Kiintoaineen ja nesteen erotusprosessit lignoselluloosaetanolin tuotannossa

Työn tarkoituksena on tehdä kirjallisuuskatsaus kiintoaine-neste-erotusprosesseihin lignoselluloosaetanolin tuotannossa. Työssä keskitytään hydrolysoidun ligniinipitoisen lignoselluloosamateriaalin kiintoaine-neste-erotukseen. Tarkoituksena on tutkia lignoselluloosamateriaalin suodatus- ja sentrifugointiprosesseja sekä niiden vaikutusta lignoselluloosaetanolin tuotantoon.

Biomassahydrolysaattien puhdistus uutolla

Lignoselluloosasta koostuvasta biomassasta valmistetaan hydrolysoimalla sokereita, jotka jatkojalostetaan fermentoimalla bioetanoliksi. Bioetanolia käytetään fossiilisten polttoaineiden korvaajana esimerkiksi ajoneuvoissa. Bioetanolin valmistuksessa pyritään mahdollisimman hyvään saantoon, jotta sen valmistus olisi taloudellisesti kannattavaa. Hydrolyysin aikana syntyy sokerien lisäksi orgaanisia happoja, furaanin johdannaisia sekä fenolisia yhdisteitä. Yleisimpiä syntyviä yhdisteitä ovat muun muassa etikkahappo, furfuraali ja hydroksimetyylifurfuraali. Nämä yhdisteet haittaavat sokerien fermentointiprosessia ja pienentävät etanolin saantoa. Fermentointiprosessia haittaavien yhdisteiden poistoon hydrolysaattiliuoksesta voidaan käyttää esimerkiksi haihdutusta, membraanierotusta, adsorptiota, saostusta, sekä uuttoa. Tämän työn tarkoituksena oli tutkia leikkaussekoittimen soveltuvuutta biomassahydrolysaatin epäpuhtauksien erotukseen. Lisäksi kirjallisuusosassa on esitetty hydrolysointiprosessissa syntyviä haitta-aineita ja niiden erotusmenetelmiä.

Aqueous-phase reforming of renewables for selective hydrogen production in the presence of supported platinum catalysts

The evolution of our society is impossible without a constant progress in life-important areas such as chemical engineering and technology. Innovation, creativity and technology are three main components driving the progress of chemistry further towards a sustainable society. Biomass, being an attractive renewable feedstock for production of fine chemicals, energy-rich materials and even transportation fuels, captures progressively new positions in the area of chemical technology. Knowledge of heterogeneous catalysis and chemical technology applied to transformation of biomass-derived substances will open doors for a sustainable economy and facilitates the discovery of novel environmentally-benign processes which probably will replace existing technologies in the era of biorefinary. Aqueous-phase reforming (APR) is regarded as a promising technology for production of hydrogen and liquids fuels from biomass-derived substances such as C3-C6 polyols. In the present work, aqueous-phase reforming of glycerol, xylitol and sorbitol was investigated in the presence of supported Pt catalysts. The catalysts were deposited on different support materials, including Al2O3, TiO2 and carbons. Catalytic measurements were performed in a laboratory-scale continuous fixedbed reactor. An advanced analytical approach was developed in order to identify reaction products and reaction intermediates in the APR of polyols. The influence of the substrate structure on the product formation and selectivity in the APR reaction was also investigated, showing that the yields of the desired products varied depending on the substrate chain length. Additionally, the influence of bioethanol additive in the APR of glycerol and sorbitol was studied. A reaction network was advanced explaining the formation of products and key intermediates. The structure sensitivity in the aqueous-phase reforming reaction was demonstrated using a series of platinum catalysts supported on carbon with different Pt cluster sizes in the continuous fixed-bed reactor. Furthermore, a correlation between texture physico-chemical properties of the catalysts and catalytic data was established. The effect of the second metal (Re, Cu) addition to Pt catalysts was investigated in the APR of xylitol showing a superior hydrocarbon formation on PtRe bimetallic catalysts compared to monometallic Pt. On the basis of the experimental data obtained, mathematical modeling of the reaction kinetics was performed. The developed model was proven to successfully describe experimental data on APR of sorbitol with good accuracy.

