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Contents
1. Overview
12
14
21
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1. Overview
A coagulant is a chemical used to effectively separate
fine suspended particles that cause pollution from water.
Minute particles that do not readily separate from water
can be separated by coagulating them into easily
separated flocs.
Coagulants are roughly divided into inorganic coagulants
and polymer coagulants. Inorganic coagulants date as far
back as ancient Egypt when alum (double salt made with
aluminum sulfate, alkaline metal, etc.) was used to make
water drinkable. Even today, aluminum salt s a popular
inorganic coagulant.
On the other hand, polymer coagulants were developed
in the 1950s. At first, they were used in industrial
processing, for example, to concentrate mining slurry.
Later, in the 1960s, when environmental problems
stemming from industrial waste water became a social
issue, anionic and nonionic polymer coagulants became
widely used to treat waste water. Then, in the 1970s,
cationic polymer coagulants became used in large
quantities as dehydrating agents in treating urban waste
water such as raw sewerage and night soil.
Current annual use of polymer coagulants in Japan is
estimated at about 11,000 ton of anionic and nonionic
types such as polyacrylamide, and about 16,000 ton of
cationic types such as polyamino alkylacrylate. Polymer
coagulants are absolutely indispensable as a chemical
agent for environmental conservation.
This paper reports on the characteristics and effective
applications of polymer coagulants in water and sludge
treatment. It cites types of organic coagulants and
polymer coagulants as well as important topics and
recent trends seen with some actual cases of use.
-2-
Polymer coagulant
Coagulating
sedimentation
Natural precipitation
Discharge
Dehydrated cake
Dehydrator
Polymer coagulant
Disposal
Aeration tank
Discharge
Sedimentation pond
Return sludge
Surplus sludge
Dehydrated cake
Dehydrator
Incineration
Polymer coagulant
(3) Soluble organic substances + Suspended substances treatment (COD, BOD, n-hex and SS)
Paper and pulp, machinery and automobiles, petroleum and petrochemicals, textiles and dyes, food products, etc.
Inorganic coagulant
Polymer coagulant
Raw water
Coagulating
sedimentation
Aeration tank
Return sludge
Discharge
Sedimentation pond
Surplus sludge
Dehydrator
Polymer coagulant
-3-
Dehydrated cake
Incineration
Disposal
Agricultural fertilizer
10 -1
10
10 -2
10 -3
10 -4
10 -5
10 -6
100nm
10nm
10 -7 (cm)
Particle size
Large particle
Plastic waste
100m
1mm
SS
1nm
Molecule
fiber waste
Sand
Screen
10mm
Bacteria
Pigment
Bentonite
Protein
Suspended
substances
Dye
Natural precipitation
Natural floatation
(API, PPI, CPI)
Coagulating sedimentation
Coagulating floatation
Electrolytic coagulation
Ordinary filtration
Treatment method
Biological treatment
(Activated sludge treatment)
Ion exchange
-4-
Size approximation
Precipitation speed
cm/sec
0.05
Sand
0.01
Fine sand
0.42
0.001
Sludge
(silt, clay)
0.0042
10.4
10 sec
4 min
7 hr
0.0001(1m m)
Bacteria
0.000042
28 day
0.00001
Colloid
0.00000042
8 year
Vg =
1 r ro d 2 g
()
m
18
Vg : Precipitation speed
r : Solid particle density
ro: Liquid density
d : Solid particle diameter
g : Gravitational acceleration
m : Viscosity coefficient of liquid
Treated water
Coagulant-added water
(Raw water)
With a raw water flow rate of 100 m3/hr and a sedimentation pond radius of a 4 m,
water surface loading is as follows.
3
100
Water surface loading = Treated water flow rate (m /hr)
=
= 2.0m2/m2h = 2.0mh
Sedimentation pond surface area (m2) 443.14
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Common name
Inorganic coagulant
Coagulant
Action
Polyvalent cations such as AL3+, Fe3+ and Fe2+
neutralize electric charge of suspended particles. At the same time,
hydroxides such as Al(OH) 3 adsorb particles,
thus having slight flocculation effect.
Slaked lime
Seawater
Anionic/Nonionic polymer
coagulant
Coagulant
Polymer
Flocculant
Dehydrator
Cationic polymer
Coagulant
Polycation,
Flocculation effect by particle electric charge neutralization and
Low molecular weight cationic polymer cross-linking though flocculation effect is not strong.
Used as dehydrating agent with special types of dehydrators
(vacuum or SL separator) and as alternative inorganic coagulant.
