M. Mladenov, Y.

Pelovski Journal of the University of Chemical Technology and Metallurgy, 45, 1, 2010, 33-38

UTILIZATION OF WASTES FROM PULP AND PAPER INDUSTRY

M. Mladenov, Y. Pelovski

University of Chemical Technology and Metallurgy 8 Kl. Ohridski, 1756 Sofia, Bulgaria E-mail: mladenov@uctm.edu

Received 05 October 2009 Accepted 12 January2010

ABSTRACT Production of pulp and paper is a stationary source of different emissions wastewaters, waste gases and solid wastes. Nowadays there are technically and economically efficient processes for chemical regeneration of used solutions in Sulfate (Kraft) and Sulfite-cellulose fabrics, incineration of some bio-wastes and secondary use of lime in Kraftcellulose plants, thermal treatment of bark, other types of utilization of wood and paper wastes minimize the sludge generated for landfilling. In this paper different techniques and practices are discussed and analyzed in order to propose sophisticated ways for achieving environmentally friendly production in this industrial sector. A book review on the different types of wastes that are generated from pulp and paper industry is made. The different directions for utilization of the various types of wastes are analyzed as well. Keywords: pulp and paper industry, solid wastes, wastes products, utilization, secondary raw material.

INTRODUCTION Pulp and paper industry producers generate considerable quantities of waste water, waste gases and solid wastes [1]. The limits in the EU for different industries require continuous improvements, applying the so called Best Available Techniques (BAT) methods, equipment and technologies. From another side, on the way to keep sustainability other factors should be taken into account the companys profitability, social status and raw materials available. Taking into account the global shortage of raw materials available, it is obvious that the priority should be given to the development of new processes and techniques, in which the rate of useful components utilization is higher and in which the emissions generation is minimized [2-4]. In many cases the

technologies from type on the end of pipe do not cover the requirements for sustainability, because the cleaning processes applied just transfer the problems from one component of the environment to the other [5]. This is the reason that the selection of BAT, according to the IPPC directive requirements and life cycle analysis is an uneasy task and it could be made on the basis of analysis of the different techniques and technologies, where not only the investment and operation cost is important but also other factors are taken into account [6]. The aim of the present work is to review the progress made in the sector of pulp and paper industry, available BAT and on the basis of analysis to show and recommend some effective suitable for implementation options as a good practice [7-9].

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Journal of the University of Chemical Technology and Metallurgy, 45, 1, 2010

Table 1. Type of plant mass used for cellulose production.

Raw material Coniferous wood Broad-leaved wood (beech, birch, poplar) Straw (stems on wheat and rye) Flax Cotton Cellulose content 36 50 % 40 50 % : 30 % : 80 % : 90 %

EXPERIMENTAL Main characteristics of the resources and the processes in the pulp and paper production Paper, cellulose pulp, board, cardboard, corrugated cardboard, wrapping, cellophane, artificial silk filament, plastics and other usefully products, used in the every day life and economic activities of people, are mainly presenting that sector of the industry. The use of these products on a world-wide scale is increasing continuously. The main raw material for that production is different plant mass. Details are given in Table 1. Despite the fact, that in the stems of flax and cotton the larger percent of cellulose is held, more often used are wood and straw, because of their wider availability and the higher yield they provide. Industrial production of cellulose pulp in general lines, consist of processing of raw materials (wood, straw and other) with different chemical reagents, which entirely or partiality extract supplementary substances, without destructing of cellulose. Regretfully, at nowadays it is not found universal chemical reagent with which can be to fully extract supplementary substances, without to destruct cellulose [10]. According to the type of the used chemical reagents, contemporary methods for extraction on cellulose can be classified as: alkaline include the natrone (NaOH) and sulfate (NaOH + Na2S); acid include the sulfite (Ca(HSO3)2) and nitric-acid (HNO3); combined methods chlorine-alkaline, mono-sulfite, method with hydro-trope soils and other. More wide application have the sulfate (Kraft) and sulfite methods. The main technological phases in the production of cellulose pulp are: preparation of raw materials (removing of bark from trees, cutting in shivers with size 10 15 mm, separation and sorting of shivers); decoction on wood, for extraction of the cellulose;

