OVERALL

MATERIAL BALANCE

Overall percent loss is calculated by multiplying the percent loss of material per equipment (0.05%) by the
number of major equipment (12).

Overall Percent Loss:

Fluorspar feed rate required to achieve target production rate of 171 kg/hr derived from market share:

Actual feed rate:

1
 OVERALL
MATERIAL BALANCE
Equipment Name Fluorspar Grinding Mill Equipment Tag B-100
Objective To reduce the particle size from 30 mm to 0.044 mm (325 mesh)

Calculation Basis

45% of the milled particles are retrained through 325 mesh (Boscak, 1978)

S3 Calculations

CaF2 =(0.45)(CaF2 in S1 ) Percent retained of 45% is used calculate

CaF2 =(0.45)(450.33) for the amount of CaF2 recycled back from
the classifier to the ball mill for further
CaF2 =202.65 kg grinding.

SiO2 = (0.45)(SiO2 in S1 ) Percent retained of 45% is used calculate

SiO2 = (0.45)(450.33) for the amount of SiO2 recycled back from
the classifier to the ball mill for further
SiO2 = 32.38 kg grinding.

2
 OVERALL
MATERIAL BALANCE

H 2O (0.45)(SiO2 in S1 ) Percent retained of 45% is used calculate

H 2O (0.45)(450.53) for the amount of H2O recycled back from
the classifier to the ball mill for further
H 2O 2.38 kg grinding.

S2 Calculations

CaF2 CaF2 in S1 CaF2 in S 3 Calculated CaF2 material balance around

CaF2 450.33 202.65 Ball Mill B-100
CaF2 652.98 kg

SiO2 SiO2 in S1 SiO2 in S3 Calculated SiO2 material balance around

SiO2 = 74.17 +33.38 Ball Mill B-100
SiO2 = 107.55 kg

H 2O H 2O in S1 H 2O in S3 Calculated SiO2 material balance around

H2O = 5.30+ 2.38 Ball Mill B-100
H2O = 7.68 kg

3
 OVERALL
MATERIAL BALANCE
Equipment Name Cross-flow Classifier Equipment Tag S-100
Objective To separate and recover -325 mesh particles and recycle coarse particles
back to the ball mill for further grinding.

Calculation Basis

The classifier is to produce 25% solids slurry prior to fluorspar flotation (Metso Corporation, 2015)

Stream 5 Calculations

CaF2 CaF2 in S2 CaF2 in S3 Calculated CaF2 material balance around

CaF2 652.98 202.65 Classifier S-100
CaF2 450.33 kg

SiO2 SiO2 in S2 SiO2 in S3 Calculated SiO2 material balance around

SiO2 107.55 33.38 Classifier S-100

4
 OVERALL
MATERIAL BALANCE
SiO2 74.17 kg

75 Calculated H2O material balance around

H 2O CaF2 in S5 SiO2 in S5 Classifier S-100
25
75
H 2O= 450.33+74.17
25
H2O = 1573.51 kg

Stream 4 Calculations

H 2O H 2O in S5 H 2O in S1 Calculated H2O material balance around

H 2O 1573.51 5.30 Ball Mill B-100 and Classifier S-100 closed
circuit.
H 2O 1568.21 kg

5
 OVERALL
MATERIAL BALANCE
Equipment Name Flotation Machine Equipment Tag S-101
Objective To float most of the CaF2 compound out of fine fluorspar using several
flotation reagents.

Calculation Basis

Reagents to be used have a flotation index of 81.4. (US Patent No. 3893915)
Maximum of 1% content allowed for SiO2 as impurity (Kirk)
Ratio of CaF2 to H2O in the tailings is 1. (Gujarat Mineral Development Corporation Ltd)
The number of cells to be used is 6. (Metso Corporation, 2015)

Grade Actual Recovery Actual

Flotation Index Equation (1)
Grade Perfect Separation Recovery Perfect Separation

Using the flotation reagents presented by US Patent No. 3893915, a flotation index of 81.4 can be
achieved. The grade of a perfect separation would be 100 percent and recovery would be 100 percent.
Since 1 percent is the maximum allowed for SiO2 for an acid-grade fluorspar (dry-basis), therefore the
maximum CaF2 grade that can be attained is 99%. Therefore, using equation (1)

