No description available.

We have successfully investigated the use of CO2 as a miscibility switch to create an environment in which we can run a homogeneously catalyzed reaction while maintaining a heterogeneous separation. We explored the use of this technique with fluorous biphasic systems, a fluorous solid support, and aqueous biphasic systems. In the case of the fluorous systems, CO2 was added to induce solubility of the fluorous catalyst. When the reaction was completed, CO2 was vented and the system returned to a biphasic state, making the separation easy. For the aqueous biphasic systems, the organic phase is chosen such that it is fully miscible with water at ambient conditions. Examples include acetonitrile, THF, and dioxane. The addition of CO2 reduces the polarity of the solvent and causes a phase split. The recovery of the water-soluble catalyst is once again heterogeneous. The application to aqueous biphasic systems is the most exciting studied. Aqueous biphasic systems are used industrially in the hydroformylation of propylene. With our technique, these systems can be extended to more hydrophobic substrates. We have shown a rate increase of 65 fold and 99% product recovery at modest pressures for the hydroformylation of 1-octene. These aqueous biphasic systems also show much promise in the arena of enzyme catalyzed reactions. We can create an environment in which the enzyme kinetics will no longer be mass transfer limited.

Organic solvent production plants emit waste gases containing volatile organic compounds (VOCs) which are usually harmful to the environments and public healths. Plant managers are obligated to control the VOC emission to meet regulations at reasonable costs. A solvent plant located in southern Taiwan emits VOC-containing gas streams from some distillation columns and storage vessels with a total ventilation gas flow rate of 2.6-3.6 m3/min which contains VOCs with concentrations of less than 1,000 mg C/m3. Due to a concern of plant¡¦s safety, the plant managers constructed a full-scale biofilter for eliminating a part of the VOCs and the associated odors in the waste gas. This study aimed to investigate the effects of operation parameters such as EBRT (empty bed retention time) of the gas through the biofiltration media and organic loading to the media on the VOC removal efficiency. The biofilter is constructed of RC (reinforced concrete) with outer dimensions of 8.45 mL ¡Ñ 3.30 mW ¡Ñ 3.00 mH. The filter was also instrumented with inverters for control of speed of induced fans, and with thermometers, hygrometers, and wind speed meters. Fern chips with a total packing volume of 36 m3 was used as the biofiltration media. After inoculation with suitable microorganisms, the waste gas was introduced to the filter for VOC elimination. Nutrients (urea, milk, and a phosphate salt) and water were supplemented to the media on a daily basis. The investigation period is July, 2008 to May, 2010. In the period, THC (total hydrocarbon) concentrations for the influent and effluent gases to and from the reactor were daily measured. In addition, on a weekly basis, compositions of the VOCs in gas samples were detected by a gas chromatography equipped with a flame ionization dector (FID). On the same time basis, pH, COD (chemical oxygen demand), SS (suspended solids) in a sample of the trickled liquid from the media was analyzed. Media pH and moisture content were also analyzed for understanding the environmental conditions around the microorganisms for the VOC degradation. Results indicated that the media was in conditions of pH = 4.5-7.0, moisture = 11-61 % in the experimental phase. Trickled liquid had low COD and SS contents which can be easily treated by the existing wastewater unit in the plant, or be recycled to the media. Avarage THC, NMHC (nonmethane hydrocarbon), and VOCs were 71, 73, and 79%, respectively, with gas EBRTs of 4.2-6.3 min. With media pH of 4-5 and moisture contents 51-57%, over 90% of the influent VOCs coulb be eliminated. However, nearly dried media (moisture around 10%) had VOC removal efficiencies of lower than 30%. Nutrition tests indicate that the VOC removal efficiency was nearly proportional to milk supplementation rate. Removal of ethnaol and acetic could easily be removed with an efficiency of over 97% while 2-pentane was only 74%. Odor intensities of the treated gas could be controlled to <1,000 (dilutions to threshold) according to 3 test data.

