IUVA UV Oxidation Conference: UV Oxidation for Recalcitrant Contaminants
IUVA Americas Conference 2018...RDX Name IUPAC Hexahydro 1,3,5 Trinitro 1,3,5 triazine 2, 4-dinitro...
Transcript of 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
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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)
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•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
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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
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Fig. 2 MS1 spectra of IM wastewater
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Treatment of IM wastewater
Fig. 3 Reactor Set up
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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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Treatment of IM wastewater
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.
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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
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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 .
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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 .
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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 .
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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 .
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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
Photo-Fenton oxidation of IM wastewater: ferrous concentration effect
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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
Photo-Fenton oxidation of IM wastewater: ferrous concentration effect
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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 .
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Photo-Fenton oxidation of IM wastewater: by-products
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Treatment of IM wastewater
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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
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