13

CHAPTER 2 LITERATURE REVIEW

2.1

PULP AND PAPER INDUSTRY The rapid increase in population and increased demand for

industrial establishments to meet human requirements have resulted overexploitation of available resources, leading to pollution of the land, air and water environments. The pulp and paper industry is one of the oldest and core industrial sector in India. It is a highly capital, energy, and water intensive industry. It is also a highly polluting process and requires substantial investments in pollution control equipments. It is the sixth largest polluter (after oil, cement, leather, textile, and steel industries) discharging a variety of gaseous, liquid, and solid wastes into the environment (Ali et al 2001). Since the pulp produced corresponds to only approximately 40-45 % of the original weight of the wood, the effluents are heavily loaded with organic matter (Nagarathnamma et al 1999). These effluents cause considerable damage to the receiving waters if discharged untreated. While some of these pollutants are naturally occurring wood extractives (tannins, resin acids, lignin), others are xenobiotic compounds that are formed during the process of pulping and paper making (chlorinated lignin, phenols, dioxins and furans), thereby turning pulp and paper mill effluents into a Pandoras box of waste chemicals (Peck et al 1994). Chloro-organic compounds tends to persist in nature because of their inherent recalcitrance; they are often toxic to aquatic live; many are genotoxic and have the potential to migrate widely

14

throughout the ecosystem, ultimately accumulating in the fatty tissues of organisms (Suntio et al 1988). Some of the pollutants listed above, notably, polychlorinated dibenzodioxins and dibenzofurans (dioxins and furans), are highly toxic, recalcitrant to degradation and tend to persist in nature. They are thus known as persistent organic pollutants (POPs) and have been classified as priority pollutants by the United States Environmental Protection Agency (USEPA 1998) and figure in the Priority Substances List 1 (PSL-1) of the Canadian Environmental Protection Act as well as the dirty dozen group of persistent organic pollutants (POPs) identified by United Nations Environment Program (UNEP 1995). Legislations were introduced to limit the levels of these toxic compounds in effluents (Sierka et al 1994, Thompson et al 2001). Additionally, during bleaching treatments chromophoric, highly oxidised, polymeric lignin/chlorolignin derivatives are formed that give rise to a dark colourisation in the effluent (Livernoche et al 1983, Bergbauer et al 1991). 2.2 MANUFACTURE OF PAPER Wood, one of the major raw materials used in the pulp and paper industry, is composed of cellulose fibres, carbohydrates such as starch and sugars, as well as lignin which act as an adhesive for cellulose fibres. The pulp and paper industry breaks down the wood to separate the cellulose from the non-cellulose substances. The raw material is dissolved chemically so as to form a pulp. The pulp slurry is bleached and subsequently dried on a paper machine to produce a paper sheet. The addition of dyes, coating materials or preservatives can occur at some point of the process to produce the required quality of paper or associated product. Papermaking involves five basic steps and each step can be carried out by a variety of methods. The effluent from pulp and paper industry, thus, has a combination of wastewaters from each of the five different unit processes and the methods employed therein, viz.:

15

1.

Debarking In this step the plant fiber is converted into smaller pieces called

chips and removes the bark. The nature of the raw material used, i.e. hard wood, softwood, agro-residues, results in the transfer of tannins, resin acids, etc. present in the bark to process waters. For instance, softwoods contain a much higher quantity of resin acids than hardwoods (Leach et al 1977), whereas agro-residues may not contain resin acids at all. 2. Pulping This process removes the majority of lignin and hemicellulose content from the raw material, resulting in a cellulose-rich pulp. Wood pulp is prepared by three main processes. Mechanical pulping: The process involves passing a block of wood, usually debarked, through a rotating grindstone where the fibres are stripped off and suspended in water. Chemical pulping: It utilizes significantly large amounts of chemicals to break down the wood in the presence of heat and pressure. The spent liquor is then either recycled or disposed of by burning for heat recovery. Kraft pulping is the most common chemical delignification procedure (Addleman et al 1993), in which the chips are digested in white liquor (sodium hydroxide and sodium sulphide) in order to separate the fibres and dissolve lignin. In thermo-mechanical pulping: The wood is softened chemically first and then subjected to mechanical pulping.

16

3.

Bleaching The process of bleaching is employed on the brown pulp obtained

after pulping in order to meet the desired color dictated by product standards. Several bleaching agents, including chlorine, chlorine dioxide, hydrogen peroxide, oxygen, ozone, etc. may be used either singly or in combination. In bleaching, the lignin, phenol, resin acid, etc. are chlorinated and transformed into highly toxic xenobiotics. Chlorination is generally the first stage in kraft pulping and during this treatment phase chlorinated organic compounds are produced. The chlorinated substances are extracted with dilute alkali from the pulp in the subsequent extraction phase (Prasad et al 1991). In later seventies, there was concern over the emissions of chlorinated organic substances, such as dioxins and furans, from the use of chlorine in pulp bleaching. Facing market and environmental demands for ``Elementary Chlorine Free'' (ECF) and ``Totally Chlorine Free'' (TCF) bleached pulps, industries adopted bleaching processes which use chlorine dioxide (ECF pulp) or oxygen-containing compounds such as molecular oxygen, peroxide and ozone (TCF pulp) (Lovblad et al 1999). 4. Washing In this step, the bleaching agents removed from the pulp. Generally, alkali (caustic soda) is used to extract color and bleaching agents from the pulp and hence this process is known as the alkali extraction stage (E1). 5. Paper machine Paper and paper products are finally produced by mixing the washed pulp with appropriate fillers (clay, titanium dioxide, calcium carbonate) and sizing agents (rosin, starch).

17

2.3

BLEACHING EFFLUENT Various stages of the pulping process give rise to aqueous effluents

in kraft mills. Comparative water usages at given stages and states of technology for bleached hardwood kraft pulp are given by Edde et al (1994) and these figures are reproduced in Table 2.1. It can be noticed that whatever the design, the bleach plant effluents comprise a highly significant proportion of the total process effluent (Upendra et al 2008). In the case of advanced future designs, the bleaching effluent will make up 71 % of the effluent flow although the total volume generated per tonne of air dried pulp could be around a third of current levels. Table 2.1 Effluent arising from various mill processes with various design concepts Effluent generated (m3/tonne of air dried pulp) Newer Current Possible Mills designs Future 0.3 0.3 0.3 1.0 1.0 0.2 1.8 0.5 0.2 21.1 10.6 10.6 6.6 0.6 0.1 0.7 3.3 1.4 0.8 8.1 0.0 16.6 62.4 1 0.4 0.1 0.2 1.0 1.1 0.3 2.7 1.2 0.0 20.4 1 0.2 0.1 0.2 0.5 0.5 0.2 0.8 0.2 0.0 15

Process Area Wood room Digestion Washing and Screening Bleach Plant Pulp Machine Evaporators Demineralization Recovery Power Boiler Recausticising Chemical Preparation Water Supply Effluent Treatment Clear water by-pass TOTAL

