Caracterização cromatográfica de compostos orgânicos presentes nos resíduos sólidos provenientes de indústria de reciclagem de papel e sua aplicação na produção de briquetes de carvão vegetal

Recycling of paper in industrial scale has become an established practice worldwide. In this work, organic compositions of three different kinds of sludge generated in recycle paper industry were studied, and the incorporation of one of those sludge in briket was also investigated. The characterization of organic compounds in sludge samples and briket was performed using Gas Chromatography coupled with Mass Spectrometry after a Soxhlet extraction. Different chemical classes were identified in each type of sludge, but just the sludge composed by cellulose residue did not presented polyaromatic hydrocarbons. Four formulations of sludge incorporated with charcoal for briket production were evaluated.

Ozonólise: a busca por um mecanismo

The ozonolysis reaction is widely used in the academy and in industry. The first reports about the existence of the ozone molecule were made over 200 years ago. Several ideas and assumptions were made to understand the chemical properties of the ozone molecule and the ozonolysis mechanism. The intent of this paper is not to be an extensive review about ozone chemistry or ozonolysis reactions, but to highlight how the rational process was developed and how conclusions were drawn at a time with limited instrumentation.

Magnesiumhydroksidialkalin käytön vaikutukset päällystämättömän aikakauslehtipaperin valmistukseen

Magnesiumhydroksidin on havaittu soveltuvan natriumhydroksidin korvaajaksi mekaanisen massan peroksidivalkaisun alkalina. Työssä selvitettiin, miten magnesiumhydroksidi vaikuttaa paperin valmistukseen ja valmiin paperin ominaisuuksiin. Laboratoriokokeet osoittivat magnesiumhydroksidin soveltuvan mekaanisen massan peroksidivalkaisun alkaliksi, sillä vaaleustavoite saavutettiin sen avulla. Valkaistun massan varaustila, johtokyky sekä ζ -potentiaali laskivat magnesiumhydroksidin vaikutuksesta. Nämä johtivat huomattavasti korkeampaan paperin täyteaineretentioon. Massan vedenpidätyskyky kasvoi korvattaessa natriumhydroksidi magnesiumhydroksidilla. Arkkien ominaisuuksista vetoindeksi, valonsirontakerroin ja taivutusjäykkyys kasvoivat. Kaikki edellä mainitut ominaisuudet viittaavat siihen, että magnesiumhydroksidin käyttö parantaa hienoaineen sitoutumista paperiin.

Nosturin kuormauselimen liitynnän suunnittelu

Paperiteollisuuden prosessituotteista paperia varastoidaan erikokoisina rullina esim. pystyrullavarastoihin. Tämän diplomityön tavoitteena oli kehittää Konecranesin prosessinosturille liityntä paperirullia käsittelevän kuormauselimen ja nosturin välille. Tavoitteena oli löytää kiinnitysmenetelmä, joka mahdollistaa nosturien joustavan käytön mahdollisimman pienin muutoksin itse nosturin standardoituun rakenteeseen. Pääasiallisena syventymisen kohteena oli alipaineella paperirullia nostettavan kuormauselimen liityntä. Liitynnän on kyettävä joustamaan ja vaimentamaan paperirullia nostavaan kuormauselimeen nosturin liikkeelle lähdöstä ja pysähtymisestä syntyvät herätteet ja voimat. Nosturin liikenopeus on kyettävä pitämään mahdollisimman suurena lyhyen rullienkäsittelyajan saavuttamiseksi. Liitynnältä vaaditaan kykyä ottaa kuormauselin vastaan mahdollisimman suurella nostonopeudella. Lisäksi kuorman ja kuormauselimen oskillaatio on vaimennettava mahdollisimman nopeasti samalla rajoittaen heilunnasta aiheutuvaa maksimi siirtymää. Liitynnän suunnittelu pohjautuu nosturin, kuormauselimen ja paperirullan muodostaman systeemin teoreettiseen tarkasteluun. Systeemistä laadittiin dynaaminen malli, jonka avulla tutkittiin oskillaation ja syntyvien kiihtyvyyksien suuruutta. Näiden teoriaan perustuvien tuloksien pohjalta suunniteltiin vaimennukseen tarvittavat vaimennuselementit ja liitynnän rakenne. Suunnittelutyön tuloksena saatiin liitynnälle alustava rakenne, joka mahdollistaa käytettävien vaimennuselementtien vaihtamisen ja siten tehokkaan heilunnan vaimmennuksen. Suunnittelutyön lähtökohtana oleva teoreettinen tarkastelu vaatii tuekseen esim. prototyypin kokeellisten tulosten saamiseksi ennen lopullisen tuotteen valmistamista. Suunnitteluprosessissa noudatettiin järjestelmällisen tuotesuunnittelun vaiheita ja menetelmiä.

