Environmental Engineering –

Industrial water
Dr. Md Salatul Islam Mozumder
Professor
Department of Chemical Engineering and
Polymer Science
Shahjalal University of Science and Technology
Sylhet 3114
Industrial water

- Boiler water
- Cooling water
- Process water
Technical demands for water

Industrial water: Boiler feed water

Hardness

What is hardness of water?

Hardness:
Ca2+ + Mg2+ Total hardness
Temporary hardness:
hardness due to HCO3-
2HCO3- → CO32- + H2O + CO2↑
Ca(HCO3)2→ CaCO3 ↓ + H2O + CO2↑
Permanent hardness:
Total hardness – temporary hardness
Which one is more dangerous?
Permanent hardness or temporary hardness

HCO3- = temporary hardness = alkalinity

 Alkalinity

Carbonic acid mainly HCO3-

The concentration of HCO3- depends on
- temperature
- pH
- equilibrium with dissolved CO2 and CO32-
Carbonic acid equilibrium:

H2CO3 → HCO3- + H+
HCO3− H+ HCO3−
𝐾𝑎1 = → 𝑝𝐻 = 𝑝𝐾𝑎1 + 𝑙𝑜𝑔
H2CO3 H2CO3
How to find this relationship?
HCO3- → CO32- + H+
CO32− H+ CO32−
𝐾𝑎2 = → 𝑝𝐻 = 𝑝𝐾𝑎2 + 𝑙𝑜𝑔
HCO3− HCO3−
Alkalinity H2CO3 → HCO3- + H+
HCO3− H+ HCO3−
𝐾𝑎1 = → 𝑝𝐻 = 𝑝𝐾𝑎1 + 𝑙𝑜𝑔
H2CO3 H2CO3

HCO3- → CO32- + H+
CO32− H+ CO32−
𝐾𝑎2 = → 𝑝𝐻 = 𝑝𝐾𝑎2 + 𝑙𝑜𝑔
HCO3− HCO3−
 Alkalinity

Carbonic acid mainly HCO3-

The concentration of HCO3- depends on
- temperature
- pH
- equilibrium with dissolved CO2 and CO32-
Carbonic acid equilibrium:

H2CO3 → HCO3- + H+
HCO3− H+ HCO3−
𝐾𝑎1 = → 𝑝𝐻 = 𝑝𝐾𝑎1 + 𝑙𝑜𝑔
H2CO3 H2CO3
How to find this relationship?
HCO3- → CO32- + H+
CO32− H+ CO32−
𝐾𝑎2 = → 𝑝𝐻 = 𝑝𝐾𝑎2 + 𝑙𝑜𝑔
HCO3− HCO3−
 Acid base reaction in water/
determination of alkalinity

CO32- → HCO3- → H2CO3 by adding acid

TA : p-value
OH- + H+ → H2O
CO32- + H+ → HCO3-
The quantity of acid used is called TA value (P-value)

OH- + H+ → H2O TAC : M-value

CO32- + H+ → HCO3- + H+ → H2CO3
HCO3- + H+ → H2CO3
The quantity of acid used is called TAC value (M-value)

TA = (OH- )+ (CO32-)
TAC = (OH- ) + (CO32-) + (HCO3-) + (CO32-)*
Calculation of (OH- ), (CO32-) and (HCO3-)) from the value of
TA and TAC

1. If TA =0 and TAC≠ 0
TA = (OH- )+ (CO32-)= 0 → (OH- ) = (CO32-) = 0
TAC = (OH- ) + (CO32-) + (HCO3-) + (CO32-)* → (HCO3-) = TAC

2. If 2TA < TAC

2(OH- )+ 2(CO32-) < (OH- ) + (CO32-) + (HCO3-) + (CO32-)*
→ (OH- ) < (HCO3-)
OH- + HCO3- → H2O + CO32-
All OH- is consumed but some HCO3- is left
X - )+ (CO32-)
TA = (OH → (CO32-) = TA
X - ) + (CO32-) + (HCO3-) + (CO32-)*
TAC = (OH → (HCO3-) = TAC – 2TA
3. If 2TA = TAC
2(OH- )+ 2(CO32-) = (OH- ) + (CO32-) + (HCO3-) + (CO32-)*
→ (OH- ) = (HCO3-)

