saan 14™ REGIONAL SYMPOSIUM ON CHEMICAL ENGINE! ISBN 978-979-16978-0-4 KINETIC OF PULP BLEACHING BY HYDROGEN PEROXIDE A.MFuadi', W. B. Sediawan’, Rochmadi”, 8. Purwono? * Chemical Engineering Deparment. Muhanmadiyah University of Surakarta, [email protected] * Chemical Engineering Department, Gadjah Mada University ABSTRACT As the result of increasing environmental concern, new technologies for bleaching pulps have been developed. Chlorine containing bleaching agents have been replaced by more environmentally benign chemical, and the Importance of hydrogen peroxide in pulp bleaching has rapidly increased. This paper reports the results of experimental and kinetics studies of pulp bleaching. About 20 g of dry pulp was, treated by using sulfuric acid and ethylene diamine tetra acetate (EDTA) at chelating stage. The treatment was carried out in plastic bags placed in a pre-heated water bath, The bleeching was performed with addition of H:O; and NaOH at 70°C and 90°C. After the bleaching, the pulp was ewatered and washed carefully. The ftrate obtained from the intial dewatering was used to determine ‘the pH and residual H,O;, The pulp was anslyzed Its lignin content. Two kinetles models were proposed. Both models assume that the process consist of two consecutive reactions, which are decomposition of HO; producing HOO" and reaction of lignin with HOO. Further, the first model assumes that decomposition of H;0; producing H;0 and O; does not occur, while the second model does. The results of the two models were verified by the experimental data. Ie curas out that the fist model works well at the temperature up to 70°C, while the seeond model work well until 90°C. Key words: mathematical modeling, kinetics, bleaching, hydrogen peroxide L INTRODUCTION ‘The world’s paper consumption has increased by SO % during the last decade. Consequently, the consumption of bleaching agent for pulp bleaching has increased as well [1]. Pulp and paper has long been recognized as a significant source of polluion. Especially the use of chlorine based bleaching agent has had a ‘negative impact on the environment. When gaseous Ci; is used in bleaching. considerable amount of organ chlorine compounds are formed, Gaseous Cla has largely been replaced by chlorine dioxide (CIO,) in bleaching in recent year, to reduce the formation of lipophilic organ chlorine and volatile molecular chlorinated compounds. However, the use of ClO; in bleaching does not toully eliminete the formation of some harmful ‘material, so from an environmental point of view, it could be advantageous ifthe use of CIO; was decreased [7] Society awareness of the environment has urged the use of environmentally ftiendly compounds in bleaching sequences. Such a bleaching concept is usualy refered to as totally chlorine free (TCF) bleaching. The use of bleaching chemical must be considered in the context of the health and safety of workers and inhabitant ofthe ‘neighboring environment and in the context of responsible environmental management. Hydrogen peroxide is ‘one ofthe key chemicals in TCF bleaching [4]. The principle of pulp bleaching isto achieve a high brighness, with secondary objective, for particular end ‘uses, being high brightness stability, high pulp clesaliness and high cellulose content, These objectives must be achieved with out cellulose degradation, because it can ead to significant loss of strength in product paper sheet. ‘The strength of paper is due in pat tothe strength of individual cellulose chains and in part to hydrogen bound formed between adjacent cellulose molecule, within fber, and between fibers, which are responsible for the strength of paper sheet. Cellulose has a great capacity to form hydrogen bounds and, asa result, has a great affinity for water. Cellulose is essentially colorless and does not require bleaching. However, during the bleaching of pulp fibers, to decolorize other component, cellulose degradation can occur, This