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THESE

présentée à

L’INSTITUT NATIONAL DES SCIENCES APPLIQUEES DE TOULOUSE

pour l’obtention du

DOCTORAT

SCIENCE DES PROCEDES

SPECIALITE : GENIE DES PROCEDES ET DE L’ENVIRONNEMENT

par

Srayut RACHU

Master of Environmental Engineering – Chulalongkorn University, Bangkok, Thaïlande

CONTRIBUTION A LA MISE AU POINT D’UN LOGICIEL DE


CALCUL DE PROCEDES ET FILIERES DE TRAITEMENT D’EAUX
RESIDUAIRES HUILEUSES

Soutenance prévue le 16 Décembre 2005 devant la commission d’examen:

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 de LIPE

M. R. BEN AIM Professeur Emérite, INSA, Toulouse

M. S. SAIPANICH PDG, Progress Technology Consultants Co.,Ltd., Thaïlande

M. H. ROQUE Professeur Emérite, INSA, Toulouse Invité


Executive summary
Sommaire

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.

2. Généraliser et proposer le modèle de chaque procédé relatif.

3. Composer le textbook sur les eaux résiduaires hydrocarbure-polluées ou les procédés


de traitement des eaux résiduaires huileuses, basés sur le résultat des 1er et 2ème
objectifs.

4. Développer le prototype du logiciel pour la recommandation de sélection du procédé,


le design des unités procédé et la simulation du plan de procédé de traitement des eaux
résiduaires huileuses.

Sommaire des procédés de traitement des eaux résiduaires huileuses


Les trois premiers objectifs sont accomplis dans la Partie 1 à la Partie 3 de cette thèse.
Tous les filières de procédé de récupération d’huile, étudiées dans le laboratoire GPI, avaient
été réexaminées ; et ses modèles mathématiques correspondantes aussi bien que la limitation
du design et les paramètres influents avaient été établis. Ces procédés qui sont réexaminés
sous les buts et objectifs du travail de cette thèse sont ;

1. L’Écrémeur déshuileurs

Ce dispositif est développé pour récupérer sélectivement la couche d’huile de la


surface de l’eau sans entraînant de l’eau avec lui. On a trouvé que le moyen pour réaliser la
bonne sélection d’huile dépend de l’énergie de surface ou de la tension superficielle critique
du matériel écrémeur. Le matériel avec la basse tension superficielle critique convient à être
utilisé comme matériel écrémeur.

[1]
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Les modèles mathématiques de deux types d’écrémeur : le tambour et le disque


déshuileurs sont vérifiés ;
Pour le tambour déshuileur,

0.486
3.035D1.541N1.541ν o L
P= m3/s {1.1}
g 0.514

Pour le disque déshuileur,

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

Où P = Productivité en huile du tambour ou du disque (relative à une


surface) (m3/s)
D = Diamètre du tambour ou du disque (m)
N = Vitesse de rotation (rev/s)
2
νo = Viscosité cinématique de l’huile (m /s)
L = Largeur du tambour (m)
I = Hauteur d’immersion totale du disque dans le liquide (m), I ≤
D/2.
g = Accélération de la pesanteur (m/s2)
γo = Tension superficielle tension de l’huile (kg/s2 or N/m = 1000
dyne/cm)

Tambour

Racleur Disque Moteur


Goulotte
de collecte
Vis d’Archimede

Racleur
Nappe d’huile
Phase aqueuse

Fig. 1-1 Tambour déhuileur Fig. 1-2 Disque déhuileur (Par: Abanaki)

Les modèles sont valides dans ces hypothèses ;


• La tension superficielle de l’huile est dans l’intervalle de 27 à 34 dynes/cm, ce qui
couvre pratiquement toute huile ordinaire.
• Le nombre capillaire (Ca = μo V/γo) est de 0.04 à 3.6.
• La densité de l’huile est d’environs 0.79 à 0.83 kg/m3. La viscosité dynamique d’huile
expérimentée est entre 1.35x10-3 et 291x10-3 (N.s)/m2 (1.35-291 cp).

[2]
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• Pour le tambour déshuileur, la vitesse périphérique ne devrait pas être supérieure de


0.8 m/s. En fin d’éviter l’entraînement d’eau, la vitesse de 0.44 m/s ou moins est
recommandée.
• Pour le disque déshuileur, la vitesse périphérique ne devrait pas être supérieure de 1.13
m/s. En fin d’éviter l’entraînement d’eau, la vitesse de 0.5 m/s ou moins est
recommandée.
• Les modèles se prouvent valides pour les écrémeurs faites de SS, PP, PVC et PTFE.

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

Figure. 2-1 Schéma et courbe caractéristique de l’efficacitéd’un décanteur

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 :

Pour d ≥ diamètre coupure, dc ηd = 100 % {2.1}


Pour d ≤ dc ηd =
Ud
⋅ 100 %
{2.2}
U dc
La vitesse ascensionnelle d’une Δρ ⋅ g ⋅ d 2 {2.3}
Ud =
gouttelette (Ud) 18 μ c
La diamètre de coupure, c’est-à-dire la plus petite taille de gouttelette dont l’efficacité de
séparation est de 100%, est déterminée par les équations suivantes,
Le décanteur simple, 1/2 {2.4}
⎛ 18HQμ c ⎞
(A = aire ecoulement, Q = debit d c = ⎜⎜ ⎟⎟
d’eau) ⎝ ΔρgLA ⎠

[3]
Sommaire

Le PPI, 1/2 {2.5}


⎛ 18Qμ c ⎞
dc = ⎜ ⎟
⎜ ΔρgS (N + 1) ⎟
⎝ P ⎠
Pour un décanteur compact qui 1/2 {2.6}
⎛ 18Qμ ⎞
hauteur de décantation n’est pas dc = ⎜ c ⎟
bien connu. ⎜ Δρ ⋅ g ⋅ S ⎟
⎝ d⎠

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

Le coalesceur est le procédé de séparation accéléré, conçu pour favoriser la


coalescence entre les gouttelettes d’huile en but de former les plus grosses gouttelettes
d’huile. Selon la loi de STOKE, la vitesse ascensionnelle est proportionnelle au carré de
diamètre de la gouttelette. Ainsi, en agrandissant la taille de la gouttelette, l’efficacité de
séparation d’huile est augmentée considérablement.

A partir du coalesceur de lit granulaire, AURELLE a proposé que les mécanismes de


fonctionnement du coalesceur puissent être divisés en 3 étapes ;
• 1ère étape : La Transportation, qui se constitue de 3 phénomènes de transport
principaux : la sédimentation, l’interception directe et la diffusion. Le modèle
mathématique de chaque phénomène est basé sur le modèle de filtration. Ces modèles
fournissent les idées claires concernant les paramètres influents sur la performance du
coalesceur.
• 2ème étape : L’Adhésion-Coalescence. L’efficacité de cette étape dépend
principalement de la mouillabilité du matériel coalesceur.
• 3ème étape : La Relargage de la phase dispersée. Cette étape dépend de 4
paramètres, i.e. la mouillabilité du matériel coalesceur à la surface de relargage, la
vitesse d’écoulement, la tension interfaciale, et la proportion de la phase dispersée et
la phase continue dans l’émulsion à traitée.

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

Fig. 3-1 Schéma d’un coalesceur

[4]
Sommaire

Lignes de courant Collecteur


Gouttelette

V U
V
U
U= Vitesse ascensionalle
V= Vitesse d’ecoulment
a) Transport par interception b) Sédimentation c) Diffusion

Fig. 3-2 Schéma des 3modes de transport de l’étape 1

Les mécanismes à 3-étapes peuvent être utilisés également pour décrire la


performance d’autres types du coalesceur, par exemple le coalesceur de lit fibreux et celui de
lit dynamique. Toutefois, pour la prédiction de l’efficacité par classe de goutte, les modèles
empiriques sont recommandés car elles sont vérifiées par un ensemble de données plus large.

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%.

Pour le coalesceur de lit granulaire,

d H ρ dpV −0.08 μd 0.09 Δρ 0.09 {3.1}


η = (0.58( ) 0.2 ( ) 0.12 ( c ) ( ) ( ) ) ⋅ 100%
d dp dp γ μc ρc
o/w

Les modèles sont valides dans ces hypothèses ;


• La diemètre de collecteur (dp) = 0.36 - 0.94 mm.
• Tension interfacielle (γow) = 11 - 42 dyne/cm.
• Vitesse d’écoulement (V) = 0.09 - 0.54 cm/s.
• La différence de mass spécifique entre deux phases (huile/eau) (Δρ) = 83 - 314 kg/m3.
• Le lit est oleophile.
• La concentration initiale de hydrocarbure < 1,000 mg/l.

Pure le coalesceur fibreux,

ρ VD d d 0.35 H 0.694 {3.2}


η = (104.5( c ) −0.77 ( ) 0.18 ( F ) −0.18 (1 − ε ) ( ) ) ⋅ 100 %
d μc D D D

[5]
Sommaire

Les modèles sont valides dans ces hypothèses ;

• 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.

Pour le coalesceur dynamique (ou brosse tournante),

0.67d 0.58 (1 − ε) 0.35 H0.35 N0.53 {3.3}


η =( ) ⋅ 100 %
d
D0.03 d 0.58 V0.74
F

Les modèles sont valides dans ces hypothèses,

• 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.

Pout le coalesceur fibreux non-ordonnée (laine d’acier),

ρ cVD −0.23 d 0.03 d F −0.. 03 H 0.36 {3.4}


ηd = ( 3 . 35 ( ) ( ) ( ) ( ) ) ⋅ 100 %
μc D D D

Les modèles sont valides dans ces hypothèses,

• Re est entre 840 - 2470.


• La diamètre de fibre (dF) = 40-75 microns.
• Coefficient de vide (ε) est environ 0.95.
• La diamètre de coalesceur (D) = 5 cm.
• La hauteur d’intercepteur tournant (H) = 0.07 - 0.21 m.
• Vitesse (V) = 1 - 2.5 cm/s (36 to 90 m/h).
• Le modèle est valide pour la diamètre de gouttelette (d) de 1 microns ou plus.
• La concentration initiale de hydrocarbure est environ 1000 mg/l.
• Le lit est oleophile.

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Les modèles des pertes de charge sont aussi proposées ;

Pour le coalesceur granulaire, l’équation de Kozeny-Carman’s est proposée,

180 Hμ cV (1 − ε ) 2 {3.5}
P= m
ρ ⋅ g ⋅ dp 2 ⋅ ε 3
ε = 0.13 à 0.23.

Pour les coalesceurs fibreux, l’équation de Hazen-William est utilisée,

⎛ V ⎞ ⎛ 5L ⎞
1.85 1.167 {3.6}
P = 6.82⎜⎜ ⎟⎟ ⎜ ⎟ m
⎝ C HW ⎠ ⎝ D ⎠
CHW = 130. L = hauteur de l’intercepteur.

Finalement, plusieurs idées initiatives pour améliorer la performance du coalesceur,


c’est-à-dire l’utilisation du guide pour augmenter la concentration d’huile entrante du
coalesceur et l’utilisation du matériel de lit mélangée dans le coalesceur de lit granulaire pour
traiter simultanément la mélange d’émulsion directe/inverse, sont réalisées.

4. La flottation à air dissous

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

Bulle Gouttelette Concentration


=C
(en tenant compte Section de la
de la dilution) colonne = Ao

Fig. 4-1 Representation schématique de vitesses at vitesse relative et schéma de la


colonne flottation

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Sommaire

Vr= vitesse relative d’ecoulement


Ur= vitesse relative de decantation
Ur
Vr
Vr
Ur

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

Où μc = Viscosité de phase contenue (eau) (L2/T)


K = Constante de Boltzman (1.38*10-23)
T = Température absolue (Kelvin)
db = Taille de bulle (L)
d = Diamètre de gouttelette (L)
Vr = Vitesse relative enter des bulles et des gouttelettes (L/T)

Quant à l’équation de généralisation du modèle de SIEM, fondée sur le concept de


l’équilibre de population, sa forme générale est comme montrée ci-dessous. Le κ2, ref est la
constante, calculée par ηd,ref dans le modèle de SIEM. Mais, le point clé est le moyen
d’adapter la valeur de Φ et τ pour s’approprier à la condition du design et contribue à la
prédiction correcte de l’efficacité, c’est-à-dire, utiliser le Φ de SIEM avec le design τ, ou vice-
versa, dans la calcul. La logique est assez compliquée pour résumer en un paragraphe court, et
donc n’est pas citée ici. Pour de plus ample information, veuillez consulter le rapport principal
de la thèse (Chapitre 6, Partie 3). La logique est d’ailleurs disponible dans le logiciel.

[8]
Sommaire

ηd = (1 − e
( − κ 2 , ref Φ τ )
) ⋅ 100 % {4.8}

Les équations pour le design du pressurisateur ou du système de l’eau pressurisé


sont aussi proposées et vérifiées dans cette thèse ;
La concentration du gaz dissous,
Conc .( gas ) = y ⋅ P ⋅ MW ( gas ) ⋅ H ' mg/l {4.9}
Le débit du gas ou d’ air dégazé,
Φ = y ⋅ H '⋅R ⋅ Q ⋅ ( P − P atm ) ⋅ T ⋅ ( 0 . 082 × 10 −3
m 3
/( mol ⋅ K )) m3/s {4.10}
où H’ = constante de Henry (molair/(m3water-atm)) et y = fraction molaire du gaz
dans l’air. Pour l’air, y = 1.
La consommation énergétique de la compresseur,
Q pw ⋅ ( P − Patm ) Q pw ⋅ P( gauge ) Watt {4.11}
Power = =
η pump η pump

La consommation énergétique du pressurisateur au débit Qpw,


⎡ (
1 . 4 −1
) ⎤
1 R air ⋅ T ⎢ ⎡ P ⎤ 1 . 4 ⎥ ⋅ Conc ( gas ) ⋅ Q Watt {4.12}
Power = ⋅ ⎢ ⎥ − 1
η comp 0 . 4 ⎢ ⎣ Patm ⎦ ⎥ MW ( gas ) pw

⎣⎢ ⎥⎦

Où Rair = Constante universal du gaz. T = température absolue

5. L’Hydrocyclone

L’hydrocyclone est le procédé de séparation accéléré. Son concept de travail principal


est de remplacer l’accélération gravitationnelle qui dirige la vitesse de décantation au moyen
de l’accélération centrifuge supérieure. MA et AURELLE ont proposé une approche nouvelle
de prévoir l’efficacité hydrocyclone, appelée le modèle d’analyse trajectoire pour
l’hydrocyclone biphasique (liquide-liquide), fondée sur la loi de STOKE. En fait, ce modèle
peut prévoir, par l’équation théorique, l’efficacité de séparation par classe des gouttelettes
d’huile de toute taille dans les eaux résiduaires ; à la différence des autres modèles qui sont
basés sur les concepts du modèle empirique et de la similarité. Ainsi, il est très pratique de
comprendre l’effet des paramètres reliés à la performance d’hydrocyclone. Le modèle est
constitué des équations qui dirigent 3 éléments de vitesse des gouttelettes d’huile à l’intérieur
du cyclone, comme montré ci-dessous.
R
d dR L dZ
∫ =∫ {5.1}
R U 0W
zvv
Δρd 2 V 2
U= {5.2}
18μ R
Q D n 0.65 {5.3}
V=( )( )
πD 2 R
i
2 3
W R ⎛ R ⎞ ⎛ R ⎞
= −3.33 + 12 − 8.63⎜⎜ ⎟⎟ + 1.19⎜⎜ ⎟⎟ {5.4}
Wz Rz ⎝ Rz ⎠ ⎝ Rz ⎠

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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)

Pour le hydrocyclone de type THEW, quand Z = L:

RVZZ = 0.186( Dn / 2) {5.8}


R
Paroi
s

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

Fig. 5-1 Trajectories of oil droplets and typical efficiency curve


from trajectory analysis model
L’efficacité par classes peut être calculée par les relations:

Pour d ≥ diamètre de coupure,dc ηd = 100 % {5.9}


Pour d < dc Dn 2 {5.10}
Rd2 − ( 0 . 186 )
ηd = 2 ⋅ 100 %
D D
( n ) 2 − ( 0 . 186 n ) 2
2 2

Les modèles sont valides dans ces conditions,

• 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.

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• 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.

MA et AURELLE a également inventé une nouvelle type d’hydrocyclone pour la


séparation simultanée de l’huile, des matières en suspension (MES) et de l’eau, appelée
l’hydrocyclone triphasique. Le modèle pour cet hydrocyclone est établi nouvellement dans
cette thèse et également basé sur le concept d’analyse trajectoire.

Solid-liquid Liquid-liquid (de type Thew)


Di
Du
Dp D Do
Ds
L4
L5 L3
L3 L1

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

Fig. 5-2 Hydrocyclone triphasique

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)

Fig. 5-4 Profils des vitesses axiales dans le hydrocyclone triphasique

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Généralement, les équations pour l’hydrocyclone triphasique sont similaires à celles


pour l’hydrocyclone biphasique avec un peu de modifications, c’est-à-dire ;
• Remplacer l’éq. 5.3 par l’éq. 5.11.
⎛ ⎞
⎜ (Q/2) ⎟ D
V = 0.676⎜ ⎟( n ) 0.65 {5.11}
⎜ π D2 ⎟ R
⎜ ⎟
⎝4 i ⎠
• Remplacer, dans l’éq. 5.1, « Dn » par « Do » et « L » par « L5 ».

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.

Finalement, les équations de la fuite de pression ou la perte de charge pour


l’hydrocyclone biphasique ou triphasique sont établies dans cette thèse :

Pour l’hydrocyclone biphasique, la perte de charge dans l’entrée/surverse (Po) et


l’entrée/sousverse (Pu) peuvent être calculée par les équations suivantes,
0.1611
Q 2.3 ⎛ 2.6 ⎞⎟
ΔPo = 16 4 ⋅ ⎜ bar (V : m/s et D : meter) {5.12}
Dn ⎜⎝ (1 − R f ) ⎟⎠
Q 2 . 2 bar {5.13}
ΔPu = 4 . 6
Dn 4
Pour l’hydrocyclone triphasique, la perte de charge entre l’entrée et la sortie d’huile
(Poil), entre la sortie d’eau (Pw) et la sortie de MES (PSS) peuvent être calculée par les
équations suivantes,
Q 2.12 bar {5.14}
ΔPwater = 49.8
D4
Q 2.34
ΔPss = 21 bar {5.15}
D4
Q 2.03 bar {5.16}
ΔP = 55
oil
D4

6. Les procédés membranaires


Le principe de travail

Le procédé membranaire est le procédé de séparation qui est basé, principalement


mais non entièrement, sur le concept de filtration. Physiquement, la membrane est le matériel
perméable ou semi-perméable qui restreindre la motion de certaines espèces. Théoriquement,
on peut toujours séparer certains composants d’émulsion à condition que la membrane choisie
convient à la différence dimensionnelle.

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Fig. 6-1 Classification des techniques membranaires de filtration selon la taille des pores

(Par Osmonics)

Les applications des procédés membranaires, c’est-à-dire, la microfiltration (MF),


l’ultrafiltration (UF), le nanofiltration (NF) et l’osmose inverse (OI), au traitement d’eaux
résiduaires huileuses dans le laboratoire GPI ont été réexaminées. Plusieurs techniques utiles
émanant de ces recherches sont réalisés et les techniques de calcul sont établies dans cette
thèse :

• L’augmentation du flux pour l’UF dans le traitement d’émulsion de l’huile de


coupe par la déstabilisation partielle. L’addition du sel, de moindre quantité
que celle pour la déstabilisation totale, dans l’alimentation contribue à
l’augmentation du flux de perméat, et donc économiser la consommation
d’énergie ainsi que la taille de la membrane. L’inconvénient de ce technique,
inclus dans cette thèse, est que l’huile déstabilisée peut colmater la membrane
si elle n’est pas correctement partitionnée ou séparée du courant d’alimentation
recirculé.

• La régénération de la membrane UF après le traitement de l’huile de coupe


par la microémulsion. Il peut efficacement laver de l’huile accumulée ou les
foulants restant sur la membrane. Il peut être réutilisé pour plusieurs fois
jusqu’à ce qu’il est saturé par l’huile.

• Le technique pour généraliser les données de la performance UF dans une


seule condition pour couvrir des autres conditions, basé sur la combinaison du
modèle de la couche de gel et modèle des résistances en série. Ce technique
est proposé et vérifié dans cette thèse. Il est utile quand les données limitées sur
des eaux résiduaires examinées sont disponibles. Il nous permet d’estimer
l’évolution du débit ainsi que celle du volume de perméat en fonction du
temps, lequel est utile pour le design du procédé.

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• Le technique pour prévoir le débit du mélange de 2 émulsions différentes. Ce


technique est également proposé et vérifié dan cette thèse. Il est utile quand
l’émulsion mélangée peut être prévue et sa proportion tend à varier.

Retentat

Po Membrane
Pp
Permeat
Reservoir
d’alimentation
Pi
Alimentation

pompe Echangeur de chaleur

Fig. 6-2 Schéma de l’unité ultrafiltration tangentielle en “batch”

Quant au modèle mathématique des procédés membranaires, on met l’accent sur le


modèle de l’UF dans l’opération batch car il joue un rôle majeur dans le traitement d’eaux
résiduaires huileuses. On a adopté deux modèles largement utilisés : le modèle de la couche
de gel et le modèle des résistances en série. Les équations des deux modèles sont comme
montrées ci-dessous,
Le modèle de la couche de gel
Cg 2
J = kV β ln( ) l/(m -h) {6.1}
C
Le modèle de résistance en série,
Pt
J= α
l/(m2-h) {6.2}
R ' m +φ ⋅ V ⋅ Pt
Les valeurs de k, α ,β, φ, R’m, et Cg varient selon les caractéristiques des eaux
résiduaires et les types de la membrane.

7. Le procédé thermique

L’intérêt principal du procédé de ce type est à la distillation hétéroazéotropique (DH).


L’application de la DH au traitement des slops de raffinerie ainsi que des retentats issus de
l’UF de l’huile de coupe est réalisée par LUCENA et AURELLE. Le procédé est accompli par
l’addition du produit chimique qui favorise la formation azéotropique (appelée extractant),
généralement les hydrocarbures, dans l’eau résiduaire. Ceci réduira la température d’ébullition
du système, et donc économisera l’énergie. Ces applications apportent la possibilité de
revaloriser ces matériels résiduaires potentiels. Son application inverse, à savoir le stripping
(pour récupérer la substance volatile de l’eau au moyen de l’addition du vapeur), est
également réalisée.

L’hétéroazéotrope est l’un des phénomènes liés au équilibre vapeur-liquide-liquide


(VLLE). Le diagramme isobare du mélange immiscible hétéroazéotropique est démontré dans
la figure 7-1. Il est constaté que la courbe de bulle de ce diagramme est représentée par une
ligne horizontale à la température constante, appelée « la température azéotropique ». A
cette température, les deux liquides dans le mélange évaporent, quelle que soit la composition
du mélange. La composition de la vapeur est toujours yH jusqu’à ce que il reste seulement une
espèce de liquide dans la phase liquide.

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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.

Table 7-1 Heteroazeotropic temperature and composition des certaines hydrocarbures

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,

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(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

Au cas où les eaux résiduaires huileuses contiennent l’émulsion stabilisée, c’est-à-dire


la macro/microémulsion, les tailles des gouttelettes sont si petites et stables qu’elles ne
peuvent pas être séparées par les procédés basés sur la loi de STOKES, par exemple le
décanteur, le coalesceur ou l’hydrocyclone. A moins que les procédés membranaires ou
thermiques soient appliqués, les gouttelettes doivent suivre un procédé chimique qui détruit
sa stabilité et favorise la coalescence de ces gouttelettes. Ainsi, le procédé chimique dans ce
cas s’appuie sur la déstabilisation chimique et la coagulation/floculation chimique. Selon ces
recherches, on peut conclut que la stabilité de l’émulsion est fondée sur les facteurs suivants,

• La barrière électrique, laquelle peut être décrite par la théorie DLVO et la


théorie de la couche double, comme montrée dans les figures 8-1 et 8-2.

• La barrière stérique, causée par la localisation des molécules tensioactives à la


surface des gouttelettes d’huile. Elle s’agira comme un film qui empêche la
coalescence des gouttelettes.

