Preparation and characterization of some ionic liquids and their use in the dimerization reaction of 2-methylpropene

Abstract This study concentrates on the preparation and characterization of some ionic liquids and their use in dimerization reaction of 2-methylpropene. Ionic liquids consist of cations and anions, and are commonly understood as green solvents. By definition their melting points should be lower than 100 °C. Prepared ionic liquids were used as catalytic solvents in dimerizations of 2-methylpropene to a high octane compound, isooctene. The monograph consists of two parts: the literature survey and the practical work. The literature survey reviews the preparation and characterization of ionic liquids as well as their environmental aspects, such as toxicity, biodegradability and recyclability. In addition, the acid catalyzed dimerization of butenes is discussed together with the dimerizations of light olefins carried out in ionic liquids. The practical work consists of three entities: The environmentally benign preparation of 1-alkyl-3-methylimidazolium-based ionic liquids under microwave activation, the characterization of ionic liquids and the use of the ionic liquids in the dimerization reaction. Ionic liquids absorb efficiently microwave irradiation and the most beneficial aspect in the microwave-assisted preparations was the considerably shortened reaction time compared to the conventional methods. In addition to the microwave-assisted preparations, [Cnmim][InCl4] ionic liquids were prepared successfully without microwave irradiation. A special attention was paid to the characterization of ionic liquids since impurities are known to affect on the properties of the ionic liquids. Ionic liquids were analysed with the following methods: 1H and 13C NMR, MS(ESI+ and ESI-), GC and elemental analysis. Characterization of ionic liquids was done by determining the thermal stability, the melting point and the crystal structure of each solid ionic liquid. The determination of the liquid range of ionic liquid is necessary in order to know the temperature limits for each ionic liquid. Novel InCl3-based ionic liquids revealed to be the more efficient than Brønsted acidic ILs as a catalytic reaction media in the dimerization of 2-methylpropene. It was preferable to apply [C6mim]Cl/InCl3 (x(InCl3) = 0.55) as a catalytic IL since then the conversion of 2-methylpropene and the product distribution revealed to be good. In order to maximize the production and the separation of dimers reaction should be carried out continuously at temperature high enough, such as 160 °C. Neutral InCl3-based ionic liquid did not catalyze reaction of 2-methylpropene, but it had to be acidic x(InCl3) > 0.5. Excess of InCl3 did not leach out from the IL and the recycling of IL was possible

Production of 5-hydroxymethylfurfural from apple pomace in deep eutectic solvent

Abstract 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

Furfural and 5-Hydroxymethylfurfural production from sugar mixture using deep eutectic solvent/MIBK System

Abstract 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

Removal of cobalt and copper from aqueous solutions with sulfonated fruit waste

Abstract 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

Selective hemicellulose hydrolysis of Scots pine sawdust

Abstract The depletion of fossil resources is driving forward the search for new and alternative renewable feedstocks in the production of renewable chemicals, which could replace the petroleum-based ones. One such feedstock is pine (Pinus sylvestris) sawdust, which is generated enormous amounts in Finnish sawmills yearly. However, prior to the utilization in high-value applications, it needs to be fractionated into its constituents. In this work, the objective was to produce monomeric hemicellulose sugars from pine sawdust without degrading cellulose or lignin simultaneously. The influence of the reaction temperature and time, as well as acid type and concentration, was studied. Based on the results, the temperature was the main distinguishing feature between cellulose and hemicellulose hydrolysis. Promising results were achieved with acid mixtures consisting of 0.5% sulfuric acid and 5.5 or 10% formic acid. At 120 °C with the reaction time of 2 h, the mixtures produced hemicellulose sugars with the yields of 62%. These yields were comparable to the yields achieved in similar conditions with 1.5% sulfuric acid or 40% formic acid. Therefore, by using an acid mixture, the concentration of a single acid could be reduced significantly. The solid fractions remaining after the hydrolysis consisted mainly of cellulose and lignin, which verified the selectivity of the hemicellulose hydrolysis. Also, the fractionation of the remaining solids confirmed that the utilization of all the sawdust components is feasible

Conversion of xylose to furfural over lignin-based activated carbon-supported iron catalysts

Abstract 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

Preparation of cationized starch from food industry waste biomass and its utilization in sulfate removal from aqueous solution

Abstract 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

Catalytic conversion of glucose to 5-hydroxymethylfurfural over biomass-based activated carbon catalyst

Abstract 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

Brønsted and Lewis acid catalyzed conversion of pulp industry waste biomass to levulinic acid

Abstract 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

Azepanium based protic ionic liquids:synthesis, thermophysical properties and COSMO-RS study

Abstract Protic ionic liquids (ILs) with seven-membered azepanium cation were synthesized and characterized. The molecular structure of the synthesized ILs was confirmed using 1H NMR and 13C NMR spectroscopy. In one hand, sulfonic acid (SO3H) group was tethered to the azepanium moiety combined with HSPO4 or H2PO4−anion and on the other hand azepanium based alkyl sulfate ILs were synthesized by reacting azepane with corresponding dialkyl sulfates. Thermo-physical properties (density, viscosity, glass transition temperature, thermal decomposition temperature) of the synthesized ILs were measured. All the studied ILs showed good thermal stability. From the viscosity and density data of alkyl sulfate ILs, the volumetric properties such as molar volume, lattice energy and standard molar entropy were calculated. COSMO-RS was used to predict hydrogen bonding energy, interaction energy, Van der Waals energy and H-bond accepting and H-bond donating nature of these pure ILs. Activity coefficient values have also predicted for these ILs with cellulose