IUVA Americas Conference 2018...RDX Name IUPAC Hexahydro 1,3,5 Trinitro 1,3,5 triazine 2, 4-dinitro...

Oxidation of IM explosives by UV/H2O2 and photo-Fenton

processes

Distribution A: Approved for Public Release; Distribution is Unlimited

IUVA Americas Conference

2018

Amalia Terracciano1

Xiaoguang Meng1

Christos Christodoulatos1

Tsan-Liang Su1

Benjamin Smolinski2

Per Arienti2

1Center for Environmental Systems, Stevens Institute of Technology, Hoboken, NJ 07032US Army RDECOM-ARDEC, Picatinny, NJ 07806-5000, USA

2Distribution A: Approved for Public Release; Distribution is Unlimited

Oxidation of IM explosives by UV/H2O2 and photo-Fenton

processes

1. IM explosives

2. IM wastewater

3. UV/H2O2 oxidation: H2O2 concentration effect

4. UV/H2O2 oxidation: pH effect

5. Photo-Fenton: Ferrous concentration effect

6. Summary and highlights

Outline

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Insensitive Munitions(IMX)


•An insensitive munition is “one that will not detonate under anyconditions other than its intended mission to destroy a target”.

•Beginning in 1987, the Army undertook a program to developinsensitive munitions to replace conventional energetics such asTNT and RDX which are more sensitive to shock.

•Insensitive Munitions formulations such as IMX-101 and IMX-104are significantly less sensitive than TNT, which increases safetyduring manufacturing, transporting and handling.

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IM constituents


NTO

NQ

DNAN

RDX

Name IUPAC

Hexahydro

1,3,5

Trinitro

1,3,5

triazine

2, 4-dinitro

anisole

3-nitro-

1, 2, 4

triazol-5-one

Nitroguanidine

Solubility in water (25 C°)StructureFormula

C3H6N6O6

130 g/mol

CH4N4O2

104 g/mol

C7H6N2O

198 g/mol

C3H6N6O6

222 g/mol45 mg/L

270 mg/L

5000 mg/L

16000 mg/L

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IM wastewater

Fig.1 IM wastewater

IM wastewater characteristics (pH=3.6±0.1)

NTO

(mg/L)

NQ

(mg/L)

DNAN

(mg/L)

RDX

(mg/L)

NO2-[N]

(mg/L)

NH4-[N]

(mg/L)

NO3-[N]

(mg/L)

TOC

(mgC/L)

Tot N

(mgN/L)

Th-TOC

(mgC/L)

Th-TN

(mgN/L)

774±8 512±14 423±25 106±3 0.024±0.006 1.63±3 3.30±0.57 307±30 443±33 398 708


Fig. 2 MS1 spectra of IM wastewater

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Treatment of IM wastewater

Fig. 3 Reactor Set up


Conditions and Setup

•UV light bulb (UVC, germicidial, 254 nm), 13 W, irradiance=8.5±0.5 mW/cm2

•Open reactor of 1000 ml volume, 800 ml wastewater

•Mixer with magnetic bar as stirrer

•Set up place in a dark chamber without natural light penetration

•H2O2 (34-36%) and/or Ferrous (Fe(II)) (Fe2SO4 solution)

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Preliminary tests

Fig. 4 (a)NTO, (b)NQ, (c)DNAN and (d)RDX concentrations vs time in IM wastewaterfor different treatment conditions; Fe(II)=50 mg L-1; H2O2=3200 mg L-1.


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Fig. 5.TOC concentrations vs time in IM wastewater fordifferent treatment conditions; Fe(II)=50 mg L-1;H2O2=3200 mg L-1.


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UV/H2O2 oxidation of IM wastewater : H2O2 concentration effect

Fig. 6 (a)NTO, (b)NQ, (c)DNAN and (d)RDX concentrations vs time in IM wastewatertreated with different H2O2 concentrations.


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Fig. 7 (a)NTO, (b)NQ, (c)DNAN and (d)RDX log concentrations vs timein IM wastewater treated with different H2O2 concentrations.


