Light Metals 2009 Edited by: Geoff Bearne

TMS (The Minerals, Metals & Materials Society), 2009

EVALUATION OF THE NECESSARY AMOUNT OF QI IN BINDER PITCH

Robert H. Wombles, John Thomas Baron, Stacey McKinney
Koppers Inc., Harmarville Technical Center, 1005 William Pitt Way, Pittsburgh, PA 15238
Keywords: coal tar pitch, anode, QI, binder pitch

Abstract
Quinoline Insolubles
The role of quinoline insoluble (QI) in a binder pitch has long
been the topic of discussion and disagreement. Throughout the
world, especially in Asia, QI levels in crude coke oven tar are
decreasing. This is largely due to coke battery age and operating
conditions. What was once thought to be the lowest acceptable
amount of QI in a binder pitch may have to be adjusted. This
study was conducted to determine the effect of the QI content of
the binder pitch on the physical properties of aluminum anodes.
This study used coal tar pitches blended to QI levels of 2 weight
percent (wt.%), 4 wt.% and 6 wt.%. as well as a petroleum pitch
containing 0 wt.% QI. This paper will present the results of this
laboratory anode study by comparing the physical properties of
the resulting anodes.

The importance or the lack of importance, of QI on the quality of

coal tar pitch has been a debated over many years. QI impacts on
pitch properties such as viscosity and wetting, coke yield, binder
penetration, ash, anode shrinkage and strength as well as electrical
properties. Although much research has been reported in the
(4)
literature, no clear conclusion has been drawn.
It is generally agreed that an anode binder should contain some
level of QI. The presence of QI affects the following:

Wetting of the filler particles

Helps control the penetration of pitch into the petroleum

coke particles since QI aggregates on or in the open
areas of the surface of filler coke

Provides a pathway for the release of volatiles from the

binder during baking

Increases coking value of the pitch because of QIs high

coking value since the QI is high in fixed carbon (5)

Introduction
Coal tar pitches typically contain a QI content of between 2 and
15 wt.%. QI is very beneficial, if not essential, to the satisfactory
performance of anodes. (1)
It is projected that there will be a 7 to 8% increase in the demand
for coal tar pitch annually. Although the coal tar supply in North
America and Europe is diminishing, there is sufficient coal tar
worldwide to meet these demands. (2) However, most of the
available coal tar is in China and typically contains a QI content
of 1 3 wt.%.

The reviewed literature suggests that a minimum QI level is less

than 2%, but this has not been confirmed experimentally.

Coal tar pitch is produced from coal tar by a distillation process.

In North America and Europe the majority of the anode binder
(2)
pitch is produced by vacuum flash distillation.
Using this
method of vacuum distillation results in a doubling of the amount
of QI contained in the crude coke oven tar. Therefore, coal tar
pitches produced from the crude coke oven tar that is currently
available in China may contain much lower amounts of QI than
typically found in North America (12 16 wt. % QI).

Laboratory Scale Anode Study

In order to investigate the differences in the properties of anodes

produced with low QI pitches, a laboratory anode study was
conducted. The remainder of this paper is dedicated to presenting
the results of that study.

A laboratory anode study was performed comparing the properties

of laboratory anodes produced using coal tar pitches with varying
amounts of QI. The pitches used for this study were produced by
blending a filtered coal tar pitch and a coal tar pitch containing a
QI of 13 wt%. The properties of the pitches used in the study are
given in Table I.

Current coal tar pitch specifications have been based on historical

QI levels for various regions around the world. The satisfactory
use of binder pitch that contains various levels of QI has been well
established, but not the optimum level of QI. Most agree that a
consistent amount of QI in coal tar pitch is more important than
(3)
the actual level of QI.

Sized coke fractions were received from a United States smelter

and were weighed and mixed using the following standard anode
coke formation:
Coarse
Intermediate
Fines
Butts

This paper will demonstrate the effects on anode quality by using

coal tar pitches with QIs of 2 wt%, 4 wt%, and 6 wt%. Anodes
made using petroleum pitch and 13 wt% QI pitch are also
included for comparison purposes.
These results will be
demonstrated by presenting the results of a small scale laboratory
anode study.

31.5 %
14.6 %
37.0 %
16.9 %

A series of cylindrical laboratory size anodes (10.2 cm in diameter

and 15.2 cm in height) was prepared using each of the pitches.
The details of the anode mixing, molding, and baking protocol are
given in Table II.

