Thursday, 14 March 2019

How to reduce or remove ammoniacal ammonia

Image result for ammonia stripping from waste water fertilizer industry
VOL. 62, 2017
A publication of
The Italian Association
of Chemical Engineering
Online at www.aidic.it/cet
Guest Editors: Fei Song, Haibo Wang, Fang He
Copyright © 2017, AIDIC Servizi S.r.l.
ISBN 978-88-95608- 60-0ISSN 2283-9216
Research on Mechanism of Air Stripping Enabled Ammonia
Removal from Industrial Wastewater and Its Application
Dan Jiaa, Wenlong Lua, Yanfu Zhangb
aJilin Institute of Chemical Technology, Jilin 132022, China
bPetrochina Jilin Petrochemical Company Wastewater Treatment Plant, Jilin 132000, China
jiadan@126.com
In this paper, the stripping method was used to deal with the wastewater with high concentration of ammonia
generated in the industrial production process, and the effects of blowing time, waste water pH, stripping
temperature and gas-liquid volume ratio on the maximum removal rate of ammonia were investigated by
experiments. The experimental results show that the gas - liquid ratio is linear to the stripping efficiency at 50
°C and strongly alkaline. And it can be deduced that the effect of different air flow rates on the blowout
efficiency at gas-liquid ratio below 1000 is not significant. In this paper, the maximum air flow rate is 2L/min,
and the maximum reaction time (stripping time) is 120min, so the maximum gas-liquid ratio is only 800. At the
same time, this paper also explored the reaction mechanism of ammonia removal via the stripping method
and its application in ammonia removal from industrial wastewater produced by monosodium glutamate.
1. Introduction
With the development of industry and agriculture and the improvement of people's living standards, the
emission of nitrogenous compound wastewater has increased dramatically, which has attracted much
attention as the main source of the environment pollution. Ammonia is an important pollutant to the water
eutrophication and environmental pollution. Upon entering water, the ammonia can lead to water hypoxia,
breeding harmful aquatic organisms that poison fish, and humans who eat such fish tend to be slightly
poisonous or even dead (Hu et al., 2003). In addition, ammonia also affects the oxygen transport by fish gills,
and the high concentration of ammonia will even kill fish. A large amount of ammonia wastewater discharged
into the rivers and lakes has brought difficulties in the industrial wastewater treatment. When the chlorine
disinfection is adopted, ammonia and chlorine will produce chloramine, which clearly have increases chlorine
consumption rate and further drives great demands for chlorine. Ammonia is converted to nitric acid, and
nitrates are further converted to ammonium nitrite with a serious three-pronged effect that directly affects
human health, for which the treatment of ammonia nitrogen wastewater has become a hot issue in today's
water treatment (Huang et al., 2014). At present, ammonia nitrogen wastewater treatment methods are as
follows: air stripping, ion exchange, chemical precipitation, membrane separation, chemical oxidation,
biological method, etc. As for the treatment of ammonia wastewater, domestic researches mainly focus on the
materialization method, while biological methods are rarely used. It is of great practical significance to seek
practical treatment technology with small investment, reliable operations and high efficiency for the processing
of industrial ammonia wastewater (Wilfried and Chakkrit, 2015).
1.1 Classification of industrial ammonia wastewater
According to the different concentrations, industrial ammonia wastewater can be divided into three categories,
namely (1) low concentration of ammonia nitrogen wastewater: NH<50mg/L; (2) moderate concentration of
ammonia nitrogen wastewater: NHis 50-500mg/L; (3) low concentration of ammonia nitrogen wastewater:
NH3> 500mg/L. High ammonia concentration wastewater is generally derived from the production process of
coke, ferroalloy, coal gasification, hydrometallurgy, oil refining, animal husbandry, chemical fertilizers, man-
made fibers and incandescent lamps that are all extremely complex and have different types of industrial
wastewater ammonia concentration in the ever-changing state (Xiang H, et al., 2011). Moderate concentration
DOI: 10.3303/CET1762020
Please cite this article as: Dan Jia, Wenlong Lu, Yanfu Zhang, 2017, Research on mechanism of air stripping enabled ammonia removal from
industrial wastewater and its application, Chemical Engineering Transactions, 62, 115-120 DOI:10.3303/CET1762020
115


of ammonia wastewater is generally derived from fertilizer, oil refining, rubber, synthetic rubber, dairy
production, pharmaceutical, farming, paper, leather and other industries; Low concentration of ammonia
wastewater generally comes from canned food, vegetables, starch, grain food processing industry and anti-
corrosion, paint ink, and other industries.
