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Owing to the abundance of availability, low cost, and environmental-friendliness, biomass waste could serve as a prospective renewable source for value-added chemicals. Nevertheless, biomass conversion into chemicals is quite challenging due to the heterogeneous nature of biomass waste. Biomass-derived chemicals are appealing sustainable solutions that can reduce the dependency on existing petroleum-based production. Metal-organic frameworks (MOFs)-based catalysts and their composite materials have attracted considerable amounts of interest in biomass conversion applications recently because of their interesting physical and chemical characteristics. Due to their tunability, the catalytic activity and selectivity of MOF-based catalyst/composite materials can be tailored by functionalizing them with a variety of functional groups to enhance biomass conversion efficiency. This review focuses on the catalytic transformation of lignocellulosic biomass into value-added chemicals by employing MOF-based catalyst/composite materials. The main focus is given to the production of the platform chemicals HMF and Furfural from the corresponding (hemi)cellulosic biomass, due to their versatility as intermediates for the production of various biobased chemicals and fuels. The effects of different experimental parameters on the conversion of biomass by MOF-based catalysts are also included. Finally, current challenges and perspectives of biomass conversion into chemicals by MOF-based catalysts are highlighted.

In this study, orange peel waste was successfully sulfonated with SO₃-pyridine complex in 1-allyl-3-methylimidazolium chloride ionic liquid in various reaction conditions. ¹H NMR was used to verify the occurrence of the reaction and to select the most promising material for the adsorption experiments. The degree of substitution of the sulfonated orange peel waste used for cobalt and copper removal was found to be 0.82. It was prepared with the reaction temperature and time of 70 ℃ and 60 min respectively and with the SO₃-pyridine complex to-peel waste ratio of 5:1. The selected material combined with ultrafiltration removed 98% of copper and 91% of cobalt from single metal solutions and 93% of copper and 83% of cobalt from binary metal solution at pH 5 with adsorbent dosage of 12.5 mg/100 mL and initial metal concentration of 8 mg/L. Preliminary experiments were also performed with apple pomace which was sulfonated in the conditions found best for the orange peel waste. The prepared sulfonated apple pomace proved to be almost as effective in cobalt and copper removal as sulfonated orange peel waste, removing 82% of copper and 77% of cobalt from binary metal solution with 12.5 mg/100 mL dosage at pH 5 and an initial metal concentration of 8 mg/L.

Apple pomace is a waste stream produced by fruit processing industry millions of tons annually. It is rich in carbohydrates making it a potential feedstock for the production of 5-hydroxymethylfurfural (HMF), one of the most valuable platform chemicals. In this work, the conversion of apple pomace carbohydrates to HMF was studied in a choline chloride:glycolic acid (1:3) deep eutectic solvent. To prevent undesired side reactions of HMF methyl isobutyl ketone was added to the reaction system as an extractive phase. The effect of reaction conditions, i.e., the amount of water added to the reaction system, the presence of Lewis acid co-catalyst, as well as the reaction temperature and time, on HMF yield were studied. The highest total HMF yield (44.5%) was achieved at 110 °C in 10 min with 15 wt% H₂O, and 0.01 g CrCl₃ as co-catalyst. Without the co-catalyst, the highest achieved HMF yield was 37.3% (120 °C, 20 min, 15 m% H₂O). The results indicated that apple pomace can be used as the feedstock for HMF production but the reaction procedure, especially the extraction process of HMF from deep eutectic solvent needs to be studied further.

