USE OF AGRICULTURAL WASTE FOR THE REMOVAL OF HEAVY METALS

SUBMITTED BY

Mohammad Haseeb Azam Student ID: 20500531

A Term paper submitted in Partial fulfillment of the Requirements of CHE 674 (Industrial Wastewater Pollution Control) Course

Chemical Engineering Department University of Waterloo

8th April, 2013

Table of Contents

1. 2.

INTRODUCTION .......................................................................................................................... 3 REMOVAL OF CR (VI) FROM AQUEOUS SOLUTION ........................................................... 4 2.1 2.2 Materials ................................................................................................................................. 5 Results and discussion ............................................................................................................ 5 Effect of Contact Time..................................................................................................... 5 Effect of initial Cr (VI) concentration ............................................................................. 6 Effect of pH ..................................................................................................................... 7 Effect of Temperature...................................................................................................... 7 Effect of particle size ....................................................................................................... 8

2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.3 2.4

Adsorption Isotherm ............................................................................................................... 9 Adsorption Kinetics Modelling ............................................................................................. 12 Pseudo-first-order model .............................................................................................. 13 Pseudo-second-order model ......................................................................................... 13

2.4.1 2.4.2 2.5 3.

Fourier transform infrared analysis (FT-IR) ......................................................................... 15

BIOSORPTION OF HEAVY METALS BY PAPER MILL WASTE ......................................... 16 3.1 Materials and Method ........................................................................................................... 17 Chemicals and reagents ................................................................................................ 17 Preparation of Biosorbent ............................................................................................ 17

3.1.1 3.1.2 3.2

Results and Discussion ......................................................................................................... 17

3.2.1 Effect of pH on the removal of the heavy metal ions.......................................................... 17 3.2.2 3.2.3 3.3 4. 5. Effect of Biomass concentration.................................................................................... 18 Effect of contact time and initial concentration of metal ions on % removal ............... 18

Adsorption Isotherm ............................................................................................................. 21

CONCLUSION ............................................................................................................................. 23 REFERENCES ............................................................................................................................. 25

1.

INTRODUCTION

Today, with the rapidly increasing population, water resources becoming scarcer, there is a strong need to reconsider the patterns of our consumption and the way we use our water resources (1). Heavy metals have been excessively released into the environment due to rapid industrialization and have created a major global concern (2). Ecological systems around the world are at risk from human activities. These delicate systems need to be conserved so that we dont disturb the natural balance of processes and therefore continue to make the earth a Greener Planet. The pollutants in the waste water are classified into two main types: (I) Organic Pollutants, which can easily biodegrade and present a low risk factor. (II) The other type is the NonOrganic Pollutants, which also contain the Heavy Metal Ions. These heavy metals do not biodegrade into harmless end products and therefore are the main contributors toward contamination. Moreover, these heavy metals ions are a big concern in the waste water due their toxicity. Much of the aquatic life is badly affected due the high quantities of the metal ions being present in this water, and many water-borne diseases have posed serious risk to the general public. Strong exposure of Cr (VI) causes cancer in the digestive tract and lungs and may cause epigastric pain, nausea, vomiting, severe diarrhoea, and haemorrhage
(3)

. The

higher concentration of Ni (II) in ingested water may cause severe damage to lungs, kidneys, gastrointestinal distress, e.g., nausea, vomiting, diarrhoea, pulmonary fibrosis, renal edema, and skin dermatitis (4). Metal contaminated waters may contain ions of copper, zinc, nickel, lead, cadmium, mercury, chromium and uranium; originating from industries like metal plating, tanneries, mining operations, smelting, alloy industries, textiles, microelectronics, petroleum refining, pesticides and battery manufacture.

Conventional bioremediation technologies viz. precipitation-filtration, ion exchange, reverse osmosis, oxidationreduction and membrane separation are not economical and inadequate to bring down the level of contaminants in wastewater to permissible. Further, these traditional protocols generate huge quantity of noxious chemical sludge
(5)

. Adsorption technology by

activated carbon has gained wide acceptance and patronage among researchers, more than any other form of wastewater treatment technologies, due to their low cost, simplicity, ease of implementation and effective removal of heavy metals at trace level in effluent streams or wastewater (6). The other technique widely used is Biosorption. Biosorption is an innovative technology using living or dead biomasses to remove toxic heavy metals from aqueous solution. The major advantages of biosorption technology are its effectiveness in reducing the concentration of heavy metal ions to very low levels and the use of inexpensive biosorbent material (7). Low cost agricultural waste by-products such as sugar cane bagasse, rice husk, saw dust, coconut husk, oil palm shell, neem bark have been investigated for use as novel adsorbents. Agricultural wastes are characterized by ready availability, affordability, ecofriendliness and high uptake capacity for heavy metals due to the presence of functional groups which can bind metals to effect the removal of heavy metal from effluents (8).

