MATERIAL BALANCE

ML-001
Titanium Slag Pan Miller
1
TiO2
FeO
SiO2

kg/hr

%
85.00
10.00
5.00
100.00

1270.21
149.44
74.72
1494.37

2
TiO2
FeO
SiO2

Basis: 30 000 kg per day of 98% TiO2

Assume: 1494.37

0.05% loss

At stream 2:
2 = 1270.21
2 = 74.72

0.9995 = 1269.58

0.9995 = 74.68

= 149.44

0.9995 = 149.36

kg/hr
1269.58
149.36
74.68
1493.62

%
85.00
10.00
5.00
100.00

ML-002
Titanium Slag Vibrating Miller
2
TiO2
FeO
SiO2

kg/hr
85.00
10.00
5.00
100.00

1269.58
149.36
74.68
1493.62

At stream 3:
2 = 1269.58
2 = 74.68

0.9995 = 1268.94

0.9995 = 74.64

= 149.36

0.9995 = 149.29

3
TiO2
FeO
SiO2

kg/hr
1268.94
149.29
74.64
1492.88

%
85.00
10.00
5.00
100.00

Cl2 Electric Gas Preheater

HEX-001
kg/hr
Cl2
O2

%
99.81
0.19
100.00

2666.19
4.96

2671.15

At stream 26:
2 = 2666.19

2 = 4.96

0.9995 = 2664.86

0.9995 = 4.96

26
Cl2
O2

kg/hr
2664.86
4.95
2669.81

%
99.81
0.19
100.00

26
Cl2
O2
R 01

kg/hr
2667.53
4.96
2672.49

%
99.77
0.19
100.00

Fluidized Bed Reactor Chlorinator

3
TiO2
FeO
SiO2

kg/hr
1268.94
149.29
74.64
1492.88

kg/hr

C
H2
O2
N2
Ash
S

313.35
0.45
0.06
0.70
0.06
3.82
318.45

5
TiO2
C
Cl2
CO2
CO
TiCl4
SiCl4
FeCl3
O2
N2
SO2
HCl
FeO
SiO2
S
H2
Ash

%
85.00
10.00
5.00
100.00
%
98.40
0.14
0.02
0.22
0.02
1.20
100.00

2 TiO2 + 4 Cl2 + 3C
-Reaction1

2 TiCl4 + CO2 + 2CO

kg/hr

25.37
6.26
53.27
440.68
435.74
2951.97
206.73
330.15
1.27
0.70
7.49
15.92
2.98
1.49
0.08

0.57
0.14
1.19
9.84
9.73
65.89
4.61
7.37
0.03
0.02
0.17
0.36
0.07
0.03
0.00
0.00
0.00
100.00

0.01
0.06
1493.39

Assuming 98% conversion (KIrk-Othmer, 2007)

