" & " "ΕΠΙΣΤΗΜΗ & ΤΕΧΝΟΛΟΓΙΑ ΥΔΑΤΙΚΩΝ ΠΟΡΩΝ", 2010

- " & ". "ΕΠΙΣΤΗΜΗ & ΤΕΧΝΟΛΟΓΙΑ ΥΔΑΤΙΚΩΝ ΠΟΡΩΝ", 2010 :.

- " & ". "ΕΠΙΣΤΗΜΗ & ΤΕΧΝΟΛΟΓΙΑ ΥΔΑΤΙΚΩΝ ΠΟΡΩΝ", 2010 :.

,.,,..,,,.,,,,,.,,.

Περίληψη,, (Granular Activated Carbon, GAC)., (COD).,,,,.,.,.,,,. H, GAC.,,,. ( =0.60 cm, =19.63cm 2, COD=400mg/l). COD 30% ii

Περίληψη COD (125mg/l)., Bohart & Adams COD.. COD. Hutchins Bohart & Adams,,. Hutchins., Hutchins.. 575nm. COD..,. iii

Περίληψη., COD., COD 90%. iv

Abstract Abstract Introduction Increasingly affluent lifestyles, continuing industrial and commercial growth in many countries around the world in the past decade has been accompanied by rapid increase in the municipal solid waste production. The sanitary landfill method for the ultimate disposal of solid waste material is widely accepted and used due to its economic advantages. As the landfills are open places, the rain water infiltrating through a landfill leaches with it the decomposing organic and inorganic matter and heavy metals by physical extraction. This contaminant laden concentrated effluent from the landfill is called landfill leachate. Its composition will vary from site to site, depending on many factors such as the nature of the waste in the landfill, the engineering design of the landfill and the rainfall of the region. Untreated leachate can percolate through the soil, mix with surface or permeate through the ground water and can contribute to the pollution of surface and ground water. A range of biological and chemical treatment processes for landfill leachate have been studied (J.M. Abdul et el., 2008). The biological methods are probably the most efficient and cheapest process to eliminate organic and inorganic matter from leachate. However, biological treatment is inhibited by the specific toxic substances and by the presence of bio-refractory organics. On the other hand, advanced oxidation processes and membranes processes are often costly in terms of energy requirements and use of additional chemicals. Over the last few years, adsorption, a surface phenomenon by which a multi components fluid mixture is attracted to the surface of a solid adsorbent and forms attachments via physical or chemical bonds, is recognized as the most efficient approach in the landfill leachate processes (K.Y. Foo & B.H. Hameed, 2009). The most frequently used adsorbent is granular or powered activated carbon. Granular activated carbon (GAC) owns an ability for removal of a wide variety of organic and inorganic pollutants dissolved in leachate. Adsorption by activated carbon often used v

Abstract along with biological treatment for effective treatment of landfill leachate (S. Renou et al., 2008). The objective of the present work is to study the removal of organic matter (COD) and color-causing components from landfill leachate using granular activated carbon. Experimental details The specifications of the activated carbon which was selected as the adsorbent for this study, i.e. Filtrabarb CC60, are presented in Table 1. The non-treated landfill leachate (from landfill in Ano Liosia) which was used had the physicochemical characteristics listed in Table 2. Table 1 Activated carbon specifications Manufacturer CHEMiTEC, Greece Size of carbon 12 x 40 mesh Type of carbon Granular Raw material Coal Ash content <10% Surface area 1050 m 2 /g Iodine number 1000 mg/g Bulk density 0.45 g/cm 3 Pore volume 1,105 cm 3 /g Table 2 Chemical characteristics of non-treated leachate COD 5500 mg/l BOD 5 27 mg/l BOD 5 /COD 0.005 Conductivity 2.6 ms/cm TSS 17500 mg/l VSS 720 mg/l ph 8.2 Color Brown Laboratory GAC columns should be about the same height as the full-scale unit. Short columns need to be arranged in series to achieve the desired depth. In this vi

Abstract work, a four column pilot plant was operated in series. Four columns of 5cm inside diameter and 60cm height were the major elements of the test equipment. Flow through the columns was provided by a small variable speed peristaltic pump. Experimental data were collected on COD and color, influent and effluent, and the analyses were carried out as per Standard Methods. Column experiments A series of column experiments were performed to evaluate the feasibility of carbon adsorption as a treatment process for leachate. Initially, glasswool was placed at the bottom of every column and then the activated carbon fed into. After this, deionized water provided in the column. This is done to remove air trapped in the carbon pores that would otherwise prevent the feed leachate from contacting the entire carbon surface. The leachate that gone treated was collected and delivered from a 100 liters container by a variable speed peristaltic pump to the columns which were operated in a downflow mode. The testing procedures adopted for the three columns studies, which were realized, are presented in Table 3. Table 3 Summary of testing procedures 1 st column test 2 nd column test 3 rd column test Mode of flow Downflow Downflow Downflow Influent COD (C 0 ) 400 mg/l 400 mg/l 400 mg/l No. Of columns 4 4 4 Height of columns 0.6 m 0.6 m 0.6 m Diameter of column 0.05 m 0.05 m 0.05 m Flow rate 46 lt/min m 2 17 lt/min m 2 27 lt/min m 2 Linear flow rate 2.8 m/hr 1.0 m/hr 1.6 m/hr Regular effluent samples were collected from the bottom of each column and analyzed for COD and color. The effluent concentration equal to 30% of inlet concentration was taken as the breakthrough point. vii

