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The spherical cellulose nanocrystals (CNCs) with high purity were prepared, the processes included composite enzymolysis of pulp fibers and the purification of product. The impurities in the crude product CNCs were analyzed with FTIR, coomassie brilliant blue-G250 and ionic chromatography. The pure CNCs were characterized with SEM, XRD, DLS and TGA. The results indicated that the crude CNCs was flocculated and washed twice with a dilute acid solution (pH = 2) to get pure spherical CNCs, the purity was approximate 99.99%. The obtained pure spherical CNCs had a narrow particle size distribution with diameter 15–40 nm. FTIR and XRD analyses proved that the crystal phase of the spherical CNCs did not change, but the crystallinity decreased slightly compared with pulp fibers. The thermal degradation showed that the spherical CNCs had better thermal stability than one from other methods, and the temperature of maximum weight loss rate (Tmax) was 329.2 °C.

Utilization of lignocellulosic biomasses for biobutanol fermentation usually requires costly processes of pretreatment and enzymatic hydrolysis. In this study, paper pulp (93.2% glucan) was used as a starting biomass material to produce biobutanol. We conducted enzymatic semi-hydrolysis of paper pulp without pretreatment and with low enzyme loading, which produced high concentrations of cellobiose (13.9 g L−1) and glucose (21.3 g L−1). In addition, efficient fermentation of the semi-hydrolysate was achieved similar to that with the use of commercial sugars without inhibitors. Finally, we designed a novel non-isothermal simultaneous saccharification and fermentation with in situ butanol recovery, which was composed of a repeated semi-hydrolysis process and successive butanol-extractive fermentation process under the respective optimal conditions. The consolidated system improved butanol production, butanol yields, and butanol productivities and enabled repeated use of medium when compared with other integrated hydrolysis and fermentation processes.

Paper mill sludge (PMS) was assessed as cheap renewable lignocellulosic biomass for lipid production by the oleaginous yeast Cryptococcus vishniaccii (MTCC 232). The sonicated paper mill sludge extract (PMSE) exhibited enhanced lipid yield and lipid content 7.8±0.57g/l, 53.40% in comparison to 5.5±0.8g/l, 40.44% glucose synthetic medium, respectively. The accumulated triglycerides (TAG) inside the lipid droplets (LDs) were converted to biodiesel by transesterification and thoroughly characterized using GC-MS technique. The fatty acid methyl ester (FAME) profile obtained reveals elevated content of oleic acid followed by palmitic acid, linoleic acid and stearic acid with improved oxidative stability related to biodiesel quality.

This paper presents the technical–economic and environmental assessment of four lignin extraction processes from two different raw materials (sugarcane bagasse and rice husks). The processes are divided into two categories, the first processes evaluates lignin extraction with prior acid hydrolysis step, while in the second case the extraction processes are evaluated standalone for a total analysis of 16 scenarios. Profitability indicators as the net present value (NPV) and environmental indicators as the potential environmental impact (PEI) are used through a process engineering approach to understand and select the best lignin extraction process. The results show that both economically and environmentally process with sulfites and soda from rice husk presents the best results; however the quality of lignin obtained with sulfites is not suitable for high value-added products. Then, the soda is an interesting option for the extraction of lignin if high quality lignin is required for high value-added products at low costs.

The aim of this work was to study the impact of shortening kraft pulping (KP) process integrated with extended oxygen delignification (OD) on the biorefinery process performance of eucalyptus. Data showed that using kraft pulps with high kappa number could improve the delignification efficiency of OD, reduce hexenuronic acid formation in kraft pulps. Pulp viscosity for a target kappa number of ∼10 was comparable to that obtained from conventional KP and OD process. The energy and alkali consumption in the integrated biorefinery process could be optimized when using a KP pulp with kappa number of ∼27. The process could minimize the overall methanol formation, but greater amounts of carbonate and oxalate were formed. The information from this study will be helpful to the future implementation of short-time KP integrated with extended OD process in actual pulp mill applications for biorefinery, aiming at further improvement in the biorefinery effectiveness of hardwood.

Mixed sludge from a pulp and paper mill was hydrothermally carbonized at 180–260 °C for 0.5–5 h with the use of HCl or NaOH for determining the effect of acid and base additions during sludge carbonization. Based on the results carbonization was mainly governed by dehydration, depolymerization and decarboxylation of sludge components. Additive type had a statistically significant effect on hydrochar carbon content and carbon and energy yield, of which especially energy yield increased through the use of HCl. The theoretical energy efficiencies of carbonization increased with decreasing reaction temperature, retention time and the use of HCl and suggested that the energy requirement could be covered by the energy content of attained hydrochar. The BOD5/COD-ratios of analyzed liquid samples indicated that the dissolved organic components could be treated by conventional biological methods.

A modified process consisting of an initial mechanical refining (R) followed by a low-alkali (5.5% NaOH) cold caustic extraction (CCE) and finally an endoglucanase (EG) treatment (R-5.5%CCE-EG) was investigated for upgrading paper-grade pulp to dissolving pulp. Results showed that compared to the conventional process (9%CCE-EG), the modified process can decrease the alkali concentration (from 9% to 5.5%) to achieve a similar hemicelluloses removal while simultaneously enhancing the Fock reactivity (from 62.2% to 81.0%). The improved results were due to the fact that the mechanical refining resulted in favorable fiber morphological changes, including increased pore volume/size, water retention value and specific surface area. Consequently, the hemicelluloses removal was enhanced even under the subsequent low-alkali CCE condition. A synergic effect of refining, low alkali concentration and enzymatic activation was responsible for the higher reactivity of resulting dissolving pulp.

