Innovation management of biorefineries in Finnish forest sector

The aim of this report is to give a comprehensive overview of the opportunities integrated biorefining can offer to Finnish forest industry companies and to assess what changes it would require from these companies to implement biorefining into their business. Also the strengths and weaknesses of the Finnish forest industry companies connected to biorefining are examined through innovation management theory frames, industry comparisons, company examples and couple of case-examples. The conclusions of the report include the statement that the Finnish forest industry has a good starting point for biorefinering and many advantages compared to other countries and industries. Unfortunately the history of the industry is holding it back and the thinking patterns would have to be altered to a more innovative and co-operational direction.

The Competitive Analysis of Selected Biorefineries in Finland

Biorefineries is a perspective field of study that covers many opportunities of a successful business unit with respect to sustainability. The thesis focuses on the following key objective: identification of a competitive biorefineries production process in small and medium segments of the chemical and forest industries in Finland. The scope of the research relates to the selected biorefineries operations in Finland and the use of hemicellulose, as a raw material. The identification of the types of biorefineries and the important technical and process characteristics opens the advantage in the company’s competitive analysis. The study concentrates on the practical approach to the scientific methods of the market and companies research with the help of Quality Function Deployment and House of Quality tool. The thesis’s findings provide mindset version of the expert’s House of Quality application, identification of crucial biorefineries technical and design characteristics’ correlation and their effect on the competitive behavior of a company. The theoretical background helps to build the picture of the problematic issues within the field and provides scientific possible solutions. The analysis of the biorefineries’ market and companies operations bring the practical-oriented aptitude of the research. The results of the research can be used for the following investigations in a field and may be applied as a company’s management analytic and strategic application.

Metsäpolttoaineiden vesitiekuljetus proomukalustolla

Metsäpolttoaineiden käyttö kasvaa lämpö- ja voimalaitoksissa ja mahdollisissa biojalostamoissa. Metsäpolttoaineilla voidaan saavuttaa päästövähennyksiä korvaamalla päästöintensiivisempiä polttoaineita. Metsäpolttoaineen kysynnän kasvu suurkäyttöpaikoilla luo uusia vaatimuksia metsäbiomassan hankintaan. Metsäpolttoaineiden vesitiekuljetuksen sisältämiä logistiikkajärjestelmiä kehittämällä toimitusvarmuutta pystytään parantamaan ja hankintaa laajentamaan kustannustehokkaasti ja ympäristöystävällisesti. Kuljetuskokeilut antoivat uutta tietoa vesitiekuljetuksen sisältämästä hankinnasta. Lastikapasiteetti nykyisen kaltaisessa Eurooppa IIa -suurproomussa vaihtelee 1200 tonnista jopa 1800 tonniin (kosteus 40 %) riippuen tiivistymisestä ja proomun modifiointiasteesta. Metsähakkeen energiatiheys oli suurproomukuljetuksissa keskimäärin 1 MWh/i-m3, joka oli 25 % parempi kuin vertailun hakerekkakuljetuksissa. Vesitiekuljetuksen kustannukset olivat kuljetuskokeiluissa lastauksineen ja purkuineen 0,02 €/MWh/km, ollen noin 20 % ketjun kokonaiskustannuksista. Simuloinnin edullisimpien vesitiekuljetusvaihtoehtojen vaihteluvälin kustannukset olivat vastaavasti 0,013 - 0,026 €/MWh/km. Lastauksen ja purun kustannus oli 0,4 - 0,6 €/MWh ja vesitiekuljetus 0,9 - 2,0 €/MWh (100 km). Ketjun kokonaiskustannukset hakkuutähdehakkeelle vaihtelivat simuloinnin edullisimpien vaihtoehtojen perusteella välillä 10,8 - 12,1 €/MWh (30 km rekka, 100 km proomu). Kuljetusketjujen simuloinnin kustannukset osoittivat proomukuljetusketjun olevan kilpailukykyinen vaihtoehto hakerekkakuljetusketjulle kalustosta ja vuosittaisista käyttötunneista riippuen kuljetusetäisyyden ylittäessä 100 km. Kustannustehokkain ratkaisu vesitiekuljetuksessa saavutettiin pienen aluksen ja suuren kokoluokan proomuyksikön kytkyeellä. Haketus kannattaa toteuttaa ennen proomukuljetuksen osuutta metsähakkeen paremman tiiviyden ja käsiteltävyyden perusteella. Logistiikkajärjestelmiä pitää kehittää tapauskohtaisesti käyttöpaikan tarpeet ja olosuhteet huomioon ottaen. Metsäpolttoaineiden vesitiekuljetuksen sisältämän logistiikan liiketoimintamallien vertailussa arvioitiin vaihtoehtoiset ulkoistetut toimintamallit paremmaksi kuin nykyinen urakointimalli. Tämä mahdollistaa paremman metsähakkeen saatavuuden ja logistiikan tehokkuuden lastausterminaaleissa. Terminaalitoiminnot ja proomukuljetukset lisäävät uusia liiketoimintamahdollisuuksia ja mahdollistavat metsäpolttoaineiden