Pumppukäyttöjen energiankulutuksen määrittäminen prosessimittauksia käyttäen

Pumppukäytöt vastaavat noin neljännestä Euroopan alueen sähkömoottoreissa kuluvasta energiasta. Energian hinnan nousun vuoksi energian säästäminen ja energiatehokkuus ovat nousseet tärkeään asemaan paljon energiaa kuluttavassa teollisuudessa. Pumppukäyttöjen hyötysuhteen parantaminen on noussut olennaiseen osaan paperi- ja kartonkiteollisuuden energiatehokkuustarkasteluissa. Tässä työssä tarkastellaan kartonkikoneen pumppukäyttöjen toiminnan energiatehokkuutta moottorin virtamittausten perusteella. Analyysi perustuu moottorin akselitehon määrittämiseen ja sen perusteella tehtävään pumpun toimintapisteen laskentaan. Työssä esitellään käytetyt estimointimenetelmät ja niillä saadut tulokset kartonkikoneen pumppukäytöille. Lisäksi työssä arvioidaan kolmen yksittäisen pumppukäytön energiankulutuksen säästöpotentiaalia. Työssä käytettyä menetelmää voidaan käyttää sekä vakio- että vaihtonopeuspumppukäyttöjen toiminnan ja hyötysuhteen analysointiin.

Taivekartongin sävytys ja jälkikellertyminen

Taivekartongilta vaaditaan nykyisin korkealaatuista ja tasaista ulkonäköä. Pakkauksen tehtävänä on parantaa myyntiä hyvällä ulkonäöllä ja siisteydellä sekä antaa informaatiota ja käyttöohjeita. Tässä diplomityössä tutkittiin taivekartongin sävyttämistä, optisia ominaisuuksia sekä vaaleuden ja sävyjen pysyvyyttä. Kirjallisuusosassa käsiteltiin paperin ja kartongin optisia ominaisuuksia sekä esiteltiin Kubelka-Munkin teoria. Teoriaa voidaan käyttää mm. monikerroskartongin vaaleuden ja sävyjen mallintamisessa. Esillä oli paljon eri prosessitekijöitä, massoja ja kemikaaleja, jotka vaikuttavat kartongin vaaleuteen ja sävyyn. Työssä kärsiteltiin myös keinoja vaikuttaa kartongin sävyyn sävytyksellä ja sävytyksen eri tapoja. Toisaalta vaaleuden ja sävyn pysyvyyteen vaikuttaa kartongin jälkikellertyminen. Työssä tarkasteltiin jälkikellertymisen mekanismeja ja siihen vaikuttavia tekijöitä sekä esitettiin keinoja ennalta ehkäistä ja estää kellertymistä. Kokeellisessa osassa käsiteltiin massan ja päällystyspastan värjäyksen vaikutuksia ulkonäköön ja optisiin ominaisuuksiin. Sinertävillä tai violeteilla sävyväreillä voidaan pienentää mekaanisten massojen luonnollista kellertyvyyttä, jolloin valkoisuuden vaikutelma lisääntyy. Värien lisääminen heikentää vaaleutta, koska värien lisäys nostaa valon absorptiota. Tämän takia on tärkeää lisätä väri mielellään siihen kerrokseen, jossa kellertävä massa on, joka on tyypillisesti kartongin keskikerros. Pintakerrokset ovat valkaistua sellua ja niillä on tärkeä merkitys kartongin vaaleudelle, joten värin lisäys pintaan alentaisi vielä merkittävämmin kartongin kokonaisvaaleutta. Pastan värjäyksellä saadaan tasaisuutta värjäykseen, mutta sävyn säätö on tehtävä edelleen massavärjäyksellä. Pigmenttivärien käytöllä pystytään lisäämään mm. valonkestoa kartongille. Kartongin ja paperituotteiden valonkeston tutkimiseen ei ole olemassa standardia. Työssä tutkittiin laboratorio-olosuhteissa ja huonevalossa vanhentuneiden kartonkinäytteiden vertailtavuutta. Materiaalivalinnoilla pystytään vaikuttamaan valon-kestoon. Siihen vaikuttavat mm. massan laatu, lateksivalinta sekä pigmenttivärin käyttö. Mekaanista massaa sisältävät tuotteet kellertyvät pääasiassa ligniinin takia. Ligniini sisältää paljon UV-säteilyyn reagoivia ryhmiä, jotka muuttuvat värilliseksi lisäten kellertymistä. Valkaistujen sellujen vanhentuminen on suhteessa mekaaniseen massaan erittäin vähäistä. SA-lateksin havaittiin suojaavan vaaleuden menetykseltä ja lisäävän sävyn pysyvyyttä paremmin kuin SB-lateksi.

