بررسی کارایی جذب زیستی پوست انار در بهبود شاخص های آلودگی پساب صنعتی و بهینه سازی فرآیند با روش سطح پاسخ
محورهای موضوعی : بیوتکنولوژی و میکروبیولوژی موادغذایینسرین هاشمی 1 , مسعود هنرور 2 * , الهه قره خانی 3
1 - دانش آموخته کارشناسی ارشد، گروه علوم و صنایع غذایی، واحد علوم و تحقیقات، دانشگاه آزاد اسلامی، تهران، ایران.
2 - دانشیار، گروه علوم و صنایع غذایی، واحد علوم و تحقیقات، دانشگاه آزاد اسلامی، تهران، ایران.
3 - استادیار، گروه شیمی، واحد ساوه، دانشگاه آزاد اسلامی، ساوه، ایران.
کلید واژه: آلودگی آب, جذب زیستی, تصفیه فاضلاب, پوست انار.,
چکیده مقاله :
بحران آب و آلودگی محیط زیست ناشی از پسابهای صنعتی باعث ایجاد توجه ویژه به تصفیه و استفاده مجدد از پسابهای صنعتی شده است. در این پژوهش تأثیر پوست انار پودر شده بهعنوان جاذب زیستی ارزان قیمت جهت بررسی شاخصهای کدورت، غلظت جامدات معلق (TSS)، سختی(TDS)، اکسیژن خواهی شیمیایی (COD)و اکسیژن خواهی بیولوژیکی (BOD) استفاده شد. اندازهگیری شاخصهای آلودگی در شرایط pH=4-8، زمان 100-20 دقیقه، دما 50-20 درجه سانتیگراد و غلظت جاذب7-1 گرم بر لیتر انجام شد. نتایج این پژوهش از طریق نرم افزار دیزاین اکسپرت مورد تجزیه و تحلیل قرارگرفت. نتایج بررسی نشان داد که اثر دما روي کل مواد جامد معلق بیشتر از سایر پارامترهاي دیگر است؛ درحالی که اکسیژن خواهی شیمیایی و pH داراي بیشترین اثر روي اکسیژنخواهی بیولوژیکی هستند. علاوه بر این، عملکرد روش سطح پاسخ براي دادههاي اکسیژنخواهی بیولوژیکی بهتر از دادههاي کل مواد جامد معلق بود. در کاهش میزان اکسیژن خواهی شیمیایی، اکسیژنخواهی بیولوژیکی و کل جامدات محلول از محلول، pH بیشترین اثرگذاری را داشت؛ به گونهای که در pH معادل 4کمترین میزان اکسیژن خواهی شیمیایی، اکسیژنخواهی بیولوژیکی و کل جامدات محلول مشاهده شد (اکسیژن خواهی شیمیایی543، اکسیژنخواهی بیولوژیکی2/245 و کل جامدات محلول 148 میلیگرم در لیتر). آنچه از نتایج مشخص است، میزان اکسیژن خواهی شیمیایی و اکسیژن خواهی بیولوژیکی به صورت چشمگیری کاهش داشت اما میزان کل جامدات محلول نسبت به پساب خام افزایش داشت. همچنین با افزایش جاذب، افزایش اکسیژنخواهی شیمیایی و اکسیژن خواهی بیولوژیکی مشاهده شد. تاثیر هر یک از پارامترها بر روی شاخصهای آلودگی اکسیژنخواهی بیولوژیکی، اکسیژن خواهی شیمیایی، کل جامدات محلول، کل مواد جامد معلق، کدورت و مقادیر p-value کمتر از 05/0 نشان می دهد که مدل، معنی دار بوده است.
