CHAPTER1: INTRODUCTION

1.1 Heavy Metal Waste from Industries

Indias environment is becoming fragile and environmental pollution is one of the undesirable side effects of industrialization, urbanization, population growth and unconscious attitude towards the environment. At present, environmental protection is the main need of the society. Though industrialization and development in agriculture are necessary to meet the basic requirement of people, at the same time it is necessary to preserve the environment. In India, too, the environmental pollution has become a cause of concern at various levels (Navneet Joshi, 2003). In India, due to lack of sewage treatment plants, generally untreated sewage effluents are released either on agricultural land for irrigation or disposed of in nearby water bodies. In general, sewage effluents from industries and of municipal origin contain appreciable amounts of plants nutrients and variable amount of metallic cations2 like Zn, Cu, Fe, Mn, Pb, Ni, Cd, etc (Ajay Kumar et al 2009). Long-term irrigation with such effluents increases EC, organic carbon content and heavy metals accumulation in soils and the chances of their entrance in food chain, and this ultimately causes significantly health concern.

Towards this direction, several conventional wastewater technologies were developed and are in use successfully at large scale, to reduce hazardous compounds concentration in wastewater from higher to lower level. Application of such traditional treatments demands high investment cost and continuous inputs of chemicals which becomes impractical and uneconomical and causes further environmental damages. Hence, easy, effective, economic and eco-friendly techniques are required for fine-tuning of wastewater treatment.

1.2 Sources of discharge of metals

Lead: present in petrol-based materials and many other industrial facilities (Sag and Kutsal 1997). Chromium: industrial operations including chrome plating, petroleum refining, leather, tanning, wood preserving, textile manufacturing and pulp processing. It exists in both hexavalent and trivalent forms. Iron: Iron and steel units, electroplating industries and galvanizing units. Zinc: widely used in industry to make paint, rubber, dye, wood preservatives, and ointments and electroplating industries. Nickel: galvanized, paint and powder batteries processing units.

Table 1.1: Health Hazards Due to Various Metals Metal Iron Health Hazard The lack of iron in the diet may lead to iron-deficient anemia, fatigue, weakness, drowsiness, pallor (paleness), cold extremities, Brittle nails, loss of appetite, constipation, headaches, irritability, difficulty concentrating, depression, loss of libido, tinnitus (ringing in the ears), spots before eyes, bizarre behavior, gastrointestinal complaints, cessation of menstruation, jaundice. Chromium Irritation, nausea and vomiting; carcinogen (Oxidation state of +6), Lowlevel exposure can irritate the skin and cause ulceration. Long-term exposure can cause kidney and liver damage, and damage too circulatory and nerve tissue. Zinc Nausea and vomiting. Zinc combines with other elements to form zinc compounds; common zinc compounds found at hazardous waste sites include zinc chloride, zinc oxide, zinc sulfate, zinc phosphide, zinc cyanide, and zinc sulfide. Lead Damage to nervous system, circulatory system, blood forming system,

reproductive system, gastrointestinal tract and kidney Lead is known for its harmful affect on the living world, enters the organism by breathing, swallowing, or absorption through the skin. The greatest danger from lead comes from its tendency to accumulate in the human organism. The central nervous system is most sensitive to the effects of lead. Nickel Short-term overexposure to nickel is not known to cause any health problems, but long-term exposure can cause decreased body weight, heart and liver damage, and skin irritation. The EPA does not currently regulate nickel levels in drinking water.

1.3 Methods of Effluent treatment

Commonly used methods for the removal of heavy metals from effluents includes ultra filtration, reverse osmosis, chemical precipitation, ion exchange, electro dialysis, pyrotermediation and solvent extraction. Given below are the description of the conventional methods and disadvantages associated with them. Ultra filtration: It involves the use of a semi-permeable membrane with pore sizes in the range of micrometers for the filtration of the effluent causing removal of metal ions. A major disadvantage is the cost of the membrane and the formation of large amounts of sludge. Reverse osmosis: Slurry containing the heavy metal is passed through a semi permeable membrane at a pressure higher than the osmotic pressure causing its separation. A disadvantage of this method is that it is very expensive at a higher scale owing to the cost of membranes. Electro dialysis: There are two regions separated by a pair of semi permeable membranes, on the application of an electric potential, causing the movement of cations and anions in separate directions thereby causing separation. A major drawback of this method along with

the high cost of membranes is the formation of metal oxides which cause choking of the membrane. Ion exchange: In this process, metal ions from dilute solutions are exchanged with ions held by electrostatic forces on the exchange resin. A disadvantage of this method again along with high cost is the partial removal of ions. Chemical Precipitation: This method involves the addition of coagulants such as lime, alum, iron salts and other organic polymers which cause the metal ions to coagulate and then be precipitated out of the solution. The disadvantage with this process is the formation of a large amount of toxic sludge which will be difficult to dispose. Pyrotermidiation: This method involves the use of certain plants to cleanse the soil, sediments and water that are contaminated with metals. Disadvantages with this method are the long time taken to remove the metals and the regeneration of the plants for further biosorption.

Table 1.2: Comparison of Effluent Treatment Processes Technology Concentrati on dependence Hydroxide Precipitation Sulfide Precipitation Ion Exchange Evaporation Reverse Osmosis Adsorption Biosorption Yes yes Some Yes Yes yes 1-5 <1 Yes Yes No No Yes No Yes Some Yes No 1-5 1-5 --No No No Yes Some No <1 Yes Yes No No Yes <1 No Yes No no Yes 2-5 No yes pH dependence Suspende Effluent d solids concetration Regenerati Sludge on generation

1.4 Biosorption
1.4.1 Introduction: The search for new technologies involving the removal of toxic metals from wastewaters has directed attention to biosorption, based on metal binding capacities of various biological materials. Biosorption can be defined as the ability of biological materials to accumulate heavy metals from wastewater through metabolically mediated or physicochemical pathways of uptake. Biosorption involves a solid phase (sorbent or biosorbent) and a liquid phase (solvent, normally water) containing a dissolved species to be sorbed (sorbate, metal ions). Due to higher affinity of the sorbent for the sorbate species, the latter is attracted and bound there by different mechanisms. The process continues till equilibrium is established between the amount of solid-bound sorbate species and its portion remaining in the solution. The degree of sorbent affinity for the sorbate determines its distribution between the solid and liquid phases. Strong biosorbent behaviour of certain micro-organisms towards metallic ions is a function of the chemical makeup of the microbial cells. This type of biosorbent consists of dead and metabolically inactive cells. Some types of biosorbents would be broad range, binding and collecting the majority of heavy metals with no specific activity, while others are specific for certain metals. Some laboratories have used easily available biomass whereas others have isolated specific strains of microorganisms and some have also processed the existing raw biomass to a certain degree to improve their biosorption properties. Recent biosorption experiments have focused attention on waste materials, which are by-products or the waste materials from large-scale industrial operations. An inexpensive source of biomass where it is available in copious quantities is in oceans as Sea Weeds, representing many different types of marine macro-algae. However most of the contributions studying the uptake of toxic metals by live marine and to a lesser extent freshwater algae focused on the toxicological aspects, metal accumulation, and pollution indicators by live, metabolically active biomass. Focus on the technological aspects of metal removal by algal biomass has been rare.

Although abundant natural materials of cellulosic nature have been suggested as biosorbents, very less work has been actually done in that respect.

