A relevante potencialidade dos centros básicos nitrogenados disponíveis em polímeros inorgânicos e biopolímeros na remoção catiônica

This review reports the application of inorganic and organic polymeric materials for cation removal by using nitrogenated basic centers. The data demonstrate the importance of the desired groups when free or immobilized on natural or synthesized inorganic polymers through silanol groups. Thus, the most studied silica gel is followed by natural crysotile and talc polymers, and the synthesized mesopore silicas, talc-like, silicic acids, phosphates and phyllosilicates. The organic natural biopolymeric chitin and cellulose were chemically modified to improve the availability of the amine groups or the reactivity with desirable molecules to enlarge the content of basic centers. The cation removal takes place at the solid/liquid interface and some interactive effects have their thermodynamic data determined.

Efeito da composição das correntes do conversor das unidades de FCC no desempenho catalítico de aditivos DESOx

Hydrotalcite-like compounds having Mg partially replaced by Cu or Mn were prepared and used as precursors for two mixed oxides (Cu-OM50 and Mn-OM50) that were evaluated for SOx removal in the presence of O2, NO and CO. Under SO2/O2 reaction system, SOx removal was slightly higher over Cu-OM50. The addition of CO and NO to the feed markedly hindered the SO2 oxidation over Cu-OM50 while no significant effect was observed for Mn-OM50. For the regeneration step, the use of propane instead of H2 reduces regeneration capacity, mainly for Cu-OM50. Mn-OM50 was less affected by the feed composition, suggesting that it was a promising additive for SOx removal.

Degradação de espécies nitroaromáticas e remediação de efluentes da indústria de explosivos, utilizando-se processos redutivos-oxidativos fundamentados no uso de ferro metálico

In this work the potentiality of reductive-oxidative processes based on zero-valent iron was studied aiming the degradation of nitroaromatic compounds and the remediation of residues from the explosive industry. The reductive process was applied as a continuous treatment system, using steel-wool as zero-valent iron source. The process permitted an almost total degradation of nitrobenzene, nitrophenol, nitrotoluene, dinitrotoluene and trinitrotoluene, probably with generation of the respective amine-derivative. The yellow-water residue, containing soluble trinitrotoluene, was notably modified by the reductive process, a fact that permitted a substantial enhancement of its biodegradability. Furthermore, the subsequent photo-Fenton process allowed TOC removal of about 80%.

Contaminação de produtos de higiene e cosméticos por n-nitrosaminas

N-nitrosamines are carcinogenic compounds that have been found during the last three decades in a variety of consumer products, including cosmetic and personal care products, and their raw materials. These compounds are formed from amine precursors and nitrosating agents present in the formulations. This paper reviews the formation and occurrence of N-nitrosamines in cosmetic products, as well as presents considerations about analytical, toxicological and regulatory aspects.

Removal of copper(II) from sugar-cane spirits employing chitosan

A method employing chitosan as complexant agent in the removal of copper(II) ions generally present in the Brazilian cachaça samples is herein proposed. The efficiency of this method is attributed to its high capacity of metal cations adsorption, mainly due to presence of hydroxyl and amine groups that can serve as chelating sites. The removal of copper(II) ions from this alcoholic beverage was efficient employing either in column and batch system. The analysis were carried out employing the flame atomic absorption spectrometry and the remaining copper(II) concentrations in the treated cachaça were lower than LOD of FAAS technique.

Poisoning and regeneration of Pt-Pd/WO3-ZrO2 short paraffin isomerization catalysts

WO3-ZrO2 catalysts promoted with Pt and Pd were tested as paraffin isomerization catalysts using n-hexane as model compound. Sulfur and amine poisoning and regeneration tests were used to assess the impact of the addition of Pt and Pd on the deactivation resistance and regenerability. Pt and PtPd catalysts were the most active for n-hexane isomerization. The low activity of the Pd catalyst was attributed to poor Pd metal properties when supported over WO3-ZrO2 and to a decrease of the number of BrQnsted acid sites. PtPd was the only catalyst capable of full regeneration after S poisoning. Amine poisoning completely supressed the isomerization activity and the original activity could only be restored by calcination and reduction.

