Project Report Mitesh & Grp.docx

GUJARAT TECHNOLOGICAL UNIVERSITY Chandkheda, Ahmedabad Affiliated

Pacific School of Engineering, Surat A PROJECT REPORT ON “Removal of colour impurities from effluent water by using natural adsorbents or Biosorbents” Under subject of PROJECT-I (2170001) B.E.-IV, Semester - VII Submitted by GROUP ID: 13420

NAME

ENRROLMENT NO

Mitesh Chaudhari

151120105025

Asodariya Dishant

151120105004

Sabhadiya Nikunj

141120105079

Pinjara Tanvir

141120105073

Guided by,

Prof. Akhilesh Yadav (Assistant Professor of chem. Engg. Dept.)

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“Removal of colour impurities from effluent water by using natural adsorbents or Biosorbents” A PROJECT REPORT Submitted by NAME

ENRROLMENT NO

Mitesh Chaudhari

151120105025

Asodariya Dishant

151120105004

Sabhadiya Nikunj

141120105079

Pinjara Tanvir

141120105073

In fulfillment for the award of the degree

BACHELOR OF ENGINEERING IN CHEMICAL ENGINEERING DEPARTMENT

Pacific School of Engineering, Surat

Gujarat Technological University, Ahmedabad October, 2018 Pacific School Of Engineering, Surat Chemical Engineering Department, 2018 Page | 2

CERTIFICATE Date: This is to certify that the project entitled “Removal of colour impurities from effluent water by using natural adsorbents or Biosorbents” has been carried out by NAME

ENRROLMENT NO

Mitesh Chaudhari

151120105025

Asodariya Dishant

151120105004

Sabhadiya Nikunj

141120105079

Pinjara Tanvir

141120105073

Under my guidance in fulfillment of the degree of bachelor of engineering in chemical (7th semester) of Gujarat Technological University, Ahmedabad during the academic year 2018-19.

Guide: - Prof. Akhilesh Yadav (Assistant Professor of chem. Engg. Dept.)

Head of the Department Mr. Piyush Modi (Assistant Professor of chem.Engg.Dpt.) Pacific School of Engineering-Surat CHEMICAL ENGINEERING DEPARTMENT 2018 Page | 3

EXAMINER’S CERTIFICATE OF APPROVAL This is to certify that the project entitled

“Removal of colour impurities from effluent water by using natural adsorbents or Biosorbents”

Submitted by: Group ID (13420)

NAME

ENRROLMENT NO

Mitesh Chaudhari

151120105025

Asodariya Dishant

151120105004

Sabhadiya Nikunj

141120105079

Pinjara Tanvir

141120105073

In partial fulfillment of the requirement for the PROJECT-I (2170001) in Chemical Engineering Department of Pacific School of Engineering, Surat is hereby approved.

Date: - ……………… Place: SURAT EXAMINER’S SIGN: -………………

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UNDERTAKING ABOUT ORIGINALITY OF WORK

“Removal of colour impurities from effluent water by using natural adsorbents or Biosorbents” NAME

ENRROLMENT NO

Mitesh Chaudhari

151120105025

Asodariya Dishant

151120105004

Sabhadiya Nikunj

141120105079

Pinjara Tanvir

141120105073

Submitted by: Group ID (13420)

In partial fulfillment of the requirement for the PROJECT-I (2170001) in Department of Chemical Engineering of Pacific School of Engineering, Surat is recorded on our own work carried out under supervision and guidance of Akhilesh Yadav. The matter embodied here is not being submitted elsewhere for award of any degree.

NAME

ENRROLMENT NO

Mitesh Chaudhari

151120105025

Asodariya Dishant

151120105004

Sabhadiya Nikunj

141120105079

Pinjara Tanvir

141120105073

Date: …………………. Place: - SURAT

Page | 5

ACKNOWLEDGEMENT We would like to take this opportunity to express our gratitude to our project guide Akhilesh Yadav, Asst. proff. of Chem. Engg. Dept. for his guidance all the time. We are extremely grateful for assigning this topic. We would like to thanks all the staff member of the department for their support of completion of the project work.

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LIST OF TABLES Table No.

Table Description

Page No.

1

Comparison of physical and chemical activation method.

15

2

Adsorption capacity of different bio adsorbent at various condition.

18

LIST OF FIGURES Figure No.

Figure Description

Page No.

1.

Chemical structure of methylene blue

2

2.

Chemical structure of crystal violet

3

3.

Chemical structure of Congo red

3

4.

Chemical structure of Basic blue 3 dye

4

5.

Chemical structure of Aniline blue dye.

4

6.

Process chart for sugarcane bagasse adsorbent

9

7.

Process chart for rice husk adsorbent

11

8.

process chart for FPW adsorbent preparation

12

9.

Preparation of adsorbent from saw dust

13

10.

General preparation of several natural adsorbents.

14

11.

Experimental setup

15

12.

Adsorption of (a) 12 mg/l (b) 50 mg/l of MB at different mass

16

of catalyst. 13.

