Electrochemical and physical characterization of Ni-Cu-Fe alloy for chlor-alkali hydrogen cathodes

This work describes the development of an alternative acetate bath for the electrochemical codeposition of Ni-Cu-Fe electrodes at low pH that is stable for several weeks and produces electrodes with good performance for chlor-alkali electrolysis. Physical characterization of the electrode surface was made using X ray absorption spectroscopy (XAS), scanning electron microscopy (SEM) and energy dispersive analysis (EDX). The evaluation of the material as electrocatalyst for the hydrogen evolution reaction (her) was carried out in brine solution (160 g L-1 NaCl + 150 g L-1 NaOH) at different temperatures through steady-state polarization curves. The Ni-Cu-Fe electrodes obtained with this bath have shown low overpotentials for the her, around 0.150 V at 353 K, and good stability under continuous long-term operation for 260 hours. One positive aspect of this cathode is that the polarization behavior of the material shows only one Tafel slope over the temperature range of 298 - 353 K.

Contaminação por mercúrio no Brasil: fontes industriais vs garimpo de ouro

This paper reviews the history of Hg contamination in Brazil by characterizing and quantifying two major sources of Hg emissions to the environment: industrial sources and gold mining. Industry was responsible for nearly 100% of total Hg emissions from the late 1940's to the early 1970's, when efficient control policies were enforced, leading to a decrease in emissions. Gold mining, on the other hand was nearly insignificant as a Hg source up to the late 1970's, but presently is responsible for over 80% of total emissions. Presently, over 115 tons of Hg are released into the atmosphere in Brazil annually. Nearly 78 tons come from gold mining operations, 12 tons come from chlor-alkali industry and 25 tons come from all other industrial uses. Inputs to soils and waters however, are still unknown, due to lack of detailed data base. However, emissions from diffuse sources rather than well studied classical industrial sources are probably responsible for the major inputs of mercury to these compartments.

Vedyn käytön tarkastelu Kemira Chemicals Oy:n Joutsenon tehtailla

Kemira Chemicals Oy:n Joutsenon tehtailla valmistetaan lipeää, suolahappoa, natriumhypokloriittia sekä natriumkloraattia. Lipeää, suolahappoa ja natriumhypokloriittia valmistetaan lipeätehtaassa. Natriumkloraattia valmistetaan kloraattitehtaassa. Kloraatti- ja lipeätehtaan tuotteet valmistetaan elektrolyysimenetelmällä. Elektrolyysien sivutuotteena syntyy vetykaasua, joka voidaan käyttää suolahapon valmistukseen, vetyvoimalaitoksen polttoaineena tai myydä asiakkaalle. Työn tavoitteena oli tarkastella vedyn käyttöä Joutsenon tehtailla. Tarkastelun tavoitteena oli löytää mahdollisia kehitys- tai jatkotutkimuskohteita vety- ja höyryjärjestelmästä. Koska vetyä käytetään myös vetyvoimalaitoksen polttoaineena, joka tuottaa tehtailla tarvittavan prosessihöyryn, tarkasteltiin työssä myös höyryn käyttöä tehtailla. Tarkastelua varten tehtiin Microsoft Excel-pohjainen taselaskentamalli, jolla simuloitiin vedyn ja höyryn käyttöä tehtailla. Työn tuloksena saatiin Excel-pohjainen simulointimalli, jolla pystyttiin tutkimaan vedyn ja höyryn käyttöä. Vedyn ja höyryn käyttöä tutkittiin viidessä eri skenaariossa. Skenaariossa yksi määritettiin pienimmät mahdolliset elektrolyysiin syötettävät sähkövirran arvot, joilla tehtaita on turvallista käyttää. Skenaariossa kaksi määritettiin pienimmät mahdolliset elektrolyysiin syötettävät sähkövirran arvot, joilla voimalaitoksen turbiini pysyisi ajossa. Skenaariossa kolme määritettiin tehtaiden tämän hetkinen maksimi kapasiteetti. Skenaarioissa neljä ja viisi tutkittiin, miten mahdollinen tehtaiden tuotantojen kasvattaminen vaikuttaisi vety- ja höyryjärjestelmään. Työn tuloksien perusteella kehitys- ja jatkotutkimuskohteita olisivat lipeän haihdutuksen höyryn kulutuksen pienentäminen, turbiinin käyttöajan kasvattaminen sekä eri lähteistä saatavan hukkalämmön parempi hyödyntäminen kaukolämmön tuotannossa. Tehtaiden tuotantoja kasvatettaessa on syytä kiinnittää huomioita myös voimalaitoksen pääkattilan ja turbiinin kapasiteettiin.