2
1 2
4 2
70.91 2

79.87 2 2 2
1 2

= 2253.18

2 = 1268.94

= 1268.94

2
1 2
3
12

= 285.98

79.87 2 2 2 1

2
1 2
1 2
44 2

0.98

79.87 2 2 2 1 2

= 342.54

2 = 1268.94


2
1 2
2 0
28
= 1268.94

0.98 0.9995

79.87 2 2 2 1

= 435.96

4
2
1 2
2 4 189.69 4
= 1268.94

0.98 0.9995

79.87 2
2 2
1 4

= 2951.97

SiO2 + 2Cl2 + C

SiCl4

+ CO2

--Reaction 2

2
1 2
2 2
70.91 2

60.09 2 1 2
1 2

= 176.35

2 = 74.64

= 74.64

2
1 2
1
12 2

= 14.92

60.09 2 1 2 1 2

4
2
1 2
1 2
169.90 4
= 74.64

0.98 0.9995

60.09 2 1 4
1 4

= 206.73

2
1 2
1 2 44 2

0.98

60.09 2 1 2 1 2

= 342.54

2 = 74.64

2FeO + 3Cl2 + C

2FeCl3 + CO2

--Reaction 3

1
3 2
70.91 2

71.84 2
1 2

= 221.03

2 = 149.29

= 149.29

1
1
12

= 12.47

71.84 2 1

 3

1
2 3
162.204 3
= 149.29

0.98 0.9995

71.84
2
1 3

= 330.15

1
1 2
44 2

0.98

71.84
2
1 2

= 44.80

2 = 149.29

= 1 + 2 + 3
= (12.47 + 14.91 + 285.98)
= 313.15

H2 + Cl2

2 HCl

--Reaction 4

2 = 0.45

2
1 2 1 2 70.91 2

= 15.82

2 2
1 2
1 2

= 0.45

2
1 2 2
36.46

0.98 = 15.95

2 2
1 2
1

2
= 2 1 + 2 2 + 2 3
+ 2 4
2 = (2253.18 + 176.17 + 221.03 + 15.81)
2 = 2666.19

S + O2

SO2

2 = 3.82

--Reaction 5

1 1 2 64.07 2

0.98 = 7.50

32
1
1 2

2 2 = 4.96

2
1 2 1 2 64.07 2

0.98 = 9.72

32 2
1 2
1 2

Thus, S is limiting reactant.

2
2

2
1 2
1 2
32 2
3.83

0.9995

64.07 2 1 2 1 2

= 0.40

= 4.96

At outlet:
For unreacted feed at outet:
2 = 2 1 + 2 2 + 2 3
2 = (342.54 + 53.56 + 44.80)
2 = 440.68

0.9995

2% of the materials that will enter will be unreacted from the first Reaction.
2 = 1269.58
= 313.35

2 = 2671.15
2 = 0.45

0.02 0.9995 = 6.276

0.02 0.9995 = 53.27

0.02 0.9995 = 0 - negligible

= 149.36
2 = 74.68

0.02 0.9995 = 25.37

0.02 0.9995 = 2.98

0.02 0.9995 = 1.49

= 3.82 0.02 0.9995 = 0.08

= 0.06 0.02 0.9995 = 0.06

negligible

negligible

CO 001
Gas-solid Rotary Cooler
5
TiO2
C
Cl2
CO2
CO
TiCl4
SiCl4
FeCl3
O2
N2
SO2
HCl
FeO
SiO2

kg/hr

25.37
6.26
53.27
440.68
435.74
2951.97
206.73
330.15
1.27
0.70
7.49
15.92
2.98
1.49

0.57
0.14
1.19
9.84
9.73
65.89
4.61
7.37
0.03
0.02
0.17
0.36
0.07
0.03
100.00

4480.12

6
TiO2
C
Cl2
CO2
CO
TiCl4
SiCl4
FeCl3
O2
N2
SO2
HCl
FeO
SiO2

Vapor:

0.9995 = 53.24

2 = 440.68
= 435.74

0.9995 = 440.46

0.9995 = 435.52

4 = 2951.97
4 = 206.73
2 = 1.27
2 = 0.7

0.9995 = 2950.50

0.9995 = 206.62

0.9995 = 1.27

0.9995 = 0.70

2 = 1.49

0.9995 =

%
0.57
0.14
1.19
9.84
9.73
65.89
4.61
7.37
0.03
0.02
0.17
0.36
0.07
0.03
100.00

4477.81

Iron chloride and unreacted solids settle down.

2 = 53.27

kg/hr
25.35
6.26
53.24
440.46
435.52
2950.50
206.62
329.99
1.27
0.70
7.49
15.91
2.98
1.49

0.9995 = 15.91

= 15.92

Unreacted solids.
2 = 25.37
= 6.26

0.9995 = 25.35

0.9995 = 6.26

3 = 330.15

0.9995 = 329.99

= 2.98

0.9995 = 2.98

2 = 1.49

0.9995 = 1.49

F-001
Gas-Solid Bag Filter
6
TiO2
C
Cl2
CO2
CO
TiCl4
SiCl4
FeCl3
O2
N2
SO2
HCl
FeO
SiO2

kg/hr

%
0.57
0.14
1.19
9.84
9.73
65.89
4.61
7.37
0.03
0.02
0.17
0.36
0.07
0.03
0.57

25.35
6.26
53.24
440.46
435.52
2950.50
206.62
329.99
1.27
0.70
7.49
15.91
2.98
1.49

