Abstract
Paper is produced mainly from wood fibrous pulps, which has been increasingly replaced by pulps from fast growing plants due to limited wood resources. In this work, properties of cellulosic pulps produced by the sulfate method from four fast growing grasses, poplar cultivar ‘Hybrid 275’, and European larch, as well as pine and birch wood chips, were compared. In addition, the cellulosic pulp yield, dimensions of fibers contained in the pulps and mechanical and optical characteristics of paper sheets produced from the pulps were compared. The pulp yield of the poplar cultivar ‘Hybrid 275’ (51.6%) was almost 5% higher than birch pulp (47.0%). Moreover, all of the investigated tensile properties of paper made from ‘Hybrid 275’ pulp were higher than for paper produced from birch pulp. Fast growing grasses, despite lower pulp yield (34.0 to 47.1%), showed comparable tensile properties to birch. Therefore, these pulps are promising raw materials for papermaking.
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Yield of Pulp, Dimensional Properties of Fibers, and Properties of Paper Produced from Fast Growing Trees and Grasses
Kamila Przybysz,a Edyta Małachowska,b Danuta Martyniak,c Piotr Boruszewski,d,* Jolanta Iłowska,eHalina Kalinowska,f Piotr Przybysz d,*
Paper is produced mainly from wood fibrous pulps, which has been increasingly replaced by pulps from fast growing plants due to limited wood resources. In this work, properties of cellulosic pulps produced by the sulfate method from four fast growing grasses, poplar cultivar ‘Hybrid 275’, and European larch, as well as pine and birch wood chips, were compared. In addition, the cellulosic pulp yield, dimensions of fibers contained in the pulps and mechanical and optical characteristics of paper sheets produced from the pulps were compared. The pulp yield of the poplar cultivar ‘Hybrid 275’ (51.6%) was almost 5% higher than birch pulp (47.0%). Moreover, all of the investigated tensile properties of paper made from ‘Hybrid 275’ pulp were higher than for paper produced from birch pulp. Fast growing grasses, despite lower pulp yield (34.0 to 47.1%), showed comparable tensile properties to birch. Therefore, these pulps are promising raw materials for papermaking.
Keywords: Format; Poplar cultivar ‘Hybrid275’; European larch; Fast growing grasses; Papermaking
Contact information: a: Natural Fibers Advanced Technologies, 42A Blekitna str., 93-322, Lodz, Poland; b: Lodz University of Technology, Faculty of Process and Environmental Engineering, 213 Wolczanska str., 90-924 Lodz, Poland; c: Plant Breeding and Acclimatization Institute – National Research Institute, Department of Grasses, Legumes and Energy Plants, Radzikow, 05-870 Blonie, Poland; d: Faculty of Wood Technology, Warsaw University of Life Sciences – SGGW, Nowoursynowska str. 159, 02-776 Warsaw, Poland; e: Institute of Heavy Organic Synthesis “Blachownia”, 9 Energetykow str., 47-225; f: Lodz University of Technology, Institute of Technical Biochemistry, 4/10 Stefanowskiego str., 90-924 Lodz, Poland Kędzierzyn-Koźle, Poland;
* Corresponding author: piotr_boruszewski@sggw.pl, piotrprzybysz@interia.pl
INTRODUCTION
Paper is used in many branches of industry and almost every aspect of our daily lives. Global paper production has reached 400 MM tons annually. In the future (by 2050), paper production is expected to increase in the world to approximately 700 MM tons (low estimate) and 900 MM tons (high estimate) (Bajpai 2016). Currently paper is manufactured mostly from wood cellulosic pulps (Fornalski 2015). One ton of paper is produced from around 2.5 tons of wood. Because of the limited wood resources that have been increasingly used not only for papermaking but also for production of furniture, plywood and many other goods, it is necessary also to consider other sorts of fibrous biomass for paper manufacturing. One of most attractive renewable fiber resources is the biomass of fast-growing perennials and annual plants (Saikia et al. 1997; Boruszewski et al. 2017; Mirski et al. 2017).
Fast-growing trees such as eucalyptus (Almeida et al. 2007) and poplar hybrids (Christersson 2008) as well as fast growing grasses such as Miscanthus giganteus (Milovanovic et al. 2012) are particularly promising plants for the paper industry. Production of paper commodities from these resources has been growing (Zalesny et al. 2011).
