MATERIAL BALANCE

Introduction:
The material balance calculation is basic tool for many chemical engineering problems. It
gives information regarding material entering, leaving, accumulated or depleted during unit
operation or unit process. Material balance helps in designing new process because designing
of equipment starts only after material balance is performed. To produce a particular amount
of product it is necessary to find out required quantity of raw material. For this material
balance calculation is necessary. In chemical industries it is possible to produce a desired
product from different rout. Therefore, by performing material balance calculation we can
select the particular rout for efficient use of equipment or effective rout for economic point of
view.
The basis of material balance calculation is law of conservation of mass. It states that the
total mass of various components involved in a unit operation or unit process remains
constant. Thus, for any unit process or operation,
Input – Output = Accumulation
Material balance calculation is classified as:
(1) Steady state or unsteady state
(2) With chemical reaction or without chemical reaction
(3) Overall balance or component balance.

Overall Reaction:
2NaCl + CaCO3 Na2CO3 + CaCl2
Basis: To produce 3000 MT per day Na2CO3
= 125 MT/hr.
= 1179.24 kmol/hr.
Overall plant efficiency = 68.5%
Material balance over Section – 100

Ca(OH)2 Na2CO3

Raw Salt Pure Brine

Section - 100
Water Waste

Figure 3.1 Material balance over Section – 100

Preparation of Raw Brine:

From Overall reaction,
To produce 1 mol of Na2CO3 = 2 mol of NaCl required

Therefore, for 1179.24 kmol Na2CO3

= 2358.48 kmol of NaCl required

At overall plant efficiency,

= 2358.48/0.685 = 3443.03 kmol

= 201.41 MT NaCl required.
%NaCl in salt (by wt.) = 94.6%
Therefore, salt has to be buy = 201.41/0.946 = 212.9 MT
Therefore, remaining waste = 212.9 – 201.41 = 11.49 MT
Conc. Of NaCl in raw brine = 5.3 mol/liter
From 5.3 mol NaCl = 1 liter brine is form
Therefore, from 3443.03 kmol NaCl
= 649628 liters
= 649.628 m3 raw brine is form
Purification of raw brine:
Mg+2 + Ca(OH)2 Mg(OH)2 + Ca+2

Concentration of Mg+2 in raw brine = 20 mmol/liter = 20 mol/m3

Mg+2 present in raw brine = 20*649.628 = 13 kmol = 13*24/1000
 = 0.312 MT
Ca(OH)2 required = 13 kmol = 13*74/1000 = 0.962 MT
Mg(OH)2 form = 13 kmol = 0.754 MT
Ca+2 form = 13 kmol = 0.52 MT

CaO + H2O Ca(OH)2

From above reaction,
CaO required = 13 kmol = 13*56/1000 = 0.728 MT
But, purity of CaO coming from section – 200 is = 60%
Therefore, CaO from section – 200 required = 0.728/0.6
= 1.213 MT

Ca+2 + Na2CO3 CaCO3 + 2Na+

Concentration of Ca+2 = 20 mmol/liter from raw brine + 20 mmol/liter from above reaction
= 40 mmol/liter
= 40 mol/m3
Ca+2 present = 40*649.628 = 25.98 kmol = 25.98*40/1000 = 1.0392 MT
Na2CO3 required = 25.98 kmol = 25.98*106/1000 = 2.7538 MT
CaCO3 form = 25.98 kmol = 25.98*100/1000 = 2.598 MT
Na+ form = 51.96 kmol = 51.96*23/1000 = 1.195 MT

Material balance over Section – 100

Input (kg/hr ) Output (kg/hr)
Salt 212900 Brine solution 851038
Water 649628 Waste 15206
Ca(OH)2 962
Na2CO3 2754
Total 8,66,244 Total 8,66,244
Material balance over Section – 200
CO2
N2
O2

Raw CaCO3

Coal Section - 200

Air

CaO
CaCO3
C
Residue of C
Residue of CaCO3

Figure 3.2 Material balance over Section – 200

CaCO3 CaO + CO2

C + O2 CO2

From overall reaction,

For 1 mol Na2CO3 = 1 mol pure CaCO3 required

Therefore, for 1179.24 kmol Na2CO3

= 1179.24 kmol pure CaCO3 required.