1.2 Introduction to the blowout method
The air stripping method is currently used for the treatment of ammonia waste. The blown off ammonia can be
recycled, but most is directly discharged into the air. Therefore, when using the air stripping method, we
should not only pay attention to how to improve the efficiency of ammonia bleed, but also take the initiative to
prevent secondary pollution. If the emitted ammonia is discharged directly into the atmosphere, it is necessary
to consider whether the total amount of free ammonia emitted is in line with the ammonia emission standards
(Lee et al., 2013). Ammonia returns to the earth in the atmosphere by gas deposition (60%), aerosol
deposition (22%), rainfall (18%), etc. After the set of animals and animals have a stimulating and toxic effect;
When there are sulfur dioxide emissions near the point, the atmosphere of ammonia, the atmosphere of sulfur
dioxide and water generate ammonium sulfate aerosol. The air stripping process of ammonia refers to that
adjusting the PH value of wastewater to transform the ammonia in the ion state into molecular ammonia, and
then blowing the air into the wastewater (Zhang et al., 2009). For the ammonia in the wastewater is usually
present in equilibrium with the state of ammonium ions (NH4
+) and free ammonia (NH3), the equilibrium
relationship between NH4
and NHin water is as follows:
4
3
2
NH
OH
NH H O
+
-
+
+
ƒ
(1)
The percentage distribution between ammonia and ammonia ions can be calculated by using the following
formula:
3
4
a
/
(
. )/
W
b
NH
H
NH
K
K
K
C
C
C
+
+
=
=
(2)
Where: K- ionization constant; K- water ionization constant; K- Ionization of ammonia; C - substance
concentration
This equilibrium is related to pH and temperature. At pH 7, only NH4
ions are present in the solution, and
when pH is 12, the solution is fully soluble NH3. Ammonia stripping is to raise the pH and temperature of the
wastewater, and then provide sufficient gas and water to blow the ammonia from the solution. The air stripping
ammonia removal method is stable and easy to control, with simple operations. But this method is also easy to
fill the fouling, affecting the operations of the equipment. When the water temperature is low, the air stripping
efficiency is low, blowing off after the completion of the callback value. In addition, the wastewater after
stripping treatment still contains a small amount of ammonia and cannot meet the discharge standard. So the
air stripping method is often used for the pretreatment of high concentration of ammonia nitrogen wastewater
(Ma H R, et al., 2010). How to improve the efficiency of air stripping, how to avoid secondary pollution and
how to control the production process and scale production in the process of industrialization call for much
attention.
1.3 The ammonia removal process by air stripping
The air stripping method has the advantages of high denitrification rate, flexible operations and small
footprints. The stripping method is often domestically used for treating high concentration ammonia nitrogen
wastewater, and the ammonia can be recycled. In order to ensure the continuous operations of the production
line, the sewage treatment system must be implemented in three stages. (Wu et al., 2010).
When the water level reaches the high level, the industrial wastewater is discharged into the accident pool.
When the regulation tank’s water level reaches the low level, the accident pool lift pump will lead wastewater
in the accident pool to the adjustment pool. Adjust the pool lift pump to transfer the wastewater from the
conditioning tank to the primary stripping tower, which is controlled by the regulating valve of the lift pump
outlet. The wastewater is added to the primary stripping tower before adding NaOH to adjust the pH of the
wastewater to 11. The wastewater enters the tower from the top of the first-stage stripping tower and flows
from the top of the tower along the gap in the packing. The air is entrained with steam from the bottom of the
tower into the tower, forming convection with the wastewater. Air will waste water in the ammonia nitrogen
blown off the wastewater into the bottom of the bottom of the collection tank. Similarly, the wastewater flows
through the secondary stripping tower and the tertiary stripping tower. Three-stage stripping tower lift pump
will strip the bottom of the wastewater to the mixing reaction tank, with HCl added to adjust the pH between 6
to 9 (Song et al., 2008). Ammonia content in wastewater is detected by the ammonia nitrogen analyzer. If the
discharge standard is reached, it will be transported to the park sewage treatment plant for further treatment. If
116


failing to meet the discharge standard, the wastewater will be transported to the regulating tank and be re-
stripped (Wang et al., 2013).
