présentée à
pour l’obtention du
DOCTORAT
par
Srayut RACHU
Sommaire
Le traitement des eaux résiduaires huileuses est l’un des sujets de recherche majeurs
dans le laboratoire GPI. L’hydrocarbure ou l’huile est l’un des polluants de l’eau les plus
importants. Une petite quantité de l’huile peut produire le film vastement couvrant la surface
de l’eau, lequel affecte le transfert de l’oxygène et par conséquence ruine l’écosystème. Même
s’il est biodégradable, il contribue à la demande biologique en oxygène (DBO) importante. En
plus, étant donné ses propriétés, à la haute concentration, il cause l’effet nuisible dans le
procédé de traitement biologique. Toutefois, l’hydrocarbure ou l’huile peut avoir la valeur ou
être récupérée ou recyclée à condition où il peut être séparé de l’eau. En cet effet, les
techniques de la séparation huile/eau sont parmi des recherches principales dans le laboratoire
GPI. Il y a plusieurs études sur les techniques, les procédés et les innovations de la séparation
d’huile initiée par le laboratoire GPI. Chaque étude peut être appropriée à certaine condition
de l’opération ou certain caractéristique des eaux résiduaires.
Ainsi, les buts de cette thèse sont de réexaminer les recherches du laboratoire GPI,
réalisées dans l’Equipe du Professeur AURELLE, sur le procédé de traitement des eaux
résiduaires huileuses ; d’établir le design du procédure générale avec les précautions de tels
procédés ; et, ensuite, valoriser et maximiser l’utilisation de ces connaissances établies sous
forme du logiciel. Ainsi, les objectifs de la thèse ont été définis pour réaliser ces buts ci-
dessus :
1. Réexaminer les technologies de traitement pour les eaux résiduaires huileuses ou les
eaux résiduaires polluées par l’hydrocarbure, dans les recherches de doctorat réalisées
dans l’Equipe du Professeur Yves AURELLE, du commencement jusqu’ au présent.
1. L’Écrémeur déshuileurs
[1]
Sommaire
0.486
3.035D1.541N1.541ν o L
P= m3/s {1.1}
g 0.514
0.486
3.464N1.541 ν o ⎡(0.5 D )2.54 − (0.5 D − I ) 2.54 ⎤ m3/s
P= {1.2}
⎢⎣ ⎥⎦
g 0.514
Tambour
Racleur
Nappe d’huile
Phase aqueuse
Fig. 1-1 Tambour déhuileur Fig. 1-2 Disque déhuileur (Par: Abanaki)
[2]
Sommaire
2. Le Décanteur
Sa théorie importante, à savoir la loi de STOKE, est citée. Selon cette théorie, les
gouttelettes peuvent être récupérées à condition qu’elles entrent dans le décanteur à la
distance ascensionnelle nécessaire pour atteindre la surface de décantation, comme la surface
de l’eau ou la surface de l’intercepteurs d’huile intérieurs, avant d’être entraînées hors du
réservoir par l’eau. D’après ce concept, la relation typique de la taille de gouttelette et son
efficacité de séparation par classe de goutte (ηd) est comme celles montrées dans la fig. 2-1.
L
ENTREE Q SORTIE
H API
V H, D
d > dc U
d = dc
H PPI (n plaques)
d < dc
L
H1
ηd
Zone 1 Zone 2 H2 La cellule “Spiraloil”
(section transversale)
d < dc d = or > d c Hauteures sont
d differentes.
dc
Les modèles mathématiques générales pour les procédé de 3 variétés différentes, c’est-
à-dire le décanteur classique (API), le décanteur lamellaires (PPI), et le décanteur compacte
(Spiraloil) sont proposées et vérifiées :
[3]
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Les modèles sont valides à condition que la loi de STOKE soit valide (Re = 10-4 à 1).
Pour le PPI, si les plaques sont inclinées, le paramètre « Sd » dans l’éq. 2.5 sera remplacé par
« Sp cos α » (pour les plaques horizontales, α = 0o). Le Sd , pour le décanteur compacte, est
l’espace totale de la surface de décantation qui peut intercepter de l’huile, sans regardant aux
distances ascensionnelles des goulettes d’huile.
3. Le Coalesceur
SORTIE:
Goutte grosse La surface de relargage
V
Le diametre du collecteur
H =dp,
Coefficient de vide = ε
ENTREE: La grilles
Gouttelette V
Dia. = d
[4]
Sommaire
V U
V
U
U= Vitesse ascensionalle
V= Vitesse d’ecoulment
a) Transport par interception b) Sédimentation c) Diffusion
Les modèles empiriques, vérifiées par le biais d’une gamme de données relativement
large, sont proposées pour les coalesceurs de 4 variétés : coalesceur de lit granulaire,
coalesceur fibreux type brosse, coalesceur fibreux dynamique (brosse tournante), et
coalesceur fibreux nonordonnée (laine d’acier). Veuillez noter que l’efficacité calculée
supérieure de 100% sera comptée pour 100%.
[5]
Sommaire
• 48 < Re < 1100. Re est le terme (ρcVD/μc) dans l’équation. 1 < H/D < 10.
• La diamètre de coalesceur (D) est environ 5.0 cm. Pour le coalesceur de diamètre
important, il y a un risque de court-circuit par entrainant despassages préférentiels le long
des parois du coalesceur.
• Le modèle est valide pour la diamètre de gouttelette (d) de 1 micron ou plus.
• Vitesse d’écoulement (V) est entre 0.5 et 2.0 cm/s (1.8 - 120 m/h).
• Le diamètre de fibre (dF) = 100 - 200 microns.
• Coefficienct de vide (ε) est 0.845 - 0.96.
• La concentration initiale de hydrocarbure < 1000 mg/l.
• Les lits sont de type brosse et sont oleophiles.
• 52 < Re < 1164. Re est le terme (ρcVD/4c) dans l’équation. 1 < H/D < 2.
• Vitesse de rotation (N) = 0.167 - 3.33 rps (10 to 200 rpm).
• Vitesse d’écoulement (V) = 0.1 - 1.1 cm/s (3.6 to 39.6 m/h).
• Diamètre de fibre (dF) = 100 - 300 microns.
• Diameter de coalesceur (D) < 11.5 cm.
• Le modèle est valide pour la diamètre de gouttelette (d) de 10 microns ou plus.
• Les lits sont de type brosse et sont oleophiles.
[6]
Sommaire
180 Hμ cV (1 − ε ) 2 {3.5}
P= m
ρ ⋅ g ⋅ dp 2 ⋅ ε 3
ε = 0.13 à 0.23.
⎛ V ⎞ ⎛ 5L ⎞
1.85 1.167 {3.6}
P = 6.82⎜⎜ ⎟⎟ ⎜ ⎟ m
⎝ C HW ⎠ ⎝ D ⎠
CHW = 130. L = hauteur de l’intercepteur.
La flottation à air dissous est le procédé de séparation accéléré, qui s’opère par
l’augmentation de la différence masse volumique entre la phase continue et la phase
dispersée. Ceci est accompli moyennant la création des bulles du gaz ou de l’air dans les eaux
résiduaires en fin de favoriser la formation des agglomérats air-solides ou air-huileux.
Le modèle mathématique basé sur le concept de filtration, proposé par SIEM est
réexaminé. Ce modèle est utile pour comprendre les effets des paramètres influents sur la
performance de la DAF. Les équations de généralisation du modèle de SIEM, fondées sur la
théorie de l’équilibre de population, sont établies dans cette thèse pour agrandir la gamme
valide du modèle de SIEM et, donc couvrir la gamme des eaux résiduaires huileuses
fréquemment trouvée. Les modèles sont comme montrés ci-dessous ;
V
Concentration after
intercepted by bubbles
= C- dC
x
Ub Ud
Vitesse relative = Vr Hauteur de la colonne
=H
Vitesses d’ecoulement = V Taille de bulle = db
y dH
[7]
Sommaire
Gouttelette
Bulle
Lignes de
courant
a) Interception directe b) Sédimentation c) Diffusion
Fig. 4-2 Schéma des 3modes de transport
SIEM’s model,
3 Φ H
(− ( αη exp ) )
ηd , ref = (1 − e 2 AV db
) ⋅ 100 % {4.1}
(αη exp ) = 0.009005(η theo ) 0.5919
{4.2}
ηtheo = ηsed + ηInt + ηdiff
{4.3}
3 d
ηInt = ( ) 2 {4.4}
2 db
Δρ gd 2
ηsed = oil / water {4.5}
18 μcVr
KT
η Diff = 0 . 9( )2 / 3 {4.6}
μdV r d b
Δρair / water gd b2
Vr = U b = {4.7}
18 μc
[8]
Sommaire
ηd = (1 − e
( − κ 2 , ref Φ τ )
) ⋅ 100 % {4.8}
⎣⎢ ⎥⎦
5. L’Hydrocyclone
[9]
Sommaire
Q {5.5}
Wz =
π(0.5D n − Z ⋅ tan( β / 2)) 2
D β {5.6}
R z = n − Z ⋅ tan( )
2 2
0.25( D n )
L= {5.7}
tan(1.5 o / 2)
0.5Dn d > dc
d < dc
d = dc
Rd LZVV
0.186Dn
Z
L
ηd
100%
Zone 1 Zone 2
d < dc d = or > d c
dc d
• Veuillez noter que les équations sont fondées sur la géométrie d’hydrocyclone liquide-
liquide initiée par Professeur THEW, en Angleterre. Pour les utiliser avec d’autres
types d’hydrocyclone, certaines constantes numériques (par exemple 0.63, 3.33, etc.)
dans les éq. 5.3, 5.4 et 5.8 doivent être réexaminées pour s’approprier aux géométries
nouvelles.
• Le modèle est valide pour la taille des gouttelettes (d) de 20 microns et plus.
• Les équations sont valides pour l’hydroclone ayant seulement 2 entrées.
[10]
Sommaire
• Le débit de purge huile à surverse (Qoveflow) est généralement petite, pas plus de 10%.
Son effet sur les profils de vitesse et d’efficacité est petit, et donc, négligeable. La
Qoveflow recommandée est de 1.8 à 2 fois du débit entrant de l’huile.
• Le modèle tend à prévoir l’efficacité plus basse quand d < d80%, et celle plus haute
quand d > d80%. L’erreur dans la prédiction de la diamètre de coupure est environs
10-20%, c’est-à-dire, si la diamètre de coupure prévue est 50 microns, la diamètre de
coupure constatée devrait être environs 40-45 microns. Pour de plus ample
information, veuillez consulter la référence.
Note: Di/D=0.25 pour 1- entrée et 0.175 for 2- entrée, Do/D=0.43,Ds/D=0.28, Du/D=0.19, Dp/D=0.034,
L1/D=0.4,L2/D=5, L3/D=15, L4/D=0.3, Solid-liquid :angle =12o, liquid-liquid angle =1.5o
Entree
Purge huile
Sortie eau
Purge MES
Entree
Fig. 5.-3 Trajectoires de l’huile (sphere) and MES (cube) dans le hydrocyclone triphasique
Solide-liquide Liquide-liquide
(RIETEMA) (THEW)
[11]
Sommaire
Pour l’efficacité solide-liquide, elle peut être calculée par le model de RIETEMA ou
d’autres modèles compatibles dont la partie solide-liquide de l’hydrocyclone est conforme à la
géométrie de l’hydrocyclone de RIETEMA.
[12]
Sommaire
Fig. 6-1 Classification des techniques membranaires de filtration selon la taille des pores
(Par Osmonics)
[13]
Sommaire
Retentat
Po Membrane
Pp
Permeat
Reservoir
d’alimentation
Pi
Alimentation
7. Le procédé thermique
[14]
Sommaire
T P = const.
A Point d’ebullition
Point d’ebullition Vapeur (V)
d’eau
de B D
Eau + V
Huile +V yw,6 xw,6=1
Azeotrope (H) yw,5 xw,5=1
xw,2
TH B yw,1’ to yw,4 xw,1’
C
xw,3 xw,4=1
= yH
Huile+eau xw,1
Huile pur Eau pur
xw = 0 xw , yw xw = 1
yw = 0 xw = xH yw = 1
yw = yH
Fig. 7-1Diagramme d’équilibre isobar: température-concentration de l’eau residuaires
huileuses
Dans le cas des eaux résiduaires huileuses, spécialement celles concentrées comme le
slop ou le retentat de l’UF dérivant de l’UF de l’huile de coupe, si l’extractant est choisi
correctement, elles formeront une condition azéotropique et, pendant son évaporation, extraira
le teneur en eau des eaux résiduaires. L’eau sera extraite jusqu’à ce que le résidu devienne
l’hydrocarbure sans eau. Le vapeur condensera pour former le distillat contenant deux
couches séparées du extractant (la couche supérieure) et l’eau (la couche inférieure) de la
composition xH (= yH). Plus la valeur de yH est haute, mieux la capacité de l’extraction d’eau
est. Les données théoriques de yH, basées sur la loi de Raoult et la loi de Dalton, sont
également proposées comme montrées dans la table 7-1.
Molecular
TH yH yH y H observed
Extractant weight
(deg. C) (by molar) (by volume) (by volume)
(g/mol)
C6H14 56 61.6 0.209 0.0351
C7H16 100 79.2 0.452 0.0922
C8H18 114 89.5 0.616 0.188
C9H20 128 94.8 0.827 0.3255
C10H22 142 97.6 0.914 0.495 0.468
C11H24 156 98.9 0.959 0.6663
C12H26 170 99.5 0.98 0.7953 0.767
C13H28 184 99.8 0.991 0.890
C14H30 198 99.95 0.996 0.9542
C15H32 212 99.999 0.998 0.9702
C16H34 226 ≈ 100 0.999 0.9840
Les équations utilisées dans le calcul de l’entraîneur ou extractant, dans le cas des
eaux résiduaires huileuses et la vapeur, dans le cas du stripping, sont comme montrées ci-
dessous,
[15]
Sommaire
(1 − y H ) {7.1}
Volume entrainer = Volume water
yH
yH {7.2}
Volume = Volume pollu tan ts
(1 − y H )
steam
8. Le procédé chimique
En fin de déstabiliser l’émulsion, les deux barrières doivent être éliminées. Selon les
recherches du GPI, le mécanisme de déstabilisation (ou cassage) de l’émulsion par l’addition
de plusieurs produits chimiques, c’est-à-dire du sel monovalent, des sels bivalents, les
polyélectrolytes, l’acide et les agents adsorbants, sont réexaminées. Les mécanismes de
déstabilisation des ces produits chimiques, fondés sur l’émulsion stabilisée par les agents
tensioactifs anioniques, sont résumés comme ci-dessous,
[16]
Sommaire
Potentiel +
+ +
- +
+ + - + +
Plan de cisaillement
Couch de diffusion
+
-
+ + + + - + + -
agents TA/COTA
+ +
+- - -+ - +
+ - +
Huile avec
+ - - + - +
+ + - Huile - + - - + +
- + + -
+-- tensioactif - + - + +
+ + -
- -(TA)- - - + + + - + +
+ + + +- - + + + -
+ - + + +
+ + +
+ - + +
+ + -
+
- + Potentiel de Stern
-
Couche Stern
Potentiel zeta
Couch de Couch Stern Distance
diffusion
+ Ion de charge positif avec
la solvation d’eau
Force repulsive
Repulsive electrostatique
+ +
+ + Force attractive de
+ + Force total
+- - -+ - + Van Der Waal +- - -+ - +
+ - - + + - -- +
+- - (court) +-
- - + - -+
+ + Gouttelette
-- -
- + + + Gouttelette
-- -
- + Distance
-- - - + -- - +
+ - - + Repulsive + + +- - + + - Force de
+ + +
+ electrostatique + Val Der Waal
+ + +
+
(Long) Force attractive prevaloir
Force attactive
Fig. 8-2 Interaction et bilan de forces entre gouttelette
• Les électrolytes multivalents : Les mécanismes principaux de déstabilisation
sont une combinaison de la précipitation des agents tensioactifs et la
coagulation de type “sweep”. La concentration réelle est donc moins que
celle calculée uniquement sur le produit de solubilité et est généralement le
moins des trois premiers électrolytes. Les exemples de produit chimique de
ce type sont le chlorure ferrique (FeCl3) et le sulfate d’aluminium.
• Les agents tensioactifs de la charge opposée : Le mécanisme principal de
déstabilisation est l’adsorption et la neutralisation de la charge. Le surdosage
doit être évité pour prévenir la restabilisation de l’émulsion par l’inversion
des charges électriques. Les exemples des agents tensioactifs cationiques qui
peuvent être utilisés dans la déstabilisation de l’émulsion sont le chlorure N-
cetylpyridinium et des sels de l’hydroxyde d’ammonium quaternaire.
[17]
Sommaire
Toutefois, il faut noter que il n’existe pas les produits chimiques et les doses
universels qui sont valides pour toute émulsion. Les types des produits chimiques efficaces,
de la concentration optimal et du niveau des polluants résiduaires doivent être évalués d’abord
d’échelle de laboratoire avant le design du procédé chimique complet.
En tout cas, à l’égard des design du réacteur, ils sont identiques, quel que soit le
produit chimique appliqué. Ils sont pratiquement identiques au réacteur utilisé pour la
coagulation/floculation dans le traitement d’eau. Les équations utilisées pour l’évaluation du
réacteur et de l’agitateur, c’est-à-dire 8.1 à 8.3, sont incluses dans le logiciel.
0. 5
⎛ P ⎞
G = ⎜⎜ ⎟⎟ {8.1}
⎝ μV ⎠
Où Np = Nombre de puissance
ρ = Mass volumique de l’eau usée (= celle de l’eau)
n = Vitesse de rotation (rev/s) (e.q. 8.2)
n = Nombre de pales (e.q. 8.3)
D = Impeller diameter (m)
A = Surface d’une pale (m2)
v = vitesse périphérique (m2)
Cd = Coefficient de traînée des pales (normalement = 0.6)
Produit
chemique
Emulsion
M G = 50 s-1 G = 30 s-1 G = 20 s-1
Separateur
M
G = 100-300 s-1
[18]
Sommaire
Bien que l’huile soit récupérée de l’eau par les procédés précédents, il y a
normalement de l’huile laissée dans l’eau traitée. En plus, les polluants d’autres formes
généralement présents dans les eaux résiduaires huileuses, surtout les agents tensioactifs/co-
tensioactifs, sont encore présents dans l’eau traitée, et contribue au haut niveau de la DOT.
Ainsi l’eau traitée est normalement transmise au procédé de finition avant de se décharger au
corps d’eau recevant. Deux procédés de finition largement utilisés, c’est-à-dire le traitement
biologique et l’adsorption sur le charbon actif, sont réalisés.
Les équations du design du filtre CAG, ainsi que la capacité d’adsorption (q) de
certains co-tensioactifs, sont réexaminées et incluses, c’est-à-dire,
Quand l’isotherme (q. VS.C relation) et les données du front d’adsorption (Qa et Ha
comme les fonctions de C) sont disponible ;
HA ⋅ ρ b ⋅ q − Qa {9.1}
tT =
Q (Co − Ce )
[19]
Sommaire
ENTREE
Ce Co Ce Co
C C
Satured
zone
Ha Vitesse =V
d’adsorption
Lit fixe
de HT
Zone
Ha
charbon
actif
Regeneration
H SORTIE H de lit est necessaire.
t=0 t = tT
180 Hμ cV (1 − ε ) 2
P= m {9.4}
ρ ⋅ g ⋅ dp 2 ⋅ ε 3
[20]
Table 10-1 La méthodologie générale pour la sélection des procédés
[21]
Sommaire
Sommaire
Buc Permeate
d’alimentation Pi Pi
Alimentation
Permeat
Retentat
Pompe Echangeur Pompe Echangeur
Retentat
de chaleur de chaleur
Ultrafiltration Osmose inverse
TI Echangeur M
de chaleur SORTIE
X
Fig. 10-1 Schéma d’une filière de traitement des émulsions d’huile de coupe
Charbon actif
huile huile
ENTREE M
(se necessaire)
SORTIE
X
Recyclage boue
Bassin d’aerationClarificateur
[22]
Sommaire
Développement du logiciel
L’objectif final de cette thèse est de développer un logiciel de design et calcul d’une
filière de traitement adoptée à l’épuration des eaux résiduaires huileuses. Ceci vise à valoriser
et appliquer le savoir-faire ainsi que les résultats importants de la recherche, en les présentant
de façon conviviale. Pour réussir à ces objectifs, le logiciel, à savoir le logiciel GPI, est divisé
en 4 modes majeurs, c’est-à-dire,
• Le mode de design (calcul) : est utilisé pour évaluer l’unité procédé. Les
modèles utilisés dans le calcul sont comme résumés dans la Partie 3.
Cette thèse est accomplie par les supports considérables de Professeur AURELLE,
mon directeur de thèse, et M. Surapol SAIPANICH, PD-G de la société Progress Technology
Consultants Co.,Ltd. (Thailand). Je suis très reconnaissant pour leur conseil et
encouragement.
[23]
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Main menu
Tool bar
Project window
Main program
[24]
Sommaire
[25]
Sommaire
Category selection
[26]
Résumé
Nom : RACHU Prénom : Srayut
CONTRIBUTION A LA MISE AU POINT D’UN LOGICIEL DE CALCUL DE
PROCEDEDS ET FILIERES DE TRAITEMENT D’EAUX RESIDUAIRES
HUILEUSE
562 pages
Thèse de Doctorat : Science des procédés
Spécialité :Génie des Procédés et de l’Environnement
I.N.S.A. Toulouse, 2005, n°
Résumé :
L’objectif de cette thèse est valorisation des diverses recherches développées au sein du
Laboratoire d’Ingénierie des Procédés de l’Environnement de l’INSA dans le domaine
spécifique du traitment des eaux résiduaires huileuse. Cette thèse résume les diverse
recherchers rélisées et permet d’établir une procédure générale de calcul associée à un “Know
-how” pour chaque procédé étudié qui permet l’utilisation de ces connaissances dans la mise
au point d’un logiciel spécifique de design et de calcul de fillières de traitemant des eaux
huileuse.
La première partie du manuscript résume les principaux résultats obtenue dans chaque thèse
relative au traitement des eaux huileuses réalisées dans l’Equipe du Professeur Y.AURELLE.
Le deuxième partie est relative à la généralisation des modèles et procédures de calcul de
chaque type de procédés. Dans cette partie, les modèles de calucul proposés dans les diverse
thèses sont comparés aux autres données bibliographiques et généralisaés. Ainsi de nouveaux
modèles de calcul sont proposés dans les cas où aucun modèle n’exist où dans les cas
spécifiques où les modèles existants ont besoin d’être modifiés.
La troisième partie permet d’établir un “textbook” qui intègre tous les rèsultats significatifs de
chaque procédé ainsi que leur procédure généralisée de dimensionnement et leurs limitations.
Ce textbook prend en compte les divers procédés de deshuilage des eaux susceptibles d’être
intégrés dans une filière de traitement à savoir : les deshuileurs de surface ou écrémeurs de
type tambours et disques déhuileurs, les décanteurs, les coalesceurs, les flottation à air
dissous, les hydrocyclones, les procédés membranaires, les procédés thermique type
distillation hétéroazéotropique, les procédés biologiques ainsi que l’adsorption sur charbon
actif. Enfin ce textbook propose une méthodologie générale permettant la sélection des
procédés selon le type d’eaux huileuses à traiter.
La dernière partie de la thèse propose le développement d’un logiciel spécifique et original de
design et calcul d’une filière de traitement adaptée à l’èpuration des eaux résiduaires huileuse
notamment de l’industrile pétrolière s’appuyant sur le textbook précédent.
Mots clés : Déshuiluer, Décanteur, Coalesceur, Flottation, Hydrocyclone, Membrane,
Distillation, Déstabilisation, Traitement biologique, Absorption, Logiciel, Eaux huileuses
Jury et date de soutenance : 16 Décembre 2005 à l'I.N.S.A. de Toulouse
M. D. HADJIEV Professeur, IUT, Lorient Rapporteur
M. J. ROLS Professeur, UPS, Toulouse Rapporteur
M. Y. AURELLE Professeur, INSA, Toulouse Directeur de thèse
M. A. LINE Professeur, INSA, Toulouse Directeur du LIPE
M. R. BEN AIM Professeur Emérite, INSA Toulouse
M. S. SAIPANICH PDG, Progress Technology Consultants Co., Ltd., Thaïlande
M. H. ROQUES Professeur Emérite, INSA Toulouse Invité
Dépôt à la Bibliothèque Universitaire en 4 exemplaires.
Nom : RACHU Prénom : Srayut
Résumé :
The aims of this thesis is to summarize the researches of GPI lab on oily wastewater
treatment processes and establish general design procedure and consideration for such
processes, and then, value and maximize the use of these established knowledge in the form
of computer program.
The first part of the thesis contributes to reviewing the related researches in GPI lab,
directed by Prof. Y. AURELLE. Significant finding of each thesis is realized.
The second part of the thesis is generalization of models. In this part, models proposed
in the researches are cross-verified with other researches and generalised. New models are
also proposed when there is no existing model or the existing models need to be revised.
The third part of thesis contributes to composure of a textbook that includes all
significant finding from every research as well as the generalized models and their limitations
of every process found in the second part. The textbook includes these processes, i.e.
skimmer, decanter, coalescer, dissolved air flotation, hydrocyclone, membrane processes,
thermal process, chemical process, biological treatment and carbon adsorption, as well as
guideline for process selection.
The final part of the thesis is program development. The program developed in this
thesis consists of 4 main features, i.e. process recommendation for the wastewater being
considered, design of unit process, simulation of process train and provision of knowledge on
process design in the form of e-book, based on the text book in the third part.
The textbook, the program and its source code may be available upon request. For
more information, please contact Pr. Y. AURELLE or gpi_program@yahoo.com
Mots clés : Skimmer, Decanter, Coalescer, Dissolved air flotation, Hydrocyclone, Membrane,
Distillation, Destabilization, Biological treatment, Adsorption, Program, Oily wastewater
PRODUCTION SCIENTIFIQUE
Publications dans des actes de congrès avec comité de lecture, sur texte complet
et à toute ma famille
Remerciements
Contents
Page
Part I Introduction and bibliography
Chapter 1 Introduction 2
Chapter 2 Objectives 4
Chapter 3 Bibliography
3.1 Categories of hydrocarbon-polluted wastewater and treatment 6
processes
3.2 STOKE’s law 7
3.3 Decanting 7
3.4 Coalescer 10
3.4.1 Thesis of AURELLE [3] 10
3.4.2 Thesis of SANCHEZ MARTINEZ [6] 11
3.4.3 Thesis of DARME [7] 12
3.4.4 Thesis of TAPANEEYANGKUL [8] 14
3.4.5 Thesis of DAMAK [9] 15
3.4.6 Thesis of MA [16] 17
3.4.7 Thesis of SRIJAROONRAT [10] 17
3.4.8 Thesis of WANICHKUL [11] 18
3.5 Flotation 18
3.5.1 Thesis of SIEM [12] 18
3.5.1 Thesis of AOUDJEHANE [13] 19
3.5.1 Thesis of DUPRE [14] 20
3.5.1 Thesis of PONASSE [15] 21
3.6 Hydrocyclone 22
3.6.1 Thesis of MA [16] 22
3.6.2 Thesis of CAZAL [17] 24
3.6.3 Thesis of SRIJAROONRAT [10] 25
3.6.4 Thesis of WANICHKUL [11] 25
3.6.5 Thesis of PUPRASERT [25 ] 26
3.7 Ultrafiltration and other membrane processes 26
3.7.1 Thesis of BELKACEM [18] 27
3.7.2 Thesis of TOULGOAT [19] 29
3.7.3 Thesis of MATAMOROS [20] 30
3.7.4 Thesis of SRIJAROONRAT [10] 32
3.7.5 Thesis of WANICHKUL [11] 33
3.8 Thermal treatment 33
3.8.1 Thesis of LUCENA[24] 33
3.8.2 Thesis of LORRAIN[23] 34
3.8.3 Thesis of WANICHKUL [11] 34
3.9 Chemical treatment 34
3.9.1 Thesis of ZHU[21] 35
3.9.2 Thesis of YANG[22] 37
3.10 Biological treatment 38
3.9.10 Thesis of WANICHKUL [11] 38
-i-
Contents
Contents (Con’t)
Page
3.11 Skimmer 38
3.12 Application researches 39
3.12.1 Thesis of SRIJAROONRAT [10] 40
3.12.2 Thesis of WANICHKUL [11] 41
Chapter 4 Conclusion 44
- ii -
Contents
Contents
Page
Part II Generalization of models for oil-water separation process design
Chapter 1 Decanting
1.1 Simple decanter or API tank 48
1.2 Lamella decanter or Parallel Plate Interceptor (PPI) 49
1.3 Model verification 50
1.4 Conclusion and generalized model of decanter 51
Chapter 2 Skimmer
2.1 Drum skimmer 53
2.2 Disk skimmer 54
Chapter 3 Coalescer
3.1 Granular bed coalescer 55
3.1.1 Filtration-based model 55
3.1.2 Dimensional analysis-based model 56
3.1.3 Model verification 57
3.1.4 Conclusion and generalized model of granular bed 58
coalescer
3.1.5 Generalized model for guide coalescer 59
3.1.6 Generalized model for mixed bed coalescer 60
3.1.7 Generalized model for pressure drop of granular bed 60
coalescer and guided coalescer
3.2 Fibrous bed coalescer 62
3.2.1 Dynamic fibrous bed coalescer model 62
3.2.2 Simple fibrous bed coalescer model 62
3.2.3 Model verification 62
3.2.4 Conclusion and generalized model of fibrous bed coalescer 65
3.2.5 Generalized model of random or disorderly fibrous bed 67
coalescer
3.2.6 Generalized model for pressure drop of fibrous bed 68
coalescer
Chapter 4 Dissolved air flotation
4.1 Dissolved Air Flotation (DAF) model for oily wastewater 69
treatment
4.2 Model verification 70
4.2.1 Modification of filtration-based model 70
4.2.2 Population balance method 72
4.3 Generalized model for DAF 74
4.4 Generalized equations for pressurized water system calculation 79
Chapter 5 Hydrocyclone
5.1 Two-phase hydrocyclone 81
5.1.1 Trajectory analysis-based model 81
5.1.2 Other models 82
5.1.3 Model verification 83
- iii -
Contents
Contents (Con’t)
Page
5.1.4 Conclusion and generalized model of two-phase 84
hydrocyclone
5.1.5 Generalized model for pressure drop of two-phase 85
hydrocyclone
5.2 Three-phase hydrocyclone 87
5.2.1 Model development and verification for liquid-liquid 87
section
5.2.2 Model development and verification for solid-liquid section89
5.2.3 Generalized Model for pressure drop of three-phase 90
hydrocyclone
Chapter 6 Membrane process
6.1 Ultrafiltration 93
6.1.1 Resistance model 94
6.1.2 Film theory based model 96
6.1.3 Model verification 97
6.1.4 Flux prediction for mixture of cutting oil microemulsion 102
and macroemulsion
6.1.5 Theoretical flux prediction for batch cross-flow UF process 104
6.1.6 UF efficiency 107
6.1.7 Minimum and maximum transmembrane pressure and 108
power required
6.1.8 Conclusion and generalized model of UF 110
6.2 Nanofiltration and Reverse osmosis 110
Chapter 7 Heteroazeotropic Distillation
7.1 Theoretical model 113
7.2 Model verification 116
7.3 Conclusion and generalized model of heteroazeotropic distillation 116
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Contents
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Reference 540
Annexe 546
- xii -
Nomenclatures
Nomenclature
Nomenclature
a Constant for population balance equation
A Flow area (Cross sectional) area of decanter L2
A Cross section area of flotation column L2
A Flow area in membrane module (= HW) L2
C Considered or required or design oil concentration ML-3
C’g The 1st (or lower or pseudo) gel concentration in film model, ML-3
used at the lower range of concentration before inflection
point in flux vs. Log (Concentration) curve (in mass/ volume
or volume/volume)
Ca Capillary number = μo V/γo
Cg Gel concentration in film model (in mass/ volume or ML-3
volume/volume)
Co Initial oil concentration of feed or influent wastewater ML-3
Cod Inlet concentration of the droplet diameter “d” M/L3
Cod Inlet concentration of the droplet diameter “d”, dilution effect M/L3
from addition of pressurized water is not included.
Conc(Air) Concentration of dissolved air in pressurized water M/L3
Conc(O2) Concentration of dissolved oxygen in pressurized water M/L3
Cy50 Cyclone number of d50%
d Diameter of dispersed phase, in our case, oil L
D Water depth or L
Diameter of the skimmer or L
Diameter of coalescer bed, such as diameter of brush or L
Nominal diameter of 3-phases hydrocyclone (the largest L
diameter of the cyclone) or
Hydraulic diameter of flow channel in membrane module L
(Channel between membrane surface and membrane module
wall)
db Average diameter of air bubble L
dc Cut size of the decanter or API tank L
dF Diameter of fiber in fibrous-bed coalescer L
Di Diameter of inlet port of hydrocyclone L
Dn Nominal diameter of hydrocyclone. ( = diameter of inlet of L
lower conical part for Thew type hydrocyclone)
dp Diameter of collector or coalescer bed material, such as resin L
dxx% , dxx Diameter of droplet corresponding to removal efficiency of M
“xx”%, such as d75%, etc. d100% or dc stands for cut size
e Surface roughness of flow channel L
f Friction factor of Darcy-Weisbach’s equation
g Gravitational acceleration L/T2
G Turbulent intensity
H Travelling or rising distance of oil drop, depending on L
configuration of the decanter. Exp. For PPI, H = distance
between plates or
Height of bed, or bed depth of coalescer or L
Height of flow channel in membrane module or L
Height of contact (or effective) zone of flotation column. If L
both pressurized water and wastewater are fed at the bottom
of the column, the contact zone is equal to column height.
Href H at reference operating condition of DAF reactor L
Hreq H at design or required operating condition of DAF reactor L
I Immersion depth of the disk in liquid or L
xiii
Nomenclature
xiv
Nomenclature
Greek Letter
Φ Air flowrate in flotation column L3/T
Π Vapor pressure (some references use “Psat”.) LT-2M-1
α Probability of collision or
Exponent of recirculation velocity in gel resistance equation
α.ηexp Corrected experimental removal efficiency factor of the tank
for the droplet diameter “d”
α, α3φ, αThew Correction factor for inlet velocity of hydrocyclone
β Conical angle of lower part of hydrocyclone or
Exponent of recirculation velocity in film model of
membrane
β0, β1, … , βi Adhesion efficiency between bubbles and oil drop/ bubble
agglomerate for population balance equation
ε Porosity or void ratio
φ Constant in gel resistance equation
γo Superficial tension of oil M/T2
γo/w Interfacial tension between oil and water M/T2
γo/w Interfacial tension between oil and water MT-2
ηoverall Overall efficiency of pump
κ Collision rate constant for population balance equation T-1
κ2 Modified collision rate constant for population balance T-2
equation (κ = κ2Φ)
κ2,ref Modified collision rate constant at reference condition T-2
κ2,req Modified collision rate constant at design or required T-2
condition
μ Dynamic viscosity ML-1T-1
μC Dynamic viscosity of continuous phase, in our case, water L2/T
μd Dynamic viscosity of dispersed phase, in our case, oil L2/T
μo Dynamic viscosity of oil M/(L.T)
νo Kinematic viscosity of oil L2/T
θo/w Contact angle between oil and water surface (180o means the
oil drop in perfectly sphere.)
xv
Nomenclature
ρ Density ML-3
ρair Density of air at required operating condition M/L3
ρc Density of continuous phases M/L3
ρm Density of emulsion M/L3
Δρ Difference between density of dispersed and continuous M/L3
phases
τ Retention time T
ηd Removal efficiency of the tank for the droplet diameter “d” %
ηd,ref Removal efficiency of DAF process for the droplet diameter %
“d” at the reference retention time (25 minutes)
ηDiff Efficiency factor from diffusion
ηInt Efficiency factor from direct interception
ηSed Efficiency factor from sedimentation
ηSed Efficiency factor from sedimentation
ηt Total Removal efficiency %
ηtheo Theoretical removal efficiency factor of the tank for the
droplet diameter “d”
?A, ?B B Subscript indicating component A and B respectively
?H Subscript indicating heteroazeotropic point
?mac Subscript indicating macroemulsion
?mic Subscript indicating microemulsion
?mix Subscript indicating mixture
?o Subscript indicating initial condition
?ref Subscript indicating reference condition
?θb Superscript indicating boiling temperature
xvi
Part I Introduction and bibliography
Part I Introduction and bibliography
Contents
Page
Part I Introduction and bibliography
Chapter 1 Introduction I-2
Chapter 3 Bibliography
3.1 Categories of hydrocarbon-polluted wastewater and treatment I-6
processes
3.2 STOKES law I-7
3.3 Decanting I-7
3.4 Coalescer I-10
3.4.1 Thesis of AURELLE [3] I-10
3.4.2 Thesis of SANCHEZ MARTINEZ [6] I-11
3.4.3 Thesis of DARME [7] I-12
3.4.4 Thesis of TAPANEEYANGKUL [8] I-14
3.4.5 Thesis of DAMAK [9] I-15
3.4.6 Thesis of MA [16] I-17
3.4.7 Thesis of SRIJAROONRAT [10] I-17
3.4.8 Thesis of WANICHKUL [11] I-18
3.5 Flotation I-18
3.5.1 Thesis of SIEM [12] I-18
3.5.1 Thesis of AOUDJEHANE [13] I-19
3.5.1 Thesis of DUPRE [14] I-20
3.5.1 Thesis of PONASSE [15] I-21
3.6 Hydrocyclone I-22
3.6.1 Thesis of MA [16] I-22
3.6.2 Thesis of CAZAL [17] I-24
3.6.3 Thesis of SRIJAROONRAT [10] I-25
3.6.4 Thesis of WANICHKUL [11] I-25
3.6.5 Thesis of PUPRASERT [25 ] I-26
3.7 Ultrafiltration and other membrane processes I-26
3.7.1 Thesis of BELKACEM [18] I-27
3.7.2 Thesis of TOULGOAT [19] I-29
3.7.3 Thesis of MATAMOROS [20] I-30
3.7.4 Thesis of SRIJAROONRAT [10] I-32
3.7.5 Thesis of WANICHKUL [11] I-33
3.8 Thermal treatment I-33
3.8.1 Thesis of LUCENA[24] I-33
3.8.2 Thesis of LORRAIN[23] I-34
3.8.3 Thesis of WANICHKUL [11] I-34
3.9 Chemical treatment I-34
3.9.1 Thesis of ZHU[21] I-35
3.9.2 Thesis of YANG[22] I-37
3.10 Biological treatment I-38
3.9.10 Thesis of WANICHKUL [11] I-38
I-i
Part I Introduction and bibliography
Contents (Con’t)
Page
3.11 Skimmer I-38
3.12 Application researches I-39
3.12.1 Thesis of SRIJAROONRAT [10] I-40
3.12.2 Thesis of WANICHKUL [11] I-41
Chapter 4 Conclusion I-44
I-ii
Part I Introduction and bibliography
Table
Page
Table 3.1 Summary of characteristics of wastewaters and sludges for “on site” I-24
experiment
Table 3.2 Summary of characteristics of synthetic wastewaters I-24
Table 3.3 Membranes test by MATAMOROS I-31
Figure
Page
Fig. 1-1 Summary of researches of Prof. AURELLE on hydrocarbon-polluted I-3
wastewater treatment
Fig. 3.1 Schematic of decante I-8
Fig. 3.2 Schematic of Phase inversion coalescer I-15
Fig. 3.3 Three- phase hydrocyclone I-23
Fig. 3.4 Hydrocyclone tested by WANICHKUL I-26
Fig. 3.5 Ultrafiltration models used by BELKACEM I-29
Fig. 3.6 Treatment processes for macro- and microemulsion, recommended I-32
by MATAMORS
I-iii
Part I Introduction and bibliography
1 I-1
Chapter 1 Introduction
Chapter 1 Introduction
Water pollution is one of the most important environmental problems. Wastewater
from agriculture and industrial processes, as well as domestic wastewater, is the main
pollutant source that causes water pollution problem. There are many substances that can
deteriorate water quality, thus classified as water pollutants, such as, organic matter from
domestic wastewater, chemicals from industrial wastewater. Some valuable substances, such
as sugar, flour, oil, will become major pollutants when discharged into water bodies.
Among various kinds of pollutants, hydrocarbon, or simply called oil, is one of the
most severe pollutants because of its intrinsic properties. Small amount of hydrocarbon can
spread over wide area of water surface and affect the oxygen transfer, so cause adverse effect
to marine or water ecology. Furthermore, the hydrocarbon contributes to very high
biochemical oxygen demand and is relatively difficult for biodegradation, which is the major
natural self-purification process. So it can last relatively long in the water and causes long -
term effect.
Our laboratory has researched for various treatment processes that cover various types
of wastewater polluted by hydrocarbons. In the few decades of researches, many theses had
been accomplished as shown in Fig. 1.1. Among these, many innovations had been created
and some had been patented and commercialized. Some researches are the key steps to
understand or improve the treatment efficiency and process design. However, because there
are many kinds of oily wastewater, as well as, there are many kinds of treatment processes.
Moreover, treatment efficiency of each treatment process will vary with characteristic of
wastewater. Then, it may cause some difficulties in selecting or designing appropriate process
train that can deal with the wastewater considered as well as predicting effluent quality
accurately.
According to the difficulty stated above, this thesis had been initiated to provide the
solution and tool about how to select and optimize the process or processes train to treat the
specified wastewater to meet required effluent standard, as well as providing details about
hydrocarbon polluted wastewater and each treatment process. It can be, also, applied for
designing the process to recover valuable hydrocarbons from hydrocarbon/water mixtures in
some industries, such as perfume or pharmaceutical industries.
2 I-2
Fig. 1-1 Summary of researches of Prof. AURELLE on hydrocarbon-polluted wastewater treatment
3
polluted or oily Application
wastewater “Deep shaft DAF”
“2 & 3-phase hydrocyclone”
treatment Hydrocyclone PONASSE [15], 1997
MA [16], 1993
“Treatment of
“Hydrocyclone with grit pot” &
“2-phase hydrocyclone stabilized emulsion”
“Combination Coagulation
for stormwater treatment” WANICHKUL [11]
-DAF-Hydrocyclone” separator
CAZAL [17], 1996 , 2000
PUPRASERT [25], 2004
“Heteroazeotropic distillation”
LUCENA [24], 2004
I-3
Part I Introduction and bibliography
Chapter 2 Objectives
Chapter 2 Objectives
The objectives of this study are as described below;
To design and select the suitable treatment process or processes, firstly, one has to
know of all applicable processes and understand their working mechanisms. So it becomes the
first objective of this study to review these data. However, as previously described in Chapter
1, there are many processes for hydrocarbon-polluted wastewater treatment. For example,
decanter can be subdivided into many types, such as simple API decanter, decanter with plate
settler, etc. So there are many researches all over the world that had been conducted to study
the mechanism or working principle of these processes and, then, to predict their efficiencies.
Among these researchers, Professor Yves Aurelle, with his team of researchers at GPI,
INSA Toulouse, has dedicated his studies to oily and hydrocarbon-polluted wastewater
treatment for a few decades. Through many years of study, the researches, conducted and led
by him, cover relatively the whole processes of hydrocarbon-polluted wastewater treatment.
So, to value and make ultimate use of these researches, the processes taken into account in
this thesis are exclusive based on the researches of Professor Yves Aurelle with additional
supports in some parts from related literatures for completeness of this study.
Each treatment process has its own variations, adapted to improve working efficiency
or to suit some certain circumstances. Thus results or models from the researches, which
intended to study in detail of these variations can not be used or extrapolated beyond their
experimental operating conditions. In order to provide the solution to the widest range, if not
the entire range, of hydrocarbon-polluted wastewater, we set the 2nd objective to generalize or,
if case arises, propose the model or models that allow the prediction of efficiency of each
treatment process over the determined range of hydrocarbon-polluted wastewater.
As previously described that there are a lot of researches dedicated to specific aspects
of various treatment processes, it is very interesting to combine these researches together to
get the whole picture. After we had reviewed and generalized all related researches as
described in the 1st and 2nd objective, we set out to work on our 3rd objective of this thesis to
compose the textbook. This textbook will feature the following topics;
4 I-4
Part I Introduction and bibliography
treatment processes and key parameters affected their designs and operations, that can lead to
proper design and selection of treatment processes or creating their own variation of process
that suit their own situation.