2.

REMOVAL OF CR (VI) FROM AQUEOUS SOLUTION

Chromium exists in either +3 or +6 oxidation states, as all other oxidation states are not stable in aqueous systems. Chromium (VI) is 100-1000 times more toxic to organisms than Cr (III) and more readily transported in soils (3). The main industrial sources of chromium pollution are leather tanning, electroplating, metal processing, wood preservatives, paint and pigments, textile, dyeing, steel fabrication and canning industry (3).
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In this case, Adsorption technique is employed for the removal of Cr (VI) ions from waste water. This study encompasses the use of activated carbon, almond and apricot shells as adsorbent for Cr (VI) to determine adsorption efficiency as a function of contact time, initial concentration, particle size, pH, temperature and constants of adsorption isotherm.

2.1 Materials
Almond and apricot shells were collected from different sites and prepared from agricultural solid wastes as adsorbents. The samples were washed several times with deionized water and dried under the sun. After this the adsorbents were ground in a blender and stored for further use. Potassium dichromate and other chemicals were used of analytical reagent grade and were obtained from standard sources (3). The physical properties of activated carbon have been listed in Table 1. Table 1: Physical Properties of activated carbon* (3)

2.2 Results and discussion 2.2.1 Effect of Contact Time

The figure below (Figure 1) shows the adsorption of Cr (VI) by almond shell, apricot shell and activated carbon as a function of time. From the figure it can be clearly seen that rapid adsorption took place in the initial 15 min for all biosorbent but then adsorption gradually

decreases with time until it reaches equilibrium. Further increase in contact time did not show an increase in biosorption (3). Figure 1: Effect of contact time on the removal of Cr (VI) (3)

2.2.2

Effect of initial Cr (VI) concentration

Fig. 2 shows the effect of Cr (VI) concentration on the sorbent by varying the initial Cr (VI) concentration (0.5, 1, 2, 4 and 5 mg/l) for a 30 min time interval. It was observed that the percentage removal decreased with increase in Cr (VI) concentration. At low concentrations the ratio of available surface to the initial Cr (VI) concentration is larger, so the removal becomes independent of initial concentrations. However, in the case of higher concentrations this ratio is low; the percentage removal then depends upon the initial concentration (3). Figure 2: Effect of Initial Cr (VI) concentration on the removal of Cr (VI) (3)

2.2.3

Effect of pH

One of the most important controlling parameter in the adsorption process is pH. The results indicate that adsorption of Cr (VI) was higher at lower pH and decreased with increasing pH (Fig. 3). Also, the results show the optimum initial pH which was observed at pH 2.0. Removal of Cr (III) at pH 2.0 is zero whereas its removal percentage is very high at pH 5.0; however, percentage removal of Cr (VI) is significantly low. At low pH values active sites are positively charged. Therefore, negative metals adsorption increases significantly whereas increasing the pH value causes the surface of the adsorbent to become neutral and hence a decrease in the adsorption is observed.

Figure 3: Effect of pH on the removal of Cr (VI)

2.2.4

Effect of Temperature

Adsorption is normally considered an exothermic process; therefore you would expect the equilibrium concentration to increase (i.e. the amount of adsorbed material decreases) with increasing temperature. But some chemical adsorption processes are endothermic processes;

therefore, increase in temperature leads to increase in both adsorption rate and amount of adsorbed materials (3). This was the case observed in this study. As shown below (Fig. 4), adsorption of Cr (VI) at different temperatures showed an increase in adsorption capacity with increase in temperature. Figure 4: Effect of temperature on the removal of Cr (VI) (3)

2.2.5

Effect of particle size

Fig. 5 shows the effect of particle size on the Cr (VI) adsorption capacity of almond shell, apricot shell and activated carbon. It is apparent from Fig. 5 that the particle size of sorbents has a considerable effect on Cr (VI) sorption. The larger sorbent size shows lesser Cr (VI) removal as compared to the smaller sorbent size. This can be inferred from the available surface area for adsorption which decreases as the particle size increases for the same dose or sorbent, providing less active surface sites for adsorption of sorbate.

Figure 5: Effect of particle size on the removal of Cr (VI) (3)

2.3 Adsorption Isotherm

Adsorption equilibrium data were fitted to the Langmuir, Freundlich and Temkin isotherms. Langmuir isotherm is based on the monolayer adsorption of chromium ions on the surface of absorbent sites and is expressed in the linear form as (3):

Where Ce is the equilibrium solution concentration, x/m the amount adsorbed per unit mass of adsorbent, m the mass of the adsorbent, Vm the monolayer capacity, and K is equilibrium constant related to the heat of adsorption by equation:

Where, q is the heat of adsorption.

