Lannoitetehtaan typenoksidipäästöjen hallintamahdollisuudet

Työssä tarkasteltiin lannoitetehtaan typenoksidipäästöjen hallintamahdollisuuksia Kemira GrowHow Oy:n Uudenkaupungin tehtailla. Työn tavoitteena oli lannoitetehtaalta muodostuvien typen oksidien syntymekanismien etsiminen. Lisäksi työssä etsittiin sellaisia keinoja, joilla typenoksidipäästöjä voitaisiin hallita. Tutkimusosassa tehtiin mittauksia kannettavalla FT-IR kaasuanalysaattorilla teoreettisen tarkastelun tueksi sekä prosessikohtaisten päästöjen selvittämiseksi. Prosessista tehtyjen mittausten lisäksi työssä on hyödynnetty lannoitetehtaan piippuun asennettua kiinteää FT-IR analysaattoria. Prosessikohtaiset mittaukset rajattiin lannoite 2-tehtaaseen. Mittauksia suoritettiin kuudesta prosessin pisteestä. Hallintamahdollisuuksien selvittämiseksi tehtiin tutkimuksia tietyillä raaka-aineiden syötöillä. Päästöjen prosessikohtaista arvioimista varten suoritettiin myös pitot-mittauksia kaasumäärien selvittämiseksi. Mittauksissa havaittiin, että typenoksidipäästöt riippuvat valmistettavasta lajikkeesta. Suurimmaksi typenoksidipäästöjen lähteeksi osoittautuivat reaktorit, joiden osuus oli jopa 95 % typenoksidipäästöistä. Tärkein oli biotiittireaktori, jonka osuus typenoksidipäästöistä oli noin 60-90 %. Lajikkeilla, joilla ei käytetä biotiittireaktoria, osoittautui suurimmaksi typenoksidipäästöjen lähteeksi ammonointireaktorit. Hallintamahdollisuuksia pyrittiin etsimään reaktoreilta. Suurimmaksi typen oksidien hallintamahdollisuudeksi osoittautui ureafosfaatin syöttö liuotus- ja biotiittireaktoreille. Tutkimuksissa havaittiin myös laimean rikkihapon käyttämisen, väkevän sijasta, auttavan hallitsemaan typenoksidipäästöjä.

