Correlation of wood-based components and dewatering properties of waste activated sludge from pulp and paper industry.

Large amounts of wet sludge are produced annually in municipal and industrial wastewater treatment. Already in pulp and paper industry, more than ten million tons of primary sludge, waste activated sludge, and de-inking sludge is generated. Waste activated sludge contains large quantities of bound water, which is difficult to dewater. Low water content would be a matter of high calorific value in incineration but it also has effects on the volume and the quality of the matter to be handled in sludge disposal. In this research waste activated sludges from different pulp and paper mills were chemically characterised and dewatered. Correlations of chemical composition and dewatering properties…

Combustion properties of spruce black liquor droplets : Sulfur-free pulping and influence of hot-water pretreatment

Hot-water pretreatment of lignocellulosics prior to sulfur-free alkaline pulping is an interesting approach for recovering value-added carbohydrate- and lignin-derived materials. This paper investigated the chemical composition variations and combustion properties of the black liquors (BLs) from three different cooking processes: two sulfur-free soda-anthraquinone (soda-AQ) and oxygen-alkali (O2-NaOH) cooks and kraft cook, before and after hot-water pretreatment of the spruce sawdust. Relatively less aliphatic acids but more lignin were present in the BLs after hot-water pretreatment as cooking time prolonged. In general, the burning time decreased as follows: soda-AQ BL > O2-NaOH BL ≅ kraf…

Advanced Biorefinery Concepts Integrated to Chemical Pulping

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

Agricultural residues, such as giant miscanthus (Miscanthus × giganteus, a hybrid of Miscanthus sinensis and Miscanthus sacchariflorus), show a great potential for use in lignocellulosic biorefiner...

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…

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 diffe…

Sulfur-free pulping of hot-water-extracted spruce sawdust

Softwood (Picea abies) sawdust was hot-water-extracted with two multi-phase processes (160-180°C, 100-280 min, and liquor-to-wood ratio 5 l/kg) corresponding to P-factors of ~780 (yield 80.0%) and ~4580 (yield 72.4%). The pre-treated materials were then pulped with the soda-AQ cooking (170°C, NaOH charge 20%, AQ charge 0.1%, 30-150 min, and liquor-to-wood ratio 5 l/kg), resulting in a yield range of 36.1-61.4% (for reference cooks without pre-extraction 47.9-60.0%). It was observed that the pre-extraction under moderate conditions enhanced the dissolution especially of large-molar-mass lignin during cooking, and the total amount of the dissolved lignin was also higher than that removed from…

Alkaline Pre-treatment of Hardwood Chips Prior to Delignification

Scots pine (Pinus sylvestris) chips were pre-treated with alkaline solutions (alkali charges of 1, 2, 3, 4, 6, and 8% of NaOH on the oven-dried wood material) at 130°C and 150°C for various treatment times (30, 60, 90, and 120 minutes). Under these conditions, 2.0–13.6% of the wood d.s. was dissolved into the aqueous hydrolysates. The soluble organic fraction was primarily characterized in terms of carbohydrates (monosaccharides and oligo-/polysaccharides) and their alkali-catalyzed degradation products: aliphatic carboxylic acids containing, besides non-volatile hydroxy carboxylic acids, volatile formic and acetic acids. With increasing alkali charge, temperature, and time, the enhanced fo…

Chemical Pretreatments of Wood Chips Prior to Alkaline Pulping - A Review of Pretreatment Alternatives, Chemical Aspects of the Resulting Liquors, and Pulping Outcomes

The chemical industry is being forced to evaluate new strategies for more effective utilization of renewable feedstocks to diminish the use of fossil resources. In this literature review, the integration of both acidic and alkaline pretreatment phases of hardwood and softwood chips with chemical pulping is discussed. Depending on the pretreatment conditions, high-volume sulfur-free fractions with varying chemical compositions can be produced. In case of acidic pretreatments, the major products include carbohydrates (mono-, oligo-, and polysaccharides), whereas under alkaline (i.e., aqueous NaOH) pretreatment conditions, the sulfur-free fractions of aliphatic carboxylic acids, lignin, and ex…

