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Refinery wastewater treating
1- General
2 _ Pre- treating
3_ Primary treaing
3.1 Oil-water separation
3.2 Equalization of wastewater
4_ Intermediate treating
4.1 pll adjustment
_A.2 Coagulation
4.3 Dissolved air flotation
4.4 Combination type clarifier
4.5 Pre-aeration
5. Secondary treating
5.1 Activated sludge process (ASP)
5.1.1
5.1. 2
5.1. 2
Overview
Operation of ASP
Operating factors of ASP
5.2 Activated carbon adsorption
6. Appendix
- 1 -
1. Genera I
Processes water, cooling water, wash water, tank drain,etc. are included in refinery
wastewater . Those waters are classified into several groups according to the contamin-
ated components and are treated by treating processes.
Over -all refinery water balance is shown in Table-1, and component data of process
-
wastewaters are shown in Table-2. Classification of refinery effluent water is sl1own
n
in Fig-}, and process wastewater flow scheme is shown in Fig-2. Refinery
treating system usually is based on existing wastewater treating units currently used
in industry, although various options are possible. Our refinery wastewater tr ea ti ng
systems are shown in Fig-3.
The treating system usually make provision for storm water diversion and tox ic was t-
es reduction in process effluent; initial oil and solids removal in API or PPI separa-
tors and equalization of quality and quantity In wastewater; further oil and solids
)
--- -------- --- -- ------- ----------
removal in clarifiers or dissolved air flotation units; carbonaceous wast es removal by
-
----------------- - --
1
biochemical oxidation process or activated carbon adsorption; remain wastes removal by
--:_-:: -=-==:::::::-=:::.::::::...7-:::
activated carbon adsorption or final coagulation-clarification units.
treating facilities must be operated by competent personnel and mu s t be
given the same close attention as any other price of refinery equipment. is
a product of refinery. The quality of this product, like any other, must be car efully
controll ed; and if it does not meet required specifications, it should not be released.
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\'(pf:' o'\=
.../Refineries A B c D E
Fresh
Sea water (%) 89 92 86 I 95 93
River water . (%)
11 8 14 5
7 .
Waste
Clean water (%) 98.5 98.5 99.0 99.0 99.5
Contaminated water(%) 1.5 1.5 1.0 1.0 0.5
Total quantity (m
3
/d) 130,000 750,000 700,000 240,000 370,000
w
Table-1. Refinery water balance
L._ :.........i
c.
-
l.;.....;.J
.....,
--;;

Components ( ppm )
Process
HzS Oil
Crude unit 500 ,.._, 11500 100 ,..__ 200
10 .....,
50
Cat. reforming 100 ,.._, 200 100 -- 200
10 ,.._,
20
gas oil cat. hydrotreating 1. 000 ,.._, 3 I 000 1. 000 -- 21000
10 ....... 20
Heavy gas oil H.D.S. 21000 "-'201000 21000 --151000
100 ,.._,
500
Residual crude H.D.S. 21000 "-'20,000 21000 "-'15,000 100 ....., 500
Vacuum distillation 300 "-' 500 100 "-' 200 100 ,.._, 200
Fluid cat. cracking 51000 ---151000 1. 000 "'-- l, 500 L 000 --- 1. 500
* Remarkes *
H.D.S. : Hydrodesulfurization
COD : Chemical oxygen demand
Table-2. Component data of process wastewaters


Phenolics
10 ,.._,
30
0"-' 1
0"-' 1
0"-' 10
0"-' 10
10 ,..__
30
300 ....__ 2.000
r . --;
......___
=.::3
COD
100 ,.._,
200
100 ,.._,
200
300 ,.._, 11500
l, 000 ,.._, 10 I 000
1, 000 "-' 10 I 000
100 ,.._,
200
500 "-' 31000
E./:

L_
~ ~
CJ1
~ ~
Eff 1 uen t water ---....-
~
Contaminated water Process water
~ Tank drain
Power units
&; ,_.,_.,
Stripping steam
Ejector steam
lvash water
Oily water
Crude tank
Slop oi 1 tank
:.:.....;JI llii.irJ
Boiler blowoffs
Polisher blowoffs
Sanitary and laboratory effluents
Clean effluents Cooling water for product coolers
Fig-1. Classification of refinery effluent water
, .
..___
--,-,:;; ~
L_
t.....W
m

"-- iiiilll iiiliiil
unit .. -]stripping steam
Naphtha cat. hydrotreating I Washing water
u.; Cl k
.. hi ng water --+1 ?l:>l Wastewater Stripper
I Residual crude H.D.S. J __J . .
.. Rec1rculatlon
::0-- ------- --------- -- ---------- ---- ----- -- ------------------ ---
__ ____ __ ____ __ _,.:;

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Stripping steam
Fluid cat. cracking . . -1 1
.. InJeCtion water
Recirculation


r
i...____
E -:J
I .
'------'
" .:1 cr- ' l
Was ter treating system
Fig-2. wastewater treating and recirculation flow sheme

L......_
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"--ri
116-.
;..._.,j ioi...- ...
: I
....__
-- e;@
ViiRJ
-- -::J

: .,
- -_.J
primary
treating
Type-1
CPI
separator
'----------
Type-2
CPI
separator
Type-3
CPI
separator
Type-4
API
separator
Intermediate Secondary
I treating l treating I
I
Chemical Activated
coagulation carbon
-filtration adsorption
Dissolved Pre- Ac ti va ted
air sludge !----?
fl ota ti on aeration process
----- L....-
l
pH