2. Object of study, purpose and experimental program
2.1 Research objects
The research object of this paper is to simulate the industrial high concentration ammonia wastewater
(concentration> 500m/L) produced by the fertilizer industry. This kind of waste water generally has the
characteristics of high temperature, high ammonia, high flow rate, low organic matter and it is difficult to
conduct biochemical treatment.
2.2 Research purposes
High concentration of ammonia wastewater treatment in domestic is always difficult to solve. Different regions,
different seasons, different industrial enterprises’ emissions of ammonia nitrogen wastewater conditions are
different, and the existing governance methods are difficult to achieve a high degree of unity of social benefits,
environmental benefits and economic benefits of (Min and Yi, 2016). Therefore, the purpose of this paper is to
try a new method for the treatment of high concentration of industrial ammonia wastewater, to explore its
application feasibility and reaction mechanism, which lays the foundation for further researches.
2.3 Experimental program
Based on the physical and chemical properties of ammonia volatilization and oxidation, and through the
comparison, this study adopts the method of gas-phase ammonium oxidation as the follow-up method based
on the stripping method. Under the action of the catalyst and a certain temperature range, we will strip the
ammonia for oxidation, and the possible oxidation products are NOx, N2, H2O, hydrazine and so on. And the
oxidation products are mainly Nand H2O by temperature control. The wastewater treated by the experiment
was made by artificial dispensing, and the NHconcentration was 1024 m/L. The effects of pH value, water
temperature, stripping time and addition amount of No. 1 denitrification on the denitrification rate were
obtained by the static test, and the reasonable design parameters were provided for the engineering design.
The experimental protocol is as follows:
(1) In the atmospheric pressure, strong alkaline conditions, by heating and drumming into the excess air, the
NHin the waste water is transformed to the gas phase;
(2) with air as the carrier gas, through its carrying NHinto the catalyst with quartz catalyst tube, heating with
electric heating, digital temperature control equipment to control the reaction temperature, in a certain
temperature range, the oxygen and ammonia in the air produce oxidation reaction in a series of catalytic; (3)
The concentration of NHand NOin the reaction tube was measured by the atmospheric sampler, and the
NHconcentration in the water samples before and after the reaction was measured.
(3) Study on Treatment of High Concentration Ammonia Wastewater by Stripping Method under Normal
Pressure and Gas - phase Ammonia Catalytic Oxidation.
According to the change of NHconcentration in the gas phase, the conversion rate of NHwas calculated,
and the removal rate of ammonia in ammonia-containing wastewater was calculated according to the change
of NHconcentration in the liquid phase and the amount of NHin the gas phase. The formation rate of N2
was calculated according to the concentration of NOin the gas phase. The experimental flow diagram is
shown in Figure 2.
Air
pump
Ammonia Wastewater
Water Sample Constant
Temperature Water Bath
Device
Reactor
Atmospheric
Collector
Liquid phase
extraction
analysis
Heating and
temperature
control
equipment
Gas sampling
analysis
Figure 2: Analysis of Ammonia Catalytic Oxidation Process for Treatment of Ammonia Wastewater at Normal
Pressure
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3 Test results and discussion
3.1 Effect of temperature and pH on stripping effect
Take the amount of ammonia wastewater, and control the amount of NaOH dosage for different pH. The gas-
liquid ratio is 3000:1; stripping time is 9h; and select the different temperature and solution pH to carry out the
experiment. The experimental results are shown in Figure 3 and Figure 4.
Figure 3: Effect of Temperature on the Stripping Effect
Figure 4: Effect of pH on the Stripping Effect
It can be seen from Fig.3 that the stripping efficiency increases with the stripping time, and the temperature
change has obvious effect on the stripping efficiency. Stripping at 25 °C and 40 °C can only reach about 44 %,
and when the water temperature rose to above 50 °C, after stripping 6h, the efficiency can reach 54%. From
the effect of pH change on the stripping efficiency in Fig. 4, it can be seen that the pH is above 9.5 and
stripping after 6h can guarantee more than 50% of the blowing efficiency.
3.2 Effect of gas - liquid ratio on stripping experiment of ammonia - nitrogen wastewater
According to the results of the stripping method for the treatment of high concentrations of ammonia
wastewater, pH and temperature are two key factors in the removal of NHfrom water. The higher the water
temperature and the pH value, the more favorable the NHescape. When the temperature and pH value are
constant, the gas-liquid ratio also has a certain impact. Therefore, we conduct experiment to study the
relationship between gas-liquid ratio and blow-off effect. Experimental conditions: simulated ammonia waste
water 300ml, pH = 14, water temperature 50 °C, temperature 25 °C, stripping time 120min. The measured
water sample is diluted by 100 times, so the calculated NHconcentration multiplied by 100 is the actual water
sample concentration, and the experimental results are shown in Table 1.
