WO2018187812A1 - Traitement à haut débit de 3-nitro -1,2,4-triazol-5-one (nto) et d'autres composés de munitions - Google Patents

Traitement à haut débit de 3-nitro -1,2,4-triazol-5-one (nto) et d'autres composés de munitions Download PDF

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Publication number
WO2018187812A1
WO2018187812A1 PCT/US2018/026751 US2018026751W WO2018187812A1 WO 2018187812 A1 WO2018187812 A1 WO 2018187812A1 US 2018026751 W US2018026751 W US 2018026751W WO 2018187812 A1 WO2018187812 A1 WO 2018187812A1
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WO
WIPO (PCT)
Prior art keywords
stage
mineral
ato
materials
minerals
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Application number
PCT/US2018/026751
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English (en)
Inventor
James A. Field
Jonathan D. CHOROVER
Maria Reyes SIERRA-ALVAREZ
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Arizona Board Of Regents On Behalf Of The University Of Arizona
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Application filed by Arizona Board Of Regents On Behalf Of The University Of Arizona filed Critical Arizona Board Of Regents On Behalf Of The University Of Arizona
Publication of WO2018187812A1 publication Critical patent/WO2018187812A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/02—Preparation of nitrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms

Definitions

  • IMC insensitive munitions compound
  • NTO 3-nitro-l,2,4-triazol-5-one
  • Organohalogens such as perchloroethylene, trichloroethylene, cis- dichloroethylene and vinyl chloride have also been shown to be reductively dehalogenated by GR to ethylene, and ethane. Trichloronitromethane has also been observed to be rapidly degraded to methylamine, and several other disinfection byproducts were also been shown to be reductively dehalogenated by GR to ethylene, and ethane. Trichloronitromethane has also been observed to be rapidly degraded to methylamine, and several other disinfection byproducts were also
  • Pentachlorophenol has also been shown to be reductively dechlorinated by GR.
  • GR are responsible for reducing the radionuclide Np(V) to Np(IV), the metal Cr(VI) to Cr(III) and selenate to elemental selenium. Nitrate is reduced to ammonium.
  • Organic amines such as aromatic amines are very susceptible to oxidation by manganese oxide minerals such as birnessite (Mn02). Birnessite can also oxidize aliphatic amines.
  • the original parent compounds of the explosives have standard reduction potentials that are too high to be oxidized; however, as the explosive parent compounds are progressively reduced their reduction potential decrease which increases the oxidation of the molecules.
  • the present invention provides a system and method for the pretreatment for 3-Nitro-l,2,4-triazol-5-one (NTO), which is an insensitive munitions compound (IMC), that poses an important environmental concern due to its high aqueous solubility enabling to it to be very mobile in the environment.
  • NTO 3-Nitro-l,2,4-triazol-5-one
  • IMC insensitive munitions compound
  • the present invention provides a system and method that convert NTO to mostly benign gaseous products (CO2 and N2) with a hydraulic retention time in the time scale of minutes.
  • a first stage reduces NTO stoichiometrically to 3-amino- l,2,4-triazol-5-one (ATO) with the Fe n /Fe in containing mineral, green rust.
  • a second stage converts ATO to CO2 and N2 with birnessite.
  • the present invention provides a system or method that is ideal for treating NTO in munitions wastewater or groundwater and works for other IMCs such as 2,4-dintroanisole (DNAN).
  • IMCs such as 2,4-dintroanisole (DNAN).
  • the present invention provides a pretreatment step that assists in the degradation of aromatic compounds with nitro substituents (explosives, TNT, plasticizers, dinitroluene).
  • the present invention provides a system and method that converts NTO or other nitro-heterocylic insensitive munitions to mostly benign gaseous products (CO2 and N2) with a hydraulic retention time in the time scale of minutes by using a reduction step followed by an oxidation step.
  • a first stage reduces NTO stoichiometrically to 3-amino-l,2,4-triazol-5-one (ATO) with the Fe n /Fe in containing mineral, green rust and the second stage converts ATO to CO2 and N2 with the
  • the present invention provides a system and wherein NTO is reductively transformed stoichiometrically to the amine containing daughter product, ATO.
  • the present invention provides a system and method wherein DNAN is reductively transformed to MENA.
  • the present invention provides a system and wherein MENA is reductively transformed to DAAN.
  • the present invention provides a system and wherein a complete to near complete abiotic reductive transformation of IMCs to reduced daughter products in a matter of minutes is achieved.
  • the present invention provides a system and wherein NTO is transformed by a first stage of sequentially one or more packed bed reactors, the first stage reactors contain solid phase mineral materials, mineral-based electron donating materials, GR, ZVI or iron minerals with adsorbed Fe 2 + or combinations thereof and create an effluent of ATO. Also provided is a second stage of one or more reactors that receive the ATO effluent and the second stage reactors oxidize the ATO.
  • the present invention provides a system and wherein one or more second stage reactors are continuously feed permanganate (MnO3 ⁇ 4) that oxidize ATO (or other reduced munitions compounds) even faster than Mn02 and at the end of the reaction, MnO3 ⁇ 4 forms Mn02.
  • MnO3 ⁇ 4 permanganate
