Papers by Dra. Tamara Llano Astuy
ABSTRACT: Physico-chemical and biological processes can be used to transform different pulp and p... more ABSTRACT: Physico-chemical and biological processes can be used to transform different pulp and paper industries through integrated forest biorefineries in order to valorise all of the main fractions of the lignocellulosic biomass (cellulose, hemicellulose and lignin). In this work, hydrolysis and fractionation processes have been studied in a sulphite pulp mill to obtain not only dissolving pulp from the cellulose but also lignosulphonates from the lignin and fermentation products from the hemicellulose. Delignification and hydrolysis experiments have been carried out at laboratory scale in order to increase the valorization opportunities and trying to decrease the inhibitors in the final by-product. In addition, detoxification or separation treatments have been developed in order to separate the lignosulphonates and other inhibitors from the sugar substrate.RESUMEN:Diferentes procesos físico-químico y biológicos se pueden utilizar para transformar la industria de la pasta y celulo...
Análisis del grado de implantación en la aplicación de los criterios de admisión en vertederos para residuos peligrosos en la Unión Europea
VII Simposio Iberoamericano #R##N#en Ingeniería de Residuos : #R##N#Hacia una economía circular, Santander, Universidad de Cantabria, 2017, 2017
VII Simposio Iberoamericano #R##N#en Ingeniería de Residuos : #R##N#Hacia una economía circular, Santander, Universidad de Cantabria, 2017, 2017
Materials, 2016
The complete bioconversion of the carbohydrate fraction is of great importance for a lignocellulo... more The complete bioconversion of the carbohydrate fraction is of great importance for a lignocellulosic-based biorefinery. However, due to the structure of the lignocellulosic materials, and depending basically on the main parameters within the pretreatment steps, numerous byproducts are generated and they act as inhibitors in the fermentation operations. In this sense, the impact of inhibitory compounds derived from lignocellulosic materials is one of the major challenges for a sustainable biomass-to-biofuel and-bioproduct industry. In order to minimise the negative effects of these compounds, numerous methodologies have been tested including physical, chemical, and biological processes. The main physical and chemical treatments have been studied in this work in relation to the lignocellulosic material and the inhibitor in order to point out the best mechanisms for fermenting purposes. In addition, special attention has been made in the case of lignocellulosic hydrolysates obtained by chemical processes with SO 2 , due to the complex matrix of these materials and the increase in these methodologies in future biorefinery markets. Recommendations of different detoxification methods have been given.
Biomass and Bioenergy, 2021
The transformation of fermentable sugars provided from lignocellulosic wastes into biofuels or bi... more The transformation of fermentable sugars provided from lignocellulosic wastes into biofuels or bioproducts is a key point at second-generation biorefineries. Spent sulfite liquor is a xylose-rich hydrolysate constituting the main residue of sulfite mills producing dissolving cellulose. Due to the presence of the inhibitors in the spent liquor, the most promising valorization options require detoxification before sugars bioconversion. In this work, a multi criteria analysis was implemented to select techno-economic and socio-environmental feasible detoxification alternatives that can be adapted to a wide variety of fermenting scenarios. Total inhibitors removal, phenolics removal, acetic acid removal, lignosulfonates removal, total sugar losses, fixed capital invested, manufacturing costs, waste toxicity, social acceptance, and employment were chosen as the most relevant criteria. The maximum allowable concentration of undesirable inhibitors cannot be established with a general character, and thereby decision-making tools result in feasible and efficient solutions. From a technical viewpoint best solution was anionic resins with a score of 0.68; the most economical alternative was the overliming with a score of 0.76; finally, from a socio-environmental perspective, overliming reached the highest score of 0.78. In addition, three spent liquor biorefinery models were proposed. Based on the multicriteria analysis and based on the inhibitor's concentration affecting fermentation yields and productivity, the best detoxification alternatives were (1) anionic resins for polyhydroxyalkanoate production; (2) activated carbon for ethanol biorefinery; (3) overliming for xylitol biorefinery.
