Synergic Adsorption for Heavy Metal and Dye Removal using Zeolite Clinoptilolite Powder - Desklib

SYNERGIC ADSORPTION IN SIMULTANEOUS REMOVAL OF DIFFERENT
HEAVY METALS IN MULTI-COMPONENT EFFLUENT AND REMAZOL NAVY
BLUE USING ZEOLITE CLINOPTILOLITE POWDER.
JENNIFER
(201272008)
SUPERVISORS: TIMOTHY HUNTER, DAVID HARBOTTLE,
UNIVERSITY OF LEEDS
SCHOOL OF CHEMICAL AND PROCESS ENGINEERING
JULY 2019
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ABSTRACT
Heavy metals and dyes from textile effluent have a significant ecological impact on
the ecosystem and can modify the physical and chemical properties of water affecting the
aquatic and human lives. The removal of these pollutants from wastewaters is difficult to
achieve using conventional methods but it is one of the most important environmental tasks
for research and technology development on water management. Therefore adsorption has
been reported as most efficient using adsorbents. Clinoptilolite is one of the adsorbents that
have been reported with the potential of removing the heavy metals. The clinoptilolite was
characterized to determine its particle size, elemental compositions, and its nature.
It was activated with salt (NaCl) and acid (HCl). In the adsorption technique,
adsorption kinetics, adsorption equilibrium and adsorption isotherm of the heavy metal were
investigated. The results showed that the natural clinoptilolite has a particle size of 11μm
with the potential to remove the heavy metals. It was revealed that the adsorption of the
heavy metals suited well with Freundlich isotherm model while the adsorption data fitted to
the second-order kinetic model. The process will be repeated for adsorption of dye and in
combination with the heavy metals in the future study.
Table of Contents
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Contents
ABSTRACT.............................................................................................................. 2
Table of Contents........................................................................................................ 3
Table of figures.......................................................................................................... 5
List of tables.............................................................................................................. 6
1. INTRODUCTION................................................................................................... 7
1.1 Overview...................................................................................................... 7
1.2 Research aim and objectives........................................................................9
1.3. Outline of the report..................................................................................10
CHAPTER 2 LITERATURE REVIEW..........................................................................11
2.1 Heavy Metal................................................................................................ 11
2.1.1 Source of Metallic Waste............................................................................... 11
2.1.2Waste Water Characteristics............................................................................13
2.1.3 Heavy Metal Toxicity................................................................................... 13
2.2 Zeolite........................................................................................................ 16
2.2.1 Metal ion Removal by Natural Zeolites clinoptilolite.............................................19
2.3 Azo farbstoff (remazol navy RGB 150%).....................................................24
2.4 Adsorption.................................................................................................. 25
2.4.1 Parameters Effecting Adsorption......................................................................27
2.4.2 Adsorption Isotherm..................................................................................... 28
2.4.3 Batch Adsorption Kinetics............................................................................. 31
2.5 Review of Related Works............................................................................33
2.6 Application of clino, the chemicals and dye................................................38
2.7 Importance of your materials and chemicals used in the experiment........39
3. Materials and Methodology...................................................................................... 40
3.1 Materials..................................................................................................... 40
3.2 Methodology............................................................................................... 40
3.2.1 Rinsing and drying....................................................................................... 42
3.2.2 Particle size measurement..............................................................................42
3.2.3 Particle size imaging..................................................................................... 42
3.2.4 Examination of surface morphology.................................................................42
3.2.4 Zeta potential measurement............................................................................43
3.2.5 Activation of the clinoptilolite.........................................................................43
3.3. 6 Cu, Cr and Pb adsorption equilibrium experiment................................................43
3.2.7 Cu, Cr and Pb adsorption kinetics experiment......................................................49
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4. Results and Discussion............................................................................................ 63
4.1 Clinoptilolite particle characterization........................................................63
4.2 Adsorption Isotherm and equilibrium effects..............................................68
4.2.1 Langmuir isotherm....................................................................................... 68
4.2.2 Freunlich isotherm....................................................................................... 69
4.2.3 Equilibrium effects....................................................................................... 74
4.3 Adsorption kinetics modelling.....................................................................75
5. Conclusion and Future Work.................................................................................... 77
5.1 Conclusion.................................................................................................. 77
5.2 Future Work................................................................................................ 77
6.0 Gantt chart..................................................................................................... 78
Reference................................................................................................................ 78
Table of figures
Figure 1: Showing Structure of Remazol navy blue............................................................32
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Figure 2: Showing graphical representation of Freundlich equation........................................39
Figure 3: Showing Schematic diagram of experimental design...............................................49
Figure 4: Showing Equilibrium uptake pre mass of ion – exchange resin in (mg/g)
for lead nitrate salt concentration onto natural and pre- activated Clinoptilolite.