6
 OVERALL
MATERIAL BALANCE

81.4 99 Recovery Actual

100 100 100
Recovery Actual 66.93%

This recovery pertains to a single cell operation. According to Metso Corporation (2015), in application for
fluorspar processing the minimum number of cells that is used is 6. The overall percent recovery is
calculated as follows

Overall Recovery = 1 RecoveryCell (1 RecoveryCell )no. of cells1

Overall Recovery = 1 0.6693(1 0.6693)61
Overall Recovery = 0.9974

Stream 7 Calculations

CaF2 0.9974 CaF2 in S5 Calculated overall percent recovery of

99.74% is used to compute for the amount
CaF2 0.9974 450.33
of CaF2 floated along with the overflow
CaF2 = 449.16 kg concentrate.

1 Used the dry-basis gravimetric ratio of

SiO2 CaF2 in S7 SiO2 to CaF2 that is 1/99 to calculate the
99
SiO2.
1
SiO2 449.16
99
SiO2 4.54 kg

H 2O H 2O in S5 H 2O in S6 Calculated H2O material balance around

H 2O 1573.51 1.17 Flotation Cells S-101.
H 2O 1548.74 kg

7
 OVERALL
MATERIAL BALANCE
Stream 6 Calculations

CaF2 1 0.9974 (CaF2 in S5 ) Used the subtracted percent recovery to

account for the amount of CaF2 loss in
CaF2 1 0.9974 (450.33) Stream 6.
CaF2 1.17 kg

H 2O CaF2 CaF2 in S6 Based on the final tailing composition data

H 2O 1.17 kg taken from Gujarat Mineral Development
Corporation Ltd, the ratio of CaF2 and H2O
is approximately 1.

SiO2 SiO2 in S5 SiO2 in S7 Calculated SiO2 material balance around

SiO2 74.17 4.54 Flotation Cells S-101.
SiO2 69.64 kg

8
 OVERALL
MATERIAL BALANCE
Equipment Name Thickener Equipment Tag S-102
Objective To thicken the flotation final concentrate up to 60% solids.

Calculation Basis

The thickener is to produce 60% solids slurry by dewatering. (911metallurgist.com)

Stream 9 Calculations

CaF2 CaF2 in S7 Calculated CaF2 material balance around

CaF2 449.16 kg Thickener S-102.

SiO2 SiO2 in S6 Calculated SiO2 material balance around

SiO2 4.54 kg Thickener S-102.

9
 OVERALL
MATERIAL BALANCE
40 Used the dry-basis gravimetric ratio of H2O
H 2O CaF2 in S9 SiO2 in S9 to solids CaF2 and SiO2 that is 40/60 to
60
calculate the H2O.
40
H 2O 449.16 4.54
60
H 2O 302.47 kg

Stream 8 Calculations

H 2O H 2O in S7 H 2O in S9 Calculated H2O material balance around

H 2O 1572.34 302.47 Thickener S-102.
H 2O 1269.88 kg

10
 OVERALL
MATERIAL BALANCE
Equipment Name Rotary Vacuum Drum Filter Equipment Tag S-103
Objective To dewater the thickened slurry up to 6% moisture.

Calculation Basis

The filter is to produce 6% moisture slurry by dewatering. (911metallurgist.com)

Stream 11 Calculations

CaF2 CaF2 in S9 Calculated CaF2 material balance around

CaF2 449.16 kg Filter S-103.

SiO2 SiO2 in S9 Calculated SiO2 material balance around

SiO2 4.54 kg Filter S-103.

6 Used the dry-basis gravimetric ratio of H2O

H 2O CaF2 in S11 SiO2 in S11 to solids CaF2 and SiO2 that is 6/94 to
94
calculate the H2O.

11
 OVERALL
MATERIAL BALANCE
6
H 2O 449.16 4.54
94
H 2O 28.96 kg

Stream 10 Calculations

H 2O H 2O in S9 H 2O in S11 Calculated H2O material balance around

H 2O 302.47 28.96 Filter S-103.
H 2O 273.51 kg

12
 OVERALL
MATERIAL BALANCE

Equipment Name Rotary Dryer Equipment Tag S-104

Objective To reduce the moisture content from 6% to 0.05%.

