Papermaking Chemistry

Fundamental & Practical Aspects

of Wet-End Chemistry for Papermakers

OBAs and their effect on Wet

End Chemistry
Mariela Gauto, Pointe-Claire
March 28-30, 2006

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 Topics to cover
• Disulphos in Wet End: a little bit of theory
– Wood-free grades
– Wood-containing applications
– High Whiteness vs Lightfastness

• Producing High White grades

– Practical experiences
– Effect of Disulpho OBAs on Retention
– Benefits

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 Disulphos in Wet End:
a little bit of theory

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 Wet-End Application of OBAs

• Already known benefits

– Improve Whiteness / Brightness of the paper
– Process control
– Help to achieve better lightfastness
– Wood- containing grades

• OBA types for the Stock

– Tetrasulphos 4 sulphonic groups
– Disulphos 2 sulphonic groups

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 Wet-End Application of OBAs

• Tetrasulpho OBAs are usually used close to the

saturation point in High White papers

• Laboratory experiments and trials on paper machines

often confirm that di-sulpho OBAs are the most cost
effective within this area

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 Disulpho OBAs

• Market needs
– Urea free product: Several reasons
– Glycol free product: Lower COD in Backwater
– True liquid: Easy to handle

• Traditionally it has been difficult to produce these low solubility

OBAs with the above requirements

• Leucophor AHF liquid is the only urea free/ glycol free di-sulpho
OBA on the market today which is in a true liquid form

• Leucophor AHF liquid is unique to Clariant

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 Disulpho OBAs
• More efficient
– Can be more cost effective

• More Substantive
– Can be used at short contact times => Process flexibility
– It is less affected by other additives => Cationic Additives
– No OBA in the backwaters => Less anionic charge
– Can be used in soft water conditions

• Wood-free & Wood-containing grades

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 Unsized and Unloaded Wet End Application
100% Chemical Pulp
Di vs Tetra with 100g/t shading dyestuff

Clariant 2-sulpho Standard 4-sulpho

185
180
175
170
165
160
CIE Whiteness

155
150
145
140
135
130
125
120
115
110
0 0.2 0.4 0.8 1.2 1.6 2

OBA Concentration, % of dry fibre

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 Unsized and Unloaded Wet End Application
100% Chemical Pulp
Di vs Tetra with 100g/t dyestuff.

-6 4 5 6 7 8 9
Yellower
Base Paper
-8
Clariant 2-sulpho
-10 Standard 4-sulpho
CIELAB b* Values

-12

-14

-16

-18

Bluer -20

-22

Greener
CIELAB a* Values Redder
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 Effect of Contact Time
Water at 12 dH Water at 1 dH
20 70

18
60
16

% OBA in Backwater
% OBA in Backwater

14 50

12
40
10
30
8

6 20

4
10
2

0 0
0 5 10 15 20 0 5 10 15 20

Minutes Minutes

Leucophor AHF liquid M in u te s

Standard 4-sulpho

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 Effect of Cationic additives
100 100

90 90

% Fluorescence
80 80
% Fluorescence

70 70

60 60

50 50

40 40

30 30
0 0.1 0.2 0 0.1 0.2

Polyethylene-imine Concentration, % Polyamide- amine Concentration, %

Leucophor AHF liquid Standard 4-sulpho

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 Quick Response

Pulper

Wire

Leucophor AHF liquid

(can be added as late as fan pump)

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 Facts

• A survey is been run recently

• Uncoated Woodfree Papers

• Several objectives
– OBAs used
– Shading system
– Furnish composition
– Lightfastness

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 Facts
Wet End OBA in Uncoated grades
WCIE > 160 160 > WCIE > 150 150 > WCIE >130
70

61.3
60
55.55

50
50
Type of OBA applied, %

40
33.33
29.03
30
22.22
20
16.66
11.11
10
6.45

0
None 2-sulpho 4-sulpho
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 High Whiteness vs Lightfastness
• Wet End addition would help to achieve a better lightfastness

• A correct Wet End / Surface ratio would improve the Whitening

process

• Highly dependant on several variables

– Paper grade
– OBA type and concentration
– OBA addition points
– Application type
– Furnish composition
– etc.

