Fluctuations in wood chip properties in kraft pulp mills, which often follow seasonal patterns, can lead to changes or disruptions in the operation of the recovery cycle whereby the root causes are not immediately obvious. In some cases, these changes are attributed to operational adjustments in the digester or brownstock washing areas resulting from the variability in wood characteristics. Varying wood chip characteristics that have the most significant impact on the recovery cycle operation include the content of non-process elements (NPEs), extractives, and properties influenced by chip storage conditions. Elevated levels of NPEs, often associated with a higher influx of wood bark into the digester, can negatively affect the entire recovery cycle. Increased levels of chlorine and potassium can lead to severe fouling and corrosion in the recovery boiler. Higher concentrations of silicon, aluminum, phosphorus, magnesium and calcium in the chips may accelerate scaling in the evaporation plant, impair dregs and lime mud settling and filtering, reduce lime mud solids content and lime availability, and increase the amounts of dregs, grits, and purged lime mud. This technical review provides an overview of the most significant effects that changes in wood chip quality can potentially exert on various processes within the kraft recovery cycle. Application: This technical review presents insights into the associations between wood chip quality and recovery cycle operation, relationships that are often not immediately apparent. It may therefore assist mills aiming to identify the root cause(s) of process deterioration.
Studies on the impact of anaerobic digestion on biosludge dewatering are conflicting and mechanisms are poorly understood, with significant implications to both wastewater costs and environmental impact. To identify the mechanisms that improve dewaterability and to amplify the impacts of anaerobic digestion, biosludge was first sonicated to deteriorate dewaterability. Sonicated biosludge was next anaerobically digested under mesophilic conditions in three experiments, and the roles of extracellular polymeric substances (EPS) and supracolloidal particles on dewaterability were explored. Dewaterability, as measured by capillary suction time, improved with anaerobic digestion from 84.7 ± 11.3 s-L/g to 31.6 ± 3.2 s-L/g. The loosely-bound fraction of EPS saw only a minor decrease from 6.4 % ± 1.1 %-1.2 % ± 0.3 % and total EPS protein did not change significantly. On the other hand, in a separate experiment, significant removal of supracolloidal particles under 10 μm was observed within 6 days of anaerobic digestion, coinciding with an improvement in a capillary suction time from 116.0 ± 6.7 s-L/g to 69.8 ± 1.1 s-L/g and Crown Press filtrate total solids from 13.7 ± 0.2 g/L to 8.4 ± 0.5 g/L. In addition, in a third experiment, raw biosludge as well as sonicated at five different intensities, saw significantly faster capillary suction time and decreased Crown Press filtrate total solids which coincided with a decrease in the volume % of particles under 16 μm. The results suggest the net removal of small supracolloidal particles is a mechanism that occurs during anaerobic digestion to improve biosludge dewaterability.
Applying the optimal polymer dose to biosludge prior to dewatering can help minimize the economic and environmental costs of disposal. However, measuring the polymer demand is a time-intensive process for wastewater treatment plants, and biosludge characteristics vary over time. A novel, rapid image-based polymer demand estimation tool was developed by designing a simple and accessible image capture station and applying transfer learning of an open-source image classifier. Images were captured with a smartphone fixed in an enclosed structure above a biosludge sample dosed with polymer in a 150 mm petri dish. To facilitate collecting the required image database, the entire structure was fastened to an orbital shaker to intermittently apply shakesteps between image capturing that simulate replicates. Using TensorFlow in Python, image databases were constructed and used to retrain EfficientNetV2 to classify images of dosed biosludge as either underdosed, welldosed, and overdosed. Two image-based models were constructed, one for pulp and paper mill biosludge, and the other for municipal biosludge, which achieved 86 % and 83 % accuracy against an unseen set of images.
