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Alkaline Sulfite Anthraquinone and Methanol (ASAM) Pulping Process of Tropical Bamboo (Gigantochloa scortechinii)
Abstract
his chapter explores the characteristic potentials of alkaline sulfite anthraquinone andmethanol (ASAM) pulping of bamboo culms (Gigantochloa scortechinii) in the industrialproduction of pulp and paper for packaging. The biometric characterization results of thebamboo culms show that bamboo has fiber length of 1980–4000μm, Runkel ratio of 0.86,and flexibility ratio of 50.19, while the chemical compositions of the bamboo contain47.67% cellulose, 68.33% holocellulose, 26% lignin, and 3.69% solvent extractive, whichgive good paper quality fiber and also falls within the range of wood from softwoodsspecies. The study revealed that the optimum ASAM pulping parameters was at 16%NaOH and 90 min cooking time, resulting in Kappa number of 14.17 and pulp yield of49.06%, while the paper tensile index of 20.86 Nm/g, tear index of 22.64 mN.m2/g, andbrightness of 39.32% were obtained. The biometric and chemical characterizations of theASAM pulped bamboo have shown that ASAM pulped bamboo produces high-qualitypulp and paper suitable for packaging and printing paper. Hence, the use of bamboomaterials can reduce the burden on the forest, due to the increasing demand for paperand paper products, while supporting the natural biodiversity.
... The greener and more environmentally friendly alkaline sulfite anthraquinone methanol (ASAM) pulping process is derived from the conventional alkaline sulfite process with adding of anthraquinone and methanol to increase the delignification rate and pulp product selectivity [13]. The anthraquinone accelerates delignification and acts as a stabilizer for polysaccharides. ...
... Alkaline sulfite anthraquinone methanol pulping process is considered as a greener and more environmentally friendly method, which is obtained from the traditional alkaline sulfite method and is augmented with anthraquinone and methanol to improve delignification rate and pulp product selectively [13]. ASAM pulping process combines the durability of kraft pulp with simplicity of sulfite pulp bleaching. ...
... For example, sodium sulfate and sodium hydroxide are the main raw materials used to separate the fibers in the alkaline sulfate process. In contrast, both AQ and methanol are used as catalyst to expedite chemical penetrating and delignifying of lignocellulosic biomass [13]. When used in specific proportions and cooked at certain conditions, high yield and relatively bright pulps are produced. ...
The manufacturing of pulps and papers from wood material via conventional processes has led to forest degradation, which has consequently caused adverse environmental impacts and disrupted the ecological balance. Hence, there has been an increased interest in using non-woody biomass as an alternative raw material for paper production. Alkaline sulfite anthraquinone methanol (ASAM) pulping process is cleaner, greener, and more environmentally, because the process does not involve sulfur compounds. It also offers better pulp and paper properties, especially for non-woody biomass. In the current review, pertaining to the production of high-quality papers and paperboards from non-woody biomass via ASAM pulping process was covered. Some of the non-woody biomass include kenaf, bamboo, elephant grass, jute, corn stalks, cotton stalks, and pearl millet stalks. As a whole, the ASAM pulping process exhibits higher pulp yield, delignification rate, and brighter, as well as enhanced pulping strength properties, with minimal air and water pollution. To the best of my knowledge, this review is the first in the field of this research. Therefore, this review highlighted the in-depth knowledge about the potentiality of non-woody biomass for pulp and paper production via ASAM pulping process.
... The chemical materials that make up the alkaline sulfite-anthraquinone-methanol (ASAM) process are sodium sulfite, sodium hydroxide (NaOH), anthraquinone (AQ), and methanol. These materials play a unique role in pulping because, sodium sulfite and NaOH are the major ingredients of the alkaline sulfite process while AQ and methanol act as catalysts to enhance the chemical penetration delignification of the lignocellulose biomass (Paridah et al., 2018). ...
... On the other hand, the tensile strength of soda pulps was higher than the ASAM (Figure 4) pulps which was supported further by the high viscosity and the same pattern for burst ( Figure 5) when comparing the different properties versus beating time. It was also found that the pulp properties of bamboo subjected to the ASAM pulping process were significantly affected by the cooking conditions (P≤0.05) (Paridah, et al. 2018 (Paridah, et al. 2018). The overall strength properties of whole and core pulps indicated no need to separate the fiber core from the bark as it seemed more or less similar in morphological and chemical properties. ...