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Cross-linking (Flocculation)
Nonionic/
Anionic polymer
Suspended particle
Primary floc
Inorganic coagulant Aluminum ion polymer
Coagulated floc
(High sludge generation)
Cross-linking (Flocculation)
Nonionic/
Anionic polymer
Coagulated floc
Primary floc
Low sludge generation
Organic coagulant
Types of coagulants
Molecular weight
Applicable pH
Aluminum sulfate
5~8
Polyalminium chloride
(PAC)
5~8
Inorganic coagulant
Coagulant
Clarifying agent
Iron chloride ()
Organic coagulant
Coagulant
Precipitant
Polymer coagulant
Several
100 - 1,000
4 or higher
Polyiron sulfate ()
4 or higher
Iron chloride ()
9 or higher
Several 1,000
- Several 100,000
-7-
4~7
4~8
Several 1,000,000
- 10,000,000
6~12
10 or higher
Characteristics
Coagulant
Use
Merits
4 5 6 7 8 9 10 11 12
Aluminum sulfate
(Al2[SO4]3)
Liquid product: Al2O3 8%
Solid product: Al2O3 16%
Working pH range
Effective pH range
Polyalminium
chloride (PAC)
Al2O3 10 - 11%
Iron chloride
(FeCl3)
FeCl3 38%
iron sulfate
Fe(SO4)7H2O
Demerits
Inexpensive
Lightweight flocs
High substance
Less effective
removal rate
at pH 8 or higher
Low corrosion and
stimulation
Heavy flocs
(Good compression point)
Effective ever at
alkaline range
Inexpensive
Heavy flocs
-8-
190
122
380
245
60
153
280
250
280
323
-CH2-CHCOONa
Structural Formula
Solution viscosity
and dissolving
concentration
Anionic polymer
-CH2-CHCOONa
Nonionic polymer
-CH2-CHCONH2
n:m
15 or more85 or less
n:m
15~585~95
n:m
5~095~100
High viscosity
0.05~0.10%
Medium viscosity
0.05~0.15%
Low viscosity
0.05~0.30%
High viscosity
0.05~0.10%
4
10 12 14
10 12 14
10 12
10 12
-CH2-CHC=O
CH3
NH-C-CH2SO3Na
CH3
Medium viscosity
0.05~0.15%
2
10 12
Applicable pH range
Floc strength
High
Fast
Fast
Good
Good
Manufacturing process
(Soda production,
paper and pulp, aluminum)
Protein recovery
(Fish meat recovery)
Applicable waste water
Propylene
CH2 = CHCN
Acrylonitrile
CH2 = CHCONH2
Acrylamide
Polyacrylamide
CH2 CH
CONH2
n
-9-
Good
Colored waste water
Other low to medium pH waste water
(effective with waste water of highly
fluctuating pH)
120
100
600104
80
60
40
900104
20
1200104
0
0.5
Coagulant amount added (ppm)
-10-
1.0
Constant pH (= 6.5)
Coagulation effect (Precipitation speed)
Anionic polymer
Nonionic polymer
6
pH
8
Aluminum sulfate amount added
Low pH
Excessive aluminum sulfate added
Polymer diffusion Adsorption to particles
Effect
Nonionic polymer
High pH
Insufficient aluminum sulfate added
Polymer diffusion Adsorption to particles
Anionic polymer
Excessive adsorption
Anionic
(Sulfonic group charged)
copolymer
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Effect
Dimethyl dialuric
ammonium chloride
R
N CH3CHCH3
R CI
OH
Alkylamine epichlorohydrin
condensation product
Ethyleneimine
(CH2CH3NH) n
NH2RNH2R
CICI-
NH
OCH2NHCNCONH2CH2
Dicyandiamide formalin
condensation product
CH2CO
Dischargeable if COD is
Polymer coagulant
20 mg/l or less
Organic coagulant C
Aluminum sulfate Polymer coagulant
Slaked lime
Raw water
Discharge
Reaction tank
Mixed waste water
pH7.5
SS150 mg/l
COD40 mg/l
Drainage volume
6,000 m3/day
Scum pit
Sludge thickener
Dehydrated cake
transportand disposal
Sludge storage tank
Vacuum dehydrator
Anionic
polymer
coagulant
(mg/l)
pH
SS
(mg/l)
COD
(mg/l)
Dehydrated cake
amount generated
TP
(t/day)
(mg/l)
800~1000
160
0.5
7.4
<5
12~20 0.14~0.25
10
150~200
0.5
7.0
<5
11~21
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0.6~2.7
Fig. ( potential and treatment effect when inorganic coagulant used alone and when used in conjunction with polycation
(Specimen: Automobile factory mixed waste water)
-15
potential (mv)
-10
sed with 5 mg/l organic coagulant
-5
0
100
200
300
400
500
400
500
10
100
200
300
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SS
(Heavy metals)
Phenomenon
Cause
Countermeasure
Yes
No
Clarity: NG
SS
Color
COD
BOD
n-hex
Yes
Yes
Yes
No
Yes
No
COD
BOD
n-hex
Yes
Yes
No
Consideration of addition of chemical
other than inorganic coagulant
Yes
Adsorbent (Activated carbon, bentonite)
Jar test Application of COD decreasing agent etc.