  • the present invention provides a system and wherein one or more reactors contain sand mixed with GR, ZVI or iron minerals with adsorbed Fe 2 + or combinations thereof and said second stage reactors contain sand mixed with MnO3 ⁇ 4 or Mn02.
  • the present invention provides a system and wherein Mn02 coated sand particles provide a lasting reservoir of the Mn02 oxidant in a packed bed reactor.
  • the present invention provides a system and wherein one or more second stage reactors contain a solid phase mineral oxidant.
  • Figure 1 illustrates the structures of NTO and ATO.
  • Figure 2A shows for DNAN the transformation of IMCs (0.5 mM) by GR at 10 g kg -1 solid to solution ratio at pH 8.4.
  • Figure 2B shows for NTO the transformation of IMCs (0.5 mM) by GR at 10 g kg "1 solid to solution ratio at pH 8.4.
  • Figure 3A shows, for the oxidation of DNAN and its daughter products, MENA and DAAN, a comparison of IMC and daughter product oxidation by birnessite (Mn02) at a SSR of 15 g kg -1 , pH 7, room temperature.
  • Figure 3B shows, for the oxidation of NTO and its daughter compound, ATO, a comparison of IMC and daughter product oxidation by birnessite (Mn02) at a SSR of 15 g kg -1 , pH 7, room temperature.
  • Figure 4 illustrates for one embodiment of the present invention a sequence of reactions with GR and Mn02 minerals, respectively.
  • Figure 5 illustrates for one embodiment of the present invention packed bed reactors for the reduction of NTO to ATO, and subsequent and oxidation of ATO to CO2 and
  • the present invention recognizes that both DNAN and NTO may be susceptible to reduction by GR at 10 g kg -1 solid to solution ratio (SSR).
  • SSR solid to solution ratio
  • NTO was reductively transformed stoichiometrically to the amine containing daughter product.
  • DNAN was reductively transformed to MENA, which was then further reduced to DAAN over time.
  • MENA 2-methoxy-5-nitroaniline
  • DAAN 4-methoxy-5-nitroaniline
  • Fe-XANES Fe-X-ray absorption near edge structure
  • a complete to near complete abiotic reductive transformation of IMCs to reduced daughter products in a matter of minutes is achieved by the present invention. While the reduced daughter products are not safe end products because many of them are also toxic compounds, such compounds are highly susceptible to oxidation in a matter of minutes with common, occurring manganese mineral, birnessite.
  • DAAN and ATO were also found to be oxidized in less than 5 minutes with 15 g kg -1 solid to solution ratio (SSR) as shown in Figures 3A and 3B. It has also been found that ATO is mineralized to a large extent to benign gaseous end products (CO2 and N2) .
  • the present invention provides a sequence of reductive and oxidative reactions.
  • One or more reactors packed with the reactive minerals GR and Mn02 are provided which can rapidly remediate NTO with cumulative hydraulic retention times of less than 10 minutes.
  • the sequence of reaction is shown in Figure 4.
  • the packing in each reactor may contain minimally 20% mass to volume of the reactive minerals.
  • the products of the reaction will be a mixture of mostly benign gasses.
  • the gasses may be CO2 and N2.
  • benign urea is also formed in the aqueous phase.
  • the present invention is suited for treating NTO contaminated groundwater or munitions wastewater.
  • FIG. 5 provides, for one embodiment of the present invention, an exemplary system 500 that may be used in the treatment of an IMC such as NTO.
  • System 500 may include a first stage of one or more sequentially packed bed reactors 502.
  • the first stage reactors may be filled with green rust mixed with sand 504 (for permeability).
  • the first stage reactors may contain solid phase mineral material and/or mineral-based electron donating materials.
  • Inlet 506 receives an IMC influent such as NTO which first flows past glass beads 508.
  • Effluent from reactor 502 which may be ATO, is sent to one or more packed bed reactors 510 comprising a second stage via pathway 509 through glass beads 512.
  • Reactor 510 may be filled with birnessite (Mn0 2 ) mixed with sand 514.
  • the second stage reactors may contain solid phase mineral oxidants.
  • Effluent from reactor 510 is mainly benign gasses such as CO2 and N2.
  • the sequentially connected reactors may contain other materials.
  • a precursor such as zero valent iron (ZVI) which corrodes to green rust.
  • ZVI zero valent iron
  • one reactor of the first stage may contain green rust and another reactor in the sequence may use a precursor such as ZVI.
  • Another reactor in the sequence of the first stage may further contain iron minerals with adsorbed Fe 2 + .
  • This material may also be provided for use with or as an alternative to green rust and ZVI.
  • the first stage reactors may contain GR, ZVI, iron minerals with adsorbed Fe 2+ or combinations thereof in one or more reactors of the first stage.
  • One or more of the second stage reactors may be operated by slowly and/or continuously feeding permanganate (MnO ⁇ ) which is a powerful oxidant that can oxidize ATO (or other reduced munitions compounds) even faster than ⁇ 2 ⁇
  • MnO3 ⁇ 4 forms MnC>2 which would coat the sand particles and provide a lasting reservoir of the MnC>2 oxidant in a packed bed reactor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention concerne un procédé et un système pour convertir un composé de munitions à risques atténués (IMC) en produits gazeux en soumettant l'IMC à une étape de réduction suivie d'une étape d'oxydation.
PCT/US2018/026751 2017-04-07 2018-04-09 Traitement à haut débit de 3-nitro -1,2,4-triazol-5-one (nto) et d'autres composés de munitions WO2018187812A1 (fr)

