Nitric Acid Dehydration Using Perfluoro Carboxylate and Mixed Sulfonate/Carboxylate Membranes

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Perfluoro ionomer membranes are tetrafluoro ethylene-based materials with microheterogeneous structures consisting of a hydrophobic polymer backbone and a hydrophilic side-chain cluster region. Due to the ionomer cluster morphology, these films exhibit unique transport properties. Recent investigations with perfluoro sulfonate and perfluoro sulfonate/carboxylate composite polymers have demonstrated their value in the dehydration of nitric acid and they show potential as an alternative to conventional, energy intensive unit operations in the concentration of acid feeds. As a result, investigations were conducted to determine the feasibility of using pure perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films for the dehydration of nitric acid because ... continued below

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162 pages

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Ames, R.L. September 1, 2004.

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  • Los Alamos National Laboratory
    Publisher Info: Los Alamos National Lab., Los Alamos, NM (United States)
    Place of Publication: Los Alamos, New Mexico

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Perfluoro ionomer membranes are tetrafluoro ethylene-based materials with microheterogeneous structures consisting of a hydrophobic polymer backbone and a hydrophilic side-chain cluster region. Due to the ionomer cluster morphology, these films exhibit unique transport properties. Recent investigations with perfluoro sulfonate and perfluoro sulfonate/carboxylate composite polymers have demonstrated their value in the dehydration of nitric acid and they show potential as an alternative to conventional, energy intensive unit operations in the concentration of acid feeds. As a result, investigations were conducted to determine the feasibility of using pure perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films for the dehydration of nitric acid because of the speculation of improved water selectivity of the carboxylate pendant chain. During the first phase of these investigations the effort was focused on generating a thin, solution cast perfluoro carboxylate ionomer film, to evaluate the general, chemical and physical characteristics of the polymer, and to assess the material's aqueous transport performance (flux and nitrate separation efficiencies) in pervaporation and high-pressure environments. Results demonstrated that generating robust solution-cast films was difficult yet a number of membranes survived high trans-membrane pressures up to 700 psig. General characterization of the solution cast product showed reduced ion exchange capacities when compared with thicker, ''as received'' perfluoro carboxylate and similar sulfonate films. Small angle x-ray scattering analysis results suggested that the solution cast carboxylate films contained a small fraction of sulfonate terminated side-chains. Aqueous transport experimentation showed that permeate fluxes for both pure water and nitric acid were approximately two orders of magnitude smaller for the carboxylate solution cast membranes when compared to their sulfonate counterparts of similar thickness (Nafion{trademark} 111). Additionally, nitric acid separation efficiencies ({alpha}) were approximately one order of magnitude higher for the carboxylate solution cast films when compared to Nafion{trademark} 111. The second phase of our work included the generation of thin carboxylate films made by the chemical synthesis perfluoro sulfonate and mixed sulfonate/carboxylate polymers from a perfluoro sulfonyl fluoride precursor, the characterization of the newly generated material, and a study of the transport characteristics of these membranes. Transport studies consisted of the dehydration of nitric acid feeds by pervaporation. In addition, the initial hypothesis was expanded to include demonstration that transmembrane flux and separation efficiencies are a function of the ratio between sulfonate and carboxylate terminated side chains of the perfluoro ionomer. Investigations demonstrated the ability to generate in- house films with varying sulfonate/carboxylate concentrations from commercially available perfluoro sulfonyl fluoride material, and showed that the converted films could be characterized using Fourier transform infrared (FTIR) and x-ray fluorescence (XRF) spectroscopy. Finally, the mixed films where subjected to nitric acid dehydration transport tests and a relationship was found to exist between sulfonate/carboxylate pendant chain ratio and both flux and water separation capability. In summary, experimental results confirmed that, when compared to Nafion 111{trademark}, the mixed film's bulk fluxes decrease by approximately three orders of magnitude and the water separation factor increases by as much as two orders of magnitude as the carboxylate side-chain content was increased from 0 (pure sulfonate film) to 53 mole%, supporting the hypothesis given for this effort. It was observed that the water selectivity improved for both the solution cast perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films when judged against similar perfluoro sulfonate materials. Of great benefit was that during the investigation a number of research tools were utilized including, but in no way limited to, basic chemical operations, procedure development and refinement, the use of a number of analytical systems (FTIR, XRF, thermal gravimetric analysis, nuclear magnetic resonance, etc.), data interpretation and analysis, and presentation and debate (defense) of results.

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162 pages

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OSTI as DE00836112

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  • Other Information: TH: Thesis (Ph.D.); Submitted to Department of Chemical Engineering, Colorado School of Mines, Golden, CO (US)

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  • Report No.: LA-14178-T
  • Grant Number: W-7405-ENG-36
  • Office of Scientific & Technical Information Report Number: 836112
  • Archival Resource Key: ark:/67531/metadc777008

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  • September 1, 2004

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  • Dec. 3, 2015, 9:30 a.m.

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  • March 22, 2016, 9:39 p.m.

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Ames, R.L. Nitric Acid Dehydration Using Perfluoro Carboxylate and Mixed Sulfonate/Carboxylate Membranes, thesis or dissertation, September 1, 2004; Los Alamos, New Mexico. (digital.library.unt.edu/ark:/67531/metadc777008/: accessed August 17, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.