The pollution of soil and groundwater have increased due to the leakage of ptrolium products and organic chemicals in the country recently,and Taiwan face with small region and dense population,so the pollution maybe exposed through relevant way such as quality of water,soil,air,crop and fish and so on to affect human health and cause risk of jeopardise directly or indiretly. The study is to aimed at chlorinated compounds for domestic,and use methods of risk assessment to analyze necessity and urgency of renovation for be contaiminted compound and downstream influence.And then according to result to make relevant management strategies and projets to control risk level and influence for contaiminated compound. In this study,we collect information relate to case,in accordence to health and risk assessment methods for soil and groundwater contaminated sites and some softwares of CRYSTAL BALL and BIOCHLO by Environmental Protection Bureau to estimate the site which was evaluated chlorinated compound (trichloroethylene,TCE),and considerate whether they affect residents healy nearby,use some hydrogeological survey of sites to process second-level health risk assessments. First,use commercial software of CRYSTAL BALL execute uncertainty and sensitivity analysis. Not only does the analysis probe into overall parameters variaty how to affect risk value but also they process analysis and results by different combinations of paremeter.From this result, we can confirm that the large parameter values for affecting risk is transmission of pollutants and is similar to previous studies assessment and analysis.Other parameter cause less influence for risk variaty such as age level of receptor,group,the way of contact,time and water quntity.The study discovers TCE pollutants concentration will make change of risk value by accompany with groundwater move to downstream distance. That means receptor of distance of contamination resource cause large influence. The far distance represents can product the larger function for TCE pollutant, and causes less cancer risk for receptor, conversely, it causes higher cancer risk. Subsequently, we also use BIOCHLOR assessment software by U.S.A Enviromental Protection Bureau. from the result to determine whether the site have potential of anaerrobic reductive dechlorination or not and estimate natural attenuation possibility.The actual situation of the site gets the three score in the weight total.This display do not prove that chlorinated compounds can procedd biogical decomposition in the anaerobic invironment without more correct value in the stage.We recommend looking for another renovations. The study selects more important sensitive parameters through risk assessment result for the site and work out the way of renovations which is suitable for this case by schedule of object. The investigation has found that residents indeed extracted groundwater for agriculture irrigation, but not drank water directly. In order to avoid the worst situation happens from the view of risk, we will consider two aspects of regulation and technology for plan. First, in order to administration control for the aspect of regulation we will consider how to prohibit residents to extract groundwater effectively. For instance, prohibit or limit to set up underground well, provide substitute drink water, set up notice sign and underground water quality monitor measure regularity. Second, for the sake of preventing pollutant group spread and adopt measure for the aspect of technology, for example pollution remediation technology (include soil gas extraction, air injection method at present) and containment control technology (include hydraulic containment, permeability reactive barrier, natural biological remediation, etc) to manage effectively possible events in the site and prepare well prevention in advance. We also adopt good communication with local residents to let residents understand executive content for renovation and reduce their resistance in favor of making progress for renovation and achieve risk management objective.

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No description available.

Naturally occurring bacterial populations are capable of detoxifying chlorinated compounds and immobilizing the radionuclide uranium via reductive processes. This study addressed the following three knowledge gaps in the fields of chlorinated solvent and uranium bioremediation, 1) the risks and benefits of coupling bioremediation with thermal treatment for clean-up of chlorinated ethene-contaminated sites, 2) the accuracy of available techniques for the monitoring of chlorinated solvent bioremediation, and 3) the role of gram positive Desulfitobacterium spp. in uranium immobilization. Experiments demonstrated that thermal treatment increases electron donor availability, but the increased electron donor was not used to fuel reductive dechlorination and was actually consumed for methanogenesis. Two approaches for monitoring chlorinated solvent bioremediation were investigated, molecular techniques and compound-specific isotope analysis (CSIA). Results demonstrated that while Dehalococcoides (Dhc) gene expression was up-regulated under conditions inhibitory to dechlorination, the isotope effects associated with dechlorination reactions catalayzed by Dhc populations in consortia and in pure cultures were similar. U(VI) reduction by multiple Desulfitobacterium isolates was demonstrated. Interestingly, while almost all U(VI)-reducing populations have been reported to produce uraninite (UO2), the product of U(VI) reduction by Desulfitobacterium isolates was a unique form of insoluble mononuclear U(IV).