No
Yes
* To investigate floc size and clarity, sample suspended water in coagulating reaction tank and treated water, judging their appearance.
-14-
Cause
Countermeasure
Yes
Situation
Improve coagulation.
Scum floating
Localized SS discharge
Scum floating
Scum floating
No
Yes
No
Yes
Scum generation
No
Yes
Scum generation
Channeling in sedimentation
tank
Yes
Yes
No
Air inclusion because of
high inflow head
Yes
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Direct dye
Reactive dye
Dye, sodium hydroxide, sodium phosphate, sodium hydrogencarbonate, mirabilite, urea, surface active agent
Acidic dye
Dye, mirabilite, ammonium sulfate, acetic acid, sulfuric acid, surface active agent
Metal complex salt dye Dye, sulfuric acid, sodium acetate, ammonium sulfate, mirabilite, surface active agent
Cationic dye
Dye, sodium acetate, sodium carbonate, ammonium acetate, surface active agent
Sulfide dye
Vat dye
Naphthol dye
Dye, sodium hydroxide, hydrochloric acid, sodium nitrite, sodium acetate, surface active agent
Disperse dye
Pigment
NaO3S
N
NH
NH2
NHCOCH3 N
SO3Na
SO3Na HO
N N
Yellow 3
Cu
N
NaO3S
Cl
N
NH
SO3Na
NaO3S
N
N
Cl
Orange 1
N
NH
NaO3S
Cl
Cl
NH2
SO3Na
N
N
Cl
NH
SO2CH2CH2O SO3Na
Blue 19
Red 6
-16-
Dye structure
exchange
N
O
C
O3
C
CH3
H2N
H2N
H
N
CH3
NH2
NH2
Basic Violet 14
O
HSO3
C
N
H
C C
H
N
SO3H
SO3H
O3
HSO3
C
N
H
Ingigo Trisulfonate
(Blue)
Oxidative decomposition of dye by O3
-17-
C O
O C
H
N
SO3H
SO3H
Dye molecule
Electric charge neutralization
3(R2N(CH3)2)Cl
NaSO3
SO3Na
N
OH OH
(R2N(CH3)2)SO3
SO3Na
SO3(R2N(CH3)2)
N
NaCl
OH OH
SO3(R2N(CH3)2)
-18-
1000
100
10
10
0
9 10 11 12 13 14 15 16 17 18 19 20
-19-
max=530mm
Alizarin Rubinol R
PAC
Poly-Cation A
Poly-Cation B
Kuriflock PA365
150rpm for 60sec
50rpm for 60sec
Separation
Sedimentation separation/filtration
Absorbance measurement
N
N
N
N O
N
O
N
N
O
N O
O O
N N
O
N
N
N
N
O
-20-
N
O
Cucurbituril structure
N
O
1) Features
Compared to conventional powder polymers, the
Emulsion Polymer has the following features.
Fine particles like that seen with conventional powder
polymers do not occur, which improves the work
environment.
Dissolution process
Original state
Immediately after
dispersion
After 10 min
After 30 min
After 60 min
Dissolution starts
immediately.
Completely
dissolved
Dispersed only.
No major changes
observed
Small particle:
Dissolves.
Powder
Powder
Particle size: 1 - 0.1 mm
Large particle:
Completely
Dissolution starts. dissolved
Large particle:
Swells.
Emulsion Polymer
(EC/EN/EA)
Dissolution rate (%)
100
Powder polymer
(Anionic polymer)
50
10
20
30 40
Time (min)
50
60
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Continuous dissolution
Dissolution tank
Stirrer
Powder polymer
Dissolution tank
Stirrer
Deconcentrator
Deconcentrator incidental
equipment
0.7 ~ 0.8
After filling water
Weighing
Adding
Dissolution stirring
Total
1.0
After filling water
2 - 3 min Weighing and adding in hopper 2 - 3 min
5 - 10 sec Deconcentrator monitoring 5 - 10 sec
5 - 10 min Dissolution stirring 30 - 60 min
7 - 13 min
37 - 73 min
0.2
1.0
Work environment
No scattered dust
simple scaffolding
Easily performed outdoors
(in rain)
Dusty
Requires slip prevention.