18

2.4

BLEACHING EFFLUENT MANAGEMENT Following the recognition of large scale environmental

contamination in bleach plants, the industry implemented a number of process internal changes and continued to develop external treatment processes. In the internal water treatment of pulp mills, process waters are purified in order to circulate water to the other stages. The methods that have been studied for internal water treatment in kraft pulp mills include membrane processes (Rosa et al 1995, Falth et al 2001, Tavares et al 2002, Cortinas et al 2002), ion exchange (Knocke et al 1986, Brown et al 1999), adsorption (Knocke et al 1986) and coagulationflocculation (Knocke et al 1986, Beulker et al 1993, Rampotas et al 1999, Lombardo et al 1997). In the external treatment, effluent is purified before it is released into the receiving water system. Various treatment processes, such as sedimentation, coagulationflocculation, adsorption, chemical oxidation, and membrane processes, as well as biological (both aerobic and anaerobic) processes and fungal treatment, have been studied for the treatment of pulp and paper mill wastewaters (Pokhrel et al 2004). Wastewater treatment in pulp and paper mills is typically carried out using sedimentation as the primary treatment, and activated sludge process as the secondary treatment. The activated sludge process is designed to remove organics from wastewater using micro-organisms under aerobic conditions, and thereby producing well settleable sludge. Due to the inability to remove non-biodegradable organics and its vulnerability to disturbances, there is a need for supplemental treatment steps in pulp and paper mill wastewater treatment. In the most common biological treatment system -activated sludge process- considerable removal of biochemical oxygen demand (BOD), chemical oxygen demand (COD), adsorbable organic halides (AOX) and

19

chlorinated phenolics can be achieved (Tsang et al 2007). Extensive research has been conducted on the ability of fungal species on the degradation of the kraft pulp bleaching effluent. The specific cultivation conditions necessary for white-rot fungi to degrade lignin (Boman et al 1988) have led to the employment of different strategies to overcome these difficulties. Various cultivation methods have been devised. For instance: the patented MyCoR process, MYCOPOR-system (Jaklin-Farcher et al 1992), continuous-flow systems and various other immobilisation techniques employing white-rot fungi (Livernoche et al 1983). Conventional biological treatments cannot effectively remove the pollutants available in kraft pulp bleaching effluent and research efforts are directed into solving this problem (Boman et al 1988, Prasad et al 1991). The reason traditional methods have failed to remove pollutants from bleach plant effluents can be attributed to the recalcitrance of chlorolignin (Mehna et al 1995, Bajpai et al 1997, Ali et al 2001). Moreover, the brownish color of the effluent is not completely removed by the treatment. The components of wastewater causing color (lignin and its derivatives) are difficult to degrade naturally because of the strong linkages in their molecular structure (especially biphenyl type carbon- carbon bond). The presence of hard-tobiodegrade and refractory materials in the waste makes the process very slow. Lignin cannot serve as the sole carbon source for the microorganisms because; the degradation of lignin is apparently a very energy intensive process (Leisola et al 1983, Boman et al 1988). Chemical coagulation using aluminium, polyaluminium and ferric salts with bleaching filtrates has been studied widely. Beulker et al (1993) found aluminium salt to be the most effective chemical against lime and magnesium hydroxide in the effluents from the oxygen and chlorine stages of

20

a bleach plant. Aluminium removed only high molecular weight substances from oxygen bleaching effluent, whereas low molecular weight substances were also partly removed from chlorine bleaching effluent. Barton et al (1992) reported 5070 % AOX removal from softwood bleach plant filtrates with aluminium sulphate, while chlorinated phenolic compounds were not effectively removed. Ferric chloride and polyaluminium salts removed 7080 % COD from alkaline ECF bleaching effluent (Lombardo et al 1997). GarciaHeras et al (1989) reported high colour removal (99 %) with ferric chloride from eucalyptus kraft pulp bleaching effluent (mixture of wastewater from chlorination and caustic extraction stages). However, there was poor settling velocity and a high sludge volume. More efficient removal of colour/ COD can be attained using aluminium or ferric coagulants together with flocculants. Chou et al (1998) used polyaluminium chloride (PAC) together with cationic polyelectrolyte (dimethyl diallyl ammonium chloride) and observed higher solid removal efficiency in the coagulation of pulp wastewater than using PAC alone, due to the better floc formation. Lombardo et al (1997) reported a marginal increase in COD reduction and a substantial improvement in floc settling when bentonite or organic flocculants were used together with ferric chloride or polyaluminium salts. Furthermore, enhanced reduction of turbidity, total suspended solids (TSS) and COD was obtained when an aluminium salt and PAC were used together with polyacrylamide (PAM) in the treatment of pulp and paper mill wastewater (Ahmad et al 2008). Cationic PAM performed better than anionic PAM in that it resulted in a lower sludge volume. Frizzo et al (1996) studied the use of solid residues from the kraft pulp industry (dregs, grit and heavy ash) and of active carbon as a flocculating aid, in the coagulation of kraft pulp bleaching effluent with ferric chloride and aluminium sulphate. This gave an appreciable reduction in the colour and

21

AOX content of the final effluent. Although chemical coagulation is efficient in removing the wastewater contaminants, the sludge generated in the treatment can cause soil, ground and underground water pollution. A variety of physical and chemical treatments have also been tested for pulping effluents. These include: adsorption (Shawwa et al 2001), wet oxidation (Verenich et al 2000), ozone treatment (Kreetachat et al 2007), fractional precipitation (Run et al 2001), ultra filtration (Chiranjib et al 2006), combined biological and membrane based treatment (Bhattacharya et al 2005) ion-exchange (Boman et al 1988). Even though the methodologies are technically feasible on lab scale operations they are questionable for their technical and economic feasibility in large scale operations. Thus, it can be observed that the problem involving the proper management of the kraft pulp bleaching effluent has not been solved. This reflects, to a great extend, the technical difficulties encountered when treatment of bleach plant effluent is attempted and the problems of setting up an effective but also an economic process for the bioremediation of the effluent. 2.5 ADVANCED OXIDATION PROCESSES Advanced oxidation processes (AOP) are attractive alternative for the treatment of industrial organic effluents containing hardly biodegradable anthropogenic substances (Legrini et al 1993, Hoffmann et al 1995, Robertson et al 1996). Generally, biological treatment of wastewater is the most

economical process and it is used for the elimination of readily degradable organic pollutants. The situation is different when the wastewater contains toxic and refractory (resistant to biological treatment) organic pollutants. One of the possibilities is to use a coupled process: partial oxidation followed by