Municipal and industrial wastewater, along with organic waste, can be transformed into valuable bioproducts using purple phototrophic bacteria. This study compares the performance of three machine learning models (Random Forest, XGBoost, and CatBoost) in predicting and optimizing the formation of key bioproducts: polyhydroxybutyrate, polyhydroxyvalerate, 5-aminolevulinic acid, coenzyme Q10, carotenoids, bacteriochlorophylls, and biomass. The models were trained on a dataset compiled from previous studies, using input variables such as reaction time, concentration of organic matter, ethanol, bicarbonate, levulinic acid, ferric citrate, mineral medium, and N, C/N ratio, illumination conditions (continuous or intermittent), operation mode (batch or semicontinuous), and volume exchange percentage. Bayesian optimization was applied to train and tune the models. Performance was assessed using R2, Pearson correlation, RMSE, and MAPE. CatBoost outperformed the others, showing higher predictive correlation and lower error. It was subsequently used for further optimization. Feature importance analysis identified reaction time, mineral medium concentration, and volume exchange percentage as key drivers of bioproduct synthesis. The Particle Swarm Optimization algorithm was applied to determine optimal conditions for each target compound. Under the conditions studied, predicted maximum yields were: 569 mg polyhydroxybutyrate/L, 45 mg polyhydroxyvalerate/L, 79 µmol 5-aminolevulinic acid/L, 13 mg coenzyme Q10/g dw, 7 mg carotenoids/g dw, 17 mg bacteriochlorophylls/g dw, and 2040 mg biomass/L. Optimization suggests that operating as a sequencing batch reactor and employing discontinuous illumination for most targets, along with a reduced mineral medium concentration, is beneficial. Results highlight that each bioproduct requires distinct operational settings, supporting the idea of clustering target compounds.
We present a dataset of six metagenomes and 323 metagenome assembled genomes (MAGs) describing the microbial community of anaerobic digesters at three Canadian pulp and paper mills. Our objective was to assess the coding potential of the microbial community and obtain draft genomes of key organisms in the digesters.
Amplicon sequencing data and operating data from anaerobic wastewater treatment plants from three Canadian pulp and paper mills were explored using correlation and network modularization approaches to study the microbial community organization and identify relationships between organisms and operating conditions. Each of the digesters contains two or three modules, or functional units, consisting of organisms that cover all trophic stages of anaerobic digestion. The modules function independently from each other, and their relative abundance changes in response to changing operating conditions. The modules show antagonistic responses, with one module associated with stable operation and another module linked to periods of environmental stress. Operating parameters correlated to module abundance include sulfide concentration in the digester influent and biogas sulfide flow rate as well as anaerobic treatment performance metrics such as COD removal efficiency and volatile fatty acid-to-alkalinity ratio. Elevated sulfide levels notably impact the microbial community composition and the anaerobic treatment performance and seem to be the primary driver of process inhibition. The time delay between a change in digester operation and a change in the abundance of microorganisms was investigated using time-lagged operating parameters. This time delay ranged between 2 and 4 days and is likely influenced by the growth rates of the anaerobic microorganisms and the digester hydraulic retention time. The application of lagged parameters appeared to be necessary for identifying numerous correlations that would otherwise have remained undetected. This is because correlations with operating parameters without a time lag tend to be smaller and are often not significant. Digester upsets due to plant shutdown periods and organic overload caused a drastic increase in acetoclastic methanogenesis and the population of acidogenic fermenters and syntrophic acid degraders. In response to impaired process conditions, the same Methanothrix amplicon sequence variants (ASVs) dominated methanogenesis in the digesters of all three mills, with its maximum relative abundance within the archaeal population reaching 68 at mill A, 58 at mill B, and 27% at mill C. The common characteristics of the organisms represented by this ASV should be further investigated for their role in alleviating the impact of digester upset conditions. Across all three mills, biogas production predominantly relied on acetoclastic methanogenesis. Methanothrix were the most abundant methanogenic ASVs, accounting for on average 63% of all archaea in mill A, 52% in mill B, and 73% in mill C over the investigation period. Also, each reactor contained at least three ASVs of high abundance from the archaeal class Bathyarchaeia. The presence of Bathyarchaeia, ranging from 10 to 20% of the total archaeal community in all digesters, may be associated with the higher lignin content present in the mill wastewater.
