REMOVING POLLUTANTS FROM WASTEWATER USING AN ADVANCED METHOD

Purpose: Preparation of Nano cellulose from cotton lint and pear peels instead of throwing it as waste and cause damage to environment and Comparison between the efficiency of the product of Nano cellulose prepared from cotton lint and NC prepared from pear peels through the characterization of both type of NC by using technique Field emission scanning electron microscopy (FESEM) . finally Applying Murexide dye from the aqueous solution to the surface of both types of extracted Nano cellulose from cotton lint and pear peels for industrial Methodology: Agricultural wastes is the: cotton lint collected from Diyala, Iraq. Linter is an important by product of the textile industry and pear peels collected from Local market of Iraq as raw material to synthesis of Nano cellulose compound Extraction of cellulose from the cotton lint in several steps as follows: A: Purification step B: Grinding step preparation NC product: The product has been prepared by acid hydrolysis. Results and Discussion: In the present study, nanocellulose was successfully isolated from various plant fiber sources (cotton lint and pear peels) using acid hydrolysis . The results indicate that the FE-SEM formation of cellulose nano particles followed this method. However, the best results under sonication conditions used are coming from treatment of 30% acid hydrolysis sonicated for 120 min. Nanocellulose for cotton lint is more efficient than nanocellulose for pear peels in removing murexide dye from the aqueous solution, because percentage of the removal of murexide dye from the aqueous solution by NC of cotton lint is higher than the percentage of the removal of murexide dye from the aqueous solution by pear peels. Therefore, nanocellulose for cotton lint will be more efficient in removing pollutants from water.


INTRODUCTION
Dyes are not readily biodegradable and are frequently not removed from wastewater by traditional wastewater treatment systems (Abd El-Latif et al., 2010).(Kargi And Ozmıhcı, 2004).Since organic dyes are a common component of industrial effluents, it is important to dispose of them properly.Biodegradation, advanced oxidative degradation, and photo-catalytic degradation are frequently suggested methods for these solutions (Walker et al.,2003;Malik et al., 2003).(Chen et al.,2003;Rauf et al., 2005).
Recently, there has been a lot of interest in employing the adsorption approach to remove certain dyes from solutions.Although adsorbent materials can be expensive and some cannot be recycled for large-scale applications, adsorption techniques are flexible and simple to use.Thus, it is obvious that low-cost, renewable, and simple energy sources are needed.One of the most notable green materials of the modern era has emerged in recent years as Nano cellulose (NC), or cellulose in the form of nanostructures.Their abundance, high aspect ratio, superior mechanical properties, renewability, and biocompatibility, among other alluring and exceptional qualities, make them an ideal material for use in a variety of contexts (Lefebvre, 2016).
Growing interest has been shown in NC materials as an ideal replacement (Doğan, 2007).For the current, expensive techniques for removing dyes from wastewater.This study aims at: (1) Preparation of Nano cellulose from cotton lint and pear peels instead of throwing it as waste and cause damage to environment; (2) Comparison between the efficiency of the product of Nano cellulose prepared from cotton lint and NC prepared from pear peels through the characterization of both type of NC by using technique Field emission scanning electron microscopy (FESEM); (3) Showing the great potential for Nano cellulose to have distinctive characteristics; (4) Applying Murexide dye from the aqueous solution to the surface of both types of extracted Nano cellulose from cotton lint and pear peels for industrial; (5) Utilizing agricultural waste recycling for practical reasons, particularly chemical adsorption; and, (6) Minimizing and managing agricultural waste.

THEORETICAL FRAMEWORD
A brand-new and extensively researched variety of cellulose called nano-cellulose is present in fibers that can be obtained from trees, plants, some types of bacteria, algae, and some marine animals.Nanocellulose is not one of them.kind of substance.Despite being a family of compounds, it is distinguished by its various characteristics.This diversity is brought on by the different sources from which nanocellulose was acquired as well as the different preparation techniques (Clemons, 2016).
The original cellulose is converted into nanocellulose crystals, which have nanostructures with tiny dimensions.The substance from which the nanocellulose crystals were made determines their diameters.Nanocellulose is defined as isolated cellulose molecules that are smaller than 100 nm in size, have at least one nanometer-scale dimension, and have unique properties due to their nanostructures (Li, 2012).