22

biological treatment. The goal is to decrease the toxicity and to increase the biodegradability of the wastewater before the biological treatment. However, the optimization of this coupled process is complex. Depending on the operating temperature, the type of oxidant used, and the concentration of the pollutants in the wastewater, the possible partial oxidation step can be classified into three main categories: (a) Incineration. Incineration takes place in the gas phase at high temperature (8201100 0C). Its main characteristic is a direct combustion with excess oxygen from air in a flame and the process is nearly instantaneous. Incineration by-products are mainly in the gas (including NOx; SO2, HCl, dioxins, furans, etc.) and solid phases (bottom and fly ashes). The technology is applied mainly for concentrated wastewater with chemical oxygen demand, (COD) > 100,000 mg/l. (b) Wet air oxidation process (WAO). WAO can be defined as the oxidation of organic pollutants in an aqueous media by means of oxygen from air at elevated temperature (2503000C) and high pressure (100150 bar). Usually Cu2+ is used as a catalyst in order to increase the reaction rate. The efficiency of the mineralization is more than 99 % and the main byproducts formed in the aqueous phase after the treatment are acetone, methanol, ethanol, pyridine, and methanesulfonic acid. The technology is attractive for treatment of wastewater with moderate concentration, COD between 15,000 to 50,000 mg/l. (c) Oxidation with strong oxidants. The oxidation of organic pollutants with strong oxidants (H2O2, O3 etc.) takes place generally at room temperature. In order to increase the efficiency of mineralization, the oxidation takes place in the presence of catalyst and UV radiation. This

23

technology is interesting for the treatment of dilute wastewater with COD < 5,000 mg/l. One of the important constituent of kraft pulp bleaching effluent that causes the recalcitrance and toxicity are phenols and substituted phenols such as chlorinated phenols and related aromatic compounds. Many phenolic compounds are thought to be highly toxic and carcinogenic so they are considered to be priority pollutants (Rao et al 2002). Because of their high environmental impact, the removal process of phenolic compounds from wastewaters was widely investigated by means of different technologies and a very large number of papers can be found in the literature, some of them as an example are Posada et al (2006), Meng et al (2006), Suarez-Ojeda et al (2005), Beltran et al (2005) and Yermakova et al (2006). Although AOP use different reacting systems, all are characterized by the same chemical feature: production of OH radicals. There radicals are extraordinarily reactive species, they attach the most part of organic molecules with very high rate constants (Hoigne et al 1997). OH radicals are also characterized by a low selectivity of attach which is a useful attribute for an oxidant used in wastewater treatment and to solve pollution problems. The versatility of AOP is also enhanced by the fact that they offer different possible ways for OH radical production thus allowing a better compliance with the specific treatment requirements. AOP are usually classified according to the reaction phase (homogeneous or heterogeneous) or to the OH radical generation method (chemical, electrochemical, sonochemical or photochemical). The commonly used AOP are represented in Figure 2.1.

24

Figure. 2.1 Advanced Oxidation Processes for wastewater treatment 2.6 COUPLING CHEMICAL AND BIOLOGICAL TREATMENT Chemical oxidation technologies are employed where the treatment of complex industrial effluents are not amenable to conventional biological methods. The role of chemical oxidation depends on the treatment objectives and may vary from partial remediation to complete mineralization. In the case of partial treatment, chemical oxidation aims at the selective removal of the more bioresistant fractions and their conversion to readily biodegradable intermediates that can subsequently be treated biologically. Coupling chemical pre-oxidation with biological post-treatment is conceptually beneficial as it can lead to increased overall treatment efficiencies compared with the efficiency of each individual stage (Dionissios et al 2004).

25

Chemical oxidation method aiming at complete mineralization might become extremely cost-intensive since the highly oxidized endproducts that are formed during chemical oxidation tend to be refractory to total oxidation by chemical means. A potentially attractive alternative to complete oxidation through chemical means is the use of a chemical oxidation pre-treatment step to convert biorecalcitrant organics to more readily biodegradable intermediates, followed by biological oxidation of these intermediates to biogas, biomass and water. For instance, organic macromolecules such as soluble polymers may simply be too large to permeate cell walls, which preclude their effective biological oxidation. Chemical oxidation break these molecules into smaller compounds (eg shortchain organic acids) that can enter cells and may be more readily biodegradable, since the rate of biological oxidation is generally thought to increase with decreasing molecular size. Conversely, total chemical oxidation of these intermediates to carbon dioxide and water may be difficult and require severe oxidative conditions, since the rate of chemical CC bond scission seems to decrease with decreasing molecular size. Putting these two separate observations together in a qualitative sense, the concept of an integrated chemical and biological treatment process can be worked out. 2.6.1 Biodegradability Wide varieties of parameters have been used in the literature in order to express biodegradability. It is possible to measure biodegradability by means of a respirometric test (Amat et al 2005) or an inhibition test by means of measuring oxygen uptake rate (OUR). The Zahn-Wellens test has been reported as a good method (Sarria et al 2002). Other biodegradability measures including substrate destruction, EC50 toxicity measurements, cell

26

growth counts and intracellular ATP levels has been used in many works (Scott et al 1995). It is also possible to perform a direct test in a biological reactor. Among the different existing parameters to study the

biodegradability enhancement and consequently the integration possibilities, the ratio between the BOD5 and COD is used in many works (Arslan et al 2004, Chamarro et al 2001, Park et al 2001, Yeber et al 1999a). The BOD5/COD ratio, referred to as the biodegradability index (BI) points out which part of the matter is capable of being readily decomposed by biological means, especially by bacterial action, among the total oxygen demanding matter. Thus BI ranges from zero to unity. Morais et al (2005) reported that samples with biodegradability index smaller than 0.3 are not appropriate for biological degradation. According to Chamarro et al (2001) for complete biodegradation, the effluent must present a biodegradability index of at least 0.4. Metcalf and Eddy (1991) suggest that a municipal wastewater can be considered biodegradable if the BI is greater than 0.4. The BI provides useful information for water monitoring concerning its self-purification ability. An identification guide may be as follows. BI > 0.59: easily and entirely biodegradable organic matter 0.1<BI<0.59: incomplete biodegradation BI <0.1: persistent organic pollutants, not biodegradable The analytical methods to measure COD and BOD5 are well standardised. Furthermore, as compared with other methods, the measure does not require complicated systems.

27

Total Organic Carbon (TOC) is another parameter of importance in order to measure pollution or degradation. It is a measure of all carbon related to organic substances. Since it indicates the amount of carbon that the bacterial population can use for growth purposes, it is a basic information of biodegradation process. Another method of assessing the performance of the process is by means of the average oxidation state. AOS is a comparison of COD and TOC values in molar concentrations. It is an indicator of the stage of oxidation of the organic matter in a certain stage of the degradation process. This parameter is calculated according to equation

AOS 4

(TOC COD) TOC

(2.1)

where TOC and COD are in molar units. This equation is normalised to values from -4, which corresponds to the least oxidized species (methane), to +4, for the complete oxidized situation (CO2). Table 2.2 shows the studies on pulp and paper industry effluent and various phenolic compounds by the method of AOP followed by biological process.

