58 resultados para ALUMINIUM CHLORIDES


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Acid mine drainage (AMD) presents a serious problem for the environment for the massive formation of acidic leachates containing heavy metals. The present work deals with the AMD treatment using neutralizing limestone side-products. The conventional methods for prevention, mitigating and control of AMD formation are described. The experimental testing of Nordkalk Oy calcite-containing side-stones for acid neutralizing and removal of nickel from solutions presents the research objective. The batch experiments in acid neutralizing with subsequent metal content analysis were carried out. The results showed the dependence of pH on the dose of neutralizing material and the exposure time. The nickel removal, unlike iron, within the pH range from 1.2 to 6.0 appeared to be inadequate. The further research on nickel co-precipitation with iron and aluminium may appear to be necessary together with testing of alkalinity strengthening materials.

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Joining processes and techniques need to meet the trend of new applications and the development of new materials. The application in connection with thick and thin plates in industrial fields is wide and the joining technology is in very urgent need. The laser-TIG hybrid welding technology can play the respective advantages of both of them. One major advantage of the hybrid laser-TIG welding technology is its efficient use of laser energy. Additionally, it can develop into a high and new advanced welding technology and become a hot spot in both the application and research area. This thesis investigated laser –TIG hybrid welding with the aim of enlightening the reader on its advantages, disadvantages and future areas of improvement. The main objective is to investigate laser-TIG hybrid on the welding of various metals (steels, magnesium, aluminium etc.). In addition, it elaborates on various possible combinations on hybrid laser-TIG welding technology and their benefits. The possibility of using laser-TIG hybrid in welding of thick materials was investigated. The method applied in carrying out this research is by using literature review. The results showed that hybrid laser-TIG is applicable to almost all weldable metals. Also it proves to be effective in welding refractive metals. The possibility of welding with or without filler materials is of economic advantage especially in welding of materials with no filler material. Thick plate’s hybrid laser-TIG welding is showing great prospects although it normally finds its used in welding thin materials in the range of 0.4 to 0.8 mm. The findings show that laser-TIG hybrid welding can be a versatile welding process and therefore will be increasingly used industrially due to its numerous advantages and the development of new TIG arc that enhances its capabilities.

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Lehmijärvi on 63 ha laajuinen kirkasvetinen ja vähähumuksinen latvajärvi Salossa. Lehmijärven suojeluyhdistys pyysi Varsinais-Suomen ELY-keskukselta ja Suomen metsäkeskukselta apua järvivedessä havaittujen korkeiden alumiinipitoisuuksien ja happamuuspiikkien sekä mahdollisten metsätaloustoimenpiteiden haittojen ehkäisemiseen valuma-alueella. Suomen metsäkeskuksen ja Varsinais-Suomen ELY-keskuksen yhteistyönä selvitettiin maanäytteiden avulla maaperän happamuutta ja alumiinipitoisuutta Lehmijärven valuma-alueella. Tulokset ja johtopäätökset on esitetty tässä raportissa. Tulosten perusteella näyttää siltä, että Lehmijärven happamuuspiikit (pH:n jyrkät laskut vedessä) johtuvat pääosin happamista lumensulamisvesistä, johon on jo aiemmissakin selvityksissä viitattu eikä alunamaa ongelmasta valuma-alueella. Myös ojitettujen soiden suuri osuus valuma-alueesta ja turvemaiden yleinen happamuus lisäävät osaltaan valuma-alueelta virtaavien vesien happamuutta varsinkin tulva-aikoina. Mustikkasuon eteläpuolisella suokuviolla, jonka läpi pääosa pohjoispuolen valumavesistä virtaa, voi kuitenkin esiintyä ohuen turpeen alla pienialaisesti alunamaata. Vertailtaessa tämän aineiston liukoisen alumiinin määriä turpeessa aikaisempien tutkimusten vertailulukuihin, voidaan sanoa Lehmijärven valuma-alueen ojitetuilla soilla olevan keskimääräistä korkeampia alumiinipitoisuuksia. Paikoin liukoiset alumiinipitoisuudet olivat jopa erittäin korkeita. Mustikkasuon eteläpuolisella suokuviolla, jonka kautta vedet suurelta osin virtaavat, alumiinipitoisuus oli korkeimmillaan 11 267 mg/kg ja Miilussuolla 7 044 mg/kg, kun Niemisen ja Jarvan (1996) tutkimuksessa alumiinipitoisuuden maksimiarvo oli 5 577 mg/kg. Alumiinin ajoittain korkeat pitoisuudet Lehmijärvessä johtuvat tämän raportin tulosten perusteella todennäköisesti pääosin valuma-alueen soiden turpeen korkeista alumiinipitoisuuksista. Voimakas maanmuokkaus kivennäismailla lisää alumiinin liukoisuutta ja samalla alumiinin huuhtoutumisriskiä vesistöihin. Lehmijärven valuma-alueella on suositeltavaa käyttää metsänuudistamisessa kevyitä maanmuokkausmenetelmiä (laikutus, kääntömätästys ja laikkumätästys) ja välttää ojitusmätästystä. Luontainen uudistaminen (erityisesti alikasvosten hyödyntäminen) pitäisi olla ensisijainen uudistamismenetelmä Lehmijärven valuma-alueella. Kunnostusojituksia toteutettaessa pitäisi ottaa käyttöön mahdollisimman tehokkaat vesiensuojelutoimet. On muistettava, että korkeat alumiinipitoisuudet Lehmijärvellä eivät ole pelkästään negatiivinen asia, koska alumiini sitoo tehokkaasti fosforia ja pahasti rehevöityneitä järviä (esim. Köyliön Ilmijärvi) on yritetty kunnostaa alumiinisulfaatti käsittelyllä. Lisätutkimusta tarvitaan selvittämään, onko Lehmijärven veden alumiinipitoisuus ajoittain jo niin korkea, että siitä on haittaa kalakannalle tai, että se jopa estää rapukannan palauttamisen istuttamalla järveen.