The other common type of adsorption isotherm used for waste water analysis and calculations is the Freundlich isotherm. This describes the heterogeneous surface energies by multilayer adsorption and is expressed in linear form as:

Log

Log

Log Ce

Where, Kf and 1/n are Freundlich constants related to adsorption capacity and intensity of adsorption, and other parameters are the same as in the Langmuir isotherm. Finally, Temkin isotherm is based on the heat of adsorption of the ions, which is due to the adsorbate and adsorbent interactions taken in linear form, is given by (3):

Where, b= Temkin Constant- Related to heat of adsorption (J/mol), A= Temkin isotherm constant (L/g), R= Gas constant (8.314 J/mol K), T= Absolute temperature (K) The theoretical parameters of the above three isotherms along with regression coefficient have been given in Table 2.

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Table 2: Isotherm constants for various adsorption isotherms (3)

Figs. 6, 7 and 8 show the comparison of the three isotherms with each other. The results indicate that the Freundlich equation fits the experimental data better than the Langmuir and Temkin equations (3). Figure 6: Equilibrium isotherms of Cr (VI) onto almond shell (3)

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Figure 7: Equilibrium isotherms of Cr (VI) onto activated carbon (3)

Figure 8: Equilibrium isotherms of Cr (VI) onto apricot shell (3)

2.4 Adsorption Kinetics Modelling

Kinetic modelling of the different adsorbents is carried out to determine the potential ratecontrolling steps involved in the process of biosorption. In this study, pseudo-first-order and pseudo-second-order kinetic models have been tested for each of the adsorbents (i.e. almond shell, apricot shell and activated carbon).

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2.4.1 Pseudo-first-order model

The pseudo-first-order kinetic model was described by Lagergren (3):

Where qe (mg g-1) and qt (mg g-1) are the amounts of the Cr (VI) adsorbed on the adsorbent at equilibrium and at time t, respectively; and k1 (min-1) is the rate constant of the first order model. After integrating the above equation and applying boundary conditions, it can be expressed as follows:

ln (qe- qt) = lnqe k1t

It is important that that the experimental qe must be known for the application of this model. The pseudo-first-order constants, qe and k1, along with the corresponding correlation coefficients for initial Cr (VI) concentration of 5 ppm are shown in Table 3. The calculated qecal value is not in good agreement with the experimental value of qeexp. These observations suggest that the pseudo-first-order model is not suitable for modelling the adsorption of Cr (VI) onto almond shell, apricot shell and activated carbon (3).

2.4.2

Pseudo-second-order model

The pseudo-second-order model is based on the assumption that the rate-limiting step is chemical sorption or chemisorption involving valance forces through sharing or exchange of electrons between sorbent and sorbate as covalent forces (3). The equation of this model can be expressed in the following form:

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Where k2 (g mg-1 min-1) is the rate constant of the second-order equation; qe (mg g-1) is the maximum adsorption capacity; qt (mg g-1) is the amount of adsorbed at time t (min). After integrating and applying boundary conditions, the above equation will yield:

Values of K2 and qe cal along with the corresponding correlation coefficients for the initial Cr (VI) concentration of 5 ppm are presented in Table 3. The correlation coefficient was nearly equal to unity and calculated qe cal value was very close to the experimental value of qe
exp.

The results indicated that the pseudo-second-order

adsorption mechanism is predominant for the adsorption of Cr (VI) onto almond shell, apricot shell and activated carbon, and it is considered that the rate of the Cr (VI) adsorption process is controlled by the chemisorption process (3).

Table 3: Calculated kinetic parameters for pseudo first-order and second-order kinetic models for the adsorption of Cr (VI) (3)

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2.5 Fourier transform infrared analysis (FT-IR)

Fourier transform infrared spectroscopy is a very useful technique to determine the changes in the functional groups and surface properties of the adsorbent
(4)

. The FT-IR spectra of

almond and apricot shells before and after adsorption of chromium have been given in Figs. 9-12. The spectra were measured within the range of 500-4000 cm-1 wave number. The results of the FT-IR spectra clearly indicate that were various functional groups detected on the surface adsorbents before and after adsorption. These results are presented in Table 4. As seen in Table 4, these band shifts indicated that it was the bonded OH groups and aliphatic CH groups in particular which played a major role in chromium (VI) biosorption on almond shell (3). Table 4: Some fundamental frequencies of the studied adsorbents (before and after use) (3)

Figure 9: The FT-IR spectra of almond shell before adsorption (3)

Figure 10: The FT-IR spectra of almond after adsorption (3)

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Figure 11: The FT-IR spectra of apricot shell before adsorption (3)

Figure 12: The FT-IR spectra of apricot after adsorption (3)

3.