Pulp and paper mill wastewater contains lignin related synthetic, aromatic and chlorinated chemical compounds. Extracting lignin from pulp and paper mill wastewater is one way of recovering valuable organic material. Due to its complex structure, lignin is difficult to break and provides economical and technical provocations in biomass recovery. The conventional wastewater treatment processes are seldom efficacious for the complete removal of lignin from paper mill effluents. A wide range of thermal, mechanical and physico-chemical methods have been reported for the removal of lignin. Moreover, biological method of lignin removal employed microorganisms including bacteria and fungi as a one-step treatment and/or amalgamation of various physico-chemical techniques. Compared with other methods, biological process for degradation of lignin is regarded as eco-friendly, cost-effective and sustainable. Therefore, this review will provide insight into the recent breakthroughs and future trends in lignin removal with special emphasis on biological treatment and scope of lignin utilization.

The process parameters for xylanase biobleaching of mixed hardwood pulp like, reaction time (6–35 h), pulp consistency (2.5–15%) and xylanase dose (5–35 U) were optimized using OFAT approach and hybrid statistical tools viz. GA-ANN and GA-ANFIS. The biobleaching ability of xylanase in terms of reducing sugar yield increased up to 28.16 mg g−1 (28.05%) than OFAT optimization (21.99 mg g−1 of pulp) after employing hybrid statistical tools. After TCF bleaching of xylanase treated pulp, we observed that lignin content reduced to 0.29% whereas it was still 0.41% in the untreated pulp. Moreover, the brightness level achieved up to 70.4% in xylanase treated pulp while it was only 53.60% in the chemically treated pulp. The kappa number for xylanase treated, chemically treated, and xylanase-chemical treated pulp was recorded 9.90, 7.10 and 4.70, respectively. The present study reports an improved eco-friendly biobleaching method using novel GA-ANN and GA-ANFIS hybrid statistical tools.

In this study we investigated the technical feasibility of convert paper mill sludge into fuel ethanol. This involved the removal of mineral fillers by using either chemical pretreatment or mechanical fractionation to determine their effects on cellulose hydrolysis and fermentation to ethanol. In addition, we studied the effect of cationic polyelectrolyte (as accelerant) addition and hydrogen peroxide pretreatment on enzymatic hydrolysis and fermentation. We present results showing that removing the fillers content (ash and calcium carbonate) from the paper mill sludge increases the enzymatic hydrolysis performance dramatically with higher cellulose conversion at faster rates. The addition of accelerant and hydrogen peroxide pretreatment further improved the hydrolysis yields by 16% and 25% (g glucose / g cellulose), respectively with the de-ashed sludge. The fermentation process of produced sugars achieved up to 95% of the maximum theoretical ethanol yield and higher ethanol productivities within 9h of fermentation.

For enzymatic treatment of dissolving pulp, there is a need to improve the process to facilitate its commercialization. For this purpose, the high consistency cellulase treatment was conducted based on the hypothesis that a high cellulose concentration would favor the interactions of cellulase and cellulose, thus improves the cellulase efficiency while decreasing the water usage. The results showed that compared with a low consistency of 3%, the high consistency of 20% led to 24% increases of cellulase adsorption ratio. As a result, the viscosity decrease and Fock reactivity increase at consistency of 20% were enhanced from 510 mL/g and 70.3% to 471 mL/g and 77.6%, respectively, compared with low consistency of 3% at 24h. The results on other properties such as alpha cellulose, alkali solubility and molecular weight distribution also supported the conclusion that a high consistency of cellulase treatment was more effective than a low pulp consistency process.

The aim of the study was to grow microalgae on mixed municipal and industrial wastewater to simultaneously treat the wastewater and produce biomass and lipids. All algal strains grew in all wastewater mixtures; however, Selenastrum minutum had the highest biomass and lipids yields, up to 37% of the dry matter. Nitrogen and phosphorus removal were high and followed a similar trend in all three strains. Ammonium was reduced from 96% to 99%; this reduction was due to algal growth and not to stripping to the atmosphere, as confirmed by the amount of nitrogen in the dry algal biomass. Phosphate was reduced from 91% to 99%. In all strains used the lipid content was negatively correlated to the nitrogen concentration in the algal biomass. Mixtures of pulp and paper wastewater with municipal and dairy wastewater have great potential to grow algae for biomass and lipid production together with effective wastewater treatment.

This study investigated the autohydrolysis pre-treatment prior to chemi-thermomechanical pulping (CTMP) process including the effects of autohydrolysis pretreatment with a lower severity on characteristics of the autohydrolysis liquor and hydrolyzed chips. The intensity of autohydrolysis, characterized by the severity factor, increased from 1.76 to 3.54, the hydrolyzed chips yield decreased from 99.0% to 86.7% and the xylose extraction yield increased from 0.8% to 44.0%. The content of holocellulose, pentosan and acid soluble lignin remained in the hydrolyzed chips decreased dramatically with increasing the treatment severity. After the autohydrolysis pretreatment, the resultant poplar chemi-thermomechanical pulp with a severity factor of 2.37 could obtain a 15.3 Nm/g tensile index, 58.6% ISO brightness and a 2.39 cm(3)/g bulk.

