Combinación de sistemas de flujo de baja y alta presion para la determinacion de Mg, Ca y Sr en salmueras por espectrofotometria de absorcion atomica con llama

This article describes the combination of low- and high-pressure flow systems for the determination of Magnesium, Calcium and Strontium by flame atomic absorption spectrometry (FAAS). In the low-pressure system a short C-18 RP column (length 0,5 cm) was utilized for the preconcentration/matrix separation step, xylenol orange was used as chelating agent and tetrabutylamonium acetate for ion pair formation. The hydraulic high pressure nebulization (HHPN) was used for sample transport and sample introduction in the high pressure system. The repeatabilities and detection limits for Mg, Ca and Sr were determined and compared with those obtained by pneumatic nebulization (PN). The results show that the detection limits obtained using the HHPN for Mg, Ca and Sr are between 1.5 to 2 times better than those obtained by PN when the signal transient was measured in area. The system presented a sampling frequency of 130 h-1 for direct determination of Mg, Ca or Sr in samples of saturated sodium chloride used in the production of chlorine and sodium hydroxide.

Paperin puhtauden parantaminen lajittelun ja muiden prosessiteknisten keinojen avulla

Tämä työ suoritettiin UPM- Kymmene Oyj:n Tervasaaren tehtaan PK 5:llä. PK 5 valmistaa tarrantaustapaperia. Tämän työn tarkoituksena oli löytää eri keinoja paperin puhtauden parantamiseksi. Puhtaamman paperin valmistaminen parantaa paperikoneen kilpailukykyä kilpailijoihinsa nähden sekä vähentää asiakasvalituskustannuksia. Työn kirjallinen osa koostuu kolmesta suuremmasta kokonaisuudesta, joiden tarkoituksena on luoda teoriapohjaa kokeellisen osan suoritusta varten. Kirjallisuusosan pääpaino on kohdistettu PK 5:llä esiintyviin saostumanaiheuttajiin, kuten uuteaineisiin, ASA- liimaan ja mikrobeihin. Tarkemmassa tarkastelussa on kirjallisuusosassa myös painelajittelu ja pyörrepuhdistus. Kokeellisessa osassa suoritettiin PK 5:n prosessissa syntyvien epäpuhtauksien karakterisointi. Suurimmat saostuman aiheuttajat analyysien perusteella olivat puuperäiset uuteaineet ja ASA- liima. Epäorgaanisista aineista päällystyskomponenttina toimiva kaoliini ja sellun mukana tuleva pihkatalkki esiintyi useimpien saostumien komponentteina. Selvityksessä havaittiin, että prosessille vieraita aineita ei löydetty muista, kuin kalanteroidusta paperista analysoiduista tummista täplistä. Tummista täplistä analysoitu styreenin alkuperä voi selittyä mm. prosessiin päässeellä kumilla tai muovilla. PK 5:n prosessissa selvityksen mukaan silikonipohjainen vaahdonestoaine aiheuttaa erittäin suuria tummia saostumia, joten sen pääsy prosessiin tulee estää sellutehtaalla tarkoin. Epäpuhtauksien määrä on suurin PK 5:n prosessissa hylkylinjassa ja lyhyessä kierrossa. Hylyn painelajittelu poistaa hyvin roskia syöttömassasta. Hylyn lajittelun toisen portaan lajittimen rejektin roskapitoisuus on suhteellisen suuri. Rejektin ohjaaminen ulos prosessista vähentää roskaisuuden rikastumista prosessiin. Sakeamassalajittelun sijoittaminen PK 5:n konekyypin jälkeen vähentää roskien päätymistä paperiin. Hylyn painelajittelun ja PP- laitoksen rejektin ohjaaminen sakeamassalajittelun toiseen portaaseen vähentäisi priimakuitutappiota ja roskien määrää käytetyissä massoissa. Seisokin aikaisen putkilinjojen pesujen lopputulos parani huomattavasti BA- pesuaineen käyttöönoton jälkeen. Kyseisen pesuaine soveltuu liuottamaan putkistosta mm. PK 5:llä esiintyvät uuteaine- ja ASA- saostumat. BSA- sellun pH- säädön lopettamisella oli suuri vähentävä vaikutus tummien täplien esiintymistiheyteen. pH- säädössä BSA- tornin pohjalaimennukseen annosteltu lipeä edesauttoi tummien saostumien syntymistä saippuoiden uuteaineita.

