Atomikerroskasvatuksen soveltaminen kemiantekniikassa

Tässä kirjallisuustyössä tutkittiin atomikerroskasvatuksen (ALD) soveltamista kemiantekniikassa. Työn alussa kerrottiin atomikerroskasvatuksesta, sen toimintaperiaatteista ja prosessitekniikasta. Tämän jälkeen tutkittiin viittä eri kemiantekniikan sovellusta, jotka olivat polymeerien pinnoittaminen, heterogeenisten katalyyttien syntetisointi, membraanien modifiointi, korroosionesto ja kaasunilmaisimet. ALD on ohutkalvotekniikka, jolla voidaan valmistaa nanometrin tai jopa Ångströmin (1 Å = 0.1 nm) tarkkuudella epäorgaanisia materiaalikerroksia, jotka yleensä ovat metallioksideja, kuten alumiinioksidi. ALD perustuu kaasu-kiintoainereaktioihin, joissa kaasumaiset kemialliset prekursorit reagoivat vuorotellen kasvualustan kanssa. Tyypilliset prekursorit ovat metalliligandi ja vesi, joka on yleisin hapen lähde ALD-reaktioissa. ALD−reaktiot suoritetaan yleensä matalassa paineessa (100−200 Pa) ja korkeassa lämpötilassa (200–400 °C) suljetussa reaktorikammiossa. ALD-prosesseissa voidaan hyödyntää myös plasmaa alentamaan reaktiolämpötiloja. Plasman avulla prekursoreista luodaan hyvin reaktiivisia radikaaleja, jotka voivat reagoida jopa huoneenlämmössä. Lämpöherkkiä polymeerejä voidaan pinnoittaa ohutkalvoilla, joilla voidaan lisätä esimerkiksi pakkausmateriaalien suojaa happea ja vesihöyryä vastaan. ALD:llä voidaan syntetisoida tarkasti nanomittakaavan heterogeenisiä katalyyttejä, joilla on korkea dispersio tukimateriaalin pinnalla. ALD:n avulla voidaan säästää katalyyttimateriaalia menettämättä katalyytin aktiivisuutta, mikä on tärkeää monien katalyyttisovellusten taloudellisuuden kannalta, esimerkiksi polttokennot. ALD soveltuu hyvin membraanien modifiointiin, koska kaasumaiset prekursorit leviävät tasaisesti membraanin huokosiin. Membraanien pinnoittamisella pyritään vaikuttamaan, selektiivisyyteen, hydrofiilisyyteen, liuotinkestävyyteen, huokoskokoon ja sen jakaumaan. Lisäksi membraaneja voidaan pinnoittaa katalyyttisillä ohutkalvoilla, mikä on tärkeää nanoreaktoreiden kehityksen kannalta. ALD:llä voidaan pinnoittaa esimerkiksi terästä, ja vähentää täten teräksen korroosiota. Puolijohtavia metallioksideja voidaan käyttää kaasunilmaisimina, joiden valmistuksessa ALD:n tarkkuudesta on suurta hyötyä.

Kinetic behavior of nitrification in the post-treatment of poultry wastewater in a sequential batch reactor

A sequential batch reactor with suspended biomass and useful volume of 5 L was used in the removal of nutrients and organic matter in workbench scale under optimal conditions obtained by central composite rotational design (CCRD), with cycle time (CT) of 16 h (10.15 h, aerobic phase, and 4.35 h, anoxic phase) and carbon: nitrogen ratio (COD/NO2--N+NO3--N) equal to 6. Complete cycles (20), nitrification followed by denitrification, were evaluated to investigate the kinetic behavior of degradation of organic (COD) and nitrogenated (NH4+-N, NO2--N and NO3--N) matter present in the effluent from a bird slaughterhouse and industrial processing facility, as well as to evaluate the stability of the reactor using Shewhart control charts of individual measures. The results indicate means total inorganic nitrogen (NH4+-N+NO2- -N+NO3--N) removal of 84.32±1.59% and organic matter (COD) of 53.65±8.48% in the complete process (nitrification-denitrification) with the process under statistical control. The nitrifying activity during the aerobic phase estimated from the determination of the kinetic parameters had mean K1 and K2 values of 0.00381±0.00043 min-1 and 0.00381±0.00043 min-1, respectively. The evaluation of the kinetic behavior of the conversion of nitrogen indicated a possible reduction of CT in the anoxic phase, since removals of NO2--N and NO3--N higher than 90% were obtained with only 1 h of denitrification.