filtration of the cellulose pulp (the solution from the decoction of cellulose is separated); washing of the cellulose pulp; whitening and improvement. Manufacturing of paper and board has additional operations, like for example, preparation of the cellulose pulp, refilling, coloration, drying. When the manufacturing of paper and board is from waste papers, for processing of the raw material additional operations are used. Product from the pulp and paper industry and quantities of generated wastes In 1992 world-wide the 164059000 tonnes cellulose pulp and 246507000 tonnes paper and board are produced. In Western Europe the productions are 31640000 t cellulose and 64530000 t paper and board, in Eastern Europe 9035000 t pulp and 10072000 t paper and board, and for North America 82123000 t cellulose and 91323000 t paper and board [11]. Though with different rate for the different parts of the World, production and consumption of cellulose, paper and board continuously grows. In our country the production of these products is concentrated in the cities of Svishtov, Belitsa, Pazardzhik, Nikopol, Lukovit and Stamboliiski [12, 13]. Production of cellulose, paper and board in Bulgaria for the 1997 2006 period is showed in Table 2. As seen from Table 2, the products from the pulp and paper industry in Bulgaria increase. The connection between the quantity of the products and the quantity of production wastes, suggests increase of the latter as well. The quantity of the generated wastes from the pulp and paper industry in Bulgaria, for the same period are given in Table 3. The type and quantities of generated wastes are different and depend on the used production method

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M. Mladenov, Y. Pelovski

Table 2. Production of cellulose, paper and board in Bulgaria during 1997 2006[14, 15].

Year

Chemical wood mass, natrone or sulfate cellulose (90 % dry matter), t 92 400 88 696.3 74 187.1 77 224.5 72 622.4 82 566.6 119 127.4 128 708.2 -

Paper and board, t

Wavy paper and board, and packages from paper and board, t 94 200 157 465 123 470 121 627 128 361 158 150 178 961 216 153 245 024 290 244

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
* **

178 400 167 091 125 705 136 031 162 278 201 955 248 035 323 371 365 400 313 394

Household, sanitaryhygienic and toilet products from paper and board, t 13 541 11 318 12 441 13 670 12 178 15 655 17 801 21 709 21 633

Total quantity of production from pulp and paper industry, t 365 000,0 426 793.3 334 680.1 352 323.5 376 931.4 454 849.6 561 778.4 686 033.2 632 133.0 625 271.0

Cellulose (base 88 % absolutely dry matter) [14]. The value is sum of paper and board individual [14]. *** Includes production of cardboard and corrugated cardboard [14]. **** The value is sum of the values in the preceding four columns.

Table 3. Generated solid wastes from the Bulgarian industry and contribution of the pulp and paper industry during 1997 2006 [16].

Year 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

Generated industrial wastes, thousand tonnes 230 669 218 437 175 603 92 335 86 397 79 632 84 313 250 957 276 902 238 771

Wastes from the pulp and paper industry, thousand tonnes 24 31 22 23 13 31 117 144 127 186

and capacity of the particular plants. Scheme of the generated emissions from pulp and paper industry are shown on Figs. 1 and 2. As seen from Fig. 1, the separate technological modules are generating wastes beginning with wood barks in the first stage. Biomass of barks and

sludges are potential secondary sources of raw material and on energy resource, which can be utilized. The generated condensate and ash have also potential as a secondary raw material resource. The generated wastes from the paper production are similar (Fig. 2).

