혼합 하드우드 칩으로부터 녹액(Green Liqour)선-펄핑추출 공정에 관한 연구

엄병환; Byung-Hwan Um

Korean Chemical Engineering Research, Vol.51, No.5, 561-567, October, 2013

DOI10.9713/kcer.2013.51.5.561 Export Citation

혼합 하드우드 칩으로부터 녹액(Green Liqour)선-펄핑추출 공정에 관한 연구

A Comparative Study on Green Liquor Pre-Pulping Extraction of Mixed Hardwood Chips

엄병환^†

한경대학교 화학공학과, 화학기술연구소, 456-749 경기도 안성시 중앙로 327

Byung-Hwan Um^†

Department of Chemical Engineering and Research Center of Chemical Technology, Hankyong National University, 327 Chungang-no, Anseong-si, Gyeonggi 456-749, Korea

E-mail:

초록

본 연구에서는 바이오연료 생산을 위한 헤미셀룰로오스의 회수 목적으로 혼합 하드우드 칩을 크라프트(kraft) 펄핑 공정 전에 녹액(green liquor)으로 선-펄핑추출(pre-pulping extraction) 하였다. 본 실험에 사용된 녹액은 황화나트륨과 탄산나트륨이 주요 성분이며, 이 녹액에 목재 건조 질량당 0, 1, 3, 5%의 알칼리(Na2O)를 각각 충진하였다. 가혹 조건에 따른 선-펄핑추출액의 구성 성분을 알아보기 위해 추출은 반응시간은 1~2 h로 달리하면서 160 ℃ 조건에서 실험을 수행하였다. 선-펄핑추출공정은 헤미셀룰로오스 추출시간과 녹액 주입 정도의 가혹도(severity)에 따라서 하향류 공정(downstream process)에서 활용 가능한 아세트산(acetic acid)과 단당류 농도, 그리고 유기산과 퓨란(furan)과 같은 분해 생성물의 축적 정도가 변한다. 본 연구 결과에서는 알칼리 주입 양이 증가할수록 헤미셀룰로오스에 존재하는 아세테이트(acetate)의 곁사슬과 용해성 및 리그닌의 양은 증가하지만, 추출액에서 탄수화물과 당류는 상당히 감소하였다. 특히 고온수(hot water)로 추출(알칼리 주입 0%)하는 경우 29.80 g/L 이상의 가장 많은 양의 탄수화물이 추출되었으나, 펄프 수율은 가장 많이 감소하였다. 또한 3% 녹액의 추출은 펄프 수율은 증가하였으나 당은 7.08 g/L로 많은 양이 감소하였다. 이 논문에서 얻어진 데이터를 통해 크라프트 펄핑공정에 추출공정 통합을 위한 헤미셀룰로오스 추출 조건을 최적화할 수 있을 것이다.

Mixed hardwood chips were pre-pulping extracted with green liquor prior to kraft pulping in order to recover hemicelluloses for use as biofuels. This green liquor solution containing mainly sodium sulfide and sodium carbonate was applied at different alkali charges (expressed as Na2O) of 0, 1, 3, and 5% on dry wood weight. The extractions were performed at 160 ℃ for residence times ranging from about 1-2 h to determine the effect of extraction severity on composition of the pre-pulping extract. The severity of hemicellulose extraction time and green liquor charge controls the concentration of acetic acid and monosaccharide sugars available for downstream processing, the accumulation of degradation products such as organic acids and furans in the extract. As the alkali charge was increased, the amount of acetate side chains on the hemicelluloses and the dissolved lignin in the extract increased but the carbohydrate and sugars in the extract decreased appreciably. Hot water extraction (0% alkali addition) released the greatest amount of carbohydrates, up to 29.80 g/L measured as component sugars, but resulted in the greatest decrease in pulp yield. Meanwhile, pre-pulping extraction with 3% green liquor increased the pulp yield while greatly reducing the component sugars to 7.08 g/L. Fundamental data obtained in this study will allow selection of optimum hemicellulose extraction conditions for integrating the extraction operation into the Kraft pulping process.

Keywords:Acetic Acid;Green Liquor;Hemicellulose;Furan;Pre-pulping Extraction

[References]