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,

• Les produits chimiques monovalents : Le procédé principal de


déstabilisation est fondé sur la réduction de la couche diffuse au moyen de
l’augmentation des ions chargés opposés. L’inconvénient principal des
produits chimiques de ce groupe est la formation du saline ou des polluants
acides au terme de la déstabilisation. Les exemples de ces produits chimiques
sont NaCl, H2SO4.
• Les produits chimiques bivalents : Le mécanisme principal de
déstabilisation est basé sur la précipitation des tensioactifs ; l’équilibre des
tensioactifs est donc modifié. Les tensioactifs focalisants à la surface des
gouttelettes d’huile seront retransmis dans la phase d’eau. Ainsi, la
gouttelette est déstabilisée. La performance est dirigée par le produit de
solubilité des tensioactifs. Les exemples des produits chimiques sont CaCl2,
MgSO4 et MgCl2. Même si la dose requise pour ce cas est inférieure à celle
des produits chimiques monovalents, elle cause encore les polluants
résiduaires de saline. Des sels organiques, comme le formiate de calcium
(Ca(COOH)2) seraient plus intéressants car les polluants résiduaires sont
(COOH)2 qui est organique et biodégradable.

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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

Fig. 8-1 Diagramme de potentiel électrique de gouttelette

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.

Dans le cas des émulsions stabilisées par des tensioactifs nonioniques, le


mécanisme principal de déstabilisation doit se fonder sur la précipitation des tensioactifs pour
former des composés insolubles. ZHU a proposé la méthode classique de la déstabilisation
chimique de l’émulsion stabilisée par les tensioactifs nonioniques de l’acide gras, basée sur
l’addition des tensioactifs anioniques (comme l’akylsulfate des alcools gras) et les
électrolytes trivalents cationiques (comme le sulfate d’aluminium, le chlorure ferrique).

[17]
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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 G = Gradient de vitisse (t-1, normalement en sec –1)


μ = Viscosité d’eau,
P = Consommation énergétique d’agitateur(ML2s-3,e.g. watt)
V = Volume de réacteur (L3)

Pour les turbines,


P = N p n3 D5 ρ {8.2}

Pour les pales tournantes ,


nAv 3 C d ρ
G= {8.3}
2Vμ

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

Bassin de coagulation Bassin de floculation

Fig. 8-3 L’example de design de coagulation-floculation

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9. Les procédés de finition

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.

Comme le procédé biologique est lui-même la science majeure, le calcul détaillé


n’est pas inclus dans les buts et objectifs du travail de cette thèse. Seulement les données
utiles sur le procédé biologique, concernant le traitement des eaux résiduaires huileuses, sont
réexaminées et incluses dans le rapport principal de cette thèse (Partie 3, Chapitre 11).

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,

Le temps d’opération totale avant le remplacement de lit (tT):

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 )

Où tT = Temps d’opération totale avant le remplacement de lit


H = Hauteur de lit
A = Section de la colonne
ρb = Mass volumique de charbon actif
q = Capacité d’adsorption
Qa = Capacité d’adsorption disponible dans la zone de
l’adsorption
Q = Débit
Co,Ce = Concentration initiale et concentration de la solution en
soluté en équilibre avec l’adsorbant
Quand les données mentionnées ci-dessus ne sont pas disponibles ;
E ⋅ HA ⋅ ρ b ⋅ q {9.2}
tT =
Q (Co − Ce )

E est la saturation efficace de lit. La valeur recommandée est environs 50-95%.

[19]
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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

Fig. 9-1 Evolution du front d’adsorption


Temps de séjour (τ):
H {9.3}
τ=
(Q / A)

Perte de charge (P):

La parte de charge peut être calculée par l’équation Kozeny-Carman.

180 Hμ cV (1 − ε ) 2
P= m {9.4}
ρ ⋅ g ⋅ dp 2 ⋅ ε 3

10. La méthodologie générale pour la sélection des procédés

En fin de achever le premier objectif, la méthodologie sur la sélection du procédé


de traitement des eaux résiduaires huileuses est proposé, comme montré dans la table 10-1.
Les filières de procédé recommandés pour le traitement d’émulsion de l’huile de coupe et
l’émulsion secondaire, fondés sur les recherches GPI, sont également proposés, comme
montrés dans les figures 10-1 et 10-2.

[20]
Table 10-1 La méthodologie générale pour la sélection des procédés

[21]
Sommaire
Sommaire

ENTREE Retentat Retentat


SORTIE
Po Membrane Po Membrane
Pp Pp (Si possible)

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

Extractant Recyclage boue


Bassin d’aerationClarificateur
Chauffage Distillat
Distillation heteroazeotropic Traitement biologique

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

API Coalesceur/ Traitement biologique


hydrocyclone/
coalesceur

Fig. 10-2 Schéma d’une filière de traitement des émulsions non-stabilisées

[22]
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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 documentation électronique : fournit les connaissances de


fond ainsi que une base de données utile sur la pollution d’huile et les
procédés de traitement. En fait, le textbook dans la Partie 3 est transformé en
directoire « e-book » du logiciel.

• Le mode de recommandation du procédé : fournit les recommandations


pour restreindre la gamme des procédés faisables pour tout influents débits.
Le critère de sélection est comme proposé dans les méthodologies dans la
Partie 3, Chapitre 12.

• 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.

• Le mode d’analyse (simulation) : permet l’utilisateurs d’intégrer tout


procédé de séparation qui est inclus dans la base de données du logiciel, en
but d’établir leur propre filières de procédé de traitement. Et le logiciel va
simuler la filière de procédé pour prévoir l’efficacité de chaque unité.

Le logiciel est développé pour être « upgradable ». Son architecture compose de la


base de données sous forme de fichier texte ordinaire et les « sub-programmes ». Pour
« upgrader » le logiciel, il peut se faire facilement en ajoutant les données, comme le nom de
nouveau procédé et son paramètre de lien nécessaire pour le calcul, à la base de données. Le
logiciel liera automatiquement le nouveau procédé à l’interface graphique d’utilisateur. Quant
au calcul du « sub-programme » du nouveau procédé, il peut être développé séparément en
utilisant la langue de programmation Visual Basic. Le moyen le plus facile est de copier le
code de source d’un procédé existant et modifier l’équation pour convenir au nouveau
procédé. Après la compilation dans un fichier exécutable, il peut être copié pour remplacer
l’ancien fichier de logiciel GPI sans réinstaller le logiciel. Ainsi le logiciel pourrait se
développé davantage jusqu’à ce qu’il peut couvrir plus de recherches et procédés dans
l’avenir. Les interfaces du logiciel pour chaque mode sont comme montrées dans les figures
suivantes.

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]
Sommaire

Main menu
Tool bar

Project window

Main program

Fig 1 L’interface graphique d’utilisateur du programme “GPI”

Fig. 2 L’interface graphique d’utilisateur du mode de documentation électronique

[24]
Sommaire

Fig. 3 L’interface graphique d’utilisateur du mode de recommendation

Fig. 4 Resultat du mode de recommendation

[25]
Sommaire

étape 1 “Wastewater data input” étape 2 “Process selection”

étape 3 “Process data input” étape 4 “Result”


Fig. 5 L’interface graphique d’utilisateur du mode de design
Calculation button
Basic drawing tool bar

Category selection

Input and result screen


(displayed when double clicking at the icon)

Process selection Graphic editing area

Fig. 6 L’interface graphique d’utilisateur du mode d’analyse

[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

COMPUTER PROGRAM DEVELOPMENT FOR OILY WASTEWATER


TREATMENT PROCESS SELECTION, DESIGN AND SIMULATION
562 pages
Thèse de Doctorat : Science des procédés
Spécialité :Génie des Procédés et de l’Environnement
I.N.S.A. Toulouse, 2005, n°

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

¾ S. Rachu, Y. Aurelle, S. Saipanich .

Simulation program on hydrocarbon polluted wastewater treatment processes

16th International Congress of Chemical and Process Engineering (CHISA 2004),


Prague, Czech Republic, 22-26 August 2004
A mes Parents

et à toute ma famille
Remerciements

Je remercie sincèrement Monsieur le professeur Yves AURELLE pour


m'avoir accueilli dans son équipe, pour m'avoir fait partager ses
connaissances et ses idées innovantes et pour son assistance tout au long
de ce travail.

I would like to thank Dr. Surapol SAIPANICH for his overwhelming


support and encouragement. If not because of him, this work would never happen.

J'adresse également tous mes remerciements à :

¾ Monsieur Dimitre HADJIEV , professeur à l'USB de Lorient, , et


Monsieur Jean Luc ROLS, professeur à l'UPS de Toulouse pour avoir accepté
de juger ce travail en faisant partie du jury,

¾ Monsieur BEN AIM, professeur émérite à l'INSA et Monsieur Alain


LINE, professeur à l'INSA, pour avoir accepté de participer au jury de
cette thèse,

¾ Monsieur Henry ROQUES professeur émérite à l'INSA pour sa présence


au jury de cette thèse,

I would like to thank my colleagues at Progress Technology


Consultants Co., Ltd (Thailand) for their support and their kindness. Many
thanks to Krisana KHWANPAE for his great support on programming. My
gratitude to Bowornsak WANICHKUL, Chaiyaporn PUPRASERT and Pisut
PAINMANAKUL for their priceless advice. I owe you guys a boon.

Thank to the French Embassy in Thailand for their financial support


during the first two years of my studies. Thanks to the embassy personnels,
particularly, Khun Hataiporn, Khun Wanpen for their assistance, Khun
Chanida for her superb translation.

Mes remerciements s'adressent également à toutes les personnes qui


m'ont beaucoup aidé tant à Monsieur Louis LOPEZ, Monsieur Gilles HEBRARD,
Madame Eugénie BADORC, Madame Danièle CORRADI et Madame AURELLE. Je
remercie également mes amis du labo, particulièrement, Oliver LORAIN et
Eduardo LUCENA.

Enfin, je remercie mes amis Thaïlandais de Toulouse (P’Lek, P’Tou,


P’Aote, A, Pond, Por, Pew, Golf, Mon, Aey-Alexandre, 1, Fon, Chin, Chat,
Pat, Vee, Choke, Sith, Ju, Bomb, etc.) qui m'ont assuré par leur humour,
une ambiance sympathique et permis d’effectuer de grandes fêtes pendant mon
séjour en France.
Table des matières
Contents

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

- iv -
Contents

Content
Page

Part III Summary of researches: Oily wastewater treatment


Chapter 1 Oily or hydrocarbon-polluted wastewater
1.1 Introduction 119
1.2 Hydrocarbons and oils 119
1.2.1 Hydrocarbons 119
1.2.2 Fats and oils 124
1.2.3 Petroleum and petroleum products 124
1.2.4 Oils in term of oily wastewater 126
1.3 Other compositions of oily wastewater 126
1.3.1 Surfactants 126
1.3.2 Soaps 127
1.3.3 Co-surfactants 128
1.3.4 Suspended solids 1281
1.3.5 Other components 128
1.4 Categories of oily wastewater 128
1.4.1 Classification by the nature of the continuous phase 128
1.4.2 Classification by the stability of oily wastewater 128
1.4.3 Classification by the degree of dispersion 129
1.5 Characteristics of certain oily wastewaters 132
1.6 Standards, Laws, and Regulations 133
Chapter 2 Overview for oily wastewater treatment process design
2.1 Decantation velocity and STOKE’s law 138
2.2 Application of surface chemistry for oily wastewater treatment 139
2.2.1 Liquid-gas and liquid-liquid interfaces 139
2.2.2 Liquid-solid and liquid-liquid-solid interfaces 142
2.2.3 Capillary pressure and LAPLACE’s law 146
2.3 Important parameters in oily wastewater treatment and 147
their method of analysis
2.3.1 Oil concentration 147
2.3.2 Size distribution , spectrum or granulometry 149
2.3.3 Other parameters 155
2.4 Overview of oily wastewater treatment processes 155
2.4.1 Decanter 156
2.4.2 Coalescer 156
2.4.3 Hydrocyclone 156
2.4.4 Dissolved air flotation (DAF) 157
2.4.5 Skimmer 157
2.4.6 Membrane processes 157
2.4.7 Thermal processes 157
2.4.8 Chemical process 158
2.4.9 Finishing processes 158

-v-
Contents

Content (Con’t)
Page

2.5 Determination of degree of treatment 158


2.5.1 Overall degree of treatment 158
2.5.2 Degree of treatment of each process 158
Chapter 3 Oil skimmer
3.1 General 162
3.2 Oil drum skimmer 164
3.2.1 Working principles 164
3.2.2 Design calculation and design consideration 169
3.3 Oil disc skimmer 171
3.3.1 Working principles 171
3.3.2 Design calculation and design consideration 173
3.4 Productivity comparison between drum and disc skimmer 173
3.5 Advantage and disadvantage of drum and disc skimmer 174
Chapter 4 Decanting
4.1 General 176
4.2 Simple Decanter or API tank 177
4.2.1 Working principles 177
4.2.2 Design calculation 179
4.2.3 Design considerations 182
4.2.4 Construction of simple decanters 183
4.3 Compact decanter 186
4.3.1 Working principles 186
4.3.2 Design calculation 190
4.3.3 Design considerations 192
4.3.4 Variations, advantage and disadvantage of compact 193
decanters
Chapter 5 Coalescer
5.1 General 195
5.2 Granular bed coalescer 195
5.2.1 Working principles 195
5.2.2 Design calculation 209
5.2.3 Design consideration 211
5.2.4 Variations, advantage and disadvantage of granular 212
bed coalescer
5.3 Guide coalescer 213
5.3.1 Working principles 213
5.3.2 Design calculation 215
5.3.3 Design consideration 215
5.4 Fibrous Bed coalescer 216
5.4.1 Working principles 216
5.4.2 Design calculation 226
5.4.3 Design consideration 227
5.4.4 Variations, advantage and disadvantage of fibrous bed 229
coalescer

- vi -
Contents

Content (Con’t)
Page

Chapter 6 Dissolved air flotation


6.1 General 232
6.2 Working principles 233
6.2.1 Filter based model 233
6.2.2 Population balance model 238
6.2.3 Generalized model of DAF from combination of 240
filtration based model and population balance model
6.2.4 Influent parameters 241
6.3 Design calculation 244
6.4 Design consideration and construction of DAF reactor 254
6.5 Pressurized water system or saturator 262
6.5.1 Working principle and design calculation 262
6.5.2 Type of saturator and injection valve 267
6.6 Variations, advantage and disadvantage of DAF 270
Chapter 7 Hydrocyclone
7.1 General 272
7.2 Two-phase hydrocyclone 273
7.2.1 Working principles 273
7.2.2 Design calculation 289
7.2.3 Design considerations 292
7.2.4 Variations, advantage and disadvantage of 295
hydrocy clone
7.3 Three-phase hydrocyclone 295
7.3.1 Working principles 295
7.3.2 Design calculation and design consideration 299
7.3.3 Advantage and disadvantage of three-phase 299
hydrocyclone
Chapter 8 Membrane process
8.1 General 300
8.1.1 Classification of membrane processes 300
8.1.2 Mode of operation of membrane processes 302
8.1.3 Membrane structure 302
8.1.4 Membrane material 303
8.1.5 Membrane module type 306
8.2 Ultrafiltration (UF) 311
8.2.1 Basic knowledge and working principles 311
8.2.2 UF process design for oily wastewater treatment 323
8.2.3 Design consideration and significant findings from 338
GPI’s researches
8.3 Microfiltration (MF) 349
8.3.1 Basic knowledge and working principles 349
8.3.2 Significant findings on MF for oily wastewater 350
treatment from GPI researches

- vii -
Contents

Content (Con’t)
Page

8.4 Reverse osmosis (RO) 352


8.4.1 Basic knowledge and working principles 352
8.4.2 Significant findings on RO for oily wastewater 353
treatment from GPI’s researches
8.5 Nanofiltration (NF) 356
8.5.1 Basic knowledge and working principles 356
8.5.2 Significant findings on NF for oily wastewater 356
treatment from GPI’s researches
8.6 Comparison of membrane processes on emulsion treatment 359
Chapter 9 Thermal processes
9.1General 362
9.2Basic knowledge on distillation 362
9.2.1 Basic knowledge on vapor/liquid equilibrium of 362
mixtures
9.2.2 Equilibrium of various mixtures 365
9.3 Heteroazeotropic distillation of oily wastewater 367
9.3.1 Working principles 367
9.3.2 Raoult’s law and Dalton’s law 368
9.3.3 Calculation of azeotropic temperature and composition, 369
dew curve and bubble curve.
9.3.4 Application of heteroazeotropic distillation on 371
treatment of inverse emulsion or concentrated oily
wastewater
9.3.5 Application of heteroazeotropic distillation on 374
treatment of the wastes polluted by trace hydrocarbons:
Steam stripping
9.3.6 Design calculation and design considerations 374
9.4 Classical or conventional distillation of oily wastewater 376
9.4.1 Working principles 376
9.4.2 Significant findings on classical distillation for oily 376
wastewater treatment from GPI’s researches
Chapter 10 Chemical treatment processes
10.1 General 380
10.2 Basic knowledge 381
10.2.1 Stability of the emulsion 381
10.2.2 Surface-active agents 381
10.2.3 Important properties to obtain stable emulsion 383
10.2.4 Destabilization of emulsion 385
10.3 Process design 391
10.3.1 Rapid mixing 392
10.3.2 Flocculator 393
10.4 Design consideration 395

- viii -
Contents

Chapter 11 Finishing processes


11.1 General 397
11.2 Biological treatment 397
11.2.1 Basic knowledge 397
11.2.2 Design consideration and significant finding on 404
biological treatment for oily wastewater from GPI’s
researches
11.3 Adsorption 405
11.3.1 Activated carbon (AC) 406
11.3.2 Basic knowledge 407
11.3.3 Design calculation 412
Chapter 12 Guideline for treatment process selection and examples of treatment
processes for certain oily wastewaters
12.1 Guideline for treatment process selection 414
12.1.1 Oil film 414
12.1.2 Primary emulsion 416
12.1.3 Secondary emulsion 417
12.1.4 Macroemulsion and microemulsion 418
12.1.5 Concentrated oily wastewater or refinery slops 418
12.2 Examples of treatment processes for certain oily wastewaters 419
12.2.1 Treatment of cutting oil emulsion 419
12.2.2 Treatment of non-stabilized secondary emulsion 420

- ix -
Contents

Contents
Page

Part IV Computer program development


Chapter 1 Program overview
1.1 Introduction 423
1.2 Conceptual design of the program 423
1.2.1 E-book mode 424
1.2.2 Recommendation mode 426
1.2.3 Design mode 427
1.2.4 Analysis mode 428
1.3 Development tools 432
1.3.1 Main development software package 432
1.3.2 Special graphic user interface (GUI) component 433
1.3.3 The third party software 433
1.4 Program architecture 434
1.4.1 Forms 434
1.4.2 Modules 437
1.4.3 Modules 437
1.4.4 Class modules 437
1.4.5 Add-in project 437
1.5 Program development 438
Chapter 2 Program reference and user manual
2.1 Overview of the program 439
2.1.1 Main program 439
2.1.2 Project window 441
2.1.3 E-books worksheet 441
2.1.4 Recommend worksheet 442
2.1.5 Design worksheet 444
2.1.6 Analysis mode 445
2.1.7 Warning dialog box 447
2.2 Program capability 447
2.3 Program limitation 447
2.4 System requirement 449
2.5 User instruction 449
2.5.1 Program Installation 449
2.5.2 Starting the program 450
2.5.3 Using E-book mode 450
2.5.4 Using Recommend mode 450
2.5.5 Using Design mode 452
2.5.6 Using Analysis mode 454
2.5.7 Printing and file operation 457
2.6 Upgrading procedure and recommendation for further 458
development
2.6.1 Upgrading procedure 458
2.6.2 Recommendation for further development 460

-x-
Contents

Contents
Page

Chapter 3 Process references


1) Drum skimmer 463
2) Disk skimmer 465
3) Simple decanter 467
4) Compact decanter 470
5) Customized decanter 473
6) Granular bed coalescer 476
7) Brush type bed coalescer 480
8) Dynamic fibrous bed coalescer 484
9) Metal wool bed coalescer 488
10) Dissolved air flotation 492
11) Two-phase hydrocyclone 498
12) Three-phase hydrocyclone 502
13) Ultrafiltration 506
14) Reverse osmosis 510
15) Heteroazeotropic distillation 513
16) Stripping 515
17) Chemical destabilization, coagulation-flocculation 517
18) Biological treatment 520
19) GAC filter 522
20) Customized concentrator 526
21) Customized oil separator 528
22) Customized inline concentrator 530
23) Inlet 532
24) Outlet 533
25) Flow merge 534
26) Flow split 536

- xi -
Contents

Contents
Page

General conclusion 537

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

The number of bubbles attached to the agglomerate


J Permeate flux of membrane L/T
K Boltzman constant (1.38*10-23)
k Constant in film model
L Length of inserted plates or interceptor surface or L
Length of lower conical part for Thew type hydrocyclone or L
Length of flow channel in membrane module L
L3 Total length of RIETEMA part in 3-phases hydrocyclone, L
includes conical and straight section.
L4 Length of lower straight section of RIETEMA part in 3-phases L
hydrocyclone, which locate oil and solid outlet ports.
MW Molecular weight g/mol
N Numbers of inserted plates or
Rotational speed or T-1, such as rev/s
(not rad/s)
Rotational speed of fibrous bed or T-1, such as rev/s
(not rad/s)
Total number of bubbles
n0, n1 The number of oil droplet attached by 0, 1, … air bubles
P Oil productivity of the skimmer or L3/T
Absolute pressure of the pressurized water system or MT-2 L-1
Pressure drop or LT-2M-1
Pressure LT-2M-1
p Partial pressure LT-2M-1
Pcap Capillary pressure LT-2M-1
Psat Vapor pressure (some references use “Πθb”) LT-2M-1
Pt Transmembrane pressure LT-2M-1
Q Wastewater flowrate or L3/T
Inlet flow or L3/T
Recirculation flowrate of membrane L3T-1
Qpw Pressurized water flowrate L3/T
Qt total water flowrate (= Qpw + Qwastewater) L3/T
R Universal gas constant (8.314 Pa. m3 / (mol.K))
r Radius of membrane pore L
R Distance in radial axis of hydrocyclone L
R’m Modified membrane resistance (= Rm+Rf) MT-1 L-2
Rd Distant from center line of hydrocyclone in radial axis to L
particle “d” considered
rd Radius of oil droplet L
Re Reynolds number (ρVD/μ)
Rf Split ratio (= Qoverflow/Q)
Rf Fouling resistance MT-1 L-2
Rg Gel (or polarization) resistance MT-1 L-2
Rm Membrane resistance MT-1 L-2
Rz Distant from center line of hydrocyclone in radial axis to the L
wall of hydrocyclone at the axial distance “Z”
S Bottom projection area of the tank L2
Sp Inserted plate area L2
t Time T
T Absolute temperature
U Radial velocity of particle or oil drop in hydrocyclone L/T
Ub Rising velocity of bubble L/T
Ud Rising velocity of the droplet diameter “d” L/T
Ud Rising velocity of oil droplet L/T
V Tangential velocity or tip speed of the skimmer L/T

xiv
Nomenclature

V Empty bed velocity or L/T


Empty bed velocity of DAF (based on sum of pressurized water L/T
and wastewater flow) or
Tangential velocity of particle or oil drop in hydrocyclone or L/T
Recirculation velocity in cross-flow membrane process L/T
Vol Volume L3
Vr Relative velocity between bubble and oil drop L/T
W Axial velocity of particle or oil drop in hydrocyclone or L/T
Width of flow channel in membrane module L
x Molar fraction in liquid (water) Mol/mol
y Molar fraction in vapor Mol/mol
Z Distance in axial axis of hydrocyclone L
ΔP Pressure drop, (in m of water, for Kozeny-Carman’s equation)
Or pressure drop in bar, for hydrocyclones
ΔPo Pressure drop across inlet and overflow port Bar
ΔPoil Pressure drop across inlet and oil outlet port Bar
ΔPSS Pressure drop across inlet and suspended solids outlet port Bar
ΔPu Pressure drop across inlet and underflow port Bar
ΔPwater Pressure drop across inlet and water outlet port Bar

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 2 Objectives I-4

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

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

“Guided & Mixed bed coalescer”


SANCHEZ MARTINEZ [5], 1982
“Granular bed coalescer”
Coalescer
AURELLE [3], 1980
“Granular bed coalescer for
stabilized emulsion”
DARME [6], 1983
“Spiraloil” decanter
Decanter
CHERID [4], 1986 “Dynamic fibrous bed coalescer”
TAPANEEYANGKUL [8], 1989

“Drum skimmer” & “Pulsed granular bed coalescer” &


Skimmer “disk skimmer” “Phase inversion coalescer”
THANGTONGTAWI [5], 1988 DAMAK [9], 1992

“Flotation for oil-water “Application of flotation on oily “Treatment of non-


Flotation separation” wastewater treatment” stabilized emulsion”
SIEM [12], 1983 AOUJEHANE [13], 1986 SRIJAROONRAT [10]
, 1998
“Mathematics model of DAF”
Hydrocarbon- DUPRE [14], 1995

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

Ultrafiltration “Ultrafiltration for cutting oil “Ultrafiltration for thermal


& membrane emulsion treatment” emulsion treatment”
processes BELKACEM [18], 1995 TOULGOAT [19], 1996

“Crystallization for oil-water “Membrane processes for cutting


Thermal
separation” oil emulsion treatment”
treatment
LORRAIN [23], 2002 MATAMOROS [20], 1997

“Heteroazeotropic distillation”
LUCENA [24], 2004

Chemical “Destabilisation of emulsion” “Low-pollution emulsion”


treatment ZHU [21], 1990 YANG [22], 1993

I-3
Part I Introduction and bibliography
Chapter 2 Objectives

Chapter 2 Objectives
The objectives of this study are as described below;

1. To review the treatment technologies for oily wastewater or wastewater polluted


by hydrocarbon from doctorate researches, directed by Professor Yves
AURELLE in LIPE-GPI, from the beginning to the present.

