Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons (1999) / Chapter Skim
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Appendix E: Neutalization of Energetic Materials by Hydrolysis
Appendix E: Neutalization of Energetic Materials by Hydrolysis
Pages 213-229
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From page 213... ...
(1995) have demonstrated base hydrolysis of a composite propellant containing HMX, ammonium perchlorate, nitrate esters, and aluminum powder.
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From page 214... ...
Finally, the technology providers must scale up a robust process that can meet the Army's requirements for various weapon types and processing rates. The scalability of operating parameters for base hydrolysis of energetic materials is not universal and will depend on the specific chemical munitions being demilitarized.
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From page 215... ...
Because destruction of TNT was not the goal, the quantitative chemical reaction kinetics for the alkaline decomposition of TNT were not determined. The base hydrolysis of TNT is probably an extremely complex series of reactions (Newman, 1999~.
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From page 216... ...
An excess of strong base should, however, drive hydrolysis to completion. A plausible overall mechanism for the alkaline decomposition of tetryl can be hypothesized from the work previously cited for TNT.
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From page 217... ...
, so attempts to increase the alkaline decomposition rate by performing base hydrolysis at temperatures above 120°C should be avoided, because these reactions may be difficult to control. Because hydrolysis is masstransfer limited, reducing the chunk size of the tetryl feedstock and inducing vigorous agitation in excess base are probably better ways to increase the rate of hydrolysis once a threshold temperature and base concentration have been achieved.
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From page 218... ...
C, and D, which are all various resonance structures. Jones also proposed the following equation for the rate of alkaline decomposition (dx/dt)
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Simple experiments in alkaline decomposition were performed with 1.5 M NaOH solutions at both laboratory and pilot scale. These results are summarized in Table E-7.
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From page 220... ...
Insufficient size reduction may adversely impact the effectiveness and scalability of processing parameters and may increase safety concerns, such as clogging of the reactor and exothermic runaway at full scale. Therefore, the ACWA technology providers must demonstrate processing conditions for realistic feeds before the alkaline decomposition of RDX, Composition B
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From page 221... ...
, and alkaline solutions. Therefore, the residence time required for alkaline decomposition of NC (14 percent N)
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From page 222... ...
NG readily plasticizes NC to form a gel that will solidify and provide useful mechanical properties, making it attractive as a rocket propellant. Unfortunately, this plasticizing effect makes alkaline decomposition of double-base propellants much more difficult than merely performing base hydrolysis of its components.
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From page 223... ...
percent of the nitrogen in P2 is decomposed to gaseous products, TABLE E-13 Results for the Pressured Alkaline Decomposition of Propellants P1-P5 % of the Total Carbon and Nitrogen in the Propellant Residue P1 P2 P3 P4 P5 Solid residue containing DPA, graphite, centralite, lead oxide, dibutylphth al ate Liquid residue containing NO2, NO3, DNT emulsion DPA emulsion, COD, HCO3 Gaseous residue containing N2, N2O, NO, CO2, CO, CHn 2-3 3-12 10 5-16 10 40-70 20-50 Source: Bunte et al., 1997.
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during pressurized alkaline decomposition of propellant P2.
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From page 225... ...
Some technology providers propose using base hydrolysis of all of the energetic materials from ACW ordnance in a single batch reactor during a demilitarization campaign 1:1 2.3:1 ,: , , , , , ~ , ' , ' , Ores C ~ jq COD HCO3 Cgas CO CO2 CH n Csum FIGURE E-4 Conversion of carbon (C) during pressurized alkaline decomposition of propellant PS under different alkaline conditions.
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In any event, the technology providers will have to demonstrate that the hydrolysate product from base hydrolysis of energetic materials is an appropriate feedstock for the next unit operation. Some of these emulsions, such as TNT.
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From page 227... ...
decomposing a heterogeneous feed stream consisting of energetic materials, metal, and contaminants via alkaline decomposition. The hydrolysate produced must be an appropriate feed stream for the next unit operation, which may be another emerging technology (supercritical water oxidation and biotreatment have been proposed)
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1954. Mechanism of the homogeneous alkaline decomposition of cyclomethylenetrinitramine: kinetics of consecutive second- and first-order reactions.
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1994. An Engineered System using Base Hydrolysis for Complete Disposal of Energetic Materials.
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