Catalysis by gold for biomass transformations

The development of new technologies to supplement fossil resources has led to a growing interest in the utilization of alternative routes. Biomass is a rich renewable feedstock for producing fine chemicals, polymers, and a variety of commodities replacing petroleumderived chemicals. Transformation of biomass into diverse valuable chemicals is the key concept of a biorefinery. Catalytic conversion of biomass, which reduces the use of toxic chemicals is one of the important approaches to improve the profitability of biorefineries. Utilization of gold catalysts allows conducting reactions under environmentally-friendly conditions, with a high catalytic activity and selectivity. Gold-catalyzed valorization of several biomass-derived compounds as an alternative approach to the existing technologies was studied in this work. Isomerization of linoleic acid via double bond migration towards biologically active conjugated linoleic acid isomers (CLA) was investigated. The activity and selectivity of various gold catalysts towards cis-9,trans-11-CLA and trans-10,cis-12-CLA were investigated in a semi-batch reactor, showing that the yield of the desired products varied, depending on the catalyst support. The structure sensitivity in the selective oxidation of arabinose was demonstrated using a series of gold catalysts with different Au cluster sizes in a shaker reactor operating in a semibatch mode. The gas-phase selective oxidation of ethanol was studied and the influence of the catalyst support on the catalytic performance was investigated. The selective oxidation of the lignan hydroxymatairesinol (HMR), extracted from the Norway spruce (Picea abies) knots, to the lignan oxomatairesinol (oxoMAT) was extensively investigated. The influence of the reaction conditions and catalyst properties on the yield of oxoMAT was evaluated. In particular, the structure sensitivity of the reaction was demonstrated. The catalyst deactivation and regeneration procedures were studied. The reaction kinetics and mechanism were advanced.

Metsäenergian liiketoimintojen kehittäminen ja käytön kasvun vaikutukset Kaakkois-Suomessa

Kaakkois-Suomen alueella uusiutuvan energian käyttö ja erityisesti metsäenergian käyttö on kasvanut merkittävästi 2000-luvulla. Tulevaisuudessa metsäenergia nähdään edelleen potenti-aalisimpana vaihtoehtona korvattaessa fossiilisia polttoaineita lämpö- ja voimalaitoskokoluo-kassa. Muita uusiutuvan energian vaihtoehtoja ovat mm. tuuli- ja aurinkovoima, biokaasu sekä erilaiset kiinteät ja nestemäiset polttoainejalosteet. Tulevaisuudessa alueella voi olla mahdollis-ta tuottaa niin kansalliseen kuin kansainväliseen vientiin esim. biopolttonesteitä, biokaasua ja biohiiltä. Tutkimushankkeen tavoitteena oli selvittää metsäenergia-alan alueelliset toimijat sekä metsä-energian soveltuvuus ja liiketoimintamahdollisuudet Kaakkois-Suomen alueen energian tuo-tannossa. Tutkimus koostui seuraavista osatehtävistä: metsäsektorin toimijakentän kartoitus, metsäenergian alueelliset liiketoimintamahdollisuudet, puuperäisten polttoainejalosteiden käyttö- ja liiketoimintamahdollisuudet, muiden uusiutuvien energialähteiden käyttömahdolli-suudet ja vaikutukset Kaakkois-Suomessa. Tutkimuksessa arvioitiin myös Kaakkois-Suomen metsäenergian hankinnan työllisyysvaikutuksia. Tutkimuksen ohjausryhmänä toimi Kaakkois-Suomen metsäenergianeuvottelukunta. Tutkimuksessa kyselytutkimuksella selvitettiin metsäenergian tuottajien ja käyttäjien mielipi-teitä ja kehittämiskohteita toimialalta. Kaakkois-Suomessa hyödynnettävistä uusiutuvista energialähteistä selvitettiin nykyinen käyttö sekä arvioitiin tulevaisuuden hyödyntämismah-dollisuuksia vuonna 2020. Nämä tulokset esitettiin Kaakkois-Suomen energiataseen avulla. Kaakkois-Suomessa uusiutuvista energialähteistä puupolttoaineilla on merkittävin rooli metsä-teollisuuden johdosta ja alueen metsäenergian käyttö voi kasvaa jopa 1,7 TWh:in, mikäli fos-siilisia energialähteitä korvataan edelleen voimalaitoksissa ja lämpökeskuksissa. Metsäenergian käytön kasvussa alueen kunnilla on merkittävä rooli. Viime vuosina erityisesti tuulivoiman tuotanto on kasvanut ja tulee kasvamaan edelleen. Samoin aurinkoenergian hyödyntäminen kiinteistökokoluokassa on lisääntynyt voimakkaasti. Lisäksi maakuntaan on suunnitteilla kiin-teiden, nestemäisten ja kaasumaisten polttoainejalosteiden tuotantolaitoksia. Toteutuessaan laitokset voivat lisätä metsäenergian käyttöä merkittävästi.