At overall plant efficiency,
= 1179.24/0.685
= 1721.52 kmol CaCO3 required
But, degree of calcination = 88%
Therefore, pure CaCO3 required = 1721.52/0.88
= 1956.27 kmol = 195.627 MT
% CaCO3 present in raw CaCO3 = 87%
Therefore, raw CaCO3 has to be fed = 195.627/0.87
= 224.86 MT
 Pure CaO form = 1956.27 * 0.88 = 1721.51 kmol = 96.4 MT
Pure CO2 produced from CaCO3 = 1721.51 kmol = 75.746 MT
Coal/Raw CaCO3 = 0.08
Coal fed in kiln = 0.08 * 224.86 = 18 MT
% Fixed carbon in coal = 86%
Fixed carbon = 18 * 0.86 = 15.48 MT = 15.48*1000/12 = 1290 kmol
= 15.48 MT
Conversion of combustion of coal = 90%
Pure CO2 from combustion of coal = 1290 * 0.9 = 1161 kmol = 51.084 MT
Unburnt CaCO3 = 1956.27 * 0.12 = 234.75 kmol = 23.475 MT
Residue from CaCO3 = 224.86 – 195.627 = 29.233 MT
Unburnt carbon = 1290 * 0.1 = 129 kmol = 1.548 MT
Residue from coal = 18 – 15.48 = 2.52 MT
CaO produced with impurity = 96.4 + 23.475 + 29.233 + 1.548 + 2.52
= 153.176 MT
O2 required for burning coal = 1290 kmol
Air required = 1290/0.21 = 6142.86 kmol
= 6142.86*28.84/1000 = 177.16 MT
N2 in output = 6142.86*0.79 = 4852.86 kmol = 135.88 MT
O2 in output = 1290*0.1 = 129 kmol = 4.128 MT
Total pure CO2 in output = 1721.51 + 1161 = 2882.51 kmol = 126.83 MT
Amount of gas outgoing from kiln = 4852.86 + 129 + 2882.51
= 7864.37 kmol

Therefore, % CO2 in output gas (mole fraction) = 2882.51 / 7864.37 = 36.66%

%N2 = 4852.86/ 7864.37 = 61.69 %
%O2 = 129/ 7864.37 = 1.64%
Density of CO2 = 1.98 kg/m3
Therefore, volume of CO2 = 126.83*1000/1.98
= 64055.55 m3
%CO2 in gas outgoing from kiln = 36.66%
 Therefore, gas outgoing from kiln = 64055.55/0.3662
= 174919.58 m3

Material balance over Section – 200

Input (Kg/hr) Output (Kg/hr)
Raw CaCO3 2,24,860 CaO 96,400
Coal 18,000 CO2 1,26,830
Air 1,77,160 Unreacted CaCO3 23,475
Unreacted carbon 1,548
Residue from
29,233
CaCO3
Residue from coal 2,520
Nitrogen 1,35,880
Unreacted Oxygen 4,128
Total 4,20,020 Total 4,20,020

Material balance over Section – 300

Pure Brine A – liquor (NaCl + NH4OH)

Section -
300
NH3 (Recovered + NH3
makeup)

Figure 3.3 Material balance over Section – 300

NaCl + H2O + NH3 NH4OH + NaCl

NaCl present in purified brine = 3443.03 kmol
= 201.41 MT
Density of water = 1000 kg/m3
Amount of water = 649.628 m3 = 649.628*1000/1000
= 649.628 MT
= 649.628*1000/18 = 36090.44 kmol
From above reaction,
 Ammonia absorbed = 3443.03 kmol = 58.53 MT
But, absorption efficiency = 95.4%
Ammonia added = 3443.03/0.954 = 3609.046 kmol
= 61.35 MT
Make up ammonia = 1.3% of total ammonia added.
Make up ammonia = 61.35 *0.013 = 0.797 MT = 797 kg
Recovered ammonia = 61.35 – 0.797 = 60.553 MT
NH4OH form = 3443.03 kmol = 120.5 MT
NaCl in output = 3443.03 kmol = 201.417 MT
NH3 in output = 61.35 – 58.53 = 2.82 MT
Water in output = 36090.44 – 3443.03 = 32647.41 kmol
= 587.65 MT
This NaCl + NH4OH mixture is called A-liquor.