Performance of an anaerobic-aerobic reactor and kinetic study of organic matter removal of cattle slaughterhouse effluent

This paper sought to evaluate the behavior of an upflow Anaerobic-Aerobic Fixed Bed Reactor (AAFBR) in the treatment of cattle slaughterhouse effluent and determine apparent kinetic constants of the organic matter removal. The AAFBR was operated with no recirculation (Phase I) and with 50% of effluent recirculation (Phase II), with θ of 11h and 8h. In terms of pH, bicarbonate alkalinity and volatile acids, the results indicated the reactor ability to maintain favorable conditions for the biological processes involved in the organic matter removal in both operational phases. The average removal efficiencies of organic matter along the reactor height, expressed in terms of raw COD, were 49% and 68% in Phase I and 54% and 86% in Phase II for θ of 11h and 8h, respectively. The results of the filtered COD indicated removal efficiency of 52% and k = 0.0857h-1 to θ of 11h and 42% and k = 0.0880h-1 to θ of 8h in the Phase I. In Phase II, the removal efficiencies were 59% and 51% to θ of 11h and 8h, with k = 0.1238h-1 and k = 0.1075 h-1, respectively. The first order kinetic model showed good adjustment and described adequately the kinetics of organic matter removal for θ of 11h, with r² equal to 0.9734 and 0.9591 to the Phases I and II, respectively.

Application of response surface methodology to study the biological removal of nitrogen from effluent of cattle slaughterhouse in a sequencing batch reactor

The aim of this study was to evaluate the efficiency of a sequencing batch reactor (SBR) on biological removal of nitrogen from cattle slaughterhouse wastewater by nitrification/denitrification processes. The effects of initial concentration of ammoniacal nitrogen were investigated at 100; 150 and 200 mg L-1 and air flow rate at 0.125; 0.375 and 0.625 L min¹ Lreactor-1 on the nitrogen compounds removal, by a Central Composite Rotational Design (CCRD) configuration. There were variations from 9.2 to 94.9%, 4.0 to 19.6% and 20.8 to 92.0% in the conversion of ammoniacal nitrogen to nitrate and nitrite concentration and removal of total nitrogen, respectively. The increase of air flow rate and decrease of the initial concentration of ammoniacal nitrogen resulted in higher efficiencies of total nitrogen removal, as well as the conversion of ammoniacal nitrogen to nitrate. During the pre-established intervals of this study, the removal and conversion efficiencies of nitrogen compounds above 85% were achieved in air flow rate variations from 0.375 to 0.725 L min-1 Lreactor-1 and initial concentration of ammoniacal nitrogen from 80 to 200 mg L-1. On denitrification process, we obtained efficiencies from 91.5 to 96.9% on the removal of nitrite/nitrate and from 78.3 to 87.9% on the removal of organic matter.

Cassava starch extraction effluent treatment in a one phase tubular horizontal pilot reactor with support medium

The cassava starch industries generate a large volume of wastewater effluent that, stabilized in ponds, wastes its biogas energy and pollutes the atmosphere. To contribute with the reversion of this reality, this manipueira treatment research was developed in one phase anaerobic horizontal pilot reactor with support medium in bamboo pieces. The reactor was excavated into the ground and sealed with geomembrane in HDPE, having a volume equal to 33.6 m³ and continuous feeding by gravity. The stability indicators were pH, volatile acidity/total alkalinity ratio and biogas production. The statistical analyses were performed by a completely randomized design, with answers submitted to multivariate analysis. The organical loads in COD were 0.556; 0.670; 0.678 and 0.770 g L-1 and in volatile solids (VS) of 0.659; 0.608; 0.570 and 0.761 g L-1 for the hydraulic retention times (HRT) of 13.0; 11.5; 10.0 and 7.0 days, respectively. The reductions in COD were 88; 80; 88 and 67% and for VS of 76; 77; 65 and 61%. The biogas productions relatively to the consumed COD were 0.368; 0.795; 0.891 and 0.907 Lg-1, for the consumed VS of 0.524; 0.930; 1.757 and 0.952 Lg-1 and volumetric of 0.131; 0.330; 0.430 and 0.374 L L-1 d-1. The reactor remained stable and the bamboo pieces, in visual examination at the end of the experiment, showed to be in good physical conditions.