... On the other hand, the tensile strength of soda pulps was higher than the ASAM (Figure 4) pulps which was supported further by the high viscosity and the same pattern for burst ( Figure 5) when comparing the different properties versus beating time. It was also found that the pulp properties of bamboo subjected to the ASAM pulping process were significantly affected by the cooking conditions (P≤0.05) (Paridah, et al. 2018 (Paridah, et al. 2018). The overall strength properties of whole and core pulps indicated no need to separate the fiber core from the bark as it seemed more or less similar in morphological and chemical properties. ...
Pennisetum glaucum pearl millet as whole stalks and core were examined for suitability in the production of pulp and
paper. Fiber dimensions, morphological, and chemical characteristics are reported. The pulping trials with soda-AQ, ASAM, and
soda as reference were carried out. ASAM pulping gave good results in yield, degree of delignification, and mechanical
properties. The best screened yield, lowest kappa number, highest brightness, and viscosity were obtained by ASAM cooking.
Soda-AQ gave pulps with good screened yield, kappa number, and viscosity compared with soda cooking. The separation of bark
and core is not recommended.
... Moreover, ASAM pulping produces pulps that are easier to bleach compared to kraft pulps [34]. Paridah et al. [35] state that the ASAM pulping method has many benefits. These include excellent pulp qualities such as a high yield of pulp, low kappa content, bright pulp color, and high strength of paper. ...
Bamboo is a versatile and fast-growing plant that generates cellulose with long fibers. This study examined the fiber morphology, chemical composition, and pulp and paper qualities of the bamboo Oxytenanthera abyssinica culm. The purpose was to assess their potential as an alternative feedstock for pulping and papermaking. The fiber characteristics were determined using the maceration method and the chemical analysis using the TAPPI standard method. The bamboo chips were pulped via the alkaline sulfite anthraquinone methanol (ASAM) pulping process, which involved charges of 15, 17, and 19% alkali, 15% methanol, 0.1% antraquinone, and 170 °C cooking temperature for 90 min. The screened yield went through the beating process at 2000, 4000, 6000, and 8000 revolutions. The mechanical properties of the hand sheets (60 g/m²) laboratory scale papers were assessed in accordance with TAPPI standards. The results showed that the bamboo fiber’s length is 1835 μm similar to those of softwood, and had led to stronger paper properties. The flexibility and Runkel ratios, at 51.71 and 0.94, respectively. Besides, the bamboo contained 71.25% holocellulose, 50.19% cellulose, and 25.67% lignin. The highest tensile index and burst index, calculated at 75.13 and 78.71 Nm/g and 7.10 and 7.40 kPa.m²/g respectively, were produced by the optimum pulp yield (45.24%) under 17% active alkali and kappa number 11.70 in 6000 and 8000 revolutions. We conclude that bamboo, with its excellent fundamental characteristics and the pulps derived from it through the ASAM pulping process, are suitable for the application of packaging paper grades.
... The alkaline sulfite, anthraquinone, and methanol (ASAM) pulping method was selected because it is a well-established method for obtaining fiber with superior strength. The bamboo chips were pulped using the MK Twin Digester, in accordance with some modifications in pulping conditions developed by the authors Khristova et al. (2006) and Paridah et al. (2018). Pulping parameters for the alkaline sulfite anthraquinone methanol (ASAM) process were set at 17% active alkali, 70/30 Na 2 SO 3 /NaOH chemical ratio, 15% methanol, and 0.1% anthraquinone. ...
... Bamboo is mainly composed of cellulose, hemicellulose and lignin. In addition, it contains a small number of extracts such as hydrocarbons, carboxylic acids, esters, and polyphenols (Tahir et al., 2018). It could be seen from Fig. 3 that the peak at 1047 cm − 1 was the C-O stretching vibration group. ...
