Adsorption capacity of pollutants by using local clay mineral from urban wastewater Touggourt (South-East Algeria)
Serraoui Mabrouk1, Ahmed Abdelhafid Bebba1, Abasse Kamarchou1, Ammar Zobeidi2
1Laboratory of Water and Environmental Engineering in the Saharan Region, University of Kasdi Merbah Ouargla. P.O. Box 511, 30000, Algeria.
2Laboratory of Valorization and Promotion of Sahara Resources (LVPSR), University of Kasdi Merbah
Ouargla. P.O. Box 511, 30000, Algeria
*Corresponding Author E-mail: abasselazhar@gmail.com
ABSTRACT:
The accurate, the city Touggourt is a huge mine of clay minerals, mostly exploited in the traditional pottery industry, ceramic and brick. The purpose of this work is to value these minerals in the field of environmental conservation by using them in wastewater treatment., in the first step, we determined the clay ratio in the soil where found 52%. The study of physical and chemical properties by XRD and FTIR showed that the clay is a mixture of kaolinite and illite also we found the surface area specific 113.76 m3/g, the cation exchange rate is 20 mm/100g. The second step is studies the adsorption of organic and inorganic pollutants in wastewater.
Clay is used as a rock term and as a particle-size term in the mechanical analysis of sedimentary rocks, soils, etc. As a rock term, it is difficult to define precisely, because of the wide variety of materials that have been called clays. Clay refers to a naturally occurring material composed primarily of fine-grained minerals. The minerals found in clay are generally silicates less than 2 microns in size [1-3].
The interest given in recent years to the study of clays by numerous laboratories throughout the world is justified by their abundance in nature, their low cost, and the presence of electrical charges on their surfaces and, above all, the exchangeability of the interfoliar cations. All these properties make clay a material of exceptional quality [4].
Several previous works [5-10], worldwide have shown that clay minerals of smectite, montmorillonite, bentonite, illite, vermiculite, kaolinite or sepiolite have heavy metal and organic compounds adsorption capacities in effluents and waters contaminated.
The mineralogical and physic-chemical properties of clays are of particular interest in many applications such as paint, the barrier for pollutants, adsorbent, catalyst, water and wastewater treatment, etc [11-13].
Water is indispensable in the living world for many reasons. Wastewater may be defined as ‘a combination of liquid or water-carried wastes removed from residences, institutions and commercial and industrial establishment together with such groundwater, surface water, and storm water as may be present [14].
Most industries are water based and release a considerable volume of wastewater which is generally discharged into water courses either untreated or inadequately treated and causes water pollution [15].
Among the different species causing water pollution is organic compounds. Organic pollutants are toxic molecular compounds and can cause significant diseases in humans when exposed to high concentration levels.
The industrial produces a variety of effluents in water containing large quantities of biological oxygen demand (BOD) and chemical oxygen demand (COD). Traditionally, aerobic treatment systems such as aerated lagoons and activated sludge plants were used to remove BOD [16].
Adsorption is an effective and well-known process and has been widely explored as an alternate technique compared with the other waste removal methods due to the lower cost, flexibility, and simplicity of design, and ease of operation. Moreover, adsorption does not result in the production of any harmful substances.
Several materials are used for the adsorption of polluting compounds. Natural materials are well known as adsorbents from the beginning of recorded human development. In particular, clays have been utilized as an adsorbent and as an ion-exchange material for the removal of ions and organics due to their low cost, natural abundance, high adsorption capacity, and ion-exchangeable property [17-20]. In the past decades, clay minerals such as bentonite, diatomite, and kaolin have garnered increasing interest due to their ability to remove both inorganic and organic materials.
Inattention towards wastewater treatment operations can lead to contamination of water and soil resources and, consequently, infectious and chronic diseases. Physical, chemical, and biological wastewater treatment methods are of special importance.
Moreover, given the limitation of water sources, when wastewater is treated appropriately and is compatible with environmental standards, the treated wastewater can be reused in different fields such as agriculture [21].
Protection of valuable sources, like bentonite soil, and their use in the treatment of industrial wastewater are from effective solutions for improving the level of environmental cleanliness [22].
2. MATERIAL AND METHODS:
2.1 Instrumentation:
The physical chemical characterization of the purified clay was performed by: X-ray diffraction with a copper anticathode (λ =1.540598Å). Generator settings 40 mA to 45 kV. Divergence slit size 0.4354°. Fourier-transform infrared spectroscopy (FTIR), from SHIMADZU type IR Affinity-1 was used. The wavelength range was 4000 - 400 cm-1. The BET technique, BET apparatus type ASAP 2020 V4.03 (V4.03 J) was used. The specific surface area was determined by measuring adsorption and desorption of nitrogen at 77.123 K. MEB model JSM- 6100. To determine Cation Exchange Capacity (CEC), the procedure described in the French standard AFNOR NFX 31-130.
2.2 Purified clay:
The sample clay was taken from area called "Beldet Omar" (Latitude 56 ° 32'32" N 55 ° 5'37.82" E) (Fig.1).