Abstract Results and discussion During regular intervals the removal of COD and color was measured in each column. Effluent impurity concentration for all columns were plotted against elapsed time generating breakthrough curves. The results of the removal of COD in each column for the first column test are shown in Fig. 1. Figure 1 is a plot showing when each column breakthrough curve exceeded the effluent limit of 30% COD remaining. The line through the data points in Fig. 2 is the Bed Depth Service Time (BDST) curve. 1st column test 100 column 1 column 2 column 3 column 4 COD remaining %, (C/Co) 80 60 40 20 0 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 service time, hr Figure 1 : Breakthrough curves for leachate (1 st column test) 1st column test service time, hr 30,0 25,0 20,0 15,0 10,0 5,0 0,0 q = 46 l/min m2 22,0 y = 11,033x - 6,4 R 2 = 0,9467 11,0 6,0 1,6 0 0,5 1 1,5 2 2,5 bed depth, m Figure 2 : Bed depth service time relationship (1 st column test) viii

Abstract In the same way, the effluent impurity concentration for the four columns is plotted against elapsed time. Breakthrough and BDST curves, for the second and third column test, are shown in Fig. 3 and in Fig. 4 respectively. COD remaining %, (C/Co) 2nd column test 100 80 60 40 20 0 column 1 column 2 column 3 column 4 0 20 40 60 80 100 120 140 160 180 200 220 240 service time, hr (a) service time, hr 160 140 120 100 80 60 40 20 20 2nd column test y = 68,333x - 20 R 2 = 0,9917 60 0 0 0,5 1 1,5 2 2,5 bed depth, m (b) 110 q = 17 l/min m2 140 Figure 3 : (a) Breakthrough curves and (b) BDST curve (2 nd column test) COD remaining %, (C/Co) 3rd column test 100 column 1 column 2 80 column 3 column 4 60 40 20 0 0 20 40 60 80 100 120 140 160 180 200 220 240 260 service time, hr (a) service time, hr 3rd column test 70 65 60 y = 32,167x - 15,5 50 R 2 = 0,9809 40 38 30 22 q = 27 l/min m2 20 10 6 0 0 0,5 1 1,5 2 2,5 bed depth, m (b) Figure 4 : (a) Breakthrough curves and (b) BDST curve (3 rd column test) Bohart & Adams Model The bed depth service time equation is based on work by Bohart & Adams (1920). It has the following form : t = ax+b (1.1) where, t service time, hr x bed depth, m ix

Abstract a b N 0 C 0 v slope = N 0 /C 0 v, hr/m adsorption rate, hr adsorptive capacity, mg COD/g AC influent concentration, mg/l linear flow rate, m/hr The slope (a) of the BDST line represents the time required to exhaust one meter of the carbon bed, which can also be defined as the time required for the adsorption wave front to move through one meter of the carbon bed. The reciprocal of the slope is the rate at which the carbon bed is spent. The adsorptive capacity N 0 can be determined from the slope of a linear plot of service time versus bed depth (equation 1.2). The rate constant K is then calculated from the intercept of this plot (equation 1.3). and N 0 = 0 C va (1.2) K 1 C 0 = ln 1 C 0b C ef (1.3) where, K rate constant, m 3 /kg hr C ef allowable effluent concentration, mg/l The bed depth, which theoretically is just sufficient to prevent penetration of concentration in excess of C ef at zero time, is defined as the critical bed depth (L critical ) and is determined from equation (1.4) : L critical = v KN 0 C 0 ln( C ef 1) (1.4) From the equations above, N 0, K and L critical is computed and the results for each column test is presented in Table 4. x

Abstract Table 4 Values of N 0, K and L critical for each column test 1 st column test 2 nd column test 3 rd column test Flow rate (l/min m 2 ) 46 17 27 BDST equation y = 11.033x 6.4 y = 68.333x 20 y = 30.333x 11.5 N 0 (kgcod/m 3 AC) 12.36 27.3 19.41 K (m 3 /kgcod hr) 0.31 0.098 0.17 L critical (m) 0.58 0.29 0.38 The results from the table above show that both K and critical bed depth increases with the flow rate. Using the results from the second column test (because they have the highest correlation coefficient), the required carbon column for the treatment of landfill leachate can be calculated. The flow of landfill leachate in Ano Liosia is 100m 3 /day. t = 68.333x 20 with correlation efficient R 2 = 0.9917 Adsorption velocity : 1 = α 1 68,033 = 0,015 m / hr The time to exhaust a column of 2.4 m height is : 2.4m COP = = 160 hr 0.015 m / hr At a flow rate of 17 l/min m 2 the total volume treated before breakthrough point is (160 100)= 667 m 3. For a yearly volume of 36500 m 3, 55 carbon charges are required. The area which required is : Diameter = 2.3m Q 70 l / min A = = = q 17 l / min m The carbon used for the treatment per hour is : CUR = 1/ 4. 1 2 CUR = 4.1 m 3 0.015 m/hr 450 kg/m 3 m 2 xi

