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Supporting Information for a Review on Development and Application of Plant-Based Bio-Flocculants and Grafted

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Supporting Information for a Review on Development and Application of Plant-Based Bio-Flocculants and Grafted Supporting Information for A review on development and application of plant-based bio-flocculants and grafted bio- flocculants Chai Siah Leea,b, Mei Fong Chonga*, John Robinsonb, Eleanor Binnerb aDepartment of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham Malaysia Campus, 43500 Semenyih, Selangor, Malaysia bDepartment of Chemical and Environmental Engineering, University of Nottingham, Nottingham NG7 2RD, UK * Corresponding author. Tel.: +60 3 8924 8347; fax: +60 3 8924 8017. E-mail addresses: [email protected] (M.F. Chong), [email protected] (C.S. Lee), [email protected] (J. Robinson), [email protected] (E. Binner) S1 Background of processing industries involving clarification/flocculation process Beverage industry Clarifying or flocculating agents are widely needed in beverage production, especially vinegar and wine clarification, clarification of dates extract, sugar cane juice and fruit juices. By referring to Figure S1, clarification is a routine part in the wine manufacturing process, as well as in the vinegar production to reduce the turbidity, total solids in suspension and various iron compounds which are largely responsible for the clouding in wines and vinegars.1-3 Fresh fruits (e.g. grapes) Destemming/crushing Mash thermal treatment Thermovinification Juice extraction Juice fermentation Wine clarification/filtration Wine stabilisation Bottling and packaging Figure S1. Process flow diagram of wine production As shown in Figure S2, clarification by means of clarifying agents plays a vital role in the production of clear and high quality fruit juice. It is used to remove colloidally suspended particles and turbidity which are caused by proteins, polyphenols, pectins, and carbohydrates in the juices.4, 5 In addition, clarification and discoloration of dates extract is one of the most important steps to free the extracted raw juice from non-soluble matter, soluble (e.g. colouring matter) and semi-soluble (e.g. pectin) materials in production of several products such as syrup, jam, date-jelly, date butter, vinegar and wine.6, 7 In the processing of sugar from sugar cane juice, clarification is essential to remove the organic and inorganic constituents in soluble, suspended and colloidal form and minimise colour formation.8 S2 Fresh fruits Washing and sorting Screw press Heating Clarification and filtration Evaporation Concentrated fruit juice Figure S2. Process flow diagram of fruit juice production As reported in Table 3, clarifying agents such as activated carbon, gelatin, albumen, bentonite and etc. are commonly used as clarification agents in beverage processing. However, they have generally been found unsatisfactory in terms of the cost involved, trouble of treatment, and lack of permanency in the results attained.1 Inadequate or improper use of these materials generally results in a reclouding of the clarified product.3 Chitosan has been investigated as an alternative option in fruit juice clarification.9-11 However, its use is hindered and shows limited potential for industrial acceptance because of seasonal and limited supply, inconsistent physical chemical properties and environmental problems.12, 13 In sugar industry, the use of lime and synthetic polymers as clarifying agents is not recommended nowadays due to the hidden toxicity effect to human health. In addition, the use of lime, chemical polymers, activated carbon and bentonite will generate solid waste which is difficult to dispose. Plant-based bio-flocculants are suggested to be used as clarifying agent in aiding the separation of suspended particles and turbidity from beverage, fruit juice or fruit extracts. Further, it is non-toxic and biodegradable, derived and extracted from natural sources, easily dissolved in water at room temperature; the treated effluent and the sludge have no negative environmental impact. Thus, it may be used as an alternative agent to the current clarifying agents for refining of fruit juices and fruit extracts. Food industry Flocculation process could be used in seafood or meat processing industry to recover the muscle proteins from the by-products (meat left over on bones, head, skin, etc.). Processing of the by- products would enable the food processing industry to diversify its product offerings and offer another source of highly nutritious proteins for human consumption beside minimising environmental stresses due to their processing waste.14 As shown in Table 3, isoelectric solubilisation or precipitation has been applied to remove the impurities such as bones, scales, skin, etc., from by-products and resulting in protein