4477.81

8
Cl2
CO2
CO
TiCl4
SiCl4
O2
N2
SO2
HCl

= 6.26

7
FeCl3
C
TiO2
FeO
SiO2

kg/hr
329.82
6.26
25.34
2.98
1.49
366.03

0.9995 = 25.34

0.9995 = 6.26

3 = 329.99

53.22
440.24
435.30
2949.02
206.52
1.27
0.70
7.49
15.91

4109.66

At Stream 7:
2 = 25.35

kg/hr

0.9995 = 329.82

= 2.98

0.9995 = 2.98

2 = 1.49

0.9995 = 1.49

%
90.14
1.71
6.93
0.81
0.41
100.00

%
1.29
10.71
10.59
71.75
5.02
0.03
0.02
0.18
0.39
100.00

At Stream 8:
2 = 53.24

0.9995 = 53.22

0.9995 = 440.24

2 = 440.46
= 435.53

0.9995 = 435.30

4 = 2950.50
4 = 206.62
2 = 1.27
2 = 0.7

0.9995 = 2949.02

0.9995 = 1.27

= 15.91

0.9995 = 206.52

0.9995 = 0.7

2 = 7.49

0.9995 = 7.49

0.9995 = 15.91

CD 01
TiCl4 Condenser
8
Cl2
CO2
CO
TiCl4
SiCl4
O2
N2
SO2
HCl

kg/hr

9
Cl2
CO2
CO
TiCl4
SiCl4
O2
N2
SO2
HCl

%
1.29
10.71
10.59
71.75
5.02
0.03
0.02
0.18
0.39
100.00

53.22
440.24
435.30
2949.02
206.52
1.27
0.70
7.49
15.91

4109.66

0.9995 = 53.24

2 = 440.68
= 435.74

0.9995 = 440.46

0.9995 = 435.52

4 = 2951.98
4 = 206.73
2 = 1.27
2 = 0.7

0.9995 = 2950.51

0.9995 = 0.4

= 15.92

0.9995 = 206.62

0.9995 = 0.7

2 = 7.49

53.19
440.02
435.09
2947.55
206.42
1.27
0.70
7.49
15.91

4107.62

At stream 9:
2 = 53.27

kg/hr

0.9995 = 7.49

0.9995 = 15.92

%
1.29
10.71
10.59
71.75
5.02
0.03
0.02
0.18
0.39
100.00

TiCl4 Knock Out Drum

10
Cl2
CO2
CO
SiCl4
O2
N2
SO2
HCl

KN-001

kg/hr
53.16
439.80
434.87
206.31
1.27
0.70
7.48
15.90

1159.90

9
TiCl4
Cl2
CO2
CO
SiCl4
O2
N2
SO2
HCl

kg/hr
53.19
440.02
435.09
2947.55
206.42
1.27
0.70
7.49
15.91

4107.62

%
1.29
10.71
10.59
71.75
5.02
0.03
0.02
0.18
0.39
100.00

15
TiCl4

At stream 10:
2 = 53.19

0.9995 = 53.16

2 = 440.02
= 435.09

0.9995 = 439.80

4 = 206.42
2 = 1.27
2 = 0.7

0.9995 = 434.87

0.9995 = 206.31

0.9995 = 1.27

0.9995 = 0.70

%
4.58
37.92
37.49
17.79
0.10
0.06
0.64
1.37
100.00

kg/hr
2947.55

%
100

2 = 7.49

= 15.91

0.9995 = 7.48

0.9995 = 15.90

At stream 14:
4 = 2947.55

0.9995 = 2946.07

Reactor 2 Preheater
HEX-002

11
O2

kg/hr
248.74

%
100

From reactor 2 calculation:

