Lipeäkierron kemiallisesti parhaat käytännöt

Diplomityön tavoitteena oli kartoittaa kemiallisesti parhaita käytäntöjä sellutehtaiden kemikaalien talteenottoprosessissa. Kirjallisuudesta ei löytynyt lipeäkiertoon liittyvää kemiallista tietoutta. Laiteteknisten ratkaisujen kautta yritettiin saada selville parhaat käytännöt. Teoriaosassa on myös käsitelty lipeäkierrossa esiintyvien vierasaineiden lähteitä, rikastumista ja poistumista prosessista. Työ tehtiin Stora Enson Suomessa sijaitseville tehtaille. Kokeellisessa osassa on suoritettu tehtailta saadun materiaalin perusteella tunnuslukujen laskentaa sekä PCA-analyysin teko. Työssä tarkastelualueena on lipeäkierto liuottajasta meesauuniin. Kaukopäässä on käytössä lipeäkierrossa kaksi lipeälinjaa ja muilla tehtailla vain yksi. Saatujen tunnuslukujen perusteella tehtaille on annettu pisteitä nollasta viiteen. Viisi pistettä on saanut parhaan arvon saanut tehdas ja nolla pistettä kaukana parhaasta arvosta olevat. Tunnuslukuja on valittu 14 ja edellä esitetyllä tavalla pisteytettynä on parhaaksi tehtaaksi saatu Kaukopään 1-lipeälinja ja huonoin on Kemijärvi. Huomioitavaa on Kaukopään 2-lipeälinjan sijoittuminen vasta neljänneksi, vaikka lipeälinjoilla on valkolipeän ja meesan käsittelyssä yhteiset syöttösäiliöt. PCA-analyysin perusteella havaittiin, että kuukausikeskiarvoja käytettäessä tulokset tasoittuvat verrattuna päiväarvoilla tehtyyn analyysiin. Analyysi osoittaa, että tehtailla lipeäkierto ei ole täysin hallinnassa. Tämä ilmenee suurina objektien liikkeinä kuvissa. Päiväarvoilla analyysi tehtiin vain Oulun tehtaalle. Tarkastelussa valittiin kuukauden mittainen ajanjakso niin hyvää kuin huonoakin jaksoa. Mallien selitysasteista voidaan nähdä eroja hyvän ja huonon jakson välillä. Tämä ilmenee niin, että hyvän jakson mallin selitysaste on korkeampi kuin huonon jakson. Objektien sijoittuminen kuvissa on myös erilainen. Hyvän jakson aikana objektit ovat pieninä ryhminä, kun huonon jakson objektit ovat hajonneet yksittäisiksi arvoiksi ja päivien väliset erot ovat suuret.

Factors Affecting Filterability

In this thesis the factors affecting lime mud filterability were studied. In the literature part there is information about recausticizing process, lime mud properties and filterability, and general filtration theory. In the experimental part the properties of lime mud particles and the properties of lime mud filter cake were investigated and the behavior of lime mud precoat was studied. The experiments were also carried out with R-PCC (rhombohedral precipitated calcium carbonate). The filtration and precoat studies were performed with a laboratory scale pressure filter. The pressure differences used were between 0.25-1.50 bars. Six different lime mud samples with varying amount of impurities and two R-PCC samples were used in the experiments. The average specific cake resistance of different lime mud samples varied quite extensively. The most influential factor affecting the lime mud filterability and dry solids content was found to be silica content. As the lime mud contained silica, the average specific cake resistance was high and the lime mud dryness was low. If the lime mud samples containing silica were not taken into account, the smaller the mean particle size, the higher the average specific cake resistance of the lime mud. The R-PCC had also a high average specific cake resistance, which was because of small particle size. In addition, the pressure difference affected the average specific cake resistance of some lime mud samples. In those cases lime mud was compressible material. During the precoat experiments the lime mud samples having the largest mean particle sizes, compressed. However, the average specific cake resistances of the filtration and precoat part were approximately the same magnitude. A brief displacement by air did not affect the behavior of the precoat. Instead, vibration and a brief but relatively great change in pressure difference had a slight influence.