Pressure filtration characteristics of enzymatically hydrolyzed biomass suspensions

Enzymatic hydrolysis of lignocellulosic polymers is likely to become one of the key technologies enabling industrial production of liquid biofuels and chemicals from lignocellulosic biomass. Certain types of enzymes are able to hydrolyze cellulose and hemicellulose polymers to shorter units and finally to sugar monomers. These monomeric sugars are environmentally acceptable carbon sources for the production of liquid biofuels, such as bioethanol, and other chemicals, such as organic acids. Liquid biofuels in particular have been shown to contribute to the reduction of net emissions of greenhouse gases. The solid residue of enzymatic hydrolysis is composed mainly of lignin and partially degraded fibers, while the liquid phase contains the produced sugars. It is usually necessary to separate these two phases at some point after the hydrolysis stage. Pressure filtration is an efficient technique for this separation. Solid-liquid separation of biomass suspensions is difficult, because biomass solids are able to retain high amounts of water, which cannot be readily liberated by mechanical separation techniques. Most importantly, the filter cakes formed from biomaterials are compressible, which ultimately means that the separation may not be much improved by increasing the filtration pressure. The use of filter aids can therefore facilitate the filtration significantly. On the other hand, the upstream process conditions have a major influence on the filtration process. This thesis investigates how enzymatic hydrolysis and related process conditions affect the filtration properties of a cardboard suspension. The experimental work consists of pressure filtration and characterization of hydrolysates. The study provides novel information about both issues, as the relationship between enzymatic hydrolysis conditions and subsequent filtration properties has so far not been considered in academic studies. The results of the work reveal that the final degree of hydrolysis is an important factor in the filtration stage. High hydrolysis yield generally increases the average specific cake resistance. Mixing during the hydrolysis stage resulted in undefined changes in the physical properties of the solid residue, causing a high filtration resistance when the mixing intensity was high. Theoretical processing of the mixing data led to an interesting observation: the average specific cake resistance was observed to be linearly proportional to the mixer shear stress. Another finding worth attention is that the size distributions of the solids did not change very dramatically during enzymatic hydrolysis. There was an observable size reduction during the first couple of hours, but after that the size reduction was minimal. Similarly, the size distribution of the suspended solids remained almost constant when the hydrolyzed suspension was subjected to intensive mixing. It was also found that the average specific cake resistance was successfully reduced by the use of filter aids. This reduction depended on the method of how the filter aids were applied. In order to obtain high filtration capacity, it is recommended to use the body feed mode, i.e. to mix the filter aid with the slurry prior to filtration. Regarding the quality of the filtrate, precoat filtration was observed to produce a clear filtrate with negligible suspended solids content, while the body feed filtrates were turbid, irrespective of which type of filter aid was used.

Biopolttoaineiden ongelmat

Biopolttoaineilla on tärkeä rooli tulevaisuuden energiahuollossa. Biopolttoaineiden käyttöä pyritäänkin lisäämään monin keinoin. Ensimmäisen sukupolven biopolttoaineet ovat jo olleet aikansa markkinoilla ja toisen sukupolven polttoaineet ovat saapumassa markkinoille. Tässä työssä tutkitaan eri biopolttoaine vaihtoehtoja ensimmäisestä toiseen sukupolveen sekä tutkitaan niiden käytön ongelmia. Biopolttoaineiden käyttö on lisääntynyt huomattavasti viime vuosien aikoina, jonka myötä on tullut esiin monia ongelmia. Ongelmia aiheuttavat niin ilmastolliset, taloudelliset, teknologiset kuin valtapoliittiset asiat.