Kartoitus kloori-alkalitehtaan tuotantokapasiteetin kasvattamisesta / Kemira Chemicals Oy Joutseno

Kemira Chemicals Oy:n Joutsenon kloori-alkalitehtaalla valmistetaan elektrolyysin avulla lipeää, suolahappoa, natriumhypokloriittia ja vetyä. Tämän työn tavoitteena on kartoittaa kloori-alkalitehtaan tuotantokapasiteetin kasvatuksen yhteydessä esiin tulevat pullonkaulat, lähitulevaisuuden kunnossapitotarpeet sekä parhaat käytettävissä olevat teknologiavaihtoehdot kloori-alkalitehtaan osa-alueille, joihin tuotantokapasiteetin kasvatuspaineet kohdistuvat: elektrolyysi, lipeän haihdutus ja suolahappopolttimet. Pullonkaulojen kartoittaminen toteutettiin rakentamalla taulukkolaskentamalli kloori-alkalitehtaan prosesseista. Mallin avulla simuloitiin elektrolyysin kloorin tuotantoa, jota kasvatettiin asteittain 54 kt:sta/a aina 100 kt:iin/a asti ja tutkittiin prosessien käyttäytymistä. Tarkastelun pohjalta havaittiin, että kloorin tuotantoa kasvattaessa, tulee lisätä myös tuotantokapasiteettia suolahapon valmistukseen, elektrolyysiin, demineralisoidun veden valmistukseen ja lipeän haihdutuslaitokseen sekä suolahapon ja lipeän varastointikapasiteetteihin. Vaihtoehtoiset teknologiat määritettiin kirjallisuudesta ja laitetoimittajien esitteistä. Lähivuosien kunnossapitotarpeet kartoitettiin haastattelemalla tehtaan henkilökuntaa. Työstä eskaloitui useita jatkotutkimuskohteita, joita ovat bipolaari-teknologian soveltuvuus Joutsenon kloori-alkalitehtaalle, uusien HCl-polttimien esisuunnittelu, höyryn käytön tehostaminen nykyisessä lipeän haihdutuslaitoksessa sekä uusien haihdutusteknologioiden soveltuvuus Joutsenon kloori-alkalitehtaalle, höyry- ja jäähdytysverkostojen kartoitukset sekä demineralisoidun veden valmistuskapasiteetin kasvattaminen.

Consequence modelling,vulnerability assessment and fuzzy fault tree analysis of hazardous storages in an industrial area

The hazards associated with major accident hazard (MAH) industries are fire, explosion and toxic gas releases. Of these, toxic gas release is the worst as it has the potential to cause extensive fatalities. Qualitative and quantitative hazard analyses are essential for the identitication and quantification of the hazards associated with chemical industries. This research work presents the results of a consequence analysis carried out to assess the damage potential of the hazardous material storages in an industrial area of central Kerala, India. A survey carried out in the major accident hazard (MAH) units in the industrial belt revealed that the major hazardous chemicals stored by the various industrial units are ammonia, chlorine, benzene, naphtha, cyclohexane, cyclohexanone and LPG. The damage potential of the above chemicals is assessed using consequence modelling. Modelling of pool fires for naphtha, cyclohexane, cyclohexanone, benzene and ammonia are carried out using TNO model. Vapor cloud explosion (VCE) modelling of LPG, cyclohexane and benzene are carried out using TNT equivalent model. Boiling liquid expanding vapor explosion (BLEVE) modelling of LPG is also carried out. Dispersion modelling of toxic chemicals like chlorine, ammonia and benzene is carried out using the ALOHA air quality model. Threat zones for different hazardous storages are estimated based on the consequence modelling. The distance covered by the threat zone was found to be maximum for chlorine release from a chlor-alkali industry located in the area. The results of consequence modelling are useful for the estimation of individual risk and societal risk in the above industrial area.Vulnerability assessment is carried out using probit functions for toxic, thermal and pressure loads. Individual and societal risks are also estimated at different locations. Mapping of threat zones due to different incident outcome cases from different MAH industries is done with the help of Are GIS.Fault Tree Analysis (FTA) is an established technique for hazard evaluation. This technique has the advantage of being both qualitative and quantitative, if the probabilities and frequencies of the basic events are known. However it is often difficult to estimate precisely the failure probability of the components due to insufficient data or vague characteristics of the basic event. It has been reported that availability of the failure probability data pertaining to local conditions is surprisingly limited in India. This thesis outlines the generation of failure probability values of the basic events that lead to the release of chlorine from the storage and filling facility of a major chlor-alkali industry located in the area using expert elicitation and proven fuzzy logic. Sensitivity analysis has been done to evaluate the percentage contribution of each basic event that could lead to chlorine release. Two dimensional fuzzy fault tree analysis (TDFFTA) has been proposed for balancing the hesitation factor invo1ved in expert elicitation .

