Advanced chemometric methods: Applicability on industrial data

Recent years have produced great advances in the instrumentation technology. The amount of available data has been increasing due to the simplicity, speed and accuracy of current spectroscopic instruments. Most of these data are, however, meaningless without a proper analysis. This has been one of the reasons for the overgrowing success of multivariate handling of such data. Industrial data is commonly not designed data; in other words, there is no exact experimental design, but rather the data have been collected as a routine procedure during an industrial process. This makes certain demands on the multivariate modeling, as the selection of samples and variables can have an enormous effect. Common approaches in the modeling of industrial data are PCA (principal component analysis) and PLS (projection to latent structures or partial least squares) but there are also other methods that should be considered. The more advanced methods include multi block modeling and nonlinear modeling. In this thesis it is shown that the results of data analysis vary according to the modeling approach used, thus making the selection of the modeling approach dependent on the purpose of the model. If the model is intended to provide accurate predictions, the approach should be different than in the case where the purpose of modeling is mostly to obtain information about the variables and the process. For industrial applicability it is essential that the methods are robust and sufficiently simple to apply. In this way the methods and the results can be compared and an approach selected that is suitable for the intended purpose. Differences in data analysis methods are compared with data from different fields of industry in this thesis. In the first two papers, the multi block method is considered for data originating from the oil and fertilizer industries. The results are compared to those from PLS and priority PLS. The third paper considers applicability of multivariate models to process control for a reactive crystallization process. In the fourth paper, nonlinear modeling is examined with a data set from the oil industry. The response has a nonlinear relation to the descriptor matrix, and the results are compared between linear modeling, polynomial PLS and nonlinear modeling using nonlinear score vectors.

Estudo da eletrocristalização de Ni e Ni-P sobre ultramicroeletrodo de platina

This work describes a comparative study of the electrocrystallization of Ni and Ni-P on Pt ultramicroelectrodes using chronoamperometric measurements. It was possible to confirm that in all cases a progressive nucleation was the predominant mechanism. Moreover, the application of the Atomistic Theory to the experimental rate of nuclei formation showed that the number of atoms in the critical nucleus was zero, except for Ni-P on Pt at low overpotentials were a value of one was observed. Furthermore, the physical characterisation of the different deposits on Pt by atomic force microscopy allowed observing the coalescence of the hemispherical nuclei of Ni and Ni-P at t max thus confirming the results obtained from the current-time analysis.

Yield in double cropping system as affected by N fertilization rate with pig slurry in a Catalonia dryland region

Intensive swine production is an important agricultural and economical activity in Europe. The high availability of pig slurry (PS) lead to attractive fertilization strategy to reduce costs, therefore is mainly applied as fertilizer in agricultural systems. The optimization N fertilization in these areas should be taken in into to avoid nitrates losses by lixiviation and to achieve maximum efficiency in crop nutrition. Many studies have shown that PS applications can achieve satisfactory yields in different crops by partially or completely replacing synthetic fertilizers. In addition, for the last years, in Northeast Spain (Catalonia) has been widely extended the double-cropping forage system.

Alteração da atividade enzimática em organismos aquáticos por poluentes de origem agrícola: uma abordagem geral e sobre a suscetibilidade da fosfatase ácida

The input of agrochemicals in the aquatic compartment can results in biochemical injuries for living organisms. In this context, the knowledge of alterations of enzymatic activities due the presence of agriculture pollutants contributes for the elucidation of the mechanisms of toxicity, implementation of economic methods for monitoring purposes and establishment of maximum allowed concentrations. In the present work, the above considerations are discussed, and data concerning changes in enzymatic function by pesticides and fertilizer contaminants are reviewed. Also, we focused on the acid phosphatase due its susceptibility to several pollutants and diversity in cellular functions.

Análise por componentes principais de espectros nexafs na especiação do molibdênio em catalisadores de hidrotratamento

Bulk and supported molybdenum based catalysts, modified by nickel, phosphorous or tungsten were studied by NEXAFS spectroscopy at the Mo L III and L II edges. The techniques of principal component analysis (PCA) together with a linear combination analysis (LCA) allowed the detection and quantification of molybdenum atoms in two different coordination states in the oxide form of the catalysts, namely tetrahedral and octahedral coordination.