Table 2.2 Literature collection on AOP followed by biological treatment

Chemicals degraded/ source of the effluent Industrial effluent with various chlorocarbons, phenols and anilines 2,4-Dichlorophenol Measure of pretreatment effect BOD5/TOC ratio

Ref. Bozzi et al (2003) Contreras et al (2003) Entezari et al (2003) Gonze et al (2003) Hong et al (2002)

Initial concentration COD 1.3 g/l, TOC 0.5 g/l

AOP (FeSiO2)/H2O2/UV light, Fe3+/H2O2/ UV light O3

Biological degradation Biological oxygen demand

C = 0.1 g/l

Phenol, p-chlorophenol, p-bromophenol, p-iodophenol Sodium pentachlorophenate, paper mill effluents (three streams) Pentachlorophenol

C = 1.6 mmol/l

Ultrasound at 423 kHz

Biological oxygen demand, acclimated and nonacclimated activated sludge in aerated reactors Enzymatic degradation (horseradish peroxidase with H2O2) Biological oxygen demand, incubation for 5 min with Vibrio fischeri Biological oxygen demand, E coli toxicity test (HACH, 19881995b)

BODx/COD ratio (x = 5, 10, 21), TOC removal Substrate removal

COD = 0.16 g/l for NaPCP, COD = 2, 3 and 15 g/l for the three streams
C

Ultrasound at 500 kHz

BOD5, BOD5/COD ratio, toxicity as percent inhibition of bioluminescence BOD5/COD ratio, toxicity as percent inhibition to bacteria

0.0250.05 g/l

O3 at pH = 5, 7, 10 and 12

28

Table 2.2 (Continued)

Chemicals degraded/ source of the effluent 4-Chlorophenol, 2,4dichlorophenol Chlorobenzene, 2,4dichlorophenol Pentachlorophenol Measure of pretreatment effect BOD5/COD ratio COD removal, oxygen uptake Increase in biomass COD removal COD removal, BOD5/COD ratio, increase in biomass, toxicity as 100/EC50 Toxicity as EC50

Ref. Chamarro et al (2001) Tiehm et al (2001) Nagata et al (2000) Helble et al (1999) Yeber et al (1999b)

Initial concentration
C = 0.3 g/l

AOP Fe2+/H2O2 Ultrasound at 360 or 618 kHz Ultrasound at 200 kHz

Biological degradation Biological oxygen demand

0.0750.15 g/l

Activated sludge Incubation with Salmonella typhimurium strains TA98 and TA100 Biofiltration Acclimated activated sludge culture, biological oxygen demand, incubation for 5 15min with Photobacterium phosphoreum Incubation for 515min with Photobacterium phosphoreum Incubation with Daphnia magna for 48 h and Vibrio fischeri for 30min, Zahn Wellens biodegradability test

C = 26.710 3 g/l

Paper mill effluents (two streams) Bleaching effluents from wood processing (two streams)

Chiang et al (1997) Pintar et al (2004)

Lignin, tannic acid, chlortetracycline, EDTA Kraft-pulp bleaching effluents (two streams)

COD 0.4 g/l (either stream) COD 1.6 g/l, AOX = 7.7mg/l (stream A) and COD 2.3 g/l, AOX = 73 mg/l (stream B) COD = 2.5 0.2 g/l COD = 2.9 and 3.6 g/l, AOX = 24.1 and 19.6 mg/l for the two streams

O3 TiO2/UV light/O2, ZnO/UV light/O2

Electrochemical oxidation
P tot = 5.5MPa, T = 190 C, trickle bed and batch recycle reactors with TiO2 or Ru/TiO2

Toxicity as EC50, COD removal 29

Table 2.2 (Continued)

Chemicals degraded/ source of the effluent 2,4-Dichlorophenol Measure of pretreatment effect BOD5/COD ratio

Ref. Lee et al (2002)

Initial concentration
C = 0.2 g/l

AOP
P O2 = 1MPa, T = 125 160 C, upflow fixed bed reactor, with or without Mn/Ce heterogeneous catalyst P O2 = 0.41.5 MPa, T = 110165 C, treatment time = 2 h, batch stirred reactor, with NaOH P O2 = 0.51.5MPa, T = 170200 C, treatment time = 2 h, batch stirred reactor P O2 = 1MPa, T = 130 200 C, treatment time = 2 h, batch stirred reactor, with or without catalysts (Cu/Co/Bi, Co/Bi, Fe/Mn on various supports, Cu2+)

Biological degradation Biological oxygen demand

Verenich et al (2002a)

Lignin

0.3 g/l

Biological oxygen demand

BOD/COD and IABOD/BOD ratios

Verenich et al (2002b) Verenich et al (2000)

Pulp and paper mill effluent

COD = 68 g/l, TOC = 1.21.9 g/l

Biological oxygen demand

BOD/COD and IABOD/COD ratios BOD/COD ratio

Pulp and paper mill effluent (two streams)

COD = 1019 g/l for stream A and COD = 6.57.3 g/l for stream B

Biological oxygen demand

30

31

2.7

ELECTROCHEMICAL TREATMENT The electrochemical method for the mineralization of organic

pollutants is a relatively new technology and has attracted a great deal of attention recently. This technology is interesting for the treatment of dilute wastewater (COD < 5,000 mg/l) and it is in competition with the process of chemical oxidation using strong oxidants. The main advantage of this technology is that chemicals are not used. In fact, only electrical energy is consumed for the mineralization of organic pollutants. Using electricity to treat water was first proposed in UK in 1889. The electro coagulation of drinking water was first applied on a large scale in the US in 1946 (Stuart et al 1946, Bonilla et al 1947). Because of the relatively large capital investment and the expensive electricity supply, electrochemical treatment of water or wastewater technologies did not find wide application worldwide then (Kobya et al 2003). However due to extensive research in US and USSR during the following half century, the process has gained large amount of knowledge. With the ever-increasing stringent environmental regulations regarding the wastewater discharge, electrochemical technologies have regained their importance worldwide (Lin et al 1998). At present, the electrochemical technologies have reached a state that they are not only comparable with other technologies in terms of cost but also potentially more efficient, and for some situations, electrochemical technologies may be the indispensable step in treating wastewaters containing refractory pollutants (Chen et al 2004). Electrochemical technologies offer various treatment processes such as electro oxidation, electro coagulation, electro disinfection, and electro deposition. An extensive research has been done by many researchers in treating various wastewaters by using electrochemical technologies.