The archaeal class Bathyarchaeia is widely and abundantly distributed in anoxic habitats. Metagenomic studies have suggested that they are mixotrophic, capable of CO2 fixation and heterotrophic growth, and involved in acetogenesis and lignin degradation. We analyzed 35 Bathyarchaeia metagenome-assembled genomes (MAGs), including the first complete circularized MAG (cMAG) of the Bathy-6 subgroup, from the metagenomes of three full-scale pulp and paper mill anaerobic digesters and three laboratory methanogenic enrichment cultures maintained on pre-treated poplar. Thirty-three MAGs belong to the Bathy-6, lineage while two are from the Bathy-8 lineage. In our previous analysis of the microbial community in the pulp mill digesters, Bathyarchaeia were abundant and positively correlated to hydrogenotrophic and methylotrophic methanogenesis. Several factors likely contribute to the success of the Bathy-6 lineage compared to Bathy-8 in the reactors. The Bathy-6 genomes are larger than those of Bathy-8 and have more genes involved in lignocellulose degradation, including carbohydrate-active enzymes not present in the Bathy-8. Bathy-6 also shares the Bathyarchaeal O-demethylase system recently identified in Bathy-8. All the Bathy-6 MAGs had numerous membrane-associated pyrroloquinoline quinone-domain proteins that we suggest are involved in lignin modification or degradation, together with Radical-S-adenosylmethionine (SAM) and Rieske domain proteins, and AA2, AA3, and AA6-family oxidoreductases. We also identified a complete B12 synthesis pathway and a complete nitrogenase gene locus. Finally, comparative genomic analyses revealed that Bathyarchaeia genomes are dynamic and have interacted with other organisms in their environments through gene transfer to expand their gene repertoire.
In kraft pulp mills, foul condensates are often steam-stripped to produce clean condensate for use as process water. The formation of organic deposits in the stripped condensate is a common problem. A systematic study was conducted to examine the deposit composition and the most likely operating parameters responsible for stripped condensate contamination experienced at a kraft mill in Brazil. Daily averaged data of 170 operating parameters over a 15-month period were analyzed by means of multivariate discriminant analysis and random forest classification analysis. The results showed that the deposit formation is related to high temperature, pressure, and dry solids operations in various evaporator effects. These conditions, combined with the poor demisting efficiency in these effects, may have increased black liquor carryover mist in the vapor. Deposit formation also appeared to be related to increased throughput of the foul condensate stripping system and increased pressure in the stripper. Results of Fourier transform infrared spectroscopy (FTIR) and pyrolysis-gas chromatography mass spectrometry (Py-GCMS) analyses show that the deposit consists of mostly organic matter that likely originated from wood extractives and lignin.
In pulp and paper mills, effective biosludge dewatering is essential in wastewater treatment to reduce the large volume of biosludge that needs to be treated and disposed. The dewatering process normally requires the use of polymers from petroleum-based sources. This study explores the potential of using cationic proteins such as protamine for biosludge dewatering through dual conditioning with a small amount of a synthetic anionic polymer such as anionic polyacrylamide (APAM). The results show that dual conditioning provides substantial synergistic enhancements in dewatering. The maximum cake solids content of biosludge achieved by adding protamine (7.5%) alone was 12%. By dual conditioning with a small amount of APAM (0.1%), not only the cake solids content was increased to 16%, but also the amount of protamine addition was substantially lowered to 2%. These results, coupled with the change in zeta potential of the particles in the biosludge samples, suggest that the cationic protamine reduced the negative charge of the particles, allowing smaller particles to agglomerate and providing a positively charged framework for the subsequent addition of the negatively charged APAM. After adding APAM, substantial floc-bridging occurred, allowing smaller flocs to aggregate into larger flocs. These synergistic effects can lower the wastewater treatment cost by reducing the amount of synthetic polymer and by applying low-value proteins from natural sources.