As a high-strength biomass composite material, the development of bamboo scrimber (BS) was limited by its flammable characteristics. In this study, different immersion orders of ammonium polyphosphate (10 wt%, APP solution) for bamboo bundles were selected in order to evaluate its influence on the interphase behavior, mechanical and combustion properties of BS. The flattened bamboo bundles, phenol-formaldehyde (PF) and APP solution were utilized to fabricate the BSs. The interphase behavior of the treated bamboo bundles was characterized by the contact angle measurement, Fourier transform infrared spectroscopy (FTIR) analysis, fluores-cence microscope and SEM-EDS measurement. Thermogravimetric analysis, limiting oxygen index (LOI), mechanical properties before and after combustion test were assessed for various BSs. The results showed that significantly increased equilibrium contact angle of PF droplet on the surface of bamboo after immersed in APP solution while the decrement was for APP solution droplet on the surface of bamboo after immersed in PF. Varied intensities of chemical bonds and distribution forms of APP and PF were observed for the treated BSs depending on the immersion orders. These variations have a great effect on the mechanical and combustion properties. No significant decrement of compressive strength and bending strength was observed for APP-treated BSs with different immersion orders compared with the control sample. Higher compressive strength, bending strength, and modulus of elasticity (MOE) were found for the APP-PF-BS with increments of 31.60%, 21.70%, and 29.01%, respectively. Significantly increased thermal stability was observed for bamboo bundles after immersed in APP and PF especially for the temperature over 300 • C. After the combustion test (duration of 40 min), a higher LOI of 35.4, retention rates of mechanical properties of 39.96-78.97%, and lower mass loss of 15.93% were obtained for the PF-APP-BS. Finally, the immersion order of low concentration of APP solution has a great effect on the interphase behavior, mechanical and combustion properties of BSs, which plays a significant role in the optimized fabrication of fire-resistant BSs.
... Bamboo is non woody plant has been utilized in wide range of uses include food, furniture, medicines and building materials [1][2][3][4][5][6]. Application of bamboo in pulp and paper technology was heavily investigated with different methods of pulping include soda [7][8][9][10] alkaline sulfite [11,12] organosolv pulping [13,14]. ...
Pulping of with soda and soda anthraquionone was designed to investigate the applicability these methods for the Oxytenanthera abyssinica, bamboo stalks cooking trails, and to examine the effect a crude extract of Senna obtusifolia as source for anthraquinone. The chemical components of the Oxytenanthera abyssinica were carried out with high pentosans 18.3%, Kurchner-Hoffer cellulose 48.7% and lignin 29.0%. The cooking conditions were applied to compare the soda and soda anthraquinone with high screened yield 61.3% low Kappa number 25.0 and good pulp properties suitable for different types of end products of paper. When application of crude extract of Senna obtusifolia as source for anthraquinone during cooking gave results more than those of soda but less than those of soda with anthraquinone. The purification of the crude extract will result in better utilization and application of these extracts.
Pulp and paper manufacturing covers approximately 15% of the non-energetic utilization of wood. The roughly 3000 existing paper and board grades require advanced processes of mechanical and chemical defibration and fibrillation as well as paper and board manufacturing and converting machinery, representing a high-tech industry with strong focus on bio-economy, sustainability, and renewability. The main raw material for virgin fibers derives from selected wood species, but also many non-wood plants can be exploited for paper and board production.This chapter gives essential information and facts to the current pulp and paper industry and substantial paper manufacturing processes, a biobased sector using wood fibers manifold thanks to a worldwide-established paper recycling system.KeywordsPaper raw materialsChemical pulpMechanical pulpPaper recyclingPaper manufacturingBiorefineryFinishing of paperPaper gradesPaper properties
Biorefineries integrate processes for the sustainable conversion of biomass into chemicals, materials, and bioenergy so that resources are optimized and effluents are minimized. Despite the vast potential of lignocellulosic biorefineries, their success depends heavily on effective, economically viable, and sustainable biomass fractionation. Although efficient, organosolv pretreatment still faces challenges that must be overcome for its widespread utilization, mainly related to solvent type and recycling, robustness regarding biomass type and integration of hemicellulose recovery and use. This review shows the recent advances and state-of-the-art of organosolv pretreatment, discussing the advances, such as the use of biobased solvents, whilst also shedding light on the perspectives of using the streams — cellulose, hemicellulose, and lignin — to produce biofuels and products of high added value. In addition, it presents an overview of the existing industrial implementations of organosolv processes and, lastly, shows the main scientific and industrial challenges and opportunities for this process.