recovery yields.14, 15 However, the last step S3 of this method which is dewatering of the precipitated protein is inefficient and requires a high gravity force and extended time. Therefore, scale up to pilot plant is limited by this disadvantage because industrial settings require short centrifugation time in order to maintain economic feasibility.15 A study has been conducted to determine the separation efficiency of fish proteins recovered from fish processing by-products by means of isoelectric solubilisation/precipitation enhanced with a wide range of polymeric flocculants (anionic, non-ionic and cationic).15 The results proved that this method could potentially be used to recover muscle proteins from the by- products. However, the safety of proteins recovered from fish with the aid of the synthetic flocculants on human and animal health has limited its usage. In this respect, the use of plant- based bio-flocculants that exhibit the similar flocculating property as polymeric flocculants is proposed to aid in dewatering of the precipitated protein after isoelectric solubilisation treatment. The dewatering efficiency can be enhanced, hence reduce the energy consumption and centrifugation time. Additionally, the safety concern of the products recovered using bio- flocculants is eliminated. Mineral industry Natural occurring kaolin clays vary considerably in their colour properties. As shown in Figure S3, selective flocculation is one of the widely used techniques to remove the discolouring contaminants (e.g. titanium and iron minerals, and impurity clay minerals), thereby improving the brightness and making the kaolin acceptable for pigment, coatings, cosmetic and pharmaceutical applications. 16-19 Crude kaolin clay Formation of aqueous kaolin suspension or slurry Fractionation to remove the coarser fraction Selective flocculation Bleaching Dewatering Rinsing of the filter cake Drying Figure S3. Process flow diagram of kaolin clay production20 Anionic flocculants such as polymers of sodium acrylate, acrylamide and also sulphonate polymers are widely used for flocculating mineral suspensions.21, 22 Nuntiya et al.23 has studied the application of electrolytes (NaCl and CaCl2), low molecular weight polymer (polyvinyl S4 alcohol, PVA) and high molecular weight polyacrylamide (PAM) on kaolin flocculation process. It was found that the floc size and floc strength increased with increasing cation valency in the electrolytes and increasing molecular weight in the polymers. However, conventional flocculants have the problems of non-biodegradable and dispersion of monomers or residual polymers in the kaolin slurry that may represent a health hazard.24-26 In addition, contamination of the clay product by the presence of the flocculating agent, may require additional processes to remove the flocculant and is significantly deleterious to the product theology.19 The flocculating ability of plant-based bio-flocculants in synthetic wastewater (kaolin suspension) has been verified.27 Therefore, it can be used to replace polymers as selective flocculants to flocculate the kaolin and leave the discolouring contaminants in the supernatant due to its advantages of green and biodegradable characteristics. The flocculated kaolin has no chemical contamination and is safe to be applied in production of consumer products. Papermaking industry Flocculating agent systems are generally and extensively used to improve the retention of fibre fines and fillers in papermaking process,28, 29 as shown in Figure S4. It promotes the flocculation by aggregating the fine particles and fibres to form flocs that are large enough to be retained within the finer network or could be attached to fiber surfaces by attractive forces.30, 31 Generally, the flocculating agents/retention aids are often polyelectrolytes whose mechanisms of operation depend on the molecular weight and charge density.32, 33 Pulp materials Preparation of aqueous slurry of pulp or wood cellulosic fibers (stock) Dilution (“thin”) of the stock Addition of filler and sizing materials (e.g. clay and titanium oxide) Addition of cationic polymers Addition of retention aid (e.g. anionic polymer) Wet end system with papermaking machine (water removal, beating and refining) Formation of paper product Pressing and drying Dry paper roll/sheet Figure S4. Process flow diagram of papermaking process34 S5 The application of bio-flocculants in papermaking retention is gaining much more attention lately. Bio-flocculants such as modified starch, modified celluloses and chitosan have been studied as papermaking retention and dewatering aids because it has the ability to bind coating fillers and pigments as well as to retain the cellulose fibres.28, 31, 35 However, starch modification has the challenge to produce starch modified products that are safe to the consumer and kind to the environment.36
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