Pilhas de combustíveis microbianas utilizadas na produção de eletricidade a partir de rejeitos orgânicos: uma perspectiva de futuro

In this review is presented an innovative technology for use of animal and vegetable waste with high pollution levels in microbial fuel cell (MFC) as an alternative to waste remediation and simultaneously producing electricity and fertilizer for agriculture. A brief history of MFC, the studies about the electron transfer mechanisms, discussion of the biological nanowires in bacteria and the use of chemical mediators or carriers of electrons are explained. The factors influencing the performance of MFCs, the application in waste and sewage treatment and power generation are also discussed.

Reciclagem do crômio de resíduos químicos provenientes da determinação de carbono oxidável em fertilizantes orgânicos

This work proposes a separation, recovery and reuse procedure of chemical residues with chromium. This residue was generated by the determination of oxidizable carbon in organic fertilizers samples. The Cr(VI) of the residue was reduced with ethanol and precipitated with NaOH. The Cr(OH)3 precipitate was separated and oxidized to dichromate ions with hydrogen peroxide. This solution was used another time in organic carbon determination. The uses of recycled dichromate solution were appropriated in four successive recycling. The accuracy was proven using potassium hydrogen phthalate and ten organic fertilizer samples. The organic carbon results, determined with recycled solutions, were similar the conventional solution.

Removal of high-molecular weight polycyclic aromatic hydrocarbons

Alternatives for the removal of high-molecular weight polycyclic aromatic hydrocarbons (HWM-PAH) from soil were tested by adding fertilizer or glycerol, as well as the combination of both. Experiments were carried out for 60 days in reactors containing a HWM-PAH-contaminated soil (8030 μg kg-1), accompanied by pH monitoring, humidity control and quantification of total heterotrophic bacteria and total fungus. Fertilizer addition removed 41.6% of HWM-PAH. Fertilizer and glycerol in combination removed 46.2%. When glycerol was added individually, degradation reached 50.4%. Glycerol also promoted the increase of degradation rate during the first 30 days suggesting the HMW-PAH removal occurred through cometabolic pathways.

Nitrato de amônio ocluído em zeólita 4A: lixiviação e absorção de nitrogênio no cultivo de milho

Systematic studies were undertaken in the intra zeolitic media to better understand the ability of zeolite type LTA in occluded nitrogen used in fertilizer and soil conditioning. We have measured the dry matter production from the cultivation of corn in a greenhouse for about 40 days, and also the amounts of nitrogen absorbed, retained and lost by leaching. The dry matter production in the cultivation with different concentrations of nitrogen occluded in the zeolite, was more efficient than the traditional fertilizer, which demonstrated better use of nitrogen to reduce leaching losses, which implies a possible reduction of costs for nitrogen.

Avaliação físico-química de efluente gerado em biodigestor anaeróbio para fins de avaliação de eficiência e aplicação como fertilizante agrícola

The use of biodigester for basic and environmental sanitation has large demand in Brazil. A biodigester was built to treat conjunctly the human and pig feces and urine, regarding to its future application in rural small towns. The results show that the biodigester can reduce 90% of COD and BOD and, up to 99.99% of thermotolerant coliforms. The treated effluent has variable quantities of macro- and micro-nutrients; and organic matter. However, the concentration variability of the nutrients makes difficult a dosed application into soil. The soluble salts (mainly as Na+ form) make necessary a controlled use to avoid environmental degradation.

Hidroformilação do oleato de metila catalisada por complexos de ródio

In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H2 ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes.