............................................................................................................................ 52
Figure 5: Showing Equilibrium uptake pre mass of ion – exchange resin in (mg/g)
for chromium chloride salt concentration onto natural and pre- activated
Clinoptilolite......................................................................................................... 53
Figure 6: Showing Equilibrium uptake pre mass of ion – exchange resin in (mg/g)
for copper cholride salt concentration onto natural and pre- activated
Clinoptilolite......................................................................................................... 54
Figure 7: Showing Equilibrium uptake pre mass of ion – exchange resin in (mg/g)
for copper chloride salt concentration onto natural Clinoptilolite. Right and open
symbol is the adsorption percent........................................................................55
Figure 8: Showing Equilibrium uptake pre mass of ion – exchange resin in (mg/g)
for lead nitrate salt concentration onto natural Clinoptilolite. Right and open
symbol is the adsorption percent........................................................................56
Figure 9: Showing Equilibrium uptake pre mass of ion – exchange resin in (mg/g)
for chromium chloride salt concentration onto natural Clinoptilolite. Right and
open symbol is the adsorption percent................................................................57
Figure 10: Showing Uptake of 10ppm Chromium chloride solution after
adsorption times, from 15mins to 48hours onto natural clinoptilolite.Left vertical
lines shows the adsorption pre mass of ion exchange, while the right vertical
shows total removal percentages........................................................................59
Figure 11: Showing Uptake of 10ppm lead nitrate solution after adsorption
times, from 15mins to 48hours onto natural clinoptilolite .Left vertical lines
shows the adsorption pre mass of ion exchange, while the right vertical shows
total removal percentages...................................................................................59
Figure 12: Showing Uptake of 10ppm Copper chloride solution after adsorption
times, from 15mins to 48hours onto natural clinoptilolite.Left vertical lines shows
the adsorption pre mass of ion exchange, while the right vertical shows total
removal percentages........................................................................................... 60
Figure 13: Showing Uptake of 100ppm Chromium chloride solution after
adsorption times, from 15mins to 48hours onto natural clinoptilolite.Left vertical
lines shows the adsorption pre mass of ion exchange, while the right vertical
shows total removal percentages........................................................................61
Figure 14: SHowing Uptake of 100ppm Copper chloride solution after adsorption
times, from 15mins to 48hours onto natural clinoptilolite.Left vertical lines shows
the adsorption pre mass of ion exchange ,while the right vertical shows total
removal percentage............................................................................................ 62
Figure 15: Showing Uptake of 100ppm lead nitrate solution after adsorption
times, from 15mins to 48hours onto natural clinoptilolite.Left vertical lines shows
the adsorption pre mass of ion exchange,while the right vertical shows total
removal percentage............................................................................................ 63
Figure 16: Showing Pseudo second order model fit for 10ppm chromium chloride
solution after different adsorption times from 15mins to 48hours......................65
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Figure 17: Showing Pseudo second order model fit for 10ppm Lead nitrate
solution after different adsorption times from 15mins to 48hours......................65
Figure 18: Showing Pseudo second order model fit for 10ppm chromium chloride
solution after different adsorption times from 15mins to 48hours......................66
Figure 19: Showing Pseudo second order model fit for 100ppm chromium
chloride solution after different adsorption times from 15mins to 48hours.........67
Figure 20: Showing Pseudo second order model fit for 100ppm copper chloride
solution after different adsorption times from 15mins to 48hours......................68
Figure 21: Showing PSO Qt(mg/g)/ time(min) 100PPM for lead ,chromium and
copper ................................................................................................................ 70
Figure 22: Showing PSO Qt(mg/g)/ time(min) 10PPM for lead ,chromium and
copper................................................................................................................. 71
Figure 23: Showing The morphology of natural clinoptilolite with a magnification scale of 50um...73
Figure 24: Showing Particle size distribution of the clinoptilolite...........................................73
Figure 25:Showing Natural clinoptilolite (a) before adsorption (b) after adsorption.....................74
Figure 26:Showing Zeta potential for (a) natural clinoptilolite (b) acid activated clinoptilolite (c) salt
activated clinoptilolite................................................................................................ 76
Figure 27: Showing Langmuir Isotherm of the adsorption of lead clinoptilolite..........................76
