Pengolahan Kimia

 Penyisihan unsur pencemar dengan cara pen

ambahan chemical agent/bahan kimia sehing
ga terjadi reaksi kimia, contoh : koagulasi da
n presipitasi
 Prinsip dasar: perubahan bentuk terlarut/ters
uspensi menjadi bentuk yang terendapkan (k
ecuali desinfeksi) sehingga lumpur yang teren
dapkan termasuk kategori B3 (perlu treatmen
t khusus)
 Kelebihan pengolahan secara kimia:
 Efisiensi tinggi (dapat mencapai angka yang diingi
nkan)
 Waktu dentensi relatif singkat sehingga volume re
aktor/unit pengolahan relatif lebih kecil
 Kekurangan
 Ada penambahan zat aditif sehingga meningkatka
n konsentrasi Total Dissolved Solid (TDS). Penyisih
an TDS relatif sulit dan mahal: membran atau dest
ilasi
 Meningkatkan beban pengolahan
 Biaya bahan kimia cukup mahal = biaya untuk ene
rgi
 Softening

Benno Rahardyan

Faculty of Civil and Environmental Engineering - ITB

Private Water System Resources
Hard water
What is "Hard Water"?
 Perhaps you have on occassion noticed mineral deposits on your
cooking dishes, or rings of insoluble soap scum in your bathtub.
These are not signs of poor housekeeping, but are rather signs
of hard water from the municipal water supply.
 Hard water is water that contains cations with
a charge of +2, especially Ca2+ and Mg2+.
 These ions do not pose any health threat, but they can engage i
n reactions that leave insoluble mineral deposits. These deposits
can make hard water unsuitable for many uses, and so a variety
of means have been developed to "soften" hard water; i.e.,remo
ve the calcium and magnesium ions.
 water hardness

Hard water is water contaminated with compounds of c

alcium and magnesium. Dissolved iron, manganese, a
nd strontium compounds can also contribute to the "t
otal hardness" of the water, which is usually expresse
d as ppm CaCO3.

Water with a hardness over 80 ppm CaCO3 is often trea

ted with water softeners , since hard water produces
scale in hot water pipes and boilers and lowers the ef
fectiveness of detergents.
T
abl
e1.H ar
dnes
sC l
assi
fica
tion
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ngrai
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ter(mg/l
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all
on(gp
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elofH a
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ssp ar
tsperm i
llio
n( p
pm)
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b
elo
w1.0 so
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Problems with Hard Water
 Mineral deposits are formed by ionic reactions resulting in the
formation of an insoluble precipitate. For example, when hard
water is heated, Ca2+ ions react with bicarbonate (HCO3-) ions
to form insoluble calcium carbonate (CaCO3), as shown in Equ
ation 1.
 This precipitate, known as scale, coats the vessels in which the
water is heated,
 reduce the efficiency of heat transfer
 serious effect for industrial-sized water boilers
 scale can accumulate on the inside of appliances, such as dishwa
shers, and pipes.
Softening
Precipitation
Neutralization
CO2+Ca(OH)2  CaCO3(s) + H2O

Ca+2 Precipitation at pH 10
Ca+2 +2HCO3-+Ca(OH)2  2CaCO3(s) + 2H2O
Mg+2 Precipitation at pH 11
Mg+2 +2HCO3-+Ca(OH)2  2MgCO3 + CaCO3(s) + 2H2O
Mg+2 + CO3= +Ca(OH)2  Mg(OH)2((s) + CaCO3(s)

Ionic Balance: addnon non hardness ionic (Na+) :