1.4.2 Biosorption Mechanism: The mechanism of biosorption is complex and mainly includes ion exchange, chelation, adsorption by physical forces, entrapment in inters and intrafibrilliar capillaries and spaces of the structural polysaccharide network as a result of the concentration gradient and diffusion through cell walls and membranes. There are several chemical groups that would attract and sequester the metals in biomass: acetamido groups of chitin, structural polysaccharides of fungi, amino and phosphate groups in nucleic acids, amido, amino, sulphhydryl and carboxyl groups in proteins, hydroxyls in polysaccharide and mainly carboxyls and sulphates in polysaccharides of marine algae that belong to the divisions Phaeophyta, Rhodophyta and Chlorophyta. However, it does not necessarily mean that the presence of some functional group guarantees biosorption (Ramchandra et al 2003). This may be due to steric, conformational or other barriers.

Biosorption mechanism is mainly of two types based on if micro organisms or dead biomass is used. They are: 1. Metabolism based, and 2. Non-Metabolism based.

Many microorganisms and bacteria have been studied and found to possess a good capacity for metal adsorption. Their mechanism is mainly metabolic based. Our focus will be more on the mechanism involved in the case of dead biomass who cellular surface contains various functional groups. During non-metabolism dependent biosorption, metal uptake is by physico-chemical interaction between the metal and the functional groups present on the cell surface. This is based on physical adsorption, ion exchange and chemical sorption, which is not dependent

on the cells' metabolism. Cell walls of the biomass, mainly composed of polysaccharides, proteins and lipids have abundant metal binding groups such as carboxyl, sulphate, phosphate and amino groups (Yadav et al). This type of biosorption, i.e., non-metabolism dependent is relatively rapid and can be reversible.

Physical adsorption: In this category, physical adsorption takes place with the help of Van der Waals' forces. Kuyucak and Volesky (1988) hypothesized that uranium, cadmium, zinc, copper and cobalt biosorption by dead biomasses of algae, fungi and yeasts takes place through electrostatic interactions between the metal ions in solutions and cell walls.

Ion Exchange: Cell walls contain polysaccharides and bivalent metal ions exchange with the counter ions of the polysaccharides. For example, the alginates of marine algae occur as salts of K+, Na+, Ca2+ and Mg2+. These ions can exchange with counter ions such as Co2+, Cu2+, Cd2+ and Zn2+ resulting in the biosorptive uptake of heavy metals.

Complexation: The metal removal from solution may also take place by complex formation on the cell surface after the interaction between the metal and the active groups.

Factors that affect adsorption are 1. Temperature: It is generally observed that the adsorption capacity of dead biomass does not vary between the temperature ranges of 20-35oC and slowly increases with further increase. 2. pH: This is one factor that greatly affects the adsorptive capacity. It is generally observed that the capacity is lower in the acidic region. 3. Adsorbent dosage: The amount of metal absorbed increases with the increase in dosage. 4. Time: Time also plays a crucial role. After a particular optimum point the adsorptive capacity becomes constant. 5. Concentration of the metal in the solution also affects the adsorption.

Table 1.3: Metal Adsorption by Various Bio-Adsorbents Bio-adsorbent Bagasse Fly Ash Activated Carbon Tea Factory Waste RHA Silica Hyacinth roots Agriculture residue Saw dust Coconut Fiber Metal adsorbed Cd+2, Ni+2 Pb+2, Cd+2, Ni+2, Hg+2, Cr+2 Ni+2 Ni+2 Cr+2 Cd+2,Cr+2 Cd+2,Cr+2,Pb+2 Cr+2

Apart from this, we have many more materials on which bio-sorption studies have been done like sago, sugar beet pulp, tree fern, wood waste, etc. A major Bio-adsorbent that has shown good activity as well as economic feasibility are under the category of Citrus peels. They are generally waste generated from the citrus juice manufacturers.

1.5 Citrus Peel as Bio-adsorbent

Conventional method such as chemical precipitation, chemical oxidation or reduction, filtration, electrochemical treatment, ion-exchange, adsorption, membrane processing and electrolytic methods, have been traditionally employed for heavy metal removal from industrial wastewater. However, the shortcomings of most of these methods are high operational and maintenance costs, generation of toxic sludge and complicated procedure involved in the treatment. Comparatively, adsorption process is considered better

in water treatment because of convenience, ease of operation and simplicity of design. Furthermore, this process can remove/minimize different type of pollutants and thus it has a wider applicability in water pollution control. Activated carbon is undoubtedly considered as universal adsorbent for effluent treatment and is commonly used for the removal of various pollutants from water. However, its widespread use in wastewater treatment is sometimes restricted due to its higher cost. A large variety of nonconventional adsorbents have been examined for their ability to remove various types of pollutants from water and wastewater and have been reviewed extensively. It has been found that various low-cost adsorbents developed from different origins show little or poor sorption potential for the removal of aquatic pollutants as compared to commercial activated carbon. Therefore, the search to develop efficient sorbents is still going on. From last few decades, bio-sorption process has emerged as a cost effective and efficient alternative for water and wastewater treatment utilizing naturally occurring and agricultural waste materials as bio-sorbents as these are cheaper, renewable and abundantly available. At present, bio-sorption field has been enriched by a vast amount of studies published in different journals. Various bio-sorbents have been examined for the removal of diverse type of pollutants from water. Agricultural materials contain proteins, polysaccharides and lignin which are associated with functional groups responsible for metal ion adsorption2. The abundant natural occurrence and presence of large amount of surface functional groups make various agricultural wastes good alternatives to expensive synthetic adsorbents. In recent years, agricultural by-products have been widely studied for metal removal from water. These include peat, wood, pine bark, banana pith, soybean and cottonseed hulls, peanut, shells, hazelnut shell, rice husk, sawdust, wool, orange peel, and compost and leaves. The use of citrus peel as a bio-sorbent material presents strong potential due to its high content of cellulose, pectin (galacturonic acid), hemicellulose and lignin. As a low cost, citrus peel is an attractive and inexpensive option for the bio-sorption removal of dissolved metals.

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It was found out that the affinity sequence Pb2+ > Cu2+ > Co2+ > Ni2+ > Zn2+ > Cd2+ ion exchangers for cation binding to pectin3. Ni2+ had a higher affinity to orange peels than Cu2+, Pb2+, Zn2+ and Cr2+ (Patil et al 2008).

Table 1.4: Comparison of percentage of pectin in its various sources FRUITS APPLE APRICOT CHERRIES ORANGES CARROTS LIME/SWEET LIME PERCENTAGE 1-1.5 1 0.4 0.5-3.5 1.4 30

Economical Aspects about Sweet lime fruits

(Source: NATIONAL HORTICULTURE BOARD REPORT 2011)

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Figure 1.1: Leading Mosambi Producing States During 2011

The major Mosambi producing belt in Maharashtra is as follows: Ahmed Nagar, Aurangabad, Nagpur, Jalgaon, Amravati, Pune

All of the sweet lime peel is thrown away as Bio waste. Most of the beverage industries after utilizing the fruit for making juices throw these peels. On the other hand, these peels are a liability towards these companies as they cannot straight away dump this peel in debris, so utilizing this peel serves various purpose. It will certainly avoid dumping problems also the raw material used for adsorption will be cheap as compared to other adsorbents. The purpose of this present study was to assess the ability of sweet lime peel to adsorb Ni (II) ions from aqueous solutions. The experiments were done in a batch system and nickel adsorption was investigated with respect to time, temperature, initial metal ion concentration and adsorbent dose.