Figure 28: Showing Langmuir Isotherm of the adsorption of chromium clinoptilolite..................77
Figure 29: Showing Langmuir Isotherm of the adsorption of Copper clinoptilolite......................77
Figure 30: Showing Freundlich Isotherm of adsorption of Lead............................................78
Figure 31: Showing Freundlich Isotherm of adsorption of chromium.......................................78
Figure 32: Showing Freundlich Isotherm of adsorption of copper...........................................79
Figure 33: Showing Equilibrium plot of the adsorption of (a) Pb (b) Cr (c) Cu on clinoptilolite......83
Figure 34: Showing Uptake of Pb2+, Cr3+ and Cu2+ on natural clinoptilolite at 100ppm salt solution
from 15minutes to 48hours.......................................................................................... 84
List of tables
Table 1: Showing Toxicities of heavy metal ions...............................................................14
Table 2: Showing Materials used for the study..................................................................40
Table 3 : Showing Chemical composition of natural clinoptilolite..........................................66
Table 4:Showing Isotherm data of the adsorption of Lead on clinoptilolite...............................71
Table 5: Showing Isotherm data of the adsorption of Cr on clinoptilolite..................................72
Table 6: Showing Isotherm data of the adsorption of Cu on clinoptilolite.................................73
Table 7: Showing Pseudo second order kinetics data...........................................................76
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1. INTRODUCTION
1.1 Overview
The contamination of water with organic and inorganic compounds by natural and
human activities is considered as a serious environmental problem worldwide. The incessant
increase in contamination of water with the aforementioned pollutants is as a result of rapid
development in human civilization such as industrialization, urbanization, mining operation,
atomic power plants etc i.Dyes and heavy metals are common and dangerous pollutants,
emanating in large quantities from dye manufacturing, textile, pulp, and paper industries.
They are emitted into wastewaters and are difficult to treat, as the colour tends to persist even
after the conventional removal processes.
Most of these dyes are difficult to remove from the effluent using a traditional
method of purification because they are stable, non-degradable, hazardous and carcinogenic.
Many researchers identified adsorption methods as the most efficient technique that removes
dye easily. Ahmad and Alrozi (2011) studied the removal of malachite green dye from
aqueous solution by adsorption using rambutan peel-based activated carbon. Dawood (2010)
examined the removal of orange (G) dye from aqueous solution by adsorption on bentonite.
Lin et al., (2008) investigated the adsorption of basic dye from aqueous solution on fly ash.
The presence of heavy metals in textile effluent can contribute to the difficulty faced
in the removal of dye using traditional methods .Heavy metals belong to elements with
atomic weights between 63.546 and 200.590 and specific gravity above 4.0 . Living
organisms require trace amounts of some heavy metals including Co, Cu, Fe, Mn, Mo, V, Sr
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and Zn. They are known as essential metals but their excessive levels can be detrimental to
organisms. Heavy metals including Hg, Cr, Cd, As, Pb, Sr, Cu etc are non-essential metals
and considered to be a great threat for aquatic life as well as humans, plants and other
animal's life. These toxic metal ions are directly released into natural water by various
industrial applications and by other human activitiesii. Many researchers have adopted
different conventional methods in the treatment of industrial effluent to remove heavy metals
before discharging them into water bodies .
The conventional methods such as coagulation, chemical precipitation, solvent
extraction, electrolysis, ultra-filtration membrane separation, phytoextraction, reverse
osmosis, adsorption, electrodialysis, irradiation, and ion exchange are been employed in
removing heavy metals but their application at large scale is limited. Nevertheless, among
these methods adsorption is better because it has a percentage removal of inorganic and
organic waste and it is easy to handleiii. Moreover, the adsorption technique is cheap and
efficient in terms of its physical properties, chemical properties, and cost. Several researchers
have examined the efficacy of cheap and affordable adsorbents in removal of heavy metals
and dyes from multicomponent effluents. One of these adsorbents that have gained interest is
zeolite.
Zeolites are crystalline, hydrated aluminosilicates of alkali and alkali earth metals that
possess infinite crystal structure in a three-dimensional pattern that accounts for their
adsorptive nature . They are neutral but their anions are exchanged with cations present in the
effluent during adsorptioniv. The zeolites occur in different natural species as follows;
mordenite, clinoptilolite, stilbite, scolecite, analcime, erionite, heulandites, and chabazite .
The most abundant naturally occurring zeolite among the aforementioned species is
clinoptilolite. Its tubular structure helps it to adsorb pollutants easily from effluents and send
it to the inner pore structure.
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