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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
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Introduction Literature review Experimental Results and discussions Conclusion Positive outcome of the thesis Recommendations
CONTENTS
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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
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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
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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
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Environmental regulations in different countries have been set a limit of the amount of effluent (its components) discharges.
Introduction
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Pulp mill effluentSource: http://www.ecofootage.com/06-08.html
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River pollution by effluentSource: http://www.ecofootage.com/06-08.html
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River pollution by effluentSource: http://www.ecofootage.com/06-08.html
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Pulp mills release toxins such as dioxin and furan and other organochlorines in their effluent Source: http://ian.umces.edu/imagelibrary/displayimage-1083.html
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Picture of Boreal forest
Source: Save Our Boreal Forests, the Mystery and the Heritage, Wilderness Committee Educational Report, Vol.11 - No.07, Fall 1992
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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
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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
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Objectives of the study
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
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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.
Objectives of the study
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● 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
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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
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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
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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).
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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.
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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.
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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.
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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.
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Experimental
Chemicals as additives
AnthraquinoneUrea Phosphonates (1-Hydroxyethylene-1,1-di-phosphonic acid) Methanol
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Experimental
Cook: To find out the most effective charge of additive
Reference
Additive AQCharge 0.04%
Additive AQCharge 0.06%
Additive AQCharge 0.08%
Additive AQCharge 0.10%
Most effective charge
Reference
AQ, charge 0.04% +MeOH, Charge 10%
AQ, charge 0.10% +MeOH, Charge 10%
AQ, charge 0.08% +MeOH, Charge 10%
AQ, charge 0.06% +MeOH, Charge 10%
Optimum charge of AQ + MeOH
Cook-3: To find out the most effective charge of Additive and surfactant
Additive AQCharge 0.12%
AQ, charge 0.12% +MeOH, Charge 10%
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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
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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 %
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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 %
HEDP + MeOH - Pulping
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 %
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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 %
Urea + MeOH - Pulping
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 %
Different Alkali + Urea - Pulping
0.02.04.06.08.010.012.014.016.018.0
Ref. 22 + 6 23 + 6 24 + 6 25 + 6 26 + 6Additive %
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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 %
HEDP + MeOH - Pulping
25
27
29
31
33
35
37
39
Ref. 0.1 + 10 0.15 + 10 0.2 + 10 0.25 + 10 0.3 + 10Additive %
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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 %
Urea + MeOH - Pulping
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 %
Different Alkali + Urea - Pulping
0.005.0010.0015.0020.0025.0030.0035.0040.0045.00
Ref. 22 + 6 23 + 6 24 + 6 25 + 6 26 + 6Additive %
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Major results are found
High pulp yield in cooking Both high and low cooking kappa number Higher strength pulp than reference pulp
CONCLUSIONS
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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
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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
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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
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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
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