Identification of extractives and polysaccharides as foulants in membrane filtration of pulp and paper mill effluents

The search for new renewable materials has intensified in recent years. Pulp and paper mill process streams contain a number of potential compounds which could be used in biofuel production and as raw materials in the chemical, food and pharmaceutical industries. Prior to utilization, these compounds require separation from other compounds present in the process stream. One feasible separation technique is membrane filtration but to some extent, fouling still limits its implementation in pulp and paper mill applications. To mitigate fouling and its effects, foulants and their fouling mechanisms need to be well understood. This thesis evaluates fouling in filtration of pulp and paper mill process streams by means of polysaccharide model substance filtrations and by development of a procedure to analyze and identify potential foulants, i.e. wood extractives and carbohydrates, from fouled membranes. The model solution filtration results demonstrate that each polysaccharide has its own fouling mechanism, which also depends on the membrane characteristics. Polysaccharides may foul the membranes by adsorption and/or by gel/cake layer formation on the membrane surface. Moreover, the polysaccharides interact, which makes fouling evaluation of certain compound groups very challenging. Novel methods to identify wood extractive and polysaccharide foulants are developed in this thesis. The results show that it is possible to extract and identify wood extractives from membranes fouled in filtration of pulp and paper millstreams. The most effective solvent was found to be acetone:water (9:1 v/v) because it extracted both lipophilic extractives and lignans at high amounts from the fouled membranes and it was also non-destructive for the membrane materials. One hour of extraction was enough to extract wood extractives at high amounts for membrane samples with an area of 0.008 m2. If only qualitative knowledge of wood extractives is needed a simplified extraction procedure can be used. Adsorption was the main fouling mechanism in extractives-induced fouling and dissolved fatty and resin acids were mostly the reason for the fouling; colloidal fouling was negligible. Both process water and membrane characteristics affected extractives-induced fouling. In general, the more hydrophilic regenerated cellulose (RC) membrane fouled less that the more hydrophobic polyethersulfone (PES) and polyamide (PA) membranes independent of the process water used. Monosaccharide and uronic acid units could also be identified from the fouled synthetic polymeric membranes. It was impossible to analyze all monosaccharide units from the RC membrane because the analysis result obtained contained degraded membrane material. One of the fouling mechanisms of carbohydrates was adsorption. Carbohydrates were not potential adsorptive foulants to the sameextent as wood extractives because their amount in the fouled membranes was found to be significantly lower than the amount of wood extractives.

SOIL COVER AND CHEMICAL AND PHYSICAL ATTRIBUTES IN OXISOL IN THE ATLANTIC FOREST BIOME

ABSTRACT The objective of this study was to evaluate the chemical and physical attributes of different soil cover in a Oxisol with a strong wavy relief in the Atlantic Forest Biome, in which were selected three watersheds, employed with grazing (watershed P), forest (watershed M) and coffee (watershed C). Deformed and not deformed samples were collected in three depths for physical and chemical characterization. The chemical characteristics of soil in different watershed studies presented low levels of fertility. It was observed an elevation of pH in the soil and contents of Ca2+ and Mg2+ in the watersheds P and C in relation to the watershed M. Due to deforestation and the establishment of agriculture and livestock, there was a decrease in the contents of soil organic matter in the watershed P and C, not altering the physical characteristics of the soil in the watershed P. The implementation of coffee plantation is causing a reduction in the soil quality of watershed C in comparison to the watershed P and M, therefore indicating a need to adequate soil management in this area.

COMPARISON OF PROCEDURES FOR IMMEDIATE CHEMICAL ANALYSIS OF CHARCOAL

ABSTRACT The climate change, the quest for sustainability and the strong environmental pressures for alternatives to traditional fossil fuels have increased the interest in the search and use of renewable energy sources. Among them stands out the biomass of charcoal coming from renewable forests, widely used as a thermal reductant in the steel industry in the detriment of the use of mineral coal coke. This study aimed to compare different operating procedures of immediate chemical analysis of charcoal. Seven essays to immediate chemical analysis were compared, spread between procedures performed by Brazilian companies and laboratories, the test described by NBR 8112 and one realized with a thermogravimetric analyzer (TGA) using the parameters of the NBR 8112. There were significant differences in the volatiles matter content and consequently in the fixed carbon contents found. The differences between the procedures and the NBR 8112 were caused by an excess burning time, a mass sample above or below the standard or inappropriate container used for burning. It observed that the TGA appraisal of the volatiles content must be carried out with a burning time equal to 2 minutes to obtain results similar to those of the NBR 8112 norm. Moreover, the ash content values were statistically identical and the particles size did not influence the differences between means.