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CHAPTER 2: THEORY

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2.1 Citrus Peel Anatomy

Citrus peel has shown a reasonable metal uptake capacity. Metal adsorption on the peel depends on the radical groups present in the cell membrane. A study of the structure and composition of the peel helps understand the mechanism of metal uptake on the peel surface. Citrus peels mainly consist of those obtained from Orange, Lemon, Sweet Lime, Grape fruit, Grapes, etc. The general structure and components that constitute the citrus peel are found to be the same.

Figure 2.1: Cross Section of a Orange Peel

Any fruit peel, including citrus fruits, is composed mainly of two parts: 1. Albedo 2. Flavedo Albedo is the inner white part of the fruit mostly comprised of fibrous components. Flavedo is the external part that is exposed to the atmosphere. The flavedo contains a lot of the essential oil associated with citrus fruits.

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2.2 Essential Oil

Essential oil is a major commercial product obtained from citrus peels. For example, lemon oil is one of the most important flavoring oils, used widely in all kind of beverages, soft drinks, soft drinks powders and tablets, and in baked goods, such as cakes, pastries, pie fillings, confectionery, soft and hard center candies, gelatin desserts, ice creams, etc. The oil is also employed in perfumes, toilet waters, Eaux de Cologne, and in cosmetics to which it imparts a refreshing aroma.

2.2.1 Composition: Essential oils are composed mainly of three main classes of compounds namely Terpenes, Oxygenates and Sesquiterpenes. Under this classification we have complex mixtures of chemical compounds like limonene, terpinene, citral, linalol and caryophyllene among others.

2.2.2 Extraction: These oils can be extracted by many methods such as steam distillation, solvent extraction, cold pressing, and extraction using super critical CO2. Among these, steam distillation is the most common method and has been in use for a long time. Steam distillation involves the passing of high pressure steam through a packed bed of citrus peel. The Steam ruptures the pores in the flavedo and the oil vaporizes and flows along with the steam. This steam is condensed and in most cases, a stable oil-in-water emulsion is formed. Steam is again passed over this emulsion and the oil droplets that are now separated do not form an emulsion (Mishra et al 2005). Another method will be to directly boil water with the peels in it and to condense the outlet steam. The Clevengers apparatus uses this method. Currently, extraction of oil using super critical CO2 has shown greater promise than any of the other methods. A major benefit of this method as compared to other conventional methods is the high degree of extraction and the solvent being gaseous in standard conditions, leaves the mixture and the oil obtained is in no way contaminated with solvent impurities.

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Essential oil yield usually is around 4-5ml per 100gm of peel. Various methods are being researched upon to increase the overall yield which is normally around 5%. One such method is to rupture the external pores and to remove first the terpenes. Once they are removed the rest of the oil is better soluble in water and can be easily extracted to yield better results even by steam distillation.

2.3 Pectin
2.3.1 Composition Another extremely essential product obtained from the peel is Pectin. Pectin is found in the white albedo part. Pectin is a polysaccharide that acts as a cementing material in the cell walls of all plant tissues. The white portion of the rind of lemons and oranges contains approximately 30% pectin. Pectin is the methylated ester of polygalacturonic acid, which consists of chains of 300 to 1000 galacturonic acid units joined with 14 linkages. The Degree of Esterification (DE) affects the gelling properties of pectin. The structure shown here has three methyl ester forms (-COOCH3) for every two carboxyl groups (-COOH), hence it is has a 60% degree of esterification, normally called a DE-60 pectin. Pectin is an important ingredient of fruit preserves, jellies, and jams.

Figure 2.2: Structure of pectin as a galacturonic acid with variable number methyl esters (Loureiro et al).

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2.3.2 Stability Structure: As can be seen in the structure of pectin, there are many OH and COOH sites that facilitate the adsorption of cations including metal cations. The carboxlate groups tend to expand the size of the molecule owing to their charge. They interact with negative charges in the near surrounding, mainly the divalent cations, and then stop extending. Thus there is a considerable amount of negative charge. The methylation of these carboxylic groups also occurs to form methyl esters as can be seen in the above figure. These methyl esters also have their own expansion effect. They have similar structure but are highly hydrophobic and tend to behave differently in the presence of water in the surrounding. The properties of pectin depend upon the amount of esterification that has occurred. t Generally 70% esterification occurs on the peel. The properties of the pectin depend upon the degree of esterification. Low methoxyl pectins (< 35% esterification) tend to form gels by reacting with the divalent Ca ions. The strength of the gel increases with increase in Ca the concentration. High methoxy pectins (> 65% esterification) gel formation happens by the interaction of hydrogen in the presence of hydrophobic group, acids, and sugars present in the peel.

Figure 2.3: Stabilised polymer of pectin (Loureiro et al). Loureiro

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Thus it can be seen that pectin tends to stabilze itself either by gelling with Ca2+-ion or with hydrogen atoms in the water. This property of its affinity to divalent positive charge can be used in the adsorption of divalent metal ions on its surface. Because of the competition of H+ ions and Ca2+ ions in it, it is required to first reduce the acidity of the solution. By doing this, the active sites on pectin are open for other metal ions. Also highly esterified pectin is will first have to be reduce by controlled reduction so that it can be used for metal adsorption. 2.3.3 Adsorptioon Mechanisms/ Egg Box Model: Different Citrus peels have shown varying levels of affinity towards different metal ions. The basic mechanism behind their adsorption remains constant. Increasing the pH reduces the number of cations available for reaction with the hydroxyl group or for assisting in methylation. Thus adsorption of metal ions becomes easier. Numerous physiochemical studies have been performed to study the mechanism of gelation by the Ca2+ ions. The mechanism is best described by the Egg box model. This model describes the mechanism for gelation in low ester pectins by Ca2+ ions. In low-ester pectins, ionic bridges are formed between calcium ions and the ionised carboxyl groups of the galacturonic acid. Low-ester pectins need calcium to form a gel, but can do so at lower soluble solids and higher pH-values than high-ester pectins.

Figure 2.4: Egg box model showing calcium distribution (Morris et al, J. Mol. Biol. 155:507 -516, 1982).

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Figure 2.5: Ca+2 ion inside the egg box, (Morris et al, J. Mol. Biol. 155:507 -516, 1982).

The same egg box model was proposed by Grant et al for the adsorption of other heavy metals like zinc, cadmium, nickel, lead on powdered citrus peel. Based on the study the following order of affinity of heavy metals to the citrus peel was obtained: Pb2+ > Cu2+ > Co2+ > Ni2+ > Zn2+ > Cd2+. Various studies have been done mainly on apple pomace, sugar beet pulp, lemon peel, orange peel, grape skin, etc.

2.4 Peel Life Cycle

Throughout the process, we see that peel as a waste is being utilized in various ways and it may be possible to extend its usefulness by converting it into a substrate for a nickel based catalyst. Study has been done on the usage of Nickel catalyst on silica based support by Chang et al. The Nickel was first adsorbed on silica and the material was calcined at a temp range of 573-763K and at this temperature the reduction of nickel takes place. Nickel was mainly found in the Ni (II) oxide (nickel oxide) (Chang et al 1997). Thus a similar idea was conceptualized using citrus peel as a substrate. The key here is to remove all the hydrates and the carbonates leaving only Carbon and Nickel oxide. Nickel Nitrate was first adsorbed on the powdered peel surface and filtered. The retintate was after air drying was calcined at 520oC. At that temperature all the volatilities like hydrates and carbonates go off and the nickel in it is converted into its oxide. Some amount of unburnt carbon will also remain.