The annual global increase in the area of fast-growing high-yield plantations has reached 3 million hectares, which is a small share of total forest area (Del Lungo et al. 2006), since 30% of the land on the Earth is covered by forests and only 5% of that area are plantations. Those plantations are capable of supplying more than 800 MM tons of lignocellulosic biomass (Carle and Holmogren 2009). So far, the largest plantations have been established in China, USA, and India (West 2006).
Currently, a large portion of harvested wood is incinerated to produce energy. This biomass is derived mainly from natural forests and managed plantations of fast growing tree species (Del Lungo et al.2006; Carle and Holmgren 2009). However, because of the regulations leading to reduction of energy production from forest resources, it has become necessary to search for novel sorts of fibrous plant biomass (Tilman et al. 2006; Arias et al. 2011). This biomass may be derived from plantations of perennial grasses (Muylle et al. 2015).
Particularly attractive are fast growing grasses adapted to the European moderate climate, such as tall wheatgrass, smooth bromegrass, tall fescue, and switchgrass. All these species are inexpensive sources of lignocellulosic biomass (Aase and Siddoway 1974; Kai-yun et al. 2015). Their seeding provides productive crops for a few or even more than 10 years (80 to 150 tons/ha) at relatively low costs (Coffey et al. 1997). Plantations of such plants may be located in areas that cannot be used for production of food because of ecological (e.g. soils that need recultivation) and economic reasons (e.g. class V – VI soils) (Martyniak and Żurek 2014).
Non-wood biomass such as grass biomass outperforms other materials, e.g. wood from forests, because it can be harvested every year and used for papermaking; this makes it possible to reduce the demand for wood and prevent devastation of forests (Leblois et al. 2017). Neither cultivation nor harvesting of grasses requires application of expensive machines that are necessary for cutting and chopping of trees.
The objective of this work was to assess the potential of two fast growing trees, poplar cultivar ‘Hybrid 275’ and European larch (Larix decidua Mill.), and four grasses, tall wheatgrass (Agropyron elongatum(Host). Beauv.), smooth brome (Bromus inermis Leyss.), tall fescue (Festuca arundinacea Schreb.), and switchgrass (Panicum virgatum L.) as materials for papermaking. Properties of pulps derived from these six plants were compared with properties of pulps obtained from three materials that are used in papermaking such as pine (Pinus sylvestris L.) wood, birch (Betula pendula Roth) wood and miscanthus (Miscanthus giganteus J. M. Greef & Deuter ex Hodk. & Renvoize) biomass.
The main aim of this work was to investigate susceptibility of investigated fast-growing grasses and trees for production of paper. Comprehensive analysis of pulp and paper properties is performed in order to verify if these raw materials can be a substitute for commonly used birch and pine wood used by pulp and paper industry.
EXPERIMENTAL
Raw Materials
The biomass of the grasses tested (Miscanthus giganteus J. M. Greef & Deuter ex Hodk. & Renvoize, Agropyron elongatum (Host). Beauv., Festuca arundinacea Schreb., Bromus inermis Leyss., and Panicum virgatum L.) were harvested using a reel lawn mower ALKO 5001 R-II (ALKO, Germany), in the generative (blooming) phase when the contents of cellulose and other fibrous polymers were the highest. The biomass was dried to the humidity of 10% and chopped to 1.5-2.0 cm chaff using a MTD 475 (Briggs & Stratton, Germany) petrol powered shredder, dedicated for disintegration of tree branches.
Woodchips of poplar cultivar ‘Hybrid 275’, European larch (Larix decidua Mill.), pine (Pinus sylvestrisL.), and birch (Betula pendula Roth) were obtained from trunks with a diameter of around 25 cm. Material used in the tests was obtained from plantations managed by the State Forests National Forest Holding.
Before pulping, wood (poplar cultivar ‘Hybrid 275’, larch, pine, and birch) was manually debarked and deprived of knots. Wood logs were sawn using an electric Milwakee MD 304 saw (Milwakee Corp, Germany) to 25 mm slices and chopped manually to 25 x16 x 8 mm chips.
Chemical Composition of Raw Material
Raw materials were disintegrated in laboratory mill Retsch SM 100. Materials were screened through 0.63mm wire and retained on 0.5 mm wire using custom designed vibration screener (CBKO-Hydrolab, Poland) and then prepared lignocellulosic materials were subjected to analysis.
