Sellutehtaan kemiallisen hapenkulutuksen hallinta integroidulla kalvosuodatustekniikalla

The pulp industry generates high volumes of wastewater from 10 to 90 m3 per tonne of produced pulp. The wastewater contains large quantities of various organic compounds which total amount can be measured, for example, with a chemical oxygen demand test. The organic compounds can cause environmental degradation if they are discharged into the near water bodies, and because of that, the treated wastewater has to have high and consistent quality. This result can be achieved, for example, with membrane filtration process, which can be in use in the tertiary treatment of the wastewater treatment. The membrane processes include micro-, ultra-, nanofiltration and reverse osmosis, which can remove contaminants from water very effectively. The effectiveness of the membrane filtration is, however, highly affected by membrane fouling, which restrains the usage of the membrane processes in the field of the wastewater treatment. During the membrane fouling process, the membrane flux is decreased fast, which causes a decline in the filtration performance of the membrane. The aim of this thesis is to investigate the suitability of the integrated membrane filtration system for the wastewater treatment of the case study’s pulp mill. The integrated membrane filtration system contains a membrane bioreactor, that combines biological wastewater treatment with membrane filtration, and a membrane filtration unit, which can be, for example, ultrafiltration. In this study, the compounds of the pulp mill’s wastewater, which can still cause membrane fouling in the membrane filtration unit, are also investigated. For example, lignin, adsorbable organic halides, colored compounds and wood extractives, are the possible foulants, because they are challenging to remove from the wastewater with the conventional wastewater treatment processes. The suitable options for the membrane fouling reduction are also suggested from the aspect of the case study’s pulp mill. The suggested options, which are simple, effective and cost-effective, include optimizing the operating conditions of the membrane filtration unit and the membrane bioreactor and elevating the hydrophilicity of the membrane surface by the membrane material selection or precoating the membrane surface with a surfactant. With a help of the above-mentioned methods, the lowest level of the membrane fouling can be obtained, when the integrated membrane filtration system can be a very suitable option for the wastewater treatment of the pulp mill.Selluteollisuus muodostaa huomattavia määriä jätevettä, jonka määrä vaihtelee välillä 10–90 m3 tuotettua sellutonnia kohden. Jätevesi sisältää runsaasti erilaisia orgaanisia yhdisteitä, joiden kokonaismäärää voidaan kuvata esimerkiksi jäteveden kemiallisen hapenkulutuksen avulla. Orgaanisten yhdisteiden päästessä valumaan läheisiin vesimuodostumiin, ne voivat aiheuttaa ympäristön tilan heikentymistä, jonka johdosta puhdistetun jäteveden laatu tulee olla korkea ja yhtenäinen. Kyseiseen puhdistustulokseen voidaan päästä esimerkiksi käyttämällä kalvosuodatustekniikkaa jäteveden puhdistuksen tertiäärivaiheessa. Kalvosuodattimiin kuuluvat mikro-, ultra-, nano- ja käänteisosmoosisuodatus, jotka puhdistavat jätevettä tehokkaasti. Kalvosuodatuksen tehokkuuteen vaikuttaa kuitenkin suuresti kalvon tukkeutuminen, joka rajoittaa kalvojen käyttöönottoa jäteveden puhdistuksessa. Kalvon tukkeutuessa kalvon vuo pienenee nopeasti, mikä aiheuttaa kalvosuodatuksen suorituskyvyn laskua. Työn tarkoituksena on tutkia integroidun kalvosuodatussysteemin soveltuvuutta tapaustutkimuksen sellutehtaan jäteveden puhdistukseen. Integroitu kalvosuodatussysteemi sisältää membraanibioreaktorin, joka yhdistää jäteveden biologisen puhdistuksen kalvosuodatukseen, sekä erillisen kalvosuodattimen esimerkiksi ultrasuodattimen. Työssä selvitetään myös ne sellutehtaan jäteveden yhdisteet, jotka voivat vielä aiheuttaa kalvopinnan tukkeutumista kalvosuodatimessa. Näihin mahdollisesti tukkeutumista aiheuttaviin yhdisteisiin kuuluvat esimerkiksi ligniini, orgaaniset halogeeniyhdisteet, värilliset yhdisteet sekä puun uuteaineet, jotka ovat haastavia poistaa puhdistettavasta jätevedestä tavallisilla puhdistusmenetelmillä. Työssä esitellään myös tapaustutkimuksen sellutehtaan näkökulmasta suositeltavat vaihtoehdot kalvon tukkeutumisen vähentämiseen. Näihin yksinkertaisiin, tehokkaisiin ja kustannustehokkaisiin vaihtoehtoihin kuuluvat kalvosuodattimen ja membraanibioreaktorin käyttöolosuhteiden optimointi, kalvopinnan hydrofiilisyyden kasvattaminen kalvomateriaalin valinnalla tai kalvopinnan esipäällystyksellä. Näiden edellä mainittujen vaihtoehtojen avulla voidaan saavuttaa alhaisin taso kalvon tukkeutumiselle, jolloin integroitu kalvosuodatussysteemi vaikuttaa olevan hyvin sopiva vaihtoehto sellutehtaan jäteveden puhdistukseen

Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298K, sulfuric acid concentrations between 5x10(5) and 1x10(9)cm(-3), and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximum of -1400 parts per trillion by volume (pptv). We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75ion pairs cm(-3)s(-1) to study neutral and ion-induced nucleation. We found that the contribution from ion-induced nucleation is small at temperatures between 208 and 248K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248K with zero added ammonia, and for higher temperatures independent of NH3 levels. We compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.Peer reviewe

Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

4 pages 359-363 in the print version, additional 7 pages online.Peer reviewe

The effect of acid-base clustering and ions on the growth of atmospheric nano-particles

The growth of freshly formed aerosol particles can be the bottleneck in their survival to cloud condensation nuclei. It is therefore crucial to understand how particles grow in the atmosphere. Insufficient experimental data has impeded a profound understanding of nano-particle growth under atmospheric conditions. Here we study nano-particle growth in the CLOUD (Cosmics Leaving OUtdoors Droplets) chamber, starting from the formation of molecular clusters. We present measured growth rates at sub-3 nm sizes with different atmospherically relevant concentrations of sulphuric acid, water, ammonia and dimethylamine. We find that atmospheric ions and small acid-base clusters, which are not generally accounted for in the measurement of sulphuric acid vapour, can participate in the growth process, leading to enhanced growth rates. The availability of compounds capable of stabilizing sulphuric acid clusters governs the magnitude of these effects and thus the exact growth mechanism. We bring these observations into a coherent framework and discuss their significance in the atmosphere.Peer reviewe

Estenomiyhdistyksen perustaminen

Tämän opinnäytetyön tarkoitus oli kerätä tietopaketti yhdistyksen perustamiseen ja ylläpitoon liittyvistä toimista estenomiyhdistyksen perustamista varten. Työn tavoitteena oli perustaa yhdistys, jonka avulla kasvatetaan estenomien tunnettuutta kauneudenhoitoalan asiantuntijoina ja täten parantaa estenomien asemaa työmarkkinoilla. Opinnäytetyön teoriaosuudessa käsiteltiin estenomitutkinnon rakennetta, yhdistystoimintaa ja digitaalista markkinointia keskittyen erityisesti sisältömarkkinointiin verkkosivuilla ja sosiaalisen median kanavissa. Aineistohankinnassa suoritettiin Suomen Kosmetologien Yhdistyksen puheenjohtajan haastattelu, jonka pohjalta tehtiin yhdistystoiminnan vertailukehittämistä. Työssä toteutettiin Estenomit Pro -Facebook-yhteisössä kysely, jossa estenomit ja estenomiopiskelijat saivat mahdollisuuden vaikuttaa yhdistyksen toimintaan. Toiminnallisessa osuudessa luotiin kerätyn aineiston perusteella toimintasuunnitelma työn aikana perustetun Estenomit ry:n toiminnalle ja sen tuleville verkkosivuille.The purpose of this thesis was to collect information to establish and maintain an association for the students and graduates of the Degree Programme in Beauty and Cosmetics. The aim of this thesis was to constitute an association to enhance the awareness of the Bachelors of Beauty and Cosmetics as experts in the beauty and cosmetics field. The theoretical part of this thesis examined the structure of the Degree Programme in Beauty and Cosmetics and the functions of an association. Digital marketing was also explored, especially focusing on content marketing via various social media channels. In this thesis, the Chairman of Association of Finnish Beauty Therapists was interviewed and benchmarking was performed with acquired answers. A survey was conducted in a closed Facebook group, Estenomit Pro, where graduates and students were able to influence the activities of the association with their answers. Based on the theoretical framework Estenomit ry was founded and an action plan was created in the functional part

