Lignin-Degrading Bacteria in Paper Mill Sludge.

The effluents generated in the paper industry, such as black liquor, have a high content of lignin and other toxic components; however, they represent a source of lignin-degrading bacteria with biotechnological potential. Therefore, the present study aimed to isolate and identify lignin-degrading bacteria species in paper mill sludge. A primary isolation was carried out from samples of sludge present in environments around a paper company located in the province of Ascope (Peru). Bacteria selection was made by the degradation of Lignin Kraft as the only carbon source in a solid medium. Finally, the laccase activity (Um-L-1) of each selected bacteria was determined by oxidation of 2,2'-azinobis-(3-etilbencenotiazolina-6-sulfonate) (ABTS). Bacterial species with laccase activity were identified by molecular biology techniques. Seven species of bacteria with laccase activity and the ability to degrade lignin were identified. The bacteria Agrobacterium tumefasciens (2), Klebsiella grimontii (1), and Beijeinckia fluminensis (1) were reported for first time. K. grimowntii and B. fluminensis presented the highest laccase activity, with values of 0.319 ± 0.005 UmL-1 and 0.329 ± 0.004 UmL-1, respectively. In conclusion, paper mill sludge may represent a source of lignin-degrading bacteria with laccase activity, and they could have potential biotechnological applications.

Synthesis of a biobased resin and its screening as an alternative adsorbent for organic and inorganic micropollutant removal.

The sol-gel route was used to synthesize a biophenolic resin from a blend of Kraft black liquor and condensed tannin. The biobased resin has an amorphous structure and diversified surface functional groups. The biomaterial thermal stability was improved by Kraft black liquor, which increased the fixed carbon yield by 19.78% in an oxidant medium and 9.07% in an inert medium. Moreover, the presence of fixed carbon and char is positively related to the material flame retardant property. Additionally, impedance measurements were used to understand the physical phenomena occurring at the polymeric matrix's interface and the material's final properties. The biobased resin characterization and the considerable increase in the presence of micropollutants in surface and water bodies suggest the new biomaterial application in the adsorption process. Thus, its adsorption capacity toward several organic and inorganic micropollutants and its effectiveness in complex water matrices were evaluated. Methylene blue was used as a model compound to assess the influence of the resin composition on the adsorption capacity, and the type H isotherm indicates the high affinity of the biobased resin toward the micropollutant. The adsorption occurs in multilayer by intermolecular interaction and electrostatic forces. The amount of Kraft black liquor favored the adsorption, and the adsorption capacity was greater than 1250 mg g-1. When inorganic compounds were evaluated, the carboxyl and phenol groups favor the biomaterial affinity toward metal ions. Cu2+ and Ni2+ were completely removed from the contaminated water, and the adsorption capacity of the other inorganic compounds was: Pb2+ (36.97 mg g-1), Al3+ (22.17 mg g-1), Ba2+ (12.76 mg g-1), Ag1+ (33.85 mg g-1), and Fe2+ (19.44 mg g-1). In contrast, the adsorption capacity of the organic micropollutants was: 2,4-D (3.09 mg g-1), diuron (5.89 mg g-1), atrazine (2.71 mg g-1), diclofenac (2.04 mg g-1), caffeine (5.79 mg g-1), acetaminophen (4.80 mg g-1), methylene Blue (106.66 mg g-1), and methyl orange (30.48 mg g-1). The results pointed that the adsorption efficiency of organic micropollutants increases with the distribution coefficient (logD), indicating the biobased resin affinity toward more lipophilic compounds and ionized species.

Forward Black Liquor Acid Precipitation: Lignin Fractionation by Ultrafiltration.

Lignin recovery from black liquor is an important task for producing valuable chemical products. Acidification processes are currently applied by pulp and paper industries for black liquor treatment, in which two main streams are produced: the precipitated lignin fraction and a lignin-lean black liquor. Membrane filtration is a suitable alternative for lignin recovery from black liquor, but studies on lignin-lean black liquor filtration are scarce. Here, we evaluated the ultrafiltration process for lignin recovery from the both fractions of black liquor acidification. The lignin-lean black liquor presented 22 wt% of total solids with 4.6 wt% of lignin. Lignin retention from the lignin-lean black liquor by the 5 kDa ultrafiltration membrane was equal to 85%, with reduction in total solid concentration from 219.8 to 68.1 g L-1. Due to the relatively high solid concentration in the lignin-lean black liquor, cake formation was the main fouling mechanism during ultrafiltrations. The precipitated lignin solution presented 4.8 wt% of total solids with equivalent lignin concentration (4.7 wt%). The used membrane was able to retain almost 100% of solids and lignin from the solution prepared from the precipitated lignin. All fouling mechanisms were responsible for flux decay in ultrafiltration of the precipitated lignin solution. Steady state fluxes for lignin-lean black liquor and precipitated lignin solution were 0.9 and 15.9 L h-1 m-2, respectively. According to TGA analyses up to 800 °C, precipitated lignin and lignin-lean black liquor presented total mass losses of 63.5% and 44.3%, respectively. Also, the permeate samples presented lower mass losses than their respective feed samples. The ultrafiltration process reduced the average weight molar mass (Mw) of the precipitated lignin solution and lignin-lean black liquor from 1817 to 486 g mol-1and from 2876 to 1095 g mol-1, respectively. Thus, the 5 kDa ultrafiltration membrane was efficient for lignin recovery from the lignin-lean black liquor, while membranes with lower cut-off should be proposed for lignin purification from the precipitated fraction.