Sustainability
Solidification/stabilization (S/S) of acid waste using Ordinary Portland Cement (OPC) is widely i... more Solidification/stabilization (S/S) of acid waste using Ordinary Portland Cement (OPC) is widely implemented, but, due to the impact on climate change, alternative methods are being investigated. In this work, first, the feasibility of using coal fly-ash/clay-based geopolymers for the S/S of Zn plant residues (ZPR), Cadmium Sponge (CS), and Anode Mud (AM) is proposed as a treatment prior to disposal in landfills. Different variables, such as the type of processing, molding (as-received waste), and pressing (dried waste), and activators, a commercial and an alternative residual sodium carbonate, have been studied. The technical and environmental assessments of the S/S process by means of compressive strength and the leaching of critical pollutants have been monitored. Immobilization efficiencies of Cd and Zn higher than 99% have been obtained by dosing 50% of the acid waste, 6 M NaOH solution (20 min contact time), cured at 75 °C (48 h) and at room temperature (28 days), achieving in ...
Applied Sciences
The incorporation of coal fly ash (CFA) in fired clay bricks (FCBs), as a clay replacement, contr... more The incorporation of coal fly ash (CFA) in fired clay bricks (FCBs), as a clay replacement, contributes toward cleaner production practices. CFA disposal is an important issue worldwide due to its huge volume and to its potential negative environmental impacts, and currently does not have a recovery route due to its high concentration in unburned materials. In this study, the impact of the incorporation of two CFA, with different content of unburned carbon, FAA (low LOI) and FAB (high LOI) in FCBs, from a technical and environmental point of view was conducted. Unburned carbon plays an important role on the final properties of FCBs. The thermal decomposition during the firing process promotes an increase of water absorption, decreasing the flexural strength as the porosity increases, although the technical and mechanical properties of samples containing up to 30% FAA and percentages of 20% FAB are acceptable. The leaching behaviour showed an immobilisation of Cr and Se in FCBs while...
Use of green solvents as pre-treatment of dissolving pulp to decrease CS2 consumption from viscose production
Cellulose, 2020
Choline chloride-based deep eutectic solvents are widely used in biomass processing. In this work... more Choline chloride-based deep eutectic solvents are widely used in biomass processing. In this work, four different green solvent mixtures were used as pre-treatment of acid sulphite dissolving pulp with the hypothesis of increasing the possibilities to produce viscose fibres and decreasing the use of the harmful and toxic carbon disulphide in the process. The experiments were performed at two different pulp to solvent mass ratios. Pulp quality parameters were also measured to determine the suitability of the pre-treatment: α-cellulose, viscosity, lignin and pentosan content. In addition, X-ray diffraction analysis of pulps at the best solid to liquid ratio was performed to obtain the influence of the crystallinity index. Best results were obtained with the use of lactic acid, with reactivity values close to 94%, giving a reduction of CS2 usage of 15.83%. Furthermore, a linear relationship between the crystallinity index calculated by the XRD and reactivity with a regression factor of 0.87 was found.
Journal of Chemical Technology & Biotechnology, 2021
In 1817, the fifth Earl of Selkirk and certain Saulteaux chiefs negotiated the Selkirk Treaty to ... more In 1817, the fifth Earl of Selkirk and certain Saulteaux chiefs negotiated the Selkirk Treaty to secure the existence of a fragile Euro-Canadian settlement near the confluence of the Red and Assiniboine Rivers. Selkirk died soon after, and his agents and successors disputed the content of the treaty with the Indigenous negotiating parties. The historiography of the Selkirk Treaty has not reached a consensus on these disputes, in part due to the number of ostensibly contradictory sources it draws upon. This thesis argues that these disputes can be best answered, and these ostensibly contradictory sources best reconciled, by situating them and the Selkirk Treaty within the context of the Indigenous and Imperial land frameworks that operated in Red River in 1817. This thesis first identifies unresolved questions in the historiography of the Selkirk Treaty. Using primary sources cited in the historiography, it then outlines the ideas acting within the Indigenous and Imperial land frameworks operative over Red River. It argues these ideas and frameworks remained intact during the negotiation of the Selkirk Treaty. On the basis of these frameworks, this thesis further argues that neither Lord Selkirk nor the Saulteaux negotiators intended the Selkirk Treaty to consist of a permanent alienation of Indigenous land. However, after Selkirk's death, his agents and successors came to trust the Indenture of the Selkirk Treaty, a written and signed record of the treaty, as the only trustworthy record of the agreement. Selkirk's agents and successors then read the Indenture as a permanent alienation of land, but this thesis argues that, on the basis of the borders specified in the Indenture, that document alone is inadequate to interpret the Selkirk Treaty.