Calculation Basis

The dryer is to produce 0.05% moisture product. (911metallurgist.com)

Stream 13 Calculations

CaF2 CaF2 in S11 Calculated CaF2 material balance around

CaF2 449.16 kg Dryer S-104.

SiO2 SiO2 in S11 Calculated SiO2 material balance around

SiO2 4.54 kg Dryer S-104.

13
 OVERALL
MATERIAL BALANCE
0.05 Used the dry-basis gravimetric ratio of H2O
H 2O CaF2 in S13 SiO2 in S13 to solids CaF2 and SiO2 that is 0.05/99.95
99.95
to calculate the H2O.
0.05
H 2O 449.16 4.54
99.95
H 2O 0.23 kg

Stream 12 Calculations

H 2O H 2O in S11 H 2O in S13 Calculated H2O material balance around

H 2O 28.96 0.23 Dryer S-104.
H 2O 28.73 kg

14
 OVERALL
MATERIAL BALANCE
Equipment Name Rotary Kiln Equipment Tag R-100
Objective To effect the generation of HF by allowing an endothermic reaction between
acid-grade fluorspar and H2SO4.

Calculation Basis

The conversion of CaF2 is 98% (Boscak)

H2SO4 is supplied as 5% excess (US EPA)
Assumption

All SiO2 will be converted to SiF4

Main Reaction CaF2 + H2SO4 2HF + CaSO4
Side Reaction SiO2 + 4HF SiF4 + 2H2O
Overall Reaction 2CaF2 + 2H2SO4 + SiO2 2CaSO4 + SiF4 + 2H2O

15
 OVERALL
MATERIAL BALANCE
Converting the material balance in terms of mole

Compound Molecular Weight

(kg/kmol) Since the limiting reactant in the main reaction is CaF2,
HF 20.01
therefore all calculations will be based on the amount of
CaF2 78.07
H2SO4 98.08 CaF2 that is to react.
SiO2 60.08
H2O 18.02
CaSO4 136.14
CO2 44.01
SiF4 104.08
H2S2O7 178.14
SO3 80.07

16
 OVERALL
MATERIAL BALANCE

We are given the amount of CaF2 charged:

CaF2 charged 5.7533 kmol

The amount of CaF2 that will react is calculated given that the main reaction proceeds with 98% conversion of
CaF2 to HF:

CaF2 to react (0.98)(5.7533) 5.6382 kmol

Correspondingly, the unreacted CaF2 will be:

CaF2 unreacted (1 0.98)(5.7533) 0.1151 kmol

The H2SO4 required to react with the amount of CaF2 available to react is:

H2SO4 required CaF4 to react 5.6382 kmol

According to US Environmental Protection Agency (US EPA), the H2SO4 is usually supplied in 5% excess.
Using this information, the H2SO4 that will be supplied in excess of what is required stoichiometrically is:

H2SO4 supplied in excess (0.05)(5.6382 ) 0.2819 kmol = 27.6499 kg

Note that the main and side reactions are occurring as series reactions. For the sake of calculations, an
over-all reaction is derived in order to account for the loss of CaF2 and H2SO4 due to the presence of SiO2
in the reactant phase. The stoichiometric calculations for the reactions are shown below.

Over-all reaction:
0.15 0.15 0.08 0.15 0.08 0.15 kmol
11.79 14.81 4.54 20.56 7.86 2.72 kg

Main reaction:
5.64-0.15=5.49 5.49 10.97 5.49 kmol
428.39 538.19 219.60 747.03 kg

17
 OVERALL
MATERIAL BALANCE
Compounds shown in red are considered as the limiting reactants thus the stoichiometric equivalencies are
derived from the given values of these compounds. From the results shown above, it can be seen that the
loss in CaF2 and H2SO4 due to the presence of SiO2 are 0.15 kmoles for each.