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Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations.

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Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.

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Tämä kandidaatintyö on kirjallisuuden pohjalta laadittu yhteenveto alumiinin oksidikerroksen vaikutuksesta hitsauksessa. Työssä käsitellään alumiinia alkuaineena, alumiinin oksidikerroksen muodostumista ja rakennetta, seosaineiden vaikutusta oksidikerrokseen, alumiinin hitsattavuutta teräkseen vertaillen, alumiiniseosten hitsattavuutta, oksidikerroksen merkitystä hitsauksessa, alumiinin yleisiä hitsausvirheitä, oksidikerroksen poistotapoja sekä alumiinin eri hitsausmenetelmiä. Hitsausmenetelmistä käsitellään pääasiassa alumiinin MIG-, TIG- ja plasmahitsausta.

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Diplomityön taustana oli oletus suorituskyvyn mittaamisen vähäisyydestä lasi- ja alumiinirakentamisen pk-yrityksissä. Tämän takia haluttiin tutkia mitataanko suorituskykyä ja jos mitataan, miten sitä tehdään sekä minkälainen järjestelmä sopisi kyseisille yrityksille. Lasi- ja alumiinirakentamisen suorituskyvyn analysoinnin tilannetta kartoitettiin haastattelututkimuksella, jossa kävi ilmi, että se tosiaan on vähäistä. Tutkimukseen osallistuneissa yrityksissä seurattiin pääasiassa liiketaloutta ja tulosta, ja näitäkin suppeasti. Laajemmalle mittaamiselle todettiin kuitenkin olevan tarvetta. Tämän jälkeen haastattelututkimuksen pohjalta suunniteltiin työssä mukana olleelle Case-yritykselle mittaristo. Suunnitteluvaiheessa valittiin yrityksen visioiden ja strategian mukaisesti neljä mitattavaa suorituskyvyn osa-aluetta ja näille mittarit. Mittariston suunnittelun jälkeen siirryttiin rakennusvaiheeseen. Järjestelmäksi valittiin SAKE, joka on helppokäyttöinen ja erityisesti pk-yritysten tarpeisiin suunniteltu työkalu. Tämän suorituskyvyn mittariston avulla lasi- ja alumiinirakentamisen yritykset voivat tehostaa toimintaansa ja ulottaa suorituskyvyn mittauksen osa-alueilla joita ei aiemmin ole huomioitu.

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Atomic Layer Deposition (ALD) is the technology of choice where very thin and highquality films are required. Its advantage is its ability to deposit dense and pinhole-free coatings in a controllable manner. It has already shown promising results in a range of applications, e.g. diffusion barrier coatings for OLED displays, surface passivation layers for solar panels. Spatial Atomic Layer Deposition (SALD) is a concept that allows a dramatic increase in ALD throughput. During the SALD process, the substrate moves between spatially separated zones filled with the respective precursor gases and reagents in such a manner that the exposure sequence replicates the conventional ALD cycle. The present work describes the development of a high-throughput ALD process. Preliminary process studies were made using an SALD reactor designed especially for this purpose. The basic properties of the ALD process were demonstrated using the wellstudied Al2O3 trimethyl aluminium (TMA)+H2O process. It was shown that the SALD reactor is able to deposit uniform films in true ALD mode. The ALD nature of the process was proven by demonstrating self-limiting behaviour and linear film growth. The process behaviour and properties of synthesized films were in good agreement with previous ALD studies. Issues related to anomalous deposition at low temperatures were addressed as well. The quality of the coatings was demonstrated by applying 20 nm of the Al2O3 on to polymer substrate and measuring its moisture barrier properties. The results of tests confirmed the superior properties of the coatings and their suitability for flexible electronics encapsulation. Successful results led to the development of a pilot scale roll-to-roll coating system. It was demonstrated that the system is able to deposit superior quality films with a water transmission rate of 5x10-6 g/m2day at a web speed of 0.25 m/min. That is equivalent to a production rate of 180 m2/day and can be potentially increased by using wider webs. State-of-art film quality, high production rates and repeatable results make SALD the technology of choice for manufacturing ultra-high barrier coatings for flexible electronics.