Concentration of A-liquor = 5.1 mol/liter

Moles of A-liquor = 3443.03 kmol = 3443.03*(58.5 + 35)/1000 = 321.92 MT
Volume of A-liquor = 3443.03*1000/5.1 = 675103.92 liter
= 675.103 m3

Material balance over Section – 300

Input (Kg/hr.) Output (Kg/hr.)
NaCl 2,01,410 NaCl 2,01,410
Water 6,49,628 NH4OH 1,20,500
NH3 61,350 NH3 (unreacted) 2,820
Water 5,87,650
Total 9,12,388 Total 9,12,388
Material balance over Section – 400

CO2
A – liquor N2
(NaCl + NH4OH) Vent O2
NH3
Kiln Gas Section - 400
Draw liquor NaHCO3
Calciner Gas NH4Cl
NaCl
NH4OH

Material balance over Section – 400

NH4OH + NaCl + CO2 NH4Cl + NaHCO3

Amount of NaCl available = 3443.03 kmol = 201.41 MT

Amount of NH4OH available = 3443.03 kmol = 120.5 MT
Therefore, total CO2 required = 3443.03 kmol = 151.49 MT
Cleaning Tower:
Volume of A-liquor in = 675.103 m3
Volume of C-liquor out = 675.103 m3

Concentration of CO2 in C-liquor to be maintained = 1.5 mol/litre = 1.5 kmol/m3

CO2 need to be added in cleaning tower = 1.5 * 675.103 = 1012.65 kmol
= 44.55 MT

Composition of kiln gas (mole fraction): CO2 = 36.66 %

N2 = 61.69 %
O2 = 1.64 %
Amount of kiln gas required for cleaning tower = 1012.65/0.3666
= 2762.27 kmol
= 93.72 MT
Output gas from cleaning tower,
 N2 = 2762.27*0.6169 = 1704.04 kmol = 47.713 MT
O2 = 2762.27*0.0164 = 45.3 kmol = 1.45 MT

Density of CO2 = 1.98 kg/m3

Therefore, volume of CO2 = 44.55*1000/1.98 = 22500 m3
Volume of kiln gas = 22500 /0.3666 = 61374.8 m3
Volume of outgoing gas = 61374.8 – 22500 = 38874.8 m3

Production Tower:
Conversion = 71%
From above reaction,
NH4Cl form = 3443.03*0.71 = 2444.55 kmol = 2444.55*53.5/1000
= 130.78 MT
NaHCO3 form = 3443.03*0.71 = 2444.55 kmol = 2444.55*84/1000
= 205.342 MT
CO2 reacted = 3443.03*0.71 = 2444.55 kmol = 107.56 MT
CO2 unreacted = 3443.03 – 2444.55 = 998.48 kmol = 43.93 MT
NaCl unreacted = = 3443.03*0.29 = 998.48 kmol = 58.41 MT
NH4OH unreacted = 998.48 kmol = 34.94 MT
CO2 added in production tower = 3443.03 – 1012.65 = 2430.38 kmol
= 106.936 MT
CO2 added from calciner gas = 1178.65 kmol = 51.86 MT
CO2 added from kiln gas = 2430.38 – 1178.65 = 1251.73 kmol = 55.06 MT

% CO2 in kiln gas = 36.66%

Amount of kiln gas required for production tower = 1251.73/0.3666
= 3414.43 kmol
= 115.846 MT
Composition of calciner gas: CO2 = 95%
NH3 = 5%
Amount of calciner gas required for production tower = 1178.65/0.95
 = 1240.68 kmol
= 52.915 MT
Output gas from production tower,
CO2 unreacted = 998.48 kmol = 43.93 MT
N2 = 3414.43*0.6169 = 2106.36 kmol = 58.97 MT
O2 = 3414.43*0.0164 = 56 kmol = 1.792 MT
NH3 = 1240.68*0.05 = 62.034 kmol = 1.0545 MT
Total = 43.93 + 58.97 + 1.792 + 1.0545 = 105.7465 MT