Checking of Assumption:

According to Kirk, there will be a 3.9% loss of CaF2 per % silica present in the reacting fluorspar. The
reacting fluorspar contains 1% silica thus 3.9% of CaF2 is expected to be lost as it proceeds with the side
reaction. Using this information, the amount of CaF2 loss due to SiO2 is:

CaF2 loss due to SiO2 (0.039)(5.6382) 0.2199kmol

Performing stoichiometric calculations on the over-all reaction,

0.2199 0.2199 0.1099 0.2199 0.1099 .2199

From the stoichiometric calculations shown above, the amount of SiO2 expected to react with CaF2 is
0.1099 kmoles which is equivalent to 6.60 kg of SiO2. However, the amount of SiO2 present in the reactant
is only 4.54 kg thus SiO2 will serve as a limiting reactant. Therefore, the assumption made that all SiO2
present are converted is valid. Other literatures also support that the impurity SiO2 actively reacts with CaF2
forming the major by-product SiF4 gas (Boscak).

Stream 14 Calculations

H2SO4 H2SO4 (main) + H2SO4 (overall) + H2SO4 excess H2SO4 material

H2SO4 538.19+ 14.81 + 27.65 balance based on
the results of
H2SO4 580.65 kg stoichiometric
calculations on
main and overall
reactions

2 Used the dry-basis

H 2O (580.65) gravimetric ratio of
98
H2O to H2SO4 that
H 2O 11.85 kg
is 2/98 to calculate
the H2O.

18
 OVERALL
MATERIAL BALANCE

Stream 16 Calculations

HF 219.60 kg From the results of stoichiometric

calculations on main reaction

SiF4 7.86 kg From the results of stoichiometric

calculations on overall reaction

H2O = H2O in S13 + H2O in S14 + H2O (overall) H2O material balance based on the
H2O = 0.23 + 11.85 + 2.72 results of stoichiometric
calculations on main and overall
H2O = 14.58 kg reactions.

Stream 15 Calculations

CaSO4 = CaSO4 (overall) + CaSO4 (main) From the results of

CaSO4 = 20.56 + 747.03 stoichiometric calculations on
CaSO4 = 767.59 kg main and overall reactions.

CaF2 = (0.1151 kmol)(78.07) = 8.98 kg From the calculated unreacted

CaF4

H2SO4 = 27.65 kg From calculated H2SO4 excess

19
 OVERALL
MATERIAL BALANCE
Equipment Name Acid Scrubber Equipment Tag A-100
Objective To absorb most of the HF from the reaction gas by running with oleum.

Calculation Basis

SiF4 is not absorbed by H2SO4. (US Patent No. 1960347)

219.60
H2SO4 to be used = = 2.24 kmol
98.08

20
 OVERALL
MATERIAL BALANCE
Converting the material balance in terms of moles

Addition of oleum to the absorbing liquid produces more concentrated sulfuric acid since the SO 3 present in
the oleum readily reacts with water or moist air.

The amount of SO3 in the form of oleum to be added is equivalent to the amount of water or water vapor
present to be reacted. In this case, the total amount of water to be removed in the acid scrubber is

Total H2O to be absorbed = H2O in product gas

Total H2O to be absorbed = 0.8093

Total H2O to be absorbed = 0.8093 kmol

The reaction and the stoichiometric calculations are as follows:

0.08 0.08 0.80 kmol

64.80 14.58 79.38 kg

21
 OVERALL
MATERIAL BALANCE

Calculation of H2SO4 present in the oleum

Based on the stoichiometric calculations shown for the reaction between SO 3 and H2O to yield
H2SO4, the required amount of SO3 to dehydrate the product gas is 0.80 kmol or equivalent to
about 64.80 kg of SO3. Using 30% Oleum, the composition and amount of oleum to be supplied
would therefore be that shown in the table below.

Compound % Weight Amount

(kg/hr)
SO3 30 64.80
H2SO4 70 151.21
Total 100 216.01

Therefore, the amount of H2SO4 that will be present in this oleum grade is

H2SO4 present in oleum = 151.21 kg

Calculation of V

V' = V1 (1 y1 ) V2 (1 y2 )

From the material balance based on moles: V1 11.8593 y1 0.9254

V ' (11.8593)(1 0.9254)

V ' 0.8843

Calculation of L

L ' L1 (1 x1 ) L2 (1 x2 )

From the material balance based on moles: L2 0.8093 1.54 2.35

x2 0

Note that this L2 only pertains to the main absorbing liquid which is the concentrated H2SO4.