Pseudo-second-order model fit for the adsorption of MB and

17

GV dyes by sugarcane bagasse adsorbent.

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TABLE OF CONTENTS

SR. NO.

CHAPTER 1

CHAPTER 2

TOPIC

PAGE NO.

ACKNOWLEDGEMENT

5

LIST OF TABLE

7

LIST OF FIGURES

7

ABSTRACT

10

INTRODUCTION

11

1.1 Effluent water containing various dyes

12

1.1.1 Methylene blue

12

1.1.2 Crystal violet (Gentian violet)

13

1.1.3 Congo red

13

1.1.4 Basic blue 3

14

1.1.5 Aniline blue

14

1.2 Adsorption

15

1.3 Adsorbents

15

1.3.1 Activated carbon

15

1.3.2 Biosorbents (natural adsorbent)

16

1.4 Aim

17

1.5 Objectives

17

LITERATURE REVIEW

18

2.1 Use of neem leaf powder as an adsorbent

18

2.1.1 Preparation of Neem leaves adsorbent 2.2 Use of sugarcane bagasse as a biosorbent

18 19

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2.2.1 Preparation of sugarcane bagasse adsorbent 2.3 Use of Rice husk ash as a biosorbent 2.3.1 Preparation of Rice hush ash adsorbent 2.4 Use of Fruit peel waste as an adsorbent 2.4.1 Preparation of fruit peel waste adsorbent 2.5 Use of saw dust as an adsorbent 2.5.1 Preparation of saw dust adsorbent CHAPTER 3

CHAPTER 5

20 20 21 22 23 23

METHODOLOGY

24

3.1 Bio-adsorbent Preparation

24

3.2 Dye solution preparation

25

3.3 Experimental setup

25

3.4 Adsorption of dyes by various adsorbent

26

3.4.1 Removal of methylene blue by using Rice husk ash adsorbent

26

3.4.2 Removal of Methylene blue and gentian violet by sugarcane bagasse

26

3.4.3 Removal of acid yellow 36 by Sawdust adsorbent CHAPTER 4

19

27

CANVAS SHEET

29

4.1 AEIOU CANVAS

29

4.2 IDEATION CANVAS

30

4.3 EMPATHY MAPPING CANVAS

31

4.4 PRODUCT DEVELOPMENT CANVAS

32

CONCLUSION

33

REFERNCES

34

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ABSTRACT In this project, Adsorption process has been found to be one of the best treatment methods for removal of various dye molecules and impurities from industrial effluent water. As the control of water pollution has become an increasing importance in recent years, the use of physical/chemical treatments such as membrane filtration, reverse osmosis, coagulation is not economically feasible. The use of natural adsorbent or biosorbent as an alternative low cost adsorbent in the removal of dye particles. And they act as an alternative replacement for the activated carbon which is very costly. So our projects aim is to use the natural or synthetic adsorbent which can use as an alternative option for other costly adsorbent.

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CHAPTER 1 INTRODUCTION In textile industry, dyes are important in dying process. Dye is difficult to biodegrade because it contains complex aromatic molecular structures which make it stable in water. Dye also can bring a bright and firm colour to materials. Textile industries consume large quantities of water and chemicals, especially in dyeing and finishing process. The effluent that discharge from the industries contains highly colours synthetic dye which can affect the water bodies although at low concentration because dyes possess as high water solubility. Dyes also can cause various diseases such as allergy, dermatitis, skin irritation and cancer because it is resistant to natural biological degradation. It is needed to remove dye from wastewater. There are several methods has been used to improve a sustainable method for dye removal from industries effluents such as biological treatment, adsorption, chemical oxidation, photolysis, suspended or supported photo catalysis degradation and electro photo catalysis. Among those methods, adsorption is the most efficient, economical, low cost, and low energy requirement. In the previous study, activated carbon is the most common adsorbent used to remove dyes. The widespread use of activated carbon in industries is restricted due to high cost and difficulties in removal from the sludge. The new alternative adsorbent was studied in order to replace activated carbon such as biomaterial which is by products or agriculture waste material. Agriculture waste material was economic and eco-friendly adsorbent because of their unique chemical composition, availability in abundance, renewable, low in cost and more efficient. In previous study, there are several types of agriculture waste some like wood, neem leaf, Asoka leaf, cotton seed plant, peanut hull, sugarcane bagasse, maize, mango seed, soya bean seed hull, pista hull, potato peel, palm leaf, orange peel, banana peel, some like agriculture flower waste were used as adsorbent to remove dye such as marigold, Thevetia neriifolia Joss, rose, holly basil, daisy, periwinkle, sun flower. Most of the adsorbent were modified with physical and chemical method to increase the adsorption capacity. The chemical treat that used to modify the adsorbent is hydrochloric acid (HCl), sodium hydroxide (NaOH), and potassium hydroxide (KOH).