Dissolved Pre- Ac ti va ted

!-----'> a1r
r----:;. ----;.
sludge
-)
adj us tmen t - clarifier flotation aeration process
L___ __ _ ___ ----
pH Dissolved Pre- Activated
----;.
air
t---)
sludge
adj us tmen t f Iota ti on aeration process
L_ ____
Fi g-3. Type of refinery treating system
1{_0
f i.D a.-o

bA-1=' u \ . l i b <:;,) /1 v; I vvv\ ...-,

Tertiary
treating
Chemical
coagulation
- clarifier
Chemical
coagulation
- clarifier
-----
Chemical
coagulation
-
Activated]
f--)
carbon
adsorption
IA:.o("' ,; L <s. rl<C<t),
2. Pre-treating
The function of pre-treating section in wastewater treating system is to reduce toxic
or nuisance contaminants in process effluents and to reduce waste- load and to control
components in flow to downstream systems . Phenolics, cyanides, hydrogen sulfide(llzS),
ammonia(NHJ), amines, etc. are contaminated as toxic or nuisance wastes. The process
effluents which are contaminanted by toxic or nuisance weastes include casutic effluent '
-from FCC unit, slop-oil tank drain, etc . Usually those wastewaters are diluted by less :
contaminated wastewaters, and are introduced to the primary or intermediated treating
section.
J
Oxygen demand of refinery waste streams is generally reduced by means of biochemical
oxidation procedures. However, nonbiochemical or chemical ' oxidation techniques are also
applied to refinery wastewaters.
Oxidation by chemical - Hydrogen peroxide
Unit flow scheme is shown in Fig-4 with its chemical reaction.
In chemical coagulation unit, toxic or nuisance wastes are formed to inert or less
reactive wastes with flocculating chemicals, and are flocculated, and are removed in
thickner. Unit flow scheme is shown in Fig-5 with its chemical reaction.
Usually pre-treating method requires high running cost. It is essential to reduce
volumes of influent as much as possible.
- 8 -
&...........
L..-; ~
'-
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Chemicals
Obj ec ti ves
Reaction
---
~
Hydrogen peroxide and NaOII
Hydrogen Su If ide ( llzS )
HzS + 3 HzOz + NaOll -----7 NaHS03 + 4 HzO
,.,...- ---...,.,
....____,
........iii
i.,____:
I surge tank I
1
1
to
t Line mixer > intermediate treating section
/
NaOH tank t----"7'
/
HzOz tank r------_,.
*** Remarkes : Intermittent operating***
Fig-4 Chemical treating of llzS in processes wastewater or slop-oil tank drain
.......;.;.JI ~
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L._
1 ::.

ij.._
-0
--l W-...
....._____
......Iii ' ....,.___;
Chemical
( Reactant and Coagulant )
Obj ec ti ve ; llzS
+1-\o.Ob\- .
Reaction
System
Influent
3 HzS + 2
Spent caustic
Surge tank
Chemicals
Fe.,Cl :1
7 FezSl + 6 HCl + fe ,j_ .
Mixing
Tank
v
Thickner
Effluent
Sludge
1
+ Fe (OH) :1
Dosage ratio
: HzS = 8.5 : 1
** Remarkes ; Continuous operating system
Fig-5. Reaction of llzS with and coagulation system
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3. Primary treating
In the wastewater treating system, there are very important problems to separate oil
in the wastewater contaminated oils (oily water), to separate suspended solids (SS) in
wnstewaters, and to equalize of waste-loads to protect downstream from shock of fluctu -
at ion.
Refinery wastewaters contain sludges of contaminants-resulting from batch processing,
operational procedures, or equipment cleaning-minimize the extreme fluctuations that cause
unit upsets. Primary treating helps to smooth out sudden feed- temperature and waste-load
fluctuation.
Facilities used in the primary treating are rather simple process, although the step
affects the over-all performance of the wastewater system.
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3. 1 Oi 1 water separation
The purpose of oil-water separator is to remove oil from wastewater. Operation of the
oil-water separator is made possible becasue of the difference in specific gravity of oil
and water. Oil-water separator does not prevent the escape of all emulsified oil. Oily
water must be demulsified before going into the separator system in order to remove oil
satisfactorily, Moreover hydrocarbons dissolve in water in a limited amount, and skips
the separator unremoved. And the separator presents an envionment in which suspended sol-
ids (SS) will be settled coincident with the separation of the oil.
An oil separator installation also includes auxiliary facilities to recover oil for
reprocessing and a means for removing and disposing solid material which settles to the
bottom of the separator. The API oil-water separator flow scheme is illustrated in Fig-6,
and the data of liquid medium is sh6wn in Table-3.
Because of reliance on gravity differential phenomena, these is practical limitation to
separator effectiveness. In terms of oil globule size, API separator is effective for the
globule having diameter larger than 0.015cm (lsebicrons), and for CPI separator case, the
'
is 0.006cm (60 microns). v
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' - . 'j;j lii...r- L_
........
w
..-..J w....,_
.... lliiiJaj :....__j ........ ..... L_j .__j
to
Air-driven pump sludge pit
Sludge catcher
Fig-6
I
API recycle water > Recovered oil

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" API oi !-water seof-rator
\
Sediment
pit
-- -- r
.. -- I
L'bdnt


