Joni Lehto

Alkaline Pre-treatment of Hardwood Chips Prior to Delignification

Abstract Hardwood (Betula pendula) chips were extracted having alkaline aqueous solutions with varying chemical charges (1, 2, 3, 4, 6, and 8% of NaOH on wood), treatment times (30, 60, 90, and 120 minutes), and temperatures (130°C and 150°C). The total amount of material removed was in the range 2.1–16.5% of the original dry feedstock. This fraction was characterized in terms of carbohydrates and their degradation products (mainly aliphatic carboxylic acids together with some furanoic compounds), lignin, and extractives. Low alkali charges (1–4% of NaOH) were not sufficient to neutralize all the acids formed (mainly acetic acid from the acetyl groups of xylan). In contrast, an increase in alkali charge (6% and 8% of NaOH) more intensively facilitated the alkali-catalyzed degradation reactions of polysaccharides to various hydroxy acids, which were then typically present as one of the main constituents in the dissolved organic matter, along with other aliphatic carboxylic acids (acetic and formic acids), lignin, extractives, and carbohydrates.

Characterization of Lignin Dissolved During Alkaline Pretreatment of Softwood and Hardwood

Various alkaline pretreatments were applied to Scots pine (Pinus sylvestris) and silver/white birch (Betula pendula/pubescens) wood chips and the characterization of sulfur-free lignin dissolved was performed. The behavior of lignin during these pretreatments (alkali charge 1–8% NaOH, time 30–120 minutes, and temperature 130–150°C) was studied mainly in terms of lignin removal efficiency and molar mass distribution of dissolved lignin. The amount of lignin in pretreatment liquors increased along with an increase in the alkali charge of 0.8–4.4% and 0.6–3.4% of o.d. pine and birch wood, respectively. The most significant parameter affecting the molar mass of the dissolved lignin was shown to be the alkali charge, since an increase in this parameter clearly increased the -values of dissolved lignin, varying from 2,260 g/mol to 7,050 g/mol and from 2,200 g/mol to 5,550 g/mol for pine and birch lignin, respectively.

Organic materials in black liquors of soda-AQ pulping of hot-water-extracted birch (Betula pendula) sawdust

Abstract The chemical composition of black liquors obtained from the soda-AQ pulping of birch (Betula pendula) sawdust was studied as a function of cooking time, effective alkali content, and hot-water pretreatment of the sawdust prior to delignification. Special attention was paid on the formation of lignin-derived materials and low-molecular-mass carbohydrate-derived degradation products containing aliphatic carboxylic acids. In the case of the hot-water-pretreated feedstock, less acetic acid and formic acid and more nonvolatile hydroxy acids (especially monocarboxylic acids) were obtained. The observations can be interpreted as a result of the extensive removal of hemicelluloses during the hot-water pretreatment.

Combustion Properties of Birch (Betula pendula) Black Liquors From Sulfur-Free Pulping

Sulfur-free pulping has an environmental advantage over the traditional kraft process. This article describes the combustion properties of the black liquors produced from silver birch (Betula pendula) sawdust using three different cooking processes: two sulfur-free cooks (soda-anthraquinone and oxygen-alkali), and one reference kraft cook. It also considers the corresponding black liquors from an integrated forest biorefinery, in which a hot-water pretreatment of feedstock was performed prior to pulping. With the same cooking time, the total burning times for the sulfur-free black liquors were higher (15–55%) than those for the conventional kraft black liquors. However, no significant differences were noted between the total burning times for black liquors from pretreated feedstock and those from untreated feedstock. Especially in the case of untreated feedstock, the results showed that the kraft black liquors typically swelled more (25–45%) than the sulfur-free black liquors. It was further observed that the kraft and soda-anthraquinone black liquors from the untreated feedstock swelled more than those from the pretreated feedstock, while the oxygen-alkali black liquors swelled less.

Spectroscopic analysis of hot-water- and dilute-acid-extracted hardwood and softwood chips

Hot-water and dilute sulfuric acid pretreatments were performed prior to chemical pulping for silver/white birch (Betula pendula/B. pubescens) and Scots pine (Pinus sylvestris) chips to determine if varying pretreatment conditions on the original wood material were detectable via attenuated total reflectance (ATR) infrared spectroscopy. Pretreatment conditions varied with respect to temperature (130°C and 150°C) and treatment time (from 30min to 120min). The effects of the pretreatments on the composition of wood chips were determined by ATR infrared spectroscopy. The spectral data were compared to those determined by common wood chemistry analyses to evaluate the suitability of ATR spectroscopy method for rapid detection of changes in the wood chemical composition caused by different pretreatment conditions. In addition to determining wood species-dependent differences in the wood chemical composition, analytical results indicated that most essential lignin- and carbohydrates-related phenomena taking place during hot-water and acidic pretreatments could be described by applying this simple spectral method requiring only a small sample amount and sample preparation. Such information included, for example, the cleavage of essential lignin bonds (i.e., mainly β-O-4 linkages in guaiacyl and syringyl lignin) and formation of newly condensed lignin structures under different pretreatment conditions. Carbohydrate analyses indicated significant removal of hemicelluloses (especially hardwood xylan) and hemicelluloses-derived acetyl groups during the pretreatments, but they also confirmed the highly resistant nature of cellulose towards mild pretreatments.

Hot-water extraction of Miscanthus × giganteus prior to soda-AQ pulping: a biorefining perspective

ABSTRACT Agricultural residues, such as giant miscanthus (Miscanthus × giganteus, a hybrid of Miscanthus sinensis and Miscanthus sacchariflorus), show a great potential for use in lignocellulosic biorefineries. In this study, various hydrolysates were prepared from miscanthus stalks under varying temperatures (140 and 150°C) and reaction times corresponding to P-factors of 50 and 200, prior to undergoing sulfur-free soda-anthraquinone (AQ) pulping (alkali charge 15% and AQ charge 0.05% on oven-dried feedstock) to recover carbohydrate-derived material. During hot-water extraction, a significant mass removal (10%) of the initial miscanthus was obtained at 150°C with a reaction time of 240 min (P-factor 200). Hydrolysates were characterized in terms of pH and the amounts of carbohydrates, volatile acids (acetic and formic acids), and furans. Hot-water extraction also influenced the delignification stage; the highest pulp yield (62%) for the hot-water-extracted miscanthus (at 150°C with a P-factor of 200) was obtained at 165°C with a cooking time of 60 min (effective alkali charge 15% and AQ charge 0.05% on oven-dried feedstock). Results revealed that giant miscanthus is an attractive feedstock for this kind of integrated biorefining.