4. To develop the prototype of program for the design, comparison and simulation
of hydrocarbon-polluted wastewater treatment processes.
At the present, computer comes to play major role in every field and become standard
equipment in almost every household, office and academic institute. Because of its powerful
logical and mathematical calculation, as well as its presentation and interaction capability, it is
very interesting to use computer in the field of hydrocarbon-polluted wastewater treatment.
Up till now, there are many commercial softwares on industrial and wastewater treatment
process calculation. Anyway, those programs are not specifically designed to deal with
hydrocarbon-polluted wastewater treatment. Furthermore, the commercial softwares are
normally developed for expert users, so they do not provide much basic data, thus, render it
difficult for non-expert users to use efficiently. Besides, they normally do not provide any
data for decision supporting, for example they can not compare the efficiency between various
processes or recommend the feasible processes for considered wastewater.
So for our 4th objective, we intend to develop the prototype of program for design,
comparison and simulation of hydrocarbon-polluted wastewater treatment processes. The
program will feature;
• E-book: provides background knowledge and useful database about the oil
pollution and the treatment processes,
• Process recommendation part: provides recommendation or narrows the range of
feasible processes for any input influent,
• Design (or calculation) part: used for sizing the process unit,
• Simulation part: allows users to integrate any separation processes, included in
the program database, to build their own treatment process train. And the program
will simulate the process train to forecast the efficiency of each unit.
The treatment processes, which can be calculated or simulated by the program built-in
database, will then be based mainly upon the researches reviewed in the 1st to 3rd objective.
However, the source code of the program will be available upon request to allow upgrading to
include more processes in the future.
5 I-5
Part I Introduction and bibliography
Chapter 3 Bibliography
Thus, it is more suitable to categorize the oily wastewater by its physical properties.
Among these properties, the degree of dispersion of oil phase in water or the size of oil
droplet is the key parameter that plays an important role in separation process selection. So we
will categorize the oily wastewater into 4 groups, in accordance with its droplet size, i.e.,
For treatment processes, each process has its own characteristic or limitation so it can
be used to separate some certain ranges of oil droplet. So each group of the oily wastewater
may require certain process or train of processes to separate the oil from the water to the
accepted degree. The treatment processes, studied by Professor AURELLE’s researchers,
covered the entire range of the oily wastewater stated above and can be summarized as
follow;
• Decanting
• Skimmer
• Coaleser
• Flotation
• Hydrocyclone
• Ultrafiltration
• Distillation
• Biological treatment
Moreover, there are researches on chemical treatment, which relates to “breaking” the
emulsion to allow the micro droplet to coalesce and make it possible to separate by the
processes stated above. There, also, are some researches contributed to formulation of
environmental-friendly oil product, which can be easily treated and still have the same
essential working properties as the existing product’s.
Furthermore, some researches can be extensively used to solve the problems of some
special types of oily waste, such as slop (viscous mixture between crude oil and water) or
inverse emulsion (fine drops of water dispersed in oil)
6 I-6
Chapter 3 Bibliography
In case of oily wastewater, the dispersed phase is hydrocarbon or oil and the
continuous phase is water. Because the density of hydrocarbons in our wastewater is normally
lower than water’s. It is prone to rise to surface of the water. Even though the STOKES
equation is valid only for certain flow regimes, the equation covers the range of flow
regime normally encountered in wastewater problem. It can be used to explain important
phenomena or applied to many types of processes, even a bit beyond its valid regime, with
satisfactory result. There are few modifications of STOKES law brought about by applying
some correction factors into basic STOKES law. But the core equation usually remains the
same as shown in eq. 3.1.
Form eq. 3.1, one can increase the rising velocity of the oil drop by modifying 4
variables properly. The separation processes, which are based on the results of STOKES law
or modification of the variables in STOKES law, are decanting, coalescer, flotation process
and hydrocyclone or various types of centrifugal process. The researches on each process can
be summarized as follows.
3.3 Decanting
Decanting (or sedimentation) is the simplest separation process. It makes use of
gravity force and density difference between oil and water to separate them. Rising velocity of
oil or hydrocarbon drop in wastewater depends on its size, density, viscosity of water and
gravity constant, as described by STOKES equation. As shown in fig. 3.1, when the
homogeneous oil/water mixture flows uniformly pass through a control volume, some big oil
drops will rise to the water surface and can be retained, then, separated from the water by
means of proper equipment, such as overflow weir or skimmer. The small oil drop that can
not reach the water surface will be entrained with the water and exit the control volume
without separation.
7 I-7
Part I Introduction and bibliography
V
Influent d > cut size U Effluent
d = cut size
d < cut size
When the size of the decanter (or settling tank) and the distribution of oil droplets in
the wastewater are known, we can calculate the separation efficiency of the tank by
comparing the time required for each size of oil droplet to reach the surface of the tank within
hydraulic retention time of the tank. The time required for oil droplet to reach the surface can
be calculated from STOKES equation and vertical travelling distance of the droplet. If the
droplet can reach the surface before the wastewater will flow off the tank, we can say that the
droplet can be separated by that decanter. American Petroleum Institute had recommended the
geometry of the decanter, generally known as API tank. This type of decanter has been widely
used.
Because all variables in STOKES equation are practically unchanged during the
separation process by decanter. Then, the efficiency of decanter can be enhanced only by
reducing the vertical travelling distance of oil droplet to the decanting surface. This fact leads
to the modification of simple decanter by inserting submerged plates into the tank. These
plates will act as oil interceptor. Instead of rising up to the water surface, oil droplets that
reach the surfaces of these plates are intercepted, collected, and then separated from the tank.
It can be said that these insertions reduce the vertical travelling time of oil drop without the
reduction of hydraulic retention time.
• Study of interaction between oil drop and surface of lamella plate, and influence of
wettability of lamella material, inclination of lamella plate and characteristic of
wastewater to decanter operation
• Model development for lamella decanter
8 I-8
Chapter 3 Bibliography
Experimental procedure
Result
The result of this study provides models for sizing and calculating the efficiency of
two lamella decanters “SPIRALOIL”. The microscopic observation clearly shows the
interaction between oil and surface of lamella plate and influence of wettability and
inclination of the plate. The result leads to optimum configuration of the SPIRALOIL.
Significant findings
1. In this thesis, mathematical models for sizing and calculating efficiency of the
decanters are proposed. The models are based upon theoretical model of classical
decanters.
2. The microscopic study shows that the operation of the decanters consists of 2
steps, i.e., decanting and coalescing.
3. For hydrophobic plate, decanted oil will adhere to the surface of the plate, then
coalesce to form a film on the surface. However, the following decanted oil drop
will adhere and coalesce with the oil film with more difficulty than adhering to
the plate itself.
4. For hydrophilic lamella plate, decanted oil will not form a film at the surface of
the plate, but will accumulate in the form of big drop. This oil drop will be
entrained with the water when it reaches sufficient size and, then, separated from
water at the ends of the plate.
5. The inclination of the plate will affect the coalescing step. For hydrophobic
plate, there is a possibility that the decanted oil drop will not coalesce with the
film, but roll over the film until reaching the end of the plate. However, at the
end of plate will appear the big oil drop, because the point will play the role of
drip point or salting-out point. This big drop can intercept those non coalesced
drops and becomes one larger oil drop until it reaches sufficient size to be
snapped off by the water flow.
6. For hydrophilic inclined plate, the decanted oil drop will move along, rather than
adhere to, the inclination of the plate. Anyway it can coalesce with other
decanted oil drop along its way to be a larger drop in the same manner as a
“snowball”.
7. Presence of surfactant will decrease the oil droplet size, thus hinder good
decanting step. Furthermore, it will lower the interfacial tension, thus hinder
good coalescing step and cause decreasing in the efficiency of decanter.
9 I-9
Part I Introduction and bibliography
8. From the study, the optimum SPIRALOIL configuration is the one with
combination of corrugated hydrophilic and smooth hydrophobic plate insertion,
installed in horizontal position. This configuration will combine the advantage of
enlarging of the oil drop both at the end of the plate (drip point enlargement) and
within the plate (snowball enlargement). Furthermore, the horizontal installation
(inclination = 0) will favor coalescing step.
3.4 Coalescer
From STOKES law (eq. 3.1), rising velocity of the oil droplet is proportional with
square of droplet diameter. So increasing the droplet diameter will make rising velocity
increasing at greater rate than other parameters in the equation. To increase the diameter, we
need a process that can integrate small droplets into the big one. Coalescer is very effective
process that enables coalescing or integrating of a number of small oil droplets in the
wastewater into relatively big drops, which can be easily separated by ordinary decanter.
Because coalescer operation depends upon several parameters or mechanisms and each of
them can be optimized to obtain better efficiency or to fit some specific working conditions,
then there are several theses related to coalescer, in order to cover every aspect of the process.
Some researches are dedicated to detailed study of mechanism of the process. Some are
contributed to various type of coalescer bed or modes of operation. While some are devoted to
application on some specific wastewater or working condition. All of these related theses on
coalescer can be outlined as follow.
Experimental procedure
The experiment was carefully planned to cover every aspect of coalescer operation,
i.e.,
10 I-10
Chapter 3 Bibliography
Result
The result of this study indicate the important parameters which influent the efficiency
of coalescer. It also shows complex phenomena in coalescer operation by means of
visualization or photographic technique. Model for sizing the coalescer was proposed. The
study also provided significant criteria to select the material of bed and guideline for
optimization and for further development of coalescer
Significant findings
1. The main parameters, which effect the efficiency of the coalescer, consist of :
• Wettability of bed material,
• Bed height,
• Empty bed velocity,
• Granulometry of bed,
• Ratio of hydrocarbon in the wastewater
2. The phenomena or mechanism occur in the coalescer can be divided into 3
fundamental steps as follow.
• Step 1: Interception, which consists of 3 major transport phenomena, i.e.,
sedimentation, direct interception and diffusion. This step is normally the
efficiency-determining step of coalescer. The research makes it possible to
develop the model, based on model of filtration process, which governs all
phenomena in this step.
• Step 2: Adhesion-Coalescence. The efficiency of this step depends mainly on
wettability of bed material. So, this step can be optimized by using oleophilic
material as coalescer bed.
• Step 3: Salting out or enlargement of coalesced liquid. This step depends on
4 parameters, i.e. wettability of bed material at the discharge surface, empty
bed flow velocity, interfacial tension and ratio of dispersed phase and
continuous phase in emulsion treated. So, for any given wastewater and bed
material, one can optimize this step only by varying feed flowrate. However,
the research shows that installation of guide, such as woven fibrous metal,
attached to discharge surface of granular bed, can eliminate influences of the
4 parameters described above and allow the coalescer to operate at much
higher velocity. This guide suppresses the limiting step 3 by channeling
coalesced oil directly into decanted oil layer at the decanter surface.
This thesis provides very important concepts and mechanisms of coalescer that leads
to further studies on various types of coalescer.
This research contributed to extensive study on granular bed coalescer, first researched
by AURELLE [3]. The research was emphasized on granular bed coalescer with guide, and
mixed bed coalescer.
11 I-11
Part I Introduction and bibliography
Experimental procedure
The experiment was conducted with transparent glass coalescer models. Coalescer bed
materials used during the experiment were sand and glass bead. Both materials were specially
coated to acquire oleophilic or hydrophilic property. 2 guides of different sizes of woven fiber
and different porosity were tested. The author intended to study the operation of coalescer for
liquid/liquid extraction. So he chose phenol extraction in this study. Phenol in wastewater can
be extracted by dissolving into appropriate hydrocarbon solvent. Solvent and wastewater will
be intensely agitated to maximize contact, thus, mass transfer. So, they normally become
emulsion, both direct and inverse. Hydrocarbons used as solvent in the experiment were
L.C.O, medium-cut petroleum, and gasoline.
Significant findings
12 I-12
Chapter 3 Bibliography
Experimental procedure
The experiment was conducted with transparent glass coalescer models. Coalescer bed
materials used during the experiment were oleophilic resin and glass bead. To study about
influence of surfactant on wettability, glass, resin and steel were tested. For the study on
mixed bed electrocoalescer, mixed material of aluminium and resin was tested. Emulsion of
kerosene and water was used throughout the experiment, with various dosages of cationic,
anionic and non-ionic surfactants.
Significant findings
13 I-13
Part I Introduction and bibliography
Experimental procedure
The experiment was conducted with transparent glass coalescer model. Coalescer bed
materials used during the experiment were of brush type, made of nylon (polyamine) and
polypropylene fiber with various fiber diameters, brush sizes, and void ratios. The brush was
mounted to a variable speed motor, so the rotation of the brush can be adjusted. Emulsion
used in the experiment was kerosene emulsion.
Significant findings
1. The main parameters, which effect the efficiency of the coalescer, consist of;
• Granulometry of emulsion (sizes of droplets)
• Bed height
• Bed diameter
• Void ratio or porosity of the bed
• Diameter of fiber of the fibrous bed
• Empty bed velocity
• Rotating speed of bed
2. In this thesis, mathematical model for sizing and calculating efficiency of fibrous
bed coalescer was proposed, i.e.;
0.67d 0.58 (1 − ε) 0.35 H0.35 N0.53
η =( E ) ⋅ 100 %
D0.03 d 0.58 V0.74
d
F P
Where ηd = Efficiency of coalescer
dE = Diameter of dispersed phase
ε = Void ratio or porosity of bed
H = Bed height
N = Rotating speed
D = Diameter of bed
dF = Diameter of fiber
Vp = Empty bed velocity
14 I-14
Chapter 3 Bibliography
This model is valid when 52<Re<1164. However, scaling-up of the model will
be limited by bed construction itself because the fiber elements of the bed tend to
compact by their own weight. Moreover, if the bed is too large, void ratio at the
tips of fibers will be very different from center’s. This may cause error in
calculation. So, it is recommended to use a number of small coalescers instead of
a single large one.
3. This coalescer has several advantages as follow;
• Anti-clogging. No regeneration or backwashing required
• High void ratio, thus, head loss is very low
• Very small size of fiber, compared to granular bed material, ensures good
interception of oil droplets
• Treatment efficiency is adjustable by mean of adjusting rotating speed of bed
This research was intended to study another variation of coalescer, i.e., “Pulsed
granular bed coalescer”. This type of coalescer had been initiated to enable the granular bed
coalescer to treat oily wastewater with high suspended solids concentration without
regeneration or backwashing process. This coalescer, in fact, is a classical up-flow coalescer,
except it bottom end is equipped with rubber diaphragm, driven by pneumatic piston. The
diaphragm will be periodically driven up, then released to go back down. This action will
cause brief fluidization of bed and the trapped solids will be released from the bed.
The author also studied a new type of coalescer, called “Phase inversion coalescer”.
For its operation principle, the wasted emulsion will be forced downward through small tubes,
equipped at the top of coalscer column, to produce emulsion drops of required size. These
drops will flow through thick layer of hydrocarbon, which is of the same type as dispersed
phase in the emulsion. The drops play the role of micro decanter. Theoretically, hydrocarbon
droplets in the emulsion drops will float to the top of the drops, then, coalesce with
surrounding hydrocarbon layer. With appropriate depth of hydrocarbon layer and size of
emulsion drop, the dispersed phase in emulsion drop will be totally separated and become
only the drop of water phase when it flow out off the hydrocarbon layer into water phase
underneath. The schematic of phase inversion coalescer will be as shown in Fig 3.2.
Influent
emulsion
Hydrocarbon
Emulsion
layer
droplets in emulsion
drop
drop
Bottom of hydrocarbon
layer
Water layer
Effluent Decanting of droplets in
emulsion drop
15 I-15
Part I Introduction and bibliography
Experimental procedure
For the phase inversion coalescer, the experiment was conducted with transparent
glass coalescer model. Furthermore, to achieve a better visual study, a special tube equipped
with micro-syringe was used to study internal phenomena in droplet. The tube was fixed at the
tip of the syringe, to be within hydrocarbon stream. Emulsions, used in the experimental, were
kerosene/water emulsion, hexane/water emulsion and T.I.O.A./water emulsion. T.I.O.A/water
emulsion is the solution of kerosene, triisooctylamine (T.I.OA) and tributylphosphate. This
solution is normally used as extracting solvent in hydro-metallurgical industries.
For up-flow pulsed granular bed coalescer, the experiment was conducted with glass
coalescer with rubber diaphragm bottom. The diaphragm was connected to pneumatic piston
that can drive the diaphragm up and down at preset interval. Coalescer materials were
hydrophilic glass bead and stainless steel. Emulsion tested were kerosene/water emulsion and
T.I.O.A./water emulsion with an addition of fly ash as suspended solids.
For model development of granular bed coalescer, transparent glass coalescer was
used. Hydrophobic and hydrophilic glass beads were used as coalescer material.
Hydrocarbons used in the experiment were kerosene, T.I.O.A., heptane, anisole and toluene.
Significant findings
1. The efficiency of phase inversion coalescer will increase with the modification
of these parameters, i.e.;
• Increasing in height of hydrocarbon layer (until certain limiting height)
• Decreasing in size or diameter of emulsion drop that will be forced through
the hydrocarbon layer (again, until lower limit)
• Incresing in flowrate of treated emulsion
• Increasing in height of emulsion-drop-accumulated or dense layer
The efficiency will also depend on characteristics of emulsion e.g. viscosity,
interfacial tension, granulometry of emulsion etc.
2. While the emulsion drop travels pass through hydrocarbon layer, internal
turbulence or circulation flow will be induced within the emulsion drop, which
then disturbs good decanting of oil droplets, thus causes the decrease in the
efficiency.
3. To avoid this turbulence, the flowrate should be increased to produce more
emulsion drops. The rate of production has to be greater than the rate of
coalescence of the drops, at the bottom of hydrocarbon layers. So, this results in
formation of emulsion-drop dense bed or layer at the bottom of hydrocarbon
layer. This layer will dampen the downward velocity of the drop, which results
in decreasing of internal turbulence. The efficiency, then, will be improved.
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Chapter 3 Bibliography
4. This coalescer is suitable for treatment of primary emulsion (dE ≥50 μm). And
the study shows that the efficiency is better than that of the classic decanter.
5. For pulsed coalescer, the study shows that brief pulsation, which causes the bed
to fluidize, can regenerate the bed and clean up the accumulated matters.
6. In classical coalescer, coalescer bed material is usually lightweight resin, which
requires the top grill to keep the bed in place without carrying over with the
wastewater. However, in this study, it shows the possibility of using of relatively
high density coalescer bed, e.g., stainless steel, without the top grill can replace
the use of lightweight material. When the grill is not required, it allows us to use
pulsating motion to fluidize, thus, regenerate the bed.
7. In this thesis, a mathematical model for sizing and calculating efficiency of
granular bed coalescer was proposed. Unlike the model of AURELLE, which
derived from theoretical mechanisms of coalescence, this model is based on
dimensional analysis. So physical properties of wastewater, which are not shown
in AURELLE’s model, are taken into account. Hence, it covers wider range of
wastewater.
This thesis was the main research on hydrocyclone for hydrocarbon/water separation.
So it will be described in detail in section 3.6. However, the author had tested, for the first
time, the efficiency of the combination process of hydrocyclone and coalescer, which worth
describing here.
Significant findings
1. This study shows, for the first time, the possibility to use the combination
process of hydrocyclone/coalescer and coalescer/hydrocyclone to improve the
total efficiency of oil/water separation.
Significant findings
1. At high empty bed velocity, the coalescer with random bed will coalesce and
enlarge the droplets into relatively large drop, while the coalescer with brush
type bed tends to produce stream of jet, containing small oil drop.
2. However, the disorderly fibrous (steel wool) bed coalescer tends to be clogged
by suspended solids, usually presence in the oily wastewater. So the author
proposed new configuration of fibrous bed in form of combination of 2 brushes.
The internal one is of ordinary brush. The external one will look like coil spring
17 I-17
Part I Introduction and bibliography
with its fiber elements protruding inward and toward the center. This type of bed
is believed to provide good interception, as same as the disorderly bed, yet
remain its anti-clogging properties, like brush-type bed.
3. Combination between coalescer/ hydrocyclone is proven to provide good
efficiency on the wider range of feed flowrate and size of oil droplet.
Significant findings
3.5 Flotation
Flotation is the separation process that makes use of increasing the density difference
to increase the rising velocity of droplets of dispersed phase. The density difference can be
increased by mean of integrating air or gas bubble with oil droplets. The bubble/droplet
agglomerate will have lower density than droplet alone, thus, result in increasing of the rising
velocity. Because flotation mechanisms are very complex, then there are several theses related
to flotation, in order to cover every aspect of the process. All of related theses on flotation can
be outlined as follow.
• Study on the interaction between hydrocarbon droplets and air bubble, and
overview of efficiency of dissolved air flotation and induced air flotation.
• Influence of essential parameters, coagulant dosage, pH, etc. to efficiency of
flotation
• Model development for dissolved air flotation, based on filtration model.
18 I-18
Chapter 3 Bibliography
Experimental procedure
Visual study of interaction between oil droplets and bubble had been conducted in
special transparent model, equipped with a microscope and a VDO camera. For the study on
flotation, transparent flotation model was used. Emulsion used during the experiment was gas-
oil/water emulsion.
Significant findings
1. From visual study on interaction between oil droplet and air bubble, it shows that
the bubble will agglomerate within the inside of oil droplet or the oil will form a
thin skin, as a shell, around the air bubble.
2. In this thesis, mathematical model for sizing and calculating efficiency of
dissolved air flotation is proposed. The model is based on filtration model by
assuming that the air bubble is collector (sand or filter media in case of filter).
Prediction results of the model fit well with experimental results. Anyway, the
author did not account for the quantity of pressurized water that used to generate
the bubbles. This amount of water can cause dilution effect, thus, contribute to
reducing in wastewater concentration. So, the model proposed in this research
should be reconsidered again to clarify the efficiency of interception of air
bubble and the efficiency from dilution effect of pressurized water. The revised
model will be described in Part 2 of this thesis.
Experimental procedure
Visual study of the interaction between oil droplets and bubble had been conducted in
special transparent models, equipped with a microscope and a VDO camera. The models are
equipped with 2 syringes, located close to each other. These 2 syringes were used to supply
air (or gas) and oil to form immobilized bubble and oil droplet respectively. Bubble and oil
droplets were brought into contact to study the formation of the agglomerate. For study on
flotation, transparent flotation model was used. Hydrocarbon used in this study was kerosene.
For transfer compounds, ammonia gas, cationic surfactant and methanol were used as
promoter of mass transfer between phases.
Significant findings
1. From visual study on interaction between oil droplet and air bubble, it confirms
the result of SIEM [12] that the bubble will agglomerate within the inside of oil
19 I-19
Part I Introduction and bibliography
droplet or the oil will form a thin skin, as a shell, around the air bubble. The
agglomerate in from of bubble and droplet locating side by side of each other,
which is exist in case of bubble/particle interaction, occurs only in unstable,
transition forms. It also shows that coalescence time between bubble and oil
droplet is less than that of the same species.
2. From the study with static transparent model, it shows that addition of transfer
compound (as gas to bubble air or as transfer compound to water) affects, more
or less, probability of coalescence between bubble/droplet, bubble/bubble and
droplet/droplet. It can be described that mass transfer of these transfer compound
from one phase to another (for example, bubble gas from bubble toward water,
etc.) can cause disturbance in local surface tension and thinning of film, then,
help increasing coalescence. This effect is well known in liquid-liquid extraction
process as the Marangoni effect.
3. From the study with flotation lab-scale model, it shows that the effect of
turbulence, caused by movement of air bubble, promotes the probability of
collision both inter-species and same species of bubbles and oil droplets.
However, this augmentation in collision increases flotation efficiency only
slightly because the number of bubble, somehow, decreases from the effect of
collision and coalescence, that leads to depletion of the number of bubble/droplet
agglomerate. Anyway, the author notes that, because coagulation-flocculation
process is not applied, the number of oil droplets is, then, always greater than the
number of bubbles. Then, it may be interesting to study further on coalescence
or coagulation of oil droplets.
Experimental procedure
To study the precipitation of dissolved gas, the author tested several pressure-reducing
venturi tubes (convergence-divergence nozzles) of various divergent angles. Tube materials
tested consisted of stainless steel (hydrophilic) and plastic (hydrophobic). Influence of
divergent angle, wettability of tube, length of pipe after the pressure reducing device and
addition of some chemicals were studied.
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Chapter 3 Bibliography
various particles were added. Then, the air was pumped out to create vacuum. This apparatus
was used to observe nucleation of bubble. The 3rd one was a transparent flotation model.
Significant findings
Experimental procedure
To study the influence of pressure reducing valve on formation of bubble, the author
tested several pressure-reducing venturi tubes (convergence-divergence nozzles) of various
divergent angles. Tube materials tested consisted of stainless steel (hydrophilic) and plastic
(hydrophobic). Influence of divergent angle, wettability of tube, length of pipe after the
pressure reducing device and addition of some chemicals were studied.
For study on deep well flotation unit, a 30-m depth deep well unit was tested. The unit
consisted of 2 concentric pipes. The external pipe diameter was 0.15 m. On the top of the
pipes placed settling tank of 1.2*1.2 m, water depth 0.7 m. The wastewater was charged with
various suspended solids, both hydrophobic and hydrophilic. The air was introduced into the
system by several methods, i.e.,
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Part I Introduction and bibliography
• Via ejector
• Injection in form of pressurized water via pressure reducing valve to form bubble,
then mix with inlet wastewater at the top of deep well reactor
Significant findings
3.6 Hydrocyclone
From STOKES law (eq. 3.1), rising velocity of the oil droplet is proportional to
gravitational acceleration. So if one increases the acceleration, the rising velocity will be
increased as well. To increase the acceleration, it can be achieved by replace gravitational
acceleration with centrifugal acceleration. This can be done mechanically, such as the use of
rotating machine like centrifuge, or by converting hydrodynamic force to centrifugal motion.
Hydrocyclone is the process that uses the latter principle to increase the acceleration.
This thesis was the main research on hydrocyclone for hydrocarbon/water separation.
22 I-22
Chapter 3 Bibliography
Experimental procedure
To study on a new approach for calculation on 2-phase hydrocyclone, the author based
his experiment on “THEW” type hydrocyclone, initiated by Professor Thew, UK. For 3-phase
hydrocyclone, he had initiated this hydrocyclone by integrating the liquid/liquid hydrocyclone
of “THEW” type and the solid/liquid hydrocyclone of “RIETEMA” type to one unit. For
coalescer tested, he used coalescers with various sizes of “brush” type beds. The emulsions
used in the experiment were based on petroleum from the “Sud-Ouest” french oil rig, with
various additions of very fine bentonite (3.7 μm) and calcium carbonate powder (6.2 or 16
μm). Average oil droplet in the emulsion tested was 15 to 50 μm.
Significant findings
Di
Du
Dp D Do
Ds
L4
L5 L3
L3 L1
23 I-23
Part I Introduction and bibliography
Experimental procedure
For the feasibility study on hydrocyclone for wastewater treatment and sludge
thickening, the author had performed the experiment “on site”, using a pilot plant. The pilot
plant was equipped with storage tank, pumps and piping system that allow to test 2
hydrocyclones instantaneously, both in series and parallel. The hydrocyclones used in the
experiment were product of NEYRTEC, equipped with replaceable outlet. The sizes of
cyclones were tested, i.e., nominal diameter of 75 and 50 mm. Outlet ports of the cyclones can
be changed to study the influence of their sizes on cyclone operation. The wastewater and
sludges were provided by the wastewater treatment plant at Ginestous. Characteristics of
wastewater were as summarized in table 3.1. For study in laboratory, The same pilot plant was
used with synthetic wastewaters, summarized in table 3.2.
Table 3.1 Summary of characteristics of wastewaters and sludges for “on site”
experiment
Domestic Biological
Storm water Primary sludge
wastewater sludge
SS (mg/l) 150-490 41-700 22000-16000 4170-6660
Median diameter, d50 24-37 10-28.8 160 36-96
(μm)
Ion Ion
Calcium
Talc Talc exchange exchange
carbonate
resin 1 resin 2
Name CaCO3 A60 Steamas 29 IRP 69 OG 4B
3
Density (g/cm ) 2.7 2.7 2.7 1.57 1.57
Median diameter, 10 25 32 78 56
(μm)
24 I-24
Chapter 3 Bibliography
Significant findings
Significant findings
25 I-25
Part I Introduction and bibliography
Significant findings
1. The results shows that key parameters that govern the efficiency of co-current
hydrocyclone are influent flowrate, recovered oil draw-off rate and ratio between
outlet velocity of oil and outlet velocity of treated water, calculated at each
corresponding outlet port.
2. The author recommended that the velocity ratio of oil/ treated water mentioned
above should be greater than 1.5, which can be precisely adjusted by using of oil
draw-off pump.
3. Testing of the 2 types of the combination in industrial pilot plants showed
satisfactory result. These combinations provide promising alternatives for
industrial wastewater treatment process. Furthermore an advanced combination
of coalescer-hydrocyclone-coalescer is tested. It promisingly shows that 2
coalescers can be used, one before the hydrocyclone to increase droplet size
entering the cyclone, and another at downstream of the cyclone to coalesce the
concentrated oil/water mixture from the outlet of the hydrocyclone. The oil in
this case is separated, not just concentrated, from the wastewater.
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Chapter 3 Bibliography
or emulsion to pass. The rest will be retained by the membrane. Working principle of
membrane process can be approximately compared to that of filtration.
Membrane processes can be divided into several categories according to the pore size
of membrane, i.e., microfiltration, ultrafiltration, nanofiltration and reverse osmosis. Each
category has different permeability and can retain different size of components. So it is crucial
to select the most appropriate membrane process to achieve the required effluent quality. Then
several researches are contributed to membrane selection.
27 I-27
Part I Introduction and bibliography
Experimental procedure
The experiment was conducted with a batch model and a pilot-scale model. For batch
model, the author used AMICON membrane test module, (fig. 3.5). The batch model was
transparent container with pressure-tight cover. The membrane was placed at the bottom of
the container. Wastewater was added into the container, then the cover was locked in place
and compressed air line was connected to the inlet port at the cover. The wastewater was
forced through the membrane by mean of air pressure, then collected and examined. During
ultrafiltration process, the wastewater was continuously stirred by mean of magnetic stirrer.
For pilot-scale model, the author used commercialized cross flow ultrafiltration test
module, model PLEIADE UFP2 of Tech Sep co,.ltd. (fig. 3.5).Wastewater was circulated
through narrow gap between membrane and transparent wall of the model. In this manner,
wastewater flow was tangential, not perpendicular to, the membrane surface. Some
components would pass through the membrane and become permeate. The rest would be
returned to storage tank, then circulated pass membrane again until it reached some certain
concentration. After being circulated for many times, the concentrate would gain in
temperature, so heat exchanger was provided to cool down the flow before re-entered the
UFP2 module.
He also tested the porous fiber membrane in the same way as the plain membrane,
described before. For the membranes, he used plain and porous fiber membrane of various cut
sizes, ranged from 40 to 150 Kdalton.
Significant findings
28 I-28
Chapter 3 Bibliography
the ultrafiltrate. The result shows that reverse osmosis can treat this wastewater
with very high efficiency (approx. 98%).
1 Air compressor
1 3 2 Pressure reducing valve
2
3 Pressure guage
4 AMICON test module
4 5 Agitator
6 Balance
7 Computer
5 7
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Part I Introduction and bibliography
Experimental procedure
To study on the entraining of volatile compounds with steam, the author used glass
distillation apparatus, equipped with microscope to observe the condensate. She had tested
several hydrocarbon compounds, such as alcanes with the number of C atoms from 5 to 12
(pentane to dodecane), toluene, benzaldehyde, isobutanol, series of primary alcohols, etc.
For ultrafiltration, she used tubular ceramic membrane of 10 nm. pore size. The
experiment was conducted with membrane test module, model MEMBRALOX T1-70 of SCT
co., ltd. For the emulsion treated, she used synthetic emulsion of kerosene/water as well as
thermal emulsion from extraction of cinnamon, aniseed and celery with various doses of
surfactants.
Significant findings
1. In this thesis, it shows that the most important parameter in thermal emulsion
formation is the variation of solubility of essential oil with changes in
temperature. She also proposed the minimum variation of solubility that can
cause the formation of thermal emulsion.
2. Condensation time is the important parameter that governs the size distribution
of the emulsion. If the condensation is relatively slow, average diameter of
droplet in the emulsion will increase.
3. The author shows that if the following compounds are present in the essential oil,
thermal emulsion will not be formed;
• Hydrocarbon of high vapor tension
• Hydrophobic hydrocarbon that solubility is not sensitive to temperature
change.
4. To avoid formation of thermal emulsion, she proposed the process called
“hydrodistillation under reduced pressure (sub-atmospheric pressure)”.
5. The study shows that “white water” or milky thermal emulsion, in fact, contains
natural surfactants. So its properties are close to that of stabilized emulsion.
6. Under carefully selected operating condition, ultrafiltration can provide good
separation efficiency between water and essential oil.
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Chapter 3 Bibliography
Experimental procedure
The experiment in laboratory scale was conducted with two batch test modules, one
was fabricated in GPI Lab, and another was AMICON test module. For pilot-scale
experiment, the author used cross flow membrane test module, model PLEIADE UFP2 from
Tech Sep co., ltd., for micro- and ultrafiltration process. For nanofiltration and reverse
osmosis, he used test module from OSMONICS.
The membranes used in the research were as tubulated in table 3.3. For emulsions, he
used various commercialized cutting oil of macro- and microemulsio typesn.
Significant findings
1. The results from this research show that the combination between chemical
destabilization process with micro- or ultrafiltration can increase working
permeate fluxes of the membranes and still obtain good efficiency.
2. For the combination of chemical destabilization and microfiltration, the system
can operate at relatively high flux with moderate transmembrane pressure. This
leads to development of continuous treatment process of cutting oil because, in
the past, working pressure is always the limiting factor of the process. However,
it requires high amount of salt.
3. For the combination of chemical destabilization and ultrafiltration, the result
conforms to BELKACEM’s [18] that the salt added plays important role, by
double layer compression, and/or adsorption/partial neutralization, in the
reduction of repulsive force and promotion of coagulation and coalescence of
droplets to form a free oil layer. This oil layer can be entrained by recirculation
stream, and then removed at the concentrate storage tank.
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Part I Introduction and bibliography
4. The permeates from the combination of two processes stated above contain high
concentration of TOD, which is the result of dissolved pollutants, especially co-
surfactants.
5. Combination between ultrafiltration and reverse osmosis shows good result both
in oil separation and dissolved pollutant elimination in permeate. However,
operating cost is relatively high.
6. The use of nanofiltration shows good efficiency result in good oil separation, as
well as dissolved pollutant elimination, at lower energy consumption than
reverse osmosis.
7. From experimental results, the author recommended 2 treatment process trains
for micro- and macroemulsion as shown in fig. 3.6
Surfactant +
CaCl2
Microfiltrtion
Microfiltrtion Reverse
Reverseosmosis
osmosis Granular
Granularactivated
activated
Macroemulsion ++ or
or carbon
carbonoror Effluent
CaCl
CaCl22 Nanofiltration
Nanofiltration Biological
Biologicaltreatment
treatment
Recycle
Decanter
Decanter Decanted oil
Surfactant +
Oil
Granular
Granularactivated
activated
Microemulsion Nanofiltration
Nanofiltration carbon
carbonoror Effluent
Biological
Biologicaltreatment
treatment
Significant findings
32 I-32
Chapter 3 Bibliography
Significant findings
1. The result on the treatment of cutting oil emulsion by ultrafiltration confirms the
result of MATAMOROS that the process is feasible and efficiency of the process
is satisfying. The author recommended that operating condition should be in
permanent regime to avoid influence of concentration factor.
2. Using microemulsion with under-saturated oil concentration is an effective
method to regenerate the membrane.
3. The author had studied the efficiency of reverse osmosis on ultrafiltrate
treatment. The result shows that the process provides remarkable efficiency.
4. The result of the comparison on efficiency between ultrafiltration and distillation
on cutting oil emulsion treatment can be concluded that ultrafiltration is suitable
for macroemulsion treatment, while distillation is more efficient for
microemulsion treatment. However, from economic point of view, energy
consumption of ultrafiltration is always lower than distillation’s.
33 I-33
Part I Introduction and bibliography
Experimental procedure
The experiment in laboratory scale was conducted with a simple glass distillation
apparatus. The author also used the pilot-scale model for on-site treatment tests.
Significant findings
1. The result on the treatment of slop shows that the water is totally separated from
the slop. The residue consists of relatively water-free hydrocarbon. Distillate
consists of 2 separate layers of entrainer and water.
2. Observed quantity of entrainer is slightly different (5-8%) from theoretical value.
So the theoretical method for calculating entrainer quantity is accurate enough
for practical use.
3. Kerosene and gasoline are proven to be good entrainer. Their water-extracting
capacities are almost identical to that of decane and dodecane, respectively.
This research is contributed to crystallization. However, this process has just been
studied by GPI lab for the first time. So we will not include it in this research.
Significant findings
34 I-34
Chapter 3 Bibliography
hydrocarbon is present in the form of very stable emulsion, which will not be naturally
coalesced. So it is impossible or very difficult to separate them by mean of physical process
alone. Example of oily wastewater that requires chemical treatment process is stabilized
emulsion, such as cutting oil emulsion.
This research is contributed to the study on influence of cutting oil emulsion formula
on its physico-chemical treatment.
Experimental procedure
The author had performed the experiment using 2 commercial macroemulsions and 2
microemulsions. Some used emulsions, provided by mechanical workshops, were also tested.
For chemical reagents for destabilizing (so-called “breaking”) the emulsions, he had tested
several chemicals, i.e.,
• Inorganic electrolytes: Sulfuric acid and several salts, such as NaCl, CaCl2, Alum,
FeCl3
• Organic electrolyte: Ca(HCOO)2
• Commercial adsorption reagents
• Cationic polyelectrolytes
• Anionic polyelectrolytes
• Cationic surfactants
Each chemical reagent was added to the emulsions, stirred, and left to decant for 20
hours. Decanting results were carefully observed. If the oil in the emulsion was separated
easily within 1 hour, the author concluded that the reagent used for destabilization was
effective.
For the study on the elimination of residual pollution, the author proposed to use
adsorption treatment by activated carbon. The experiment had been conducted with batch and
continuous lab scale models.
Significant findings
35 I-35
Part I Introduction and bibliography
36 I-36
Chapter 3 Bibliography
Experimental procedure
The author had tried to formulate low pollution cutting oil emulsion, using carefully
selected base components, i.e.,
• Base oil: commercial naphthene (cyclic aliphatic compound) based oils and
paraffin based oils,
• Surfactants: various succinic and sulfonate surfactants,
• Co-surfactants: alcohol-based, ester-based, and other co-surfactants with low water
solubility,
• Corrosion inhibitors: fatty acid alcanolamide, oleylsarcosinic acid, and fatty acid
polydiethanolamide,
• Anti-mousse reagents: polysiloxane and a commercial reagent,
• Bactericides: 4-chloro-3methylphenol, isothiazolinone, and parahydroxybenzoic
ester with phenoxyethylic alcohol,
Significant findings
37 I-37
Part I Introduction and bibliography
There are many studies, includes some from our lab, on the effect of oil contents in
wastewater to biological treatment process and possibility or optimum condition to use
biological treatment to treat oily wastewater. However, none of doctoral thesis, directed by
M.Aurelle, is fully devoted to biological treatment of oil wastewater. So we will work on this
process by reviewing the available data from our lab researches as well as outside data.
Anyway, only our lab researches will be summarized here. Synthesized result from reviewing
will be presented as a section of textbook in Part 3 of this thesis.
This all-purpose thesis is also contributed to biological treatment. The author had
performed biodegradability test of permeate from ultrafiltration of cutting oil emulsion.
Significant findings
1. The study shows that ultrafiltrate of cutting oil emulsion can be treated by
aerobic biological process. The result from biodegradability test shows very high
TOC reduction efficiency (82 to 90% at the retention time of 2 to 5 hours).
3.11 Skimmer
When hydrocarbon is in the form of layer on water surface. It can be simply removed
from the surface by mean of overflow weir, overflow pipe or be scooped out manually. There
is one thesis on skimmer, which is the thesis of THANGTONGTAWI [5]. This research is
38 I-38
Chapter 3 Bibliography
contributed to study on oil drum skimmer and disk skimmer, which are very effective to
recover film or layer of oil or hydrocarbon on the surface of water.
Experimental procedure
The experiment was conducted with various sizes of disc and drum skimmers to verify
effect of skimmer geometry. Various types of skimming material were tested, i.e., stainless
steel, PVC, polypropylene and fluorocarbon coated material. Kerosene and 2 types of
lubricant oil, as well as real wastewater from 4 refineries, were used in the experiment. Effect
on interfacial tension was also considered by varying concentration of a commercial
surfactant.
Result
The result of this study provides models for sizing and calculating oil quantity,
recovered by the skimmers. The study, also, provides significant criteria for skimmer material
selection to obtain selective property, which allow the devices to recover only oil, not water.
Design consideration, such as limitation of model, working condition to be avoided, etc. is
included in this study.
Significant findings
1. In this thesis, mathematical models for sizing and calculating oil productivity of
the skimmer are proposed.
2. Influence of skimming material is studied and can be summarized as follow,
• Material of high surface energy, such as stainless steel, which is conditioned
by submerging in oil, will effectively recover or separate the oil from water.
However, when oil film on the surface of the tank is broken and the skimmer
is exposed to water, it will start recover the water immediately. Even after the
oil layer is present again, it will not resume its function of oil recovering.
• Material of low surface energy, such as PVC and PP, can effectively recover
oil. But it will start recovering water after the oil film is broken and the
skimmer is allowed to expose to the water surface for some times. Anyway,
it will resume its function after the presence of oil layer.
• From the study, fluorocarbon coated material, which is patented by ELF, is
the best oil-water selectivity. It always recovers only oil.
39 I-39
Part I Introduction and bibliography
kind of research provides very useful information for process selection or process design. All
of related theses on membrane process can be outlined as follows.
Experimental procedure
The experiment on ultrafiltration was conducted with 3 models, i.e. commercial batch
test module (effective area 37 cm2), lab scale cross flow model (effective area 100 cm2) and
pilot scale cross flow model (effective area 1 m2). The non-stabilized emulsions tested
consisted of synthetic emulsion kerosene/water and crude oil/water emulsion. However, the
author also tested the emulsion with presence of surfactant to study the effect of surfactant on
ultrafiltration. These stabilized emulsions were cutting oil emulsion and wastewater from
textile factory, which contained oil, water, dye and some surfactant from cleansing chemical
in form of emulsion.
For ultrafiltration membrane, she had tested various membrane materials, i.e.,
inorganic, organic and ceramic. She also used 2 forms of membrane, i.e. plain and tubular.
Significant findings
Results of this thesis are described in previous sections, corresponding to each process
that had been studied in this thesis. However, to get the whole picture of this thesis, we will
summarize overall significant findings of this thesis again as follow;
40 I-40
Chapter 3 Bibliography
Experimental procedure
The experiment on ultrafiltration was conducted with 3 models, i.e. commercial batch
test module (effective area 37 cm2), lab scale cross flow model (effective area 100 cm2) and
pilot scale cross flow model (effective area 1 m2). For reverse osmosis, he used commercial
test module from OSMONIC co., ltd.
41 I-41
Part I Introduction and bibliography
used in the experiment as a cleansing reagent. He also used water to rinse the membrane after
each test.
For ultrafiltration membrane, he used the asymmetric type organic membrane from
ORELIS S.A., pore size 50 Kdaltons. For reverse osmosis, he used hydrophilic organic
membrane, cut size 150-200 Daltons.
For distillation, lab-scale glass distillation apparatus was used. For biodegradation, the
apparatus, custom-made by our lab, called “Respirometer BIOS-R” was used. This apparatus
can track reduction of organic material and convert to biodegradability.
Significant findings
Results of this thesis are described in previous sections, corresponding to each process
that had been studied in this thesis. However, to perceive the whole picture of this thesis, we
have summarized overall significant findings of this thesis again as follows;
1. The result on the treatment of cutting oil emulsion by ultrafiltration confirms the
result of MATAMOROS that the process is feasible and the efficiency of the
process is satisfying. The author recommended that operating condition should
be in permanent regime to avoid influence of factor of concentration.