( \\
\ ... \
..... \ .PI -
Flow scheme of API ' _. } -
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. C) _ .- . //...-
\ p . <'"-
\ \ J' ' - ,.r'
\ \ _,./ //'- .
I,..,., ...\
' "'./ ,,,.-4) '
-- . , . .
.. --":."'../ //
I l ;.r / :.,...-- _;y<. .
I y v.-'?
\ .A
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L._;_
~ Iii.-
,........
""'-
~ I-....
: ; . . . . . . . . ~
~ -
........ .. ~ ..
"
.....___
~ iWill L.._j
AEElication of Strokes' Law
1. Velocity of particle precipitation
v = 18.5 oz ( p I - p z ) I /1 (1)
where:
v = Velocity of precipitation, ( ft/sec )
D = Diameter of particle, ( inches )
pI = Density of particle, ( 1 b/ft
3
)
Pz = Density of fluid, ( lb/ff
1
)
/1 = Viscosity of fluid, ( centipoise )
2. Effect of decreasing size of spheres
Diam. of Order of Total surface Time required
particle, size
area * 'to preci pita te
mm
+
10 Gravel 0.487 in
2
0.3 sec
1 Coarse sand
4.87 in
2
3 sec
0.1 Fine sand 48.7 in
2
38 sec
0.01 Silt 3.38
ftZ
33 m1n
0.001 Bacteria 33.8
ft'Z
55 hr
0.0001 Colloidal solids 3.8
ydZ
230 days
-
*: Area for particles of indicated size produced from a particle 10 mm in diameter
with a specific gravity of 2.65.
+;Time to precipitate 1.0 ft long for spheres with a specific gravity of 2.65.
I
SOURCE: S.T.Powe ll,"watcr conditioning for industry, McGra w- Hill, NeW York,1954.
Table-3. Velocity of particle precipitation
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3. 2 Equalization of wastewater
It is assumed that refinery wastewater will have received primary treatment in a
gravity-type oil-water separator before they are charged to a flocculation-clarifier
unit. Such treatment will remove most of the oil and removable solids.
llowever,it is required that a retention or equqlization system be provided where
wastewaters of varying feed rate and composition are mixed to make feed water to a
flocculation unit less fluctuated in quantity and quality. By mixing wastewaters from
such facilities as batch processing, operational procedures, and cleaning,
pll values, temperature and component of feed water to the unit is equalized.
Typical equalization system is shown in Fig.-7 .
-- Wastewater from batch processing, or equipment cleaning goes to surge tank, anrl is
mixed with API effluent. Oil-free process wastewater is mixed after pre-treating wi lh
API effluent. These waters have a surge tank or a surge pond for stable flo1v and
qua 1 i ty.
- 15 -
L..__
L......:.l
.........
0)

,. ' . l
..........
Surge tank
----------------------- ---
API separator
Level control -----
-----------A---------
'5 ' 71
F1ow
control
'
L__
- .--,, 1
t;;.''' l
Oily water
----:------ to intermediate
API separator I I \% ,, Line-mixing I ) treating section
Desai ter separator
I
J
control
. i '
Spent c:as tic
from FCC

Flow
, Pre-treating I --t,J,........ 1
. --------.-----.
. .
control '
Slop oil tank
Q Flow
: :
drain l Surge tank "' :.1
Spent-chemicals
Equipment cleaning.
----
. .
Flow
control
------o1 Surge tank
Fig-7. Wastewaters equalization in quality and quantity

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4. Intermediate treating
The characteristics of oil-water separator effluents are: oil content, oxygen demand,
toxicity, and pll. The extent to which receiving waters may be affected by any or all
threse characteristics determines whether intermediate treating is required. The import-
ance of these effects is related to the uses served by the receiving waters and the
regulation imposed to maintain
As the intermediate treating -method pH adjustment, chemical-coagulation, flocculation
-flotation, circular flocculator-clarifier, and pre-aeration are used. These methods
may be used singly or in combination, depending on the contamination degree of feed
water.
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4. l pH adj us tmen t
pH adjustment of feed water is required to obtain a good result of coagulation in the
flocculation unit and biochemical oxidation unit. Generally speaking, pll value of 6 to 8
is preferable for optimum operation of the unit. Acid or caustic is added to the feed
water and mixed thoroughly in the pll adjustment vessel.
However, the best range of pi! changes by the concentration of ammonia and arnine tn
the feed In our refinery, the best range of pll is 8.0 to 9.0.
Typical pll adjustment and coagulation flow scheme is shown in Fig-8.
J 4. 2 Coagulation
] 14ith pll adjustment, the coagulant chemical is added to the in the mixing
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zone. Ferric chloride or poly-aluminium chloride (PAC), etc. is used as coagulant chemi ca l.
If certain soluble metallic salts are added to the wastewaters in the presence of suffic-
ient alkalinity to produce the equrvalent hydrous oxides, finely divided precipitates or
microflocs are formed by caogulation.
In our refinery, ferric chloride hydrate is used to coagulate and to l{zS remove (in chap.2).
OvJ
Coagulant chemicals should be quickly brought into contact with the waste to achieve
a good coagulation. This requires rapid and thorough mixing which is often referred to as
flash mixing.
Chemical Coagulants
Ferric chloride hydrate
Poly aluminum chloride
Aluminum sulfate
Joo -I
l
FeCl3 6Hz0
AlClJ nl!zO
A I z (S04) 3 .18IIz0
l \
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0 - -1--
L 18 -
=-+-----rf
4. g I(),
Pl+
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4. 3 Dissolved-air flotation (01\F)
Dissolved-air flotation (OAF) is the supplemental process for oil-water separator
effluents to reduce oil and suspended solids to a low level . In this processes very
fine air bubbles force suspended prticles to float to the surface for removal. OAF
can be used alone or in combination with flocculation (flocculation- flotation).
As is illustrated in Fig-3, OAF follows oil separator, and the operation of the
preceeding oil separator greatly the operation of 01\F. Sufficient removal of
oil and solid at the oil separator stage could result in the reduction of air and
flocculant and so economical operation.
High pressure or low pressure air is used in forming air bubbles. As for the high
pressure method, air is blown into the water at 3 to 4 atm of pressure. As the pressure
is released to atomosphere, fine bubbles are formed. On the other hand, in the l ow pres-
sure system air is blown in at atomospheric pressure, and then fine bubbles are formed by
applying a vacuum of approximately 9 in. Jig. The first one is preferable for refinery
wastewater treating.
Flocculation when combined with flotation reduces biochemical oxygen demand(BOD) and /
I '\l- I
chemical oxygen demand(COD) by 30 to 50 percent and total oil to the range of 10 to 25 mg
per liter, which is close to the limit of oil soluble in the water. \1
Fig-9 shows a flow scheme of OAF.
In the high pressure system with recycle stream as is illustrated in Fig-9, the coag-
ulant is added to the feed water at the mixing tank. Then it goes to the mixer hhere it com-
blnes with the recycle stream down and the flotation chamber 1vhere oil is flotat ed as scum
and is removed. High pressure air is introduced in the recycle stream and the pressure is
released at the accumulator to form fine bubbles. Approximately of feed rate
is circulated as recycle stream.
*
rn\ W
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L...._ W..... L_
--.I i...-
and acid ( 'P Qd k
10
+)
'(Coagulant 4
Effluent
<:>1 separa ,_
I1Ixing I I Scum
tank
( pH adjustment )
c.x..A.-0--v\ .
Dr\;:-.
i.......__
L:.___j - "-;a lii 'f- . -!! __j
Flotation chamber
Driver
-,.... , M Effluent
Blow-out
""'" I cn v s 1 udge
Air from atmosphere
Compressor
ecycle stream
accumulator
( Operating pressure : 3 -- 4 atm )
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OAF is becoming a popular form of secondary oil removal from wastewater becasue of its
advantages. First the retention time of flotation method is much shorter than those of plain
sedimentation. For example, retention time for flotation is !0 to 20 min against 40 min to 90
"' .
In for plain sedimentation. The second advantage is that flotation is less susceptible to
upsets by temperature or flow fluctations. The thrid advantage is the lower chemical dosage.
The fourth advantage is the higher concentration ~ f scum obtained.
Principai disadvantages is the cost of pressuring part of the waste to about 3 to 4 atm.
- 22 -
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4. 4
fWt.tS.S: COtJ1
Combination type of Clarifier ( Accelerator-Clarifier) A-P--n:;'Q.. ACT\ VA lt::D
D q :Pw cess
I
or activated sludge process effluents. Use of flocculants to increases . the rate of pre-
cipitation of suspended particles.
After coagulation and flocculation, the treated water pass through a sedimentation
zone where the floc settles as sludge, The sludge is mechanically scraped into a sump
from and is drawn off as slurry.
The unit is arranged so that flash-mixing, coagulation, flocculation, and sludge set-
tling and collection is carried out in one compact vessel. Raw water is introduced into
the central cylindrcal compartment, where the coagulants and caogulant aids are flash-mi-
xed with the water. These chemicals can be added to the unit with the raw water or may be
introduced into the flash-mixing zone separately. The coagulant can be brought into the
unit with the raw water, and the coagulant aids added in the flash-mixing zone.
Flash-mixing usually is acieved mechanically by impellers that mix and circulate the
chemicals and waters. From the flash-mixing zone, the waters pass into a larger central
zone. Here they are slowly circulated to induce floc growth. The waters proceed radially
and upward into the sedimentation zone. As the waters rise, their velocity decreases per-
mitting the floc to settle and concentrate at the bottom of the unit. In the recirculating
clarifier, a portion of the settled sludge is returned to the flocculation zone where the
sludge acts as a seed to aid in floc formation and growth.
The sludge-blanket type clarifier is arranged to maintain a suspension of sludge bed
in the settling zone through which the water must pass. The combination type clarifi er
provides both sludge recirculation and sludge-blanket contact.
The floor of clarifier is usually conical to encourage accoumulation of sludge at tlt c
center for easy removal. In some sludge is removed to central pit or hopper by mechanical
scrapers powered by a driving unit . Then the sludge is removed by a sludge pump. In any
case, the level of suspended sludge bed must be carefully controll ed.
Typical combination type of clarifier flow scheme is shown in Fig-10.
- 23 -
L.....;..,._ - - - - - ........., ...___ ;_ I qr-_,, ., ,

,:::...
Coagulant
( A1Cl3 )
Influent
coagulant aid recycle sludge
--;]
Polymer- Driver
""' / ll ';---I , f ........ :'i'?+.----.. J ' , Effluen \
MIXIng
tank
J
Sludge pump out
bottom zon ixing zone
operating conditions : pH range 6.5 7.5
Sludge concentration
at mixing zone
at bottom zone
Chemical dosage
1.500 ppm
15,000 ppm
coagulant (A1Cl3); 100 ppm on feed
coagulant aid ; 1 ppm on feed
Fig-10. Combination type of Clarifier flow scheme
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Operation of combination type-clarifier
1. Coagulant and coagulant aid dosage
Normally, coagulant dosage is about 100 ppm on feed-water and coagulant aid dosage
is about 1 ppm on feed.
2. Feed rate fluctuation
Feed equalization to smooth out sudden feed-rate fluctuation prevents sedimentation
interfere.
3. Suspended solid concentration
In case the concentration is low, sludge recirculation rate should be increased
for a quick floc growth.
4. pll range
Optimum pll range is from 6.5 to 7.5. Maximum allowable pH value to prevent floc
destruction is 9.0.
5. Feed temperature change
Feed equalization helps to smooth out sudden feed temperature change that inter-
o
feres sedimentation. Maximum allowable change rate is 4 F per hour.
6. Suspended sludge recirculation
Excessive recirculation may cause unstable suspension of sludge bed, and formed
floes are carried out and SS concentration of effluent is increased.
- 25 -
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4. 5 Pre-aeration (Oxygenation)
p72.o U:
The term aeration refers to the means by which air is applied to water; oxygenation
refers to the process wherein oxygen is dissolved in water. Air is mechanically impelled,
or dispersed, into wastewater for the purposes of stripping odorous gases and facilitating
oil water separation.
Aeration floats some of the oil that is left unremoved in a conventional gravity type
oil water separator. In air mixing type, quiescent zone should be provided in the basin
for accumulating and skimming.
Pre-aeration flow scheme is shown in Fig- ll. '
-f' T J-. ' r A-: I
-i--T IS 1'-.0 p ItO 4 fh_ '(?-O Cf>S, ,
1
0 t::'-7\ v 'lS"v
At12.-k \ \.,0\--\ L lt l ('; (_ T ?t-N.'L I A"1 rL-
- 26 -
tr--s owr---.1
U Tt -e h . )
'--- r *' L__ --....l w......


!'.:)
-..l
Foul air
* River water
-------- ------ -- ------------------::>:
* Blower
I V I';'Adsorber
( for HzS removal )
( for over-load protection in ASP )
Drain to API separator
Injection nozzle
* Steam (for temperature control)
to
Feed wa te --I+.;Y.;--.;--.;--.;.; .;.;.;.;--.;-- -,--1 ) Activated sludge .process (ASP)
...
Air
Compressor Air-nozzle Optional units
** Operating **
....._
1. Reduced oxygen demand
2. Reduced HzS etc.
3. Temperature control ( ar6und lOO"F)
Fig-11. Pre-aeration Flow Scheme
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5. Secondary treating
The purpose of secondary treating is to redu
:chemical or chemical oxygen demand, and toxicity
oxidation process or activated carbon adsorption process is used in this step.
.. .. ..... --- - ----.. ...-------- ......
Biochemical oxidation is a for removing organic components in
wastewater. The benefits of biochemical process for treating refinery ts
as follows.
a. Reduction of oxygen demand.
b. Reduction of aquatic toxicity
Biochemical waste treating system uses bacteria and other microorganisms to reduce
the crganic wastes present in the wastes.
The removal of pollutant from wastewater by adsorption onto a fixed bed of granular
activated carbon is a relatively new by developed process. Of the numerous adanced
processes evaluted for treating of wastewater, activated carbon adsorption has emerged
as one the most pratical and most promising process in terms of perfromance.
The running cost and performance data for activated sludge process, combination type
clarifier, and activated carbon adsorption process are shown in Table-4.
- 28 -
L......._ L.....ij "'- ,_ -- ........... i....wj
L_j ~ ltiilil L.._j ~ 5' '' ~
Treating method
I
activated sludge
I
activated carbon
I activated s 1 udge and
with reactivator combination-clarifier
Percent of removed
pollutant
BOD 90
(%)
99 (%)
I 93
(%)
Total organics 80 99 I 85
suspended solids 90 99 I 95
Phosphorous 30 95 I 95
I'U
<.;;) I
Nitrogen 50 55 I 50
Inorganics 5 15 I 10
..:r-;?
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Runing cost
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( yen/m
3
)
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10 I 70 I I 20
Table-4 Running cost and performance data
of activated sludge process, combination-clarifier, and activated carbon process.

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5. 1. Activated Sludge Process(ASP)
5. 1. 1 Activated Sludge Process(ASP)
The activated sludge process(ASP) is an aerobic biochemical treating process in
wastewater is treated microorganisms that are suspended uniformly in a reaction tank,
into which oxygen is introduced mechanically, The activity of microorganisms in the reac-
tion -tank is maintained by recycling activated sludge which is formed by the microorgan-
isms in the process. Essentially, the organic matter is removed from the wastewater by
synthesis and oxidation. An aerobic environment is necessary to maintain the proper micro-
bial activity in the system.
Activated sludge is formed by aerating the waste water, until the bacteria stabilizes
all of the organic In most diluted wastes, the activated sludge formed is micro-
scopic. Replacement of a portion of the aerated mixture with fresh waster accelerates to
stabilize the organic matter in the system and to build up an activated sludge visible to
the naked eye. With a period of settling, the activated sludge settles to the bottom of
vessel leaving a relatively clear water above the activated sludge,
Typical activated sludge process flow sheme is shown 1n Fig-12.
The basic process consists of a rectangular aeration tank and a sedimentation lank.
The activated sludge removed from the sedimentation tank is recycled to the aeration lank
to maintain an activity of activated sludge. The excess activated sludge will be discard.
- 30 -
'--- t.....J . L__ .__j \riooo.o-
Activated Sludge recirculation
(for AS concentration control)
Aeration Tank
'--- - ....... ....____ ___..... .........
Sludge
Pit
'"
Excess
1----7 Sludge
Feed
water o -o--o -;-o- o- ;--o -.-o ;--o--o --o- ---- -

Blower
c.o
Sedimentation Tank Effluent
. . . . . . . . . . . . . .
. . . . . . . . . . . . . .
Air-nozzle
;: =-= 1 n f n r r n n f n 1 n rn 1 n rn;: n In 1 =
** operation **
1. Dissolved oxygen
2. AS recirculation range
3. Sludge Volume Index (SVI) range
4. Sludge age
5. Operating temperature range
6. pH range
0. 5 ,_ 1. 0 ppm
0.5 : 1.0 1.5 : 1.0
50 ,_ 120
3 ,_ 5 days
70 ,.... 90 F ;_, r}o"LQ.,..
6.5 ,_ 7.5
7. Mixed Liquor SuspendTd Solids (MLSS) Goncentration
at aeration tank : 3.000 ,_ 4,000 ppm
at sedimentation tank bottom : 7.000 ,_ 9, 000 ppm
Fig-12 Ac t ivated Sludge Process (ASP) Flow Scheme
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5. 1. 2 Operation of Activated Sludge Process(ASP)
A. Endogenous Metabolism and Endogenous Respiration.
The metabolism of organic waste by activated sludge is accomplished by the conversion
of the organic matter into cellular protoplasm. By increasing the aeration period beyond
the time for metabolizing the organic wastes, the activated sludge oxidizes its own pro-
toplasm. This is called endogenous metabolism or endogenous respiration. Endogenous meta-
holism lakes place continuously but masked when rapid synt!Jesis is occurring. Extended
endogenuous metabolism results in eventual death of the cell, hydrolysis of certain cel-
lular components, and release of nutrient components back into the environment. These
products can be used by other cells for energy, prolonging their existence. These mater-
ials are biochemically inert and accumulate in the activated sludge mass. The inert com-
ponents represent apprpoximately 25 percent of the initial cell mass.
B. Organic (BOD) loads
Activated sludge systems have little capability for handling shock loads. Toxic metals
have sufficient period of contact with all of the microorganisms in the aeration system
to destroy the entire microbial Shock organic loads usually result in over-
loading the system with the development of filamentous microorganisms and, hence, poor
settling characteristics. Complete mixing has resulted in a reduction of the effect of
] shock organic loads. The use of the aeration tank as a surge tank tends to level out the
shock load.
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BOD loads Lr * Q I ( MLSS * V )
Lr
g
MLSS
v
Concentration of removed BOD
Flow rate of feed
Concentration of activated sludge
Volume of aeration tank
C. Excess sludge
(ppm )
(m
3
/d)
(ppm )
( m3 )
When receiving streams are large, the excess solids may be discharged with the treated
effluent. Where a highly treated effluent is required.
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D. Sedimentation
,.
Continuous operation of
1
activated sludge system requires separation of the microbial
I
solids ;from the liquid and the return to the aeration tank. It is important that the
activated sludge be returned as rapidly as possible. Activated sludge normally 5ettles
quite quickly so that the sedimentation time does not need to be longer than 1 hr acco-
to combined factors of flow, raw water, and recirculation.
wastes may be high in ammonia content. With a high dergree of stabilization,
the ammonia will be oxidized to nitrates in the aerati on tank. When the activated sludge
---------------------------- .. ---------- ---------- --------
enters the sedimentation tank, it will utilize all of the dissolved oxygen that was carr-
..___ _______ ,_ ... ... -- --- --.. --.. ------ ... . ..- .. -.. . ---p ...--..... ... _ .. __________ ,.._......-
ied with it from the aeration tank. The nitrates will become the next source of oxygen
. ____ .. _____ ,. _______ , .. . .. __, ______ ,._,r_..__,_. ,..,.,....- _,__. , ..... -..,,-or------"'-.----
for the microorganisms in the activated sludge and denitrification will result. Denitrif-
------.. --.. ......................... ---' ..... -....... .. -.. .....------ ..... -------:-.----- ... ..,......... _.; .................. . - """"''' _____ .......,. ........ - ..
ication causes the nitrate nitrogen to be reduced to gaseous nitrogen which is insoluble
----------- - ..... - - .. ---oOoOo .... ---- -- --- ..... __ ___,.-po, -...- -...--.. -- --.. ..... . .. .._. .. , - -' 0 .. M0 0 o0--- -..-- .. ------
in water. As the nitrogen gas comes out of solution, it is trapped under the activated
_ _ ________ , .,.., , ,._.,,..., -- - -'""' ,., .... -.-, , ,..,_._ .... , __ .,,,_._,,, __ , _.,... _,,,.No ,,_ ,_..,,.__ ' - v
sludge and causes the sludge to rise to the surface of the sedimentation tank. Rising s l-
.... - .. ' ........ _______ ., ............____,.. .... -... ,. ,. ...-- ... --..... --- - .. --... .... .. -.... -... ..... - .... -. . .. - .- .. .... ---- ------......... . --- ........... .. - .; ... --------- ................. _
udge is quite common in activated sludge systems in which nitrogen content is high.
_____ ,. ____ .. _ ............ , .. _ ..... _.., .... ... ,. ,., ......... ... ..... .... ..-. .... ...., ,_, ..... _. ,., .......-.-:.-...- _,_..,.. ..,. _ __ .,..,.., __ ,.,..,,_. .........,....,... _____ .. - -n._.,., ... l.,..._,.._.
E. Sludge recirculation
Sludge recirculation from the sedimentation tank to the aeration tank maintains the
microbial population in the aeration tank for rapid me tabolism of the organic wastes.
The rate of recirculation depends in part on the concentration of microorganisms in the
aeration tank and in part on the settling characteristics of the activated sludge. To
maintain the same microbial solids content, the rate of recirculation with a good-settl -
ing sludge should be smaller than with a poor -settling sludge.
With activated sludge, the rate of recirculation ranges from 0.5:1.0 to 3.0:1.0. The
sludge volume index that is used to measure the settling of sludge can be cal culated by
dividing the volume of sludge settling in 30 min, measured as percent, by the weight of
suspended solids, measured as percent. With normal opera tions, the sludge volum index
(SVI) should be 100 or less.
- 33 -
5. 1. 3 Operation of Activated Sludge Process (ASP)
A. Temperature
Temperature controls the rate of microbial reaction. Increased the temperature results
in increased rate of metabolism until a limiting level is reached. Certain bacteria grow
readily to a limit of 100'F and then die rapidly with increased temperature. While other
b'O""C
bacteria can grow up to 140 F before they start to die. Although it is possible to
ate a oiochemical treating system above or below lOO"F, ' it will not be efficient if the
tempera lure fluctuates wide 1 y around 100 oF. ( rv B C), .
B. Suspended solids
Suspended solids often represent material that, in any case, should be removed from the
wastewater prior to its discharge into the receiving body of water. Generally speaking,
suspended solids in the feed will be incorporated into the biochemical mass if they are
not removed prior to biochemical treating.
C. Sulfides
Sulfides in concentrations greater than 10 mg per liter have been indicated as toxic to
------- -
the microbial mass. However, it has been shown that treating plants with adequate aeration

and holding time can handle wastes containing as much as several hundred milligrams per
liter of sulfides.
D. Phenolics
Phenolics are important soluble organic compounds in process wastewater streams, and they
are readily destroyed by bacteria in biochemical systems. Feed concentration of phenolics
as high as 800 mg per liter have been handled in a system treating process
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be avoided, particularly if the concentration is in excess of about 30 mg per liter.
E. BOD Biochemical oxygen demand
Reduction in oxygen demand accomplished by both the trickling filter and activated slud-