Designing a new type of support for rotary kilns

Lime kiln is used as a part of the modern kraft pulp process in order to produce burnt lime from lime mud. This rotating kiln is supported by support rollers, which are traditionally supported by journal bearings. Since the continuous growth in the production of pulp mills requires larger lime kilns, the traditional bearing construction has become unreliable. The main problem especially involves the running-in phase of the bearings. In the present thesis, a new type of support roller was developed by using the systematic approach of machine design. Structural analysis was conducted on the critical parts of the selected structure by the finite element method. The operation of hydrodynamic bearings was examined by analytical methods. As a result of this work, a new type of support for rotating kilns was designed, which is more reliable and easier to service. A new support roller geometry is described, which pro¬vides for significant cost savings.

Intercalação Eletroquímica de Cátions Hexilamínio na Matriz Lamelar 1T-TiS2

The electrochemical synthesis of a ternary compound obtained by the intercalation of hydrated hexilaminium cations into the layered compound 1T-TiS2 is reported. Two different compounds were detected by cyclovoltammetry and studied by X-ray diffractometry. Models showing the steric arrangement of the hydrated hexilaminium cations into the Van der Waals gaps were proposed.

Troca iônica no estado sólido de európio3+ em zeólita Y: influência do tempo de reação

Rare earth elements supported in zeolites are the most important catalysts in the fluid cracking of petroleum. The solid state ion exchange of Eu3+ in Y zeolite was investigated. First of all, the hydrated EuCl3 was well mixed in a ball mill and was then heated at 300ºC for different times. The quantitative determination of Eu3+ showed that the degree of ion exchange depends on the reaction time at constant temperature, being ~95% in 4 h. The X-ray study showed that the crystallinity of the zeolite is little affected by the exchange procedure. The study of spectroscopic properties of Eu3+, emission spectra and lifetime, give information about the migration and position of the ion in the zeolite cages.

Fontes, reatividade e quantificação de metanol e etanol na atmosfera

In the last two decades, the use of oxygenated fuels, like methanol and ethanol, pure or in mixture with gasoline, has been growing due to benefits introduced into the air quality. In Brasil, the fraction of light duty vehicles powered by pure hydrated ethanol is estimated at about 4 million, while the remaining vehicles actually utilize a mixture (22:78 v/v) of ethanol:gasoline. As a consequence, there's a need for the availability of methods that can provide the evaluation of possible impacts of alcohol emissions in the formation of chemical species in the atmosphere, as ozone, aldehydes, carboxylic acids and so on. In this paper, methanol and ethanol are discussed in their general aspects, as well as their atmospheric sources, chemical reactivity and available methods of analysis.

Preparation and thermal decomposition of copper(II), zinc(II) and cadmium(II) chelates with 8-hydroxyquinoline

When the compounds are heated in an inert atmosphere it can be verified the consecutive partial sublimation, fusion, partial volatilization and partial thermal decomposition of the anhydrous complexes. When in an oxidating atmosphere the above process is only verified to Cu(II) chelates. Anhydrous copper(II) complexes present a monoclinic structure in the b form and the volatilized compound in a a form. Zinc(II) and cadmium(II) hydrated complexes are isomorphous and they present different cell dimensions from those reported previously.