Gas-phase photocatalytic oxidation of volatile organic compounds

Substances emitted into the atmosphere by human activities in urban and industrial areas cause environmental problems such as air quality degradation, respiratory diseases, climate change, global warming, and stratospheric ozone depletion. Volatile organic compounds (VOCs) are major air pollutants, emitted largely by industry, transportation and households. Many VOCs are toxic, and some are considered to be carcinogenic, mutagenic, or teratogenic. A wide spectrum of VOCs is readily oxidized photocatalytically. Photocatalytic oxidation (PCO) over titanium dioxide may present a potential alternative to air treatment strategies currently in use, such as adsorption and thermal treatment, due to its advantageous activity under ambient conditions, although higher but still mild temperatures may also be applied. The objective of the present research was to disclose routes of chemical reactions, estimate the kinetics and the sensitivity of gas-phase PCO to reaction conditions in respect of air pollutants containing heteroatoms in their molecules. Deactivation of the photocatalyst and restoration of its activity was also taken under consideration to assess the practical possibility of the application of PCO to the treatment of air polluted with VOCs. UV-irradiated titanium dioxide was selected as a photocatalyst for its chemical inertness, non-toxic character and low cost. In the present work Degussa P25 TiO2 photocatalyst was mostly used. In transient studies platinized TiO2 was also studied. The experimental research into PCO of following VOCs was undertaken: - methyl tert-butyl ether (MTBE) as the basic oxygenated motor fuel additive and, thus, a major non-biodegradable pollutant of groundwater; - tert-butyl alcohol (TBA) as the primary product of MTBE hydrolysis and PCO; - ethyl mercaptan (ethanethiol) as one of the reduced sulphur pungent air pollutants in the pulp-and-paper industry; - methylamine (MA) and dimethylamine (DMA) as the amino compounds often emitted by various industries. The PCO of VOCs was studied using a continuous-flow mode. The PCO of MTBE and TBA was also studied by transient mode, in which carbon dioxide, water, and acetone were identified as the main gas-phase products. The volatile products of thermal catalytic oxidation (TCO) of MTBE included 2-methyl-1-propene (2-MP), carbon monoxide, carbon dioxide and water; TBA decomposed to 2-MP and water. Continuous PCO of 4 TBA proceeded faster in humid air than dry air. MTBE oxidation, however, was less sensitive to humidity. The TiO2 catalyst was stable during continuous PCO of MTBE and TBA above 373 K, but gradually lost activity below 373 K; the catalyst could be regenerated by UV irradiation in the absence of gas-phase VOCs. Sulphur dioxide, carbon monoxide, carbon dioxide and water were identified as ultimate products of PCO of ethanethiol. Acetic acid was identified as a photocatalytic oxidation by-product. The limits of ethanethiol concentration and temperature, at which the reactor performance was stable for indefinite time, were established. The apparent reaction kinetics appeared to be independent of the reaction temperature within the studied limits, 373 to 453 K. The catalyst was completely and irreversibly deactivated with ethanethiol TCO. Volatile PCO products of MA included ammonia, nitrogen dioxide, nitrous oxide, carbon dioxide and water. Formamide was observed among DMA PCO products together with others similar to the ones of MA. TCO for both substances resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide and water. No deactivation of the photocatalyst during the multiple long-run experiments was observed at the concentrations and temperatures used in the study. PCO of MA was also studied in the aqueous phase. Maximum efficiency was achieved in an alkaline media, where MA exhibited high fugitivity. Two mechanisms of aqueous PCO – decomposition to formate and ammonia, and oxidation of organic nitrogen directly to nitrite - lead ultimately to carbon dioxide, water, ammonia and nitrate: formate and nitrite were observed as intermediates. A part of the ammonia formed in the reaction was oxidized to nitrite and nitrate. This finding helped in better understanding of the gasphase PCO pathways. The PCO kinetic data for VOCs fitted well to the monomolecular Langmuir- Hinshelwood (L-H) model, whereas TCO kinetic behaviour matched the first order process for volatile amines and the L-H model for others. It should be noted that both LH and the first order equations were only the data fit, not the real description of the reaction kinetics. The dependence of the kinetic constants on temperature was established in the form of an Arrhenius equation.

Suomen metsäteollisuuden päästökehitys vuoteen 2020

Metsäteollisuudessa on käynnissä rakennemuutos, joka tuo haasteita toimialan ympäristöasioiden hallintaan sekä ympäristölupia myöntävän ja valvovan viranomaisen toimintaan. Lähivuosina tulee myös runsaasti voimaan uutta lainsäädäntöä, joka vaikuttaa metsäteollisuuden ympäristöasioiden hallintaan. Tämän työn tarkoituksena oli arvioida Suomen kemiallisen metsäteollisuuden päästökehitystä vuoteen 2020 huomioiden metsäteollisuuden uusi tuotanto sekä lähivuosina voimaan tuleva ympäristölainsäädäntö, erityisesti päivitettävänä oleva massa- ja paperiteollisuuden BREF-asiakirja. Päästökehitystä arvioitiin viiden skenaarion avulla. Vesistöpäästöjen osalta tarkasteltiin COD- ja AOX-päästöjä sekä typpi- ja fosforipäästöjä, ja ilmapäästöjen osalta sellun tuotannon rikki- ja typpioksidi- sekä hiukkaspäästöjä. Massan- ja paperintuotannon oletettiin pysyvän muutaman prosentin nykyistä tasoa korkeammalla tasolla. Uuden tuotannon osalta kahdessa skenaariossa huomioitiin nestemäisten biopolttoaineiden tuotanto kolmella laitoksella, yhteensä 600 000 t/a. Päästölaskennassa käytettiin päivitettävänä olevan massa- ja paperiteollisuuden BREF-asiakirjan BAT-päätelmissä annettuja luonnoksia uusista päästötasoista. Skenaarioiden pohjalta havaittiin, että massa- ja paperiteollisuuden BAT-päätelmien mukaiset päästötasot eivät tuo merkittäviä muutoksia metsäteollisuuden vesistöpäästöihin vuoteen 2020 mennessä. Biojalosteiden tuotannon vaikutus vesistöpäästöihin todettiin myös hyvin vähäiseksi. Sen sijaan ilmaan johdettavat päästöt pienenevät huomattavasti: hiukkaspäästöt vähenivät 42–50 prosenttia uusien päästötasojen myötä. Biojalosteiden tuotannon vaikutus oli myös merkittävämpi kuin ilmapäästöihin kuin vesistöpäästöihin. Prosentuaalisesti eniten biojalostus lisäsi rikkidioksidipäästöjä.