Abstract where, bulk density of carbon, g/cm 3 Using the equation (1.5) the total volume of the column can be calculated : ( CUR COP ) SF V = ρ (1.5) (27,7 160 ) 1,5 V = 450 15 m 3, CUR carbon use, kg/hr COP time to exhaust a column, hr SF safety factor, 1,5 bulk density of carbon, kg/m 3 Hutchins Methodology Hutchins and co-workers (1973) have used the Bohart & Adams equation (1.1) in the form of bed depth service time for interpretation of column data and process design, including data extrapolation to conditions other than tested. A new BDST equation must be developed if the flow rate through the columns changes. Applying Hutchins equation (1.6), additional column tests will not required. The new equation for a change in flow rate is developed as follows : V 1 t = ax + V 2 b (1.6), V 1 original flow rate V 2 new flow rate From this work indicates that the results obtained by this simplified method were not in close agreement with results obtained by tests performed under actual flow rate conditions (Fig. 5). xii

Abstract 160 140 Actual BDST equation at q=17 l/min m2 (y = 68,333x - 20) service time, hr 120 100 80 60 40 BDST equation at q=46 l/min m2 Calculated BDST equation at q=17 l/min m2 (y = 29,789x - 6,4) Actual BDST equation at q=27 l/min m2 (y = 30,333x - 11,5) (y = 11,033x - 6,4) Calculated BDST equation at q=27 l/min m2 (y = 18,618x - 6,4) 20 0 0 0,5 1 1,5 2 2,5 3 bed depth, m Figure 5 : Effect of flow rate change on the BDST curve (Hutchins) Removal of color Summarizing the results of COD and color removal show that they have a parallel move during the time (Fig. 6). The relationship between COD and color is presented in Fig. 7. COD, mg/l 450 400 350 300 250 200 150 100 50 0 COD Abs 1 9 17 25 33 41 49 57 65 73 81 89 97 105 113 121 129 137 145 service time, hr 45 40 35 30 25 20 15 10 5 0 Abs, nm Figure 6 : Plots of color and COD versus service time xiii

Abstract COD, mg/l 450 400 350 300 250 200 150 100 50 0 y = 11,018x - 75,462 R 2 = 0,8732 0 5 10 15 20 25 30 35 40 45 Abs, nm Figure 7 : Relationship between COD and color Determination of Microbial flora After the end of each column test the development of microbial flora was measured at the surface of activated carbon grains (Fig.8). The results show that the number of colonies (cfu) per gram activated carbon increases with the elapsed time. This might happen because when the service time increases the microorganisms have the time required for their development. Millions 600 500 Microbial flora, cfu/g 400 300 200 100 column 1 column 2 column 3 column 4 0 1st column test service time 390 hr 2nd column test service time 218 hr 3rd column test service time 285 hr Figure 8 : Microbial flora xiv

Abstract Conclusions The carbon column adsorption study shows that organic matter and colorcausing components may be reduced to acceptable levels by using carbon adsorption technique. Nearly 90% COD removals were achieved with GAC. The results from the breakthrough and BDST curves show that the critical bed depth increases with the flow rate. The results from Hutchins methodology were not in close agreement with the results obtained by column test in this work. The column tests also show that the color has an almost parallel trend with the concentration of COD. Finally, it is shown that the number of microorganisms which grow on the carbon s granules increases with the increase of the elapsed time of the system. xv

ii Abstract v xvi xx xxii 1. 1 2. 4 2.1 4 2.2 5 2.3 6 2.3.1 6 2.3.2 6 2.3.3 8 2.3.4 9 3. 11 3.1 11 3.2 11 3.2.1 12 3.2.1.1 12 3.2.1.2 12 3.2.2 13 3.2.2.1 13 3.2.2.1.1 13 3.2.2.1.2 14 3.2.2.1.3 15 3.2.2.1.4 17 3.2.2.1.5 18 3.2.2.2 18 3.2.2.2.1 18 3.2.2.2.2 20 xvi

3.2.3 21 3.2.3.1 21 3.2.3.2-22 3.2.3.3 23 3.2.4 : 23 3.2.4.1 26 3.2.4.2 26 3.2.4.3 27 3.2.4.4 27 3.2.5 28 3.2.5.1 Fenton Fenton UV (Photo-Fenton) 29 3.2.5.2 30 3.2.5.3 30 4. 32 4.1 32 4.2 33 4.2.1 Freundlich 35 4.2.2 Langmuir 37 4.2.3 Brunauer, Emmet Teller (BET) 38 4.3 39 4.4 41 4.5 (Breakthrough curve) 41 4.6 45 5. 47 5.1 47 5.2 48 5.3 50 5.4 52 5.5 54 5.5.1 (PAC) 55 5.5.2 (GAC) 58 xvii

5.6 GAC 60 5.7 64 5.8 GAC 65 5.8.1 Bohart Adams 68 5.8.2 Hutchins 70 5.9 72 74 6. 76 6.1 76 6.2 (GAC) 77 6.2.1 77 6.2.2 (GAC) 78 6.2.3 GAC 79 6.3 82 6.4 85 6.4.1 86 6.4.3 OD (Biochemical Oxygen Demand) 93 6.4.4 97 6.4.5 104 6.4.6 (T), ph 108 7. 109 7.1 110 7.2 Bohart & Adams 112 7.2.1 ( ) 112 7.2.2 118 7.2.3 121 7.2.4 124 7.3 GAC 129 7.4 Hutchins 132 xviii