Analysis of chemical composition of raw materials included quantification of extractives, lignin, cellulose, hemicelluloses, and ash. The content of lignin was determined by a gravimetric method in compliance with the TAPPI T222 standard after the removal of extractives according to the TAPPI T204 standard. The content of holocellulose was determined according to the TAPPI T249 standard. Cellulose was quantified as alpha cellulose, according to the TAPPI T203 standard. The content of hemicelluloses was calculated as the difference between the holocellulose and cellulose contents. Ash content was determined by gravimetric method in compliance with TAPPI T211 standard. All these assays were performed in triplicate for each raw material.
Cellulosic Pulps
Cellulosic pulps were prepared as described by Modrzejewski et al. (1969). Pulping conditions were as follows: active alkali 26% (to b.d. lignocellulosic material), sulfidity 30%, liquid module 4.0 for wood and 10 for grasses, maximal digestion temperature 165 °C (for pine and European larch wood 172 °C), heating up-time 2 h, digestion time in maximal temperature 2 h, cooling time to ambient temperature 15 min. It should be noted that pulping conditions were optimized within the scope of our previous (unpublished) research activities. The pulps obtained were used to produce paper. Paper was also produced from the pulps subjected to refining to the freeness of 30°SR, to determine the impact of the latter process on paper characteristics.
Pulping was carried out using a 15 L laboratory heated digester PD-114 (Danex, Poland) with agitation (3 swings per minute, swinging angle of 60°). The temperature was controlled using a dedicated ESM-4950 driver governed by a computer program that enabled recording of the data.
Dry weight of all materials was determined before pulping. Wood samples (1000 g d.w.) were suspended in 4 dm3 of alkaline sulfate solution and heated as described in Table 1. Grass biomass (500 g d.w.) was suspended in 5 dm3 of alkaline sulfate solution and treated as described above.
At the end of cooking, the content of the digester was cooled with 240 dm3 of cold water (to decrease the temperature), and a sample of residual base (0.5 dm3) was withdrawn. Then the pulp was washed with 50 dm3 of water and soaked overnight in 10 dm3 of water to remove base residues. Then the fibrous biomass was disintegrated using a laboratory JAC SHPD28D propeller pulp disintegrator (Danex, Poland) at 10000 rpm, and screened using a PS-114 membrane screener (Danex, Poland) (0.2 mm gap). After screening, the pulps and shives were dried at room temperature (20 to 22 °C) for 48 h, and weighted to determine the yield of pulps and shives contents. The dry pulps were stored in hermetically closed vials before further experiments.
The pulps and samples of base residues from the digester were characterized. The pulps were characterized in terms of the yield from the digester, the yield after screening, the contents of shives, and the residual lignin content, expressed as the Kappa number. The average polymerization degree of cellulose contained in the pulps was determined by the viscometric method (ISO 5351 (2010)). The consumption of bases was expressed as the percentage of bases that underwent reaction with the fibrous materials.
Sheets of paper were produced under laboratory conditions from rewetted pulp samples (22.5 g d.w. samples were soaked in water for 24 h) that were subjected to disintegration using the laboratory JAC SHPD28D propeller pulp disintegrator (Danex, Poland) at 23000 rpm, according to ISO 5263-1 (2004). The disintegrated pulps were concentrated to the dry weigh content of 10% and refined in a PFI mill under standard conditions (ISO 5264-2 (2011)). The ultimate standard freeness of the pulps was around 30°SR. This parameter was determined according to ISO 5267-1 (2000). Values of WRV were determined according to ISO 23714 (2014). Dimensions of fibers were measured according to ISO 16065-2 (2016) using a Morfi Compact Black Edition apparatus (Techpap, France). Paper sheets (the grammage of around 75 g/m2) were produced from the refined and not refined pulps using a Rapid-Koethen apparatus (according to ISO 5269-2 (2004)). Mechanical properties of paper were determined only for the sheets with the grammage of 74 to 76 g/m2. The sheets were stored for 24 h at the relative humidity of 50 ± 2% and temperature of 23 ± 1 °C (ISO 187 (1990)) before determination of mechanical properties such as tensile index, stretch, TEA (ISO 1924-2 (2008)), burst index (ISO 1974 (2012)), and tear index (ISO 2758 (2014)). The other parameters measured were the bulk (ISO 534 (2011)), brightness (TAPPI T452), and opacity (TAPPI T519).
Paper sheets were also characterized using an electron microscope SEM/EDS Hitachi S-4700 after coating with carbon.