OH- + HCO3- → H2O + CO32-

All OH- and HCO3- are consumed
OH- = 0
HCO3- = 0

X - )+ (CO32-)
TA = (OH → (CO32-) = TA

5. If TA = TAC
4. If 2TA > TAC
(OH- ) = TA
(OH- )= 2TA - TAC
(CO32-) = 0
(CO32-) = TAC - TA
(HCO3-) = 0
(HCO3-) = 0
Calcium carbonate/carbonic acid equilibrium

Coexistence of the equilibrium Ca2+ and CO32-

Scale formation
Scale re-dissolve
Corrosiveness of water
CaCO3→ Ca2+ + CO32 - 𝐾𝑆 = Ca2+ CO32 −
HCO3− H+
H2CO3 → HCO3 + - H+ 𝐾𝑎1 =
H2CO3
CO32− H+
HCO3 → CO3 +
- 2- H+ 𝐾𝑎2 =
HCO3−
H2O → OH- + H+ 𝐾𝑤 = OH− H+ = 10-14
+
𝐾𝑎2 CO32− H𝑆
At equilibrium condition, =
𝐾𝑆 HCO3− Ca2+ CO32 −
𝐾𝑎2
H𝑆+ = HCO3− Ca2+
𝐾𝑆
𝐾𝑎2
−𝑙𝑜𝑔 H𝑆+ = −𝑙𝑜𝑔 − 𝑙𝑜𝑔 HCO3− − 𝑙𝑜𝑔 Ca2+
𝐾𝑆
Calcium carbonate/carbonic acid equilibrium
𝐾𝑎2
−𝑙𝑜𝑔 H𝑆+ = −𝑙𝑜𝑔 − 𝑙𝑜𝑔 HCO3− − 𝑙𝑜𝑔 Ca2+
𝐾𝑆
𝐾𝑆
𝑝𝐻𝑆 = 𝑙𝑜𝑔 + 𝑝 𝐴𝑙𝑘 + 𝑝 Ca2+
𝐾𝑎2

Saturation index (S.I.) = 𝑝𝐻 − 𝑝𝐻𝑆

S.I. = 0; water is in equilibrium
S.I. > 0; CaCO3 scale will be formed
S.I. < 0; CaCO3 scale will be re-dissolved
𝐾𝑆 and 𝐾𝑎2 are the function of temperature and salt concentration
- make differ in saturation pH
Ca2+ can be removed by
- Membrane (reverse osmosis)
- Ion exchange
 Ion exchange

Solid, non-soluble, high molecular poly-electrolytes, containing mobile

ions which can be exchanged
- cation exchange
- anion exchange

Types of ion exchanger

Cation exchanger
Strong acid: type –SO3-H+
Weak acid: type –COO-H+
Anion exchanger
Strong base: secondary/tertiary amines
Weak base: primary amines
Synthesis of ion exchanger: Cation exchanger

Strong acid: type –SO3-H+

Synthesis of ion exchanger: Cation exchanger

Weak acid exchanger: type –COO-H+

+ →
Acrylic acid Divinyl benzene
Synthesis of ion exchanger: Anion exchanger

Weak base exchanger

+ NH3 →
NH3+Cl-
Chlorinated divinyl benzene

Strong base exchanger

+ N(CH3)3 →
Chlorinated divinyl benzene
Ion exchange reaction

MF.C1+ + C2X → MF.C2+ + C1+ + X-

MF.H+ + C2X → MF.C2+ + H+ + X-

MF.H+ + C2OH → MF.C2+ + H+ + OH- → MF.C2+ + H2O

irreversible

Normally reversible exchanger is used

→ important for the regeneration of the resin
Apparent capacity and working condition

Apparent capacity and the maximum capacity are not the same
𝐶
𝑞 = 𝑞𝑚𝑎𝑥
𝐾+𝐶

Strong acid and base are completely dissociated with a wide range of pH
Weak acid do not work at low pH and weak base do not work at high pH
The workability depends on the dissociation constant (pK)
For acid; pH > pKa
For base; pH < pKb
Weak acid exchanger and weak base electrolyte; pKexchanger < pH < pKbase
Weak base exchanger and weak acid electrolyte; pKacid < pH < pKexchanger
Selectivity