A granular analysis of the soil was conducted in the Southern General Laboratory in the Ouargla region with NFP,
5 Mai 1992 method. Organic compounds were removed by treatment with H2O2 (6%) and calcite were removed with hydrochloric acid. Clay minerals were then separated using sodium hexametaph -osphate solution (5%) as dispersion material. In order to obtain clay minerals granules less than 2 μm in diameter, we used the Robinson pipette method.
Fig. 1: The geographical location of the city of Touggourt (Google Earth 2017)
Fig. 2: the located astronomically of wastewater treatment plant in the city of Touggourt
2.3. Wastewater treatment:
The samples were taken from wastewater treatment plant of Touggourt city, located astronomically on the longitude 5 ° 04 'E and latitude 33 ° 16' (Fig. 2).
During all the treatment operations, a volume of 800 mL of the wastewater was taken as fixed. To determine the optimal treatment conditions: stirring speed (200-800) rpm, contact time (30-150min), pH (5.15-8.1), mass (0.01-2) g and temperature (20-41) °C, the variation of chemical oxygen demand (COD), biochemical oxygen demand after 5 days (BOD5) and suspended solids (TSS) according to the parameters mentioned above have been monitored (NFP 94-057 ).
COD was measured by cuvette test model: LCK314, LCK114 and P-PO4-3 by cuvette test model: P-1K, P-2K with Spectrometer model: HACH DR 3900. As for the BOD5 is measured by OXITOP-WTW-2.
3. RESULTS AND DISCUSSION:
3.1. Physico-chemical characteristics of the clay sample:
The obtained results of the physico-chemical characterization of the studied clay are summarized in table 1.
Table 1. Physical and chemical properties of the studied clay sample
|
soil texture |
clay |
52℅ |
|
silt |
20.5℅ |
|
|
Fine sand |
18℅ |
|
|
Clay sample composition |
illite |
65.5℅ |
|
kaolinite |
21.8℅ |
|
|
quartz |
12.7℅ |
|
|
Isotherm type |
IV |
|
|
The average size of nanoparticles (Å) |
527.416 |
|
|
BET Surface Area (m2/g) |
113.7622 |
|
|
Langmuir Surface Area(m2/g) |
166.3105 |
|
|
Pore volume (cc/g) |
0.123026 |
|
|
Pore size (Å) |
81.846 |
|
|
Cation exchange capacity (mmol/100g) |
20 |
|
3.2. Influential parameters:
3.2.1. Effect of stirring speed:
We note in the curves represented in figure .4, when the stirring speed increased until 700 rpm, the rate of COD, BOD 5, P-PO4-3 increase and for the TSS increase at the value 500 rpm.
We discuss that the stirring speed blends all pollutants with the clay, this leads to increase the contact between the surface of clay and the pollutants, also the adsorption increases between pollutant and the clay, so the rate of adsorption augments. The rate of adsorption controlled by the spread of pollutant inside the clay surface [23].
After 700 rpm the rate of adsorption decreases because there is a desorption phenomene that are caused by a generation resistance prevents from being installed on the mud surface[25-24] .so we choose the 700 rpm as a optimal speed stirring.
Fig. 3: Effect of stirring speed on removal rate for COD, BOD, P-PO4, TSS (pH = 7.5 ± 0.2, T = 25±1°C, m = 1g, t=60min)
3.2.2. Effect of contact time:
We note in the curve Fig.5 that the removal rate of COD and BOD5 increases in the timeframe between 30 – 150 min, As the previous works of some researchers have shown.[27-24]
The removal rate of COD and BOD5 increases until happening the equilibrium between the clay and the pollutants. However, these results were applied in water solutions. In this case, the removal payoff continues to rise, This increase is due to a time difference allowing the remaining bacteria in the water to work and digest a high amount of organic pollutants, the fixes of removal rate due to a time difference allowing the remaining bacteria in the water to work and digest a quantity of organic pollutants.
The removal yield P-PO4-3 increases up to 90 minutes and decreases at 120 minutes and then re-increases, This due to the impact of the nature of the clay and absorption locations available to the removal rate of P-PO4-3.
The mechanism of the transfer of the solvent to the solid is carried out according to the spread through the liquid film about the adsorpants particles.
In the premery steps of phosphate absorption, the combination of film and available pore locations is large, so the absorption rate is faster. The rate of absorption decreases in late stages of adsorption due to the slow spread of dissolved ions in most of the adsopants pores [28- 29].
Fig. 4: Effect of contact time on removal rate for COD, BOD, P-PO4, TSS (pH = 7.50±0.2, T = 25±1°C, m = 1g, V=700rpm)
3.2.3. Effect of mass:
From the results of the four curves in Figure. 6, the removal rate for COD, BOD5, P-PO4-3, TSS, is shown to increase the mass of the pollutants by a clear increase to a mass of 1.5g.