2. Using microemulsion with under-saturated oil concentration is an effective
method to regenerate the membrane.
3. The author had studied the efficiency of reverse osmosis on ultrafiltrate
treatment. The result shows that the process provides remarkable efficiency.
4. Comparison on efficiency between ultrafiltration and distillation on cutting oil
emulsion treatment, the author concluded that ultrafiltration is suitable for
macroemulsion treatment, while distillation is more efficient for microemulsion
treatment. However, from economic point of view, energy consumption of
ultrafiltration is always lower than distillation’s.
5. Heteroazeotropic distillation is proven to be an effective way to treat
“mayonnaise-like” retentate from ultrafiltration of cutting oil emulsion. The
residue of distillation process is clear liquid, composed of oil without water.
6. The research results shows that key parameters that governs the efficiency of co-
current hydrocyclone are;
• Influent flowrate
• Recovered oil draw-off rate
• Ratio between outlet velocity of oil and outlet velocity of treated water,
calculated at each corresponding outlet port
7. The author recommended that the velocity ratio mentioned above should be
greater than 1.5.
8. Testing of the 2 types of the combination in industrial pilot plants shows
satisfying result. These combinations provide promising alternatives for
42 I-42
Chapter 3 Bibliography
43 I-43
Part I Introduction and bibliography
Chapter 4 Conclusion
In this part, we have reviewed all of the researches in our lab, directed by Professor
AURELLE. We can see the attempts to study many aspects of treatment processes to cope
with various type of oily wastewater. The results of each thesis make us understand working
principles and limitation of the processes in many specific cases or frameworks. In the next
part, we will analyze these specific data from these theses. And then try to integrate and
generalize them to formulate design criteria or mathematical models that can be used with the
entire (or as wide as possible) range of oily wastewater.
44 I-44
Part II Generalization of models for
oil-water separation process design
Part II Generalization of models for oil-water separation process design
Contents
Page
Part II Generalization of models for oil-water separation process design
Chapter 1 Decanting
1.1 Simple decanter or API tank II-2
1.2 Lamella decanter or Parallel Plate Interceptor (PPI) II-3
1.3 Model verification II-4
1.4 Conclusion and generalized model of decanter II-7
Chapter 2 Skimmer
2.1 Drum skimmer II-9
2.2 Disk skimmer II-10
Chapter 3 Coalescer
3.1 Granular bed coalescer II-11
3.1.1 Filtration-based model II-11
3.1.2 Dimensional analysis-based model II-12
3.1.3 Model verification II-13
3.1.4 Conclusion and generalized model of granular bed II-14
coalescer
3.1.5 Generalized model for guide coalescer II-15
3.1.6 Generalized model for mixed bed coalescer II-16
3.1.7 Generalized model for pressure drop of granular bed II-16
coalescer and guided coalescer
3.2 Fibrous bed coalescer II-18
3.2.1 Dynamic fibrous bed coalescer model II-18
3.2.2 Simple fibrous bed coalescer model II-18
3.2.3 Model verification II-18
3.2.4 Conclusion and generalized model of fibrous bed coalescer II-21
3.2.5 Generalized model of random or disorderly fibrous bed II-23
coalescer
3.2.6 Generalized model for pressure drop of fibrous bed II-24
coalescer
Chapter 4 Dissolved air flotation
4.1 Dissolved Air Flotation (DAF) model for oily wastewater II-25
treatment
4.2 Model verification II-26
4.2.1 Modification of filtration-based model II-26
4.2.2 Population balance method II-28
4.3 Generalized model for DAF II-30
4.4 Generalized equations for pressurized water system calculation II-35
Chapter 5 Hydrocyclone
5.1 Two-phase hydrocyclone II-37
5.1.1 Trajectory analysis-based model II-37
5.1.2 Other models II-38
5.1.3 Model verification II-39
II-i
Contents
Contents (Con’t)
Page
5.1.4 Conclusion and generalized model of two-phase II-40
hydrocyclone
5.1.5 Generalized model for pressure drop of two-phase II-41
hydrocyclone
5.2 Three-phase hydrocyclone II-43
5.2.1 Model development and verification for liquid-liquid II-43
section
5.2.2 Model development and verification for solid-liquid section II-45
5.2.3 Generalized Model for pressure drop of three-phase II-46
hydrocyclone
Chapter 6 Membrane process
6.1 Ultrafiltration II-49
6.1.1 Resistance model II-50
6.1.2 Film theory based model II-52
6.1.3 Model verification II-53
6.1.4 Flux prediction for mixture of cutting oil microemulsion II-58
and macroemulsion
6.1.5 Theoretical flux prediction for batch cross-flow UF process II-60
6.1.6 UF efficiency II-63
6.1.7 Minimum and maximum transmembrane pressure and II-64
power required
6.1.8 Conclusion and generalized model of UF II-66
6.2 Nanofiltration and Reverse osmosis II-66
Chapter 7 Heteroazeotropic Distillation
7.1 Theoretical model II-69
7.2 Model verification II-72
7.3 Conclusion and generalized model of heteroazeotropic distillation II-72
II-ii
Part II Generalization of models for oil-water separation process design
Table
Page
Table 1.1 Summary of tested decanters and operating conditions II-6
Table 6.1 Summary of parameters of resistance model from UF researches on II-51
oilywastewater treatment (reference temperature = 20O C)
Table 6.2 Summary of parameters of film model from UF researches on oily II-54
wastewater treatment (reference temperature = 20O C)
Table 6.3a Summary of RO data on oily wastewater treatment II-67
Table 6.3b Summary of NF data on oily wastewater treatment II-68
Table 7.1 Heterotropic temperature and composition from various extractants II-72
II-iii
Contents
Figure
Page
Fig. 1.1 Schematic and typical removal efficiency curve of simple decanter II-3
Fig. 1.2 Schematic of PPI decanter II-4
Fig. 1.3 “Spiraloil” decanter a) Simple spiral b) Mixed spiral II-5
Fig. 1.4a Comparison between observed efficiency (1',2',3') and predicted II-6
efficiency (1,2,3) for Simple Spiral "Spiraloil" decanter
Fig. 1.4b Comparison between observed efficiency (1',2') and predicted II-6
efficiency (1,2) for Mixed Spiral "Spiraloil" decanter
Fig. 2.1 Drum and disk skimmer II-10
Fig. 3.1(a) Schematic diagram of granular bed coalescer, (b) photo of bed material II-11
with coalesced oil on their surface and (c) coalesced oil drops at the
discharge surface of bed
Fig. 3.2a Relation between droplet diameter VS. model's error II-14
Fig. 3.2b Comparison between observed efficiency and predicted efficiency from II-14
DAMAK's model
Fig. 3.3 Relation between observed pressure drop of granular bed coalescer and II-17
predicted upper & lower limits from Kozeny-Carman's porosity = 0.13 and 0.23
Fig. 3.4 Comparison between observed efficiency and predicted efficiency from II-19
SRIJAROONRAT's model, Verified by MA's and WANICHKUL's data
Fig. 3.5 Comparison between observed efficiency and predicted efficiency by II-
20TAPANEEYANGKUL's model for simple fibrous bed (Assume rotating speed = 450
rpm)
Fig. 3.6 Comparison between observed efficiency and predicted efficiency from II-21
modified SRIJAROONRAT's model (eq. 3.8b)
Fig. 3.7 Relation between observed efficiency and predicted efficiency from random II-23(or
disorderly) fibrous bed coalescer model and simple fibrous bed model
Fig. 4.1 Schematic diagram of DAF II-25
Fig. 4.2 Relation between theoretical efficiency factor and observed efficiency II-27
factor
Fig. 4.3 Relation between obseved efficiency and predicted efficiency of DAF II-27
from modified SIEM's model
Fig. 4.4 Relation between absolute pressure in pressure tank and dissolved quantity II-36
and released air volume
Fig. 5.1 Schematic diagram and trajectories of droplets in two-phase hydrocyclone II-37
Fig. 5.2 Comparison between observed efficiency and predicted efficiency from II-39
Ma's and Thew-Colman's models
Fig. 5.3a Relation between observed pressure drop (inlet/overflow) of Thew cyclone II-42
and predicted pressure drop
II-iv
Part II Generalization of models for oil-water separation process design
Fig. 5.3b Relation between observed pressure drop (inlet/underflow) of Thew cyclone II-42
and predicted pressure drop
Fig. 5.4 Three-phase hydrocyclone II-43
Figure (Con’t)
Page
Fig. 5.5 Relation between observed efficiency and predicted efficiency of II-44
liquid-liquid (Thew) part of three-phase hydrocyclone
Fig. 5.6a Relation between observed pressure drop (bar) across inlet and water outlet II-47
and predicted value from 2 approaches
Fig. 5.6b Relation between observed pressure drop (bar) across inlet and SS outlet II-48
and predicted value from 2 approaches
Fig. 5.6c Relation between observed pressure drop (bar) across inlet and oil outlet II-48
and predicted value from 2 approaches
Fig. 6.1 Typical schematic diagram of Cross-flow membrane process II-49
Fig. 6.2 Typical relation between flux and various parameters II-52
Fig. 6.3a Relation between flux and concentration at any recirculation velocity [38] II-52
Fig. 6.3b Typical characteristic curve of concentration VS. Flux II-
53(Log-Normal scale) [38]
Fig. 6.4 Relation between UF permeate flux and Transmembrane pressure at II-56
reference concentration (C) of = 4%, V = 1.4 m/s and Predicted relations at C = 2 and 8%
Fig. 6.5 Relation between observed and predicted flux by resistance model for II-57
ultrafiltration of macroemulsion 4% conc. and extend to cover other conc. by film model
Fig. 6.6 Comparison between predicted flux and observed flux for UF of micro/ II-59
macroemulsion mixture (Conc. shown as % by volume of concentrate)
Fig. 6.7 Relation between observed and predicted flux of micro/macroemulsion II-60
mixture from weighted average method between flux of whole micro and macroemulsion at the same total oil
concentration
Fig. 6.8a Relation between Flux VS. theoretical and observed permeate volume II-62
Fig. 6.8b Relation between time VS. theoretical and observed permeate volume II-62
Fig. 6.8c Relation between theoretical flux VS. concentration of oil in retentate II-63
Fig. 6.9 Relation between oil concentration VS. viscosity of emulsion II-65
Fig. 7.1 Isobar equilibrium diagram : Temperature-Concentration characteristic of II-70
immiscible binary mixture
Fig. 7.2 Graphical method to find heteroazeotropic temperature II-70
Fig. 7.3 Graphical method to find dew curves II-71
II-v
Part II Generalization of model for oil-water separation process design
45 II-1
Chapter 1 Decanting
Chapter 1 Decanting
Decanting or sedimentation is a non-accelerated process, which every input
parameters in STOKES law are not modified. According to the researches reviewed in Part I,
there are several types of decanters studied in GPI laboratory, i.e.,
The model that governs the operation of the process is derived from comparing the
time required for the droplet to reach the surface with retention time of the tank. Fig. 1.1
shows again the diagram of decanting process. From the figure, the longest path to reach the
surface is the path starts at the bottom of the tank. The smallest droplet size that can reach the
surface is called the cut size. The droplet of cut size or bigger is always separated from
wastewater stream with 100% removal efficiency.
The smaller droplet can be also separated providing that it enters the tank near the
water surface. When uniformly distributed influent flow is valid, which is true for almost all
of properly designed tank, the removal efficiency of the droplets smaller than cut size is
proportional to its corresponding rising velocity. From these concepts, the models of
decanting process are as shown in eq. 1.1 to 1.4.
⎛Q⎞ {1.1}
U =⎜ ⎟
dc ⎝S⎠
From STOKES law
Δρ ⋅ g ⋅ d 2 {1.2}
U =
d 18μ c
1/2
⎛ 18Qμ c ⎞
Then d c = ⎜⎜ ⎟⎟ {1.3}
⎝ Δρ ⋅ g ⋅ S ⎠
For oil droplet size, d ≥ cut size,dc
η = 100% {1.4a}
d
For oil droplet size, d ≤ cut size,dc
U
η = d ⋅ 100% {1.4b}
d U
dc
1 d max
ηt =
Q
Q
C
(
∑ η d ⋅ C od ⋅ 100% ) {1.4c}
out o d min
d max
Q out = Q −
Q
∑η C od {1.4d}
ρd
d
d min
46 II-2
Part II Generalization of model for oil-water separation process design
U
Influent d > cut size V Effluent
d = cut size
d < cut size
ηd
Zone 1 Zone 2
d < dc d = or > d c
d
dc
Fig. 1.1 Schematic and typical removal efficiency curve of simple decanter
Typical characteristic of the removal efficiency of decanter is as shown in fig. 1.1. The
equations are valid while these conditions are satisfied i.e.,
1. Reynolds number, Re, of droplet is between 10-4 to 1, which is the range that
STOKES law is valid.
2. The oil droplets are uniformly distributed across the cross section area of the
tank.
3. The oil droplet is spherical, which is normally true.
The model that governs the operation of the process is modified from the model of
simple decanter, as shown in eq. 1.5. From the equation and figure, it can be implied that the
simple tank is divided into (N+1) small decanters.
47 II-3
Chapter 1 Decanting
H
Influent Effluent
D
Inserted plates
(No. of plates = N)
1/2
⎛ 18Qμ ⎞
dc = ⎜ c ⎟ {1.5}
⎜ ΔρgS (N + 1) ⎟
⎝ P ⎠
Where Sp =
Inserted plate area
N =
Numbers of inserted plates
L =
Length of inserted plates
H =
Rising distance of oil drop, in this case, distance between inserted
plates
α = Inclination angle, related to horizontal axis
When incline plates are used, replace Sp with Sp cos α.
Removal efficiency can be calculated using eq. 1.4. Typical characteristic of the
removal efficiency of decanter is identical to simple decanter’s, as shown in fig. 1.1.But the
cut size of PPI tank will be smaller than the simple decanter’s, providing that they are the
same size. The equations are valid while these conditions are satisfied i.e.,
1. The tank is operated under laminar flow regime. Reynolds number, Re, is
between 10-4 to 1, which is the range that STOKES law is valid.
2. The oil droplets are uniformly distributed across the cross section area of the
tank.
3. The oil droplet is spherical, which is normally true.
4. The plates are identical in size and are inserted evenly and in parallel.
General model for calculating the cut size, when H, L and A can be clearly defined.
1/2
⎛ 18HQμ c ⎞
d c = ⎜⎜ ⎟⎟ {1.9a}
⎝ ΔρgLA ⎠
48 II-4
Part II Generalization of model for oil-water separation process design
Removal efficiency can be calculated using eq. 1.4. From the equations, we can see
that the models of simple decanters and PPI are modified forms of eq. 1.9 by simple relations
of flow velocity and tank geometry. However the models described before are derived from
basic rectangular tank and flat insertion plates.
But, in real life situation, decanters are designed or produced in various forms, such as
corrugated plate inserted tank, concentric annular insertion decanter, etc. So, sometimes, it is
very difficult to define H. Then, we propose to simplify the general model by neglecting
complicate analyzing to define H, and using concept of decanting area (Sd) instead. Sd is
calculated from the sum of every surface area within the decanter that can intercept oil
without considering whether the values H of these areas are identical or not. The other form
of general model is shown in eq. 1.9b.
1/2
⎛ 18Qμ ⎞
dc = ⎜ c ⎟ {1.9b}
⎜ Δρ ⋅ g ⋅ S ⎟
⎝ d ⎠
To verify the theoretical model, we select the research of CHERID [4] on 2 sets of the
“SPIRALOIL” decanter, i.e.,
• “Simple Spiraloil”; fabricated from concentric annular plates as shown in fig. 1.3a
• “Mixed-spiral Spiraloil”; ”; fabricated from concentric annular plates with
corrugated plates spacer as shown in fig. 1.3b
We will use these decanters to compare the removal efficiency calculated from model
to experimental result from the research. Geometry of the decanter and operating parameters
used in the experiment are summarized in Table 1.1 and Annex A1.
Annular plates
H
Solid core,
radius = r
a) b)
49 II-5
Chapter 1 Decanting
100.00%
90.00%
1 1' 3 3'
80.00%
V = 0.4 cm/s (1, 1')
Removal efficiency (%)
70.00%
V = 0.8 cm/s (2, 2')
60.00%
V = 1.6 cm/s (3, 3')
50.00%
2 2'
40.00%
30.00%
20.00%
10.00%
0.00%
0 10 20 30 40 50 60
Droplet diameter (micron)
Fig. 1.4a Comparison between observed efficiency (1',2',3') and predicted efficiency (1,2,3) for Simple Spiral "Spiraloil" decanter
100.00%
90.00%
1' 1 (V = 0.5 cm/s)
80.00%
Removal efficiency (%)
70.00%
60.00%
2' 2 (V = 1.5 cm/s)
50.00%
40.00%
30.00%
20.00%
10.00%
0.00%
0 10 20 30 40 50 60
Droplet diameter (micron)
Fig. 1.4b Comparison between observed efficiency (1',2') and predicted efficiency (1,2) for Mixed Spiral "Spiraloil" decanter
50 II-6
Part II Generalization of model for oil-water separation process design
Comparison graphs between observed efficiency and predicted efficiency from model
for both Spiraloil decanters are shown in fig. 1.4. These graphs show that;
1. To solve oil or hydrocarbons removal efficiency of decanter, the cut size of the
decanter will be determined first. Then, graded efficiency (efficiency of each size
of droplet) and then total removal efficiency can be determined.
2. The cut size of the decanter can be determined from eq. 1.9. When configuration
of decanter is not complicate and rising distance of oil drop to interceptor can be
clearly determined, Using eq. 1.9a will give very accurate prediction. However,
when configuration of the decanter is so complicate to determine the rising
distance accurately, eq.1.9b provides relatively accurate result for the cut size.
For PPI tank, the cut size can be calculated from eq. 1.5, which is the modified
form of eq. 1.9a.
1/2
⎛ 18HQμ c ⎞
d c = ⎜⎜ ⎟⎟ {1.9a}
⎝ ΔρgLA ⎠
1/2
⎛ 18Qμ ⎞
dc = ⎜ c ⎟ {1.9b}
⎜ Δρ ⋅ g ⋅ S ⎟
⎝ d ⎠
1/2
⎛ 18Qμ ⎞
dc = ⎜ c ⎟ {1.5}
⎜ ΔρgS (N + 1) ⎟
⎝ P ⎠
51 II-7
Chapter 1 Decanting
4. To use the models described above, the following conditions need to be satisfied
and the assumptions and limitations would be noted.
1) Reynolds number, Re, of oil droplet is between 10-4 to 1, which is the range
that STOKES law is valid.
2) The oil droplets are uniformly distributed across the cross section area of
the tank, which can be achieved by proper design of inlet chamber. And the
oil droplet is spherical, which is normally true.
3) For PPI or others forms of plate inserted decanter, the plates are identical in
size and are inserted evenly and horizontally. For PPI tank with incline
plates, Sp in eq. 1.5 will be replaced by Sp cos α. α is the inclination angle,
related to horizontal axis.
4) If the decanter or the inserted plates are inclined, the rising distance will be
the spacing between plates, but will be measured in vertical direction. So
the shortest distance is obtained from the same spacing between plates,
when the plates are located horizontally.
5) Prediction of cut size from eq.1.9b, even with its simplification, is
relatively accurate for the cut size larger than 20 microns.
6) For droplets smaller than 20 microns, they are subject to Brownian motion
and cause error in the prediction of the efficiency. So it is recommended to
avoid using the decanter for the wastewater with majority part of oil
droplets smaller than 20 microns. However, if these small droplets are the
minority part of pollutants, the models can be used to predict the efficiency
without any harm because its prediction is usually lower than observed
value, thus make the prediction result on the safe side.
52 II-8
Part II Generalization of model for oil-water separation process design
Chapter 2 Skimmer
Skimmer is the equipment designed to remove oil film or layer from water surface. It
is superior to basic hydraulic elements such as bell-mouth pipe or weir for its oil-water
selectivity. It will remove relatively water-free oil. According to the researches reviewed in
Part I, there are 2 types of skimmers studied in GPI laboratory, i.e., drum skimmer and disk
skimmer.
0.486
3.035D1.541N1.541ν o L
P= {2.1}
g 0.514
η t = 100% {2.2}
The model will be valid when these conditions are satisfied, i.e.;
53 II-9
Chapter 2 Skimmer
D Scrapper Scrapper
Oil layer I
Water Oil layer
Water
a) b)
0.452 1.17
1.328D 1.258 N 1.212 ν o I
P= {2.3}
g 0.332
η t = 100% {2.2}
The model will be valid when these conditions are satisfied, i.e.;
54 II-10
Part II Generalization of model for oil-water separation process design
Chapter 3 Coalescer
Coalescer is an accelerated separation process that is designed to promote coalescing
of oil droplets into bigger oil drop, which can be separated easily by relatively small decanter.
There are several types and modification of coalescer studied in GPI laboratory, i.e.,
OUT:
Large drop Discharge
V screen
Collector
H size =dp,
Void ratio = ε
IN: Inlet
Micro drop V screen/support
Dia. = d
a) b) c)
Fig. 3.1 (a) Schematic diagram of granular bed coalescer, (b) photo of bed material
with coalesced oil on their surface and (c) coalesced oil drops at the
discharge surface of bed
The method is proposed by AURELLE [3]. In his study, AURELLE divided the
mechanisms taking place with in coalescer bed into 3 steps, i.e.;
AURELLE suggested that step 2 and step 3 can be optimized by using oleophilic and
hydrophilic material as coalescer bed and discharge screen, respectively, as well as keeping
the feed flowrate within optimum range. Then step 1 will become rate determining step of the
55 II-11
Chapter 3 Coalescer
1 d max
ηt =
Q
Q
⋅
C
⋅ ∑ η ⋅C
d od
% ( ) {3.4a}
d
out o min
d max
Q =Q −
Q
∑η C od {3.4b}
ρd
out d
d min
The model will be valid when these conditions are satisfied, i.e.;
• The model is valid when the shape of the collector is relatively spherical.
• The collector shall be wetted by dispersed phase. In case of direct emulsion (oil in
water emulsion), the collector, then, shall be oleophilic. In this case, oleophilic
resin is recommended.
• Range of empty bed velocity shall not be greater than 0.35 cm/s (12.6 m/h)
• Density difference between dispersed phase and continuous phase shall be
approximately 200 kg/m3.
• The model is developed for inlet oil concentration between 100-200 mg/l.
• At velocity < 0.35 cm/s, efficiency of the coalescer is independent of velocity.
Beyond this range, The efficiency will decrease when the velocity increases. The
rate of the decreasing of efficiency varies with size and wettability and surface
roughness of collector.
• The key assumption of this model is that mechanisms in steps 2 and 3 of the
coalescer are optimized.
This research has been studied thoroughly and covered every important parameter. But
the last assumption, related to mechanisms in steps 2 and 3, is difficult to verify. The evident
is clearly shown in eq.3.2 where the relation between ηexp and ηtheo is not linear. This means
there are other factors, besides the 3 interception steps, which should be included in the ηtheo.
However this filtration-based model is good for understanding the effect of various
parameters on coalescer efficiency.
The method is proposed by DAMAK [9]. The model is based on classic dimensional
analysis, which is the efficient tool when exact theory of the processes can not be established,
as described in the section 3.1.1. DAMAK’s model is shown in eq.3.5.
56 II-12
Part II Generalization of model for oil-water separation process design
⎛ d H ρ dpV μd Δρ ⎞
η = ⎜ 0.58( ) 0.2 ( ) 0.12 ( c ) − 0.08 ( ) 0.09 ( ) 0.09 ⎟ ⋅ 100% {3.5}
d ⎜ dp dp γ μc ρ ⎟
⎝ o/w c ⎠
1 d max
ηt =
Q
Q
⋅
C
⋅ ∑ η ⋅C
d od
% ( ) {3.4a}
out o d min
d max
Q =Q −
Q
∑η C od {3.4b}
ρd
out d
d min
• The model is tested at the range of dp from 0.36 to 0.94 mm. and interfacial tension
of dispersed phase (oil) 11 to 42 dyne/cm. (T.I.O.A, heptane, anisole, toluene and
kerosene)
• The velocity tested is in the range of 0.09 to 0.54 cm/s.
• Different density between dispersed phase (oil) and continuous phase (water) is
between 83 to 314 kg/m3.
• The bed material used is spherical glass bead with silicon coated.
• The inlet concentration of hydrocarbon tested is around 1,000 mg/l.
Inspite of the fact that AURELLE’s model is theoretical based and understandable,
from experimental conditions of the two models stated above, DAMAK’s model covers wider
range of oil and accounts for every parameter that affects coalescer operation. So, from
application and design point of view, it is more reasonable here to use the second model as the
generalized model of coalescer.
However, DAMAK’s model is tested at greater concentration of inlet oil (1,000 mg/l)
than AURELLE’s (100-200 mg/l). In theory, the greater the concentration, the higher the
probability of coalescing between droplets. So it is interesting to verify DAMAK’s model
using AURELLE’s test data. The data used for model verification is tabulated in Annex A2.1.
However, firstly, difference between predicted and observed efficiency of both models
have been checked to eliminate inaccurate or error data. Fig. 3.2a shows that, at droplet size
smaller than 10 microns, the differences between predicted and observed efficiency of both
models are very high. This may be caused by the re-fragmentation of coalesced oil by shear
force, which both models can not predict. The error may also come from inaccurate
measurement of these tiny droplets. Then, to be on the safe side, the droplet smaller than 10
microns will not be considered and assumed that their removal efficiencies are zero.
Comparison between AURELLE’s observed data and predicted data from DAMAK’s
model (after error data removal) is as shown in fig. 3.2. From the graph, it shows that the error
in prediction of DAMAK’s model for the whole range of wastewater tested by AURELLE
and DAMAK is not greater than 10%. So DAMAK’s model can be used as the generalized
model for granular bed coalescer.
57 II-13
Chapter 3 Coalescer
100%
90%
80%
70%
60%
50%
Error (%)
40%
30%
20%
10%
0%
-10%
-20%
-30%
0.0E+00 5.0E-06 1.0E-05 1.5E-05 2.0E-05 2.5E-05 3.0E-05 3.5E-05 4.0E-05 4.5E-05
Droplet diameter (m)
80%
70%
60%
50%
+10%
40%
30% -10%
20%
10%
0%
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Observed efficiency %
Fig. 3.2b Comparison between observed efficiency and predicted efficiency from DAMAK's model
From model verification result, we can conclude and propose the generalized model as
well as its limitation as follow,
⎛ ρ dpV ⎞
⎜ d H μd Δρ ⎟
η = ⎜ 58( ) 0.2 ( ) 0.12 ( c ) − 0.08 ( ) 0.09 ( ) 0.09 ⎟⎟ ⋅ 100 %
{3.5}
d ⎜ dp dp γ μc ρ
⎝ o/w c ⎠
58 II-14
Part II Generalization of model for oil-water separation process design
1 d max
ηt =
Q
Q
⋅
C
⋅ ∑ η ⋅C
d od
% ( ) {3.4a}
out o d min
d max
Q =Q −
Q
∑η C od {3.4b}
ρd
out d
d min
2. To use the models described above, the following conditions need to be satisfied
and the assumptions and limitations would be noted;
For guide coalescer, high porosity oleophilic material, such as steel wool, will be
placed next to downstream end of the granular and extended up to water surface (actually, up
to oil/water interface of the decanter). Coalesced oil drop will channel along this material until
it combines with oil layer at the water surface. This material is called “guide”.
Installation of guide helps preventing formation of oil mousse or jet, which normally
occurs in classical coalescer at high velocity or high concentration of oil. Thus, the maximum
velocity before formation of mousse or jet will occur (so called critical velocity) of the guide
coalescer is, at least, 1.5 times greater than usual [6].
Unfortunately, we do not have sufficient recorded data to develop the model for guide
coalescer. However, it is proven that, at velocity range below critical value, the efficiency is
approximately velocity-independent [3], [6]. It, also, can be confirmed by eq. 3.5, which
shows that the exponent of V is very low (–0.08). Then, at recommended range of velocity,
V-0.08 is approximately constant.
So, from this fact, we can estimate the efficiency of guide coalescer by using classical
model of coalescer (eq. 3.5) with additional precautions and assumptions as follow,
• When V < 0.54 cm/s: Use eq. 3.4 and 3.5 directly.
• When 0.54 < V < 0.8 cm/s (1.5 times of 0.54): Use eq. 3.4 and 3.5 by using V =
0.54 cm/s for calculation. Using the real velocity instead of 0.54 cm/s will result in
59 II-15
Chapter 3 Coalescer
Mixed bed coalescer is another modified form of granular bed coalescer, used for
mixed direct/inverse emulsion separation, which is usually found in liquid-liquid extraction
process. In mixed bed coalescer, the bed will consist of separate layers of oleophilic and
hydrophilic materials, placed in series in the same column. From research [6], ratio of
oleophilic and hydrophilic material and order or configuration of column (upper hydrophilic
layer/lower oleophilic layer or vice versa) depends on wastewater characteristic. So it is
difficult to determine the efficiency of the coalescer by fixed equation. In this case, it is
recommended to perform pilot test to find optimum design criteria.
3.1.7 Generalized model for pressure drop of granular bed coalescer and guided
coalescer
Many GPI researches provide data of pressure drop of granular bed coalescers. But
there is no model proposed and, unfortunately, there is insufficient data to develop new
pressure drop model by dimensional analysis. So we have to develop the model based on
available theory. According to the structure of coalescer, its components are similar to that of
a deep bed filter. Then, we will use pressure drop models of deep bed filter as basis to develop
coalescer’s pressure drop model.
From normal practice, porosity may be used more often to describe the bed. So we
will use Kozeny-Carman’s equation (eq. 3.6) to predict coalescer pressure drop (ΔP), in m of
water.
180Hμ c V(1 − ε) 2
ΔP = {3.6}
ρ m ⋅ g ⋅ dp 2 ⋅ ε 3
All variables except porosity (ε) will be determined by designer. For the porosity of
coalescer bed, from our literature review, there is no data provided in any research. Then we
will use the pressure drop data from researches to calculate back to find corresponding
porosity. From many researches [3], [26], [27], it shows that bed porosity varies with bed
depth and can be divided into 2 zones, i.e.,
60 II-16
Part II Generalization of model for oil-water separation process design
• Lower zone or critical zone: This zone represents effective zone of coalescer bed.
The maximum height of this zone is called “critical height (Hc)”. When bed height
is greater than critical height, the efficiency will increase only slowly (From eq.
3.5: η ∝ H 0.12). In this zone, the bed will be soaked with oil so the porosity will be
low.
• Upper zone: If the bed is higher than Hc, practically, all of oil will be trapped in
critical zone. Then in higher zone, there will be enough oil in lower zone to flow
continuously through the bed in form of “flow channeling”. So the porosity in this
zone will be lower than critical zone.
We use data from various researches [3], [26], [27] to verify the value of bed porosity.
The verification result is shown in Annex A2.2 and fig. 3.3. We can conclude that pressure
drop of granular bed can be calculated by Kozeny-Carman’s equation (eq. 3.6), using the
following recommendations, i.e.,
• When Hc is known (from literatures, etc.), pressure drop in the lower and upper
part of bed can be calculated separately, using eq. 3.6. Recommended porosity (ε)
for the lower (critical) part of bed (H<Hc) is between 0.14 to 0.19. Recommended
porosity for the upper part of bed (H>Hc) is between 0.23 to 0.30.
• If it is certain that H design < Hc, use single step calculation with ε = 0.14 - 0.19.
• However, Hc is usually unknown, then it is recommended to use single step
calculation with ε = 0.13 and 0.23 to estimate minimum and maximum pressure
drop respectively (as shown in fig. 3.3).
• Because of the fact that “guide” of guided coalescer has relative high porosity (0.9
approx.), then, The pressure drop is very low, compared to granular bed, and can
be negligible. So eq. 3.6 can also be used for guided coalescer.
160
Observed data
140
Upper limit (porosity = 0.13)
120 Lower limit (porosity = 0.23)
Pressure drop (m)
100
80
60
40
20
0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31
Run number
Fig. 3.3 Relation between observed pressure drop of granular bed coalescer and predicted upper & lower limits from Kozeny-
Carman's porosity = 0.13 and 0.23
61 II-17
Chapter 3 Coalescer
There are 2 main categories of fibrous bed coalescers, i.e., simple fibrous bed
coalescer and dynamic (or rotating) fibrous bed coalescer. The latter is the modified form of
the former, by the installation of driving unit to drive the bed.
After reviewing existing experimental data, it shows that each research presents only
some parameters related to its own objectives. However we have tried to develop a model,
62 II-18
Part II Generalization of model for oil-water separation process design
using dimensional analysis method, from SRIJAROONRAT’s data [10], which provided more
details than others. And then we verified the model with the data from other researches [11],
[16]. The proposed model is shown in eq. 3.8a. In our research, we will call it
“SRIJAROONRAT’s simple fibrous bed model”.
⎛ ρ VD d d H ⎞
η = ⎜ 45.005( c ) − 0.77 ( ) 0.18 ( F ) − 0.18 ( ) 0.694 ⎟ ⋅ 100 % {3.8a}
d ⎜ μ D D D ⎟
⎝ c ⎠
100.0%
90.0%
80.0%
70.0%
Predicted efficiency (%)
60.0%
+20 %
50.0%
40.0%
30.0% -20 %
SRIJAROONRAT's data
20.0%
MA's data
10.0% WANICHKUL's data
0.0%
0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0%
Observed efficiency (%)
Fig. 3.4 Comparison between observed efficiency and predicted efficiency from SRIJAROONRAT's model, Verified by MA's
and WANICHKUL's data
Comparison between observed and predicted efficiency is shown in fig. 3.4. From the
graph, it shows that;
• The proposed model is valid for empty bed velocity up to 2 cm/s (72 m/h) and
concentration of inlet oil up to 1000 mg/l.
• For higher empty bed velocity, there is not any detailed data on graded efficiency
to verify the model. However, SRIJAROONRAT’s research shows that the total
(or average) efficiency, more or less, still conforms to eq. 3.8 at the velocity as
high as 5 cm/s and that the equation tends to underestimate the efficiency.
• For high inlet oil concentration, for example in case of WANICHKUL’s research,
The model, again, tends to underestimate the efficiency.
• Because of the fact that there is not enough data to find the effect of porosity,
porosity is omitted in the proposed model.
From the observations above, SRIJAROONRAT’s simple fibrous bed model does not
include effect of porosity. However, from TAPANEEYANGKUL [8] research, he shows that
the efficiency of dynamic coalescer, operating at low speed, is almost identical to the simple
coalescer’s and his model readily includes the effect of porosity. So it may be a matter of
interest to verify if the model of dynamic coalescer is possible to apply to simple coalescer by
assuming a low rotational speed into the model.
63 II-19
Chapter 3 Coalescer
For this, data from several researches [10], [11], [16] have been used to verify
TAPANNEYANGKUL’s model. The data, used to verify the model, has been limited to the
droplet size of 10 microns and greater. For smaller droplet, it is difficult to measure the
concentration of these droplets accurately. So observed data is not complete and seems
erroneous. Comparison between observed and predicted efficiency is shown in fig. 3.5.
⎛ ρ VD d d H ⎞
η = ⎜104.5( c ) − 0.77 ( ) 0.18 ( F ) − 0.18 (1 − ε )0.35 ( ) 0.694 ⎟ ⋅ 100 % {3.8b}
d ⎜ μ D D D ⎟
⎝ c ⎠
120.0%
100.0%
Predicted efficiency (%)
80.0%
+20%
60.0%
40.0%
-20%
20.0%
0.0%
0.0% 20.0% 40.0% 60.0% 80.0% 100.0% 120.0%
Observed efficiency (%)
Fig 3.5 Comparison between observed efficiency and predicted efficiency by TAPANEEYANGKUL's model for simple
fibrous bed (Assume rotating speed = 450 rpm)
64 II-20
Part II Generalization of model for oil-water separation process design
100.0%
90.0%
80.0%
70.0%
Predicted efficiency (%)
60.0%
+20 %
50.0%
40.0%
30.0% -20 %
SRIJAROONRAT's data
20.0%
MA's data
10.0% WANICHKUL's data
0.0%
0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0%
Observed efficiency (%)
Fig. 3.6 Comparison between observed efficiency and predicted efficiency from modified SRIJAROONRAT's model (eq.
3.8b)
From model verification result, we can conclude and propose the generalized model as
well as its limitation as follows,
1 d max
ηt =
Q
Q
⋅
C
⋅ ∑ η ⋅C
d od
% ( ) {3.4a}
out o d min
d max
Q =Q −
Q
∑η C od {3.4b}
ρd
out d
d min
65 II-21
Chapter 3 Coalescer
• Diameter of fiber is around 100 to 300 microns and diameter of coalescer bed
is around 11.5 cm. Using bigger coalescer diameter may cause deflection at
the end of fibers from longer overhung length, which may cause error in
calculation.
• The beds, used in the experiment, are “bottle brush” types, made of
polyamide or polypropylene with stainless steel shaft.
• It is recommended to use the model only for the droplet size of 10 microns or
greater. For smaller droplet, the model can also be applied, but for
comparison purpose only.
3. Internal diameter of coalescer casing, which contains the bed, should be as close
to the diameter of the bed as possible to avoid channeling problem.
1 d max
ηt =
Q
Q
⋅
C
⋅ ∑ η ⋅C
d od
% ( ) {3.4a}
out o d min
d max
Q =Q −
Q
∑η C od {3.4b}
ρd
out d
d min
66 II-22
Part II Generalization of model for oil-water separation process design
• Diameter of coalescer bed tested is around 5.0 cm. Using larger coalescer
diameter may cause deflection at the end of fibers from longer overhung
length, which may cause error in calculation.
• The beds used in these researches vary from “bottle brush” type, simple
spiral type and combination of internal bed of “simple spiral” and concentric
“coil spring” –like external bed with the tip of the fibers pointed to center
line. However, they are all oleophilic. There is some difference in efficiency
between each type, but there is too few data to make a conclusion. However,
because of its rigidity, the “simple spiral in coil spring- like” bed tends to
operate more stable without the decrease in efficiency with time, while others
tend to be deflected by weight of accumulated oil drops. In fact, this type of
bed is invented to take advantage of spiral bed for its non-clogging and
disorderly bed for its rigidity.
3. Internal diameter of coalescer casing, which contains the bed, should be as close
to the diameter of the bed as possible to avoid channeling problem.
There is another special case of simple fibrous bed coalescer that uses random or
disorderly fibrous material (such as metal wool, etc.) as coalescer bed. SRIJAROONRAT also
studies this type of coalescer. In her research, she shows that the removal efficiency of this
coalescer is higher than that of coalescer that uses brush type bed. For this, it can be
concluded that tortuosity of bed also affects the removal efficiency. We use her data to
develop the model, based on dimensional analysis, as shown in eq. 3.9. So we will call it
“SRIJAROONRAT’s random fibrous bed model”. However, this model is developed from
rather small set of data. So we have tried to apply the generalized model in eq. 3.8b to this
type of coalescer. Comparison between eq. 3.9, 3.8b and observed value is shown in fig. 3.7.
⎛ ρ VD d d H ⎞
η = ⎜ 3.35( c ) − 0.23 ( ) 0.03 ( F ) − 0.03 ( ) 0.36 ⎟ ⋅ 100 % {3.9}
d ⎜ μ D D D ⎟
⎝ c ⎠
110.0%
100.0% SRIJAROONRAT's disorderly
bed model
90.0%
Predicted efficiency (%)
Fig. 3.7 Relation between observed efficiency and predicted efficiency from random (or disorderly) fibrous bed coalescer
model and simple fibrous bed model
67 II-23
Chapter 3 Coalescer
From the graph, it shows that SRIJAROONRAT’s random fibrous bed model (eq. 3.9)
can accurately predict the efficiency of the coalescer. SRIJAROONRAT’s simple fibrous bed,
(eq. 3.8b) is used to calculate the efficiency of the coalescer for comparison. However, from
the graph, it shows that the result from eq. 3.8b tends to underestimate the efficiency from 2 to
6 times. From this, we recommend the following procedure to calculate the efficiency of
metal wool bed coalescer.
3. Internal diameter of coalescer casing, which contains the bed, should be as close
to the diameter of the bed as possible to avoid channeling problem.
Many researcher [8], [10], [11], [16] observed pressure drop of fibrous bed coalescers
and reported that these coalescer causes very low pressure drop due to very high porosity of
their beds. There is no proposed model on pressure drop.
In order to calculate the pressure drop, we recommend to use any general piping loss
equations, such as Darcy’s, Colebrook-White’s or Hazen-William’s equation with the safety
factor of 2 to 5, multiplied to the actual length of the bed. However, the pressure drop of
fibrous bed coalescer is normally low (< 104 N/m2), compared to piping system pressure drop.
68 II-24
Part II Generalization of model for oil-water separation process design
4.1 Dissolved Air Flotation (DAF) model for oily wastewater treatment
For Dissolved Air Flotation, air bubbles are generated from pressurized (or air –
saturated) water. At GPI laboratory, the model of DAF for oily wastewater treatment is
proposed by SIEM [12]. In his study, SIEM applies filtration-based model for granular bed
coalescer, proposed by AURELLE [3], by assuming the air bubble as collector (or filter
media), as shown in eq. 4.1. However, in this case, the media is also moving. Schematic
diagram of DAF is shown in fig. 4.1.
Clarified Separated
water Droplet
/ bubble
agglomerate
Air
bubble
Oil droplet
Pressurized Oily
water system wastewater
⎛ 3 Φ H ⎞
⎜ (− (α η ) )⎟
2 AV exp d
⎜
η = ⎜1 − e b ⎟ ⋅ 100 % {4.1}
d ⎟
⎜ ⎟
⎜ ⎟
⎝ ⎠
η =η + η Int + η {4.2a}
theo sed diff
Δρgd 2 {4.2b}
η =
sed 18μ8 r
69 II-25
Chapter 4 Dissolved air flotation
3 d
η Int = ( ) 2 {4.2c}
2 d
b
KT 2/3 {4.2d}
η = 0.9( )
Diff μdVr d
b
Vr = |V-Ub| {4.2e}
(αη exp ) = 0.0074(η ) 0.507 {4.3a}
theo
From the model in section 4.1, air or gas flowrate (Φ) and the term “AV” can be
written in form of Qt as shown in eq. 4.4.
Φ Q pw Conc(air)
= ⋅ {4.4a}
AV Qt ρ
air
Qpw
=( )x {4.4b}
Qt
Normally, under certain design condition, Qpw/Qt is constant. Solubility of air in water
(Conc(air)) and air density are intrinsic (internal) property, depends on pressure, and
temperature of pressurized water, which are constant for any given pressurized water system.
Then, from eq. 4.4, it shows that the term “Φ/(AV)” is flow-independent.
From, eq. 4.2, it shows that the effciency factors vary with flowrate via relative
velocity between air bubble and oil droplet. Rising velocity of bubble (Ub) is calculated by
STOKE’s law, so it does not depend on wastewater flowrate. However, if we consider eq.
4.2d, it can be implied that if we lower the flowrate until V = Ub, Vr is, therefore, equal to 0.
Or when V >> U, it will seem to some one that happen to be on an oil droplet, which will be
carried along with the flow, that he run pass very slow bubble, or bubble will stay in the
reactor longer than oil drop. This cannot be true because the bubble will be carried along with
the flow as well. Furthermore, from its lower density and its bigger size, the bubble will
usually rise up faster than oil drop at the same diameter.
In fact, relative velocity (Vr) is equal to difference between absolute velocity of bubble
(V+Ub) and flow velocity of water (V) (eq. 4.2f). If we replace Vr with Ub, it will cause some
changes in eq. 4.3a. We have already recalculated the eq. 4.3a (see fig. 4.1) and found that it
can be rewritten as shown in eq. 4.3b (modified SIEM’s model). Fig. 4.2 shows comparison
between observed efficiency and predicted efficiency calculated from eq. 4.1, 4.2a to 4.2d,
4.2f and 4.3b. From the graph, prediction error is about 20%.