The water crisis and environmental pollution caused by industrial wastewater have led to special attention to the treatment and reuse of industrial effluents. In this research, the impact of powdered pomegranate peel as a low-cost biosorbent was studied for the examination of turbidity, total suspended solids (TSS), hardness (TDS), chemical oxygen demand (COD), and biological oxygen demand (BOD) indices. Pollution indices were measured under conditions of pH=4-8, time 20-100 minutes, temperature 20-50 degrees Celsius, and adsorbent concentration of 1-7 grams per liter. The results of this study were analyzed using the Design Expert software. The analysis showed that the temperature had the most significant effect on TSS (total suspended solids) compared to other parameters, while COD (chemical oxygen demand) and pH had the highest impact on BOD (biological oxygen demand). Furthermore, the response surface method performed better for BOD data than TSS data. The reduction in chemical oxygen demand, biological oxygen demand, and total dissolved solids from the solution, as well as pH, had the most significant effects. The lowest levels of chemical oxygen demand, biological oxygen demand, and total dissolved solids were observed at pH 4 (543, 2.245, and 148 mg/L, respectively). The results indicate a significant reduction in chemical oxygen demand and biological oxygen demand, while total dissolved solids increased compared to raw wastewater. Additionally, an increase in the adsorbent led to an increase in chemical oxygen demand and biological oxygen demand. The impact of each parameter on pollution indices (BOD, COD, TDS, TSS, Turbidity) and p-values less than 0.05 demonstrate the significance of the model
Introduction
Water has always been a strategic and vital resource that has attracted much attention in every era. As statistics show, the annual volume of water consumed in Iran is 3.5 billion cubic meters, of which 50 to 70% is returned to the environment as wastewater. The discharge of non-standard industrial wastewater and its use in agriculture or discharge into surface waters will lead to many health and environmental hazards. In order to prevent threats to public health, soil contamination, the entry of pollutants into water sources, and contamination of agricultural products, wastewater quality control and identification of its components in order to select the appropriate treatment method are of great importance (3). There are various methods for removing pollutants from wastewater, among which the surface adsorption process has been recognized as a suitable alternative to other expensive wastewater treatment methods (1).Ghaneian et al. used pomegranate seed powder in a study to remove hexavalent chromium from an aqueous medium. The results showed that increasing the mass of the adsorbent and contact time led to an increase in the removal efficiency, and increasing the pH and initial concentration of chromium led to a decrease in the removal efficiency. According to the results, the best removal efficiency occurred at acidic pH and the adsorption reached equilibrium in 120 minutes. At an adsorbent mass of 0.6 g/100 ml, pH=2, and a hexavalent chromium concentration of 2 mg/L, the removal efficiency was 99.5%. The results showed that pomegranate seed powder is a suitable natural adsorbent for the removal of hexavalent chromium (2). Hadigol et al. (2019) used pomegranate peel activated carbon as an adsorbent for dyes and divalent and trivalent metals in liquid media. The results showed that the highest metal absorption occurred at pH=3.5, for 200 minutes and an adsorbent concentration of 2.5 g/L.Under optimal conditions, the adsorption of heavy metals lead, mercury and arsenic was also evaluated and the results showed that the adsorbent reduced these ions by 80%. In the next step, the decolorization and heavy metal reduction ability of the activated carbon produced in the oil environment was investigated. The results showed that this adsorbent has a good ability for decolorization and oxidation stability of oil. In relation to the reduction of heavy metals in oil, the adsorbent produced from pomegranate peel showed better performance than commercial decolorizing soil (4). In a study, the potential of using pomegranate peel as an economical and environmentally friendly solution for the removal of chromium (VI) from aqueous solution was investigated by Giri (2021) and its adsorption properties were studied. The prepared materials were characterized using Fourier transform red spectroscopy and scanning electron microscopy with energy dispersive X-ray analysis.The removal efficiency of pomegranate peel and the effect of experimental parameters on the adsorption of chromium (VI) were evaluated through continuous experiments. The removal efficiency of pollutants by pomegranate peel is dependent on the pH of the chromium (VI) solution and is optimal at pH=2. Furthermore, it was observed that the removal of chromium (VI) increased with increasing adsorbent amount, temperature, contact time and stirring speed, while it decreased with increasing pH, initial concentrations and ionic strength. Excellent removal capacity (96%) was observed at pH=6, adsorbent amount of 300 mg and contact time of 30 min. The adsorption kinetics of chromium (VI) were well fitted by a pseudo-second-order kinetic model and the calculated adsorption capacity of the model showed good agreement with the experimental values. The Langmuir isotherm described the adsorption mechanism of chromium (VI) on pomegranate peel, indicating monolayer adsorption of chromium (VI) with an adsorption capacity (qmax) of 20.87 mg/g. Thermodynamic studies further demonstrated the spontaneous and endothermic adsorption of chromium (VI) on the adsorbent surface.The findings of this study indicate that pomegranate peel can be used as an efficient, environmentally friendly and low-cost biosorbent for the removal of chromium (VI) from contaminated wastewater (13). In a study by Bhatti et al. (2015), various agricultural biomasses such as corn, sugarcane bagasse, cork, sunflower and peanut shells were used to remove pollutants from textile mill wastewater. Various parameters such as adsorbent amount, agitation speed and temperature were optimized. For dye removal, corn biomass is the best adsorbent with a removal efficiency of 79%. The removal efficiency of adsorbents is maximum under the conditions of 0.3 g/500 ml of adsorbent, agitation speed of 120 rpm and temperature of 300°K. Also, thermodynamic studies of Gibbs free energy, enthalpy and entropy changes were carried out, and the results showed that the biological process is exothermic.In wastewater color removal using particulate adsorbents in amounts of 0.05, 0.1, 0.15, 0.2, and 0.3 g, the removal efficiency at 0.3 g was the highest, 40.4%, while the removal efficiency was reported to be 14.4% for sugarcane adsorbent (7). Sharafi Nasab et al. (2021) investigated the removal of chemical oxygen demand from olive factory wastewater using sugarcane bagasse. A factorial design of experiments was used to obtain optimal conditions for each parameter that affects the absorption process. The effects of sugarcane bagasse concentration, solution pH, reaction time, temperature, and stirring speed on the removal percentage of chemical oxygen demand were considered. Removal efficiency above 55.07% of chemical oxygen demand removal occurred at 60 °C, 10 g/L adsorbent, pH = 12, 1 hour contact time, and 80 rpm stirring speed (23).In a study by Rabbani et al. (2023), a mixture of charcoal (60%) and alluvial soil (40%) mixed with laccase enzyme was used to reduce the load of pulp and paper industry wastewater. The mixture of charcoal (60%) and alluvial soil (40%) adsorbent was used to absorb biological oxygen demand, chemical oxygen demand, dye and lignin of the wastewater. The effect of pH, temperature, adsorbent concentration and adsorption time on the removal method was studied. The adsorption equilibrium was achieved after 50 minutes with a stirring speed of 500 rpm at a pH of 0.6 at 25 degrees. The results showed that chemical oxygen demand, biological oxygen demand, dye and lignin were removed by 86, 80, 60 and 62%, respectively. In addition, laccase enzyme also increased the reduction of these parameters as chemical oxygen demand by 95%, biological oxygen demand by 93%, dye by 83% and lignin by 75%.Experimental batch equilibrium adsorption for chemical oxygen demand and biological oxygen demand was discussed by Freundlich and Langmuir models and the kinetics were also discussed with pseudo-first and pseudo-second order. The results of thermodynamic parameters of Gibbs free energy changes, enthalpy and entropy showed that the adsorption process is endothermic and non-spontaneous. Consequently, the use of laccase enzyme in combination with an adsorbent mixture provides promising results and is feasible (20). Pomegranate peel has advantages such as being cheap and available, environmentally friendly, containing pectin and polysaccharides, and due to its negative charge, it adsorbs positive ions. It also has a positive effect on various pollutants. For the reasons mentioned in this study, pomegranate peel was used as a biosorbent.