Regional potential for collaborative implementation of small CHP plants in bioenergy technology

This thesis is a preliminary study targeting South-Eastern Finland. The objective was to find out the financial and functional readiness and willingness of the small and medium-sized enterprises of the region to manufacture and sell distributed bioenergy solutions collaboratively as a business network. In this case these solutions mean small-scale (0.5 - 3 MW) woodchips-operated combined heat and power (CHP) plants. South-Eastern Finland has suffered from a decline in the recent years, mostly due to the problems of the traditionally strong industrial know-how area of the region, the paper industry. Local small and medium-sized companies will have to find new ways to survive the toughening competition. A group of 40 companies from suitable industries were selected and financial and comparative analysis was performed on them. Additionally 19 managing directors of the companies were selected for an interview to find out their views on networking, its requirements, advantages and the general interest in it. The studied companies were found to be generally in fairly good financial condition and in that sense, fit for networking activities. The interviews revealed that the companies were capable of producing all the needed elements for the plants in question, and the managers appeared to be very interested in and have a positive attitude towards such business networks. Thus it can be said that the small and medium-sized companies of the region are capable of and interested in manufacturing small bio-CHP plants as a production network.

BimTwin - Two component continuous process hygiene concept

The aim of this study was to examine suitability of BimTwin cleaning concept in card board machine to control microbiological activity and describe microbiological balance of the machine. In a review of literature is examined microbe and spore caused problems in paper industry. Biggest problems are deposits, which decrease runnability and cause quality errors. In this chapter is also introduced most common oxidizing biocides used in paper industry and described ATP assay as a microbiological monitoring method. In an experimental part are included BimTwin mill trial results, chemical condition monitoring methods and microbiological balance in a card board machine. In a second part are examined possibilities to effect hygiene of card board by chemical treatment of the surface size and coating. Result showed that BimTwin concept is suitable for card board machine as a cleaning concept, when chemical dosing is fitted right. For proper dosing and secure tolerable hygiene level, chemical and microbiological monitoring is significant. Determining of the microbiological balance would have need more sampling. According to acquired results, broke turned out to be the biggest microbe source. Sizing and coating experiments showed that it is possible to improve hygiene of card board by chemically treated surface size and coating color.