Vr = V+Ub-V = Ub {4.2f}
(αη exp ) = 0.009005(η ) 0.5919 {4.3b}
theo
70 II-26
Part II Generalization of model for oil-water separation process design
η η
-9.0E+00
-8.0E+00
-7.0E+00
ln (Observed efficiency)
-6.0E+00
y = 0.5919x - 4.71
-5.0E+00 R2 = 0.9821
-4.0E+00
-3.0E+00
-2.0E+00
-1.0E+00
0.0E+00
0.0E+00 -1.0E+00 -2.0E+00 -3.0E+00 -4.0E+00 -5.0E+00 -6.0E+00 -7.0E+00
ln(Theoritical efficiency)
Fig. 4.2 Relation between theoretical efficiency factor and observed efficiency factor
120.0%
110.0%
100.0%
90.0%
Predicted efficiency
80.0%
70.0%
60.0%
50.0%
+ 20%
40.0%
30.0%
20.0%
- 20%
10.0%
0.0%
0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0%
Observed efficiency
Fig. 4.3 Relation between obseved efficiency and predicted efficiency of DAF from modified SIEM's model
However, since we replace Vr with Ub, it is interesting to note that the proposed model
(eq. 4.1 to 4.2a to d) is mathematically flow-independent. In fact, the effect of wastewater
flowrate, sometimes described in form of velocity or retention time, is studied by many
researchers. It is widely accepted that DAF efficiency varies with retention time. So,
considering SIEM’s research, it can be interpreted that the effect of retention time is already
included in eq. 4.3. Since eq. 4.3 is evaluated from one set of operating condition and
retention time (approx. 25 minutes), it may be valid only for that condition.
To expand valid range of model, we need to verify or adjust the model by other sets of
data. However, from literature review, we cannot find enough data to do so. Then we have to
find theoretical criteria or equation that allow us to estimate the effect of retention time on
removal efficiency.
71 II-27
Chapter 4 Dissolved air flotation
i = 0 to imax
Φ {4.5c}
N=
π 3
d
6 b
no and ni represent the number of oil droplet which is free and attached by i bubbles
respectively. κ represents collision rate constant, from Saffman and Turner’s (1956)
coagulation theory, and β represents adhesion efficiency or probability that the collision
between oil drop and bubble will be successful. Removal efficiency can be written as (ni/n0),
which can be achieved by integrating eq. 4.5.
To integrate eq. 4.5, complex numerical method is required. MATSUI and LEPPINEN
[34], [37] solve the equation by Laplace transforms and suggest the solution as shown in eq.
4.6.
i
⎛ ⎛⎜ κτ ⎞⎟ ⎞
⎜ ⎜ ⎟ ⎟
⎜ ⎟
n ⎜ ⎜ d 2 /d 2 ⎟ ⎟
i = x : i ⋅ e (− κτ) ⎜ e ⎝
⎜ ⎟
b ⎠ − 1⎟ {4.6a}
N ⎜ ⎟
⎜ ⎟
⎜ ⎟
⎝ ⎠
i = 0 to imax –1
x(x − 1)...(x − (i − 1))
x :i = {4.6b}
i(i − 1)...(2)(1)
x = d 2 /d 2 {4.6c}
b
72 II-28
Part II Generalization of model for oil-water separation process design
It should be noted that eq. 4.8 is about the same form as eq. 4.1, but the value of κ,
represented by eq. 4.6d, clearly represents effect of every interesting parameter, including
retention time. The collision rate κ can be compared to the exponent term in eq. 4.1, as shown
in eq. 4.9a and 4.9b.
6 3 Φ H
κτ = aG(1 + (d/d )) 3 Φβ τ = (α η exp ) {4.9a}
π b 0 2 AV d
b
If “x” represents the variable Φ or τ that we want to vary from SIEM’s while another
variable still conforms to SIEM’s condition, eq. 4.9c can be rewritten as show below.
η = 1 − e − A⋅x {4.9d}
Where A= constant
If
x = B.x ref {4.10a}
Where B = Constant
Xref = x at SIEM’s condition
Then
( − Ax)
η 1− e {4.10b}
=
η (− Ax )
ref 1 − e ref
(− ABx )
η 1− e ref
= {4.10c}
η (− Ax )
ref 1− e ref
73 II-29
Chapter 4 Dissolved air flotation
η = 1 − (1 − η )B {4.10d}
ref
However, changing of τ or Φ will also cause some parameter in eq. 4.6d change. For
example, increasing of retention time from SIEM’s condition will make V decrease. Then G
will decrease. So the constant “A” at design condition is not equal to “A” at SIEM’s
condition. In this case, eq. 4.10 is not valid. And it is not possible to know the value of “A” at
design condition. So, the best estimation in this case is to use the value of A at some condition
that we are sure that will underestimate efficiency at design condition. Design reactor in this
case will be larger than it should be. Then it can be considered as safety factor.
Criteria to predict the efficiency from combination of SIEM’s model and population
balance model will be described again in details in section 4.3.
In case of inlet oil concentration, SIEM’s model is verified at inlet oil concentration of
800 mg/l before adding pressurized water or around 400 mg/l after adding pressurized water,
which is moderate value. If inlet oil concentration increases, the collision rate κ would
increase since probability of bubble collision (a) will be increased. However, DUPRE’s study
[14] shows that inlet concentration less than 600 mg/l does not have significant effect on the
efficiency. So, to be on the safe side, we can imply that modified SIEM’s model is still valid
when inlet concentration is not greater that 600 mg/l (dilution included) or 1,200 mg/l
(dilution not included). Using the model for higher oil concentration will result in
underestimating of efficiency.
74 II-30
Part II Generalization of model for oil-water separation process design
Δρ gd 2
oil/water {4.2b}
η =
sed 18μ8 r
3 d 2 {4.2c}
η Int = ( )
2 d
b
KT 2/3 {4.2d}
η = 0.9( )
Diff μdVr d
b
Δρ gd 2
air/water b {4.2f}
Vr = U =
b 18μ c
2. To use the models described above, the following conditions need to be satisfied;
1) Inlet oil concentration should not be greater than 1,200 mg/l (before
dilution) or 435 mg/l (after dilution). Using the model with higher oil
concentration will result in underestimating the efficiency.
2) The model is tested at the following operating conditions;
• Φ/AV = 0.0516. Only this value must be used in the equations. As
long as this value is fixed, SIEM’s operating condition still holds and
the model is still valid.
• Retention time (τ), based on Qt, is around 25 minutes.
• Droplet diameter (d) tested is between 2 to 40 microns.
• Diameter of air bubbles (db) varies from 15 to 130 microns. Tested
average diameter is 70 microns, which is used to verify the model, and
standard deviation of bubble diameters is 34.5 microns. The range of
bubble sizes is common for commercial pressurized water system or
saturator. The pressure of the test system is 4 atm (absolute).
• Tested air flowrate (Φ) is 0.42 cm3/s (4.2e-7 m3/s).
• Tested wastewater flowrate (Q) is 3.9 cm3/s (3.9e-6 m3/s)
• Tested effective water depth (H) is 0.70 m. The value of H can be
freely changed as long as (Φ/AV) is fixed. However, H between 1.8 to
2.7 is recommended by API [45].
• Diameter of flotation column is 0.15 m Cross section area of column
(A) is 0.01767 m2.
• Ratio of pressurized water to wastewater (Qpw/Q) is 1.76.
• Air to pollutants ratio used is around 0.12 kg. air/ kg. oil.
• Ratio of number of bubble/ oil droplet tested is around 1.4 oil droplet/ 1
air bubble.
• Hydraulic loading rate or flow velocity (V), based on Qt, is 1.6 m/h
3. Because of the limitation of the pilot model, tested ratio of pressurized water to
wastewater is quite high (around 92%), compared to that of general DAF for
solid/liquid separation (less than 50%) [13]. However, API [45] recommended
air/wastewater ratio of 0.35 std. ft3/ 100 gal of total flow for full-flow DAF
process. This value is equivalent to 84% of 4-atm (abs) pressurized water/
75 II-31
Chapter 4 Dissolved air flotation
76 II-32
Part II Generalization of model for oil-water separation process design
(− κ Φ τ )
η = 1− e 2,ref req ref {4.15a}
d
Because we use τref, instead of τreq, the calculated efficiency will be
lower than the real value.
• To decrease Φ (Φreq < Φref), as well as, τ (τreq < τref):
This will cause increasing of V, so G will increase. Then κ2 (see eq.
4.9) will be higher. Again, we do not know how much exactly. So, to
be on the safe side, we will assume that κ2 = κ2,ref. The efficiency can
be calculated by eq. 4.15b. And again, the calculated efficiency will be
lower than the real value.
(− κ Φ τ )
η = 1− e 2,ref req req {4.15b}
d
• To increase Φ(Φreq > Φref) and decrease τ(τreq < τref):
This can be done by increasing pressurized water flowrate. However,
the ratio of pressurized water/ wastewater is already high (176%). Thus,
this case is unlikely to heppen. In this case, κ2(see eq. 4.9) will be
higher. Like the former case, the efficiency can be calculated by eq.
4.15b.
• To increase Φ(Φreq > Φref), as well as, τ(τreq > τref):
This case does not exist because it means that we have to decrease
wastewater flowrate. As stated above, the ratio of pressurized water/
wastewater is already high (92%). If we decrease wastewater flow,
quantity of pressurized water flow will exceed that of wastewater,
which is not feasible because we have to recycle effluent at 100% plus
additional makeup water to feed the pressurized water system.
There is no obvious limit for the 4 adaptations, shown above. However
we recommend using the values within general range, shown in item 2. to
4.
7) Outlet concentration can be calculated from eq. 4.16a. If DAF effluent is
recycled to pressurized system, Cod,dil will be calculated as shown in item
8. If pressurized water comes from additional clean water, Outlet
concentration can be calculated by eq. 4.16b. In this case, effluent
quantity is equal to Qt, not Q. The subscript “dil” represents the condition
after dilution with pressurized water.
C =
Q
⋅ (1 − η )C {4.16a}
d Q d od, dil
out
C =
Q
⋅ (1 − η )C (
Q
) {4.16b}
d Q d od Q
out t
d max
Q out = Q −
Q
⋅ ∑η C od {4.16c}
ρd
d
d min
77 II-33
Chapter 4 Dissolved air flotation
d max
∑ ⎛⎜ (1 - η d ) ⋅ C od, dil ⎞⎟
d ⎝ ⎠
η DAF = min ⋅ 100% {4.16d}
C
o, dil
In case that, additional clean water is used as pressurized water, eq. 4.16d
can be rewritten as follow.
d max d max
d
∑
⎛
⎜ (1 - η ) ⋅ C
⎜ d
(
od Q
Q ⎞
)⎟
⎟ d
( )
∑ (1 - η d ) ⋅ C od
min ⎝ t ⎠ min
η DAF = = ⋅ 100%
Q Co
Co ( )
Qt
{4.16e}
Total removal efficiency, which is the efficiency calculated from ratio
mass between oil removed and initial mass of oil, can be calculated by
eq. 4.16e.
Co − C {4.16f}
ηt = ⋅ 100%
Co
In case that, additional clean water is used as pressurized water, eq. 4.16e
and be rewritten as follow.
Qt
Co Q − C ⋅ Q t C o − C( )
Q {4.16g}
ηt = = ⋅ 100%
Co Q Co
78 II-34
Part II Generalization of model for oil-water separation process design
The power for pressurized water pump can be calculated by normal pump equation
(Power =ρgQpwH/ηpump). Head of pump (H) can be assumed to equal the absolute pressure of
the pressurized water system. For the power required for an air compressor as well as the
quantity of air released by the pressurized water will be as show below.
To calculate quantity of pressurized water that can supplied the required amount of air
bubbles, our researches show that theoretical equations based on Henry’s and Dalton’s law
give relatively accurate result. The equations can be summarized as follows,
1. To predict molar fraction of dissolved gas in the water (x), Henry’s law (eq.
4.18) will be applied. Normally, we use the molar fraction of air (yair), which
equals to 1 , to calculate. Anyway, if we need to know the quantity of some
certain gases, i.e., oxygen or nitrogen, etc. It can also be calculated by Henry’s
law, using molar fraction of oxygen gas and nitrogen gas in air (yO2 and yN) of
0.11 and 0.89 respectively (in permanent regime). For the absolute pressure of
the saturator or pressurized water system (P), it is recommended to use pressure
within the standard of commercial equipment range (around 4 atm(abs)). The
higher the pressure, the more the amount of bubble generated and the greater the
energy required. Henry’s constant (H) of air, oxygen, and nitrogen are 4.04 x104,
8.04 x104, 6.64 x104 atm/mole respectively
yP {4.18}
x=
H
2. When we know the molar fraction of dissolved air or gas (x) in water, we can
convert it to mg/l of dissolved air or gas or volume of air or gas per unit volume
of water by general conversion factor. The equation for calculating mg/l of
dissolved oxygen or air in pressurized water is shown in eq. 4.19a and 4.19b
respectively (using P in atm). Ratio of air flow to pressurized water flow at 20 o
C, assuming %saturation of air or gas in water is equal to 95%, are as shown in
eq. 4.20 (using P in atm).
Conc.(O 2 ) = 4.5893P {4.19a}
79 II-35
Chapter 4 Dissolved air flotation
180.0 0.14
160.0 0.12
120.0
(l gas/ l water)
y = 22.965x y = 0.0191x - 0.0191
100.0 0.08
R2 = 1 R2 = 1
80.0 0.06
60.0
y = 4.5893x 0.04
40.0 R2 = 1
20.0 0.02
0.0 0.00
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Absolute pressure (atm)
Dissolved oxygen Dissolved air Released air per volume of pressurized water
Fig. 4.4 Relation between absolute pressure in pressure tank and dissolved quantity and released air volume
3. To estimate power required for the air compressor, SIEM shows that theoretical
equation (eq. 4.20a), based on adiabatic process (PV1.4 = const.), can be applied
with acceptable accuracy. Please note that the equation does not include the
overall efficiency (ηoverall) of the system, which can be safely assumed to be
around 60-70%. So the overall power required can be calculated by eq. 4.20b.
⎡ 1.4 −1 ⎤
RT ⎢ P 2 ( 1.4 ) Conc(air) {4.20a}
Power = ( ) − 1⎥ ⋅ ⋅ Q pw
theo ⎢
0.4 Patm ⎥ MW(air)
⎣ ⎦
Power
Power = theo {4.20b}
η
overall
Using R = 8.314 Pa.m3/(mol. K), Conc(air) in g/l and Qpw in m3/s will result in
Power theo in Watt. Molecular weight (MW) of air is 28.95 g/mol. For power
consumption of pressurized water pump, it can be calculated by the following
equation (P as atm).
80 II-36
Part II Generalization of model for oil-water separation process design
Chapter 5 Hydrocyclone
Hydrocyclone is an accelerated separation process by replacing gravitational
acceleration with higher centrifugal acceleration. Hydrocyclones are widely used in many
processes, i.e., classification and separation between solid-liquid and liquid-liquid. In our
scope of work, we will consider mainly on the mathematical model of liquid-liquid
hydrocyclone. There are 2 main types of hydrocyclones studied in GPI laboratory, i.e., two-
phase hydrocyclone and three-phase hydrocyclone.
Every commercial hydrocyclone has its own shape and ratio between each component.
So it is difficult to develop the model to cover every type of them. In our lab, main research
on hydrocyclone is based upon MA’s study [16] on two-phase hydrocyclone for oil/water
separation. In his research, he bases his experiment on “THEW” type hydrocyclone, which is
initiated by Prof. THEW, UK. So, in our research, we will emphasize only on this type of
hydrocyclone.
Do
d < dc d = dc d > dc
Di D
Rd
R R R
Dn
R
U L
V
W
β
Z Z Z
Ds η = 100 % η = 100 %
Z
a) Schematic diagram b) Trajectory of each size of oil droplets
Note: Dn/D=0.5, Ds/D=0.25, Do/D<0.05, Di/D=0.25, β=1.5 deg
81 II-37
Chapter 5 Hydrocyclone
MA’s model is presented in eq. 5.1 to 5.2. Steps of calculation of the model will be
identical to decanter’s, beginning with cut size calculation. After finding the cut size, graded
and total removal efficiency, then, can be calculated.
R
d dR L dZ
∫ =∫ {5.1a}
R U 0W
zvv
Δρd 2 V 2
U= ⋅ {5.1b}
18 μ R
⎛ ⎞
⎜ (Q/2) ⎟ D
V = 0.5⎜ ⎟( n ) 0.65 {5.1c}
π
⎜ D2 ⎟ R
⎜ ⎟
⎝4 i ⎠
2 3
W R ⎛ R ⎞ ⎛ R ⎞
= −3.33 + 12 − 8.63⎜⎜ ⎟⎟ + 1.19⎜⎜ ⎟⎟ {5.1d}
Wz Rz ⎝ Rz ⎠ ⎝ Rz ⎠
Q {5.1e}
Wz =
π(0.5D n − Z ⋅ tan( β /2)) 2
Cut size (dc) is the smallest oil droplet diameter that moves from Rd = Dn/2 (eq.5.1a)
and can reach the central core of cyclone at Z = L. When d ≥ dc, removal efficiency will be
100%. For THEW’s hydrocyclone, RZVV = 0.186 (Dn/2) at Z = L.
η = 100% {5.2a}
d
For d < dc, the oil drops that enter the hydrocyclone at relatively short distance from
the center line can also be separated, while those that enters at further distance will be carried
over with wastewater through the underflow outlet. The efficiency in this case can be
calculated by ratio of the area corresponding to the entering distance “Rd” to the whole cross
section area, as shown in eq. 5.2b. We can assume ηd (η50%, η75%, etc.) and calculate the
corresponding Rd, then use eq. 5.1 to calculate corresponding d (d50%, d75%, etc.) from the Rd.
2 Dn 2
(R − (0.186) )
d 2 {5.2b}
η = ⋅ 100 %
d Dn 2 Dn 2
(( ) − (0.186 ) )
2 2
Advantage of the concept of trajectory is that the concept can be applied to other shape
of hydrocyclone, if the equation of tangential velocity V and W are known, since the
equations of U is assumed to conform to STOKE’s law. For the equation of V, the general
form is normally as shown in eq. 5.1c except the exponent (for THEW type, = 0.65) that will
vary with the shape of the hydrocyclone.
There are several researches that suggests the model to predict the efficiency of
hydrocyclone, both theoretical and empirical based, such as Bradley’s, Rietema’s,
Dahlstrom’s, Chebelin’s, Plitt’s, Lynch’s, etc. [16],[28]- [34]. However, most of models are
developed from solid-liquid hydrocyclone. Some models are developed for specific
82 II-38
Part II Generalization of model for oil-water separation process design
commercial liquid-liquid hydrocyclone, such as Vertoil. So it should be applied only with that
specific hydrocyclone. Extrapolation of model is normally not guaranteed.
For THEW hydrocyclone, used by MA in his research, Prof. THEW, himself, and his
colleague, COLMAN, have proposed the model for the hydrocyclone (eq. 5.3a). However, it
is an empirical model, which seems to be obtained from curve fitting. CHEBELIN [29]
quoted THEW-COLMAN’s correlation for solving d75% in his research, as shown in eq.
5.3b.
d
( −1.8( − 0.19))
η = (1 − e d 75%
) ⋅ 100 % {5.3a}
d
0.5
⎡ 0.00001μ ⋅ (0.001D ) 3 ⎤
d 75% = 10 6 ⎢ n ⎥ {5.3b}
⎢⎣ Δρ ⋅ Q ⎥⎦
To verify the models, we will compare predicted efficiency, calculated from MA’s
model, with observed data. Moreover, since MA’s model is developed from THEW
hydrocyclone. So it will be interesting to compare the MA’s model with THEW’s model. We
use the data from MA’s study, based on THEW hydrocyclone, nominal diameter 2 cm.
Operating condition used is tabulated in table 5.1. For COLMAN’s model, we used observed
value of d75% in eq. 5.3.Comparison between result from the 2 models and observed data is
shown in fig. 5.2.
110%
100%
90%
80%
Efficiency (%)
70%
60%
50%
40%
30%
Colman's model
20% Observed data
10% Ma's trajectory analysis
0%
0.00 10.00 20.00 30.00 40.00 50.00 60.00
Droplet diameter (micron)
Fig. 5.2 Comparison between observed efficiency and predicted efficiency from Ma's and Thew-Colman's models
From the graph, it shows that, at droplet size > 20 microns, MA’s and COLMAN’s
models give relatively accurate result (± 10% error). However, at d > d 80%, COLMAN’s
model seems to cause higher degree of error and predict too high value of cut size. This may
because the researchers used different assumptions or operating condition to develop their
models. In effect, it is very difficult to point out that which model is more accurate.
83 II-39
Chapter 5 Hydrocyclone
However, Ma’s model is developed from theoretical assumption and does include
many parameters, such as viscosity, feed flowrate, and size of the hydrocyclone, etc., which
can be used to explain or verify the effect of these parameters to the efficiency. So, in this
research, we will base our model on MA’s.
From model verification result, we can conclude and propose the generalized model as
well as its limitation as follows,
Δρd 2 V 2
U= ⋅ {5.1b}
18 μ R
Q D
V=( )( n ) 0.65 {5.1c}
πD 2 R
i
2 3
W R ⎛ R ⎞ ⎛ R ⎞
= −3.33 + 12 − 8.63⎜⎜ ⎟⎟ + 1.19⎜⎜ ⎟⎟ {5.1d}
Wz Rz ⎝ Rz ⎠ ⎝ Rz ⎠
Q {5.1e}
Wz =
π(0.5D n − Z ⋅ tan( β /2)) 2
The equations are, somehow, very complex and require complicate numerical
method, such as Range-Kutta, to solve. However, our computer program,
developed in scope of work of this thesis, will be able to calculate these
equations.
84 II-40
Part II Generalization of model for oil-water separation process design
3. To use the models described above, the following conditions need to be satisfied
and the assumptions and limitations would be noted;
1) The model is valid for THEW hydrocyclone or other cyclones with relative
identical geometry.
2) It is recommended to use the model only for droplet diameter of 20
microns or greater. For smaller droplet, it can also be applied, but for
comparison only.
3) Eq. 5.2c is valid for the hydrocyclone with 2 inlet ports only. If the
hydrocyclone has only 1 inlet port, Q in eq. 5.1c will be modified as shown
in eq. 5.1c’. However, using 2 inlet ports is recommended for its hydraulics
stability. Please note that the size of 2 inlet ports will be smaller than a
single inlet port to keep the inlet area constant.
Q D
V = 2( )( n ) 0.65 {5.1c’}
πD 2 R
i
4) Overflow quantity is usually small, not greater than 10%. Its effect on
velocity profiles and efficiency is small, thus, negligible.
Many literatures [16], [28] – [34] have studied pressure drop of hydrocyclone. Some
researchers also proposed models of pressure drop, obtained from their experimental data, i.e.,
Bradley’s, Hotta’s, Rietema’s. From these models, we find that, even derived from different
assumptions, the general form of pressure drop equation is as shown in eq. 5.4
4
ΔP = f(Q 2.xx /D n ) {5.4}
We use the data from MA [16] and THEW [28] to find the constant in eq. 5.2. The
model, developed from these data, is as shown in eq. 5.5 (Q in m3/s and Dn in meter).
Comparison between observed data and predicted data is shown in fig. 5.3.
For pressure drop (bar) across inlet and overflow port (oil outlet);
Q 2.3 {5.5a}
ΔPo = 16
4
Dn
For pressure drop (bar) across inlet and underflow port (water oultet);
Q 2.2 {5.5b}
ΔPu = 4.6
4
Dn
85 II-41
Chapter 5 Hydrocyclone
2.3 4
Δp o (bar) = 16 Q /Dn
6.0
5.0
Predicted pressure drop (bar)
4.0
3.0 +10%
2.0
-10%
1.0
0.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00
Observed pressure drop (bar)
Fig. 5.3a Relation between observed pressure drop (inlet/overflow) of Thew cyclone and predicted pressure drop
2.2 4
Δp u (bar) = 4.6 Q /Dn
7.0
6.0
5.0
Predicted pressure drop (bar)
4.0
+10%
3.0
2.0
-10%
1.0
0.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0
Observed pressure drop (bar)
Fig 5.3b Relation between observed pressure drop (inlet/underflow) of Thew cyclone and predicted pressure drop
From THEW’s research [28], Split ratio (Rf) or ratio between overflow and inlet flow
has some effect on pressure drop. However the effect of this parameter on under flow pressure
drop is very small, thus, negligible. There is more effect on overflow pressure drop. From
THEW’s and MA’s data, we can find the empirical correlation between split ratio and then
can transform eq. 5.5a to account for the split ratio. The modified equation is as follow;
0.1611
Q 2.3 ⎛ 2.6 ⎞
⎟
Δp o = 16 ⋅⎜ {5.5c}
Dn
4 ⎜ (1 − R ) ⎟
⎝ f ⎠
However, the correlation is developed from relatively small set of data. Furthermore,
range of split ratio, generally used, is around 1 to 10%. Within this range, eq. 5.5a alone can
predict the efficiency with an error of only 10-20%. So we recommend using eq. 5.5a and
86 II-42
Part II Generalization of model for oil-water separation process design
5.5b to predict the pressure drop of the hydrocyclone. Anyway, to allow for prediction error,
safety factor of 1.2 should be applied.
Note: Di/D=0.25 for 1- inlet and 0.175 for 2- inlet, Do/D=0.43,Ds/D=0.28, Du/D=0.19, Dp/D=0.034,
L1/D=0.4,L2/D=5, L3/D=15, L4/D=0.3, Solid-liquid part cone angle=12o, for liquid-liquid part=1.5o
MA testd the performance of the prototype of this hydrocyclone. It showed very good
efficiency, which relatively conforms to the efficiency obtaining from separate solid-liquid
and liquid-liquid hydrocyclone. He also studied the influence of important parameters to
efficiency of this new hydrocyclone. However he did not propose the model. So we have to
develop new model for three-phase hydrocyclone. Model development detail will be
described in section 5.2.1.
From the fact that three-phase cyclone is the combination between THEW and
RIETEMA hydrocyclone. New model for liquid-liquid and solid-liquid part should conform
to that of each separate hydrocyclone.
For liquid-liquid hydrocyclone, we will apply the model of MA’s, as stated in section
5.1, to three-phase hydrocyclone. The problem is how to adapt MA’s model to this new
hydrocyclone. From MA’s research, he observed that the phenomena in three-phase
hydrocyclone, such as oil central core formation, etc., are relatively identical to THEW
hydrocyclone. From this, we assume that the driving force of oil part in the hydrocyclone
should be identical to normal THEW hydrocyclone at the same flowrate and nominal diameter
(Dn in fig.5.1 = Do in fig. 5.4 = ND.). The driving force in hydrocyclone is generated by
energy of feed flowrate. From geometry in fig. 5.1 and 5.4, we get the following equations.
α 3φ ⋅ V =α ⋅V
i(3φ ) Thew i(Thew)
87 II-43
Chapter 5 Hydrocyclone
⎛ ⎞ ⎛ ⎞
⎜ 4Q ⎟ ⎜ 4Q ⎟
α 3φ ⋅ ⎜ ⎟ = 0.5 ⋅ ⎜ ⎟
⎜ π(D )2 ⎟ 2
⎜ π(D i(Thew) ) ⎟
⎝ i(3φ ) ⎠ ⎝ ⎠
⎛ ⎞ ⎛ ⎞
⎜ ⎟ ⎜ ⎟
4Q 4Q
α 3φ ⋅ ⎜ ⎟ = 0.5 ⋅ ⎜ ⎟
⎜ ND 2 ⎟ ⎜ ND 2 ⎟
⎜ π(0.25( )) ⎟ ⎜ π(0.25( )) ⎟
⎝ 0.43 ⎠ ⎝ 0.5 ⎠
2
⎛ 0.5 ⎞ {5.6}
α 3φ ⋅ = 0.5 ⋅ ⎜ ⎟ = 0.676
⎝ 0.43 ⎠
We use α3φ in eq. 5.6 with the model in eq. 5.1 and 5.2 to predict the efficiency of the
oil part of three-phase hydrocyclone and compare the result with observed value from MA’s
data [16]. Comparison result in fig. 5.5 shows that the error from prediction is ± 20%, which
is acceptable. We have tried to select the value of α3φ arbitrarily and found that;
• If the value of α3φ is lower, the model will predict too low efficiency.
• For higher value of α3φ, it may provide better curve fitting but we do not have any
data to support the use of it. The value of 0.676 seems more appropriate.
120.0%
100.0%
Predicted efficiency (%)
80.0%
+20%
60.0%
40.0%
-20%
20.0%
0.0%
0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0%
Observed efficiency (%)
Fig. 5.5 Relation between observed efficiency and predicted efficiency of liquid-liquid (Thew) part of three-phase
hydrocyclone
From model verification result, we can conclude and propose the model of liquid-
liquid part of three-phase hydrocyclone as well as its limitation as follows,
88 II-44
Part II Generalization of model for oil-water separation process design
Δρd 2 V 2
U= ⋅ {5.7b}
18 μ R
⎛ ⎞
⎜ (Q/2) ⎟ D
V = 0.676⎜ ⎟( n ) 0.65 {5.7c}
⎜ π D2 ⎟ R
⎜ ⎟
⎝4 i ⎠
2 3
W R ⎛ R ⎞ ⎛ R ⎞
= −3.33 + 12 − 8.63⎜⎜ ⎟⎟ + 1.19⎜⎜ ⎟⎟ {5.7d}
Wz Rz ⎝ Rz ⎠ ⎝ Rz ⎠
Q {5.7e}
Wz =
π(0.5D n − Z ⋅ tan( β / 2)) 2
For d ≥ dc,
η = 100% {5.8a}
d
For d < dc,
2 Dn 2
(R − (0.186
) )
d 2 {5.8b}
η = ⋅ 100 %
d Dn 2 Dn 2
(( ) − (0.186 ) )
2 2
2. To design the hydrocyclone by the model, it is recommended to select the cut
size that covers majority of oil droplet in the wastewater and provide a safety
factor around 10% to 25%, because the model is apt to predict too small cut size.
For example, if the desired cut size is 50 microns, it is recommended to select
50(1-0.25) = 37.5 microns for eq. 5.7 and 5.8.
3. To use the models described above, the following conditions need to be satisfied
and the assumptions and limitations would be noted;
1) The model is valid for three phase hydrocyclone with geometry of the oil
part conforms to that of THEW.
2) It is recommended to use the model only for droplet diameter of 20
microns or greater. For smaller droplet, the model can also be applied, but
for comparison purpose only.
3) Eq. 5.7c is valid for the hydrocyclone with 2 inlet ports only. If the
hydrocyclone has only 1 inlet port, replace Q/2 with Q. However, using 2
inlet ports is recommended for its hydraulics stability. Please note that the
size of 2 inlet ports will be smaller than single inlet port to keep the inlet
area constant.
From the same reason as oil-part model development, we will base our model for
solid-liquid separation on RIETEMA hydrocyclone’s model. In MA’s research, he used only
2 sizes of suspended solids. So the data is not sufficient to develop the model. However,
geometry of this part of three-phase hydrocyclone is identical to RIETEMA’s. So RITEMA’s
model should be applied without any modification.
89 II-45
Chapter 5 Hydrocyclone
RIETEMA [30] defined the performance of the hydrocyclone in form of d50% and the
dimensionless number Cy50, as shown in eq. 5.9. To find graded efficiency besides d50%,
correlation of YOSHIOKA and HOTTA [30], for 2% < ηd <98%, may be applied (eq. 5.10).
2
d 50 (ρ ss − ρ c )(L 2 − L 4 ) ⋅ Δp
= Cy 50 {5.9}
ηcρ c Q
−( d −0.115) 3
d
η = (1 − e 50% ) ⋅ 100 % {5.10}
d
The value of Cy50 of MA’s hydrocyclone can not be calculated due to lacking of data.
However, RIETEMA recommended the value of Cy50 around 3.5 for RIETEMA type
hydrocyclone, which MA used in his hydrocyclone. So we recommend to use Cy50 =3.5 to
calculate the efficiency of solid part of three-phase hydrocyclone.
MA proposed the model for pressure drop calculation for his prototype hydrocyclone.
For the prototype, he used Do = 14 mm and D = 32 mm. Pressure drops across various ports of
the prototype (in bar, m3/s) can be calculated from the following equations,
ΔPwater = 1.364Q 2.11 {5.11a}
The equations are valid only for 14/32-mm. three-phase hydrocyclone. Thus, to extend
the valid range of the equations or to develop generalized model. We consider 2 approaches,
i.e.,
• Similarity approach
So combination of eq. 5.11 and 5.12 can be used to predict the pressure drops of
any size of three-phase hydrocyclone by calculating the pressure drops of 14/32-mm.
hydrocyclone at given flowrate by eq. 5.11 first, then use eq. 5.12 to find the flowrate at given
hydrocyclone diameter and given characteristic of wastewater.
• Empirical approach
Similarity approach is theoretical based. In practice, many factors may cause some
discrepancies from theoretical value. To account for these factors, empirical approach is
introduced. We base our model on eq. 5.4 that we successfully applied for two-phase
hydrocyclone.
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Part II Generalization of model for oil-water separation process design
To develop and verify empirical model, we use the data from MA’s and THEW’s
research [16], [18]. The empirical models are as shown in eq. 5.13 (ΔP in Bar, Q in m3/s, D in
m.).
Q 2.12 {5.13a}
ΔPwater = 49.8
D4
Q 2.34
ΔPss = 21 {5.13b}
D4
Q 2.03 {5.13c}
ΔP = 55
oil
D4
Comparisons between the predicted pressure drops of the 2 approaches are shown
in fig. 5.6. The graphs show that the two approaches give very accurate results. However,
using eq. 5.11 and 5.12 may cause some difficulty because it requires calculation for d50%
first. So using eq. 5.13 may be more convenient.
4.000
3.500
Predicted pressure drop (bar)
3.000
2.500
2.000
1.500
1.000
Fig. 5.6a Relation between observed pressure drop (bar) across inlet and water outlet and predicted value from 2 approaches
91 II-47
Chapter 5 Hydrocyclone
3.00
Predicted pressure drop (bar)
2.50
2.00
1.50
1.00
Fig. 5.6b Relation between observed pressure drop (bar) across inlet and SS outlet and predicted value from 2 approaches
8.00
7.00
Predicted pressure drop (bar)
6.00
5.00
4.00
3.00
2.00
Fig. 5.6c Relation between observed pressure drop (bar) across inlet and oil outlet and predicted value from 2 approaches
92 II-48
Part II Generalization of model for oil-water separation process design
Membrane process design depends mainly on wastewater characteristics. So, the best
way to design the membrane process is to perform feasible study in lab scale or pilot scale.
However, our lab has several researches on UF. From these researches, we have gained some
understanding of phenomena taking place in the process. Then we can use our result to set a
guideline for conceptual design or preliminary evaluation of membrane process.
6.1 Ultrafiltration
Because of their pore sizes, MF and UF are suitable for finely dispersed emulsion,
such as, secondary emulsion, macroemulsion and microemulsion. However, there is only one
research on MF of oily wastewater treatment in Prof. AURELLE’s team. Then, despite of its
feasibility on cutting oil emulsion treatment, which is one of the important applications of
membrane processes on oily wastewater treatment, we will not include MF in our thesis for
there is insufficient data. So we will emphasize on UF.
There are 2 main types of UF, as well as other, membrane processes, based on flow
pattern, i.e., dead-end and cross-flow. In dead end reactor, wastewater will be fed in
perpendicular direction to membrane surface. So this mode of operation is rather like cake
filtration. Dead-end process is normally used in bench scale experiment. For cross-flow,
wastewater will be fed in tangential direction, parallel to membrane surface. It is this mode of
operation that is widely used in real life situation. So our researches are related to this process.
For wastewater treatment, our aim is to reduce the quantity of the wastewater as much
as possible while the effluent quality still meets effluent standard. So wastewater will be
recycled repeatedly until its volume reaches required limit. In this case, UF system is
normally designed as batch processes, as shown in fig. 6.1.
Retentate
Permeate
Storage
tank
Membrane
Feed pump
93
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Chapter 6 Membrane process
From fig. 6.1, we have to apply enough pressure to force components that can pass
through the membrane pores to the other side. The components of influent that can pass
through the membrane is called permeate. The rest that can not pass is called retentate. The
pressure difference between retentate side and permeate is called transmembrane pressure (Pt).
The retained components will accumulate at the surface of membrane and its concentration
will be increased. This accumalation and high concentratio, called concentration polarization
or gel polarization, will hinder the permeate flow. Some components may lodge in the pores.
These phenomena will make the membrane clog and rate of permeate passing through the
membrane or permeate flux will decrease. In cross-flow process, we can alter the superficial
(or recirculation) velocity at the membrane surface (V) by changing recirculation flowrate to
reduce the effect of polarization. From this brief operating principle, we can see that there are
several parameters, relates to membrane process design. So models of membrane will be
developed to describe the relation between these parameters.
There are several researches in our lab [10], [11], [18]-[22] on membrane processes.
However, they were based mainly on application. Only some of them provided models.
Furthermore those models are limited by their scopes of the experiment, then they are not in
general forms to apply to general case. In this thesis, we will try to develop the generalized
models, based on well-accepted theoretical models, i.e. resistance model and film model.
General form of resistance model [38], [54], [18], [11] is similar to the equation for
electrical calculation as shown in eq. 6.1.
Pt
J= {6.1a}
Rm + R + Rg
f
Membrane resistance (Rm) and fouling resistance (Rf) are property of membrane and
relatively unaffected by operating condition [38]. So it is normally be summed together and
called intrinsic membrane resistance (R’m). Eq. 6.1a , then, will become,
Pt
J= {6.1b}
R 'm + R g
Gel resistance (Rg) is the function of Pt and V as shown in eq. 6.2. α and φ are
numerical constants.
R g = φ ⋅ V α Pt {6.2}
This model can give the accurate evolution of flux with Pt, starting from pressure
controlled region, which the flux varies with Pt, to mass transfer controlled region, which the
flux is relatively constant, as shown in fig. 6.2.
From researches in our lab, we can summarize the value of R’m, φ and α for many
operating conditions, as tabulated in table 6.1. φ and α are dependent of wastewater inlet
concentration so it can be applied only to their corresponding concentration only.
94
II-50
Table 6.1 Summary of parameters of resistance model from UF researches on oily wastewater treatment (reference temperature = 20O C)
95
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Part II Generalization of model for oil-water separation process design
Chapter 6 Membrane process
r flux
Higer temperature
Lower concentration
Wate
This model is developed under the assumption that the process is in the mass transfer
controlled region. So flux is assumed to be controlled by mass transfer phenomena and
independent of Pt. Operating UF in this region will maximize the flux, thus minimize the size
of membrane. The general form of film theory based model [38], [54] is shown in eq. 6.3.
β Cg {6.3}
J = kV ln( )
Co
For the first type, the curve is flat without inflection point. This type of curve will
cross the horizontal axis at Cg. This Cg remains constant for the whole range of retentate
concentration.
For the second type, The curve presents an inflection point. In this case, we can say
that there are two Cg. The first one is obtained from extending the steeper part of the graph to
cross the X-axis. But it is not the real Cg and used only for flux calculation at lower range of
retentate concentration. The real Cg is obtained from the graph after inflection point. UF of
cutting oil emulsion will be in this category. In this case, the real Cg normally crosses the X-
axis at approximately 100% concentration. This can imply that, theoretically, we can use UF
to filter the oily wastewater until the retentate become water-free oil. However, the flux will
become very low and the operation may become unacceptable from economic point of view.
Flux V2>V1
V1
Cg Log (Concentration)
Fig. 6.3a Relation between flux and concentration at any recirculation velocity [38]
96
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Part II Generalization of model for oil-water separation process design
Flux
1 2
Fig. 6.3b Typical characteristic curve of concentration VS. Flux (Log-Normal scale) [38]
From researches in our lab, we can summarize the value of k, Cg and β for various
kinds of membranes for many types and inlet concentration of wastewater, as tabulated in
table 6.2.
From section 6.1.1, it shows that the resistance model can predict flux at any pressure.
However, the constants in eq. 6.2 are valid for only their own specific operating conditions,
esp. the influent oil concentration. On the other hand, eq. 6.3, even though it is supposed to be
valid only in mass transfer region, can be used to predict flux at any influent oil concentration,
providing that the Cg is known. So, it is interesting to combine eq. 6.2 and 6.3 to see if they
can be used to predict flux at any influent concentration and pressure or not. The procedures
used to combine film theory and resistance theory, which are divided into 2 cases, are as
shown below.
1. Find JC,Vref
If we know the value of k and β at one known velocity (called reference velocity,
Vref), we can calculate limiting flux at any required concentration (called C) by the film
theory.
β Cg {6.4a}
J = kV ln( )
C,Vref ref C
In this case, we have tried to verify if the film theory is still valid. We studied the
flux/concentration relation of cutting oil macroemulsion (Elf SeraftA) at P = 2 and 3.5 bar, V
from 0.7 to 2.8 m/s from Belkacem’s data [18]. We found that eq. 6.3 is valid at P = 3.5 bar,
where is in the mass transfer controlled region. And we also found that the form of eq.6.3 still
holds at P = 2, where flux does not yet reach fully mass transfer controlled region at low C
and/or high V. But there are some little differences in the values of k, β and Cg.
97
II-53
Table 6.2 Summary of parameters of film model from UF researches on oily wastewater treatment (reference temperature = 20O C)
Chapter 6 Membrane process
98
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Part II Generalization of model for oil-water separation process design
So we conclude that eq. 6.3 is valid even when the mass transfer controlled
region is not fully reached in some condition at the reference pressure. However, it is
recommended to select the reference pressure as high as possible, at the very least, more than
50% of recommended operating range of the membrane. It should be noted that, in this case,
JC,Vref from eq. 6.4a may not exactly be limiting flux but it represents the flux at required
concentration at the reference velocity and pressure. The equation may be rewritten as
β Cg {6.4b}
J = kV ln( )
C,Vref,Pref ref C
2. Find JC,V
Again from the film theory, we can find flux at required concentration and
velocity and at reference pressure by eq. 6.5.
β Cg {6.5}
J = kV ln( )
C,V,Pref C
3. Find αC and φC
From the resistance theory, if we know at least 2 fluxs at the same concentration
but at different velocity, we can find α and φ at that concentration (αC and φC) by the
following equations.
⎛J ⎞
C,V R m − Pref K J ⎟
ln⎜⎜ ⎟
J C,V R m − P
⎝ ref ⎠ {6.6a}
αC =
V
ln( ref )
V
J V β
C,V,Pref {6.6b}
KJ = =( )
J V
C,Vref,Pref ref
99
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Chapter 6 Membrane process
Besides using the reference velocity and required velocity, other dummy velocities
can also be used to cross-check the value of αc and φc. Calculated values of the two
parameters may not be exactly the same as those calculated from Vref and V, since there is
normally some calculation error. Using average values of these αc and φc is recommended.
From αc and φc, we can calculate flux at any transmembrane pressure and at the required
concentration by the resistance theory (eq. 6.7).
Pt
J C,V,Pt = {6.7}
R m + φ C V αc Pt
To verify the procedure from eq. 6.4 to eq. 6.6, we use data from many researches
[10], [11], [18], [20], which φ, Cg, and α of corresponding cases are available. Example of
verification data is provided in Annex A5. In this case, we use φ, Cg, and α obtained from UF
test of cutting oil macroemulsion (Elf SeraftA) at influent concentration (Cref) of 4% V/V, Pref
= 2 bar, Vref = 1.4 m/s as a reference condition to predict flux/ pressure relation at C = 2 and 8
% V/V. Predicted relations and comparison between observed flux and predicted flux are as
in fig. 6.4 and 6.5. From the graphs, it shows that eq. 6.4 to 6.6 can be effectively used to
extend the range of eq. 6.1, 6.2 and 6.3 to cover any influent concentration.
180
160
140
Predicted Flux (l/ (h.m ))
2
120
100
80
60
40
20
0
0 0.5 1 1.5 2 2.5 3
Transmembrane Pressure (Bar)
Fig. 6.4 Relation between UF permeate flux and Transmembrane pressure at reference concentration (C) of = 4%, V = 1.4 m/s
and Predicted relations at C = 2 and 8%
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Part II Generalization of model for oil-water separation process design
180.00
160.00
140.00
Predicted Flux (l/ (h.m ))
2
120.00
+10%
100.00
80.00
-10%
60.00
40.00
20.00
0.00
0 20 40 60 80 100 120 140 160 180
2
Observed flux (l/ (h.m ))
Fig. 6.5 Relation between observed and predicted flux by resistance model for ultrafiltration of macroemulsion 4% conc. and
extend to cover other conc. by film model
1. Find JCref,V
From resistance theory, we can find JCref,V, when φCref and αCref are known, by the
following equation.
