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World of Coal Ash (WOCA) Conference - May 9-12, 2011, in Denver, CO, USA

http://www.flyash.info/

Fly Ash Substrates for Complex Wastewater


Treatment
Maria Visa1, Mihaela Nacu1 Radu Adrian Carcel1
1
Transilvania University of Brasov, RTD Dept. Renewable Energy Systems and
Recycling, Romania, Eroilor 29, 500036 Brasov

KEYWORDS: fly ash, wastewater, cadmium, copper, dyes adsorption

ABSTRACT

Dyeing and finishing processes applied in the textile industry are among the most
common source of surface water pollution. The waste water resulted in the dye industry
contains a mixture of pollutants with variable structure, including dyes, heavy metals,
surfactants. To remove these toxic compounds, the design of a treatment plant must
combine adsorption on mixed substrates or adsorption with photo-catalysis or other
advance treatment process.

For understanding the complex process involving many pollutants, preliminary tests on
binary (dye heavy metal) and ternary (dye and two heavy metals) were developed and
are presented. Experiments were done on synthetic wastewaters containing methyl
orange, cadmium and copper, using alkali modified fly ash.

The adsorption mechanisms are corroborated with the ash structure (XRD) and surface
morphology (AFM). The dye, cadmium and copper adsorption isotherms on modified fly
ash can be described using the Freundlich isotherm, proving the heterogeneous
distribution of the active sites with different affinity on the substrate.

The adsorption efficiency was studied on systems with different pollutant concentrations
and the optimized conditions (contact time, amount of substrate for 50mL of pollutant)
were evaluated in batch experiments using fly ash dispersions. Higher heavy metal
removal efficiencies were obtained in dye containing systems, comparing to the
systems without dyes proving that the dye acts as complexion agent.

1. INTRODUCTION

Heavy metals and dyes are common pollutants, resulting from specific industries
(electroplating, fertilizers, pesticides, pigments manufacturing and textile dye finishing)
in huge amounts of wastewaters, with compositions ranging from tenth up to thousands
of mg/L. For avoiding flora, fauna and health problems, the discharge limits are strict
and require advanced wastewater treatment processes.

Depending on the initial composition, many alternatives are proposed: adsorption,


chemical precipitation, coagulation and flocculation, ion-exchange, reverse osmosis,
membrane nanofiltration4, photo-degradation using wide band gap semiconductors:
TiO22, WO326 choosing one or a complex of solutions is subject of efficiency and cost
analysis. Among these, adsorption technologies have several advantages: easy
operation and well known technology, inexpensive equipments, less sludge, adsorbents
reuse after desorption.

For fulfilling the industrial requirements, low-cost adsorbents are intensively studied,
mainly based on natural compounds or on wastes. Heavy metals (cadmium, cooper,
zinc, nickel, iron) and dyes (methylen blue and methyl orange)23,24,25 removal was
reported on inorganic oxides (natural zeolites11,19 , red mud20 resulted from the
aluminium processing)18,6, wheat straw, or barley husks5. Organic artificial or synthetic
wastes are also reported for these applications, like, bone char7 scrap rubber8, humus21
or bituminous coal.

Ash, resulting from coal burning coal is a mixture of oxides with unburned carbon, with a
predominant negative surface charge, having thus a good affinity for cations or polar
substances/pollutants. The ash resulted from biomass (wood) burning has a larger
amount of carbon but preserves the negative surface charge due to the oxides.

Part of the oxides in fly ash are water soluble, therefore, washing the substrate before
use is a prerequisite. Even so, the result is a rather heterogeneous surface with variable
composition from one batch of fly ash to another, depending on the coal properties and
burning conditions. Therefore, a further conditioning process must be developed to
obtain a substrate with a larger degree of reproducibility. Previous studies proved the
efficiency of alkali modified fly ash and optimized conditions were identified for cadmium
and copper removal25.

Previous studies investigated FA as substrate for heavy metals (cadmium, cooper, zinc,
nickel) and dyes (methylen blue and methyl orange) removal, from mono, - bi or three-
component (Cu2+, Cd2+, Ni2+ and MB) wastewaters, resulted from the dye finishing
industry. The results showed that raw fly ash has limited efficiency, thus the surface of
fly ash was modified with 1N, 2N, 4N NaOH solution25 with NaOH and Methylen Blue24
and with Methyl Orange23.

