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

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

Introduction Now pulp and paper industries have two major problems 1.Environmental problem 2.Economic problem To reduce deforestation To protect environment To reduce cost To make the process more environment friendly

Introduction 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.

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

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

River pollution by effluent Source: 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

Objectives of the study 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.

Introduction 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

Objectives of the study Table: Chemical Composition of E. urophylla and E. camaldulensis. 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 ● 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).

Objectives of the study 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.

Scope of study ● 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

Literature review 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 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 Anthraquinone Urea Phosphonates  (1-Hydroxyethylene-1,1-di-phosphonic acid) Methanol

Optimum charge of AQ + MeOH Experimental Cook: To find out the most effective charge of additive Cook-3: To find out the most effective charge of Additive and surfactant Reference Reference Additive AQ Charge 0.04% AQ, charge 0.04% + MeOH, Charge 10% Additive AQ Charge 0.06% AQ, charge 0.06% + MeOH, Charge 10% Most effective charge Optimum charge of AQ + MeOH Additive AQ Charge 0.08% AQ, charge 0.08% + MeOH, Charge 10% Additive AQ Charge 0.10% AQ, charge 0.10% + MeOH, Charge 10% Additive AQ Charge 0.12% AQ, charge 0.12% + MeOH, Charge 10%

Results and Yield Yield of different cooks

Results and Yields Yield of different cooks

Results and Cooking Kappa no. Kappa of different cooking

Results and Cooking Kappa No. Kappa of different cooking

Results and Pulp strength properties Tensile index of different cooking

Results and Pulp strength properties Tensile index of different cooking

CONCLUSIONS 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.

Positive outcome from thesis 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 %

RECOMMENDATIONS 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

Thank You !