Reduction of nitrogen oxide emissions in lime kiln

Different nitrogen oxide removal technologies for rotary lime kiln are studied in this thesis, the main focus being in commercial technologies. Post-combustion methods are investigated in more detail as potential possible NOx removal with combustion methods in rotary lime kiln is more limited or primary methods are already in use. However, secondary methods as NOx scrubber, SNCR or SCR technologies are not listed as the Best Available Technologies defined by European Union. BAT technologies for NOx removal in lime kiln are (1) Optimised combustion and combustion control, (2) Good mixing of fuel and air, (3) Low-NOx burner and (4) Fuel selection/low-N fuel. SNCR method is the most suitable technique for NOx removal in lime kiln when NOx removal from 50 % to 70 % is required in case primary methods are already in use or cannot be applied. In higher removal cases ammonia slip is an issue in SNCR. By using SCR better NOx reduction can be achieved but issues with catalyst materials are expected to arise because of the dust and sulphur dioxide which leads to catalyst poison formation in lower flue gas temperatures. NOx scrubbing has potential when simultaneous NOx and SO2 removal is required. The challenge is that NO cannot be scrubbed directly, but once it is oxidized to NO2 or further scrubbing can be performed as the solubility of NO2 is higher. Commercial installations have not been made regarding SNCR, SCR or NOx scrubbing regarding rotary lime kiln. For SNCR and SCR the closest references come from cement industry.

Carponate precipitation with carbon dioxide gas

The aim of this thesis research work focused on the carbonate precipitation of magnesium using magnesium hydroxide Mg(OH)2 and carbon dioxide (CO2) gas at ambient temperature and pressure. The rate of dissolution of Mg(OH)2 and precipitation kinetics were investigated under different operating conditions. The conductivity and pH of the solution were inline monitored by a Consort meter and the solid samples gotten from the precipitation reaction were analysed by a laser diffraction analyzer Malvern Mastersizer to obtain particle size distributions (PSD) of crystal samples. Also the Mg2+ concentration profiles were determined from the liquid phase of the precipitate by ion chromatography (IC) analysis. Crystal morphology of the obtained precipitates were also investigated and discussed in this work. For the carbonation reaction of magnesium hydroxide in the present work, it was found that magnesium carbonate trihydrate (nesquehonite) was the main product and its formation occurred at a pH of around 7-8. The stirrer speed has a significant effect on the dissolution rate of Mg(OH)2. The highest obtained Mg2+ concentration level was 0.424 mol L-l for the 470 rpm and 0.387 mol L-1 for the 560 rpm which corresponded to the processing time of 45 mins and 40 mins respectively. The particle size distribution shows that the average particle size keeps increasing during the reaction as the CO2 is been fed to the system. The carbonation process is kinetically favored and simple as nesquehonite formation occurs in a very short time. It is a thermodynamically and chemically stable solid product, which allows for a long-term storage of CO2. Since the carbonation reaction is a complex system which includes dissolution of magnesium hydroxide particles, absorption of CO2, chemical reaction and crystallization, the dissolution of magnesium hydroxide was studied in hydrochloric acid (HCl) solvent with and without nitrogen (N2) inert gas. It was found on the dissolution part that the impeller speed had effect on the dissolution rate. The higher the impeller speed the higher the pH of the solution, although for the highest speed of 650rpm it was not the case. Therefore, it was concluded that the optimum speed of the stirrer was 560rpm. The influence of inert gas N2 on the dissolution rate of Mg(OH)2 particles could be seen based on measured pH, electric conductivity and Mg2+ concentration curves.