Ilmaan johdettavien päästöjen tarkkailun luotettavuus sellutehtaalla

Suomen ympäristönsuojelulaki (86/200) velvoittaa toiminnanharjoittajia olemaan selvillä päästöistään ja hakemaan ympäristöluvan ympäristön pilaantumisen vaaraa aiheuttavalle toiminnalle. Sellutehtaat tuottavat tietoa merkittävimmistä ilmaan johdettavista päästöistään mittaamalla niitä jatkuvatoimisesti. Tuloksia käytetään tiedottamisessa ja päätöksenteossa. Yksi tärkeimmistä käyttökohteista on ympäristöluvan ehtojen täyttymisen seuranta. Mittaustulosten on oltava luotettavia. Luotettavuutta voidaan arvioida vertailumittauksien ja mittausepävarmuustarkastelujen avulla. Tässä työssä määritettiin mittausepävarmuudet Imatran tehtaiden kuorikattilan (LCP-kattila) NOX-mittaukselle sekä sellutehtaan meesauunien ja soodakattiloiden mittauksille. Tämän jälkeen tarkasteltiin, kuinka mittausepävarmuus huomioidaan ympäristö¬luparajaseurannassa. Lopuksi arviointiin, kuinka jatkuvatoimisten mittalaitteiden laadunvarmistusstandardia SFS-EN 141481 voidaan soveltaa Imatran tehtailla. Tarkastellut jatkuvatoimiset mittaukset todettiin varsin luotettaviksi. Etenkin NOx¬mittaukset ovat luotettavia. Kuorikattila 2:lla luotettavuutta heikentää mittauspaikan epä¬edustavuus. Rikin yhdisteiden (SO2 ja TRS) mittausten luotettavuus on alhaisempi, koska mitattavat pitoisuudet ovat pieniä. Mittausten luotettavuus on kuin vertailumittausten. Kuorikattila 2:lla Mittausepävarmuus huomioidaan NOX-pitoisuuden lupaseurannassa LCP-asetuksen mukaisesti. Sellutehtaan TRS-päästöillä mittausepävarmuus voidaan huomioida joko LCP-asetuksen mukaisesti tai tilastomatemaattisesti. Kummallakin tavalla saadaan negatiivisia luparajaan verrattavia keskiarvoja. Standardia SFS-EN 141481 voidaan soveltaa kuorikattilalla mutta sellutehtaalla se voi olla epäkäytännöllistä, eikä välittömästi paranna mittausten luotettavuutta

Determinação condutométria de carbonato residual do calcário aplicado no solo por análise em fluxo

The objective of this study was to evaluate a flow injection system for determination of residual CO3(2-) in soil amended with lime material. It was used a closed system were the CO2 released from soil sample acidified with 0.5 mol L-1 HCl was capted in a 0.2 mol L-1 NaOH solution. After 16h the capted CO2 was determined by conductivimetry using a flow injection system. The results obtained by the proposed method were significantly correlated with those reported in soil samples used by the International Soil Analytical Exchange Programe. The regression equation was: y = 0.987x -- 0.075 r = 0.996, P > 0.01. For acid soils amended with CaCO3 the method showed a deviation error of 2.7%, detection limit was 0.077 mmol kg-1 of CO3(2-), and a recovery of 99.7% of the total CO3(2-) added in soil sample. The method was easily adapted for routine determination of residual CO3(2-) in soil samples with an analytical frequency of 40 samples per hour.

Esfoliação e hidratação da caulinita após intercalação com uréia

Well-ordered Georgia kaolinite (Kga-1b) obtained from the source Clay Repository of the Clay Minerals Society (USA) was intercalated with urea using grinding procedures. To achieve complete intercalation 20% of urea (in weight) was used, producing Al2Si2O5(OH)4 (N2H4CO)0,86 with an interplanar basal spacing of 1,08nm. After washing with water under ultrasound stirring at 363K, urea was completely removed and kaolinite was partially exfoliated. After drying under air, the material was converted to hydrated kaolinite with the composition Al2Si2O5(OH)4 (H2O)0,64 and an interplanar basal spacing of 0,84nm. In this compound, water molecules positioned between the layers of the silicate can be removed after calcination at 573K, regenerating structurally disordered kaolinite.

Determinação em fluxo do carbonatoresidual do solo empregando pervaporação

The objective of this study was to develop a method for the direct determination of residual CO3(2-) in acid soil using a flow system coupled with pervaporation. The gas released from the acidified sample was separated though a hydrophobic membrane and detected by conductivimetry. The detection limit was 0.054 mmol c kg-1 for CO2/CO3(2-) with relative error of 3.1%. The analytical frequency was 20 samples per hour. The method is recommended for studying the reactions and kinetics of lime applied in acid soils.