Many physical, chemical, and/or enzymatic treatments have been used to open the structure of lignocellulosic biomass, separate its components and obtain cellulose. The alkaline-bleaching treatment is most preferred in terms of reagent availability. In terms of cellulose yield and quality, however, there are inconsistencies with the alkaline-bleaching treatment. Similarly, the optimum conditions for carboxymethylcellulose (CMC) synthesis from cellulose mercerization and etherification are vague. This review paper investigates and compares the various conditions applied in CMC synthesis and recommends efficient processes and optimal conditions for increasing CMC yield and quality. Recommended mercerization parameters are 25-30% (w/v) NaOH, 1-1.5 h and 25-28 °C. Recommended etherification parameters are 1.2 g chloroacetic acid (CAA) or sodium chloroacetate (SCA)/g cellulose, 3-3.5 h and 50-55 °C. The source material and extraction process determines the quality of the cellulose produced. Therefore, identifying the most efficient methods and underlying conditions for various cellulose sources is important.
Crystalline nanocellulose was prepared from Semantan bamboo (Gigantochloa scortechinii) via acid hydrolysis and was used to synthesize a nanocomposite of polyaniline/crystalline nanocellulose (PANi/CNC) via in situ oxidative polymerization of aniline in the presence of crystalline nanocellulose. The electrochemical properties of the nanocomposite were studied using a modified PANi/CNC electrode via cyclic voltammetry, and higher current response was observed for the PANi/CNC-modified electrode compared to that for the modified electrode with PANi. The results obtained from EIS displayed lower value of Rct for the PANi/CNC-modified electrode, indicating that the incorporation of CNC into the PANi structure could enhance the electron transfer rate. The characteristic peaks of PANi and CNC were observed in the FTIR spectra of the nanocomposite, indicating the incorporation of CNC inside the nanocomposite structure. Moreover, in the XRD diffractogram, lower crystallinity was observed at the 2 theta values of 22.6 and 16.1 for PANi/CNC compared to that for pure CNC. The FESEM images showed high porosity of the nanostructure with no phase separation, revealing the homogenous polymerization of the monomer on the surface of the crystalline cellulose. Aggregation of PANi particles was observed with the increasing aniline concentration.
Background
Bamboo is a highly abundant source of biomass which is underutilized despite having a chemical composition and fiber structure similar as wood. The main challenge for the industrial processing of bamboo is the high level of silica, which forms water-insoluble precipitates negetively affecting the process systems. A cost-competitive and eco-friendly scheme for the production of high-purity dissolving grade pulp from bamboo not only requires a process for silica removal, but also needs to fully utilize all of the materials dissolved in the process which includes lignin, and cellulosic and hemicellulosic sugars as well as the silica. Many investigations have been carried out to resolve the silica issue, but none of them has led to a commercial process. In this work, alkaline pretreatment of bamboo was conducted to extract silica prior to pulping process. The silica-free substrate was used to produce high-grade dissolving pulp. The dissolved silica, lignin, hemicellulosic sugars, and degraded cellulose in the spent liquors obtained from alkaline pretreatment and pulping process were recovered for providing high-value bio-based chemicals and fuel.
Results
An integrated process which combines dissolving pulp production with the recovery of excellent sustainable biofuel and biochemical feedstocks is presented in this work. Pretreatment at 95 °C with 12% NaOH charge for 150 min extracted all the silica and about 30% of the hemicellulose from bamboo. After kraft pulping, xylanase treatment and cold caustic extraction, pulp with hemicellulose content of about 3.5% was obtained. This pulp, after bleaching, provided a cellulose acetate grade dissolving pulp with α-cellulose content higher than 97% and hemicellulose content less than 2%. The amount of silica and lignin that could be recovered from the process corresponded to 95 and 77.86% of the two components in the original chips, respectively. Enzymatic hydrolysis and fermentation of the concentrated and detoxified sugar mixture liquor showed that an ethanol recovery of 0.46 g/g sugar was achieved with 93.2% of hydrolyzed sugars being consumed. A mass balance of the overall process showed that 76.59 g of solids was recovered from 100 g (o.d.) of green bamboo.