Novel solvents utilizing a reversible CO₂ induced property switch are presented. The synthetic procedure for designing the solvents is discussed, along with detailed characterizations on both solvent forms to serve as a tool for optimal solvent identification as well as future solvent design. A reflectance infrared spectroscopic technique is introduced to allow for the examination of CO₂ and solvent composition under high pressures and temperatures. The magnitude of solvent property changes afforded by this "switch" creates opportunities for sustainable processing; discussed are the application to coupling reactions and separations, and CO₂ capture. The switchable solvents are shown to serve as effective media for running reactions, with the switch providing facile recovery of products and catalysts for solvent recycling. Lastly, the switch itself is exploited to provide for the separation of CO₂ from low partial pressure feed streams, and structure-property relationships were successfully used to develop next generation materials with enhanced absorption capacities. The viscosity of the solvents, as a function of temperature and composition, is also presented.

This thesis focuses on the development of new compounds or new processes that are more environmentally friendly and economical than those currently in use. The decomposition of hydrazine, a well established liquid rocket fuel for both the aerospace and defense industries, to the product ammonia is studied. Control of this reaction will allow hydrazine to be used as a propellant for both chemical and electric propulsion. From this a dual stage thruster will be developed that will be more efficient than current systems decreasing the amount of propellant needed and allowing for either a larger mission payload or a longer duration of individual missions. Hydrazine, while beneficial and well established, is also highly toxic, so other work in this thesis focuses on the synthesis of the novel molecule 1,1-dimethyl-2-[2-azidoethyl]hydrazine or DMAEH and its hydrazone intermediate 1,1-dimethyl-2-[2-azidoethyl]hydrazone or De-DMAEH as less toxic hydrazine replacements. Novel "switchable" ionic liquids have been investigated in this research. These are solvents that can change from molecular liquids to ionic liquids and back, simply with the addition or removal of CO₂ from the system. They can be used for a variety of applications, including as solvents for a reaction and separation system. Due to the recyclable nature of these solvents, waste is decreased making their development and implementation both environmentally and economically beneficial. Finally, the grafting reaction of vinyl silanes onto a hydrocarbon backbone is investigated. Fundamental work is being performed to study the graft distribution, selectivity and mechanism by which this reaction occurs. A more thorough understanding of how this reaction proceeds will allow for the development of a more efficient industrial process.

Cross-linked polyethylene has higher upper use temperature than normal polyethylene and is used as an insulating material for electricity carrying cables and hot water pipes. The most common method of inducing crosslinks is by reaction with silanes. After incorporation of silanes into polyethylene and upon hydrolysis with ambient moisture or with hot water, Si-O-Si crosslinks are formed between the various linear polyethylene chains. Industrially, this reaction is performed routinely. However, the efficiency of this reaction with respect to the silane is low and control of product distribution is difficult. A precise fundamental understanding is necessary to be able to manipulate the reactions and thus, allow for the facile processing of the polymers. Hydrocarbon models of polymers - heptane, dodecane - are being used to study this reaction in the laboratory. For the reaction, vinyltrimethoxysilane is used as the grafting agent along with di-tert-butyl peroxide as the radical initiator. MALDI, a mass spectrometric technique is used for the analysis of the product distribution after work-up. Advanced NMR techniques (COSY, HSQC, DEPT, APT, HMBC) are being conducted on the grafted hydrocarbon compounds to gain an in-depth understanding of the mechanism and regiochemistry of the grafting reaction. Scalable and cost effective methods to capture CO2 are important to counterbalance some of the global impact of the combustion of fossil fuels on climate change. The main options available now include absorption, adsorption and membrane technology. Amines, especially monoethanolamine, have been the most commercialized technology. However, it is not without disadvantages. House et al have investigated the energy penalty involved in the post-combustion CO2 capture and storage from coal-fired power plants and found that 15-20% reduction in the overall electricity usage is necessary to offset the penalty from capturing and storing 80% of United States coal fleet's CO2 emssions1. Novel non-aqueous amine solvents, developed by the Eckert Liotta group, react with CO2 to form ionic liquids. The ionic liquids readily desorb CO2 upon heating, regenerating the reactive amines and this cycle can be carried out multiple times. An iterative procedure is being adopted to develop amine solvents for CO2 capture. Thermodynamic information like reversal temperature and boiling point of the solvents are collected; they are then used to formulate structure property relationships which allow for new molecules to be engineered. On reaction with CO2, there is a sharp increase in viscosity which is unfavorable from a processing standpoint. Many approaches to mitigate and control viscosity are being studied as well. 1House et al, Energy Environ Sci, 2009, 2, 193-205