Not easily performed
outdoors (in rain)
Maintenance
Not required
Deconcentrator cleaning
Removal of coagulant
scattered on scaffolding.
Dissolution equipment
0.2
Can be used outdoors.
1.0
Basically, designed for
indoor use.
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Liquid polymer
conventional polymer,
high molecular weight
Dissolution tank
Stirrer
0.9
After filling water
Weighing and adding 5 - 10 min
Dissolution stirring 60 - 120 min
Total
65 - 130 min
1.8
No scattered dust
Requires scaffolding because
of carrying about twenty times
as much as weight of powder
polymer.
Easily performed outdoors
(in rain)
Dissolving water
M
LS
LS
H
M
L
(3 m3)
Stock solution
storage tank
P
Stock solution
feed pump
(Mainly a kind
of screw pump)
L
LL
P
Feeding pump
(1 m3)
Dissolution-Storage tank
-23-
Metal
EP stock
solution
Material
EPDM, EPT
(Ethylene, propylene rubber)
NBR
(Acrylonitrile-butadiene rubber)
EP
Powder polymer
solution
solution
Material
SS41
BC-2 (Bronze)
Hyperon (CSM)
SUS304
Polyethylene
Hastelloy C
Polypropylene
Dylite
Byton
Hard polyvinyl chloride
FRP
Can be used.
Cannot be used.
-24-
EP stock
solution
EP
Powder polymer
solution
solution
Settling tank
or
conical tank
Supernatant tank
Asbestos
Raw materials Cement
Pulp
Raw material recovery
Product
Vacuum
Wet machine
Waste water
Beater
2. Results
Applicable coagulant
Amount added
(mg/l)
Chemicals cost
(1,000/month)
1.0
50 - 100
123
Kurifloc EA333
2.0 - 2.5
50 - 100
150
3. Merits
[1] Greatly improved dissolution work Dissolution work: once every hour, 20 to 24 times a day
(Dissolution tank: 100 l, storage tank: 200 l, no deconcentrator)
In case of anionic powder polymer of Company K
Weighing and adding: 10 min/cycle (200 min/day), stirring: 1 hr/cycle (24 hr/day)
In case of Kurifloc EA333
Weighing (Ladle) and adding: 0.5 min/cycle (10 min/day), stirring: 10 min/cycle (4 hr/day)
[2] Decrease of impurities (clods)
in products
Some clods of approx. 1 mm in size, believed to be undissolved coagulant, had been found in
products. After changing to Kurifloc EA333, most impurities were eliminated
-25-
Target sludge
Surplus sludge
SS
0.7 to 0.8%
VSS
70 to 75%
Sludge amount ... 120 m3/day
Dehydrator
BP
Applicable
dehydrating agent *
Treatment effect
Chemicals cost
Addition rate
(%/SS)
Treatment amount Cake water (1,000/month)
(kg-ds/m/hr)
content (%)
2. Merits
Dissolution work improvement
Labor reduction
Before, 5 kg of a conventional powder polymer was
prepared from a 15 kg bag in a 3m3 tank 2 to 3 times a
day. It took 2 hours to dissolve the polymer using a
deconcetrator. However, the dissolution tank was located
in a humid room and the deconcetrator sometimes
clogged, requiring frequent maintenance and checks.
Also, because the dissolution tank stirrer performed
poorly, it took time (5 to 10 min/cycle) to carefully
dissolve all undissolved clods.
With Kurifix EC153, a deconcentrator is unnecessary
and the polymer was dissolved in about 10 min without
clods even just after adding it, which improved the work
environment.
* Kurifix EC153: Cationic EP (Emulsion Polymer)
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1.0
90 - 100
85
320 - 350
2.0 - 2.5
100
85
380 - 420
Coagulant
After use
Before use
Treatment
rate m3/hr
Water
content %
Operating schedule
H/D D/M
Price
/kg
Amount used
Various cationic
powder polymers
(Various manufactures)
1.5450
7.5
83
725
1,300
590
Kurifix EC253
3.0900
7.5
83
725
850
1,180
2. Merits
Centrifugal dehydrator
Container loading
Dissolving water
(Ground water)
Sludge feed
3 m3 stock
solution tank
4 m3 stock
solution tank
P
P
P
Added part
Dehydrator A
Cake
Dehydrator B
Cake
Dehydrator C
Cake
Existing equipments
New equipments delivered by KWI ---3 m3 stainless steel stock solution tank (stirrer),
stock solution feed pump: a kind of screw pump, stator: synthetic rubber
Existing equipments used --- Dissolution tank (stirrer), solution feed pump
* Kurifix EC253 = Cationic EP (Emulsion Polymer)
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