METHODOLOGY
Agricultural wastes is the: cotton lint collected from Diyala, Iraq.Linter is an important by product of the textile industry.And pear peels collected from Local market of Iraq as raw material to synthesis of Nano cellulose compound.

Preparation of nanocellulose from agricultural waste (cotton lint)
Extraction of cellulose from the cotton lint in several steps as follows: (a) Purification step: In this step the cotton lint was washed with distilled water in several times (exactly five times).After that cotton fiber was dried until the cotton became completely dry; (b) Bleaching step: In this step the sample (15 gm) added to sodium hypochlorite (4%) for 3h under a strong stirred, filtered and washed with, the distilled water several times, then the sample were dried at (40 ˚C) for 3h; (c) Preparation NC product: The product has been prepared by acid hydrolysis (Wijnhoven et al.,2009).Where the product which from bleaching step has been hydrolysis in 100 ml of sulfuric acid in concentration (30 %), when the sample added to each concentration of H2SO4 the sample must dissolved under strong stirred until the sample completely dissolved at 35˚C with strong stirring, then to finish reaction, added 150 ml of deionized water to solution.After that the solution cooled to 8˚C.After that prepared solution contains (1%) of NaOH for neutralization the sample to pH =7 by adding Sodium hydroxide (1%).
After neutralization the solution was The prepared suspended solution was centrifuged at 10,000 × g for 15 min and it was collected .To production nanocellulose (NC), 200ml of deionized water was added to the sample with stirring.After addition the solution sonicated by ultrasonic processor (Zhou et al., 2012).For three different times (60, 120, and 180) min.When the sonication was completed the solution was collected finally the sample dried at 60˚C for 12h, and get a perfect powder.The fine powder Were put in plastic tube and ready to measurement.

Preparation of nanocellulose from agricultural waste (pear peels)
Extraction of cellulose from the pear peels in several steps as follows: (a) Purification step: In this step the Pear peels was washed with distilled water in several times (exactly five times).After that pear peels was dried for two week until the peels became completely dry; (b) Grinding step: In this step the pear peels was grinded for several time until the pear peels was grinded well.The grinded sample passed through sieves 75 µm to get a good powder; (c) Bleaching step: In this step the sample (30 gm) added to sodium hypochlorite (4%) for 3h with strong stirred, filtered and washed with, the distilled water several times, then the sample were dried at (60 ˚C) for 10h.Then the sample grinded to get a fine powder; (d) Preparation NC product: The product has been prepared by acid hydrolysis (Wijnhoven 2009).Where the product which from bleaching step has been hydrolysis in 100 ml of sulfuric acid in concentration (30 %), when the sample added to each concentration of H2SO4 the sample must dissolved under strong stirred until the sample completely dissolved at 35˚C with strong stirring, then to finish reaction, added 150 ml of deionized water to solution.After that the solution cooled to 8˚C.The produce left at room temperature for one day to separate of cellulose until the separation completed well.Then solution was filtered, and it was washed with distilled water many times.After that prepared solution contains (1%) of NaOH for neutralization the sample to pH =7 by adding Sodium hydroxide (1%).After neutralization the solution was filtered and it was collected (Maiti et al., 2013) To production nanocellulose (NC), 200ml of deionized water was added to the sample with stirring.After addition the solution sonicated by ultrasonic processor (Zhou et al., 2012).for three different times (60, 120, and 180) min.When the sonication was completed the solution cooled to 8˚C for one day.After that the sample filtered and kept the sample at 8˚C.Finally the sample dried at 60˚C for 12h, and get a perfect powder.The fine powder were put in plastic tube and ready to measurement, Figure (3.2) showed all steps.