Applied Sciences, 2021
The recent recovery processes of electric arc furnace dust (EAFD) include stabilization within ma... more The recent recovery processes of electric arc furnace dust (EAFD) include stabilization within materials with potential uses in the construction sector. The stabilization of EAFD by alkaline activation of different alumina-silicates, resulting in low-cost and environmentally friendly materials. The leaching standards within the different European regulations allow evaluating waste materials and products. This work aims to study the introduction of EAFD in FA–clay geopolymers, assessing the environmental and geochemical behavior in two different scenarios, disposal, and utilization. For it, the compliance equilibrium-based batch test (EN 12457-2) and pH dependence test (EN 14429) have been used. The dosages of EAFD in the geopolymeric matrix are 5% to 20% with curing temperatures of 75 °C and 225 °C. The introduction of EAFD favors the development of the flexural strength. From the environmental point of view, metals related to EAFD, such as Zn, Pb, or Cu, are retained in the matrix....
BioResources, 2018
A totally chlorine free (TCF) bleaching sequence was studied for an acid sulfite pulp mill that p... more A totally chlorine free (TCF) bleaching sequence was studied for an acid sulfite pulp mill that produces dissolving pulps. Laboratory analyses of the last two bleaching stages, an oxidant-reinforced alkaline extraction stage (EOP), and a subsequent pressurized peroxide with oxygen stage (PO), were performed on a eucalypt pulp that had been delignified by an ozone (Z) stage in the pulp mill. The goal was to predict the optimal costs and operational conditions for the (EOP)(PO) partial bleach sequence for three different specialty pulp products. Four independent variables affecting the pulp quality properties were examined for each stage (i.e., reaction temperature, reaction time, NaOH dosage and H2O2 dosage). The dependent variables were various pulp properties, such as intrinsic pulp viscosity, alpha-cellulose content, kappa number, and GE brightness. Three scenarios were considered to optimize the bleaching process, which related to a regenerated cellulose product (viscose) that is...
Cellulose, 2020
Reactivity of dissolving pulp is one of the main parameters to determine its availability to be t... more Reactivity of dissolving pulp is one of the main parameters to determine its availability to be transformed into viscose. It is related to the use of carbon disulphide (CS2). An industrial sequential totally chlorine free bleaching process is used as case study. It is carried out in two stages: 1) Alkaline extraction (EOP) and 2) peroxide bleaching (PO). In order to assess how to decrease the use of carbon disulphide, several experiments were performed at laboratory scale for the two stages mentioned before by modifying the operating conditions: NaOH and H2O2 dosages, time and temperature. Reactivity using a modified Fock's method and pentosan content was analysed along with quality pulp parameters: α-cellulose, viscosity and lignin content (kappa number). Results showed that reactivity increases through the bleaching process and varies with the chemical dosage in both stages. Pulp obtained at the best conditions had the following characteristics: reactivity, 95.3 %; α-cellulose 91.17 %; intrinsic viscosity, 448 mL/g; kappa number, 1.81 and pentosan content 2.86 %, and as a result, CS2 usage was reduced by 11.88 %. At the best conditions obtained in this work, NaOH dosage in PO stage was reduced to zero and temperature was slightly lower, when compared with industrial operating conditions.
Energies, 2017
Detoxification is required for sugar bioconversion and hydrolyzate valorization within the bioref... more Detoxification is required for sugar bioconversion and hydrolyzate valorization within the biorefining concept for biofuel or bio-product production. In this work, the spent sulfite liquor, which is the main residue provided from a pulp mill, has been detoxified. Evaporation, overliming, ionic exchange resins, and adsorption with activated carbon or black carbon were considered to separate the sugars from the inhibitors in the lignocellulosic residue. Effectiveness in terms of total and individual inhibitor removals, sugar losses and sugar-to-inhibitor removal ratio was determined. The best results were found using the cation exchange Dowex 50WX2 resin in series with the anion exchange Amberlite IRA-96 resin, which resulted in sugar losses of 24.2% with inhibitor removal of 71.3% of lignosulfonates, 84.8% of phenolics, 82.2% acetic acid, and 100% of furfurals. Apart from exchange resins, the results of evaporation, overliming, adsorption with activated carbon and adsorption with black carbon led to total inhibitor removals of 8.6%, 44.9%, 33.6% and 47.6%, respectively. Finally, some fermentation scenarios were proposed in order to evaluate the most suitable technique or combination of techniques that should be implemented in every case.