913

The laboratory anodes were cored and the cores were tested for
the typical anode properties as shown in Table III.

After baking, the laboratory anodes were measured for baked

apparent density, coking value in situ and shrinkage. Plots of the
results of the testing are given in Figures 1 - 13.

Table I Physical Properties of Pitches in Laboratory Anode Study

Method
ASTM
D3104
D2318
D4072
TI-QI
D2416
D71
D5018

Property
Softening Point, C
QI, wt.%
Toluene Insolubles, wt.%
Beta Resins, wt.%
Coking Value, wt.%
Density, g/cc
Viscosity, cps
150C
165C

Pitch
0%
QI

Pitch
2%
QI

Pitch
4%
QI

Pitch
6%
QI

Pitch
13%
QI

115.5
0
3.8
3.8
49
1.20

115.3
2
23.9
21.9
56.0
1.28

113.3
3.6
25.2
21.6
55.0
1.32

114.7
6.3
26.2
19.9
55.9
1.33I

109.4
13.1
27.5
14.4
57.8
n/a

4380
1060

5680
1377

4450
1170

6225
2200

n/a
n/a

Table II Anode Production Protocol

Mixing and Molding Conditions
Materials
Not Preheated
Mixing Time
20 -25 Minutes
Mixing Temperature
160C +/-3C
Molding Temperature
145-150C
Vibrating Time
55 Seconds
Baking Protocol:
0-600C
10C/hr
600-1170C
25C/hr
1170C
20 hr hold
Center Retort Temperature ~
1100-1120C
Note: Anodes are packed in fluid coke with a nitrogen purge sweep.

Table III Typical Anode Properties

Laboratory Block Data

Preferred
Value
Ranges (6)

Pitch
0% QI

Pitch
2% QI

Pitch
4% QI

Pitch
6% QI

Pitch
13% QI

15.5

15.5

15.5

15.5

15.5

1.40 1.65

1.592
57.51
.03
1.488

1.622
68.97
1.44
1.572

1.619
68.6
1.40
1.57

1.625
69.37
1.47
1.582

1.592
70.60
2.18
1.573

1.40 1.65
50 - 75

1.49
70.77

1.57
60.59

1.57
61.27

1.58
58.99

1.57
68.38

.5 1.5
Excellent
90%
Excellent
80%
34 - 49
68
3.5 5.5
3.5 5.0

0.97
84.73

.32
84.51

.30
86.78

.33
85.36

.50
81.10

65.48

68.25

70.89

69.86

67.90

33.28
4.33
3.88
2.12

41.80
9.72
4.234
2.44

46.52
7.72
4.304
2.43

53.08
8.30
4.281
2.48

43.55
4.98
4.260
2.28

Pitch Percent
Green Apparent Density
Coking Value In-Situ
Shrinkage
Baked Apparent Density
Laboratory Core Data
Baked Apparent Density
Electrical Resistivity

g/cc
wt.%
Vol. %
g/cc

Air Permeability
CO2 Reactivity

g/cc
Ohmsmm
nPm
% Residue

Air Reactivity

% Residue

Crush Strength
Flexural Strength
Thermal Conductivity
Coefficient of Thermal
Expansion

MPa
MPa
W/mK
*10^-6
@300C

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Conclusions:

Anode quality is acceptable at the QI levels tested.

Petroleum pitch does not produce an acceptable
quality anode.
Slight decrease in coking value in situ for the lower QI
pitches since QI solids increase coke yield
Aromaticity of the binder pitch appears to have a
greater influence on anode quality than the QI level.
This needs validated in future studies.
Anode quality is similar over the range of QI levels
tested. Future evaluations will continue to verify these
findings.

1.64
1.62
1.6
g/cc

Green Aparent Density

1.66

1.58
1.56
1.54
1.52
1.5
13.5

14

14.5

15

15.5

16

16.5

% Pitch

0% QI

2.0% QI

4.4% QI

6.3% QI

13.1% QI

Figure 1. Block Green Apparent Density

Acknowledgements
Coking Value in Situ

Ralph And Daniel Gray provided information regarding effects

of QI on anode quality. P. K. Sickels, and G. D. Wall assisted
the authors in providing data and preparing this report. Their
contributions are gratefully appreciated.

75

Wt. %

70
65
60
55

References

50
13.5

(1) Irwin, Charles, et. al.