Density of CO2 = 1.98 kg/m3

Volume of CO2 in kiln gas = 55.06*1000/1.98 = 27808.08 m3
Volume of kiln gas = 27808.08/0.3666 = 75854 m3
Volume of CO2 in calciner gas = 51.86*1000/1.98 = 26191.92 m3
Volume of calciner gas = 26191.92/0.95 = 27570.4 m3
Total kiln gas added in carbonation = 61374.8 + 75854 = 137228.8 m3

Material balance over Section – 400

Input (Kg/hr.) Output (Kg/hr.)
NaCl 2,01,410 NH4Cl 1,30,780
NH4OH 1,20,500 NaHCO3 2,05,342
Kiln gas 2,09,566 NaCl (unreacted) 58,410
Calciner gas 52,915 NH4OH (unreacted) 34,940
Water 5,87,650 CO2 43,930
N2 1,06,683
O2 3,242
NH3 1,055
Water 5,87,650
Total 11,72,041 Total 1172041
Material balance over Section – 500

NH4Cl

Draw Section - 500 Na2CO3

liquor

Calciner gas

Figure 3.5 Material balance over Section – 500

Filtration:
Material balance over filtration
Input (Kg/hr.) Output (Kg/hr.)
NH4Cl 1,30,780 NH4Cl 1,30,780
NaHCO3 2,05,342 NaHCO3 2,05,342
NaCl (unreacted) 58,410 NaCl (unreacted) 58,410
NH4OH (unreacted) 34,940 NH4OH (unreacted) 34,940
Water 5,87,650 Water 5,87,650
Total 10,17,122 Total 10,17,122
From this 98 wt.% NaHCO3 goes to calcination, 2 wt.% are loss in washing and
mother liquor (NH4Cl + NaCl + NH4OH + water) goes to ammonia recovery section.

Calcination:
2NaHCO3 Na2CO3 + H2O + CO2

Amount of NaHCO3 available = 205.342*0.98 = 201.235 MT

= 2395.65 kmol

Conversion = 98.4%
Light Na2CO3 form = 2395.65*0.984/2 = 1178.65 kmol = 124.93 MT
CO2 in output = 1178.65 kmol = 51.86 MT
 H2O in output = 1178.65 kmol = 21.215 MT
NaHCO3 unreacted = 2395.65*0.016 = 38.33 kmol = 3.22 MT

Density of CO2 = 1.98 kg/m3

Density of H2O vapor = 0.804 kg/m3
Volume of CO2 in output = 51.86*1000/1.98 = 26191.92 m3
Volume of H2O in output = 21.215*1000/0.804 = 26386.8 m3
Total gas outlet flow = 26191.92 + 26386.8 = 52578.72 m3

Material balance over Calciner

Input (Kg/hr.) Output (Kg/hr.)
NaHCO3 201235 Na2CO3 124930
CO2 51860
H2O 21215
NaHCO3 3220
Total 201235 Total 201235

Conclusion
From above calculation of material balance, we can say that to produce 3000 MT/day of
soda ash, 2,12,900 kg/hr raw salt, 6,49,628 kg/hr water, 2,24,860 kg/hr raw CaCO 3, 18,000
kg/hr coal and 1,77,160 kg/hr air is required. We can also design an equipment of required
capacity.
 Recovered NH3 + Makeup NH3
Ca (OH)2 = 962 kg/hr Na2CO3 = 2754 kg/hr
= 61350 Kg/hr

Salt =212900 Kg/hr

Section 100 Section NH3 = 2820 kg/hr

H2O =649628 Kg/hr Pure Brine = 300

851038 Kg/hr
Sludge = 15206 Kg/hr
A-liquor = 909560 Kg/hr

CO2 = 43930 Kg/hr

57260
209566 Kg/hr
NH3 = 1055 Kg/hr

Kiln gas O2 = 3242 Kg/hr

N2 = 106683 Kg/hr
Coal = 18000
Section
Raw CaCO3 =224860 Kg/hr 200
Section
Air = 177160 Kg/hr 400