Effects of Battery Chemical Process Liquors on Heap Bioleaching Microorganisms

During coming thirty years, the quantity of electric vehicles will increase by eight-fold according to International Energy Agency. For the batteries of electric vehicles, metal-based battery chemicals, such as nickel and cobalt sulfate, are used as a raw material, therefore, increasing quantities of these chemicals will be needed in near future. In nickel and cobalt sulfate production process, ammonium sulfate is formed as a side product when ammonium-rich process liquors, containing ammonium sulfate, are associated with the process. These ammonium-rich side streams are a potent source of nitrogen for heap bioleaching. Therefore, in this thesis, possible negative and positive effects of ammonium sulfate (AS) bleed and feed (ammonium-rich side streams, originating from the battery chemical production process) and their constituents on biological iron and sulfur oxidation was under investigation. The experiments of this study were performed as small-scale batch studies (shake flask). The enriched indigenous acidophilic microorganisms, present in the irrigating leach liquor obtained from a heap bioleaching plant of Terrafame Oy, were used as an inoculum. The effects of battery chemical process liquors: AS bleed and feed, and their constituents (ammonium sulfate, carboxylic acid (neodecanoid acid), Nessol D100, Cyanex 272, and Baysolvex D2EHPA), on biological iron and sulfur oxidation were investigated separately. In addition to these experiments, possible stimulatory effect of ammonium-rich AS bleed and feed, as nitrogen supplement, on biological iron oxidation was also studied. Both AS bleed and feed process liquors negatively affected the biological iron oxidation. The process liquors resulted in a lag phase in biological iron oxidation and decrease of iron oxidation rate at concentrations higher than 2% (v/v), whereas at AS bleed and feed concentrations of 20% (v/v) and 50% (v/v), respectively, the biological iron oxidation was completely and irreversibly inhibited. With AS bleed, it was recognized that AS bleed enhanced biological sulfur oxidation at concentration of 8% (v/v) and below. The highest sulfate production yield and rate of 27% and 0.38 g/L/d, respectively, were achieved with AS bleed concentration of 4% (v/v). Ammonium sulfate concentrations higher than 20 g/L resulted in a lag phase in biological iron oxidation, whereas 250 g/L resulted in full and irreversible inhibition. Of the organic solvents (neodecanoid acid, Nessol D100, Cyanex 272, and Baysolvex D2EHPA) only neodecanoid acid affected biological iron oxidation. Neodecanoid acid resulted in a lag phase in iron oxidation with concentration of 2.5% of its water solubility (6.3 mg/L) or higher. Organic solvents Nessol D100, Cyanex 272, and Baysolvex D2EHPA were nonbioavailable for the microbial culture in experimental conditions of this study and, therefore, did not affect biological iron oxidation. In ammonium deficiency experiment, 0.079 g/L ammonium supplementation with 0.1% (v/v) AS feed, and 0.11 g/L ammonium supplementation with 0.09% (v/v) AS bleed enhanced biological iron oxidation. With 1% (v/v) AS bleed and feed concentration, the iron oxidation rate was not significantly increased. Iron oxidation rate of iron oxidizing culture, incubated in ammonium deficit medium, was 2.0 g/L/d, whereas iron oxidation rates of cultures supplemented with AS bleed or feed were over 2.3 g/L/d. In conclusion, ammonium-rich process liquors have a potential to enhance bioleaching, however, potential nitrogen deficiency in the heap bioleaching liquors (of Terrafame) should be studied to estimate the actual demand for nitrogen supplementation. Furthermore, the battery chemical process liquors and some of their constituents may potentially inhibit heap bioleaching process. Ammonium and organic solvents, present in the process liquors, can result in drastic harmful effects in recipient waters, therefore, their release to the environment must be prevented