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ge process vary directly with the waste load, within design limits. Load in the activated
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sludge process is stated as weight of BOD per unit weight of active sludge per unit
-- ------ - -----------------
of contact time.
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F. COO Chemical oxygen demand
The effluent from a properly operating activated sludge system is made up largely of
nonbiochemically oxidizable compounds after the microorganisms and other suspended solids
have been removed. The microbial solids in the treated effluent can be removed by passing
through a membrane filter.
G. pll
The pll of the microbial environment is very important for the stabilized operation.
Fundamental studies have shown that an excess of hydrogen ions or hydroxyl ions is toxic.
For biochemical systems, the optimum pH lies between 6.5 and 8.5 with little trouble bet-
ween 6.0 and 9.0. Should the pll drop much lower than 5.5 or rise much above 9.5, toxic
conditions will result.
II. Oi I
Too -much oil causes problems in the biochemical system because it is adsorbea-by the
microorganisms faster than it can be metabolized. In the activated sludge process, the
adsorbed oil impairs sludge settling characteristics. Resulting sludge loss mny be so
high that reduce the microbial level in the systm to such level as to impair its effici-
ency and may cause system failure. The microbial metabolism of oil is limited by the low
solubility of the oil, the chemical configuration of the oil molecules, and the microbial
surfaces, The concentration of oil or hydrocarbons that can be assimilated by biochemical
l systems have not been well -established. However, experience has indicated that for:
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~ Activated sludge systems :Oil concentrations up to 30 mg per liter have no effect.
----------------- .. ---------------------------
I. Nitrogen and Phosphorous Nutrients
The growth of microorganisms requires a balance of certain nutrient elements in the syst-
em. Two major nutrient elements necessary for microbial growth are nitrogen and phosphorus.
Rifinery wastes generally have ample nitrogen in the form of ammonia, but many be deficient
ln phosphorus. For activated sludge, the nitrogen required is approximately 1 lb for every
20 lb of BOO stabilized; the phosphorus required is approximately 1 lb for every 100 lb
of BOO stnbilized.
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J. Chlorides
Chlorides, in the concentration range found in refinery waste, do not adversely affect
the chemicroorganisms in biochemical waste treating systems .
K. Toxicity
Toxicity refers to the deleterious effects on the microorganisms involved in the bio-
chemical treating process. Biochemical oxidation of some organic can be accom-
plished only if concentration of such toxic substance in the system is carefully control-
led and the microorganisms have adapted to their presence. Examples of such compounds
found in refinery wastes are phenolics and cyanides. Little is known about the toxicity
of other organics present in wastes from refinery and petrochemical operations.
L. Sludge Discharge
Biochemical systems actually adapt resonably well to some extent of variability in the
waste characteristics. llowever, the and microorganisms involved in the process
can be destroyed or their efficiency is reduced by sudden, sharp changes in environmental
conditions or by slug discharges of various materials. Among the causes of difficulty are
sudden temperature rise above tolerable level; high concentration of sulfides, alkalies,
J and acids; and addition of heavy metals.
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5. 2 Activated carbon adsorption
The removal of pollutants from wastewater by adsorption onto a fixed bed of granular
activated carbon . is a relatively new process.
The basic components of an activated carbon adsorption unit are:
1. The adsorber in which the wastewater stream is contacted with a bed of granular
carbon, and wherein the solute pollutants measured by the biochemical oxygen
demand, the chemical oxygen demand, total organic carbon, etc., are transferred
from the stream to the carbon.
2. A hydraulic transport system for moving spent carbon to regeneration furnace and
for returning reactivated carbon back to the adsorber.
3. The regeneration system consisting of dewatering facilities for spent carbon, a
furnace, and reactivated carbon quenching and slurrying facilities.
Fixed beds in ser ies are downflow, and the influent bed is taken offstream for
regeneration when it becomes saturated or spent. A fresh carbon bed is then brought onst-
ream at the effluent end of the series. In this manner, the carbon beds are utilized coun-
tercurrent to the flow of wastewater.
The stepwise moving bed is a modification of the countercurrent operation of fixed
beds. The wastewater flow is upward through the bed and spent carbon is periodically
removed from the bottom of the vessel. Fresh carbon make up is made at the top of the
bed or effluent portion.
Typical activated carbon adsorption process (fixed beds in series) scheme is
shown in Fig-13.
- 37 -
L._
t......ow
w
co
Iii.-
'
'-- -.- .........1 ..........

...... ..... .
..... liliil ....
,
...____

..,
L..__.

................................
. .
. .
:-....... -... ............ , ......
.................. L Back-wash-1
'----------------------
Back-wash-2
_ ......... ________ ......... ___ _
.
. .
X- ............. -.. ----- .. -.. -- ............. .. ....................... ----------- .... --- J

................. t Back-wash-1 :
lllllllllllll!lll -l
11111111111111111
B 2 '
::::::::::::::::: ack-wash- :
::::::::::::::::: .-: .. --- .. -- ......... --- .. -...... :
' .
.
.
water temperature
about 150 F
t------?1::::::::
::::::.: .. ::::
:::: ::: : :: ::::
.... ........ ..
. ............ .
Back wash water pit
steam
'"
.,
to -----'"'
C!arif ier ( lmm:w i I Washed water pit
,lr
) Ef f I uen t
Treated water pit
... ... ... ...... .
::: ::::::: :::: ::::

** Back-wash frequency **
Back-wash-1 2....,3 days
Back-wash-1 + weekly
Fig-13 Activated Carbon Process (ACP) Flow Scheme (Fixed Bed case)

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React iva Lion
lihen an adsorber bed becomes saturated with solute pollutants, the carbon is usually
' I
'reactivated by burning off the adsotbed material. Reactivation is effected in a multiple
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-hearth furnace at temperatures 1700 F and residence time in U1e furnace is appro-
.' .
ximately one hour. The furnace
oxygen atmosphere that assures
is closely controlled to provide a high-temperature, Jow-
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the comp 1-e te remova 1 and des true t ion of the adsorbed mate-
l
rial wllile restoring adsorption cae_acity without burning the carbon. During tire reactiva-
tion process 1 kg of stenm I kg activated carbon is induced into the furnace. The stenm
is an effective oxidizing agent. The adsorbed materials are volatilized and selectively
oxidized from the surface of the carbon.
The granular carbon should be sufficiently hard lq nllow hydraulic transport to and
from .the furnace, as well as mechanical handling wilhin the furnace, without suffering
excessive attrition losses. Usually the overall loss, i.e., the sum .of the handling loss
and furnace Joss, are about 4-8 % in reactivation.
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Adsorption zone
I
Fig.l4 is an idealized representation of the adsorption process in a single fixed
bed of carbon nnd illustrates lhe downward moving adsorption zone. At the bottom of
the figure, the solute concentration has been plotted against time to illustrate the
I
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break-U1rough lhal occurs when the adsorption zone reaches the bottom. If the bed \\'ere
I
not removed from service, the adsorption zone would disappear and the solule concent-
ration would soon be equal to the solute in the influent, thnt is, lite
entire carbon bed would be
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.,
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z
0
;:::

