Simultaneous chemical reaction and distillation of formaldehyde

The thesis is concerned with the development and testing of a mathematical model of a distillation process in which the components react chemically. The formaldehyde-methanol-water system was selected and only the reversible reactions between formaldehyde and water giving methylene glycol and between formaldehyde and methanol producing hemiformal were assumed to occur under the distillation conditions. Accordingly the system has been treated as a five component system. The vapour-liquid equilibrium calculations were performed by solving iteratively the thermodynamic relationships expressing the phase equilibria with the stoichiometric equations expressing the chemical equilibria. Using optimisation techniques, the Wilson single parameters and Henry's constants were calculated for binary systems containing formaldehyde which was assumed to be a supercritical component whilst Wilson binary parameters were calculated for the remaining binary systems. Thus the phase equilibria for the formaldehyde system could be calculated using these parameters and good accuracy was obtained when calculated values were compared with experimental values. The distillation process was modelled using the mass and energy balance equations together with the phase equilibria calculations. The plate efficiencies were obtained from a modified A.I.Ch.E. Bubble Tray method. The resulting equations were solved by an iterative plate to plate calculation based on the Newton Raphson method. Experiments were carried out in a 76mm I.D., eight sieve plate distillation column and the results were compared with the mathematical model calculations. Overall, good agreement was obtained but some discrepancies were observed in the concentration profiles and these may have been caused by the effect of limited physical property data and a limited understanding of the reactions mechanism. The model equations were solved in the form of modular computer programs. Although they were written to describe the steady state distillation with simultaneous chemical reaction of the formaldehyde system, the approach used may be of wider application.

The design of a high pressure solvent extraction process using liquid ammonia as solvent

The literature on the potential use of liquid ammonia as a solvent for the extraction of aromatic hydrocarbons from mixtures with paraffins, and the application of reflux, has been reviewed. Reference is made to extractors suited to this application. A pilot scale extraction plant was designed comprising a Scm. diameter by 12Scm. high, 50 stage Rotating Disc Contactor with 2 external settlers. Provision was made for operation with, or without, reflux at a pressure of 10 bar and ambient temperature. The solvent recovery unit consisted of an evaporator, compressor and condenser in a refrigeration cycle. Two systems were selected for study, Cumene-n-Heptane-Ammonia and Toluene-Methylcyclohexane-Ammonia. Equlibrium data for the first system was determined experimentally in a specially-designed, equilibrium bomb. A technique was developed to withdraw samples under pressure for analysis by chromatography and titration. The extraction plant was commissioned with a kerosine-water system; detailed operating procedures were developed based on a Hazard and Operability Study. Experimental runs were carried out with both ternary ammonia systems. With the system Toluene-Methylcyclohexane-Ammonia the extraction plant and the solvent recovery facility, operated satisfactorily, and safely,in accordance with the operating procedures. Experimental data gave reasonable agreement with theory. Recommendations are made for further work with plant.

Oil bearing seasonal crops in India:energy and phytoremediation potential

Purpose: A variety of biomass plantations are being raised for energy production. This case study is on energy production potential of seasonal oil bearing crops in India. These crops have the advantage of producing oil (liquid fuel) as well as biomass as agro residue (solid fuel). The purpose of the study is to estimate total energy yields of oil bearing crops and compare with other types of energy plantations. Also oil bearing crops bioaccumulate metals and thus phytoremediate soil. This provides scope for waste water irrigation. Design/methodology/approach: Relevant published papers on energy production by raising oil bearing crops have been analyzed. The effect of waste water irrigation and agronomic practices on increasing productivity is given special attention. Findings: It is shown that the seasonal oil bearing crops such as castor have a high potential to generate energy and this is comparable to energy produced by many perennial grasses. The energy yields of castor under irrigated condition was 196×103 MJ/ha and this is comparable to the reed canary grass which yields 195×103 MJ/ha. Some of the oil bearing crops are also super accumulators of certain toxic metals. Research limitations/implications: In this study, only all the accessible papers on the topic could be analyzed. Practical implications: This case study indicates that raising oil bearing crops such as castor using waste water has many advantages which include high energy yields, utilization of waste water for productive purpose and phytoremediation of soil. Originality/value: The comparison made between various types of energy crops for their energy generation is an original contribution. Findings of economic and environmental benefits by waste water irrigation are also of value. © Emerald Group Publishing Limited.

