Effect of chemical charges in cooking and their effectiveness on pulp bleaching
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1 Journal of Scientific & Industrial Research Vol. 63, June 2004, pp Effect of chemical charges in cooking and their effectiveness on pulp bleaching M N Islam Forestry and Wood Technology Discipline, Khulna University, Khulna 9208, Bangladesh Received: 14 October 2003; accepted: 03 February 2004 The screened Eucalyptus camendulensis chips were cooked in the laboratory at various alkalinities (14, 16, 18 and 20 per cent) and sulphidity (20, 30 and 40 per cent). Due to the variation in chemical charge, the pulp yield was found to be different. The average pulp yield was 50.6 per cent after washing and the final yield was obtained 40 per cent, which followed the normal kraft yield trend. Bleaching was done with the pulp of maximum final yield obtained. By avoiding oxygen delignification stage, pulp was bleached directly by using D 0 ED 1 sequence of elementary chlorine free bleaching. The average brightness and viscosity after final stage were 79.9 per cent ISO and 614 ml/g, respectively. Improvement in brightness was remarkable, but the viscosity decreased. Keywords: Alkalinity, Bleaching, Brightness, Chemical charge, Sulphidity, Viscosity IPC Code: Int.Cl 7 : D 062 1/02 Introduction In chemical pulping, fibres are separated from the wood matrix as the lignin is dissolved and removed by cooking chemicals at a high temperature and a part of the hemi-celluloses may also dissolve 1. At present, kraft pulping process is the dominating chemical pulping process worldwide 2 because of better pulp quality, applicable to most of the species, efficient chemical recovery and less environmental hazardous compared to other system 2, 3. This process depends largely on chemical components, chemical concentration, chemical charge, chip cleanliness, dimensions, time of cooking, temperature, and pressure 1, and proper combination of chemicals and energy is vital for uniform cooking 4. Alkalinity is the most important driving force for kraft pulping reaction and large amount of chemical is needed to carry the cooking reaction to completion 5. Sulphidity enhances the rate of delignification without affecting the carbohydrates 4. Sodium hydroxide (NaOH) and sodium sulphide (Na 2 S) are the active cooking chemicals in kraft pulping. The initial ph lies between 13 to 14 due to sodium hydroxide, which decreases with time as the organic acids are liberated from wood during cooking. Bleaching is a purification process in which coloured substances are modified so that they both either loose their light absorption ability or they dissolve 3. Also the aim is to further reduce solid contaminants that have not been separated out in earlier operations and to improve the hygienic properties of the product. Chemical pulp, especially pulp made by alkaline processes, is darker in colour than the original wood, despite a high degree of lignin separation. The light absorption properties of residual lignin increase during the cooking. The study was conducted to find out the effect of pulp yield and quality by different EA profile during cooking. It was also done to find out the effect of optimum EA profile in terms of pulp yield on bleaching of that pulp. Materials and Methods Chip Screening Air dried Eucalyptus camaldulensis chips were used for this study. The chips were screened as per SCAN-CM Address for correspondence: Md. Nazrul Islam, Mail Box. 505, Asian Institute of Technology, P O Box 4, Klong Luang, Pathumthani Thailand, Phone: nazrul17@yahoo.com, st037108@ait.ac.th 40: 94. Screened chips were stored in plastic bag in cold room. Dry matter content of chips was determined, according to SCAN-CM 39: 94. The amount of chips in each fraction was calculated and reported as percentage of the whole batch.