Extração e caracterização da lignina proveniente do pré-tratamento de biomassa para produção de etanol de 2a geração / Extraction and characterization of lignin from the pre-treatment of biomass for 2 nd generation ethanol production

RESUMO A biomassa destaca-se como um dos poucos recursos disponíveis com potencial de desenvolvimento de biorrefinarias para a inclusão de rotas alternativas sustentáveis na produção de energia e produtos químicos. A lignina é um subproduto do pré-tratamento da biomassa na produção de etanol de segunda geração, basicamente composta de cadeias de carbono e que pode ter alto valor agregado. Contudo, tem sido tradicionalmente utilizada para geração de energia por queima direta. Sendo assim, o objetivo do presente estudo foi investigar a influência do pH na precipitação do licor negro, variando o pH de 1 a 7, bem como caracterizar os componentes da sua estrutura química para possíveis usos futuros. Após a obtenção da massa precipitada, procedeu-se às análises espectrofotométricas no infravermelho e no ultravioleta, além da quantificação de fenóis totais, nas frações sólidas e líquidas das ligninas provenientes dos diferentes pH. Os resultados demonstram que as maiores concentrações de lignina foram obtidas nos menores valores de pH. As análises instrumentais indicaram diferenças nos componentes de cada lignina, sugerindo que sua composição química é influenciada pela alteração do pH. Ainda, a concentração total de fenóis no sobrenadante das amostras foi menor em pH mais baixos, confirmando que há maiores concentrações desses na fração sólida das ligninas.

ABSTRACT Biomass appears to be one of the few resources available with the potential of developing bio refineries for the inclusion of sustainable alternative routes in the production of energy and chemicals. Lignin is a 2nd generation by-product of biomass pre-treatment on ethanol production, and consists of carbon chains, which can have a high added value. However, lignin is being considered just for energy generation. Therefore, the aim of this study was to investigate the influence of pH in the precipitation of black liquor through its acidification of in different pH values (1-7), and to characterize the components of its chemical structure for possible future use. After determining the precipitated mass, a spectrophotometric analysis was carried out on infrared and ultraviolet, along with the quantification of total phenolic compounds in the solid and liquid fractions of lignin derived from different pH ranges. The results showed that the higher lignin concentrations were obtained at lower pH values. The instrumental analysis indicated significant differences in each lignin's components, suggesting that its chemical composition is influenced by pH change. To conclude, the total concentration of phenolic compounds in the supernatant of the samples was lower at lower pH ranges, indicating that there are higher concentrations of these in lignin's solid fraction.

Effects of black liquor shocks on activated sludge treatment of bleached kraft pulp mill wastewater.

Kraft pulp mills use activated sludge systems to remove organic matter from effluents. Process streams may appear as toxic spills in treatment plant effluents, such as black liquor, which is toxic to microorganisms of the activated sludge. The present study evaluates the effects of black liquor shocks in activated sludge systems. Four black liquor shocks from 883 to 3,225 mg chemical oxygen demand-COD L(-1) were applied during 24 hours in a continuously operating lab-scale activated sludge system. Removal efficiencies of COD, color and specific compounds were determined. Moreover, specific oxygen uptake rate (SOUR), sludge volumetric index (SVI) and indicator microorganisms were evaluated. Results show that the addition of black liquor caused an increase in COD removal (76-67%) immediately post shock; followed two days later by a decrease (-19-50%). On the other hand, SOUR ranged between 0.152 and 0.336 mgO2 g(-1) volatile suspended solids-VSS• min(-1) during shocks, but the initial value was reestablished at hour 24. When the COD concentration of the shock was higher than 1,014 mg/L, the abundance of stalked ciliates and rotifers dropped. Finally, no changes in SVI were observed, with values remaining in the range 65.8-40.2 mL g(-1) total suspended solids-TSS during the entire operating process. Based on the results, the principal conclusion is that the activated sludge system with the biomass adapted to the kraft pulp effluent could resist a black liquor shock with 3,225 mgCOD L(-1) of concentration during 24 h, under this study's conditions.

Ozonização em meio básico para redução de cor do licor negro de indústria de celulose de algodão / Color reduction of black liquor from cotton cellulose industry using ozonation in an alkaline medium

As indústrias de papel e celulose descartam no ambiente um grande volume de efluente contendo grande quantidade da substância lignina, que atribui coloração e apresenta considerável potencial de toxicidade. Neste trabalho, foi avaliada a ozonização em meio básico para a redução de cor do licor negro gerado por uma indústria de celulose de algodão. Face aos resultados, foi possível observar que, para menores concentrações iniciais de ozônio (0,4 gO3 L-1 h-1), foi necessário um tempo mais longo de ozonização para se obter a redução desejada de 80 por cento da cor. O consumo específico de ozônio, entretanto, em comparação a experimentos com dosagens mais elevadas (4,3 gO3 L-1 h-1) foi menor. Sugere-se que o oxigênio molecular desempenhe, também, um importante papel na oxidação dos compostos, participando do mecanismo de oxidação iniciado por radical hidroxila, •OH, formado na ozonização em meio básico.

Pulp and paper mills discharge large amounts of wastewater containing high concentrations of lignin, a coloring substance that is dangerous and presents high toxicity to the environment. In this study, ozonation in alkaline ambience was evaluated for color reduction in black liquor, generated in a cotton linter mill. It was observed that the ozonation time to reach 80 percent color reduction was higher at a lower initial ozone dose (0,4 gO3 L-1 h-1) in comparison to a higher initial ozone dose (4,3 gO3 L-1 h-1). On the other hand, the amount of consumed oxidant was lower at the lower ozone dose. It is suggested that molecular oxygen participates in the oxidation mechanism of colored compounds, which is initiated by hydroxyl radicals (•OH) formed during ozonation in alkaline ambience.