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CHAPTER 3: LITERATURE REVIEW

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3.1 Adsorption Studies

Recent research works on effluent treatment are focused more on finding cheaper materials with reasonable adsorptive capacity. Various studies have been done one using different biomaterials as biosorbents. Among these a greater part of the work has been focused on using micro-organisms as biosorbents. The use of other substances like citrus peel, fly ash bagasse, RHA, etc are relatively new. The studies show that biomaterials do not have an adsorptive capacity as good as activated carbon or other strong adsorbents, but they are extremely cheap and abundantly available. Schiewer et al worked on the comparative study of adsorption of cadmium on different citrus peels like apple pomace, lemon peel, orange peel, grapefruit peel, apple kernel, apple core, etc. Citrus peels were identified as the most promising biosorbent due to high metal uptake in conjunction with physical stability. Uptake was rapid with equilibrium reached after 3080 min depending on the particle size (0.180.9 mm). Sorption kinetics was found to follow second-order model. Sorption equilibrium isotherms could be described by the Langmuir model in some cases, whereas in others an S-shaped isotherm was observed, that did not follow the Langmuir isotherm model. The metal uptake increased with pH, with uptake capacities ranging between 0.5 and 0.9 meq/g of dry peel. Feng et al worked on the study of modified pectin as a biosorbent for different heavy metals. Pectin was modified using adipic acid. Modified pectin cross-linked with adipic acid, was synthesized and used for heavy metal removal from wastewater. SEM and FTIR were used to investigate its structure and morphology. The modified pectin had a rough, porous phase covered with carboxy groups, resulting a high adsorption capacity. And at the room temperature, the saturated loading capacity for Pb2+, Cu2+ and Zn2+ reached 1.82 mmol/g, 1.794 mmol/g and 0.964 mmol/g, respectively. The results proved its potential application to remove of the heavy metal. Research has also been done on identifying the specific affinities of a particular metal ion for particular peel for process intensification. Amel et al has studied the adsorptive capacity of copper on orange peel. The solid support was first thermally pre treated before carrying out the adsorbtion of Cu (II) ions on it. The influence of various parameters such as initial copper Concentration, Temperature, Amount of peel used per liter of solution, pH, etc

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on the retention of Copper on the citrus peel were studied. The study showed solid liquid ratio did not have an effect on adsorption capacity. Kinetics of the process was found to be second order. Yadav et al studied the production of extracellular pectin lyase, on mandarin peel meal by Penicillium oxalicum. The partially purified preparation showed a pH optimum at 8.0 and was stable at a whole pH range of 4.0 8.0. The optimum temp of the substance was found to be around 40oC and it quickly lost activity at temperature greater than 50oC. The Km of the enzyme was found to be 2.08 mg/ml of citrus pectin which substantially lower the values already reported. Phenolic compounds except tannic acid and several divalent ions and other inhibitors were examined and showed no significant effect on the activity. Gonen et al worked on the adsorption of Ni(II) on dried orange peel. Adsorption of Ni (II) ions from aqueous solution onto a low cost adsorbent-orange peel was investigated to evaluate the effects of pH, initial nickel ion concentration and adsorbent dose on the removal of Ni (II) systematically. The optimal pH value for Ni(II) adsorption onto the orange peel was found to be 5.0. Greater percentage of metal ion was removed with decrease in the initial concentration of metal ion and increase in amount of adsorbent used. Adsorption data was modeled using the Langmuir and Freundlich adsorption. The adsorption kinetics was found to follow pseudo-second-order rate kinetic model. Malkoc et al worked on the adsorption of Ni on Tea waste. The study was based on the effect of adsorbent dose, initial metal concentration, solution pH, agitating rate and temperature on the adsorption of nickel(II) on waste tea. Batch adsorption studies have been carried out. The equilibrium nature of nickel(II) adsorption at different temperature (2560 C) has been described by the Freundlich and Langmuir isotherm. The adsorption capacity (Q0) calculated from Langmuir isotherm was 15.26 mg Ni (II) g1 at initial pH of 4.0 at 25 C. The results of the thermodynamic investigations indicate that the adsorption reactions are spontaneous (G0 < 0), slightly endothermic (H0 > 0) and irreversible (S0 > 0). Chang et al studied the adsorption of nickel on PHA silica and the use of nickel supported on RHA as a catalyst for CO2 methanation. RHA supported nickel was prepared by incipient wetness impregnation for methanation of CO2 in a gas stream of H2/CO2 (4:1) mixture. High selectivity (80-90%) for CH 4 formation was found to proceed in the reaction

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at 623-973 K with the supported nickel. During the investigations of preparation conditions, effects of nickel loading, immersion time, calcination and reaction temperature on catalytic performance were also examined. According to these results, the metal dispersion increases with a decreasing nickel loading. The conversion of CO2 and the yield of CH4 depend on calcinations conditions. In addition, the nickel catalyst activity is independent of immersion time; the CH 4 yield achieves a maximum value in CO2 methanation at 773 K. Moreover, rice husk ash is found to be a preferable catalyst support over silica gel by TPD techniques and the reaction test.

3.2 Bio-Sorption
Kalyani et al studied the removal of nickel ions from a solution using microalgae as a sorbing material. In the present study biosorption technique, the passive accumulation of metals by biomass, was used for the removal of nickel from aqueous medium. The brown algae, Sargassum sp., in its natural and acid treated forms was used as a low cost sorbent. The adsorption characteristics of nickel on Sargassum sp. were evaluated as a function of time, pH, adsorbent dosage and initial concentration of nickel. The equilibrium adsorption data was fitted to Freundlich and Langmuir adsorption isotherm models and the model parameters was evaluated. Both the models fitted the experimental data satisfactorily. The adsorption follows Lagrangian first order kinetic model. The monolayer adsorption capacities of natural and acid treated forms of algae as obtained from Langmuir adsorption model are found to be 181 and 250mg/g. Ajaykumar et al presented a review on biosorption at various parameters. An investigation has been undertaken to determine the removal of heavy metals (Cd2+, Cu2+, Ni2+ and Zn2+) of high environmental priority due to their toxicity, from dilute aqueous solutions studied in the present work by biosorption using inexpensive biomaterials like activated sludge. Activated sludge is used widely in water treatment plants and is easily available. To understand the action of bio metals uptake, the essential role played by extra cellular polymeric substance (EPS) needs to be understood.

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Ramchandra et al carried out a comprehensive review of adsorption of various heavy metals on different biomaterials. They have presented the various possible adsorption mechanisms. Compartive study also has been presented of different materials mainly enzymatic micro-organisms.

3.3 Essential oil

Essential oil extraction studies have been done that have focused mainly on first improving the yield of essential oil extracted from various organic sources. Gamarra et al carried out the extraction of essential oil at 25oC and 1.0bar. Steam was sent in at 110oC for 10 hrs. The composition of the extracted oil was studied and also the aldehyde content before and after steam distillation. Mishra et al studied the aqueous enzymatic extraction of oil from mandarin peels. They have also shown a comparative study of the amount of oil extracted by this process and by steam distillation. Povh et al studied the essential oil extraction from turmeric that is Curcuma Longa by steam distillation and by extraction using other volatile substances. Highest essential oil yield of 0.46%wt was obtained.