Biochemical Modification of Thermomechanical Pulp Fibers

The first objective of this study was to find out reliable laboratory methods to predict the effect of enzymes on specific energy consumption and fiber properties of TMP pulp. The second one was to find with interactive software called “Knowledge discovery in databases” enzymes or other additives that can be used in finding a solution to reduce energy consumption of TMP pulp. The chemical composition of wood and enzymes, which have activity on main wood components were presented in the literature part of the work. The results of previous research in energy reduction of TMP process with enzymes were also highlighted. The main principles of knowledge discovery have been included in literature part too. The experimental part of the work contains the methods description in which the standard size chip, crushed chip and fiberized spruce chip (fiberized pulp) were used. Different types of enzymatic treatment with different dosages and time were tested during the experiments and showed. Pectinase, endoglucanase and mixture of enzymes were used for evaluation of method reliability. The fines content and fiber length of pulp was measured and used as evidence of enzymes' effect. The refining method with “Bauer” laboratory disc refiner was evaluated as not highly reliable. It was not able to provide high repeatability of results, because of uncontrolled feeding capacity and refining consistency. The refining method with Valley refiner did not have a lot of variables and showed stable and repeatable results in energy saving. The results of experiments showed that efficient enzymes impregnation is probably the main target with enzymes application for energy saving. During the work the fiberized pulp showed high accessibility to enzymatic treatment and liquid penetration without special impregnating equipment. The reason was that fiberized pulp has larger wood surface area and thereby the contact area between the enzymatic solution and wood is also larger. Standard size chip and crushed chip treatment without special impregnator of enzymatic solution was evaluated as not efficient and did not show visible, repeatable results in energy consumption decrease. Thereby it was concluded that using of fiberized pulp and Valley refiner for measurements of enzymes' effectiveness in SEC decrease is more suitable than normal size chip and crushed chip with “Bauer” refiner. Endoglucanase with 5 kg/t dosage showed about 20% energy consumption decrease. Mixture of enzymes with 1.5 kg/t dosage showed about 15% decrease of energy consumption during the refining. Pectinase at different dosages and treatment times did not show significant effect on energy consumption. Results of knowledge discovery in databases showed the xylanase, cellulase and pectinase blend as most promising for energy reduction in TMP process. Surfactants were determined as effective additives for energy saving with enzymes.

Computational Evaluation of Print Unevenness According to Human Vision

Print quality and the printability of paper are very important attributes when modern printing applications are considered. In prints containing images, high print quality is a basic requirement. Tone unevenness and non uniform glossiness of printed products are the most disturbing factors influencing overall print quality. These defects are caused by non ideal interactions of paper, ink and printing devices in high speed printing processes. Since print quality is a perceptive characteristic, the measurement of unevenness according to human vision is a significant problem. In this thesis, the mottling phenomenon is studied. Mottling is a printing defect characterized by a spotty, non uniform appearance in solid printed areas. Print mottle is usually the result of uneven ink lay down or non uniform ink absorption across the paper surface, especially visible in mid tone imagery or areas of uniform color, such as solids and continuous tone screen builds. By using existing knowledge on visual perception and known methods to quantify print tone variation, a new method for print unevenness evaluation is introduced. The method is compared to previous results in the field and is supported by psychometric experiments. Pilot studies are made to estimate the effect of optical paper characteristics prior to printing, on the unevenness of the printed area after printing. Instrumental methods for print unevenness evaluation have been compared and the results of the comparison indicate that the proposed method produces better results in terms of visual evaluation correspondence. The method has been successfully implemented as ail industrial application and is proved to be a reliable substitute to visual expertise.