2 ISLAM: EFFECT OF CHEMICAL CHARGES IN COOKING & THEIR EFFECTIVENESS ON PULP BLEACHING 523 Kraft Cooking Kraft cooking was carried out in a digester consisting of six autoclaves. Each autoclave contained 400g of OD chips. White liquor was prepared from fresh chemicals after necessary titration, according to SCAN-N 2: 88. The detailed cooking conditions are given in Table 1. Table 1 Cooking conditions for the experiment Amount of chips (OD basis) in g 400 g Alkali charge (AA) as percent of 14, 16, 18 and 20 per cent OD chips Sulphidity, percent 20, 30 and 40 per cent Liquor to wood ratio 4 Cooking temperature, 0 C 160 C Time to C 1 C/min Cooking time at C, min 80 min Washing After cooking the black liquor sample was collected to measure residual alkali. The pulp was poured into filter bag for washing. Black liquor was taken out by squeezing the pulp and 8 L of fresh water was added to the pulp and washed. This washing process continued until the colour of the water remained unchanged. The suspension was dewatered and excess water removed from the pulp. After washing the pulp was centrifuged until water came out from it and then homogenized. Dry matter content was determined, according to SCAN-C 3: 78 and the total yield of pulp was determined. Screening The pulp was disintegrated for 10 min before screening and was screened on flat screen using 0.30mm slot, in order to separate the undesired materials from the pulp. Pulp was centrifuged and homogenized. The rejects was collected to determine the percentage of undesired matter. Dry matter content and yield of screened pulp were measured. Kappa Number Determination The kappa number was measured with the screening yield. It was measured, as per SCAN-C 1: 77. Bleaching For bleaching the maximum amount of unbleached pulp was bleached with a short sequence, i.e., D 0 ED 1. Bleaching was carried out in plastic bags in water bath. Before bleaching, pulp and distilled water were preheated in microwave oven. The ph was measured at the beginning and after completion in each stage of bleaching. The residual alkali charge was measured after completion of D stage. After each stage, washing was done several times by using distilled water in a container with wire screen fitted to suction pipe. The conditions for bleaching are given in Table 2. Viscosity and Brightness Measurement The viscosity and brightness of the bleached and unbleached pulp were measured, according to SCAN CM 15: 88 and SCAN CM 11: 95 respectively. In the case of bleached pulp, those properties were measured after both E-stage and D 1 -Stage. Results and Discussions Chip Screening Chip thickness is the most important factor for chemical impregnation 3. No ideal chip size was established, but advantage was demonstrated by the removal of undersize and oversize fractions 6 and irrespective of the type of wood and chipping conditions, chips of 2-6mm thick showed the best results in the cooking 7. The accepted amount of chip was per cent in 7-mm hole screen plate and it is the optimum chip size 8. There were no oversized chips but it had over thick, pin and fines. The Dry Matter Content of this chip obtained per cent. Those chips were prepared cautiously to avoid unwanted chip sizes. The results of chip screening are given in Table 3. Kraft Cooking and Yield Lower sulphidity and alkalinity increased the washing yield which may be due to partial lignin removal in cooking than other groups and similar result have been reported by Bhandari and Bhatnagar 9. Though cooking yield increased but screening yield decreased due to the presence of higher amount of shives in the cooking
3 524 J SCI IND RES VOL. 63 JUNE 2004 Table 2 Bleaching condition for different stages Conditions Name of the stage D 0 stage E stage D 1 stage Amount of pulp 60 g OD pulp 60 g OD pulp (Assume that no loss after D 0 -stage) 40 g OD pulp (2/3 of the E-stage yield) Kappa number 19.8 Kappa factor 0.20 Percent of DMC per cent The ClO 2 -charge 0.20 kappa number per cent 2 per cent on pulp on pulp as active chlorine NaOH charge - 2 per cent on pulp 0.4 per cent on pulp Temperature 60 0 C 60 0 C 70 0 C Time 40 min 60 min 180 min Consistency 8 per cent 8 per cent 10 per cent Table 3 Chips in different fractions after screening Chip categories Weight (g) Chip (per cent) Oversized (Mesh size 45 mm) 0 0 Over thick (mesh size 08 mm) Accepted chip (Mesh size 7 mm) Pin chip (Mesh size 3 mm) Fines (Last tray) Total yield. From these results, it is evident that sulphidity and alkalinity bring better result. Mamers, et al., 11 found that per cent active alkali produced screened pulp yields between per cent with a kappa number of 20 but Correia 11 suggested that per cent alkali charge is optimum for hemp pulp yield. From Figure 1, it is evident that lower the sulphidity and alkalinity, higher the yield. It is evident that screening yield increased with sulphidity (Figure 2). The effects of sulphide have increased by 20 per cent sulphidity and the normal range been, per cent 4. It also increased with alkalinity but decreased after certain level of alkalinity (Figure 2). The reverse phenomenon has been found in case of undesired matter but it is gentle (Figure 3). Kappa Number Fig. 1 Effect of Sulphidity and alkalinity on cooked yield Fig. 2 Effect of Sulphidity and alkalinity on screening yield