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Bauksiittijäte on alumiinin jalostuksessa syntyvä sivutuote, jonka alkalisuus on riski lähiympäristön ekosysteemeille. Alkalisuuden aiheuttamaan riskiin etsittiin ratkaisua perehtymällä bauksiittijätteen käsittelyyn. Kandidaatintyössä esitettiin eri menetelmiä bauksiittijätteen neutraloimiseksi, stabiloimiseksi ja varastoimiseksi. Menetelmien periaatteet määritettiin kirjallisuudesta löytyvien tutkimusten pohjalta, joiden perusteella voitiin määrittää toimivimmat menetelmät bauksiittijätteen käsittelemiseksi. Käytännöllisimmiksi käsittelymenetelmiksi osoittautuivat meriveden ja/tai hiilidioksidin lisääminen bauksiittijätteeseen sen neutraloimiseksi. Bauksiittijätteen stabiloimiseksi siihen tulee lisätä kiinteää materiaalia, kuten kalkkia, kiintoainepitoisuuden nostamiseksi sekä kovettuvien yhdisteiden muodostumiseksi.

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Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.

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Tässä työssä testattiin partikkelikokojakaumien analysoinnissa käytettävää kuvankäsittelyohjelmaa INCA Feature. Partikkelikokojakaumat määritettiin elektronimikroskooppikuvista INCA Feature ohjelmaa käyttäen partikkeleiden projektiokuvista päällystyspigmenttinä käytettävälle talkille ja kahdelle eri karbonaattilaadulle. Lisäksi määritettiin partikkelikokojakaumat suodatuksessa ja puhdistuksessa apuaineina käytettäville piidioksidi- ja alumiinioksidihiukkasille. Kuvankäsittelyohjelmalla määritettyjä partikkelikokojakaumia verrattiin partikkelin laskeutumisnopeuteen eli sedimentaatioon perustuvalla SediGraph 5100 analysaattorilla ja laserdiffraktioon perustuvalla Coulter LS 230 menetelmällä analysoituihin partikkelikokojakaumiin. SediGraph 5100 ja kuva-analyysiohjelma antoivat talkkipartikkelien kokojakaumalle hyvin samankaltaisen keskiarvon. Sen sijaan Coulter LS 230 laitteen antama kokojakauman keskiarvo poikkesi edellisistä. Kaikki vertailussa olleet partikkelikokojakaumamenetelmät asettivat eri näytteiden partikkelit samaan kokojärjestykseen. Kuitenkaan menetelmien tuloksia ei voida numeerisesti verrata toisiinsa, sillä kaikissa käytetyissä analyysimenetelmissä partikkelikoon mittaus perustuu partikkelin eri ominaisuuteen. Työn perusteella kaikki testatut analyysimenetelmät soveltuvat paperipigmenttien partikkelikokojakaumien määrittämiseen. Tässä työssä selvitettiin myös kuva-analyysiin tarvittava partikkelien lukumäärä, jolla analyysitulos on luotettava. Työssä todettiin, että analysoitavien partikkelien lukumäärän tulee olla vähintään 300 partikkelia. Liian suuri näytemäärä lisää kokojakauman hajontaa ja pidentää analyysiin käytettyä aikaa useaan tuntiin. Näytteenkäsittely vaatii vielä lisää tutkimuksia, sillä se on tärkein ja kriittisin vaihe SEM ja kuva-analyysiohjelmalla tehtävää partikkelikokoanalyysiä. Automaattisten mikroskooppien yleistyminen helpottaa ja nopeuttaa analyysien tekoa, jolloin menetelmän suosio tulee kasvamaan myös paperipigmenttien tutkimuksessa. Laitteiden korkea hinta ja käyttäjältä vaadittava eritysosaaminen tulevat rajaamaan käytön ainakin toistaiseksi tutkimuslaitoksiin.

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Alumiiniseosten käyttö konstruktiomateriaalina lisääntyy johtuen sen lukuisista variaatioista lujuuden ja muovattavuuden suhteen. Alumiinin keveys on merkittävä kilpailuetu teräkseen nähden. Alumiiniseosten hitsattavuus on parantunut hitsausmenetelmien kehittyessä. Uusilla menetelmillä lämmöntuontia hallitaan paremmin, kuten myös alumiinin huokoisuutta sekä lujuuden laskua hitsauksen yhteydessä. Tässä diplomityössä tutkitaan alumiinin metallurgiaa, hitsausmenetelmiä, sekä alumiinin ja teräksen sekaliitoksen toteutusta. Tutkimuksella pyritään tekemään hitsatun alumiinirakenteen suunnittelua ymmärrettävämmäksi. SFS-EN standardit antavat perustuksen alumiinirakenteen suunnittelulle. Tässä diplomityössä tehdään suunnitteluesimerkki hitsatun alumiinirakenteen hitsien suunnittelusta. Suunnitteluesimerkissä tutkitaan alumiiniseoksen lujuuden laskua hitsattaessa, ja etsitään standardien antamia ratkaisuja toimivan hitsatun rakenteen toteuttamiseksi.