The CET Brasov is a CPH plant which works with two boilers (420 t/h capacity) and two
turbo-aggregates which generate 50 MW/each. Every year 6*105 tons of coal is burned
and the fly ash resulted is 2*105 tons/year. Part of the ash is used in cement
manufacturing but large amounts are still free and represent a major pollutions source.
One possible application is to develop alternative processes (like wastewater
treatment), involving the use of this waste.

This paper presents a comparative study developed on fly ash (collected from the CET
Brasov, Romania CHP), investigating the efficiency and optimization in removing heavy
metals cations (cadmium and/or cooper) and methyl orange (MO) from multi-component
solution.
The fly ash was conditioned by washing and by optimized alkali treatment and the
efficiency of these two substrates is kinetically and thermodynamically discussed.
2. ADSORPTION EXPERIMENTS

2.1. THE SUBSTRATES

We collected only fly ash, from the electro-filters (FA-ELF).

Raw fly ash was analysed by S.C. Prospecting S.A. Bucharest, Roman using AAS
(Al2O3, Fe2O3, CaO, MgO, K2O, Na2O, MnO), gravimety (SiO2, SO3, PC) and
colorimetry (TiO2 and P2O5) methods.

The major oxides from fly ash with role in heavy metals and dyes removal are presented
in Table 1. Using emission spectrometry other metals were also identified in small
amounts (Ba, Cu, Sn, Pb, Cr, Ni, V, Zn, Ti).

According to the ASTM standards, the raw fly ash (FA-ELF) pertains of class F because
the sum of the SiO2, Al2O3 and Fe2O3 is above 70%14. This has as direct consequence
the lack of agglomeration in water (and in any water environment with reduced CaO-
derivates content), with positive influence on the use of this powder as adsorbent.

Table 1. Raw fly ash composition


FA Composition [%]
SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O TiO2 MnO LOI*
53.32 22.05 8.97 5.24 2.44 2.66 0.63 1.07 0.08 1.58
*LOI: loss of ignition

The fly ash was washed in ultra pure water, by stirring 200 g fly ash with 2000 mL ultra
pure water, at room temperature (20-250C), for 48 h, till the filtrate solution had constant
values of pH (10.2), and conductivity (1.710 mS/cm) with a TDS value of 850 mg/L. The
washed fly ash was dried at 105-1200C, till constant mass and this substrate is further
denominated as FA-W.

Part of FA-W was further conditioned by stirring 48 h in with NaOH solution 2N (mFA-W :
VNaOH2N = 1:10 g/mL), followed by filtration washing and drying and this substrate was
notated (FA-NaOH).

Both FA-W and FA-NAOH were separately sieved and the 40-100m fractions were
selected as substrate for experiments.

The FA crystalline structure was evaluated by XRD (Bruker D8 Discover Diffractometer)


and for morphology studies the images AFM were take using (Ntegra Spectra, NT-MDT
model BL222RNTE). The surface area of the fly ash was measured by using Analyser
Tri Star II 3020 Micromeritics, Debaser flow Prep 060- micromerics.
2.2 ADSORPTION EXPERIMENTS

Two series of tests were done on multicomponent solutions of Cd2+, 0700 mg/L,
(CdCl2, Scharlau Chemie), Cu2+, 0320 mg/L, (CuCl2, Scharlau Chemie), Methyl
orange (MO) C14H14N3SO3Na, Merck), 0 - 1.999 mmol/L. The first set of experiments
used FA-W as substrate and the second set used FA-NaOH.

In both applications, the mixtures were stirred up to 240 min at room temperature, then
the substrate was removed by vacuum filtration and the supernatant was analyzed.

Heavy metals concentration was measured using AAS (Analytic Jena, ZEEnit 700), at
Cd = 228.8nm, Cu = 324.75, while MO quantitative analysis was done by uv-vis
spectroscopy at max = 464 nm (Perkin Elmer Lambda 25).

3. RESULTS AND DISCUSSION

3.1. THE SUBSTRATES

The silicon-alumininous composition in the ash was confirmed by XRD spectra, Fig. 1.
The major components of both ashes are: carbon (graphite), SiO2 (quartz) combined
with Al2O3, (as rhombo H, mullite (3Al2O3.2SiO5), cristobalite and -Al2O3), hematite
(Fe2O3) and MnO2 (ramsdellite), along with bixbyite (Mn2O3), TiO2 brookite. The traces
of Cd2+, (0.00166 mg/l), and Cu2+ (0.00033 mg/L) were founded in washed water of fly
ash.