Preparação e caracterização de pós cerâmicos de aluminatos de lítio

The preparation of gamma-LiAlO2 by coprecipitation and sol-gel synthesis was investigated. Ceramic powders obtained by coprecipitation synthesis were prepared from aqueous solutions of aluminum and lithium nitrates using sodium hydroxide as precipitant agent. By sol-gel synthesis, the ceramic powders were prepared from hydrolysis of aluminum isopropoxide. The materials obtained by two routes of synthesis were dried at 80ºC and calcined at 550, 750, 950 and 1150ºC. The characterization was done by X-ray diffraction, infrared spectroscopy, emission and absorption atomic spectrometry, helium picnometry, specific surface area (BET method) and scanning electronic microscopy. Mixtures of crystalline phases were obtained by coprecipitation synthesis: 80ºC- LiAl2(OH)7.2H2O + Al(OH)3; 550 and 750ºC- alpha-LiAlO2 + eta-Al2O3; 950 and 1150ºC- gamma-LiAlO2 + LiAl5O8. Chemical analysis showed molar ration Al/Li @ 3. Crystalline single-phases were obtained by sol-gel synthesis above 550ºC: 550ºC-alpha-LiAlO2; 750, 950 and 1150ºC-gamma-LiAlO2. These powders presented molar ration Al/Li @ 1. Thus, gamma-LiAlO2 crystalline phase was obtained at 750ºC by sol-gel synthesis while by coprecipitation synthesis, a mixture of crystalline phases was obtained. These results showed the superiority of the sol-gel synthesis for the preparation of pure gamma-LiAlO2.

Determinação espectrofotométrica por injeção em fluxo de paracetamol (acetaminofeno) em formulações farmacêuticas

A flow injection spectrophotometric procedure is proposed for the determination of paracetamol (acetaminophen) in pharmaceutical formulations. Powdered and liquid samples were previously dissolved/diluted in 0.05 mol L-1 hydrochloric acid solution and a volume of 250 µL was injected directly into a carrier stream of this same acid solution, flowing at 2.5 mL min-1. Paracetamol reacts with sodium hypochlorite forming N-acetyl-p-benzoquinoneimine which then reacts with sodium salicylate in sodium hydroxide solution yielding a blue indophenol dye which was measured at 640 nm in the pH range of 9.5-10.0. Paracetamol was determined in pharmaceutical products in the 1.0 to 100.0 mg L-1 (3.3x10-6 a 6.6x10-4 mol L-1) concentration range, with a detection limit of 0.5 mg L-1 (1.6x10-6 mol L-1). The recovery of this analyte in five samples ranged from 98.0 to 103.6 %. The analytical frequency was 80 determinations per hour and the RSDs were less than 1% for paracetamol concentrations of 25.0, 50.0 and 75.0 mg L-1 (n=10). A paired t-test showed that all results obtained for paracetamol in commercial formulations using the proposed flow injection procedure and a spectrophotometric batch procedure agree at the 95% confidence level.

Construção e aplicação de eletrodo de aço inoxidável UNS S31254 como eletrodo indicador em titulações condutimétricas

UNS S31254 SS electrodes have been built to substitute platinum in conductimetric titrations. The electrodes were tested in both acid-basic titration (chloridric acid and sodium hydroxide) and precipitation titration (sodium chloride and argentum nitrate as titrant). The practical application was exemplified from conductimetric tritations of HF ¾ HNO3 mixtures used in metalurgical industry to passivate stainless steels. The results were compared with those obtained using commercial platinum electrodes. The equivalent volumes obtained were comparable within 3% experimental error. Its application depends on the nature of electrolyte. These results have shown that stainless steel, less expensive than platinum (about three order of magnitude), can substitute platinum electrodes in routine analyses and didactic laboratories.

Biohajoavat kompleksinmuodostajat mekaanisen massan peroksidivalkaisussa

Mekaanisen massan peroksidivalkaisussa on perinteisesti käytetty kahta kompleksinmuodostajaa, jotka ovat dietyleenitriamiinipentaetikkahappo (DTPA) ja etyleenidiamiinipentaetikkahappo (EDTA). Kompleksinmuodostajat saavat aikaan hyvän kelatointituloksen muodostamalla valkaisulle haitallisten metalli-ionien kanssa kompleksin ja estäen näin metalli-ionien valkaisutulosta huonontavan vaikutuksen. Perinteiset kompleksinmuodostajat DTPA ja EDTA eivät kuitenkaan ole biohajoavia ja niiden epäillään irrottavan metalleja vesistöjen sedimenteistä. Työssä selvitettiin kolmen eri biohajoavan kompleksinmuodostajan valkaisuteho verrattuna perinteisiin kompleksinmuodostajiin. Laboratoriossa suoritetut pesukokeet osoittivat, että mikään biohajoava kompleksinmuodostaja ei saavuttanut samaa pesutehoa kuin perinteiset kompleksinmuodostajat. Valkaisukokeet kuitenkin osoittivat, että biohajoava kompleksinmuodostaja ISA pääsi hyvin lähelle perinteisten kompleksinmuodostajien valkaisutuloksia suoritettaessa valkaisu siten, että massa esipestään kompleksinmuodostajalla ja sen jälkeen valkaistaan vakiokemikaaliannoksella alkalina ollessa natriumhydroksidi. Kaksi muuta biohajoavaa kompleksinmuodostajaa, ISA+EDDS ja HAS, eivät saavuttaneet samaa tasoa. HAS toimi kyllä stabilaattorina, muttei pystynyt nostamaan massan vaaleutta.

Gerenciamento de resíduos químicos e águas servidas no laboratório de isótopos estáveis do CENA/USP

A system for disposal and recovery of the main effluents and chemical waist from isotope separation plants and enriched compounds-15N and 34S production has been carried out at the Stable Isotope Laboratory (LIE) of the CENA/USP. Around four hundred thousand liters of effluents has been recovered yearly. Among the recovered chemical wastes, the more relevant are: ammonia; brome; ammonium and sodium sulfate; sodium hydroxide; sulfur dioxide; and hydrochloric acid. Chemical wastes containg recoverable heavy metals (Ag, Cr and Cu) and solvents (methanol, ethanol and acetone) are processed and recovered. Gaseous emissions, mainly H2S are used for recovery of heavy metals solutions. The minimization of the residues waters, as well the reduction of electric energy consume was established using a water deionization system. A cost/effect balance of the process is reported.

Determinação eletroanalítica de corante reativo presente como contaminante em proteínas purificadas por cromatografia de afinidade

Procion Green HE-4BD is a reactive dye currently used in affinity purification, and commonly present as a contaminant in the final biological preparation. An assay method is described to determine trace amounts of the dye in the presence of human serum albumin(HSA) and leakage from agarose as affinity sorbent by cathodic stripping voltammetry. The proposed method is based on the reductive peak at -0.55V in B-R buffer pH 3 (E=0V and t= 240s), obtained when samples of HSA 2% (m/v) containing dye concentrations in sodium hydroxide pH 12 are submitted to a heating time of 330 min at 80 ºC. Linear calibration curves can be obtained for RG19 dye concentrations from 5x10-9 mol L-1 to 8 x10-8 mol L-1. The detection limit (3sigma) is 1x10-9 mol L-1.

Jatkuvatoimisen natriumhypokloriittireaktorin mallinnus

Natriumhypokloriittia voidaan valmistaa kloorista ja lipeästä jatkuvatoimisessa absorberissa. Tässä työssä tutkittiin kokeellisesti, miten kaasun ja nesteen virtausnopeudet vaikuttavat täytekappalekolonnin tulvimiseen ja painehäviöön, kuinka nopeasti kloori absorboituu lipeään ja kuinka suuri hypokloriittiliuoksen kierrätys tarvitaan, ettei hypokloriitti ala hajota. Lisäksi luotiin matemaattinen malli, jolla voidaan mitoittaa jatkuvatoiminen vastavirtaperiaatteella toimiva natriumhypokloriittireaktori. Kloori–lipeäsysteemin havaittiin tulvivan suuremmilla virtausnopeuksilla kuin ilma–vesisysteemin. Tosin osa kloorista absorboituu jo ennen täytekappalekerrosta, minkä vuoksi kaasun todellinen virtausnopeus täytekappalekerroksen alaosassa on pienempi kuin mitattu arvo. Kolonnin painehäviö nousee erittäin jyrkästi tulvimispisteen läheisyydessä. Koska kloori absorboituu lähes täydellisesti ja vain kolonnin alaosa tulvii, voidaan kolonnia painehäviön kannalta operoida lähellä tulvimispistettä. Sekä mallinnuksen että koetulosten perusteella yli 99,99 % kloorista absorboituu koeolosuhteissa kahden metrin täytekappalekerroksessa. Nopea absorptio johtuu erittäin nopeasta, irreversiibelistä kloorin reaktiosta ja prosessille tyypillisestä natriumhydroksidikonversion rajoittamisesta alle 94 %:iin. Jotta varmistetaan, ettei hypokloriitti ala hajota, valmista hypokloriittiliuosta täytyy kierrättää kolonniin vähintään noin 4-kertainen määrä tuoreen lipeän syöttömäärän nähden.