7.4.1 Hutchins 2 133 7.4.2 Hutchins 3 135 7.4.3 Hutchins 4 138 7.5 142 7.5.1 143 7.5.2 145 8. 150 153 154 156 164 : COD 165 : 178 : 181 xix

2.1 7 3.1 25 4.1 Freundlich 36 5.1 GAC 52 6.1 77 6.2 GAC 78 6.3 80 6.4 82 6.5 99 6.6 101 6.7 _ 101 7.1 1 112 7.2 1 115 7.3 2 118 7.4 2 119 7.5 3 121 7.6 3 123 7.7 4 124 7.8 4 126 7.9 129 7.10 Hutchins 2 134 7.11 Hutchins L critical (2 ) 135 7.12 Hutchins 3 137 xx

7.13 Hutchins L critical (3 ) 137 7.14 Hutchins 4 140 7.15 Hutchins L critical (4 ) 140 xxi

2.1 : 5 2.2: 9 3.1 : SBR 16 3.2 : OD, COD 20 3.3 : 22 4.1 : 43 4.2 : 44 5.1 58 5.2 : 59 5.3 : 62 5.4 : ( ) ( ) COD 72 5.5: COD MAACFB 74 6.1 : (GAC) 78 6.2: 79 6.3 : GAC 80 6.4 : 81 6.5 : µ 87 6.6 : ( ) COD REACTOR ( ) µ µ HACH DR/2010 88 6.7 : 92 6.8 : 92 6.9 : ( ) ( ) 94 6.10 : 100 6.11 : 102 6.4.5 104 6.12 : 108 7.1 : 1 113 xxii

7.2 : GAC (1 ) 114 7.3 : 2 118 7.4 : GAC (2 ) 119 7.5 : 3 122 7.6 : GAC (3 ) 122 7.7 : 4 125 7.8 : GAC (4 ) 125 7.9 : GAC _ 127 7.11 : Hutchins 2 134 7.11 : Hutchins 3 136 7.12 : Hutchins 4 139 7.13 : COD 2 143 7.14 : 144 7.15 : COD 3 145 7.16 : COD 4 146 7.17 : COD 147 7.18 : 148 xxiii

Κεφ. 1 Εισαγωγή 1.,.,.,,,...,.,...,...., 1

Κεφ. 1 Εισαγωγή,.,.., (Granular Activated Carbon - GAC)..,.,.. COD. ( GAC, COD ). Bohart & Adams COD. 2

Κεφ. 1 Εισαγωγή,,..... 3

Κεφ. 2 Διαχείριση στερεών αποβλήτων 2. 2.1 : ),, ),,,. (, 2007). ( ),,,. 50910/2727/2003,,,,,,,,.,, (,, ).,. 4

Κεφ. 2 Διαχείριση στερεών αποβλήτων 2.2, ( ). ( ),,.., ( ).,.,,,, (, 2007).,, (CH 4 ) CO 2. 50. 2.1. 2.1 : (, 2007) 5

Κεφ. 2 Διαχείριση στερεών αποβλήτων 2.3 2.3.1 ( ) : a. ( ), b. c..,.,.,,,.. 2.3.2.,,,,.,. 6

Κεφ. 2 Διαχείριση στερεών αποβλήτων. 2.1,. 2.1 (S. Renou et al., 2008) ( ) <5 5-10 >10 ph <6.5 6.5-7.5 >7.5 COD (mg/l) >10000 4000-10000 <4000 BOD 5 /COD >0.3 0.1-0.3 <0.1 - - 80% 5-30% &,.,.,. BOD 5 /COD. 0,3. 0,1. 7

Κεφ. 2 Διαχείριση στερεών αποβλήτων (. BOD 5 /COD)., (J.M. Abdul et al., 2008). 2.3.3 ( - ),..,. 100 (,,..),.. 56, 32, 10 21 (K.Y. Foo & B.H. Hameed, 2009).,, (, 2005). 2.2. 8

Κεφ. 2 Διαχείριση στερεών αποβλήτων 2.2: (, 2005).,,. 2.3.4,,... 9

Κεφ. 2 Διαχείριση στερεών αποβλήτων,,,. 10

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 3. 3.1,.,,,.,,.. 3.2 : a., b. c.. 11

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 3.2.1 3.2.1.1,..,,, (S. Renou et al., 2008).,,.. 9:1, 95% BOD 50% (S. Renou et al., 2008). 3.2.1.2.... 12

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων, 2-3.,.,, (S. Renou et al., 2008). 3.2.2 ( ) BOD. CO 2. BOD 5 /COD (>0,3)., ( ). 3.2.2.1 3.2.2.1.1 (Lagoons),., 13

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων. (1-1,2 m) ( / ) (, 2001).. : i. ph ( ), ii. BOD 5 /N/P ( 100/5/1), iii. COD/BOD 5 ( 1,5 2), iv. v.. COD 55-64% (K. Orupold et al., 2000).,,., (S. Renou et al., 2008). 3.2.2.1.2 (Activated sludge).. 14

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων :,, -, (Metcalf & Eddy, 2006).,.,.,..,.,.,,,,. 3.2.2.1.3 (sequencing batch reactor SBR) ( ),. 15