Effect of temperature, wetness duration and cultivar on the development of anthracnose in guava fruits

The development of a large number of postharvest diseases is closely associated with fruit ripeness. Environmental conditions may affect both the pathogen development and the fruit ripening rate. The aim of this study was to determine the most favorable temperature and wetness duration to the development of anthracnose in guava fruits. Cultivars 'Kumagai' (white pulp) and 'Pedro Sato' (red pulp) were inoculated with a conidial suspension of Colletotrichum gloeosporioides and C. acutatum and incubated at constant temperature ranging from 10 to 35ºC and wetness duration of 6 and 24 hours. Disease severity and incidence were evaluated at every two days during 12 days. No infection occurred at 10 and 35ºC, regardless of the wetness duration. The optimum conditions for fruit infection were 26 and 27ºC for 'Kumagai' and 25 and 26ºC for 'Pedro Sato', adopting 24 hours of wetness. In general, the disease development in 'Kumagai' cultivar was more affected by the wetness period, compared to 'Pedro Sato'. Disease severity for 'Kumagai' fruits was maximal between 25 and 30ºC , depending on the Colletotrichum species. Regarding 'Pedro Sato', the mean diameter of lesions was greater in fruits stored at 20, 25 and 30ºC , compared to 'Kumagai' cultivar, depending on the wetness period and the species. The incubation period (between 6 and 7 days) and the latent period (between 8 and 10 days) were minimal at 30ºC. The data generated in this study will be useful either for the development of a disease warning system or for the increase in the shelf life of guavas in the postharvest.

The True Brand Loyalty in the Finnish Tabloid Industry

Asiakas- ja brandiuskollisuutta on tutkittu 1920-luvulta alkaen ja sitä käsittelevän kirjallisuuden kirjo on hyvin laaja. Empiirisiä tutkimuksia löytyy kattava joukko aina pankkimaailmasta päivittäiskaupan tuotteisiin. Iltapäivälehtimarkkinaa tutkivaa empiiristä asiakas- tai brandiuskollisuustutkimusta ei kuitenkaan toistaiseksi ole tieteellisen tutkimuksen saralla tehty. Tässä tutkimuksessa perehdytään asiakas- ja brandiuskollisuuden maailmaan ja tutkitaan brandiuskollisuuden toteutumista suomalaisien iltapäivälehtien keskuudessa. Tutkimuksen keskeisin tavoite on selvittää, voidaanko todeta asiakas- ja brandiuskollisuutta olevan suomalaisien iltapäivälehtien keskuudessa ja mikäli sitä todetaan olevan, mitkä ovat ne tekijät, jotka tämän uskollisuuden muodostumiseen vaikuttavat. Tutkimus toteutettiin yhteistyössä toisen suuren suomalaisen iltapäivälehtitalon kanssa. Empiirinen tutkimus toteutettiin strukturoituna Internet-kyselynä, josta saatu aineisto analysoitiin kvantitatiivisin tutkimusmenetelmin. Tutkimuksen tulokset osoittavat, että asiakas- ja brandiuskollisuutta löytyy suomalaisien iltapäivälehtien keskuudessa. Tärkeimmät havainnot osoittavat, että muun muassa uskollisuus iltapäivälehden verkkosivustoa kohtaan vaikuttaa positiivisesti uskollisuuteen ja toistuvaan ostokäyttäytymiseen samaa iltapäivälehteä kohtaan. Tämä on merkittävä löytö, sillä asian on monissa aiemmissa tutkimuksissa oletettu olevan päinvastoin. Myös luottamus brandiin, sitoutuneisuus brandiin, asiakkaan kokemat hyödyt ja asiakastyytyväisyys todettiin tutkimustuloksien pohjalta vaikuttavan positiivisesti sekä asenteellisen että behavioristisen uskollisuuden muodostumiseen iltapäivälehtiä kohtaan.

Germination and vigor of Dimorphandra mollis benth. seeds under different temperatures and substrates

The Dimorphandra mollis Benth. - Caesalpiniaceae is a native forest species coming from the Cerrado and Caatinga due to its economical and ecological use, which justifies the studies on seed germination. In this work, germinative performance of D. mollis seeds were studied in different conditions of temperature regime and substrate. The experimental delineation used was completely randomized in factorial 4 x 4 (4 substrates -sand, coconut fiber, vermiculite and paper towel; and 4 temperatures: 25, 30, 35 and 20-30ºC), with four replications of 25 seeds each. The following parameters were evaluated: seed moisture content, final germination, first germination count, germination speed index, length and dry matter weight. The best germination and vigor is obtained at 30 and 35ºC. The substrates paper towel and vermiculite allow satisfactory germinative performance of seeds, being suitable to evaluate the physiological quality of D. mollis seeds.