3.4 Pectin Characterization

Nari et al studied the interaction of metal ions on the cell walls of organic citrus peels. Various mechanisms of metal interaction with pectin were presented as different mnodels. It was found that metal ions interact with negative groups present on the pectin and forms bonds. Kumar et al extracted pectin from apple pomace using steapsin enzymatic inhibitor. The extracted pectin was treated with acetic acid and hydrochloric acid and its characterization was carried out. XRD, NMR, FTIR or Raman spectroscopy was carried out over the extracted pectin. Loureiro et al has presented theoretical study on the structure of pectin compounds. He has shown their structure and described conditions under which they attain stability. Totlani et al studied the adsorption of Ni(II) on Rise husk Ash Silica and on Carbon

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CHAPTER 4: MATERIALS

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4.1 Mosambi Peel and Preparation of the MPP

Mosambi Peel was obtained from a local fruit juice centre. It was cleaned with distilled water to remove the dust and dirt on its surface. It was then kept in the oven for 24 hours to dry the peel and to remove all the moisture from it. A temperature of 400c was maintained in the oven. This operation has to be done at a low temperature because the organic bonds in the peel may get broken and the fibre, which helps in the adsorption of Nickel will get disturbed or distorted completely. At high temperatures, methylation of carboxyl groups will increase and we get highly esterified pectin. This drastically decreases the adsorptive capacity of the peel.

Figure 4.1: Peel after drying in the Oven.

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After the peel was taken out of the oven, it was hard enough to be grounded in a ball mill. Ball mill ensured a very fine particle size. Sometimes, the ball mill was found to be ineffective in grinding the peels. The peel particles remained coarse and the desired size for the powder was not obtained. Therefore, a domestic grinder was used for grinding the dried peel. Thus, a fine Mosambi Peel Powder (MPP) was obtained. Further characterization of MPP was performed using sieve shaker in the laboratory. For this purpose we used 14.42 grams of dried MPP. Three sieves were used for this purpose with sieve numbers as 85 , 120 and 170. Following size distribution was found. Table 4.1: Characterization of MPP, Particle Size Sr. No. 1 2 3 4 Sieve Number (BSS) >85 85-120 120-170 <170 Size (mm) >0.178 0.178-0.120 0.120-0.089 <0.089 Weight (grams) 4.70 3.83 1.56 4.33 Percentage 32.6 26.56 10.81 30.03

Figure 4.2: Mosambi Peel Powder (MPP)

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4.2. Nickel Nitrate Solution

To carry out the adsorption studies, a solution of Nickel Nitrate was prepared, with 1000ppm concentration of Nickel. This was done by mixing 4.93 grams of Nickel Nitrate salt, Ni (NO3)2.6H2O in 1000 ml water.

Model calculations: Molecular weight of NiNO3.6H2O = It contains 58.7 grams of Nickel. 20 ppm solution of Nickel ~ 20 milligrams per liter solution Now, 20 / 1000 = 0.02 grams. Moles of Nickel = 0.02/58.7 = 0.00034071 gram moles Weight of NiNO3.6H2O (nickel nitrate) required = 0.00034071 X 290.81 = 0.099 grams. Therefore 0.099 grams of nickel nitrate powder is required in 1 liter of solution for 20 ppm solution of nickel. 290.81 grams

28

Figure 4.3: Nickel Nitrate Solution (1000 ppm of Nickel)

Actual calculations done in laboratory: 4.95 grams of Nickel Nitrate powder was taken. 0.099 grams 4.95 grams Thus, we obtained 1000 ppm solution of nickel. 20 ppm 1000 ppm.

29

Figure 4: Sample Bottles containing Nickel Nitrate solution and MPP.

4.3 HNO3 Solution for Dilution

For finding out the amount of Nickel adsorbed by the peel, we find out the difference in the concentration of Nickel in the Nickel Nitrate Solution before and after the adsorption. Concentration of the solution is measured in ppm of Nickel with the help of Atomic Absorption Spectroscopy (AAS Model GBS Scientific Equipments, SensAA DUAL). This equipment measured the ppm of Nickel below 25 ppm. Therefore, the concentration of Nickel Nitrate Solution was diluted from 1000 ppm to 25 ppm with the help of Nitric Acid Solution. A 1% HNO3 solution was made by adding 10 ml of conc. HNO3 (99%) to 990 ml distilled water. This was used to dilute the Nickel Nitrate solution according to the following calculations.

30

1000 ppm

25 ppm

1000 ppm * x ml = 25 ppm * 25 ml x = 0.627 ml. Here, x represents the volume of our filtrate (nickel nitrate solution) and (25-x) ml the HNO3 solution. So, for the required dilution, x ml of Nickel Nitrate Solution was taken and mixed with (25-x) ml of HNO3 solution. Dilution Factor = Volume Of Sample Solution Total Volume (25 ml)

4.4 Industrial Dye Effluent

Acid Orange Dye (Effluent) was procured from a local dye manufacturing industry which supplies dyes for Paper Industry. The MPP was used for decolourisation of this effluent by adsorption of OMe (Methyl Orange) by the peel. The initial pH of the dye was 8.5.

Figure 4.5: Industrial Dye.

31

CHAPTER 5: PROCEDURE

32

5.1 Oil Extraction

Following were the steps followed for the extraction of oil from the Peel. The peel was cleaned in distilled water. It was then placed in a vessel containing water and was boiled. The steam rising from it contains the volatile oil particles. This product when condensed was found to contain a stable emulsion of both oil and water. To further purify the oil, steam distillation was done on this emulsion wherein steam was passed over the emulsion and the volatile oil droplets area carried forward by the steam. When this was condensed, clear layers of oil and water were obtained.

5.2 Adsorption Analysis

To study the effect of various parameters on Adsorption for optimization of the process, several tests were carried out by varying the parameters like 1. time, 2. temperature, 3. dosage, 4. concentration of the Nickel Nitrate solution, 5. pH, etc.

33

The basic steps followed for the adsorption study are listed below The Nickel Nitrate solution was taken in 100ml sample bottles and the powdered peel was added to these bottles for the study of different parameters of Adsorption. The samples were kept for a specific time at a specific temperature in a mechanical shaker assembly. Enough time was given for the adsorption to take place and then the samples were taken out of the shaker. The samples were then filtered with the help of a vacuum pump and both the filtrate and the retinate were procured. The filtrate was used to measure the amount of Nickel that was adsorbed by the Peel. The retinate which was collected in filter papers after filtration was placed in the oven and dried for around 16 hours at 400c. Moisture was thus removed from the peel. The peel was then scrapped out of the filter papers and transferred into air-tight containers. This peel was then kept in air tight containers to prevent moisture to enter into the peel again.

5.2.1 Time Study: During the initial stage of sorption, a large number of vacant surface sites are available for adsorption. After a lapse of time, the number of vacant sites decreases and adsorption becomes difficult because of the repulsive forces between the solute molecules on the solid surface and the bulk phase. The metal ions are adsorbed into the mesopores that almost get saturated with metal ions during the initial stages of adsorption. Thereafter the metal ions have to travel farther and deeper into the pores encountering much more resistance. This results in slowing down of adsorption process with time.

34

If the time that the samples are kept for is very large, the adsorbent might start desorbing from the surface of the adsorbate. Therefore, an optimum time has to be found out for carrying out the adsorption for maximum adsorption of Nickel on the MPP. 100ml of Nickel Nitrate Solution (1000 ppm nickel concentration) was taken in the sample bottles and 1g of the peel powder was added to it. The samples were kept in a mechanical shaker at a specific temperature of 400c for 1, 2, 4, 6 and 24 hours. These samples were then taken for filtration and testing as stated above.

Table 5.1: Observation Table for Time Study Sample No. Nickel Volume of Time (hours) Temperature ( c)
0

Dosage (grams)

pH

Concentration Ni(NO3)2 (ppm) (ml) 100 100 100 100 100 100 100 100 100 100

1 2 3 4 5 6 7 8 9 10

1000 1000 1000 1000 1000 1000 1000 1000 1000 1000

0.33 0.5 1 2 4 6 6 12 21 30

40 40 40 40 40 40 29 29 29 29

1 1 1 1 1 1 1 1 1 1

3.15 3.15 3.15 3.15 3.15 3.15 3 3 3 3

All the samples were diluted to 25 ppm by adding 24.37 ml of HNO3 solution to 0.63 ml of Nickel Nitrate Solution.