Hiilidioksidin talteenottoon soveltuvan anioninvaihtohartsin valmistus ja karakterisointi

Tämän työn tarkoituksena oli tutkia hiilidioksidin talteenottoon soveltuvan anioninvaihtohartsin valmistusmenetelmiä, kokeilla eri menetelmiä käytännössä ja tutkia sekä itse valmistettujen että valmiina saatujen hartsien adsorptiokykyä ja muita ominaisuuksia. Kemiallinen adsorptio amiiniryhmän omaavien hartsien avulla on yksi tapa sitoa hiilidioksidia ilmasta. Primäärinen amiiniryhmä sitoo hiilidioksidia parhaiten. Primäärisen amiiniryhmän omaava anioninvaihtohartsi voidaan valmistaa pohjapolymeeristä halogeenialkyloimalla ja aminoimalla, aminoalkyloimalla tai suoraan aminoimalla. Aminoalkylointi voidaan suorittaa erilaisilla reagensseilla ja katalyyteillä. Tässä työssä hartseja valmistettiin aminoimalla polymetyyliakrylaattidivinyylibentseenipohjaista polymeeriä etyylidiamiinilla ja propyylidiamiinilla. Lisäksi suoritettiin polystyreeni-divinyylibentseenipohjaisen polymeerin aminoalkylointi bis(ftaali-imidometyyli)eetterin avulla. Reaktio tehtiin kahdella eri katalyytillä; rikkitrioksidilla ja rautakloridilla. Aminoalkylointireaktioissa tarvittava eetteri piti ennen varsinaista reaktiota valmistaa N-hydroksymetyyliftaali-imidistä. Myös tämän reagenssin syntetisointia ftaali-imidistä kokeiltiin. Kaikki synteesit onnistuivat melko hyvin, paitsi aminoalkylointi rautakloridikatalyytillä. Hartsien valmistuksen lisäksi itse valmistettuja primäärisen amiiniryhmän omaavia hartseja sekä erilaisia amiiniryhmiä omaavia valmiita hartseja karakterisoitiin eri tavoin. Erityisesti haluttiin tutkia hiilidioksidin adsorptiokapasiteettia ja hartsien termistä kestävyyttä. Kaikista tutkituista hartseista lähimpänä haluttuja ominaisuuksia olivat kaksi kaupallista primäärisen amiiniryhmän omaavaa PS-DVBpohjaista makrohuokoista hartsia. Rakenteeltaan samanlainen itse valmistettu hartsi (rikkitrioksidikatalyytin läsnä ollessa aminoalkyloitu) oli myös ominaisuuksiltaan lupaava. Valmistusmenetelmää pitää kuitenkin tutkia ja kehittää lisää vielä parempien tulosten aikaansaamiseksi. Myös kaupallinen polyetyleeni-imiinirakenteen omaava silikapohjainen hartsi oli ominaisuuksiltaan hyvä.

In situ synthesis of nanoclay filled polyethylene using polymer supported metallocene catalyst system

In situ ethylene polymerizations were performed using bis(cyclopentadiene)titanium dichloride supported on polyethersulfone as catalyst. The bis(cyclopentadiene)titanium dichloride supported on polyethersulfone catalyst activity estimated by ethylene polymerization was 360 kgPE/molTi/h. During polymerization the fillers used were montmorillionite nanoclays having surface modifications with 35-45 wt% dimethyl dialkyl(14-18)amine (FA) and 25-30 wt% trimethyl stearyl ammonium (FB). These fillers were pretreated with methylaluminoxine (MAO; cocatalyst) for better dispersion onto the polymer matrix. The formation of polyethylene within the whole matrix was confirmed by FTIR studies. It was found that the nature of nanofiller did not have any remarkable effect on the melting characteristics of the polymer. TGA study indicates that nanoclay FB filled polyethylene has higher thermal stability than nanoclay FA filled polyethylene. The melting temperature of the obtained polyethylenes was 142 ºC, which corresponds to that synthesized by the polyether sulfone supported catalyst.

Estudo espectroscópico de compósito obtido da reação no estado sólido entre um complexo mononuclear de vanádio(IV) e caulinita

The use of probes, such as paramagnetic species diluted in diamagnetic materials in EPR spectroscopy, and mathematical tools such, as the Kubelka-Munk function in DRUV-VIS spectroscopy are strategies in the analysis of complex mixtures of solid materials. The results obtained here show that the solid state reaction between the complex, [VO(acac)(BMIMAPY)] [ClO4], BMIMAPY = [(bis(1-methylimidazole-2-yl)methyl)(2-(pyridyl-2-yl)ethyl) amine] and acac = acetilacetonate, with kaolinite turns possible to obtain anisotropic EPR spectrum of the complex with a reasonable level of resolution. The study by DRUV-VIS using the method of second derivative mode of the Kubelka-Munk function revealed new complex structural arrangements, a solid hitherto unknown.

A general A³: coupling reaction based on functionalized alkynes

A range of hydroxypropargylpiperidones were efficiently obtained by a one-pot three-component coupling reaction of aldehydes, alkynols, and a primary amine equivalent (4-piperidone hydrochloride hydrate) in ethyl acetate using copper(I) chloride as a catalyst. The developed protocol proved to be equally efficient using a range of aliphatic aldehydes, including paraformaldehyde, and using protected and unprotected alkynols.

VIS-NIR SPECTROMETRY, SOIL PHOSPHATE EXTRACTION METHODS AND INTERACTIONS OF SOIL ATTRIBUTES

The objective of this study was to evaluate the relationships between the spectra in the Vis-NIR range and the soil P concentrations obtained from the PM and Prem extraction methods as well as the effects of these relationships on the construction of models predicting P concentration in Oxisols. Soil samples' spectra and their PM and Prem extraction solutions were determined for the Vis-NIR region between 400 and 2500 nm. Mineralogy and/or organic matter content act as primary attributes allowing correlation of these soil phosphorus fractions with the spectra, mainly at wavelengths between 450-550, 900-1100 nm, near 1400 nm and between 2200-2300 nm. However, the regression models generated were not suitable for quantitative phosphate analysis. Solubilization of organic matter and reactions during the PM extraction process hindered correlations between the spectra and these P soil fractions. For Prem,, the presence of Ca in the extractant and preferential adsorption by gibbsite and iron oxides, particularly goethite, obscured correlations with the spectra.

DERIVATIZACIÓN Y CARACTERIZACIÓN ESPECTROSCÓPICA DE UN BIOPOLÍMERO A BASE DE L -LISINA CON ANÁLOGOS DE LA D-BIOTINA: CO -POLI(L-LISINA)-GRAFT -(ε-N-[X-D -BIOTINIL]-L-LISINA)

We report the single-step derivatization reaction of a biopolymer based onL -lysine with D -biotin analogs:Co -poly(L -lysine)-graft-(ε-N -[X-D-biotinyl]-L -lysine) (PLL-X-Biotin). The valeric acid carboxylate of D -biotin is activated to an NHS ester for direct modification of amine groups in proteins and other macromolecules. NHS esters react by nucleophilic attack of an amine in the carbonyl group, releasing the NHS group, and forming a stable amide linkage. NHS-X-Biotin is the simplest biotinylation reagent commercially available. In contrast withD -biotin, it has a longer spacer arm off the valeric acid side chain allowing better binding potential for avidin or streptavidin probes. Derivatization of poly(L -lysine) (PLL) with NHS-X-Biotin led to a copolymer PLL-X-Biotin. UV-Visible, IR-FT and 1H NMR characteristics derived from synthesis are briefly discussed.