The unburned carbon graphite, and carbon hexagonal (chaoite or white), along with
compounds as micro-sized crystallites represents a significant part of the FA and can
explain the versatility of this material in adsorption processes of heavy metals, dyes and
surfactants10.

9000 SiO2quartz
Cgraphit FA-NaOH
8000 FA-W
7000
maghemite Fe2O3
6000 Hematite Al2O3, SiO2cristobalite
Intensity [a.u.]

5000
Cchaoitehexagonal (2)
4000
Cchaoitehexagonal
3000 Al2O3,

2000
(1)
1000
20 30 40 50 60 70 80
2 theta [degree]
Fig. 1 XRD of raw FA-W and modified with NaOH 2N (FA-NaOH)
The FA-NaOH specific surface is 10.95 m2/g, and has an average pore diameter of
25nm. During long time washing under stirring in ultra pure water, the soluble alkaline
oxides, (K2O, Na2O, MgO, CaO) from raw fly ash were removed from the substrate in
the solution, thus the pH raised up to 10.2, conductivity up to 1.710 and TDS up to 850,
and a new surface appears with various roughness values, Fig. 2, good for adsorption
heavy metals and dyes. This is confirmed also by the roughness decrease, ranging from
72.7 nm (FA-W), down to 30.5 nm (FA-NaOH). The changes in morphology are evident
and the surface leveling is obvious the result of preferential dissolution of the high
energy sites.

Based on the results presented by Otero et al17. AFM data were used to get
supplementary information about the FA pore association, density and size distribution,
Fig. 3. The surface data show large mesopores, which are filled during the dye
adsorption, Fig. 3. Still, the roughness after adsorption is increased, supporting the idea
of preferential adsorption on corners and edges.

One may conclude that there are adsorption sites with different affinity for the pollutants,
both on FA-W and on Fa-NaOH. This effect is more pronounced on FA-W, with very
large pores and, consequently, with lower specific surface.

(a) FA -W (b) FA - NaOH (c) FA - NaOH after


Average Roughness: Average Roughness: adsorption
72.7nm 30.5 nm Average Roughness: 98.9
nm

Fig. 2 The AFM topography and average roughness


FA C ET N aOH FA-W
FA C ET N aOH M O FA-N aO H after adsorption
Counts [a.u.]

Counts [a.u.]
0 50 100 150 200 250 300 0 250 500 750 100 0
M e s o p o re s d ia m e te r [n m ] M eso p ores d iam eter [n m ]

a) FA-NaOH before and after adsorption b) FA-W before and after adsorption

Fig. 3 The pore size distribution

3.2. UPTAKE KINETICS OF THE HEAVY METALS AND METHYL ORANGE

For metal removal kinetics studies, the metal uptake qe (mg/g) was evaluated by using
i t
the initial and current heavy metal concentrations ( ccation and ccation ), in a given solution
volume, V, for a given amount ms of FA (eq. 1):

i t
( c cation - c cation )V
qe = ms (1)

Kinetics of heavy metals adsorption was modelled by the follows equations:

- pseudo first-order Lagergren equation13,

KL
t
log (q0 qt) = log (q0) 2,303 (2)

where KL is the Lagergreen constant, and qt the metal uptake at moment, t.

- pseudo-second order reaction model, developed by Ho and McKay9 :

t 1 t
= +
q t k 2 q e2 q e
(3)

where k2 is the equilibrium rate constant for the pseudo second-order adsorption
(g mg-1min-1) and can be evaluated from the slope of the plot.

While the first model corresponds to a substrate with very high affinity for the adsorbed
species, the second one describes a process where the concentration of both
participants (adsorbent adsorbed specie) is of the same order of magnitude and
supports the idea of binary interactions. The model is mentioned in literature for heavy
metals24 including Cu2+.

A third adsorption mechanism is likely on porous substrates, the interparticle diffusion


model, described by1.

q = k id t 1/2 + C (4)

Good results were previously reported by22, in pollutants removal from binary
component solutions, when the most likely model proved to be the pseudo-second order
kinetics:

(Cd2++MO /FA-NaOH 2N), with qe = 16.921 [mg/g] and k2 = 0.0972 [g/mg min]

and (Cu2+ MO /FA-NaOH 2N) with: qe = 14.880 [mg/g] and k2 = 0.1046 [g/mg min].