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.

2. To generalize or propose the model of each related process.

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.

3. To compose the textbook on hydrocarbon-polluted wastewater or oily wastewater


treatment process, based on the result from the 1st and 2nd objective.

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;

• Background knowledge on oily and hydrocarbon-polluted wastewater


• Treatment technology overview
• Chapters devoted to details of each treatment process
• Guidance for selection and combination of processes

If we could compose it well as we intended. This textbook would provide readers


sufficient practical data to understand properties oily wastewater, working mechanisms of

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

3.1 Categories of hydrocarbon-polluted wastewater and treatment


processes
As hydrocarbon or oil requires a great amount of oxygen or oxidizing agent to oxidize,
moreover, the hydrocarbon is relatively difficult to biodegrade, thus, it becomes clear that the
use of the biological treatment with high-concentration oily wastewater is not the economical
alternative. Besides there are possibilities to reuse or recover the hydrocarbons in the
wastewater. Then almost all of treatment processes that have been studied in our laboratory
are based on separation, both physical and physico-chemical, techniques in order to separate
oil from water.

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.,

• Hydrocarbon in form of film or layer on the surface of wastewater, or hydrocarbon


in form of big oil drops in the wastewater
• Emulsion without surfactants, by the word “emulsion”, it can be easily described
as the water with very fine dispersed oil drops
• Emulsion with surfactants
• Dissolved hydrocarbon

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

Details of wastewater characteristics and treatment processes are thoroughly described


in Part 3. So, this part emphasizes on reviewing of related researches, categorized by process,
about their scope of work and significant finding, as described in next sections.

3.2 STOKES law


It is important to mention about STOKES law (eq. 3.1), because almost all of
separation processes considered here are based upon modification of parameters in this
equation. The STOKES equation is the relation between rising (or settling) velocity of
spherical object (in our case, droplet of dispersed phase) with very small Reynolds number
(10-4 to 1) and properties of dispersed phase and continuous phase.
Δρ ⋅ g ⋅ d E2
V= {3.1}
18μ c

Where V = rising or settling velocity (based on density of the 2 phases)


Δρ = Difference between density of dispersed phase and continuous
phase
dE = Diameter of dispersed phase
μC = Dynamic viscosity of continuous phase

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

Fig. 3.1 Schematic of decanter

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.

Theoretical efficiency of plate-inserted decanter, known as lamella decanter, parallel


plate interceptor (PPI), etc., can be calculated using the same equation as for API tank with a
little modification on decanting area. However, the selection of the shape and installation of
these plates are the state-of-art processes. The spacing between the plates should be as small
as possible to minimize the size of decanter. However, the flow of water and the collected oil
between the plates shall be taken into account to minimize shear force, thus minimize the
effect of surface distortion or “snap-off”.

Thesis of CHERID [4] is contributed to study on the compact lamella decanter,


known as “SPIRALOIL”, that shows far greater efficiency compared to the simple decanter of
the same size.

The research consisted of,

• 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

The experiment of phenomena in the lamella decanter was conducted in transparent


model. Interaction between oil and surface of the lamella plate, as well as the influence of
wettability of plate and inclination of plate, could be observed clearly in this model. The
experiment to test the operation and efficiency of lamella decanter was conducted with 2
models of “SPIRALOIL”, the first one with normal spiral hydrophobic plate insertion, the
other with the combination of corrugated hydrophilic plate and smooth hydrophobic plate
insertion, also in spiral form. Kerosene/ water mixture was used for the research, with the
addition of surfactant in some tests to vary the interfacial tension.

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.

3.4.1 Thesis of AURELLE [3]

This research contributed to the study on fundamental mechanism of granular bed


coalescer, which was used as a basis and guideline for following researches.

The research consisted of,

• Influence of essential parameters, i.e., geometry of bed, and operation parameters,


such as feed rate to efficiency of coalescer
• Fundamental mechanisms or phenomena, take place with in coalescer during its
operation
• Model development for granular bed coalescer

Experimental procedure

The experiment was carefully planned to cover every aspect of coalescer operation,
i.e.,

• Wastewater characteristic : Hydrocarbons, used in the research, included gasoline,


kerosene at various concentrations, in form of both direct and inverse emulsion.
• Collector material : Alternatives of collector or bed material included;
• Type of material : glass beads, resin, sand, chamotte (porous dried clay)
• Wettability : Oleophilic or Hydrophilic
• Granulometry or size and size distribution of the collectors
• Geometry of colaescer
• Diameter or size of the coalescer tank
• Bed height
• Empty bed flow velocity

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.

3.4.2 Thesis of SANCHEZ MARTINEZ [6]

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

The research consisted of,

• Influence of essential parameters, i.e., geometry of guide, and operation


parameters, such as feed rate and ratio of oil in wastewater to efficiency of
classical coalescer and guided coalescer
• Study on mixed bed coalescer to treat direct and inverse emulsion simultaneously
• Application on mixed bed coalescer with guide in phenol extraction

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

1. Installation of guide, porous material preferably wetted by dispersed phase, helps


optimizing the 3rd mechanism “salting out or enlarging of dispersed phase”, thus,
allow the granular bed coalescer to work at the flowrate of 1.5 - 6 times higher
than classical coalescer without guide. It helps preventing formation of mousse,
jet at the bed outlet. It also prevents formation of zone of non-coalesced drops
between decanted solvent and clarified water zone. The guided coalescer can be
operated at higher ratio of dispersed phase/ continuous phase than the classical
coalescer. The research confirms the advantage of guided coalescer proposed by
Prof. AURELLE.
2. When both direct and inverse emulsion are simultaneously present in the
wastewater, two-stages process of hydrophilic bed and hydrophobic bed
coalescers, connected in series, may encounter a problem of re-dispersion or re-
fragmentation, thus, lower the total efficiency.
3. Mixed bed coalescer, using combination of both hydrophilic and hydrophobic
bed material, is proven to be the effective way to treat direct and inverse
emulsion simultaneously.
4. Application of mixed bed coalescer with guide shows satisfactory result and is
proven to be a good alternative in the field of liquid-liquid extraction process.

3.4.3 Thesis of DARME [7]

This research contributed to the application of coalescer on treatment of stabilized


emulsion. This work was one of successions of the research of AURELLE [3] in order to
understand profoundly about working mechanism, limitation and application of granular bed
coalescer.

12 I-12
Chapter 3 Bibliography

The research consisted of,

• Influence of surfactant on coalescer operation


• Trials on optimization of each basic mechanisms of coalescer
• Study on mixed bed electrocoalescer

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

1. Surfactants have important effects on emulsion and operation of coalescer as


follow;
• Decreasing average size of droplet in emulsion, then, results in limiting the
efficiency of the 1st mechanism “Interception step” of coalescer.
• Decreasing interfacial tension, increasing electric charge at the surface of the
droplets and increasing viscosity of surface of the droplets, then, result in
poor adhesion between droplets and bed, as well as, ineffective collision
(collision without coalescence) between droplets. These leads to limiting the
efficiency of the 2nd mechanism “Adhesion-coalescence step” of coalescer.
• Decreasing interfacial tension and adsorption of surfactant on enlargement
surface (or grill) results in limiting the efficiency of the 3rd mechanism
“Enlargement step”
2. Trials to optimize the 1st and 3rd mechanism were conducted by;
• Optimization of the 1st mechanism: increasing bed depth
• Optimization of the 3rd mechanism: installation of “guide”
The efficiency of the coalescer after these 2 modifications is not improved.
Hence, it shows that the 2nd mechanism “Adhesion-Coalescence” is the limiting
step in this case.
3. The 2nd mechanism can be optimized by destabilizing the emulsion, chemically
or electrically. To apply only the coalescer to treat stabilized emulsion, without
additional chemical process to destabilize or “break” the emulsion, the author
propose to destabilize the emulsion by electrostatic effect. To achieve the
electrostatic effect required, the author proposes to use the combination of
oleophilic resin and metal (such as aluminium) as coalescer bed. With carefully
selected bed materials, the electrostatic effect, caused by electrical potential of
the 2 materials, will be sufficient to subdue the surface charge of droplets,
caused by surfactants. Then, it will improve adhesion and coalescence within the
coalescer.
4. However, this mixed bed is effective only when the emulsion is stabilized by
ionic surfactant. In case of non-ionic surfactant, coalescence is hindered by

13 I-13
Part I Introduction and bibliography

mechanical, not electrical, barrier, caused by adsorption of the surfactant at the


surface of droplets. This barrier cannot be subdued by electrostatic effect.

3.4.4 Thesis of TAPANEEYANGKUL [8]

This research was intended to study on a variation of coalescer, i.e., “Dynamic


fibrous bed coalescer”. This type of coalescer has advantage in its anti-clogging property
which allows it to be used with oily wastewater with high suspended solids concentration.

The research consisted of,

• Influence of essential parameters, i.e., geometry of fibrous bed, and operation


parameters, such as feed rate, rotating speed of fibrous bed to efficiency of
coalescer
• Model development for fibrous bed coalescer

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

3.4.5 Thesis of DAMAK [9]

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

Orifice plate Top of hydrocarbon


layer
Emulsion jet
from orifice
Hydrocarbon

Hydrocarbon
Emulsion
layer

droplets in emulsion
drop
drop

Bottom of hydrocarbon
layer
Water layer
Effluent Decanting of droplets in
emulsion drop

Fig. 3.2 Schematic of Phase inversion coalescer

15 I-15
Part I Introduction and bibliography

The research consisted of,

• Influence of essential parameters, i.e.,diameters of droplets, height of hydrocarbon,


etc. to efficiency of Phase inversion coalescer
• Study on up-flow pulsed granular bed coalescer
• Model development for granular bed coalescer, based on dimensional analysis

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.

16 I-16
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.

3.4.6 Thesis of MA [16]

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.

3.4.7 Thesis of SRIJAROONRAT [10]

This thesis is an application research on treatment of non-stabilized oil/water


emulsion. This type of thesis provides important data that can be applied in real life situation.
So we will devote one section to review these theses. However, as one part of her thesis,
SRIJAROONRAT had studied on comparison between fibrous bed coalescer of brush type
and random, disorderly type (like a steel wool). She also studied on combination of
coalescer/hydrocyclone to treat non-stabilized emulsion. The idea is to use coalescer to
increase droplet size, permitting a good separation by the following hydroclclone. Her study
on coalescer will be briefly mentioned here to complete the entire coalescer studies.

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.

3.4.8 Thesis of WANICHKUL [11]

This thesis is an application research on treatment of stabilized oil/water emulsion.


Details of this thesis will be described in the section devoted to application thesis. However,
as one part of his thesis, WANICHKUL had studied on the combination of
coalescer/hydrocyclone and hydrocyclone/coalescer to treat non-stabilized emulsion, as well
as the efficiency of multi stage fibrous bed coalescer.

Significant findings

1. Testing of the 2 types of the combination in industrial pilot plants shows


satisfactory result. These combinations provide promising alternatives for
industrial wastewater treatment process. Furthermore 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.
2. Result from multi stage fibrous bed coalescer test shows that this “modified
bottlebrush” bed provides better efficiency than classic bottlebrush bed. This is
because the gaps between each stage cause turbulance, then promote coalecence
between droplets that, somehow, fail to coalesce in the previous stage of bed.

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.

3.5.1 Thesis of SIEM [12]

This research contributed to the study on fundamental mechanism of Flotation for


hydrocarbon/water separation, which was used as a basis and guideline for other followed
researches.

The research consisted of,

• 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.

3.5.2 Thesis of AOUDJEHANE [13]

This research contributed to application of flotation on treatment of hydrocarbon-


polluted wastewater. This work was one of successions of the research of SIEM [12] in order
to understand profoundly about working mechanism, limitation and application of flotation.

The research consisted of,

• Study on structure of bubble/droplet agglomerate and influence of additional of


flotation reagent in form of the transfer compound( composé transferable)
• Influence of hardness and salinity of pressurized water on production of air bubble
• Study on probability of collision and coalesce of air bubble and oil droplet

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.

3.5.3 Thesis of DUPRE [14]

This research contributed to the study on related mechanisms and mathematical


model development of dissolved air flotation. Even though the author intended to study on
solids/ liquid separation, some parts of the study on formation of air bubble and some general
ideas can be applied in the field of hydrocarbon/water separation.

The research consisted of,

• Study on precipitation of dissolved gas to form bubbles


• Study on formation of bubble/particle agglomerate
• Model development for dissolved air flotation

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.

To study the formation of bubble/particle agglomerate and operation of flotation, the


experiment was conducted using 3 apparatuses. The 1st one was a glass container with
syringes and holders, for supplying bubbles and particles. Bubble can be fixed in place while
particles were brought to contact with it or vice versa. The 2nd apparatus was glass container
with sealed cover, connected to a vacuum pump. The container was filled with water and

20 I-20
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

1. The study result, which can be applied to hydrocarbon/water separation, is the


one about formation of bubble at pressure reducing valve. The study shows that
efficiency of flotation can be improved if the design of pressure reducing valve is
optimized to generate microbubble in majority.
2. The use of hydrophobic venturi or pipe can cause the increase in size of the
largest bubble generated. These large bubbles, though small in the number,
consume almost all of the gas volume. So the number of generated
microbubbles, which plays an important role in flotation, is left but only in small
proportion.
3. Addition of surfactant in pressurized water can cause augmentation in population
of microbubbles. On the contrary, addition of polyelectrolyte will cause a
decrease in electric charge, which is favorable for the coalescence of bubbles.

3.5.4 Thesis of PONASSE [15]

This research contributed to study and trial on improvement of flotation efficiency.


The author had tested several ways to improve formation of microbubble, such as addition of
chemicals, using ultrasound vibrator to create microbubble. She also performed a feasibility
study on “Deep shaft” flotation unit.

The research consisted of,

• Study on the influence of pressure reducing valve on formation of bubble


• Feasibility study on deep shaft flotation unit
• Feasibility study on combination of pressure reducing valve and ultrasound
vibrator.

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.,

• Direct injection into the wastewater at static mixer


• Via porous plate, located inside the wastewater pipe before enter the deep shaft
reactor
• Via injection chamber, air will forced through small orifice into the chamber
• Via membrane

21 I-21
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

1. We are interested only in the result that can be applied to hydrocarbon/water


separation, i.e., formation of bubble. From the study, it shows that precipitation
of dissolved gas appears firstly in form of big gas pocket within pressure
reducing valve. Then the pocket is broken or fragmented by hydrodynamic force
to form bubble.
2. Geometry of pressure reducing valve, which determines hydraulic condition, is
the key parameter to obtain microbubbles.
3. To obtain good efficiency, pressure reducing device should be placed as close as
possible to mixing zone between wastewater and pressurized water

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.

In our lab, we emphasize on hydrocyclone, rather than the centrifugal machine,


because of its simplicity and economy. Furthermore, for most of oily wastewater we
encounter, the centrifugal acceleration induced by hydrodynamic force alone is sufficient to
provide satisfying separation. The hydrocyclone have no moving part. Its structure is
relatively much more simple than centrifugal machine. And it uses the driving force only from
its feed flowrate. So it is more economic than centrifuge both in investment cost and operating
cost. Now, there are various types of hydrocyclone, commercialized by many manufacturers.
Even so, basic concept of these products is identical. Understanding of the concept including
related mechanisms and limitation of the process will lead to appropriate design, selection and
operation, as well as improvement of the process. There are several theses related to
hydrocyclone, in order to cover various aspects of the process. All of related theses on
hydrocyclone can be outlined as follows.

3.6.1 Thesis of MA [16]

This thesis was the main research on hydrocyclone for hydrocarbon/water separation.

22 I-22
Chapter 3 Bibliography

The research consisted of,

• Study on new approach for calculating two-phase hydrocyclone, used for


liquid/liquid separation application
• Study on three-phase hydrocyclone, used for liquid/liquid/solid separation
• Feasibility study on the combination process of three phase hydrocyclone and
coalescer

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

1. In this thesis, a mathematical model for sizing and calculating efficiency of


THEW type hydrocyclone was proposed. This model, based on calculation of
decanter, can be used to calculate trajectories of oil droplets in the cyclone, as
well as the separation efficiency for each size of oil droplet. Difference between
model prediction and experimental result is around 10%.
2. It is recommended that the optimum angle of conical section of THEW
hydrocyclone should be 8° to 12°. And ratio Dn/D (nominal diameter of cyclone/
diameter of cylindrical part of the hydrocyclone) should be around 0.5.
3. The author had designed the 3-phase hydrocyclone by integrating THEW type
hydrocyclone with RIETEMA type hydrocyclone. To do so, the vortex finder of
RIETEMA hydrocyclone is replaced by THEW hydrocyclone, as shown in fig.
3.3. Test results show that the hydrocyclone is capable to separate, efficiently
and simultaneously, lightweight hydrocarbon and heavy suspended solids from
water.
4. The study shows that separation efficiency of hydrocyclone will drop rapidly if
the diameter of oil droplet is smaller than 20 μm.
Solid-liquid part (Rietema’s part) Liquid-liquid part (Thew’s part)

Di
Du

Dp D Do
Ds
L4
L5 L3
L3 L1

Fig. 3.3 Three- phase hydrocyclone


Note: Di/D=0.25, 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

23 I-23
Part I Introduction and bibliography

3.6.2 Thesis of CAZAL [17]

This research contributed to the feasibility study of solid/liquid separation


hydrocyclone on treatment of storm water, domestic wastewater, and thickening of sludge. In
spite of the fact that this research is mainly related to solid/liquid separation process, it
provides useful details about model development and basic concepts of hydrocyclone.
Furthermore, oily wastewater always contains some amount of suspended solids. So, some
parts of this thesis can fulfil the study of hydrocyclone for oily wastewater treatment charged
with suspended solids.

The research consisted of,

• Feasibility study on application of hydrocyclone for treatment of storm water,


domestic wastewater, thickening of primary sludge and biological sludge
• Model development for solid/liquid separation hydrocyclone and study on
influence of shape of suspended solids to separation efficiency
• Study and proposal on multi-hydrocyclone processes for treatment of storm water

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)

Table 3.2 Summary of characteristics of synthetic wastewaters

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

1. In this thesis, it shows that the efficiency of hydrocyclone for wastewater


treatment and sludge thickening application are relatively low, compared to
classic decanter or gravity thickener. Main reasons for poor efficiency consist of;
• Shear force from flow pattern in hydrocyclone, which causes deflocculation
effect or decreasing in size of biological floc
• Nature of the wastewater, which normally contains high contents of fiber
agglomerates. These fibers hinder separation phenomena in hydrocyclone
2. The author had tested the operation of hydrocyclones using the range of influent
SS concentrations from 10 mg/l to 20 g/l and maximum purge ratio of 2%. The
result shows that efficiency will increase if influent flowrate is increased.
3. Shape of suspended solid affects the efficiency of hydrocyclone. This influence
is the function of particle’s size. The smaller the size is, the less the influence is.
4. In this study, mathematics model of hydrocyclone is proposed and form
coefficient is introduced.
5. The author proposed the combination of 3 hydrocyclones in series as the
recommended process for storm water treatment. She also proposed installation
of grit pot (the short cylindical chamber), connected to discharge port of the
hydrocyclone, to minimize the influence of particle shape.

3.6.3 Thesis of SRIJAROONRAT [10]

This thesis is an application research on treatment of non-stabilized oil/water


emulsion. SRIJAROONRAT, as one part of her thesis, had studied on the combination of
coalescer/hydrocyclone to treat non-stabilized emulsion. The hydrocyclone used in this
research is the product of Dorr Oliver, model DOXIE 5, nominal diameter of 1 cm, 10 cm
long. Her study on hydrocyclone is briefly mentioned here to complete the entire
hydrocyclone studies.

Significant findings

1. Combination between coalescer/ hydrocyclone is proven to provide good


efficiency on the wider range of feed flowrate and size of oil droplet.

3.6.4 Thesis of WANICHKUL [11]

This thesis is an application research on treatment of stabilized oil/water emulsion.


Details of this thesis will be described in the section devoted to application thesis. However,
as one part of his thesis, WANICHKUL had studied on the combination of
coalescer/hydrocyclone and hydrocyclone/coalescer to treat non-stabilized emulsion. It will be
briefly mentioned here. WANICHKUL had been tested the combination of
coalescer/hydrocyclone and hydrocyclone/coalescer. In his experiment, he used Plexiglas
hydrocyclone as shown in fig. 3.4. The influent will be fed through 2 tangential inlet ports,
located at the upper cylindrical section. The oil and treated water will be discharged at each
corresponding outlet port. Because the oil and treated water outlet port locates at the same end
of hydrocyclone, so this configuration of hydrocyclone is called “co-current”.

25 I-25
Part I Introduction and bibliography

Fig. 3.4 Hydrocyclone tested by WANICHKUL

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.

3.6.5 Thesis of PUPRASERT [25 ]

This thesis is contributed to study on the efficiency of hydrocyclone equipped with


“grit pot”, as recommended by CAZAL [17]. It is also related to the feasibility study of an
innovation on solid/liquid separation, which is a hybrid of 3 processes, i.e., coagulation-
flocculation, dissolved air flotation and centrifugal separation. However, it seems that this
thesis is not related directly to oily wastewater treatment. So we will not mention about the
result of this research here. Anyway, some information and ideas presented in PUPRASERT’s
thesis will be integrated in the stage of textbook composing in Part 3 of this thesis.

3.7 Ultrafiltration and other membrane processes


Membrane process seems to be the future of separation technology. Main component
of every membrane process is the membrane, which can be briefly described as a porous
material that plays the role of selective barrier. Under appropriate transmembrane pressure,
the membrane of appropriate characteristic will allow only certain components in wastewater

26 I-26
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.

In membrane treatment system, wastewater will be circulated on one side of


membrane. The water and some components that can be passed through membrane pore will
flow to another side of membrane. This portion is called “filtrate” or “permeate”. The portion
that can not pass the membrane will have higher oil concentration because it losses its water
component. It is called “concentrate” or “retentate”. So, the membrane can be considered as a
concentrating process because the pollutant, in our case, oil, is not exactly separated, just
concentrated. Increasing in oil contents of concentrate will cause important phenomena called
polarization concentration. This can be described as oil rich layer that can obstruct flow of
permeate. Solid content or some components in wastewater can be trapped in membrane pore
and cause clogging. Concentration polarization and clogging of membrane are the main
problems of this process. So many researches are devoted to solve this problem. All of related
theses on membrane process can be outlined as follows.

3.7.1 Thesis of BELKACEM [18]

This research is contributed to the application of ultrafiltration on treatment of cutting


oil emulsion. This type of emulsion is one of important oily wastewater. In metal industries,
especially metal forming plants and mechanical workshops, machine tools and products needs
good lubrication and cooling to ensure good quality of products and prolonged working life of
the tools. Water, by its property, is very good cooling liquid and a cost-effective choice. As
well as oil is very good lubricant and anti-corrosion substance. So the combination of oil and
water in form of emulsion provides users with both properties required. To fulfil this purpose,
the emulsion is charged with surfactants and co-surfactants to increase its stabilization. From
user point of view, it yields satisfying result.

However, from environmental point of view, presence of these surfactants or


emulsifiers makes separation process very difficult. This is because the oil phase in the
emulsion is dispersed in form of very fine droplets, which impossible to be decanted naturally.
So it requires special treatment.