P
J = ref {6.8}
Cref,V
R 'm + φ ⋅ V αCref P
Cref ref
2. Find JC,V
3. Find JC,Vref
In the same way as 1 and 2, we can find JC,Vref, when φCref and αCref are known,
by the following equation.
101
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Chapter 6 Membrane process
⎛ C ⎞
⎜ ln( g ) ⎟
⎛ P ⎞ ⎜ ⎟
⎜ ref ⎟ C {6.10}
J =⎜ ⎟ ⋅⎜ ⎟
C,Vref αCref Cg ⎟
⎜ R 'm + φ ⋅V P ⎟ ⎜
⎝ Cref ref ref ⎠ ⎜ ln( )⎟
⎜ C ⎟
⎝ ref ⎠
4. Find αC and φC
6.1.4 Flux prediction for mixture of cutting oil microemulsion and macroemulsion
Wasted cutting oil emulsion is one of the most difficult-to-treat oily wastewater,
mainly because its stability and its very tiny oil droplet. From the researches stated above, we
could see that treatment of this wastewater is the main application of UF on oily wastewater
treatment. From table 6.1 and 6.2, we have some information on UF of microemulsion and
macroemulsion, summarized from many researches. However, in real life situation, some
mechanical workshops or factories may use more than 1 type of cutting oil, to meet individual
process requirement. So it will be interesting to predict the flux of the mixture of them.
To do this, we start with components of the cutting oil emulsion. Two main
components of cutting oil concentrate are base oil and surfactants/co-surfactants. Other
additives are also present but their quantities are usually very low. For macroemulsion, the
ratio of oil in cutting oil concentrate is around 80%. For microemulsion, the ratio of oil is
around 30 to 40%. The surfactants and co-surfactants are the components that give the
emulsion its characteristic.
When 2 types of emulsion are mixed. The oil components will be summed up.
Concentration of oil in the mixture is, therefore, the summation of oil concentration in each
emulsion. Excess surfactants/co-surfactants in microemulsion part will reduce oil droplet size
of macroemulsion, as they do in microemulsion. However, their quantities will not be
sufficient to convert all of macroemulsion into microemulsion. The resultant flux, then, will
be neither the same as the flux of pure microemulsion, nor that of pure macroemulsion. But it
will surely fall between these 2 extreme cases. Accurate prediction may require the
knowledge of the chemistry of surfactants/co-surfactants.
However, if the concentrations are presented in %V of oil (not concentrate), total oil in
the mixture is a simple summation of the two concentrations (eq. 6.10b).
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Part II Generalization of model for oil-water separation process design
C =C +C {6.10b}
oil,mix oil,mac oil,mic
C J +C J
oil,mac mac:Coil,mix oil,mic mic,Coil,mix {6.11}
J =
mix C
oil,mix
To verify this idea, we used reference data of flux of pure macroemulsion and
microemulsion, as used in section 6.1.3, to predict flux of various ratios of
micro/macroemulsion mixture. Relations between predicted values and observed data are
presented in fig. 6.6 and 6.7. Even though, the error from prediction is around 20%, this
procedure will be a useful tool for the preliminary estimation of mixture flux, especially when
UF test data on the wastewater is not available
o
(Module: UFP2, Membrane: IRIS 3042, T = 20C., data from [11]. The lines show predicted value.)
180.00
4% Macro
160.00 1% Micro
V = 2.8 m/s
140.00
120.00
Flux (l/(sq.m.h))
100.00 4% Macro
4% Micro
80.00 V = 2.0 m/s
60.00
4% Macro
40.00 2% Micro
V = 1.0 m/s
20.00
0.00
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50
Pressure (bar)
Fig 6.6 Comparison between predicted flux and observed flux for UF of micro/ macroemulsion mixture (Conc. shown as
% by volume of concentrate)
103
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Chapter 6 Membrane process
180.00
160.00
+20%
140.00
Predicted flux (l/(sq.m.h)
120.00
100.00
80.00
60.00
40.00
20.00
0.00
0.00 20.00 40.00 60.00 80.00 100.00 120.00 140.00 160.00 180.00
Observed flux (l/(sq.m.h)
Fig 6.7 Relation between observed and predicted flux of micro/macroemulsion mixture from weighted average method
between flux of whole micro and macroemulsion at the same total oil concentration
Models in section 6.1.1 and 6.1.2 are developed under the condition that permeate is
recycled back to feed storage tank, so the inlet concentration is kept constant. For real
situation, the process may be designed as batch process, continuous process, single stage
process or multi stage process. In these cases, mass balance will be taken into account.
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Part II Generalization of model for oil-water separation process design
C o Vol o
C= {6.14}
(Vol o − Vol)
However, the system may not be operated in the mass transfer controlled region for the
whole time. In this case, the function J(c) in eq. 6.12 can be calculated by eq 6.7. Eq. 6.12 and
6.15b are in the form of integration of [1/ln (x)], so they can not be written in general form
since the equation will be infinity at x =1. However, a definite integration is possible, using
numerical method that can be calculated by computer.
In this thesis, we have compared the theoretical result, using reference data stated in
section 6.1.3, with observed results from UF test on used cutting oil macroemulsion (3% V of
concentrate or 2.4%V of oil, from Willamette SAS factory) from WANICHKUL’s research
[11], as shown in fig. 6.8a. The x-marked circles indicate the observed flux of fresh emulsion.
From the graph, it shows that the model can accurately predict flux of fresh (unused) emulsion
as the circles are closed to the theoretical flux curve.
Comparing with observed flux of the used emulsion, the graph shows that, at low
concentration, theoretical flux is greater than observed value. This simply because additional
fouling from foreign material in the emulsion. However, at high concentration, theoretical
flux is, somehow, lower than observed value. This can be explained by partial degradation of
the used emulsion. During its working lifetime, cutting oil emulsion will subject to many
foreign material, such as coated oil on specimen surface, small scraps of specimen, leaked
lubricant, and heat. So its quality, as well as its stability, will gradually deteriorate. This is
proven by milky appearance of used emulsion, compared with the translucent or transparent
characteristic of fresh emulsion. When partial oil is destabilized to be free oil, this means the
concentration of oil in emulsion form may be lower than its initial value. At lower
concentration, the effect of fouling overwhelms the effect of reduced concentration, so the
theoretical flux is higher than the observed value. However, at higher concentration where the
concentration effect is stronger, the theoretical flux shows lower value.
Fig. 6.8b shows evolution of permeate volume with time, the result from integration of
eq. 6.12. From the observed data, it confirms that the macroemulsion can be ultrafitrated until
the retentate is relatively pure oil. In this case, initial volume of 1643 l of 2.4%V of oil is
ultrafiltrated to the final volume of 40 l. The theoretical time required to do so is 45 hours,
compared to observed value of 34 hours. However, the theoretical volume of permeate is
higher until almost at the end of the operation. Fig.6.8c shows evolution of theoretical flux
with concentration. It must be noted that eq 6.12 to 6.15 are based on the assumption that no
additional emulsion is added to the storage tank. If the emulsion is added, eq. 6.12 must be
modified to account for it.
105
II-61
Chapter 6 Membrane process
70.00
P = 1.0 bar, v = 1.17 m/s P = 1.5 bar, v = 1.40 m/s
60.00
50.00
flux (l/(sq.m.h))
40.00
30.00
20.00
10.00
0.00
0 200 400 600 800 1000 1200 1400 1600 1800
= Observed data from UF test ofnew
Permeate volume (l) cutting oil at the same condition
Theoretical data at P = 1.0 Bar, v = 1.17 m/s) Observed data Theoretical data at P = 1.5 Bar, v = 1.40 m/s)
Fig. 6.8a Relation between Flux VS. theoretical and observed permeate volume
1800
1600
P = 1.0 bar, v = 1.17 m/s P = 1.5 bar, v = 1.40 m/s
1400
Permeate volume (l)
1200
1000
800
600
400
200
0
0.000 5.000 10.000 15.000 20.000 25.000 30.000 35.000 40.000 45.000 50.000
Time (h)
Theoretical data at P = 1.0 Bar, v = 1.17 m/s) Theoretical data at P = 1.5 Bar, v = 1.4 m/s) Observed data
Fig 6.8b Relation between time VS. theoretical and observed permeate volume
106
II-62
Part II Generalization of model for oil-water separation process design
o
(Elf SeralfABS cutiing oil macroemulsion: Membrane IRIS 3042, 20
C)
80.00
70.00
60.00
Permeate flux (l/m .h)
2
50.00
40.00
30.00
20.00
10.00
0.00
1 10 100
Retentate concentration (% V of oil)
Fig. 6.8c Relation between theoretical flux VS. concentration of oil in retentate
6.1.6 UF efficiency
From many researches, with appropriate UF membrane pore size, it clearly shows that
oil, even in form of very tiny droplets in macroemulsion and microemulsion, cannot pass the
membrane. We can say that the removal efficiency of UF is 100%. Selection of membrane
involves many parameters. However, AURELLE [quoted by [18]] have grouped these
parameters and proposed 3 brief criteria, i.e.,
• Pore size of membrane: To prevent oil droplets to pass through the membrane
pore, the size of the pore, firstly, must be smaller than the droplets. From
researches in our lab, we recommend that minimum pore size should be 1/4 to 1/3
of average droplet size.
• Characteristic of membrane: for oil/water separation, membrane should be
hydrophilic. Membrane material should not react with the wastewater, which can
cause pour clogging. Hydrophilic material, such as polyacrylic, cellulose acetate,
zirconium oxide, etc., is recommended. Naturally without special treatment or
coating, polysulfonate tends to be fouled by oil, resulting in low flux and frequent
washing.
• Operating condition: Operating pressure should be less than capillary pressure
required to force the oil droplets through the membrane pores. Capillary pressure
increases with the hydrophilicity of membrane and decreasing of pore size.
However, if pore size and hydrophilicity are carefully selected, the capillary
pressure is normally higher than recommended maximum pressure of the
membrane.
107
II-63
Chapter 6 Membrane process
However, other soluble pollutants, especially surfactants and co-surfactants, can pass
through the membrane. So, after UF, these chemicals are still present in permeate, resulting in
high TOD, and require further treatment.
Thus, the minimum transmembrane pressure required for any recirculation velocity
will be equal to pressure drop caused by that velocity. The pressure drop can be calculated, as
a friction loss of retentate flowing through narrow channel between membrane surface and UF
module wall, by general pressure drop formula, such as Darcy-Weisbach’s equation. It must
be noted that the friction factor (f) depends on Reynolds number, which, in turn, depends on
viscosity of liquid. For oily wastewater, the viscosity varies with concentration of oil. Fig. 6.9
shows relation of viscosity and oil concentration (as % V of concentrate) of the cutting oil
macroemulsion (Elf Seraft ABS). So the pressure drop will be calculated using the highest
viscosity in the selected operating range of concentration.
L V2
P =f {6.16a}
min D 2
e/D is ratio of roughness to diameter. For plate membrane, the flow channel is usually
rectangular. D of this channel can be calculated as hydraulic diameter, as shown in eq. 6.16d.
H and W are height and width of the rectangular channel respectively.
4HW
D= {6.16d}
2(H + W)
However, since L of the UF module is small, even though the velocity is as high as 3
m/s and D is as low as 1.0 mm., Pmin is still well below 0.5 bar.
108
II-64
Part II Generalization of model for oil-water separation process design
⎡ 1/3 ⎤
⎢⎛⎜ ⎞
⎟ ⎥
⎢⎜ 3 ⎟ ⎥
cosθ 3cosθ − cos θ −2
Pcap = 2γ o/w ⎢⎜ o/w o/w ⎟ ⎥
− 1⎥ {6.17}
o/w ⎢⎜ 3 ⎟
r ⎢⎜ ⎛ rd ⎞ ⎥
⎟
⎢⎜ 4⎜⎜ ⎟ cosθ + (2 − sinθ + sin 3θ )⎟ ⎥
⎢⎜⎝ ⎝ r ⎟ o/w o/w o/w ⎟
⎥
⎠ ⎠
⎣ ⎦
Normally, the value of the capillary pressure is higher than the maximum operating
pressure. For example, for UF of macroemulsion, θo/w= 135o, γo/w = 0.033 N/m, rd = 150 nm
and r = 100 nm, the capillary pressure is 11.45 bar while the maximum pressure
recommended by the manufacturer is only 4 bar.
o
(Elf SeralfABS cutiing oil macroemulsion, 20
C, 100% = pure cutting oil concentrate = 80% V(approx) oil )
350.00
300.00
250.00
Viscosity (cp)
200.00
150.00
100.00
50.00
0.00
0 10 20 30 40 50 60 70 80 90 100
Oil concentration (% V of cutting oil concentrate in water)
For the power requirement of UF system, main power consumption is the power
required to maintain transmembrane pressure at require flowrate (or recirculation velocity).
This power can be calculated straightforwardly by the basic equation
P⋅Q P⋅V⋅A {6.19}
Power = =
η η
overall overall
Q in this case means recirculation flowrate, not the permeate flowrate. V is the
recirculation velocity and A is the flow area of liquid in UF module (the channel between the
membrane surface and the UF module wall). P in the equation is pump discharge pressure,
which is the summation of transmembrane pressure and other headloss from pipe and values
system. It should be noted that transmembrane pressure is average value of the pressure at
the inlet and outlet of UF module. Overall efficiency of pump depends on pump type. For
progressive cavity pump or progressive screw pump, the efficiency should be around 50-70%.
109
II-65
Chapter 6 Membrane process
Both resistance and film theory based models can give accurate result if the numerical
constants from table 6.1 and 6.2 are chosen correctly. So both models can be used as
generalized models for UF process. It should be noted before using any parameters from any
UF researches that every parameter varies with type of emulsion and membrane. Experimental
procedure (such as recycling of permeate, preparation of emulsion by tap water or
demineralised water, reporting concentration of oil concentration as %V of concentrate or %
V of oil, etc.), as well as the difference from lot-to-lot of membrane manufacturing, also
affects the result. So, if possible, we strongly recommend performing a feasibility test in
bench scale or pilot scale, using real wastewater.
In this thesis, the combination of resistance and film models (section 6.1.3) is
proposed and verified. Advantage of this combine model is that, if we know k, β and Cg and
the flux at one influent concentration (Co), we can find flux at any concentration. This fact is
very useful to extend the resistance model (section 6.1.1) at specific concentration to any
concentration. The constant in table 6.1 and 6.2 can be used to preliminarily calculate UF
process of cutting oil emulsion.
The phenomena, taking place in NF and RO, are more complex than those of MF and
UF. They involve osmotic pressure. So the model of RO and NF will be relatively complicate.
However, because we use them only as post treatment, which the characteristic of influent is
quite typical, so the process can be safely designed using simple criteria, such as aerial
loading rate. From researches of our lab, we can summarize such criteria, as tabulated in table
6.3.
110
II-66
Part II Generalization of model for oil-water separation process design
111
II-67
Table 6.3b Summary of NF data on oily wastewater treatment
Chapter 6 Membrane process
112
II-68
Part II Generalization of model for oil-water separation process design
Our lab studies find that it is feasible to apply heteroazeotropic distillation process on
treatment of oil/water emulsion by adding proper entrainer or extractant, which is relatively
volatile hydrocarbons, into the mixture. The distillate in this case will consist of 2 separate
layers, one of extractant on the top, and another of water at the bottom. The residue from
distillation is water-free hydrocarbons (efficiency = 100%), which can be reused or recycled.
Anyway, due to its relatively high-energy consumption, its application should be considered,
also, from economic point of view, especially for relatively dilute wastewater.
Our lab emphasizes on its application for highly viscous emulsion treatment, like
wasted slop from refineries and retentate left from emulsion treatment by membrane
processes. These applications are feasible because it provides a chance to valorize these
suppose-to-be-wasted materials.
Researches in our lab are based mainly on the study on types of entrainers and influent
parameters, rather than developing distillation column. Main researches on heteroazeotropic
distillation in our lab are thesis of LUCENA [24] on slop treatment and thesis of
WANICHKUL [11] on retentate treatment. However, the concept of calculation, based on
classical theory, can be applied to other oil/water mixtures.
113 II-69
Chapter 7 Heteroazeotropic Distillation
Temperature
Boiling point 2 ph.vapor Dew curves
of hydrocarbon
Boiling point
1 ph.vapor + of water
1 ph. liquid Bubble curve
TH
Azeotrope (H)
Pure 2 ph. liquid
hydrocarbon yH x,y Pure H2O
From the figure, we can set the steps of calculation to create isobar diagram as
follows,
Relations between vapor pressures (Πθb or Psat) and boiling temperature of A and
B, in our case, water and hydrocarbons, can be found in any standard property tables, such as
PERRY’s [2]. Then, we obtain the relation between vapor pressure and boiling temperature of
the mixture from the summation of the vapor pressure of A and B, as shown in eq. 7.1. This
can be done easily by a graphical method, as shown in fig. 7.2. When we select our design
pressure (normally 1 atm), we can obtain heteroazeotropic temperature (TH) from the graph.
Pressure
A+B
Pdesign Pure A
Pure B
TH Temperature
114 II-70
Part II Generalization of model for oil-water separation process design
On the dew curves, partial pressure is equal to vapor pressure, then For
condensation of A
θd Π θd
pA = yA ⋅ P = ΠA → yA = A {7.3a}
P
For condensation of B
Π θd
p B = y B ⋅ P = Π θd
B → y B = B {7.3b}
P
Pure
T2 T1 Temperature hydrocarbon yB 1 yH yA 1x,y Pure H2O
yB 2 y A 2
Heteroazeotropic composition (yH) can be calculated, based on eq. 7.1 and 7.3,
as shown in eq. 7.4,
Π θb
A
yH = yA = {7.3a}
P
115 II-71
Chapter 7 Heteroazeotropic Distillation
Vapor pressures of A and B (water and hydrocarbons) can be obtained from any
standard property tables [2]. yH indicates capability of extractant to extract water from
wastewater. For example, if yH = 0.5 mole/mole, it means 1 mole of extractant can extract 1
mole of water. The higher the yH , the better the extractant.
Molecular y H observed
TH yH yH
Extractant weight (by volume)
(deg. C) (by molar) (by volume)
(g/mol) [24]
C6H14 56 61.6 0.209 0.0351
C7H16 100 79.2 0.452 0.0922
C8H18 114 89.5 0.616 0.188
C9H20 128 94.8 0.827 0.3255
C10H22 142 97.6 0.914 0.495 0.468
C11H24 156 98.9 0.959 0.6663
C12H26 170 99.5 0.98 0.7953 0.767
C13H28 184 99.8 0.991 0.890
C14H30 198 99.95 0.996 0.9542
C15H32 212 99.999 0.998 0.9702
C16H34 226 ≈ 100 0.999 0.9840
116 II-72
Part II Generalization of model for oil-water separation process design
On the other hand, for stripping, we can find the theoretical quantity of steam or water
required for extracting the design volume of volatile hydrocarbons from the following
equations. Please note that the calculated volume of steam is the quantity required for
heteroazeotropic distillation only. Additional heat may be required to raise the temperature up
to the design point. Stripping is suitable to treat the waste polluted by small amount of volatile
substance. The concept is also applied to essential-oil extraction from herbs or flowers in
perfume or chemical industries.
yH
Volumesteam = S.F ⋅ Volume {7.6a}
hydrocarbon (1 − y )
H
Or
yH
Volumesteam = S.F ⋅ Concentration Volume wastewater {7.6b}
hydrocarbon (1 − y H )
117 II-73
Part III Summary of researches :
Oily wastewater treatment
Part III Summary of researches: Oily wastewater treatment
Content
Page
III-i
Chapter 1 Oily or hydrocarbon-polluted wastewater
Content (Con’t)
Page
III-ii
Part III Summary of researches: Oily wastewater treatment
Content (Con’t)
Page
III-iii
Chapter 1 Oily or hydrocarbon-polluted wastewater
Content (Con’t)
Page
III-iv
Part III Summary of researches: Oily wastewater treatment
Content (Con’t)
Page
III-v
Chapter 1 Oily or hydrocarbon-polluted wastewater
Table
Page
III-vi
Part III Summary of researches: Oily wastewater treatment
Table (Con’t)
Page
Table 8.2.2-4 Procedure to predict flux/pressure relation for case 1: Know k, III-211
β, Cg and R’m
Table 8.2.2-5 Procedure to predict flux/pressure relation for case 2: Know φ, α, III-213
Cg and R’m
Table 8.2.3-1 Composition of the special cleaning microemulsion concentrate [18] III-230
Table 8.4.2-1 Summary of RO data on oily wastewater treatment III-240
Table 8.5.2-1 Summary of NF data on oily wastewater treatment III-243
Table 8.6-1 Comparison of membrane processes on cutting macroemulsion III-244
treatments (based on Elf Seraft ABS at 4% by V of oil)
Table 9.3.3-1 Heterotropic temperature and composition from various III-254
hydrocarbons [24]
Table 9.3.4-1 Water extracting performance of various commercial hydrocarbons [24] III-257
Table 10.2.4-1 Results from ZHU’s research on destabilization of various emulsions III-272
Table 10.3.2-1 Recommended value of gradient and detention time III-277
Table 11-2.1-1 Rate coefficient for selected wastewaters [51] III-282
Table 11.2.1-2 Biodegradability and biotoxicity data [51] III-284
Table 11.2.1-3 Concentration of certain metals affecting biological systems [45] III-287
Table 11.2.2-1 Case studies on biological treatment of oily wastewater [66] III-287
Table 11.3.1-1 Examples of PAC and GAC properties III-289
Table 11.3.1-2 Adsorptive capacity of AC for some hydrocarbons [65] III-291
Table 11.3.3-1 Adsorption isotherm and MTZ data of some co-surfactants [21] III-295
Table 12.1-1 Guideline for oily wastewater process selection (based on III-298
GPI’s researches)
III-vii
Chapter 1 Oily or hydrocarbon-polluted wastewater
Figure
Page
Fig. 1.2.1-1 Examples of normal alkanes and derivatives with equal number of III-4
carbon atoms
Fig. 1.2.1-2 Examples of benzene series III-6
Fig. 1.4.3-1 Relation between droplet sizes and rising velocity of primary and III-13
secondary emulsion [11]
Fig. 1.4.3-2 Classification of oily wastewater by degree of dispersion III-14
Fig. 2.1-1 Free body diagram of oil drop in water and relation between III-21
Cd and Re [55]
Fig. 2.2.1-1 Force diagram of oil drop in water III-23
Fig. 2.2.1-2 Model for visualization of γ [40][42] III-24
Fig. 2.2.1-3 Model for visualization of adhesion work III-25
Fig. 2.2.2-1 Diagram of Oil drop on solid surface in water III-25
Fig. 2.2.2-2 Model for visualization of cohesion work III-26
Fig. 2.2.2-3 Effect of surface roughness on contact angle III-27
Fig. 2.2.3-1 Section of air bubble in water III-29
Fig. 2.2.3-2 Diagram for visualizing the capillary pressure III-30
Fig. 2.3.2-1 Example of the size distribution of oil droplet in cutting oil III-32
macroemulsion (Elf Seraft 4% V of concentrate), measured by Coultronics nanosizer NDM4 [11]
Fig. 2.3.2-2 Granulometer (Source: above - Ankermid Techcross / below - CILAS) III-33
Fig. 2.3.2-3 Decanting test column III-33
Fig. 2.3.2-4 Relation between accumulated C/Co (% of C/Co when the droplet size III-36 is
equal or smaller than the given dE) and oil droplet size
Fig. 2.3.2-5 Example of estimated size distribution of oil droplets from III-37
decanting test
Fig. 2.5.2-1 Cut size determination III-43
Fig. 2.2.5-2 Economics of processes (least cost criteria) III-44
Fig. 3.1-1 Examples of oil skimming devices III-46
Fig. 3.2.1-1 Lab-scale drum skimmer: Major components are shown. III-47
(Source: GPI lab)
Fig. 3.2.1-2 Surface energy or superficial tension of materials, oil and water III-48
Fig. 3.2.1-3 Influent parameters on drum skimmer performance III-52
Fig. 3.2.2-1 Occurrence of eddy currents from drum operation and no oil zone III-54
or non-productive zone that affects the productivity of the skimmer
(Source: Oil Spill Cleanup)
Fig. 3.5-1 Application of the skimmers III-58
III-viii
Part III Summary of researches: Oily wastewater treatment
III-ix
Chapter 1 Oily or hydrocarbon-polluted wastewater
Fig. 5.4.3-3 Characteristics of oil and water drops on silicon coated (oleophilic) III-112
steel fibers and non-coated (hydrophilic) steel fibers
Fig. 6.2-1 Example of schematic diagram of DAF (Source: Aquatec Maxcon) III-115
Fig. 6.2.1-1 Diagram for considering relative velocity of bubble and oil in flotation III-117
column
Fig. 6.2.1-2 Schematic diagram of the 3 transport phenomena III-117
Fig. 6.2.1-3 Schematic of single bubble and entire height of flotation column III-118
Fig. 6.2.1-4 Relation between theoritical efficiency factor and observed efficiency III-120
factor
Fig. 6.2.4-1 Typical relation between efficiency of DAF and various parameters III-124
Fig. 6.2.4-2 Solid-bubble agglomerate and formation of oil-bubble agglomerate [14] III-126
Fig. 6.3-1 Pilot-scale DAF test and Flota-test III-135
Fig. 6.4-1 Example of necessary equipment and component details of DAF system III-
140(Source: Environ Treatment System)
Fig. 6.4-2 Necessary equipment and reactor components of DAF system III-141
Fig. 6.4-3 Examples of characteristics of scum from DAF processes III-145
Fig. 6.5-1 Example of good bubble formation from pressurized water III-146
(Source: Cornell DAF pump)
Fig. 6.5-2 Relation between power required for pump, compressor and absolute III-149
3
pressure of saturator for pressurized water flowrate of 10 m /h (assume %air saturation = 95%)
Fig. 6.5-3 Schematic diagrams of saturator systems (Source: Edur pump) III-151
Fig. 6.5-4 Examples of saturator system III-152
Fig. 6.5-5 Examples of injection valve III-153
Fig. 7.1-1 Basic flow pattern and examples of hydrocyclones III-155
Fig. 7.2.1-1 General flow pattern and features of hydrocyclones III-158
Fig. 7.2.1-1 General flow pattern and features of hydrocyclones III-159
Fig. 7.2.1-2 Velocity components in hydrocyclone III-159
Fig. 7.2.1-3 Tangential velocity profile in hydrocyclone and various typed of vortex III-160
Fig. 7.2.1-4 Examples of tangential velocity profile III-161
Fig. 7.2.1-5 Example of axial or vertical velocity profile III-162
Fig. 7.2.1-6 Example of radial velocity profile [30] III-163
Fig. 7.2.1-7 Forces on oil droplets or particles in hydrocyclone III-163
Fig. 7.2.1-8 Components of velocity of oil droplets or particles in hydrocyclone III-163
III-x
Part III Summary of researches: Oily wastewater treatment
Fig. 7.2.1-9 Trajectories of oil droplets and typical efficiency curvefrom trajectory III-166
analysis model
Fig. 7.2.1-10 Comparison between observed efficiency and predicted efficiency III-168
form MA’s model and THEW-COLMAN’s model
Fig. 7.2.1-1 Corresponding flowrate and velocities of various sizes of hydrocyclones III-173
at overflow pressure drop (Po) = 3 and 5 bars
Figure (Con’t)
Page
Fig. 7.2.3-1 An example of the coupling between solid-liquid and liquid III-176
hydrocyclone for the treatment of oily wastewater containing suspended
solids (Source: Ultraspin)
Fig. 7.2.4-1 Relation between oil and water outlet velocity in co-current III-177
hydrocyclone
Fig. 7.3.1-1 Three-phase hydrocyclone III-178
Fig. 7.3.1-2a Oil drop (sphere) and particle (cube) trajectories in three-phase III-179
hydrocyclone
Fig. 7.3.1-2b Typical vertical velocity profiles in three-phase hydrocyclone III-179
Fig. 7.3.1-3 Comparison between observed pressure drop and predicted valued from III-182
the 2 approaches (similarity and semi-empirical model)
Fig. 8.1.1-1 Material sizes and corresponding membrane processes III-
184(Source: Osmonics)
Fig. 8.1.1-2 Separation characteristic of membrane processes (Source: III-184
Koch membrane system)
Fig. 8.1.2-1 Mode of operation of membrane process [11] III-185
Fig. 8.1.3-1 Membrane structures (Source: SCT, Millipore) III-186
Fig. 8.1.4-1 Membrane materials (Structures depend on manufacturing processes.) III-187
(Source: Millipore, Orelis, WWW.Scienceinafica.co.za)
Fig. 8.1.5-1 Membrane modules III-191
Fig. 8.2.1-1 Relation between pore sizes and MWCO [59] III-194
Fig. 8.2.1-2 Typical characteristic curves of UF membrane III-195
Fig. 8.2.1-3 Oil drop at membrane pore III-196
Fig. 8.2.1-4 Typical schematic of cross-flow UF for wastwater treatment III-196
Fig. 8.2.1-5a Examples of pure water flux and solution flux characteristics III-197
Fig. 8.2.1-5b Typical characteristic curves of water and solution flux VS. III-197
transmembrane pressure when feed conc. is constant
Fig. 8.2.1-6 Characteristic curves of permeate flux and feed concentration III-198
Fig. 8.2.1-7 Typical characteristics of permeate flux VS. time for constant feed conc III-198
system
Fig. 8.2.1-8 An example of characteristic of flux VS. time for non-constant feed III-199
conc. system
III-xi
Chapter 1 Oily or hydrocarbon-polluted wastewater
Fig. 8.2.1-9 Diagram of polarization layer and effect of velocity on flux in film III-201
theory
Fig. 8.2.1-10 Various resistances in UF processes III-203
Fig. 8.2.2-1 Examples of flux VS. oil concentration in UF of macroemulsion III-211
Fig. 8.2.2-2 Case 1: find flux/pressure relation when k, β, Cg and R’m are known III-211
Fig. 8.2.2-3 Relation between UF permeate flux and Transmembrane pressure III-212 at
Cref = 4% by volume of oil , V = 1.4 m/s and Predicted relations at C = 2 and 8% (Oil: Elf SeraftA
cutting oil macroemulsion, Membrane: IRIS 3042 PAN )
Figure (Con’t)
Page
Fig. 8.2.2-4 Relation between Flux VS. theoretical and observed permeate volume III-216
Fig 8.2.2-5 Relation between time VS. theoretical and observed permeate volume III-217
Fig. 8.2.2-6 Calculation of required storage volume of equalization tank by III-218
graphical method
Fig. 8.2.2-7 Relation between oil concentration VS. viscosity of emulsion III-220
Fig. 8.2.3-1a Flux of non-stabilized emulsion III-222
Fig. 8.2.3-1b Photographs of non-stabilized emulsion influent, retentate and permeate III-
222(from left) [10]
Fig. 8.2.3-2 Typical relation between CaCl2 concentration and flux at low Pt III-223
Fig. 8.2.3-3a Partially destabilization by salt and coalesce of oil droplets III-224
Fig. 8.2.3-3b Magnified images (x100) of oil droplets from original (left) and III-224
partially destabilized macroemulsion (right) [11]
Fig. 8.2.3-3c Magnified images of new membrane surface (left) and the surface after III-224
UF of macroemulsion at 3 bars without salt (middle) and with salt
addition (600 mg/l CaCl2) [11]
Fig. 8.2.3-4 Relation between fluxes VS. pressure and calculated VS. observed oil III-225
concentration in retentate for partially destabilized emulsion
Fig. 8.2.3-5 Examples of feed emulsions and their corresponding UF permeates III-226
Fig. 8.2.3-6 Examples of flux enhance techniques [38] III-228
Fig. 8.2.3-7 Example of evolution of flux of macroemulsion UF with periodical III-229
cleaning with macroemulsion (membrane IRIS 3042, P = 1 bar,
V=1.5 m/s. 25oC) and schematic of interaction between membrane/
surfactants [18]
Fig. 8.2.3-8 Examples of UF test modules III-231
Fig. 8.3.1-1 Examples of MF membranes III-232
Fig. 8.3.2-1 Evolution of flux from MF (with salt addition) of macroemulsion [20] III-234
Fig. 8.4-1 Examples of RO membranes III-235
Fig. 8.4.1-1 Working principles of reverse osmosis III-235
Fig. 8.4.2-1a Typical relation between flux and pressure of RO III-237
Fig. 8.4.2-1b Typical relation between flux and log of concentration III-237
III-xii
Part III Summary of researches: Oily wastewater treatment
Fig. 8.4.2-2 Examples of flux evolution from RO of the UF permeates of various III-237
emulsions(the RO permeate are not recycled) [11]
Fig. 8.4.2-3a Relation between rejection, TOD of permeate and concentration factor III-238
Fig. 8.4.2-3b Relation between rejection and transmembrane pressure III-238
Fig. 8.4.2-2 Examples of permeate TOD evolution from RO of the UF permeates III-238
of various emulsions (the RO permeate are not recycled) [11]
Fig. 8.5.2-1 Relation of flux and transmembrane pressure of NF for macroemulsion III-
241(Elf Seraft ABS) and microemulsion treatment (Elf Emulself G3 EAB),
using desal5 membrane at 20oC [20]
Figure (Con’t)
Page
Fig. 8.5.2-2 Relation of flux and theoretical feed concentration of NF for macro- III-242
and microemulsion treatment [20]
Fig. 9.2.1-1 Diagram of a binary mixture system III-246
Fig. 9.2.1-2 Evolution of temperature of a binary mixture at a constant P III-246
Fig. 9.2.1-3 Examples of P-T diagram III-246
Fig 9.2.1-4 Examples of T-x-y and P-x-y diagrams III-247
Fig. 9.2.1-5 An example of P-T-x-y diagram III-247
Fig. 9.2.1-6 An example of T-x-y diagram III-247
Fig. 9.2.2-2 Examples of evolution of VLE and VLLE with pressure III-248
Fig. 9.2.2-1 Examples of various types of vapor/liquid equilibrium III-249
Fig. 9.3.1-1 Typical isobar diagram oily wastewater III-250
Fig. 9.3.3-1 Graphical method to find heteroazeotropic temperature III-252
Fig. 9.3.3-2 Graphical method to find dew curve III-253
Fig. 9.3.4-1 Examples of lab-scale apparatus for heteroazeotropic III-255
distillation [11], [24]
Fig. 9.3.4-2 Example of evolution of temperature with time from the treatment of UF III-255
permeate of cutting oil emulsion, using decane as entrainer [11]
Fig. 9.3.4-3 Pictures of feed, residue and retentate of slop and UF retentate of used III-256
macroemulsion (30% by volume of oil) [24], [11]
Fig. 9.4.2-1 Evolution of temperature, volume of distillate, TOD of mixed distillate III-260
and TOD of water part of the distillate (Based on Elf Seraft ABS, 4%
by volume of concentrate) [11]
Fig. 9.4.2-2 The feed, residue and distillate from distillation of the III-260
macroemulsion [11]
Fig. 9.4.2-3 Evolution of temperature, volume of distillate , TOD of mixed distillate III-261
and TOD of water part of the distillate (Based on Elf G3 EAB, 4% by
volume of concentrate) [11]
Fig. 9.4.2-4 The feed, residue and distillate from distillation of the III-261
microemulsion [11]
Fig. 9.4.2-5 Evolution of temperature, volume of distillate, and TOD of distillate III-
262(Based on UF of used macroemulsion, TOD of feed =4400 mg/l) [11]
III-xiii
Chapter 1 Oily or hydrocarbon-polluted wastewater
Fig. 10.2.2-1 Symbols of surface active agent and its localization at oil/water III-264
interfaces
Fig. 0.2.2-2 Diagram of the electrical double layer III-266
Fig. 10.2.3-1 Interfacial of oil and water with the presence of surfactants III-266
Fig. 10.2.3-2 Coalescence and redistribution of droplets in thermodynamiclly III-266
stabilized emulsion
Fig. 10.2.3-3 Diagram of the electrical double layer III-267
Fig. 10.2.4-1 Force diagram of oil droplets and relation of repulsive, attractive and III-268
resulting force with the distance between oil droplets
Figure (Con’t)
Page
Fig. 10.3-1 Schematic diagram of chemical process for emulsion destabilization III-274
Fig. 10.3.1-1 Static mixer (leftmost) and impeller types (from left): flat turbine, III-275
pitched blade turbine, propeller type (Source: Memko, Sharp mixers)
Fig. 10.3.1-2 Relation between Np and Re [63] III-276
Fig. 10.3.2.1 Paddle type mixers (Source: Norfolk WTP, Aqua Pak) III-277
Fig. 10.4-1 Jar test equipment (Source: ECE engineering) III-278
Fig. 10.4-2 Example of stabilized emulsion before (right) and after chemical III-279
treatment (left)
Fig. 11.2.1-1 General schematic diagram of activated sludge III-281
Fig. 11.3-1 Schematic diagram of adsorption III-289
Fig. 11.3.2-1 Examples of adsorption isotherm diagrams III-291
Fig. 11.3.2-2 Evolution of pollutant concentration along the bed depth III-292
Fig. 11.3.2-3 C/V curve and C/H curve III-292
Fig. 11.3.3-1 Examples of AC and GAC filter III-296
Fig. 12.2.1-1 Schematic diagram of cutting oil emulsion treatment system III-303
Fig. 12.2.2-1 Schematic diagram of conventional oily wastewater treatment system III-304
Fig. 12.2.2-2 Schematic diagram of compact oily wastewater treatment system for III-304
Non-stabilized secondary emulsion
III-xiv
Part III Summary of researches: Oily wastewater treatment
118 III-1
Chapter 1 Oily or hydrocarbon-polluted wastewater
1.1 Introduction
Water pollution is one of the most important environmental problems. Wastewater
from agriculture and industrial processes, as well as domestic wastewater, is main pollutant
source that causes water pollution problem. There are many substances that can deteriorate
water quality and, then, can be counted as water pollutants, such as, organic matter from
domestic wastewater, chemicals from industrial wastewater. Some valuable substances, such
as sugar, flour, oil, will become major pollutants when discharged into water bodies.
Among various kinds of pollutants, hydrocarbon or oil is one of the most severe
pollutants because of its intrinsic properties. Examples of adverse effects of hydrocarbons or
oil when it is discharged into water bodies or environment can be summarized as follow;
• Even the small amount of oil can cause unpleasant odor and taste, so the water can
not be used in potable water production system. Some hydrocarbons, such as
benzene series, are noted for their carcinogen property.
• Presence of oil or hydrocarbons in visible form on the water surface is
objectionable from aesthetic and recreation point of view.
• For ecosystem, floating oil layer is dangerous for it can directly harm aquatic
animals such as fishes and waterfowls. It may coat and destroy algae thereby
destroying food sources of aquatic animals.
• Small amount of hydrocarbon can spread over wide area of water surface. API
reports that only 40 liters of oil can cover 1 km2 of water surface in form of visible
film. It can affect photosynthesis and oxygen transfer, so causes adverse effect to
marine or water ecology.
• The hydrocarbon contributes to very high biochemical oxygen demand (BOD) and
is relatively difficult for biodegradation, which is main natural self-purification
process. So it can last relatively long in the water and cause long term effect.
The first step to proper oily wastewater treatment design is to have basic knowledge
on types and characteristics of oily wastewater, which are described in the following sections
1.2.1 Hydrocarbons
Chemically, the hydrocarbons are compounds of carbon and hydrogen. They are also
in the family of organic compounds, thus can be divided into 3 types, according to formation
of characteristic groups i.e., aliphatic hydrocarbons, aromatic hydrocarbons and heterocyclic
hydrocarbons.
119 III-2
Part III Summary of researches: Oily wastewater treatment
The aliphatic hydrocarbons are the hydrocarbon compounds those in which the carbon
atoms are linked to a straight line. There can be subdivided into 2 groups i.e., saturated and
unsaturated aliphatic hydrocarbons.
Nomenclature: The hydrocarbons that form to a straight line are the basic form,
called normal alkanes or n-alkanes, such as n-butane. The names and properties of some
normal alkanes are shown in table 1.2.1-1. There are also another formations of hydrocarbons
with the same number of carbon atoms as shown in fig. 1.2.1-1. These hydrocarbons are
named differently from n-alkanes. To name such hydrocarbons, the IUPAC system is
commonly used, somehow, will not be presented here.
120 III-3
Chapter 1 Oily or hydrocarbon-polluted wastewater
H H H H H H H
H C C C C H H C C C H
H H H H H CHC H
C
a) n-Butane b) Isobutane
Fig. 1.2.1-1 Examples of normal alkanes and derivatives with equal number of
carbon atoms
Basic chemical reactions: The hydrocarbons in this category are quite inert. In
ambient, they do not react with strong bases, acids or aqueous solutions of oxidizing agents.
However, at elevated temperature, strong oxidizing agents, such as concentrated sulfuric acid,
oxidize the compounds to CO2 and water. Other important reactions of the compounds are as
follow;
Alkenes: The hydrocarbons in this category contain one double bond between
two adjacent carbon atoms. Their general formula is CnH2n, such as Ethylene (C2H4), Butene
(C4H8). They are also called “Olefins”. The compounds are produced in large number during
the cracking of petroleum.
Diolefins: The hydrocarbons in this category contain two double bonds, such as
1,3-butadiene (CH2=CHCH=CH2), which has been used to make polymers.
121 III-4
Part III Summary of researches: Oily wastewater treatment
Specific Solubility
Melting point Boiling point gravity
Name Formula (at 25
(°C/ 1 atm) (°C/1 atm) (20/4°) °C)(mg/l)
Ethene CH2=CH2 -169 -103.7 0.568-104C
Propene CH2=CHCH3 -185.2 -47.6 0.50525C
1-Butene CH2=CHCH2CH3 -185.3 -6.2 0.58825C
1-Pentene CH2=CH(CH2)2CH3 -165.2 29.9 0.640
1-Hexene CH2=CH(CH2)3CH3 -139.7 63.4 0.673 50
1-Heptene CH2=CH(CH2)4CH3 -119.7 93.6 0.697
1-Octene CH2=CH(CH2)5CH3 -101.7 121.2 0.715 2.7
1-Nonene CH2=CH(CH2)6CH3 -81.3 149.9 0.72525C
1-Decene CH2=CH(CH2)7CH3 -66.3 170.5 0.741
Alkadienes: The hydrocarbons in this category contain more than two doubles,
such as the red coloring matter of tomatoes, lycopene. Example of presence of these
compounds in industrial wastes is wastewater from vegetable canneries. They require
extremely high demand of oxidant.
Alkynes: The hydrocarbons in this category contain one triple bond, for
example, H-C≡C-H. They are found to some extent in industrial wastes, such as synthetic
rubber industries. Solubility
These compounds are the special cases of aliphatic hydrocarbons. They are also
called “Naphthenes” and can be count as saturated hydrocarbons. The compounds can be
easily described as a ring of CH2 molecules. They are found in petroleum product. Examples
122 III-5
Chapter 1 Oily or hydrocarbon-polluted wastewater
of these compounds are cyclopropane, cyclopentane, cyclohexane, etc. At the same number of
carbon atoms, naphthenes have higher density and lower melting point than paraffins.
The aromatic hydrocarbons are the hydrocarbon compounds that contain ring
structure. The difference between these compounds and the cyclic aliphatic compounds is that
a carbon atom has one single bond and one double bond to the adjacent carbon atoms (see fig.
1.2.1-2). For the cyclic aliphatic compounds, they do not have double bond. There are 2 major
series of the aromatic hydrocarbons, i.e., Benzene and Polyring series.
1. Benzene series
Benzene (C6H6) ring is the simplest aromatic ring, containing 6 carbon atoms.
Benzene ring is knows as the parent compound of the aromatic series. The formula of benzene
is shown in fig. 1.2.1-2. The compounds in benzene series are made up of alkyl (CnH2n+1)
substitution product of benzene. Examples of the compounds in benzene series are as shown
in table 1.2.1-3 and fig .1.2.1-2.