2 = 248.74

0.9995 = 248.62

12
O2

kg/hr
248.62

%
100

R 002
Carbon Monoxide Converter
10
Cl2
CO2
CO
SiCl4
O2
N2
SO2
HCl

kg/hr

53.16
439.80
434.87
206.31
1.27
0.70
7.48
15.90

4.59
37.93
37.50
17.79
0.11
0.06
0.65
1.37

1159.9

100.00

12
O2

kg/hr

%
100

248.62

13
Cl2
CO2
SiCl4
O2
N2
SO2
HCl

Converter reaction:
CO + O2

kg/hr

%
3.77
79.77
14.64
0.09
0.05
0.53
1.13

1408.41

100.00

CO2

= 440.24
2 = 435.09

= 248.74

2 = 435.30

1
28

1
28

1 2 44 2

= 684.05
1
1 2

0.5 2 32 2

1
1 2

At outlet:
2 = 2 + 2
2 = (684.05
2 = 53.16

+ 439.8
) 0.9995 = 1123.72

0.9995 = 53.14

4 = 206.42
2 = 1.27

53.14
1123.73
206.21
1.27
0.70
7.48
15.89

0.9995 = 206.31

0.9995 = 1.27

2 = 0.70
2 = 7.49

0.9995 = 0.70

= 15.91

0.9995 = 7.48

0.9995 = 15.90

Gaseous Stream Cooler

CO 02
13
Cl2
CO2
SiCl4
O2
N2
SO2
HCl

kg/hr

14
Cl2
CO2
SiCl4
O2
N2
SO2
HCl

%
3.77
79.78
14.65
0.09
0.05
0.53
1.13
100.00

53.14
1123.73
206.21
1.27
0.70
7.48
15.89

1408.41

1407.71

At stream 15:
2 = 1123.73
2 = 53.14

0.9995 = 1123.17

0.9995 = 53.11

4 = 206.21

0.9995 = 206.11

2 = 1.27

0.9995 = 1.27

2 = 0.70

0.9995 = 0.70

2 = 7.498 0.9995 = 7.48

= 15.89

kg/hr
53.11
1123.17
206.11
1.27
0.70
7.48
15.88

0.9995 = 15.88

%
3.77
79.78
14.65
0.09
0.05
0.53
1.13
100.00

Reactor 3 Preheater
HEX-03

16
O2

kg/hr
496.99

%
100

From reactor 3 calculation:

2 = 469.99

0.9995 = 496.74

17
O2

kg/hr
496.74

%
100

TiCl4 Electric Arc Furnace

R-003
17
O2

15
TiCl4

kg/hr
2946.07

kg/hr
496.74

%
100

18
TiO2
Cl2
O2
TiCl4

%
100.00

kg/hr
1227.44
2179.49
4.97
29.45
3441.34

%
35.67
63.33
0.14
0.86
100.00

Assuming 99% conversion (United States of America Patent No. US7476378 B2, 2009)
TiCl4 + O2

TiO2

2Cl2 - Reaction 0

4
1 4
1 2
32 2

189.69 4
1 4 1 2

= 496.99

2 = 2946.07

2 = 296.07
63.33

1 4
189.69 4

2 2
1 4

70.91 2
1 2

0.99 0.9995 =

2
4
1 4
1 2 70.87 2
= 2946.07

0.99 0.9995

189.69 4
1 4
1 2

= 1228.67

From burner reaction calculation conversion is 99%. Thus, 1% of the materials that will enter will be
unreacted:
At outlet:
4 = 2946.07
2 = 497.49

0.01 0.9995 = 29.45

0.01 0.9995 = 4.97

C0- 003
Gas-solid Cooler

18
TiO2
Cl2
O2
TiCl4

kg/hr
1227.44
2179.49
4.97
29.45
3441.34

%
35.67
63.33
0.14
0.86
100.00

19
TiO2
Cl2
O2
TiCl4

The off gas from the burner will be rapidly 1000 OC to 900 OC.

At stream 19:
2 = 1227.44

0.9995 = 1226.83

2 = 2179.49

0.9995 = 2178.40

4 = 29.45

0.9995 = 29.43

2 = 4.97

0.9995 = 4.96

kg/hr
1226.83
2178.40
4.96
29.43
3439.62

%
35.67
63.33
0.14
0.86
100

CY-01
TiO2 Separator
19
TiO2
Cl2
O2
TiCl4

kg/hr
1226.83
2178.41
4.96
29.46
3439.66

%
35.67
63.33
0.14
0.86
100.00

20
Cl2
O2
TiCl4

27
TiO2
TiCl4

kg/hr
1226.21
25.02
1251.24

kg/hr
2177.31
4.96
4.39
2186.67

%
98.00
2.00
416.67

Titanium Dioxide is completely removed from oxide burner outlet by passing the mixture through a porosity
filter. (Management, 2001)