can lead to cellulose fragments being dissolved, Further, if cellulose degradation is sufficiently sufered, pulp sength will decrease [6 Lignin is material which gives a greet contribution in dackener pulp. Pulping process can not remove all lignin in wood, and the residual lignin i often dasker than the original lignin. Lignin conteat must be measured during chemical pulping and blesching. Because of its complex structure and relatively low concentration, Yogyakarta-Indonesia, 4-5 December 2007 Chemical Engineering Department, Gadjah Mada Universi eep@eapeacin: ri a; oan aoa 35| 14™ REGIONAL SYMPOSIUM ON CHEMICAL ENGINEERING 2007 ISBN 978-979-16978-0-4 lignin is difficult to measure directly and therefore relative lignin content is measured by standaedized reaction of potassium permanganate with pulp. There are several types of this test; one of them is termed kappa number. ‘There is linier relationship between kappa number and lignin content. Lignin content (in weight percent) is approximated by multiplying the kappa number by 0.15 (3. ‘The goals when using hydrogen peroxide in bleaching are to maximize delignification, brightness and selectivity toward lignin, and fo minimize the consumption of hydrogen peroxide. Hydrogen peroxide is very fable under acidic conditions, but under alkaline conditions, it has a propensity for decomposition. The decomposition of hydrogen peroxide is also accelerated by temperature. The active bleaching species in alkaline hydrogen peroxide systems is the perhydroxyl anion, HOO’, which is formed under alkaline conditions [8]. The dissociation of hydrogen peroxide (the formation of the perhydroxyl anion) is shown in equation (1), HOOH+ 16} —-HOO'+H,0 o ‘This anion is a song nucleophile and is primarily responsible forthe bleaching effect of alkaline hydrogen peroxide. There are two competing reactions in hydrogen peroxide bleaching: the first leads to delignification land a brightness increase while the second parallel reaction leads to the decomposition of hydrogen peroxide {nto water and oxygen. The decomposition of hydrogen peroxide into water and oxygen is extalyzed by ‘transition metal ions and is usually claimed to involve the formation of reactive intermediates (HO, and Ox). ‘The overall reaction can be writen as in equation (2). H:Os+ HOY —» 1,0 +0:+ HO" @ Kinetic management in using hydrogen peroxide as bleaching agent is very important. The decomposition should be directed to equation 1, For this purpose, the metal ions in a pulp which catalyze to decompose of hydrogen peroxide (equation 2) must be removed from pulp; it can be done by chelating stage [I Hydrogen peroxide blesching is usually performed at pH 10-11.5. Under these conditions transition metals ‘can hardly exist as free ions. Collodee [2] has studied the solubility of Fe", Cu! and Mn** in the pH range of ‘98 to 118. After aging at $0°C for 120 minutes, the solutions were subjected to ultrafiltration (cut off >1000 MW) and snalysis of the firates showed that no amounts of iron, copper or manganese above the detection, Fimit (10 ppb) could be found inthe solution, The rte of peroxide decomposition was shown to be considerably lower in the filtrates than in the original solution, which implies thatthe devompesition is surface-catalyzed by colloidal transition metal-oxides/nydroxides (2). IL. THEORETICAL DEVELOPMENT CCtiulose has great capacity to form hydrogen bounds, so it has a great affinity for water. Based on this characteristic, the concentration of system in the solution is assumed homogenous. Bleaching mechenism is Started by formation of HOO". This anion is believed to be the principal active species involved in the limination of chromophores ia lignin structure. This anion then reacts with lignin: HOO’ + lignin. —— lignin-0 +08 @ ‘This paper proposes 2 kinds of model in bleaching process by using hydrogen peroxide. The first model assumed that no side reaction producing HO and oxygen, and the second model considers that the side reaction producing HO and oxygen is occurred as an equation (4). 