Conclusions
The present work proposes an integrated biorefinery process that contains alkaline pre-extraction, kraft pulping, enzyme treatment and cold caustic extraction for the production of high-grade dissolving pulp and recovery of silica, lignin, and hemicellulose from bamboo. This process could alleviate the silica-associated challenges and provide feedstocks for bio-based products, thereby allowing the improvement and expansion of bamboo utilization in industrial processes.
Increasing concerns over the unstable and uncertain petro-based reserves, global warming and energy insecurity have led to a resurgence in the development of an environmentally-responsive greener approach for biofuel production. Exploration of renewable bio-resources for producing biofuels as well as industrially-commodity chemicals has become a universal research theme and attracted massive scientist’s impetus over the last decade. Inarguably, lignocellulosic biofuel represents a renewable, sustainable, and the sole foreseeable alternative energy source to transportation fuels. Nevertheless, the lignocellulose recalcitrance postures technical hurdles to develop a cost-competitive bio-refinery process. To do this, the fuel-producing microbial hosts and their metabolic pathways must be engineered/tailored and optimized. Protein engineering has been used to amplify the biocatalytic performance of lignocellulose-modifying enzymes, but only a modest outcome has seen in biotransforming the lignocellulose-to-biofuels than that of its great success in other industrial applications. Recent advancements in metabolic engineering and synthetic biology will provide novel tools for biotechnologists and metabolic engineers to create an efficient and well-performing biocatalyst with desired phenotypes for producing economically viable biofuels. The present review article describes various technical obstacles, advances, and bio-economic aspects in the research arena of lignocellulose to biofuel which is crucial in the future biofuel industry to respond inevitably accelerating oil prices and depleting oil assets.
World is facing challenges to reduce global environmental issues including waste management, green house gas emissions, pollution, deforestation and depletion of non renewable resources originated due to speedy industrial and urban development. To protect environmental resources, strict legislations are being made by the governments of developing and developed world. Due to such issues, pulp and paper industry is sarcastically facing shortage of forest based raw materials for paper production. Most of the mills have either start up with non wood based raw materials or recycled papers in place of conventional forest based resources. Rice straw, a lignocellulosic residue is abundantly available in wood short countries like India and China and can be utilized in pulp and paper industry. In present study it was found that rice straw consisted of cellulose (33.3 ± 0.47%), pentosan (27.3 ± 0.36%), lignin (13.0 ± 0.07%), ash (12.6 ± 0.11%) and silica (11.7%). The higher amount of carbohydrates and less lignin content in rice straw in comparison to hardwoods and softwoods can be made as a alternate raw material for pulp and paper mills. Out of soda and soda anthraquinone - methods for converting rice straw to pulp, -Later was found to be a better option as it gives high pulp yield (62.4%) and better strength properties of the pulp. The bleaching of soda--anthraquinone rice straw pulp with chlorine dioxide based bleaching sequence was found better over elemental chlorine based sequence as it improved the pulp strength properties and reduced the bleaching effluent load. The adsorbable organic halides - indicative of biorefractory, accumulative and toxic compounds were reduced by 66% when chlorine dioxide bleaching was used. Such approach of using agricultural waste as a raw material for making paper can prove to be valuable towards waste utilization, pollution control and for sustainable growth of industry.
The interest in using nanofibrillated cellulose (NFC) in packaging is exponentially increasing thanks to (1) the recent industrialization of cellulose nanofibers (CNF), (2) the improvement in coating process, (3) their excellent barrier properties but also thanks to (4) the strong expectation from industry for innovative and high-performance biobased solutions. Furthermore their price and the societal expectations lead researchers to focus on new functionalities. This chapter presents very recent innovations using CNF in active packaging like antimicrobial packaging.