Trained Neural Network Characterizing Variables for Predicting Organic Retention by Nanofiltration Membranes

Many organic compounds cause an irreversible damage to human health and the ecosystem and are present in water resources. Among these hazard substances, phenolic compounds play an important role on the actual contamination. Utilization of membrane technology is increasing exponentially in drinking water production and waste water treatment. The removal of organic compounds by nanofiltration membranes is characterized not only by molecular sieving effects but also by membrane-solute interactions. Influence of the sieving parameters (molecular weight and molecular diameter) and the physicochemical interactions (dissociation constant and molecular hydrophobicity) on the membrane rejection of the organic solutes were studied. The molecular hydrophobicity is expressed as logarithm of octanol-water partition coefficient. This paper proposes a method used that can be used for symbolic knowledge extraction from a trained neural network, once they have been trained with the desired performance and is based on detect the more important variables in problems where exist multicolineality among the input variables.

Composition of zooplankton assemblages along the Zagyva River

The species composition, longitudinal distribution and seasonal dynamics of zooplankton were studied in the Zagyva River, Hungary. A total of 108 taxa was recorded from which 61 were new for the river. Rotatoria was the most abundant group, microcrustaceans were less important, only nauplii and copepodites were represented in similar individual numbers. Frequent species included Anuraeopsis fissa, Pompholyx spp., Keratella cochlearis, Brachionus angularis, Bdelloida sp., Bosmina longirostris. Dominance of cosmopolitan species was observed both in the river and its reservoir, and species characteristic of eutrophic waters were of major importance in the latter. There was a downstream decrease in zooplankton densities, which was explained by modified conditions. The relatively large number of individuals in autumn months, and the characteristic large number of individuals in the upper section contrasted general findings of potamoplankton dynamics. On the basis of the species abundance matrix, three river sections can be distinguished (upper, middle, lower section). Due to waste water discharges - received from the Tarján Stream - we found extremely high number of individuals and the lowest diversity at the sampling site Nagybátony (148 rkm).

Eco-innovation – does additional engagement lead to additional rewards?

Purpose: Eco-innovation is any form of product, process or organisational innovation that contributes towards sustainable development. Firms can eco-innovate in a variety of ways. The purpose of this paper is to identify nine different eco-innovation activities – including such items as reducing material use per unit of output, reducing energy use per unit of output, reducing carbon dioxide (CO2) “footprint” – and the authors ask whether these act as substitutes or complements to one another. Design/methodology/approach: Eco-innovation is any form of product, process or organisational innovation that contributes towards sustainable development. Firms can eco-innovate in a variety of ways. In this paper the authors identify nine different eco-innovation activities – including such items as reducing material use per unit of output, reducing energy use per unit of output, reducing CO2 “footprint” – and the authors ask whether these act as substitutes or complements to one another. Findings: Introducing only one eco-innovation activity has little payoff (in terms of turnover per worker) with only those firms who reduce their CO2 “footprint” having higher levels of turnover per worker. When introducing more than one eco-innovation activity the authors find that certain eco-innovation activities complement one another (e.g. reducing material use within the firm at the same time as improving the ability to recycle the product after use) others act as substitutes (e.g. reducing material use within the firm at the same time as recycling waste, water or materials within the firm). Practical implications: The results suggest that firms can maximise their productive capacity by considering specific combinations of eco-innovation. This suggests that firms should plan to introduce eco-innovation which act as complements, thereby, boosting productivity. It also suggests that eco-innovation stimuli, introduced by policy makers, should be targeted at complementary eco-innovations. Originality/value: The paper analyses whether eco-innovations act as complements or substitutes. While a number of studies have analysed the importance of eco-innovation for firm performance, few have assessed the extent to which diverse types of eco-innovation interact with each other to complement or substitute for one another.