In this work, corn stover was refined by a pulp refining instrument (PFI refiner) after NaOH pretreatment under varied conditions. The quantitative characterization of the influence of PFI refining on enzymatic hydrolysis was studied, and it was proved that the enhancement of enzymatic saccharification by PFI refining of the pretreated corn stover was largely due to the significant increment of porosity of substrates and the reduction of cellulose crystallinity. Furthermore, a linear relationship between beating degree and final total sugar yields was found, and a simple way to predict the final total sugar yields by easily testing the beating degree of PFI refined corn stover was established. Therefore, this paper provided the possibility and feasibility for easily monitoring the fermentable sugar production by the simple test of beating degree, and this will be of significant importance for the monitoring and controlling of industrial production in the future.

The effects of lime mud from papermaking process (LMP) addition as buffer agent and inorganic nutrient on the anaerobic digestion stability of food waste (FW) were investigated under mesophilic conditions with the aim of avoiding volatile fatty acids accumulation, and inorganic elements deficiency. When LMP concentration ranged from 6.0 to 10g/L, the FW anaerobic digestion could maintain efficient and stable state. These advantages are attributed to the existence of Ca, Na, Mg, K, Fe, and alkaline substances that favor the methanogenic process. The highest CH4 yield of 272.8mL/g-VS was obtained at LMP and VS concentrations of 10.0 and 19.8g/L, respectively, with the corresponding lag-phase time of 3.84d and final pH of 8.4. The methanogens from residue digestates mainly consisted of Methanobrevibacter, coccus-type and sarcina-type methanogens with LMP addition compared to Methanobacteria in control. However, higher concentration of LMP inhibited methanogenic activities and methane production.

Mechanical refining has been shown to improve biomass enzymatic digestibility. In this study industrial high-yield sodium carbonate hardwood pulp was subjected to lab, pilot and industrial refining to determine if the mechanical refining improves the enzymatic hydrolysis sugar conversion efficiency differently at different refining scales. Lab, pilot and industrial refining increased the biomass digestibility for lignocellulosic biomass relative to the unrefined material. The sugar conversion was increased from 36% to 65% at 5 FPU/g of biomass with industrial refining at 67.0 kWh/t, which was more energy efficient than lab and pilot scale refining. There is a maximum in the sugar conversion with respect to the amount of refining energy. Water retention value is a good predictor of improvements in sugar conversion for a given fiber source and composition. Improvements in biomass digestibility with refining due to lab, pilot plant and industrial refining were similar with respect to water retention value.

The hemicelluloses fraction of black liquor is an underutilized resource in many chemical pulp mills. It is possible to extract and separate the lignin and hemicelluloses from the black liquor and use the hemicelluloses for biochemical conversion into biofuels and chemicals. Precipitation of the lignin from the black liquor would consequently decrease the thermal load on the recovery boiler, which is often referred to as a bottleneck for increased pulp production. The objective of this work is to techno-economically evaluate the production of sodium-free lignin as a solid fuel and butanol to be used as fossil gasoline replacement by fractionating black liquor. The hydrolysis and fermentation processes are modeled in Aspen Plus to analyze energy and material balances as well as to evaluate the plant economics. A mathematical model of an existing pulp and paper mill is used to analyze the effects on the energy performance of the mill subprocesses.

This work describes the production of alternative adsorbents from industrial residues and their application for the removal of a highly consumed antidepressant (citalopram) from water. The adsorbents were produced by pyrolysis of both primary and biological paper mill sludge at different temperatures and residence times. The original sludge and the produced chars were fully characterized by elemental and proximate analyses, total organic carbon, specific surface area (BET), N-2 isotherms, FTIR, C-13 and H-1 solid state NMR and SEM. Batch kinetic and equilibrium experiments were carried out to describe the adsorption of citalopram onto the produced materials. The fastest kinetics and the highest adsorption capacity were obtained using primary sludge pyrolysed at 800 degrees C during 150 min. The use of pyrolysed paper mill sludge for the remediation of contaminated waters might constitute an interesting application for the valorization of those wastes. (C) 2014 Elsevier Ltd. All rights reserved.

Fibres fractionated from solid recovered fuel (SRF), a standardised market combustion fuel produced from sorted waste, were considered as a source of lignocellulosic fermentable sugars. The fibre yield from four samples of SRF was 25-45%, and the separated material consisted of 52-54% carbohydrates, mainly glucan, with a high content of ash (12-17%). The enzymatic digestibility of recovered fibres was studied at low and high solids loading and compared with model substrates containing only chemical and mechanical pulps. Above 80% hydrolysis yield was reached at 20% solids loading in 48. h, but variation was observed between different samples of recovered fibres. Surfactants were found to improve the hydrolysis yield of recovered fibres especially in tumbling-type of mixing at low solids loading, where hydrolysis was found to stagnate without surfactants. The results suggest that SRF is a potential source of easily digestible lignocellulosic carbohydrates for use in biorefineries.