Ion exchange equilibrium → ion exchange isotherm

For a binary mixture of A and B :

Equivalent ion fraction of A Equivalent ion fraction of ion B

𝑍𝐴 𝐶𝐴 𝑍𝐵 𝐶𝐵
In exchanger: 𝑋𝐴 = In exchanger: 𝑋𝐵 =
𝑍𝐴 𝐶𝐴 +𝑍𝐵 𝐶𝐵 𝑍𝐴 𝐶𝐴 +𝑍𝐵 𝐶𝐵
𝑍𝐴 𝐶𝐴 𝑍𝐵 𝐶𝐵
In solution: 𝑋𝐴 = In solution: 𝑋𝐵 =
𝑍𝐴 𝐶𝐴 +𝑍𝐵 𝐶𝑩 𝑍𝐴 𝐶𝐴 +𝑍𝐵 𝐶𝑩
Selectivity

Equivalent ion fraction of A Equivalent ion fraction of ion B

𝑍𝐴 𝐶𝐴 𝑍𝐵 𝐶𝐵
In exchanger: 𝑋𝐴 = In exchanger: 𝑋𝐵 =
𝑍𝐴 𝐶𝐴 +𝑍𝐵 𝐶𝐵 𝑍𝐴 𝐶𝐴 +𝑍𝐵 𝐶𝐵
𝑍𝐴 𝐶𝐴 𝑍𝐵 𝐶𝐵
In solution: 𝑋𝐴 = In solution: 𝑋𝐵 =
𝑍𝐴 𝐶𝐴 +𝑍𝐵 𝐶𝑩 𝑍𝐴 𝐶𝐴 +𝑍𝐵 𝐶𝑩

The relation 𝑋𝐴 /𝑋𝐴 or 𝑋𝐵 /𝑋𝐵 is the ion exchange isotherm

𝛼𝐵𝐴

Separation factor
𝑋𝐴
𝑋𝐴 𝑋𝐴 .𝑋𝐵 𝐶𝐴 .𝐶𝐵
𝛼𝐵𝐴 = 𝑋𝐵
= = 𝑋𝐴
𝑋𝐵 .𝑋𝐴 𝐶𝐵 .𝐶𝐴
𝑋𝐵

𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐼
=
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐼𝐼
Selectivity constant – equilibrium constant
+ + + +
𝑍𝐴 (𝐵 𝑍𝐵 𝑀𝐹 − )𝑍𝐵 + 𝑍𝐵 𝐴 𝑍𝐴 = 𝑍𝐵 (𝐴 𝑍𝐴 𝑀𝐹 − )𝑍𝐴 + 𝑍𝐴 𝐵 𝑍𝐵
𝐶𝐴 𝑍𝐵 .(𝐶𝐵 )𝑍𝐴
𝐾𝐶 𝐴 = Which one is constant 𝑲𝑪𝑨 or 𝜶𝑨𝑩 ?
𝐵 𝐶𝐵 𝑍𝐴 .(𝐶𝐴 )𝑍𝐵 𝑩
𝑍𝐵
𝐶𝐴 . (𝐶𝐵 )𝑍𝐴 𝐶𝐴 𝑍𝐴
. (𝐶𝐴 )𝑍𝐴
= .
𝑍𝐴 . (𝐶 ) 𝑍𝐵 𝐶 𝑍𝐴 . (𝐶 ) 𝑍𝐴
𝐶𝐵 𝐴 𝐴 𝐴

(𝐶𝐴 . 𝐶𝐵 )𝑍𝐴 𝐶𝐴 𝑍𝐵 −𝑍𝐴

= .
(𝐶𝐵 . 𝐶𝐴 )𝑍𝐴 (𝐶𝐴 )𝑍𝐵 −𝑍𝐴
𝑍𝐵 −𝑍𝐴
𝐶𝐴
= (𝛼𝐵𝐴 )𝑍𝐴 .
𝐶𝐴
𝜶𝑨𝑩 = Not constant,
𝑲𝑪𝑨 =constant, f(Temperature) f(concentration)
𝑩