Forest-based sectors such as sawmills and pulp and paper play an important role in Finnish industry. Lignocellulosic side stream fractions from these activities, such as wood sawdust and lignin, are primarily used for energy. However, these fractions could be used more efficiently in biorefinery concepts like the production of value-added bio-based materials and chemicals instead of energy production. In biorefinery concepts, catalysis is an important tool for creating more sustainable processes. Efforts to develop novel catalytic systems for biomass valorization to obtain platform chemicals from biomass feedstock are worth pursuing. In catalytic applications, novel bio-based activated carbon catalysts could be used to replace the non-renewable catalytic materials currently used. In this thesis, the application of lignocellulose-based side stream materials as a raw material for activated carbon catalysts and their use in catalytic applications are studied, and the physical and chemical characteristics of the activated carbon catalysts prepared using various methods are examined. Catalysts prepared for catalytic conversion reactions to produce value-added chemicals for biorefinery applications are investigated: specifically, the conversion of the biomass-based molecules furfural and glucose into 2-methylfuran, 5-hydroxymethylfurfural, lactic acid and its ester, ethyl lactate. This research provides new insights into the preparation of lignocellulose-based activated carbon catalysts and their suitability for catalytic conversion reactions to produce important value-added chemicals for industrial applications. The present study found that lignocellulosic side stream materials can be used in preparing high-quality activated carbon catalysts or supported catalysts. Prepared carbon-based catalysts showed promising results in the conversion reactions studied, indicating that tailored catalyst supports for specific applications are needed., Tiivistelmä Suomessa metsä- ja sahateollisuus sekä paperi- ja selluteollisuus ovat keskeisiä teollisen tuotannon toimialoja. Tuotannossa syntyvät arvokkaat sivuvirrat, kuten sahanpuru- sekä ligniinifraktiot hyödynnetään tänä päivänä suurelta osin energiantuotannossa polttamalla. Nämä arvokkaat sivuvirrat voidaan hyödyntää energiatuotannon sijaan biojalostamokonsepteissa korkeamman lisäarvon tuotteiksi, kuten uusiksi biomassapohjaisiksi biomateriaaleiksi ja -kemikaaleiksi. Biojalostamokonsepteissa katalyyttiset menetelmät ovat tärkeässä roolissa mahdollistaen energiatehokkaammat prosessit. Uusien katalyyttisten menetelmien kehittäminen biomassan konvertoimiseksi biokemikaaleiksi ja -materiaaleiksi on tavoiteltavaa. Biopohjaisilla aktiivihiilikatalyyteillä voidaan myös korvata nykyisiä ei-uusiutuvia katalyyttejä. Tässä väitöskirjatutkimuksessa on tutkittu lignoselluloosapohjaisten sivuvirtamateriaalien soveltuvuutta aktiivihiilipohjaisten katalyyttimateriaalien valmistukseen sekä näiden katalyyttien käyttöä sovelluksissa. Aktiivihiilten fysikaalisten ja kemiallisten ominaisuuksien vaikutusta katalyyttimateriaaleihin ja sovelluksiin on tutkittu. Valmistettujen katalyyttien soveltuvuutta konversioreaktioissa korkean lisäarvon tuotteiksi biojalostamosovelluksiin on tutkittu: erityisesti biomassapohjaisten molekyylien kuten furfuraalin ja glukoosin konversiota 2-metyylifuraaniksi, 5-hydroksimetyylifurfuraaliksi, maitohapoksi sekä maitohapon esteriksi etyylilaktaatiksi. Tutkimus tuo uutta tietoa lignoselluloosapohjaisten sivuvirtamateriaalien hyödyntämisestä ja soveltuvuudesta biopohjaisten aktiivihiilikatalyyttien valmistuksessa sekä käytöstä katalyyttisissä sovelluksissa korkean lisäarvon kemikaalien tuotannossa. Tutkimuksessa havaittiin, että lignoselluloosapohjaisia sivuvirtoja voidaan hyödyntää korkealaatuisten aktiivihiilikatalyyttimateriaalien valmistuksessa. Valmistetut hiilipohjaiset katalyytit osoittivat potentiaalia tutkituissa sovelluksissa ja tutkimus viittasi

Choline chloride (ChCl) / glycolic acid (GA) deep eutectic solvent (DES) media with high water content but without any additional catalyst are introduced in furfural and 5-hydroxymethylfurfural (HMF) production. The effects of water content, reaction time, and reaction temperature are investigated with two feedstocks: a glucose/xylose mixture and birch sawdust. Based on the results, 10 equivalent quantities of water (32.9 wt.%) were revealed to be beneficial for conversions without rupturing the DES structure. The optimal reaction conditions were 160 °C and 10 minutes for the sugar mixture and 170 °C and 10 minutes for birch sawdust in a microwave reactor. High furfural yields were achieved, namely 62 % from the sugar mixture and 37.5 % from birch sawdust. HMF yields were low, but since the characterization of the solid residue of sawdust, after DES treatment, was revealed to contain only cellulose (49 %) and lignin (52 %), the treatment could be potentially utilized in a biorefinery concept where the main products are obtained from the cellulose fraction. Extraction of products into the organic phase (methyl isobutyl ketone, MIBK) during the reaction enabled the recycling of the DES phase, and yields remained high for three runs of recycling.