Waste and Biomass Valorization, 2015
This paper contains data related to the research paper entitled "Organic two-phase system based o... more This paper contains data related to the research paper entitled "Organic two-phase system based on acetonitrile þ water þ polyvinylpyrrolidone, a novel concept of liquid-liquid equilibrium: phase diagrams and phenolic compounds partitioning". Data of phase equilibrium were obtained using the cloud point method. After this step, some blending points were chosen to perform the phenolic compounds partitioning (gallic acid, quercetin dihydrate and cyanidin 3-O-glucoside chloride)
Journal of Chemistry, 2015
The evolution of lignin, five- and six-carbon sugars, and other decomposition products derived fr... more The evolution of lignin, five- and six-carbon sugars, and other decomposition products derived from hemicelluloses and cellulose was monitored in a sulfite pulp mill. The wastewater streams were characterized and the mass balances throughout digestion and total chlorine free bleaching stages were determined. Summative analysis in conjunction with pulp parameters highlights some process guidelines and valorization alternatives towards the transformation of the traditional factory into a lignocellulosic biorefinery. The results showed a good separation of cellulose (99.64%) during wood digestion, with 87.23% of hemicellulose and 98.47% lignin dissolved into the waste streams. The following steps should be carried out to increase the sugar content into the waste streams: (i) optimization of the digestion conditions increasing hemicellulose depolymerization; (ii) improvement of the ozonation and peroxide bleaching stages, avoiding deconstruction of the cellulose chains but maintaining i...
Monosaccharide production in an acid sulfite process: Kinetic modeling
Carbohydrate Polymers, 2015
Spent sulfite liquor is a lignocellulosic waste obtained after the sulfite pulping process. It is... more Spent sulfite liquor is a lignocellulosic waste obtained after the sulfite pulping process. It is mainly formed by sugars and lignosulfonates which are isolated from the pulp during the cooking process. The current work investigates the kinetic modeling of the sulfite process from a biorefinery point of view since monosaccharides present in the spent liquor can be used as a raw material in further biorefinery processes to produce other value-added products. Kinetic parameters of carbohydrate degradation have been determined following sugar and inhibitors from wood to spent liquor, using laboratory scale reactors and different temperatures, 130, 140 and 150 °C. Three types of reaction schemes were developed. Kinetic parameters were obtained for each one using first and n order reactions, using Aspen Custom Modeler. Results show that the best temperature to be used in the process is 130 °C, giving the maximum sugar conversion, 33.91 mol% and obtaining 13.81 mol% of decomposition products.
Journal of Biotechnology, 2012
Spent sulphite liquor is a lignocellulosic residue obtained in the acid sulphite pulping process ... more Spent sulphite liquor is a lignocellulosic residue obtained in the acid sulphite pulping process after the digestion of hardwood chips, and composed mainly by lignosulphonates and hemicelluloses. The aim of this work is to study the main process variables at different digestion conditions: maximum temperature, heating rate, and total SO 2 content, which affect the delignification process of hardwood chips to obtain dissolving pulp and to increase the total amount of fermentable sugars and lignosulphonates presented in this lignocellulosic waste. The best results are 210.5 g/L of lignosulphonates and 47.26 g/L of total monosaccharides obtained at higher temperatures of 1.058T and 1.072T, low heating rates of 0.334R and 0.285R, and total SO 2 content of 6.20%. Furthermore, concentrate-acid hydrolysis of the liquor with sulphuric acid was performed in order to study the evolution of the sugar content and the release of the inhibitors. Temperature, acid concentration, acid/liquor ratio and time were modified, showing that acid/liquid ratio is the most influential variable. Although increase in the content of sugars in neither case, a notable furfural and acetic acid concentration decrease is registered, 97.88% and 36.57% respectively, at 20 • C, 60% (w/w) sulphuric acid and acid/sample ratio of 1/0.1 (v/v).
Biotechnology Reports, 2017
Waste from pulp and paper mills consist of sugar-rich fractions comprising hemicellulose derivati... more Waste from pulp and paper mills consist of sugar-rich fractions comprising hemicellulose derivatives and cellulose by-products. A complete characterisation of the waste streams is necessary to study the possibilities of an existing mill. In this work, four chromatographic methods have been developed to obtain the most suitable chromatographic method conditions for measuring woody feedstocks, lignocellulosic hydrolysates and cellulose pulp in sulphite pulping processes. The analysis of major and minor monosaccharides, aliphatic carboxylic acids and furfurals has been optimised. An important drawback of the spent liquors generated after sulphite pulping is their acidic nature, high viscosity and adhesive properties that interfere in the column lifetime. This work recommends both a CHO-782Pb column for the sugar analysis and an SH-1011 resin-based cross-linked gel column to separate lowmolecular-weight chain acids, alcohols and furfurals. Such columns resulted in a good separation with long lifetime, wide pH operating range and low fouling issues.