These compounds are widely used as solvents and in chemical synthesis. They
are commonly found in petroleum products, such as gasoline. The compounds are hazardous
for human health. They are known to be carcinogenic and cause leukemia. Eventhough they
are relatively insoluble in water, there are limits of these compounds, such as xylene, toluene,
set in drinking water standards.
Boiling Specific
Melting Solubility
Name Formula point(°C/1 gravity
point(°C) (at 20 °C)
atm) (20/4°)
Benzene C6H6 5.5 80.0 0.877 1,600
Toluene C6H5CH3 -94.9 110.6 0.867 500
o-Xylene C6H4(CH3)2 -25.2 144.5 0.88 170
m-Xylene -47.8 139.1 0.864
p-Xylene 13.2 138.3 0.861
Ethybenzene C6H5C2H5 -94.9 136.1 0.867 130
H
C CH3
HC CH CH3 CH3
HC CH
C
H
a) Benzene ring b) simplified formula c) Toluene d) o-Xylene
of benzene
123 III-6
Part III Summary of researches: Oily wastewater treatment
2. Polyring series
The compounds contain more than 1 benzene ring. Some compounds are in
from of solids at ambient, such as Naphthalene (mothball). Other examples of the compounds
in this group are Anthracene and Phenanthrene (C14H10). They are known as carcinogen, thus
also hazardous to human health. Furthermore, the larger compounds (5 or more rings) are very
difficult to be biodegraded.
The heterocyclic hydrocarbons are the hydrocarbon compounds that have one other
element in the ring in addition to carbon. An important hydrocarbon in this group is epoxides.
Epoxides are three-membered rings where oxygen is bonded with two carbons. They are very
reactive. Example of epoxides is ethylene oxide, which is in synthetic surfactant and pesticide.
Chemically, fats and oils are esters (product formed by reaction between acid and
alcohol) of the trihydroxy alcohol, glycerol. They are also described as glycerides of fatty
acids. These glycerides that are liquid at room temperature are called oils and those that are
solids are called fats. The oils, here, are mainly vegetable or animal oil and normally edible.
• Oxidation: For some oils, such as linseed oil, oxygen may be added to the double
bonds and forms resin-like material. These drying oils are major component in all
oil-based paints.
• Hydrolysis: since they are esters, oils can be easily hydrolyzed into glycerol plus
fatty acids. If hydrolysis is accomplished by using of NaOH, it is called
saponification. The product from saponification is soap.
• Addition: Oils containing unsaturated acids can add chlorine at the double bonds.
This process is normally slow. However, it may represent a significant part of
chlorine demand in some wastes. Oils that contains large amount of oleic and
linoleic acids may be converted to fats by the process of hydrogenation. Thus, low-
priced oils can be converted into magarine.
Petroleum and petroleum products are one of the major sources of oil in oily
wastewater. Petroleum is the mixture of various hydrocarbons, as well as other chemicals. If
contains (by weight) about 80% of carbon, 10-15% of hydrogen, 1.55 of oxygen, 0.1-t% of
124 III-7
Chapter 1 Oily or hydrocarbon-polluted wastewater
sulfur, 0.65 of nitrogen and also trace amount of iron, calcium, sodium, potassium, and other
elements [39]. The density of crude oils is around 650 to 1,200 kg/m3.
Olefins are found relatively rarely and in significant amount. Because of their highly
reactive and easily polymerizing, they are relatively undesirable components in fuels and
lubricant oils.
Naphthenes are normally found in forms of cyclo-pentane and cyclo-hexane. They are
also important components of fuels and lubricant oils for their temperature resistance
property.
Aromatic hydrocarbons of 1 to 4 rings are also found in crude oils. These compounds
have the greatest density, compared to other hydrocarbons. They provide good viscosity-
temperature property to petroleum product. They are also good solvents
Solubility of crude oils is low. The solubility of petroleum fractions decreases in the
following order: aromatic compounds – naphthenes – paraffins. It also decreases with
increasing in molecular weight.
Petroleum products are the product derived from crude oils through processes such as
catalytic cracking and fractional distillation. These products have physical and chemical
characteristics that differ according to the type of crude oils and subsequent refining
processes. Several examples of refined petroleum products and their physical properties are as
follow:
Gasoline: a lightweight product that flows easily, spreads quickly, and may evaporate
completely in a few hours under temperate conditions. It poses a risk of fire and explosion
because of its high volatility and flammability, and is more toxic than crude oil. Gasoline is
amenable to biodegradation, but the use of dispersants is not appropriate unless the vapors
pose a significant human health or safety hazard.
Kerosene: a lightweight product that flows easily, spreads rapidly, and evaporates
quickly. Kerosene is easily dispersed, but is also relatively persistent in the environment.
No. 2 Fuel Oil: a lightweight product that flows easily, spreads quickly, and is easily
dispersed. This fuel oil is neither volatile nor likely to form emulsions, and is relatively non-
persistent in the environment.
No. 4 Fuel Oil: a medium weight product that flows easily, and is easily dispersed if
treated promptly. This fuel oil has a low volatility and moderate flash point, and is fairly
persistent in the environment.
125 III-8
Part III Summary of researches: Oily wastewater treatment
No. 5 Fuel Oil (Bunker B): a mediumweight to heavyweight product with a low
volatility and moderate flash point. Preheating may be necessary in cold climates, and this
fuel oil is difficult, if not impossible, to disperse.
No. 6 Fuel Oil (Bunker C): a heavyweight product that is difficult to pump and
requires preheating for use. This fuel oil may be heavier than water, is not likely to dissolve, is
difficult or impossible to disperse, and is likely to form tar balls, lumps, and emulsions. It has
a low volatility and moderate flash point.
Lubricating Oil, a medium weight product that flows easily and is easily dispersed if
treated promptly. This oil has a low volatility and moderate flash point, but is fairly persistent
in the environment
From section 1.2.1 to 1.2.3, the definitions and properties of hydrocarbons and other
substances have been described. Those substances can be accounted as “oil” in oily
wastewater. Even though they are some discrepancies in their chemical formula, their source
of origin or some or their properties, they are some physical properties in common. Since the
treatment processes studied in GPI lab are based on separation process, which depends mainly
on these physical properties, it can be concluded that substances that have identical properties
can be accounted as “oil” by the meaning of this book. These properties include:
• Liquidity: oils, in our case, must be liquids only. So some solids hydrocarbons and
fats will not be accounted as “oil” in our case.
• Solubility: oils, in our case, must have very low solubility in water. So it can be
treated as non-miscible binary mixture, which is main assumption or condition that
governs operating principles of most separation processes. However, dissolved
pollutants in oily wastewater are considered in some treatment processes, even
though their major components come from other additives in oil, rather than the
dissolved portion of oil its self.
• Specific gravity or density: oils, in our case, must have less density or specific
gravity than water.
So, after this section, the word “oils” found herein this book will normally refer to the
substances that conform to the above criteria.
1.3.1 Surfactants
126 III-9
Chapter 1 Oily or hydrocarbon-polluted wastewater
interfaces), it means the work required to form new surfaces. The substances that can decrease
the level of surface energy are called “surface-active substances” or “surfactants”. They are
also called by other names, such as, detergents (for solid/liquid interface, e.g. in washing or
cleaning process), emulsifier, or dispersant, etc. With proper amount of surfactants, surface
energy can be substantially decreased until almost to zero. This makes it possible to create a
lot of new surface.
In our interest, surfactants can help making a lot of new surfaces of oil in the water.
This means the oils can be divided into very small droplets, which contributes to many new
surfaces, in the water, called emulsion. Theory of surface energy will be described in chapter
2. Effect and some further details of surfactants and co-surfactants will be described again
in chapter 10 “Chemical treatment processes”.
All surfactants have rather large functional groups. One end of the molecule, which
normally is organic group, is particularly soluble in oil. The other (polar group) is soluble in
waters. There are 4 main types of surfactants i.e., cationic, anionic, non-ionic and ampholytic
surfactants
These surfactants are generally salts of quaternary ammonium hydroxide. The surface-
active properties are contained in the cations. Besides their surface-active properties, the
compounds are known for their disinfecting properties.
These surfactants are generally sodium or potassium salts. The common ones are
sulfates and sulfonates. The surface-active properties are contained in the anions.
These surfactants do not ionize and have to depend upon groups in the molecule to
render them soluble. All depend on polymers of ethylene oxide (C2H4O) to give them this
property.
For these surfactants, they contain both cationic and anionic functional groups.
1.3.2 Soaps
Ordinary soaps are derived from fats and oils by saponification with sodium
hydroxide. Saponification is the special case of hydrolysis in which an alkaline agent is
present to neutralize the fatty acids as they are formed. The fats and oils are split into glycerol
and sodium soaps. The nature of the soap depends on the type of fat and oil used. Sodium and
potassium soaps are normally soluble. If the water contains hardness, calcium, magnesium
and other hardness-causing ions will precipitate soap to form metallic soap. Soap will
precipitate all hardness ions first, after that it becomes a surfactant.
127 III-10
Part III Summary of researches: Oily wastewater treatment
1.3.3 Co-surfactants
Suspended solids are commonly found in oily wastewater, especially when combined
collection systems are used. Types and concentration of suspended solids, present in oily
wastewater, depends on the sources of the wastewater. Some oil separation processes, esp. the
ones that are based on filtration concept such as granular bed coalescer and membrames, are
sensitive to the suspended solids. Suspended solids can cause adverse effect on oil separation
processes, unless it has already accounted for and mitigation measure is provided.
Others components found in oily wastewater depend on their source. Normally they
are the additives of the oil product, such as anti-foaming agents, anti-mousse agents,
bactericides, dyes, or anti-corrosion agents, etc. Some can present adverse effect on treatment
processes. Some may be present as residual pollutants in the effluent after oil separation
processes. So it will be very helpful if we know in advance the components of the oily
wastewater considering.
In binary mixture systems of oil and water, their components can be divided into 2
main phases, i.e., continuous phase, which is the majority of the two, and dispersed phase.
Direct emulsion: If continuous phase is the water, the mixture will be called “direct
emulsion”, and can be written as “o/w emulsion”, which stands for emulsion of oil in water.
Inverse emulsion: On the other hand, if the continuous phase is oil, the mixture will
be called “inverse emulsion” or “w/o emulsion”.
The treatment processes described herein this book will emphasize on oily wastewater,
which is direct emulsion. However, some processes can also be applied to inverse emulsion.
128 III-11
Chapter 1 Oily or hydrocarbon-polluted wastewater
1. Non-stabilized emulsion
This type of wastewater mainly consists of 2 components, i.e., oil and water,
without presence of surfactants. So its stability is not enhanced by surfactants and depends
mainly on degree of dispersion (the size of oil droplets) in the wastewater. If the droplet size
is small, the oil drop will take long time to rise to the surface, so it stays relatively long within
the water phase. As long as there are oil dispersed in the water, the mixture is still called
emulsion. The longer the time that droplets stay in the water, the greater the stability of the
emulsion. Without surfactants, the degree of dispersion depends on energy added to the
system to disperse the oil phase. This energy is normally supplied by mechanical means, such
as agitation, pump, or hydraulic mixing, such as venturi.
2. Stabilized emulsion
This type of wastewater contains oil, water and surface-active agent, which may
consists of only one surfactant or both surfactant and co-surfactant. Presence of these surface-
active substances cause decrease in interfacial tension between oil and water, thus make the
oil disperse into very fine droplets, down to micron size. Furthermore, localization or
orientation of the surface-active agents causes electric barrier as well as mechanical barrier
that prevent collision and coalescence between droplets. So the droplets remain small (See
chapter 10). Their rising velocity is then very small and can be negligible, compared to
Brownian motion. So this type of emulsion is stable, as it is called, and not prone to decant
naturally.
This type of wastewater is relatively easy to treat for the oil and the water are
readily separated. However, extraction or removal of oil from the water surface should be
carefully performed to prevent entraining of water with oil.
2. Primary emulsion
Oily wastewater will be categorized into this type if the oil droplets are greater
than 100 microns.
3. Secondary emulsion
Oily wastewater will be categorized into this type if the oil droplets are smaller
than 20 microns.
129 III-12
Part III Summary of researches: Oily wastewater treatment
10-3
Primary
10-4 emulsion
Secondary
emulsion
10-5
Rising velocity (m/s)
10-6
10-7
Primary
10-8 emulsion
Secondary
emulsion
10-9
10-10
1 10 100 1000
Droplet diameters (microns)
Oil 0.60 0.70 0.75
density 0.80 0.98 0.90
Fig. 1.4.3-1 Relation between droplet sizes and rising velocity of primary
and secondary emulsion [11]
4. Macroemulsion
This type of emulsion contains droplet size between 0.06 to 1.0 microns. It
usually contains surfactant (and co-surfactant). This type of emulsion has a milky appearance.
A common example of this emulsion is cutting oil macroemulsion.
5. Microemulsion
From the three criteria stated above, some classes of oily wastewater from
different criteria might be overlapped. So, to summarize all of three criteria, oily wastewater
can be categorized as shown in fig. 1.4.3-1 and table 1.4.3-2.
130 III-13
Chapter 1 Oily or hydrocarbon-polluted wastewater
Soluble
Soluble
Oil
Oil
Non
Non Non
Non
Film
Film
soluble
soluble stabilized
stabilized
> 100 μ Primary
Emulsion Inverse Stabilized Primary
Emulsion Inverse Stabilized emulsion
emulsion
Degree of dispersion
Continuous
Stability Primary Secondary
phase Macroemulsion Microemulsion
emulsion emulsion
Direct Non-stabilized Exist Exist Exist Not exist
emulsion emulsion
(o/w)
Stabilized Exist Exist Exist Exist
emulsion
131 III-14
Table 1.5-1a Data of pollution from certain oils, oil products and serfactants.
132
III-15
Part III Summary of researches: Oily wastewater treatment
Chapter 1 Oily or hydrocarbon-polluted wastewater
Table 1.6-1 shows effluent standards data from various sources. It must be noted that,
• Applicable effluent standards or laws for individual site usually depend on type of
pollutant source and receiving water body as well as location of the source. The
same type of industries locating at different towns may subject to different effluent
standards.
• Summary of standards that should be considered for each site generally consists of,
• National standards (e.g. “Normes françaises pour les eaux useé” in France,
“Notification of the Ministry of Science, Technology and Environment” in
Thailand, or “Code of Federal Regulations on Environment” in the USA)
• Regional and specific industrial standard (e.g. standards of Toulouse, Bangkok
metropolitan administration standard, standards for petroleum industries, etc.)
• Receiving water body standards (e.g. standards for coastal aquaculture, etc.)
• Generally, there are many conditions and exceptions in the laws. In some
countries, such as the USA, the standards are meticulous categorized based on
treatment technology, e.g. the best available technology (BAT) and the best
practicable technology (BPT), which makes it more complicate to select the right
applicable standard. Thus, conditions of the laws shall be studied carefully.
133 III-16
Part III Summary of researches: Oily wastewater treatment
134 III-17
Chapter 1 Oily or hydrocarbon-polluted wastewater
135 III-18
Part III Summary of researches: Oily wastewater treatment
(2) CFR 40 part 437—The centralized waste treatment point source category
136 III-19
Chapter 1 Oily or hydrocarbon-polluted wastewater
Table 1.6-1c Industrial effluent standards of USA, categorized by pollutant sources (Cont.)
(3) CFR 40 part 417—Soap and detergent manufacturing point source category
(4) CFR 40 part 438—Metal products and machinery point source category
TSS 62.0
Oil and grease (as HEM) 46.0
General note: 1 The standards may be amended and some special remarks for each type of
receiving water and type of industry, which refers to other notification or decree,
are not completely included in this chapter.
137 III-20
Part III Summary of researches: Oily wastewater treatment
F1
V
A Oil drop,
dia. = d
F2 Water
πd 3 {2.1.1}
F1 = (ρ − ρc )g
6
1 {2.1.2}
F2 = C d ρ c AV 2
2
Fig. 2.1-1 Free body diagram of oil drop in water and relation between Cd and Re [55]
Cd is a numerical constant, called drag coefficient, which depends on the flow region,
represented by Reynolds number (Re) as shown in fig. 2.1-1. A is the projection area of oil
drop. In this case, the oil drop is spherical, then A is the cross sectional area of the sphere.
The oil drop will start to rise from a stationary position (V = 0 m/s, F2 = 0). After
some time, it will reach the terminal velocity or rising velocity, which will remain constant
along its course. At this velocity, F1 = F2. So, from this condition, the rising velocity (V) can
be written as follows.
1/ 2
⎛4 d ρ ⎞
V = ⎜⎜ ( − 1) g ⎟⎟ {2.1.3}
⎝ 3 cd ρ c ⎠
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Chapter 2 Basic theory for oily wastewater treatment process design
By substituting the relation between Cd and Re at various ranges of Re into eq. 2.1.3
[41], The rising velocity can be calculated by the equations, summarized in table 2.1-1. In
most of oil separation processes described hereafter, they normally operate in laminar flow
regime. So rising velocity are governed by STOKES law (Table 2.1-1, eq. 2.1.4).
From STOKES law, one can increase the rising velocity by modifying related
parameters in eq. 2.1.4. To increase the rising velocity is to increase the oil separation
efficiency. Several treatment processes in this book are based upon this idea of modification.
And because some parameters in STOKES law have been modified from natural condition,
these processes will be called “accelerated separation process”. Examples of these processes
include coalescer, flotation and hydrocycloning.
In liquid, there are short-length attraction forces (Van de waal and polar forces)
reacting between adjacent liquid molecules. The molecules located inside the bulk of liquid
are subject to equal force in all direction, as shown in Fig 2.2.1-1. However, the molecules
located at the surface of air/liquid are subject to unbalanced force, resulting in net inward pull
(R) (see fig. 2.2.1-1). From this force, the molecules will try to move from the surface into
bulk liquid. The surface of liquid, thus, tends to contract spontaneously. That is the reason
why the oil or air present in the water tends to form a sphere shape, as oil drop or bubble
(Laplace’s law).
This phenomenon is identical for the surface between 2 liquids. To avoid confusion,
when talking about the surface between 2 substances, not the surface between one substance
and air, this surface will be called “interface”
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From this definition, interfacial tension between oil and water (γow) and between oil
and air can be written in form of the following equations. Interfacial tension of liquid
normally decreases with increasing temperature in a nearly linear fashion [40]. Data of surface
tension and interfacial tension for some liquids are presented in table 2.2.1-1
W
γ ow = {2.2.1a}
Aow
W
γo = {2.2.1b}
Ao
W represents effective work required to increase the interfacial area between oil and
air or water by Ao or Aow (or Ao/w) m2 respectively. For emulsion, Aow is the total area of every
oil droplet. This effective work will be used to calculate mechanical work of the mixer to
create the emulsion providing that the efficiency of the mixer is known. This concept will be
used to create the emulsion of required degree of dispersion.
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Chapter 2 Basic theory for oily wastewater treatment process design
Tip To visualize the surface tension [42], we will consider a tank that one side
wall can be moved as shown in fig. 2.2.1-2. If we try to move the wall to extend the
surface of liquid, we have to apply the force F. Then, the wall move by the distance dl.
From this, the work done or effective work can be written as:
W = F ⋅ dl {2.2.2a}
When the wall is moved, we increase the surface area of the liquid, which can
be written as shown in eq. 2.2.2b.The increasing in energy of the system is as shown in
eq. 2.2.2c.
A = L ⋅ dl {2.2.2b}
ΔG = γ ⋅ A {2.2.2c}
F
We assume the process is isothermal and
reversible, so there is no heat loss. Then,
Section work done will be equal to energy (eq.
dl 2.2.2d). From this, we will see that the
surface tension can be derived as shown in
eq. 2.2.2e and eq. 2.2.1
F ⋅ dl = γ ⋅ L ⋅ dl {2.2.2d}
L F
F ⋅ dl W F
γ= = or = {2.2.2e}
L ⋅ dl A L
Plan
Table. 2.2.1-1a Data of surface and interfacial tension (N/m) for some liquids at 20°C
[40][42]
Interfacial Interfacial
Surface Surface
Name tension Name tension
tension tension
(/water) (/water)
Water 72.8 Ethanol 22.3
Benzene 28.9 35 n-Octanol 27.5 8.5
Acetic acid 27.6 n-Hexane 18.4 51.1
Acetone 23.7 n-Octane 21.8 5038
CCl4 26.8 45.1 Mercury 485 375
Polar organic 22-50 Aqueous 24-40
compounds detergent
solutions
Hydrocarbon 18-30 Fluorocarbon 8-15
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Part III Summary of researches: Oily wastewater treatment
Adhesion work: Interfacial tension between oil and water (or any two liquids) can
relate to surface tension of each liquid by DUPRE’s equation (eq. 2.2.3a). This equation can
be also applied to solid-liquid interface, as shown in eq. 2.2.3b. γs represents surface energy of
solid.
γ ow = γ o + γ w − Wadh (ow) {2.2.3a}
γ so = γ s + γ o − Wadh ( so ) {2.2.3b}
Tip To visualize the concept of adhesion work [42], we will consider a tank that
one side wall can be moved, filled with 2 liquids (oil and water). When we move the
wall, from eq. 2.2.2, it can be described that:
Wetting is the displacement from a surface of one fluid by another [40]. Therefore, it
involves three phases and, at least two phases must be fluid. To understand this, we will
consider the oil drop on a solid surface in water, as shown in fig. 2.2.2-1.
Water
Solid
Contact angle: The angle between tangential line of oil drop’s surface and the surface
of solid is called “contact angle”. In case that the oil remains as a drop, it means the system is
in equilibrium. We will have definite contact angle θso. Equilibrium of force on the droplet
can be written as shown in eq. 2.2.4, known as YOUNG’s equation.
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Chapter 2 Basic theory for oily wastewater treatment process design
If we combine DUPRE’s equation (eq. 2.2.3) with YOUNG’s equation, we will get an
equation, called YOUNG-DUPRE equation, as shown in eq. 2.2.5. This equation allows us
to calculate the adhesion work of the system.
To define the degree of wetting or “wettablity”, we use the simple criteria as follow:
• If the contact angle is equal or less than 90°, it can be said that the solid is wetted
by oil. So it has “oleophilic” property.
• If the contact angle is greater than 90°, it can be said that the solid is not wetted by
oil. So it has “hydrophilic” property. The shape of oil drop is almost spherical in
this case.
When applied to oil/water system, cohesion work, in order to separate oil in presence
of water, can be written as follows:
Wc (o) w = 2γ ow {2.2.6b}
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Part III Summary of researches: Oily wastewater treatment
From eq. 2.2.7, it shows that adhesion work, in this case, is equal to cohesion work.
From this fact, HARKINS [quoted by AURELLE [42]] sets the criteria to consider if the
liquid will spread over the solid or not, by a constant called “spreading coefficient”(φ).
φ = Wadh ( so ) w − Wc ( o ) w {2.2.8}
• If φ ≥ 0, or Wadh(so)w ≥ Wc(o)w, then the oil will spread over the solid.
• If φ < 0, or Wadh(so)w < Wc(o)w, then the oil will not spread over the solid.
Concept of spreading is very useful for oil/water separation process. When we bring
the emulsion to contact with the solid, if the solid is olephilic or the oil prefer to spread over
the solid, the oil that collides with the solid will attach to solid surface, thus, be separated
from the emulsion. From this concept, we can define the relation between contact angle,
adhesion work, interfacial tension, and spread coefficient as shown in table 2.2.2-1.
Critical surface tension (or critical surface energy): Zisman [quoted by AURELLE
[42]] studies that if the oil drop is placed on the solid surface, the contact angle will decrease
linearly with decreasing surface tension of oil. When the surface tension of the oil is low
enough, the contact angle will be zero, then that oil will spread over the surface. That surface
tension will be called “Critical surface tension” of the solid. The value can be interpreted that
any oil will spread over the solid surface when surface tension of that oil is equal or lower
than critical surface tension of the solid, as shown in eq. 2.2.9. This concept is very useful for
material selection in several separation processes, such as skimmer (chapter 3).
If γo ≤ γc , the oil can spread over the solid surface. {2.2.9}
Effect of roughness of solid surface: Surface roughness of solid can effect its
wettability. If the surface is not smooth, the contact angle will increase as described by
WENZEL’s equation (eq. 2.2.10, fig 2.2.2-3). r represents the roughness coefficient and is
equal to ratio between actual surface area to geometrical surface area . The value of r is equal
to 1, when the surface is smooth. Otherwise, r will always be greater than 1. The effect of
roughness should be considered when design the oil/water separation process.
θ θ θ θ
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Chapter 2 Basic theory for oily wastewater treatment process design
Table 2.2.2-1 Relation between contact angle, work adhesion, interfacial tension and spread
coefficient of oil/water/solid system [42]
γow
0°<θso<90o γow <W< 2γow <0 γsw > γso θ
γso γsw
γow
= 90o W = γow <0 γsw = γso θ
γso γsw
γow
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Part III Summary of researches: Oily wastewater treatment
LAPLACE’s law is the relation of pressure difference across the surface of liquid of
surface tension γ. If we consider the air bubble in water, at one fraction of the bubble with the
radius of curvature R1, and R2 on 2 perpendicular plains (fig. 2.2.3-1), the pressure
difference, by LAPLACE’s law, will be as shown in eq. 2.2.11:
1 1
ΔP = P − P ' = γ ( + ) {2.2.11}
R1 R 2
From the equation, we can calculate the
P (Outside pressure) pressure difference of the following
systems, i.e.,
• A soap bubble of radius R in air
γ
P’ ΔP = 4
(Inside pressure) R
Because there are 2 interfaces of air/soap.
R
Section of 1 R2 • An air bubble of radius R in water
surface of air γ
bubble in water ΔP = 2
R
• A cylindrical jet of water in air
γ
ΔP =
R
Fig. 2.2.3-1 Section of air bubble in water Because R2 is infinity.
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Chapter 2 Basic theory for oily wastewater treatment process design
From eq. 2.2.14, it shows that the value of Pc or h will vary with the size of capillary
tube. In case that the contact angle is greater than 90o, the surface of the liquid in the tube will
be lower than that outside of the tube. So if we want to force the liquid through the tube, the
applied force must be greater than capillary pressure plus the resistance of tube. This concept
is very useful to understand membrane process.
a) b)
For the methods of analysis, if the result will be used to report to authorities, such as
effluent quality report, method of analysis used has to be those that are approved by
authorities or related standards. However, if the result is used for preliminary consideration, or
standard method is not available, this section will provide simple technique that can be
performed by basic or commonly available apparatus.
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Part III Summary of researches: Oily wastewater treatment
Method of analysis
This method is the standard method of examination of oil and grease. They are at
least 4 variations. However, they all involve an initial extraction of oil and grease by hexane
or CFC-113. The 4 variations include,
2. Turbidity measurement
Oil concentration can be measured by light loss (turbidity) or light scatter from
oil droplets in the wastewater [43]. The main advantage of this method is its simplicity and
fast response. However, it will be difficult to distinguish between oil droplets and other
particles. Some manufacturer claim that this effect can be minimized by the selection of the
angle of scatter and detector. In GPI lab, some researchers use this method to measure the oil
concentration. It is suitable to use for relatively clear wastewater, such as condensate.
However, in most situations, oily wastewaters are usually contaminated by color materials and
suspended solids. This method, thus, may not provide accurate result on oil concentration.
3. TOD measurement
4. Other methods
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Chapter 2 Basic theory for oily wastewater treatment process design
There are also others techniques to measure the oil concentration. However, some techniques
are developed for specific application. Some are not widely used or not suitable for
wastewater analysis. So they will not be described in detail here. Such techniques include
direct infrared absorption, ultraviolet absorption, optical fiber sensor, gas chromatography,
etc.
The size distribution, spectrum or granulometry is the data on the number of each size
of oil drop, air bubbles, particles or other dispersed material in continuos phase. Normally, it
is reported in the form of percent of total number of dispersed material or percent by volume
or percent by weight. Example of the size distribution of oil droplet in cutting oil
macroemulsion is shown in fig. 2.3.2-1.
45.0
40.0
35.0
Percent by weight (%)
30.0
25.0
20.0
15.0
10.0
5.0
0.0
10.0 17.8 31.6 56.2 100.0 178.0 316.0 562.0 1,000.0 1,780.0
Droplet diameter (nm)
Fig. 2.3.2-1 Example of the size distribution of oil droplet in cutting oil macroemulsion (Elf Seraft 4% V of
concentrate), measured by Coultronics nanosizer NDM4 [11]
Oil drop or particle’s diameter is one of the parameters in the STOKES equation.
Since treatment efficiency of several separation processes, which will be described in the
following chapters, are based on the rising velocity that is governed by STOKES law. So the
diameter is one of the key parameters to calculate the efficiency of the process. Furthermore,
each process can provide acceptable or competitive efficiency in only a certain range of
droplet size. So the size distribution is an important data to select feasible treatment process.
Method of analysis
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Part III Summary of researches: Oily wastewater treatment
distribution, both by number and by volume or weight. An example in fig. 2.3.2-1 was also
measured by the granulometer. Fig. 2.3.2-2 shows the picture of granulometer.
2. Decanting test
h4
h3
h2
h1
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Chapter 2 Basic theory for oily wastewater treatment process design
Analytical procedure
1) Pour the wastewater into the decanting test column and stir. Make sure it is
homogeneous.
2) Leave the wastewater to decant, taking the water samples from various
heights of the column at preset interval.
3) Analyze the samples to find the oil concentration or other parameters that
are directly proportional to the oil concentration, such as TOD, turbidity,
etc.
4) From the collected data, we can calculate the granulometry, using this
procedure:
• At t = 0, the wastewater is homogeneous, then the oil concentration is
Co throughout the column.
• At t = t1 and height (from the bottom of the column) = h1, the
corresponding rising velocity Vh1t1 = h1/t1.
• So at this point, the oil drop that have rising velocity greater than Vh1t1
will rise past the height h1 then will not be found in the sample taken
from h1. From Vh1t1, we can calculate the corresponding droplet
diameter dh1t1 by STOKES law.
• If the oil concentration at this point is Ch1t1, and the calculated droplet
diameter is dh1t1, we can conclude that:
The fraction of d < dh1t1 = Ch1t1/Co
5) Repeat step 4), at other t and h. then, use the fraction of d < dhx tx to plot the
size distribution curve.
6) Concentration of each droplet size can be roughly represented by the
differences between value of adjacent % of accumulated C/Co. Please note
that the size and %C/Co are estimated values only. But it can provide an
idea of how the sizes of droplet are distributed.
An example of the analysis of decanting test data is shown in tab. 2.3.2-1 and fig.
2.3.2-4 and 2.3.2-5.
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Part III Summary of researches: Oily wastewater treatment
Note: Assume the oil is kerosene so the density (20o C) = 790 kg/m3. Water dynamic
viscosity = 1.08E-3 (N.S)/m2.
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Chapter 2 Basic theory for oily wastewater treatment process design
Table. 2.3.2-1b Example of the decanting test of oil/water emulsion: sorting of the result
from table 2.3.2-1a
% accumulated C/Co
Estimated C/Co for
Corresponding droplet size Corresponding rising velocity when d
each droplet size
< dEht
100
90
80
% Accumuleted C/Co
70
60
50
40
30
20
10
0
0.00 20.00 40.00 60.00 80.00 100.00 120.00 140.00
Oil droplet size (dE) (micron)
Fig. 2.3.2-4 Relation between accumulated C/Co (% of C/Co when the droplet size is equal or smaller than the
153 III-36
Part III Summary of researches: Oily wastewater treatment
20
% by weight
15
10
0
26 30 36 41 42 47 51 58 66 73 81 115
Droplet size (micron)
Fig. 2.3.2-5 Example of estimated size distribution of oil droplets from decanting test
3. Visual observation
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Chapter 2 Basic theory for oily wastewater treatment process design
Table 2.3.2-3 Criteria for visual observation of surface oil film [45]
Each treatment process may require some special data for its calculation. However,
common data required by several processes include:
• Interfacial tension
• Viscosity of oil
Thus almost all of treatment processes that have been studied in GPI laboratory are
based on separation process, both physical and physico-chemical, techniques in order to
separate oil from water. From chapter 1, it shows that oily wastewaters can be divided into
several categories, mainly depending on their stability and degree of dispersion. And in the
previous sections on this chapter, it shows that physical separation of oil from water depends
on STOKES law.
Thus, to enhance separation between water and oil, it can be archived by modification
of parameters in STOKES law in the manner that make the rising velocity of oil droplets
increase. Actually, almost all of oil/water separation processes covered by Prof. AURELLE’s
research team are STOKES law-based processes, i.e. decanter, coalescer, hydrocyclone, and
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Part III Summary of researches: Oily wastewater treatment
dissolved air flotation (DAF). Thus each process will has its own limitation, bound by
assumptions of STOKES law as well as its unique working characteristic.
Apart from STOKES law-based processes, there are other oil/water separation
processes that based on other physical properties between oil and water. In GPI lab, Prof.
AURELLE’s teams also studied these processes, i.e. skimmer (which is based on interfacial
tension concept), membrane process (which depend on mass transfer phenomena), thermal
process (which depends on thermodynamic properties), and chemical process (which depends
on chemical reaction).
2.4.1 Decanter
Decanter is an oil separation process that depends purely on STOKES law without
modification of their parameters. The oil droplets in wastewater will allow to decant (or rise)
naturally to the surface of water .It is very simple and proven to be very good process for
separation of free oil and primary emulsion. Rising velocity depends mainly on the droplet
size. In case of very small droplets, it may take too long time for the droplets to reach the
surface or it may need so large tank to become economical. However, performance of
decanter can be enhanced by reducing of rising distance of droplets, such as by lamella-plate
insertion. Actually, GPI lab had initiated a very compact decanter by this concept, called
“Spiraloil”, which is commercialized by Elf Total Fina. Decanter is described in details in
chapter 4.
2.4.2 Coalescer
2.4.3 Hydrocyclone
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Chapter 2 Basic theory for oily wastewater treatment process design
operate. So it is noted for its increase in efficiency with the increase of inlet flow, which is
unique advantage of the system. It can handle secondary emulsion effectively. However, its
operation has high shear characteristic. Furthermore, it driving force come only from its inlet
flow so the centrifugal force is limited. So it can not separate very small droplets (<10
microns). It must also be noted that hydrocyclone is actually a concentrator. It can not
separate water-free oil. Separated oil usually contains some water. Thus it need to be further
treated by other process. Hydrocyclone is described in details in chapter 6.
Other processes
2.4.5 Skimmer
Skimmer is the device designed to remove oil film from the water surface. GPI lab had
studied and perfected skimmer’s oil performance so it can selectively remove only oil without
drawing the water with it. Operating principle of the oleophilic oil skimmer is based on
surface tension concepts. The skimmer studied in GPI lab was also commercialized. Details
about skimmer are described in chapter 3.
Membrane processes are the promising separation processes that gain popularity in
these recent years. The key part of the processes is the membrane, which is porous material
with various ranges of pore size to suit the sizes of material to be retained or separated. Its
working principle can be compared, but not exactly identical, to that of filtration process.
With properly selected pore size, membrane processes can separate target materials with
relatively high efficiency. GPI lab had studied application of various membrane processes,
i.e., microfiltration, ultrafiltration, nanofiltration and reverse osmosis on oily wastewater
treatment. The lab also initiated studies on capacity (or flux) enhancement of membrane
process for cutting oil emulsion treatment. Membrane processes are described in details in
chapter 8.
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Part III Summary of researches: Oily wastewater treatment
process of oily wastewater treatment. Thus it provides opportunity to recover these supposed-
to-be-wasted oil and treat the most problematic waste. Thermal processes are described in
details in chapter 9.
Chemical process for oily wastewater treatment is mainly destabilization process for
destabilizing of stable emulsion. It consists of 2 main mechanisms, i.e. destabilization of oil
droplets and coalescence or flocculation of destabilized oils. This process is necessary when
the wastewater to be treated contains stable or stabilized emulsion, otherwise it can not be
treated by STOKES law-based processes. Destabilization chemicals includes salts, acids, and
polyelectrolytes. GPI lag had studied destabilization mechanisms of each chemical which
provide understanding and knowledge on chemical selection. The detail is discussed in
chapter 10.
To meet the effluent standards, effluent from aforementioned processes may need
further treatment before discharge to receiving water body. The most widely used processes
for finishing propose are biological treatment and adsorption (by activated carbons). These
processes are not the main interest in Prof. AURELLE’s team, which emphasize of physical
processes. However, to fulfil the whole oily wastewater treatment processes, biological
treatment and adsorption are briefly described in chapter 11.
The theories and details of each processes described in section 3 to 11 will, then, be
used to develop the software for design and simulation of oily wastewater process train,
which is the scope of work of this thesis.
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Chapter 2 Basic theory for oily wastewater treatment process design
Example A: consider wastewater from in-land refinery contains 230 mg/l of non-
stabilized secondary emulsion and 10 mg/l of emulsified oil. If applicable effluent standard in
this case is 12.0 mg/l, in this case, the degree of treatment of the system is (10+230-
12)/(10+230)*100 = 95%. We can separate the secondary emulsion by compact decanter,
coalescer or DAF, which secondary emulsion removal efficiency is expected at 90%. So it
requires further treatment and the degree of treatment required in the next stage is at least 100-
((100-950)/(100-80)) = 50%. In this case, It can be archieved by sending to the water to mix
with domestic wastewater and treat by biological treatment. The concentration of 12.0 mg/l
may be met by dilution effect of domestic wastewater alone. Moreover the biological process
can be reduced the oil concentration at least 50%. Thus it can be certain that the effluent
concentration of 12 mg/l is guaranteed at all times.
As stated before that efficiency of most separation process depends on the size of oil
droplets, most of researches in GPI lab had common aim to establish the relation between
the efficiency and droplet size, which will be shown in the following chapters. If
granulometry data (see fig. 2.3.2-5) is available, it will provide clear data on percentage of
each size of oil droplets. So it is very useful for removal efficiency calculation of each droplet
size (graded removal efficiency) of each process. Summation of graded efficiency of each
process results in total removal efficiency of that process corresponding to that particular
wastewater, which is more accurate than the estimated value from literatures alone. In case
that the treatment system consists of several processes, overall efficiency can be determined
from summation of greaded effeciecny of ecah process, as shown in eq. 2.5.1.
∑ (η )
d max
d ,i ⋅ C od ,i
η t ,i =
d min
⋅ 100 % {2.5.1b}
C o ,i
∑ (η )
d max
d , overall ⋅ C od
η overall =
d min
⋅ 100 % {2.5.1b}
Co
To achieve the required effluent standard, overall efficiency of the system must be
equal of higher than the required degree of treatment, established in section 2.5.1.
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Part III Summary of researches: Oily wastewater treatment
Since the bigger oil drops are realtively easier to remove than the smaller ones, it is
recommended to select the treatment process to handle the range of oil drops from the biggest
to the smallest size that contributes to the required degree of treatment (in case that the
granulometry data is known). This smallest size in the range described above is called cut
size.
For example, if the granulometry of the wastewater is as shown in fig. 2.3.2-4, if the
required degree of treatment is 90%, from the curve, the cut size will be 90 microns.
The cut size is very useful in process design for it can be used as a representation of
the whole wastewater to calculation the required size of separation process. It can save
calculation time when many processes are to be compared. However, sizing of the process
calculated from this theoretical cut size may not be exactly equal to the degree of treatment
since the cut size is selected based on the assumption that the graded removal efficiency of
droplet equal to larger than cut size is 100% (see fig. 2.5.2-1). Thus some adjustments should
be made after detailed calculation of the efficiency by eq. 2.5.1.
100%
100%
ηR
Required degree
of treatment
Theo. eff
Real eff.
Performance of each separation process also depends on other parameters apart from
the droplet size. Change in these parameters will also make the performance of the process
change. Thus the process train can be optimized by changing influent parameters, usually the
geometry, of each process in the process train to make the overall efficiency as close to the
required degree of treatment as possible.
Treatment capability of processes may overlap in some range of droplet sizes, which
will be summarized again in chapter 12. For example, droplet size around 20 microns can be
treated by coalescer or compact decanter. This leads to several combinations of process trains.
For example, the process train in example A may be divided into 2 alternatives, i.e. (1)
Compact decanter+activated sludge (AS), (2) Coalescer+Activated sludge. In each alternative,
the sizes of equipment and reactors can be varied within its own valid range. Thus, to select
the best alternative and process sizes, economics of each alternative should be compared.
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Chapter 2 Basic theory for oily wastewater treatment process design
Since the expected degree of treatment is identical, least cost criteria are usually adopted.
The most suitable process train is practically the system that can treat the water to meet the
required degree of treatment at the least capital cost and operating expense (see fig. 2.5.2-2).
Required degree
of treatment
Overall eff.
Hydrocyclone
Coalescer
Size or cost
Most suitable
(economic) size
However, to select such a system, many alternatives must be calculated. This is the
reason that the computer program for oily wastewater treatment process calculation,
according to the scope of work of this thesis, is developed. The program will help perform
complex calculation and handle calculation of many alternatives within very short time. So
the results will lead to the effective oily wastewater treatment system design. Details of the
program is described in Part 4.
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Chapter 3 Oil skimmer
3.1 General
The most basic form of oily wastewater is the presence of oil film or layer on the
water surface. The most severe case of this form of oily wastewater is the large-scale oil spill,
caused by tanker or offshore platform accident. The oil will spread over wide area and cause
adverse effect on ecosystem. When the accident occurs, the oil confinement, such as booms, is
arranged to limit the spreading area. Then, the spilled oil is, sometimes, dispersed by chemical
dispersant to form tiny droplets, then left to biodegrade. Biological accelerating agents may
be added to promote biological degradation. Sometimes, specific adsorbents are added to the
oil to make it settleable or in more manageable form, such as floating agglomerate scum.
These methods may still cause adverse effect on the environment. Thus, if possible, the oil
layer is preferably removed in form of water-free oil for it can be reused.
In oily wastewater treatment process, the goal of almost all of the separation processes
is to separate the oil droplets and form an oil layer on the water surface. After that, it is also
crucial to remove this oil layer as water-free oil, otherwise it will become new oily
wastewater. In a small container, the oil layer can be removed manually or by simple devices,
such as weir, bell mouth pipe. Anyway, in case of oil spill at sea, or upscale tank, it is difficult
to remove only oil without getting water with it even though the oil film is visibly stratified
from the water. In these cases, specific devices that have good oil selectivity are required.
There are many variations of these devices as shown in fig. 3.1-1. However, they can be
generally divided into 2 concepts i.e.,
• Pumping or hydraulic devices: The oil will be directly pumped out or intercepted
by controlled hydraulic devices, such as adjustable-weir. Important factor that
governs the performance is the oil layer thickness. So, some mechanisms are
provided to locally thicken the oil layer before removing it. Examples of the
devices include pump skimmer and weir skimmer.
• The devices based on adsorption property: This group of devices makes use of
difference between oil and water adsorption property of material to remove the oil.
The oil selectivity of material is based on the concept of interfacial tension, as
described in chapter 2. When design properly, the device can remove virtually
water-free oil from the wastewater. Examples of the devices include drum
skimmer, disc skimmer, belt skimmer, etc.
This chapter emphasizes on the drum and disk skimmer, which are thoroughly
researched in GPI lab.
162 III-45
Part III Summary of researches: Oily wastewater treatment
163 III-46
Chapter 3 Oil skimmer
Oil drum skimmer is the equipment that has a rotating drum which its surface acts as
an oil-skimming surface (fig. 3.2.1-1). The oil will adhere to the skimming surface, lift up
from the surface by the skimmer’s rotating movement, and then be scraped off by a scrapper
blade into a receiving channel or container.
Drum skimmer
Scrapper
Oil receiving
trough
Oil layer
Water
Fig. 3.2.1-1 Lab-scale drum skimmer: Major components are shown. (Source: GPI lab)
The working principle of oil drum skimmer, as well as other absorption based devices,
is based on surface energies of hydrocarbon, water and skimmer material. To obtain water-
free oil, the material must have good oil selectivity. THANGTONGTAWI [5] had studied the
effect of surface energies on oil selectivity and concluded that oil selectivity of the material
depends on the difference between its critical surface tension (see chapter 2) and the
superficial (surface) tensions of hydrocarbon and water.