BIOSORPTION OF HEAVY METALS BY PAPER MILL WASTE

Biosorption is a relatively new process that has shown a significant contribution for the removal of contaminants from aqueous effluents. Biosorption can be defined as the removal of metal or metalloid species, compounds and particulates from solution by biological materials or a by-product or waste material from another industry (9). Both living and dead biomass as well as cellular products such as polysaccharides can be used for metal removal (9). The process of biosorption involves a solid phase (sorbent) and a liquid phase (solvent) containing a dissolved species to be sorbed. Due to the high affinity of the sorbent for the metal ion species, the latter is attracted and bound by a rather complex process affected by several mechanisms involving chemisorption, complexation, biosorption on surface and pores, ion exchange, chelation, biosorption by physical forces, entrapment in inter and intrafibrillar capillaries and spaces the structural polysaccharide networks as a result of the concentration gradient and diffusion through cell walls and membranes (10).

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3.1 Materials and Method 3.1.1 Chemicals and reagents

The stock solutions were prepared by dissolving lead nitrate, cadmium iodide, nickel sulphate and copper sulphate respectively in milli Q water; each containing 1000 mg l-1 concentration of lead, cadmium, nickel and copper.

3.1.2 Preparation of Biosorbent

The paper mill sludge used in this study is collected from the filter bed of effluent treatment. It is mainly composed of primary clarified sludge (Kraft pulp & paper based mill). The sludge is first washed with distilled water to remove the particulate matter before carrying out the metal adsorption experiments. The sludge is oven-dried at 100oC overnight, pulverized and stored in a polyethylene bag for further studies.

3.2 Results and Discussion 3.2.1 Effect of pH on the removal of the heavy metal ions
The effect of pH is given in Fig. 13. It can be clearly seen that the maximum removal took place at pH 4.5. This indicates that the maximum adsorption affinities take place in moderately and slightly acidic medium (1). Figure 13: Effect of pH on the % removal of different metals by paper mill waste (1)

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3.2.2

Effect of Biomass concentration

Each of the metals exhibited similar behaviour with change in biomass concentration. Biosorption of each metal was found to be better with 1% concentration of biomass. The results are presented in Fig. 14. Figure 14: Effect of Biomass concentration (w/v) on the % removal of different metals (1)

3.2.3

Effect of contact time and initial concentration of metal ions on % removal

The results showed some analogous characteristics; adsorption was sharp and up to 70%-89% of the metal ions were adsorbed within 15 minutes from 100 mg l-1 and 5 mg l-1 initial concentration respectively. Though Cd, Cu at 50 mg l-1 and Pb, Ni at 20 mg l-1 showed a decrease in absorption in the first 15 minutes, with increase in contact time the adsorption increased. At equilibrium, adsorption was 99.8% of Ni, 98.0% of Pb, 99.2% of Cu and 99.8% of Cd by dried paper mill sludge with an initial conc. of about 5 mg l-1 of aqueous solution (1). Even though at higher initial concentration i.e. from 10-100 mg l-1 of metals, the adsorption decreased but it was well above 90% (Fig. 15-18).

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Figure 15: Effect of initial concentration (Ci) of Cd with time of agitation on residual concentration (1)

Figure 16: Effect of initial concentration (Ci) of Cu with time of agitation on residual concentration (1)

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Figure 17: Effect of initial concentration (Ci) of Pb with time of agitation on residual concentration (1)

Figure 18: Effect of initial concentration (Ci) of Ni with time of agitation on residual concentration (1)

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3.3 Adsorption Isotherm

Biosorption of heavy metals is a rapid process and equilibrium is established between the adsorbed metal ions on the surface of the adsorbent (qeq) and unadsorbed metal ions in solutions (Ceq) (1). Langmuir and Freundlich adsorption constants evaluated from isotherms and correlation coefficients (R2) are given in Table 5. The results clearly indicate that both physico-chemical adsorption and ion exchange interaction plays a role in binding of lead, copper, nickel and cadmium from aqueous solution simultaneously. Paper mill sludge is composed of both organic and inorganic constituents therefore mechanism of adsorption involves both ion exchange interactions as well as physico-chemical adsorption. The equilibrium constants of Langmuir and Freundlich adsorption models for each of the metals (Lead, Nickel, Copper and Cadmium) show a good correlation when compared with the experimental data, resulting in ( which shows that Freundlich sorption model

fitted well as compared to Langmuir adsorption model throughout the concentration range of Pb, Ni, Cu and Cd. However, the results show that Cd has favoured Freundlich model relatively more than the Langmuir.