L ' (2.35)(1 0)

22
 OVERALL
MATERIAL BALANCE
L ' 2.35

Calculation of X1

x1
X1
1 x1

From the material balance based on moles: x1 0.8326

0.8236
X1
1 0.8236
X1 4.6689

Calculation of X2

x2
X2
1 x2

From the material balance based on moles: x2 0

0
X2
1 0
X2 0
Calculation of Y1

y1
Y1
1 y1

From the material balance based on moles: y1 0.9254

0.9254
Y1
1 0.9254
Y1 12.4048

23
 OVERALL
MATERIAL BALANCE
Calculation of y2
V '(Y1 Y2 ) L '( X1 X 2 )
y
V ' Y1 2 L '( X 1 X 2 )
1 y2
y
(0.8847) 12.4048 2 2.35(4.6689 0)
1 y2
y2 0.0029

Stream 17 Calculations

SiF4 = SiF4 in S16 SiF4 material balance around

SiF4 = 7.86 kg = 0.0755 kmol the HF Absorption Tower A-100.

Using the calculated value of y2

0.0029
HF 0.0755
1 0.0029
HF 0.000222 kmol = 0.004395 kg

Stream 22 Calculations

HF = HF in S16 - HF in S17 SiF4 material balance around

HF = 219.60 - 0.004395 the HF Absorption Tower A-100.
HF = 219.59 kg

H2SO4 = H2SO4 supplied + H2SO4 produced H2SO4 material balance

H2SO4 = 151.2074 + 79.3792
H2SO4 = 230.59

Stream 21 Calculations

SO3 64.80 kg From the calculation of H2SO4

H2SO4 = 151.21 kg present in oleum

24
 OVERALL
MATERIAL BALANCE
Equipment Name Water Scrubber Equipment Tag A-101
Objective To recover SiF4 as H2SiF6 by running with water.

Calculation Basis

99% conversion of SiF4 (New Zealand Institute of Chemistry)

25
 OVERALL
MATERIAL BALANCE
Converting the material balance in terms of moles

We are given the amount of SiF4 charged:

SiF4 charged 0.075516 kmol

The amount of CaF2 that will react is calculated given that the main reaction proceeds with 98% conversion
of CaF2 to HF:

SiF4 to react (0.99)(0.075516) 0.07476 kmol

Correspondingly, the unreacted SiF4 will be:

SiF4 unreacted (1 0.99)(0.075516) 0.000755 kmol

The H2O required to react with the amount of SiF4 available to react is

26
 OVERALL
MATERIAL BALANCE
2 2
H2O required SiF4 to react (0.07476)kmol) = 0.04984 kmol
3 3

The stoichiometric calculations for the reactions occurring inside the water scrubber are shown below

SiF HO H SiF SiO

4

0.07476 0.04984 0.04984 0.02492

7.7811 0.8981 7.1815 1.4972

Stream 19 Calculations

H 2 SiF6 7.18 kg From stoichiometric calculations

H2O = unreacted H2O=H2O required(1-%conversion)

H2O 0.050344(1 0.99)
H2O 0.0005 kmol 0.0091kg

SiO2 1.50 kg

Stream 18 Calculations

3 From stoichiometric calculations

H 2O SiF4 charged
2
3
H 2O (0.075516)
2
H 2O 0.050344 kmol 0.9072 kg

Stream 20 Calculations

SiF4 0.00076 kmol 0.08 kg From unreacted SiF4

HF HF in S17 0.0044 kg

27
 OVERALL
MATERIAL BALANCE
Equipment Name Vaporizer Equipment Tag E-100
Objective To vaporize the HF-H2SO4 solution prior to entering the flash column.

Stream 23 Calculations

4 4

28
 OVERALL
MATERIAL BALANCE
Equipment Name Flash Column Equipment Tag S-106
Objective To ultimately separate HF and H2SO4 by flash distillation.

Calculation Basis

The flash temperature is 140oC and pressure is 1 atm. (US Patent No. 7371363)

The table below shows the Antoine coefficients for the calculation of vapor pressures of HF and H2SO4.