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων : (1), (2) ( ), (3) ( / ), (4) ( ) (5).,,.,.,,.. COD SBR 75% (S. Renou et al., 2008).. SBR 95% Loukidou & Zouboulis. 3.1. 3.1 : SBR (Loukidou & Zouboulis, 2001) 16

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 3.2.2.1.4,.., (, 2001). (, 1986).,.,., -,..., BOD. 17

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 3.2.2.1.5 (Rotating Biological Contactors RBC). 40%..,..... :,,. 3.2.2.2 3.2.2.2.1,. : ( ) ( ) 18

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων.,., ( ) (CH 4 ), (CO 2 ).,.,. 30-35 C ( ) 50-55 C ( ). 35 C ( ).,,..,,..,.., ph,.,.. COD 80-90% 55% 35 C (S. Renou et al., 2008). 19

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 3.2 BOD COD 35 C. 20 BOD ( 42%) COD ( 55%).. 3.2 : OD, COD (C.Y. Lin, 1991). 3.2.2.2.2... 20

3.2.3 Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων,.. 3.2.3.1. ( )... (Metcalf & Eddy, 2003).... 80%. 3.3. 21

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 3.3 : (Zouboulis et al., 2003). 3.2.3.2 - (coagulation). (flocculation),...,.,, ph. COD 22

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 50%. COD (S. Renou et al., 2008). 3.2.3.3.,. COD...,,,.,. 3.2.4 :, (, 2005). : i. (microfiltration, MF), 23

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων ii. iii. iv. (ultrafiltration, UF), (nanofiltration, NF) (reverse osmosis, RO).. - (Metcalf & Eddy, 2007). 3.1. 24

3.1 Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων (Metcalf & Eddy, 2007) ( m) MF UF NF RO 0.08-2.0 0.005-0.2 0.001-0.01 0.0001-0.001 TDS ( ) TSS ( ) TSS NF RO. MF UF NF RO 25

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 3.2.4.1,., (UF, NF RO). COD ( 25-35%) (A. A. Abbas et al., 2009). 3.2.4.2.,,. UF. COD 50%., UF. 26

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων 3.2.4.3 0,001 m.,. 60-70% COD. 70-80% (A. A. Abbas et al., 2009). 3.2.4.4,., ( ).. ( ).,.... 27

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων,,., (Metcalf & Eddy, 2007).... COD 98% 99%., 30 60 bar (S. Renou et al., 2008). 3.2.5,. ( ), " (Advanced Oxidation Processes - AOPs)". (UV-,C), ( 3, 3 /UV-, 3 / 2 2 ), 2 2 /UV-, ( i 2/UV- ), Fenton Photo-Fenton,,..,,. 28

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων ( ) (CO 2, H 2, ),.,., (AOPs). AOPs -. (Hydroxyl free radical),,, (Metcalf & Eddy, 2007). 3.2.5.1 Fenton Fenton UV (Photo- Fenton) Fenton ( Fe +2 2 2 )... ( Photo-Fenton)... Fenton, UV. Fenton photo-fenton COD, 45-75% 70-78% (A.A. Abbas et al., 2009). COD 60%, 75% Fenton. (J. Wiszniowski et al., 2005). 29

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων ph. ph 2,8 photo-fenton. 3.2.5.2., TiO 2,. (.. i 2 ),,., CO 2. UV/TiO2. 80% COD ph (J. Wiszniowski et al., 2005). 3.2.5.3.., 30

Κεφ. 3 Μέθοδοι επεξεργασίας στραγγισμάτων,, (Maldonado et al., 2006)., 50%.,,, ( 3 /UV), ( 3 /H 2 O 2 ), ( ),.. 90%., COD. (J.J. Wu et al., 2004). 31

Κεφ. 4 Προσρόφηση 4. 4.1..,.,,,..,,.,.,..,,,, (Schalekamp, 1987). 32

Κεφ. 4 Προσρόφηση 4.2 : a. b. c. d. ( ).,.,.,.,..,, (, 1996)., Coulomb, Van der Waals. Van der Waals..,. 33

Κεφ. 4 Προσρόφηση, (, 2005).,.,,.,., (Metcalf & Eddy, 2007). -.,..,.,,.,,.. 4.1. 34

Κεφ. 4 Προσρόφηση q e = ( C 0 C m e ) V (4.1), q e, g/g moles/kg C 0 C e, mg/l,, mg/l V m, l, g. Freundlich Langmuir (W. Wesley Eckenfelder, 1989). 4.2.1 Freundlich Freundlich 1912 : q e = X m = K f C 1 n e (4.2), q e, mg/g moles/kg ( m X ) m, mg, g K f Freundlich, ( /m)(v/x) 1/n C e, mg/l 1/n Freundlich ( ) 35

Κεφ. 4 Προσρόφηση Freundlich log(x/m) logc e, 4.2, 4.3, : X log q e = log( ) = log K f + m 1 log n C e (4.3) f n. 1.3 C e. q e, q e. ( ), 4.1. 4.1 Freundlich (Metcalf & Eddy, 2007) ph K f (mg/g)(l/mg) 1/n 1/n 5,3 1,0 1,6-2,9 5,3 19,6 0,52 5,3 11 0,83 7,4 91 0,99 5,3 0,59 0,95 5,3 2,6 0,73 DDT 5,3 322 0,50 5,3 4,8 0,34 5,3 7,9 0,61 36