Water normally has higher superficial tension (around 72 dyne/cm, depending on the
temperature) than oil (25 – 40 dyne/cm). The diagram in fig. 3.2.1-2 shows surface energy of
water, oil and various materials. Adhesion of oil or water at the material surface can be
explained in term of the adhesion work (see chapter 2, eq. 5.2.5) as shown in table 3.2.1-1. If
the adhesion work of oil on solid surface in presence of water (Wadh(so)w ) is greater than that
of water on the surface in presence of oil (Wadh(sw)o), the oil film will adhere to the skimmer
surface and not be replaced by water film when the skimmer is rotated until the oil film
submerges in water. Thus, it still adheres to the surface when it is lifted from the liquid and
then removed by the scraper.
From this concept, the oil selectivity of materials can be summarized as follows,
• Material of high surface energy (or critical surface tension), such as stainless steel
(γ > 72 dyne/cm), tends to be adhered by water, rather than oil.
• Material that have the surface tension in the vicinity of oil’s, such as
polyvinylchroride (PVC), polypropylene (PP), tends to adhered by oil, rather than
water. It can be adhered by water if the oil film is not present. However, it will
start recovering oil once the oil is present again.
164 III-47
Part III Summary of researches: Oily wastewater treatment
• Material that has very low critical surface tension (lower than surface tension of
oil), such as PTFE and fluorocarbon variations, is proven to have very good oil
selectivity since its surface energy is so low that it is hardly adhered by water.
When used as a skimmer material, it recovers only oil and hardly or does not
recover water.
oil
Surface energy
10 20 30 40 50 60 70 (dyne/cm)
25 35
Material of low Material of high
surface energy surface energy
Fig. 3.2.1-2 Surface energy or superficial tension of materials, oil and water
Table 3.2.1-1 Work adhesion and contact angles of oil, water and various materials
It is interesting to note that the stainless steel, which is the most oleophilic material
(oil can spread over its surface), makes the worst oil selectivity. This, sometimes, causes
confusion since the device is, sometimes, called oleophilic oil drum skimmer. So, It should be
reminded that the device got its name from its oil selectivity, but the skimming material itself,
even though can considered as oleophilic (contact angle < 90o), is selected from its low
surface energy, rather than its oleophilicity.
• Even the high critical surface tension material can remove oil if it is exposed to
pure oil first. Performance from SS, PVC, PP and PTFE skimmers in this case are
about identical. In case of SS, this does not seem to conform to the adhesion work
165 III-48
Chapter 3 Oil skimmer
calculation result. This can be explained by the effect of “masking”. The oil film
covers overall surface of the skimmer so the water cannot contact directly to the
skimmer to form a water film.
• However, if the oil is entirely recovered, or oil film locally raptures, the SS will be
immediately adhered by water and stop recovering oil. Then it will recover
substantial amount of water.
• Even though the water film is removed by scrapper, there is always a thin film left
due to very high adhesion work of the film that causes by chemi-sorption or polar
bond to the solid surface. When the oil is present again, the oil cannot contact
directly to the solid surface, then cannot be recovered.
• When oil film is present, PVC or PP skimmer will recover oil. After the oil is
totally removed, the skimmer is still not immediately adhered by water film. This
can be explained by the presence of residual oil film on the surface of the skimmer.
• The residual oil film will gradually disappear. So, after some times (about 24
hours), the skimmer will be wetted by water and start recover water.
• If the oil is present again, the skimmer will immediately resume oil recovery since,
from concept of work adhesion, it is preferably adhered by oil.
• Because of its low critical surface tension, this type of material is not affected by
exposure history for it is hardly adhered by water. PTFE skimmer always recover
oil without water even when it is left to operate without the presence of oil layer
for a long period of time.
0.486
3.035D1.541N1.541ν o L
P= {3.2.1}
g 0.514
166 III-49
Part III Summary of researches: Oily wastewater treatment
The model will be valid when these conditions are satisfied, i.e.;
Oil removal efficiency of the skimmer is usually 100%, if the conditions stated above
are satisfied.
η t = 100% {3.2.2}
Parameters that affects the performance of drum skimmer are as summarized below.
Graphical presentation of effect of various parameters on the performance of the skimmer is
shown in fig. 3.2.1-3.
1. Diameter of drum
2. Length of drum
Oil layer thickness on the water surface will affect the oil productivity of the
skimmer when it is thinned out until it cannot supply the oil fast enough to the skimmer. Then
there will be some part of skimmer that does not contact with the oil layer and has no
167 III-50
Chapter 3 Oil skimmer
productivity. So the overall productivity will drop. The layer thickness of 0.4 – 0.5 cm is
considered thick enough to ensure continuous supply of oil to the skimmer.
Immersion depth means the height of the part of the drum that is lower than
water surface, measured from the bottom of oil layer. At immersion depth of 1-2 cm.
THANGTONGTAWI reported that this parameters does not practically affect the
performance of the skimmer. The author has tested at the immersion depth around 5 - 7 cm.
The result still confirmed THANGTONGTAWI’s conclusion.
Immersion depth means the height of the part of the drum that is lower than
water surface, measured from the bottom of oil layer. At immersion depth of 1-2 cm.
THANGTONGTAWI reported that this parameters does not practically affect the
performance of the skimmer. The author has tested at the immersion depth around 5 - 7 cm.
The result still confirmed THANGTONGTAWI’s conclusion.
7. Velocity of drum
Rotating velocity directly affects the oil productivity as shown in eq. 3.2.2. The
higher the velocity, the higher the productivity. However, the velocity also governs the
entraining of water by the dynamic force. If the velocity is too high, the rotation of the drum
will draw the water up too fast until it can reach the scrapper blade and entrain with the
skimmed oil. It is recommended to use peripheral velocity (or tip speed) of 0.44 m/s or less to
prevent water entraining.
8. Viscosity of oil
Oil productivity, as well as the oil film thickness on the surface of the drum, will
increase if the viscosity of the oil increase, as clearly shown in eq. 3.2.1.
• When oil layer is present: The efficiency of the drum skimmer is proven to
be practically independent of the presence of the surfactant [5]. So change in
superficial tension of water and the interfacial tension of oil/water does not
affect the performance of the skimmer.
168 III-51
Part III Summary of researches: Oily wastewater treatment
• When oil layer is absent: After the oil is removed and the skimming surface
is exposed to water. The surfactant will lower superficial tension of water
until it is close to naturally interfacial tension of oil/water. So there is no
difference between oil and the water. Thus the skimmer will lose its
selectivity, even in the case of PTFE, and start recovering the water.
The size of the skimmer can be calculated by eq. 3.2.1. If oil concentration or
quantity of inlet oil is known, it could be used as required oil productivity of the skimmer.
Then, the oil productivity, geometry of tank (width, length), tank freeboard and available
installation space of the skimmer and oil outlet pipe should be taken into account in order to
select a suitable size of the skimmer.
Energy requirement of the skimmer is the energy for driving the skimmer. It can
be calculated by simple product of torque and speed. The torque required depends on the
structure, weight and size of the drum.
2 Design consideration
The mathematical model of drum skimmer (eq 3.2.1) is valid only under its
limitations shown in section 3.2.1. Application of the model beyond its limitation may cause
unpredictable error.
Besides the limitations of models shown in section 3.2.1, there are some
assumptions or operating condition that affect the performance of the skimmer but cannot be
expressed in the form of equation. To design a skimmer, these assumption and precaution, as
described below, should be taken into account to ensure good performance of the skimmer.
169 III-52
Chapter 3 Oil skimmer
1) The model is developed under the assumption that the scrapper can
totally remove or scrape the oil film from the drum surface. So in the
real situation, scrapper should be designed properly to make sure that
it will not be a limiting factor in the operation. Scrapper should be
made of flexible material to ensure its close contact to the entire
length of the drum. However it should have good abrasive resistance.
2) The oil productivity in eq. 3.2.1 is valid under the condition that the
oil layer is not the limiting factor and the entire length of drum can
contact to the oil film. To ensure these condition, the following
precaution should be considered;
• The drum should be properly sized to accommodate the inlet oil
quantity. So it can operate continuously without the problem
about lack of oil layer.
• Automatic control should be provided to stop the skimmer when
the oil layer in the tank is too thin to avoid the recovery of water,
esp. when high or moderate critical surface tension is used as
skimming material, or when there is a risk of the presence of
surfactant in wastewater.
• If possible, the skimming surface should be of low critical
surface tension material, such as variants of flouorocarbon, to
guarantee good oil selectivity and avoid exposure history
problem. Critical surface tensions of certain materials are listed in
table 3.2.2-1.
• Operation of the skimmer can cause eddy current around the ends
of the drum that causes the oil layer in this area vanished quicker
than other area. It results in non-productive zone of the skimmer
(see fig. 3.2.2-1). To avoid this, the oil layer should be kept at
170 III-53
Part III Summary of researches: Oily wastewater treatment
No oil zone
Eddy
Fig. 3.2.2-1 Occurrence of eddy currents from drum operation and no oil zone or non-
productive zone that affects the productivity of the skimmer (Source: Oil Spill Cleanup)
Oil disc skimmer is the equipment that has a rotating disc or discs, instead of drum,
which surface act as oil-skimming surface (fig. 3.3.1-1). The oil will adhere to the skimming
surface, lift up from the surface by the skimmer’s rotating movement, and then be scraped off
by a scrapper blade into a receiving channel or container.
Working concept of the disc skimmer is identical to that of the drum skimmer except
the skimming surface. The concept of surface tension and exposure history described in the
previous is still valid. For the skimming surface area, in case of disc skimmer, it is circular
surface of the disc.
Oil trough
Eddy
Scrapper
171 III-54
Chapter 3 Oil skimmer
0.452 1.17
1.328D1.258 N1.212 ν o I
P= {3.3.1}
g 0.332
The model will be valid when these conditions are satisfied, i.e.;
The major difference between drum and disc model is that the disc model is the
function of immersion depth while this parameter hardly affects the drum skimmer
performance.
Oil removal efficiency of the skimmer is usually 100%, if the conditions stated above
are satisfied.
η t = 100% {3.3.2}
Parameters that affect the performance of disc skimmer are identical to that of the
drum skimmer, as described in section 3.2.1.2, except the immersion depth. Graphical
presentation of effect of various parameters on the performance of the skimmer is shown in
fig. 3.2.1-2.
Immersion depth of disc skimmer, in this case, represents the depth of a part of the
disc that is under the liquid free surface. From eq. 3.3.1, it shows that oil productivity incerase
172 III-55
Part III Summary of researches: Oily wastewater treatment
with increase in the immersion depth. However the immersion depth is limited by the
diameter of the disc (I ≤ D/2)
The size of the skimmer can be calculated by eq. 3.3.1. If oil concentration or
quantity of inlet oil is known, it could be used as required oil productivity of the skimmer.
Then, the oil productivity, geometry of tank (width, length), tank freeboard and available
installation space of the skimmer and oil outlet pipe should be taken into account in order to
select a suitable size of the skimmer.
Like the drum skimmer, energy requirement of the skimmer is the energy for
driving the skimmer. It can be calculated by simple product of torque and speed. The torque
required depends on the structure, weight and size of the drum.
2 Design consideration
The mathematical model of disc skimmer (eq 3.3.1) is valid only under its
limitations shown in section 3.3.1. Application of the model beyond its limitation may cause
unpredictable error.
It must be noted that the oil productivity from eq. 3.3.1 is for two sides of
the disc. If scrapper is installed at only one side of the disc, the productivity can be safely
assumed to be 50 % of the value from eq. 3.3.1. Productivity of several discs are the product
of the result from eq. 3.3.1 and the number of the disc “n”.
Like the case of drum skimmer, besides the limitations of models shown in
section 3.3.1, there are some assumptions or operating condition that affect the performance
of the skimmer but cannot be expressed in the form of equation. The precaution proposed for
the drum skimmer can also be applied for the disc skimmer. Like the drum skimmer,
operation of disc skimmer also results in non-productive zone of the skimmer, starting at the
axis of the skimmer (see fig. 3.3.1-1), when the oil layer is almost totally recovered. To avoid
this, the oil layer should be kept at certain thickness to cope with this effect. The thickness of
1.0 cm is considered safe [5].
0.486
3.464N1.541 ν o ⎡(0.5 D )2.54 − (0.5 D − I ) 2.54 ⎤
P= {3.4.1}
⎢⎣ ⎥⎦
g 0.514
173 III-56
Chapter 3 Oil skimmer
From eq. 3.4.1 and 3.2.1, it the productivity of the two skimmers are assumed to be
equal, we can write the relation between the length of the drum and immersion depth of the
disc at the same diameter as shown in eq. 3.4.2. This equation is useful for comparison the
dimensions of the two devices. The dimension can be used for preliminary cost estimation,
which can help determining which type of skimmer is more suitable for the project.
174 III-57
Part III Summary of researches: Oily wastewater treatment
a) Drum skimmers and booms for oil spill b) Installation of skimmer in variable water level
recovery (ELF/ GPI lab) tank. An oil pump (below) is used to lift the
skimmed oil. (Source: SkimOil, Ro-clean Desmi
175 III-58
Chapter 4 Decanting
Chapter 4 Decanting
4.1 General
Decanting or sedimentation is the most basic separation process. Its working principle
bases only upon properties of oil and water, which tend to separate from each other naturally.
This process is widely used, even becomes legal standard for some industries, such as
refineries in USA. Because of its working principle, which bases on natural unadapted
properties, decanting is suitable for separating oil in form of big oil drop or primary emulsion.
There are many variations of decanting process, however they can be categorized into 2
groups, i.e.,
• Simple decanter: This group of decanter is the most basic process. They may vary
in geometry and details of some components. But they all use the same working
principle of natural unadapted decanting. The well known example of this type of
decanter is API tank, as shown in fig. 4.1-1.
• Compact decanter: This group of decanter is the modified version of the first
group, intended to upgrade the capacity of the existing simple decanter. Or it can
be newly designed equipment. The objective of compact decanter design is to
enhance the efficiency of decanter, making it handle more capacity, using smaller
footprint. This can be achieved by the modification of decanter geometry, such as
the insertion of lamella plates. However, the working principle is still identical to
that of the simple decanter as, theoretically, there is no modification of any natural
properties. Examples of this type of decanter are shown in fig. 4.1-1. Among these,
GPI lab has developed one of the most compact decanter, called “Spiraloil”. Its
special features and technical design consideration will be presented hereinafter.
176 III-59
Part III Summary of researches: Oily wastewater treatment
e) Graphical image of lamella plate decanter f) Corrugated plate module of corrugated plate
(Source: USFilter) decanter (Source: Dewaterworks)
Simple decanter, which is made well known and standardized by the American
Petroleum Institute (API), is the simplest oil-water separation process. Its working principle
bases on classical STOKES law (cf. Chapter 2). Concept of the operation of the process is to
provide sufficient time for oil droplets to float to the water surface and accumulate into oil
layer before they have a chance to flow out with the water at the water outlet. The equation
that governs the operation of the process is derived from comparing the time required for the
droplet to reach the surface with retention time of the tank (τ), as shown in eq. 4.2.1.
177 III-60
Chapter 4 Decanting
L Separated
Q oil layer
Ud H, D
Influent V Effluent
d > cut size
d = cut size
d < cut size
Oil droplets
ηd
Zone 1 Zone 2
d < dc d = or > d c
d
dc
Figure. 4.2.1-1 Schematic and typical removal efficiency curve of simple decanter
Figure 4.2.1-1 shows the diagram of decanting process. From the figure, the longest
path to reach the surface is the path starts at the bottom of the tank. The smallest droplet size
that can reach the surface is called the cut size (dc). The droplets of cut size or bigger are
always separated from wastewater stream with 100% removal efficiency.
The smaller droplets can be also separated providing that it enters the tank near the
water surface. When uniformly distributed influent flow is valid, which is true for almost all
of properly designed tanks, the removal efficiency of the droplets smaller than cut size are
proportional to theirs corresponding rising velocity. From these concepts, the models of
decanting process are as shown in Eq. 4.2.2 to 4.2.5.
For the simple decanter of the length “L”, the width “W” and the water depth “D”,
from eq. 4.2.1, we have,
L H
τ= = {4.2.2a}
(Q ) U dc
WD
For the simple decanter, rising distance of the droplet (H) is equal to the water depth
(D), then
⎛ Q ⎞ ⎛Q⎞
U dc = ⎜ ⎟=⎜ ⎟ {4.2.2b}
⎝ LW ⎠ ⎝ S ⎠
In laminar flow regime (Re < 1), STOKES law is applicable. So, rising velocity of
droplet of diameter “d“ (Ud) can be written as shown in eq. 4.2.3.
Δρ ⋅ g ⋅ d 2
Ud = {4.2.3}
18 μ c
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Part III Summary of researches: Oily wastewater treatment
Then
1/2
⎛ 18Qμ c ⎞
d c = ⎜⎜ ⎟⎟ {4.2.4}
⎝ Δρ ⋅ g ⋅ S ⎠
Design procedure for simple decanter is based upon the equations, shown in the
previous section. To design the simple decanter, the required cut size will be determined first.
After that, the size of the tank can be calculated. Then, graded efficiency (efficiency of each
size of droplet) and then total removal efficiency can be determined. Calculation in each step
is described below.
The cut size can be determined from the degree of treatment required as well as
from the limitation of the decanting processes. Cut size determination from the degree of
treatment is described in chapter 3. For the limitations of the decanting process, they come
from 2 main parts, i.e.,
179 III-62
Chapter 4 Decanting
Thus, the suitable cut size will be considered by accounting for the 2 limitations
above. API recommends the cut size of 150 microns for API tank.
2. Decanter sizing
The size of the decanter can be determined, based on the equation in section
4.2.1, as follow:
Bottom surface area (S): The decanter size is based mainly on its bottom
surface area. In general case, it is identical to the tank surface area. Presence of some
structures or components, such as effluent trough or gutter or tank cover (at the water
surface), may affect the efficiency of the decanter. However, if these structures are present in
the ways that make the rising distance of oil droplets decrease, they will help enhancing the
efficiency. However, their effects are normally small, thus, negligible, unless they
substantially reduce the rising distance of oil drops. In latter case, the tank will become a
compact decanter, which will be described in the next section. Bottom surface area of the
simple decanter can be calculated from the rising velocity of the cut size, as shown in eq.
4.2.6. The example of relation between kerosene droplet size and its corresponding rising
velocity as shown in fig. 4.2.2-1.
⎛ Q ⎞
S = ⎜⎜ ⎟⎟ {4.2.6a}
⎝ U dc ⎠
Δρ ⋅ g ⋅ d c2
U dc = {4.2.6b}
18 μ c
Flow velocity (V): Flow velocity means the velocity of total wastewater along
the tank, determined from wastewater flowrate and cross sectional area of the tank. Using
high flow velocity may cause turbulent or eddy current, especially when the wastewater
collides to the far end of the tank. Turbulence in the tank may interfere the decanting of
droplets, as well as suspended solids, which are usually present in the wastewater. This may
cause carry-over of oil drop and suspended solids with the effluent of the tank.
API recommends that V should not be greater than 0.15 m/s or greater than
15Vdc, whichever is smaller.
Water depth (D) and width (W): Theoretically, the efficiency of the tank does
not depend directly on these parameters. However, they have some effects on the tank
operation since they are ones of the parameters that govern the flow regime of the tank.
Furthermore, if they are not selected properly, they can cause adverse effect, such as eddy, or
short circuit.
180 III-63
Part III Summary of researches: Oily wastewater treatment
200
160
120
0.03
100
80
0.02
60
40 0.01
20
0 0
0 100 200 300 400 500 600 700 800
Cut size (micron)
Fig. 4.2.2-1 Relation between rising velocity, hydraulic loading rate of simple decanter and kerosene droplet size
API recommends that the ratio D/W should not be smaller than 0.3. The value of
0.5 is recommended. The depth (D) should be in the range of 0.9 to 2.5 m.
3. Removal efficiency
It must be noted that the graded efficiency described above is not yet accounted
for effect of flow splitting between water outlet flow and separated oil outlet flow. To
calculate graded outlet oil concentration, the effect must be taken into account, as shown in
eq. 4.2.7c.
Q {4.2.7c}
Cd = (1 − η d ) C od
Q out
Qout is outlet flow at treated water outlet port of the process. Qout is calculated
from difference between inlet flow and separated oil (in relatively pure condition) as shown
below.
d max
Q ∑ (η d ⋅ C od )
Q out = Q −
d min {4.2.7d}
ρd
181 III-64
Chapter 4 Decanting
∑ (η d ⋅ C od )
ηt =
d min
⋅ 100 % {4.2.7e}
Co
4. Energy required
The simple decanter does not require extra energy to make it function. The
energy is required only to feed the water into the tank, then the water will flow, naturally,
through the tank by gravity. Pressure drop across the tank and piping system depend on tank
and piping design. This pressure drop can be calculated by general hydraulic equations, such
as Darcy-Weisbach’s, Manning’s, or Hazen-William’s equation, thus will not de described
here.
The equations described above are developed from the following assumptions.
Thus, it is necessary to ensure that these assumptions are valid when design your decanter.
2. Safety factors
API recommends the safety factor for turbulent flow (Ft) as the function of
(V/U), as shown in eq. 4.2.9. U represents hydraulic loading rate or overflow rate, based on
total flow and bottom area. For effect of short circuit, API recommends the safety factor (Fs)
182 III-65
Part III Summary of researches: Oily wastewater treatment
of 1.2. Then the total safety factor (F), by API recommendation, is the product of Ft and Fs
(eq. 4.2.9c). Factor F will be used to multiplied the value of S, calculated from eq. 4.2.6.
V 2 V {4.2.9a}
Ft = − 0 . 0005 ( ) + 0 . 0355 ( ) + 0 . 9617
U U
F = Ft ⋅ F s = 1 . 2 ⋅ Ft {4.2.9b}
There are many variations of simple decanters, as shown in fig. 4.2.4-1. The most
famous one is API tank, which is the rectangular tank. However, they use the same working
principles, can be calculated by the same equations and consists of relatively the same
components.
To design the decanter, besides the sizing stated above, proper details of construction
of decanter components are also important to guarantee good efficiency. Design
considerations for important components of decanter are described hereby.
1. Inlet chamber
2. Separation section
Sizing of this section is obtained from the equations. In this section, not only the
oil will be separated, suspended solids will also settle. So sludge hopper or sludge draw-off
pipe, or other provisions for sludge removal should be provided. Geometry of this section
should be as recommended in the previous section to ensure good hydraulic condition. This
section may be covered, if necessary, to prevent accidental ignition and to prevent the loss of
volatile hydrocarbons by evaporation. Sludge hopper, sludge scrapper and surface skimmer,
should be provided, as shown in fig. 4.2.4-2.
Effluent and oil will be removed at the downstream end of the tank. Normally oil
retention underflow baffle is installed to prevent the oil to flow out with the effluent. API
recommends that this baffle should be installed with a maximum submergence of 55% of the
water depth and should be located as close as possible to the oil removal device. The baffle
should be extended to the top of the tank or, at least, higher than water surface.
For oil removal devices, in small unit, the weir or slotted pipe is sufficient. For
upscale tank, those simple devices may draw the water off along with the oil. So the separated
oil still contains some water, and may not be suitable for downstream reuse or recycle
process. In this case, the device with more selective property, such as rotating slotted pipe or
oil skimmer, is required. There is a chapter in this book, devoted to oil skimming process.
183 III-66
Chapter 4 Decanting
For effluent, it is normally removed from the tank by a weir. In some small units,
bell mouth pipe is acceptable. Design consideration for effluent removal device is that it
should be of sufficient size to prevent undesired turbulence and provide good flow
distribution in the tank. Normally, the weir across the width of the tank is sufficient.
a) Example of up-scale simple decanter with inlet diffuser wall, equipped with
mechanical skimmer (Source: Monroe)
b) Example of small to medium size simple decanter with simple elbow type inlet
diffuser and weir for collecting oil (Source: Pan American)
184 III-67
Part III Summary of researches: Oily wastewater treatment
Flow
15o
Plan
Elevation
e) Example of rotating skimmer pipe f) Chain and flight scrapper and oil drum
(Source: Environmentalleverage) skimmer (Source: US Filter)
185 III-68
Chapter 4 Decanting
This type of decanter is the modification of the simple decanter. The concept is to
decrease the rising distance of droplet to intercepting surface without decreasing the retention
time. This can be achieved by inserting plates into the simple decanter to act as the
interceptors for the rising oil droplets. Rising or travelling distance (H) is the distance
between the plates, not the depth of water (D) as shown in fig. 4.2.1-1. There are several
variations of this type of decanter. Normally they are named after configurations of their
inserted plates, such as:
Parallel plate interceptor (PPI), which its inserted plates are flat sheets, placed
parallel to each other.
Tilted plate separator (TPS), which its inserted plates are tilted or inclined.
Corrugated plate interceptor (CPI), which used corrugated plates instead of flat
plates.
The equation that governs the operation of the process is modified from the model of
simple decanter, as shown in Eq. 4.3.1. From the equation and the figure, it is implied that, in
a compact decanter, the simple tank is divided into (N+1) small decanters but the flow
velocity through the tank remains the same.
H
Influent Effluent
D
Inserted plates
(No. of plates = N)
Removal efficiency can be calculated using eq. 4.2.5. Typical characteristic of the
removal efficiency of the compact decanter is identical to the simple decanter’s, as shown in
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Part III Summary of researches: Oily wastewater treatment
fig. 4.2.1-1.But the cut size of this tank will be smaller than the simple decanter’s, providing
that they are of the same geometry.
According to the concept of decanting model that derived from comparing detention
time with rising time of droplet to intercepting surface, we can formulate the general model to
calculate dc for any decanter as shown in eq. 4.3.2
General model for calculating the cut size, when H, L and A can be clearly defined, is
as shown in eq 4.3.2.
1/2
⎛ 18 HQμ c ⎞
d c = ⎜⎜ ⎟⎟ {4.3.2}
⎝ ΔρgLA ⎠
GPI lab has also developed a decanter, called “Spiraloil” (see fig. 4.3.1-2) This special
decanter has its lamella plates placed very close to each other. Then the rising distance is
reduced dramatically. For the spiraloil, the plates are rolled into cylindrical shape, so it is very
compact in size. However, it is difficult to determine the rising distance (H). GPI lab has been
studies the model that governs this type of decanter and found that the modified theoretical
model, as shown in eq. 4.3.3, can provide good result. This model is developed from the
general model (eq. 4.3.2) by neglecting the complicated analysis to define H, and using the
concept of decanting area (Sd) instead. Sd is calculated from the sum of every surface area
within the decanter that can intercept oil without considering if the values H of these areas are
identical or not. This model or equation has been confirmed by CHERID [4] for its accuracy,
as shown in fig. 4.3.2-3.
1/2
⎛ 18Qμc ⎞
d c = ⎜⎜ ⎟⎟ {4.3.3}
⎝ Δρ ⋅ g ⋅ S d ⎠
Annular plates
H
Solid core,
radius = r
a) b)
187 III-70
Chapter 4 Decanting
100.00%
90.00%
1 1' 3 3'
80.00%
Removal efficiency (%)
Fig. 4.3.1-3a Comparison between observed efficiency (1',2',3') and predicted efficiency (1,2,3) for Simple Spiral
"Spiraloil" decanter
100.00%
90.00%
1' 1 (V = 0.5 cm/s)
80.00%
Removal efficiency (%)
70.00%
60.00%
2' 2 (V = 1.5 cm/s)
50.00%
40.00%
30.00%
20.00%
10.00%
0.00%
0 10 20 30 40 50 60
Droplet diameter (micron)
Fig. 4.3.1-3 Comparison between observed efficiency (1',2') and predicted efficiency (1,2) for Mixed Spiral "Spiraloil"
decanter
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Part III Summary of researches: Oily wastewater treatment
tank with relatively high accuracy. So it is reasonable to select the cut size to
cover the majority of droplet size distribution. The predicted efficiency of
smaller droplets, which is the minority part, will cause no harm but slightly
underestimation on the total efficiency.
Because of its very close spacing, This type of decanter provides the separation both
from decanting phenomenon and coalescing phenomenon. So the oil drops from the decanter
is relatively big (> 2 mm), and easy to separate at the downstream end of the decanter.
Phenomena taking place in the decanter have also been studied by CHERID. It shows
that, besides the decanting phenomenon, coalescing of oil drop is also taking place. From the
study, it shows that there are 3 parameters that affect the decanting and coalescing
phenomenon in the plate inserted decanter, i.e.,
• Oleophilic plates: The oil will adhere and then coalesce to form a film at the
surface of the plates. However, when the film is totally coated the plate
surface, it will be more difficult for the following oil drops to coalesce to the
film than adhere to the surface. These following oil drops, sometimes, roll
along the film, rather than coalesce into it, along with the wastewater flow.
However, at the end of plates, the oil film, driven by the hydraulic force of
the wastewater, will form big oil drops. It can be said that these points will
play the roles of the drip points or salting-out points, the same as in the
coalescer. These big oil drops can intercept those non-coalesced oil drops to
form even bigger drops until they reach certain size that can be snapped off
by the water flow.
• Hydrophilic plates: The oil will not form a film on the plate surface. But
they will accumulate as an oil droplet and coalesce with other droplets to
form big oil drops. Then they will roll along with the wastewater flow and
coalesce with other drops along their ways like snowballs. These big oil
drops will leave the plate for the surface when they reach sufficient size.
alesc
e point point
ot co Drip Dr i p
dr o p s do n
il lm
ing o t he fi
m e follow roll along
So ut
fi l m b fect
with ball e
f
Snow
lm
O i l fi
Hydrophilic plate
Oleophilic plate
189 III-72
Chapter 4 Decanting
In many designs, the plates are tilted for the designers believe that it will help
increasing the oil separation efficiency. CHERID has studied the effect of inclination. From
theory and research result, the influent of the inclination to the decanter can be concluded and
described below:
U (Rising velocity) H
H U
Rising distance =
=V( Flow velocity) (H/ cos θ) > Η V
θ
3. Presence of surfactants
The presence of surfactant will decrease the sizes of decanted oil drops, thus
hinder good decanting phenomenon. Furthermore, it will prevent coalescing between oil
drops. As a result, the total efficiency of decanter will be decreased. It has been reported that
[4], when tested with kerosene-water emulsion at the concentration of 100 mg/l with the
concentration of surfactants around 100 mg/l and the average droplet size of 40 microns, the
efficiency of spiraloil will decrease about 15 – 20%. The interfacial tension between kerosene
and water will drop from 42 N.m to 8.5 – 32.1 N.m, depending on the type of the surfactants.
Non ionic surfactant is the most effective surfactant for lowering the interfacial tension. The
second best is cationic surfactant, then anionic surfactant, respectively.
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Design procedure for compact decanter is relatively similar to the simple decanter’s
and based upon the equations shown in the previous section.
1. Cut size determination
The cut size can be determined from the degree of treatment required as well as
from the limitation of the decanting processes. Cut size determination from degree of
treatment is described in chapter 3. For the limitations of the decanting process, they come
from 2 main parts, i.e., theoretical and economic limitations, as stated in section 4.2.2.
2. Decanter sizing
The size of the decanter can be determined, based on the equation in section
4.3.1, as follows:
Decanting area (Sd), inserted plate area (Sp), footprint area (S): The decanter
area of the compact decanter depends on the types or configuration of the decanter. However
the decanting area (Sd) in this case is not equal to footprint area (S).
S d = S p ( N + 1) {4.3.4c}
S =Sp {4.3.4d}
N represents the number of plates. Please note that the plates must be inserted at
an evenly interval throughout the water depth.
General compact decanter that rising distance (H) can not be exactly specified.
⎛ Q ⎞
S d = ⎜⎜ ⎟⎟ {4.3.5a}
⎝ U dc ⎠
Δρ ⋅ g ⋅ d c2
U dc = {4.3.5b}
18 μ c
In this case, the footprint area has to be specially calculated, based on the
geometry of the decanter. Sd can be specifically calculated, depending on the shape of the
decanter. Surface of material or free water surface that can intercept oil drops will be
accounted for calculating the decanting area (Sd). In case of commercial decanter, required Sd
calculated from eq. 4.3.5a will be used to select the model and/or the number of the product
required for the design flowrate.
Flow velocity (V): Flow velocity means the velocity of total wastewater along
the decanter, determined from wastewater flowrate and full cross sectional area of the
decanter. Velocity is the main parameter that governs flow regime and hydraulic condition,
191 III-74
Chapter 4 Decanting
such as hydraulic force, head loss, etc., in the decanter. CHERID [4] recommends the value of
0.4-1.6 cm/s or 14.4-54 m/h., 2.6 to 10.6 times higher than simple decanter.
3. Removal efficiency
5. Energy required
The compact decanter does not require extra energy to make it function. The
energy is required only to feed the water through the decanter. Pressure drop across the
decanter and piping system depends on decanter and piping design. This pressure drop can be
calculated by general hydraulic equations, such as Darcy-Weisbach’s, Manning’s, or Hazen-
William’s equation, thus will not de described here. However, velocity through decanter is
relatively low, compared to velocity in pipe (0.6-2.5 m/s). So the estimated value of pressure
drop across the decanter around 0.5-1.0 m. is normally acceptable, regardless of its size and
configuration.
The equations described above are developed from the following assumptions
and limitations. Thus, it is necessary to ensure that these assumptions are valid when design
your decanter.
1) The tank is operated under laminar flow regime. Reynolds number, Re, is
between 10-4 to 1, which is the range that STOKES law is valid.
2) The oil droplets are uniformly distributed across the cross section area of
the tank, which can be achieved by the proper design of inlet chamber.
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Part III Summary of researches: Oily wastewater treatment
2. Material selection
There are many variations of compact decanters. However, the components of the
decanter can be designed by the same concept as that of the simple decanter. Nowadays, there
are several suppliers that commercialize these products, such as ELF, Johnson lamella
separator, etc. So designers can find further information from these suppliers. Some examples
of these decanters are shown in fig. 4.3.4-1
Disadvantages: Because of its relatively small flow passage, esp. for closely inserted
decanter, it may have a chance of clogging by suspended solids. So this fact should been taken
into account before design or select the decanter.
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Chapter 4 Decanting
194 III-77
Chapter 5 Coalescer
Chapter 5 Coalescer
5.1 General
From STOKES law, particle or oil droplet diameter is the most influent parameter because
it is powered by 2. Thus, if we have a process that can increase the size of the oil droplet 2 times,
the rising velocity will be 4 time higher. This can be achieved by making the oil drops combine
or coalesce to each other. Coalescer is the process that is designed to promote coalescing of oil
droplets into bigger oil drops, which can be separated easily by relatively small decanter. Because
of its working principle involves the modification of parameters of STOKES law. So it is one of
accelerated or adapted separation process, along with other processes such as hydrocyclone and
flotation. There are several types and modification of coalescers. However, they can be
categorized into 2 groups, based on the type of the media used, i.e.,
• Granular bed coalescer: This group of coalescer uses granular material, such as
resin, sand or glass beads, as a coalescer bed.
• Fibrous bed coalescer: This group of coalescer uses fibrous material, such as metal
wool or plastic brush, as a coalescer bed.
This type of coalescer uses granular material as a bed to promote coalescing between oil
droplets. The concept of the process is that the oily wastewater will flow through the coalescer
bed, as shown in fig. 5.2.1-1. Oil droplets in the wastewater will undergo several steps to coalesce
them into big oil drops. Then, these big oil drops will be separated by a small integrated decanter
at the downstream of the bed.
Professor AURELLE [3] is the pioneer on coalescer research. He establishes the 3-step
working mechanisms of the coalescer and the model for efficiency prediction, based on YAO’s
filter model [35]. Then there are several follow-up researches on coalescer , based on
AURELLE’s research
To understand the working principles of coalescer, the 3-step working mechanisms of the
coalescer ise described hereby.
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Part III Summary of researches: Oily wastewater treatment
a) Graphical image of Granular bed coalescer b) Graphical image of one type of fibrous bed
(Source: Elf, GPI lab) coalescer (Source: Knit mesh)
c) Granular bed coalescer installation for d) Photo of coalesced oil drop of dynamic
refinery’s condensate treatment (rotating) fibrous bed coalescer
(2x125m3/h)(Source: Donges refineries, Elf) (Source: GPI lab)
OUT:
Large drop Discharge
V screen
Collector
H size =dp,
Void ratio = ε
IN: Inlet
Micro drop V screen/support
Dia. = d
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Chapter 5 Coalescer
AURELLE divided the mechanisms taking place with in coalescer bed into 3 steps, i.e.;
This step is the step of transportation of the oil droplets through the bed of coalescer.
AURELLE considered that this step is identical to the mechanism of in-depth filtration. So he
applied the phenomena taking place in the filter to the colescer. This step will be divided into 3
transport phenomena, i.e., sedimentation, direct interception and diffusion. Other transport
phenomena, such as that of electrical force, might take place, but it is proven that their effect is
small, thus, negligible. To simplify the model, we will consider the phenomena, taking place at 1
collector or 1 piece of media. Schematic diagram of the 3 phenomena is shown in fig. 5.2.1-1.
V U
V
U
U= Rising velocity
V= Flow velocity
a) Direct interception b) Sedimentation c) Diffusion
1. Direct interception
When oil drops of diameter “d” flow along with the streamline, the oil drops that
pass within the distance less than d/2 from the media will be intercepted by the media, as shown
in fig. 5.2.1-1a. The efficiency factor for this phenomenon can be calculated by eq. 5.2.1. dp is the
diameter of collector or media particle.
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Part III Summary of researches: Oily wastewater treatment
3 d 2
η Int = ( ) {5.2.1}
2 dp
2. Sedimentation
Consider oil drops of diameter “d” flow along with the streamline. Because of its
density, the droplets will be subjected to rising velocity (U), calculated by STOKES law. When
they are far from the media, the rising velocity and flow velocity (V) will have the same
direction. When they come close to the media, the flow velocity will deviate, as shown by the
streamline, while the oil drops will be subjected to both flow velocity and their own rising
velocity. So the resultant velocity will not totally conform to streamline. And in some cases, it
will make the oil drops collide to, thus, sediment on the media. The efficiency factor for this
phenomenon can be calculated by eq. 5.2.2.
U Δρgd 2
η sed = = {5.2.2}
V 18μ cV
3. Diffusion
For very small droplets (d < 5 microns), They will be subjected to Brownian’s
motion. These random motions can cause the droplets to collide to the media. The efficiency
factor for this phenomenon can be calculated by eq. 5.2.3. K , in this equation, represents the
Bolzmann constant and T represents the absolute temperature.
2/3
⎛ KT ⎞
η Diff = 0.9⎜⎜ ⎟
⎟ {5.2.3}
⎝ μ c d ⋅ dpV ⎠
Thus
2/3
Δρgd 2 3 d 2 ⎛ KT ⎞
ηtheo = + ( ) + 0.9⎜⎜ ⎟
⎟ {5.2.4}
18μ cV 2 dp ⎝ μ c d ⋅ dpV ⎠
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Chapter 5 Coalescer
1.00E-01
1.00E-02
Effciecncy factor
1.00E-03
1.00E-04
1.00E-05
0.01 0.1 1 10 100
Droplet diameter (micron)
Fig. 5.2.1-3 Relation between oil droplet diameter and efficiency factors of each
transportation phenomena
From the graph, the range where the theoretical efficiency factors are minimal is
between 0.25 to 5 microns. So the droplets in this range is theoretically the most difficult to
separate.
To adapt the efficiency of a single collector to the entire coalescer bed, we will
consider the simplified diagram of single spherical collector, placed in laminar flow regime, as
shown in fig. 5.2.1-3a. V represents the flow velocity. The fraction of wastewater flowing pass
the single collector will be the flow that passes through the projected area of the collector (q), as
shown in eq. 5.2.5a. Then, some oil drops in this fraction of the wastewater will be intercepted by
the collector. The quantity of intercepted oil drops of the single collector (c’) will be calculated
from the theoretical efficiency factor, as shown in eq. 5.2.5b.
π
q= d 2p ⋅ V {5.2.5a}
4
π
c' = η theo ⋅ d 2p ⋅ V ⋅ C {5.2.5b}
4
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Part III Summary of researches: Oily wastewater treatment
OUT:
Large drop Discharge
V screen
dp Collector
H size =dp,
V Void ratio = ε
IN: Inlet
Micro drop screen/support
q = Vπdp2/4 V
Dia. = d
a) b)
Fig. 5.2.1-4 Schematic of a single collector and the entire bed of coalescer
C is the inlet concentration of oily wastewater. For the entire coalescer bed, we will
consider a very small slice of bed of the height dH (see fig. 5.2.1-3b). The number of collector
particles in this slice can be calculated from the cross sectional area of bed (Ao), the size of
collector (dp) and the void ratio of the bed (ε), as shown in eq. 5.2.5c.
Then, the total concentration of intercepted oil for this slice of bed will be equal to
the product of c’ and the number of collector particles. However, not all of the intercepted oil
drops will adhere to the collector. So the probability coefficient (α) will be applied to adapt the
quantity of intercepted oil drops to the quantity of adhered oil drops (c”), as shown in eq. 5.2.5d.
dH (1 − ε ) Ao
The number of collector particles in the slice dH = {5.2.5c}
π
d 3p
6
π dH (1 − ε ) Ao
c" = α ⋅η theo ⋅ d 2p ⋅ V ⋅ C ⋅ ,α<1 {5.2.5d}
4 π
d 3p
6
If dC represents the concentration of oil reduced after passing through the bed dH,
then we have got eq. 5.2.5e and f;
− V ⋅ Ao ⋅ dC = c" {5.2.5e}
π dH (1 − ε ) Ao
− V ⋅ Ao ⋅ dC = α ⋅η theo ⋅ d 2p ⋅ V ⋅ C ⋅ {5.2.5f}
4 π
d 3p
6
Therefore,
dC 3
=− (1 − ε )αη theo dH {5.2.5g}
C 2d p
Integration of eq. 5.2.5g will give the value of the oil concentration reduced by the
entire bed, as shown in eq. 5.2.6.
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Chapter 5 Coalescer
C 3 H
log( ) = − (1 − ε )αη theo {5.2.6}
Co 2 dp
⎛ C ⎞ ⎛ − (1 −ε ) ( α ⋅ηtheo ) ⎞
3 H
After being intercepted from step 1, the oil droplets will be separated from the wastewater
stream if they can adhere to the surface of the collectors. After that, in good coalescers, the
adhering oil drops will coalesce to each other and flow separately from the water stream, as oil
stream within the bed. Phenomena taking place in this step is shown in fig. 5.2.1-4. So the
mechanism in this step depends mainly on the wettability of the bed. AURELLE had tested the
effect of wettability, using hydrophilic and olephilic material as coalescer bed for secondary o/w
emulsion treatment. The result shows that:
• For Oleophilic material: The oil droplets will adhere to the collector surfaces then
form the oil film around the collectors. The oil films will accumulate in the bed until it
reaches saturate level at certain height of the bed, called “critical height” (Hc). After
that the oil will start to flow as a separated oil stream, called “channeling”.
• For Hydrophilic material: The oil droplets will be trapped in the void between
collectors. These trapped oil droplets will, then, be play the role of collectors by their
own to intercept the following oil droplets. Then they will coalesce into bigger drops
and flow through the void with the wastewater stream.
Even though both materials can cause coalescence, from test result, the oleophilic material
yields good efficiency up to higher range of flow velocity. It means that oleophilic bed coalescer
can be used at higher loading rates, thus makes it more compact in size. So it is recommended to
use oleophilic material as the bed for direct emulsion treatment.
The coalesced oil that flows through the bed in the manner of channeling will finally
reach the topmost of the bed. Then it will leave the bed for the water surface. In good coalescer,
the coalesced oil will leave the bed in the form of big oil drops (diameter 2-3 mm or more).
Characteristic or size of the oil drops that leave the bed depends on the phenomenon, taking place
at the top surface of the bed. AURELLE has studied this phenomenon, comparing between
oleophilic material and hydrophilic material. The result shows that:
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Part III Summary of researches: Oily wastewater treatment
a) Oil drops adhere to collectors b) Several oil drops coalesce to form oil film or
stream, separating from water stream
Oleophilic bed
a) Oil drops are intercepted or lodge between b) Intercepted oil drops coalesce to form bigger
interceptor. Note that contact angles > 90o. drops in the void between collectors
Hydrophilic bed
• For Oleophilic material: The coalesced oil will flow along its preferable “channels”
out of the bed, called “drip points”. At the drip point, the oil will adhere and cover the
top surface of the material as a film. To flow out of the bed, the water has to flow
inevitably through the covering oil film, then forms the “oil mousse”, as shown in fig.