Compound C1 C2 C3 C4 C5 Boiling Point

HF 59.544 -4143.8 -6.1764 1.42E-05 2 292.65
H2SO4 13.4515 8107.94 9.26851 610.15

29
 OVERALL
MATERIAL BALANCE
The summary of the calculations are shown as follows for vapor pressure of HF and H2SO4 at different
temperatures ranging from 292.65 K (19.5oC) and 610.15 K (337oC) which are the boiling points of HF and
H2SO4, respectively using antoines equation and the corresponding mole fractions by means of Daltons
Law of Partial Pressures and Raoults Law.

Temperature Vapor Pressure (Pa) Mole Fraction

(K) A B Xa Ya
292.65 100870.5184 0.02606999 1.004505595 1.000000001
303.2333333 145171.6943 0.07302877 0.69796649 0.999999782
313.8166667 204253.9777 0.190438706 0.496073101 0.999999053
324.4 281727.9229 0.465647354 0.359654452 0.999997057
334.9833333 381857.928 1.074298947 0.265345311 0.999992211
345.5666667 509676.6019 2.351481654 0.198798838 0.999981406
356.15 671125.8248 4.906796796 0.150971443 0.999958885
366.7333333 873230.1163 9.80253685 0.116024783 0.999914481
377.3166667 1124309.025 18.81891747 0.09010679 0.999831007
387.9 1434236.695 34.83500686 0.070624762 0.999680486
398.4833333 1814758.61 62.35826088 0.055801428 0.999418914
409.0666667 2279877.83 108.2390239 0.044397803 0.998979191
419.65 2846325.975 182.6086413 0.035536647 0.998261837
430.2333333 3534137.864 300.0806639 0.028587877 0.997123099
440.8166667 4367353.29 481.2538098 0.023092902 0.995360076
451.4 5374875.155 754.5527923 0.018713843 0.992692502
461.9833333 6591520.351 1158.438848 0.015198947 0.988740866
472.5666667 8059308.78 1744.015923 0.012358695 0.98300062
483.15 9829047.226 2578.051204 0.010049077 0.974812295
493.7333333 11962279.03 3746.420352 0.008159745 0.963327407
504.3166667 14533688.51 5357.978614 0.006605509 0.947470156
514.9 17634071.84 7548.849502 0.005320173 0.925895008
525.4833333 21374014.81 10487.11308 0.004252008 0.896940323
536.0666667 25888454.61 14377.86661 0.003360396 0.858578324
546.65 31342349.23 19468.62163 0.002613309 0.808361766
557.2333333 37937737.35 26054.99346 0.001985404 0.74336774
567.8166667 45922547.46 34486.63273 0.001456552 0.660139145
578.4 55601611.93 45173.34236 0.001010714 0.554624377
588.9833333 67350465.84 58591.31967 0.00063505 0.422115852
599.5666667 81632670.69 75289.46007 0.00031923 0.257188005
610.15 99021608.47 95895.65711 5.4883E-05 0.05363539

30
 OVERALL
MATERIAL BALANCE
Generating the T-xy Diagram of HF-H2SO4 system at a pressure of 1 atm

T-x,y diagram for HF-H2SO4 system

592.65
572.65
552.65
532.65
512.65
492.65
472.65
452.65
432.65
412.65
392.65
372.65
352.65
332.65
312.65
292.65
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

From the graph, the corresponding mole fractions of HF in liquid (x) and vapor phase (y) at 140oC (413 K)
are

x = 0.04098
y = 0.9987

Converting these into mass fractions,

x = 0.1732
y = 0.9997

Performing HF Balance:

0.9997S27 (1 0.9997) S28 219.59

31
 OVERALL
MATERIAL BALANCE

Performing H2SO4 Balance:

(1 0.8268)S27 0.8268S28 230.59

Solving the above equations simultaneously,

S27 = 171.35

S28 = 278.83

Stream 26 Calculations

Stream 25 Calculations

32
 OVERALL
MATERIAL BALANCE
Equipment Name Condenser Equipment Tag E-101
Objective To condense and liquefy the distillate product.

Stream 27 Calculations

4 4

33