35

5.2.2 Temperature Study: Adsorption has the tendency to increase with temperature. To study the effect of temperature on adsorption, experiments were carried out at 3 different temperatures. The temperature was controlled by the agitation assembly in the orbital shaker. 100ml of Nickel Nitrate Solution (1000 ppm nickel concentration) was taken in the sample bottles and 1g of the peel powder was added to it. The sample bottles were kept in the mechanical shaker for 24 hours at different temperatures of 290c, 400c and 500c. These samples were then taken for filtration and testing as stated above.

Table 5.2: Observation Table for Temperature Study Sample No. Nickel Volume of Time (hours) Temperature (0c) Dosage (grams) pH

Concentration Ni(NO3)2 (ppm) (ml) 100 100 100

1 2 3

1000 1000 1000

24 24 24

29 40 50

1 1 1

3 3.15 3.17

All the samples were diluted to 25 ppm by adding 24.37 ml of HNO3 solution to 0.63 ml of Nickel Nitrate Solution

5.2.3 Concentration Study: Concentration of the Nickel Nitrate solution was changed by adding Nitric Acid to it. This decreased the amount of Nickel present in the solution. But as an acid was being added to the solution, the pH of the solution also decreased. This is very undesirable as adsorption takes place in a basic range of pH.

36

Table 5.3: Observation Table for Concentration Study Sample No. Nickel Volume of Time (hours) Temperature (0c) Dosage (grams) pH

Concentration Ni(NO3)2 (ppm) (ml) 100 100 100 100

1 2 3 4

1000 750 500 250

24 24 24 24

40 40 40 40

1 1 1 1

3.15 3 2.87 2.64

Table 5.4: Dilution for AAS Analysis Sample No. HNO3 Taken Nickel Nitrate Taken 1 2 3 4 24.37 24.17 23.75 22.50 0.63 0.83 1.25 2.5 Current ppm of Solution 25 24.799 24.898 24.848 39.68 30.12 20 10 Dilution Ratio

5.2.4 Dosage Study: Dosage is the amount of the peel powder taken for adsorption of Nickel. Generally, higher dosage of the MPP will result in higher adsorption capacity. But, there is a limit to the amount of MPP that can be taken for adsorption. The volume of the container used for adsorption puts a maximum limit to the amount of MPP that can be used for adsorption. Theoretically, increasing the adsorbent dosage increases the adsorption and hence, more metal ion removal. The reason governing this principle is the availability of more vacant adsorption sites due to large surface area available for adsorption initially. During adsorption a point is reached after which an increase in the dosage brings about no change in

37

the adsorption of metal ion. This was taken as the optimum dose for adsorption of the peel at a particular ppm concentration. The bottles were filled with 100 ml of Nickel Nitrate solution (1000 ppm nickel concentration) and known amounts of powder were added to it. To carry out the dosage studies, 1g, 2 g, 4 g, 6 g, 8 g, 9.6 g, 12 g and 16 grams of the peel was added to the sample bottles. The samples were kept in a mechanical shaker at a specific temperature of 400c for a specific time of 24 hours. These samples were then taken for filtration and testing as stated above.

Table 5.5: Observation Table for Dosage Study Sample No. Initial Nickel Concentration (ppm) 1 2 3 4 5 6 7 1000 1000 1000 1000 1000 1000 1000 Volume of Ni(NO3)2 (ml) 100 100 100 100 100 100 100 24 24 24 24 24 24 24 40 40 40 40 40 40 40 1 2 5 8 9.6 12 16 3.15 3.15 3.15 3.15 3.15 3.15 3.15 Time (hours) Temperature (0c) Dosage (grams) pH

All the samples were diluted to 25 ppm by adding 24.37 ml of HNO3 solution to 0.63 ml of Nickel Nitrate Solution

38

5.2.5 pH Study: The removal of metal ions from an aqueous solution by adsorption depends on the pH of the solution since it affects the adsorbent surface charge, degree of ionization of the functional groups, and metal ion speciation (Flaviane et al., 2010). The optimal pH varies with diverse metal ions. At lower pH value, the H+ ions compete with metal cation for the exchange sites in the system, thereby partially releasing the latter. The heavy metal cations are completely released under circumstances of extreme acidic conditions. To find a suitable pH for the effective adsorption of Ni (II) ions, experiments were performed over a pH range of 3.0 to 6.0. Following table shows the adsorption parameters.

Table 5.6: Observation Table for pH Study Sample No. Nickel Volume of Time (hours) Temperature (0c) Dosage (grams) pH

Concentration Ni(NO3)2 (ppm) (ml) 100 100 100

1 2 3

1000 1000 1000

24 24 24

40 40 40

1 1 1

3.15 4.2 6.13

5.3 Effluent Treatment

The effluent was obtained from a nearby industry, which produced an orange dye for a newspaper printing press. The composition of the dye is unknown. We used the MPP for de-colorization of the effluent. Two bottles were filled with 50 ml and 100ml of effluent. This was followed by addition of MPP in both the bottles. The following tables give process condition data.

39

Table 5.7: Observation Table for Effluent Treatment Sample No. Volume of Effluent (ml) 1 2 50 100 2 2 40 40 2 7 8.5 8.5 Time (hours) Temperature (0c) Dosage (grams) pH

5.4 Calcination
Calcination is done at high temperature to remove hydrates and carbonates along with water and other volatile materials. The presence of any metal during calcinations may result in formation of its oxide, as oxides are stable. After Nickel was successfully adsorbed on the MPP, the loaded powder was kept in a silica crucible for air drying at ambient atmospheric condition for a period of 48 hours. After the stipulated time, the loaded MPP inside silica crucible was kept in a muffle furnace to be calcined at 520oC.The ramp rate of the furnace was set at 5oC/min. The soaking time was adjusted to 180 minutes. After 4 hours and 45 minutes, the calcined powder was taken out and stored for further testing. This was characterized in SEM imaging.

5.5. Use of Calcined Nickel Adsorbed MPP for Bio Diesel Preparation
Synthesis of Biodiesel was carried out separately using the calcined powder. Soyabean oil and methanol was used along with the calcined powder. 50 ml of soyabean oil and 20 ml of methanol were taken. To this solution, 2 grams of calcined powder was added as a catalyst. The process was carried out at 40oC.

40

CHAPTER 6: RESULTS AND DISCUSSIONS

41

6.1 Effect of Time on Adsorption

The variation of percentage of Nickel removed with time was studied at two different temperatures and over a time range of 1hr 30mins. It was observed that the percentage removal is very high in the initial stages and it slowly decreases at time increases. Beyond 12hrs the maximum removal has occurred and it attains steady value by 30hrs. Also it was found that the isotherm at 29oC showed greater rate than that at 40oC. These isotherms were regressed into different adsorption isotherms models and the most suitable model was found.

