NOVEL SUPERABSORBENT HYDROGEL COMPOSITE BASED ON POLY(ACRYLAMIDE-CO-ACRYLATE)/NONTRONITE: CHARACTERIZATION AND SWELLING PERFORMANCE

A novel superabsorbent hydrogel (SH) composite based on a poly(acrylamide-co-acrylate) matrix filled with nontronite (NONT), a Fe(III)-rich member of the smectite group of clay minerals, is described in this manuscript. A variety of techniques, including FTIR, XRD, TGA, and SEM/EDX, were utilized to characterize this original composite. Experimental data confirmed the SH composite formation and suggested NONT was completely dispersed in the polymeric matrix. Additionally, NONT improved the water uptake capacity of the final material, which exhibited fast absorption, low sensitivity to the presence of salt, high water retention and a pH sensitive properties. These preliminary data showed that the original SH composite prepared here possesses highly attractive properties for applications in areas such as the agriculture field, particularly as a soil conditioner.

PYROLIGNEOUS LIQUOR PRODUCED FROM ACACIA MEARNSII DE WILD WOOD UNDER CONTROLLED CONDITIONS AS A RENEWABLE SOURCE OF CHEMICALS

Acacia mearnsii de Wild (black wattle) is one of the most important trees planted in Southern Brazil for tannin extraction and charcoal production. The pyrolysis of the black wattle wood used for obtaining charcoal is performed in brick ovens, with the gas fraction being sent directly into the environment. The present study examines the condensable compounds present in the liquor produced from black wattle wood at different thermal degradation conditions, using gas chromatography coupled with mass spectrometry (GC/MS). Branches of black wattle were thermally degraded at controlled ambient and temperature conditions. Overall, a higher variety of compounds were obtained under atmospheric air pressure than under synthetic air pressure. Most of the tentatively identified compounds, such as carboxylic acids, phenols, aldehydes, and low molecular mass lignin fragments, such as guayacol, syringol, and eugenol, were products of lignin thermoconversion. Substituted aromatic compounds, such as vanillin, ethyl vanillin, and 2-methoxy-4-propeny-phenol, were also identified. At temperatures above 200 ºC, furan, 2-acetylfuran, methyl-2-furoate, and furfural, amongst others, were identified as polysaccharide derivatives from cellulose and hemicellulose depolymerization. This study evidences the need for adequate management of the condensable by-products of charcoal production, both for economic reasons and for controlling their potential environmental impact.

Pinnoiteteollisuudessa syntyvien maalijätteiden hyötykäyttö ja uudet liiketoimintamahdollisuudet

Tämän diplomityön tavoite on kartoittaa maalien ja lakkojen valmistuksessa syntyvien sivuvirtojen hyötykäyttöä ja hyötykäyttöpotentiaalia nykyisellään. Työn tarkoitus on toimia esiselvityksenä pinnoiteteollisuuden sivuvirtojen hyötykäyttöön liittyvien liiketoimintamahdollisuuksien syvemmälle analyysille. Teollisuuden sivuvirtoihin liittyvää tietoa kerätään tilastoista ja olemassa olevista raporteista sekä haastattelemalla teollisuus- ja palveluyritysten edustajia sekä alan asiantuntijoita. Sivuvirtojen teknisten hyötykäyttömahdollisuuksien ja liiketoiminnallisten mahdollisuuksien tarkastelua varten järjestetään työpajoja asiantuntijoille Apila Group Oy Ab:n asiantuntijaverkostossa. Neljässä haastatellussa tuotantolaitoksissa syntyi vuonna 2008 yhteensä 6 662 tonnia kiinteää jätettä ja lietteitä. 68 % näistä sivuvirroista hyötykäytettiin energiana tai polttoaineen valmistuksessa. Materiaalina sivuvirtoja hyötykäytettiin 16 % sivuvirroista, pääasiassa pahvia, paperia, metalleja sekä tynnyreitä ja kontteja. Myös merkittävä osa liuottimista otettiin talteen uudelleenhyödyntämistä varten. Tässä diplomityössä hyötykäyttömahdollisuuksien tarkempaa tarkastelua varten valittiin tavanomaisiksi jätteiksi luokiteltuja maalisivuvirtoja, joita haastatelluissa tuotantolaitoksissa syntyi noin 1 500 tonnia. Maalisivuvirtojen tärkeimmät materiaaliominaisuudet liittyvät niiden sisältämiin täyte- ja sideaineisiin, jotka muodostavat merkittävän osan maalien koostumuksesta. Selvityksen mukaan nämä ominaisuudet voidaan ottaa hyötykäyttöön erilaisissa yhdistelmämateriaaleissa, esimerkiksi ekstruusiopuristetuissa tai ahtopuristetuissa muovikuitukomposiiteissa. Komposiittien raaka-aineena käytetään jo erilaisia sivuvirtoja ja lisäksi erilaisten komposiittien markkinoiden ennustetaan kasvavan. Tämä voi tarjota mahdollisuuksia uusille palvelu-, t&k- tai tuotteistusliiketoiminnoille. Kuivilla maalijätteillä on myös hyvä lämpöarvo, jolloin energiahyötykäytön ja palamisjäännöksen materiaalihyötykäytön yhdistäminen mm. keramiikka- tai sementtiteollisuudessa voi tarjota mahdollisuuksia uusille liiketoiminnoille.