Water circulations for effective bleaching of high-brightness mechanical pulps

The amount of water available is usually restricted, which leads to a situation where a complete understanding of the process, including water circulations and the influence of water components, is essential. The main aim of this thesis was to clarify the possibilities for the efficient use of residual peroxide by means of water circulation rearrangements. Rearranging water circulations and the reduction of water usage may cause new problems, such as metal induced peroxide decomposition that needs to be addressed. This thesis introduces theoretical methods of water circulations to combine two variables; effective utilization of residual peroxide and avoiding manganese in the alkaline peroxide bleaching stage. Results are mainly based on laboratory and mill site experiments concerning the utilization of residual peroxide. A simulation model (BALAS) was used to evaluate the manganese contents and residual peroxide doses. It was shown that with optimum recirculation of residual peroxide the brightness can be improved or chemical costs can be decreased. From the scientific perspective, it was also very important to discover that recycled peroxide was more effective pre-bleaching agent compared to fresh peroxide. This can be due to the organic acids i.e. per acetic acid in wash press filtrate that have been formed in alkaline bleaching stage. Even short retention time was adequate and the activation of residual peroxide using sodium hydroxide was not necessary. There are several possibilities for using residual peroxide in practice regarding bleaching. A typical modern mechanical pulping process line consist of defibering, screening, a disc filter, a bleach press, high consistency (HC) peroxide bleaching and a wash press. Furthermore there usually is not a particular medium consistency (MC) pre-bleaching stage that includes additional thickening equipment. The most advisable way to utilize residual peroxide in this kind of process is to recycle the wash press filtrate to the dilution of disc filter pulp (low MC pre-bleaching stage). An arrangement such as this would be beneficial in terms of the reduced convection of manganese to the alkaline bleaching stage. Manganese originates from wood material and will be removed to the water phase already in the early stages of the process. Recycling residual peroxide prior to the disc filter is not recommended because of low consistencies. Regarding water circulations, the novel point of view is that, it would be beneficial to divide water circulations into two sections and the critical location for the division is the disc filter. Both of these two sections have their own priority. Section one before the disc filter: manganese removal. Section two after the disc filter: brightening of pulp. This division can be carried out if the disc filter pulp is diluted only by wash press filtrate before the MC storage tower. The situation is even better if there is an additional press after the disc filter, which will improve the consistency of the pulp. This has a significant effect on the peroxide concentration in the MC pre-bleaching stage. In terms of manganese content, it is essential to avoid the use of disc filter filtrate in the bleach press and wash press showers. An additional cut-off press would also be beneficial for manganese removal. As a combination of higher initial brightness and lower manganese content, the typical brightness increase varies between approximately 0.5 and 1% ISO units after the alkaline peroxide bleaching stage. This improvement does not seem to be remarkable, but as it is generally known, the final brightness unit is the most expensive and difficult to achieve. The estimation of cost savings is not unambiguous. For example in GW/TMP mill case 0.6% ISO units higher final brightness gave 10% savings in the costs of bleaching chemicals. With an hypothetical 200 000 ton annual production, this means that the mill could save in the costs of bleaching chemicals more than 400 000 euros per year. In general, it can be said that there were no differences between the behavior of different types of processes (GW, PGW, TMP and BCTMP). The enhancement of recycling gave a similar response in all cases. However, we have to remember that the utilization of residual peroxide in older mills depends a great deal on the process equipment, the amount of water available and existing pipeline connections. In summary, it can be said that processes are individual and the same solutions cannot be applied to all cases.