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1.1 Effluent water containing various dyes: The removal of dyes from wastewater is a matter of great interest in the field of water pollution. Wastewaters from industries like dyestuffs, tannery, textiles, paper and plastics, contain various kinds of synthetic dyes. There are more than 100,000 commercially available dyes and more than 700000 metric tons of dyes are produced worldwide annually. Recent studies indicate that approximately 12% of synthetic dyes are lost during manufacturing and processing operations and that 20% of the resultant colour enters the environment through effluents from industrial wastewater treatment plants. Wastewaters from these industries are highly coloured and the release of these effluents in natural waters produces serious damage to the environment. Dyes are organic compounds with a chemical complex structure that are stable to light, heat, oxidizing agents and resistant to aerobic digestion. Beyond the visual pollution, the contamination of natural waters with dyes produces modification in biological cycles affecting mainly photo-synthesis process. Many dyes are also toxic and even carcinogenic affecting aquatic living organisms. Studies showed that azo dyes and their sub-products may be carcinogenic and/or mutagenic. In this current work, the studied dyes are the cationic dyes, methylene blue (MB), gentian violet (GV), Congo red, basic blue 3, acid yellow 16, acid red 186, aniline blue, basic black 9, Rhodamine etc. 1.1.1 Methylene blue: MB is the most commonly used substance for dying natural fibres as cotton or silk. It can cause eye burns by direct contact and nausea, vomiting, profuse sweating, mental confusion and methemoglobinemia by ingestion. This compound is prepared by oxidation of dimethyl-4-phenylenediamine in the presence of sodium thiosulfate. Methylene Blue is a synthetic basic dye. Methylene blue stains to negatively charged cell components like nucleic acids; when administered in the lymphatic bed of a tumour during oncologic surgery, methylene blue may stain lymph nodes draining from the tumour, thereby aiding in the visual localization of tumour sentinel lymph nodes. When administered intravenously in low doses, this agent may convert methemoglobin to haemoglobin.

Fig.1 Chemical structure of methylene blue

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1.1.2 Crystal violet (Gentian violet): Crystal violet or gentian violet (also known as methyl violet 10B or hexamethyl pararosaniline chloride) is a triarylmethane dye used as a histological stain and in Gram's method of classifying bacteria. Crystal violet has antibacterial, antifungal, and anthelmintic properties and was formerly important as a topical antiseptic. The medical use of the dye has been largely superseded by more modern drugs, although it is still listed by the World Health Organization. It can be prepared by reaction of dimethylaniline with phosgene to give 4,4′bis(dimethylamino)benzophenone (Michler's ketone) as an intermediate. This was then reacted with additional dimethylaniline in the presence of phosphorus oxychloride and hydrochloric acid.

Fig. 2 Chemical structure of crystal violet

1.1.3 Congo red: Congo red is an acid dye used in testing for hydrochloric acid in gastric contents. It is also used histologically to test for AMYLOIDOSIS. Congo Red is the sodium salt of benzidinediazo-bis-1-naphthylamine-4-sulfonic acid; a diazo dye that is red in alkaline solution and blue in acid solution and used especially as an indicator and as a biological stain. Congo Red is an indicator dye that is blue-violet at pH 3.0 and red at pH 5.0.

Fig. 3 Chemical structure of Congo red Page | 13

1.1.4 Basic blue 3: Basic Blue 3 is a cationic type dye; Basic Blue 3 is an extremely weak base with three mesomeric structures whereby the positive charge can be allocated on the nitrogen in either one of the amine groups or on the central oxygen atom in the aromatic ring. The sorption points out range of pH 3 to pH 10 were excluded in this experiment due to precipitation overwhelmed adsorption.

Fig. 4 Chemical structure of Basic Blue 3 dye.

1.1.5 Aniline blue: Aniline Blue WS, also called aniline blue, China blue, or Soluble blue, is a mixture of methyl blue and water blue. It may also be either one of them. It is a soluble dye used as a biological dye, in fluorescence microscopy, appearing a yellow-green colour after excitation with violet light. It is a mixture of the trisulfonates of triphenyl rosaniline and of diphenyl rosaniline. Aniline blue or its constituents are used to stain collagen, as the fibre stain in Masson's trichrome, as well as to reveal callose structures in plant tissues. It can be used in the Mallory's connective tissue stain and Gömöri trichrome stain. It is used in differential staining.

Fig. 5 Chemical structure of Aniline blue dye. Page | 14

1.2 Adsorption: Adsorption is integral to a broad spectrum of physical and chemical processes and operations in the environmental field. Purification of gases by adsorption has played a major role in air pollution control and adsorption of dissolved impurities from solution has been widely employed for water purification. Adsorption is now viewed as a superior method for wastewater treatment and water reclamation. It is common to distinguish between three types of adsorption. (1) Electrical attraction of the solute to the adsorbent (exchange adsorption): (2) Van Der Waals attraction (physical or ideal adsorption) (3) Chemical reaction (chemisorption or chemical adsorption). Applications of adsorption for chemical processing air pollution control and water treatment are well known applications in wastewater treatment and water pollution control are generally not as well recognized, nor as well understood. The process has been demonstrated to be widely effective for removing dissolved organic substances from wastewaters.

