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Title: PROGRESS REPORT ON RAW MATERIALS FOR SEPTEMBER 1957

Abstract

4 5 7 9 4 1 2 3 3 5 6 8 acid extractions of several metal ions in the presence Some approximate values of the concentrations of the chlorine ion and the mean activity coefficients of HCl in of radiotracer- labeled inorganic phosphate, the phosphate accompanied extracted Fe(III) and Al, but not V(IV) or Mo(VI) in amounts that could cause significant coutamination of a vanadium product. In the extraction of thorium from sulfate solution with di(2- ethylheryl) phosphoric acid, extraction coefficients were lowered but still usable in the presence of enough decanol to prevent third-phase formation in alkaline stripping. Tri-n-octylphosphine oxide in kerosene extracted thorium effectively from 1 and 4 M HNO/sub 3/ and from 4 but not 1 M HCl. The coefficients increased rapidly with increasing phosphine oxide concentration. In measurement of acid extraction by amine diluent combinations, the aqueous pH at which enough acid was extracted to neutralize half the amine varied with amine class, primary> secondary> tertiary; with branching, straight chain 7 branched chain; with diluent, chloroform> benzene> kerosene; and with anion, HClO/sub 4/> H/sub 2/SO/sub 4/. Melting points, apparent molecular weights, aud assay test results are reported for tri-n-octylphosphine oxide batches tom several different sources.more » Process Development Studies. In continued studies of the Amex vanadium process, the effects of several extraction variables were examined and the vanadium extraction abilities of three different amines were compared. Rate tests showed rapid extraction of most of the vanadium although the final approach to equilibrium was quite slow. Vanadium coefficients, which were low at pH 1.4, increased rapidly with increasing; pH particularly in the region of pH 2. The coefflcients also increased as the sulfate concentration decreased. Isotherms for extraction of vanadiam with 0.1 M solutions of S-24, 9D-178, and tri-iso- octylamines were of uuconventional shape, showing (at least over a portion of the curves) an increase rather thau a decrease in vanadium extraction efficieucy with increase in vanadium loading. Maximum vananium loadings (0.1 M amine) were in the range 11.5-13 g/liter. Thorium was efficiently recovered from Amex carbonate strip solutions by adjusting the pH to pH > 13 with caustic or to 5-6 with sulfuric acid. Precipitates from the sulfuric acid method filtered much more readily than those produced with caustic. Under certain precipitation conditions thorium was effectively separated from the small amount of urauium in the strip solution. In the Dapex system, contact of air with the mixed organic and aqueous phases results in some oxidation of iron(II). The amount of iron oxidized, although relatively small, is of sufficient magnitude to suggest that, for best results in a vanadium recovery process, the extraction mixers should be designed to minimize contact with air. Engineering Studies. The kinetics of vanadium(IV) and iron(III) extraction by Dapex in batch mixer tests were well represented by first-order rate constants similar to those previously reported for uranium extraction. The rate of extraction for each metal increased with approximately the cube root of power input to the mixer. The relative rates of extraction, expressed as rate constants, were 1.62 for uranium, 0.95 for vanadium, aud 0.11 for iron at a power input of 30 hp per 1000 gal of mixer volume. Fundamental Studies. Comparison of the infrared spectra of n-octaue solutions of di(2ethylhexyl)phosphoric acid (D2EHFA), tributylphosphate (TBP), and tri-n-octylphosphine oxide (TOPO) showed some D2EHPA-TBP association, and considerable« less

Authors:
; ; ;
Publication Date:
Research Org.:
Oak Ridge National Lab., Tenn.; Chemical Technology Div.
OSTI Identifier:
4321820
Report Number(s):
ORNL-2443
NSA Number:
NSA-12-012310
DOE Contract Number:  
W-7405-ENG-26
Resource Type:
Technical Report
Resource Relation:
Other Information: Orig. Receipt Date: 31-DEC-58
Country of Publication:
United States
Language:
English
Subject:
CHEMISTRY; ACIDITY- ACIDS- ALKYL RADICALS- AMINES- ANIONS- BENZENE- CHEMICALS- CHLORINATED HYDROCARBONS- CHLOROFORM- EFFICIENCY- HYDROCHLORIC ACID- HYDROXIDES- KEROSENE- MEASURED VALUES- MELTING POINTS- MOLECULES- NITRIC ACID- ORGANIC PHOSPHORUS COMPOUNDS- PERCHLORIC ACID- REACTION KINETICS- SOLVENTS- SULFURIC ACID- TESTING- TOPO- WATER- WEIGHT; AIR- CARBONATES- CHEMICAL REACTIONS- DAREX PROCESS- DIAGRAMS- FILTERS- INFRARED RADIATION- LIGHT- MIXING- NITRATES- OCTANE- OXIDATION- PRECIPITATION- RARE EARTHS- RECOVERY- SCATTERING- SPECTRA- TEMPERATURE- URANIUM- VOLUME; ALCOHOLS- ALUMINUM- CONTAMINATION- DECANOL