These data show that the systems containing MO have almost constant kinetic
parameters for heavy metal removal, as consequence of the uniform surface resulted
from the dye adsorption on FA.

The adsorption processes of pollutants from more component systems (three in the
experiments here presented) can be well fitted using the pseudo second rate, for all the
investigated systems. The results are presented in Table 2.

Table 2 Kinetic parameters of the heavy metals and MO adsorption a


Pseudo first-order Pseudo-second Interparticle diffusion
reaction rate rate model
FA-W
KL k2
2 - 2 q
Parameter R [min R [g/mg . e R2 Kid C
1 [mg/g]
] min]
Cd/(Cd + Cu+ MO) 0.347 - 0.924 3.285 5.624 0.835 - -
Cu/(Cd + Cu +MO) 0.914 0.017 0.992 0.936 8.264 0.909 0.191 5.545
MO/(Cd +Cu+MO) 0.663 - 0.999 7.622 0.196 0.534 - -
FA-NaOH
Cd/(Cd + Cu+ MO) 0.971 0.011 0.175 - - 0.979 2.194 8.140
Cu/(Cd +Cu + MO) 0.969 0.031 0.995 0.354 23.585 0.930 1.227 9.860
MO/(Cd + Cu+MO) 0.408 - 0.998 266.7 0.008 0.141 - -

The data show that the adsorption capacity of FA-W and FA-NaOH for heavy metals
from the multi-component systems is decreasing, comparative to the correspondent
data for systems involving two pollutants, as result of competitive adsorption.

Parallel mechanisms, of first order and interparticle diffusion are likely for copper
adsorption. These processes are independently running, with lower rate and could be
the result of the higher copper mobility, due to its lower hydration number (4),
comparative to cadmium (6) 12. An increase in the substrate capacity for copper
adsorption was registered on Fa-NaOH, supporting the assumption of dyes (stringer)
bonding on the FA surface16, and suggesting that the ratio of ionization potential to ionic
radius (strongly influencing the hydration number) can be suitable criteria for evaluating
the relative sorption capacity.

The kinetic data were obtained using a substrate: pollutant solution ratio of 1:10 g/mL.

3.2. OPTIMIZING THE ADSORPTION EFFICIENCY ON FA

The Cd2+, Cu2+ and MO adsorption efficiency, , on the two substrates was evaluated
to optimize the contact time and the amount of dispersed FA in a given volume of
wastewater, and was calculated with equation (8):

i e
(ccation ccation ) 100
= i (8)
ccation

i e
where ccation and c cation are the initial and equilibrated cation concentrations (mg/L),
respectively mMol/L for MO.

The dynamic adsorption results are presented in Fig. 4a and 4b for the cadmium,
cooper and MO, adsorption on FA-NaOH, compared with the results obtained using FA-
W as adsorbents.

100 100

80 80
2+
Cu (M) /FA-W
Efficiency [%]
Efficiency [%]

2+
60 Cu (M)/ FA-NaOH 60 2+
2+ Cd (M) /FA-W
Cd (M)/ FA-NaOH 2+
MO (M) /FA-W
MO (M)/ FA-NaOH
40 40

20 20

0 0
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time [min] Time [min]

Fig.4 a Efficiency immobilization Fig. 4 b Efficiency immobilization


vs. contact time vs. contact time
100 100
90 90
80 80
70 70

Efficiency [%]
Efficiency [%]

60 60
50 50
40 40
30 30 2+
2+ Cu (M) /FA-W
20 Cu (M) /FA-NaOH 20 2+
2+ Cd (M) /FA-W
10
Cd (M) /FA-NaOH 10 MO (M) /FA-W
MO (M) /FA-NaOH
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 massa [g]
massa [g]

Fig. 5a Efficiency immobilization, vs. Fig. 5b Efficiency immobilization, vs.


mass of FA mass of FA-W

The low adsorption efficiency of Cd2+ and Cu2+ cations on FA-W, comparative with the
efficiencies on FA-NaOH, show that during the first hour of contact with substrate a
share of pores are occupied with methyl orange molecules, as also supported by the
AFM pictures and the average roughness values. The higher adsorption efficiency of
copper vs. cadmium confirms the idea of the diffusion control of the process, which
favors the cation with lower volume and higher mobility.

Further, it may be concluded that in such complex systems, containing (two) cations
and a dye, there are expected only average adsorption efficiencies of the heavy metals
but very good results can be expected for dyes removal.