The possibility of introducing the thermo-alkali hydrolysis of Waste-Activated Sludge (WAS) was investigated, in order to enable the use of its solid residue as a raw material in cardboard production and the use of its liquid portion for anaerobic digestion in an UASB reactor. The evaluation of the hydrolysis at pH > 12 and T = 70 °C showed that the microbe cells were disrupted with more than 90% efficiency in less than 2 h. The solid portion was hygienised, therefore making it possible to integrate it into the cardboard production as a raw material for less demanding cardboards. Up to 6% addition of the liquid portion of hydrolysed WAS to wastewater decreased the specific biogas production in a pilot-scale UASB from 0.236 to 0.212 m3/kgCOD, while the efficiency of the COD removal decreased from 80.4% to 76.5%. These values still guarantee an adequate treatment of the wastewater and an increased biogas production by 16%.

Enzymatic hydrolysis of waste paper is becoming a perspective way to obtain raw material for production of liquid biofuels. Reducing sugars solutions that arise from the process of saccharification are a precursors for following or simultaneous fermentation to ethanol. Different types of waste paper were evaluated, in terms of composition and usability, in order to select the appropriate type of the waste paper for the enzymatic hydrolysis process. Novozymes® enzymes NS50013 and NS50010 were used in a laboratory scale trials. Technological conditions, which seem to be the most suitable for hydrolysis after testing on cellulose pulp and filter paper, were applied to hydrolysis of widely available waste papers - offset paper, cardboard, recycled paper in two qualities, matte MYsol offset paper and for comparison again on model materials. The highest yields were achieved for the cardboard, which was further tested using various pretreatment combinations in purpose of increasing the hydrolysis yields.

This paper describes a new option for integrated recovery and esterification of carboxylates produced by anaerobic digestion at a pH above the pKa. The carboxylates (acetate, propionate, butyrate, valerate and lactate) are recovered using a strong anion exchange resin in the bicarbonate form, and the resin is regenerated using a CO2-expanded alcohol technique, which allows for low chemicals consumption and direct esterification. Paper mill wastewater was used to study the effect of pH and the presence of other inorganic anions and cations on the adsorption and desorption with CO2-expanded methanol. Calcium, which is present in paper mill wastewater, can cause precipitation problems, especially at high pH. Esters yields ranged from 1.08±0.04mol methyl acetate/mol of acetatein to 0.57±0.02mol methyl valerate/mol of valeratein.

Toilet-paper cellulose with rich but refractory carbon sources, are the main insoluble COD fractions in sewage. An anaerobic membrane bioreactor (AnMBR) was configured for sewage treatment at room temperature and its performance on methanogenic degradation of toilet paper was highlighted. The results showed, high organic removal (95%), high methane conversion (90%) and low sludge yield (0.08gVSS/gCOD) were achieved in the AnMBR. Toilet-paper cellulose was fully biodegraded without accumulation in the mixed liquor and membrane cake layer. Bioconversion efficiency of toilet paper approached 100% under a high organic loading rate (OLR) of 2.02gCOD/L/d and it could provide around 26% of total methane generation at most of OLRs. Long sludge retention time and co-digestion of insoluble/soluble COD fractions achieving mutualism of functional microorganisms, contributed to biodegradation of toilet-paper cellulose. Therefore the AnMBR successfully implemented simultaneously methanogenic bioconversion of toilet-paper cellulose and soluble COD in sewage at room temperature.

This study is focused on defunctionalizing monomeric phenolics from lignin into simple phenols for applications such as phenol/formaldehyde resins, epoxidized novolacs, adhesives and binders. Towards this goal, Titanium dioxide (TiO2) was used to selectively remove hydroxyl, methoxy, carbonyl and carboxyl functionalities from the monomeric phenolic compounds from lignin to produce mainly phenol, cresols and xylenols. The results showed that anatase TiO2 was more selective and active compared to rutile TiO2. Catechols were found to be the most reactive phenolics and 4-ethylguaiacol the least reactive with anatase TiO2. An overall conversion of about 87% of the phenolics was achieved at 550°C with a catalyst-to-feed ratio of 5 w/w. Over 97% conversion of phenolics is achievable at moderate temperatures (550°C or ≤ 600°C) and a moderate catalyst-to-feed ratio of 6.5:1. The reactivity of catechols on TiO2 suggests that titania is a promising catalyst in the removal of hydroxyl moiety.

Economic feasibility of steam explosion pretreatment for improvement of biogas production from wheat straw and paper tube residuals was investigated. The process was simulated by Aspen plus ®, and the economical feasibility of five different plant capacities was studied by Aspen Process Economic Analyzer. Total project investment of a plant using paper tube residuals or wheat straw was 63.9 or 61.8 million Euros, respectively. The manufacturing cost of raw biogas for these two feedstocks was calculated to 0.36 or 0.48 €/m(3) of methane, respectively. Applying steam explosion pretreatment resulted in 13% higher total capital investment while significantly improved the economy of the biogas plant and decreased the manufacturing cost of methane by 36%. The sensitivity analysis showed that 5% improvement in the methane yield and 20% decrease in the raw material price resulted in 5.5% and 8% decrease in the manufacturing cost of methane, respectively.