Potentials of process intensification in the Finnish petrochemical industry

This research was motivated by the need to examine the potential application areas of process intensification technologies in Neste Oil Oyj. According to the company’s interest membrane reactor technology was chosen and applicability of this technology in refining industry was investigated. Moreover, Neste Oil suggested a project which is related to the CO2 capture from FCC unit flue gas stream. The flowrate of the flue gas is 180t/h and consist of approximately 14% by volume CO2. Membrane based absorption process (membrane contactor) was chosen as a potential technique to model CO2 capture from fluid catalytic cracking (FCC) unit effluent. In the design of membrane contactor, a mathematical model was developed to describe CO2 absorption from a gas mixture using monoethanole amine (MEA) aqueous solution. According to the results of literature survey, in the hollow fiber contactor for laminar flow conditions approximately 99 % percent of CO2 can be removed by using a 20 cm in length polyvinylidene fluoride (PDVF) membrane. Furthermore, the design of whole process was performed by using PRO/II simulation software and the CO2 removal efficiency of the whole process obtained as 97 %. The technical and economical comparisons among existing MEA absorption processes were performed to determine the advantages and disadvantages of membrane contactor technology.

Voimalaitoksen palamisilman esilämmittimen sisäpuolisen korroosion hallinta pinta-aktiivisten amiinien avulla

Useat voimalaitokset käyttävät hiiliteräksistä valmistettuja palamisilman esilämmittimiä, joissa höyrykattilan palamisilmaa lämmitetään matalapainehöyryllä. Joissakin tapauksissa esilämmittimet ovat kärsineet sisäpuolisen korroosion aiheuttamista putkirikoista. Tämän työn tavoitteena oli selvittää korroosiovaurioiden aiheuttajat ja tarkastella eri keinoja uusien korroosiovaurioiden ehkäisemiseksi. Keskeisimpänä uusien vaurioiden ehkäisykeinona tarkastellaan pinta-aktiivisia amiineja sisältäviä höyrykattilan jälkiannostelukemikaaliseoksia, joista tarkemman tarkastelun kohteena on kaupallinen Helamin 90 H Turb- kemikaaliseos. Pääasialliseksi korroosion aiheuttajaksi on usein epäilty höyryn sisältämää hiilidioksidia. Uusimpien näkemysten mukaan orgaaniset hapot, pääasiassa etikka- ja muurahaishappo ovat kuitenkin hiilidioksidia voimakkaampia korroosion aiheuttajia ilmanesilämmittimissä. Orgaaniset hapot väkevöityvät höyryn lauhtumisen alkaessa muodostuviin lauhdepisaroihin ja alentavat pH-tasoa radikaalisti. pH-tason aleneminen nopeuttaa metallipintoja suojaavan magnetiitin liukenemista ja vaikeuttaa myös sen uusiutumista. Orgaanisia happoja ja hiilidioksidia muodostuu orgaanisten aineiden osittaisessa hajoamisessa höyrykattilan vesi-höyrypiirissä. Pääasialliset orgaanisten aineiden lähteet ovat lisäveden mukana kattilaan kulkeutuva luonnon orgaaninen aines ja käytetyt orgaaniset jälkiannostelukemikaalit. Orgaanisten aineiden kuormaa voidaan pienentää parantamalla lisäveden valmistusprosessin orgaanisten aineiden erotustehokkuutta esimerkiksi käänteisosmoosilla. Mikäli lisäveden laadun parantaminen ei ole järkevästi toteutettavissa, voidaan orgaanisten jälkiannostelukemikaalien oikeanlaisella käytöllä neutraloida orgaanisten happojen vaikutus ilmanesilämmittimissä. Tehokkaimmaksi korroosion hillitsijäksi suoritettujen mittausten perusteella osoittautuivat kemikaaliseokset, jotka sisältävät alkaloivien amiinien lisäksi kalvoa muodostavaa pinta-aktiivista amiinia.

Use of modified silica gel for concentrating Pb (II) and Cd (II) occurring in form of complex anions

The performance of silica gel, modified by the impregnation with a high molecular weight quaternary amine (triethyl octadecyl ammonium iodide), used for the concentration of heavy metals occurring in water is studied. The material under study captures Cd, Pb, which are capable of forming stable complexes with I- ions.The results obtained about the metal capture, under dynamic conditions, are described and metal ions are removed by desorption with EDTA and quantified by AAS.