1,0; —* H,0+0; o A. Development ofthe frst model ‘Atte fist model, we assume that no side reaction (4). The concentration of HOs changes as equation (1), so the rate of [H;0] depletion is: dlH,0,] = : 0.1 -1[01,0,]on-]+4,[400"] © Yogyakarta-Indonesia, 4-5" December 2007 Chemical Engineering Department , Gadjah Mada Universityeee 14™ REGIONAL SYMPOSIUM ON CHEMICAL ENGINEERING 2007 ISBN 978-979-16978-0-4 Anion of HOO" produced trom equation (1) reacts with lignin, so the inerease HOO" is equal to [HOO] eee ims ema attoo"} ee ~Ht:2:)_ 400" Viernlo © The lgnin content in pulp wil decrease equation (3), andthe content of ign can beclclated by: Mie —_- [400-Wierino o The values of H:O>, HOO" and iignin att = 0 are {#,0,]=[H,0,], [x00"]=0 [tignin]= [lignin], uations (5), (6) and (7) are calculated by Runge-Kutta method while the valves of reaction parameters (ly, hs ‘ad 4s) are optimized using Hooke-Jeeves minimization method, Ia this case, the sum of squares of errors (SSE) between the calculated and experimental results of residual of H.O; and lignin content is being minimized, B. Development of the secend model ‘The second model assumes that side reaction is occured as a reaction (4). The rate of change of [H:Os] is alHt,0,] dt Anion of HOO” produced from equation (1) reacts with lignin, so the rte of increase of HOO’ is equal to [00 | produced from equation (I) minus [HOO'] reacting with lignin. -k,[#1,0, Jou }+é,[u007|-k,{H,0,] a A100" 14,0,Jon-}-&,.400"|-& 400 Vieie © The Sit coin ani tds of scving Go etn tnd of ming th vl of ta pee se ee IIL EXPERIMENTAL METHODOLOGY ‘The raw material used in this research was oxygen-delignfied eucalypmis kraft pulp (Eucalyptus globulus) ‘with kappa number of 10.8 and brightness of 56.6 % ISO. This experimental research was divided into. two sections, which ae chelating section und bleaching section, ‘A. Chelating stage About 20 g of dry pulp was treated by using sulfuric acid and ethylene diamine tetraacetate (EDTA), The {teatments were carried out at 10 % consistency in plastic bag placed in a pre-heated water bath for 1 hour at ‘70°C. After tha, the pulps were dewatered and washed carefully. B. Bleaching stage After the treatment in the chelating stag, pulps were subjected to hydrogen peroxide bleaching immediately, ‘The bleaching was performed for various times, at 10 % consistency in plastic bag placed in water bath pres heated to 70°C and 80°C, with addition of 2.5'% H:03. After the bleaching, the puips were dewatered and washed carefully, The filtrate obtained from the initial dewatering was used for determination of pH and zesidual of H,O;, The pulps were subjected to analyses of brightness, kappa number and intrinsic viscosity, ‘BL. Determination of residual HO, Distilled water (30 mal) is put into an Exienmeyer flak together with 10 ml H,SO, (20 %), 10 ml of sample, 10 mal of KI solution (50 g/L)and some drops of saturated ammonium molybdate solution(catalyt). If 30, is resent in the sample, a formation of iodine will take place. The amount of jodine in the solution was Yogyakarta-Indonesia, 4-5 December 2007 Chemical Engineering Department , Gadjah Madu Universitymeth 14™ REGIONAL SYMPOSIUM ON CHEMICAL ENGINEERING 2007 ISBN 978-979-16978-0-4 determined by tization with Na,$,0, solution. The concentration of f1,02 in the sample can then be calculated by the formulas H,0(g/L) 'B2, Determination of fignin content Pulp (between 0.5 g to 3 &, depending onthe predicted kappa number) was put into a glass beaker together ‘with 730 ml distilled weter. This mixture was mixed using a blender to disintegrate the pulp. Then 25 ml of MnO, solution (0.1 N) and 25 ml of H:SO, (2M) was added. The reaction was carried out at 25°C. After 10 tninutes, the reaction wes terminated by the addition 6 ml of 1 M KI solution. The iodine forined was then. titrated with 0.1 