In-Digester Demethylation Kinetics for VOC/TRS Formation During the Kraft Pulping of Loblolly Pine

Sung-Hoon Yoon; Xin-Sheng Chai; Juyong Zhu; Byoung-Hyun Kim; Byoung-Kyu Song

Journal of Industrial and Engineering Chemistry, Vol.9, No.2, 125-133, March, 2003

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In-Digester Demethylation Kinetics for VOC/TRS Formation During the Kraft Pulping of Loblolly Pine

Sung-Hoon Yoon^†, Xin-Sheng Chai¹, Juyong Zhu¹, Byoung-Hyun Kim², and Byoung-Kyu Song

Research Institute of Technology, Korea Minting and Security Printing Corporation, Daejeon 305-713, Korea
¹Institute of Paper Science and Technology, 500 10th Street, N.W, Atlanta, GA, USA
²Department of Graphic Arts Technology, Joongbu University, Chungnam 312-940, Korea

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The objective of this study was to examine the reaction kinetics of demethylation and VOC/TRS formation during the kraft pulping process. The methyl mercaptan and dimethyl sulfide were taken into account as the major compounds for TRS, and methanol for the major VOC. On the basis of H-factor process variable, the kinetic analysis was conducted using the mechanistic assumptions of two parallel competing reaction and bimolecular-type second order reaction. Demethylation appeared to be proportional to the degree of delignification. The rate constants of the demethylation showed as high a value in the order of ten as the delignification rate constants. Sulfidity has a significant impact on both demethylation and delignification. Higher sulfidity-dependency was observed in demethylation rates. The VOC formation rate was highly proportional to the effective alkali charge in the kraft process, whereas TRS formation to sulfidity. VOC formation rate appeared to be about seven times higher than TRS formation at a lower level of sulfidity, but the difference between them increasingly decreased with increasing sulfidity. These results suggest that higher effective alkali charge at a given level of sulfidity should be instrumental to minimize the TRS formation during the kraft pulping.

Keywords:kraft pulping;demethylation;VOC;TRS;methyl mercaptan;sulfidity

[References]

Andersson B, Lovblod R, Grennbelt P, Diffuse Emissions of Odorous Sulfur Compounds from Kraft Pulp Mills, 1VLB145, Swedish Water and Air Pollution Research Laboratory, Gotenborg (1973)
Sableski JJ, TAPPI J., 50(8), 35A (1967)
Hendrickson ER, Robeson JE, Koogler JB, Control of Atmospheric Emissions in the Wood Pulping Industry, Vols. 1, 2, and 3, Final Report, Contract No. CPA22-69-18 HEW, Natonal Air Pollution Control Administration, March 15 (1970)
Allan MS, Industrial Environmental Control: Pulp and Paper Industry, 2nd Ed., Tappi Press, Atlanta, Georgia, 559 (1993)
Zhu JY, Chai XS, Dhasmana B, J. Pulp Paper Sci., 25(7), 256 (1999)
Dipple A, Cancer Res., 43(5), 2422 (1983)
Ruus AL, Svensk Papperstid., 19(10), 751 (1964)
Adams DF, TAPPI J., 48(5), 83A (1965)
DeHaas GG, Hansen GA, TAPPI J., 38(12), 732 (1955)
Yoon SH, Chai XS, Zhu JY, LiJ, Malcolm EW, Advances in Environmental Research, Elsevier, 5, 91 (2001)
Chai XS, Dhasmana B, Zhu JY, J. Pulp Paper Sci., 24(2), 50 (1998)
Chai XS, Liu PH, Zhu JY, J. Pulp Paper Sci., 26(5), 167 (2000)
Chai XS, yoon SH, Zhu JY, Li J, J. Pulp Paper Sci., 27(12), 407 (2001)
Ryan TA, Joiner BL, Ryan BF, Minitab Student Handbook, Duxbury Press, North Scituate, MA (1986)
Neter J, Wassermann W, Kutner MH, Applied Linear Statistical Models, Irwin Inc., Homewood, IL, Boston (1990)
Sjostrom E, Wood Chemistry: Fundamentals and Applications, Academic Press, New York, 127 (1981)
McKean WT, Ph.D. Dissertation University of Washington (1968)
Enkvist T, Turunen J, Ashorn T, TAPPI J., 45(2), 128 (1962)
Goheen DW, Forest Products J., 10, 471 (1963)
McKean WT, Hrutfiord BF, Sarkanen KV, Price L, Douglass IB, TAPPI J., 50(8), 400 (1967)
Zhu JY, Yoon SH, Liu PH, Chai XS, TAPPI J., 83(7), 65 (2000)
Shih TTC, Hrutfiord BF, Sarkanen KV, Johanson LN, TAPPI J., 50(12), 634 (1967)
Sjostrom E, Wood Chemistry Fundamentals and Applications, 2nd ed., Academic Press, New York, 145 (1993)
Sarkanen KV, Chirkin G, Hrutfiord BG, TAPPI J., 46(6), 375 (1963)
Zhu JY, Liu PH, Yoon SH, Chai SX, Thomas JT, TAPPI Engineering/Process and Product Quality Conference & Trade Fair, Vol. 1, Anaheim, California, Anaheim Hilton, 111 (1999)
Seo SG, Moon JS, J. Ind. Eng. Chem., 8(1), 17 (2002)