Applications Claiming Priority (2)

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US201762482987P 2017-04-07 2017-04-07
US62/482,987 2017-04-07

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WO2018187812A1 true WO2018187812A1 (fr) 2018-10-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115094447A (zh) * 2022-06-24 2022-09-23 西南科技大学 一种成对电化学合成偶氮***酮和含氧偶氮***酮的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090000194A1 (en) * 2006-01-12 2009-01-01 Liang-Shih Fan Systems and Methods of Converting Fuel
US20130006018A1 (en) * 2010-03-18 2013-01-03 Christopher John Mitchell Process for the conversion of aromatic nitro compound into amines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090000194A1 (en) * 2006-01-12 2009-01-01 Liang-Shih Fan Systems and Methods of Converting Fuel
US20130006018A1 (en) * 2010-03-18 2013-01-03 Christopher John Mitchell Process for the conversion of aromatic nitro compound into amines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KHATIWADA: "Mineral Surface-Mediated Transformation of Insensitive Munition Compounds", THE UNIVERSITY OF ARIZONA, vol. 1, no. 2, 2016, pages 6 - 18 , 23-25, 34-43, 59-62, 71-77, 101-111, XP055543680, Retrieved from the Internet <URL:https://repository.arizona.edu/bitstream/handle/10150/621565/azu_etd_14844_sip1_m.pdf?sequence=1&isAllowed=y> [retrieved on 20180523] *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115094447A (zh) * 2022-06-24 2022-09-23 西南科技大学 一种成对电化学合成偶氮***酮和含氧偶氮***酮的方法
CN115094447B (zh) * 2022-06-24 2023-10-13 西南科技大学 一种成对电化学合成偶氮***酮和含氧偶氮***酮的方法

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