(Table 1) Age determination of North Atlantic sediment cores

Stable isotope, trace metal, alkenone paleothermometry, and radiocarbon methods have been applied to sediment cores in the western subpolar North Atlantic between Hudson Strait and Cape Hatteras to reveal the history of climate in that region over the past ~11 kyr. We focus on cores from the Laurentian Fan, which is known to have rapid and continuous accumulation of hemipelagic sediment. Although results among our various proxy data are not always in agreement, the weight of the evidence (alkenone sea surface temperature (SST), d18O and abundance of Globigerinoides ruber) indicates a continual cooling of surface waters over Laurentian Fan, from about 18°C in the early Holocene to about 8°C today. Alternatively, Mg/Ca data on planktonic foraminifera indicate no systematic change in Holocene SST. The inferred long-term decrease in SST was probably driven by decreasing seasonality of Northern Hemisphere insolation. Two series of proxy data show the gradual cooling was interrupted by a two-step cold pulse that began 8500 years ago, and lasted about 700 years. Although this event is associated with the final deglaciation of Hudson Bay, there is no d18O minimum anywhere in the Labrador Sea, yet there is some evidence for it as far south as Cape Hatteras. Finally, although the 8200 year B.P. event has been implicated in decreasing North Atlantic ventilation, and hence widespread temperature depression on land and at sea, we find inconsistent evidence for a change at that time in deep ocean nutrient content at ~4 km water depth.

Helium and oxygen isotope ratios of ODP Sites 193-1188 and 193-1189

Fluid mixing processes and thermal regimes within the Snowcap and Roman Ruins vent sites of the PACMANUS hydrothermal system, Papua New Guinea, were investigated using 3He/4He ratios from fluid inclusions within pyrite and anhydrite and the d18O signature of anhydrite. Depressed 3He/4He ratios of 0.2-6.91RA appear to be caused by significant atmospheric diffusive exchange, whilst He-Ne diffusive fractionation precludes correction using 20Ne. 40Ar/36Ar ratios of 295-310 are elevated above seawater, indicating the majority of argon is seawater derived but with a magmatic component. d18O anhydrite ratios are 6.5 per mil to 11 per mil for Snowcap and 6.4 per mil to 11.9 per mil for Roman Ruins. Using oxygen isotope fractionation factors for the anhydrite-water system, the temperatures calculated assuming isotopic equilibrium at depth are up to 100 °C cooler than fluid inclusion trapping temperatures. It is likely that anhydrite is precipitated rapidly, preventing d18O equilibration. By comparing new d18O values for anhydrite with corresponding published 87Sr/86Sr ratios, seawater is inferred to penetrate deep into the Snowcap system with little conductive heating. A simple fluid mixing model has been constructed whereby the differing venting styles can be explained by a plumbing system at depth which favors delivery of end-member hydrothermal fluid to the high temperature sites.

Ottimizzazione della reazione di Fenton mediante l’utilizzo di un sistema automatico di reazione

The research presented in this dissertation is aimed to the automation of the Fenton process. The Fenton reaction is finalized to the waste water pre-treatment in order to promote the abatement of the organic contaminants and make it more degradable. Reagents adopted are constituted by a mixture of iron ions and hydrogen peroxide and their effect is strictly influenced by several variables, such as: the reagents molar ratio and their quantities counterpoised to the substrate, temperature, pH, agitation, etc. Therefore, the optimization is far from being considered an easy procedure. The research was carried out using a batch configuration, through which the optimal [Fe2+]/[H2O2] and [substrate]/[H2O2] ratios were identified. Then, in order to improve the process, a semibatch configuration was performed. The preliminary results show that is possible to obtain a greater abatement efficiency for high organic burden using the semibatch configuration here proposed.

Sex steroid feedback regulation of pituitary gonadotropins during early secondary oocyte growth in coho salmon (Oncorhynchus kisutch) – a potential target of endocrine disruption.

Thesis (Ph.D.)--University of Washington, 2016-06