Sawdust is an abundant but poorly utilized lignocellulosic side stream. It is mainly burned as energy despite the fact that it could be utilized in the production of biomass-based chemicals. Sawdust is composed of cellulose, hemicellulose, and lignin fractions, all of which can be separated and utilized for different applications. The production of so-called high-value-added chemicals from biomass could improve the economics associated with biorefinery and replace certain petroleum-based chemicals as well. Recently, the production of 5-hydroxymethylfurfural (HMF) and furfural has attracted a considerable amount of interest, as these substances can be prepared from sawdust-based sugars and play a key role in the production of many biomass-based products. The catalytic conversion of sawdust-based sugars into HMF and furfural was studied in this thesis. The comprehensive utilization of sawdust through stepwise fractionation, hydrolysis, and conversion were used, and all the reaction steps were geared toward high selectivity. In addition, different homogeneous and heterogeneous catalysts, such as mineral acids, organic acids, metal salts, catalysts based on activated carbon (AC), and deep eutectic solvents (DESs), were also utilized in this research. In the first part of the thesis, sawdust was selectively degraded to produce either hemicellulose sugars or furfural using acid hydrolysis or DES treatment. In the second part, sawdust-based sugars were converted into HMF and furfural using different AC-based catalysts or DES media. Based on the results obtained, it was demonstrated that hemicellulose could be efficiently separated as sugars and furfural from the sawdust. These processes could potentially be utilized in biorefinery concepts where the main products are currently obtained from cellulose. In addition, the selectivity of HMF and furfural production from sawdust-based sugars could be significantly improved with the use of AC catalysts in the conversion, Tiivistelmä Sahanpuru on laajasti saatavilla oleva mutta huonosti hyödynnetty lignoselluloosapitoinen sivuvirta. Se poltetaan pääasiassa energiana, vaikka se voitaisiin hyötykäyttää erilaisten biomassaperäisten tuotteiden valmistuksessa. Sahanpuru koostuu selluloosa-, hemiselluloosa- ja ligniinifraktioista, jotka voidaan erottaa toisistaan ja hyötykäyttää erilaisissa sovelluksissa. Niin sanottujen korkean lisäarvon tuotteiden valmistaminen biomassasta voisi sekä lisätä biojalostamoiden taloudellista kannattavuutta että korvata osan öljypohjaisista tuotteista biomassaperäisillä vastineilla. Viime aikoina 5-hydroksimetyylifurfuraalin (HMF) ja furfuraalin tuotanto on herättänyt paljon kiinnostusta, sillä ne voidaan valmistaa sahanpurun sisältämistä sokereista ja niillä on keskeinen rooli monien biomassaan perustuvien tuotteiden valmistuksessa. Tässä työssä tutkittiin sahanpurun sisältämien sokereiden katalyyttistä konversiota HMF:ksi ja furfuraaliksi. Sahanpuru hyödynnettiin kokonaisvaltaisesti vaiheittaisen fraktioinnin, hydrolyysin ja konversion avulla siten, että reaktioiden korkea selektiivisyys säilyi joka vaiheessa. Työssä hyödynnettiin erilaisia homogeenisia sekä heterogeenisiä katalyyttejä, kuten mineraalihappoja, orgaanisia happoja, metallisuoloja, aktiivihiilipohjaisia katalyyttejä ja syväeutektisia liuottimia (DES). Työn ensimmäisessä osassa sahanpurun hemiselluloosafraktio pilkottiin selektiivisesti joko sokereiksi tai furfuraaliksi. Tähän käytettiin happohydrolyysiä tai DES-käsittelyä. Työn toisessa osassa sahanpurun sisältämiä sokereita muunnettiin HMF:ksi ja furfuraaliksi käyttäen erilaisia aktiivihiilikatalyyttejä tai hyödyntäen syväeutektisia liuottimia. Saadut tulokset osoittivat, että hemiselluloosa voidaan erottaa sahanpurusta selektiivisesti sekä sokereina että furfuraalina. Tämä olisi hyödynnettävissä esimerkiksi biojalostamoissa, joissa nykyiset päätuotteet saadaan selluloosasta. Lisäksi tulokset osoittivat että HMF- ja furfuraalituotannon selekt

In this study, conversion of xylose to furfural was studied using lignin-based activated carbon-supported iron catalysts. First, three activated carbon supports were prepared from hydrolysis lignin with different activation methods. The supports were modified with different metal precursors and metal concentrations into five iron catalysts. The prepared catalysts were studied in furfural production from xylose using different reaction temperatures and times. The best results were achieved with a 4 wt% iron-containing catalyst, 5Fe-ACs, which produced a 57% furfural yield, 92% xylose conversion and 65% reaction selectivity at 170 °C in 3 h. The amount of Fe in 5Fe-ACs was only 3.6 µmol and using this amount of homogeneous FeCl₃ as a catalyst, reduced the furfural yield, xylose conversion and selectivity. Good catalytic activity of 5Fe-ACs could be associated with iron oxide and hydroxyl groups on the catalyst surface. Based on the recycling experiments, the prepared catalyst needs some improvements to increase its stability but it is a feasible alternative to homogeneous FeCl₃.

