<p>Glycerol is one of the by-products of transesterification of fatty acids for the production of bio-diesel. Value-added products such as hydrogen, wood stabilizers and liquid chemicals from catalytic treatment of glycerol can improve the economics of the bio-diesel production process. Catalytic conversion of glycerol can be used for production of value-added liquid chemicals. In this work, a systematic study has been conducted to evaluate the effects of operating conditions on glycerol conversion to liquid chemical products in the presence of acid catalysts. </p><p>Central composite design for response surface method was used to design the experimental plan. Experiments were performed in a fixed-bed reactor using HZSM-5, HY, silica-alumina and ã-alumina catalysts. The temperature, carrier gas flow rate and weight hourly space velocity (WHSV) were maintained in the range of 350-500 oC, 20-50 mL/min and 5.40-21.60 h -1, respectively. </p><p>The main liquid chemicals detected in liquid product were acetaldehyde, acrolein, formaldehyde and hydroxyacetone. Under all experimental conditions complete glycerol conversion was obtained over silica-alumina and ã-alumina. A maximum liquid product yield of approximately 83 g/100g feed was obtained with these two catalysts when the operating conditions were maintained at 380 oC, 26 mL/min and 8.68 h-1. Maximum glycerol conversions of 100 wt% and 78.8 wt% were obtained in the presence of HY and HZSM-5 at temperature, carrier gas flow rate and WHSV of 470 oC, 26 mL/min and 8.68 h-1. HY and HZSM-5 produced maximum liquid product of 80.9 and 59.0 g/100 g feed at temperature of 425 and 470 oC, respectively.</p><p>Silica-alumina produced the maximum acetaldehyde (~24.5 g/100 g feed) whereas ã-alumina produced the maximum acrolein (~25 g/100 g feed). Also, silica-alumina produced highest formaldehyde yield of 9g/100 g feed whereas HY produced highest acetol yield of 14.7 g/100 g feed. The effect of pore size of these catalysts was studied on optimum glycerol conversion and liquid product yield. Optimum conversion increased from 80 to 100 wt% and optimum liquid product increased from 59 to 83.3 g/100 g feed when the pore size of catalyst was increased from 0.54 in case of HZSM-5 to 0.74 nm in case of HY, after which the effect of pore size was minimal.

<p>Glycerol is one of the by-products of transesterification of fatty acids for the production of bio-diesel. Value-added products such as hydrogen, wood stabilizers and liquid chemicals from catalytic treatment of glycerol can improve the economics of the bio-diesel production process. Catalytic conversion of glycerol can be used for production of value-added liquid chemicals. In this work, a systematic study has been conducted to evaluate the effects of operating conditions on glycerol conversion to liquid chemical products in the presence of acid catalysts. </p><p>Central composite design for response surface method was used to design the experimental plan. Experiments were performed in a fixed-bed reactor using HZSM-5, HY, silica-alumina and ã-alumina catalysts. The temperature, carrier gas flow rate and weight hourly space velocity (WHSV) were maintained in the range of 350-500 oC, 20-50 mL/min and 5.40-21.60 h -1, respectively. </p><p>The main liquid chemicals detected in liquid product were acetaldehyde, acrolein, formaldehyde and hydroxyacetone. Under all experimental conditions complete glycerol conversion was obtained over silica-alumina and ã-alumina. A maximum liquid product yield of approximately 83 g/100g feed was obtained with these two catalysts when the operating conditions were maintained at 380 oC, 26 mL/min and 8.68 h-1. Maximum glycerol conversions of 100 wt% and 78.8 wt% were obtained in the presence of HY and HZSM-5 at temperature, carrier gas flow rate and WHSV of 470 oC, 26 mL/min and 8.68 h-1. HY and HZSM-5 produced maximum liquid product of 80.9 and 59.0 g/100 g feed at temperature of 425 and 470 oC, respectively.</p><p>Silica-alumina produced the maximum acetaldehyde (~24.5 g/100 g feed) whereas ã-alumina produced the maximum acrolein (~25 g/100 g feed). Also, silica-alumina produced highest formaldehyde yield of 9g/100 g feed whereas HY produced highest acetol yield of 14.7 g/100 g feed. The effect of pore size of these catalysts was studied on optimum glycerol conversion and liquid product yield. Optimum conversion increased from 80 to 100 wt% and optimum liquid product increased from 59 to 83.3 g/100 g feed when the pore size of catalyst was increased from 0.54 in case of HZSM-5 to 0.74 nm in case of HY, after which the effect of pore size was minimal.