Kraft pulp mills produce on average about 100 kg of solid residuals per metric ton of pulp produced. The main types of mill waste are sludge from wastewater treatment plants, ash from hog fuel boilers, dregs, grits, and lime mud from causticizing plants and lime dust from lime kilns. Of these, about half is disposed of in landfills, which highlights the need and potential for waste recycling and utilization. Sludge is either incinerated in hog fuel boilers to generate steam and power or used in various forms of land application, including land spreading, composting, or as an additive for landfill or mine waste covers. The majority of hog fuel boiler ash and causticizing plant residues is landfilled. Alkaline residuals can be conditioned for use in land application, manufacture of construction materials, and production of aggregates for road work. This technical review summarizes residuals utilization methods that have been applied in pulp and paper mills at demonstration- or full-scale, and therefore may act as a guide for mill managers and operators whose goal is to diminish the costs and the environmental impact of waste management.
In the wastewater treatment plant of pulp and paper mills, biosludge dewatering is needed to reduce the sludge handling and disposal costs. It is usually facilitated by means of the addition of synthetic polymers. There is increasing interest in replacing synthetic polymers with biopolymers derived from low value by-products or industrial residuals to improve the environmental footprint of dewatering. In this study, lignin-based flocculants (LBF) were tested for their ability to improve the biosludge dewaterability based on Capillary Suction Time (CST) and dry cake solids achieved with a Crown Press. The results demonstrate that LBFs alone can significantly enhance dewatering with a decrease in CSTs from 72.7 ± 5.1 s (unconditioned biosludge) to 23.3 ± 0.4 s and an increase in dry cake solids after pressing from 7.1 ± 0.5% to 13.9 ± 1.3% with a relatively high dosage of 7.5% w/w. However, with dual conditioning a LBF and 0.1% w/w anionic polyacrylamide (APAM), the required dosage of LBF was reduced to 3% w/w to achieve a dry cake solids content of 13.8 ± 0.4%, the same as that achieved with Zetag8165, a commercial synthetic polymer. LBF addition lowered the particle surface charge, allowing the particles to agglomerate and enhancing for the biosludge dewaterability. The application of LBFs for sludge dewatering offers novel considerable promise for providing more sustainable approaches by optimizing the use of lignin from different extraction processes, applying various types of lignin modifications in combination with anionic polymers, and exploring different methods of disposal or utilization of the dewatered sludge.
Sludges from pulp and paper mills represent a major ecological and environmental cost, and anaerobic digestion represents a method of waste reduction and energy recovery for these mills. This study compared methane production potential and microbial communities across 11 primary- and biosludges from five pulp and paper mills using various mill processes. We measured methane production from sludges in anaerobic batch reactor experiments over 64 days. Sludges were incubated with and without added substrate to test for organic substrate limitation versus inhibition of methanogens. Initial microbial communities and changes to community composition were determined using Illumina MiSeq for metabarcoding of bacterial and archaeal 16S rRNA genes. Mean methane production potential varied greatly between sludges (0.002-79 mL CH4 g-1 TS). Among primary sludges, kraft mill sludge produced more methane than other mill types. For these other mills, biosludge produced more methane than primary sludge, which had evidence of methanogen inhibition. Microbial communities and diversity were influenced by the initial community composition, and high methane production was only seen in sludges with high diversity. A number of sludges innately produced substantial methane and may be targets for further modelling and larger scale testing of anaerobic digestion.
A study was conducted to examine the most likely parameters responsible for poor dregs settling at a kraft mill over a 2.5-year period, using multivariate data analysis (MVDA) and machine learning (ML) techniques. The dregs settling behavior seems to be seasonally influenced, implying that wood quality variation can be a factor. The results from the MVDA/ML analysis show that poor dregs settling is correlated to incomplete combustion and/or low load conditions in the recovery boiler, low sulfidity in the causticizing plant, and high flow in the green liquor–weak wash cycle. Compositions of dregs and black liquor were also examined to identify correlations with impaired dregs settling. The results show that poor dregs settling strongly correlates with high silicon (Si) content in dregs and moderately correlates with high iron (Fe) and high aluminum (Al) contents, and with low bulk density in dregs. For mills that experience dregs settling or green liquor filtering issues, regular compositional analyses of dregs, green liquor, weak wash, and black liquor are recommended in order to monitor the dynamics of silicon and other constituents in the recovery cycle.