In this study, the effect of a mechanocatalytic pretreatment on the structure of willow and sugar release from pretreated willow was explored. In the mechanocatalytic approach, the pretreatment consists of solvent-free impregnation with sulfuric acid and a mechanical treatment with ball milling. Willow sawdust and pretreated samples were analyzed with field emission scanning electron microscope and X-ray diffraction. The products in the sugar solution were determined as the total reducing sugars with the 3,5-dinitrosalicylic acid method and monosaccharides with capillary electrophoresis. According to the results, milling increased the sugar production, depending on the sulfuric acid load. The milling parameters, such as the rotation speed of the mill, the catalyst-to-willow ratio, and the milling time influenced the amount of sugars in the hydrolysate and the composition of the sugar solution produced. Changes were observed in the surface of the willow particles as well as changes in the crystalline structure. Glucose and xylose yields increased after 15 min of milling and reached their maximum level after 45 min of milling with the 0.5 mmol/g sulfuric acid load.

In this work pine sawdust was converted into levulinic acid (LA) and furfural. Sawdust was first pre-treated with sulfuric acid-catalysed mechanical depolymerization. The conversion reactions were then performed with microwave heating at 180 °C. To enhance the furfural yield and the efficient separation of furfural and LA, a biphasic water-toluene reaction system was used. The effect of an additional catalyst, AlCl₃, on the yield of LA and furfural was also studied. According to the results the pre-treatment method enhanced the yields of LA. In addition, due to the microwave heating the reaction times were short. Additional AlCl₃ catalyst enhanced the LA yield, however excellent furfural yields were achieved even without it. Best LA yield (38%) was achieved with 6 h of milling combined with 30 min of microwave heating while the best furfural yield (85%) was achieved with 4 h of milling and 20 min of microwave heating.

Selective and efficient dehydration of glucose to 5-hydroxymethylfurfural (HMF) has been widely explored research problem recently, especially from the perspective of more sustainable heterogeneous catalysts. In this study, activated carbon was first produced from a lignocellulosic waste material, birch sawdust. Novel heterogeneous catalysts were then prepared from activated carbon by adding Lewis or Brønsted acid sites on the carbon surface. Prepared catalysts were used to convert glucose to HMF in biphasic water:THF system at 160 °C. The highest HMF yield and selectivity, 51% and 78%, respectively, were obtained in 8 h with a catalytic mixture containing both Lewis and Brønsted acid sites. Also, preliminary recycling experiments were performed. Based on this study, biomass-based activated carbon catalysts show promise for the conversion of glucose to HMF.

Enormous amounts of fiber sludge are generated annually by the pulp industry as a by-product. As a cellulose-rich material, its current usage, mainly as fuel, is inefficient from a material efficiency point of view. This work studied the utilization of fiber sludge from a Finnish and a Swedish pulp mill as a potential feedstock to produce levulinic acid, a valuable platform chemical. The conversion experiments of fiber sludge to levulinic acid were performed in a microwave reactor with a mixture of H2SO4 and Lewis acid as the catalyst. The reaction conditions, which included reaction time and temperature as well as the H2SO4 and Lewis acid concentrations, were studied in detail. The highest levulinic acid yield, 56%, was obtained with Swedish fiber sludge after 60 min at 180 °C with the H2SO4 concentration of 0.3 mol/L and a CrCl3 concentration of 7.5 mmol/L which indicated that the fiber sludge had the potential to be used as feedstock for levulinic acid production.

In this work, untreated starch-rich potato peel waste was used as a starting material in preparation of cationized starch (CS¹) in water solution with 2-chloro-3-hydroxypropyltrimethylammonium chloride (CHPTAC) as the cationization reagent. The impact of various factors (activation time, temperature, reaction time, the amount of CHPTAC and NaOH) on the degree of substitution (DS) of CS was studied by using experimental design. The DS values were determined by ¹H NMR. The highest DS (0.40) was obtained when the reaction time was 8 h, temperature 30 °C, the molar ratio of CHPTAC and NaOH to AGU 3 and 3.75, respectively. The prepared CS was successfully used to remove sulfate ions from an aqueous solution with ultrafiltration technique. Sulfate is a major pollutant of water bodies so development of efficient techniques for its removal is detrimental. The removal of sulfate in study was 74% at best.