32

Over the past two decades there has been a growing interest in the use of electrochemical techniques such as electro-coagulation, electroflotation and electro-oxidation for the treatment of organic effluents. Technical feasibility for the treatment of various industrial effluents such as electroplating waste water (Adhoum et al 2004b); oil mill wastewater (Apostolos et al 2007); heavy metal laden wastewater (Lai et al 2003); nitrite effluent (Koparal et al 2002); de-fluoridation (Zhu et al 2007); arsenic removal (Balasubramanian et al 2009a, 2009b); textile dyes (Saravanathamizhan et al 2007, Chithra et al 2008, Mohan et al 2007); landfill leachate (Tsai et al 1997); restaurant wastewater (Chen et al 2000a, 2000b); laundry wastewater (Ge et al 2004); surfactants (Ebru et al 2007); agro industry wastewater (Patrick et al 2008) etc has been studied. A typical electrochemical treatment process consists of electrolytic cell, which uses electrical energy to affect a chemical change. In simplest forms, an electrolytic cell consists of two electrodes, anode and cathode, immersed in an electrical conducting solution (the electrolyte), and are connected together, external to the solution, via an electrical circuit which includes a current source and control device. The processes occurring in such cells are oxidation and reduction, taking place at the electrode/electrolyte interface. The electrode at which reduction occurs is referred to as the cathode and conversely, the anode is the electrode at which oxidation processes occur. The current flow in an electrochemical cell is maintained by the flow of electrons resulting from the driving force of the electrical source. In order to allow the current to flow, there must be an electrolyte, which facilitate the flow of current by the motion of its ionic charged species. The electrolyte has significant effect on the process in the formation of oxidizing species during the process. For example, if HCl is used as the electrolyte, H+ moves toward the negatively charged electrode (cathode) in order to accept electrons and get reduced to hydrogen according to the following reaction.

33

1 H2 2

(2.2)

At the same time, Cl - moves toward the positively charged electrode (anode) to discharge electrons and gets oxidized to chlorine as the following:

Cl

1 Cl2 e 2

(2.3)

The species H+ and Cl in this example are called the principal charged species, which are responsible for current flow in the solutions. High conductivity is an added advantage to the process, which reduces the electrical resistance of the solution. On other hand, it also significantly reduces the adverse effects of HCO3- and SO4-. As the existence of the carbonate or sulfate ions would lead to the precipitation of Ca2+ or Mg2+ ions that form an insulating layer on the surface of the electrodes, which would further hinders the oxidation and reduction process (Chen et al 2004). 2.7.1 Electro-oxidation Electro oxidation of organic and inorganic compounds takes place via two principle pathways direct oxidation and indirect oxidation. The direct oxidation occurs at the anode in which the pollutants discharge its electron to the anode electrode in order to maintain the flow of current in the bulk solution. The indirect oxidation occurs as a result of the production of powerful oxidizing agents in the bulk solution such as chlorine, hydrogen peroxide and ozone. Short-lived intermediates, such as OH.2, O.2 and HO.2 also form during the electro-oxidation and could effectively destroy the organic and inorganic pollutants.

34

The electrochemical oxidation of phenolic compounds was also widely studied at different anodic materials and performing better (Comninellis et al 1993, Saracco et al 2000, 2001, Canizares et al 2002, 2004a, 2004b, 2005b, Iniesta et al 2001). Lidia et al (2005) studied the ability of the electro oxidation technique in improving the biodegradability of the tannery wastewater. Extensive research has been going on for the electro oxidation of pulp and paper industry wastewater using electrochemical process on various electrodes. El-Ashtoukhy et al (2009) studied the ability of electrochemical treatment of paper mill effluent from Raktas Pulp and Paper Company where rice straw is used to produce paper pulp. Experiments were carried out in a cylindrical agitated vessel lined with lead sheet as anode while a concentric cylindrical stainless steel sheet screen was placed as a cathode. The effect of current density, pH, NaCl concentration, impeller rotational speed and temperature on the rate of color and COD removal was studied and colour removal of 53 % to 100 % was reported. The COD was reduced from an average value of 5500 to 160 mg/l. Energy consumption ranged from 4 to 29 kWh/m3 of effluent depending on the operating conditions. Upendra et al (2008) studied the removal of pentachlorophenol (PCP) as a model AOX compound in pulp bleaching effluent of a bamboo based mill by electrochemical treatment in batch mode and reported that 10 mg/l of PCP in water removed almost completely in less than 10 min at a current density of 0.6 A/dm2 in the presence of 1000 mg/l NaCl serving as an electrolyte and source of chloride ions. The initial rate of PCP removal was found to decrease at alkaline pH (9.3) as compared to that at acidic pH (5.5). PCP removal in neutralized raw pulp bleach effluent (containing around 1830 mg/l of chloride) was very slow and incomplete even after 2 hours of electrochemical treatment at a current density of 1.5 A/dm2. Various pre-

35

treatments of raw bleach effluent such as, alkaline sulfide using sodium sulfide, alkaline reduction using ferrous sulfate and coagulation using potash alum were evaluated. Electrochemical treatment of potash alum pretreated effluent (spiked with PCP) was reported to achieve greater than 90 % removal of initial colour, COD and PCP in less than 1 hour. The estimated cost of combined treatment (potash alum coagulation + electrochemical) is 0.70.9 US$/m3 of the raw pulp bleach effluent. Dominguez et al (2008) described the electrochemical oxidation using boron-doped diamond electrodes as an efficient alternative in the treatment of biorefractory effluents. Total organic carbon (TOC) removal was reported higher than 80 % under the selected experimental conditions, where COD was in the range of 500- 1500 mg/l, current density was between 3 and 6 A/dm2, and the concentrations of sodium sulfate and sodium chloride supporting electrolytes were 2500 and 5000 mg/l respectively. Experimental conditions were selected to evaluate the technical suitability of the process and to establish a kinetic model and parameters. A first-order kinetic model and kinetic parameters were found out. Hongzhu et al (2007) investigated the electrochemical degradation of pulp and paper mill wastewater catalyzed by molybdenum and phosphate (MoP) modified kaolin with graphite electrodes. The catalyst was characterized by XRD, XPS and SEM spectra and the effects of pH, metal ion and introduction of NaCl on the efficiency of the electrochemical degradation process was studied. It was reported that the modified kaolin loaded with Fe3+ had higher electrochemical catalytic activity in the electrochemical degradation of paper mill wastewater at pH 4. A 96 % COD removal efficiency was obtained in 40 min of electrochemical treatment of the wastewater at current density 3 A/dm2. A possible mechanism for degradation of the mill wastewater constituents was also proposed.

36

Bo et al (2007a) investigated the electrochemical oxidation of pulp and paper making wastewater assisted by transition metal (Co, Cu) modified kaolin in a 200 ml electrolytic batch reactor with graphite plate as electrodes and found that when the initial pH was at 3, current density was 3 A/dm2; catalyst dose was 30 g/l, COD removal could reach up to 96.8 % in 73 min. They claimed that H2O2, which produced on the surface of porous graphite cathode, would react with the catalysts to form strong oxidant (hydroxyl radicals) that can in turn destruct the pollutants adsorbed on the surface of kaolin. The transition metal (Co, Cu) modified kaolin was also characterized by XRD and SEM before and after the modification. The mechanism was proposed on the basis of XPS analysis of the catalyst after the degradation process. Series of experiments were also done to prove the synergetic effect of the combined oxidation system and to find out the optimal operating parameters such as initial pH, current density and amount of catalyst. Bo et al (2007b), in the second work on electrochemical treatment of pulp and paper mill effluent studied the properties of the interlayer and outer layer of Ti/Co/SnO2-Sb2O5 electrode. As a result of unsatisfactory treatment using Ti/Co/SnO2-Sb2O5 electrode, electrochemical disposal of the effluent employing three-dimensional electrodes, combining active carbon granules serving as packed bed particle electrodes, with Ti/Co/SnO2-Sb2O5 anode, was performed. The residual dimensionless COD concentration reached 0.137, and color removal 75 % applying 16.7 A/dm2 current density at pH 11 and 15 g/l NaCl. The instant current efficiency, energy cost, electrochemical oxidation index (EOI) and kinetic constant of the reaction were calculated. The influence of pH and current density on COD abatement and decolorization was also investigated. Ugurlu et al (2006) investigated the removal of COD, lignin and phenol from paper mill effluents using an electrode cell consisting of graphite