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.

Enhancement of ultrafiltration process by pretreatment in recovery of hemicelluloses from wood extracts

Hemicelluloses are potential raw material for several items produced in future wood-based biorefineries. One possible method for recovering hemicelluloses from wood extracts is ultrafiltration (UF). However, low filtration capacities and severe fouling restrict the use of tight UF membranes in the treatment of wood extracts. The lack of suitable commercial membranes creates a need for pretreatment which would decrease fouling and increase the filtration capacity. This thesis focuses on the evaluation of the possibility to improve the filtration capacity and decrease fouling with the pretreatment of wood extracts. Methods which remove harmful compounds and methods which degrade them are studied, as well as combinations of the methods. The tested pretreatments have an influence on both the concentration of different compounds and the molecular mass distribution of the compounds in the extract. This study revealed that in addition to which kind of compounds were removed, also the change in molecular size distribution affected the filtration capacity significantly. It was shown that the most harmful compounds for the filtration capacity of the hydrophobic 5 kDa membrane were the ones capable of permeating the membrane and fouling also the inner membrane structure. Naturally, the size of the most harmful compounds depends on the used UF membrane and is thus case-specific. However, in the choice of the pretreatment method, the focus should be on the removal of harmful compound sizes rather than merely on the total amount of removed foulants. The results proved that filtration capacity can be increased with both adsorptive and oxidative pretreatments even by hundreds of per cents. For instance, the use of XAD7 and XAD16 adsorbents increased the average flux in the UF of a birch extract from nearly zero to 107 kg/(m2h) and 175 kg/(m2h), respectively. In the treatment of a spruce extract, oxidation by pulsed corona discharge (PCD) increased the flux in UF from 46 kg/(m2h) to 158 kg/(m2h). Moreover, when a birch extract batch was treated with laccase enzyme, the flux in UF increased from 15 kg/(m2h) to 36 kg/(m2h). However, fouling was decreased only by adsorptive pretreatment while oxidative methods had a negligible or even negative impact on it. This demonstrates that filtration capacity and fouling are affected by different compounds and mechanisms. The results of this thesis show that filtration capacity can be improved and fouling decreased through appropriate pretreatment. However, the choice of the best possible pretreatment is case-specific and depends on the wood extract and the membrane used. Finding the best option requires information on the extract content and membrane characteristics as well as on the filtration performance of the membrane in the prevailing conditions and a multivariate approach. On the basis of this study, it can be roughly concluded that adsorptive pretreatment improves the filtration capacity and decreases fouling rather reliably, but it may lead to significant hemicellulose losses. Oxidation reduces the loss of valuable hemicelluloses and could improve the filtration capacity, but fouling challenges may remain. Combining oxidation with adsorptive pretreatment was not a solution for avoiding hemicellulose losses in the tested cases.

Ultraäänen käyttö ligniinin ja hemiselluloosan ertuksessa puu-uutteesta

Puusta valmistetussa puu-uutteessa on puun polymeerejä, ligniiniä ja hemiselluloosaa, joiden käyttöä halutaan lisätä biojalostamoissa. Polymeerit tulisi erottaa mahdollisimman puhtaasti jatkojalostusta varten. Erotus voidaan tehdä ultrasuodatuksella. Puu-uutetta pitää kuitenkin esikäsitellä, sillä polymeerit ovat lähes samankokoisia. Ultraäänikäsittelyn on osoitettu kasvattavan ligniinin moolimassaa, jolloin myös erotus parantuisi. Ultraäänikäsittely on aikaisemmin käytettyihin esikäsittelymenetelmiin verrattuna ympäristöystävällisempi, sillä sen käytössä ei tarvita erillisiä kemikaaleja. Tämän työn tavoitteena oli selvittää, kuinka ultraäänikäsittely vaikuttaa ligniinin ja hemiselluloosan erotukseen PHWE-puu-uutteesta. Näytteen pH säädettiin emäksiseksi, näyte ultraäänikäsiteltiin eri koeolosuhteissa ja ultrasuodatettiin. Ultraäänikäsiteltyä näytettä verrattiin käsittelemättömään referenssinäytteeseen. Näytteet analysoitiin UV- ja TOC-analyyseillä konsentraattien ligniini- ja hiilipitoisuuksien selvittämiseksi. Lisäksi tarkasteltiin suodatusprosessin parametreja. Tulosten perusteella ultraäänikäsittely paransi ligniinin ja hemiselluloosan erotusta erilleen. Erotus parani eniten pH 12 -näytteessä, joka ultraäänikäsiteltiin 65 °C lämpötilassa, 45 minuutin ajan laiteteholla 175 W.