Table 5: Values of Langmuir and Freundlich adsorption constants evaluated from isotherms and correlation coefficients (R2). (1)

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Table 6 gives a brief comparison of the biosorption capacity of some agricultural wastes which can be used as cheap adsorbents. Table 6: Selected heavy metal adsorption capacities for selected low cost adsorbents (1)

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4.

CONCLUSION

The removal of heavy metals from waste water/effluent streams has gained much attention around the world due to the fatal effects of these metals and water becoming a scarce resource in many parts of the world. Agricultural wastes being economical and readily available make very good use as adsorbents. However, its extremely important to make sure that these agricultural wastes are treated or modified before use if necessary in order to ensure that minimum amount of waste sludge is formed. The two most common methods for the removal heavy metals have been discussed above. In the first case adsorption technique was adopted which investigated the use of almond and apricot shells as effective and inexpensive biosorbents. In the latter case, biosorption technology was used for the removal of heavy metals. Both of these removal methods depend on specific parameters such as temperature, pH, initial biomass/metal concentration, contact time, particle size etc for metal removal efficiency. The Langmuir and Freundlich adsorption models can be used to represent the experimental data and compare the adsorption capacities. Adsorption kinetics modelling can be used to determine the rate controlling steps involved in the biosorption process. In biosorption technology, living or dead biomass is used to accumulate heavy metals and this finds a major drawback of cost of growing sufficient quantity of bacterial fungal or algal biomass. One of the solutions to this problem is to use biomass of another industry for the development of inexpensive biosorbent. Further physico-chemical characterization of biomass and application in continuous system should be taken into account for future research. In addition, more stress should be given on recycling and re-use of biosorbents and the safe disposal of any toxic sludge produced. Finally, to conclude, the removal of heavy metals from waste water streams is efficient and economical if carried out using appropriate methods; hence it is important to employ this
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research at grass root levels in developing countries too where majority of the population does not have access to safe water supplies.

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5.

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3. Use of Agricultural Waste for Removal of Cr(VI) from Aqueous Solution. Khazaei, M. Aliabadi, H. T. Hamed Mosavian.: Iranian Journal of Chemical Engineering, 2011, Vol. 8 (4), pp. 11-23.

4. Use of Agricultural Waste for the Removal of Nickel Ions from Aqueous Solutions: Equilibrium and Kinetics Studies. Manjeet Bansal, Diwan Singh, V.K.Garg and Pawan Rose.: International Journal of Civil and Environmental Engineering, 2009, Vol. 1 (2), pp. 108-114.

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6. Potential application of activated carbon from maize tassel for the removal. O.F. Olorundare a, R.W.M. Krause a, J.O. Okonkwo b, B.B. Mambaa.: Physics and Chemistry of the Earth, 2012 Vols. 50-52, pp. 104-110.

7. Agricultural Waste materials as potential adsorbent for removal of heavy metals from aqueous solutions. Alfa, Y. M., Hassan H. and Nda-Umar U. I. : International Journal of Chemical Resources, 2012, Vol. 2 (1), pp. 48-54.

8. Comparative analysis of the efficiencies of two low cost adsorbents in the removal of Cr(VI) and Ni(II) from aqueous solution. O. Olayinka Kehinde, T. Adetunde Oluwatoyin, and O. Oyeyiola Aderonke.: African Journal of Environmental Science and Technology, 2009, Vol. 3 (11), pp. 360-369.

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9. Modified barley straw as a potential biosorbent for removal of copper ions from aqueous solution. E. Pehlivan, T. Altun, S. Parlayici.: Food Chemistry, 2012, Vol. 135 (1), pp. 22292234.

10. Heavy metal uptake by agro based waste materials. Qaiser. S, Saleemi A. Anwar, Ahmad. M Muhammad.: Electronic Journal of Biotechnology, 2008, Vol. 10 (3), pp. 409416.

11. Removal of Nickel ion from Industrial Waste Water using Maize Cob. Muthusamy P., Murugan S. and Manothi Smitha.: ISCA Journal of Biological Sciences, 2012, Vol. 1 (2), pp. 7-11.

12. Agricultural waste as a low cost adsorbent for heavy metal removal from wastewater. J. N. Egila, B. E. N. Dauda, Y. A. Iyaka and T. Jimoh. : Academic Journals, 2011, International Journal of the Physical Sciences, Vol. 6 (8), pp. 2152-2157.

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