Mg+2 +NaOH  Mg(OH)2((s) + Na +
Ca+2 +Na2CO3  CaCO3(s) + 2Na+
 Precipitation
 For large-scale municipal operations, a process known as the "li
me-soda process" is used to remove Ca2+ and Mg2+ from the
water supply.
 The water is treated with a combination of slaked lime, Ca(OH)2
, and soda ash, Na2CO3. Calcium precipitates as CaCO3, and m
agnesium precipitates as Mg(OH)2. These solids can be collecte
d, thus removing the scale-forming cations from the water suppl
y.
 To see this process in more detail, let us consider the reaction f
or the precipitation of Mg(OH)2.
 Consultation of the solubility guidelines in the experiment reveal
s that the Ca(OH)2 of slaked lime is moderately soluble in water
. Hence, it can dissociate in water to give one Ca2+ ion and two
OH- ions for each unit of Ca(OH)2 that dissolves.
 The OH- ions react with Mg2+ ions in the water to form
the insoluble precipitate. The Ca2+ ions are unaffected b
y this reaction, and so we do not include them in the net
ionic reaction. They are removed by the separate reactio
n with CO32- ions from the soda ash.
 Ion-exchange
 Ion-exchange devices consist of a bed of plastic (poly
mer) beads covalently bound to anion groups, such a
s -COO-.
 The negative charge of these anions is balanced by N
a+ cations attached to them. When water containing
Ca2+ and Mg2+ is passed through the ion exchanger
, the Ca2+ and Mg2+ ions are more attracted to the
anion groups than the Na+ ions.
 Hence, they replace the Na+ ions on the beads, and
so the Na+ ions (which do not form scale) go into th
e water in their place.
The ion exchange process
 Calcium (Ca2+) and magnesium (Mg2+) ions that ca
use water hardness can be removed fairly easily by u
sing an ion exchange procedure.
 Water softeners are cation exchange devices. Cations
refer to positively charged ions. Cation exchange invo
lves the replacement of the hardness ions with a non
hardness ion.
 Water softeners usually use sodium (Na+) as the exc
hange ion. Sodium ions are supplied from dissolved s
odium chloride salt, also called brine. In the ion exch
ange process, sodium ions are used to coat an excha
nge medium in the softener.
 The exchange medium can be natural "zeolites" or sy
nthetic resin beads that resemble wet sand.
The exchange medium can be natur
al "zeolites" or synthetic resin beads
that resemble wet sand.
 Softening Process
NaZeolite + Ca2+ --> CaZeolite + Na+
and
NaZeolite + Mg2+ --> MgZeolite + Na+

 Recharging Process
NaCl + CaZeolite --> NaZeolite + CaCl
and
NaCl + MgZeolite --> NaZeolite + MgCl
 Ion exchange softeners replace Ca++ and Mg++ with Na+ ions.
Zeolite medium is recharged with Na+ by NaCl brine when depleted.
 Ion Exchange Water Softeners

 Exchange sodium ions for calcium and magnesium

ions in water
 May be dietary hazard - hypertension (adds 140
mg/l of sodium in “Hard” water)
 Use potassium salt (KCl) for health reasons
 many people with high blood pressure or other h
ealth problems must restrict their intake of sodium.
 Because water softened by this type of ion exchange
contains many sodium ions, people with limited sodiu
m intakes should avoid drinking water that has bee
n softened this way. Several new techniques for softe
ning water without introducing sodium ions are begin
ning to appear on the market.
 Types of water softening equipm
ent available
Water softeners are classified in five different categories:
 Manual: There are several types of manual softeners. The oper
ator opens and closes valves to control the frequency, rate and
time length of backflushing or recharging.
 Semi-automatic: The operator initiates only the recharging cy
cle. A button is pushed when the softener needs recharging and
the unit will control and complete the recharging process.
 Automatic: The automatic softener usually is equipped with a t
imer that automatically initiates the recharging cycle and every
step in the process. The operator needs only to set the timer an
d add salt when needed. It is the most popular type of softener
used.
Types of water softening equipm
ent available

 Demand initiated regeneration (DIR): All operations are ini

tiated and performed automatically in response to the water use
demand for softened water. DIR systems generally have two sof
tening tanks and a brine tank. While one tank is softening the ot
her tank is recharging.

 Off-site regeneration (generally rental units): A used softenin

g tank is physically replaced with a recharged tank. Spent soften
ing tanks are then recharged at a central location.
Ion Exchange Water
Softener with Sensor
- Controlled Recharg
e
Softener Selection Considerations

 Required grain capacity

 Daily water use (household populatio
n)
 Water hardness
 Desired regeneration schedule
 Initial cost
 Water conservation
 Other (Iron removal, etc.)
 Ion Exchange Water
Softener Capacity
 Rated by grains of hardness treated between regeneration
s

Example:
Water hardness = 200 mg/l
Softener Capacity = 2000 gr
Household Population = 4 persons