Κεφ. 4 Προσρόφηση 1, 2-5,3 3,6 0,83 7,3 53 0,79 5,3 1220 0,95 5,3 96,5 0,38 5,3 1,3 1,16-3-9 220 0,37 PCB 5,3 14100 1,03 PCB 1221 5,3 242 0,70 PCB 1232 5,3 630 0,73 3-9 21 0,54 5,3 51 0,56 5,3 26,1 0,44 1, 1, 1-5,3 2-2,48 0,34 5,3 28 0,62 Freundlich.. n, 1/n 4.3 q e. 4.2.2 Langmuir : Langmuir X m q max bc = 1 + bc e e (4.4), q max q e, C e b, m 3 /g 37

Κεφ. 4 Προσρόφηση m C e, mg, g, mg/l q max, b. q max b 4.5 4.4 : 1 q e = q max 1 bc e + 1 q max (4.5) C q e e = q 1 max b + C q e max (4.6) Langmuir (Metcalf & Eddy, 2007): 1. 2... 4.2.3 Brunauer, Emmet Teller (BET) Brunauer, Emmet Teller 38

Κεφ. 4 Προσρόφηση. 4.7 (Farley et al., 1985) : q e = ( C s q max bc e C C e )[1 + ( b 1) C e s ] (4.7), C s, mg/l BET : 1. 2.. 4.7 : C e 1 ( b 1) C e = + ( C s C e ) q e q max b q max b C s (4.8) 4.3. (U.S. EPA,1973): 1., 2., 3. 4.. 39

Κεφ. 4 Προσρόφηση (, 2008) : a. ( ),.. b.. c.. d. ph. (Dissolved organic matter DOM) ph (Fusheng Li et al., 2003). e..,, (, 2005). f..,,.. 40

4.4 Κεφ. 4 Προσρόφηση,..,,., (Metcalf & Eddy, 2007).,. H ( ). 4.5 (Breakthrough curve),,.,, - (Mass Transfer Zone - MTZ),., L MTZ,,,,,,,, ph., 41

Κεφ. 4 Προσρόφηση, (Y.S. Al- Degs et al., 2009).,,, ( n Freundlich), L MTZ.,, L MTZ,.,,.,. (, 2005)..,,. : L MTZ = L V E V E V B 0.5( V E V B (4.9), L MTZ, m L, m V V, m 3, m 3 42

Κεφ. 4 Προσρόφηση 4.1. L MTZ.,,,., L MTZ,. 4.1 : (, 2005) : (C 0 -C)dV (4.10) V=0 V=V. C=C 0., C ef,.,. 43

Κεφ. 4 Προσρόφηση,,. 4.2. 4.2 : (, 2005) ( ). ( )., ( D)., 1 ( ), 44

Κεφ. 4 Προσρόφηση, ( C).,, 1. 4.6,.,,.,..,.,,.,.., :,, (Babel & Kurrniawan, 2003).,,,,.. 45

Κεφ. 4 Προσρόφηση,, (Suzuk,1997).,,,. 46

Κεφ. 5 Ενεργός άνθρακας 5. 5.1 1550... Scheele, 1773. 1785 Lowitz.. 1860., 50,, (U.S. EPA, 1973)...,,,,, (U.S. EPA, 1973). 20. 47

Κεφ. 5 Ενεργός άνθρακας 5.2,,,,,,,,,.,,.,.,,.., (<700 C),,,, (800-900 C) ( CO 2 ),..,,..,.. (U.S. EPA, 1973)... (U.S. EPA, 1973) : 48

Κεφ. 5 Ενεργός άνθρακας 1. 170 C 2. 170 C 3. 270-280 C, 4. 400-600 C., CO 2., 750-950 C,.,.. (Metcalf & Eddy, 2007) : >25 nm >1 nm <25 nm <1 nm,,. (powdered activated carbon, PAC), 0,074nm (granular activated carbon, GAC), 0,1nm. 49

Κεφ. 5 Ενεργός άνθρακας 5.3,,. : a., (U.S. EPA, 1973). b.. (, 2004) : i., d 10%, 10%, ii., UC, UC= d 60% / d 10%.. c.,,, (M.C. Mauguet et al.,2005). 350-500 kg/m 3. d. GAC,, 10%. GAC (, 2008). 50

Κεφ. 5 Ενεργός άνθρακας e., b, (M.C. Mauguet et al., 2005). 80-95% 80-100% (, 2004). f. GAC,. : a. (Molasses Number),. >28. (, 2004). b.,. 650-1000 mg. c., v,. 1000-1500 m 2 /g.., (, 2008). 5.1 : 51

5.1 GAC (Metcalf & Eddy, 2007) Κεφ. 5 Ενεργός άνθρακας m 2 /g 700-1300 Kg/m 3 400-44 UC 1.9 mm 1.5-1.7-850 % 8 % 4-6 5.4. (Metcalf & Eddy, 2007): 1., 2., 3. 4.... 52

Κεφ. 5 Ενεργός άνθρακας,, ( ) (650-980 C). : 1., 2. 3.. ( ), (W. Wesley Eckenfelder, 1989)., 5 10 %. (U.S. EPA, 2000)., (W. Wesley Eckenfelder, 1989).,., 2 5 %..., 4 8 %. 53