Simultaneously ultrasonic wave and microwave assisted technique (SUMAT), as a method of process intensification, was first applied to the preparation of nanocellulose whiskers (NCWs) from filter paper by sulfuric acid hydrolysis. The effects of temperature, sulfuric acid concentration, and mass of raw material and time on the yield of NCWs were investigated by single-factor experiments, and the preparation conditions were optimized with response surface methodology. The obtained NCWs were characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and thermal gravimetry. The results showed NCWs were facilely prepared by using SUMAT. However, some harsh reaction conditions such as high temperature, strong acidity and long time treatment easily induced the reduction of the yield of NCWs. Under the optimal conditions, the yield and the crystallinity of NCWs with the crystal form of cellulose Iα is 85.75% and 80%, respectively.

A bench scale biofilter packed with compost and wood chips seeded with potential DMS degrading culture (Bacillus sphaericus) could efficiently remove DMS from ambient air with removal efficiency (RE%) of 71 ± 11 at an effective bed contact time (EBCT) of 360 ± 20 s with loading rate in the range of 4–28 gDMS/m3/h. Further, the same biofilter operated for the treatment of vent gas generated from a P&P industry indicated DMS removal of 61 ± 18% at optimal EBCT of 360 ± 25 s with a loading rate in the range of 3–128 gDMS/m3/h.

A new approach for the hydrophobization of finished cellulosic substrates based on a previously reported enzymatic technique is proposed. Commercial finished paper was hydrophobized by using laccase from Trametes villosa in combination with lauryl gallate (LG) as hydrophobic compound. The efficiency of the method was increased by the use of a lignosulfonate as a natural dispersant to improve the surface distribution of LG on the paper, raise its hydrophobicity and help preserve the enzyme activity. No similar threefold effect from a single compound for the improvement of enzymatic treatments was previously reported. The influence of processing conditions including the LG dose, treatment time and temperature was also examined, resulting in further increased hydrophobicity. Efficient fiber bonding and chemical functionalization were confirmed by thorough washing and Soxhlet extraction of the paper. As shown here for the first time, enzyme treatments have the potential to improve the surface hydrophobicity of paper-based media.

Imidazolium-based ionic liquids (ILs), including 1-butyl-3-methylimidazolium chloride (BmimCl) and 1-allyl-3-methylimidazolium chloride (AmimCl), were used to improve the refining properties of pulps under mild conditions. Results showed that the macro appearance of pulps was virtually unchanged after pretreatment with ILs under mild conditions. In addition, chemical pulps pretreated with ILs are more suitable for pretreatment than chemimechanical pulps. Pretreatment with ILs facilitates the refining process by destroying hydrogen bonds, which exist extensively in fiber. At the same refining energy input, the Canada standard freeness (CSF) of refined pulp decreased with improved fiber quality. At identical CSF values, the energy consumed during refining significantly decreased because ILs pretreatment facilitated swelling and fibrillation. The viscosity of cellulose changed slightly after IL pretreatment. However, the crystallinity index and fines content decreased, and the micro appearance of the fiber surface changed. BmimCl has a stronger swelling influence on pulp than AmimCl under optimal conditions.

Aim of the study was to investigate how hydrothermal carbonization changes adsorption efficiency toward metal ions of typical sludges. Hydrothermal carbonization is a novel and green method of treating biomasses. Reactions take place in an aqueous environment at relatively mild temperature and high pressure resulting a different end biomass structure than obtained from traditional pyrolysis. Anaerobically digested sludge (ADS) and pulp and paper industry sludge (INS) were utilized as a feedstock. Adsorption behavior of ADS and INS was examined towards Pb(II), Cr(III), Cr(VI), As(III) and As(V). Both ADS and INS were found to remove Pb(II) effectively and followed Sips adsorption isotherm. Adsorption kinetics was fast and followed pseudo-second order model. Furthermore, intraparticle diffusion was observed to be partly responsible in the adsorption process. Hydrothermal carbonization indicated high potential for the production of novel carbonaceous materials for metal removal from waters.

Structural characteristics of benzene-ethanol-extracted lignin (BEL) and acetone-extracted lignin (AL) precipitated from black liquor were identified by elemental analysis, FTIR, (13)C NMR, and (1)H NMR, while the thermal behaviors were examined with thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR). The frequency of β-O-4 bonds per 100 C9 monomeric units was 28 and 17 for BEL and AL. Two-stage pyrolysis processes were observed for the two lignins. The mass loss rate of the initial solvent evolution stage (110-180 °C) of BEL was greater than that of AL. The two lignins presented slightly different mass loss curves and evolution profiles of gases in the main pyrolysis stage (280-500 °C). A global kinetic model was proposed for lignin pyrolysis and activation energies of 39.5 and 38.8 kJ/mol was obtained for BEL and AL. The results enhance understanding of lignin pyrolysis and facilitate commercial utilization of black-liquor lignin.

Black liquor from the kraft process facilitates quantitative biomass hydrolysis converting cellulose and hemicellulose into organic acids such as lactic acid (~50%), and lignin into small molecular aromatics, without gasification and black tar formation. Oxygen transfer between lignin and carbohydrates may be the mechanism. With this method, three tons of lignocellulosic biomass can potentially produce up to one ton of lactic acid, and one ton of small molecular aromatics. This novel usage of black liquor is environmentally viable because it is accompanied by significant emission reduction of particulates, sulfur and nitrogen oxides, most organic sulfur compounds and sulfites of black liquor were converted into sulfates.