Calculate:
Water Use = 4 persons x 200 l/person-day = 800 l/day
Daily Hardness Treated = 800 l/day x 200 mg/l = 160 gr/day
Regeneration Interval = 2000 gr/ 160 gr/day = 12.5 days
 Recommended Softener Sizes
Pump Capacity (l/ Softener Capacity (g Water Hardness (m
det) r) g/l)
50 750 350
80 1000 500
120 1500 850
140 2000 1200
200 3000 1500
Ion Exchange Water Softener
Recharge Control Method
Water Us Initial Cost
e
-
+
-Time Clock
-Flow Meter
-Hardness
-
- Sensor +
 Water Softening
 Permanent magnet water softeners don’
t work
 Electrostatic and catalytic descalers may
“descale” water, but don’t soften it
 Scale will not buildup on pipes, water heater
elements, bathtubs etc.
 Sudsing action of soaps is not improved
Typical Programmable Water Softener Contr
oller
 Reactions
 CO2+Ca(OH)2CaCO3+H20
 Ca(HCO3)2+Ca(OH)2=2CaCO3+2H20
 Mg(HCO3)2+Ca(OH)2=MgCO3+CaCO3+2H20
 MgCO3+Ca(OH) 2=Mg(OH)2+2CaCO3
 MgSO4+Ca(OH) 2=CaSO4 + Mg(OH)2
 CaSO4+Na2CO3=CaCO3 + Na2SO4
 CaCl2+Na2CO3=CaCO3 + 2NaCl
 MgSO4+Ca(OH)2=CaSO4 + Mg(OH)2
 MgCl2+Ca(OH)2= Mg(OH)2 + CaCl2
 CO2+Ca(OH)2Ca+2+2OH-
 CO2+2OH- HCO3-
 HCO3-+OH- CO3-2+H20
 Ca+2 +CO3-2  CaCO3
 Mg+2 + 2OH- Mg(OH)2
Pretreatment and other variati
ons
Prior to softening some preliminary treatment may be a
dvisable if
1. Raw water turbidities exceed 3,000 NTU at times
2. Raw water has high concentration of free carbon di
oxide (more than 10 mg/l)
3. The raw water is high in organic colloids of a type t
hat impedes crystallization of calcium carbonate
4. Raw water quality is highly variable over short peri
ods of time
5. Recalcining of sludge is to be practiced
Variation of process
 Single or two stage recarbonation ater conventional li
me-soda treatment
 Sludge recirculation
 Excess lime treatment with split treatment or recarbo
nation
 Post-treatment with polyphophates
 Coagulation with alum, activated silica, or polymers
 The use of three-stage treatment
 The substitution of cation exchangers for soda ash to
remove non carbonate hardness
 The use of caustic soda instead of soda ash
 CO2+2NaOHNa2CO3+H20
 Ca(HCO3)2+2NaOH=CaCO3+Na2CO3+2H20
 Mg(HCO3)2+4NaOH=Mg(OH)2+2Na2CO3+2H20
 MgSO4+2NaOH=Mg(OH)2 + Na2SO4
Systems expressing hardness
of water
 German degree = Ca and Mg equivalent
with 10 mg CaO/liter
 French degree = Ca and Mg equivalent
with 10 mg CaCO3/liter
 English degree = one grain (0.06480 g)
of CaCO3 per gallon (3.785 L)
 USA = ppm (mg/L) CaCO3
Expressing hardness in millieq
uivalent/liter
1 milli-equivalent per liter =

- 2.8 German degree

- 5.0 French degree
- 3.5 English degree
- 50 mg CaCO3/liter

< 2 meq/L  soft water

> 5 meq/L  hard water
Total hardness = amount of Ca and Mg non car
bonate hardness + carbonate hardness.

Carbonate hardness = Ca and Mg equivalent to

bicarbonate content

The difference between total hardness and bica

rbonate (also called carbonate) hardness is th
e non carbonate hardness, which corresponds
with ions like Cl-, and SO4--
 HCO3-
I
Total hardness

Ca+2 Mg+2

HCO3-
II Total hardness

Ca+2 Mg+2
Solubility in water
Substance mg/l meq/l mg CaCO3/l

Ca(OH)2 1280 34.9 1730

CaCO3 15 0.3 15

Ca3(PO4)2 Nearly insoluble

Mg(OH)2 8.4 0.29 14.5

MgCO3 110 2.62 131

Mg3(PO4)2 Nearly insoluble

Disadvantage of phosphate method
- Rather expensive (cost of sodium ortho
phosphate)
- Treated water will contain some rest of
PO43-
- For drinking water it is not necessary an
d even not reccomendable to remove all
hardness
 Lime soda process
I CO2+Ca(OH)2CaCO3+H20 1
II Ca(HCO3)2+Ca(OH)2=2CaCO3+2H20 1

IIIa Mg(HCO3)2+Ca(OH)2=MgCO3+CaCO3+2H20
IIIb MgCO3+Ca(OH)2=Mg(OH)2+2CaCO3
III Mg(HCO3)2+2Ca(OH)2=Mg(OH)2+2CaCO3+2H20 2

IV CaCl2+Na2CO3=CaCO3 + 2NaCl 1

Va MgCl2+Ca(OH)2=CaCl2 + Mg(OH)2
Vb CaCl2+Na2CO3=CaCO3 + 2NaCl
V MgCl2+Ca(OH)2+Na2CO3=CaCO3 + Mg(OH)2 + 2NaCl 1 1
II, III carbonate hardness reactions needed Ca(OH)2 in meq
IV, V non carbonate hardness reaction needed Na2CO3 in meq
 Lime soda process I II V

Lime needed : [CO2] +[HCO3-]+ [Mg+2]