The research consisted of,

• Feasibility study on the application of ultrafiltration on treatment of cutting oil


macroemulsion
• Study on treatment methodology of the cutting oil emulsion by ultrafiltration
process
• Study on membrane washing solution
• Feasibility study on the application of ultrafiltration on treatment of cutting oil
microemulsion

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.

For the emulsions, he used commercialized cutting oil emulsion of both


microemulsion and macroemulsion types. He also used cutting oil macroemulsion from
mechanical workshops.

Significant findings

1. In this thesis, the author proposed a mathematical model for calculating


ultrafiltration flux of macroemulsion, as function of non-dimensional numbers.
2. The study indicates interesting aspect in integrating ultrafiltration with partial
destabilization, using salt. From this methodology, the membrane will play the
roles of filter and coalescer, which help reducing the influence of polarization
layer and concentration factor. This leads to increasing in ultrafiltration flux for
treatment of macroemulsion.
3. To solve the problem about clogging, the author proposed to use new formulated
microemulsion, which is not saturated by oil, to wash the membrane and slow
down clogging process. With a careful selection of surfactants in the
microemulsion, it can be easily treated by the combination process of
polyelectrolyte breaking and ultrafiltration. Because the author used co-
surfactant with poor water solubility, residual pollutant concentration after
ultrafiltration, mainly in dissolved form, was relative low, compared to ordinary
microemulsion.
4. From study on treatment of microemulsion by ultrafiltration, it shows that
ultrafiltration provides good separation between oil and water. However, the
filtrate is heavily polluted by dissolved pollutant, then additional treatment is
inevitably required. The author proposed to use reverse osmosis process to treat

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

Fig. 3.5 Ultrafiltration models used by BELKACEM

3.7.2 Thesis of TOULGOAT [19]

This research is contributed to the study on formation mechanisms of thermal


emulsion and feasibility study on treatment of the emulsion by ultrafiltration. This type of
milky emulsion is generally encountered in essential oil extraction process, such as in perfume
industry. Not only this study provides information about one of the application of
ultrafiltration. It also provides the general idea of formation of thermal emulsion, which leads
to precaution to avoid it formation. This idea can be applied to heteroazeotropic distillation,
which is one of treatment processes for oily wastewater.

The research consisted of,

• Influence of essential parameters, such as temperature, condensing surface, etc., on


the formation and characteristic of thermal emulsion
• Preventive approach to avoid formation of the emulsion or, if case arise, limit its
concentration
• Feasibility study on treatment of thermal emulsion by ultrafiltration

29 I-29
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.

To study mechanisms of thermal emulsion formation, hydrodistillation apparatus was


used. It is, in fact, the same device as the first one, with an additional installation of a stirrer.
For the plants used for the experiment, she used several plants, i.e., cinnamon, aniseed, celery,
lavender, etc. Condensate was found in form of decanted essential oil, floating on the top, and
milky thermal emulsion.

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.

3.7.3 Thesis of MATAMOROS [20]

This research is contributed to the study on treatment of stabilized emulsion,


especially cutting oil emulsion, by various membrane processes. This research provides many
useful information and comparison data of several membrane processes.

30 I-30
Chapter 3 Bibliography

The research consisted of,

• Feasibility study on the application of various membrane processes for treatment


of cutting oil emulsion, of both macroemulsion and microemulsion types
• Feasibility study on the application of combination processes between one of
membranes and chemical destabilizing process for treatment of cutting oil
macroemulsion and microemulsion

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.

Table. 3.3 Membranes test by MATAMOROS

Initial permeate flux


Membrane Cut size Material
(m.s-1.pa-1)
Microfiltration 0.10 – 0.45 μm 655 - 125786 Cellulose compounds,
Polyamide and PTFE
Ultrafiltration 40-50 Kda 750*10-12 Polyacrylonitrile,
Acrylonitrile
Nanofiltration 150 – 2000 Da 1.72*10-12 - 20*10-12 Cellulose
-12
Reverse osmosis 150 Da 2.2*10 Polyamide

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.

31 I-31
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

Fig. 3.6 Treatment processes for macro- and microemulsion,


recommended by MATAMOROS

3.7.4 Thesis of SRIJAROONRAT [10]

This thesis is an application research on the treatment of non-stabilized oil/water


emulsion. As one part of her thesis, SRIJAROONRAT had studied on the application of
ultrafiltration to treat non-stabilized emulsion. In her thesis, SRIJAROONRAT had tested
several types of ultrafiltration membranes, i.e., organic, inorganic and ceramic. Wastewater
used in the experiment consisted of synthetic emulsion of kerosene/water, cutting oil
emulsion, crude oil/water emulsion, and wastewater from textile plant. The result can be
summarized as follows.

Significant findings

1. Ultrafiltration process can be used to treat non-stabilized emulsion with


remarkable efficiency (approx. 100%).
2. Major problem of the ultrafiltration is the rapid decrease in permeate flux, caused
by;
• Presence of suspended solids in wastewater, these solids will deposit on the
membrane surface and/or in the pores and cause clogging.

32 I-32
Chapter 3 Bibliography

• Presence of surfactant, the surfactant will be adsorbed or form micelles


within the membrane pores, as well as membrane surface, thus cause
changing in wettability of membrane.
3. Influence of surfactant on permeate flux also depends on material of membrane.
Inorganic (mineral) based membrane is more sensitive to surfactants than other
membranes.

3.7.5 Thesis of WANICHKUL [11]

This thesis is an application research on the treatment of stabilized oil/water emulsion.


WANICHKUL had studied on the application of ultrafiltration on cutting oil emulsion
treatment. He also studied on the treatment of ultrafiltrate by reverse osmosis.

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.

3.8 Thermal treatment


This treatment approach makes use of physical properties of hydrocarbon, water and
their mixture. Because hydrocarbon is only slightly soluble in water, we can say that the
hydrocarbon/water mixture is practically an immiscible binary system. From this fact, we can
apply the basic of phase equilibrium to develop thermal processes for hydrocarbon/water
separation. Such processes are distillation and crystallization. All related theses based on
thermal treatment can be outlined as follows.

3.8.1 Thesis of LUCENA[24]

This research is contributed to the heteroazeotropic distillation for treatment of slop,


the wasted viscous water-in-petroleum emulsion that is usually very difficult and costly to
treat. This process is very interesting innovation that allows hydrocarbon recovery by
separating from water from the slop. Certain type of hydrocarbons, considered as efficient
water extractant or entrainer, is added to the slop, then the slop undergoes distillation to
extract the water. After distillation, the distillate obtained is composed of 2 layers of clear
liquid, the entrainer in the upper layer and the water at the lower. The water can be disposed
or further treated and the entrainer can be reused for next cycle of distillation. The residue
obtained is relatively fluid, contains no water, and can be recycled to refinery unit as crude
oil.

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.

3.8.2 Thesis of LORRAIN[23]

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.

3.8.3 Thesis of WANICHKUL [11]

This thesis is an application research on the treatment of stabilized oil/water emulsion.


WANICHKUL had studied on the application of distillation for the treatment of cutting oil
emulsion and permeate from ultrafiltration. He also studied the possibility to treat concentrate
from ultrafiltration of cutting oil emulsion by heteroazeotropic distillation.

Significant findings

1. Comparison on the 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.
2. Heteroazeotropic distillation is proven to be an effective way to treat
“mayonnaise-like” retentate from the ultrafiltration of cutting oil emulsion. The
residue of distillation process is clear liquid, composed of oil without water. The
distillate consists of 2 separate layers of the entrainer (in this case, decane) on the
top and the water at the bottom. However, TOD of the distillate is still high
(around 2,800 mg/l). So the additional treatment of the distillate (either by
biological treatment or RO) is required.

3.9 Chemical treatment


When we talk about chemical treatment in oil/water separation process, we normally
refer to chemical destabilization, coagulation and flocculation. The process, then, does not
“destroy” oil. Its major role is to transform the oil into the form that facilitates oil/water
separation. So, chemical treatment process usually follows by physical separation processes as
we discussed in previous sections. Normally, chemical treatment will be required when oil or

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.

All of related theses on chemical treatment can be outlined as follows.

3.9.1 Thesis of ZHU[21]

This research is contributed to the study on influence of cutting oil emulsion formula
on its physico-chemical treatment.

The research consisted of,

• Study on chemical destabilization of various macroemulsions and microemulsions


• Study on treatment of residual pollution in treated emulsions after physico-
chemical treatment
• Feasibility study on formulation of cutting oil emulsion to minimize the residual
pollution

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

1. From the experiment on macroemulsion, it shows that destabilization mechanism


of electrolyte depends on the number of its valences, which can be described as
follows;

35 I-35
Part I Introduction and bibliography

• Mono-valence cationic electrolyte, main destabilization mechanisms are


based on Zeta potential reduction and promoting micelle formation of
surfactants.
• Bi-valence cationic electrolyte, main destabilization mechanism is based on
precipitation of surfactant to insoluble form.
• Tri-valence cationic electrolyte, main destabilization mechanisms are based
on the bridging of its cations and hydroxides and precipitation of surfactant
to insoluble form.
2. The result shows that destabilization techniques of fresh macroemulsion can also
be effective for used macroemulsion.
3. For breaking emulsion by acid, the study shows that destabilization mechanisms
for micro- and macroemulsion are different, based on type of surfactant used in
the emulsions.
• For microemulsion- surfactant used is soap. So it is sensitive to pH change.
Then, addition of acid will disturb the equilibrium of ionization of fatty acid
and make it lose its surfactant property. This type of destabilization requires
relatively small amount of acid.
• For macroemulsion- surfactant used is sulfonate type. Main destabilization
mechanisms are based on Zeta potential reduction and promoting micelle
formation of surfactants. So it requires high dosage of the acid.
4. Ferric chloride is an effective destabilization chemical for breaking
macroemulsion. However, it cannot be used to breaking microemulsion because
it will react with surfactants and form complex, which is difficult to separate.
5. High residual pollution which presents after breaking the emulsion is caused by
co-surfactant, which is fatty acid that dissolves very well in water.
6. To destabilize the emulsion stabilized by non ionic surfactant, the author
recommended to use a mixture of anionic surfactant and tri-valence electrolyte
(Alum, FeCL3) as destabilization reagent. Main breaking mechanism is based on
selective reaction between non-ionic surfactant, anionic surfactant and
electrolyte, which form insoluble complexes.
7. Breaking mechanisms of commercial adsorption reagents are based on their
components. So, their efficiencies will be known only by testing.
8. Activated carbon adsorption is proven to be an effective treatment for residual
pollution which is left after breaking the emulsion. However, investment and
operating costs of this system, esp. cost for regeneration or replacement, are
relatively high.
9. The author had proposed, for the first time, to replace fatty acid co-surfactant
with other surfactant with less water solubility to solve the problem about
residual pollutant after breaking the emulsion. In his case, he used decanol,
which is slightly soluble in water, as a co-surfactant. The new emulsion has
satisfying property. But vigorous mixing by ultrasound device is required to
disperse the oil into droplets to create the emulsion.
10. He suggested that new formula of this low pollution emulsion should be further
studied to make it soluble instantly in water, which is the way the users prefer.

36 I-36
Chapter 3 Bibliography

3.9.2 Thesis of YANG[22]

This research is a succession of ZHU’s thesis and contributed to development of low


pollution emulsion. This thesis was a new approach in pollution control because it was one of
the first researches on pollution reduction from the source, as it is presently called “cleaner
product, CP” research, which is the branch of pollution control that is well-known and widely
acceptable now.

The research consisted of,

• Study on the formulation of low pollution cutting oil emulsion


• Study on the treatment process of that new emulsion

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,

Each emulsion formula was subjected to these 5 tests, i.e.,

• Droplet size distribution measurement: using particle analyzer (granulometer)


• Emulsification test: new products were diluted by water to observe its solubility
and stability.
• Anti-rust test: new emulsions of various concentrations were used to coat on steel
chip and rust forming was observed.
• Anti-mousse test: new emulsions were manually and intensely agitated and
characteristic and stability of mousse were observed.
• Determination of residual pollutant after chemical destabilization process or
ultrafiltration.

Significant findings

1. The author proposed new formulae of low-residual-pollutant microemulsions


and macroemulsions.
2. These new emulsions can be treated efficiently by breaking with calcium
chloride or ultrafiltration. Residual pollution after treatment is 2-57 times lower
than present commercial products.
3. Concentration of emulsion and hardness of dilution water are important
parameters, which affect stability of emulsion.

37 I-37
Part I Introduction and bibliography

3.10 Biological treatment


Biological treatment is the most common wastewater treatment process. Because of its
versatile, efficiency and economic, biological treatment plants are widely used for both
domestic and industrial wastewater treatments. Its working principles depend mainly on
degradation and/or assimilation of pollutants by microorganisms, so called “biomass”, present
in the biological reactor. Key to obtain satisfying treatment efficiency is to optimize the
environment in the reactor to promote function of biomass. Even though oil or hydrocarbons
are biodegradable, presence of some hydrocarbons at some concentrations can cause adverse
effect on the biological treatment mechanisms by;

• Obstructing oxygen transfer: Oxygen content is an important factor in aerobic


biodegradation. Oil layer that covers water surface will obstruct transfer of oxygen
between air and water. Oil may surround biomass floc and impede oxygen transfer
of the floc in biological reactor. This leads to the decrease in treatment efficiency.
• Its high oxygen demand: Oil requires high amount of oxygen for biodegradation. It
will cause problem on insufficient aeration capability in some treatment plants that
did not account for this type of pollutant in the design procedure. It also increases
investment cost and operating cost for aeration system.
• Its toxicity: In petroleum product or industrial oil-based product, they, sometime,
contain toxic substance, such as sulfide, heavy metals, which may be added to the
oil product in form of inhibitor or additive to provide desired product properties.
When these products are discharged to water and become wastewater, these
substance will become toxicity to living water organisms, includes biomass.

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.

3.10.1 Thesis of WANICHKUL [11]

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.

The research consisted of,

• Influence of skimming materials, geometry of devices and characteristic of


wastewater to skimmer operation
• Model development for oil drum and disc skimmer
• Behavior of skimmers under interesting working conditions, which may affect its
efficiency

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.

3.12 Application researches


To apply treatment processes previously described in real life situation, our lab had
performed some researches that devoted to compare the efficiency of various stand-alone
processes or combination of processes on treatment of certain type of oily wastewater. This

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.

3.12.1 Thesis of SRIJAROONRAT [10]

This thesis is an application research on the treatment of non-stabilized oil/water


emulsion, which is one of the most encountered wastewaters.

The research consisted of,

• Study on treatment of non-stabilized emulsion by ultrafiltration


• Influence of operating condition, presence of surfactant and type of membrane on
ultrafiltration process
• Study on treatment of non-stabilized emulsion combination of coalescer/
hydrocyclone

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.

For combination of coalescer/hydrocyclone, two types of coalescer bed were used,


bottle brush type and disorderly fibrous bed (like metal wool). For hydrocyclone, a
commercial hydrocyclone, model DOXIE 5 of Dorr-Oliver, was used.

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;

1. Ultrafiltration process can be use to treat non stabilized emulsion with


remarkable efficiency (approx. 100%).
2. Major problem of the ultrafiltration is a rapid decrease in permeate flux, caused
by;
• Presence of suspended solids in wastewater: these solids will lodge tightly in
membrane pores and cause clogging.
• Presence of surfactant: the surfactant will be adsorbed or form micelles
within the membrane pores, as well as membrane surface, then cause
changing in wettability of membrane.

40 I-40
Chapter 3 Bibliography

3. Influence of surfactant on permeate flux, also, depends on material of membrane.


Inorganic (mineral) based membrane is more sensitive to surfactants than other
membranes.
4. Backflushing the membrane with its permeate is proven to be an effective way to
increase the limiting flux. The result shows that duration of ultrafiltrating and
backflushing cycle should be optimized to obtain best efficiency. Normally, the 2
cycles is preferred to be short.
5. 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.
6. 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 the combination of 2
brushes. The internal one is of ordinary brush. The external one will look like
coil spring with its fiber elements protruding inward and toward the center. This
type of bed is believed to provide good interception, similar to the disorderly
bed, yet remain its anti-clogging properties, like brush-type bed.
7. Combination between coalescer/ hydrocyclone is proven to provide good
efficiency on the wider range of feed flowrate and size of oil droplet.

3.12.2 Thesis of WANICHKUL [11]

This thesis is an application research on the treatment of stabilized oil/water emulsion,


one of the most encountered oily wastewaters. The author also extended the research of
SRIJAROONRAT [10] on the combination of coalescer and hydrocyclone by studying the
influence of order of the 2 processes. So, WANICHKUL tested both combinations of
coalescer/hydrocyclone and hydrocyclone/coalescer as well as the combination on
coalescer/hydrocyclone/coalescer.

The research consisted of,

• Study on treatment of stabilized emulsion by ultrafiltration and distillation


• Study on treatment of permeate from ultrafiltration by reverse osmosis, biological
treatment and distillation
• Study on treatment of retentate from ultrafiltration by heteroazotropic distillation
• Study on treatment of non-stabilized emulsion combination of coalescer/
hydrocyclone and hydrocyclone/coalescer
• Study on multi stage fibrous bed coalescer

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.

The stabilized emulsions tested consisted of 2 commercial cutting oil emulsions, 1


macroemulsion and 1 microemulsion. For membrane regeneration, he used the microemulsion

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.

For hydrocyclone/coalescer study, co-current transparent hydrocyclone and “bottle


brush” fibrous bed coalescer were used. He also tested a new type of fibrous bed, multi stage
fibrous bed”. In fact, the new bed is modified version of bottlebrush type with the rings of
fibers not placed close to each other, but placed separately.

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

industrial wastewater treatment process. Furthermore, 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
9. Result from Multi stage fibrous bed coalescer test shows that this “modified
bottlebrush” bed provides better efficiency than the classic bottlebrush bed. This
is because the gaps between each stage can cause turbulence, then promote
coalescence between oil droplets that, somehow, fail to coalesce in the previous
stage of bed.

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

Part 2 Generalization of model for oil-water separation process design


In this part, the models or researches collected and summarized in the part I are
analyzed and then generalized to obtain the model or models that governs the entire range (or
as wide as possible) of oily wastewater that we are interested in. Basic concept of each model
is briefly described here providing that it will be fully described in the next part. Then the
models and their limitations will be presented. After that, models will be tested using various
sets of data to cover the considered range of wastewater. Finally the generalized model will
then be proposed.

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.,

1.1 Simple Decanter or API tank


Simple decanter, which is made well known and standardized by American Petroleum
Institute (API), is the simplest oil-water separation process based on classical STOKES law.
Concept of operation of the process is to provide sufficient time for droplets to float to the
surface, where it will accumulate into oil layer, before it flows out with the water at the water
outlet.

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.

1.2 Lamella Decanter or Parallel Plate Interceptor (PPI)


This type of decanter is the basic 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. 1.2. Some times, the plates are
inclined with angle (α) as related to horizontal axis. In this case, rising distance will become
H / cos α.

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

L Separated oil floats


to surface
Q

H
Influent Effluent
D

Inserted plates
(No. of plates = N)

Fig. 1.2 Schematic of PPI decanter

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.

1.3 Model verification


According to the concept of decanting model that derives from comparing detention
time with rising time of droplet to intercepting surface, we can formulate the general model to
calculate dc for any decanters as shown in eq. 1.9

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

Where Q = Wastewater flowrate


H = Rising distance of oil drop, depends on configuration of the decanter
L = Length of interceptor surface
A = Flow area (Cross sectional) area of decanter

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)

Fig. 1.3 “Spiraloil” decanter a) Simple spiral b) Mixed spiral

49 II-5
Chapter 1 Decanting

Table 1.1 Summary of tested decanters and operating conditions

Description Simple spiral “Spiraloil” Mixed spiral “Spiraloil”


Geometry
Nominal radius R (mm) 50 50
Core radius r (mm) 10 10
Length of decanter L (mm) 300 300
Total length of inserted plates (m) 3.88 N/A
Spacing between concentric annular plate (mm) 2 3
Plate thickness (mm) 0.3 0.2 for annular plates
0.4 for corrugated plates
Interceptor (decanting) area (m2) 1.66 2.1
Inclination of decanter Horizontal Horizontal
Operating conditions
Flow velocity (cm/s) 0.4-1.6 0.5-1.5
(m/h) 14.4-57.6 18-54
Wastewater used Kerosene-water mixture Kerosene-water mixture

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. Predicted values for cut size are relatively accurate.


2. Predicted efficiencies of the droplets smaller than cut size are always lower than
observed value because, in our simplified model, coalescing between rising oil
drops is not accounted. Furthermore, in case that the plates are placed very close
to each other like in “Spiraloil”, oil film will accumulated at the surface of plate,
then helps reducing rising height oil droplet, thus increasing the efficiency.
3. Correction factor for efficiency prediction of these small droplets may not be
established accurately. However, the predicted cut size can be used to design the
tank with relative 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.

1.4 Conclusion and Generalized Model of decanter


From model verification result, we can conclude and propose the generalized model,
as well as, its limitation as follows,

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 ⎠

3. To determine graded and total removal efficiency, use eq. 1.4.


For oil droplet size, d ≥ cut size, dc
η = 100% {1.4a}
d

51 II-7
Chapter 1 Decanting

For oil droplet size, d ≤ cut size,dc


U
η = d ⋅ 100% {1.4b}
d U
dc

For total removal efficiency


1 d max
ηt =
Q
Q

C
⋅ ∑ η ⋅C
d od
(
⋅ 100% ) {1.4c}
d
out o min
d max
Q out = Q −
Q
∑η C od {1.4d}
ρd
d
d min

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.

2.1 Drum skimmer


Drum skimmer is rotating drum or cylinder with specially selected surface material,
which can adhere to oil, not water. The oil will adhere to the drum as a film and, then, lift up
from water surface by The skimmer’s rotating movement. The skimmer will be equipped with
scrapper blade to scrape the oil film from drum surface into receiving trough or gutter. Fig.
2.1 shows the schematic of oil drum skimmer.

The generalized model of drum skimmer had been proposed by THANGTONGTAWI


[5]. His proposed model was developed by similarity analysis, using Buckingham Pi theory.
He had conducted his research thoroughly and covered every necessary aspect of drum
skimmer. So his model and its limitation will be quoted here again, as shown in eq.2.1,
without the need for further verification.

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.;

• Superficial tension of oil is in the range of 27 – 34 dynes/cm, which practically


covers all common oil.
• Capillary number (Ca = μo V/γo) is in the range of 0.2 – 1.0.
• Oil density is around 0.8 g/cm3.
• Peripheral or tip velocity should not be greater than 0.8 m/s. To avoid water
entraining, velocity of 0.44 m/s or less is recommended.
• Recommended immersion depth is 1.0-2.0 cm.
• Presence of surfactant has only little effect on skimmer’s operation.
• Total removal efficiency of the equipment is always 100%, providing that above
conditions are satisfied, and then recovered oil is water-free.

53 II-9
Chapter 2 Skimmer

D Scrapper Scrapper

Oil layer I
Water Oil layer
Water
a) b)

Fig. 2.1 Drum and disk skimmer

2.2 Disk skimmer


Disk skimmer’s operating principle is the same as drum skimmer’s. Major difference
is the replacement of the drum with thin circular disk. fig. 2.1 shows the schematic of oil disk
skimmer.

The generalized model of disk skimmer had been proposed, also, by


THANGTONGTAWI [5]. His proposed model, as shown in eq. 2.3, was developed by
similarity analysis, using Buckingham Pi theory.

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.;

• Superficial tension of oil is in the range of 27 – 34 dynes/cm, which practically


covers all common oil.
• Capillary number (Ca = μo V/γo) is in the range of 0.04 – 3.6.
• Oil density is around 0.8 g/cm3.
• Peripheral or tip velocity should not be greater than 1.13 m/s. To avoid water
entraining, velocity of 0.5 m/s or less is recommended.
• Presence of surfactant has only little effect on skimmer operation.
• Total removal efficiency of the equipment is always 100%, providing that above
conditions are satisfied, and then recovered oil is water-free.

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.,

3.1 Granular bed coalescer


This type of coalescer uses granular material as a bed to promote coalescing between
oil droplets, as shown in fig. 3.1. AURELLE [3] is the pioneer on coalescer study. He
established the 3-step working mechanisms of the coalescer, based on filtration model [35].
Then there are several follow up researches on coalescer, based on AURELLE’s research.
However, for mathematics model of coalescer, there are only 2 major mathematical models
for coalescer. The first one is based on filtration concept and another is based on dimensional
analysis.