6.2 Effect of Temperature on Adsorption

Study was done on the variation of Ni adsorbed at different temperatures namely 29 C, 40oC, 50oC keeping all other parameters constant. It was observed that with increase in temperature the amount of nickel adsorbed decreased. This suggests that the adsorption phenomenon may be exothermic. Thus providing extra energy by increasing the temperature only hinders adsorption and decreases the adsorptive capacity. It was found that MPP shows reasonable capacity between 30-40oC indicating that it can be used at atmospheric ambient temperature conditions.
o

6.3 Effect of Dosage on Adsorption

Variation of Nickel removed was also studied by variation of the dosage keeping other parameters constant at a temperature of 40oC. Different samples of dosage at 10, 20, 50, 80, 96, 120, 180 g/L and it was observed that the amount of nickel adsorbed initially increases at a high rate and the rate decreases becoming almost constant at very high dosages. This is because the overall volume of the system decreases with increasing dosage and thus due to better contacting and higher area more adsorbtion takes place. But beyond a point increase in dosage only occupies space and hinders the proper intermixing and then amount Ni adsorbed does not change much.

42

Table 6.1: Variation of Percentage Extraction of Nickel with Time Initial Nickel Final Nickel Time Temperature Dosage (grams) pH % Removal

Concentration Concentration (hours) (0c) (ppm) 1 1000 2 1000 3 1000 4 1000 5 1000 6 1000 7 1000 (ppm) 970.4 934 912.4 900.4 915.6 910 864.68 1 2 4 6 6 12 30 40 40 40 40 29 29 29

1 1 1 1 1 1 1

3.15 2.96 3.15 6.6 3.15 8.76 3.15 9.96 3.03 8.44 3.03 9 3.03 13.53

160 140 120 Ni extracted (ppm) 100 80 60 40 20 0 0

Time vs. Concentration

Temperature 29c Temperature 40c

500

1000 Time (minutes)

1500

2000

Figure 6.1: Graph between Ni Extracted and Time.

43

Table 6.2: Variation of Percentage Extraction of Nickel with Temperature Initial Nickel Final Nickel Time Temperature Dosage (grams) pH % Removal

Concentration Concentration (hours) (0c) (ppm) 1 1000 2 1000 3 1000 (ppm) 744 860 918.28 24 24 24 29 40 50

1 1 1

25.6

3.15 14 3.17 8.17

Temperature vs. Concentration

300 250 Ni extracted (ppm) 200 150 100 50 0 0 10 20 30 Temperature (0c) 40 50 60

Figure 6.2: Graph between Ni Extracted and Temperature.

44

Table 6.3: Variation of Percentage Extraction of Nickel with Dosage Initial Nickel Final Nickel Time Temperature Dosage (grams) pH % Removal

Concentration Concentration (hours) (0c) (ppm) 1 1000 2 1000 3 1000 4 1000 5 1000 6 1000 7 1000 (ppm) 913.84 819.92 580.84 481.24 377.8 372 337.6 24 24 24 24 24 24 24 40 40 40 40 40 40 40

1 2 5 8 9.6 12 16

3.15 8.62 3.15 18 3.15 41.9 3.15 51.81 3.15 62.2 3.15 62.8 3.15 66.2

Dosage vs. Concentration

700 600 500 400 300 200 100 0 0 50 100 Dosage (mg/L) 150 200 Dosage vs. Concentration

Ni extracted (ppm)

Figure 6.3: Graph between Ni Extracted and Dosage.

45

6.4 Effect of pH on Adsorption

Samples were prepared with varying pH values. The pH was varied using NaOH solution and adsorption was carried out on 1g of MPP for 24 hrs. It was observed that Ni adsorbed increased with increasing pH. This is in consonance with the theory that suggests that as the pH decreases the number of acidic (positively charged) ions present, that compete with the metal and hinder its adsorption, are decreased and hence Ni2+ ions are more easily adsorbed. Table 6.4: Variation of Percentage Extraction of Nickel with pH Initial Nickel Final Nickel Time Temperature Dosage (grams) pH % Removal

Concentration Concentration (hours) (0c) (ppm) 1 1000 2 1000 3 1000 (ppm) 913.8 879.39 847.55 24 24 24 40 40 40

1 1 1

3 4.2

8.62 12.06

6.13 15.24

pH vs. Concentration
180 160 140 120 100 80 60 40 20 0 0 2 4 pH 6 8 Ni extracted (ppm)

Figure 6.4: between Ni Extracted and pH.

46

6.5 Kinetic Modelling

The kinetic study of the results obtained was carried out to find out which model best suited the adsorption of nickel on the MPP. It was assumed to offer no mass transfer (both external and internal) resistance to the overall adsorption process. Therefore kinetics can be studied through the residual metal ion concentration in the solution. Two different models were studied: 1. Pseudo First order 2. Pseudo Second order

The parameters required for the studying the kinetic model are the amount of adsorbent removed at any time t (Qt) and the amount of adsorbate removed per gram of adsorbent per liter of solution (Qe). Amount Nickel removed at any time Qt (mg/L) :

Qt = (Co Ce)
Nickel removed per gram of MPP used Qe (mg/g) = Qe = (Co Ce)V/w Here Co is the initial concentration of Nickel in the Nickel Nitrate solution. This was taken as 1000ppm or 1000mg/L in our work. Ce is the amount of Nickel adsorbed at any point in time. V is the volume of the solution used in the process of adsorption. We generally used 100ml. w is the weight of the adsorbent taken for adsorption.

6.5.1 Pseudo First Order Model: The sorption of molecules from a liquid phase to a solid phase can be considered as a reversible process with equilibrium being established between the solution and the solid phase. Assuming a non-dissociating molecular adsorption of Nickel ions on MPP, the sorption phenomenon can be described as the diffusion controlled process (Totlani et al 2011).

47

Pseudo first order model states that: = (k1) ( This can be further linearized as: ln(Qe Qt ) = ln Qe k1t where k1 is the rate constant for the pseudo first order kinetic equation and Qe and Qt are the amounts of the solute adsorbed at equilibrium and at any time t respectively. The pseudo first order model for the adsorption of nickel on MPP at two different temperatures 29oC and 40oC were fitted into the model. The values of r2 obtained were 0.759 and 0.984. This shows that the adsorption does not very closely follow the first order model and a better model may be possible. The Graphs of ln(Qe Qt) vs time was plotted for the two different temperatures and regressed as shown below. Table 6.5: First Order Calculations for 400c ln(Qe Qt) 3.28 4.08 4.37 4.5 Time t (min) 60 120 240 360 )

pseudo 1st order 400C

5 4 ln(Qe - Qt) 3 pseudo 1st order 40C 2 1 0 0 100 200 Time (Minutes) 300 400 Linear (pseudo 1st order 40C) y = 0.003x + 3.358 R = 0.759

48

Figure 6.5: Pseudo First Order Model at 400c. The k1 value was found to be 0.003 in this and r2 was 0.759.

Table 6.6: First Order Calculations for 290c ln(Qe Qt) 4.33 4.39 4.8 Time t (min) 360 720 1800

Pseudo 1st Order 290C

4.9 4.8 ln(Qe - Qt) 4.7 4.6 4.5 4.4 4.3 4.2 0 500 1000 1500 2000 Pseudo 1st Order 29c Linear (Pseudo 1st Order 29c) y = 0.000x + 4.181 R = 0.984

Time (Minutes)

Figure 6.6: Pseudo First Order Model at 290c.

The k1 value was found to 0.0001 and the r2 value was 0.984.

49

6.5.2 Psuedo Second order Model: The Pseudo Second order reaction is given by = k2(Qe Qt)2

It can be further Linearized as follows

This is the linear model of the second order that is similar to y = mx + c. Here y is t/Qt and x is time t. m is 1/Qe and 1/k2Qe2 is the k value. k2 is the rate constant for pseudo second order kinetics and Qe and Qt are the amounts of solute adsorbed per unit adsorbent at equilibrium and at any time t respectively (Totlani et al 2011). The values of Qe and Qt for the two temperatures 40oC and 29oC for the adsorption of Nickel on MPP was put into the following model and its linear regression was carried out. The k2 values obtained at 40oC was 1.28x 10-05 and that at 29oC was 1.78x 10-05. The regression value of r2was found to be 0.967 and 0.912 respectively. Following are the graphs for regression with t/Qt (L.min/mg) on the y axis and time t (min) in the xi axis.