Entsyymien talteenotto ja kierrätys selluloosaetanolin valmistuksessa

Bioetanolin valmistus selluloosapitoisista raaka-aineista vaatii selluloosapolymeerien pilkkomisen liukoisiksi sokereiksi. Tämä voidaan toteuttaa entsymaattisella hydrolyysillä. Selluloosan pilkkomiseen tarkoitetut entsyymit, sellulaasit, ovat entsymaattisen hydrolyysin jälkeen sitoutuneet joko kiintoainefaasiin tai ovat nestemäisessä faasissa ns. vapaina entsyymeinä. Prosessin taloudellisuuden kannalta on erityisen tärkeää minimoida siinä käytettävien entsyymien tarve, sillä tehokkaat entsyymivalmisteet ovat suhteellisen kalliita. Yksi varteenotettava vaihtoehto bioetanoliprosessin saamiseksi taloudellisemmaksi on käytettyjen entsyymien talteenotto ja kierrätys. Työn tarkoituksena oli selvittää kirjallisuudesta, millaisia menetelmiä on kehitetty entsyymien talteenottoon ja kierrätykseen lignoselluloosasta valmistettavan bioetanolin valmistuksessa. Työssä on keskitytty tuoreisiin tutkimuksiin ja menetelmien käyttökelpoisuuteen ja taloudellisuuteen. Viime vuosina sellulaasien talteenotto- ja kierrätysmenetelmiä koskevat tutkimukset ovat keskittyneet pääasiassa käsittelemään nanopartikkelien avulla tapahtuvaa entsyymien immobilisointia, ultrasuodatusta, erilaisia desorptiomenetelmiä, kiinteän hydrolyysijäännöksen kierrättämistä, tuoreen substraatin lisäämistä sekä myös tislausvaiheen jälkeistä entsyymien kierrättämistä. Jotta kierrätysmenetelmä olisi tehokas, tulisi sen pyrkiä säilyttämään entsyymien aktiivisuuksia, sokerisaantoa menettämättä ja sisältää sekä neste-, että kiintoainefaasista tapahtuva kierrätys. Jokaisella kierrätysmenetelmällä on hyvät ja huonot puolensa. Entsyymien talteenottoastetta saadaan kuitenkin parannettua yhdistämällä erilaisia menetelmiä. Useista tutkimuksista huolimatta, taloudellisinta ja käyttökelpoisinta entsyymien talteenotto- ja kierrätysmenetelmää ei ole vielä saavutettu.

Esikäsittelyn vaikutus sahajauhon jauhautumiseen sekä energiankulutukseen vasaramyllyllä

Tämän kandidaatintyön tarkoituksena oli perehtyä bioetanolin eri valmistusvaiheisiin ja sen valmistuksessa käytettäviin raaka-aineisiin sekä myöskin tutkia eri esikäsittelymenetelmien vaikutusta sahajauhojen jauhautumiseen sekä energiankulutukseen, kun niitä jauhetaan vasaramyllyllä. Kirjallisuusosassa keskityttiin paljon aineksen hienonnukseen, sillä varsinkin biomassat tulee hienontaa, jotta halutut kemialliset reaktiot saataisiin tapahtumaan riittävän tehokkaasti. Kokeellisessa osassa tutkittiin eripituisien vesiliotuksien sekä emäs-käsittelyn vaikutusta sahajauhon jauhautumiseen sekä jauhautumisen energiankulutukseen, kun niitä jauhettiin vasaramyllyllä. Tutkimuskysymyksinä tässä työssä oli: Miten vesiliotus sekä liotus emäksisessä liuoksessa vaikuttaa eri sahajauhojen jauhautumiseen vasaramyllyllä?, Millaisia vaikutuksia esikäsittelyillä on myllyn energiankulutukseen?, Miten esikäsittelyt vaikuttavat jauhautumistuotteiden partikkelikokoihin?. Tuloksista käy ilmi, että 1. ja 3. tunnin vesiliotukset eivät olleet riittäviä sillä mylly ei jaksanut jauhaa minkään puulaadun sahajauhoja näillä ajoilla. Yleisesti tuloksista huomattiin, että haapajauhon jauhamiseen kului kaikkein eniten energiaa, riippumatta esikäsittelytekniikasta, mutta haapa myös jauhautui parhaiten pH-esikäsittelyn tuloksena.  

Advanced biofuel production: Engineering metabolic pathways for butanol and propane biosynthesis.