Κεφ. 5 Ενεργός άνθρακας (Metcalf & Eddy, 2007).. O 2-3,.,,. 5.5, ( )..,.,.,,..,,..., 54

Κεφ. 5 Ενεργός άνθρακας.,.,.,.,. 5.5.1 (PAC)..,,..,. ( ),, (TOC) (, 2008).. 55

Κεφ. 5 Ενεργός άνθρακας.,,.,.,..,.,... Freundlich., 5.1 : PAC = C 0 C q e e (5.1), C 0, mg/l C e q e, mg/l, g/g 56

Κεφ. 5 Ενεργός άνθρακας,. (.. ) PAC (16-50mg/l)., (.. ) (500-1000mg/l) (, 2008).. COD.. COD. (O. Aktas & F. Cecen, 2001). H., (R.G. Scharf et al., 2009).,.. 57

Κεφ. 5 Ενεργός άνθρακας 5.5.2 (GAC) GAC. 5.1. 5.1 (Metcalf & Eddy,2007) ( ), ( ). ( 5.1-, ). ( 5.1- ).,....,,. 5.2.,.. 58

Κεφ. 5 Ενεργός άνθρακας 5.2 : (Metcalf & Eddy,2007),.,.,..,.,... 59

Κεφ. 5 Ενεργός άνθρακας,,.., (Metcalf & Eddy, 2007). 5.6 GAC : a. (EBCT), (L), (q = Q/A)., 5.2 : V C L L EBCT = = = Q Q / A v (5.2), Vc GAC, m 3 v, m/s Q, m 3 /s, m 2 L GAC, m, 5.2, Q. 60

Κεφ. 5 Ενεργός άνθρακας CT.,., ( L )., (q e ),..,,.,,..,, -.,., (Thi To Loan Hoang et al., 2008).. (II) (P b (II)). 61

Κεφ. 5 Ενεργός άνθρακας ( ) ( ) 5.3 : ( ) P b (II) ( ) P b (II) (J. Goel et al., 2005) b...., (, 2004)..,., (, 2004). 30 m 3 /m 2 h 62

Κεφ. 5 Ενεργός άνθρακας 30%. 5min.... ( ). 6,3-7,4 l/min/m 2 (, 2004). c. (Carbon Usage Rate, CUR)., : CUR = m V GAC B (5.3), CUR, g/m 3 m GAC GAC, g V, m 3 c. COD. (, 2005). 63

Κεφ. 5 Ενεργός άνθρακας 5.7.,.,. ( ) (BAC)...., GAC -. (H 2 S),. H 2 S (U.S. EPA, 1973). (U.S. EPA, 1973) : a., b., 64

Κεφ. 5 Ενεργός άνθρακας c., d.. (U.S. EPA, 1973) : a. GAC, b... c.. d. (.. ). 5.8 GAC, (Yung-Tse Hung et al., 2005). : a. ( cm) GAC ( g). (high pressure minicolumn, HPMC) Rosene et al (1983) Bilello and Beaudet (1983).. 65

Κεφ. 5 Ενεργός άνθρακας (Metcalf & Eddy, 2007). (rapid small-scale column test, RSSCT). b..,. : i., ii., iii. iv.. c..,.. 66

Κεφ. 5 Ενεργός άνθρακας d. : i., ii., iii., iv., v. vi....,,. (Yung-Tse Hung et al., 2005). 50%,.. 60 cm 4 cm, (Norit Americas Inc., 2001).,. 67

Κεφ. 5 Ενεργός άνθρακας 5.8.1 Bohart Adams Bohart Adams (1920). : t = ax + b (5.4), t, hr x, m = 0 /C 0 v, hr/m b, hr N 0 C o v, mg COD/g AC, mg/l, m/hr (Y.S. Al-Degs et al., 2009). Bohart-Adams 5.5 : C KN L / v ln 0 0 1 = ln( e 1 KC C ) ef 0 t (5.5) e KN0X/v 5.5 : t N 0 v C 0 N 0 1 C 0 = L ln( 1) = EBCT ln( 1) C 0v KN 0 C ef C 0 KN 0 C ef (5.6), t, hr L, m v, m/s 68

Κεφ. 5 Ενεργός άνθρακας N 0 C o C ef K, mg/g, mg/l, mg/l, m 3 /kg hr EBCT (L/v), hr t=0 (L critical ) 5.7 ( t=0) : L critical = v KN 0 C 0 ln( C ef 1) (5.7) 5.6 0 : a = N 0 C v 0 (5.8) : b = C C 1 0 ln( 0 K C ef 1) (5.9) 69

Κεφ. 5 Ενεργός άνθρακας 5.8.2 Hutchins Hutchins (1973) Bohart-Adams, BDST (Bed-depth service time, ) (Hung-Tse Hung et al., 2005). Bohart-Adams : t = ax + b t = a ' EBCT + b (5.10), ( 0 /C 0 v) b (-1/KC 0 [ln(c 0 /C ef -1)] v, BDST,.. : V1 t = ax + b V 2 (5.11), V 1 V 2, BDST.. b 70

Κεφ. 5 Ενεργός άνθρακας, C ef. : t = C C 1 2 ax + ( C 1 / C 2 ln( C ) ln( C 1 / C 2 ef / C ef 1) 1) b (5.12), C 1 C 2 71