1.3 Adsorbents: 1.3.1 Activated carbon: The adsorption properties of carbon-reach materials have been known for millennia, but only since the beginning of the twentieth century has this material been improved by activation processes. Activated carbons are applied in two different forms, Granular activated carbon - with particle sizes of 0.5 to 4 mm Powdered activated carbon - with particle sizes < 40 μm. 

The adsorption increases with increasing internal surface of the activated carbon.



The adsorption increases with increasing molecule size of the activated carbon as long as no size exclusion hinders the adsorbate molecules from entering the pore system.



The adsorption decreases with increasing temperature because adsorption is an exothermic process.



The adsorb ability of organic substances onto activated carbon increases with decreasing polarity of the adsorbate. Page | 15



Aromatic compounds are better adsorbed than aliphatic compounds of comparable size.



Organic ions are not adsorbed as strongly as the corresponding neutral compounds (pH dependence of the adsorption of weak acids and bases).



In multi component systems, competitive adsorption takes place, resulting in decreased adsorption of a considered compound in comparison with its single solute adsorption.

1.3.2 Biosorbents (natural adsorbent): Activated carbons are derived from natural materials such as wood, lignite or coal, which are commercially available. But almost any carbonaceous material may be used as precursor for the preparation of carbon adsorbents. Coal is the most commonly used precursor for AC production Because of its availability and cost effective. Coal comprises of different mixtures of carbonaceous materials and mineral matter, which results from the degradation of plants. The nature, origin and the extent of the physical– chemical changes occurring after deposition of vegetation, determines the sorption properties of each individual coal. In a research conducted by Karaka et al attention has been drawn on the use of coal as a successful sorbent for dye removal. Additionally, coal is not a pure material, and thus will have different sorption properties due to its large variety of surface properties. Recently there has been report on the use of activated carbon in the treatment of dye and heavy effluents. Material such as sugarcane bagasse, rice hush ash, fruit pills, neem leaf, peanut shell, bael shell carbon, raw pine and acidtreated pine cone powder, Calotropis procera, Coconut Shell, Super paramagnetic PVA-Alginate Microspheres were able to reduce the concentration of pollutants in wastewater successfully. Their sorption capacity increases with increasing in adsorbent dosage.

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1.4 Aim: 

The main aim of the project is to prepare low-cost natural adsorbent or biosorbent.



To find an alternative option of activated carbon which has low cost.

1.5 Objectives: 

To determine easily available natural substances which can be act as an adsorbent after proper chemical and physical treatment.



To test new naturally occurring adsorbent for the adsorption of colour impurities from effluent water.



To enhance the adsorption capacity of known biosorbent.

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CHAPTER 2 LITERATURE SURVEY Abstract: This topic deals with the literature review related to use of natural absorbent or biosorbent to remove dye particles from industrial effluent water, preparation of various natural adsorbent and its used in the removal of several dyes.

2.1 Use of neem leaf powder as an adsorbent: The surface area of carbon obtained from Neem Leaves Powder is determined by Brunauer, Emmett and Teller (BET) N2 sorption procedure with liquid N2 at 195.72℃. The specific surface area is found to be 421 m2/g. The Neem leaves commonly available waste material in India. It is useful in medicine, but utilization of Neem leaves using various treatments can be used as a low cost adsorbent instead of high cost adsorbent. The surface area and particle size are 421 m2/g and 5um respectively also studied. In the present work the Neem Leaves Powder converted into the activated carbon by chemical activation. There is a tremendous potential in these materials to be explored as industrial low cost effective adsorbents.

2.1.1 Preparation of Neem leaves adsorbent: Initially Neem leaves were washed repeatedly by using distilled water to remove moisture and soluble impurities. Then Neem leaves kept in dryer at 90℃, For 2-3 hrs till leaves turn pale yellow. Then crushed and screen by 10-15um mesh size. Neem leaves powder washed to remove moisture and free acid and kept in dryer 20-25 minute. After drying powder was mixed with ortho-H3PO4 in silica crucible and kept in furnace at 260℃ for 15-20 minute. The heating period depend on atmospheric temperature then solution was cooled & repeatedly washed using hot water to remove free acid and moisture, total 7 washing taken and kept it in dryer for 20-25 minute the prepared black coloured adsorbent kept in bottle for further use. About 20 gm sample and 10ml Ortho-H3PO4 acid taken in silica crucible and kept in furnace. The furnace is initially at normal room temperature then furnace set at 260℃. Heating was carried out for 20 minute. Then sample was removed and cool. After cooling the sample was repeatedly washed for 7 times using hot water to remove free acid and moisture. Then sample kept in dryer for 20-25 minute and the activated black coloured adsorbent stored in bottle. Reference:(Ghansyam Pandhare*, S.D. Dawande. “Neem leaves powder as a low cost adsorbent and its characteristics.” April-June,2013).

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2.2 Use of sugarcane bagasse as a biosorbent: waste product of sugar mill (bagasse) was used as low-cost adsorbent in its natural, and modified forms for the removal of malachite green (MG) dye. Chemical treatment of sugar cane bagasse (SB) was carried out with formaldehyde and sulphuric acid which produced carbonaceous bagasse (C-SB). The sugar cane bagasse (SB), carbonaceous bagasse (C-SB) and fly ash bagasse (FA-SB) were tested as adsorbents for the removal of malachite green (MG) dye from aqueous solutions. The utilization of waste material as biosorbent is an eco-friendly technique. It is a way of minimization of agricultural waste and its utilization for the removal of dyes. By adopting the adsorption process sugar cane bagasse and its modified forms were utilized for the decolourization of textile dyes and other effluents. By utilizing modified sugar cane bagasse, the removal of malachite green dye can be enhanced compared to its other forms. About 78% for MG–SB, 87.00% for MG–FA-SB and 89.60% for MG–C-SB removal were obtained by adopting the batch adsorption process. The thermodynamic parameters were also evaluated to support the spontaneity of the system. Results of the present study suggested that the C-SB system has good potential for the removal of MG dye. This model system can be operated on the industrial scale for the removal of dyes, metal and other toxic species. This is a beneficial, economical and fast method.

Fig. 6 Process chart for sugarcane bagasse adsorbent

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2.2.1 Preparation of sugarcane bagasse adsorbent: For enhancing the adsorption sites on adsorbent’s surface for the removal of basic dye the ground bagasse was treated with form aldehyde with w/v ratio of 1:5 at 54 ± 2 ℃ for 24 h. Then the content was filtered out and bagasse was separated and washed with distilled water and kept in an electric oven for 12 to 5 h at 80 ℃ for drying. After drying it was mixed with sulphuric acid (98%) in a 1:1 ratio of acid and bagasse then placed in an electric oven at 100℃ for 24 h. After the acid treatment the bagasse was washed with an excessive amount of distilled water and soaked in 1% NaHCO3 solution for overnight. Then the contents were filtered and washed with an excessive amount of distilled water till neutral pH was obtained (Ashoka and Inamdar, 2010). After air drying the contents were kept in an electric oven for 24 h at100℃ and the particle size was found to be 150 um. Reference:( Hajira Tahir*, Muhammad Sultan, Nasir Akhtar, Uzma Hameed, Tahreem Abid “Application of natural and modified sugar cane bagasse for the removal of dye from aqueous solution.” 17 September,2012.)

2.3 Use of Rice husk ash as a biosorbent: Rice husk ash (RHA) is an effective adsorbent for the removal of Indigo Carmine dye (IC) from aqueous solution. Higher percentage of IC removal by RHA was possible provided that the C0 in the solution was low. The equilibrium between the adsorbate in the solution and on the adsorbent surface was practically achieved in 8 h. Adsorption kinetics was found to follow second-order rate expression. The adsorption of IC onto RHA was found to be endothermic in nature. Equilibrium adsorption data for IC on RHA were well represented by the R-P and Freundlich isotherm models. Adsorption of IC on RHA is favourably influenced by an increase in the temperature of the operation. The adsorption capacities of RHA for IC dye were obtained as 29.3, 33.5, 40.3 and 65.9 mg/g at 293, 303, 313 and 323 K, respectively. The negative value of ∆G0 indicated spontaneous adsorption of IC on RHA. The interaction processes were accompanied by an increase of entropy value. This study concludes that the RHA could be employed as low-cost adsorbent for the removal of IC dye from aqueous solution. 2.3.1 Preparation of Rice hush ash adsorbent: Average particle size of RHA was 150.47mm. Bulk density and heating value of RHA were found to be 104.9 kg/m3 and 9.68 MJ/kg, respectively. Proximate analysis showed the presence of 0.73% moisture, 5.37% volatile matter, 88.0% ash and 5.90% fixed carbon in RHA. High amount of ash indicates that RHA is basically inorganic in nature. Elemental analyses showed 7.424% carbon, 0.061% hydrogen, 0.846% nitrogen, and rest others. The heating of rice husk at different temperatures produces RHA containing different contents of carbon and silicon dioxide. Nakbanpote et al. (2000) reported that the RHA heated at higher temperatures had reduced percentages of carbon but an increased proportion of silicon dioxide. Almost all of the carbon was lost when heated at temperatures > 400℃. In the paper mills, rice husk is heated at temperatures > 700℃ to generate steam. Therefore, it is expected that the amount of carbon will be very small in RHA. Reference:( Uma R. Lakshmi, Vimal Chandra Srivastava, Indra Deo Mall*, Dilip H. Lataye “Rice husk ash as an effective adsorbent: Evaluation of adsorptive characteristics for Indigo Carmine dye.” 4 January,2004) Page | 20

Fig.7 Process chart for rice husk adsorbent

2.4 Use of Fruit peel waste as an adsorbent: Fruit peel waste (FPW) is abundantly available from the agricultural and food processing industry and has been studied in recent past as an adsorbent. This paper critically reviews the reported work and investigates various FPW-pollutant systems. The study includes statistics of FPW generation, modification, characterization, adsorption ability, recovery/regeneration, and modelling (isotherms, kinetics, and thermodynamics) of batch adsorption. It is found that orange and banana peels are the most extensively studied adsorbents, whereas Pb2+ and methylene blue are the most efficiently removed pollutants, the Langmuir and Freundlich adsorption isotherms provide the best fit in most of the cases, and in general, pseudo-second-order kinetics is followed. There are very limited column studies and no report on commercial plant. Though the reproducibility of the results is poor, FPW has a great potential in the wastewater treatment due to its abundant and cheap availability. FPW can be used for removal of heavy metals and dyes; however, removal of organic and gaseous impurities needs further investigation.

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2.4.1 Preparation of fruit peel waste adsorbent: The use of raw FPW as an adsorbent can give rise to problems such as (1) low adsorption capacity, (2) high COD, (3) high BOD, and (4) high total organic carbon (TOC) due to leaching of soluble organic compounds present in the FPW. The increase of COD, BOD, and TOC leads to hyper-trophication. So, FPW needs to be treated or modified before use. The treatment of FPW can alter its physical and chemical properties, along with its adsorption capacity. Different physical, chemical, and other treatment or modification methods are listed in the literature. Physical treatment involves cleaning, drying, and thermal treatment of FPW. Chemical treatment is used to influence/alter properties like water sorbency, ion exchange capability, conductivity, hydrophilicity, or hydrophobicity of cellulosic materials. The chemical treatment methods include protonation, xanthanation, chemical pyrolysis, saponification, halogenation, oxidation, polymerization and removal of inhibiting groups (the groups on the surface that inhibit adsorption of the selected moieties), deamination, and decarboxylation. Some other treatment involves the use of supercritical CO2 for enhancing the significant charges on lignocellulose tissues. For the maximum adsorption of pollutants, it is necessary that an appropriate activation process is selected. Out of listed treatments, physical treatments are simple and inexpensive. However, they are less effective than chemical modifications. Generally, acid washing increases cationic or basic pollutant adsorption. Some treatment methods such as physical or chemical carbonization can cause weight loss of the biosorbent. Pretreatment is a very easy process among the other chemical processes. To enhance adsorption capacity of FPW, most of the researchers prefer only washing with acid, alkali, or some other solvent (Gaballah et al. 1994, Ngah and Hanafia 2008, O’Connell et al. 2008, Park et al. 2010, Patel 2012).

Fig.8 process chart for FPW adsorbent preparation

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2.5 Use of saw dust as an adsorbent: The potential use of Indian Rosewood (Dalbergia sissoo) sawdust, pre-treated with formaldehyde and sulphuric acid, for the removal of methylene blue dye from simulated wastewater. The effects of different system variables, viz., adsorbent dosage, initial dye concentration, pH and contact time were studied. The results showed that as the amount of the adsorbent was increased, the percentage of dye removal increased accordingly. Higher adsorption percentages were observed at lower concentrations of methylene blue. Optimum pH value for dye adsorption was determined as 7.0 for both the adsorbents. Maximum dye was sequestered within 30 min after the beginning for every experiment. The adsorption of methylene blue followed a first order rate equation and fit the Lagergren equation well. Similar experiments were carried out with commercially available activated carbon to compare the results. Sulphuric acid treated sawdust or formaldehyde treated sawdust of Indian Rosewood can be attractive options for dye removal from dilute industrial effluents. 2.5.1 Preparation of saw dust adsorbent: Formaldehyde treated sawdust (SD): Indian Rosewood (Dalbergia sissoo) tree sawdust collected from a local sawmill was washed with hot distilled water and then dried in sunlight until all the moisture evaporated. The material was ground to a fine powder in a still mill. The resulting material was sieved in the size range of 20-50 mesh ASTM. To immobilize the colour and water-soluble substances, the ground powder was treated with 1% formaldehyde in the ratio of 1:5 (sawdust: formaldehyde, w/v) at 50°C for 4 h. The sawdust was filtered out, washed with distilled water to remove free formaldehyde and activated at 80ºC in a hot air oven for 24 h. The material was placed in an airtight container for further use.

Sulphuric acid treated sawdust (SDC): One part of dried SD was mixed with one part of concentrated sulphuric acid and heated in a muffle furnace for 24 h at 150ºC. The heated material was washed with distilled water and soaked in 1% sodium bicarbonate solution over night to remove residual acid. The material was dried in an oven at 105°C for 24 h and sieved in the size range of 2050 mesh ASTM and used for the further study. SDC was characterized by adopting the standard procedures. The various physico-chemical characteristics of SDC were: surface area = 98 m2/g; apparent density = 1.45 g/ml; ash content = 1.68%; moisture content = 3.82%; CEC = 0.68 meq/g; water-soluble matter = 1.68%; acid soluble matter (4 N HCl) = 6.34%; 2 N NaOH soluble matter = 1.48%; and EC = 0.10 mS/cm. All adsorbents were dried at 110ºC overnight before the adsorption experiments.

Fig. 9 Preparation of adsorbent from saw dust Page | 23

CHAPTER 3 METHODOLOGY

3.1 Bio-adsorbent Preparation: First of all, we collected the biosorbent like sugarcane bagasse, rice hush ash, fruit pills, neem leaf, saw dust, peanut shell, bael shell carbon, raw pine and acid-treated pine cone powder, Calotropis procera, Coconut Shell etc. and wash them with distilled water and kept them for drying in the presence of sunlight for 5-6 days. Then dry them in oven around 50-100 ℃. After this process we converted it into powder form by the use of milling mill and transformed it into fine granular particles. Then give them proper chemical treatment with several solutions like hexane-ethanol solution. This treatment is known as degreasing. And then dry them in oven once again. The bio-adsorbent is ready to experimental use.

Fig. 10 General preparation of several natural adsorbents.

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There are two method of activation 

Physical activation



Chemical activation Table 1 Comparison of physical and chemical activation method.

Physical activation

Chemical activation

Two stage process

Single stage process

High energy consumption – expensive

Low energy consumption – Cheap

Longer process duration

Shorter process duration

High surface area and porosity

Modest surface area and porosity

3.2 Dye solution preparation: The dye solution can take directly from the effluent of the various textile and pharma industries. Also we can prepare various dye solution like methylene blue dye solution, gentian violet dye solution, Congo red etc. at the laboratory itself by just dissolving various dyes in hot water and cold water.

3.3 Experimental setup:

Fig. 11 Experimental setup. Page | 25

3.4 Adsorption of dyes by various adsorbent: 3.4.1 Removal of methylene blue by using Rice husk ash adsorbent: Photocatalytic and adsorption studies showed an effective removal of MB in aqueous medium. Among all the catalysts studied, RHA-10Sn10Ti showed highest photocatalytic activity with MB. The photocatalytic degradation of MB over RHA-10Sn10Ti, under UV-light causes 99% mineralization into inorganic ions such as chlorides, nitrates and sulphates. This high photocatalytic activity could relate to increase in the band gap energy (∼3.54eV) when tin and titanium are incorporated together into the silica matrix. In adsorption studies, RHA-10Sn10Ti and RHA-10Sn removed about 99.4% of MB from aqueous solution. While RHA-silica and RHA-10Ti showed lower adsorption capacity of 45.1 and 77.1% of MB, respectively. It was also demonstrated that alkaline medium favors adsorption of MB up to 98% at pH range of 9.0–10.0. All the catalysts were found to follow the pseudo-second order adsorption kinetics.

Fig. 12 Adsorption of (a) 12 mg/l (b) 50 mg/l of MB at different mass of catalyst.

3.4.2 Removal of Methylene blue and gentian violet by sugarcane bagasse: The adsorbent prepared from sugarcane bagasse proved to be effective for the removal of MB and GV dyes from aqueous solutions by an adsorption process. The FTIR spectrum of EB showed the appearance of strong band that confirmed the introduction of EDTA di anhydride into the lignocellulose matrix. Three adsorption kinetic models were tested and the pseudosecond-order model fit the experimental data well. The intra particle diffusion study yielded three linear regions, which suggested that dye adsorption involves more than one kinetic stage. The Langmuir model fit the experimental data well, suggesting the adsorption occurs in a monolayer. The maximum adsorption capacities for the adsorption of MB and GV dyes onto EB were found to be 202.43 and 327.87 mg/g, respectively. Page | 26

Fig. 13 Pseudo-second-order model fit for the adsorption of MB and GV dyes by sugarcane bagasse adsorbent.

3.4.3 Removal of acid yellow 36 by Sawdust adsorbent: Activated carbon prepared from low cost materials, mahogany sawdust and rice husk have suitable adsorption capacity with regard to the removal of Acid Yellow 36 from its aqueous solution. Mahogany sawdust carbon has better adsorption capacity than rice husk carbon. The adsorption is highly dependent on contact time, adsorbent dose and pH. The optimal pH for favourable adsorption of Acid Yellow 36 is 3 and below. Adsorption obeys both Freundlich and Langmuir isotherms. Adsorption kinetics follows Lagergren first order kinetic model. For the present adsorption process, intra-particle diffusion of dye molecule within the particle has been identified to be rate limiting. The adsorption capacities of saw-dust carbon (SDC) was found to be 183.8 mg per g of the adsorbent. The results indicate that SDC and RHC could be employed as low-cost alternatives to commercial activated carbon in wastewater treatment for the removal of acid dyes.

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Table 2 Adsorption capacity of different bio adsorbent at various condition.