Abstract Blackcurrants (Ribes nigrum L.) are widely consumed due to their favourable taste and health-promoting effects. The berries and extracts from different parts of the plant show anticarcinogenic, antioxidative and anti-inflammatory properties, and are effective in reducing the risk of cardiovascular disease and in promoting brain health. These health-promoting benefits are due to high concentrations of valuable compounds such as anthocyanins and flavonols in blackcurrants. However, these compounds are sensitive to heat and processing and some are lost when the berries are processed into products such as jams, purees and juices. Industrial processing of juices is a multistep process that typically includes enzyme treatment, pressing, pasteurisation, clarification and usually also thermal concentration. Alternative minimal processing technologies are required to preserve the health-promoting compounds in products by avoiding the use of high temperatures and extensive clarification. Integrated membrane technology, i.e. combined ultrafiltration and reverse osmosis, was used in this thesis for the production of blackcurrant juice concentrate. Pre-treatment methods, such as enzymatic treatment, ultrafiltration, enzymatic treatment combined with ultrafiltration and centrifugation to increase the filtration efficiency in reverse osmosis were evaluated. Processing was modelled to define the resistances, using the resistance-in-series model. The preservation and concentration of anthocyanins and flavonols were analysed. The results indicated that the main resistance in the reverse osmosis process was polarisation resistance, while membrane resistance was lower and fouling resistance was one order of magnitude lower than the other resistances. The filtration efficiency results showed that the highest flux was achieved by ultrafiltered blackcurrant juice, but that the resulting juices were substantially lower in anthocyanins and flavonols, which were retained on the ultrafiltration membrane. Therefore, replacing ultrafiltration with centrifugation as the clarification method for juices is recommended. Value-added processing of blackcurrant was conceptualised by valorisation of the marc left in the berry pressing process for extraction of anthocyanin compounds. Conventional extraction was compared with microwave-assisted extraction (MAE), with the latter optimised using response surface methodology to achieve maximum efficiency in extracting anthocyanins. The optimum parameters found for MAE were: microwave power 700 W, extraction time 10 minutes, pH 2 adjusted with hydrochloric acid and a solid to solvent ratio of 0.05. Conventional extraction showed the best results when carried out at 80 &#176;C for 300 minutes in aqueous solution with pH 2 adjusted by hydrochloric acid. Under these conditions, recovery of anthocyanins was still 10% lower than with MAE for only 10 minutes of extraction time. / Tiivistelmä Mustaherukoita käytetään paljon niiden hyvän maun ja terveyttä edistävien vaikutusten ansiosta. Marjoilla ja marjakasvin eri osien uutteilla on osoitettu olevan antikarsinogeenisia, antioksidatiivisia ja tulehduksia estäviä ominaisuuksia ja ne ovat tehokkaita pienentämään sydän- ja verisuonisairauksia. Ne edistävät myös aivojen terveyttä. Marjojen arvokkailla yhdisteillä kuten antosyanideillä ja flavonoleilla on terveyttä edistäviä vaikutuksia. Mustaherukassa on runsaasti näitä yhdisteitä. Hillojen, soseiden ja mehujen prosessoinnissa menetetään näitä hyödyllisiä yhdisteistä, koska ne ovat herkkiä lämmölle ja prosessoinnin vaikutuksille. Mehujen prosessoinnissa käytetään entsyymikäsittelyjä, puristusta, pastörointia, selkeytystä ja usein myös lämpökonsentrointia. Tuotteiden terveyttä edistävien yhdisteiden säilyttämiseksi tarvitaan uudenlaisia hellävaraisia prosessointitekniikoita ilman korkeita lämpötiloja ja voimakasta selkeyttämistä. Tässä työssä tutkittiin yhdistettyjen kalvotekniikoiden kuten ultrasuodatuksen ja käänteisosmoosin käyttöä mustaherukkatiivistemehun prosessoinnissa. Esikäsittelymenetelmiä, mm. entsyymikäsittelyä, ultrasuodatusta, entsyymikäsittelyn ja ultrasuodatuksen yhdistelmää sekä sentrifugointia, arvioitiin käänteisosmoosin suodatustehokkuuden parantamisessa. Suodatusvastuksen määrittämiseksi prosessi mallinnettiin käyttäen sarja -vastus mallia. Antosyanidien ja flavonolien säilyminen ja konsentroituminen prosesseissa määritettiin. Tulokset osoittivat, että suurin vastus käänteisosmoosissa aiheutui polarisaatiovastuksesta, kun taas kalvon vastus oli pienempi. Mallinnus osoitti myös, että likaantumisen aiheuttama vastus oli yhtä magnitudia alhaisempi kuin muut vastukset. Suodatusteho osoitti, että suurin virtaus saavutettiin ultrasuodatetulla mustaherukkamehulla. Ultrasuodatetussa mehussa oli kuitenkin huomattavasti vähemmän antosyaniineja ja flavonoleja, mikä johtui näiden yhdisteiden tarttumisesta ultrasuodatuskalvoon. Näin ollen, tämän työn tulokset suosittelevat ultrasuodatuksen korvaamista sentrifugoinnilla mehun kirkastusprosessissa. Mustaherukkamehun tuotannossa muodostuu sivutuotteena ns. puristekakkua, joka sisältää runsaasti antosyaaneja. Työssä kehitettiin antosyaanien talteenottoa tästä sivutuotteesta vertaamalla tavanomaista uuttotekniikkaa mikroaaltoavusteiseen uuttoon. Prosessi optimoitiin vastepintamenetelmällä mahdollisimman suuren antosyaanien uuttotehokkuuden saavuttamiseksi. Optimaaliset parametrit saatiin mikroaaltoavusteisessa uutossa teholla 700 W, uuttoajalla 10 minuuttia, kiintoaines-liuotin -suhteella 0,05 pH-arvossa 2, mikä saavutettiin lisäämällä suolahappoa. Tavanomaisessa uutossa parhaat antosyaanisaannot saavutettiin suolahappo-vesiliuoksella pH-arvossa 2 uuttamalla 300 minuuttia lämpötilassa 80 &#176;C. Antosyaanisaanto oli kuitenkin tavanomaisessa uutossa optimiolosuhteissa 10% pienempi kuin mikroaaltoavusteisessa uutossa 10 minuutin uuttoajalla.