Vermistabilization of paper mill wastewater sludge (PMS) spiked with cow dung (CD) at ratios of 0%, 25%, 50%, 75%, and 100% was carried out employing the earthworm, Eisenia fetida. A total of five treatments were established and changes in chemical and microbial properties of mixtures were observed. Vermistabilization caused decreases in total organic carbon, C:N ratio and cellulose by 1.2-1.5, 4.6-14.6, and 2.3-9.7-fold, respectively, but increases in pH, electrical conductivity, ash content, (tot)N, (avail)P, (tot)P, (exch)K, Ca, Na, and N-NO(3)(-) of 1.06-1.11, 1.2-1.6, 1.3-1.6, 3.8-11.5, 4.1-6.5, 5.7-10.3, 1.7-2.0, 1.16-1.24, 1.23-1.45, 4.2-13.4-folds, respectively. PMS with 25-50% of CD showed the maximum mineralization rate. The fungal, bacterial and actinomycetes population increased 2.5-3.71, 3.13-8.96, and 5.71-9.48-fold, respectively after vermistabilization. The high level of plant-available nutrients indicates the suitability of vermistabilized material for agronomic uses.

The feasibility of anaerobic treatment of methanol condensate from pulp and paper mill in UASB reactor was investigated and compared with the anaerobic treatment of methanol. The UASB reactor treating methanol condensate was operated for 480 days with minimum problems of overload. COD removal from methanol condensate and methanol under normal operating conditions ranged from 84-86% to 86-98%, respectively. Under optimal conditions (OLR=5.0 g COD L(-1)day(-1), COD(influent)=11.40 g L(-1)) a methane yield of 0.29 NL CH(4) per g COD(removed) (at standard temperature and pressure) was achieved during the treatment of methanol condensate. The recovery time of the microorganisms after several overloads was decreasing each time probably due to the adaptation to methanol condensate. These findings indicate that methanol condensate can be efficiently treated in a UASB reactor with the benefit of biogas production. As a bonus effect of the treatment, much of the smell of the feed was eliminated.

Eucalyptus globulus sapwood and heartwood showed no differences in lignin content (23.0% vs. 23.7%) and composition: syringyl-lignin (17.9% vs. 18.0%) and guaiacyl-lignin (4.8% vs. 5.2%). Delignification kinetics of S- and G-units in heartwood and sapwood was investigated by Py-GC–MS/FID at 130, 150 and 170 °C and modeled as double first-order reactions. Reactivity differences between S and G-units were small during the main pulping phase and the higher reactivity of S over G units was better expressed in the later pulping stage. The residual lignin composition in pulps was different from wood or from samples in the initial delignification stages, with more G and H-units. S/G ratio ranged from 3 to 4.5 when pulp residual lignin was higher than 10%, decreasing rapidly to less than 1. The S/H was initially around 20 (until 15% residual lignin), decreasing to 4 when residual lignin was about 3%.

The feasibility of cellulase recycling in the scope of bioethanol production from recycled paper sludge (RPS), an inexpensive byproduct with around 39% of carbohydrates, is analyzed. RPS was easily converted and fermented by enzymes and cells, respectively. Final enzyme partition between solid and liquid phases was investigated, the solid-bound enzymes being efficiently recovered by alkaline washing. RPS hydrolysis and fermentation was conducted over four rounds, recycling the cellulases present in both fractions. A great overall enzyme stability was observed: 71, 64 and 100% of the initial Cel7A, Cel7B and -glucosidase activities, respectively, were recovered. Even with only 30% of fresh enzymes added on the subsequent rounds, solid conversions of 92, 83 and 71% were achieved for the round 2, 3 and 4, respectively. This strategy enabled an enzyme saving around 53-60%, while can equally contribute to a 40% reduction in RPS disposal costs., The authors acknowledge the financial support of the Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of UID/BIO/04469/2013 unit, COMPETE 2020 (POCI-01-0145-FEDER-006684) and the Project RECI/BBB-EBI/0179/2012 (FCOMP-01-0124-FEDER-027462). The financial support of FCT through GlycoCBMs Project PTDC/AGR-FOR/3090/2012–FCOMP-01-0124-FEDER-027948 and the PhD grant to DG (SFRH/BD/88623/2012) is equally acknowledged. The authors also thank RENOVA (Portugal) for kindly providing the recycled paper sludge.

A mixed culture of microalgae, containing two Scenedesmus species, was analysed to determine its potential in coupling of pulp and paper mill effluent treatment and microalgal cultivation. Laboratory studies suggested that 60% concentration of wastewater was optimum for microalgal cultivation. A maximum of 82% and 75% removal of BOD and COD respectively was achieved with microalgal cultivation in outdoor open pond. By the end of the cultivation period, 65% removal of NO3-N and 71.29% removal of PO4-P was observed. The fatty acid composition of mixed microalgal culture cultivated with effluent showed the palmitic acid, oleic acid, linoleic acid and α-linolenic acid as major fatty acids. The results obtained suggest that pulp and paper mill effluent could be used effectively for cultivation of microalgae to minimise the freshwater and nutrient requirements.