37

electrode and powder-activated carbon (as working electrode). The effects of electrolyses time, voltage, initial pH, activated carbon (AC), NaCl amount and airflow were selected as parameters. The experimental results showed that removal efficiency significantly depends on the applied cell voltage, airflow, time, salt amount and pH. For electrolyses under the conditions of 25 V cell voltage, 5 min, in presence of air 2 min/l, NaCl 5 g/l at low pH and AC 20 g/l, it can be said that the removal of COD, lignin and phenol from the paper mill effluent were almost higher than 90 %. The present study proves the effectiveness of electrochemical treatment for the highly concentrated organic pollutants present in paper mill effluents. Anna et al (1997) investigated the electrochemical removal of 2chlorophenol and 2,6-dichlorophenol from aqueous solutions using porous carbon felt anodes. Operating variables including current input, ratio of electrode and solution volumes, and initial pollutant concentration were considered in order to determine their influence on the faradic efficiency of the process. The by-products of the oxidation reaction were identified, and their concentration was determined during the electrolysis. The experimental results showed a satisfactory detoxification, consisting of removal of cyclic chlorinated compounds, could be accomplished by means of this electrochemical method with a faradic efficiency of 30 % under optimized conditions. A mathematical model based on the reaction between chlorophenols adsorbed on the carbon fibers of the electrode and hydroxyl radicals produced by anodic oxidation of water has been proposed to interpret the experimental behavior of the system under different operating conditions. 2.7.2 Electro-coagulation Electrocoagulation is a process involving chemical and physical phenomena, which use sacrificial electrodes for generation of coagulants. The generation of metallic cations takes place at the anode, while H2 production

38

occurs at the cathode (Balasubramanian et al 2010). Electro coagulation technology offers an alternative to conventional coagulation process, where the metal salts or polymers are added to break the stable suspensions of the colloidal particles. In electro coagulation, coagulants are produced in situ within the reactor without direct addition of any chemicals. Coagulants are produced by the electrolytic oxidation of appropriate anode materials, such as mild steel or aluminium, which result in formation of highly charged polymeric metal hydroxyl species. These species neutralize the electrostatic charges on the suspended solids and facilitate agglomeration resulting in separation from the aqueous phase. The technology removes metals, colloids particles, and soluble organics pollutants from aqueous media by introducing highly charged polymeric hydroxide species. The treatment prompts the precipitation of certain metals and salts (Mollah et al 2001, Mollah et al 2004). The various advantages of electro coagulation process, compared to the conventional chemical coagulation process, have been reported by Mollah et al (2001). Process avoids the use of chemicals, and there is no problem of neutralizing excess chemicals and less possibility of secondary pollution. The equipment required for Electro coagulation process is simple and compact and is easy to operate and handle the problems encountered during running. Simple and compact treatment facility results in relatively low cost and there is a possibility of complete automation.

39

Electro coagulation process has the advantage of removing the smallest colloidal particles because the applied electric field sets them in faster motion thereby facilitating the agglomeration. It is a low sludge producing process, and the sludge formed during the process tends to be readily settable and easy to dewater, as it is mainly composed of metallic oxides/ hydroxides. The flocs formed during the electro coagulation process tends to be much larger, contains less bound water, is acid resistant and more stable, therefore can be separated by filtration. Electro coagulation effluent can be reused with a lower water recovery cost, due to the low dissolved solids content as compared with other chemical treatment effluent. The gas bubbles produced during electrolysis can carry the pollutant on the top of the solution where it can be more easily concentrated, collected, and removed. The process has no moving parts and most of the process is controlled electrically, therefore requires less maintenance. The electrocoagulation technique can be conveniently used in rural areas where electricity is not available, because a solar panel attached to the unit may be sufficient to carry out the process. The electrodes that are commonly used for the electrocoagulation process are aluminium and iron, in the form of plates or packed form of scraps such as steel turnings, millings etc. Usually, electrodes of iron for wastewater treatment and aluminium for water treatment are used, because

40

iron is relatively cheaper (Shen et al 2003). When mild steel is used as anode, upon oxidation in an electrolytic system, it produces iron hydroxide, Fe(OH)n, where n=2 or 3. Two mechanisms have been proposed for the production of Fe(OH)n (Balasubramanian et al 2010). Mechanism 1 Anode: Fe(s) Fe2+(aq.) + 2e
(aq.)

(2.4) Fe(OH)2(s) (2.5)

Fe2+(aq.) + 2OH Cathode: 2H2O(l) + 2e Overall: Fe(s) + 2H2O Mechanism 2 Anode: 4Fe(s)

H2(g) + 2(OH)

(aq.)

(2.6)

Fe(OH)2(s) + H2(g)

(2.7)

4Fe2+(aq.) + 8e 4Fe(OH)3(s) + 8H+(aq.)

(2.8) (2.9)

4Fe2+(aq.) + 10H2O(l) + O2(g) Cathode: 8H+(aq.) + 8e Overall: 4Fe(s) + 10H2O(l) + O2(g) 4H2(g)

(2.10)

4Fe(OH)3(s) + 4H2(g)

(2.11)

41

In addition to the above hydroxyle species, electro generated ferric ions form monomeric, ferric hydroxo complexes with hydroxide ions and polymeric species, depending on the pH range. These are FeOH2+, Fe(OH)2+, Fe2(OH)24+, Fe(OH)4-, Fe(H2O)2+,Fe(H2O)5OH2+, Fe(H2O)4(OH)2+, Fe(H2O)8(OH)24+, Fe2(H2O)6(OH)42+, which transform finally into Fe(OH)3 at pH around 8 (Kobya et al 2003, Benefield et al 1982, Rubin et al1974). The charged hydrolyzed hydroxyl can reduce the net surface charge of the colloidal particles that are in suspension due to the reduction of repulsive potential of electrical double layer. As a result of this, the repulsive forces between the colloidal particles decrease, and bring the particles close to such an extent where the Vander Waals forces predominate and facilitate agglomeration. Hydrolyzed metal species can be adsorbed on the colloids and creates bridges between the particles. In addition to that, the amorphous solid ferric hydroxide flocs that forms at elevated pH, settle down causing sweep flocculation. The destabilization mechanisms of the contaminants and particulate suspensions may be summarized as follows. 1. Compression of the diffuse double layer due to the reduction of net surface charge, which is mainly due to the reduction of repulsive potential of the electric double layer by the presence of species of opposite charge species around the charged colloidal. This is mainly achieved by the interactions of the ions generated by the dissolution of the sacrificial electrode, due to the passage of current through the solution. 2. Charge neutralization of the ionic species present in wastewater, which is caused by the counter ions produced by the electrochemical dissolution of the sacrificial electrode.