Organic material dissolved during oxygen-alkali pulping of hot-water-extracted spruce sawdust

Untreated and hot-water-extracted (HWE) Norway spruce (Picea abies) sawdust was cooked using the sulfur-free oxygen-alkali (OA) method under the following conditions: temperature, 170 °C; liquor-to-wood ratio, 5:1 L/kg; and NaOH charge, 19% on the oven-dry sawdust. In comparison with earlier studies conducted with birch sawdust, the spruce cooking yield data, together with the amount of the pulp rejects (78% to 86% for reference pulps from the initial feedstock and 73% to 83% for pulps from the HWE feedstock), revealed that the pretreatment stage prior to spruce OA pulping caused different effects on pulping performance. The analyses of the three main compound groups (i.e., lignin, volatile…

Fast pyrolysis of hot-water-extracted and delignified silver birch (Betula pendula) sawdust by Py-GC/MS

The thermochemical behavior of birch (Betula pendula) sawdust both untreated and after various chemical treatments (hot-water extraction, delignification, and hot-water extraction followed by delignification) was investigated by pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). In each case, major GC-amenable condensable products were classified into several compound groups, and the formation of these monomer-related fragments from feedstock samples with varying mass portions of the structural constituents (cellulose, hemicelluloses, and lignin) were determined at 500 °C and 700 °C at hold times of 5 s and 20 s. The formation of pyrolysis products was shown to be characteristically…

Chemometric Study on Alkaline Pre-treatments of Wood Chips Prior to Pulping

Alkaline pre-treatments were performed for the production of organics-containing effluents from silver/white birch (Betula pendula/pubescens) and Scots pine (Pinus sylvestris) chips prior to chemical pulping. Pre-treatment conditions were varied with respect to time (from 30 min to 120 min), temperature (130 °C and 150 °C), and alkali charge (1, 2, 3, 4, 6, and 8% of NaOH on oven-dried wood). The analytical data (total content, weight average molar mass, and molar mass distribution) on dissolved lignin were subjected to principal component analysis to examine the relationship between molar mass and molar mass distributions in lignin removed from different wood species under varying alkaline…

Effect of sodium borohydride and hydrogen peroxide pretreatments on soda pulping of sugar maple (Acer saccharum)

For recovering value-added wood-based organic material prior to delignification, sodium borohydride (NaBH4) and hydrogen peroxide (H2O2) pretreatments under alkaline conditions were performed before soda pulping of sugar maple (Acer saccharum) chips with sodium hydroxide (NaOH). In this investigation, it was determined whether the pulp yield could be increased by partly stabilizing the hemicelluloses by these pretreatments, and simultaneously obtains lower pulp kappa numbers. The results indicated that when aiming to the same kappa numbers (i.e., kappa numbers 14.3-20.5), roughly 3% higher pulp yield could be achieved if the chips were pretreated with alkaline 0.5% NaBH4 solutions, compared…

PURIFICATION OF HARDWOOD-DERIVED AUTOHYDROLYSATES

Carbohydrate-containing hydrolysates (1.1 to 14.9% of wood dry matter) obtained from autohydrolysis (at 130 to 150°C for 30 to 120 minutes) of birch (Betula pendula) chips prior to pulping were purified with respect to non-carbohydrate materials, without carbohydrate losses, either by ethyl acetate extraction or XAD-4 resin treatment. In the former case, about 50% of lignin and practically all the furanoic compounds (2-furaldehyde and 5-(hydroxymethyl)furfural) could be removed, whereas in the latter case, the corresponding amounts were about 30% and 50 to 90%, respectively. A partial recovery of various unsaturated impurities is of importance, because they may act as inhibitors when bioche…

Multivariate Correlation between Analysis Data on Dissolved Organic Material from Scots Pine (Pinus sylvestris) Chips and their Autohydrolysis Pre-Treatment Conditions