Calciner gas = 52915 Kg/hr

Bottom = 153176 Kg/hr

Draw liquor =

1017122 Kg/hr

Water = 21215
Condenser

Calciner gas = 74130 Kg/hr

Section
Na2CO3 = 124930
Kg/hr
500

Mother liquor = NaHCO3 = 4106.84 Kg/hr

811780 Kg/hr
Material Balance block diagram
ENERGY BALANCE
Introduction
Energy balance is application of law of conservation of energy, according to law of
conservation of energy, energy can neither created nor can be destroyed, it can be
transformed from one form to another form.

Energy in – Energy out = Accumulation

Energy balance is a calculation done to calculate the load on utilities. It is used to

calculate the amount of utilities required by the system to reach optimum conditions. Thus,
the load calculation for cooling water is used to determine the total cooling water
requirements and thus used to find the capacity of cooling tower, Similarly, the load
calculation for steam is used to determine the capacity of boiler.

Energy balance requires knowledge of thermodynamics. The heat duty on process side
and utility side is matched in order to calculate the load on the utilities. Proper values of heat
capacities, latent heat of vaporization, latent heat of condensations etc at their respective
temperatures are needed to be incorporated in the calculation.Energy balance around lime
kiln
Reaction:-

CaCO3 CaO + CO2

C + O2 CO2
Energy balance around lime kiln
Component ∆Hfo n m Cp
(kJ/mol) (kmol/hr) (MT/hr) ( KJ/kg oC)
Reaction-1
CaCO3 -1207 1956.27 195.627 0.8175
CaO -635 1721.51 96.4 0.8787
CO2 -394 1721.51 75.746 0.84625
Reaction-2
C 0 1290 15.48 0.7069
O2 0 1290 41.28 0.918
N2 0 4852.86 135.88 1.04
CO2 -394 1161 51.084 0.84625
Feed inlet Temperature is = 30°C

Product outlet Temperature is =1050 °C

Steam inlet temperature = 242°C

Steam Outlet temperature = 150°C

Rection-1:

Conversion = 88%

∆Ho Rx = (∆Hf o) Product – (∆Hf o) Reactant = – 394 – 635 + 1207

= 178 kJ/mol. (Endothermic reaction)

∆Ho Reaction = 178*1721.51*1000 = 306428780 kJ/hr.

∆H1 = mCP∆T

= 195627*0.8175*1000*(25-30)

= -799625 KJ/hr

∆H2 = miCPi∆T

= (234752*0.8175 + 96400*0.8787 + 75746*0.84625) *(1050-25)

= 348923846 KJ/hr

∆H Rx = ∆H1 + ∆Ho Rx + ∆H2

= - 799625 + 306428780 + 348923846 = 654553001 KJ/hr.

Reaction-2:

Conversion = 90%

∆Ho Rx = (∆Hf o) Product – (∆Hf o) Reactant

= - 394 – 0 – 0 = - 394 kJ/mol (Exothermic reaction)

∆Ho Rx = - 1161*1000 *394 = - 457,434,000 kJ/hr.

∆H1 = miCPi∆T
 = (15480 *0.7069 + 41280 *0.918 + 135880 *1.04) *(25-30)

= - 950,765 kJ/hr

∆H2 = miCPi∆T

= (1548*0.7069 + 4128*0.918 + 135880*1.04 + 51084*0.84625) *(30-25)

= 9,47,144 KJ/hr

∆H Rx = ∆H1 + ∆Ho Rx + ∆H2

= - 950765 – 457,434,000 + 9,47,144 = - 457,437,621 kJ/hr.

Q = ∆HReraction-1 - ∆HReraction-2

= 654,553,001 – 457,437,621

= 197,115,380 kJ/hr.