Pseudo-First Order Reaction

k (h-1)

H2O2

(mg/L)NTO NQ DNAN RDX

1500 0.2256 0.3289 0.2739 0.2993

3200 0.2368 0.2972 0.3543 0.3257

4400 0.2159 0.2832 0.2203 0.2447

5600 0.1742 0.2828 0.2318 0.1841

R2

H2O2

(mg/L)NTO NQ DNAN RDX

1500 0.9881 0.9891 0.9861 0.9886

3200 0.9985 0.9969 0.9844 0.9907

4400 0.9966 0.9816 0.9827 0.9911

5600 0.9895 0.9838 0.9909 0.9902

UV/H2O2 oxidation of IM wastewater: H2O2 concentration effect

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Fig. 8 (a) TOC concentrations (b) carbon balance vs timein IM wastewater treated with different H2O2

concentrations.Distribution A: Approved for Public Release; Distribution is Unlimited

UV/H2O2 oxidation of IM wastewater : H2O2 concentration effect

12

Fig. 9 (a) NO3-[N], (b) NO2-[N], (c) NH4-[N], (d) Total N, vs time in IMwastewater treated with different H2O2 concentrations.

•Distribution A: Approved for Public Release; Distribution is Unlimited

UV/H2O2 oxidation of IM wastewater : by-products

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Fig. 10 (a)NTO, (b)NQ, (c)DNAN and (d)RDX concentrations vs timein IM wastewater for different initial pH; H2O2=3200 mg L-1 .


pH=5.5 pH=7 pH=9

UV/H2O2 oxidation of IM wastewater: pH effect

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Fig. 11 pH vs time in IM wastewater for differentinitial pH; H2O2=3200 mg L-1 .


Fig. 12 (a) TOC concentrations (b) carbon balance vstime in IM wastewater for different initial pH;H2O2=3200 mg L-1 .

UV/H2O2 oxidation of IM wastewater: pH effect

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Fig. 13 (a) NTO, (b) NQ, (c) DNAN and (d) RDX concentrations vs time in IMwastewater for different Fe concentrations; H2O2=3200 mg L-1 .


Photo-Fenton oxidation of IM wastewater: ferrous concentration effect

Fe(OH)2+ + hv Fe2+ + HO·

H2O/hv

HO·

Fe3+

Fe2+

HO·

H2O2

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Fig. 14 (a)NTO, (b)NQ, (c)DNAN and (d)RDX log concentrations vstime in IM wastewater treated with different Fe concentrations;H2O2=3200 mg L-1 .


Pseudo-First Order Reaction

k (h-1)

Fe(II)(mg/L)

NTO NQ DNAN RDX

20 0.4912 0.5079 0.7681 0.9107

50 0.3161 0.4376 0.6472 1.117

80 0.2426 0.3313 0.3275 0.7012

100 0.2322 0.2656 0.3837 0.5415

R2

Fe(II)(mg/L)

NTO NQ DNAN RDX

20 0.9957 0.9887 0.9848 0.9919

50 0.9854 0.9879 0.9926 0.9975

80 0.9962 0.9889 0.9833 0.9923

100 0.9834 0.9858 0.9929 0.9875


17Distribution A: Approved for Public Release; Distribution is Unlimited

Fig. 15 (a) TOC concentrations (b) carbon balance vstime in IM wastewater treated with different Fe(II)concentrations.

UV

++2

0 p

pm

Fe

+32

00 p

pm

H2O

2

UV

+32

00

pp

m H

2O

2


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Fig. 16. (a) NO3-[N], (b) NO2-[N], (c) NH4-[N], (d) Total N, vs time in IMwastewater for different ferrous concentrations; H2O2=3200 mg L-1 .


Photo-Fenton oxidation of IM wastewater: by-products

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Summary and highlights

• UV/H2O2 oxidation effectively mineralized the organic carboncontent of the IM wastewater up to 98% with a H2O2 concentration of3200 mg L-1 within 24 hours of treatment

• The initial pH did not significantly affect the performance of UV/H2O2

oxidation; thus no pH adjustment is required

• The photo-Fenton technique showed more efficiency in thetreatment of the IM wastewater compared to UV/H2O2 oxidation(99%removal TOC)

• The optimal performance was obtained with the application of H2O2

equal to 3200 mg L-1 plus Fe(II) concentration as low as 20 mg L-1

Thank you


IUVA Americas Conference 2018...RDX Name IUPAC Hexahydro 1,3,5 Trinitro 1,3,5 triazine 2, 4-dinitro...

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