentration vs column operational time. Bohart & Adams model curve of a packed column 15.0×2.5
cm with sawdust spruce pretreated with brine water in 180oC, (2 & 8 repetitions), steady i.e. 21 mL min-1 MB solution inflow rate
and mean packing density 0.212 g.mL-1. The 8-repetition packing demonstrates slight superiority over the 2-repetition packing in
terms of column decoloring efficiency.

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FIGURE 6. Linearized Clark’s model for Bohart & Adams parameters ሺK୆୅ & Nሻ estimation of a packed column 15.0×2.5
cm with sawdust spruce pretreated with brine water in 180oC, (2 repetitions), steady i.e. 21 mL min-1 MB solution inflow rate and
mean packing density 0.212 g.mL-1.

FIGURE 7. Effluent concentration vs column operational time. Bohart & Adams model curve of two packed column 15.0×2.5
cm & 25.0×2.5 cm with sawdust spruce untreated and steady i.e. 21 mL min-1 MB solution inflow rate. The longer column
apparently demonstrates superiority over the shorter one since it contains greater quantities of packing material, thereof it is
expected to achieve an improved decoloring result.

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 FIGURE 8. Bohart & Adams model’s ‫ ܰ & ܭ‬parameters estimation of a packed column 15.0×2.5 cm with sawdust
spruce unpretreated, steady i.e. 21 mL min-1 MB solution inflow rate and mean packing density 0.212 g.mL-1.

FIGURE 9. Effluent concentration vs column operational time Bohart & Adams model curve of a packed column 15.0×2.5 cm
with sawdust spruce undergone hydrolysis (0.045N H2SO4, 160oC, 30 & 50 min respectively) steady i.e. 21 mL min-1 MB
(20g/100L) solution inflow rate.

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 FIGURE 10. Bohart & Adams model’s ‫ ܰ & ܭ‬parameters estimation of a packed column 15.0×2.5 cm with sawdust spruce
undergone hydrolysis (0.045N H2SO4 & 160oC for 30 min), steady i.e. 21 mL min-1 MB solution inflow rate and mean packing
density 0.212 g.mL-1.

FIGURE 11. Effluent concentration vs column operational time. Bohart & Adams model curve of packed column 15.0×2.5 cm
with twice brine treated sawdust spruce, steady i.e. 21 mL min-1 MB solution inflow rate and mean packing density 0.212 g.mL-1.

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FIGURE 12. Effluent concentration vs column operational time. Bohart & Adams model curve of packed column 15.0×2.5 cm
with twice brine treated sawdust spruce, steady i.e. 21 mL min-1 MB solution inflow rate and mean packing density 0.212 g.mL-1.

FIGURE 13. Effluent concentration vs column operational time. Bohart & Adams model curve of packed column 15.0×2.5
cm with pre-treated sawdust spruce (0.045N H2SO4, 160oC, 30min) steady i.e. 21 mL min-1 MB solution inflow rate and mean
packing density 0.212 g.mL-1.

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 FIGURE 14. Effluent concentration vs column operational time. Bohart & Adams model curve of packed column 15.0×2.5
cm with pre-treated sawdust spruce (0.045N H2SO4, 160oC, 50min) steady i.e. 21 mL min-1 MB solution inflow rate and mean
packing density 0.212 g.mL-1.

Discussion

The present manuscript demonstrates the experimental outcome of treated/untreated spruce adsorption capacity under
various operating scenarios with MB basic dye, in the laboratory scale. The very promising lignocellulosic material,
(spruce sawdust) was tested in laboratory scale, adsorption packed columns. Conclusions were drawn for potential
scaling up for industrial use. Two sizes packed columns were employed to conduct MB solution decoloring, in a
variety of experimental conditions - acid treated in different temperatures and effect time, various inflow
concentrations, column length 15 & 25cm – part of the results obtained were presented and depicted properly at
the above given FIGURES (5-7), FIGURE 9 & FIGURES (11-14).
The Bohart & Adams model was adopted to describe all 15.0×2.5cm & 25.0×2.5cm packed column breakthrough
profiles obtained at different flow rates and inlet concentrations. Breakthrough curves estimated by using the simplistic
Bohart and Adams model are considered to be in a fairly good agreement with the experimental observations. Bohart
& Adams model’s K ୆୅ & N parameters along with column adsorption capacity q ୣ was analytically estimated and
presented in TABLES 3-5 as the results of numerous conducted experimental scenarios.
Sawdust spruce acid aided hydrolysis (0.045N H2SO4, 160oC), when the processing is prolonged from 30 to 50 min
incurs a clear decoloring column’s capacity enhancement which more or less expected for the same packing
weight FIGURE 9.
Sawdust spruce pretreated twice with brine water in 180oC, when tested in packing columns, demonstrates a slight
better performance as regards decoloring capacity in comparison to the same spruce quantity, undergone the afore
mentioned brine water pretreatment 8-times. It is apparent that a repetition above a certain number reduces
the decoloring capacity FIGURE 5.
The longer column corresponds to greater adsorption packing material which explains the better decoloring
response within 100-300min operational time zone FIGURE 7. Furthermore, the longer the tube the higher
prompted packing density.

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 Conclusions

Packed-bed adsorption columns have gained great popularity amid decoloring techniques mainly for industrial dyes
removal. Great scaling up efforts have been made in laboratory designed columns to surpass operational difficulties,
concerning the proper packing size to overcome back pressure obstacles and the regeneration difficulties. The packing
material size and geometry affects severely the hydraulic column response.
The Bohart & Adams model was adopted to describe both 15.0×2.5cm & 25.0×2.5cm packed column breakthrough
profiles obtained at different flow rates and inlet concentrations. Breakthrough curves estimated by using the simplistic
Bohart and Adams model is in a fairly good agreement with the experimental observations.
Experimental results, even in small laboratory columns, indicated that spruce sawdust, through heated brine
pretreatment, achieved remarkable adsorption properties and discoloration of MB solution. Considering the
abundance, low cost and mainly the easiness to get the acquired quantities of lignocellulosic material i.e. spruce
sawdust, it is concluded that it could serve satisfactorily as a cost-effective adsorbent for basic dyes discoloration. The
use of spruce sawdust undergone special pretreatment (acid aided hydrolysis, brine effectiveness) are innovative
approaches in usage in Industrial Ecology framework and by all means compensate the cost of the additional spruce
processing.

ACKNOWLEDGMENTS

The financial support was provided by Enviroplanet Single Member Personal Company.

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