42

These counter ions reduce the electrostatic inter particle repulsion sufficiently so that the van der Waals attraction forces predominates, thus causing coagulation. A zero net charge results in the process. 3. Floc formation due to the precipitation of amorphous ferric hydroxide species at elevated pH. This forms a sludge blanket that entraps and removes the colloidal suspended particles when settling down, as a result of enmeshment phenomena. The mechanism of EC is highly dependent on the chemistry of the aqueous medium, especially the conductivity. The other characteristics such as pH, particle size, and chemical constituent concentrations will also influence the EC process. The electrolyte pH plays an important role in the separation of suspended particles; at low pH the separation is dominated by precipitation while adsorption dominates at high electrolyte pH. In addition, the following physiochemical reactions can take place in the EC cell (Balasubramanian et al 2010): cathodic and chemical reduction of organic and inorganic matter; chemical interaction between ions of iron (or aluminium), formed during the dissolution of anodes, and anions present in wastewater, resulting in the formation of insoluble compounds; flotation of solid and emulsified impurities by hydrogen gas produced on the cathode; sorption of ions and molecules of dissolved impurities on the surface of iron (or aluminium) hydroxides having considerable sorption capacity.

43

Electrocoagulation has been successfully applied on various wastewaters, and found to be the promising for solids/liquids separation (Vik et al 1984, Donnini et al 1994). Khansorthonga et al (2009) attempted to find the optimum condition for colour and total COD reduction from the pulp and paper industry effluent by electrocoagulation. The authors studied the effect of parameters including the type of polyelectrolyte, current density, initial pH of the wastewater and the flow rate. The authors observed that the polyelectrolyte had no effect on pollutant removal. At optimum conditions, greater than 97% of colour and 77% COD were effectively removed with a total operating cost of approximately 0.29 USD/m3 effluent satisfying the first order rate kinetics. For the continuous mode, the treatment process reached the steady state condition within 2.15 h and the efficiency of colour and total COD reduction reported greater than 91% and 77%, respectively. Parama Kalyani et al (2009) studied the influence of electrolysis time, applied charge density, electrolyte pH and supporting electrolyte concentration on electrocoagulation efficiency for the treatment of pulp and paper industry effluent. The maximum color removal efficiencies were reported as 92 % and 84 % for mild steel and aluminium electrode respectively. The corresponding maximum COD reduction has been recorded as 95 % and 89 %. The authors have coupled electrocoagulation with Sequential Batch Reactor (SBR) to improve the efficiency of biochemical treatment by increasing the biodegradability index through electrocoagulation. The process of electrocoagulation was modeled using various adsorption isotherms and observed that the Langmuir and Radke-Prausnitz isotherm models predictions match satisfactorily with the experimental observations. Zaied et al (2009) studied the effect of electrolysis time, current density, type of electrode material and initial pH during electrocoagulation of

44

the black liquor resulting from paper industry in an attempt to achieve a higher removal capacity. Under the optimal experimental conditions (initial pH: 7, time: 50 min and current density: 1.4 A/dm2), the treatment of black liquor by electrocoagulation has led to a removal capacity of 98 % of COD, 92 % of polyphenols and 99 % of color intensity with a good repeatability, making it possible to highlight the industrial interest of this electrochemical process. Marcela et al (2008) conducted a preliminary investigation that associates the electrocoagulationflotation (EC) method (iron electrodes) followed by photocatalysis to treat water effluents from cellulose and paper factories. For EC, the experiment with aluminium and iron electrodes showed similar efficiency. By applying 30 min of EC/Fe0, 1.53 A/dm2 and pH 6.0, the COD values, UVvis absorbance and turbidity underwent an intense decrease. For the subsequent UV photocatalysis TiO2 was employed and the favourable operational conditions found were 0.25 g/l of the catalyst and solution pH 3.0. The addition of hydrogen peroxide (50 mmol/l) highly increased the photoprocess performance. By employing the UV/TiO2/H2O2 system, the COD reductions reported, improved to 88 % compared to pre-treated effluents. The salt concentration on EC showed that the electrolysis duration can be reduced from 30 to 10 min by the addition of 5.0 g/l of NaCl. The biodegradability index (BOD/COD) increased from 0.15 (pre-treated) to 0.48 (after EC) and to 0.89 (after EC/photocatalysis irradiated for 6 h), showing that the employed sequence is very helpful to improve the water quality. This result was confirmed by biotoxicity tests performed with microcrustaceous Artemia
salina .

Beata et al (2008) experimented electrocoagulation of pulp and paper industry effluent using aluminium anode. The maximum efficiency of pollutant removal was 40 to 60 % for COD, and 90 to 99 % for turbidity,

45

colour and suspended solids. The authors commented electrocoagulation to be an effective method of wastewater treatment, offering a viable alternative to chemical coagulation. Ugurlu et al (2008) investigated the treatment of paper mill effluents using electrocoagulation. Removal of lignin, phenol, COD and BOD from paper mill effluents was investigated at various current intensities by using different electrodes. It is reported that the experiments carried out at 12 V, an electrolysis time of 2 min and a current intensity of 77.13 mA were sufficient for the removal of these pollutants with each electrode. The removal capacities of the process for aluminium anode were 80 % of lignin, 98 % of phenol, 70 % of BOD, and 75 % of COD after 7.5 min. For Fe anode the removal capacities were 92 %, 93 %, 80 % and 55 %, respectively. In addition, it was found that removal of lignin, phenol, BOD and COD increased with increasing current density. It was also found that Al electrode performs higher efficiency than Fe electrode except for COD removal. However, the time required for removal of BOD was more than that of COD. Ben et al (2007) studied the treatment of paper effluent samples by coagulation followed by electro-flotation in order to determine the best conditions of treatment which maximize the purification efficiency. The methodology of experimental research with an orthogonal central composite design was adopted in batch and continuous modes. The authors have reported the current density to be the most significant factor in the suspended solids elimination followed in decreasing order of importance by coagulant concentration and pH. Purification efficiency consisting in the elimination of suspended solids exceeded 95 %. Physicochemical characterization of the effluent was done before and after the treatment in batch and continuous mode to improve the efficiency of the process. This characterization included pH, conductivity, salinity, BOD5, COD, suspended solids and chlorides.