Characterizing the effects of turbulence on sediment oxygen and sediment nitrate demand using flow-through reactors

Onondaga Lake has received the municipal effluent and industrial waste from the city of Syracuse for more than a century. Historically, 75 metric tons of mercury were discharged to the lake by chlor-alkali facilities. These legacy deposits of mercury now exist primarily in the lake sediments. Under anoxic conditions, methylmercury is produced in the sediments and can be released to the overlying water. Natural sedimentation processes are continuously burying the mercury deeper into the sediments. Eventually, the mercury will be buried to a depth where it no longer has an impact on the overlying water. In the interim, electron acceptor amendment systems can be installed to retard these chemical releases while the lake naturally recovers. Electron acceptor amendment systems are designed to meet the sediment oxygen demand in the sediment and maintain manageable hypolimnion oxygen concentrations. Historically, designs of these systems have been under designed resulting in failure. This stems from a mischaracterization of the sediment oxygen demand. Turbulence at the sediment water interface has been shown to impact sediment oxygen demand. The turbulence introduced by the electron amendment system can thus increase the sediment oxygen demand, resulting in system failure if turbulence is not factored into the design. Sediment cores were gathered and operated to steady state under several well characterized turbulence conditions. The relationship between sediment oxygen/nitrate demand and turbulence was then quantified and plotted. A maximum demand was exhibited at or above a fluid velocity of 2.0 mm•s-1. Below this velocity, demand decreased rapidly with fluid velocity as zero velocity was approached. Similar relationships were displayed by both oxygen and nitrate cores.

Development of a Composite ion-exchange membrane for PDMS-based microfluidic devices

The purpose of this research is to investigate potential methods to produce an ion-exchange membrane that can be integrated directly into a polydimethylsiloxane Lab-on-a-Chip or Micro-Total-Analysis-System. The majority of microfluidic membranes are based on creating microporous structures, because it allows flexibility in the choice of material such that it can match the material of the microfluidic chip. This cohesion between the material of the microfluidic chip and membrane is an important feature to prevent bonding difficulties which can lead to leaking and other practical problems. However, of the materials commonly used to manufacture microfluidic chips, there are none that provide the ion-exchange capability. The DuPont product Nafion{TM} is chosen as the ion-exchange membrane, a copolymer with high conductivity and selectivity to cations and suitable for many applications such as electrolysis of water and the chlor-alkali process. The use of such an ion-exchange membrane in microfluidics could have multiple advantages, but there is no reversible/irreversible bonding that occurs between PDMS and Nafion{TM}. In this project multiple methods of physical entrapment of the ion-exchange material inside a film of PDMS are attempted. Through the use of the inherent properties of PDMS, very inexpensive sugar granulate can be used to make an inexpensive membrane mould which does not interfere with the PDMS crosslinking process. After dissolving away this sacrificial mould material, Nafion{TM} is solidified in the irregular granulate holes. Nafion{TM} in this membrane is confined in the irregular shape of the PDMS openings. The outer structure of the membrane is all PDMS and can be attached easily and securely to any PDMS-based microfluidic device through reversible or irreversible PDMS/PDMS bonding. Through impedance measurement, the effectiveness of these integrated membranes are compared against plain Nafion{TM} films in simple sodium chloride solutions.

Inputs from a mercury-contaminated lagoon: impact on the nearshore waters of the Atlantic Ocean

Ria de Aveiro, a Portuguese coastal lagoon that exchanges water with the Atlantic Ocean, received the effluent from a chlor-alkali industry for over 50 years; consequently several tons of mercury had been buried in the sediments of an inner basin. To assess the importance (and seasonal variation) of the lagoon waters as carriers of mercury to the nearby coastal area, we measured total mercury levels in several compartments: in surface sediments, in surface and deep waters (including dissolved and particulate matter!, and in biota. Dissolved (reactive and total) mercury concentrations both in surface and deep waters were low (<1 to 15 ng L '). Mean mercury values in suspended particulate matter varied hetween 0.2 and 0.6 jxg g ' and in sediments between 1 and 9 ng g '. Aquatic organisms displayed levels below regulatory limits but exhibited some bioaccumulation of mercury, with concentrations ranging from 0.05 to 0.8 ^ig g ' Idry weight (dw)|. No seasonal pattern was found in this study for mercury-related determinations. Levels found in the estuary mouth during ebb tide provide evidence for the transport of mercury to the coastal zone. No significant changes in the partition of mercury between dissolved and particulate phases were found in the coastal waters in comparison with the values found in the estuary mouth. In spite of the high levels of mercury found inside some areas of the lagoon, the wide web of islands and channels allows some spreading of contaminants before they reach the coastal waters. Moreover, the low efficiency of local marine sediments in trapping mercury contributes to a dilution of mercury transported in suspended particulate matter over a broader area, reducing the impact in the nearby manne coastal zone.