Sellutehtaan kemiallisen hapenkulutuksen hallinta integroidulla kalvosuodatustekniikalla

The pulp industry generates high volumes of wastewater from 10 to 90 m3 per tonne of produced pulp. The wastewater contains large quantities of various organic compounds which total amount can be measured, for example, with a chemical oxygen demand test. The organic compounds can cause environmental degradation if they are discharged into the near water bodies, and because of that, the treated wastewater has to have high and consistent quality. This result can be achieved, for example, with membrane filtration process, which can be in use in the tertiary treatment of the wastewater treatment. The membrane processes include micro-, ultra-, nanofiltration and reverse osmosis, which can remove contaminants from water very effectively. The effectiveness of the membrane filtration is, however, highly affected by membrane fouling, which restrains the usage of the membrane processes in the field of the wastewater treatment. During the membrane fouling process, the membrane flux is decreased fast, which causes a decline in the filtration performance of the membrane. The aim of this thesis is to investigate the suitability of the integrated membrane filtration system for the wastewater treatment of the case study’s pulp mill. The integrated membrane filtration system contains a membrane bioreactor, that combines biological wastewater treatment with membrane filtration, and a membrane filtration unit, which can be, for example, ultrafiltration. In this study, the compounds of the pulp mill’s wastewater, which can still cause membrane fouling in the membrane filtration unit, are also investigated. For example, lignin, adsorbable organic halides, colored compounds and wood extractives, are the possible foulants, because they are challenging to remove from the wastewater with the conventional wastewater treatment processes. The suitable options for the membrane fouling reduction are also suggested from the aspect of the case study’s pulp mill. The suggested options, which are simple, effective and cost-effective, include optimizing the operating conditions of the membrane filtration unit and the membrane bioreactor and elevating the hydrophilicity of the membrane surface by the membrane material selection or precoating the membrane surface with a surfactant. With a help of the above-mentioned methods, the lowest level of the membrane fouling can be obtained, when the integrated membrane filtration system can be a very suitable option for the wastewater treatment of the pulp mill.Selluteollisuus muodostaa huomattavia määriä jätevettä, jonka määrä vaihtelee välillä 10–90 m3 tuotettua sellutonnia kohden. Jätevesi sisältää runsaasti erilaisia orgaanisia yhdisteitä, joiden kokonaismäärää voidaan kuvata esimerkiksi jäteveden kemiallisen hapenkulutuksen avulla. Orgaanisten yhdisteiden päästessä valumaan läheisiin vesimuodostumiin, ne voivat aiheuttaa ympäristön tilan heikentymistä, jonka johdosta puhdistetun jäteveden laatu tulee olla korkea ja yhtenäinen. Kyseiseen puhdistustulokseen voidaan päästä esimerkiksi käyttämällä kalvosuodatustekniikkaa jäteveden puhdistuksen tertiäärivaiheessa. Kalvosuodattimiin kuuluvat mikro-, ultra-, nano- ja käänteisosmoosisuodatus, jotka puhdistavat jätevettä tehokkaasti. Kalvosuodatuksen tehokkuuteen vaikuttaa kuitenkin suuresti kalvon tukkeutuminen, joka rajoittaa kalvojen käyttöönottoa jäteveden puhdistuksessa. Kalvon tukkeutuessa kalvon vuo pienenee nopeasti, mikä aiheuttaa kalvosuodatuksen suorituskyvyn laskua. Työn tarkoituksena on tutkia integroidun kalvosuodatussysteemin soveltuvuutta tapaustutkimuksen sellutehtaan jäteveden puhdistukseen. Integroitu kalvosuodatussysteemi sisältää membraanibioreaktorin, joka yhdistää jäteveden biologisen puhdistuksen kalvosuodatukseen, sekä erillisen kalvosuodattimen esimerkiksi ultrasuodattimen. Työssä selvitetään myös ne sellutehtaan jäteveden yhdisteet, jotka voivat vielä aiheuttaa kalvopinnan tukkeutumista kalvosuodatimessa. Näihin mahdollisesti tukkeutumista aiheuttaviin yhdisteisiin kuuluvat esimerkiksi ligniini, orgaaniset halogeeniyhdisteet, värilliset yhdisteet sekä puun uuteaineet, jotka ovat haastavia poistaa puhdistettavasta jätevedestä tavallisilla puhdistusmenetelmillä. Työssä esitellään myös tapaustutkimuksen sellutehtaan näkökulmasta suositeltavat vaihtoehdot kalvon tukkeutumisen vähentämiseen. Näihin yksinkertaisiin, tehokkaisiin ja kustannustehokkaisiin vaihtoehtoihin kuuluvat kalvosuodattimen ja membraanibioreaktorin käyttöolosuhteiden optimointi, kalvopinnan hydrofiilisyyden kasvattaminen kalvomateriaalin valinnalla tai kalvopinnan esipäällystyksellä. Näiden edellä mainittujen vaihtoehtojen avulla voidaan saavuttaa alhaisin taso kalvon tukkeutumiselle, jolloin integroitu kalvosuodatussysteemi vaikuttaa olevan hyvin sopiva vaihtoehto sellutehtaan jäteveden puhdistukseen