Biermann C, Handbook of Pulping and Papermaking, 2nd ed., Academic Press, California, CA (1996)
Sjostrom E, Wood Chemistry: Fundamentals and Applications, 2nd ed., Academic Press, California, CA (1993)
Gabrielii I, Gatenholm P, Glasser WG, Jain RK, Kenne L, Carbohydr. Polym., 43, 367 (2000)
Um BH, van Walsum GP, Appl. Biochem. Biotechnol., 153(1-2), 127 (2009)
Ebringerova A, Hromadova Z, Kaucurakova M, Antal M, Carbohydr. Polym., 24, 301 (1994)
Jain RK, Sjostedt M, Glasser WG, Cellulose. Andover., 7(4), 319 (2000)
Niu W, Molefe MN, Frost JW, J. Am. Chem. Soc., 125(43), 12998 (2003)
Brasch DJ, Free KW, Tappi., 48(4), 245 (1965)
Amidon, T. and Liu, S, Biotechnology Advances., 27(5), 542 (2009)
Mendes CVT, Carvalho MGVS, Baptista CMSG, Rocha JMS, Soares BIG, Sousa GDA, Food and Bioproducts Processing., 87, 197 (2009)
Frederick WJ, Lien SJ, Courchene CE, DeMartini NA, Ragauskas AJ, Iisa K, Biomass Bioenerg., 32(12), 1293 (2008)
Um BH, van Walsum GP, Bioresour. Technol., 101(15), 5978 (2010)
Huang HJ, Ramaswamy S, Al-Dajani WW, Tschirner U, Bioresour. Technol., 101(2), 624 (2010)
Al-Dajani WW, Tschirner UW, TAPPI J., 7(6), 3 (2008)
Park YC, Kim JW, Kim JS, Korean Chem. Eng. Res., 49(3), 292 (2011)
Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Tmpleton D, Crocker D, “Determination of Structural Carbohydrates and Lignin in Biomass,” National Renewable Energy Laboratory NREL/TP-510-42618 ed. Golden, CO (2010)
Sixta, H., Handbook of Pulp Vol. 1., Wiley-VCH Verlag GmbH & Co., KGaA, Weinheim, Germany (2006)
Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Tmpleton D, “Determination of Sugars, Byproducts, and Degradation Products in Liquid Fraction Process Samples,” National Renewable Energy Laboratory NREL/TP-510-42623 ed. Golden, CO (2008)
Garrote G, Dominguez H, Parajo JC, Bioresour. Technol., 79(2), 155 (2001)
Um BH, Friedman B, vanWalsum GP, Holzforschung., 65, 51 (2011)
Um BH, Bae SH, Korean J. Chem. Eng., 28(5), 1172 (2011)
Gray MC, Converse AO, Wyman CE, Appl. Biochem. Biotechnol., 105-108, 179 (2003)
Dietrichs HH, Holzforschung., 18(1-2), 14 (1964)

[Referenced By]

[1] Biermann C, Handbook of Pulping and Papermaking, 2nd ed., Academic Press, California, CA (1996)

[2] Sjostrom E, Wood Chemistry: Fundamentals and Applications, 2nd ed., Academic Press, California, CA (1993)

[3] Gabrielii I, Gatenholm P, Glasser WG, Jain RK, Kenne L, Carbohydr. Polym., 43, 367 (2000)

[4] Um BH, van Walsum GP, Appl. Biochem. Biotechnol., 153(1-2), 127 (2009)

[5] Ebringerova A, Hromadova Z, Kaucurakova M, Antal M, Carbohydr. Polym., 24, 301 (1994)

[6] Jain RK, Sjostedt M, Glasser WG, Cellulose. Andover., 7(4), 319 (2000)

[7] Niu W, Molefe MN, Frost JW, J. Am. Chem. Soc., 125(43), 12998 (2003)

[8] Brasch DJ, Free KW, Tappi., 48(4), 245 (1965)

[9] Amidon, T. and Liu, S, Biotechnology Advances., 27(5), 542 (2009)

[10] Mendes CVT, Carvalho MGVS, Baptista CMSG, Rocha JMS, Soares BIG, Sousa GDA, Food and Bioproducts Processing., 87, 197 (2009)

[11] Frederick WJ, Lien SJ, Courchene CE, DeMartini NA, Ragauskas AJ, Iisa K, Biomass Bioenerg., 32(12), 1293 (2008)

[12] Um BH, van Walsum GP, Bioresour. Technol., 101(15), 5978 (2010)

[13] Huang HJ, Ramaswamy S, Al-Dajani WW, Tschirner U, Bioresour. Technol., 101(2), 624 (2010)

[14] Al-Dajani WW, Tschirner UW, TAPPI J., 7(6), 3 (2008)

[15] Park YC, Kim JW, Kim JS, Korean Chem. Eng. Res., 49(3), 292 (2011)

[16] Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Tmpleton D, Crocker D, “Determination of Structural Carbohydrates and Lignin in Biomass,” National Renewable Energy Laboratory NREL/TP-510-42618 ed. Golden, CO (2010)

[17] Sixta, H., Handbook of Pulp Vol. 1., Wiley-VCH Verlag GmbH & Co., KGaA, Weinheim, Germany (2006)

[18] Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Tmpleton D, “Determination of Sugars, Byproducts, and Degradation Products in Liquid Fraction Process Samples,” National Renewable Energy Laboratory NREL/TP-510-42623 ed. Golden, CO (2008)

[19] Garrote G, Dominguez H, Parajo JC, Bioresour. Technol., 79(2), 155 (2001)

[20] Um BH, Friedman B, vanWalsum GP, Holzforschung., 65, 51 (2011)

[21] Um BH, Bae SH, Korean J. Chem. Eng., 28(5), 1172 (2011)

[22] Gray MC, Converse AO, Wyman CE, Appl. Biochem. Biotechnol., 105-108, 179 (2003)

[23] Dietrichs HH, Holzforschung., 18(1-2), 14 (1964)