Continuous Method for
Increasing the QI Concentration of Liquid tar While
Concurrently Producing a QI Free Tar. UCAR
Carbon Technology Group assignee.
Patent
EP0712921. 28 July 1999.
(2) R.H. Wombles & J.T. Baron, Laboratory Anode
Comparison of Chinese Modified Pitch and Vacuum
Distilled Pitch, Light Metals 2006, 2006. 537 540.
(3) K.Krupinski & J. Windfielder, Effects of Tar
Quinoline Insolubles on Manufactured Carbon
Perfromance, Proc. Ironmaking Conference, 1992,
487-492.
(4) W. Boegnigk, A. Niehoff & R. Wildforster, Influence
of QI Content on Binder Pitch Performance, Light
Metals 1991, 1991, 615-620.
(5) R. H. Wombles & B. Sadller, The Effect of Binder
Pitch QI Content on Aluminum Anodes Physical
Properties, Eighth Australasian Aluminum Smelting
Technology, September 2004.
(6) Jones, S.S. & Bart E.F., Binder for the Ideal Carbon
Anode, Light Metals 1990, 1990, 61 1 627.

14

14.5

15

15.5

16

16.5

17

17.5

% Pitch

0% QI

2.0% QI

4.4% QI

6.3% QI

13.1% QI

Figure 2. Block Coking Value In-Situ

Anode Baked Apparent Density
1.6
1.58

g/cc

1.56
1.54
1.52
1.5
1.48
1.46
13.5

14

14.5

15

15.5

16

16.5

17

17.5

% Pitch

0% QI

2.0% QI

4.4% QI

6.3% QI

13.1% QI

Figure 3. Block Baked Apparent Density

Shrinkage
2.50

Vol. %

2.00
1.50
1.00
0.50
0.00
-0.50
-1.00
-1.50
13.5

14

14.5

15

15.5

16

16.5

17

17.5

% Pitch

0% QI

2.0% QI

4.4% QI

6.3% QI

Figure 4. Shrinkage

915

13.1% QI

17

17.5

85
80
75
70
65
60
55
50
45
40
13.5

Compressive Strength
55
50
45
MPa

--m

Electrical Resistivity

40
35
30
25

14

14.5

15

15.5

16

16.5

17

20
13.5

17.5

14

14.5

15

% Pitch

0% QI

2.0% QI

15.5

16

16.5

17

17.5

% Pitch

4.4% QI

6.3% QI

13.1% QI

0% QI

Figure 5. Electrical Resistivity

2.0% QI

4.4% QI

6.3% QI

13.1% QI.

Figure 9. Compressive Strength

Air Permeability

Flexural Strength

2.5

14
12

2.0

MPa

nPm

10

1.5
1.0

8
6
4

0.5
2

0.0
13.5

14

14.5

15

15.5

16

16.5

17

0
13.5

17.5

14

14.5

15

% Pitch

0% QI

2.0% QI

4.4% QI

6.3% QI

13.1% QI

0% QI

Figure 6. Air Permeability

2.0% QI

88

2.5

86

2.3
W/m-K

% Residue

2.7

84
82

17

17.5

4.4% QI

6.3% QI

13.1% QI

2.1
1.9

80

1.7

14

14.5

15

15.5

16

16.5

17

1.5
13.5

17.5

14

14.5

15

% Pitch

0% QI

2.0% QI

4.4% QI

6.3% QI

13.1% QI.

0% QI

Air Reactivity
Avg. Alpha * 10-6 (@ 300C)

70
68
66
64

15

15.5

2.0% QI

17

17.5

16

4.4% QI

2.0% QI

4.4% QI

6.3% QI

13.1% QI

16.5

17

17.5

4.6
4.4
4.2
4.0
3.8
3.6
3.4
3.2
3.0
13.5

14

14.5

% Pitch

0% QI

16.5

Coefficient of Thermal Expansion

72

14.5

16

Figure 11. Thermal Conductivity

74

14

15.5
% Pitch

Figure 7. CO2 Reactivity

% Residue

16.5

Thermal Conductivity

CO2 Reactivity

62
13.5

16

Figure 10. Flexural Strength

90

78
13.5

15.5
% Pitch

15

15.5

16

16.5

17

17.5

% Pitch

6.3% QI

13.1% QI

0% QI

Figure 8. Air Reactivity Residue

2.0% QI

4.4% QI

6.3% QI

13.1% QI

Figure 12 Coefficient of Thermal Expansion

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