The conversion of paper-grade pulps into dissolving pulps requires efficient strategies and process steps to remove low-molecular noncellulosic macromolecules generally known as hemicelluloses. Current strategies include alkaline extractions and enzymatic treatments. This study focused on the evaluation of extraction efficiencies in alkaline extractions of three economically interesting hardwood species: beech (Fagus sylvatica), birch (Betula papyrifera), and eucalyptus (Eucalyptus globulus). Substrate pulps were subjected to alkaline treatments at different temperatures and alkalinities using white liquor as the alkali source, followed by analyses of both pulps and hemicellulose-containing extraction lyes. The extracted hardwood xylans have strong potential as an ingredient in the food and pharmaceutical industries. Subsequent analyses revealed strong dependencies of the extraction efficiencies and molar mass distributions of hemicelluloses on the process variables of temperature and effective alkalinity. The hemicellulose content of the initial pulps, the hardwood species, and the type of applied base played minor roles.

The bleached wheat straw pulp (BWSP) accounts for about 25% of the virgin fiber supply in the Chinese Pulp and Paper Industry. As a non-wood chemical pulp, BWSP is known to have low bulk, low light scattering coefficient and poor drainage due to its high content of parenchyma cells. In this study, a high-quality aspen high-yield pulp (HYP) was used to improve the BWSP properties at the laboratory scale. The results indicate that adding 5–20% aspen HYP into unrefined or refined BWSP can minimize many of the drawbacks associated with the BWSP: improving its drainage, bulk, light scattering coefficient and opacity. The addition of a small amount (up to 20%) of aspen HYP can also significantly increase the tear index of BWSP with only a slight decrease of the tensile index.

A microbial consortium MC1 was used to pretreat filter paper, office paper, newspaper, and cardboard to enhance methane production. The results of pretreatment indicated that sCOD of hydrolysates of the four substrates increased significantly in the early stage, and peaked on day 7. During pretreatment, ethanol, acetic acid, propionic acid, butyric acid, and glycerol were the predominant volatile organic products in hydrolysates. MC1 had strong degradation ability on the four substrates, and the weight loss of filter paper, office paper, newspaper, and cardboard reached 78.3%, 80.5%, 39.7%, and 49.7%, respectively. The results of anaerobic digestion showed that methane production yields and rates of the four substrates significantly increased after pretreatment. This study is the first attempt to explore the microbial pretreatment method for anaerobic digestion of waste paper and cardboard. Microbial consortium pretreatment could be an effective method for enhancing methane production of waste paper and cardboard into bioenergy.

The aim of the present work was to find a suitable Kraft cooking process for olive tree pruning (OTP), in order to produce pulp of kappa number about 17. The Kraft pulp produced under optimized conditions showed a viscosity of 31.5 mPa·s and good physical, mechanical, and optical properties, which are suitable for paper production. The physical-mechanical and optical properties were measured before and after bleaching. Although the OTP pulp was bleached to 90.9% ISO brightness (kappa1), the process demanded a long sequence of stages, OZQPOZQPO. The bleached pulp showed a brightness reversion equal to 1.3%. Furthermore, this bleached pulp did not need a high intensity of beating due to high drainability degree in the unbeaten pulp. So that, OTP is suggested as an interesting raw material for cellulosic pulp production because its properties are comparable to those of other agricultural residues, currently used in the paper industry.

The present work targeted the understanding of the influence of nine different hardwood species as feedstock on ethanol production yield and costs. It was found that the minimum ethanol revenue (MER) ($ per gallon to the producer) to achieve a 12% internal rate of return (IRR) on invested capital was smaller for low lignin content samples and the influence of species characteristics remained restricted to high residual lignin content. We show that if the pretreatment being applied to the feedstock targets or is limited to low lignin removal, one can expect the species to have a significant impact on overall economics, playing important role to project success. This study also showed a variation of up to 40% in relative MER among hardwood species, where maple, globulus and sweet gum varied the least. Sensitivity analysis showed ethanol yield per ton of feedstock had the largest influence in MER, followed by CAPEX.

A novel integrated thermophilic submerged aerobic membrane bioreactor (TSAMBR) and electrochemical oxidation (EO) technology was developed for thermomechanical pulping pressate treatment with the aim of system closure. The TSAMBR was able to achieve a chemical oxygen demand (COD) removal efficiency of 88.6 ± 1.9-92.3 ± 0.7% under the organic loading rate of 2.76 ± 0.13-3.98 ± 0.23 kg COD/(m(3) d). An optimal hydraulic retention time (HRT) of 1.1 ± 0.1d was identified for COD removal. Cake formation was identified as the dominant mechanism of membrane fouling. The EO of the TSAMBR permeate was performed using a Ti/SnO(2)-Sb(2)O(5)-IrO(2) electrode. After 6-h EO, a complete decolourization was achieved and the COD removal efficiency was increased to 96.2 ± 1.2-98.2 ± 0.3%. The high-quality effluent produced by the TSAMBR-EO system can be reused as process water for system closure in pulp and paper mill.

