CHEMICAL ADDITIVES AND SURFACTANTS ON KRAFT PULPING OF E. CAMALDULENSIS

CHEMICAL ADDITIVES AND SURFACTANTS ON KRAFT PULPING

OF E. CAMALDULENSIS

Student : Md.Jabed Hasan

Committee : Dr. Esa Viljakainen (Chairperson) Dr. Mousa M. Nazhad Prof. Seyed Ahmad Mirshokraie Dr. Esa Lehtinen

May, 2009

Introduction Literature review Experimental Results and discussions Conclusion Positive outcome of the thesis Recommendations

CONTENTS

Now pulp and paper industries have two major problems

1.Environmental problem

2.Economic problem

Introduction

To reduce deforestationTo protect environmentTo reduce costTo make the process more environment friendly

The wood costs, almost 50% of the production costs for a pulpmill.

The average global conifer wood price reached a new all-time-high of

US$112.53/odmt (oven-dry metric ton) in the 2Q/08.

This was up 11% from 2007 and 26% higher than two years ago.

Source: according to the [2Q 2008 ] market report Wood Resource Quarterly (WRQ).

Introduction

The average non-conifer wood fiber costs were reaching a record-high of US$108.77/odmt in the 2Q,

which was up 16% from a year ago and 23% higher than in 2006.

Some of the largest increases have occurred in Brazil where costs for pulpwood traded in the open market have increased over 300 % in five years in US dollar terms, and more than 200 % as measured in the Brazilian Reais.

Source: according to the [2Q 2008 ] market report Wood Resource Quarterly (WRQ).

Introduction

Environmental regulations in different countries have been set a limit of the amount of effluent (its components) discharges.

Introduction

Pulp mill effluentSource: http://www.ecofootage.com/06-08.html

River pollution by effluentSource: http://www.ecofootage.com/06-08.html

River pollution by effluentSource: http://www.ecofootage.com/06-08.html

Pulp mills release toxins such as dioxin and furan and other organochlorines in their effluent Source: http://ian.umces.edu/imagelibrary/displayimage-1083.html

Picture of Boreal forest

Source: Save Our Boreal Forests, the Mystery and the Heritage, Wilderness Committee Educational Report, Vol.11 - No.07, Fall 1992

Science, there is no superior pulping procedure than kraft process,

We have to improve the process either by process modification like MCC, EMCC,

RDH. or by adding some chemicals to improve yield and

delignification.

Objectives of the study

Process modification requires major capital investment and increase recovery boiler load.

Digester additives are less costly alternatives for decreasing kappa number and improving yield.

Digester modifications and pulping additives do not work antagonistically but are complementary

Introduction


Table: Chemical Composition of E. urophylla and E. camaldulensis.

● In Thailand, 5-year-old E. camaldulensis gave 72% holocellulose, 29% lignin, 12% pentosan and 8% extractives.

● Cooking yield of E. camaldulensis is around 47%.

Source: Science Report of Research Institute of Pulp and Paper Industry of Vietnam, Special Issue. November 1991. Source: Pattanopast, S. Effect of sulfidity on chemical properties of sulfate pulp from the river red gum (Eucalyptus camaldulensis Dehnh.),

Master Thesis, Kasetsart University, Thailand, p 211. (1995).

Tree specie Density, g/cm3 Cellulose, % Lignin, % Pentozan, % Ash,%

E. urophilla

E. camaldulensis

0.57

0.55

47.6

48.1

25.4

27.5

19.2

19.6

0.6

0.7

Many researches have done in Europe, North and South America with different additives for their local softwood and hardwood kraft cooking

Very few researches have done in Southeast Asian hardwoods like Eucalyptus.

We wanted compare the effectiveness of different additives with traditional kraft process in local wood.


● To find out the effect of additives in kraft pulping of Eucalyptus camaldulensis.

● To find out the effect of solvent in kraft pulping of Eucalyptus camaldulensis.

● To find out the combine and synergistic effect of additives and solvent in kraft pulping of Eucalyptus camaldulensis.

● To find out the yield and quality of pulps from different additives charges

Scope of study

Inhibiting the "peeling reaction"

Oxidizing agent, converts the reducing (reactive) end group of the carbohydrates to an alkali-stable aldonic acid.

reducing agent, converts the carbonyl group in the reducing end units of carbohydrate chains to hydroxyl groups.

Literature review

The phenyl propane units of lignin are joined through carbon-carbon and carbon-oxygen bonds in a random sequence.

During pulping, most of the carbon-carbon linkages are stable, while carbon-oxygen bonds are cleaved to varying extents.

Literature review

Literature review

A proposed mechanism illustrating the function of anthraquinone as a redox catalyst.

Source: Fleming, B.I., Kubes, G.J., Macleod, J.M., and Bolker, H.I., "Soda pulping With Anthraquinone: A Mechanism", Tappi 61(6): 43-46, (1978).

Literature review

Source: Y. Copur, A. Tozluoglu, A comparison of kraft, PS, kraft-AQ and kraft-NaBH4 pulps of Brutia pine, Bioresource Technology 99 (2008) 909–913.

Literature review

Source: Minja, R. J. A., Moe, S. T., Christensen, P. K. (1996): "Extended delignification of kraft pulping by anthraquinone, methanol and black liquor", 1996 Pulping conference Vol. 1, p. 319 – 324.

Literature review

Source: Nam–Seok C., Yuji M., Et al. (2008). Effect of urea addition on Soda pulping of Oak wood. J. Fac. Agr., Kyushu Univ., 53 (1), 1–5.

Literature review

Source: Nam–Seok C., Yuji M., Et al. (2008). Effect of urea addition on Soda pulping of Oak wood. J. Fac. Agr., Kyushu Univ., 53 (1), 1–5.

Experimental

Chemicals as additives

AnthraquinoneUrea Phosphonates (1-Hydroxyethylene-1,1-di-phosphonic acid) Methanol

Experimental

Cook: To find out the most effective charge of additive

Reference

Additive AQCharge 0.04%




Most effective charge

Reference

AQ, charge 0.04% +MeOH, Charge 10%




Optimum charge of AQ + MeOH

Cook-3: To find out the most effective charge of Additive and surfactant



Results and Yield

AQ - Pulping

47.2

47.3

47.4

47.5

47.6

47.7

47.8

47.9

48

Ref. 0.04 0.06 0.08 0.1 0.12Additive %

HEDP - Pulping

47.4047.4547.5047.5547.6047.6547.7047.7547.8047.85

Ref. 0.1 0.15 0.2 0.25 0.3

Additive %

AQ + MeOH - Pulping

47.20

47.40

47.60

47.80

48.00

48.20

48.40

Ref. 0.04 + 10 0.06 + 10 0.08 + 10 0.1 + 10 0.12 + 10

Additive %

HEDP + MeOH - Pulping

47.00

47.50

48.00

48.50

49.00

Ref. 0.1 + 10 0.15 + 10 0.2 + 10 0.25 + 10 0.3 + 10Additive %

Yield of different cooks

Results and Yields

Yield of different cooks

Urea - Pulping

45

46

47

48

49

50

51

52

53

Ref. 4 5 6 7 8

Additive %

Urea + MeOH - Pulping

45

46

47

48

49

50

51

52

53

Ref. 4 + 10 5 + 10 6 + 10 7 + 10 8 + 10

Additive %

AQ + Urea - Pulping

45.00

46.0047.00

48.00

49.00

50.0051.00

52.00

53.00

Ref. 0.12 + 4 0.12 + 5 0.12 + 6 0.12 + 7 0.12 + 8Additive %

Different Alkali + Urea - Pulping

46.5

47

47.5

48

48.5

49

49.5

Ref. 22 + 6 23 + 6 24 + 6 25 + 6 26 + 6

Additive %

Results and Cooking Kappa no.