Considerable effort has been devoted to the development of biofuels from renewable lignocellulosic biomass. To resolve the challenges associated with the structural barrier of lignocellulosic biomass, hydrothermal pretreatment is applied to alter the structure and improve the accessibility of carbohydrate sugars to microorganisms or chemicals in the subsequent conversion processes. Hydrothermal pretreatment takes advantage of high moisture content of biomass and efficiently converts polysaccharides into monomeric sugars and their corresponding degradation products. To achieve this goal, multiple technologies have been explored using liquid water as the media, with or without addition of chemicals (acids or alkalis). However, there are difficulties in developing an optimized and universal treatment approach due to the heterogeneity of biomass. In this chapter, four major biomass types, wood, bamboo, agricultural residues, and agave, are discussed and compared with respect to feedstock composition and response to the various hydrothermal pretreatments. Moreover, the reaction pathways of individual biomass components (hemicellulose, cellulose, lignin, extractive, and ash) under different treatment conditions (acidic and alkaline) are also comparatively reviewed. Finally, the effects of pH, biomass solid loading, and reactor selection on pretreatment are presented.
The isolation of cellulose nanocrystals from different lignocellulosic materials has shown increased interest in academic and technological research. These materials have excellent mechanical properties and can be used as nanofillers for polymer composites as well as transparent films for various applications. In this work, cellulose isolation was performed following an environmental friendly procedure without chlorine. Cellulose nanocrystals were isolated from the exhausted acacia bark (after the industrial process of extracting tannin) with the objective of evaluating the effect of the solvent extraction steps on the characteristics of cellulose and cellulose nanocrystals. It was also assessed the effect of acid hydrolysis time on the thermal stability, morphology and size of the nanocrystals, through TGA, TEM and light scattering analyses. It was concluded that the extraction step with solvents was important in the isolation of cellulose, but irrelevant in the isolation of cellulose nanocrystals. Light scattering experiments indicated that 30 minutes of hydrolysis was long enough for the isolation of cellulose nanocrystals.
The pursuit of sustainable functional materials requires development of materials based on renewable resources and efficient fabrication methods. Hereby, we fabricated all-polysaccharides multilayer films using cationic guar gum (CGG) and anionic cellulose nanofibrils (i.e. TEMPO-oxidized cellulose nanofibrils, TOCNs) through a layer-by-layer casting method. This technique is based on alternate depositions of oppositely charged water-based CGG and TOCNs onto laminated films. The resultant polyelectrolyte multilayer films were transparent, ductile and strong. More importantly, the self-standing films exhibited excellent gas (water vapor and oxygen) and oil barrier performances. Another outstanding feature of these resultant films was their resistance to various organic solvents including methanol, acetone, N, N-dimethylacetamide (DMAc) and tetrahydrofuran (THF). The proposed film fabrication process is environmentally benign, cost-effective and easy to scale-up. The developed CGG/TOCNs multilayer films can be used as a renewable material for industrial applications such as packaging.
Cost effective pretreatment is key to commercial success of use of lignocellulosic material (LCM) as feedstock for production of bioethanol. The seasonal nature and annual variability of LCM may enforce the use of different biomass sources as feedstock to ensure round the year production. However, different processing requirements of each material may limit the success of such development and impair the use of many feedstocks due to logistic and economic reasons. The selection of pretreatment technology for different LCM sources in cost effective manner is a major challenge. The recent review articles have provided the details of different pretreatment operations. This article has tried to establish a strong connection between pretreatment options and their combination with prior and post pretreatment processes, which is pre-requisite to success of establishing the commercial facility. The key is lessening number of operations and operating cost of each unit of operation. This paper suggests ways towards appropriate pretreatment processes through process intensification leading to the prospects of sustainable biofuel production.
The present study demonstrated that the concentrated lithium bromide (LiBr) solution with acid as catalyst was able to selectively cleave β-O-4 aryl ether bond and lead to lignin depolymerization under mild conditions (e.g., in 60% LiBr with 0.3 M HCl at 110 °C for 2 h). Four industrial lignins from different pulping and biorefining processes, including softwood kraft lignin (SKL), hardwood kraft lignin (HKL), softwood ethanol organosolv lignin (EOL), and acid corncob lignin (ACL), were treated in the LiBr solution. The molecular weight, functional group, and inter-unit linkages of the lignins were characterized using GPC, FTIR, and NMR. The results indicated that the β-O-4 aryl ether bonds of the lignins were selectively cleaved, and both LiBr and HCl played crucial roles in catalyzing the cleavage of the ether bonds.