Paineviemärissä muodostuvan rikkivedyn vähentäminen kemikaloimalla

Anaerobisissa olosuhteissa muodostuva rikkivetykaasu on tyypillinen ongelma etenkin pitkillä paineviemäriosuuksilla. Sille ominainen epämiellyttävä haju aiheuttaa jätevedenkäsittelyverkostoissa ja viemärilinjojen lähialueilla merkittäviä hajuongelmia. Lisäksi rikkivedyn hapettuessa rikkihapoksi viemäri joutuu alttiiksi korroosiolle. Helsingin Etelä rannassa sijaitsevaan Munkkisaareen päätyy 4,4 km pitkä paineviemäri. Viemärin tuuletusputken kautta leviävä rikkivety on aiheuttanut hajuongelmia alueella. Korkeimmat mitatut rikkivetypitoisuudet tuuletusputken läheisyydessä olivat jopa 300 ppm. Tutkimuksessa tehtiin koeajoja erilaisilla hajunpoistokemikaaleilla rikkivetyongelman ratkaisemiseksi. Viemäriin annosteltiin sen alkupäässä jatkuvatoimisesti ferrosulfaattia ja ferrinitraattisulfaattia, sekä shokki-käsittelyllä natriumhydroksidia (lipeää). Munkkisaaressa mitatut rikkivetypitoisuudet osoittivat käytettyjen kemikaalien tehokkuuden rikkivedyn poistossa. Rikkivedyn saostamiseen tarkoitetut rautasuolat (ferrosulfaatti ja ferrinitraattisulfaatti) vähensivät 100 - 150 g annoksilla rikkivetyä yli 90 prosenttia. Natriumhydroksin annoksella 3600 g/m³ viemärin mikrobiologinen toiminta voitiin estää keskimäärin kymmeneksi päiväksi, mutta tehokas rikkivedyn muodostumisen esto vaatisi käsittelyn uusimisen noin 5 päivän välein. Normaaleissa viemärin olosuhteissa rikkivetyä muodostui vuorokauden aikana yhtä neliömetriä kohden noin 10 g. Kemikaalikäsittelyjen avulla muodostuminen aleni parhaimmillaan kymmenesosaan alkuperäisestä. Tulosten perusteella kemikaalien käytöllä viemärissä voisi välttyä kalliilta saneeraukselta Munkkisaaressa sekä muissa korroosiolle alttiiksi joutuvissa viemäreissä. Kemikalointikustannukset rautasuoloilla olivat noin 11 000 - 34 000 € ja lipeällä noin 7 000 € vuodessa.

Processamento de pilhas Li/MnO2 usadas

This work presents two recycling processes for spent Li/MnO2 batteries. After removal of the solvent under vacuum the cathode + anode + electrolyte was submitted to one of the following procedures: (a) it was calcined (500 ºC, 5 h) and the calcined solid was submitted to solvent extraction with water in order to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Manganese was recovered as sulfate; (b) the solid was treated with potassium hydrogeno sulfate (500 ºC, 5 h). The solid was dissolved in water and the resulting solution was added dropwise to sodium hydroxide. Manganese was recovered as dioxide. The residual solution was treated with potassium fluoride in order to precipitate lithium fluoride.

Desenvolvimento de um método empregando quitosana para remoção de íons metálicos de águas residuárias

In this work a method was developed for removing metallic ions from wastewaters by co-precipitation of Cu2+, Pb2+, Cd2+, Cr3+ and Hg2+ with chitosan and sodium hydroxide solution. Solutions of these metallic ions in the range from 0.55 to 2160 mg L-1 were added to chitosan dissolved in 0.05 mol L-1 HCl. For the co-precipitation of metal-chitosan-hydroxide a 0.17 mol L-1 NaOH solution was added until pH 8.5-9.5. A parallel study was carried out applying a 0.17 mol L-1 NaOH solution to precipitate those metallic ions. Also, a chitosan solid phase column was used for removing those metallic ions from wastewaters.

Recuperação de cobalto e de lítio de baterias íon-lítio usadas

The "active mass" (cathode + anode + electrolyte) of spent Li-ion batteries was submitted to one of the following procedures: (a) it was calcined (500 ºC) and submitted to extraction with water to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Cobalt was recovered as sulfate; (b) the "active mass" was treated with potassium hydrogen sulfate (500 ºC) and dissolved in water. Cobalt was precipitated together with copper after addition of sodium hydroxide. Lithium was partially recovered as lithium fluoride. Co-processing of other battery components (aluminum and copper foils) affected negatively the behavior of the recovery procedures. Previous segregation of battery components is essential for an efficient and economical processing of the "active mass".

Highly improved chromium (III) uptake capacity in modified sugarcane bagasse using different chemical treatments

The present paper focuses on improving chromium (III) uptake capacity of sugarcane bagasse through its chemical modification with citric acid and/or sodium hydroxide. The chemical modifications were confirmed by infrared spectroscopy, with an evident peak observed at 1730 cm-1, attributed to carbonyl groups. Equilibrium was reached after 24 h, and the kinetics followed the pseudo-second-order model. The highest chromium (III) maximum adsorption capacity (MAC) value was found when using sugarcane bagasse modified with sodium hydroxide and citric acid (58.00 mg g-1) giving a MAC value about three times greater (20.34 mg g-1) than for raw sugarcane bagasse.