At Stream 20:
2 = 2178.41
4 = 4.39
2 = 4.96

0.9995 = 2177.31

0.9995 = 4.39

0.9995 = 4.96

At stream 27:
2 = 1228.06
4 = 25 .02

0.9995 = 1227.44

0.9995 = 25.02

%
99.57
0.23
0.20
100.00

CO 04
Recycle stream cooler
20
Cl2
O2
TiCl4

kg/hr

2177.31
4.96
4.39
2186.67

99.57
0.23
0.20
100.00

21
Cl2
O2
TiCl4

kg/hr

2176.22
4.96
4.39
2185.57

99.57
0.23
0.20
100.00

The off gas from the burner will be rapidly 1000 OC to 900 OC.

At stream 17:
2 = 1228.67
2 = 2177.31
4 = 4.39

0.9995 = 1228.06

0.9995 = 2176.22

0.9995 = 4.39
2 = 4.96
0.9995 = 4.96

COND-02
Gaseous Components Condenser
21
Cl2
O2
TiCl4

kg/hr
2176.22
4.96
4.39
2185.57

%
99.57
0.23
0.20
100.00

At stream 22:
2 = 2176.22
4 = 4.39
2 = 4.96

0.9995 = 2176.13

0.9995 = 4.39

0.9995 = 4.96

22
Cl2
O2
TiCl4

kg/hr
2175.13
4.96
4.39
2184.48

%
99.57
0.23
0.20
100.00

KN- 002
TiCl4 Knock-out drum

22
Cl2
O2
TiCl4

kg/hr

2175.13
4.96
4.39
2184.48

99.57
0.23
0.20
100.00

24
Cl2
O2

23
TiCl4

kg/hr
4.39

At stream 23:
4 = 4.39

0.9995 = 4.42

At stream 24:
2 = 2175.13
2 = 4.96

0.9995 = 2174.04

0.9995 = 4.96

%
100

kg/hr
2174.04
4.96
2179.00

%
99.77
0.23
100.00

CO -005
TiO2 Rotary Cooler
27
TiO2
TiCl4

kg/hr
1226.21
25.02
1251.24

%
98.00
2.00
100.00

28
TiO2
TiCl4

At stream 28:
2 = 1226.21
4 = 25.02

0.9995 = 1225.60

0.9995 = 25.01

kg/hr
1225.60
25.01
1250.61

%
98.00
2.00
100.00

CO -006
Indirect Plate Cooler

28
TiO2
TiCl4

kg/hr
1225.60
25.01

1250.61

%
98.00
2.00
100.00

At stream 28:
2 = 1225.61
4 = 25.01

0.9995 = 1224.99

0.9995 = 25.01

29
TiO2
TiCl4

kg/hr
1224.99
25.01
1250.00

%
98.00
2.00
100.00

ML 03
TiO2 Jet Miller
28
TiO2
TiCl4

kg/hr
1224.99
25.01
1250.00

%
98.00
2.00
100.00

29
TiO2
TiCl4

At stream 29:
2 = 1224.39
4 = 25.01

0.9995 = 408.33

0.9995 = 25.00

kg/hr
1224.38
25.00
1249.38

%
98.00
2.00
100.00

References
KIrk-Othmer. (2007). Encyclopedia of Chemical Technology. Wiley Blackwell.
Management, I. f. (2001). Large Volume Solid Inorganic. Umwelt Bundes Amt.
Subramanian, N. S., Bernard, R. P., Hsu, Y. H., Musick, C. D., Ogunde, K., & Tilton, J. N. (n.d.).
Alfred-Herrhausen. (2001). German Notes on BAT for the Production of Large Volume Inoragnic Chemicals
- Titanium Dioxide. Federal Environmental Agency.
Gzquez, M. J., Bolvar, J. P., Garcia-Tenorio, R., & Vaca, F. (2014). A Review of the Production Cycle of
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