Investigation of adsorption of dyes onto modified titanium dioxide

Titanium dioxide (TiO2) nanoparticles with different sizes and crystalloid structures produced by the thermal method and doped with silver iodide (AgI), nitrogen (N), sulphur (S) and carbon (C) were applied as adsorbents. The adsorption of Methyl Violet (MV), Methylene Blue (MB), Methyl Orange (MO) and Orange II on the surface of these particles was studied. The photocatalytic activity of some particles for the destruction of MV and Orange II was evaluated under sunlight and visible light. The equilibrium adsorption data were fitted to the Langmuir, Freundlich, Langmuir-Freundlich and Temkin isotherms. The equilibrium data show that TiO2 particles with larger sizes and doped with AgI, N, S and C have the highest adsorption capacity for the dyes. The kinetic data followed the pseudo-first order and pseudo-second order models, while desorption data fitted the zero order, first order and second order models. The highest adsorption rate constant was observed for the TiO2 with the highest anatase phase percentage. Factors such as anatase crystalloid structure, particle size and doping with AgI affect the photocatalytic activity significantly. Increasing the rutile phase percentage also decreases the tendency to desorption for N-TiO2 and S-TiO2. Adsorption was not found to be important in the photocatalytic decomposition of MV in an investigation with differently sized AgI-TiO2 nanoparticles. Nevertheless C-TiO2 was found to have higher adsorption activity onto Orange II, as the adsorption role of carbon approached synchronicity with the oxidation role.

Titanium dioxide based nanomaterials for photocatalytic water treatment

Water treatment using photocatalysis has gained extensive attention in recent years. Photocatalysis is promising technology from green chemistry point of view. The most widely studied and used photocatalyst for decomposition of pollutants in water under ultraviolet irradiation is TiO2 because it is not toxic, relatively cheap and highly active in various reactions. Within this thesis unmodified and modified TiO2 materials (powders and thin films) were prepared. Physico-chemical properties of photocatalytic materials were characterized with UV-visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometry (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), ellipsometry, time-of-flight secondary ion mass spectrometry (ToF-SIMS), Raman spectroscopy, goniometry, diffuse reflectance measurements, thermogravimetric analysis (TGA) and nitrogen adsorption/desorption. Photocatalytic activity of prepared samples in aqueous environment was tested using model compounds such as phenol, formic acid and metazachlor. Also purification of real pulp and paper wastewater effluent was studied. Concentration of chosen pollutants was measured with high pressure liquid chromatography (HPLC). Mineralization and oxidation of organic contaminants were monitored with total organic carbon (TOC) and chemical oxygen demand (COD) analysis. Titanium dioxide powders prepared via sol-gel method and doped with dysprosium and praseodymium were photocatalytically active for decomposition of metazachlor. The highest degradation rate of metazachlor was observed when Pr-TiO2 treated at 450ºC (8h) was used. The photocatalytic LED-based treatment of wastewater effluent from plywood mill using commercially available TiO2 was demonstrated to be promising post-treatment method (72% of COD and 60% of TOC was decreased after 60 min of irradiation). The TiO2 coatings prepared by atomic layer deposition technique on aluminium foam were photocatalytically active for degradation of formic and phenol, however suppression of activity was observed. Photocatalytic activity of TiO2/SiO2 films doped with gold bipyramid-like nanoparticles was about two times higher than reference, which was not the case when gold nanospheres were used.

Effect of nitrogen fertilization, grass species and cultivar on sod production on Valkeasuo peat bog - a case study

Selostus: Typpilannoituksen, kasvilajin ja lajikkeen vaikutus siirtonurmikon tuotanto-ominaisuuksiin Valkeasuon turvetuotannon jättöalueella

Effects of variety, soil type and nitrogen fertilizer supply on the nutritive value of barley for growing pigs

Selostus: Lajikkeen, typpilannoitustason ja maalajin vaikutus ohran ruokinnalliseen arvoon lihasioilla

Effect of dietary crude protein and energy content on nitrogen utilisation, water intake and urinary output in growing pigs

Selostus: Rehun valkuais- ja energiapitoisuuden vaikutus sikojen typen hyväksikäyttöön, veden kulutukseen ja virtsan eritykseen

Modelling growth and nitrogen balance of barley under ambient and future conditions

Selostus: Ohran kasvun ja typpidynamiikan mallintaminen nykyisissä ja tulevaisuuden olosuhteissa

Carbon dioxide evolution from snow-covered agricultural ecosystems in Finland

Selostus: Hiilidioksidin kulku lumipeitteisessä ja paljaassa maassa

Nitrogen and phosphorus losses in surface runoff and drainage water after application of slurry and mineral fertilizer to perennial grass ley

Selostus: Typen ja fosforin kulkeutuminen pinta- ja salaojavalunnassa lietelannalla ja NKP-lannoitteella lannoitetulta nurmelta