Applied Sciences, 2022
The incorporation of coal fly ash (CFA) in fired clay bricks (FCBs), as a clay replacement, contr... more The incorporation of coal fly ash (CFA) in fired clay bricks (FCBs), as a clay replacement, contributes toward cleaner production practices. CFA disposal is an important issue worldwide due to its huge volume and to its potential negative environmental impacts, and currently does not have
a recovery route due to its high concentration in unburned materials. In this study, the impact of the incorporation of two CFA, with different content of unburned carbon, FAA (low LOI) and FAB (high LOI) in FCBs, from a technical and environmental point of view was conducted. Unburned carbon plays an important role on the final properties of FCBs. The thermal decomposition during the firing process promotes an increase of water absorption, decreasing the flexural strength as the porosity increases, although the technical and mechanical properties of samples containing up to 30% FAA and percentages of 20% FAB are acceptable. The leaching behaviour showed an immobilisation of Cr and Se in FCBs while Mo reduced its mobility to values below non-hazardous limits. Acid gas emission values do not exceed the reference emission value, except for SO2 emissions while the level of CO2 emissions must be estimated based on the total annual production of the ceramic factory.
Sustainability, 2022
Solidification/stabilization (S/S) of acid waste using Ordinary Portland Cement (OPC) is widely i... more Solidification/stabilization (S/S) of acid waste using Ordinary Portland Cement (OPC) is widely implemented, but, due to the impact on climate change, alternative methods are being investigated. In this work, first, the feasibility of using coal fly-ash/clay-based geopolymers for the S/S of Zn plant residues (ZPR), Cadmium Sponge (CS), and Anode Mud (AM) is proposed as a treatment prior to disposal in landfills. Different variables, such as the type of processing, molding (as-received waste), and pressing (dried waste), and activators, a commercial and an alternative residual sodium carbonate, have been studied. The technical and environmental assessments of the S/S process by means of compressive strength and the leaching of critical pollutants have been monitored. Immobilization efficiencies of Cd and Zn higher than 99% have been obtained by dosing
50% of the acid waste, 6 M NaOH solution (20 min contact time), cured at 75 C (48 h) and at room temperature (28 days), achieving in the leachates pH values of 7 to 10 and [Cd] and [Zn] < 1 and 2.5 mg/kg, respectively. However, alkaline activation increases As leaching, mainly associated with
the clay. Secondly, removing clay from the geopolymer formulation, the optimization of geopolymer parameters, acid waste/geopolymer ratio, liquid/solid ratio, and NaOH molar concentration enables obtaining a significant reduction in the release of As and Cd, and Zn is kept at
acceptable values that meet the non-hazardous waste landfill disposal limits for the S/S of both acid wastes.
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Papers by Dra. Tamara Llano Astuy
a recovery route due to its high concentration in unburned materials. In this study, the impact of the incorporation of two CFA, with different content of unburned carbon, FAA (low LOI) and FAB (high LOI) in FCBs, from a technical and environmental point of view was conducted. Unburned carbon plays an important role on the final properties of FCBs. The thermal decomposition during the firing process promotes an increase of water absorption, decreasing the flexural strength as the porosity increases, although the technical and mechanical properties of samples containing up to 30% FAA and percentages of 20% FAB are acceptable. The leaching behaviour showed an immobilisation of Cr and Se in FCBs while Mo reduced its mobility to values below non-hazardous limits. Acid gas emission values do not exceed the reference emission value, except for SO2 emissions while the level of CO2 emissions must be estimated based on the total annual production of the ceramic factory.
50% of the acid waste, 6 M NaOH solution (20 min contact time), cured at 75 C (48 h) and at room temperature (28 days), achieving in the leachates pH values of 7 to 10 and [Cd] and [Zn] < 1 and 2.5 mg/kg, respectively. However, alkaline activation increases As leaching, mainly associated with
the clay. Secondly, removing clay from the geopolymer formulation, the optimization of geopolymer parameters, acid waste/geopolymer ratio, liquid/solid ratio, and NaOH molar concentration enables obtaining a significant reduction in the release of As and Cd, and Zn is kept at
acceptable values that meet the non-hazardous waste landfill disposal limits for the S/S of both acid wastes.