Ultrasuodatuskalvon modifiointi paineen, lämpötilan ja emäksen avulla

Työssä tutkittiin polymeerisen ultrasuodatuskalvon modifiointimahdollisuuksia prosessiolosuhteita muuttamalla. Kalvon modifioimisella pyritään sen suodatusominaisuuksien muuttumiseen, joka voi lisätä kalvon käyttökohteita ja parantaa kalvon soveltuvuutta tiettyjen yhdisteiden suodatukseen. Hydrofiilisiä, tiukkoja polymeerisiä ultrasuodatuskalvoja on kaupallisesti saatavilla vähän, joten työssä tutkittiin niiden valmistusta modifioimalla markkinoilla olevaa, löysempää, hydrofiilistä, polymeeristä ultrasuodatuskalvoa. Ultrasuodatuskalvo modifioitiin paineen, lämpötilan ja emäksen avulla. Modifioinnin aiheuttamat muutokset voidaan jakaa pysyviin, osittain palautuviin tai palautuviin muutoksiin. Kalvon rakenteen muuttuessa pysyvästi voidaan kalvo modifioida ennen suodatuksen aloittamista. Tällöin modifioinnissa käytetyt olosuhteet eivät vaikuta suodatukseen kuten muissa tapauksissa. Modifioinnin vaikutusta kalvoon voidaan analysoida eri menetelmillä. Näitä ovat esimerkiksi elektronimikroskopia ja kalvon vuon tai retention analysointi. Mikroskooppikuvia ei voida ottaa suodatuksen aikana, vaan kalvosta saada tietoa ainoastaan alku- ja lopputilanteissa suodatusolosuhteista poistettuna. Vuon ja retention avulla saadaan reaaliaikaista tietoa modifioidun kalvon suodatuskapasiteetin ja erotuskyvyn muutoksista. Työssä modifioinnin vaikutusta seurattiin vuo- ja retentiomittausten avulla ja kalvon rakenteessa tapahtuvia muutoksia tutkittiin pyyhkäisyelektronimikroskooppikuvien ja mikrometrimittausten avulla. Korkeampaa painetta tai lämpötilaa käytettäessä havaittiin vuon alenevan modifioitaessa enemmän kuin matalammissa paineissa tai lämpötiloissa. Korkeampi puristuslämpötila kasvatti myös retentiota. Modifiointiolosuhteiden ollessa emäksisiä aleni permeabiliteetti neutraaleissa olosuhteissa tehtyä puristusta enemmän. Myös retentio aleni emäksen avulla tehdyssä modifioinnissa. Kalvon rakenteessa tapahtuneiden muutosten palautuminen riippui modifiointilämpötilasta, korkeassa lämpötilassa modifioidussa kalvossa palautumista ei tapahtunut. Modifioinnin aiheuttamat kalvojen paksuuden muutokset tukivat retentio- ja vuomittauksia. Pyyhkäisyelektronimikroskooppikuvista voitiin havaita kalvon huokosrakenteen puristuneen modifioinnin aikana.

Studies in offset ink setting

The offset printing process is complex and involves the meeting of two essentially complex materials, printing ink and paper, upon which the final product is formed. It can therefore be expected that a multitude of chemical and physical interactions and mechanisms take place at the ink-paper interface. Interactions between ink and paper are of interest to both the papermakers and ink producers, as they wish to achieve better quality in the final product. The objective of this work is to clarify the combined influence of paper coating structure, printing ink and fountain solution on ink setting and the problems related to ink setting. A further aim is to identify the mechanisms that influence ink setting problems, and to be able to counteract them by changing properties of the coating layer or by changing the properties of the ink. The work carried out for this thesis included use of many techniques ranging from standard paper and printability tests to advanced optical techniques for detection of ink filaments during ink levelling. Modern imaging methods were applied for assessment of ink filament remain sizes and distribution of ink components inside pigment coating layers. Gravimetric filtration method and assessment of print rub using Ink-Surface-Interaction-Tester (ISIT) were utilized to study the influence of ink properties on ink setting. The chemical interactions were observed with the help of modified thin layer chromatography and contact angle measurements using both conventional and high speed imaging. The results of the papers in this thesis link the press operational parameters to filament sizes and show the influence of these parameters to filament size distribution. The relative importance between the press operation parameters was shown to vary. The size distribution of filaments is important in predicting the ink setting behaviour, which was highlighted by the dynamic gloss and ink setting studies. Prediction of ink setting behaviour was also further improved by use of separate permeability factors for different ink types in connection to filtration equations. The roles of ink components were studied in connection to ink absorption and mechanism of print rub. Total solids content and ratio of linseed oil to mineral oil were found to determine the degree of print rub on coated papers. Wax addition improved print rub resistance, but would not decrease print rub as much as lowering the total solids content in the ink. Linseed oil was shown to absorb into pigment coating pores by mechanism of adsorption to pore walls, which highlights the need for sufficient pore surface area for improved chromatographic separation of ink components. These results should help press operators, suppliers of printing presses, papermakers and suppliers to papermakers, to better understand the material and operating conditions of the press as it relates to various print quality issues. Even though paper is in competition with electronic media, high quality printed products are still in demand. The results should provide useful information for this segment of the industry.

Sulfuric acid - glucose separation using mixed-recycle steady state recycling chromatography

Batch chromatography is a widely used separation technique in a variety of fields meeting difficult separations. Several technologies for improving the performance of chromatography have been studied, including mixed-recycle steady state recycling (MR-SSR) chromatography. Design of MR-SSR has been commonly limited on 100 % purity constraint cases and empirical work. In this study a predictive design method was used to optimize feed pulse size and design a number of experimental MR-SSR separations for a solution of 20 % sulfuric acid and 100 g/L glucose. The design was under target product fraction purities of 98.7 % for H2SO4 and 95 % for glucose. The experiments indicate a maximum of 59 % increase in sulfuric acid productivity and 82 % increase for glucose when compared to corresponding batch separation. Eluent consumption was lowered by approximately 50 % using recycling chromatography. Within this study the target purities and yields set in design were not completely met, and further optimization of the process is deemed necessary.

Metanolin tuotanto biomassasta

Tämä työ käsittelee eri tapoja, joilla biomassasta voidaan valmistaa metanolia. Työssä käydään läpi eri valmistusreitit sekä tarkastellaan biomassaa raaka-aineena. Työhön on myös koottu joidenkin maailmalla tehtyjen tutkimusten aine- ja energiataseita. Tutkimusten pohjalta mietitään onko metanolin tuotanto liikennepolttoaineeksi tällä hetkellä taloudellisesti tai energiatehokkuudeltaan järkevää. Metanolia voidaan valmistaa biomassasta pääsääntöisesti viidellä eri tavalla. Ensimmäinen tapa on kaasuttaa biomassaa, jolloin tuotetaan raaka-kaasua. Raaka-kaasusta jalostetaan synteesikaasua, josta voidaan metanolisynteesillä valmistaa metanolia. Toinen tapa metanolin valmistamiseksi on liittää tuotanto sellunkeiton yhteyteen. Tällöin raaka-aineena olisi selluprosessissa syntyvä mustalipeä, josta metanoli voidaan erottaa. Kolmas mahdollinen valmistusprosessi on biomassan mädätys. Mädätyksessä syntyy biokaasua, josta jalostetaan synteesikaasuaja siitä edelleen metanolia. Neljäs keino metanolin valmistamiseksi biomassasta on pyrolyysi. Puun pyrolyysissä puu kuumennetaan nopeasti hapettomissa tai rajallisen hapensaannin olosuhteissa. Prosessissa syntyvästä pyrolyysiöljystä voidaan erottaa metanolia tislaamalla. Viides mahdollinen reitti metanolin valmistukselle on Fischer¬–Tropsch-synteesi. Biomassasta saatu synteesikaasu johdetaan FT-synteesiin, jossa katalyyttisesti saadaan hiilivetyjen ohella tuotettua metanolia. Biopolttoaineiden kuten metanolin valmistusprosesseja tutkitaan ja kehitetään jatkuvasti, sillä uusiutumattomat energianlähteet eivät riitä loputtomasti ja niiden aiheuttamia hiilidioksidipäästöjä halutaan vähentää. Tällä hetkellä tuotantoteknologiat eivät ole vielä tarpeeksi kehittyneet, jotta tuotanto saataisiin vastaamaan kulutusta. Metanolia ei kuitenkaan vielä voida käyttää sellaisenaan liikennepolttoaineena, joten metanolin markkinat ainakin vielä ovat sillä saralla varsin kapeat.

Surface chemistry of fibres and vessel elements in chemical and recycled pulps

Den viktigaste råvaran i papperstillverkning är pappersmassa. Massan innehåller (ved)fibrer men också finmaterial och andra typers (ved)celler, så som kärlceller. Hur dessa komponenter beter sig under arkformationen i pappersmaskinen eller hur de bidrar till egenskaperna hos det färdiga pappret avgörs till stor del av massakomponenternas ytkemiska sammansättning, fysiska struktur och mängden joniserbara grupper på ytan. I denna avhandling studerades ytegenskaperna hos fraktionerade kemiska massor och returfibermassor med avancerade analystekniker. Rester av avfärgningskemikalier identifierades på både returfibrer och på kärlceller. Dessa kan påverka arkformationen och arkstyrkan på returfiberpapper. Kärlcellernas cellväggsstruktur visade sig skilja sig från fibrernas. Resultaten kan främja utvecklingen av returfiberprosessen och användningen av kärlcellsrika lövvedsmassor.

Performance during post-harvest storage of banana cv. 'prata', 'maçã' and 'nanica' exposed to physical and chemical treatments

Banana is the most consumed fruit in the world and Brazil is the second largest producer. Despite its global position, Brazil has an average of 40% losses during the post-harvest period. So, this experiment aimed at evaluating the efficiency of post-harvest treatments to improve the storage of banana cultivars cv. 'Prata', 'Maçã' and 'Nanica'. The fruits were acquired at CEASA with green peel, and were submitted to six different treatments: T- immersion in drinking water for 3 minutes (control), H3 - hot water (50 °C for 3 minutes), H8 - hot water (50 °C for 8 minutes), HP - immersion in hypochlorite 0.2% for 3 minutes, OS - immersion in soybean oil 10% for 3 minutes, and OM - immersion in mineral oil 10% for 3 minutes. The fruits were stored at room temperature at about 21 °C for 14 days and evaluated in three periods (1, 7 and 14 days) comparing peel color, flesh/peel ratio, titratable acidity (TA), soluble solids (SS), SS/TA ratio, and pH. The fruits of cv. 'Prata' and 'Maçã' submitted to the treatments H3, H8 and HP ripened at the same time as the control for peel color, which showed increased soluble solids, flesh/peel ratio, acidity and a decrease in pH. On the other hand, the cv. 'Nanica' did not respond significantly different when compared to the applied treatments and the control. The fruits treated with OM and OS were kept green for a longer time for the cultivars 'Prata' and 'Nanica', but there were some changes on peel color due dark spots in 'Prata' banana and a softening aspect in 'Nanica', indicating some level of toxicity of these treatments. Fruits of the 'Maçã' cultivar continued green with the application of mineral oil, without toxicity symptoms. In conclusion, the treatments applied did not show any advantage for storage of these fruits.

Physical, chemical and microbiological properties of a Dystrophic Yellow Latosol using manipueira

The study aimed to evaluate chemical, microbiological and hydro-physical changes of a Dystrophic Yellow Latosol, receiver of different levels of manipueira (cassava wastewater) application, in the cultivation of 'Terra Maranhão' banana. The experimental design was a randomized block with three replications in a factorial scheme 3 x 4, in which it was considered three soil depths and four levels of manipueira. It was evaluated the weighted mean diameter of the aggregate, the percentage of aggregation at different periods, soil density, particle density, porosity and soil saturated hydraulic conductivity, in addition to pH of P (mg dm -3), K (mg dm-3), Ca (cmolc dm-3), Mg (cmolc dm-3), Ca+Mg (cmolc dm-3), Al (cmolc dm-3), Na (cmolc dm -3), H+Al (cmolc dm-3), CEC (cmolc dm-3), V%, OM (g kg-1), soil microbial biomass (Ug Cg-1 dry soil), acid phosphatase (Ug PNP g-1 h-1). The use of manipueira influenced some physical characteristic of the soil, but it was not possible to specify the effect of increasing application dosage. Therefore, the application did not affect the biological indicators assessed in the soil or its pH. The use of manipueira as a fertilizer in the doses used in this study showed low increase of K, P, H+Al and Al in the soil and a good increase of Mg, Ca and Ca+Mg, Na, CEC and V%.

Tabular cusum control charts of chemical variables applied to the control of surface water quality

The aim of this study was to evaluate the application possibility of tabular CUSUM control charts in the quality control of chemical variables in surface water. It was performed bibliographic and field research to collect water samples from 2003 to 2009, totaling 30 samples, some monthly and others semi-annual in order to observe the variables that regulate water quality. It was found that these charts may be applied to control the quality of river water; showing to be effective in the perception of changes during the process, especially for small samples (n=1) which there is no repetition as in this research. It was also concluded that the Mandurim River does not presents significant levels of pollution.

Management zones definition using soil chemical and physical attributes in a soybean area

Several equipments and methodologies have been developed to make available precision agriculture, especially considering the high cost of its implantation and sampling. An interesting possibility is to define management zones aim at dividing producing areas in smaller management zones that could be treated differently, serving as a source of recommendation and analysis. Thus, this trial used physical and chemical properties of soil and yield aiming at the generation of management zones in order to identify whether they can be used as recommendation and analysis. Management zones were generated by the Fuzzy C-Means algorithm and their evaluation was performed by calculating the reduction of variance and performing means tests. The division of the area into two management zones was considered appropriate for the present distinct averages of most soil properties and yield. The used methodology allowed the generation of management zones that can serve as source of recommendation and soil analysis; despite the relative efficiency has shown a reduced variance for all attributes in divisions in the three sub-regions, the ANOVA did not show significative differences among the management zones.

Chemical attributes of soil and dry mass accumulation of maize fertilized with cassava wastewater

The aim of this study was to evaluate chemical attributes alterations of a clay-loam textured soil and dry mass accumulation of maize submitted to application of cassava wastewater doses in three assessment periods. The experiment was conducted under greenhouse using a completely randomized experimental design in a factorial 5 × 3, with four replicates. The analyzed factors of research were doses of cassava wastewater (0; 12.6; 25.2; 50.4; 75.6 m3 ha-1) andassessment periods (20, 40 and 52 days after germination). The following parameters were determined: electric conductivity of soil saturation extract, pH in water, content of available P, content of exchangeable K+, Ca2+, Mg2+ and Na+of soil, dry mass of leaves and stem. The application of cassava wastewater on soil enables increase of pH, electric conductivity of saturation extract, contents of available P, contents of exchangeable K+ and Na+ and dry mass of leaves and stem. However, only pH and content of exchangeable K+ of soil, the electric conductivity of saturation extract and dry mass of leaves and stem are influenced by assessment period.

Spatial influence of physical and chemical parameters on management zone definition in apple orchards

ABSTRACT Precision agriculture adoption in Brazilian apple orchards is still incipient. This study aimed at evaluating the spatial variability of certain soil properties as soil density, soil penetration resistance, electrical conductivity, yield, and fruit quality in an apple orchard through digital mapping, as well as assessing the correlation between these factors by means of geostatistics, establishing management zones. Forty representative points were set within 2.5 hectares of apple orchard, wherein soil samples were collected and analyzed, besides measurements of fruit quality (Brix degree, size or diameter, pulp firmness and color) to generate an overall index quality. We concluded that the fruit quality indexes, when isolated, did not show strong spatial dependence, unlike the index of fruit quality (FQI), derived from a combination of these parameters, allowing orchard planning according to management zones based on quality.

Software for design of experiments and response modelling of cake ltration applications

Filtration is a widely used unit operation in chemical engineering. The huge variation in the properties of materials to be ltered makes the study of ltration a challenging task. One of the objectives of this thesis was to show that conventional ltration theories are di cult to use when the system to be modelled contains all of the stages and features that are present in a complete solid/liquid separation process. Furthermore, most of the ltration theories require experimental work to be performed in order to obtain critical parameters required by the theoretical models. Creating a good overall understanding of how the variables a ect the nal product in ltration is somewhat impossible on a purely theoretical basis. The complexity of solid/liquid separation processes require experimental work and when tests are needed, it is advisable to use experimental design techniques so that the goals can be achieved. The statistical design of experiments provides the necessary tools for recognising the e ects of variables. It also helps to perform experimental work more economically. Design of experiments is a prerequisite for creating empirical models that can describe how the measured response is related to the changes in the values of the variable. A software package was developed that provides a ltration practitioner with experimental designs and calculates the parameters for linear regression models, along with the graphical representation of the responses. The developed software consists of two software modules. These modules are LTDoE and LTRead. The LTDoE module is used to create experimental designs for di erent lter types. The lter types considered in the software are automatic vertical pressure lter, double-sided vertical pressure lter, horizontal membrane lter press, vacuum belt lter and ceramic capillary action disc lter. It is also possible to create experimental designs for those cases where the variables are totally user de ned, say for a customized ltration cycle or di erent piece of equipment. The LTRead-module is used to read the experimental data gathered from the experiments, to analyse the data and to create models for each of the measured responses. Introducing the structure of the software more in detail and showing some of the practical applications is the main part of this thesis. This approach to the study of cake ltration processes, as presented in this thesis, has been shown to have good practical value when making ltration tests.