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Journal of the University of Chemical Technology and Metallurgy, 45, 1, 2010

Woods (timber) Barks, woods wastes

Woodpreparation

Decoction

Collection of liquid wastes Reject Evaporation

Washing

Condensate

Sorting

Incineration

Wastes from incineration (ashes)

Bleaching (Whitening)

Regeneration of reagents

Dehydration/ Drying Waste water treatment Pulp Sludges

Fig. 1. A principal scheme of the generation of emissions from the pulp production. RESULTS AND DISCUSSION Minimization and utilization of wastes from the pulp and paper industry There are different options and best techniques which are used in some countries for decreasing the quantity of secondary products (wastes). Optimization of the technological regimes and processes, and improvements of equipment are mostly used, because they achieve a higher degree of utilization of the useful components in the raw materials. Other reason is the possibility for minimization of the production cost [17]. The minimization of wastes depends on the type of production methods (respectively type of generated wastes) and the availability of good techniques for their utilization. For example, the main quantity of the generated wastes from the sulfite method is the sulfite lye. The general directions for its utilizations are: the hexozes are used for production of ethyl alcohol; the pentozes for albumen yeasts; the residuary solution after concentration is used like as a connecting substance [10]. The used decoction solution can be chemical recovered and reused. In the sulfate method secondary products can be sulfate (tall) soap; tall oil; black lye; sulfate lignin; mud. They are obtained with different technology. The dense black lye flocculates dropped and on its surface is separates the tall soap, the sludge which consist of organics substances (about 60 % content of dry substance) can be incinerated. With the production of every ton cellulose about 2050 kg tall soap is generated. It can be reprocessed (decomposition with vitriol) with the aim to obtain tall oil for the rubber, detergent (saponaceous) and other industries. In the complex treatment of the tall oil by distillation adipose can be separated from the pitch acids. Extracted tall sterols and high adipose alcohols, also have practical application. For utilization of sulfate lignin there are many methods which have not found practical application till now and because of that the lignin is incinerated. Generated mud is a high-tonnage waste, mainly consisting of crystal CaCO3 and CaSO4. Because of that they are used for

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M. Mladenov, Y. Pelovski

Pulp Waste paper preparation Mechanical pulp production

Barks/ wood wastes

Pulper

Rejects

Sorting/breaki ng

Paper machine

Product

Waste paper, sieves, felts Waste water sludge

Flotation

Incineration

Waste water treatment Waste water (processed)

Ashes

Fig. 2. A principle scheme for generation of emissions from the paper production.

neutralization (lime-treating) on sour soils and for production of lime. The general solid wastes emitted from the paper and board production are: oddments from preparation of the paper mass; little quantity of wood mass and cellulose; pieces of end production (separated from carving, sorting and transporting); technological reject (unfit products for sail). The bigger part of the solid wastes can be returned in the production cycle and they are incinerated only when this is not avoidable. The ashes like waste from the pulp and paper plants also can be used as a raw material resource. They are mineral (inorganic) remainder after incinerating plant biomass and have a well balance of content of elements for direct application in agriculture neutralizer for sours soils or for improving the structure of soils. Other methods for production of building materials, ash-glass and ash-wadding, light filler for plastics, rubber, paints, varnishes, etc. are being investigated. Unfortunately, the better part of the ashes are situated (dumped) [7].

Thermal treatment of the secondary products (wastes) Thermal treatment like an option for utilization of secondary wastes generated, by pulp and paper plants gain greater importance. Incentives for that is the possibility for satisfaction of own thermal energy and electricity needs by using one inexpensive and accessible incinerating raw material, and the possibility to reduce unnecessary waste. Practically, about 47 % of the generated secondary products are incinerated inside in plants (mainly for obtaining thermal energy) and only about 5 % outside. From the viewpoint of the thermal utilization, barks and other wood wastes are less problematic, because they have a relatively high dry matter content (> 50 %), relatively high calorific value (about 1500 kJ/ kg) and the residual ash is comparatively low (< 5 % of the primary matter). There is practical experience for incinerating of those wastes and their mixtures with other wastes (for example, the settings and the lyes).