RESULTS AND DISCUSSION
The results of analyses of chemical composition of tested raw materials – (Table 1), are presented as means and standard deviations of triplicate assays. These results demonstrate that chemical composition of these materials was different. The highest content of cellulose (52.4% d.w.) was observed in the biomass of poplar cultivar ‘Hybrid 275’. Among the grasses, the richest source of cellulose was the biomass of miscanthus (47.2% d.w.).
Table 1. Chemical Composition of the Tested Fibrous Materials
The other grasses contained more hemicelluloses than the biomass of miscanthus, hardwoods, and softwoods that may positively affect the properties of paper because hemicelluloses promote swelling of fibers (Spiegelberg 1966).
All the fibrous materials were subjected to pulping by the sulfate method. The results were collected in Table 2.
Table 2. Yields and Characteristics of Cellulosic Pulps Obtained by the Sulfate Method
These results demonstrate that the consumption of bases was above 97% in all the cases. The highest pulp yield (before and after screening) was obtained from the poplar cultivar ‘Hybrid 275’ (52.5 and 51.6%, respectively). Among the grasses, the highest pulp yields were obtained from miscanthus (above 47%) while for the other grasses these yields ranged from 34 to 40%.
All of the fibrous materials were converted to cellulosic pulps at the same concentration of bases (of 26% on a wood dry weight). Therefore, the value of kappa number, corresponding to the residual lignin content, reflects their susceptibility to pulping. The pulps derived from the grasses were characterized by the significantly lower values of kappa number compared to the pulps from the hardwoods and softwoods. The European larch wood was the least susceptible to pulping. The kappa number of the pulp derived from the larch wood was the highest, of 56.8 (by 14 units higher compared to the pine pulp). Moreover, the larch pulp was rich in shives that also provided evidence of the low susceptibility of larch wood to kraft pulping.
After screening the pulps were characterized in terms of the freeness, water retention value (WRV), fiber dimensions and fines contents. The results of these measurements are presented in Table 3.
Table 3. Characteristics of the Kraft Pulps before Refining
Then the pulps were subjected to refining in a PFI mill until their freeness reached the value of around 30°SR. Properties of the refined pulps are presented in Table 4. The refined pulps were used to produce sheets of paper under laboratory conditions. Their grammage was 75 g/m2. Mechanical and optical properties of these sheets are shown in Table 5.
Table 4. Characteristics of the Refined Pulps (freeness around 30°SR +/- 1°SR)
Table 5. Mechanical and Optical Properties of Paper Sheets Produced from Refined Pulps (freeness 30°SR +/-1°SR)
Fig. 1. Microscopic images of the tested fibrous materials recorded using a Morfi Compact Black Edition apparatus
Fig. 2. Microscopic images of the paper sheets derived from the refined pulps derived from the tested fibrous materials recorded using a SEM/EDS Hitachi S-4700 microscope
Novel, fast growing fibrous resources that may be used in papermaking instead of wood have been sought after for many years (Oggiano et al. 1997). A particularly promising crop is Miscanthus giganteus because its annual biomass harvests from one hectare may reach 30 tons (Marín et al. 2009). This biomass may be used for production of kraft cellulosic pulps as well as TMP and CTMP pulps (Cappelletto et al. 2000). These pulps may be added to the pulps obtained from recycled paper and used as replacements of hardwood pulps (Madakadze et al. 1999). The papermaking utility of Miscanthus giganteus is well documented in numerous scientific publications (Pažitný et al. 2013; Danielewicz et al. 2015). Our research indicate that higher yield of miscanthus pulp can be achieved (47.12%). Also, other grasses, byproducts of food processing such as orange and lemon peels (Żubrzak 2014; Finell 2003), and algal biomass were tested as alternative fiber resources for paper production (Ververis et al. 2007). However, commercial application of these materials at the present time is problematic because it requires modification of pulping technology and investments in a new equipment (Dietz et al. 2014). Moreover, in all of the mentioned raw materials, both pulp and paper properties were significantly lower compared to the investigated fast growing grasses and trees. From the technological point of view, this is much easier to produce paper from fast growing grasses (Law et al. 2001; Shatalov and Pereira 2006; Madakadze et al. 2010) and trees from managed plantations, e.g.fast growing poplar species (Semen et al. 2001; Francis et al. 2006; Ai and Tschirner 2010, Zamora et al. 2013). This information was confirmed also by our research. Kappa number, for all investigated grasses and poplar ‘Hybrid 275’ ranged from 12.25 (tall wheatgrass) to 14.31 (Miscanthus giganteus). Although the papermaking potential of certain grasses, such as tall wheatgrass (Smith 1996), has already been