Greenhouse gases emitted from energy production and transportation are dramatically changing the climate of Planet Earth. As a consequence, global warming is affecting the living conditions of numerous plant and animal species, including ours. Thus the development of sustainable and renewable liquid fuels is an essential global challenge in order to combat the climate change. In the past decades many technologies have been developed as alternatives to currently used petroleum fuels, such as bioethanol and biodiesel. However, even with gradually increasing production, the market penetration of these first generation biofuels is still relatively small compared to fossil fuels. Researchers have long ago realized that there is a need for advanced biofuels with improved physical and chemical properties compared to bioethanol and with biomass raw materials not competing with food production. Several target molecules have been identified as potential fuel candidates, such as alkanes, fatty acids, long carbon‐chain alcohols and isoprenoids. The current study focuses on the biosynthesis of butanol and propane as possible biofuels. The scope of this research was to investigate novel heterologous metabolic pathways and to identify bottlenecks for alcohol and alkane generation using Escherichia coli as a model host microorganism. The first theme of the work studied the pathways generating butyraldehyde, the common denominator for butanol and propane biosynthesis. Two ways of generating butyraldehyde were described, one via the bacterial fatty acid elongation machinery and the other via partial overexpression of the acetone‐butanol‐ethanol fermentation pathway found in Clostridium acetobutylicum. The second theme of the experimental work studied the reduction of butyraldehyde to butanol catalysed by various bacterial aldehyde‐reductase enzymes, whereas the final part of the work investigated the in vivo kinetics of the cyanobacterial aldehyde deformylating oxygenase (ADO) for the generation of hydrocarbons. The results showed that the novel butanol pathway, based on fatty acid biosynthesis consisting of an acyl‐ACP thioesterase and a carboxylic acid reductase, is tolerant to oxygen, thus being an efficient alternative to the previous Clostridial pathways. It was also shown that butanol can be produced from acetyl‐CoA using acetoacetyl CoA synthase (NphT7) or acetyl‐CoA acetyltransferase (AtoB) enzymes. The study also demonstrated, for the first time, that bacterial biosynthesis of propane is possible. The efficiency of the system is clearly limited by the poor kinetic properties of the ADO enzyme, and for proper function in vivo, the catalytic machinery requires a coupled electron relay system.

Modeling and kinetic study of bio-ethanol production from soy protein concentrate by-product

Abstract The aim of this work was to evaluate a non-agitated process of bioethanol production from soybean molasses and the kinetic parameters of fermentation using a strain of Saccharomyces cerevisiae (ATCC® 2345). Kinetic experiment was conducted in medium with 30% (w v-1) of soluble solids without supplementation or pH adjustment. The maximum ethanol concentration was in 44 hours, the ethanol productivity was 0.946 g L-1 h-1, the yield over total initial sugars (Y1) was 47.87%, over consumed sugars (Y2) was 88.08% and specific cells production rate was 0.006 h-1. The mathematical polynomial was adjusted to the experimental data and provided very similar parameters of yield and productivity. Based in this study, for one ton of soybean molasses can be produced 103 kg of anhydrous bioethanol.

Effets de facteurs pédoclimatiques sur la composition et l’anatomie du bois de cinq cultivars de saule destinés aux biocarburants

En 2011, cinq (5) cultivars de saules ont été sélectionnés pour leur rendement en biomasse. Ils ont été plantés sur quatre sites de la province du Québec et ont été maintenus selon le protocole de la culture intensive sur courtes rotations (CICR) afin de déterminer leur potentiel pour la bioénergie dans des environnements contrastés. La composition et l’anatomie du bois de ces cultivars ont été caractérisées et comparés en fonction des conditions environnementales caractéristiques de chaque site. La hauteur et le diamètre à la base des plantes diffèrent selon les sites. Ainsi, les cultivars répondent de façon spécifique aux conditions pédoclimatiques dans lesquelles ils sont cultivés. L’effet de l’environnement n’a pas été mis en évidence sur la teneur en lignine des cultivars. Cependant, un effet génotypique a pu être constaté soulignant l’importance de la sélectivité des cultivars. La densité du bois a étonnamment conservé la même hiérarchie génotypique entre les sites. À l’opposé, l’anatomie du bois présente des différences notamment au niveau des caractéristiques des fibres et des vaisseaux. Une forte teneur en polyphénols ainsi que des fibres moins larges et des vaisseaux plus nombreux ont été observés sur le site dont le bois est le plus dense supposant l’effet probable d’un stress abiotique. De plus, deux fois plus de fibres gélatineuses, fibres riches en cellulose, ont été identifiées sur ce site montrant un intérêt pour la production de bioéthanol.