Various chemometric techniques were used to establish the relationship between the autohydrolysis conditions prior to pulping and the chemical compositions of the soluble organic materials removed from Scots pine (Pinus sylvestris) wood chips. The aqueous chip pre-treatments (autohydrolysis) were administered at 130 °C and 150 °C for 30, 60, 90, and 120 min, and the hydrolysates obtained were characterized in terms of total carbohydrates (various mono-, oligo-, and polysaccharides together with uronic acid side groups), volatile acids (acetic and formic acids), lignin, and furans (furfural and 5-(hydroxymethyl)furfural). Based on the analytical data gathered, a relatively accurate model for…

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 30 min to 120 min). 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 spe…

Combustion behavior of kraft black liquor droplets from hot water pretreated hardwood and softwood chips

This paper describes the combustion behavior of birch and spruce kraft black liquors obtained from an integrated forest biorefinery concept in which a hot water extraction of chips was performed before pulping. This pretreatment, aiming mainly at the recovery of various hemicellulose-derived materials, increased the concentrations of lignin and hydroxy acids in black liquors, compared with those in the reference black liquors without any process modification. On the other hand, the pretreatment decreased the concentrations of volatile acids and other organics (extractives and hemicellulose residues). Because of these characteristic changes, the total burning times (pyrolysis time plus char …

Organics in soda-anthraquinone black liquors from hot-water-extracted non-wood feedstocks

The chemical compositions of black liquors (BLs) obtained from the soda-anthraquinone (AQ) pulping of untreated and hot-water-extracted non-wood feedstocks (okra stalk, miscanthus stalk, and wheat straw) were determined. These under-utilized renewable and widely available feedstocks could provide a cheaper source for producing fiber and precursors for manufacturing green chemicals. These BLs were mainly characterized in terms of carbohydrate-derived volatile carboxylic acids (acetic and formic acids) and non-volatile carboxylic acids (hydroxy acids) as well as lignin. Additionally, in each case, the average molar mass and molar mass distribution of the dissolved lignin were measured. Result…

Multivariate Correlation between Analytical Data for Various Organics Dissolved during Autohydrolysis of Silver Birch (Betula pendula) Chips and Treatment Conditions

Autohydrolysis pre-treatments were performed for the production of hemicellulose-rich autohydrolysates from silver birch (Betula pendula) chips prior to chemical pulping. Pre-treatment conditions were varied with respect to time (from 30 to 120 min) and temperature (130 and 150 °C), covering a P-factor range from 10 to 238. Hydrolysates were analyzed in terms of carbohydrates, lignin, volatile organic acids, and furanoic compounds. The analytical data were subjected to various chemometric techniques to establish the relationships between dissolved organic components, hardwood and softwood used in the experiments, and applied pre-treatment conditions. Using this method, differences between t…

Fast pyrolysis of hot-water-extracted and delignified Norway spruce (Picea abies) sawdust by Py-GC/MS

The thermochemical behavior of Norway spruce (Picea abies) sawdust as such and after various chemical treatments (hot-water extraction, delignification, and hot-water extraction followed by delignification) was investigated by analytical pyrolysis–gas chromatography–mass spectrometry. In each case, the yields of major GC-amenable condensable products were semi-quantitatively measured, and the individual compounds were classified into several compound groups. The formation of these groups from feedstock samples with varying mass portions of their structural constituents (carbohydrates and lignin) was determined at 500 °C and 700 °C with a residence time of 5 s and 20 s. The formation of pyro…

Characterization of pre-treatments on wood chips prior to delignification by near infrared spectroscopy

A near infrared (NIR) spectroscopy-based method for predicting yields and lignin contents of differently pre-treated silver/white birch (Betula pendula/B. pubescens) and Scots pine (Pinus sylvestris) chips was developed. The approach was to create multivariate calibration models from the NIR data by the partial least squares (PLS) method. Both parameters are important factors when adjusting adequate conditions for pre-treatments either with hot-water (HW) as such and slightly acidified HW (collectively referred to as autohydrolysis) or dilute alkaline aqueous solutions prior to alkaline pulping. Pre-treatment conditions were varied with respect to temperature (130 °C and 150 °C) and treatme…

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 diffe…