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

3.1.1 Filtration-based model

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.;

• Step 1: Interception, which consists of 3 major transport phenomena, i.e.,


sedimentation, direct interception and diffusion.
• Step 2: Adhesion-Coalescence. The efficiency of this step depends mainly on
wettability of bed material.
• 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 (or screen),
empty bed flow velocity, interfacial tension and ratio of dispersed phase and
continuous phase in emulsion treated.

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

coalescer. To calculate removal efficiency of step 1, he proposed the model, based on


filtration model, as shown in eq. 3.1 to 3.3.
⎛ 3 H ⎞
⎜ − (1 − ε) (α ⋅ η )⎟
2 dp exp
η = ⎜1 − e ⎟ ⋅ 100 % {3.1}
d ⎜ ⎟
⎜ ⎟
⎝ ⎠

α⋅η = 0.5484(η ) 0.5143 {3.2}


exp theo
2/3
Δρgd 2 3 d 2 ⎛ KT ⎞
{3.3}
η = + ( ) + 0.9⎜⎜ ⎟

theo 18μ V 2 dp
c ⎝ μ c d ⋅ dpV ⎠

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.

3.1.2 Dimensional analysis-based model

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 verified under these conditions i.e.;

• 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.

3.1.3 Model verification

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)

DAMAK's model AURELLE's model

Fig. 3.2a Relation between droplet diameter VS. model's error


0.2 0.12 2 -0.08 0.09 0.09
ηd = 58 (dE/dp) (H/dp) (ρc dp V / γo/w ) (μd/ μc) (Δρ/ ρc)
110%
100%
90%
Predicted efficiency %

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

3.1.4 Conclusion and generalized model of granular bed coalescer

From model verification result, we can conclude and propose the generalized model as
well as its limitation as follow,

1. To predict removal efficiency of coalescer, graded efficiency (ηd) can be


calculated by eq. 3.5. If the result from eq. 3.5 is greater than 100%, then it will
be rounded up to 100%. Total removal efficiency can be calculated by eq. 3.4.

⎛ 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;

1) Coalescer bed shall be oleophilic and relatively spherical in shape.Tested


range of bed height is between 1 to 10 cm. However, bed height 1 cm is
not recommended. The greater the bed height, the safer coalescer
operation. However, it also results in higher pressure drop.
2) The model is valid for inlet concentration between 100 - 1,000 mg/l.
3) Tested size of bed media is between 0.35 – 0.9 mm. The larger the media
size, the lower the efficiency.
4) The density difference between dispersed phase (oil) and continuous phase
(water) is between 80 to 315 kg/m3 (approx).
5) The velocity shall be in the range of 0.09 to 0.54 cm/s.(3.2 to 19.4 m/h) for
coalescer without guide.
6) 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.

3.1.5 Generalized model for guide coalescer

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

higher efficiency. However, because of the lack of verifying data, we recommend


using low prediction value for safety.
• Velocity 0.8 to 1.9 cm/s may still be applicable at low concentration of inlet oil
(phase ratio around 1-2).
• For oil inlet concentration, guide coalescer has been tested in liquid-liquid
extraction application [6] with maximum phase ratio (oil/water) of 6, the result
shows that it can operate effectively. So, for oily wastewater treatment process,
which the concentration is much lower, installation of guide can assure that the
coalescer should operate efficiently.

3.1.6 Generalized model for mixed bed 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.

Two pressure drop models are considered, i.e.,

• Kozeny Carman’s model: pressure drop is calculated from bed porosity.


• Darcy’s model: pressure drop is calculated from bed permeability.

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

3.2 Fibrous bed coalescer


This type of coalescer uses relatively porous fibrous material as a bed to promote
coalescing between oil droplets, as shown in fig. 3.4. 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, can be deflected, especially in large-scale unit, and causes unpredicted
channeling, then decreasing in efficiency. Three basic steps for granular bed coalescer,
proposed by AURELLE [3], can also be used to describe phenomena taking place within the
coalescer. However, mathematical 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. The latter is the modified form of
the former, by the installation of driving unit to drive the bed.

3.2.1 Dynamic fibrous bed coalescer model

The method is proposed by TAPANEEYANGKUL [8]. The model is based on the


classic dimensional analysis, which is an efficient tool when exact theory of the processes can
not be established. The author had conducted his research thoroughly and covered every
necessary aspect of the equipment. So his model and its limitation will be quoted here again,
as shown in eq.3.7, without the need for further verification.
⎛ ⎞
⎜ 0.67d 0.58 (1 − ε) 0.35 H0.35 N0.53 ⎟
η =⎜ ⎟ ⋅ 100 % {3.7}
d
⎜ D0.03 d 0.58 V0.74 ⎟
⎝ F ⎠

The model is verified under these conditions i.e.;

• 52 < Re < 1164.


• Rotating speed of the bed is between 10 to 200 rpm.
• Empty bed velocity is between 0.1 to 1.1 cm/s (3.6 to 39.6 m/h).
• Diameter of coalescer bed is around 11.5 cm.
• Diameter of fiber is around 100 to 300 microns.
• The beds, used in the experiment, are “bottle brush” types, made of polyamide or
polypropylene with stainless steel shaft.

3.2.2 Simple fibrous bed coalescer model

This coalescer is a predecessor of dynamic bed coalescer, described in the previous


section. 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 by
GPI researchers for this equipment.

3.2.3 Model verification

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.

From the graph, it shows that TAPANEEYANGKUL’s model can be adapted to


predict the efficiency of simple fibrous bed coalescer with acceptable degree of accuracy (±
20% error) when using the rotating speed = 450 rpm. This speed is too high to be reasonable.
This may be due to the fact that TAPANEEYANGKUL’s model is verified from relatively
short bed (H/D < 2) while other researches operate at H/D up to 10. So the exponent of (H/D)
from both models is quite different. In this case, we can conclude that TAPANEEYANGKUL
may not be applied to simple fiber bed coalescer.

However, it is still interesting to assume that the effect of porosity in


SRIJAROONRAT’s model should be the same as TAPANEEYANGKUL’s. So we add the
term “(1-ε)0.35” into eq. 3.8a and solve for a new constant to replace 45.005. The modified
model is shown in eq. 3.8b. Comparison between observed and predicted efficiency is shown
in fig. 3.6. The graph shows that MA’s data are better predicted, using eq. 3.8b. The model
still cannot cover WANICHKUL’s data for it is tested at very high oil inlet concentration
(7950 mg/l). However, the predicted efficiency is still on the safe side to use as a guideline.

⎛ 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)

3.2.4 Conclusion and generalized model of fibrous bed coalescer

From model verification result, we can conclude and propose the generalized model as
well as its limitation as follows,

Dynamic fibrous bed coalescer

1. To predict removal efficiency of coalescer, graded efficiency can be calculated


by eq. 3.7. If the result from eq. 3.7 is greater than 100%, then it will be rounded
up to 100%. Total removal efficiency can be calculated by eq. 3.4.
⎛ ⎞
⎜ 0.67d 0.58 (1 − ε) 0.35 H0.35 N0.53 ⎟
η =⎜ ⎟ ⋅ 100 % {3.7}
d
⎜ D0.03 d 0.58 V0.74 ⎟
⎝ F ⎠

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. The model is verified under these conditions i.e.;

• 54 < Re < 1164.


• 1 < H/D < 2. However, the maximum H/D shows in
TAPANEEYANGKUL’s research is 6. Using H/D > 2 in the model can be
also applied for comparison purpose only.
• Rotating speed of the bed is between 10 to 200 rpm. However, recommended
minimum rotating speed is 75 rpm. Using lower speed may not provide any
additional benefit over simple fibrous bed coalescer.
• Empty bed velocity is between 0.1 to 1.1 cm/s (3.6 to 39.6 m/h).

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.

Simple fibrous bed coalescer

1. To predict removal efficiency of coalescer, graded efficiency can be calculated


by eq. 3.8b. If the result from eq. 3.8b is greater than 100%, then it will be
rounded up to 100%. Total removal efficiency can be calculated by eq. 3.4.
⎛ 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 ⎠

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. The model is verified under these conditions i.e.;


• 48 < Re < 1100.
• 1 < H/D < 10.
• Unlike other granular bed model, eq. 3.8b is valid for droplet size of 1
microns and greater. The new technology on granulometer make it possible
to measure these very tiny droplets with high accuracy.
• Empty bed velocity used in the researches is between 0.5 to 5.0 cm/s (1.8 to
180 m/h). However detailed data used to verify the model is between 0.5 to
2.0 cm/s. Using velocity > 2.0 cm/s may cause unpredictable error on
calculated efficiency.
• Fiber size used in the researches is between 40 to 200 microns. However
detailed data used to verify the model is between 100 to 200 microns. Using
fiber size < 100 microns may cause unpredictable error on calculated
efficiency.
• The model is verified at inlet oil concentration up to 1000 mg/l. Using the
concentration > 1000 mg/l, again, will cause underestimation of predicted
efficiency.

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.

3.2.5 Generalized model of random or disorderly fibrous bed coalescer

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 (%)

80.0% SRIJAROONRAT's simple bed


70.0% model
+10%
60.0%
50.0%
-10%
40.0%
30.0%
20.0%
10.0%
0.0%
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Observed 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.

1. Apply SRIJAROONRAT’s random fibrous bed model (eq. 3.9) if these


conditions are satisfied, i.e.,
• Velocity is between 1 to 2.5 cm/s or 36 to 90 m/h.
• Inlet concentration is around 1000 mg/l.
• The model is developed from metal wool bed coalescer, diameter = 5 cm.,
fiber diameter = 40 microns, and porosity = 0.95.
• The wool is coated with silicone, so it becomes oleophilic.
2. Even though eq. 3.9 is developed from small set of data and tortuosity can not be
established in the form of numerical factor. But, from graph 3.6, it can be
estimated that the disorderly bed coalescer is 2 to 6 times more efficient that
simple bed. However, it will be clogged easily if suspended solids are present in
the wastewater.

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.

3.2.6 Generalized model for pressure drop of fibrous bed coalescer

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

Chapter 4 Dissolved air flotation


Flotation is an accelerated separation process 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, studied in GPI laboratory, such as
mechanical flotation, diffused air flotation, dissolved air flotation, etc. Here, we will consider
only the application of dissolved air flotation (DAF) on oily wastewater treatment.

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

Fig. 4.1 Schematic diagram of DAF

Removal efficiency (or probability) factor of DAF is calculated from summation of


theoretical efficiency factors of 3 transport phenomena, i.e. sedimentation, direct interception,
and diffusion, as shown in eq. 4.2, and adjusted to fit with observed data, as shown in eq. 4.3.

⎛ 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

4.2 Model verification


4.2.1 Modification of filtration-based model

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.

4.2.2 Population balance method

71 II-27
Chapter 4 Dissolved air flotation

Population balance method is one of popular concepts, used by many researchers, to


develop DAF model. In our lab, DUPRE [14] uses this method in her research on application
of DAF for liquid-solid separation. Concept of this method is that rate of change in the
number of oil droplets which are free or attached by 1, 2 or more air bubbles is the function of
the number of air bubble and oil droplet, as shown in eq. 4.5. Oil droplet that is attached by at
least 1 bubble, so-called oil-bubble agglomerate, will be separated. So the rate of change in
number of oil droplets represents removal efficiency.

Main assumption of population balance method is that the number of bubble is


assumed to be constant. From many researches [14], [34], It is proven that, for liquid-solid
separation, the number of bubble (N) can be safely assumed as constant without serious error,
because there are a lot more bubbles than pollutant if normal range of (Qpw/Qt) is applied.
However, in case of oily wastewater, many researches [12], [13] show that bubble-oil
agglomerates are in form of oil shell with air inside and these agglomerates are still able to
intercept more oil droplets. Those researches also show that coalescence of oil and bubble is
more effective than that of the same species. So it should be safely assumed that the number
of bubble in this case is more or less constant and the population balance method is, then,
applicable.
dn 0
= − kβ 0 n 0 N {4.5a}
dt
dn
i = − kβ n N − kβ n N {4.5b}
dt i−1 i−1 i i

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

When i = 0, the above function will be equal to 1.


6
κ= aG(1 + (d/d )) 3 Φβ 0 {4.6d}
π b

G is a measure of turbulence intensity, which is normally proportional to V but we do


not know the exact relation. For i = 0, ni will become n0, which represents the number of free
oil drop remaining from contacting with air bubble. So 1-(n0/N) represents removal efficiency
of the process. Using i > 0 will result in greater value of efficiency. So, to be on the safe side,
we will use i = 0. Then eq. 4.6, when i = 0, can be rewritten as shown in eq. 4.7. Removal
efficiency of DAF is, then, can be written in form of eq. 4.8.
n0 ( − κτ)
=e {4.7}
N
n (− κτ)
η = 1− 0 = 1− e {4.8}
N

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

At constant d and db, eq. 4.9a can be rewritten as;


κτ = Const ⋅ GΦ τ = κ Φτ {4.9b}
2
( − κτ) ( − κ Φτ)
η = 1− e =1− e 2 {4.9c}

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.

4.3 Generalized Model for DAF


From 2 models stated above, we can conclude and propose the generalized model as
well as its limitation as follows,

1. To predict removal efficiency of DAF, reference graded efficiency (based on Qt)


can be calculated by eq. 4.1, 4.2 and 4.3. If the result from the equations is
greater than 100%, then it will be rounded up to 100%. The values of (Φ/AV)
have to be the same as SIEM’s condition (see 2.) or its staightforward scale up.
⎛ 3 Φ H ⎞
⎜ (− (α η ) )⎟
⎜ 2 AV exp d
η = ⎜1 − e b ⎟ ⋅ 100 % {4.1a}
d, ref ⎟
⎜ ⎟
⎜ ⎟
⎝ ⎠
or
⎛ Q ⎞
⎜ 3 pw Conc(air) H ⎟
⎜ ( − ⋅ ⋅ (α η ) )
2 Q ρ exp d ⎟
η ⎜
= 1−e t air b ⎟ ⋅ 100 % {4.1b}
d, ref ⎜ ⎟
⎜ ⎟
⎜ ⎟
⎝ ⎠
η =η + η Int + η {4.2a}
theo sed diff

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

(αη exp ) = 0.009005(η ) 0.5919 {4.3b}


theo

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

wastewater. Anyway, it is interesting to adapt the model to calculate the


efficiency at lower ratio of pressurized water.
4. Tested hydraulic loading rate or overflow rate (based on Qt) is 1.6 m/h, which is
relatively low, compared to normal rate of 3-15 m/h for domestic wastewater
treatment. The value recommended by the American Petroleum Institute (API)
[45] is between 4.8-6.1 m/h. So it is also interesting to adapt the model to
calculate the efficiency at higher overflow rate.
5. To calculate graded removal efficiency at other operating condition, esp. at
higher overflow rate or lower ratio of pressurized water/wastewater, the
following procedure is recommended.
1) Calculate the reference efficiency of the model (ηd,ref) at our required
height (Hreq), average bubble diameter (db) and droplet sizes (d) using eq.
4.1 to eq.4.3. Use Φ/AV = 0.0516 in order that the operating condition of
SIEM still holds.
2) Scale up the area from 0.01767 m2 to required area (Areq), which may be
calculated from general design criteria. Other operating condition from 1)
still holds. So efficiency from 1) remains the same.
3) Find Φref, corresponding to the area Areq, by the following equation,
A req 4.2 × 10 −7 A req
Φ = ⋅Φ = m3/s {4.11}
ref A model 0.01767
model
4) Find τref, corresponding to the area Areq, by the following equation,
Hreq 25H req 1 hour
τ = ⋅τ = ⋅ {4.12}
ref H model 0.00046 3600
model
5) Find κ2,ref, corresponding to Areq, Hreq, τref and Φref from the reference
efficiency (from 1)) by the following equations. Please note that, at this
point, SIEM’s constraint still holds.
− ln(1 − η )
d,ref {4.13}
κ =
2,ref Φ ⋅τ
ref ref
Or
(− κ Φ τ )
η = 1− e 2,ref ref ref {4.14}
d,ref

6) To change Φ or τ from SIEM’s condition, the following procedure is


recommended and precaution should be noted.
• To decrease Φ (Φreq < Φref) and increase τ (τreq > τref):
This will cause decreasing of V, so G will decrease. Then κ2 (see eq.
4.9) will be lower. However we do not know how much exactly. So, to
be on the safe side, we will assume that only Φ decrease but τ = τref. In
this case, κ2 will remain the same and be equal to κ2,ref. The efficiency
can be calculated by eq. 4.15a.

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

DAF efficiency (ηDAF), which is the efficiency based on flotation effect


alone, can be calculated by the following equation.

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

8) If the effluent from flotation is recycled to use in pressurized water


system, some oil left in the effluent will be returned to the system. In this
case, mass balance of oil has to take into account. Thus, Cod will be
modified by adding this returned oil repeatedly, as shown in eq. 4.17.
Theoretically, rmax in eq.4.17 should be infinity. The value of C’od will
eventually convert to an asymptote. Anyway, for ηd greater than 50%,
using rmax between 5 to 10 will practically give the result sufficient
accuracy, esp. when ηd > 20%.
⎡ r −1 ⎤
⎢ rmax ⎛Q ⎞ ⎥ C od Q
= ⎢ ∑
⎜ pw

⎟ {4.17a}
C
od, dil ⎜⎜ Q (1 η )
d ⎟⎟ ⎥⋅
⎢ r =1 ⎥ Qt
⎝ t ⎠
⎣ ⎦

Where Qpw = RQ, Qt = Q + RQ. Then, eq. 4.17a can be simplified as


follows,
R r −1
(( (1 − η d )) max − 1) C Q
C = 1+R ⋅ od
{4.17b}
od, dil R Qt
(1 − η d ) - 1
1+R
9) It must be noted that there are many other parameters that can affect
efficiency of DAF, such as reactor hydraulic design, contact zone
configuration, design of pressurized water system (or saturator) and
pressure regulating device, etc. These parameters can cause some
discrepancies in efficiency prediction. However, the model will be a
useful tool for preliminary evaluation of the efficiency of DAF reactor.

78 II-34
Part II Generalization of model for oil-water separation process design

Batch experiment, such as Flota-test, will provide valuable result, if not


exact, for design propose and can be used to compare with model result.

4.4 Generalized equations for pressurized water system calculation


An important system that plays very significant role in DAF process is pressurized
water system, since, as shown in previous section, it is the source of air bubble and ratio of
air/oil droplet is one of the key parameters in DAF process. It is still the component that
consumes almost all of the energy required in DAF process. The other required energy is
pressure drop of the process caused by hydraulic elements of the reactor, such as pipeline,
outlet weir, etc., which can be calculated by familiar pressure drop equations. This pressure
drop is substantially lower than required energy of the pressurized water system.

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}

Conc.(air) = 22.965P {4.19b}


Φ {4.19c}
( ) = 0.0191P − .0191
Q pw

79 II-35
Chapter 4 Dissolved air flotation

180.0 0.14
160.0 0.12

volume of pressurized water


140.0

Released air volume per


0.10
mg of gas /l of water

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).

Q pw ⋅ ( P − Patm ) R ⋅ Q ⋅ ρ c ⋅ g ⋅ ( P − Patm ) ⋅ 10 watt {4.20c}


Power = =
3600 ⋅ η pump 3600 ⋅ η pump

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.

5.1 Two-phase hydrocyclone


5.1.1 Trajectory analysis-based model

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.

MA develops hydrocyclone model, based upon trajectory analysis, which is normally


used in decanter calculation. The concept of the model is that oil droplet in the hydrocyclone
is subjected to 3 velocity components, i.e., radial velocity (U), tangential velocity (V) and
axial or vertical velocity (W), as shown in fig. 5.1. For the tangential velocity, he assumed
that the oil droplet has the same tangential velocity as the liquid, which follows the free vortex
pattern (VRn = const.). In the case of THEW’s hydrocyclone, n is equal to 0.65. The equation
of V for THEW’s hydrocyclone is a sshown in eq. 5.1c. He also assumed that vertical velocity
(W) of the droplet is similar to that of the liquid. Vertical velocity profile can be devided into
2 regions. The external region, near to the wall of the hydrocyclone, has downward flow,
while the internal region has upward flow. The equation of W is in 3rd order polynomial form
as shown in eq. 5.1d and 5.1e. For the radial velocity of the droplet, he assumed that it is
governed by STOKE’s law. His assumption is that if the droplet can reach certain radial
distance where the vertical velocity starts changing from downward to upward direction (R =
RZVV, “ZVV” means zero vertical velocity), it will be carried upward to the overflow port,
then separated from the main stream, which will flow out at the bottom (underflow) outlet.

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

Fig. 5.1 Schematic diagram and trajectories of droplets in two-phase hydrocyclone

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.

5.1.2 Other models

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 ⎥⎦

5.1.3 Model verification

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.

5.1.4 Conclusion and Generalized model of two-phase hydrocyclone

From model verification result, we can conclude and propose the generalized model as
well as its limitation as follows,

1. To predict removal efficiency of the hydrocyclone, graded efficiency can be


calculated by eq. 5.1 and 5.2. If Rd in eq. 5.1a is equal to Dn/2, the corresponding
“d” will be equal to dc.
R
d dR L dZ
∫ = ∫ {5.1a}
R U 0W
zvv

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

For THEW’s type hydrocyclone, when Z = L:


RVZZ = 0.186( Dn / 2) {5.1f}
If Rd in eq. 5.1a is equal to Dn/2, the corresponding “d” will be equal to dc.
For d ≥ dc
η = 100 % {5.2a}
For d < dc,
2 Dn 2
(R − (0.186
)
d 2 {5.2b}
η = ⋅ 100 %
d Dn 2 Dn 2
(( ) − (0.186 )
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

2. To design the hydrocyclone by MA’s 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 20%, 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(1-0.20) = 40 microns for eq. 5.1 and 5.2.

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.

5.1.5 Generalized Model for Pressure drop of two-phase hydrocyclone

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.

5.2 Three-phase hydrocyclone


Prof. AURELLE and MA develop the three-phase hydrocyclone in order to create a
new type of hydrocyclone that can separate both oil and suspended solids simultaneously in
the same unit. From this concept, MA proposed the new hydrocyclone, which is the
combination between THEW liquid-liquid hydrocyclone and RIETEMA solid-liquid
hydrocyclone, as shown in fig. 5.4. Geometry of this hydrocyclone is nearly identical to the 2
originals with slight adaptation.

Solid-liquid part Liquid-liquid part (Thew’s part)


Di
Du
Dp D Do
Ds
L4
L5 L3
L2 L1

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

Fig. 5.4 Three-phase hydrocyclone

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.

5.2.1 Model development and verification for liquid-liquid section

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,

1. To predict removal efficiency of three-phase hydrocyclone, graded efficiency


can be calculated by eq. 5.7 and 5.8.Dn in this case is equal to Dc. And L in this
case is equal to L5.
R
d dR L dZ
∫ = ∫ {5.7a}
R U 0W
vzz

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.

5.2.2 Model development and verification for solid-liquid section

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.

5.2.3 Generalized Model for pressure drop 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}

ΔPss = 0.951Q 2.34 {5.11b}


ΔPoil = 3.140Q 2.03 {5.11c}

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

From TRAWINSKY [33], he suggested that hydrocyclone, like other centrifugal


machines, is subject to concept of similarity or affinity law.
−2
ΔP ∝ D −1d 50% Δρ {5.12}

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.

90 II-46
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.

(Empirical approach: Δp D 4 /Q2.12 = 49.8 )


4.500

4.000

3.500
Predicted pressure drop (bar)

3.000

2.500

2.000

1.500

1.000

0.500 Method 2- Similarlity approach


Method 1- Empirical approach
0.000
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50
Observed pressure drop (bar)

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

(Empirical approach: Δp D4/Q2.34= 21.0 )


3.50

3.00
Predicted pressure drop (bar)

2.50

2.00

1.50

1.00

0.50 Method 2- Similarity approach


Method 1- Empirical approach
0.00
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50
Observed pressure drop (bar)

Fig. 5.6b Relation between observed pressure drop (bar) across inlet and SS outlet and predicted value from 2 approaches

(Empirical approach: Δp D4/Q2.03= 55 )


9.00

8.00

7.00
Predicted pressure drop (bar)

6.00

5.00

4.00

3.00

2.00

1.00 Method 2- Similarity approach


Method 1- Empirical approach
0.00
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
Observed pressure drop (bar)

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

Chapter 6 Membrane process


Membrane process is a separation process based, mainly but not entirely, on filtration
concept. It can be said that the membrane is a very fine screen or filter. Theoretically, we can
always separate one or more components from fluid stream providing that the filter chosen is
suitable for size difference. Membranes can be categorized by their separation characteristics,
i.e., microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO).
MF and UF have relatively large pore sizes, so they work rather like screens or sieve filters.
While separation by NF and RO, which have very tiny pore sizes, is not simply by size alone
but involves more complex factors, such as osmotic pressure. So we can group the membranes
processes into 2 categories, i.e., 1) MF and UF, 2) NF and RO.

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

Fig. 6.1 Typical schematic diagram of Cross-flow membrane process

93
II-49
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.

6.1.1 Resistance 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

Pressure controlled Mass transfer


region controlled region
Flux Higher recirculation flow

r flux
Higer temperature
Lower concentration

Wate

Transmembrane pressure (Pt)

Fig. 6.2 Typical relation between flux and various parameters

6.1.2 Film theory based model

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

From the equation, k is mass transfer coefficient. Cg is gel concentration, which


depends on type of wastewater. V is recirculation velocity. Two typical characteristic curves
of flux VS. retentate concentration are shown in fig. 6.3b. (Other curves also exist, but they
are very rare cases)

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]

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Part II Generalization of model for oil-water separation process design

Flux

1 2

Cg C’g Cg Log (Concentration)


case 1 case 2 case 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.

6.1.3 Model verification

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.

Case 1: Know k, β and Cg

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

However, even the film theory is supposed to be pressure-independent, it should


be noted that k and β are obtained from experimental data, which are conducted at certain
value of pressure. At that reference pressure (Pref), the flux may not yet fully reach the mass
transfer controlled region. In fact, we frequently find that flux/concentration curve never the
reach really flat part within the recommended operating range of pressure (generally 0 to 4
bar), especially when velocity is high.

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.

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Table 6.2 Summary of parameters of film model from UF researches on oily wastewater treatment (reference temperature = 20O C)
Chapter 6 Membrane process

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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

So eq. 6.6a can be rewritten as,


⎛J V β ⎞
⎜ C,V R m − Pref ( V ) ⎟
ln ⎜ ref ⎟
⎜ J C,V R m − P ⎟
⎜ ref ⎟
αC = ⎝ ⎠ {6.6c}
V
ln( ref )
V
P −J R
ref C,V,Pref m {6.6d}
φC =
V αc P J
ref C,V,Pref

Membrane resistance (Rm) (or modified resistance R’m) depends on type of


membrane and emulsion treated. Then it is usually constant for any given membrane and
emulsion. In case of cutting oil emulsion, we found that there is, more or less, no fouling
occurred. So we can safely replace R’m by Rm, as shown in eq. 6.6.

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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)

Observed, C = 2% Predicted, C = 2% Observed, C = 8% Predicted, C = 8% Reference, C = 4%

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

Case 2: Know α, φ and Cg

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

Again, we recommend selecting the reference pressure as high as possible to


make sure that the calculated flux is in the mass transfer controlled region.

2. Find JC,V

From film theory, we can write that;


Cg
ln( )
C {6.9}
J C,V = J
Cref,V Cg
ln( )
C
ref

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.

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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

αc and φc can be calculated by the same method as shown in case 1, no. 3.

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, since the excess amount of surfactants/co-surfactants in the mixture is


directly proportional to the ratio of the microemulsion presenting in the mixture, we may
estimate that flux of the mixture is the weighted average of the two emulsions.

To formulate the equations, consider the mixture of Cmac % by V of macroemulsion


concentrate and Cmic % by V of microemulsion concentrate. Ratios of oil in the
macroemulsion and microemulsion concentrate are Rmac and Rmic %, respectively. Total oil
concentration in mixture can be written as follows.

C = C mac R mac + C R {6.10a}


oil,mix mic mic

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

Flux of macroemulsion and microemulsion at the total oil concentration (Jmac:Coil,mix


and Jmic:Coil, mix) can be calculated by the procedure described in the previous section.
Therefore, the flux of the mixture can be calculated by the following equation.

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)

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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)

Macro 4%, Micro 1% Macro 4%, Micro 2% Macro4%, Micro 4%

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

6.1.5 Theoretical flux prediction for batch cross-flowUF process

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.

However, for wastewater treatment process, UF is normally designed as batch system,


as shown in fig. 6.1. In batch process, the concentration of retentate will be increased up to
required limit or as much as possible. From film theory, flux will decrease when the
concentration increases. And from our procedure to predict flux in section 6.1.3, it will be
interesting to predict evolution of retentate volume, permeate volume, and flux with time.
These data is important to design UF process to meet the required operating time. However, it
must be noted that these evolutions are based on the assumption of fresh (not used) emulsion
thus there is no fouling from any other foreign materials, which, in practice, hardly exists.
Anyway, these data will provide the idea about the approximate size of membrane required.

To find permeate volume, we consider that a small volume of permeate (dVol),


passing through a UF membrane of area A at a small time (dt), will be defined by the
following equation.
dVol = J(c) ⋅ Adt {6.12}
If the system is operated in the mass transfer controlled region, the film theory can be
applied. Eq. 6.12 can be rewritten as follows,
β ⎛ Cg ⎞
dVol = kV ⋅ ln⎜ ⎟Adt {6.13}
⎜ C ⎟
⎝ ⎠
If we start with initial wastewater volume Volo and concentration Co and the rejection
of oil is totally completed, which is true from our every test, the concentration C will be the
function of the permeate volume at that moment V.

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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)

Eq. 6.9 can be rewritten as,


(Vol o − Vol)C g ⎞
β ⎛
dVol = kV ⋅ ln ⎜ ⎟ Adt {6.15a}
⎜ C o Vol o ⎟
⎝ ⎠
Vo l
final dVol t β
∫ = ∫ kV Adt {6.15b}
Volo ⎛ (Volo − Vol)Cg ⎞ 0
ln⎜ ⎟
⎜ Co Volo ⎟
⎝ ⎠

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.

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Chapter 6 Membrane process

(Used cutting oil macroemulsion :initial volume 1643 l, final volume 40 l,


initial concentration 2.4% by volume of oil (not concentrate): Module UFP10: membrane IRIS 3042)

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

(Used cutting oil macroemulsion :initial volume 1643 l, final volume 40 l,


initial concentration 2.4% by volume as oil (not as concentrate): Module UFP10: membrane IRIS 3042)

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

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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)

P = 1 bar, V = 1.17 m/s P = 1.5 bar, V = 1.4 m/s

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.

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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.

6.1.7 Minimum and maximum transmembrane pressure and power required

Transmembrane pressure and recirculation velocity are important factors in UF


process. In case of the pressure, many researches [11], [18] recommended that using moderate
pressure would reduce fouling, thus increasing operating time before cleaning. Increasing in
velocity will reduce polarization effect and lead to increasing of flux. However, using high
recirculation velocity inevitably cause high pressure drop, then the transmembrane pressure
will be increased accordingly.

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

For laminar flow,


64
f= {6.16b}
Re

For turbulent flow (Colebrook’s equation),


1 e/D 2.51 {6.16c}
= −2 ⋅ log( + )
f 0.5 3.7 Re ⋅ f 0.5

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.

The maximum transmembrane pressure will be controlled by the lower pressure


among 1) capillary pressure of oil droplet , 2) the maximum operating pressure, recommended
by membrane manufacturer. Capillary pressure of oil droplet of diameter rd and membrane
pore of diameter r can be calculated by the following equation [10].

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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)

Fig. 6.9 Relation between oil concentration VS. viscosity of emulsion

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

6.1.8 Conclusion and generalized model of UF

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.

Estimation of flux of mixed micro/macroemulsion is verified in section 6.1.4.


Furthermore, prediction of permeate flux of batch UF process is proven to be useful tool for
process design for it can provide general idea of evolution of permeate flux with time (section
6.1.5). The oil removal efficiency of UF is considered to be 100% providing that the pore size
is suitably chosen. Minimum transmembrane pressure is controlled by required pressure drop
across UF module at the design recirculation velocity, which is usually lower than 0.5 bar.
Maximum theoretical pressure is controlled by the lower value among capillary pressure and
manufacturer recommended maximum pressure. Normally the former is much higher than the
latter.

6.2 Nanofiltration and Reverse osmosis


NF and RO are the membrane processes that use very fine pore membranes. So it can
be retain almost all of components in the fluid stream and let only the water pass through.
Despite of their separation capability, they are normally costly and consume very high energy.
Thus, they are not economical choices for wastewater treatment. However, it is proven by our
lab [11], [18], [20] that it is useful for the post treatment of permeate from UF and MF for it
can retain dissolved pollutants such as surfactant and co-surfactant.

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

Table 6.3a Summary of RO data on oily wastewater treatment

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

Chapter 7 Heteroazeotropic Distillation


Heteroazeotropic distillation is a thermal treatment process that makes use of
vapor/liquid/liquid equilibrium (VLLE) to separate oil from water. Concepts of VLLE and
heteroazeotropic distillation are classical concepts for process engineers. However, the
application on oily wastewater treatment is not realized, or if any, very few.

Heteroazeoptropic distillation phenomena normally take place in a distillation column.


But, after condensation, evaporated water and hydrocarbons are condensed together and form
distillate mixture of hydrocarbons and water again.

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.

Another application of heteroazeotropic distillation is the steam stripping, in which


steam is supplied into mixture of relatively non-volatile and volatile components to strip the
volatile components from the mixture. The steam is this case will act as the entrainer to
extract the volatile components. This process can be viewed as the inverse process of
heteroazeotropic distillation. If the mixture is a hydrocarbon/water mixture, the water will act
as an entrainer. So it is called a self-entraining mixture.

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.

7.1 Theoretical model


Models or procedure for heteroazeotropic distillation, in our case, are based on non-
miscible mixture, like oil and water. For non-miscible binary mixture of water and
hydrocarbon, typical isobar diagram of VLLE is as shown in fig. 7.1.

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

Fig. 7.1 Isobar equilibrium diagram : Temperature-Concentration characteristic of


immiscible binary mixture

From the figure, we can set the steps of calculation to create isobar diagram as
follows,

1) Find bubble curve

For binary mixture


P = Π θb θb θb sat sat
A + B = Π A + Π B = PA + PB
{7.1}

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

Fig. 7.2 Graphical method to find heteroazeotropic temperature

114 II-70
Part II Generalization of model for oil-water separation process design

2) Find dew curves

From DALTON’s law


pA = yA ⋅ P {7.2a}
And
pB = yB ⋅ P {7.2b}

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

At any temperature between boiling points of pure substances and


heteroazotropic temperature (TH), we can find their corresponding vapor pressures (Π) from
fig. 7.3a. Then, from eq. 7.3, we can obtain yA and yB. This can be done easily, again, by the
graphical method as shown in fig. 7.3

Pressure A+B Calculate yA and yB from ΠA,ΠB


Temperature by eq. 7.3, then, plot T,y and T,y
A B
to obtain dew curves
Pure A
ΠA 1 T1
ΠB 1
ΠA 2 Pure B T2
ΠB 2 TH

Pure
T2 T1 Temperature hydrocarbon yB 1 yH yA 1x,y Pure H2O
yB 2 y A 2

Fig. 7.3 Graphical method to find dew curves

3) Find heteroazeotropic composition

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

From eq. 7.1,


Π θb
A
yH = {7.4}
Π θb +
A ΠB
θb

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.

7.2 Model verification


From section 7.1, we can find yH of pure hydrocarbon that can be used as an
extractant, i.e., alkane with the number of carbon from 6 atoms (n-Hexane) to 16 (n-
Hexadecane). Theoretical values of yH of each alkane are tabulated in table 7.1. To compare
the theoretical value to experimental result, we use data from LUCENA’s thesis on slop
treatment, using decane and dodecane. Comparison result in table 7.1 shows that the
theoretical values are slightly higher (3.5-5.5%) than observed values.

Table 7.1 Heterotropic temperature and composition from various extractants

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

7.3 Conclusion and generalized model of heteroazeotropic distillation


From data verification result, we can conclude that the theoretical model, stated in
section 7.1, provides very good prediction of heteroazotropic composition (yH). However, the
safety factor (S.F) of 1.05 or 1.1 is recommended. When we know the water volume in our
treated wastewater and determine the type of extractant, we can find quantity of extractant
required for extracting the water from the following equation. yH in eq. 7.5 will be by volume
basis, determined by the model in section 7.1. Heteroazeotropic distillation is suitable to treat
or recover valuable residue, such as slop or retentate from UF of cutting oil emulsion, which
is contaminated by relatively small amount of water.
(1 − y H )
Volumeextractant = S.F ⋅ Volume water {7.5}
yH

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

Part III Summary of researches: Oily wastewater treatment


Chapter 1 Oily or hydrocarbon-polluted wastewater
1.1 Introduction III-2
1.2 Hydrocarbons and oils III-2
1.2.1 Hydrocarbons III-2
1.2.2 Fats and oils III-7
1.2.3 Petroleum and petroleum products III-7
1.2.4 Oils in term of oily wastewater III-9
1.3 Other compositions of oily wastewater III-9
1.3.1 Surfactants III-9
1.3.2 Soaps III-10
1.3.3 Co-surfactants III-11
1.3.4 Suspended solids III-11
1.3.5 Other components III-11
1.4 Categories of oily wastewater III-11
1.4.1 Classification by the nature of the continuous phase III-11
1.4.2 Classification by the stability of oily wastewater III-11
1.4.3 Classification by the degree of dispersion III-12
1.5 Characteristics of certain oily wastewaters III-15
1.6 Standards, Laws, and Regulations III-16
Chapter 2 Overview for oily wastewater treatment process design
2.1 Decantation velocity and STOKE’s law III-21
2.2 Application of surface chemistry for oily wastewater treatment III-22
2.2.1 Liquid-gas and liquid-liquid interfaces III-22
2.2.2 Liquid-solid and liquid-liquid-solid interfaces III-25
2.2.3 Capillary pressure and LAPLACE’s law III-29
2.3 Important parameters in oily wastewater treatment and III-30
their method of analysis
2.3.1 Oil concentration III-30
2.3.2 Size distribution , spectrum or granulometry III-32
2.3.3 Other parameters III-38
2.4 Overview of oily wastewater treatment processes III-38
2.4.1 Decanter III-39
2.4.2 Coalescer III-39
2.4.3 Hydrocyclone III-39
2.4.4 Dissolved air flotation (DAF) III-40
2.4.5 Skimmer III-40
2.4.6 Membrane processes III-40
2.4.7 Thermal processes III-40
2.4.8 Chemical process III-41
2.4.9 Finishing processes III-41

III-i
Chapter 1 Oily or hydrocarbon-polluted wastewater

Content (Con’t)
Page

2.5 Determination of degree of treatment III-41


2.5.1 Overall degree of treatment III-41
2.5.2 Degree of treatment of each process III-41
Chapter 3 Oil skimmer
3.1 General III-45
3.1 Oil drum skimmer III-47
3.1.1 Working principles III-47
3.1.2 Design calculation and design consideration III-52
3.2 Oil disc skimmer III-54
3.2.1 Working principles III-54
3.2.2 Design calculation and design consideration III-56
3.3 Productivity comparison between drum and disc skimmer III-56
3.4 Advantage and disadvantage of drum and disc skimmer III-57
Chapter 4 Decanting
4.1 General III-59
4.2 Simple Decanter or API tank III-60
4.2.1 Working principles III-60
4.2.2 Design calculation III-62
4.2.3 Design considerations III-65
4.2.4 Construction of simple decanters III-66
4.3 Compact decanter III-69
4.3.1 Working principles III-69
4.3.2 Design calculation III-73
4.3.3 Design considerations III-75
4.3.4 Variations, advantage and disadvantage of compact III-76
decanters
Chapter 5 Coalescer

5.1 General III-78


5.2 Granular bed coalescer III-78
5.2.1 Working principles III-78
5.2.2 Design calculation III-92
5.2.3 Design consideration III-94
5.2.4 Variations, advantage and disadvantage of granular III-95
bed coalescer
5.3 Guide coalescer III-96
5.3.1 Working principles III-96
5.3.2 Design calculation III-98
5.3.3 Design consideration III-98

III-ii
Part III Summary of researches: Oily wastewater treatment

Content (Con’t)
Page

5.4 Fibrous Bed coalescer III-99


5.4.1 Working principles III-99
5.4.2 Design calculation III-109
5.4.3 Design consideration III-110
5.4.4 Variations, advantage and disadvantage of fibrous bed III-112
coalescer
Chapter 6 Dissolved air flotation
6.1 General III-115
6.2 Working principles III-116
6.2.1 Filter based model III-116
6.2.2 Population balance model III-121
6.2.3 Generalized model of DAF from combination of III-123
filtration based model and population balance model
6.2.4 Influent parameters III-124
6.3 Design calculation III-127
6.4 Design consideration and construction of DAF reactor III-137
6.5 Pressurized water system or saturator III-145
6.5.1 Working principle and design calculation III-145
6.5.2 Type of saturator and injection valve III-150
6.6 Variations, advantage and disadvantage of DAF III-153
Chapter 7 Hydrocyclone
7.1 General III-155
7.2 Two-phase hydrocyclone III-156
7.2.1 Working principles III-156
7.2.2 Design calculation III-172
7.2.3 Design considerations III-175
7.2.4 Variations, advantage and disadvantage of III-178
hydrocy clone
7.3 Three-phase hydrocyclone III-178
7.3.1 Working principles III-178
7.3.2 Design calculation and design consideration III-182
7.3.3 Advantage and disadvantage of three-phase III-182
hydrocyclone
Chapter 8 Membrane process
8.1 General III-183
8.1.1 Classification of membrane processes III-183
8.1.2 Mode of operation of membrane processes III-185
8.1.3 Membrane structure III-185
8.1.4 Membrane material III-186
8.1.5 Membrane module type III-189

III-iii
Chapter 1 Oily or hydrocarbon-polluted wastewater

Content (Con’t)
Page

8.2 Ultrafiltration (UF) III-194


8.2.1 Basic knowledge and working principles III-194
8.2.2 UF process design for oily wastewater treatment III-206
8.2.3 Design consideration and significant findings from III-221
GPI’s researches
8.3 Microfiltration (MF) III-232
8.3.1 Basic knowledge and working principles III-232
8.3.2 Significant findings on MF for oily wastewater III-233
treatment from GPI researches
8.4 Reverse osmosis (RO) III-235
8.4.1 Basic knowledge and working principles III-235
8.4.2 Significant findings on RO for oily wastewater III-236
treatment from GPI’s researches
8.5 Nanofiltration (NF) III-239
8.5.1 Basic knowledge and working principles III-239
8.5.2 Significant findings on NF for oily wastewater III-239
treatment from GPI’s researches
8.6 Comparison of membrane processes on emulsion treatment III-242
Chapter 9 Thermal processes
9.1 General III-245
9.2 Basic knowledge on distillation III-245
9.2.1 Basic knowledge on vapor/liquid equilibrium of III-245
mixtures
9.2.2 Equilibrium of various mixtures III-248
9.3 Heteroazeotropic distillation of oily wastewater III-250
9.3.1 Working principles III-250
9.3.2 Raoult’s law and Dalton’s law III-251
9.3.3 Calculation of azeotropic temperature and composition, III-252
dew curve and bubble curve.
9.3.4 Application of heteroazeotropic distillation on III-254
treatment of inverse emulsion or concentrated oily
wastewater
9.3.5 Application of heteroazeotropic distillation on III-257
treatment of the wastes polluted by trace hydrocarbons:
Steam stripping
9.3.6 Design calculation and design considerations III-257
9.4 Classical or conventional distillation of oily wastewater III-259
9.4.1 Working principles III-259
9.4.2 Significant findings on classical distillation for oily III-259
wastewater treatment from GPI’s researches

III-iv
Part III Summary of researches: Oily wastewater treatment

Content (Con’t)
Page

Chapter 10 Chemical treatment processes


10.1 General III-263
10.2 Basic knowledge III-264
10.2.1 Stability of the emulsion III-264
10.2.2 Surface-active agents III-264
10.2.3 Important properties to obtain stable emulsion III-266
10.2.4 Destabilization of emulsion III-268
10.3 Process design III-274
10.3.1 Rapid mixing III-275
10.3.2 Flocculator III-276
10.4 Design consideration III-278
Chapter 11 Finishing processes
11.1 General III-280
11.2 Biological treatment III-280
11.2.1 Basic knowledge III-280
11.2.2 Design consideration and significant finding on III-287
biological treatment for oily wastewater from GPI’s
researches
11.3 Adsorption III-288
11.3.1 Activated carbon (AC) III-289
11.3.2 Basic knowledge III-290
11.3.3 Design calculation III-295
Chapter 12 Guideline for treatment process selection and examples of treatment
processes for certain oily wastewaters
12.1 Guideline for treatment process selection III-297
12.1.1 Oil film III-297
12.1.2 Primary emulsion III-299
12.1.3 Secondary emulsion III-300
12.1.4 Macroemulsion and microemulsion III-301
12.1.5 Concentrated oily wastewater or refinery slops III-301
12.2 Examples of treatment processes for certain oily wastewaters III-302
12.2.1 Treatment of cutting oil emulsion III-302
12.2.2 Treatment of non-stabilized secondary emulsion III-303

III-v
Chapter 1 Oily or hydrocarbon-polluted wastewater

Table
Page

Table 1.2.1-1 Properties of some normal alkanes [1],[2] III-3


Table 1.2.1-2 Properties of some unsaturated aliphatic hydrocarbons [1],[2] III-5
Table 1.2.1-3 Properties of some benzene-series hydrocarbons [1],[2] III-6
Table 1.4.3-2 Summary of oily wastewater classification III-14
Table 1.5-1a Data of pollution from certain oils, oil products and serfactants. III-15
Table 1.6-1a Industrial effluent standard of Thailand III-17
Table 1.6-1b Industrial effluent standard of France (1998) III-18
Table 1.6-1c Industrial effluent standards of USA, categorized by pollutant sources III-19
Table 2.1-1 Summary of equations for rising velocity calculation [41] III-22
Table 2.2.1-1a Data of surface and interfacial tension (N/m) for some liquids at 20°C III-24
Table 2.2.2-1 Relation between contact angle, work adhesion, interfacial tension III-28
and spread coefficient of oil/water/solid system [42]
Table 2.3.2-1a Example of the decanting test of oil/water emulsio III-35
Table 2.3.2-1b Example of the decanting test of oil/water emulsion: sorting of the III-36
result from table 2.3.2-1a
Table 2.3.2-2 Criteria for visual observation of size distribution [22] III-37
Table 2.3.2-3 Criteria for visual observation of surface oil film [45] III-38
Table 3.2.1-1 Work adhesion and contact angles of oil, water and various materials III-48
Table 3.2.2-1 Critical surface tensions of certain materials [42] III-53
Table 5.4.1-1 Coalesced kerosene droplet size at various velocities and bed heights III-108
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 III-108
brush coalescer, hydrocyclone, theoretical and observed efficiency of the
coupling of coalescer/hydrocyclone [10]
Table 6.3-1 General design criteria of DAF from various literatures and III-130
manufactures (hydraulic loading rate us based on total flowrate)
Table 6.4-1 Data on efficiency and coagulant concentration of various oily III-141
wastewater treatments by DAF [51]
Table 6.5-1 Constant for calculation of concentration and quantity of gas for III-148
o
saturator design (Operating pressure of DAF = Patm, T = 20 C)
Table 6.5-2 Air characteristic and solubility at Patm [51] III-148
Table 8.1.4-1 Advantages and disadvantages of inorganic membrane [38] III-188
Table 8.1.4-2 Summary on membrane polymeric materials [38], [54], [57] III-189
Table 8.1.5-1 General characteristic of various membrane module [38], [54], [57] III-193
Table 8.2.2-1 General design criteria of UF process from various literatures III-208
Table 8.2.2-2 Summary of parameters of film model from UF researches on oily III-209
wastewater treatment (reference temperature = 20oC)
Table 8.2.2-3 Summary of parameters of resistance model from UF researches on oily III-210
wastewater treatment (ref. temperature = 20oC)

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

Fig. 4.1-1 Examples of decanters III-59


Fig. 4.2.1-1 Schematic and typical removal efficiency curve of simple decanter III-61
Fig. 4.2.2-1 Relation between rising velocity, hydraulic loading rate of simple III-64
decanter and kerosene droplet size
Figure (Con’t)
Page

Fig. 4.2.4-1 Variations of simple decanters III-67


Fig. 4.2.4-2 Important components of simple decanter III-67
Fig. 4.3.1-1 Schematic of PPI decanter III-69
Fig. 4.3.1-2 “Spiraloil” decanter a) Simple spiral b) Mixed spiral III-70
Fig. 4.3.1-3a Comparison between observed efficiency (1',2',3') and predicted III-71
efficiency (1,2,3) for Simple Spiral "Spiraloil" decanter
Fig. 4.3.1-3 Comparison between observed efficiency (1',2') and predicted III-71
efficiency (1,2) for Mixed Spiral "Spiraloil" decanter
Fig. 4.3.1-4 Effect of wettability of inserted plates III-72
Fig. 4.3.1-5 Schematic of inclined and horizontal decanter III-73
Fig. 4.3.4-1 Examples of compact decanters III-77
Fig. 5.1-1 Examples of coalescer III-79
Fig. 5.2.1.1 Schematic diagram of granular bed coalescer Mechanisms taking place III-79
inside the coalescer bed
Fig. 5.2.1-2 Schematic diagram of the 3 transport phenomena III-80
Fig. 5.2.1-3 Relation between oil droplet diameter and efficiency factors of each III-82
transportation phenomena
Fig. 5.2.1-4 Schematic of a single collector and the entire bed of coalescer III-83
Fig. 5.2.1-5 Phenomena in step 2: Adhesion-Coalescence III-85
Fig. 5.2.1-6 Phenomenon in step 3: “Salting out” or enlargemant of coalesced oil III-86
Fig. 5.2.1-7 Relation between experimental (or observed) efficiency factor and III-88
theoretical efficiency factor
Fig. 5.2.1-8 Typical relation between efficiency of granular bed coalescer and III-90
various parameters
Fig 5.2.2-1 Relation between cut size and coalescer dimension III-93
Fig. 5.3.1-1 Guide coalescer III-97
Fig. 5.4.1-1 Fibrous bed coalescer (Source: GPI lab) III-100
Fig. 5.4.1-2 Comparison between observed efficiency and predicted efficiency from III-102
SRIJAROONRAT's model, Verified by MA's and WANICHKUL's data.
Fig. 5.4.1-3 Relation between observed efficiency and predicted efficiency from III-104
random fibrous bed coalescer model and simple fibrous bed model
Fig. 5.4.1-4 Random or disorderly fibrous bed, used in the research of III-105
SRIJAROONRAT
Fig 5.4.1-5 Typical relation between efficiency of fibrous bed coalescer and various III-106
parameters

III-ix
Chapter 1 Oily or hydrocarbon-polluted wastewater

Fig. 5.4.3-1 Examples of fibrous bed coalescer casing III-111


Fig. 5.4.3-2 Various types of bed tested by WANICHKUL [11]: From left, a) III-112
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]
Figure (Con’t)
Page

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

Part 3 Summary of researches: Oily or hydrocarbon-polluted wastewater


treatment
In this part, we will use the data reviewed and verified in Part 1 and Part 2 to
summarize and compose the textbook that covers every research of Prof. AURELLE. The text
will consists of;

• Types and characteristics of oily wastewater


• Related theories on oily wastewater treatment
• Oily wastewater treatment processes, based mainly on researches of Prof.
AURELLE with additional data from well-proven literatures
• Special treatment process trains for some specific oily wastewater, based on
Professor AURELLE’ s researches

118 III-1
Chapter 1 Oily or hydrocarbon-polluted wastewater

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.

Therefor, it is obligatory to separate or remove oil from wastewater before disposal. In


European countries, standard for hydrocarbons in effluent is normally 5 mg/l (see section 1.6).

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 Hydrocarbons and oils


This section will provide background knowledge on definitions and basic chemistry of
various from of hydrocarbons and oils, normally present in oily wastewater.

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

1.2.1.1 Aliphatic Hydrocarbons

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.

1. Saturated aliphatic hydrocarbons

The saturated aliphatic hydrocarbons are the compounds in form of CnH2n+2.The


compounds are also called Methane series, Alkanes or Paraffins. Principle source of these
compounds is petroleum.

Properties: These saturated hydrocarbons are normally colorless, relatively


odorless, and relatively insoluble, particularly those with five or more carbon atoms. They are
present in form of gas, liquid and solid. Alkanes with 1 to 5 carbon atoms are gases at
ambient, those from C6 to C17 are liquids, and those above C17 are solids. Saturated aliphatic
hydrocarbons are quite inert toward most chemical reagents. They are readily soluble in many
solvents. However, their water solubility is relatively low. Solubility decreases with
increasing size or molecular weight, while boiling and melting point increase with increasing
molecular weight. Like common chemicals, properties of these hydrocarbons are subject to
change with pressure and temperature.

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.

Table. 1.2.1-1 Properties of some normal alkanes [1],[2]

Melting Specific Solubility


Boiling point
Name Formula point(°C/ 1 gravity (at 25
(°C/1 atm)
atm) (20/4°) °C)(mg/l)
Methane CH4 -182.4 -161.5 0.423 -162C
Ethane C2H6 -182.8 -88.6 0.545 -89C
Propane C3H8 -187.6 -42.1 0.493 25C
Butane C4H10 -138.2 -0.5 0.573 25C
n-Pentane C5H12 -129.7 36 0.626 40
n-Hexane C6H14 -95.3 68.7 0.655 10
Cyclohexane C6H14 55
n-Heptane C7H16 -90.6 98.5 0.684 3
25C
n-Octane C8H18 -56.8 125.6 0.699 0.66
Isooctane C8H18 2
Nonane C9H20 -53.5 150.8 0.718
Decane C10H22 -29.7 174.1 0.730

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;

• Oxidation with oxygen or air and heat:


Ex: CH4 + 2O2 Æ CO2 + 2H2O
• Substitution of hydrogen by halogens (scarcely occurs):
Ex: CH4 +Cl2 Æ HCl + CH3Cl
• Pyrolysis or cracking:
High-mol.-wt. Alkanes + Heat + Pressure Æ Low-mol.-wt. Alkanes + alkenes +
hydrogen + naphthenes +carbon
• Biological oxidation:
1st step: Alcohol forming (relatively slow)
Ex: 2CH3CH2CH3 + O2 +bact. Æ 2CH3CH2CH2OH
2nd step:
Ex: 2CH3CH2CH2OH + 5O2 Æ 3CO2 + 4H2O

2. Unsaturated aliphatic hydrocarbons

The unsaturated aliphatic hydrocarbons are can be divided into 4 groups,


catagorized by the number of double or triple bond in between carbon atoms, i.e., Alkenes,
Diolefins, Alkadienes, and Alkynes. Examples of these compounds and their properties are
shown in table 1.2.1-2. Solubility of these hydrocarbons is very low, normally less < 1.0
g/100g water.

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

Table. 1.2.1-2 Properties of some unsaturated aliphatic hydrocarbons [1],[2]

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

Basic chemical reactions: These compounds have many properties in common,


regardless of the type of compound in which they exist. Their important reactions are as
follow;

• Oxidation: Oxidizing agents, such as potassium permanganate, easily


oxidizes the compounds, in an aqueous solution, to glycol.
• Reduction: Hydrogen may be added to double or triple bonds under proper
temperature and pressure.
• Addition: Halohen acids, hypochlorous acids and halogens can be added at
double or triples bonds.
• Polymerization: The compounds prone to combine with each other, by their
unsaturated link, to form polymers.
• Biological oxidation: These compounds are easier to be biodegraded by
bacteria than saturated compounds.

3. Cyclic aliphatic compounds (Naphthenes)

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.

1.2.1.2 Aromatic hydrocarbons

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.

Table. 1.2.1-3 Properties of some benzene-series hydrocarbons [1],[2]

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

Fig. 1.2.1-2 Examples of benzene series

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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.

3. Chlorinated aromatic hydrocarbons

The compounds are derivatives of aromatic hydrocarbons that are of interest


because of their industrial importance, as well as, their toxicity. Well-known example of these
compounds is the polychlorinated biphenyls (PCBs), which are widely used as coolants in
transformer, plasticizer, solvents and hydraulic fluid for they are very stable. The compounds
are known to be very hazardous to human health.

1.2.1.3 Heterocyclic hydrocarbons

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.

1.2.2 Fats and oils

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.

Basic chemical reactions: Their important reactions are as follow;

• 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.

1.2.3 Petroleum and petroleum products

1.2.3.1 Petroleum or crude oils

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.

Crude oils normally consist of paraffins, olefins, naphthenes and aromatic


hydrocarbons. Oxygen, sulfur and nitrogen are present in the forms of compounds. Normally,
paraffins of 5 to 16 atoms of carbon are present in the form of liquid. They are important
components in gasoline and kerosene, as well as, desire components of diesel and lubricant
oil. Paraffins of 17 carbon atoms or more are solids.

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.

1.2.3.2 Petroleum products

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.

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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

Because of the difference in their properties, as stated above, it is helpful to know


which type of oils is present in the oily wastewater considering.

1.2.4 Oils in term of oily wastewater

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 Other compositions of oily wastewater


Apart from “oil” and water, oily wastewater can contain other substances that may
affect its properties, as well as selection and design of its treatment processes. Important
components of oily wastewater include:

1.3.1 Surfactants

In many applications, such as in cleansing processes, it is necessary to change the level


of free surface energy. By the surface energy (or interfacial tension, in case of liquid/liquid

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

1.3.1.1 Cationic 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.

1.3.1.2 Anionic surfactants

These surfactants are generally sodium or potassium salts. The common ones are
sulfates and sulfonates. The surface-active properties are contained in the anions.

1.3.1.3 Non-ionic surfactants

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.

1.3.1.4 Ampholytic (or amphoteric) surfactants

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.

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Part III Summary of researches: Oily wastewater treatment

1.3.3 Co-surfactants

In emulsions, especially microemulsion, they contain co-surfactants. These


compounds are normally alcohol, such as butyldiglycol, or benzylic alcohol. These
compounds are readily soluble in water thus provide good solubility to certain products, such
as cutting oil emulsion. They also increase the stability to the emulsion by promoting both
electrical stability and mechanical stability.

1.3.4 Suspended solids

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.

1.3.5 Other components

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.

1.4 Categories of oily wastewater


Oil/water mixture systems can be categorized by many criteria. However, as stated
before that the treatment processes summarized in this book are based mainly on separation
processes, the criteria, used to categorize these oil/water mixtures, are based upon physical
properties. There are 3 main criteria, i.e., the nature of continuous phase, the stability of oily
wastewater, and the degree of dispersion.

1.4.1 Classification by the nature of the continuous phase

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.

1.4.2 Classification by the stability of oily wastewater

By these criteria, oily wastewater can be divided into 2 groups:

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.

1.4.3 Classification by the degree of dispersion

This classification is based on rising velocity of oil droplet, which is controlled by


properties of the oil/water system and its size or its degree of dispersion. For common
treatment processes, this velocity is governed by STOKES law. Theory of rising velocity will
be described in chapter 2. By these criteria, oily wastewater can be divided into 5 groups:

1. Film or layer of oil on water surface

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.

Classification of primary and secondary emulsion can be summarized as shown


in fig. 1.4.3-1.

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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

This type of emulsion contains droplet size between 10 to 60 nm. It contains


extensive amount of surfactants and cosurfactants. Since the droplets is very small, this type
of emulsion is usually transparent (sometimes, translucent if dyes are present or amount of o-
surfactants is low). A common example of this emulsion is cutting oil microemulsion.

Details of microemulsion amd macroemulsion will be described in details in the


chapter 10, related to “emulsion destabilization”.

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

Solubility Forms of oil Continuous phase Stability Dispersion Type of emulsion

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

Non < 20 μ Secondary


Direct Non Secondary
Direct stabilized emulsion
stabilized emulsion
<1μ Macro-
Stabilized Macro-
Stabilized emulsion
emulsion
< 60 nm Micro-
Micro-
emulsion
emulsion

Fig. 1.4.3-2 Classification of oily wastewater by degree of dispersion

Table. 1.4.3-2 Summary of oily wastewater classification

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

1.5 Characteristics of certain oily wastewaters


From the previous sections, it can be concluded that the characteristics of oily
wastewater can greatly very from wide varieties of oils and compositions of oily wastewater,
as well as degree of dispersion. So, the best solution to characterize the oily wastewater is to
have it analyzed by standard methods to get important data necessary for treatment process
consideration. Important parameters and their method of analysis will be present in chapter 2.
However, in this section, data of oily wastewater from many literatures, include GPI’s
researches, will be presented as shown in table 1.5-1. These data can be used as guideline for
treatment process consideration, when the real data is not available.

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

1.6 Standards, Laws, and Regulations


To study or design wastewater treatment process, it is necessary to determine the
quality of the effluent after the treatment. In case that the effluent will be recycled or reused,
the treatment process will be designed to meet the requirement for reuse or recycle. However,
in general case, the effluent will be discharged to public collection system or receiving water
bodies. To do so, The effluent quality will have to meet the requirement of that receiving
water bodies, set by local laws, standards, or related regulations. For oily wastewater
treatment process, apart from oil concentration, other parameters that usually relate to oil or
come with oil product, e.g. BOD and COD (from surfactants in cutting oil), phenol (from
petroleum product), should be considered.

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

Table 1.6-1a Industrial effluent standard of Thailand

Parameters Standard Values Method for Examination


1. pH value 5.5-9.0 pH Meter
not more than 3,000 mg/l depending on receiving
water or type of industry under consideration of
2. Total Dissolved PCC but not exceed 5,000 mg/l Dry Evaporation 103-105
Solids (TDS) not more than 5,000 mg/l exceed TDS of receiving °C, 1 hour
water having salinity of more than 2,000 mg/l or
TDS of sea if discharge to sea
not more than 50 mg/l depending on receiving
3. Suspended solids water or type of industry or wastewater treatment
Glass Fiber Filter Disc
(SS) system under consideration of PCC but not exceed
150 mg/l
4. Temperature not more than 40°C Thermometer on-site
5. Color and Odor not objectionable Not specified
6. Sulphide as H2S not more than 1.0 mg/l Titrate
Distillation and Pyridine
7. Cyanide as HCN not more than 0.2 mg/l
Barbituric Acid Method
not more than 5.0 mg/l depending of receiving
8. Fat, Oil & Grease Solvent Extraction by
water or type of industry under consideration of
(FOG) Weight
PCC but not exceed 15.0 mg/l
9. Formaldehyde not more than 1.0 mg/l Spectrophotometry
Distillation and 4-
10.Phenols not more than 1.0 mg/l
Aminoantipyrine Method
11.Free Chlorine not more than 1.0 mg/l lodometric Method
12.Pesticides not detectable Gas-Chromatography
13.Biochemical not more than 20 mg/l depending on receiving
-Azide Modification at 20
Oxygen Demand water or type of industry under consideration of
°C , 5 days
(BOD) PCC but not exceed 60 mg/l
not more than 100 mg/l depending on receiving
14.Total Kjedahl
water or type of industry under consideration of Kjeldahl
Nitrogen (TKN)
PCC but not exceed 200 mg/l
not more than 120 mg/l depending on receiving
15.Chemical Oxygen Potassium Dichromate
water of type of industry under consideration of
Demand (COD) Digestion
PCC but not exceed 400 mg/l
16.Heavy metals
1. Zinc (Zn) not more than 5.0 mg/l
2. Chromium (6) not more than 0.25 mg/l
Atomic Absorption
3. Chromium (3) not more than 0.75 mg/l Spectro Photometry; Direct
4. Copper (Cu) not more than 2.0 mg/l Aspiration or Plasma
5. Cadmium (Cd) not more than 0.03 mg/l Emission Spectroscopy ;
6. Barium (Ba) not more than 1.0 mg/l Inductively Coupled Plama
7. Lead (Pb) not more than 0.2 mg/l : ICP
8. Nickel (Ni) not more than 1.0 mg/l
9. Manganese (Mn) not more than 5.0 mg/l
Atomic Absorption
(AA)Spectrophotometry;
10. Arsenic (As) not more than 0.25 mg/l Hydride Generation, or
Plasma Emission
Spectroscopy; Inductively
11. Selenium (Se) not more than 0.02 mg/l Coupled Plasma : ICP
12. Mercury (Hg) not more than 0.005 mg/l AA Cold Vapour

134 III-17
Chapter 1 Oily or hydrocarbon-polluted wastewater

Table 1.6-1b Industrial effluent standard of France (1998)

Parameters Standard Values Method for Examination


1. pH value 5.5-9.5, 9.5 if there is alkaline neutralization pH Meter
2. Total Dissolved Dry Evaporation 103-105
Depend on receiving water or type of industry
Solids (TDS) °C, 1 hour
100 mg/l for maximum daily rate not more than 15
3. Total suspended
kg/d, 35 mg/l for those that exceed, 150 mg/l for Glass Fiber Filter Disc
solids (TSS)
lagoon treatment system
4. Temperature Not more than 30°C Thermometer on-site
5. Color and Odor Not specified Not specified
6. Sulphide as H2S Not specified Not specified
7. Cyanide as HCN not more than 0.1 mg/l Not specified
8. Fat, Oil & Grease
Depend of receiving water or type of industry Not specified
(FOG)
9. Formaldehyde Not specified Not specified
10.Phenols not more than 0.3 mg/l Not specified
11.Organic
halogenated not more than 1.0 mg/l if discharge > 30 g/d As AOX or EOX
compounds
12.Pesticides Not specified Not specified
13.Biochemical Depend on receiving water or type of industry,
Oxygen Demand Level A to D: 30-100 mg/l, Level E: not more than At 20 °C , 5 days
(BOD) 30 mg/l, Level F: not more than 15 mg/l
Depend on receiving water or type of industry,
TKN and ammonia N not more than 10-40 mg/l for
14.Nitrogen (N) level NK1 to NK3, Kjeldahl
TKN+AmmoniaN+Nitrite+Nitrate not more than 20
mg/l for level NGL1 and NGL2.
Depend on receiving water or type of industry,
15.Chemical Oxygen Potassium permanganate
Level A to D: 125-150 mg/l, Level E: not more than
Demand (COD) Digestion
50 mg/l, Level F: not more than 90 mg/l
16.Heavy metals
1. Zinc (Zn) not more than 2.0 mg/l if discharge > 20 g/d
2. Chromium (6} not more than 0.1 mg/l if discharge > 1 g/d
3. Chromium (total) not more than 0.5 mg/l if discharge > 5 g/d
4. Copper (Cu) not more than 0.5 mg/l if discharge > 5 g/d
5. Cadmium (Cd) Not specified
6. Barium (Ba) Not specified Not specified
7. Lead (Pb) not more than 0.5 mg/l if discharge > 5 g/d
8. Nickel (Ni) not more than 0.5 mg/l if discharge > 5 g/d
9. Manganese (Mn) not more than 1.0 mg/l if discharge > 5 g/d
10. Tin not more than 2.0 mg/l if discharge > 20 g/d
11. Iron, aluminium not more than 5.0 mg/l if discharge > 20 g/d
12. Mercury (Hg) Not specified
Note: 1 Extracted form Les normes de rejet des eaux usées et d'effluents (normes guides) (Source:
Web site of Grenoble eau pure)
2. 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.

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Part III Summary of researches: Oily wastewater treatment

Table 1.6-1c Industrial effluent standards of USA, categorized by pollutant sources

(1) CFR 40 part 419—Petroleum refining point source category

Kg / 1000 m3 of feed stock


Effluent characteristics
Average of daily values for 30
Maximum for any 1 day
consecutive days shall not exceed
BOD5 34.6 18.4
COD 210.0 109.0
TSS 23.4 14.8
Oil and grease 11.1 5.9
Phenolic compound 0.25 0.120
Ammonia as N 23.4 10.6
Sulfide 0.22 0.099
Total chromium 0.52 0.30
Chromium (hexavalent) 0.046 0.020
pH 6.0-9.0 6.0-9.0
Note: 1 The limits shown in the table are to be multiplied by the process factors and size factor
to calculate the maximum for any one day and maximum average of daily values for
thirty consecutive days

(2) CFR 40 part 437—The centralized waste treatment point source category

Effluent characteristics Maximum daily (mg/l) Maximum monthly average (mg/l)


Oil and grease 127.0 38.0
pH 6.0-9.0 6.0-9.0
TSS 74.1 30.6
Metals
Arsenic 2.95 1.33
Cadmium 0.0172 0.0102
Chromium 0.746 0.323
Cobalt 56.4 18.8
Copper 0.500 0.242
Lead 0.350 0.160
Mercury 0.0172 0.00647
Tin 0.335 0.165
Zinc 8.26 4.50
Organic parameters
Bis(2-ethylhexyl) phthalate 0.215 0.101
Butylbenzyl phthalate 0.188 0.0887
Carbazole 0.598 0.276
n-Decane 0.948 0.437
Fluoranthene 0.0537 0.0268
n-Octadecane 0.589 0.302
Note: 1The limits shown in the table arebased on best practicable control technology currently
available (BPT)
General note: 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.

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

Kg / 1000 kg of anhydrous product


Effluent characteristics
Average of daily values for 30
Maximum for any 1 day
consecutive days shall not exceed

BOD5 0.90 0.30


COD 4.05 1.35
TSS 0.09 0.03
Surfactants 0.90 0.30
Oil and grease 0.15 0.05
pH 6.0-9.0 6.0-9.0

(4) CFR 40 part 438—Metal products and machinery point source category

Effluent characteristics Maximum daily (mg/l)

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.

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Chapter 2 Overview for oily wastewater treatment process design


This chapter provides basic theories, which are important to understand the
phenomena, taking place in oily wastewater, and to understand operating principle of oily
wastewater treatment processes. The analysis methods of some important parameters and
overview of oily wastewater treatment processes are also described.

2.1 Decantation velocity and STOKES law


Oily wastewater can be considered as an immiscible binary mixture system of oil and
water, with the oil as a dispersed phase, because the solubility of oil in water is very low (<
1g/ 100 g of water). So the oil will be present in the water in form of oil droplets, which is the
result of surface tension, which will be described in the next section. Because of its low
specific gravity, these droplets will try to separate themselves from the water by “floating” or
“rising” to the water surface. Consider a single oil drop, when the oil drop is rising, it will be
subject to 2 forces as shown in fig. 2.1-1. The first one (F1) is the gravitational force,
calculated from oil drop size and density difference of oil and water (eq. 2.1.1). The second
force is called “drag force”, which is the resultant of the resistance inertia force and viscous
force (eq. 2.1.2).

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.

Table. 2.1-1 Summary of equations for rising velocity calculation [41]

Equation Flow Regime Re Cd V

STOKES law Laminar 10-4 - 1 24 ( ρ − ρ c ) gd 2


2.1.4} Re or
18μ c
ρ
0.545( − 1)γ −1 d 2
ρc
ALLEN’s law Intermediate 1 - 10 26 ρ
0.57( − 1) 0.814 γ − 0.625 d 1.439
2.1.5a,b,c} Re 0.77 ρc
10 – 100 20 ρ
0.73( − 1) 0.741 γ −0.481 d 1.222
Re 0.65 ρc
100 – 1000 4.92 ρ
1.81( − 1) 0.604 γ −0.209 d 0.813
Re 0.316 ρc
NEWTON’s law Tubulent 103 - 2*105 0.44 ρ
5.40( − 1) 0.5 d 0.5
{2.1.6}
(Eddy flow) ρc
Turbulent > 2*105 Newton’s law is applicable

2.2 Application of surface chemistry for oily wastewater treatment


2.2.1 Liquid-gas and liquid-liquid interfaces

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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Fig. 2.2.1-1 Force diagram of oil drop in water

Surface tension (between liquid-air) or interfacial tension (between liquid-liquid or


liquid-solid) [40] is defined as the work required to increase, isothermally and reversibly, the
surface or interface area by 1 unit. Sometimes, it is also called “surface free energy” or
“surface energy” (esp. in case of solid surface). It is measured in unit of work per unit area
(ex. Nm/m2) or unit of force per unit length (ex. N/m or dyne/cm).

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

Fig. 2.2.1-2 Model for Visualization of γ

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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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:

Water Oil • We increase the surface of oil and water


by γo and γw, respectively.
• Then we attach the oil and water surface
γo
together. For this, we recover an amount
γo/w of energy, called “adhesion work”
F
γw
Fig. 2.2.1-3 Model for visualization of
adhesion work

2.2.2 Liquid-solid and liquid-liquid-solid interfaces

2.2.2.1 Wetting, Contact angles, Adhesion work, and YOUNG’s equation

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

Oil droplet γow


θso γso
γsw

Solid

Fig. 2.2.2-1 Diagram of Oil drop on solid surface in water

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

For oil/water/solid system


γ sw = γ so + γ ow cos θ so {2.2.4a}
For oil/air/solid system
γ s = γ so + γ o cos θ so {2.2.4b}

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.