“Studies on glucose tolerant β-glucosidases from a novel Byssochlamys fulva and their applications in biomass to ethanol conversion”

Beta-glucosidases are critical enzymes in biomass hydrolysis process and is important in creating highly efficient enzyme cocktails for the bio-ethanol industry. Among the two strategies proposed for overcoming the glucose inhibition of commercial cellulases, one is to use heavy dose of BGL in the enzyme blends and the second is to do simultaneous saccharification and fermentation where glucose is converted to alcohol as soon as it is being generated. While the former needs extremely high quantities of enzyme, the latter is inefficient since the conditions for hydrolysis and fermentation are different. This makes the process technically challenging and also in this case, the alcohol generation is lesser, making its recovery difficult. A third option is to use glucose tolerant β-glucosidases which can work at elevated glucose concentrations. However, there are very few reports on such enzymes from microbial sources especially filamentous fungi which can be cultivated on cheap biomass as raw material. There has been very less number of studies directed at this, though there is every possibility that filamentous fungi that are efficient degraders of biomass may harbor such enzymes. The study therefore aimed at isolating a fungus capable of secreting glucose tolerant β- glucosidase enzyme. Production, characterization of β-glucosidases and application of BGL for bioethanol production were attempted.

Ethanol Production From Spent Substrate Of Pleurotus Eous

Spent substrate, the residual material of mushroom cultivation, causes disposal problems for cultivators. Currently the spent substrate of different mushrooms is used mainly for composting. Edible mushrooms of Pleurotus sp. can grow on a wide range of lignocellulosic substrates. In the present study, Pleurotus eous was grown on paddy straw and the spent substrate was used for the production of ethanol. Lignocellulosic biomass cannot be saccharified by enzymes to high yield of ethanol without pretreatment. The root cause for the recalcitrance of lignocellulosic biomass such as paddy straw is the presence of lignin and hemicelluloses on the surface of cellulose. They form a barrier and prevent cellulase from accessing the cellulose in the substrate. In the untreated paddy straw, the amount of hemicelluloses and lignin (in % dry weight) were 20.30 and 20.34 respectively and the total reducing sugar was estimated to be 5.40 mg/g. Extracellular xylanase and ligninases of P. eous could reduce the amount of hemicelluloses and lignin to 16 and 11(% dry weight) respectively, by 21st day of cultivation. Growth of mushroom brought a seven fold increase in the total reducing sugar yield (39.20 mg/g) and six fold increase in the production of ethanol (6.48 g/L) after 48hrs of fermentation, when compared to untreated paddy straw

Pretreatment Of Agricultural Waste With Pleurotus Sp. For Ethanol Production

Bioethanol is a liquid fuel obtained from fermentation of sugar/starch crops. Lignocellulosic biomass being less expensive is considered a future alternative for the food crops. One of the main challenges for the use of lignocellulosics is the development of an efficient pre-treatment process. Pretreatments are classified into three - physical, chemical, and biological pretreatment. Chemical process has not been proven suitable so far, due to high costs and production of undesired by-products. Biologically, hydrolysis can be enhanced by microbial or enzymatic pretreatment. Studies show that the edible mushrooms of Pleurotus sp. produce several extracellular enzymes which reduce the structural and chemical complexity of fibre. In the present study, P. ostreatus and P. eous were cultivated on paddy straw. Spent substrate left after mushroom cultivation was powdered and used for ethanol production. Saccharomyces sp. was used for fermentation studies. Untreated paddy straw was used as control. Production of ethanol from P. ostreatus substrate was 5.5 times more when compared to untreated paddy straw, while the spent substrate of P. eous gave 5 times increase in ethanol yield. Assays showed the presence of several extracellular enzymes in the spent substrate of both species, which together contributed to the increase in ethanol yield