EMISSÕES DE ÓXIDO NITROSO E METANO DO SOLO EM ÁREAS DE RECUPERAÇÃO DE PASTAGENS NA AMAZÔNIA MATOGROSSENSE

AbstractThis study evaluates the chemical processes responsible for the nitrous oxide (N2O) and methane (CH4) fluxes in the managed pasture (PM) and unmanaged pasture (PNM). In addition, the impact of nitrogen fertilization on the N2O and CH4 fluxes was assessed. The experiments were conducted on three farms in Alta Floresta city in the state of Mato Grosso. Both regular and intensive samples were collected from PM, PNM, and forest areas for each of the properties. The gases were sampled using static chambers in the morning. Higher N2O fluxes were recorded in the PMs, whereas the CH4 fluxes showed no influence of nitrogen fertilization in both regular and intensive samples. Low fertilizer levels resulted in low N2O emissions.

Biokaasulaitoksen rejektivesien vaikutus jätevedenpuhdistamon toimintaan ja rejektivesien esikäsittelyn tarpeellisuus

Diplomityön tavoitteena oli tutkia biokaasulaitoksen rejektivesien ominaisuuksiin vaikuttavia tekijöitä ja rejektiveden esikäsittelyn tarpeellisuutta. Lisäksi tavoitteena oli tarkastella Kouvolaan suunnitteilla olevan Kymen Bioenergia Oy:n biokaasulaitoksen rejektivesien vaikutusta Kouvolan Veden Mäkikylän jätevedenpuhdistamolla. Biokaasulaitoksen rejektivedet ovat yhdyskuntajätevesiin verrattuna selvästi konsentroituneempia. Jätevedenpuhdistamoilla erityisesti rejektiveden korkea typpipitoisuus aiheuttaa lisäkuormitusta. Suomessa toiminnassa oleville biokaasulaitoksille tehdyn kyselytutkimuksen tulosten perusteella rejektiveden typpipitoisuuteen vaikuttaa syötteen typpipitoisuus sekä mädätysjäännöksen kuivauksen tehokkuus. Rejektiveden kiintoainepitoisuudella on puolestaan vaikutusta biologiseen hapenkulutukseen ja välillisesti myös rejektiveden kemialliseen hapenkulutukseen. Rejektivesien jätevedenpuhdistamoilla aiheuttamaa kuormitusta on mahdollista vähentää esikäsittelemällä rejektivedet joko biologisella tai fysikaalis-kemiallisella puhdistusmenetelmällä. Kyselytutkimus kuitenkin osoitti, että rejektivesien esikäsittelyssä ei aina päästä puhdistustavoitteeseen. Jätevedenkäsittelyn sijaan rejektivesiä on mahdollista käyttää lannoitteena, mikäli biokaasulaitoksen syöte ei sisällä jätevedenpuhdistamon lietteitä. Myös Kouvolan Veden Mäkikylän puhdistamolla biokaasulaitoksen rejektivedet tulevat lisäämään merkittävästi tulovirtaaman typpikuormaa. Typpikuorman lisäys edellyttää ilmastusaltaassa ilmastuksen tehostamista sekä kalkin syöttömäärän lisäämistä, jotta jäteveden happipitoisuus ja pH pysyvät typenpoistoreaktioille suotuisina. Lisäksi tulovirtaamasta puolet tullaan ohjaamaan esiselkeyttimen ohi, jotta ilmastusaltaassa on orgaanista ainetta typenpoistoon riittävästi. Mäkikylän puhdistamon typenpoistokapasiteettia on mahdollista kasvattaa lisähiilen syötöllä. Mikäli biokaasulaitoksen kapasiteettilisäyksen jälkeen rejektivesien typpikuoma ylittää lisähiilellä saavutetun lisäkapasiteetin, on rejektivedet esikäsiteltävä.