For oil/water/solid system


Wadh ( so ) w = γ ow (1 + cos θ so ) {2.2.5a}

For oil/air/solid system


Wadh ( so) = γ o (1 + cos θ so ) {2.2.5b}

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.

2.2.2.2 Cohesion work and Spreading

Cohesion work: If we have a tank of


oil and we want to separate the oil to create
air-oil surface of 1 unit area within the oil
bulk, we can apply eq. 2.2.1 to find the
work required. In this case, we will have 2
surface of oil. Each surface has the area of
1 unit (see fig. 2.2.2-2).

From eq. 2.2.1, the required work


will be calculated as shown in eq. 2.2.6a,
Fig. 2.2.2-2 Model for visualization of
which we call “Cohesion work”.
cohesion work
W c (o ) = 2γ {2.2.6a}

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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Spreading: From YOUNG-DUPRE’s equation, if contact angle is zero, it means that


the oil surface is parallel to solid surface. In this case, we call that the oil spreads over the
solid surface. In this case, adhesion work can be calculated as follows:
W adh ( so ) w = γ ow (1 + cos(0)) = 2γ ow {2.2.7}

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.

cos(θ ' so ) = r ⋅ cos(θ so ) {2.2.10}

θ θ θ θ

Smooth Rough Smooth Rough

Fig. 2.2.2-3 Effect of surface roughness on contact angle

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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]

Contact angle Relation beween


Wadh(so)w φ Characteristic of oil drop
θso interfacial tension

= 0° > 2γow >0 γsw > γso + γow γow


γso γsw

= 0° = 2γow =0 γsw = γso + γow γow


γso γsw

γow
0°<θso<90o γow <W< 2γow <0 γsw > γso θ
γso γsw

γow
= 90o W = γow <0 γsw = γso θ
γso γsw

γow

90°<θso<180o 0<W < γow <0 γsw < γso


θ
γso γsw

=180o W=0 <0 γso = γsw+γow γow


γso γsw

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2.2.3 Capillary pressure and LAPLACE’s law

2.2.3.1 LAPLACE’s law

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.

2.2.3.2 Capillary pressure

Capillary effect is an important phenomenon for oil/water separation process when we


consider flowing through porous media, such as ultrafiltration membrane. This phenomenon
will be described by fig. 2.2.3-2. When the tube with very small diameter (capillary tube) is
plunged into liquid surface. Because of surface tension of liquid, the liquid will rise into the
tube to the height h. From equilibrium, we can calculate the capillary pressure (Pc) as follow:
Pb − Patm = ρgh = Pc {2.2.12}
From LAPLACE’s law,
2γ 2γ cos θ
Pb − Patm = = {2.2.13}
R r
From eq. 2.2.12 and 2.2.13,
2γ cos θ
Pc = {2.2.14a}
r
And
2γ cos θ
h= {2.2.14b}
ρgr

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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)

Fig. 2.2.3-2 Diagram for visualizing the capillary pressure

2.3 Important parameters in oily wastewater treatment and their method


of analysis
From chapter 1, it shows that characteristics of oily wastewater can greatly vary,
depending on their sources, degree of dispersion and compositions. However, to design the
oily wastewater treatment process, it is, somehow, necessary to know its characteristic. In
case that characteristic data is not available, we have to have it analyzed by an acceptable
method. This chapter will suggest the important parameters necessary to consider or design
the treatment processes, esp. those that are included in this book.

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.

2.3.1 Oil concentration

Oil concentration is one of important parameters for oily wastewater treatment


consideration or design. Effluent standard is set by oil concentration. Inlet oil concentration
and effluent standard are the parameters that determine the degree of treatment required.
Furthermore, some separation processes are limited by oil concentration. Normally, the oil
concentration is reported in the form of mg/l. However, for inlet oil concentration, it may be
measured in the form of % by volume.

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Method of analysis

1. Solvent extraction [1]

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,

• Partition-gravimetric method: Hexane will be used to extract the oil. Then


it will be separated from water and then evaporated. The residue will be used
as an inditator of oil and grease content.
• Partition-infrared method: CFC-113 will be used as extractant. Then it will
be measured with infrared scanning. This method is faster than gravimetric
method. The accuracy depends on selection of oil standards for calibration.
The oil used for calibration should be the same type as oil in the wastewater.
• Soxhlet extraction: It involves the initial step of acidification and then
hexane extraction. This method tends to retain more volatile hydrocarbons.
However, it is time consuming.
• Hydrocarbon analysis: Silica gel is added to hexane to remove fatty
materials. And then the hexane will be analyzed by the first method.

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

If total oxygen demand (TOD) measuring instrument is available, oil


concentration can also be measured as TOD. Again, the main advantage of this method is its
fast response. However, it will be difficult to distinguish between TOD of oil and other
substances, especially surfactants and co-surfactants. So this fact should be taken into
account. In GPI lab, some researchers use this method to measure the oil concentration. The
data from the researches are presented in chapter 1. It must be noted that TOD includes
oxygen demand from non-organic factors, such as ammonia, sulfide. Thus its value is usually
higher than BOD.

4. Other methods

Total organic carbon (TOC) is also widely used to measure pollutant


concentration. Its working principle bases on oxidizing of the sample, usually at high
temperature, to convert carbons to carbondioxide, which will be measured by IR, UV probe.
TOC machine can cover from ppm to ppt range. It is very useful for online control. But it does
not account for nitrogen compounds, which have much higher oxygen demand than carbons.

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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.

2.3.2 Size distribution , spectrum or granulometry

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

1. Particle size analyzer or Granulometer

“Particle size analyzer” or “granulometer” or “nanosizer” is the specific


equipment designed for measuring size and quantity of particle in liquid. There are many
generations of granulometer with different operating principles. However, present
granulometers are based on laser detection technology. This equipment can be used to
measure size distribution of oil droplet or particle down to the range of submicron size
(depend on manufacturers). It can report the result in the form of table or graph of size

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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.

Fig. 2.3.2-2 Granulometer (Source: above - Ankermid Techcross / below - CILAS)

2. Decanting test

When the use of granulometer is not available, there is a simple method to


measure the size distribution, which is called “decanting test”. This method requires a simple
equipment as shown in fig. 2.3.2-3.

h4
h3
h2
h1

0 min 5 min 10 min …. t min

Fig. 2.3.2-3 Decanting test column

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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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Table 2.3.2-1a Example of the decanting test of oil/water emulsion

At sampling height % accumulated C/Co Corresponding droplet


Corresponding rising Oil concentration of
Time (from the bottom when d < size (from STOKES
velocity the sample
of column) dEht law)

h Vh,t Ch,t % Ch,t/Co dEh,t


sec m m/s mg/l % micron
0 0.5 86 100
900 0.5 5.56E-04 57 66.28 72.8
1800 0.5 2.78E-04 25 29.07 51.4
2700 0.5 1.85E-04 8 9.30 42.0
3600 0.5 1.39E-04 3 3.49 36.4
5400 0.5 9.26E-05 1 1.16 29.7
7200 0.5 6.94E-05 0 0.00 25.7
0 1.25 86 100
900 1.25 1.39E-03 83 96.51 115.0
1800 1.25 6.94E-04 63 73.26 81.3
2700 1.25 4.63E-04 49 56.98 66.4
3600 1.25 3.47E-04 37 43.02 57.5
5400 1.25 2.31E-04 16 18.60 47.0
7200 1.25 1.74E-04 6 6.98 40.7
7200 1.25 2.06E-03 80 93.02 140.0

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

dE Vh,t % Ch,t/Co %C/Co


micron m/s % %
25.72 6.94E-05 0
29.70 9.26E-05 1.16 1.16
36.38 1.39E-04 3.49 2.33
40.67 1.74E-04 6.98 3.49
42.00 1.85E-04 9.30 2.33
46.96 2.31E-04 18.60 9.30
51.44 2.78E-04 29.07 10.47
57.52 3.47E-04 43.02 13.95
66.41 4.63E-04 56.98 13.95
72.75 5.56E-04 66.28 9.30
81.34 6.94E-04 73.26 6.98
115.03 1.39E-03 96.51 23.26

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)

Accumulated conc. curve h = 0.5 m h = 1.25 m

Fig. 2.3.2-4 Relation between accumulated C/Co (% of C/Co when the droplet size is equal or smaller than the

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Part III Summary of researches: Oily wastewater treatment

given dE) and oil droplet size


25

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

To roughly estimate the granulometry of oily wastewater, there are simple


criteria for visual observation as shown in table 2.3.2-2. However, these criteria may be used
only when the wastewater is not polluted by suspended solids or other substances that makes
it opaque. In case of surface oil layer, API [45] recommended useful guide to evaluate oil
thickness as shown in table 2.3.2-3.

Table 2.3.2-2 Criteria for visual observation of size distribution [22]

Visual aspect Average particle size Example


Particles visible by eye 500 micron Very fine sand
Not clearly visible by eye 100 micron Starch
Opaque milky 10 micron Milk
Whitish milky 1 micron Homogenized milk
Bluish milky 0.1 micron Macroemulsion
Semitransparent 50 nm Microemulsion
Transparent 10 nm Microemulsion
Transparent 2-6 nm Micelles
Transparent 1 nm Molecules

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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]

Film thickness Approximate volume of oil


Appearance
(micron) for film 1 km2 in area (l)
38.1 Barely visible under most 37
favorable light conditions
76.2 Visible as silvery sheen on 74
surface of water
152.4 First trace of color may be 148
observed
304.8 Bright bands of color are visible 296
1016 (1 mm) Colors begin to turn dull 985
2032 (2 mm) Colors are much darker 1970

2.3.3 Other parameters

Each treatment process may require some special data for its calculation. However,
common data required by several processes include:

• Interfacial tension
• Viscosity of oil

These data can be analyzed by specialized laboratories. However, if we know the


source of the oily wastewater, we can estimate these parameters. Even when we can not
specify the exact source of oil, we still can estimate them, using the general data of oil or from
references, without too much error. These data can also be found in chapter 1 and this chapter.

2.4 Overview of oily wastewater treatment processes


As hydrocarbon or oil requires a great amount of oxygen or oxidizing agent to oxidize,
moreover, the hydrocarbon is relatively difficult to biodegrade, thus, it becomes clear that the
use of biological treatment with high-concentration oily wastewater may not be the
economical alternative. Besides there are possibilities to reuse or recover the hydrocarbons
in the wastewater. Then, if possible, it is reasonable to separate oil from the wastewater,
rather than destroy or change them into other forms.

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).

Thus, to design an efficient oily wastewater treatment process, designer should


understand working principle and limitation of each process. The following chapters will
devote to each oily wastewater treatment processes studied and perfected by Prof.
AURELLE’s team within 3 decades. However, in this section, description of each process will
be described briefly as follows,

STOKES law-based processes

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

Coalescer is a modified or accelerated STOKES law-based separation process by


increasing the size of oil droplet. Since rising velocity is proportional to square of droplet
size, theoretically, coalescer can enhance oil separation efficiency more rapidly than other
process that work on other parameters. AURELLE is one of the pioneers on granular bed
coalescer, which was patented and, later, commercialized by Elf Total Fina. He also initiated
other type of coalescer, i.e, granular bed coalscer with guide to handle wastewater with high
oil concentration, fibrouse bed coalescer that can handle wastewater with SS. Coalescer can
handle secondary emulsion effectively. However, its performance with stabilized emulsion is
not so good since the droplets are very table and unlikely to coalesce with each other.
Coalescer is described in details in chapter 5.

2.4.3 Hydrocyclone

Hydrocyclone is a modified or accelerated STOKES law-based separation process by


increasing the acceleration of the system. Hydrocyclone replaces gravity acceleration (g)
with centrifugal acceleration, which can reach several hundreds times of g. Thus it is very
compact separation process. AURELLE and MA had initiated three-phase hydrocyclone that
can separate oil, solids and water simulteneously. Hydrocyclone use its inlet flow energy to

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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.

2.4.4 Dissolved air flotation (DAF)

DAF is a modified or accelerated STOKES law-based separation process by


decreasing density difference between oil and water. It can be obtained by addition of gas
bubble or air bubble to wastewater to form agglomerates with oil droplets. Since air or gas has
low density the agglomerates, then, has lower density than oil drops, resulting in higher rising
velocity. DAF is noted for its versatility. It can separate both solids and oil. Its efficiency
depends on formation of oil-bubble agglomeration. Thus its performance is low if droplets are
very small, since collision between air bubble and oil drops is difficult. In practice, DAF will
be used after coagulation-flocculation process, which can increase the droplet sizes
chemically. DAF is described in details in chapter 7.

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.

2.4.6 Membrane processes

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.

2.4.7 Thermal processes

Thermal process is the separation process based on thermodynamic properties of


oil/water mixture. GPI lab emphasizes on heteroazeotropic distillation, which can be carried
out at the temperature that is lower than those of pure water and pure hydrocarbons. It is
achieved by addition of proper hydrocarbons, called entrainer or extractant, into the
wastewater to azeotrope point, where oil, water and vapor co-exist, during distillation. The
process can be used to separate water from refinery slops and permeate from membrane

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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.

2.4.8 Chemical process

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.

2.4.9 Finishing processes

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.

2.5 Determination of degree of treatment


2.5.1 Overall degree of treatment

Before designing oily wastewater process, required overall degree of treatment or


effluent quality of the treatment system must be set. In case that the effluent is discharged to
public receiving water body, such as sewage system or natural stream, the final effluent
quality must conform to every applicable law. Examples of effluent standards are shown in
chapter 1. In case that the water is recycled or reused, required water quality for those
purposes, such as standard of recycled water quality, standard of recycled cooling water, etc.,
will determine the overall degree of treatment.

2.5.2 Degree of treatment of each process

Since the performance of every treatment process depends mainly on wastewater


characteristic, for existing facilities, wastewater must be thoroughly analyzed to obtain its
detailed characteristic. For new facilities, its characteristic must be carefully estimated. In
case of oily wastewater, performances of oil separation processes are based on degree of
dispersion and stability of the wastewater. When these data are available and limitation as
well as expected performance of each treatment process is thoroughly understand, it is
possible to select feasible process train that can treat the wastewater to meet the required
degree of treatment.

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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.

2.5.2.1 Graded efficiency and total removal efficiency

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 ,overall = (1 − (1 − η d ,1 )(1 − η d .2 )....( 1 − η d ,i )) ⋅ 100 % {2.5.1a}

∑ (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

Where ηoverall = Overall efficiency of the treatment process train


ηd,overall = Graded removal efficiency of the treatment process train
ηd,i = Graded removal efficiency of the process “i”, calculated by
equation of each process shown in the following chapters
ηt,i = Total removal efficiency of the process “i”
Co = Oil inlet concentration of the treatment process train
Co,i = Oil inlet concentration of the process “i”
Cod,i = Graded oil inlet concentration of the process “i”
i = the number of processes in the process train, i ≥ 1

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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2.5.2.2 Cut size determination

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.

Acc. % ηR = Required degree


ηoverall
(by weight) of treatment

100%
100%
ηR
Required degree
of treatment

Theo. eff
Real eff.

Real Droplet diameter


Theo. Droplet size cut size
Theo.
cut size
cut size

Fig. 2.5.2-1 Cut size determination

2.5.2.3 Economics of the processes

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).

Technical acceptable range


η

Required degree
of treatment

Overall eff.
Hydrocyclone
Coalescer

Size or cost
Most suitable
(economic) size

Fig. 2.2.5-2 Economics of processes (least cost criteria)

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

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.

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Part III Summary of researches: Oily wastewater treatment

a) Disc skimmer (source: Highland tank) b) Belt skimmer (Source: Ultraspin)

c) Drum skimmer (source: ELF/GPI lab) d) Mop skimmer (source: Ultraspin)

e) Weir skimmer (Source: Skimoil) f) Pump skimmer (Source: Ro cleandesmi)

g) Dispersant spray (Source: Ro-cleandesmi) h) Absorbent (Source: Ro-cleandesmi)

Fig. 3.1-1 Examples of oil skimming devices

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Chapter 3 Oil skimmer

3.2 Oil drum skimmer


3.2.1 Working principles

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.

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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.

PTFE PP PVC Water Stainless steel


(19) (30) (39) (72) (> 72)

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

Contact angle of oil Wadh(so)w = Wadh(sw)o =


Material
drop in water (θ) (γow(1+cos θ)) (γow(1+cos (180−θ))
Stainless steel (SS) 124o 0.01543 N/m 0.05457 N/m
o
PVC 26 0.06650 N/m 0.0035 N/m
PP 17o 0.0685 N/m 0.0015 N/m
PTFE 47o 0.0589 N/m 0.0111 N/m

Note: The oil used is kerosene. γow (at 20o C) = 35 dyne/cm.

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.

3.2.1.1 Exposure history

Another important characteristic of material related to oil selectivity is the “exposure


history” or the order and duration of contact between solid and liquids. THANGTONGTAWI
study shows that,

Material of high critical surface tension

• 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.

Material of medium critical surface tension (PVC, PP, etc.)

• 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.

Material of very low critical surface tension (PTFE, etc.)

• 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.

3.2.1.2 Mathematical model of drum skimmer

Mathematical model of oil drum skimmer, proposed by THANGTONGTAWI, was


derived from dimensional analysis approach, using Buckingham Pi theory under a wide range
of material and wastewater properties as well as operating parameters. The model is as shown
below.

0.486
3.035D1.541N1.541ν o L
P= {3.2.1}
g 0.514

Where P = Oil productivity of the skimmer (m3/s)


D = Diameter of skimmer (m)
N = Rotational speed of the skimmer (rev/s)
νo = Kinematics viscosity of oil (m2/s)
L = Length of the skimmer (m)
G = Gravitational acceleration (m/s2)
γo = Superficial tension of oil (kg/s2 or N/m = 1000 dyne/cm)

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Part III Summary of researches: Oily wastewater treatment

The model will be valid when these conditions are satisfied, i.e.;

• Superficial tension of oil is in the range of 27 – 34 dynes/cm, which practically


covers all common oil.
• Capillary number (Ca = μo V/γo) is in the range of 0.2 – 1.0.
• Oil density is around 0.79 – 0.83 kg/m3. Oil dynamic viscosity (μ) tested is
between 1.35x10-3 to 291x10-3 (N.s)/m2 (1.35-291 cp).
• Peripheral or tip velocity should not be greater than 0.8 m/s. To avoid water
entraining, velocity of 0.44 m/s or less is recommended.
• Recommended minimum immersion depth is 1.0-2.0 cm.
• Drum skimmer surface used for model development is polypropylene. But it is
proven to be valid for SS, PVC, and PTFE [5]. As shown in fig. 3.2.1-2.

Oil removal efficiency of the skimmer is usually 100%, if the conditions stated above
are satisfied.
η t = 100% {3.2.2}

3.2.1.3 Influent parameters

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

The oil productivity is proportional to drum diameter because it directly relates


to the skimming surface area. The larger the diameter, the bigger the area, thus the
productivity. However, the study on the oil film thickness on the surface of the drum [5]
shows that the diameter has only little effect, thus negligible, on the film thickness, which
direct relates to the skimmer performance. So the diameter of the drum could be selected to
suit the tank freeboard.

2. Length of drum

The oil productivity is proportional to drum length because, again, it directly


relates to the skimming surface area. The longer the drum, the bigger the area, thus the
productivity. It does not affect the oil film thickness on the surface of the drum. So there is no
effect on the performance. However, the rotation of the drum will cause eddy current at the 2
ends of the drum. This turbulence will propel the oil film and prevent it to contact with the
parts of drum surface. If the drum is long, the area of eddy zone, compared to the entire length
of drum, will be small. So the length of drum will help improving the skimmer performance in
this sense.

3. Oil layer thickness

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.

4. Immersion depth of drum

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.

5. Immersion depth of drum

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.

6. Roughness of drum surface

Surface roughness affects the contact angle, thus wettability, as described in


chapter 2. However, in case oil skimmer, this change is overshadow its affect on difficulty to
remove film from the drum surface. Concavity on the surface may cause some difficulty to
scrape the oil film off the drum surface even though the oil thickness may be increased by the
roughness. So it is recommended to use relatively smooth drum surface.

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.

9. Superficial tension of water and interfacial tension of oil/water

Surfactant is usually present in oily wastewater. The presence of the surfactants


lowers the superficial tension of water and interfacial tension of oil/water. Effect of surfactant
on the skimmer operation can be divided into 2 cases, i.e.,

• 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.

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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.

Oil Productivity (P)


Increase D, L
Increase oil viscosity

0.44 m/s 0.8 m/s Tip speed


(recommended) (max of of drum
model)

a) Oil productivity of various drum materials b) Effect of parameters on drum skimmer


when the oil layer is not a limiting factor [5] performance

Fig. 3.2.1-3 Influent parameters on drum skimmer performance

3.2.2 Design calculation and design consideration

1 Drum skimmer sizing

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

2.1 Limitations of the equation

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.

2.2 Practical design consideration

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.

Table 3.2.2-1 Critical surface tensions of certain materials [42]

Material γc (dyne/cm, 20 oC)


Poly(1,1-dihydroperfluoroctyl methacrylate) 10.6
Polyhexafluoropropylene 16.2
Polytetrafluoropropylene 18.5
Polytrifluoretylene (PTFE) 22
Poly (vinylidene fluoride) (PVDF) 25
Poly(vinyl fluoride) 28
Polyethylene ({PE) 31
Polytrifluorchloroethylene 31
Polystyrene 33
Poly (vinyl alcohol) 37
Starch 39
Poly (methylmethacrylate) 39
Poly (vinyl chloride) (PVC) 39
Poly (vinylidene chloride) 40
Poly (ethylene terephthalate) 43
Cellulose 45
Poly (hexamethylene adipiamide) 46

• 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

certain thickness to cope with this effect. The thickness of 1.0 cm


is considered safe.
• If the length of the drum is smaller than the width of the tank to
be skimmed, guide walls should be installed to help guiding the
oil layer to the drum.

No oil zone

Eddy

a) Eddy currents b) No oil zone or non-productive zone

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)

3.3 Oil disc skimmer


3.3.1 Working principles

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.

Disc Drive unit

Oil trough
Eddy

Scrapper

Components of disc skimmer Eddy current from rotating of the disc


(Source: Abanaki) (see section 3.3.2)

Fig. 3.3.1-1 Disc skimmer

171 III-54
Chapter 3 Oil skimmer

3.3.1.1 Mathematical model of disc skimmer

Mathematical model of oil disc skimmer, proposed by THANGTONGTAWI, was


derived from dimensional analysis approach, using Buckingham Pi theory under a wide range
of material and wastewater properties as well as operating parameters. The model is as shown
in eq. 3.3.1

0.452 1.17
1.328D1.258 N1.212 ν o I
P= {3.3.1}
g 0.332

Where P = Oil productivity of two sides of the skimmer (m3/s)


D = Diameter of skimmer (m)
N = Rotational speed of the skimmer (rev/s)
νo = Kinematics viscosity of oil (m2/s)
I = Immersion depth of the skimmer (m), I ≤ D/2.
g = Gravitational acceleration (m/s2)
γo = Superficial tension of oil (kg/s2 or N/m = 1000 dyne/cm)

The model will be valid when these conditions are satisfied, i.e.;

• Superficial tension of oil is in the range of 27 – 34 dynes/cm, which practically


covers all common oil.
• Capillary number (Ca = μo V/γo) is in the range of 0.04 – 3.6.
• Oil density is around 0.79 – 0.83 kg/m3. Oil dynamic viscosity (μ) tested is
between 1.35x10-3 to 291x10-3 (N.s)/m2 (1.35-291 cp).
• Peripheral or tip velocity should not be greater than 1.13 m/s. To avoid water
entraining, velocity of 0.5 m/s or less is recommended.
• Disc skimmer surface used for model development is PVC. But it is proven to be
valid for SS, PP, and PTFE [5].

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}

3.3.1.2 Influent parameters

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)

3.3.2 Design calculation and design consideration

1 Disc skimmer sizing

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

2.1 Limitations of the equation

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”.

2.2 Practical design consideration

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].

3.4 Productivity comparison between drum and disc skimmer


To compare the productivity of drum disc skimmer, THANGTONGTAWI had
proposed the alternative model of the disc skimmer (eq. 3.4.1) that has the same exponents as
the drum skimmer except for that of geometric parameters (D, L, I).

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.

3.464 ⋅ n ⎡(0.5 D )2.54 − (0.5 D − I ) 2.54 ⎤


L= {3.4.2}
⎢ ⎥⎦
3.035 ⋅ D1.541 ⎣

Where n = the number of the disc (n ≥ 1)

3.5 Advantage and disadvantage of drum and di