Modeling the interplay between land use, bioenergy production and climate change

Land use has become a force of global importance, considering that 34% of the Earth’s ice-free surface was covered by croplands or pastures in 2000. The expected increase in global human population together with eminent climate change and associated search for energy sources other than fossil fuels can, through land-use and land-cover changes (LUCC), increase the pressure on nature’s resources, further degrade ecosystem services, and disrupt other planetary systems of key importance to humanity. This thesis presents four modeling studies on the interplay between LUCC, increased production of biofuels and climate change in four selected world regions. In the first study case two new crop types (sugarcane and jatropha) are parameterized in the LPJ for managed Lands dynamic global vegetation model for calculation of their potential productivity. Country-wide spatial variation in the yields of sugarcane and jatropha incurs into substantially different land requirements to meet the biofuel production targets for 2015 in Brazil and India, depending on the location of plantations. Particularly the average land requirements for jatropha in India are considerably higher than previously estimated. These findings indicate that crop zoning is important to avoid excessive LUCC. In the second study case the LandSHIFT model of land-use and land-cover changes is combined with life cycle assessments to investigate the occurrence and extent of biofuel-driven indirect land-use changes (ILUC) in Brazil by 2020. The results show that Brazilian biofuels can indeed cause considerable ILUC, especially by pushing the rangeland frontier into the Amazonian forests. The carbon debt caused by such ILUC would result in no carbon savings (from using plant-based ethanol and biodiesel instead of fossil fuels) before 44 years for sugarcane ethanol and 246 years for soybean biodiesel. The intensification of livestock grazing could avoid such ILUC. We argue that such an intensification of livestock should be supported by the Brazilian biofuel sector, based on the sector’s own interest in minimizing carbon emissions. In the third study there is the development of a new method for crop allocation in LandSHIFT, as influenced by the occurrence and capacity of specific infrastructure units. The method is exemplarily applied in a first assessment of the potential availability of land for biogas production in Germany. The results indicate that Germany has enough land to fulfill virtually all (90 to 98%) its current biogas plant capacity with only cultivated feedstocks. Biogas plants located in South and Southwestern (North and Northeastern) Germany might face more (less) difficulties to fulfill their capacities with cultivated feedstocks, considering that feedstock transport distance to plants is a crucial issue for biogas production. In the fourth study an adapted version of LandSHIFT is used to assess the impacts of contrasting scenarios of climate change and conservation targets on land use in the Brazilian Amazon. Model results show that severe climate change in some regions by 2050 can shift the deforestation frontier to areas that would experience low levels of human intervention under mild climate change (such as the western Amazon forests or parts of the Cerrado savannas). Halting deforestation of the Amazon and of the Brazilian Cerrado would require either a reduction in the production of meat or an intensification of livestock grazing in the region. Such findings point out the need for an integrated/multicisciplinary plan for adaptation to climate change in the Amazon. The overall conclusions of this thesis are that (i) biofuels must be analyzed and planned carefully in order to effectively reduce carbon emissions; (ii) climate change can have considerable impacts on the location and extent of LUCC; and (iii) intensification of grazing livestock represents a promising venue for minimizing the impacts of future land-use and land-cover changes in Brazil.

Análisis de factibilidad de un proyecto productivo que utilice el bagazo de caña panelera como materia prima para la producción de bioetanol y papel

El presente trabajo analiza el sector panelero colombiano y la viabilidad de implementar un proyecto productivo capaz de transformar los residuos generados en el proceso de producción de la panela en nuevos productos como bioetanol o papel, de esta manera, se busca contribuir al cierre del ciclo productivo y la generación de nuevas alternativas de trabajo para la región. Para llevar a cabo este trabajo se realizó un estudio de campo en 15 trapiches de la región de Cundinamarca, donde se encontró que este residuo es utilizado dentro del proceso como fuente de energía (combustible). Adicionalmente, se revisó información secundaria relacionada con la producción de papel y etanol; posteriormente se realizó un proceso de análisis de la información enfocado en la capacidad energética del bagazo, los costos asociados a los procesos de producción y el impacto ambiental de los mismos, con el fin de determinar mediante un análisis de factibilidad la implementación de una nueva infraestructura que permita desarrollar procesos de producción. Finalmente, después de realizar el análisis de factibilidad teniendo en cuenta el impacto ambiental y la eficiencia energética del bagazo, teniendo en cuenta la cantidad de bagazo mensual producida y la capacidad instalada de las plantas de transformación de papel y etanol, se llegó a la conclusión que es más eficiente y viable utilizar este insumo como combustible en las moliendas de la región.