Soda needed : [Ca+2] - [HCO3-] + [Mg+2]
CO2 HCO3-
I IV V

Ca+2 Mg+2

CO2 HCO3-
II

Ca+2 Mg+2 Lime needed : [CO2] +[HCO3-]+ 2[Mg+2]

I II III
Sodium hydroxide-soda process
Advantages
- Dosage of NaOH solutions is very simpl
e
- By using NaOH the amount of sludge is
much less than with Ca(OH)2 as the pre
cipitating agent)
 NaOH process
I CO2+2 NaOHNa2CO3+H20 1
II Ca(HCO3)2+ 2NaOH =CaCO3+Na2CO3+2H20 1

IIIa Mg(HCO3)2+ 2NaOH =MgCO3+Na2CO3+2H20

IIIb MgCO3+ 2NaOH =Mg(OH)2+Na2CO3
III Mg(HCO3)2+ 4NaOH =Mg(OH)2+2Na2CO3+2H20 2

IV CaCl2+Na2CO3=CaCO3 + 2NaCl 1

V MgCl2+ 2NaOH = NaCl + Mg(OH)2 1

II, III carbonate hardness reactions needed Ca(OH)2 in meq
IV, V non carbonate hardness reaction needed Na2CO3 in meq
 NaOH process I II V

NaOH needed : [CO2] +[HCO3-]+ [Mg+2]

Soda needed : ([Ca+2] - HCO3- ) – ([CO2] +[HCO3-])
CO2 HCO3- [Ca+2] - [CO2] - 2[HCO3-]
I
IV I, II

Ca+2 Mg+2

CO2 HCO3-
II

Mg+2
Ca+2 NaOH needed : [CO2] +[HCO3-]+ 2[Mg+2]

I II III
 CaSO4+Na2CO3=CaCO3 + Na2SO4
 CaCl2+Na2CO3=CaCO3 + 2NaCl
 MgSO4+Ca(OH)2=CaSO4 + Mg(OH)2
 MgCl2+Ca(OH)2= Mg(OH)2 + CaCl2
Diketahui air mengandung ion
 Cl=142 mg/l,

 HCO3-=183 mg/l

 Ca++ = 120 mg/l

 Mg++=36 mg/l

 CO2 terlarut = 66 mg/l

Harga bahan kimia

 Na2CO3 = Rp. 4500/kg

 NaOH = 4000/kg

 Ca(OH) = 2500/kg
1. Hitung tingkat kesadahan yang dapat dicapai denga
n metode pengendapan yang paling murah. Jawaba
n didasarkan atas perhitungan dan reaksi-reaksi
2. Hitunglah tingkat kesadahan yang dapat dicapai dala
m proses pelunakan menggunakan Ca(OH)2 jika dik
etahui bahan proses ini memerlukan kelebihan dosis
Ca(OH)2 sebanyak 18,5 mg/l
3. Idem soal 2 menggunakan NaOH jika diperlukan kel
ebihan dosis NaOH sebesar 16 mg/l
 Cl-=142 mg/l =142/35.5 = 4 meq/l
 HCO3-=183 mg/l = 183/61 = 3 meq/l
 Ca2+ = 120 mg/l = 120x2/40=6 meq/l
 Mg2+ = 36 mg/l = 36x2/24 = 3 meq/l
 CO2 = 66 mg/l = 66x2/44 = 3 meq/l

Ca2+ Mg2+ > HCO3-  bukan hanya kesadahan seme

ntara
Kesadahan total = 9 meq/l
Kesadahan sementara = 3 meq/l
Kesadahan tetap = 6 meq/l
Total Ca(OH)2 yang dibutuhkan
333+18,5 = 350 mg/l

Naik 350/333 = 1,05

Ksp CaCO3 < Ca2+ + CO3=

pada suhu tertentu adalah 0,3 meq/l
=[Ca2+][CO3=]/[CaCO3]
dengan memperhatikan

Ca(OH)2 = Ca2+ + OH-

350 350
---- mmol/l ----- mmol/l
74 74
Dengan kenaikan 1,05 pada ion Ca
maka Ksp  0,3 x 1,05 = 0,315 meq/l

Mg(OH)2 = Mg2+ + OH-

Ksp = 0,24 meq/l

Total 0,555 meq/l = 1,64 D CaCO3

1 D = 10 mg/L CaCO3 = 10/(40+12+48)*2
= 0,2 meq/L CaCO3

Ca(OH)2 = Ca2+ + 2OH-

18,5 mg
18,5 x 2
--------- = 0,5 meq/L
40+34
Tingkat kesadahan 0,5/0,2 = 2,5 D

NaOH = Na+ + OH-

16 mg
16/40 =
0,4 meq

Kesadahan 0,4/0,2 = 2 D