Steam required,

Q = mCp∆T

197,115,380 = m*1.9643*(242-150)

m = 10,90,749 Kg/hr.
Energy balance around ammonia absorption column
Reaction:-

NaCl + H2O + NH3 NH4OH + NaCl

Energy balance around ammonia absorber

Component ∆Hfo n m Cp
(kJ/mol) (kmol/hr) (MT/hr) ( KJ/kg oC)
NaCl - 410 3443.03 201.41 0.8597
H2O - 286 36090.44 649.628 4.1197
NH3 - 46 3443.03 61.35 2.08767
NH4OH - 80.29 3443.03 120.5 1.1486
Feed inlet Temperature is = 25°C
Product outlet Temperature is = 60°C

Cooling water inlet Temperature is = 18°C

Water outlet Temperature is = 25°C

Heat of solution of NH3 gas is 35.271 kJ/mol

Therefore, total heat released during absorption = 3443030 * 35.271

= 121,439,111 kJ/hr.

Cooling water use for this process,

Q = mCp∆T

121,439,111 = m *4.186 *(25-18)

m = 41,44,396 Kg/hr,

Energy balance around carbonation tower

Reaction:-

NH4OH + NaCl + CO2 NH4Cl + NaHCO3

Energy balance around carbonation tower

Component n m Cp
(kmol/hr.) (MT/hr.) ( KJ/kg oC)
NaCl 3443.03 201.41 0.8597
NH4OH 3443.03 120.5 1.1486
CO2 3443.03 151.49 0.84625
NaHCO3 2444.55 205.342 1.0472
NH4Cl 2444.55 130.78 1.9817

Feed inlet Temperature is = 25°C

Product outlet Temperature is = 65°C

Cooling water inlet Temperature is = 18°C

 Water outlet Temperature is = 25°C

Heat of solution of CO2 gas is 24.602 kJ/mol

Therefore, total heat released during absorption = 24602 * 2444.55

= 6,01,40,819 kJ/hr.

Cooling water use for this process,

Q = mCp∆T

60140819 = m *4.186 *(25-18)

m = 20,52,447 Kg/hr.

Energy balance around calciner

Reaction:

2NaHCO3 Na2CO3 + H2O + CO2

Energy balance around calciner

Component ∆Hfo n m Cp
(kJ/mol) (kmol/hr.) (MT/hr.) ( kJ/kg oC)
NaHCO3 -950.8 2395.65 201.235 1.0472
Na2CO3 -1130.7 1178.65 124.93 1.0515
H2O -286 1178.65 21.215 4.186
CO2 -394 1178.65 51.86 0.84625

CP (steam) = 1.9643 kJ/Kg °C

Feed inlet temperature = 30°C

Product outlet temperature = 180°C

Steam inlet temperature = 242°C

Steam Outlet temperature = 150°C

∆Ho Rx = (∆Hf o) Product – (∆Hf o) Reactant

 = - 394 – 286 – 1130.7 + (2 *950.8)

= 90.9 kJ/mol (Endothermic Reaction)

∆Ho Rx = 1178.65*1000*90.9 = 107,139,285 kJ/hr.

∆H1 = miCPi∆T

= 201235 *1.0472 *(25 – 30) = - 10,53,666 kJ/hr.

∆H2 = miCPi∆T

= (3219.75 *1.0472 + 124930*1.0515 + 21215*4.186 + 51860*0.84625) *(180 – 25)

= 4,14,51,360 kJ/hr

∆H Rx = ∆H1 + ∆Ho Rx + ∆H2

= - 10,53,666 + 107,139,285 + 4,14,51,360 = 147,536,979 kJ/hr.

Steam required,

Q = mCp∆T

147,536,979 = m*1.9643*(242-150)

m = 816,404 kg/hr.

Total steam required = 10,90,749 + 816,404 = 19,07,153 kg/hr.

Total cooling water required = 41,44,396 + 20,52,448 = 61,96,844 kg/hr.

Conclusion
By performing calculation of energy balance, we comes to know amount of steam and
water required for heating and cooling purpose for each operations. From this amount we can
say that cooling tower of capacity 43,50,553 kg/hr and boiler of capacity 19,07,153 kg/hr is
required.