Table 6.7: Second Order Calculations for 400c t/Qt (min.L/mg) 4.26 8 13.3 Time t (min) 360 720 1800

50

Pseudo 2nd Order 40c

16 14 12 y = 0.006x + 2.796 R = 0.967

t/Qt (min.L/mg)

10 8 6 4 2 0 0 500 1000 Time (minutes) 1500 2000 Pseudo 2nd Order 40c Linear (Pseudo 2nd Order 40c)

Figure 6.7: Pseudo Second Order Model at 400c.

Table 6.7: Second Order Calculations for 290c t/Qt (min.L/mg) 2.02 1.81 2.73 3.61 Time t (min) 60 120 240 360

51

Pseudo 2nd Order 29c

4 3.5 3 y = 0.005x + 1.403 R = 0.912

t/Qt (min.L/g)

2.5 2 1.5 1 0.5 0 0 100 200 Time (minutes) 300 400 Pseudo 2nd Order 29c Linear (Pseudo 2nd Order 29c)

Figure 6.8: Pseudo Second Order Model at 290c.

Thus from the study of the two models it can be seen that although the model partially fits the Pseudo First Order condition for 40oC it does not satisfy for 29oC. Whereas for the Pseudo Second Order model more reasonable value of r2 values were obtained and thus it can be said that the adsorption of Ni2+ on the surface of MPP follows pseudo second order kinetics.

52

6.6 Calcination and Catalyst activity

Various samples were kept for the adsorption of Nickel in which many parameters were varied. Thus Nickel was loaded on the MPP under different parametric conditions. It was observed that on the adsorption study with respect to dosage the maximum nickel adsorption occurred with almost all solution being adsorbed by MPP. This peel was supposed to contain maximum quantity of Nickel and was hence chosen for calcinations after drying.

Thoretical structure of the peel suggests a polymeric network of pectin which contained carboxylic sites on which metal ions and in our case nickel would be adsorbed. During adsorption, most of the water contained in the solution was also adsorbed. Thus, Calcination was carried out to remove water and water that would be stored inside the organic compound in the form of hydrates and carbonates. The process of calcination in this case was supposed to destroy most of the polymeric frame work releasing CO2 and H2O. This basically is the oxidation of carbonates and hydrates. Also in this case the temperature of calcination was maintained at 5200C and it was supposed that at this temperature the Nickel that was adsorbed would get oxidized to a stable state. Thus nickel oxide formation was predicted.

The calcined sample was characterized by a Scanning Electron Microscope (SEM) and the results obtained are shown below in the images.

53

Figure6.9: SEM Image at a scale of 100 mircrons

Figure6.10: SEM Image at a scale of 100 microns

54

Figure 6.11: SEM Image at a scale of 10 microns

Interpretation from the SEM Images: 1. SEM was carried out on a conductive carbon substrate or base on which the calcined powder was loaded. 2. The electrons that hit the substances are either reflected back or not depending on whether the material is conductive or non-conductive. It was observed that Nonconductive or insulating compounds capture the electron and are seen as bright parts of the powder. 3. Conducting materials were seen as darker parts. Thus the morphology in the first two images showed a lot of non-conductive substance that seemed to be layered on a conductive substance. 4. It was supposed that Nickel oxide will be formed during calcinations. Nickel oxide is a non-conducting and insulating material and could possibly be the bright parts seen in the image.

55

5. Carbon, if present, is generally in different allotropic structures. It may be possible that the energy of the electron beams falling on it might cause it to change forms. 6. Carbon can be in form of graphite, fullerene, diamond, carbon nanotubes, etc. Out of these, fullerene and graphite are known to be conducting. So, it may be that carbon was present in the powder in graphite form or that the energy of electrons caused it to change its form. 7. Also, the third image showed certain viscous nature on the surface of the powder.It was inferred that some low melting substance may be present that it getting heated up by the electron presence and melting. 8. The electron beam provided sufficient energy and continuous agglomeration of the particles kept taking place.

Though not conclusively, but it can be said from the images that NiO or some oxide of Nickel may have been formed in the calcinations. We know that Nickel oxides are well known catalysts. Hence it may be that this calcined ash may show catalytic properties. To test the claim the calcined powder from the same sample was used in the synthesis of biodiesel. Biodiesel synthesis is a simple trans-esterification reaction that happens in the presence of alkoxides. In the trail, oil used was soyabean oil and it was reacted with methanol with about 0.6gm of calcined powder as catalyst. It was observed that biodiesel was formed. Its quantification was not perfect. But it suggested that some acid sites were available for possible alkoxide formation suggesting Nickel may be present as Nickel Oxide or in some pseudo stable oxide structure which may have catalyzed the reaction. Conclusive proof can only be generated by carrying out more and better controlled test. Also, the characterization of the calcined powder by E-DAX might produce more conclusive evidence.

56

CHAPTER 7: CONCLUSIONS

57

Mosambi peels are available abundantly in the Vidarbh region and are a cheap and feasible candidate for adsorption of heavy metals. It can act as a good adsorbent for effluent treatment for heavy metals. The study of nickel adsorption was carried out on it and following conclusions were obtained: Most of the Ni is adsorbed by the peel within 1-2hrs and beyond this point the adsorption only decreases and reaches a steady value. If Adsorption is carried out for longer times there is also a possibility of degradation of the peel structure thereby decreasing efficiency. Also, adsorption is not economically viable beyond a certain time. Temperature study on adsorption shows that the adsorption might be an exothermic phenomenon. Hence the amount adsorbed Nickel decreases with increase in temperature. But it has been observed that the adsorption capacity is reasonable at ambient temperature conditions. Hence effluent treatment can be carried out without the need for any ancillary equipment for heat treatment. As we increase the pH of the solution the number of acidic ions or positively charged ions decrease thus there is less competition for Nickel ions and thus higher adsorptive capacity. pH conditions around 6.0 or greater are feasible. Dosage studies show that beyond 96 g/L of adsorbent, the capacity of adsorption does not increase. The graph between Dosage and Nickel extracted becomes almost a straight line parallel to the x-axis. Thus the dosage of the MPP is best lesser than or at max 96 g/L. Kinetic modelling shows that adsorption of Ni on MPP best follows the Pseudo Second Order model. Accroding to the model, the rate of removal of Nickel is proportional to the square of the amount of Nickel adsorbed at any time. Adsorptive capacity of the peel was also tested on an industrial dye and it was observed that though the dye was not decolourized, there was a significant decrease in the pH on the solution after two hours of adsorption.

58

It is proposed that the presence of Nickel on the peel can be utilized as a catalyst by some due conversions. Also, a catalyst support maybe provided to the Nickel atoms. Thus, on calcination of the adsorbed MPP it was found that there is a presence of a nonconducting and insulating material that could be Ni in a stable state, possibly nickel oxide. The calcined peel was also used as a catalyst for biodiesel synthesis to test the hypothesis of its catalyst activity and it was observed that a certain amount of biodiesel was formed. Thus it could be said that Nickel may be present in the form of some pseudo stable oxide state and could assist the formation of a CH3O- ions that reacted with the triglycerides to produce fatty acid methyl esters or biodiesel.

59

CHAPTER 8: REFERENCES

60

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