Studies in offset ink setting

The offset printing process is complex and involves the meeting of two essentially complex materials, printing ink and paper, upon which the final product is formed. It can therefore be expected that a multitude of chemical and physical interactions and mechanisms take place at the ink-paper interface. Interactions between ink and paper are of interest to both the papermakers and ink producers, as they wish to achieve better quality in the final product. The objective of this work is to clarify the combined influence of paper coating structure, printing ink and fountain solution on ink setting and the problems related to ink setting. A further aim is to identify the mechanisms that influence ink setting problems, and to be able to counteract them by changing properties of the coating layer or by changing the properties of the ink. The work carried out for this thesis included use of many techniques ranging from standard paper and printability tests to advanced optical techniques for detection of ink filaments during ink levelling. Modern imaging methods were applied for assessment of ink filament remain sizes and distribution of ink components inside pigment coating layers. Gravimetric filtration method and assessment of print rub using Ink-Surface-Interaction-Tester (ISIT) were utilized to study the influence of ink properties on ink setting. The chemical interactions were observed with the help of modified thin layer chromatography and contact angle measurements using both conventional and high speed imaging. The results of the papers in this thesis link the press operational parameters to filament sizes and show the influence of these parameters to filament size distribution. The relative importance between the press operation parameters was shown to vary. The size distribution of filaments is important in predicting the ink setting behaviour, which was highlighted by the dynamic gloss and ink setting studies. Prediction of ink setting behaviour was also further improved by use of separate permeability factors for different ink types in connection to filtration equations. The roles of ink components were studied in connection to ink absorption and mechanism of print rub. Total solids content and ratio of linseed oil to mineral oil were found to determine the degree of print rub on coated papers. Wax addition improved print rub resistance, but would not decrease print rub as much as lowering the total solids content in the ink. Linseed oil was shown to absorb into pigment coating pores by mechanism of adsorption to pore walls, which highlights the need for sufficient pore surface area for improved chromatographic separation of ink components. These results should help press operators, suppliers of printing presses, papermakers and suppliers to papermakers, to better understand the material and operating conditions of the press as it relates to various print quality issues. Even though paper is in competition with electronic media, high quality printed products are still in demand. The results should provide useful information for this segment of the industry.

Production of natural aroma by yeast in wastewater of cassava starch industry

ABSTRACT2-Phenylethanol (PE) is an aromatic alcohol with a characteristic odor of roses, widely used in food industry to modify certain aroma compositions in formulations with fruit, jam, pudding, and chewing gums, and also in cosmetic and fragrance industry. This compound occurs naturally in low concentrations in some essential oils from flowers and plants. An alternative to plants extraction are biotechnological processes. This study evaluated 2-phenylethanol’s production in cultivation of Saccharomyces cerevisiae in cassava wastewater originated from starch industry. The substrate was supplemented with glucose and L-phenylalanine in order to obtain higher 2-phenylethanol concentrations and better efficiency in glucose/2-phenylethanol conversion. It was performed using Rotatable Center Composite Design and response surface analysis. Cultures were performed under aerobic conditions in a batch system in Erlenmeyer flasks containing 50 mL of medium in shaker at 150 rpm and 24 ± 1 ºC. The highest PE values ​​were obtained with supplementation of 20.0 g.L-1 of glucose and 5.5 g.L-1 of L-phenylalanine, which has been experimentally validated, obtaining a PE production of 1.33 g.L-1 and PE/glucose yield factor of 0.070 g.g-1, equivalent to 74.3 and 89.7% ​​of desirability values according to the validated model.