estimated, the majority of studies focused on problems related to their cultivation and biomass yields. This is the first work presenting properties of pulps obtained from the selected fast growing plants and paper produced from these pulps. No comprehensive information regarding properties of pulp and paper for smooth bromegrass are presented in the scientific literature. The available information is mainly limited to biomass yield (Coffey et al. 1997). The results suggest that the most attractive materials are tall wheatgrass and poplar cultivar ‘Hybrid 275’ that may be used in papermaking as birch wood replacements. Cellulosic pulp from tall wheatgrass was characterized by lower fiber length (819 m) and higher fines content (27.7%). Tensile properties of hand sheets of paper are approximately 10% lower than for paper produced from poplar ‘Hybrid 275’ but still at acceptable level. Because of the limited resources of birch wood (Koski and Rousi 2005; Soleimani et al. 2012), the biomass of fast growing plants may be regarded a profitable and technologically attractive alternative. The alternative fiber resources may be used to produce kraft and semi-chemical pulps (Cappelletto et al. 2000). Properties of the pulps derived from grasses and birch wood are similar (Kürschner and Hoffer 1929; Thykesson et al. 1998; Albert et al. 2011). However, they are worse compared to the pine wood pulps that are characterized by the higher fiber length (2256 m) and coarseness (0.148). According to the literature, the chemical composition of pulps from biomass of grasses and length of fibers depend not only on botanical origin but also time of harvesting and site of plantation (Pahkala and Pihala 2000; Jahan et al. 2007). The chemical composition of the pulps produced in this study from the presented grass species was different than that reported by other authors, and the differences in the contents of cellulose and lignin were around 15% (Ververis et al.2004). The differences in chemical composition cause differences in the properties of pulp and paper. To minimize the effect of pulping and refining conditions on paper characteristics, the nine materials used in this study were subjected to kraft pulping under the same conditions and refined to the same freeness.
CONCLUSIONS
- Properties of cellulosic pulps from fast growing trees and grasses were investigated in this study and believed to be potentially attractive for papermaking. The pulp from wood of European larch is much less attractive despite the high length and coarseness of fibers.
- Among the woods tested, the highest and lowest pulp yields were obtained from the poplar cultivar ‘Hybrid 275’ (51.6% w/w on a wood dry weight) and European larch (36.6% w/w), respectively. The latter pulp was rich in shives that had to be discarded by screening. Among the tested grasses, the highest pulp yield was obtained from Miscanthus giganteus (7 to 13% more than from the biomass of the other grasses).
- The fibers contained in the pulps from poplar wood and biomass of grasses were only slightly shorter than the birch pulp fibers. Among the pulps from grasses, the fibers from tall wheatgrass were characterized by the greatest weighted length and coarseness.
- The lowest fines content in the pulps from the fast growing plants was observed in the pulp from the European larch (similar to the contents of fines in the pine and birch pulps). The other pulps contained around 2 to 6 times more fines. However, because of the lower fiber coarseness the high fines content had no impact on the density of paper produced from other pulps. The large part of fines in these pulps originated from the biomass subjected to pulping.
- Paper sheets produced from the poplar cultivar ‘Hybrid 275’ showed the highest tensile strength among paper sheets produced from the fast growing trees. The static strength of paper sheets from the poplar cultivar ‘Hybrid 275’ and birch were nearly the same. Paper produced from the European larch pulp exhibited the high dynamic tensile properties (by 25% higher than the paper from pine pulp), which were ascribed to the high length and coarseness of fibers.
- Paper sheets produced from the grasses tall wheatgrass, smooth brome, and tall fescue were characterized by nearly the same mechanical properties as sheets of birch paper, while properties of paper sheets from Miscanthus giganteus were only slightly worse.
- The pulps produced from fast growing trees and grasses are interesting substitutes of hardwood pulps. These fiber resources are attractive from the technological and economic points of view because of the short period of growth and productive crops.
ACKNOWLEDGMENTS
The authors are grateful for the support of the National Centre for Research and Development, Grant. No. BIOSTRATEG2/298537/7/NCBR/2016 and LIDER/002/406/L-4/NCBR/2013.
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Article submitted: October 2, 2017; Peer review completed: December 4, 2017; Revised version received: December 19, 2017; Accepted: December 20, 2017; Published: January 8, 2018.
DOI: 10.15376/biores.13.1.1372-1387