46

Yuan et al (2007) used a pilot-scale pulsed electrocoagulation (EC) system for treating specialty paper mill wastewater from central Taiwan using a pilot-scale pulsed electrocoagulation unit. The effect of controlled parameters as the use of either iron or aluminium electrodes, current density and hydraulic retention time on electrical conductivity, suspended solids (SS), COD and true color during the treatment was studied. The results indicated that electrical conductivity decreased with increasing current density and HRT; under all current densities, SS removal appeared to have no correlation with the flow rate, and a minimum of 85 % SS removal was observed. Removal of COD was dependent on the electrode materials. Under the best operational conditions (a current density of 1.07 A/dm2, and an HRT of 3.25 min) using aluminium electrodes achieved removals of 25.4, 97.14, 76.47 and 70.09 % of electrical conductivity, SS, COD, and true colour, respectively. The current dissolved air flotation unit costs 0.0812 US$/m3 of effluent to operate, while the pulsed EC unit costs 0.0733 US$/m3 of effluent. A proposed 5-stage mechanism of the EC system is also discussed. Mahesh et al (2006a) investigated the electrochemical degradation of agri-based paper mill wastewater (black liquor) in a 2 litre electrolytic batch reactor using iron plate electrodes. Of the four, six, and eight-plate configurations, a current density of 0.55 A/dm2 at neutral pH with a six-plate arrangement was found to be optimal, achieving a maximum COD and color removal of 80 % and 90 % respectively. The chemical dissolution of iron was found to be strongly influenced by the initial pH. Electrochemical treatment at higher initial pH (pH0 > 9) increases the dissolution of iron electrodes by an order of magnitude. At the optimal current density, the iron electrode consumed is 31.27 g/m2Ah, achieving maximum COD removal. An increase in salinity reported to reduce the treatment time significantly, and the sludge settling characteristics also improve. The addition of polyacrylamide (10 mg/l) to the electrochemical reactor enhanced the COD removal rate with

47

a very short treatment time with excellent sludge settleability. Specific energy consumption (SEC) reduced from 6.64 to 5.73 kWh/kg of COD removed, with the addition of NaCl (625 mg/l). The post-treatment of electrochemically treated wastewater by chemical coagulation using alum (360 mg/l) along with 20 mg/l polyacrylamide (PAA) further reduced COD values to <180 mg/l and a near 100 % (<5 PCU) color removal. An overall COD removal of 91 % and color removal of near 100 % was reported achieved by electrochemical treatment followed by coagulation/flocculation. In second part of the same work Mahesh et al (2006b) reported the characteristics and the management of the sludge generated. The settling velocity of the sludge obtained from the EC treatment without any additive was satisfactorily correlated with the model of Richardson and Zaki. The results of the gravity filtration of the treated black liquor showed that the addition of NaCl (625 mg/l) improved the filtration characteristics and reduced the values of the specific cake resistance. The values of the specific cake resistance and the resistance of the filter medium were in the range of 3.25-4.67 1011 m/kg and 2.37- 2.98 109/m, respectively. Prolonged use of iron anodes produces a large number of dents on their surface. SEM images of the electrodes showed that the dents formed because of the anode dissolution during the EC process. The sludge has lower ash content and fixed carbon and higher volatile matter than that of Indian coal. Thermal analysis showed good combustion characteristics and complete oxidation of the EC process sludge at about 400C, with a heating value of 11.33 MJ/kg. They have also concluded by commenting to dispose the ash by blending with organic manure or with clay/coal fly ash to make bricks/ceramic tiles. Thus, it has been reported repeatedly that electrochemical degradation of the pulp and paper industry effluent is technically feasible, the advantages being superior rate, less amount of side product etc. But the

48

consumption of electricity, the costliest form of energy, makes the process economically infeasible in most of the cases. Complete mineralization of such a heavily loaded effluent is not acceptable because of energy cost. The trend of growing stringent environmental regulations will overtake the growing energy and electrode cost and makes the process economically viable soon. The extra-ordinary ability of the technique in removing organic part, colour, odour and improving biodegradability is noticeable. In the present work, these abilities are optimally utilized, in order to make a conventional biological treatment process of the kraft pulp bleaching effluent from typical large-scale pulp and paper industries, performing more efficiently and economically. 2.8 RESPONSE SURFACE METHODOLOGY In conventional multifactor experiments, optimization is usually carried out by varying a single factor while keeping all other factors fixed at a specific set of conditions. It is not only time-consuming, but also usually incapable of reaching the true optimum due to ignoring the interactions among variables. On the other hand, the response surface methodology (RSM) has been proposed to determine the influences of individual factors and their interactive influences. The RSM is important in designing, formulating, developing, and analyzing new scientific studying and products. It is also efficient in the improvement of existing studies and products. The most common applications of RSM are in Industrial, Biological and Clinical Science, Social Science, Food Science, and Physical and Engineering Sciences. According to Hill and Hunter, RSM method was introduced by G.E.P. Box and K.B. Wilson in 1951. Box and Wilson suggested to use a first-degree polynomial model to approximate the response variable. Mead and Pike stated origin of RSM starts 1930s with use of Response Curves (Myers et al 1989).

49

According to Myers et al (1989), the orthogonal design was motivated by Box and Wilson (1951) in the case of the first-order model. For the second-order models, many subject- matter scientists and engineers have a working knowledge of the central composite designs (CCDs) and three-level designs by Box and Behnken (1960). Also, the same research states that another important contribution came from Hartley (1959), who made an effort to create a more economical or small composite design. There exist many papers in the literatures about the response surface models. One of the important facts is whether the system contains a maximum or a minimum or a saddle point, which has a wide interest in industry. Therefore, RSM is being increasingly used in the industry. Also, in recent years more emphasis has been placed by the chemical and processing field for finding regions where there is an improvement in response instead of finding the optimum response. In result, application and development of RSM will continue to be used in many areas in the future. Response Surface Methods are designs and models for working with continuous treatments when finding the optima or describing the response is the goal (Oehlert et al 2000). The first goal for Response Surface Method is to find the optimum response. When there is more than one response then it is important to find the compromise optimum that does not optimize only one response (Oehlert et al 2000). When there are constraints on the design data, then the experimental design has to meet requirements of the constraints. The second goal is to understand how the response changes in a given direction by adjusting the design variables. In general, the response surface can be visualized graphically. The graph is helpful to see the shape of a response surface; hills, valleys, and ridge lines. RSM has been received wide attention in research works, examples include, dye removal by adsorption (Ravikumar et al 2006), Biosorption of

50

dye (Pavan et al 2007), Fentons peroxidation on the removal of organic pollutants from olive oil mill wastewater (Ahmadi et al 2005), decolorization of dye using enzyme (Murugesan et al 2007) and nickel plating process (Oraon et al 2006), Chemical coagulationflocculation process of pulp and paper mill wastewater (Ahmad et al 2007), Chemical coagulation electroflotation of process of pulp and paper mill wastewater (Ben et al 2007), electrochemical treatment of textile dye wastewater (Korbahti et al 2007a), electrochemical oxidation of water-based paint wastewater (Korbahti et al 2007b), decolorization of Acid Red 14 dye by electrocoagulation process (Aleboyeh et al 2008), electro chemical oxidation of simulated textile waste water (Korbahti et al 2008) etc.