Effects of metal extraction liquors from electric vehicle battery materials production on iron and sulfur oxidation by heap bioleaching microorganisms

This study reports the effects of metal extraction liquors that are used for production of electric vehicle batteries on biological iron and sulfur oxidation. These liquors include ammonium sulfate and organic solvent constituents, and thus are potentially or inhibitory for heap bioleaching microorganisms. The effects of the liquors and their potential constituents were studied in batch bioassays at pH 2 and 27 ± 2 °C. Both metal extraction liquors had a negative effect on biological iron oxidation at >2% (v/v), whereas biological sulfur oxidation was enhanced with ≤8% (v/v) metal extraction liquor 1. Biological iron oxidation was negatively affected by ammonium sulfate at above 20 g/L. From the studied low-solubility organic solvents (neodecanoic acid, Nessol D100, Cyanex 272, and Baysolvex D2EHPA), neodecanoic acid was the only one negatively affecting biological iron oxidation, and this effect occurred at ≥ 6.3 mg/L (2.5% of its aqueous solubility). Since these extraction liquors and some of their potential constituents inhibited biological iron oxidation, they may also inhibit heap bioleaching and have adverse impacts in recipient waters, if released to the environment. With ammonium limited culture, iron oxidation was stimulated with ≤ 1% (v/v) of metal extraction liquor 1 and 2, and therefore, would also likely enhance heap bioleaching.publishedVersionPeer reviewe

Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrations between 5 × 105 and 1 × 109 cm−3, and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximum of ~1400 parts per trillion by volume (pptv). We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75 ion pairs cm−3 s−1 to study neutral and ion-induced nucleation. We found that the contribution from ion-induced nucleation is small at temperatures between 208 and 248 K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248 K with zero added ammonia, and for higher temperatures independent of NH3 levels. We compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry