Treatment of Industrial Wastewater Contaminated byNitro Compounds
Akila
K El Morsi1*, SAShokry2, AAIsmail3
2Science
and Technology, Centre of Excellence, Elsalem City, Cairo, Egypt
3Abu
Zaabal Company for Speciality Chemicals, Cairo, Egypt
Citation:ElMorsi AK, Shokry SA, Ismail AA (2017) Treatment of Industrial Wastewater Contaminated by Nitro Compounds. Arch Pet Environ Biotechnol: APEB -117. DOI: 10.29011/2574-7614. 100117
1.
Abstract
AC : Activated
Charcoal
TOC : Total
Organic Carbon
COD : Chemical
Oxygen Demand
AOPs : Advanced
Oxidation Process
% R : Percent
Removal
1.
Introduction
During
the purification stage, sodium sulphiteis added to react with the asymmetric
TNTs, resulting in the formation of Dinitrotoluene(DNT) sulphonated compounds
(for example 2,4-DNT-5-SO3Na). These
sulfonates are water soluble and are easily separated from α-TNT. The wastewater resulting from the purification
process exhibits an intense "Red"colour and is commonly referred to
as TNT Red Water. In addition to the sulfonated compounds, red water also
contains products of complete nitration (for example, priority pollutants
2,4-DNT and 2,6-DNT) and complex by products formed during the nitration and
purification stages. Currently, red water is classified by US Environmental
Protection Agency (EPA) as a Resource Conservation and Recovery Act (RCRA)-regulated
hazardous waste (K047) based on its reactivity. Furthermore, TNT and red water
are toxic to aquatic life[1-3]. Consequently,
the treatment and disposal of red water presents a significant environmental
problem for the public and private sectors involved in the manufacturing of
TNT.
4.2
Materials
Animal
bones 800ºC/5 hr (BC)
residue + steams + oils + ammonia liquor
Inert atmosphere
The
reactor was heated at constant rate (3ºC/min)
up to 400ºC. Then, hold for 60 min.
at this temperature. After that period, the electrical heater was switched off
and sample is left to cool down. This led to the virgin carbon (MC-0). This
carbon was subsequently treated chemically with HNO3 (100 ml) and heated slowly on hot plate in a fuming
cupboard till boiling near dryness, then left to cool. After the treatment, the
sample was washed with distilled water several times to remove the excess
reagent used and the pH of the filtrate was measured. Then, the sample was
dried at 105ºC in a dryer
The
red water was obtained from TNT manufacturing plant in September 2001, from Abu
Zaabal Company for Speciality Chemicals. The red water was filtered through
cotton, placed in dark bottle and stored in a refrigerator at 4ºC. The prolonged refrigeration, however,
produced crystalline flakes. The samples were kept at room temperature and
thoroughly mixed using a magnetic stirrer to re dissolve the crystals before
each experiment. A typical red water composition is shown in (Table 1). Only diluted raw red water (1:100) was used
in all of the adsorption experiments, and (AOPs), primarily for safety reasons.
4.3
Methods:
4.3.3 Photo oxidation using UV/H2O2
3.1
Equilibrium Time
3.2
Effect of
adsorbent mass
3.3
Effect of pH
Also,
the maximum % R was observed at pH=2 and reaches 90 % using BC and this will
help for treatment of some other pollutants in acidic ranges. In conclusion, it
is worth to mention that mixed adsorbents (BC and AC) will be effective in
removal of many pollutants contained in TNT red water whether pH adjusted in
ranges acidic or basic.
Isotherm data are analyzed in term of Langmuir adsorption isotherm model. Langmuir plot was obtained, (Figure 7) using the well-known equation
Where
qe is the amount of solute adsorbed
per unit mass adsorbent, Ce is
equilibrium concentration of solute and qo,
b are constants, were evaluated and their values are listed in (Table 3).
r = 1/
3.5
Second-stage
operation
3.5.2
Effect of UV
exposure time:
H2O2 + λν ---------------------->2OH-
The
destruction of red water was rapid (Figure 9).