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Journal of the University of Chemical Technology and Metallurgy, 45, 1, 2010

The sorted reject (organic reject from preparation of primary fibrous materials and reject from the paper wastes recycling) can be incinerated if its has a high dry matter content and does not have high concentrations of dangerous substances. The lower density of waste paper, its high specific surface in fragmented state and its good inflammability, define it like a very suitable raw material for incineration, and most often incineration is done with the joint use of pulverized traditional fuel. The direct thermal treatment of settlings and lyes is also practically realized. For that purpose special ovens with fluidized bed are designed and used. CONCLUSIONS The analysis and survey of the wastes generated, from the pulp and paper industry and the opportunities for their minimization and utilization, show that there are possibilities for realization of ecological improvements of this industry both by improvement of the used technologies of different products, and by utilization of some of the generated wastes like secondary raw material and energy resources. The best ecological, technical and economical solutions for the utilization of these wastes are by using of their energetic potential and their transformation in raw materials for production of soil improving materials. Acknowledgements The authors would like to thank the Science and Research Programme (SRC) of the UCTM Sofia for the financial support (Contract 10 564/09.03.09). REFERENCES 1. R. Draganova, S. Nenkova, Chemistry and structure of vegetal tissues, UCTM, Sofia, 2002, (in Bulgarian). 2. N. I. Nemerow, A. Dasgupta, Industrial and hazardous waste treatment, VNR, New York, 1991. 3. L. Zashkova, K. Spirov, N. Penkova, V. Iliev, Utiliza-

tion of industrial wastes in the composition of fireproof concrete and mortans, J. Univ. Chem. Technol. Met. (Sofia), 43, 2, 2008, 277-279. 4. S. Ganev, H. Vasileva, S. Atanasov, Using of actively sediment from waste water on pulp and paper industry, Bulletin Pulp and Paper Bulgaria, 2, 1992, 98-102, (in Bulgarian). 5. Su-Yoi Lee, Seung-Kyu Rhee, From end-of-pipe technology towards pollution preventive approach: the evolution of corporate environmentalism in Korea, Journal of Cleaner Production, 13, 2005, 387-395. 6. J. Petts, G. Eduljee, Environmental impact assessment for waste treatment and disposal facilities, John Wiley and Sons, Chichester, 1994. 7. G. Babachev, Ashes and cinders valuables raw materials and stuff, Technika, Sofia, 1984, (in Bulgarian). 8. St. Nedeva, Trends in the production of pulp and paper in Balkan countries, Bulletin Pulp and Paper Bulgaria, 3, 2006, 5-6, (in Bulgarian). 9. A. Papazov, Modernization of Svilosa An Investment in the Future of National Pulp Industry, Bulletin Pulp and Paper Bulgaria, 2, 2007, 8-10, (in Bulgarian). 10. R. Draganova, Chemistry of wood, Technika, Sofia, 1976, (in Bulgarian). 11. A. E. Hackl, G. Zehetner, in: B. Karigl (ed), Waste combustion, 1996, Conference papers, Vol.18, By-Product Utilization from Stationary Installations, Vienna, Austria, September 1996, Federal Ministry for Environment, Youthand Family, Vienna, 1996, 52-73. 12. St. Nedeva, Production, import, export of paper, board and wood pulp in Bulgaria, Bulletin Pulp and Paper Bulgaria, 2, 2007, 26, (in Bulgarian). 13. St. Nedeva, Production, import, export of paper, board and wood pulp in Bulgaria, Bulletin Pulp and Paper Bulgaria, 2, 2008, 28 (in Bulgarian); 14. National statistical institute (NSI) - Sofia, Statistical year-book 1998, (in Bulgarian). 15. NSI, Statistical year-books 1999 2007, (in Bulgarian). 16. Executive environmental agency Sofia, Year-books Environment 1998 2007, (in Bulgarian). 17. St. Ivanov, Organic chemical technologies, Science and art, Sofia, 1972, (in Bulgarian).

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