Pretreatment in membrane filtration of wood hydrolysate

Interest in recovery of valuable components from process streams has increased in recent years. Purpose of biorefinery is to utilize components that otherwise would go to waste. Hemicelluloses, for example, could be utilized in production of many valuable products. One possible way to separate and fractionate hemicelluloses is membrane filtration. In the literature part of this work membrane fouling in filtration processes of pulp and paper process- and wastewaters was investigated. Especially purpose was to find out the possible fouling compounds, after which facilities to remove or modify such components less harmful were studied. In the experimental part different pretreatment methods, mainly to remove or degrade lignin from wood hydrolysate, were studied. In addition, concentration of hemicelluloses and separation from lignin were examined with two ultrafiltration membranes; UFX5 and RC70PP. Changes in feed solution, filtration capacity and fouling of membranes were used to evaluate the effects of pretreatment methods. Changes in hydrolysate composition were observed with different analysis methods. Filtration of hydrolysate proved to be challenging, especially with the UFX5 membrane. The more hydrophilic RC70PP membrane did not seem to be fouled as severely as the UFX5 membrane, according to pure water flux measurements. The UFX5 membrane retained hemicelluloses rather well, but problems arose from rapid flux decline resulting from concentration polarization and fouling of membrane. Most effective pretreatment methods in the case with the UFX5 membrane proved to be prefiltration with the RC70PP membrane, activated carbon adsorption and photocatalytic oxidation using titanium dioxide and UV radiation. An additional experiment with PHW extract showed that pulsed corona discharge treatment degraded lignin quite efficiently and thus improved filtration capacity remarkably, even over six times compared to the filtration with untreated extract.

Utilization of retention chemicals in non-wood containing furnishes

The usage of the non-wood pulps in furnishes for various paper grades is the real alternative for substitution of wood fibres in the papermaking. This is especially important now, when the prices for wood are increasing and forest resources are depleting in many regions of our planet. However, there are several problems associated with utilization of such pulps. In terms of the papermaking process one of the main problems is the poor dewatering of the non-wood pulps. This problem can be partially solved by means of retention aids. In the literature part were described technological features of the non-wood pulps as the raw materials for paper production. Moreover, overviews of the retention chemicals and methods for retention measurement were done; special attention was paid to the mechanisms of retention and drainage. Finally, factors affecting on the drainage and retention of non-wood pulps were considered holistically. Particular emphasis was put on the possibility of enzyme treatment for drainage improvement. It was stated that retention aids can significantly improve dewatering of non-wood pulps. In the experimental part the goal was to investigate influence of various microparticle retention aids on the drainage, retention and formation of furnish containing wheat straw pulp, obtained by novel pulping process (Formico™Fib). The parallel test were performed with reference furnish containing only wood pulps. It was found that Bentonite-CPAM retention aid can significantly improve drainage and retention; however formation seems be suffer from such additives. It was stated that performance of the Silica-Starch retention aid significantly depends on the starch dosing sequence and wet-end conditions; this system have shown better formation than other tested retention aids. Silica-CPAM retention aid have provided comparable results in retention and drainage with Bentonite-CPAM, while Silica-starch did not improve dewatering and yielded in lowest filler retention among other aids. Ultimately, optimal dosages for the tested retention chemicals have been suggested.