Field emission scanning electron microscopy (FESEM)
Field emission scanning electron microscopy (FESEM) provides important visual information concerning with the morphology of cellulose.FESEM was utilized to check morphology of the nanoparticles of samples (Dima et al., 2017).
Scanning electron microscope (FESEM) shows the morphology of the external side after isolation methods.FESEM images show differences in size and shape of the samples.It showed the existence of regular crystalline regions, but also showed non-amorphous areas.The surface morphology of the NC prepared of cotton lint appear layers separarted from each other with some nanotubes.the surface morphology of the NC prepared of pear peels show the surface morphology shown in Figures (4.2) all of them show a homogeneous distribution of spherical shape like nanoparticles with irregular distribution.From FESEM images it is confirmed that the particles having small size.The smallest nano dimeter of cotton lint is (42) nm. the smallest nano dimeter of pear peels is 67 nm.

Adsorption study
The Nano-cellulose materials were prepared from lint cotton and pear peels used as adsorbent surfaces for murexide dye (adsorbate), The factors influencing adsorption were then studied in different conditions to study the adsorption behavior with murexide dye.

Determination of contact time of adsorption
This step is important in the research and aims to follow the adsorption of the dye of murexide with time and determine the time necessary to reach the state of equilibrium, the study done with a fixed concentration of dye (10 ppm), and a constant acidic function PH of 6, as well as a constant amount of adsorbent surface, which is 0.06 grams of both surfaces.The study showed that the process reaches a state of equilibrium at time 5 minutes for the nanocellulose produced from the cotton lint and 15 minutes for the nanocellulose from the pear peels.The results are shown figure (1) explains change in the percentage of the, removal of murexide dyes from aqueous solutions with change time for adsorptions of murexide dye, on surface of NC of cotton lint and NC of pear peels.

The results
Exhibited in Figure 3 that the equilibrium times for the adsorption of murexide dye on cotton lint and pear peels were 5 min and 15 min, respectively.The amount of adsorbate was seen to increase as equilibrium time increased until it reached a constant value (Trache et al., 2020).This can be explained by the fact that initially there are a large number of surface sites, which makes it very simple for adsorption to occur.However, as time goes on, active sites become saturated, slowing down the dye removal (Rehman et al., 2011).
The effects off adsorbent quantity on adsorption of murexide dye studied, by using different amounts off adsorbent for cotton lint and pear peels (0.01,0.02,0.03,0.04,0.05, and 0.06) g, with remained the concentration of the original dye (10 ppm) and constant PH and  It was found that the percentage of their removals (R%) off dyes from aqueous solutions through using nanocellulose prepared from the cotton lint.It increases with the increase of the amount of the adsorbent surface reach to 0.04g, which we find that the percentage of removal in the maxi\mum case and then begin to decrease gradually and slightly.the reason for increasing percentage of removal is too increases the surface areas of f adsorption and their presences off active adsorption sites, after that, the percentage of removal begins to decrease gradually but slightly, and this is due to the arrival of the surface to the state of saturation of dye molecules.
While (R%) of dyes from aqueous solutions through using the nano-cellulose prepared from the pear peels, The convenient weight of the adsorbent is 0.006 g, and as the dosage of the adsorbent is increased, more active sites on the NC surface become available to adsorb the dye, increasing the percentage of dye removal into the surface (Cottet et al., 2014).

Study of the effect of concentration on adsorption
The different concentrations of the murexide dye to determine the optimal concentration of dye was studied by taking different concentrations are (10 ,30,50,70,90) ppm, at quantity of adsorbent constant is (0.04g) of cotton lint and (0.06g) of pear peels and constant temperature at 25 C, and constant time 5min for nanocellulose of cotton lint and 15 min for NC pear peels and constant PH.It was found that the best concentration of murexide dye is 10 ppm, which has the maximum percentage of the removal (R%) of the dye from the aqueous solution.Information in figure 6 below: According to the aforementioned findings, the percentage of dye R% removed by increasing the initial concentration decreases.The percentage of dye removed from aqueous solution decreases as initial murexide dye concentration increases.This is explained by the decrease in active sites required for absorption caused by the buildup of dye molecules on the surface of the adsorbent (Abdeen and Mohammad,2013).(Smaranda et al.,2011).