Κεφ. 5 Ενεργός άνθρακας 5.9. GAC., 1995, COD 91% 940 mg/l (K.Y. Foo & B.H. Hameed, 2009)., Morawe, COD. 5.4 COD. ( ) ( ) 5.4 : ( ) ( ) COD (B. Morawe et al., 1995) 72

Κεφ. 5 Ενεργός άνθρακας COD,,. Imai. (Microorganism-attached activated carbon fluidized bed MAACFB)..,,. 60 70% (A. Imai et al., 1993). 85-90% COD 60-80% (S. Renou et al., 2008). 5.5 COD. 73

Κεφ. 5 Ενεργός άνθρακας 5.5: COD MAACFB (Imai et al., 1993) 74

75

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6. 6.1 ( ) 2010....,,.,. Chemitec. COD.,.. 76

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.2 (GAC) 6.2.1,.,.. 10 25. 6.1. 6.1 COD 5500 mg/l BOD 5 27 mg/l BOD 5 /COD 0.005 2.6 ms/cm TSS 17500 mg/l VSS 720 mg/l ph 8.2 77

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.2.2 (GAC) (GAC) CHEMiTEC., Filtrabarb CC60. ( 6.1) 6.1 : (GAC) GAC, 6.2. 6.2 GAC CHEMiTEC, 12 x 40 mesh <10% 1050 m 2 /g 1000 mg/g 0.45 g/cm 3 1,105 cm 3 /g 78

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.2.3 GAC. 4,..... ( 6.2). 6.2: 79

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.3. 6.3 (cm) 5 (cm) 140 (cm 2 ) 19.63 (cm 3 ) 2748. 10 cm,. ( 6.3). 6.3 : GAC 80

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης, 3.. 100. Easy-load, Master Flex L/S Model 7553-89. ( 6.4) 6.4 : 81

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.3 4.., 24. 6.4. 6.4 1 2 3 4 COD (C 0 ) 900 mg/l 400 mg/l 400 mg/l 400 mg/l 4 4 4 4 GAC 0.4 m 0.6 m 0.6 m 0.6 m GAC 0.05 m 0.05 m 0.05 m 0.05 m 27 lt/min m 2 46 lt/min m 2 17 lt/min m 2 27 lt/min m 2 3.2 l/hr 5.4 l/hr 2.0 l/hr 3.2 l/hr, COD.,,.,. 82

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης,. 6.4 COD.,.. ( ) COD. COD. (breakthrough curves). COD,. COD 125 mg/l., 91/271/, COD 125 mg/l., (breakthrough point).,, COD 900 mg/l, 14%., COD,, 14% COD.,, COD 400 mg/l, 83

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 30%., COD 125 mg/l 400 mg/l, COD 30% COD., Bohart & Adams. 84

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.4 (TSS VSS),, (COD), (BOD),, ( ) ph. Standard Methods. 85

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.4.1 µ. µ Standard Methods, 209 C 209 D Standard Methods for the Examination of Water and Wastewater, 1992,. 103-105 C., 550 C,. 105 C 550 C GF/C 4,7 cm. µ ( 6.5) ( SS), µ GF/C (m g) ( 1 : ). (V ml), 105 C 1 h., (m g), 10 min, 2. 86

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.5 : µ, (VSS), 550 C 30 min., µ (m g). 3 : 1000 TSS( mg / l) = ( m2 m1 ) (6.1) V 1000 VSS( mg / l) = ( m3 m2 ) (6.2) V, m, mg V, l 87

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης 6.4.2 COD (Chemical Oxygen Demand) 0.1 Ag 2 SO 4 H 2 SO 4. COD 5220 D Closed Reflux Colorimetric Method Standard Methods for the Examination of Water and Wastewater, 2005. COD COD REACTOR ( 6.5 ( )) µ µ HACH DR/2010 ( 6.5 ( )) (CH 3 COOH), 2000 mg/l ( ) ( ) 6.6 : ( ) COD REACTOR ( ) µ µ HACH DR/2010 88

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης. (K 2 Cr 2 O 7 ).. ( ) (IV), (III).,. (Cr 2 O 2-7 ) 400 nm, (Cr + 3 ). COD : ) AgSO4 : Ag + Cl AgCl ) Cl 2, COD, : 14 H + + Cr 2 O 7 2- + 6 Cl - 3 Cl 2 + 7 H 2 O + 2 Cr 3+, 150±2 0 C.,. 89

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης COD., COD 2,50 ml., 150±2 0 C. 150±2 0 C 120 min.,,..,,. 120 min,.,,, (optical path). (435 ) =620 nm ( ). 620 nm COD. ZERO,. 620 nm ( COD 2,50 ml ). ( ), 90

Κεφ. 6 Πειραματικό σύστημα & μέθοδοι ανάλυσης.. COD : COD (mg/l)=a*abs+b (6.3) (CH 3 COOH), 2000 mg/l. CH 3 COOH. 10, 20, 33, 50 100 mg/l 100, 200, 400, 500, 1000 1500mg/l. COD : COD (mg/l) = a * Abs+ b x (6.4), Abs., COD (mg/l).,, (10 100 mg/l) (100 1500 mg/l). 6.7, 6.8. 91