Mathematical equation correction to spectral and transport interferences in high-resolution continuum source flame atomic absorption spectrometry: determination of lead in phosphoric acid

In this work, a new mathematical equation correction approach for overcoming spectral and transport interferences was proposed. The proposal was applied to eliminate spectral interference caused by PO molecules at the 217.0005 nm Pb line, and the transport interference caused by variations in phosphoric acid concentrations. Correction may be necessary at 217.0005 nm to account for the contribution of PO, since Atotal217.0005 nm = A Pb217.0005 nm + A PO217.0005 nm. This may be easily done by measuring other PO wavelengths (e.g. 217.0458 nm) and calculating the relative contribution of PO absorbance (A PO) to the total absorbance (Atotal) at 217.0005 nm: A Pb217.0005 nm = Atotal217.0005 nm - A PO217.0005 nm = Atotal217.0005 nm - k (A PO217.0458 nm). The correction factor k is calculated from slopes of calibration curves built up for phosphorous (P) standard solutions measured at 217.0005 and 217.0458 nm, i.e. k = (slope217.0005 nm/slope217.0458 nm). For wavelength integrated absorbance of 3 pixels, sample aspiration rate of 5.0 ml min-1, analytical curves in the 0.1 - 1.0 mg L-1 Pb range with linearity better than 0.9990 were consistently obtained. Calibration curves for P at 217.0005 and 217.0458 nm with linearity better than 0.998 were obtained. Relative standard deviations (RSD) of measurements (n = 12) in the range of 1.4 - 4.3% and 2.0 - 6.0% without and with mathematical equation correction approach were obtained respectively. The limit of detection calculated to analytical line at 217.0005 nm was 10 µg L-1 Pb. Recoveries for Pb spikes were in the 97.5 - 100% and 105 - 230% intervals with and without mathematical equation correction approach, respectively.

Mädätysjäännöksen tuotteistamismahdollisuudet Kymenlaaksossa

Biokaasun tuotantoa ollaan selvästi lisäämässä Suomessa. Biokaasutuksen kokonaishyödyn kannalta on olennaista, että mädätyksen lopputuote eli mädätysjäännös saadaan lannoitekäyttöön. Tämän työn tavoitteena oli selvittää Kymenlaakson Jäte Oy:n mahdollisuuksia tuotteis-taa Kymen Bioenergia Oy:n yhteismädätyslaitoksen mädätysjäännöstä. Työssä keskityttiin hyötykäyttövaihtoehdoista lannoitekäyttöön maanviljelyssä sekä tilanteeseen jossa mädätyslaitos käsittelee sekä puhdistamolietettä että biojätettä ja mädätysjäännös kuivataan mekaanisesti. Mekaanisesti kuivatun mädätysjäännöksen ensisijaiset tuotteistamisvaihtoehdot maanviljelyyn ovat joko jäännös sellaisenaan tai termisesti kuivattuna ja rakeistettuna, eli kuivarakeena. Mäkikylän laitoksen mädätysjäännöksen arvo peltolannoitteena on syyskuun 2010 keinolannoit-teiden hintaan vertaamalla sellaisenaan noin 1–20 €/t ja kuivarakeena noin 2–60 €/t. Arvo riippuu siitä, miten tuotteiden typpeä ja fosforia huomioidaan kasveille käyttökelpoiseksi. Täl-lä hetkellä käyttökelpoisin tapa on ympäristötuen puhdistamolietetuotteita koskevien ehtojen mukaisesti ottaa huomioon vesiliukoinen typpi ja 40 % kokonaisfosforista. Tällöin mädätys-jäännöksen arvo on noin 6 €/t ja kuivarakeen n. 18 €/t. Käytön kannalta kuivarae on helpompi vaihtoehto ja alueen viljelijät ovat heille tehdyn kyselyn mukaan varsin kiinnostuneita kuivarakeesta lannoitteena. Muista tuotteistusvaihtoehdoista termisesti kuivaamalla mädätysjäännöksen tehollinen lämpö-arvo saapumistilassa on noin 10 MJ/kg. Vastaava arvo jyrsinturpeen kesäkuun 2010 hinnan mukaan on noin 30 €/t. Tuotteen soveltuvuus polttoon tulee silti varmistaa. Termisesti kuiva-tulla mädätysjäännöksellä on tuotteistamismahdollisuuksia hieman laajemmin kuin kompostoidulla. Kompostoidun mädätysjäännöksen tuotteistamisen lähtökohta on lähinnä viherrakentaminen. Maanviljelykäyttöä ajatellen mädätysjäännöstä ei välttämättä tarvitse kompostoida.