Surface Modification of Lignocellulosic Biomass based Activated Carbon with Ionic Liquids and Deep Eutectic Solvents for Adsorption of Various Dyes

Content Number: 14
Author Name: Saadat Ullah
Author I’d: SBPWNC – A14
Educational Institution: Bannu, Pakistan
Content Title: Surface Modification of Lignocellulosic Biomass based Activated Carbon with Ionic Liquids and Deep Eutectic Solvents for Adsorption of Various Dyes

1. Introduction

Environmental pollution is a challengeable issue for the whole world as it increase day by day. The population of the world is increasing and to fulfill the demand of human beings various new industries are being established. These industries produce various types of pollutants which is a threat for the whole globe [1-3]. Various types of inorganic and organic pollutants from these industries discharge into the environment which have adverse effect on living organisms. Among the organic pollutants, dyes are extensively used in various industries such as paint, textiles, rubber, leather, cosmetic, pharmaceuticals, food, plastic, photography, etc., to colorize their products. Thousands of different types of dyes are produced per year and use in various industries from textile and tanning to paper and pulp [4]. Among these dyes, between 35 and 70 thousands of these dyes end up in industrial effluents and pass into water bodies [5, 6]. The release of dyes without any treatment from industries to water bodies is a threat to living organisms. We know that dyes have stable nature and can remain in the environment for a long time. Among these dyes, some have a carcinogenic and mutagenic nature and therefore have an adverse effect on the biota [7, 8]. To protect humans and other living organism from the adverse effect of these dyes, the purification of water from such dyes is necessary.

Various types of chemical, biological and physical techniques have been applied for the purification of wastewater comprising dyes. The mentioned techniques have their own benefit and limitations. Chemical methods required expensive chemicals and sometimes cause secondary pollution. Biological methods are effective for treating water containing low ppm dyes. Biological methods require long treatment time and sometimes microbes are affected by pollutants. Among the mentioned techniques, adsorption is considered better because it requires low-cost materials and is simple, and has an easy treatment procedure. Various types of materials are applied to adsorb dyes from water-containing dyes [2, 3]. Among the tested adsorbents, activated carbon (AC) derived from lignocellulosic biomass is widely used. The biomass-based AC is promising adsorbent due to surface porosity, high surface area, economical, and tunable surface chemistry. AC has better adsorption capacity than the native biomass from it has been derived [9, 10].

To further enhance the surface and adsorption properties, recently the surface of AC has been modified with various types of chemicals [11]. Oxidation, plasma deposition, and irradiation introduce oxygen to the surface of AC to enhance the adsorption efficiency of AC [12]. The surface of AC is usually modified with traditional organic and inorganic acids. However, in-depth research is still needed to transform activating agents from chemical solvents to green solvents in order to improve the adsorption capacity of modified AC and make the process greener. In this context, alternative treatment methods are still demanded, and ionic liquids (IL) and Deep eutectic solvent (DESs) may be promising alternative approaches to modify the surface of AC [13-15].

ILs are salts formed by pairing of proper different anions and are cations and thus considered a designer solvent because their properties can be altered by changing in molecular structure (in both anions and cations or the alkyl chain length or functional groups). Similarly, DES is a eutectic mixture designed with specific properties by choosing the right H-bon donor (HBD) and the H-bond acceptor (HBA) [16]. Both ionic solvents and DESs can interact with nonionic compounds via combination of ion-dipole and dipole-dipole forces, H bonding, dispersion forces and π-π interactions. ILs and DESs can functionalize the surface of filler, does not modify the original microstructure of the filler [17, 18]. Treatment of an the surface of adsorbent with ILs and DESs would be promising approach that combines the advantages of both extraction and adsorption for recovery of various types of dyes and organic pollutants. ILs and DESs modified adsorbent have many advantages over the native free ILs and DESs, including avoiding the leaching of ILs and DESs to water, will use a small amount of ILs and DESs and recovery and reusability [18]. Modification of the surface of AC with ILs and DESs will enhance the adoption capacity of AC for dyes and be safer to adsorbents. Immobilization of ILs could provide high adsorption efficiency and capacity, as well as good safety foradsorbents [19-21]. However, very little research has been done on the modification of thesurface of AC with ILs and DESs for the removal of dyes.

2. Aims and Objectives

Based on the above mentioned problems the aim of this current research work is to modify the surface of AC derived from lignocellulosic biomass with ILs and DES for efficient adsorption of dyes. Following are the objectives of the current research work.

To modify the surface of activated carbon with various types of ionic liquids and deep eutectic solvents for efficient adsorption of dyes from aqueous media.

• To modify the surface of activated carbon with various types of ionic liquids and deepeutectic solvents for efficient adsorption of dyes from aqueous media.
• To study the surface properties of ILs and DESs treated ACs using various types of analytical techniques such as SEM-EDX, FTIR, and TGA.
• To find out that how various experimental process such as initial pH of dye solution, doseof adsorbent, contact time, initial dye concentration, and temperature effect on theextraction efficiency of AC treated with ionic liquids and DESs.
• To study kinetic, isotherm and thermodynamic study for extraction of dyes using ionicliquids and DESs treated AC.
• To recycle and reuse the ILs and DESs modified ACs.

3. Instrumental Procedure

3.1 Chemicals

Various types of chemicals such as imidazole, pyridine, various types of amine, carboxylic acid which needed for the synthesis of ILs and DESs will be purchased from various suppliers. Various types of HBDs (oxalic acid, malic acid, benzoic, 2-hydroxy benzoic acid), and HBAs (trioctylamine, trihexylamine, tributylamine, trioctylphosphine, trihexylphosphine, tributylphopsine) will be purchased from various companies. ILs will be prepared by using trioctylamine, trihexylamine, tributylamine, trioctylphosphine, trihexylphosphine, tributylphopsine and trioctylamine, trihexylamine, tributylamine, trioctylphosphine, trihexylphosphine, tributylphopsine as a source of cation and various carboxylic acids such 4- tributylbenzoic acid, 4-phenylbtanoic acid, 3,4-dimethylbenzoic acid and salicylic acid.

3.2 Instrumentation

The structure of the synthesised ILs and DESs and the surface properties of treated AC will be investigated using various analytical techniques such NMR, FTIR, DSC, TGA, and SEM-EDX.

3.3 Synthesis of ILs and DESs

Various types of ILs will be prepared in this research work. Various types of commercial ILs having functional group such as amine, carboxylic and nitrile group will be used for surface modification of ILs. Some desired function ILs will be also used in this study. Trioctylphosphine (TOP) and trioctylamine (TOA) and various types of carboxylic acid will be used for synthesis of ILs. The TOP/TOA will be added to three neck flask having reflux condenser. The reaction flask will be placed in ice bath and carboxylic acid will be added in equimolar amount at will stirred for 30 min. The temperature of reaction mixture will be increase up to 60 oC and will be stirred for another 24 h until viscous color liquids is formed. In similar way the HBD an HBA will be mixed and will be put in glass vial. The well mixed HBD and HBA will stirred until clear liquid is formed.

3.4 Surface modification of AC with ILs and DESs

Various types of ILs will be prepared in this research work. Various types of commercial ILs having functional group such as amine, carboxylic and nitrile group will be used for surface modification of ILs. Some desired function ILs will be also used in this study. Trioctylphosphine (TOP) and trioctylamine (TOA) and various types of carboxylic acid will be used for synthesis of ILs. The TOP/TOA will be added to three neck flask having reflux condenser. The reaction flask will be placed in ice bath and carboxylic acid will be added in equimolar amount at will stirred for 30 min. The temperature of reaction mixture will be increase up to 60 oC and will be stirred for another 24 h until viscous color liquids is formed. In similar way the HBD an HBA will be mixed and will be put in glass vial. The well mixed HBD and HBA will stirred until clear liquid is formed.

3.5 Characterization of AC-IL and AC-DES

Change in physicochemical propertied in the surface of AC after treatment with ILs and DESs will be characterized using different instrumental techniques such as FTIR, SEM, EDX, TGA and XRD.

4. Adsorption of dyes on AC

The native and ILs/DESs modified AC will be used for removal of dyes from aqueous phase. Specific amount of adsorbent will be added to the specific volume of dye solution having specific concentration into flask and will be stirred/shacked for predetermined time. At the completion of adsorption experiment the flask will be taken out from the shaker and the concentration of dye remaining in aqueous phase will be determined using UV-Vis spectrophotometer. The adsorption capacity of adsorbent for dyes will be determined using the below formula:

Effect of various parameters such initial pH of dyes solution, contact time, dose of adsorbent, initial concentration of dyes and temperature will be investigated to get the

maximum removal of dyes. Kinetic, isotherms and thermodynamic study for adsorption of dyes on adsorbents will be performed to know the mechanism of adsorption of dyes on the adsorbent. The adsorbents will be recycled and reused. Schematic diagram for the current research work is given below.

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