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Title: Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media

Abstract

Simulants for the Hanford Waste Vitrification Plant (HWVP) feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO{sub 3}{sup 2{minus}}, NO{sub 3}-, and NO{sub 2}- were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO{sub 2}H {yields} H{sub 2} + CO{sub 2} catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100{degree}C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO{sub 2}, H{sub 2}, NO, and N{sub 2}O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl{sub 3}{center_dot}3H{sub 2}O, was found to be the most active catalyst for hydrogen generation from formic acid above {approx}80{degree}C in the presence of nitrite ion in accord with earlier observations. The inherent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is suggested by the approximate pseudo first-order dependence of the hydrogen productionmore » rate on Rh concentration. Titration of the typical feed simulants containing carbonate and nitrite with formic acid in the presence of rhodium at the reaction temperature ({approx}90{degree}C) indicates that the nitrite-promoted Rh-catalyzed decomposition of formic acid occurs only after formic acid has reacted with all of the carbonate and nitrite present to form CO{sub 2} and NO/N{sub 2}O, respectively. The catalytic activities of Ru and Pd towards hydrogen generation from formic acid are quite different than those of Rh in that they are inhibited rather than promoted by the presence of nitrite ion.« less

Authors:
;  [1];
  1. Univ. of Georgia, Athens, GA (United States). Department of Chemistry
Publication Date:
Research Org.:
Pacific Northwest Lab., Richland, WA (United States)
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
10182540
Report Number(s):
PNL-SA-23865; CONF-940807-1
ON: DE94018724; TRN: 94:008385
DOE Contract Number:  
AC06-76RL01830
Resource Type:
Conference
Resource Relation:
Conference: 9. international symposium on homogeneous catalysis,Jerusalem (Israel),21-26 Aug 1994; Other Information: PBD: Aug 1994
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; RADIOACTIVE WASTES; CHEMICAL REACTIONS; FORMIC ACID; DECOMPOSITION; RUTHENIUM COMPLEXES; CATALYTIC EFFECTS; RHODIUM COMPLEXES; PALLADIUM COMPLEXES; HYDROGEN; CHEMICAL REACTION YIELD; NITRATES; GAS CHROMATOGRAPHY; HOMOGENEOUS CATALYSIS; 052002; 400201; WASTE DISPOSAL AND STORAGE; CHEMICAL AND PHYSICOCHEMICAL PROPERTIES

Citation Formats

King, R B, Bhattacharyya, N K, and Wiemers, K D. Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media. United States: N. p., 1994. Web.
King, R B, Bhattacharyya, N K, & Wiemers, K D. Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media. United States.
King, R B, Bhattacharyya, N K, and Wiemers, K D. Mon . "Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media". United States. https://www.osti.gov/servlets/purl/10182540.
@article{osti_10182540,
title = {Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media},
author = {King, R B and Bhattacharyya, N K and Wiemers, K D},
abstractNote = {Simulants for the Hanford Waste Vitrification Plant (HWVP) feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO{sub 3}{sup 2{minus}}, NO{sub 3}-, and NO{sub 2}- were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO{sub 2}H {yields} H{sub 2} + CO{sub 2} catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100{degree}C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO{sub 2}, H{sub 2}, NO, and N{sub 2}O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl{sub 3}{center_dot}3H{sub 2}O, was found to be the most active catalyst for hydrogen generation from formic acid above {approx}80{degree}C in the presence of nitrite ion in accord with earlier observations. The inherent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is suggested by the approximate pseudo first-order dependence of the hydrogen production rate on Rh concentration. Titration of the typical feed simulants containing carbonate and nitrite with formic acid in the presence of rhodium at the reaction temperature ({approx}90{degree}C) indicates that the nitrite-promoted Rh-catalyzed decomposition of formic acid occurs only after formic acid has reacted with all of the carbonate and nitrite present to form CO{sub 2} and NO/N{sub 2}O, respectively. The catalytic activities of Ru and Pd towards hydrogen generation from formic acid are quite different than those of Rh in that they are inhibited rather than promoted by the presence of nitrite ion.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1994},
month = {8}
}

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