𝜶𝑨𝑩 ↑ for high valence

For same valence, 𝜶𝑨𝑩 ↑ for high mass (atomic number)
Ion exchange process

1. Batch process: → lab scale experiment

→ Only acid-base exchanger in industry
2. Column process: → mostly used in industry
Ion exchange process

2. Column process: → mostly used in industry

Ion exchange regeneration

1. Downstream regeneration (co-current)

2. Upstream regeneration (counter-current)

1. Downstream: → Regeneration is not complete

→ Complete regeneration is expensive
→ Effluent with contamination
(leakage of column)

2. Upstream: → favorable for complete reuse

→ Leakage of column could be avoided

How can you explain the selectivity factor in regeneration?

Water treatment with ion exchange

1. Softening
2. Removal of alkalinity
3. De-ionizing or demineralization

1. Softening:
𝐶𝑎2+ ,𝑀𝑔2+ − 𝑁𝑎 + 𝑁𝑎+ − 𝐶𝑎 2+ , 𝑀𝑔2+
+ 𝑀𝐹𝑠𝑎 => + 𝑀𝐹𝑠𝑎
𝑆𝑂42− ,𝐶𝑙− ,𝐻𝐶𝑂3− 𝑆𝑂42− ,𝐶𝑙− ,𝐻𝐶𝑂3−

→ regenerated with 5-10% NaCl

Water treatment with ion exchange

2. Removal of alkalinity:
Week acid cation exchanger: 𝐻𝐶𝑂3− + 𝐻 +
𝐻2 𝑂 + 𝐶𝑂2
𝐶𝑎2+ ,𝑀𝑔2+ − 𝐶𝑎2+ ,𝑀𝑔2+
+ 𝑀𝐹𝑤𝑎 𝐻+ => −
+ 𝑀𝐹𝑤𝑎 (𝐶𝑎2+ , 𝑀𝑔2+ ) + 𝐻2 𝐶𝑂3
𝑆𝑂42− ,𝐶𝑙− ,𝐻𝐶𝑂3− 𝑆𝑂42− ,𝐶𝑙−

Aeration

Cation and anion exchanger in sodium cycle:

𝐶𝑎2+ ,𝑀𝑔2+ + 𝐶𝑎2+ ,𝑀𝑔2+ +
+ 𝑀𝐹𝑠𝑏 𝐶𝑙 − => + 𝑀𝐹𝑠𝑏 (𝑆𝑂42− , 𝐻𝐶𝑂3− )
𝑆𝑂42− ,𝐶𝑙 − ,𝐻𝐶𝑂3− 𝐶𝑙 −

𝐶𝑎2+ ,𝑀𝑔2+ − 𝑁𝑎 + 𝑁𝑎+ − (𝐶𝑎 2+ , 𝑀𝑔2+ )

+ 𝑀𝐹𝑠𝑎 => + 𝑀𝐹𝑠𝑎
𝐶𝑙 − 𝐶𝑙 −

→ regenerated with 5-10% NaCl

Water treatment with ion exchange

3. De-ionizing or demineralization
Strong acid and strong base :
𝐶𝑎2+ ,𝑀𝑔2+ − + 𝐻+ −
+ 𝑀𝐹𝑠𝑎 𝐻 => + 𝑀𝐹𝑠𝑎 (𝐶𝑎2+ , 𝑀𝑔2+ )
𝑆𝑂42− ,𝐶𝑙− ,𝐻𝐶𝑂3− 𝑆𝑂42− ,𝐶𝑙− ,𝐻𝐶𝑂3−

𝐻+ + 𝐻+ +
+ 𝑀𝐹𝑠𝑏 𝑂𝐻− => ( 𝑂𝐻 − = H2O) + 𝑀𝐹𝑠𝑏 (𝑆𝑂42− , 𝐶𝑙 − , 𝐻𝐶𝑂3− )
𝑆𝑂42− ,𝐶𝑙− ,𝐻𝐶𝑂3−

Strong acid and weak base :

Strong base and weak acid :

Mixed bed ion exchanger:

How to separate the mixture of resin after regeneration?

Any question?