Comportamento térmico da caulinita hidratada

Well-ordered kaolinite from the Brazilian Amazon Region (State of Pará) was initially reacted at 60 °C with a water dimethylsulfoxide mixture. After washing and characterisation, the resulting material was washed several times with methanol and in the final step with water. The water molecules displace the previously dimethylsulfoxide intercalated molecules and two different hydrated kaolinites were obtained. An unstable phase characterized by an interplanar basal distance of 0,996 nm that after drying collapse to the stable 0,844 nm hydrated kaolinite. The dehydration of the sample to disordered kaolinite was accompanied by Powder X-ray Diffractometry, thermal analysis (simultaneous TG and DSC) and FTIR spectroscopy.

Adsorção de íons dicromato nos compósitos celulose/ZrO2.nH2O preparados pelos métodos da precipitação convencional e em solução homogênea

This article describes the preparation and characterization of the cellulose/ hydrated zirconium oxide composites prepared by conventional precipitation (PC) and homogeneous solution precipitation (PSH) methods. The composite obtained by the PC method was prepared by using an ammonia solution as the precipitating agent, while the composite obtained by the PSH method was prepared by using urea as the precipitating agent. The adsorption of dichromate ions on the composites was studied using factorial design 2³. The variables were: initial concentration, agitation time and mass of the composite. The data obtained agree better for the composite obtained by the PC method.

Incorporação de CuSO4 residual em argamassa, como método de disposição final

Residual CuSO4 was incorporated into the mass utilized for cement preparation. To a cement mass with 1:0.5:5 of cement, lime and sand to 0.25, 0.50, 0.75 and 1.00% of residual CuSO4 were added. The sulfate was mixed separately with lime and water to induce metal precipitation. The hardened test bodies were submerged in Milli-Q water for three months. No Cu was detected in the water by Atomic Absorption Spectrometry. The best proportion for mechanical resistance and porosity is 0.50%. The cement is adequate for non-structural objects.

Kalkin sammutus kalsiumkarbonaatin saostuksessa

Tässä työssä tutkittiin sammutetun kalkin vaikutusta kalsiumkarbonaatin saostamiseen ja saostetun kalsiumkarbonaatin ominaisuuksiin. Työn kirjallisuusosa käsittelee mm. kalkin sammutusta yleisesti, sammutuslaitteita, sammutetun kalkin ominaisuuksiin ja agglomeroitumiseen vaikuttavia tekijöitä sekä partikkelikoon analyysimenetelmiä. Kirjallisuusosan mukaan sammutusolosuhteilla sekä sammutuslaitteilla on vaikutusta sammutetun kalkin ominaisuuksiin. Työn kokeellisessa osassa tutkittiin kalkin sammutuksen vaikutusta kalsiumkarbonaatin saostamiseen sekä saostetun kalsiumkarbonaatin ominaisuuksiin. Sammutuskokeet tehtiin neljällä eri sammutuslaitteella ja sammutettavina kalkkeina käytettiin neljää ominaisuuksiltaan erilaista poltettua kalkkia. Karbonoinnit suoritettiin sekä laboratorio- että pilot-laitteilla. Lisäksi tutkittiin neljän lisäaineen; natriumdodekyylisulfaatin, trietanoliamiinin, lignosulfonaatin sekä sakkaroosin vaikutusta kalkin sammuttamiseen sekä miten lisäaineen käyttäminen sammutuksessa vaikuttaa kalsiumkarbonaatin saostamiseen. Tulosten perusteella kalkin sammutuksella on vaikutusta kalsiumkarbonaatin saostamiseen ja saostetun kalsiumkarbonaatin ominaisuuksiin. Eri sammutusmenetelmillä sammutetuilla kalkeilla on mm. erilainen vaikutus karbonointiaikaan. Myös lisäaineet vaikuttavat mm. sammutetun kalkin ominaispinta-alaan ja partikkelin muotoon. Lisäaineet lisäksi pidentävät karbonointiaikaa ja vaikuttavat saostettujen kalsiumkarbonaattipartikkeleiden agglomeroitumiseen.