After a 2 hr reaction there was an 81.4 % reduction in TOC, 83.8 % reduction in
COD and 88.1 % at 200 nm by UV-spectrophotometer. The solution pH after the AOP
is altered, pH decreased from 2.15 to approximately 1.2. The red water has
little buffer capacity and the reduction in pH indirectly infers that SO3 groups were rapidly detached from the DNTs,
resulting in the formation of H2SO4. (I.e. acidity increases). Also, the formation
of new components due to AOP may also cause a reduction in pH,
3.6
Recommended
procedures:
Figure 1: Photo reactor
a. cooling water inlet; b. cooling water outlet; c. gas inlet (nitrogen); d.
gas outlet (Nitrogen); e. UV lap; f. sample solution; g. sampling stopcock.
Figure 2: Circulated
Fluidized-Bed.
Figure 3: Effect of
Equilibrium time on percent removal of TNT red water.
Figure 4: Effect of
adsorbent mass on percent removal of TNT red water.
Figure 5: Effect of pH on
percent removal of TNT red water adsorption isotherms.
Figure 6: Adsorption isotherms of red water on AC and
BC, (equilibrium Adsorbate uptake qe
and equilibrium Adsorbate concentration in the bulk fluid phase Ce).
Figure 7:Langmuir
adsorption isotherms of TNT red water on BC and AC.
Figure 8: Effect of H2O2
dosage on the percent removal.
Figure 9: Effect of
exposure time on percent removal of TNT red water.
Parameters |
Value |
pH units |
7.6 |
sp. Gravity |
1 |
solids |
|
Total |
2840 |
Volatile |
1020 |
Fixed |
1820 |
Organics |
36 |
Inorganic salts |
|
[NaNO2] |
209 |
[NaNO3] |
0 |
[Na2SO3] |
55 |
[Na2SO4] |
514 |
[Na2SO3+ Na2SO4] |
569 |
Alkalinity |
|
as [CaCO3] |
43 |
Organic content |
|
COD |
685 |
TOC |
544 |
Nitro bodies |
|
α-TNT |
2.27 |
2,4-DNT |
0.21 |
2,6-DNT |
0.03 |
1,3,5-TNB |
3.1 |
DNTSb |
|
2,4-DNT-3-SO3Na |
272 |
2,4-DNT-5-SO3Na |
228 |
Table1:All concentration was in mg/L for diluted red water (1:100).
BC |
AC |
||
Constituent |
(w/w%) |
Constituent |
(w/w%) |
C |
10.3 |
C |
37 |
H |
1.3 |
H |
5.1 |
N |
3.6 |
N |
0.4 |
Cl |
1.9 |
O* |
37 |
Ca3(PO4)2 |
78 |
Ash |
20.5 |
CaCO3 |
3.5 |
|
|
Others (Mg, Fe, SiO2, etc.) |
<1.0 |
|
|
SBET |
73 m2/g |
SBET |
100 m2/g |
pH |
8.2 |
pH |
2.15 |
Table 2:By differencesome data on (BC) and (AC).
Carbon type |
Surface area m2/g |
Correlation coefficient |
Dimensionless separation factor |
Langmuir constants |
|
qomg/g |
b |
||||
AC |
100 |
0.999 |
0.000102 |
181.812 |
27.5 |
BC |
73 |
0.9721 |
0.046607 |
5.614 |
0.057 |
Table 3:Langmuir constants for TNT manufacturing red water on AC and BC.
Metal |
Concentration (mgl-1) |
Removal (%) |
|
Before treatment |
After treatment |
||
Cd++ |
0.001 |
0.0001 |
90 % |
Ba++ |
ND |
ND |
|
Co++ |
ND |
ND |
|
Cr+++ |
0.041 |
0.006 |
85 % |
Cu++ |
0.043 |
0.002 |
95 % |
Fe+++ |
0.059 |
0.059 |
|
Mn++ |
ND |
ND |
|
Ni++ |
ND |
ND |
|
Pb++ |
0.05 |
0.014 |
72 % |
Sb+++ |
0.03 |
0.03 |
|
Se++++ |
ND |
ND |
|
Ti++++ |
ND |
ND |
|
V+++++ |
ND |
ND |
|
Zn++ |
0.049 |
0.016 |
67 % |
Hg++ |
ND |
ND |
|
As+++ |
ND |
ND |
|
Table 4: Concentration of metals in raw red water (1:100) before and after treatment using adsorption technique (pH=2; contact time = 12 h; 1 g BC + 0.25 g AC).
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