Biosorbent

Modified polysaccharide Mango seed kernel powder wheat shells Neem leaf powder jute Fibre carbon: Rice husk Giant duckweed Date pit Wool Fibre (sheep wool) Cotton Fibre Sugarcane bagasse Saw dust Banana stalk waste Gulmohar leaf powder Tea waste Papaya seed Bamboo Watermelon Pine saw dust Coconut husk

Q max (mg/g)

Experimental Parameters/ Result pH

48 8 142.86 8 21.50 6.5 8.76 5-8 22.5 5-10 40.58 8 144.93 9 80.3 8 94.3% 5 97% 5 95.4% 8.76 263.16 7 243.90 4-12 186.22 7.5 85.16 4.5 555.55 3-10 286.1 3.7 489.80 NA 16.75 NA 500 7.8

T( C) 25 30 50 30 28 32 25 25

25 25 30 30 29 30 25 30 35 30

Co (mg/l) 50 100 100 40 50-200 100 300 5 5 3.5 72 300 50-500 10-100 20-50 50-360 400 50 20-50 100-200

T (min) 150 60 240 250 40 144 NA 30 10 193 480 330 300 1440 30 180 30

AD (g/l) 0.5 0.02 1.0 2 1 0.12 0.2 NA 1.0 1.50 0.19 0.2 0.1 0.5-2.5 0.2 0.05-1.0 0.1 0.5 NA 0.03

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CHAPTER 4 CANVAS SHEET DESIGN ANALYSIS AND METHODOLOGY 4.1

AEIOU Summary: AEIOU Summary

Environment:

Interactions:

Objects:

    

    

      

Water pollution Soil degradation Bio accumulation Skin disease Bio degradation waste

Manager Engineer Lab assistant Worker Plant Incharge

Activities:

users:

      

    

Collect effluent of Dye industry Drying of objects Size reduction Sieves analysis of powder Filtration Adsorption using Bio-adsorbent Final product analysis

Neem leaves Sugarcane bagasse Rice Husk Ash Pineapple waste BOD, COD indicator Adsorption Column pH meter

Dye industry Textile industry Municipal corporation Effluent treatment plant Pharma industry

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4.2

Ideation Canvas: IDEATION CANAVS

People:      

Lab assistance manager ETP incharge Worker Plant incharge professor

Activities:       

Situation/context/location

Collect effluent of Dye industry Drying of objects Size reduction Sieves analysis of powder Filtration Adsorption using Bio-adsorbent Final product analysis

   

Prevention water Municipal sewage plant ETP Dye industry

Props/possible/solutions     

Use of Bio adsorbent Use of low cost adsorbent Replacement of activated carbon BOD, COD management Removal of suspended particle

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4.3

Empathy Mapping Canvas:

EMPATHY MAPPING CANVAS USER     

STAKEHOLDERS Dye industry Textile industry Municipal corporation Effluent treatment plant Pharma industry

 Government  Industrial group

ACTIVITIES       

Collect effluent of Dye industry Drying of objects Size reduction Sieves analysis of powder Filtration Adsorption using Bio-adsorbent Final product analysis

STORY BORDING HAPPY: In our project we focus on the use of bio adsorbent to removal the dye particles from waste water which is good for environment and it also having low cost so it is very helpful so it is happy moment. HAPPY: In our project the treated water is dye particle free and it also used for the various and also it can be Now free to mix with sea water it is not harmful at all SAD: In our project we take neem leaves as a first adsorbent so in the making of neem adsorbent it takes so much time and it is very hard to prepare.

SAD: We can’t make the adsorbent in very bulk at a time it’s a sad moment.

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4.4

Product Development Canvas: PRODUCT DEVELOPMENT CANVAS

PURPOSE:   

Sufficient adsorption of Dye molecules Low-cost High capacity like Activated carbon

PRODUCT EXPERIENCE: - Sufficient capacity to adsorb various dyes. - nearly less capacity then activated carbon but has low-cost than it.

CUSTOMER REVALIDATION:    

REJECT, REDESIGN, RETAIN: 

PEOPLE:    

Textile industries Dye industries Pharma industries Food industries

PRODUCT FUNCTIONS: - Use as an adsorbent for colour impurities from water. -Act as an alternative of activated carbon

It has good capacity to adsorb dye particles. Required more in quantity Small size is good Great replacement of activated carbon



Have to reduce particle size of adsorbent Have to dry more.

PRODUCT FEATURES: -Good capacity to adsorb dye. -Easily available and low-cost. -Alternative of activated carbon.

COMPONENTS: -Neem leafs -Rice husk ash -Sugarcane bagasse -Hammer mill -Adsorption tower -Sieve shaker

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CHAPTER 5 CONCLUSION

From the experiments and literature surveys we conclude that there are number of natural adsorbents which has great capacity to adsorb colour impurities from the effluent water of various industries. Some of the bio adsorbents which can be used as an alternative option for activated carbon are Neem leave powder adsorbent, Rice hush ash adsorbent, Treated sawdust. The natural adsorbent or bio-adsorbents are easily available and having very low cost comparing to the activated carbon. So, finally the bio-adsorbent is a great replacement of high cost activated carbon.

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