[Referenced By]

[1] Andersson B, Lovblod R, Grennbelt P, Diffuse Emissions of Odorous Sulfur Compounds from Kraft Pulp Mills, 1VLB145, Swedish Water and Air Pollution Research Laboratory, Gotenborg (1973)

[2] Sableski JJ, TAPPI J., 50(8), 35A (1967)

[3] Hendrickson ER, Robeson JE, Koogler JB, Control of Atmospheric Emissions in the Wood Pulping Industry, Vols. 1, 2, and 3, Final Report, Contract No. CPA22-69-18 HEW, Natonal Air Pollution Control Administration, March 15 (1970)

[4] Allan MS, Industrial Environmental Control: Pulp and Paper Industry, 2nd Ed., Tappi Press, Atlanta, Georgia, 559 (1993)

[5] Zhu JY, Chai XS, Dhasmana B, J. Pulp Paper Sci., 25(7), 256 (1999)

[6] Dipple A, Cancer Res., 43(5), 2422 (1983)

[7] Ruus AL, Svensk Papperstid., 19(10), 751 (1964)

[8] Adams DF, TAPPI J., 48(5), 83A (1965)

[9] DeHaas GG, Hansen GA, TAPPI J., 38(12), 732 (1955)

[10] Yoon SH, Chai XS, Zhu JY, LiJ, Malcolm EW, Advances in Environmental Research, Elsevier, 5, 91 (2001)

[11] Chai XS, Dhasmana B, Zhu JY, J. Pulp Paper Sci., 24(2), 50 (1998)

[12] Chai XS, Liu PH, Zhu JY, J. Pulp Paper Sci., 26(5), 167 (2000)

[13] Chai XS, yoon SH, Zhu JY, Li J, J. Pulp Paper Sci., 27(12), 407 (2001)

[14] Ryan TA, Joiner BL, Ryan BF, Minitab Student Handbook, Duxbury Press, North Scituate, MA (1986)

[15] Neter J, Wassermann W, Kutner MH, Applied Linear Statistical Models, Irwin Inc., Homewood, IL, Boston (1990)

[16] Sjostrom E, Wood Chemistry: Fundamentals and Applications, Academic Press, New York, 127 (1981)

[17] McKean WT, Ph.D. Dissertation University of Washington (1968)

[18] Enkvist T, Turunen J, Ashorn T, TAPPI J., 45(2), 128 (1962)

[19] Goheen DW, Forest Products J., 10, 471 (1963)

[20] McKean WT, Hrutfiord BF, Sarkanen KV, Price L, Douglass IB, TAPPI J., 50(8), 400 (1967)

[21] Zhu JY, Yoon SH, Liu PH, Chai XS, TAPPI J., 83(7), 65 (2000)

[22] Shih TTC, Hrutfiord BF, Sarkanen KV, Johanson LN, TAPPI J., 50(12), 634 (1967)

[23] Sjostrom E, Wood Chemistry Fundamentals and Applications, 2nd ed., Academic Press, New York, 145 (1993)

[24] Sarkanen KV, Chirkin G, Hrutfiord BG, TAPPI J., 46(6), 375 (1963)

[25] Zhu JY, Liu PH, Yoon SH, Chai SX, Thomas JT, TAPPI Engineering/Process and Product Quality Conference & Trade Fair, Vol. 1, Anaheim, California, Anaheim Hilton, 111 (1999)

[26] Seo SG, Moon JS, J. Ind. Eng. Chem., 8(1), 17 (2002)