5.2.1-5. The separated oil will contain high content of water. The water flow will also
cause “re-fragmentation” of the oil into small oil droplets again when the mousses
rapture, esp. in case that the interfacial tension is low. Thus, the efficiency is
decreased.
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Chapter 5 Coalescer
a) “Oil mousse” forming. Note that contact b) Re-fragmentation of oil when the
angle < 90o. mousse raptures
Oleophilic “salting out” surface
c) Formation of big oil drops. Note that contact d) Oil jet and re-fragmentation of oil at high
angle > 90o. velocity or high oil concentration
Hydrophilic “salting out” surface
• For Hydrophilic material: The drip points will appear as well. But the oil will not
form the film over the collector surface. But the film will locate between the collectors
and will grow to big oil drops and, then, be snapped off as big oil drops, without
forming oil mousse. However, at high flow velocity or high concentration of oil,
hydraulic force from water flowing out of the bed will be high. The oil will be
snapped off as a jet of oil and then, from the high hydraulic force, will be “re-
fragmented” to small droplets.
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Part III Summary of researches: Oily wastewater treatment
From the result described above, it shows that efficiency of this step depends on 4
parameters, i.e., wettability of discharge surface, flow velocity or empty bed velocity, interfacial
tension, and concentration or ratio of oil to water. To optimize the efficiency of this step,
AURELLE suggestd the following methods:
• Design the coalescer at the proper velocity to avoid the re-fragmentation effect.
• Use hydrophilic material as the top layer of the bed or use top grill of hydrophilic
material, to avoid mousse formation. At the same removal efficiency, it is proven that
the bed with hydrophilic material on the top layer can be operated at higher velocity
than that with the oleophilic top layer.
AURELLE had studies the relation between observed efficiency (α.ηexp) and the
theoretical efficiency and found that the observed values are quite different from the calculated
value in complex fashion, as shown in fig. 5.2.1-6. Relation between observed efficiency and
theoretical efficiency, suggested by AURELLE, is shown in eq. 5.2.8a. So the theoretical
efficiency in eq.5.2.7 can be modified by replacing αηtheo with α.ηexp. The efficiency of granular
bed coalescer, then, can be calculated by eq.5.2.8b.
⎛ C ⎞ ⎛ − (1 −ε ) ( α ⋅η exp ) ⎞
3 H
ηd = ⎜⎜1 − ⎜
⎟⎟ ⋅ 100 % = 1 − e 2 dp ⎟ ⋅ 100 % {5.2.8b}
⎝ Co ⎠ ⎜ ⎟
⎝ ⎠
• The key assumption of this model is that mechanisms in step 2 and step 3 of the
coalescer are optimized.
• The shape of the collector is relatively spherical. The size of the collector tested (dp)
is between 0.2 – 1 mm.
• The collector shall be wetted by dispersed phase. In case of direct (oil in water)
emulsion, the collector, then, shall be oleophilic. For inverse emulsion, oleophilic
resin is recommended.
• Range of empty bed velocity (V) shall be not greater than 0.35 cm/s (12.6 m/h)
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Chapter 5 Coalescer
1.00E+00
Experimental efficiency factor
1.00E-01
1.00E-02
1.00E-03
1.00E-04
1.00E+00 1.00E-01 1.00E-02 1.00E-03 1.00E-04
Theoretical efficiency factor
Fig. 5.2.1-7 Relation between experimental (or observed) efficiency factor and
theoretical efficiency factor
From fig. 5.2.1-6 and eq. 5.2.8, the relation is not in linear fashion, then it can be
interpreted that some assumptions in theoretical model are violated or not exactly true. Many
researchers had tried to fine-tune the assumptions. HAPPEL [44] had changed the flowrate
corresponding to single collector (eq. 5.2.5b) by replacing the value “dp” with an imaginary
diameter called “b” to account for the void area between collectors. The value of b is calculated
from the cross sectional area of bed (Ao) and the number of collectors by eq. 5.2.9.
π
N b 2 = Ao {5.2.9a}
4
Ao ⋅ (1 − ε )
N = {5.2.9b}
π
d 2p
4
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Part III Summary of researches: Oily wastewater treatment
• The model is tested at the range of dp from 0.36 to 0.94 mm. and interfacial tension
(γow) of 11 to 42 dyne/cm. (T.I.O.A, Heptane, Anisole, Toluene and Kerosene)
• The velocity (V) tested is in the range of 0.09 to 0.54 cm/s.
• The density difference between dispersed phase (oil) and continuous phase (water)
(Δρ) is between 83 to 314 kg/m3.
• The bed used is spherical glass bead with silicon coated to achieve oleophilicity.
• The inlet concentration of hydrocarbon tested is around 1,000 mg/l.
• If the result from eq. 5.2.10 is greater than 100%, it will be rounded up to 100%.
Verification result, using AURELLE’s experimental data, confirms that DAMAK’s model
can predict the removal efficiency with only ±10% error. It implies that the model is also valid at
the operating condition tested by AURELLE. From these test conditions, it seems that this
empirical model covers the range of the oily wastewater commonly found in real situation. Thus,
it is recommended to use this model (eq.5.2.10) for granular bed coalescer calculation.
Main parameters that affect the efficiency of the granular bed coalescer include:
Typical relation between the bed height and the removal efficiency is as shown in
fig. 5.2.1-7. From the graph, the efficiency of coalescer will increase with increasing height, then
it will stay relatively constant. This height is called “critical height (Hc)”. The occurrence of
critical height can be described by phenomena in step 2 : adhesion- coalescence, as described
before in section 5.2.1.2. If the bed height is shorter than the critical height, it can be said that
there is not enough accumulated oil film to trap the oil droplets and provide continuous coalesced
oil stream to form perfect “channeling”. Hc depends on wettability, roughness and size of media.
From eq. 5.2.10, it shows that the efficiency is proportional to H0.12
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Efficiency (η)
Efficiency (η)
100%
Increase V, dp
More hydrophilic
Less roughness
Lower limit of Droplet size (d)
the model: Hc Bed height (H)
10 microns
Fig. 5.2.1-8 Typical relation between efficiency of granular bed coalescer and various
parameters
The effect of the size of media is shown in fig. 5.2.1-7. Under the same operating
condition, the smaller the collector size, the better the efficiency. From eq. 5.2.10, it shows that
the efficiency is proportional to dp-0.4
The effect of velocity is relatively small, compared to other parameter. From eq.
5.2.10, it shows that the efficiency is proportional to V-0.08. However, this is true only within the
valid range of the model. At higher velocity, mousse or jet formation will occur, thus the
efficiency will drop rapidly and no longer conform to eq. 5.2.10. The velocity that the mousse or
jet starts appearing is called “critical velocity”. It is recommended to use velocity not more than
0.54 cm/s to avoid mousse and jet formation.
Even though this parameter is not included in eq. 5.2.10, but it is an important
parameter that limit the working range of coalescer. In fact, the model in eq. 5.2.10 is valid for oil
concentration not greater than 1,000 mg/l. Higher oil concentration will result in mousse or jet
forming, which will greatly lower the efficiency of the coalescer. To expand the working range of
granular bed coalescer, it is necessary to modify basic granular bed coalescer by additional
installation of oil guide, which will be described in the following section.
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Surfactant will lower the interfacial tension, then make the oil droplets more
stabilized. This leads to poor adhesion between droplets and surface, ineffective collision
(collision without coalescence), and re-fragmentation of oil drops. So the presence of surfactant
directly limits the efficiency of step 2 “adhesion-coalescence”. To optimize the efficiency of step
2, it is recommended to destabilize (or breaking or cracking) the emulsion before sending to the
coalescer.
7. Temperature
Surface roughness affects adhesion of oil on the surface of the solid, as shown in
chapter 2. The roughness makes the wettablity of the surface more eminent. So oleophilic
material will show more oleophilicity if its surface is rough. Contact angle of oil on the material
surface will be lower. In this case, it helps promoting direct emulsion separation.
Pressure drop across coalescer bed (p), in metre, can be calculated by Kozeny-Carman’s
equation (eq. 5.2.11) (use SI unit, e.g. m, kg, second).
180 Hμ cV (1 − ε ) 2
p= m {5.2.11}
ρ ⋅ g ⋅ dp 2 ⋅ ε 3
All variables except porosity (ε) will be determined by designer. For the porosity of
coalescer bed, from many researches [3], [26], [27], it shows that bed porosity varies with bed
depth and can be divided into 2 zones, i.e.,
• Lower zone or critical zone: This zone represents an effective zone of coalescer bed.
The maximum height of this zone is called “critical height (Hc)”. When bed height is
greater than the critical height, the efficiency will increase only slowly (from eq.
5.2.10: η ∝ H 0.12). In this zone, the bed will be soaked with oil so the effective
porosity will be low.
• Upper zone: If the bed is higher than Hc, practically, all of oil will be trapped in
critical zone. Then in the higher zone, there will be enough oil in lower zone to flow
continuously through the bed in form of “channeling”. So the effective porosity in this
zone will be lower than critical zone.
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From data of various researches [3], [26], [27], it can be concluded that the pressure drop
of granular bed can be calculated by Kozeny-Carman’s equation, using the following
recommendations, i.e.,
• When Hc is known (from literatures, etc.), pressure drop lower and upper part of bed
can be calculated separately, using eq. 5.2.11 and corresponding H of each zone. For
example, if Hc is 0.1 m. and total bed height is 0.15 m, H for lower zone will be equal
to Hc because Hc is lower the total height. And H for the upper zone will be 0.15 - 0.1
= 0.05 m.
• Recommended porosity for the lower (critical) part of bed (H<Hc) is between 0.14 to
0.19.
• Recommended porosity for the upper part of bed (H>Hc) is between 0.23 to 0.30.
• If it is certain that H design < Hc, use single step calculation with ε = 0.14 - 0.19.
• However, Hc is usually unknown, then it is recommended to use the single step
calculation with ε = 0.13 and 0.23 to estimate minimum and maximum pressure drop,
respectively.
• The value of ε described above can be used for the range of dp from 0.20 to 1.0 mm.
Design procedure for granular bed coalescer is based upon the equations, shown in the
previous section. To design the coalescer, the required cut size will be determined first. After that,
the size of the coalescer can be calculated. Then, graded efficiency (efficiency of each size of
droplet) and, hence, the total removal efficiency can be determined. Calculation procedure for
each step is described below.
The cut size can be determined from the degree of treatment required as well as
from the limitation of the coalescing processes. The cut size determination from degree of
treatment is described in chapter 3. For the limitations of the process, it is mainly model
limitation. Since the model used for calculation is based on empirical data, it can be applied only
within its valid range. Extrapolation of model may cause unpredictable errors. The limitation of
model will be described in section 5.2.3. It should be noted that the cut size must be greater than
10 microns since it is the lower limit of the model. For smaller droplets, the efficiency will be
very low and unpredictable.
2. Coalescer sizing
The size of the granular bed coalescer can be determined, based on the equation in
section 5.2.1. The main equation for coalescer designed will be based on the empirical model, as
shown is eq. 5.2.10. Design cut size will be used to calculate the dimension of the coalescer by
assuming that the graded efficiency at the cut size is 100%.
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Dimension of the coalescer can be arbitrarily selected under the limitations of the
model, as shown in section. 5.2.3, to make eq. 5.2.10 consistent. However, it is recommended to
select the lowest possible media diameter and highest velocity for the first trial because it will
give the most compact diameter of the coalescer. If the result is acceptable, it can be fine-adjusted
to get the most suitable dimension. If the result is unacceptable, normally too big, it may be
necessary to increase the number of units.
Fig. 5.2.2-1 shows the result of calculation from eq. 5.2.10 at various cut sizes. The
calculation is based on kerosene-water emulsion, which may be used as a guideline for coalescer
size estimation. The collector diameter, used in the graph, is 0.35 mm.
1.4
1.3
1.2
1.1
1
0.9
Bed height (m)
3. Removal efficiency
To determine the removal efficiency, the graded efficiency (ηd) will be calculated
first by eq. 5.2.10. If the result from eq. 5.2.10 is greater than 100%, then it will be rounded up to
100%.
It must be noted that the graded efficiency from the equation is not yet accounted for
effect of flow splitting between water outlet flow and separated oil outlet flow. To calculate
graded outlet oil concentration, the effect must be taken into account, as shown in eq. 5.2.12a.
Q {5.2.12a}
Cd = (1 − η d ) C od
Q out
Qout is outlet flow at treated water outlet port of the process. Qout is calculated from
difference between inlet flow and separated oil (in relatively pure condition) as shown below.
d max
Q ∑ (η d ⋅ C od )
Q out = Q −
d min {5.2.12b}
ρd
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∑ (η d ⋅ C od )
ηt =
d min
⋅ 100 % {5.2.12c}
Co
4. Pressure drop
Pressure drop (in metre) can be calculated from Kozeny-Carman’s equation (eq.
5.2.11). Recommended value of bed porosity (ε) and other criteria are as shown in section
5.2.1.7. For diluted wastewater, the values of μ and ρ can be replaced by those of water (μc, ρc).
180 HμV (1 − ε ) 2
p = m {5.2.11}
ρ ⋅ g ⋅ dp 2 ⋅ ε 3
The equations described above are developed from the following assumptions and
limitations. Thus, it is necessary to make sure that these assumptions are valid when design your
coalescer.
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Granular bed coalescer consists of 2 major components, i.e., casing and bed.
1) The casing
The casing is the component that contains the bed and other important
appurtenances, such as wastewater inlet, wastewater outlet, oil outlet, clean out, etc. Researches
in GPI lab normally emphasize on working mechanisms and developing of a model so there is no
direct study on characteristic of the casing. However, because of the fact that the coalescer is
usually designed as a pressure vessel in the same manner as a pressure filter, then, casing or tank
construction criteria of the pressure filter can be readily applied to the coalescer. However, some
details, such as oil outlet pipe, water outlet pipe and internal baffle should be adapted to ensure
good separation between oil and water. As outlined in chapter 4 “Decanting”, the internal baffle
should be installed in the manner that it can promote oil drop decanting, prevent short circuit of
oil drops to the water outlet pipe. The pipe and baffle arrangement shown in fig. 5.1-1 can be
used as a guideline for casing design.
2) The bed
From many GPI researches, it is recommended that resin is the most suitable
material for coalescer bed, because:
Other materials that have been used as coalescer bed include glass beads, small
stainless steel balls. Material that is heavier than water, such as stainless steel, has an advantage
for it can be used without installation of top grille to prevent it from carry-over. So it can be
cleaned by backwash process or scouring process because the material is not retained by top
grille, then can be expanded or floated freely.
For wettability, oleophilic bed with thin layer of hydrophilic material on the
top or with hydrophilic top grille is recommended (see section 5.2.1.2). Guideline on
oleophilicity of materials is described in chapter 2. Some hydrophilic material that has good
mechanical properties can acquire oleophilic property by coating with proper substance, such as
silicone. Oleophilicity of bed may change with time from deterioration of the coating or reaction
with wastewater. It may need re-coating or replacement if decreasing in efficiency is
unacceptable.
Variations of granular bed coalescer: There are several modifications of granular bed
colaescers, normally, on bed materials, such ad resin bed coalescer, glass bead bed coalescer.
There are 3 major modified granular bed coalescer studied at GPI lab, i.e., mixed bed coalescer,
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down-flow coalescer and guide coalescer. The latter will be fully described in the next section.
Mixed bed coalescer is another modified form of granular bed coalescer, used for mixed
direct/inverse emulsion separation, which is usually found in liquid-liquid extraction process. In
mixed bed coalescer, the bed will consist of separate layers of oleophilic and hydrophilic
materials, placed in series in the same column. From research [6], ratio of oleophilic and
hydrophilic material and order or configuration of column (upper hydrophilic layer/lower
oleophilic layer or vice versa) depends on wastewater characteristic. So it is difficult to
determine the efficiency of the coalescer by fixed equation. In this case, it is recommenced to
perform pilot test to find optimum design criteria.
Furthermore, there are also variations of coalescers, based on flow patterns i.e., up-flow
coalescer and down-flow coalescer. The researchs conducted in GPI lab are generally based on
up-flow coalescer. For down-flow coalescer, the flow pattern in this case will be identical to that
of deep-bed filter. This type of coalescer is intentionally designed to use with the oily wastewater
that contains suspended solids. The wastewater will be fed from the top of the bed. The oil will be
coalesced in the same manner as the up-flow coalescer. However, the coalesced oil will flow up
against the wastewater stream to the inlet water surface, then be skimmed out of the reactor. This
flow patterns can eliminate the top grille that is used for preventing carry-over of bed media in
up-flow coalescer. This allows us to clean the bed by air scouring, back washing or any proper
mechanism, such as pneumatic pulsation that can make the bed move up or partially fluidize to
unclog the trapped solids. Working principles of this coalescer is generally identical to that of up-
flow coalescer. However, there is not enough research data to develop the math model. So it is
recommended to use the equation of up-flow coalescer for roughly estimation of efficiency.
Anyway, the exact efficiency would be obtained from pilot scale testing.
Advantage: Granular bed coalescer has a major advantage in its compactness. Tested
loading rate of coalescer is 3.2 – 19.4 m/h and it can be used with the droplet size from 10
microns while, for simple decanter, the loading rate is about 0.04 m/h for 10-micron droplet
separation.
Disadvantage: The bed of this type of coalescer has relatively low porosity (0.14-0.19).
So, at high loading rate, the pressure drop may be very high. Moreover, it can make the bed clog
relatively easily. So the granular bed coalescer is sensitive to the presence of suspended solids.
Guide coalescer is the modified form of simple granular bed coalescer. In guide coalescer,
high-porosity oleophilic material, such as woven metal fiber or woven mesh, will be placed next
to downstream end of the granular and extended up to water surface. Coalesced oil drop will be
guided along this material until it combines with oil layer at the water surface. So, this material is
called “guide”. Structure of the guide shall be self-sustained or installed in perforated structure,
so the treated water can flow freely out of the guide structure, then be discharged from the
coalescer. The pictures of guide coalescer are shown in fig. 5.3.1-1.
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Working principles of guide coalescer is relatively identical to those of basic granular bed
coalescer. However, iinstallation of guide helps preventing formation of oil mousse or jet, which
normally occurs in classical coalescer at high velocity or high concentration of oil because it
virtually eliminates the drip point (step 3 of the 3 mechanisms, see section 5.2.1). Thus, the
maximum velocity before formation of mousse or jet will occur (so called critical velocity) of the
guide coalescer is 1.5 times greater than usual [6]. Furthermore, it can be operated at ratio of oil
to water (Phase ratio) as high as 6 [6].
a) Graphic image of “guide” coalescer b) Steel wool or steel mesh that can be used as a guide
From literature review, there is no proposed model for guide coalcescer. However, it is
proven that, at velocity range below critical value, the efficiency is approximately velocity-
independent [3], [6]. It, also, can be confirmed by eq. 5.2.10, which shows that the exponent of V
is very low (–0.08). Then, at recommended range of velocity, V-0.08 is approximately constant.
So, from this fact, the efficiency of guide coalescer could be calculated by the model of
basic granular bed coalescer (eq. 5.2.10) with additional precautions or assumptions as follows,
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efficiently. To apply to higher concentration or beyond the limit stated above, bench
scale or pilot scale testing is highly recommended
This type of coalescer have been developed for 2 purposes, 1) to increase the hydraulic
loading rate of the granular bed coalescer, 2) to make it possible to use the granular bed with the
water containing very high concentration of oil, such as in liquid-liquid extraction process.
Steps of calculation, as well as cut size determination, for the guide coalescer is identical
to those of basic granular bed coalescer. However, there are some difference in details of sizing
and pressure drop calculation as described below.
1. Coalescer sizing
The size of guide coalescer can be calculated by eq. 5.2.10. For velocity less than
0.54 m/s, actual velocity will be used in the equations. However, if design velocity is greater than
0.54, the velocity of 0.54 m/s will be used, regardless of the actual velocity. The size from the
calculation can be, theoretically, used at velocity from 0.54 to 0.8 cm/s.
2. Removal efficiency
The removal efficiency can be calculated from the selected dimension, using eq.
5.2.10 and 5.2.12.
3. Pressure drop
Because of the fact that the “guide” in guided coalescer has relative high porosity
(0.9 approx.), then, The pressure drop is very low, compared to the granular part, and can be
negligible. So Kozeny-Carman’s equation (eq. 5.2.11) and recommended value of porosity from
section 5.2.2 can also be used to predict pressure drop of guided coalescer.
The limitations in this case are identical to those of granular bed coalescer (see
section 5.2.3) except for the velocity and oil concentration, which will conform to section 5.3.1.
2. Material selection
For direct emulsion treatment, granular bed in guide coalescer shall be oleophilic
material. However, instead of top layer or grill of hydrophilic media, guide will be placed on the
top of the granular bed. The guide should be made of metal or rigid material and properly coated
to obtain oleophilic property. It should have high porosity and self-sustained structure because it
is not supported by the wall of the coalescer. If the selected guide is not self-sustained, perforated
oleophilic material shall be provided to support the guide. Commercial woven wire-meshes or
metal wool, such as MuitiKnit™, Knit meshTM, 3MTM, etc., can be efficiently used as a guide.
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This type of coalescer uses high porous fibrous material, such as fibrous bottle brush, as a
bed to promote coalescing between oil droplets. Due to its high porosity, this type of bed is
hardly clogged and can handle wastewater containing suspended solids efficiently. It also causes
much less pressure drop than granular bed coalescer. However, fibrous element, which is
normally very small, may deflect at its tip, especially in large-scale unit, and causes unpredictable
channeling of untreated wastwater, then decreasing in efficiency.
From other point of view, this coalescer can be considered as a modified form of guide
coalescer that granular bed is removed and the guide is additionally used to intercept oil, besides
its role to provide coalesced oil flow channel.
Three basic steps for granular bed coalescer, proposed by AURELLE [3], can also be
used to describe phenomena taking place within the coalescer. However, mathematics models,
derived from dimensional analysis, are proven to be more accurate.
There are 2 main categories of fibrous bed coalescers, i.e., Simple fibrous bed coalescer
and dynamic (or rotating) fibrous bed coalescer, as shown in fig. 5.4.1-1. The latter is the
modified form of the former, by installation of driving unit to drive the bed.
This type of coalesceruses uses fibrous material, normally, in the form of “bottle brush”
as a coalescer bed. The brush has relatively high porosity, compared to granular material. So this
coalescer causes much lower pressure drop and is hardly clogged. Furthermore, from the three-
step phenomena of coalescer, described in section 5.2.1, it shows that the efficiency of coalescer
will increase if the size of the bed media is small. For fibrous bed coalescer, the size of fiber is
around 100- 200 microns, much smaller than granular media’s. By this way, the efficiency can be
improved.
GPI lab has been studied the possibility to use this type of material as a bed for some
times. However, the researches on this type of coalescer are based mainly on its application and
design consideration, rather than model development. So there is no model proposed for this
coalescer. Anyway, these researches, especially the study of SRIJAROONRAT [10], provide
sufficient raw data to formulate an empirical model. This newly formulated model, which will be
called “SRIJAROONRAT’s model”, is as shown in eq. 5.4.1. The model has been verified, using
data from MA’s and WANICHKUL’s researches, as shown in fig. 5.4.1-2.
⎛ ρ VD ⎞
η d = ⎜⎜104 . 5 ( c ) −0.77 ( ) 0.18 ( F ) −0.18 (1 − ε ) ( ) 0.694
d d 0 . 35 H
⎟⎟ ⋅ 100 % {5.4.1}
⎝ μc D D D ⎠
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a) Simple fibrous bed coalescer [11] b) Graphical image of dynamic fibrous bed
coalescer
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Chapter 5 Coalescer
100.0%
90.0%
80.0%
Predicted efficiency (%)
70.0%
60.0%
+20 %
50.0%
40.0%
-20 %
30.0%
SRIJAROONRAT's data
20.0%
MA's data
10.0% WANICHKUL's data
0.0%
0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0%
Observed efficiency (%)
Fig. 5.4.1-2 Comparison between observed efficiency and predicted efficiency from
SRIJAROONRAT's model, Verified by MA's and WANICHKUL's data.
Dynamic brush coalescer is the modified form of simple fibrous brush coalescer by
installing the prime mover to drive the brush. From TAPANEEYANGKUL [8], rotating motion
of the brush provides 2 major benefits, i.e.,
• It can increase the probability of interception or collision between fiber elements and
oil droplets. Thus, the efficiency will be improved. Furthermore, if the variable speed
driving system is installed, the efficiency of the coalescer will be adjustable.
• Rotating motion also helps reducing possibility of clogging.
⎛ ρ VD d D ⋅ N 0.53 ⎞
η d = ⎜⎜1.76( c ) − 0.21 ( ) 0.58 ( F ) − 0.58 (1 − ε )0.35 ( ) 0.35 (
d H
) ⎟⎟ ⋅ 100% {5.4.2a}
⎝ μc D D D V ⎠
Or
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There is another special case of simple fibrous bed coalescer that uses random or
disorderly fibrous material (such as metal wool, etc.) as coalescer bed. SRIJAROONRAT’s
research shows that removal efficiency of this coalescer is higher than that of coalescer that uses
brush type bed. For this, it can be concluded that tortuosity of bed also affects the removal
efficiency. From SRIJAROONRAT’s raw data, an empirical model, based on dimensional
analysis, can be derived as shown in eq. 5.4.3. However, this model is developed from rather
small set of data. There is an effort to verify if the simple bed model (eq. 5.4.1b) is still valid for
random fibrous bed coalescer. Comparison between efficiency from eq. 5.4.1b, eq. 5.4.3 and
observed value is shown in fig. 5.4.1-3.
⎛ ρ VD d d H ⎞
ηd = ⎜⎜ 3 . 35 ( c ) −0.23 ( ) 0.03 ( F ) −0.. 03 ( ) 0.36 ⎟⎟ ⋅ 100 % {5.4.3}
⎝ μc D D D ⎠
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Chapter 5 Coalescer
110.00%
100.00%
90.00%
80.00%
Predicted Efficiency (%)
70.00%
60.00%
+10%
50.00%
40.00%
30.00%
-10%
20.00%
10.00%
0.00%
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Observed efficiency (%)
Fig. 5.4.1-3 Relation between observed efficiency and predicted efficiency from
random fibrous bed coalescer model and simple fibrous bed model
From the graph, it shows that SRIJAROONRAT’s random fibrous bed model (eq. 5.4.3)
can accurately predict the efficiency of the coalescer while the result from the simple bed model
(eq. 5.4.1b) tends to underestimate the efficiency from 2 to 6 times. This confirms that tortuosity
of the bed plays very important role in efficiency of fibrous bed coalescer. However, tortousity
can not be effectively established in form of numerical value so it can not be included as a
parameter in mathematics model. Eq. 5.4.3, then, can be applied only when design condition is
close to the test condition from SRIJAROONRAT’s research.
• The beds used in the experiment are highly disorderly bulk of stainless steel fiber, dF =
75 microns, and steel wool, dF = 40 microns (see fig. 5.4.1-4). However, only the
latter case, which raw experimental data is available, is used to develop the model.
The minimum size of oil droplet tested is 1 micron.
• Tested Reynolds number is between 840 to 2470.
• Porosity of the bed (ε) is around 0.95.
• Diameter of the coalescer (D)= 5 cm.
• Height of the coalescer bed (H) is between 0.07 to 0.21 m.
• Velocity (V) is between 1 to 2.5 cm/s or 36 to 90 m/h.
• Inlet concentration is around 1000 mg/l.
In case that the conditions stated above are not fully compliant, it is recommended to use
eq. 5.4.1b to calculate the efficiency of the coalescer because it is proven to be valid within wider
range. In this case, predicted result from eq. 5.4.1b tends to underestimate the efficiency of the
coalescer.
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Fig. 5.4.1-4 Random or disorderly fibrous bed, used in the research of SRIJAROONRAT
Even though each type of fibrous bed coalescer is governed by different equation, all of
the equations is in about the same mathematics form, as shown in eq. 5.4.4. Thus, main
parameters that affect the efficiency of the fibrous bed coalescer can be commonly summarized
as shown in fig. 5.4.1-5.
1 1 1
ηd = f ( , , , d , H , N , (1 − ε )) {5.4.4}
V D dF
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Efficiency (η)
Efficiency (η)
100%
100%
Increase V, D, dF
Decrease H, (1-ε), N
Less tortousity
Lower limit of Droplet size (d)
the model: Droplet size (d)
1 micron
Fig 5.4.1-5 Typical relation between efficiency of fibrous bed coalescer and various
parameters
However, besides the parameters shown in eq. 5.4.4, there are some important parameters
that affect the efficiency of the coalescer, i.e.,
1. Tortousity
If the bed is more tortuous, the probability to intercept oil droplets will be increased.
The efficiency, then, is increased, as clearly shown in the case of wool coalescer. However, it will
tend to be clogged if suspended solids are present in wastewater.
2. Wettability of bed
From the 3 mechanisms of AURELLE [3] (section 5.4.1.1), wettability of the bed is
the key parameter that governs the step 2 “adhesion-coalescence”. In case of direct (oil in water)
emulsion treatment, he bed material shall be oleophilic to optimize the adhesion-coalescence
phenomena.
Surfactant will lower the interfacial tension, then make the oil droplets more
stabilized. This leads to poor adhesion between droplets and surface, ineffective collision
(collision without coalescence), and re-fragmentation of oil drops. So presence of surfactant
directly limits the efficiency of step 2 “adhesion-coalescence”. To optimize the efficiency of step
2, it is recommended to destabilize, (breaking or cracking) the emulsion before sending to the
coalescer
4. Temperature
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section are developed under the temperature range between 15 to 25oC, which is general practical
operating range.
Another precaution about the bed is the ratio of bed center shaft to diameter of bed.
Since the effective part of the bed is its fibers, efficiency of coalescer of the same diameter will
decrease it the shaft is relatively large. Equations in sections 15.4.1 already include the effect of
center shaft. The sizes of the shafts used in those researches are around 1.0 to 1.5 cm., or about 20
to 30% of diameter of the bed. If the selected shaft does not conform to this criterion, diameter of
shaft used in the equations will be adapted to the equivalent diameter that has the same effective
area of fiber as the real bed with the shaft size conforms to the criterion.
Many researcher [8], [10], [11], [16] observe pressure drop of fibrous bed coalescers and
report that these coalescer causes very low pressure drop due to very high porosity of their beds.
However, there is not any proposed model on pressure drop.
In order to calculate the pressure drop, it is recommended to use any general piping loss
equations, such as Darcy’s, Colebrook-White’s or Hazen-William’s equation with the safety
factor of 2 to 5, multiplied to the actual length of the bed. However, the pressure drop of fibrous
bed coalescer is normally low (< 104 N/m2), compared to piping system pressure drop.
Observed size of coalesced oil drop from fibrous bed coalescer with oleophilic bed is
reported [3], [10] to be between 0.3 mm to 8.4 mm with the average value between 1.8 to 6.8 mm
(table 5.4.1-1). The size of the oil drop depends on operating condition, esp. velocity, and
material properties, such as interfacial tension, fiber wettability. The size will decrease if the
velocity increases or interfacial tension decreases or the fiber is hydrophilic.
From STOKES law, rising velocity of the droplet of 1.8 mm diameter is around 0.33 m/s,
which is greater than maximum tested velocity in the fibrous bed coalescer (around 5 cm/s). So
the oil drop is positively separated. Furthermore, if oil and water discharge pipes of the coalescer
is properly arranged, even the smallest drop of 0.3 mm can still be separated. So, it can be safely
said that all of coalesced oil can be decanted by downstream end of the coalescer because it
requires less decanting area than the size of the coalescer itself. However, using moderate
velocity (around 2.0 cm/s) and sufficient height (H/D>2) will guarantee sufficient size of
coalesced oil drop for good decanting.
Anyway, it is interesting to consider granulometry of remaining oil droplets that are not
fully coalesced to form big oil drops. To help considering this, there are some researches on
coupling or combination of coalescer and hydrocyclone [10], [11]. Example of the result from
[10] is show in table 5.4.1-2. From the table, it shows that the observed total efficiency of the
coupling is higher than the product of the two separate processes. So it may be implied that the
size of the smallest droplets from coalescer is increased. Therefore, with these bigger oil droplets,
the efficiency of the hydrocyclone is increased. However, there is not enough data for further
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analysis. Furthermore, if this partial coalescing exists, its effect should be already included in the
efficiency prediction models (eq. 5.4.1 to 5.4.3). So, for calculation, it is safer to assume that
there is no partial coalescing. Prediction of coupling of processes would be calculated from the
product of the efficiency of each individual process.
Table 5.4.1-1 Coalesced kerosene droplet size at various velocities and bed heights from
oleophilic “bottle brush” coalescer (dF = 100 microns, D = 0.05 m, Co = 1 g/l,
120oC) [10]
Table 5.4.1-2 Comparison between the individual efficiency of oleophilic bottle brush coalescer,
hydrocyclone, theoretical and observed efficiency of the coupling of
coalescer/hydrocyclone [10]
micron m/s % % % %
11 0.02 35% 54.19% 70% 82%
11 0.03 50% 39.65% 70% 82%
11 0.04 61% 31.78% 73% 82%
11 0.05 69% 26.76% 77% 82%
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Steps of calculation, as well as cut size determination, for fibrous bed coalescer is
identical to those of basic granular bed coalescer. However, there are some difference in details of
sizing and pressure drop calculation as described below.
The ut size can be determined from the degree of treatment required as well as from
the limitation of the coalescing processes. Cut size determination from degree of treatment is
described in chapter 3. For the limitations of the process, it is mainly model limitation. Since the
model used for calculation is based on empirical data, it can be applied only within its valid
range. Extrapolation of model may cause unpredictable error. The limitation of each model is
described in section 5.4.1.
2. Coalescer sizing
The size of various types of fibrous bed coalescer can be calculated by eq. 5.4.1 to
5.4.3. Design cut size will be used to calculate the dimension of the coalescer by assuming that
the graded efficiency at the cut size is 100%. Dimension of the coalescer can be arbitrarily
selected under the limitations of each equation, as described in section 5.4.1.1 to 5.4.1.3.
However, it is recommended to select the possible lowest fiber diameter and highest velocity for
the first trial because it will give the most compact diameter of the coalescer. If the result is
acceptable, we may try to fine-adjust the parameters to get the most suitable dimension. If the
result is unacceptable, normally too big, we may have to increase the number of units.
3. Removal efficiency
After the dimension of the coalescer is determined, graded efficiency (ηd) can be
calculated by eq. 5.4.1, 5.4.2 or 5.4.3. If the result from eq. 5.2.10 is greater than 100%, then it
will be rounded up to 100%.
It must be noted that the graded efficiency from the equation is not yet accounted for
effect of flow splitting between water outlet flow and separated oil outlet flow. To calculate
graded outlet oil concentration, the effect must be taken into account, as shown in eq. 5.2.12a.
Q {5.2.12a}
Cd = (1 − η d ) C od
Q out
Qout is outlet flow at treated water outlet port of the process. Qout is calculated from
difference between inlet flow and separated oil (in relatively pure condition) as shown below.
d max
Q ∑ (η d ⋅ C od )
Q out = Q −
d min {5.2.12b}
ρd
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∑ (η d ⋅ C od )
ηt =
d min
⋅ 100 % {5.2.12c}
Co
4. Pressure drop
The equations described above are developed from the following assumptions and
limitations. Thus, it is necessary to make sure that these assumptions are valid when design the
coalescer. Limitation of each design equation (eq. 5.4.4 to 5.4.3) is described in section 5.4.1.
Fibrous bed coalescer consists of 2 major components, i.e., casing and bed.
1) The casing
The casing is the component that contains the bed and other important
appurtenances, such as wastewater inlet, wastewater outlet, decanting section, oil outlet, clean
out, etc. Researches in GPI lab normally emphasize on working mechanisms and developing of a
model so there is no direct study on characteristic of the casing. However, the size of the fibrous
bed coalescer is usually small to avoid deflection at the tip of fibers, it is, then, designed as inline
unit or in the form of pipe (see fig. 5.4.1-1 and 5.4.3-1). Batteries or multi-coalescer unit is also
available. Downstream decanter may be integrated or placed separately from the coalescer as
shown in fig. 5.4.3-1. As described in section 5.4.1, diameter of the decanter is normally equal to
that of coalescer or a bit bigger to facilitate placement and construction of internal baffle, water
and oil outlet pipe.Casing of coalescer can be made of any material (plastic, steel, glass, etc.) that
can withstand the operating condition. If possible, it should be oleophilic.
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b) Inline-style fibrous bed coalescer [11] c) Assembly of the coalsecer and separated
decanter (Source: Elf, GPI lab)
2) The bed
The bed is the most important part in the coalescer. From section 5.4.1, there
are 2 major types of fibrous beds, i.e., simple or brush type and random or disorderly type.
Difference in operating efficiency between the two is already discussed. However, one property,
which both beds have in common, is that, for direct emulsion treatment, the bed shall be
oleophilic.
Material of the bed varies from steel, stainless steel and variety of plastic, scuh
as polyamide, polypropylene as shown in fig. 5.4.1-1, 5.4.1-4 and 5.4.3-2. For simple brush type,
the efficiency of the coalescer varies only slightly for various types of bed shown in the figure.
The factor that governs the efficiency for this type of bed is its oleophilicity. Guideline on
wettability of material is described in chapter 2. To preliminary test olephilic property of the bed,
it can be done easily by dip or have the bed contact with oil or water. If the drop of oil or water is
almost sphere, it can be approximately concluded that the material is hydrophilic or oleophilic
respectively (see fig. 5.4.3-3)
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Chapter 5 Coalescer
Fig. 5.4.3-2 Various types of bed tested by WANICHKUL [11]: From left, a) Simple spiral, b)
Double spiral, c) Solid plastic spiral, d) A module of multi-stage bed [No. of stage
can be added by increase the number of module into the same center shaft
a) water drop on b) water drop on non- c) oil drop on silicon d) oil drop on non-
silicon coated fibers coated fibers coated fibers coated fibers
Fig. 5.4.3-3 Characteristics of oil and water drops on silicon coated (oleophilic) steel fibers and
non-coated (hydrophilic) steel fibers
Variations of fibrous bed coalescer: There are several modifications of fibrous bed
colaescers, normally, on bed type and materials, such as simple fibrous bed, steel wool bed,
rotating or dynamic bed, as described in section 5.4.1. Each type of bed can be sub-divided into
sub-types, characterized by specific features of beds. The efficiencies of these “brush” beds are
almost identical, as discussed before. However, there are some variations of these coalescers
worth to mention here for their initiative idea.
Double spiral bed (fig. 5.4.3-2b) is one of the innovations of GPI lab [10], [11]. It is
designed to mitigate the fiber tips deflection effect. The bed provides homogeneous void ratio at
any radial distance. External “coil spring-like” part will help intercepting oil droplets without the
problem about defection since the fibers just protrude a short distance from their coil spring-like
support. This type of bed can also reduce undesirable channeling, taking place at high velocity at
the tips of simple fiber bed. Anyway, it tends to clog easier if suspended solids are presence.
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Multi-stage simple brush coalescer is another initiative idea to improve the efficiency of
simple fibrous bed coalescer [11]. Eq. 5.4.1 to 5.4.3 show that efficiency varies with Ha, when 0<
a <1. If a coalescer of bed height “H” and efficiency of one stage “η1-stage” is divided into n sets of
bed height (H/n), theoretical total efficiency of the series of these coalescers will be as shown in
eq. 5.4.5.
η1 −stage
η n −stages = 1 − (1 − a
)n {5.4.5}
n
From the equation, when η1-stage and “a” is lower than 1, the value of ηn-stages is always
higher than η1-stage. From this fact, WANICHKUL [11] had been developed annular brush module
(fig. 5.4.3-2d) that could be placed close to each other or with some spacing between them. When
there is a sufficient distance between modules, it can be assumed that the coalescer becomes
multi-stage. Theoretically, the efficiency will increase as shown in eq. 5.4.5. WANICHKUL use
spacing of 1.0 cm. between each module. The result shows that the total efficiency of this multi-
stage coalescer is actually higher than the single stage one. However, efficiency of the multi-stage
coalescer is approximately equal to efficiency of the single stage coalescer plus 10%, not as high
as calculated from eq. 5.4.5. This is simply because the efficiency is also a function of oil
concentration. After each stage, the oil concentration for the next stage will decrease, so eq. 5.4.5
will be no longer valid. However, this research confirms the idea of efficiency improvement by
simply adding some spacing between each module of bed.
Advantage:
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6.1 General
Flotation is an accelerated separation process, operated by increasing density
difference between continuous phase and dispersed phase. This is accomplished by mean of
adding gas or air into the wastewater to promote formation of air-solids or air-oil
agglomerates. There are several researches on flotation, its modification and applications of
various types of flotation such as mechanical flotation, diffused air flotation, dissolved air
flotation (DAF), etc. Among these, DAF, with its finest air bubble size, is the most efficient
process. So it became the main flotation process studied in GPI lab.
Δρgd 2 {6.2.1}
U=
18μ c
For dissolved air flotation, pressurized water which is (or almost) saturated with air or
gas will be fed to wastewater at lower, usually, atmospheric pressure. The air or gas will be
released from the pressurized water in form of tiny bubbles. These bubbles, while rise up to
the surface, will collide with dispersed phase, in case of oily wastewater oil droplets, in the
wastewater. Some will attach to the droplets and form oil-bubble agglomerates. Since the
bubble has much less density than oil and water. Density of these agglomerates will be lower
than that of oil droplets alone, thus, make the rising velocity increase. General schematic
diagram of DAF process is as shown in fig. 6.2-1.
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There are many attempts to predict the efficiency of DAF or to formulate mathematics
model of DAF. However, there is no general model so far that can predict the efficiency of the
process accurately at any operating condition. Almost all of the models are on empirical.
However, there are some researches in GPI lab to formulate the models of DAF that are semi-
empirical or based on some theories. So they can be used as tools to understand the effect of
some parameters on DAF operation and to adapt empirical data on DAF efficiency at one
condition to estimate, only roughly, the efficiency at other condition. There are 2 approaches
to formulate such a model, studied in GPI lab, i.e.,
From the concept that air bubbles are used to intercept oil droplets and form oil-bubble
agglomerate, AURELLE and SIEM [12] considered that this concept is relatively close to that
of filtration with the air bubbles play the role of collector. So they formulated model of DAF
based on the filtration model, proposed by YAO et al. [35]. Details of model formulation are
as shown in the following sections.
To calculate relative velocity of air bubble/ oil droplets in flotation column, consider a
flotation column which wastewater and pressurized water are fed at the bottom. This causes
flow velocity “V” in the column (see fig. 6.2.1-1). Air bubbles generated from pressurized
water, as well as, oil droplets in the wastewater will be carried along with the liquid.
However, from STOKES law, the air bubble and the oil droplets also have their own rising
velocities, “Ub“and “Ud“ respectively. So, for the observer looking from outside of the
column, the absolute velocity of bubble and oil droplets will be equal to “V+Ub“ and “V+Ud “
respectively. Then relative velocity between air bubble and water (Vr) will be as shown in eq.
6.2.2a while the relative velocity between bubble and oil droplets (Ur) is shown in eq. 6.2.2b.
Vr = (V + U b ) − (V ) = U b {6.2.2a}
U r = (V + U b ) − (V + U d ) = U b − U d {6.2.2b}
From above equations, if an observer stands on the bubble, it will seem to him that the
water is flowing past him at velocity “Ub”, while oil droplets move toward him at slightly
lower velocity “Ub-Ud”. To apply filtration model to DAF, we will consider, firstly, the
phenomena, taking place at 1 collector (or 1 bubble). Assume that frame of reference is on the
bubble, schematic diagram of the 3 transport phenomena is shown in fig. 6.2.1-2. Efficiency
of each phenomenon is described as follow.
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Part III Summary of researches: Oily wastewater treatment
x
Ub Ud
y
Bubble, Oil droplet
Collector
Fig. 6.2.1-1 Diagram for considering relative velocity of bubble and oil in flotation
column
Oil droplet
Bubble,
Stream line