Starch is one of the most abundant polysaccharides found in nature and is widely utilized in various fields of industry. Due to the complex structure of native starch it is insoluble in most organic solvents and needs modification prior utilization. In this study, ionic liquids (ILs), modern green chemistry alternatives for common solvents were used as reaction media in starch modification. At first various starch species were depolymerized in 1-allyl-3-methylimidazolium chloride ([AMIM]Cl) with p-TsOH as a catalyst. Microwave activation or conventional bath heating were used as heating methods while HPLC-ELSD was used as an analytical method. All studied starch species depolymerized similarly into water-soluble starch oligomers while microwave activation shortened the depolymerization time considerably compared to oil bath heating. Barley starch was chosen for further experiments, in which various ILs were studied as potential media for starch dissolution and depolymerization. Results suggested that both the anion and the cation part of the IL had an effect on the dissolution and depolymerization of barley starch. After the depolymerization reactions, the depolymerized barley starch was further modified by cationization. [AMIM]Cl was used as the reaction media, microwave activation as the heating method while HPLC-ELSD, 1H NMR and elemental analysis were used as analytical methods. The modified products had DS values from 0.2 to 0.5 depending on the reaction conditions. The products were studied as potential binding agents for heavy metal ions which showed that moderately substituted modified starch (DS 0.4) could be used to bind Cu(II), Fe(III) and Zn(II) ions from an aqueous solution. Finally, potato peel waste was studied as an alternative starch source to produce cationized starch for wastewater purification. Peel waste was pre-treated by alkaline depolymerization after which it was cationized in a water solution to produce cationized products with DS, Tiivistelmä Tärkkelys on yksi yleisimmistä luonnossa esiintyvistä polysakkarideista. Sitä hyödynnetään useilla eri teollisuuden aloilla. Monimutkaisen rakenteensa vuoksi tärkkelys on liukenematon useimpiin orgaanisiin liuottimiin ja veteen, minkä vuoksi sitä täytyy modifioida ennen käyttöä. Tässä väitöstutkimuksessa tärkkelyksen modifioinnissa käytettiin ionisia nesteitä reaktioväliaineena. Tutkimuksen alussa eri tärkkelyslajeja depolymeroitiin 1-allyyli-3-metyyli-imidatsoliumkloridissa ([AMIM]Cl) katalyyttinä p-TsOH. Mikroaaltoaktivointia ja haudekuumennusta käytettiin vaihtoehtoisina lämmitysmenetelminä. Reaktion edistymistä ja tuotteiden muodostumista tutkittiin HPLC-ELSD -menetelmällä. Eri tärkkelyslajit depolymeroituivat samankaltaisesti vesiliukoisiksi, lyhytketjuisiksi tärkkelysoligomeereiksi. Mikroaaltoaktivointi lyhensi reaktioaikaa haudekuumennukseen verrattuna. Tutkimuksen seuraavassa vaiheessa tutkittiin ohratärkkelyksen liukoisuutta ja depolymeroitumista eri ionisissa nesteissä. Tulosten perusteella ionisen nesteen sekä anioni- että kationiosa vaikuttivat tärkkelyksen liukenemiseen. Depolymeroidun ohratärkkelyksen modifiointitutkimuksia jatkettiin [AMIM]Cl:ssa kationisoinnilla. Lämmitysmenetelmänä käytettiin mikroaaltoaktivointia. Tuotteet tutkittiin käyttäen alkuaineanalyysiä sekä HPLC-ELSD- että 1H NMR-tekniikoita. Kationisoitujen tuotteiden substituutioaste (DS) vaihteli reaktio-olosuhteista riippuen välillä 0.2–0.5. Saatuja tuotteita tutkittiin raskasmetalli-ionien sitomisessa vesiliuoksesta. Havaittiin, että kohtalaisesti substituoitu (DS 0.4) modifioitu tärkkelys sitoi Cu(II)-, Fe(III)- ja Zn(II)-ioneja vesiliuoksesta. Tutkimuksen loppuosassa tutkittiin perunan kuorijätettä vaihtoehtoisena tärkkelyslähteenä kationisoidun tärkkelyksen valmistamisessa. Kuorijäte esikäsiteltiin kuumentamalla se emäksisessä etanoliliuoksessa, minkä jälkeen sille suoritettiin kationisointi vesiliuoksessa. Kationisten tuotteiden substituutioasteet vaihtelivat välillä 0–