• Shading system should be taken into account

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 Wood-containing grades
• Lignin absorbs UV light

• Natural yellow colour of pulp

• OBA has affinity for cellulose

• Lower effect on Wood-containing pulps

• Adding only a small amount of Chemical Bleached pulp can lead to

a bigger effect

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 Wood-containing grades
No OBA (vs. Stock A)
0.4% Standard 4-sulpho
0.4% Clariant 2-sulpho

10

Brightness lift
6

0
Stock A = 100% CTMP Stock A Stock B Stock C

Stock B = 70% / 30% CTMP/ Bleached Chemical Pulp

Stock C = 100% Bleached Chemical Pulp
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 Case Studies

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 Introduction
• The following are cases taken from machine
trials

• Note:
– The Whiteness target in every case is 160-
165WCIE
– Grade: P&W, 80-90gsm

• Optical properties were on target in every case

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 Case Study 1

• Wet End: Standard urea free 4-sulpho replaced

with urea and glycol free 2-sulpho
liquid

• Size Press: Standard urea free 4-sulpho

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21
Flow rate, l/h

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0
5
10
15
20
25
30
35

08:55

09:20
AHF ON

09:40
09:55

10:20
10:40
Case Study 1

10:55

11:12

Wet-End OBA
11:30

11:50

12:10

12:40

13:05

13:30

13:50

14:20

14:50

15:20
Size-Press OBA

15:50

16:20

17:15
AHF OFF
 Case Study 1

• Wet End: An average 40- 50% reduction with the

2-sulpho OBA was introduced

• Maintained L*a*b*, CIE whiteness and D65 brightness for

grade.

• 8% reduction in backwater solids.

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 Case Study 2

• Wet End: Standard urea free 4-sulpho replaced

with urea and glycol free 2-sulpho
liquid

• Size Press: Urea free 6-sulpho OBA

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 Case Study 2
12 AHF ON

10
OBA Concentration, kg/t

0
12 13 14 15 16 17 20 22 23 24 25 26 29

Reel Number

Wet-End OBA Size-Press OBA

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 Case Study 2

• Wet End: An average 40% reduction in wet-end

OBA when the 2-sulpho was
introduced

• Size Press: An average 12% reduction in size-

press OBA addition.

• Maintained L*a*b*, CIE whiteness and D65 brightness

for grade.

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 Case Study 3

• Wet End: Standard urea free 4-sulpho replaced

with urea & glycol free 2-sulpho liquid

• Size Press: Urea free 6-sulpho OBA

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OBA Concentration, kg/t

0
2
4
6
8
10
12
14

07:23

08:24

09:52

Wet End OBA

10:43

11:27
Case Study 3

12:25

13:26
Trial

Time
14:37

15:30

16:37

17:52

18:50

20:50

21:55
 Case Study 3
Trial

85

80

75
Retention, %

70

65

60

55

50
07:23

08:24

09:52

10:43

11:27

12:25

13:26

14:37

15:30

16:37

17:52

18:50

20:50

21:55
Time, hours

Total retention Filler Retention

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White Water Solids, ppm

1500
1700
1900
2100
2300
2500
2700
2900
3100
3300
3500

07:23

08:24

09:52

10:43

11:27
Case Study 3

12:25

13:26
Trial

14:37

15:30

Time, hours
16:37

17:52

18:50

20:50

21:55

07:30
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Head Box charge ,µeq/ l

0
50
100
150
200
250
300
350
400

07:23

08:24

10:43

11:27
Case Study 3

13:26

14:37
Trial

Time, hours
15:30

16:37

17:52

18:50

21:55

07:30
 Case Study 3
• Extremely successful.
Parameter When running with the When switching back to
2-sulpho 4-sulpho
Total Retention

Filler Retention

White Water Solids

System charge

Internal Sizing Aid

Addition
( AKD & PAC )

• Positive benefits achieved with regard to system stability

and cleanliness.
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 Case Study 4

• Wet End: Standard urea free 4-sulpho replaced

by urea and glycol free 2-sulpho
liquid

• Size Press: Modified 4-sulpho OBA

• Addition points
– Two different dosage points were tried to evaluate
the effect of the OBA on the Wet End Chemistry
a) Machine Chest ( current dosage point )
b) Fan Pump
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OBA dosage, kg/t

0
2
4
6
8
10
12
14

09:40

10:24

11:27
Standard 4-sulpho

12:04
Case Study 4

12:40

13:23
Leucophor AHF

14:46

15:49

16:52

Time, hours
09:13

09:44

10:03

10:20

11:14

12:33

14:38
 Case Study 4
Standard 4-sulpho
Leucophor AHF

100

95

90

85
Retention, %

80

75

70

65

60

55

50
09:40

10:24

10:50
11:27

12:04

12:40

13:23

14:46

15:49

16:52

09:13

09:44

10:03

10:20

11:14

12:33

14:38

13:36
Time, hours
Total Retention Filler Retention
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35
Backwater Solids, %

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0
0.2
0.4
0.6
0.8
1
1.2

09:40

10:24

10:50
Standard 4-sulpho

11:27
12:04
Case Study 4

12:40
13:23

14:46
Leucophor AHF

15:49

16:52

Time, hours
09:13

09:44
10:03

10:20

11:14
12:33

14:38

13:36
 Case 4 - Results
( in percentage of increase/decrease )
OBA consumption Total Retention Filler Retention

50%
40%
40%
30%
30%

20%
12% 10%
10%
3%
0%

-10%
-10%
-20%
-15%
-30%
-26%
-40%
-37.50%
-50%

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 The reason…..

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 Effect on Backwaters

• High anionic charge could alter all of the Wet

End Chemistry

• Surface OBAs could come out from broke, but

in a quite small amount

• Main source of anionic charge:

– 4-sulphos applied in the Stock ( even at 30-50%
broke )

• Solution: 2-sulphos in Wet End

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 Laboratory evaluation of OBA in Backwater
from broke containing different types of OBAs
Note:
Broke was generated by 36g/l Urea free 6-sulpho in
30
re-pulping suitable paper Size Press
28
samples.
26
OBA in Backwater, ppm

There was no extra OBA

24
added.
22
20
18
16 0.7% Leucophor AHF
14 in Stock
12
10
8
Build-up with Standard 6
4-sulpho in Stock
4
2
0
Standard 4-slulpho Leucophor AHF 6-sulpho
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 167 CIE Whiteness Paper Machine Trial
OBA in backwater (ppm)
140 Standard Trial
Machine running with freshwater
120 for standard conditions 30% broke

100 Saturation effect of tetra OBA

80
Worst case:
60 - close backwater loop
- 45% recycled broke
40

20

0
Tetra Hexa Leucophor AHF Leucophor SAC
liquid liquid
Note:
Both,
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effect of the normal usage of the 4-sulpho and broke management is observed in this graph
 Case Study 5
Backwaters
• Wet End Urea free 4-sulpho replaced by a urea
& glycol free 2-sulpho

• Size Press Urea free 6-sulpho

• Backwater Samples were taken during the trial.

• Grades P&W, 80-90 gsm

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 Case Study 5
400
4-sulpho 6-sulpho Leucophor AHF

350

300
AHF On Tetra On
OBA in Backwater, ppm

250

200
Broke

150

100

50

0
1 2 3 4 5 6 7 8 9 10 11 12 13
Backwter No
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 Backwater analysis

Initial Values Final Values

4-sulpho OBA >500ppm < 5ppm

6-sulpho OBA >300ppm < 10ppm

2-sulpho OBA None was detected at all, in any case

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 Case Study 5 Tetra On

90
AHF On

80

70
Retention, %

60

50

40

Filler Retention
30
Total Retention

20
Trial Development

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 Summary
OBA Consumption Wet End Size Press
- 15 to 50% - 15 to 40%
Total Retention - 5 to 6%

Filler Retention - 10 to 30%

Retention Aid -5 to 35%

Cationic Demand ->300 µeq/l

Formation
Internal Sizing √
Runnability Excellent
Grade changes were performed in few minutes instead of 30-40mins
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 Case of study 6
Backwaters
• Grade P&W, 80-90 gsm
WCIE = 161
R457 = 115
b*-value = -17
OBA Wet End, Size Press Anionic
kg/t kg/t Charge
µeq/l
4-sulpho 2 2
70
6-sulpho - 8

2-sulpho 2.3 -
12
6-sulpho - 7
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 Case of study 6
Backwaters
• Grade P&W, 80-90 gsm
WCIE = 161
R457 = 115
b*-value = -17
OBA Wet End, Size Press Anionic
kg/t kg/t Charge
µeq/l
4-sulpho 2 2
70
6-sulpho - 8

2-sulpho 2.3 -
12
6-sulpho - 7
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 Measuring Whiteness
A last but not least point

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 Measuring Whiteness

• Whiteness vs Brightness

• Calibration methods

• Machine vs Laboratory

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 Effect of UV calibration on R457
R457
110
Leucophor U liquid
100% UV
105
Leucophor U liquid
90% UV
100
Leucophor U liquid
70% UV
95
Leucophor U liquid
50% UV
90
Leucophor U liquid
25% UV
85
0 0.2 0.4 0.6 0.8 1 Leucophor U liquid
0% UV
Conc. (%)

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 Effect of UV calibration on b*

b*
Leucophor U liquid
2 100% UV

0 Leucophor U liquid
90% UV
-2
Leucophor U liquid
-4 70% UV

Leucophor U liquid
-6
50% UV

-8 Leucophor U liquid
25% UV
-10
Leucophor U liquid
0 0.2 0.4 0.6 0.8 1 0% UV

Conc. (%)

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 Case 1
Mill vs Clariant: different equipments
High White Paper sample
L* a* b* CIE R457
Whiteness
Sample A
Mill 1 93.7 0.5 -4.6 105.6 92.6
ACS Spectro'

Sample A
Clariant values 94.0 3.8 -15.5 155.1 109.1
Spectro' 1

Sample A
Clariant values 94.8 3.8 -15.9 158.0 110.8
Spectro' 2

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 Case 2
Mill vs Clariant: same equipments
High White Paper sample
L* a* b* CIE W R457 Rz

Sample B 94.4 2.4 -5.0 137.5 93.9 N/A

Mill 2 Elrepho 2000
Sample B 95.0 3.5 -13.7 149.0 107.6 N/A
Clariant Elr'o 2000
Sample C 95.0 1.5 -5.1 @110.7 95.4 N/A
Mill 3 Elrepho 2000
Sample C 95.3 1.9 -7.8 123.4 99.5 N/A
Clariant Elr'o 2000
Sample D 95.5 1.6 -3.6 @105.0 N/A 93.9
Mill 4 Elrepho 2000
Sample D 95.0 1.7 -6.3 116.0 N/A 103.6
Clariant Elr'o 2000

@ = Calculated from L*, a*, b*

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 Conclusions

• Controlling the production of high white papers

requires good knowledge of the instrument used, the
values measured and the products used to influence
whiteness

• Where OBA's are used results vary depending on the

UV component

• More inter instrument calibration is required (e.g.

TAPPI, STFI etc)

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 Final Conclusions

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 Summary
• Disulpho OBAs are the most cost-effective option for the Wet End

• They bring a wide range of benefits, control and flexibility to the

process

• Overall retention and Filler retention are improved

• Excellent runnability of the PM results from running a much “cleaner”

system

• Compatibility with different types of Wet End chemistries and machine

types

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 Thank you very much for your attention.

Questions?

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