Kappa of different cookingAQ - Pulping

11.5

12.0

12.5

13.013.5

14.0

14.5

15.0

15.5

Ref. 0.04 0.06 0.08 0.1 0.12

Additive %

HEDP - Pulping

12.5

13.0

13.5

14.0

14.5

15.0

15.5

Ref. 0.1 0.15 0.2 0.25 0.3

Additive %

AQ + MeOH - Pulping

0.0

2.04.0

6.0

8.0

10.012.0

14.0

16.0

Ref. 0.04 + 10 0.06 + 10 0.08 + 10 0.1 + 10 0.12 + 10Additive %


12.5

13.0

13.5

14.0

14.5

15.0

15.5

Ref. 0.1 + 10 0.15 + 10 0.2 + 10 0.25 + 10 0.3 + 10Additive %

Results and Cooking Kappa No.

Kappa of different cookingUrea - Pulping

0.0

5.0

10.0

15.0

20.0

25.0

30.0

Ref. 4 5 6 7 8

Additive %


0.00

5.00

10.00

15.00

20.00

25.00

30.00

Ref. 4 + 10 5 + 10 6 + 10 7 + 10 8 + 10Additive %

AQ + Urea - Pulping

0.0

5.0

10.0

15.0

20.0

25.0

Ref. 0.12 + 4 0.12 + 5 0.12 + 6 0.12 + 7 0.12 + 8Additive %


0.02.04.06.08.010.012.014.016.018.0

Ref. 22 + 6 23 + 6 24 + 6 25 + 6 26 + 6Additive %

Results and Pulp strength properties

Tensile index of different cookingAQ - Pulping

20

22

24

26

28

30

32

34

36

Ref. 0.04 0.06 0.08 0.1 0.12Additive %

HEDP - Pulping

2526272829303132333435

Ref. 0.04 0.06 0.08 0.1 0.12

Additive %

AQ + MeOH - Pulping

20

2224

2628

30

3234

36

Ref. 0.04 + 10 0.06 + 10 0.08 + 10 0.1 + 10 0.12 + 10

Additive %


25

27

29

31

33

35

37

39

Ref. 0.1 + 10 0.15 + 10 0.2 + 10 0.25 + 10 0.3 + 10Additive %

Results and Pulp strength properties

Tensile index of different cookingUrea - Pulping

20

25

30

35

40

45

50

55

Ref. 4 5 6 7 8

Additive %


20

25

30

35

40

45

50

55

Ref. 4 + 10 5 + 10 6 + 10 7 + 10 8 + 10Additive %

AQ + Urea - Pulping

20

25

30

35

40

45

50

55

Ref. 0.12 + 4 0.12 + 5 0.12 + 6 0.12 + 7 0.12 + 8Additive %


0.005.0010.0015.0020.0025.0030.0035.0040.0045.00

Ref. 22 + 6 23 + 6 24 + 6 25 + 6 26 + 6Additive %

Major results are found

High pulp yield in cooking Both high and low cooking kappa number Higher strength pulp than reference pulp

CONCLUSIONS

AQ reduced the kappa 14.6 %.

Urea increases both yield and Kappa. Yield and Kappa increased 9.5 % and 83.4 % respectively.

Tensile index of this pulp was about 47 % higher than reference pulp.

Conclusions

Combined effect of additive and surfactant does not change the result significantly.

Synergetic effect of AQ and urea gives 9.4 % higher

yield and 8 % higher Kappa than the reference cooking.

Conclusions

AQ reduced the kappa 14.6 %.

Urea increased yield 9.5 % and kappa 83.4 %

Urea increased tensile index near about 50 %

AQ + Urea increased yield 9.4 % and kappa 8 %

Positive outcome from thesis

The future research should be extended to

1. Different alkali charges

2. Lower sulphidity

3. H- factors

4. Liquor ratios

5. Bleaching

6. New practical applications

7. Tests run in industrial scale

RECOMMENDATIONS

CHEMICAL ADDITIVES AND SURFACTANTS ON KRAFT PULPING OF E. CAMALDULENSIS

Documents

wood costs

effluent source

pulping additives

chemical additives

kraft process

kraft pulping of

digester additives

production costs