A multivariate data analysis (MVDA) was conducted to identify operating parameters that affect the sludge dewatering efficiency in a Canadian pulp and paper mill. The sludge is a mixture of waste activated sludge (WAS) and three different types of primary sludge. The dewatering efficiency was defined by three target parameters: the cake solids content after dewatering, the solids capture efficiency, and the costs of dewatering aids (chemicals) used per ton of dewatered sludge solids. The results show that the most influential parameters affecting the dewatering efficiency are 1) the type and amount of primary sludge added to the sludge mix, 2) the operating parameters of the dewatering equipment and 3) the sludge solids throughput. A high proportion of fiber-rich primary sludge in the sludge mix substantially enhances dewaterability. Operating the screw press at a low torque and/or at a high screw press speed lowers the dewatering performance. The pH adjustment of the sludge prior to dewatering also significantly affects dewaterability. The effectiveness of the dewatering aids decreases notably when the pH is not within the target range. Besides the processes in the dewatering plant, the activated sludge process and the associated amount and quality of the WAS also affect the dewaterability of the sludge mix. In particular, the dewatering efficiency seems to be seasonal. The higher temperature during the summer produces less WAS, and thus increasing the proportion of primary sludge in the sludge mix and improving dewaterability. Also, WAS with high microbial activity and firm flocs, as well as a low sludge volume index enhances dewaterability.
Full-scale anaerobic digestion processes for organic solid waste are common in Europe but are generally unaffordable in Canada and the United States because of inadequate regulations to restrict cheaper forms of disposal, particularly landfill. We investigated the viability of solid-state anaerobic digestion (SS-AD) as an alternative that reduces the costs of waste pretreatment and subsequent wastewater treatment. A laboratory SS-AD digester, comprising six 10 L leach beds and an upflow anaerobic sludge blanket reactor treating the leachate, was operated continuously for 88 weeks, with a mass balance based on chemical oxygen demand (COD) of 100 ± 2% (CODout/CODin). The feed was a mixture of fibers (cardboard, boxboard, newsprint, and fine paper) with varying amounts of food waste added. The process remained stable throughout. The addition of food waste caused a synergistic effect, raising methane production from the fiber mixture from a low of 52.7 L kg-1 COD fibersadded at no food waste, to 152 L kg-1 COD fibersadded at 29% food waste, an increase of 190%. Substrate COD destruction efficiency reached 65%, and the methane yield reached 225 L kg-1 CODadded at 29% food waste on a COD basis, with a solids retention time of 42 days. This performance was similar to that of a completely stirred tank reactor digesting similar wastes, but with much lower energy input. Multiple factors likely contributed to the enhanced fiber destruction, including the action of hydrolytic enzymes derived from fresh food waste and continuous leachate recirculation between leach beds of different ages.
Dewatering and handling of pulp and paper mill sludge is challenging and often comprises more than half of the overall wastewater treatment costs at a mill. Primary sludge is usually more dewaterable than biosludge (waste activated sludge), and the ratio between both types of sludge largely determines the dewaterability of the sludge mix. This study has quantified the benefits of adding primary sludge to biosludge to enhance the dewaterability in terms of cake solids and filtrate/pressate solids content. Furthermore, the effects of the particle size distribution and the monovalent to divalent cation ratio of the various types of sludge were investigated. Biosludge and three types of primary sludge from a Canadian pulp and paper mill were mixed at various ratios and tested for dewaterability using a Crown Press (R), a bench-scale device which simulates industrial belt press dewatering. Results show that after addition of primary sludge at up to 40% mass proportion (dry solids basis) the dewatered cake solids content increased substantially, from 10.4% to 18.7-19.9%, depending on the type of primary sludge added. Further addition of primary sludge led to comparably only small improvements. Primary sludge addition also resulted in decreased total suspended solids (TSS) concentrations in the combined gravity filtrate / Crown Press pressate. Primary sludge content of only 10% in the sludge mix was sufficient to decrease the TSS concentration from 1.8 g/L to 0.2 - 0.4 g/L. The study shows that only less than half of the sludge mix needs to consist of primary sludge, in order to achieve adequate dewaterability. This opens up the possibility of retaining more primary fiber within the pulping process, without compromising downstream sludge dewatering.
