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At least 757 records · Page 42

Compositions and methods for the dissolution and depolymerization of lignin

The present invention provides for a method for dissolving and/or depolymerizing lignin comprising: (a) providing a composition comprising lignin, (b) contacting the composition with a strong hydrogen donor, such as a polyol, to form a first solution, (c) incubating the first solution at a temperature equal to or less than 100° C., whereby at least 20% by weight of the lignin is dissolved, (d) optionally introducing an oxidation agent to the first solution to form a second solution, wherein the temperature of the second solution is equal to or less than 100° C., whereby lignin is depolymerized, and (e) optionally introducing an anti-solvent to the second solution to precipitate the depolymerized lignin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solids from Fuel Dissolution, Process Solutions, and Waste Evaporation

Irradiated light water reactor (LWR) fuel contains material which is insoluble in nitric acid, and process solutions are unstable with respect to precipitation of compounds insoluble in nitric acid. Accordingly, solids will be encountered during fuel reprocessing, and operations must be conducted in a way to minimize formation of additional solids and to prevent their interference with reprocessing operations.

Campbell, D. O.↗

Metallurgical Analysis of the High Flux Isotope Reactor (HFIR) Carrier Lifting Bails (Rev.1)

The dissolution rates of the aluminum alloys in the High Flux Isotope Reactor (HFIR) element carriers and the Material Test Reactor (MTR) L-bundles in the H-Canyon facility have been identified as the possible cause of extended dissolutions that result in significant time and financial expenditures. A study, carried out by Savannah River National Laboratory (SRNL) to determine relationships between the dissolution rates and the metallurgical properties of the aluminum alloy materials of construction of the HFIR carriers and the L-bundles, considered the dissolution rates of aluminum alloy (AA) series 1100, 6061, and 6063. The study determined that the aluminum alloy compositions played a principal role in the dissolution rate of the carrier/bundle components. Higher dissolution rates were correlated with lower concentrations of the minor element additions in the alloys and with specific element concentrations. Aluminum alloys 1100 and 6063 were found to have similar dissolution rates that were approximately two orders of magnitude (100X) greater than those of AA6061. Based on the results of the dissolution behavior study, a Technical Assistance Request (TAR) was first issued to determine if the replacement of AA6061-T6 with AA6063-T6 is feasible for the HFIR carrier lifting bails. A Technical Task Request was then issued to consider AA6063-T5 as well as other alloys to improve possible supply chain issues. The metallurgical properties of the L-bundle (specifically the end caps) were not evaluated in this report because L-Bundle drawings already allow for the use of AA6063-T6 in all structural components. The HFIR carriers are composed of thin-walled components with significant surface areas that allow for relatively quick overall dissolution times. Conversely, the carrier lifting bails and the supporting constituents are composed of solid bars and thick plate regions with relatively small surface areas that experience longer overall dissolution times. While the MTR L-bundle design includes allowances for the materials of construction to be either AA6061-T6 or AA6063-T6, the HFIR carriers are specified to be constructed fully with AA6061-T6 alloy. This report analyzes the recommendations of the dissolution behavior study to replace the materials of construction of the HFIR carrier lifting bails. The analysis considers the operational requirements of the lifting bail and its supporting structures. To decrease dissolution times, the analysis considers direct replacement of the material as well as reductions in the thicknesses of the components to decrease the mass of the elements. Material reductions are considered on options for using either AA6061 and/or AA6063. The calculations are based on specifications from the American Society of Mechanical Engineer (ASME) and The Aluminum Association, Inc. design codes. The analysis finds that direct replacement of the lifting bail material of construction with AA6063-T6, and AA6063-T5 as well as reductions in the dimensions of the lifting bail components are acceptable. Note that this study considers the structural suitability of the alloys. It does not consider their dissolution rates in the dissolvers.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Immobile Pore-Water Storage Enhancement and Retardation of Gas Transport in Fractured Rock

The effect of immobile pore-water on gas transport in fractured rock has implications for numerical modeling of soil vapor extraction, methane leakage, gaseous CO 2 leakage from sequestration operations, radionuclide transport from underground nuclear explosions, and nuclear waste disposal. While the ability for immobile pore-water storage to effect gas transport has been recognized in the past, the details and specific scenarios leading to enhanced, retarded, or unaffected gas transport have not been explored. In this paper, we performed numerical investigations into the enhancement and retardation of gas transport due to immobile pore-water storage in order to identify implications for gas transport applications. To do this, we developed a numerical approach to model gas transport with a single-phase flow solution coupled to the advection–dispersion equation modified to account for immobile pore-water storage. Other than the immobility of pore water, the formulation contains all other physics included in two-phase formulations (advective and diffusive gas transport in fractures and rock matrix and dissolution in immobile pore water). The assumption of immobile pore water is valid here since for many applications involving transport of soluble gases in fractured rock, the rate of aqueous transport is insignificant compared to gas transport. We verify our modeling approach with analytical solutions of: (1) 1D gas diffusion, (2) 1D gas advection, (3) barometric pumping of a fracture, and (4) gas transport with uniform fracture flow and diffusion into the matrix. We account for pore-water storage in our model by implementing a kinetic formulation of gas dissolution wherein the dissolved (aqueous) phase is considered an immobile constituent. Using this formulation, we model the effect of dissolution rate and saturation on the retardation of gas transport during pure diffusion and pure advection. We also demonstrate that although it is commonly believed that pore-water storage will always enhance gas transport in fractures during oscillatory flow (e.g., during reversing pressure gradients such as barometric pumping cycles), our simulations indicate that this may not always be the case. Our numerical investigations indicate that scenarios with lower effective diffusion coefficients ( &#x2A85;<!-- <≈ --> 10 &#x2212;<!-- - --> 5 &#xA0;m 2 / s ) and lower dissolution coefficients (i.e., the dissolution diffusion coefficient) ( &#x2A85;<!-- <≈ --> 10 &#x2212;<!-- - --> 11 &#xA0;m 2 / s ) will result in enhanced gas transport. Other combinations of gaseous diffusion and dissolution coefficients result in delayed gas transport or insignificant effect on gas transport. Based on these results, and given the fact that the free-air diffusion coefficients for many gases are slightly above 10 &#x2212;<!-- - --> 5 &#xA0;m 2 / s (near the boundary of enhanced/non-enhanced gas transport), tortuosity would have to be significant for gas transport enhancement to occur. Similarly, if we consider the free-water diffusion coefficient of gases (around 10 &#x2212;<!-- - --> 9 &#xA0;m 2 / s for many gases of interest) to be a maximum bound for the effective dissolution coefficients (i.e., the rate of diffusion into the water away from the air/water interface will limit the dissolution rate), the effective dissolution coefficient would have to be at least 2 orders of magnitude less for enhanced gas transport to occur. Otherwise, pore-water storage will delay or have negligible effect on the gas transport. The results also indicate that the assumption of instantaneous equilibrium, often invoked in numerical codes for dissolution processes (i.e., dissolution coefficient is effectively infinite), will fail to accurately capture important details of soluble gas transport. Finally, the implication of our results is that gas breakthrough times in fractured rock during oscillatory flow may be highly dependent on the effective gaseous diffusion and dissolution coefficients.

58 GEOSCIENCES↗