A process for removing inhibitors from pre-hydrolysis liquor (PHL) of a kraft-based dissolving pulp production process by adsorption and flocculation, and the characteristics of this process were studied. In this process, industrially produced PHL was treated with unmodified and oxidized activated carbon as an absorbent and polydiallyldimethylammonium chloride (PDADMAC) as a flocculant. The overall removal of lignin and furfural in the developed process was 83.3% and 100%, respectively, while that of hemicelluloses was 32.7%. These results confirmed that the developed process can remove inhibitors from PHL prior to producing value-added products, e.g. ethanol and xylitol via fermentation.

Nine phenol derivatives, p-coumaric acid (PC), vanillin (V), acetovanillone (AV), acetosyringone (AS), syringaldehyde (SA), coniferaldehyde (CLD), ferulic acid (FRC), sinapic acid (SNC), and sinapyl aldehyde (SLD) were assayed as laccase redox mediators in the biobleaching of kenaf and sisal pulps. As a general behaviour, the phenolic mediators increased the kappa number (KN) and reduced the brightness of pulps. In particular, these changes were found to depend in a linear manner on the energy of the highest occupied molecular orbital (EHOMO) of the mediators. The phenolic mediator with the lowest EHOMO (PC) led to the highest increase of KN and the lowest reduction of brightness. On the contrary, syringyl derivatives (i.e. SA) with high EHOMO values caused small KN increases and significant losses of brightness. This behaviour was explained on the basis of a competition between grafting and polymerisation processes. The former basically affects KN, whereas the latter affects pulp brightness.

Wood from the leguminous tree, Leucaena diversifolia , was subjected to hydrothermal treatment (autohydrolysis) at 160–180 °C for 0–30 min followed by ethanol–soda–anthraquinone delignification. The liquid phase contained 18.65 g of sugars per liter, and the solid phase had a gross heating value of 19.083 MJ/kg, but could also be used as a source of cellulose pulp for the production of paper with tear, burst, and tensile indexes of 2.4 N m 2 /kg, 2.6 MPa m 2 /kg and 40.7 kN m/kg, respectively. L. diversifolia lends itself readily to valorization for energy production, and also to integral, fractional exploitation by autohydrolysis and ethanol–soda–anthraquinone delignification, which can additionally bring environmental benefits to cropping zones.

Paper sludge (PS) from the paper and pulp industry consists primarily of cellulose and ash and has significant potential for ethanol production. Thirty-seven PS samples from 11 South African paper and pulp mills exhibited large variation in chemical composition and resulting ethanol production. Simultaneous saccharification and fermentation (SSF) of PS in fed-batch culture was investigated at high solid loadings and low enzyme dosages. Water holding capacity and viscosity of the PS influenced ethanol production at elevated solid loadings of PS. High viscosity of PS from virgin pulp mills restricted the solid loading to 18% (w/w) at an enzyme dosage of 20 FPU/gram dry PS (gdPS), whereas an optimal solid loading of 27% (w/w) was achieved with corrugated recycle mill PS at 11 FPU/gdPS. Ethanol concentration and yield of virgin pulp and corrugated recycle PS were 34.2g/L at 66.9% and 45.5 g/L at 78.2%, respectively.

Corn stalk pretreated with white-rot fungus Trametes hirsute was used to produce fiberboard by hot pressing without adhesive. The moduli of rupture and elasticity of the corn-stalk-based fiberboard were increased 3.40- and 8.87-fold when bio-pretreated rather than untreated corn stalk was used. Fourier transform infra-red spectroscopy, X-ray diffraction, and chemical analysis showed that bio-pretreated corn stalk increased the mechanical properties of the fiberboard because it had more than twice the number of hydroxyl group, an 18% higher crystallinity, and twice the polysaccharide content of untreated corn stalk. Its laccase content was 4.65 ± 0.38 U/g. Corn stalk-based fiberboard production did not require adhesives, thus eliminating a potential source of toxic emissions such as formaldehyde gas.

Thermogravimetric analyses (TGA) was applied to study the effects of enzymatic bleaching of eucalyptus pulp with xylanase and a laccase–mediator system. The thermal degradation profile of the pulps was sensitive to the enzymatic treatments. Xylanase treatment produced an ordered and clean microfibril, whereas laccase oxidized surface cellulose chains and increased the amorphous (paracrystalline) cellulose content. In this case, pulp viscosity decreased from 972 to 859 mL/g and apparent pulp crystallinity calculated from TGA data decreased almost 50%. Alkaline extraction was necessary to recover pulp crystallinity and to remove oxidized lignin in the laccase-treated samples. TGA data allowed differentiating and quantifying crystalline and amorphous cellulose. This thermogravimetric approach is a simple method in order to monitor superficial changes in cellulosic microfibrils.

Effects of temperature and temperature shock on the performance and microbial community structure of a submerged anaerobic membrane bioreactor (SAnMBR) treating thermomechanical pulping pressate were studied for 416 days. The results showed that the SAnMBR system were highly resilient to temperature variations in terms of chemical oxygen demand (COD) removal. The residual COD in treated effluent was slightly higher at 55 °C than that at 37 and 45 °C. There were no significant changes in biogas production rate and biogas composition. However, temperature shocks resulted in an increase in biogas production temporarily. The SAnMBR could tolerate the 5 and 10 °C temperature shocks at 37 °C and the temperature variations from 37 to 45 °C. The temperature shock of 5 and 10 °C at 45 °C led to slight and significant disturbance of the performance, respectively. Temperature affected the richness and diversity of microbial populations.