Effect of cycle time and airflow in biological nitrogen removal from poultry slaughterhouse wastewater using sequencing batch reactor

This study aimed to evaluate the influence of airflow (0.25, 0.50 and 0.75 L.L-1.min-1) and cycle time (10.45 h, 14.25 h and 17.35 h) on a sequencing batch reactor (SBR) performance in promoting nitrification and denitrification of poultry slaughterhouse wastewater. The operational stages included feeding, aerobic and anoxic reactions, sedimentation and discharge. SBR was operated in a laboratory scale with a working volume of 4 L, keeping 25% of biomass retained inside the reactor as inoculum for the next batch. In the anoxic stage, C: N ratio was maintained between 5 and 6 by adding cassava starch wastewater. A factorial design (22) with five repetitions was designed at the central point to evaluate the influence of cycle time and airflow on total inorganic nitrogen removal (N-NH4++N-NO2-+N-NO3-) and in the whole process (nitrification and denitrification). The highest total inorganic nitrogen removal (93.3%) was observed for airflow of 0.25 L.L-1.min‑1 and a cycle time of 14.25 h. At the end of the experiment, the sludge inside the reactor was characterized by fluorescent in situ hybridization (FISH), indicating the presence of ammonia and nitrite oxidizing bacteria.

Hydrogen production from cassava processing wastewater in an anaerobic fixed bed reactor with bamboo as a support material

Attempting to associate waste treatment to the production of clean and renewable energy, this research sought to evaluate the biological production of hydrogen using wastewater from the cassava starch treatment industry, generated during the processes of extraction and purification of starch. This experiment was carried out in a continuous anaerobic reactor with a working volume of 3L, with bamboo stems as the support medium. The system was operated at a temperature of 36°C, an initial pH of 6.0 and under variations of organic load. The highest rate of hydrogen production, of 1.1 L.d-1.L-1, was obtained with application of an organic loading rate of 35 g.L-1.d-1, in terms of total sugar content and hydraulic retention time of 3h, with a prevalence of butyric and acetic acids as final products of the fermentation process. Low C/N ratios contributed to the excessive growth of the biomass, causing a reduction of up to 35% in hydrogen production, low percentages of H2 and high concentrations of CO2in the biogas.

HYDROPHOBIC MEMBRANE TECHNOLOGY FOR AMMONIA EXTRACTION FROM WASTEWATERS

ABSTRACT Total Ammoniacal Nitrogen - TAN (NH3 + NH4+) in wastewaters cause environmental degradation concerns due to their negative impacts on air, soil and water. Several technologies are available for TAN removal from the wastewaters. One emerging technology is the use of hydrophobic membrane as non-destructive NH3 extraction. In this paper the authors discuss the uses of gas permeable membrane (GPM) and its physicochemical characteristics that influence gas mass transfer rate, diffusion and recovery mechanisms of NH3 from liquid sources (e.g. animal wastewater). Several aspects of NH3 extraction from liquid manure and other TAN generation sources using GPM technology as well as its applicability for NH3 mitigation from liquid effluents and possible recovery as a nutrient for plant growth are also discussed in this review.

Use of the amniotic membrane to cover the peritoneal cavity in the reconstruction of the abdominal wall with polypropylene mesh in rats

OBJECTIVE: to evaluate the efficacy of the amniotic membrane used with polypropylene mesh against the formation of adhesions and its influence on healing. METHODS: twenty five female Wistar rats were anesthetized for creating a parietal defect in the anterior abdominal wall. Its correction was made with polypropylene mesh alone and associated with amniotic membrane. In the control group (n=11), the screen was inserted alone. In group A (n=7) we interposed the amniotic membrane between the screen and the abdominal wall. In group B, the amniotic membrane was placed on the mesh, covering it. After seven days, the animals were euthanized for macroscopic and microscopic evaluation of healing. RESULTS: adhesions were observed in all animals except one in the control group. Severe inflammation was observed in all animals in groups A and B and in three of the control group, with significant difference between them (A and B with p=0.01). Pronounced angiogenic activity was noted in one animal in the control group, six in group A and four in group B, with a significant difference between the control group and group A (p=0.002) and group B (p=0.05). The scar collagen was predominantly mature, except in five animals of the control group, with significant difference between the control group and group A (p=0.05) and group B (p=0.05). CONCLUSION: The amniotic membrane did not alter the formation of adhesions in the first postoperative week. There were also pronounced inflammation, high angiogenic activity and predominance of mature collagen fibers, regardless of the anatomical plane that it was inserted in.

Effects of topical 0.2% Cyclosporine A on corneal neovascularization induced by xenologous amniotic membrane implantation into a corneal stroma micropocket of rats

The objective of the study was to evaluate the topical effects of 0.2% Cyclosporine A (CsA) on corneal neovascularization of rats following surgical implantation of equine amniotic membrane into a corneal stroma micropocket. The implantation of xenologous amniotic membrane was performed bilaterally in 90 rats. In the same day of the surgery each right eye started receiving topical CsA twice a day. The left eye received no medication and served as a control. The evaluation of corneal neovascularization was performed by computerized image analysis and histopathological evaluation at 1, 3, 7, 15, 30 and 60 days postoperatively. For the image analysis 10 animals were used per time period, and for the histopathological examination, five animals were used per time period. Image analysis found that corneal neovascularization began on the 3rd postoperative day, reached its peak on the 7th day, and then progressively and rapidly decreased. Statistic analysis indicated that neovascularization of the CsA treated eye on the 7th day was significantly higher than that observed in untreated eyes. On the 30th day, however, this pattern was reversed with the neovascularization observed in the CsA treated eyes declining to the low levels observed on the 3rd day. The degree of neovascularization in the untreated eyes on the 30th day declined to the baseline levels found on day 3 at the 60th day. Histopathological analysis indicated that deposition of collagen in the implanted tissue was completed by the 15th day. Therefore, we concluded that (1) equine amniotic membrane in rat corneal stroma produced an intense neovascularization until the 15th day postoperatively and then regressed, (2) deposition of collagen of the implanted tissue was completed on the 15th day postoperatively, and (3) use of CsA was associated with increase in the corneal neovascularization initially, followed by a quick and intense regression.

Efficacy of bacterin-, outer membrane protein- and fimbriae extract-based vaccines for the control of Salmonella Enteritidis experimental infection in chickens

The efficacy of three vaccines was evaluated in chickens for the control of experimental infection with Salmonella Enteritidis (SE) phage type 4. The vaccines were produced with bacterin, outer membrane proteins (OMP) and fimbriae crude extract (FE). The chickens were vaccinated intramuscularly with two doses of each vaccine at 12 and 15 weeks of age. The chickens were then orally challenged with 10(9) CFU/chicken Salmonella Enteritidis phage type 4 at 18 weeks of age. Fecal swabs were performed for the recovery of shedding SE, and SE was recovered from the liver and spleen. Additionally, antibody titers were measured in the serum by micro-agglutination test. The results indicated that the vaccine produced with bacterin yielded better results and resulted in reduction of fecal shedding and organ invasion by SE after oral challenge, although no vaccine was 100% effective for the control of SE experimental infection.

Safety study of hydrogen peroxide direct synthesis

Kandidaatintyön johdantokappaleessa esitellään vetyperoksidi ja mihin sitä käytetään teollisuudessa. Työssä vertaillaan antrakinoniprosessia ja suoraa prosessia sekä selvitetään nykyisin enemmän vetyperoksidituotantoon käytetyn antrakinoniprosessin ongelmakohdat ja osoitetaan, miksi suora synteesi vetyperoksidin tuotannossa olisi parempi vaihtoehto. Kandidaatintyön käsittelee suurilta osin turvallisuusongelmia, joita esiintyy suoran synteesin yhteydessä. Kirjallisuudesta on etsitty ratkaisuja näihin ongelmiin, kuten membraaniprosessin käyttöä räjähdysvaaran välttämiseksi. Pienemmän reaktorin eli ns. mikroreaktorin käyttö tuo mukanaan monia etuja vetyperoksidin tuotantoon. Tällöin prosessi on turvallisempi ja sitä on helpompi hallita. Mikroreaktorissa voidaan käyttää korkeampia lämpötiloja ja paineita kuin makroreaktorilla ilman, että räjähdysvaara prosessissa kasvaisi. Mikroreaktorin sisällä olevat mikrokanavat luovat turvallisen ympäristön synteesille. Aspen plus – simulointiohjelmalla mallinnettiin ja simulointiin suoran prosessin kriittisiä virtoja mikroreaktorissa. Tarkoituksena oli löytää virrat, joissa kulkee mahdollisesti räjähtävä kaasuseos. Kaasumaiset prosessivirrat ovat kriittisimmät vetyperoksidin suorassa synteesissä, koska ne aiheuttavat todennäköisemmin räjähdyksen kuin nestemäiset prosessivirrat. Kaikkein eniten prosessiturvallisuutta uhkaavat ainevirrat ennen ja jälkeen mikroreaktoria.

Hydrodynamics Characteristics and Gas-Liquid Mass Transfer in a Three Phase Fluidized Bed Reactor

This paper presents the experimental characterization of hydrodynamics and gas-liquid mass transfer in a three-phase fluidized bed containing polystyrene and nylon particles. The influence of gas and liquid velocities on phase holdups and volumetric gas-liquid mass transfer coefficient was investigated for flow conditions similar to those applied in biotechnological process. The phase holdups were obtained by the pressure profile technique. The volumetric gas-liquid mass transfer coefficient was obtained adjusting the experimental concentration profiles of dissolved oxygen in the liquid phase with the predictions of the axial dispersion model. According to experimental results the liquid holdup increases with the gas velocity, whereas the solid holdup decreases. The gas holdup increases significantly with the increase in gas velocity, and it shows for the three-phase fluidized bed comparable values or larger than those of bubble column. The volumetric gas-liquid mass transfer coefficient increases significantly with an increase in the air velocity for both bubble column and fluidized beds. In addition, in the operational condition of high liquid velocity, the presence of low-density particles in the bed increased the gas-liquid mass transfer, and thus the volumetric mass transfer coefficient values obtained in the fluidized bed were comparable or larger than those of bubble column.

Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Recovery of biomass-derived valuable compounds using chromatographic and membrane separations

Utilization of biomass-based raw materials for the production of chemicals and materials is gaining an increasing interest. Due to the complex nature of biomass, a major challenge in its refining is the development of efficient fractionation and purification processes. Preparative chromatography and membrane filtration are selective, energy-efficient separation techniques which offer a great potential for biorefinery applications. Both of these techniques have been widely studied. On the other hand, only few process concepts that combine the two methods have been presented in the literature. The aim of this thesis was to find the possible synergetic effects provided by combining chromatographic and membrane separations, with a particular interest in biorefinery separation processes. Such knowledge could be used in the development of new, more efficient separation processes for isolating valuable compounds from complex feed solutions that are typical for the biorefinery environment. Separation techniques can be combined in various ways, from simple sequential coupling arrangements to fully-integrated hybrid processes. In this work, different types of combined separation processes as well as conventional chromatographic separation processes were studied for separating small molecules such as sugars and acids from biomass hydrolysates and spent pulping liquors. The combination of chromatographic and membrane separation was found capable of recovering high-purity products from complex solutions. For example, hydroxy acids of black liquor were successfully recovered using a novel multistep process based on ultrafiltration and size-exclusion chromatography. Unlike any other separation process earlier suggested for this challenging separation task, the new process concept does not require acidification pretreatment, and thus it could be more readily integrated into a pulp-mill biorefinery. In addition to the combined separation processes, steady-state recycling chromatography, which has earlier been studied for small-scale separations of high-value compounds only, was found a promising process alternative for biorefinery applications. In comparison to conventional batch chromatography, recycling chromatography provided higher product purity, increased the production rate and reduced the chemical consumption in the separation of monosaccharides from biomass hydrolysates. In addition, a significant further improvement in the process performance was obtained when a membrane filtration unit was integrated with recycling chromatography. In the light of the results of this work, separation processes based on combining membrane and chromatographic separations could be effectively applied for different biorefinery applications. The main challenge remains in the development of inexpensive separation materials which are resistant towards harsh process conditions and fouling.