>-o
:z:w
111111
uz
8-
0
0
Ill
..
L
0
..
.:-- .:i: ..
,. __ _
---
- 40 -
0
0
Ill
o(
A
>( :i
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..
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..
...
0011 >10 HOI.LYl;ll H3:>NO:>
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6. Appendix
The quality data of treated water in our refinery wastewater treating systems
are shown i ~ ~
2. The perfromance datas of the wastewater treating systems are shown in Fig-15.
Those data are normal average datas.
Type-1. Chemical-coagulation-filtration and
moving-bed activated carbon adsorption with reactivator system.
Type-3. Activated sludge process and chemical-coagulation-clarifier system.
Type-4. Activated sludge process, chemical -coagulation-clarifier and
fixed- bed activated carbon adsorption without reactivator system.
3. The performance graph of Type-4 wastewater treating system is shown in Fig-16.
( Actual influent and effluent data on each treating process at normal operation )
4. The running cost of each treating processes are shown in Table-6.
5. The running cost of wastewater systems are shown in Table-7.
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L_ ~ ~ L.
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Refinery '
pH
COD ( ppm )
Oi 1 ( ppm )
ss ( ppm )
~ ...................... --- l......o.i
- ......... . i.,.___ ..........;, ......... ~
A B c
I
D E
7.8--8.5 6.5-----7.5 6.5--7.5 6.0-- 8.0 6.0 -., '7.0
2.0--5.0 5.0-----9.0 5.0--9.0 5.0--10.0 10.0 --15.0
0.5 or less 0.5 or less 0.5 or less 0.5 or less 0.5 or lessr
1. o--s. o 1. 0'"'-4. 0 1. 0"-'4. 0 1.0-... 9.0 1. 0 ,..__ 4. 0
Table-S. Refinery treated water
L_ 1 '.'-;.:.;;
L___ -...l ........ ;;......,j
..... .... .... lr.jii;J
(
....___
- -.,&l
liiiiiiil
L__'


w
Type-1
CPI Chemical Activated
\ coagulation
' '
carbon
separator -filtration adsorption
COD (ppm)125 4 -7 COD (ppm) 65

t::--- _____ .,.
COD (ppm) 15
ss (ppm) 10

00%
(/ --7 SS (ppm) 5 ss (ppm)
4
--7 Oil (ppm)0.5 olo
Oi 1 (ppm) 0. 5 Oi 1 (ppm) 2 .,...
I S 'fo " '-
Type-3
! CPI

[-?
\
separator - clarifier
COD (ppm) 90
SS (ppm) 75
Oi 1 (ppm)150
Type-4
API
COD (ppm) 45
SS (ppm) 5
-----7
Oi 1 (ppm) 5
Dissolved
air
separator f lota ti on
Dissolved Activated Chemical
air
'
sludge coagulation
fl ota ti on process - clarifier
?< Coom)

1 ss (ppm) s
1
Oi 1 (ppm) 5
c--

Activated H Chemical
sludge coagulation
process - clarifier
'
I COD (ppm) 8
I SS (ppm) 3
0 i 1 (ppm) 0. 5
I I J Ac
1
tivated I
carbon
adsorption
-.....
COD
ss
Oi 1
.)7
(ppm) 135 <---- Ll 0
1
o
(ppm)160 80lo.J, -r
(ppm) 40 N ___:r.
COD (ppm) 70 g <7 t . -----vf COD (ppm) 8 COD (ppm) 5
SS (ppm) 30 4 --- 9
0
(. _- . _______ ____.:_;,. SS (ppm) 3 66?, SS (ppm) 1
Oil (ppm) 25 ...., __ __ Oil (ppm) 0. 5 Oi 1 (ppm) 0. 5
\
Fig-15. Performance data of wastewater treating systems
L._ L ___,j \.i........ '-..J ......... -1....-.J
- --
,.-...
E
0.
0.
-
Cl)
.._.
"'
co
3::
.......
c;)
c:
-
E
co
.......
c:
.z::,.. 0
.z::,.. u
.......
0
c:
0
- .......
1"0
I...
.......
c:
Cl)
u
c:
0
u
170
I
160
.150 t\
140 --.- \
130
120
110
100
90
80
70
60
50
\
\
\
\
\
\
\
\
\
\
\
\
'
\
\
\
\
\
\
\
'1 -s.s
',
' ..........
.......................
l
OlL ',
0: COD
: ss
.6 :. Oil
Jt... : H2S
0 : NIIJ
+ :
l::r----._- - ..
40 ---- -,
I I '',,,
30 ...___ __ ... ',,, -j
""-,?;;>f _____________________
t t"'o-.Ve<. --r---- 4
0
API
separator
Dissolved
air
f Iota lion
Ac ti va ted
sludge
process
Chemical
coagulation
- clarifier
Fig-16. Performance graph of wastewater treating system.
oh-.IH' ,
Ac ti va ted
carbon
adsorption
............ii "-"""'" .____j
L..:........:_
.S -::.: .:_,
~
.z::,.
CJ1
L-
I
L_ __
~ .......
- ~
i Treating processes
API separator
CPI separator
Dissolved air flotation
Combination-clarifier
activated sludge process
activated carbon process
with reactivator
activated carbon process
without reactivator
Table-6 Running cost
~
-
"-..i ~
_____..
--.... - ~ ~ '
Running cost
0.5
0.5
5
I
10
10
70
100
I
( yen/m
3
)

\.i.-...
,b.
m
'
L - .........i
-7- '8 .. -7'

'
---,
\-c be_.

; >J ....
Combination of
treating process
Dissolved air flotation
+
activated sludge process
+
combination-clarifier _
Dissolved air flotation
+
activated sludge process
+
combination-clarifier
+
activated carbon process
without reactivator
Combination-clarifier
+
activated carbon process
with reactivator
Combination-clarifier
+
activated carbon process
without reactivator
---- -- ----- -- ----- - - -
Table-7. Running cost ( yen/m
3
)
4
.......
Running cost
25
50
80
110
Combination of treating process
, .
fJFF'
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