Anaerobic digestion of biosludge has not yet been implemented in pulp mills due to low biogas yields. Enzymatic pretreatment of biosludge has shown improvements in biogas yields but results are varied. A key limitation of previous studies is that they fail to consider the COD contribution from the enzyme solutions. The aim of this study was to systematically investigate the potential for enzymatic pretreatment on the anaerobic digestibility of pulp mill biosludge. Out of the six enzymes tested, four enhanced the anaerobic digestibility of biosludge. At the end of the BMP, a maximum improvement of 26% in biogas yield was observed with protease from B. licheniformis. There was no correlation between enzymatic activities on standard substrates and/or on biosludge and the effect of enzymes on biogas yields. Enzymes have potential for improving biosludge anaerobic digestibility but more research on optimal conditions and potential synergies with other pretreatment is needed.
Poor black liquor burning results in decreased steam production, increased TRS emissions, unstable lower furnace operation, and in severe cases, boiler blackouts. In this case study, an attempt was made to identify the most likely parameters responsible for sudden changes in black liquor burnability in a Canadian hardwood dissolving pulp mill. Multivariate data analysis methods were used to identify correlations between black liquor combustibility and pulping and recovery process parameters. Poor black liquor burning appeared to be strongly seasonal, with the greatest number of incidents taking place during spring. Analytical results and anecdotal evidence point to wood chip quality, and in particular chip pitch content, as factors affecting cooking and eventually black liquor combustion. Extended periods of poor liquor burning lead to higher variability in white liquor total titratable alkali and effective alkali and in most cases also lower sulphidity. These effects on white liquor quality may act as a self-reinforcing cycle, prolonging periods of impaired burning.
Dewatering of pulp and paper mill biosludge is challenging, and it can make up half of overall wastewater treatment costs. By harvesting energy provided by nature, freezing-thawing can notably alter the physical structure of sludge flocs, thereby influencing dewaterability and anaerobic digestibility. Samples of biosludge from three pulp and paper mills (sulfite, kraft, and semi-chemical pulping) as well as biosludge digestate (i.e., biosludge after anaerobic digestion) were subject to freeze-thaw treatment, and they were subsequently tested in terms of dewaterability by using a gravity filtration-crown press unit, and anaerobic digestibility by means of biochemical methane potential assays. Gravity filtrate from dewatering of freeze-thaw treated biosludge was also tested for anaerobic digestibility. Freeze-thaw treatment improved the dewaterability of biosludge mill samples to a larger extent than dewatering polymer. Treatment at -10 degrees C before dewatering increased the dry solid content of the dewatering cake from 13% to 21% (sulfite mill), from 7% to 26% (kraft mill), from 10% to 20% (digestate after 35 days of digestion), and from 17% to 23% (digestate after 60 days of digestion). Biosludge from the semi-chemical pulping mill was only dewaterable after freeze-thaw treatment, which enabled a final cake solid content of 45%. In contrast, the anaerobic digestibility of biosludge and digestate improved, if at all, only to a relatively small extent. A strong improvement in digestibility was only observed in the case of gravity filtrate from dewatering of freeze-thaw treated biosludge (sulfite mill), where the specific biogas yield increased from 111 to 310 mL/g chemical oxygen demand added. Visual inspection on untreated and freeze-thaw treated biosludge confirmed the assumption that the strong effect on dewaterability was caused by irreversible compaction and dehydration of sludge particles. Evidence for widespread rupture of bacterial cells was not confirmed, which may explain the comparably small effect on anaerobic digestibility.