An additional increase in the amount of the clay up to 2g leads to a slight increase in each of the COD, BOD5; we note decreases in rate of P-PO4-3, TSS.
We interpret the initial acute increase in adsorption as an increase in the adsorption locations available on the surface relative to the concentration of pollutants [30].
The least effect of an increase in the mass of clay can be the result of the assembly of adsorpants particles that lead to a decrease in effective surface area [31]. Through the results we take the mass 1.5 g as the optimal value.
Fig. 5: Effect of mass on removal rate for COD, BOD5, P-PO4-3, TSS (pH = 7.50±0.2, T = 25±1°C, t = 90min, V=700rpm)
3.2.4. Effect of pH:
from the results obtained and shown in Figure 7, we note that the increases of pH between 5.15 – 8.1 leads to increases the removal rate of COD, BOD5.
It is known that the hydrogen number of the solution is an important parameter that affects the properties of the clay and pollutants as well as the process of adsorption in water solutions [32- 33].
This is because the crystal structure is a characteristic of the main surface which is a factor in the surface charge and reactive sites that are located primarily above the edge surface. it also determines the adsorption process.
The variable charge of clay minerals lies primarily from the disintegration of Al-OH and Si-OH in the broken edge, at a higher pH, the surface of the mud carries more negative charges [34], the adsorpants matters effected with pH converting into negatives and positives charges.
We note that pH effect on the process of adsorption, so that the ratio of adsorption of orthophosphate is increasing between the values of pH 5.15- 6.15, then decline thereafter .in a high pH value the dominant category is PO4-3, The dominant category in weak basic conditions is HPO4-2, the category H2PO4- is dominate in a weakly acidic conditions, the main category in highly acidic conditions is H3PO4. The Previous research has shown that increasing acidity decreases phosphate adsorption [35].
At highly pH values the clay surface has negative charges, which increase the repulsion of negative phosphate types in solution, by a less adsoption capacity, this leads to electrostatic dissipating between phosphate ions and negatively charged surface molecules.
It is known that the total soluble phosphorus in the waste water is found in different forms of organic and non-organic phosphate, Decomposition reactions also affect it. Organic phosphates may depend on some structural differences such as number, variety of functional groups, and number of phosphate groups.
when the pH value increases the yield of TSS increases, This is due to the high activity of the amino functions, The presence of H+ ions in the solution has reduced the charge of the negative surface of the particles due to the acid nature of the solution, This led to molecules associated with self-groupings [39], at the pH = 8.1 there is a negative electrostatic multiplier, maybe that will stop to neutral kind only in the water, This is due to the attractiveness of static electric.
Fig. 6: Effect of pH on removal rate for COD, BOD, P-PO4-3, TSS (m =1.5g, T = 25±1°C, t = 90min, V=700rpm)
3.2.5. Effect of temperature:
from the results obtained and shown in Figure 8, we note that the increases of pH between 20 – 41 C0 leads to increases the removal rate of COD, BOD5, P-PO4-3 , this results are closely aligned with[38-37], It is known that increasing temperature increases the rate of spread of pollutants across the outer layer, This is due to the decrease of solution viscosity, Thus, the change in temperature will change the equilibrium between adsorpate and adsorpant , In most of pollutant-clay mineral adsorption systems, the temperature possesses a positive effect on the uptake of solute, with the increase of temperature, the amount of pollutant adsorbed by clay also increase.
Fig.7: Effect of temperature on removal rate for COD, BOD, P-PO4-3, TSS (pH = 8.1V = 700rpm, m = 1.5g, t=90min)
4. CONCLUSIONS:
Clays have been utilized as an adsorbent and as an ion-exchange material for the removal of ions and organics due to their low cost, natural abundance, high adsorption capacity, and ion-exchangeable property.
The granulometric analysis study showed that the soil contains 52 % clay minerals; the latter contains mostly illite, some kaolinite and a bit of quartz, and has a specific surface area 113.7622 m2/g and has also a cation exchange capacity of 20 m Eq/100g.
These properties enable the clay to be used for the removal of organic pollutants in significant amounts of urban wastewater. For that reason it was sought to find the optimal conditions for the removal of organic pollutants to obtain water that has standards that make it suitable for agricultural and industrial use.
By studying the factors affecting adsorption (speed of stirring, contact time, pH, clay mass and temperature) it is possible to select optimal conditions for reducing organic pollutants by adding a concentration of 3.33 g/L with an acidity of around 8.1. The operation is carried out at 30 °C near normal temperature and 700 rpm for 90 minutes and m= 1.5 g.
These optimal conditions showed a good elimination results by reducing COD, BOD5, P-PO4-3and TSS with removal rates of 69.16℅, 71.59℅, 73.10℅, and 85.81℅respectively
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Received on 03.02.2020 Modified on 20.02.2020
Accepted on 28.02.2020 ©AJRC All right reserved
Asian J. Research Chem. 2020; 13(2): 85-90.
DOI: 10.5958/0974-4150.2020.00018.8