M of Nay$.0) solution. The kappa number can be calculsted by: (10) (x—y)*d kappa = 2=2) a ct) ante ‘The lignin content ean be then calculated by multiplying the kappa number by 0.15 (3} IV. RESULT and DISCUSSION ‘The accuracy of this model is examined by comparison between the residual of H,O> and lignin content of cxperimental data and calulation using the models proposed. The results aze presented in figure I and. a. The first model, NaOH = 1.75 % 08 ee 2s Fa iS | ia roe '. The second model, NaOH= 1.75% teat | oat ‘Higue J, Compari a 0% Figure 1 shows the residual of H,Os and lignin content at various time of bleaching, Tt can be clearly observed thatthe results of calculation of both models not only have similar trend line but also the same values ‘vith the experimental data. The average error of the fist model is 4.9%, while the second model i 5.3%. Based tn this calulation, it ean be concluded that both models work well upto 70°C. The two models were now tested at a higher temperature (90°C). The results ae presented at figure 2 Figure 2 shows thatthe second model still works wel at 90°C. Its proved by he similarities of trend tines between the experimental data and the calculation results using the second model. The average eror of the second model is 9.97% Meanwhile the first model looks poor at 90°C. The results imply that decomposition as in reaction (4 snot significant at 70°C, but significant at 90°C. Yogyakarta-Indonesia, 4-5" December 2007 Chemical Engineering Department , Gadjah Mada Universisae 14™ REGIONAL SYMPOSIUM ON CHEMICAL ENGINEERING 2007 ISBN 978-979-16978-0-4 a. The first model, N8OH = 1.75 % | oat 3a fos | Bos os ° ‘Figure 2, Comparison between the first model andthe second model at 90°C V. CONCLUSION 1. The first model, which assumes no decomposition of HO» producing HzO and O, works well up to 70°C. 2. The sevond model, which assumes decomposition of HO: producing H,0 and 0; does take place, works ‘well up to 90°C. VI. SYMBOL volume of sample (ml) volume of NapS:0; solution (rm) d= corection factor, 10%0™Me-9)/08-8) ‘volume of Na,$,0; solution used to irate sample (rl) sme (mins) mass.of fiber P= olumeofrolution Vil ACKNOWLEDGMENT ‘The authors thank the Indonesian Government for suportng ths research via Hibah Bersaing research grant of 2007-2008, and also PT. PIP for providing H:O>, VIL. REFERENCES [1] Bayer, J., Dilme, and Femandez-Zapico, JM. 1999, “Tendenciaous on in Industria Papelera en Los Inicious”, del Singlo XXIIngeneria Quimico 3, 177-181 Yogyakarta-Indonesia, 4-5" December 2007 Chemical Engineering Department , Gadjah Mada Universitybi 14™ REGIONAL SYMPOSIUM ON CHEMICAL ENGINEERING 2007 Q) G1 4 [5] (6) 0) ISBN 978-979-16978-0-4 Colodete, J4., Rothenberg, S., and Dence, C.W,, 1988, Factor Affecting Hydrogen Peroxide Stability in the Brightening of Mechanical and Chemimechanical Pulp Pact Tl: Hydrogen Peroxide in Presence Sodium Silicate, Journal Pulp and Paper Science, 15(1) J3-J10. Denve, C.W., and Reeve, D.W., 1996, “Pulp Bleaching Principle and Practice”, Tappi Peres, Atlanta, Page:349-415. Fengel, D., and Wegener, G., 1983, "Wood: Chemistry, Ultrastructure, Reaction’ ‘University Perss,Jogjakarta, Fuad, A.M., and Harald, B., 2006, “Benefits of Chelating Stage Prior to Peroxide Bleaching”, Gelagar, 17, 91-97, Khan, L, Bigot, Y.L., Delmas, M., and Avigron, G., 2005, “Delignification of Wheat Straw Using & Mixture of Carbanilic Acids and Peroxoacids”, Industrial Crops and Products, 21, 9-15. [Natatama, K., Motoe, Y., and Ohi, 2004, “Evaluation of Chloroform Formed in Process of Kraft Pulp ‘Bleaching Mill Using Chlorine Dioxide”, J. Wood Sei, $0, 242-247. dal, Gagjah Mada Yogyakarta-Indonesia, 4-5" December 2007 Chemical Engineering Department, Gadjah Mada University{ N-PEKIK KIMMIA LAS TEKNIK IPAS GADJAH MADA, hampton kepads | Ahmad M Fuadi | as peron sertanyasebagat | Pemakalah so ‘Sirposivm Polmer Nasional Vit 207 Yomyatarta, 4 Agustin 2007 De Sunt Hendon