Effect of temperature on adsorption
Their effects off temperatures only adsorptions of dyes was studied at different temperature (25,35,45,55,65) C, with remained the concentration of dye constant (10 ppm) and a constant time 5 minutes for NC cotton lint and 15 minutes for NC of pear peels.Results are appeared into) and figure (4).In the results, indicate that the amount of adsorption (Q e) and the percentage of removal (R%) to the dye of the murexide on the surface of NC of cotton lint and pear peels decrease when the temperature increase where the maximum the percentage removal at 25˚C, then increases into temperature s leads into decreases (R%) gradually of this is because the increases into temperatures leads , to reduce in speed off the spread of molecules on the surface and thus weaken the adsorption of dye molecules on the active sites of the surface where the adsorption occurs (Bazrafshan et al., 2016;Wambu et al., 2012) It is also the result of the assumption that only adsorbent surfaces can experience instantaneous adsorption (Jadhav et al., 2001).

Effect off pH only adsorption
Their effects of pH on adsorptions off dye on nanocellulose produced from cotton lint and pear peels was studied by changing the acidic function PH (2,4,6, 8, and 10) with a constant concentration of dye (10 ppm) and constant temperature 25C°for 5 min for cotton lint and 15 minutes for Pear peels and results are shown in figure (5).It is obvious that a key factor in controlling the adsorption process is the pH of the aqueous solution.In the pH range of 2-10, the percentage of adsorption was investigated.The outcomes are displayed in Figure 8.
The minimum and maximum adsorption values for the nanocellulose made from cotton lint and pear peels were 64% and 70%, respectively, at pH=10, and 98% and 90%, respectively, at pH=2. and in the acidic media, adsorption was greatest.This may be because of the hydrogen bonds formed by the oxygen atoms in the adsorbate and the hydroxyl groups in the adsorbent, which ultimately cause an increase in the percentage of adsorption (Baig et al.,2014).

CONCLUSIONS
Nanocellulose product was prepared from cotton lint and pear peels waste as raw materials .NC product was obtained from cellulose found in the raw materials with simple methods without having an expensive processes such as bleaching, acid hydrolysis, freeze and drying processes.Ultrasonic device was used to has be done sonication process of the raw materials and it was obtained a powdered with good properties that could have been used in other processes and techniques The aim of this study was to evaluate the efficiency of nanocellulose (NC) obtained from cotton lint and pear peels for the adsorption of murexide dye.
The adsorption experiments were carried out in the context of the batch process, based on the following experimental conditions: the time, the adsorbent dose, the initial dye concentration and the pH, In this study, an excellent removal of the murexide dye from the aqueous solution by adsorption process using NC as adsorbent surface of dye.Thus, NC can be used to remove pollutants from the environment, therefore NC environmentally friendly.
Nanocellulose for cotton lint is more efficient than nanocellulose for pear peels in removing murexide dye from the aqueous solution, because percentage of the removal of eosin dye from the aqueous solution by NC of cotton lint is higher than the percentage of the removal of murexide dye from the aqueous solution by pear peels.Therefore, nanocellulose for cotton lint will be more efficient in removing pollutants from water.

Figure 1 :
Figure 1: The Fe-SEM images of (NC) produced from cotton Lint Source: The authors (2022).

Figure 3 :
Figure 3: explains effects off contact times, on adsorption of dye on surface of NC of cotton lint and pear peels at 298 K. Source: The authors (2022).

Figure 5 :
Figure 5: explains effect of adsorbent quantity on adsorption of murexide dye on surface of NC of cotton lint and pear peels at 298 K Source: The authors (2022).

Figure 6 :
Figure 6: Shows the effects off initially concentrations on adsorption to Murexide dye on surface off NC of cotton lint and pear peels at 298 K. Source: The authors (2022).

Figure 7 :
Figure 7: explains effects of temperatures on adsorptions off dyes only surface of NC of cotton lint and pear peels at different temperature.Source: The authors (2022).

Figure 8 :
Figure 8: explains, effects off pH on adsorptions of eosins dyes on NC of cotton lint and pear peels.Source: The authors (2022).