The rate of adsorption is also depending on the amount of fly ash. While the dyes
requires rather low amounts of ash, for efficient heavy metal removal (> 90%) the
amount of FA should rise up to 3g/50mL solution. The results are presented in Fig.5a
and 5b.

By increasing the amount of adsorbent, the initial pH increases up to 5.8 (bellow the
precipitation value) while the adsorption efficiency of the heavy metals increases due to
a larger amount of active centres in the system.

The recommended parameters for simultaneous removal of the heavy metals and dyes
are:
(a) the FA-NaOH substrate: mFA-NaOH = 1.25 g for 50 mL solution; contact time: 60 min

(b) the FA-W substrate:. mFA-W = 1.5 g for 50 mL solution; contact time: 90 min

3.3. ADOSRPTION THERMODYNAMIC STUDY

The adsorption isotherm data were experimentally obtained after optimising the
adsorption processes and the absorption parameters were calculated considering the
Langmuir and Freundlich equations, respectively, as given below27.
The Langmuir isotherm - linearization:

C eq 1 C eq
= + (9)
q eq qmax a qmax

Where qmax (mg/g) represents the monolayer adsorption capacity, is a constant related
to the free energy of adsorption, qeq is the amount of metal adsorbed from a solution
with the equilibrium concentration, Ceq.

The Freundlich isotherm - linearisation:

1
ln q eq = ln k F + ln C eq (10)
n

Where kF is Freundlich adsorption constants, being an indicator of the adsorption


capacity and 1/n dimensionless parameter is a measure of the adsorption density.

Table 3 presents the adsorption parameters for the heavy metal ions (Cd2+, Cu2+ and
MO) calculated from the slope of the linearization plots of the two isotherm equations.

Table 3 Adsorption isotherm parameters


Langmuir Isotherm Freundlich Isotherm

Parameters qmax a
R2 n KF R2
[mg/g] [L/mg]
FA -W
Cd/(Cd + Cu+ MO) 7.502 0.017 0.999 2.060 0.00006 0.972
Cu/(Cd + Cu +MO) 7.236 0.015 0.917 5. 201 0.002 0.903
MO/(Cd +Cu+MO) - - 0.196 1.242 0.001 0.903
FA_NaOH
Cd/(Cd + Cu+ MO) 8.968- 0.002 1 1.928 0.037 0.969
Cu/(Cd + Cu +MO) - - 0.737 2.705 0.167 0.960
MO/(Cd +Cu+MO) - - 0.196 0.926 1.878 0.957

The data show that the Freundlich model could better describe the adsorption on FA-
NaOH and FA-W as result of heterogeneous substrates resulted after washing and after
treating with the NaOH 2N modifier.

The higher surface energy on FA-W, confirmed by the higher surface roughness allows
strong interactions with the heavy metals, thus the Langmuir model can also apply.
Methyl orange, a significantly less ionic molecule, although adsorbs well, does not
exhibit chemi-sorption and the Langmuir model is not suited for describing this process.
The Langmuir model could well describe the adsorption of cadmium and cooper ions
attendance MO with bill of the homogenous of the substrate.

The cadmium and copper behavior is quite different, again supporting the diffusive
control that allows a larger amount of copper to be linked on the substrate.

CONCLUSIONS

Fly ash was investigated as substrate for complex adsorption processes, involving tri-
component pollutant system: two heavy metals (copper and cadmium) and a dye
(methyl orange).

The washed fly ash has a rough surface with a large amount of high energy sites. By
further alkali treatment the surface becomes smoother with a larger amount of small
meso-pores. These changes result in a controlled adsorption affinity. The substrates
proved to be highly efficient in the dyes adsorption: methyl orange adsorbs fast and
forms a rather homogeneous substrate. Therefore, the adsorption conditions were
optimised considering the heavy metals uptake and are presented in the paper.

The adsorption process of heavy metals in the experimental conditions is significantly


controlled by diffusion and the low volume high mobile copper cation has a faster
adsorption rate, comparing to cadmium.

The data show that, if optimized, fly ash can be a suitable substrate for efficient
adsorption of a complex pollutants load from wastewaters. Considering its low cost, up-
scaling will be further studies.

AKNOWLEDGEMENTS

This paper is supported by the Sectoral Operational Programme Human Resources


Development (SOP HRD), financed from the European Social Found and by the
Romanian Government under the contract number POSDRU ID 59323.

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