Citation Formats

Brown, K. B., Coleman, C. F., Crouse, D. J., and Ryon, A. D. PROGRESS REPORT ON RAW MATERIALS FOR SEPTEMBER 1957. United States: N. p., 1958. Web. doi:10.2172/4321820.
Brown, K. B., Coleman, C. F., Crouse, D. J., & Ryon, A. D. PROGRESS REPORT ON RAW MATERIALS FOR SEPTEMBER 1957. United States. doi:10.2172/4321820.
Brown, K. B., Coleman, C. F., Crouse, D. J., and Ryon, A. D. Wed . "PROGRESS REPORT ON RAW MATERIALS FOR SEPTEMBER 1957". United States. doi:10.2172/4321820. https://www.osti.gov/servlets/purl/4321820.
@article{osti_4321820,
title = {PROGRESS REPORT ON RAW MATERIALS FOR SEPTEMBER 1957},
author = {Brown, K. B. and Coleman, C. F. and Crouse, D. J. and Ryon, A. D.},
abstractNote = {4 5 7 9 4 1 2 3 3 5 6 8 acid extractions of several metal ions in the presence Some approximate values of the concentrations of the chlorine ion and the mean activity coefficients of HCl in of radiotracer- labeled inorganic phosphate, the phosphate accompanied extracted Fe(III) and Al, but not V(IV) or Mo(VI) in amounts that could cause significant coutamination of a vanadium product. In the extraction of thorium from sulfate solution with di(2- ethylheryl) phosphoric acid, extraction coefficients were lowered but still usable in the presence of enough decanol to prevent third-phase formation in alkaline stripping. Tri-n-octylphosphine oxide in kerosene extracted thorium effectively from 1 and 4 M HNO/sub 3/ and from 4 but not 1 M HCl. The coefficients increased rapidly with increasing phosphine oxide concentration. In measurement of acid extraction by amine diluent combinations, the aqueous pH at which enough acid was extracted to neutralize half the amine varied with amine class, primary> secondary> tertiary; with branching, straight chain 7 branched chain; with diluent, chloroform> benzene> kerosene; and with anion, HClO/sub 4/> H/sub 2/SO/sub 4/. Melting points, apparent molecular weights, aud assay test results are reported for tri-n-octylphosphine oxide batches tom several different sources. Process Development Studies. In continued studies of the Amex vanadium process, the effects of several extraction variables were examined and the vanadium extraction abilities of three different amines were compared. Rate tests showed rapid extraction of most of the vanadium although the final approach to equilibrium was quite slow. Vanadium coefficients, which were low at pH 1.4, increased rapidly with increasing; pH particularly in the region of pH 2. The coefflcients also increased as the sulfate concentration decreased. Isotherms for extraction of vanadiam with 0.1 M solutions of S-24, 9D-178, and tri-iso- octylamines were of uuconventional shape, showing (at least over a portion of the curves) an increase rather thau a decrease in vanadium extraction efficieucy with increase in vanadium loading. Maximum vananium loadings (0.1 M amine) were in the range 11.5-13 g/liter. Thorium was efficiently recovered from Amex carbonate strip solutions by adjusting the pH to pH > 13 with caustic or to 5-6 with sulfuric acid. Precipitates from the sulfuric acid method filtered much more readily than those produced with caustic. Under certain precipitation conditions thorium was effectively separated from the small amount of urauium in the strip solution. In the Dapex system, contact of air with the mixed organic and aqueous phases results in some oxidation of iron(II). The amount of iron oxidized, although relatively small, is of sufficient magnitude to suggest that, for best results in a vanadium recovery process, the extraction mixers should be designed to minimize contact with air. Engineering Studies. The kinetics of vanadium(IV) and iron(III) extraction by Dapex in batch mixer tests were well represented by first-order rate constants similar to those previously reported for uranium extraction. The rate of extraction for each metal increased with approximately the cube root of power input to the mixer. The relative rates of extraction, expressed as rate constants, were 1.62 for uranium, 0.95 for vanadium, aud 0.11 for iron at a power input of 30 hp per 1000 gal of mixer volume. Fundamental Studies. Comparison of the infrared spectra of n-octaue solutions of di(2ethylhexyl)phosphoric acid (D2EHFA), tributylphosphate (TBP), and tri-n-octylphosphine oxide (TOPO) showed some D2EHPA-TBP association, and considerable},
doi = {10.2172/4321820},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1958},
month = {1}
}