4 ISLAM: EFFECT OF CHEMICAL CHARGES IN COOKING & THEIR EFFECTIVENESS ON PULP BLEACHING 525 There is a negative relationship between kappa number and alkalinity and sulphidity, i.e., sulphidity or alkalinity or both decrease with the increase of kappa number and the vice versa (Figure 4), and Bhandari and Bhatnagar 9 obtained the same results. Pressure, pulp consistency and alkali charge variations, all influenced kappa number reduction and brightness significantly 12. Bleaching After completion of the three stages bleaching the brightness was found to be quite high. The chlorine dioxide charge was high as there was no oxygen delignification which might be the cause of significant increase of brightness. The variation was due to different chemical charges and hot bathing time. Brightness had increased with chemical charge Figure 5 and 6 and similar results were reported by Axelsson, et al. 13 and Daniel et al. 14. For hot bathing, brightness had increased with time but decreased after 40 min (Figure 5 and 6). But the strong use of chemical in bleaching chemical pulps decreased the length of cellulose molecules, resulting in scale from 0 per cent (absolutely black) to 100 percent (relative to a MgO standard, which possesses brightness of about 96 per cent) by reflectance of blue light from the paper 15. Thus, D 0 ED 1 bleaching sequence has proved quite useful for the supplied kraft pulp. The average viscosity after D 0 E stage and E 1 stage was 706 and 614 ml/g, respectively. The viscosity had increased slightly with the increase in chemical charge but decreased sharply after a certain level for D 0 E stage but started to fall initially and increased to a certain level after E 1 stage (Figure 7 and 8). Though the variation is high but it follows the trend of viscosity, i.e., viscosity decreases with the increases of bleaching stage, as stated by Doyle, et al. 16. The viscosity of the unbleached supplied pulp was also Fig. 3 Effect of Sulphidity and alkalinity on rejects measured. It was found that brightness had increased largely (Figure 9) after bleaching and viscosity had decreased (Figure 10). Thus, it has tracked the customary targets of bleaching. Conclusion Fig. 4 Effect of Sulphidity and alkalinity on Kappa number Fig. 5 Effect of ClO 2 charge and time brightness
5 526 J SCI IND RES VOL. 63 JUNE 2004 Different chemical charges were used for cooking and the average yield was about 40 per cent and had the same yield like, chemical pulping. Bleaching process makes pulp brighter and the used bleaching sequence of this study was D 0 ED 1, which has increased brightness of pulp from 24.3 to 79.9 per cent ISO. However the viscosity of bleached pulp decreased from 795 ml/g to 614 ml/g. Brightness remarkably improved without losing viscosity Fig. 6 Effect of ClO 2 charge and time on brightness after E 1 stage Fig. 10 Decrease of viscosity with bleaching significantly. References 1 Biermann C J, Hand book of pulping and paper making, 2 nd ed (Academic Press Inc., California, USA) 1996, Grace T M & Malcolm E W, Pulp and paper manufacture, Vol.5, Alkaline pulping (Canadian Cataloguing in Publication Data, Canada) 1989, 5. 3 Gullichsen J & Fogelholm C J, Chemical pulping: paper making science and technology, Book 6A (Helsinky, Finland) 2000, Smook G A, Hand book for pulp and paper technologies (Angus Wilde Publications, Vancouver) 1997, 5. 5 Christensen P K, Wood and pulping chemistry (Norwegian Institute of Technology, NTNU, Torndheim, Norway) 1991, Wood J R, Chip quality effects in mechanical pulping a selected review, Pulp Conf, Nashville, TN, USA (27-31 October 1996) Book 1, Wehr T R & Barrichelo L E G, Kraft cooking with Eucalyptus grandis wood with different basic densities and chipping dimensions, Paper presented at Twenty Fifth Annu Pulp Paper Meet, Sao Paulo, Brazil (23-27 November 1992) Sacia W K, Chip screening and cleaning, chip preparation and quality short course, Atlanta, GA, USA, 1995, Bhandari K S & Bhatnagar A, Indian Foretr, 127(3) (2001) Mamers H, Balodis V, Garland C P, Langfors N G, Menz D N J & Chin C W J, An assessment of the kraft pulping properties of residual mature eucalypt roundwood from East Gippsland, Appita, 44(4) (1991) Correia F M C, Fibre characteristics and chemical pulping of Canadian industrial hemp (Cannabis sativa L.) (UMI Dissertation Services, University of Toronto) 1999, Roost C, Larsson P & Gellerstedt G, Nord Pulp Pap Res J, Fig. 7 Effect of ClO 2 charge and time of viscosity Fig. 8 Effect of ClO 2 charge and time on viscosity Fig. 9 Increase of brightness with bleaching
6 ISLAM: EFFECT OF CHEMICAL CHARGES IN COOKING & THEIR EFFECTIVENESS ON PULP BLEACHING (3), 2000, Axelsson P, Ek M & Teder A, Nord Pulp Pap Res J, 17(3), 2002, Daniel A I D, Evtuguin D V, Silvestre A J D & Pascoal Neto C, Influence of active alkali on the chemical composition and bleachability of Eucalyptus globulus kraft pulps, Sixth Workshop Lignocellulos Pulp, Bordeaux, France, (3-6 September 2000) Casey J P, Pulp and paper chemistry and chemical technolog, 3 rd ed (A Wiley-Interscience Publication, John Wiley and Sons, New York) 1980, Doyle C, Dever M & Byrd M V, Pulp and paper properties of kudzu vines pulped with the kraft-aq process, TAPPI Pulp Conf, Orlando, FL, USA, (31 October-4 Novemebr 1999) 359. Address for correspondence: Md. Nazrul Islam, Mail Box. 505, Asian Institute of Technology, P O Box 4, Klong Luang, Pathumthani Thailand, Phone: nazrul17@yahoo.com, st037108@ait.ac.th
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