Parametric model for the analysis of concrete expansion due to alkali-aggregate reaction

The alkali-aggregate reaction (AAR) is a chemical reaction that provokes a heterogeneous expansion of concrete and reduces important properties such as Young's modulus, leading to a reduction in the structure's useful life. In this study, a parametric model is employed to determine the spatial distribution of the concrete expansion, combining normalized factors that influence the reaction through an AAR expansion law. Optimization techniques were employed to adjust the numerical results and observations in a real structure. A three-dimensional version of the model has been implemented in a finite element commercial package (ANSYS(C)) and verified in the analysis of an accelerated mortar test. Comparisons were made between two AAR mathematical descriptions for the mechanical phenomenon, using the same methodology, and an expansion curve obtained from experiment. Some parametric studies are also presented. The numerical results compared very well with the experimental data validating the proposed method.

Sodium distribution in mixed alkali K-Na metaphosphate glasses

The local order and distribution of Na in the mixed alkali metaphosphate glasses K(x)Na(1-x)PO(3) were analyzed, with the aim to identify segregation or a random mixture of both cation species. X-Ray photoelectron spectroscopy and several nuclear magnetic resonance (NMR) techniques were applied, including (31)P and (23)Na high-resolution spectroscopy, (23)Na triple quantum-MAS NMR, rotational echo double resonance between (31)P and (23)Na, and (23)Na NMR spin echo decay. The structural picture emerging from these results reveals the similarity in the local Na environments in the glasses but also subtle structural adjustments with increasing degree of K replacement. While both cations are intimately mixed at the atomic scale, the (23)Na spin echo decay data suggest a detectable like-cation preference in the spatial distribution of the ions. These structural properties are consistent with those determined in Li-Rb metaphosphates, indicating that the origin of the mixed alkali effect observed in the conductivity of Na-K metaphosphate glasses may also be explained by structurally blocked ion diffusion.

Xylooligosaccharides Production from Alkali-Pretreated Sugarcane Bagasse Using Xylanases from Thermoascus aurantiacus

Sugarcane bagasse hemicellulose was isolated in a one-step chemical extraction using hydrogen peroxide in alkaline media. The polysaccharide containing 80.9% xylose and small amounts of L-arabinose, 4-O-methyl-D-glucuronic acid and glucose, was hydrolyzed by crude enzymatic extracts from Thermoascus aurantiacus at 50 degrees C. Conditions of enzymatic hydrolysis leading to the best yields of xylose and xylooligosaccharides (DP 2-5) were investigated using substrate concentration in the range 0.5-3.5% (w/v), enzyme load 40-80 U/g of the substrate, and reaction time from 3 to 96 h, applying a 22 factorial design. The maximum conversion to xylooligosaccharides (37.1%) was obtained with 2.6% of substrate and xylanase load of 60 U/g. The predicted maximum yield of xylobiose by a polynomial model was 41.6%. Crude enzymatic extract of T. aurantiacus generate from sugarcane bagasse hemicellulose 39% of xylose, 59% of xylobiose, and 2% of other xylooligosaccharides.

Comparative analysis of the gas-phase reactions of cylindrospermopsin and the difference in the alkali metal cation mobility

Cylindrospermopsin (CYN) belongs to a group of toxins produced by several strains of freshwater cyanobacteria. It is a compact zwitterionic molecule composed of a uracil section and a tricyclic guanidinium portion with a primarily hepatotoxic effect. Using low multi-stage and high-resolution mass spectrometry, the gas-phase reactions of this toxin have been investigated. Our data show that collision-induced dissociation (CID) spectra of CYN are dominated by neutral losses, and three major initial fragmentation pathways are clearly distinguishable. Interestingly, comparative analysis of protonated and cationizated molecules showed a significant difference in the balance of the SO(3) and terminal ring elimination. These data indicate that the differential ion mobility of H(+), Li(+), Na(+) and K(+) leads to different fragmentation pathways, giving rise to mass spectra with different profiles. Copyright (C) 2008 John Wiley & Sons, Ltd.

Dehydromonocrotaline generates sequence-selective N-7 guanine alkylation and heat and alkali stable multiple fragment DNA crosslinks

Monocrotaline is a pyrrolizidine alkaloid known to cause toxicity in humans and animals. Its mechanism of biological action is still unclear although DNA crosslinking has been suggested to a play a role in its activity. In this study we found that an active metabolite of monocrotaline, dehydromonocrotaline (DHM), alkylates guanines at the N7 position of DNA with a preference for 5'-GG and 5'-GA sequences; In addition, it generates piperidine- and heat-resistant multiple DNA crosslinks, as confirmed by electrophoresis and electron microscopy. On the basis of these findings, we propose that DHM undergoes rapid polymerization to a structure which is able to crosslink several fragments of DNA.