Materials and Methods
In this study, pomegranate peel was used as a biosorbent to reduce wastewater pollution indices. The materials used were of analytical purity and were purchased from Merck. The list of materials used is as follows:
Sodium hydroxide, concentrated sulfuric acid, mercury sulfate, silver sulfate, phenanthroline, ammonium iron sulfate, potassium hydrogen phthalate
Pomegranate peel collected from a fruit concentrate factory was washed and after drying using a desiccator (0.019% humidity), it was ground with a planetary ball mill of Amin Asia Fanavar Pars Company, model NARYA-MPM-2*250 H, and was added to the wastewater under different conditions of temperature, time, pH, and adsorbent with a concentration of 1-7 g/liter.The turbidity indices, suspended solids concentration, total dissolved solids hardness, chemical oxygen demand and biological oxygen demand were measured before and after adding the adsorbent using standard methods.
Preparation of the adsorbent
After preparing the adsorbent in powder form, the collected powder was washed several times with distilled water until the solution became colorless and then dried at room temperature. Then, 100 g of dried pomegranate peel was stirred with 50 ml of 0.50 M sodium hydroxide solution in a beaker at room temperature for one day to activate its surface (13).
Measurement of biological oxygen demand
The biological oxygen demand of the samples was measured using a biological oxygen demand meter WTW model (BSB-620-T). To measure biological oxygen demand, the sample was first diluted to a level that could be measured by the device.164 ml of the diluted solution was poured into a special container for biological oxygen demand testing, and then two sodium hydroxide crystals were placed in a special place on top of the container. The indicator was set to zero. The device was turned on for 5 minutes while the connections were loose. After the time had elapsed, the connections were tightened and the device was capped. After 5 days, the biological oxygen demand was recorded (21).
Measurement of chemical oxygen demand
To measure chemical oxygen demand, the glass tubes and caps were washed with 20% sulfuric acid before use to prevent contamination. For greater accuracy, volumetric measuring devices with class A were used. The sample was poured into a glass tube and the digestion solution was added to it. The sulfuric acid solution was carefully added into the tube so that an acid layer formed under the digestion solution of the sample.The tubes were placed in the digestion chamber of the Photometer model AL100, which had been preheated to 150°C, and the digestion process was carried out for 2 hours. 0.05 to 0.1 ml (1 to 2 drops) of freoon indicator was added to the solution and titration was carried out with 0.1 M standard ammonium ferric sulfate solution FAS while stirring with a magnetic stirrer. A control solution containing a volume of distilled water equal to the sample volume and all reagents added to it was digested and titrated in a similar manner (21).
(1)
COD as mg O2/L=
A: Volume of FAS used for the control
B: Volume of FAS used for the sample
M: Molarity of FAS
8000= milliequivalents of oxygen×1000 ml/liter
Measurement of total dissolved solids
To measure total dissolved solids, the evaporation dish (Plate) was dried in an oven at a temperature of 180±2°C for one hour and placed in a desiccator. Then the weight was recorded.The sample volume for determining total dissolved solids was selected to yield between 10 and 200 mg of dry residue. After thorough mixing, the sample was filtered and washed three times with distilled water. Then, time was given for each wash to be completed, and finally, time was given again three minutes after the completion of filtration. The filtered solution was placed in a drying container and placed on a dry steam bath. Then, the evaporation container (plate) was placed in an oven at a temperature of 180 ± 2 °C for at least one hour and placed in a desiccator until the temperature stabilized and the weight was recorded (21).
(2)
TSS( ) =
=A Weight of container and suspended matter
B = Weight of container
V = Sample volume (ml)
Measurement of total suspended solids
First, the filter paper was dried in an oven at a temperature of 103-105 °C
.
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