Table 1: Gas-liquid Ratio Test Data
Test number Gas-liquid ratio Absorbance Concentration of NHin wastewater
Stripping
efficiency
1
2000
0.576
366
66.8
2
2200
0.481
322
71.2
3
2500
0.434
289
76.7
4
2800
0.339
190
81.4
5
3000
0.256
123
88.3
The graph shows that the gas-liquid ratio is linear with the stripping efficiency at 50 °C and strongly alkaline,
and it can be deduced that the effect of different air flow rates below 1000 on the stripping-out efficiency is not
significant. In this experiment, the waste water volume is 300ml; the maximum air flow rate is 2L/min during
118


stripping and catalytic oxidation; the maximum reaction time (stripping time) is 120min, so the maximum gas-
liquid ratio is only 800. It can be argued that, for the purposes of this experiment, the total amount and volume
change of NHare negligible under different conditions of flow (<2 L/min) of air at the same time, and
ammonia is actually "boiled out." Different air flows only bring about different concentration of gas phase NH3.
4 Study on the Reaction Mechanism of Ammonia by Stripping
It is generally believed that the reaction of NH3 and 02 can be expressed as a stoichiometric equation:
3
2
2
3
2
2
2
3
2
2
2
:4
5
4
6
:4
4
4
6
:4
3
2
6
A NH
O
NO
H O
B
NH
O
N O
H O
C
NH
O
N
H O
+
=
+
+
=
+
+
=
+
(3)
The reaction of NHwith NO can be expressed as:
3
2
2
4
6
5
6
NH
NO
N
H O
+
=
+
(4)
The reaction of A, B, and C can occur at 900 °C. The equilibrium constant is K= 1053; K= 1061; K= 1063.
The equilibrium constant of the three reactions is large, so the reaction to the left can be regarded as
irreversible. From K3> K2> K1, it is known that the reaction of NHoxidation to Nis the most complete, and the
final product of NHoxidation can be all N(Hao et al., 2008). When there is a catalyst, the reaction of NH3
with Ohas the mechanism of "selective catalytic oxidation(SCO)". Denote NH(a) and O (a) to represent the
ammonia and oxygen in the adsorbed state, and the two reaction mechanisms are described below:
3
3
2
3
2
2
3
2
2
2
2
2
2
2
( )
2
2 ( )
( )
( )
( )
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a) (
)
X
Y
X Y
X Y
NH
s
NH a
O
O a
NH a
NH a
OH a
NH
O
NH
OH
NH
OH
NH
H O
NH
OH
NH
H O
NH
OH
N
H O
NH
O
N
OH
NH
NH
N H
N H
X Y OH
*
+
+
+ ↔
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
2
2
( )
( ) (
)
a
N g
X Y HO
+
+
(5)
Foreign scholars tend to believe that, under the condition of excessive oxygen oxidation, the SCO mechanism
is suitable for describing the way of ammonia catalytic oxidation. This experiment detects the presence of NO
and confirms this view (Shaji, et al., 2012).
5 Application of Stripping Method
MSG production process can be divided into high, medium and low concentrations of organic wastewater.
High concentration of wastewater, which is glutamic acid mother liquor, has a strong acid, high COD,
ammonia nitrogen, and sulfate and a series of characteristics, so it brought more difficulties for the
management work especially that the high concentration of ammonia nitrogen will produce a strong inhibition
of biological activity. In this experiment, the ammonia removal experiment of high concentration monosodium
glutamate wastewater was carried out by stripping method, which provided the basis for its application in
actual production.
5.1 Primary ammonia bleaching purification process
Because of the low cost of running, mature process, high stripping efficiency, stable operation and suitable for
the treatment of high concentration ammonia nitrogen, it is widely used at home and abroad. Therefore, this
method uses stripping method to remove high concentration ammonia in wastewater (Wu et al., 2001). Due to
the high ammonia content in alkaline solution, it will react with heavy metal ions to produce complexes that is
difficult to deal with, and will play a buffer in the regulation of the time.
5.2 Secondary ammonia bleaching purification process
Ammonia stripping tower selects polypropylene ladder ring as packing tower. The best pH value is 11, and the
best temperature is room temperature. It directs high gas to water than the free ammonia in the waste water to
the air, and then uses dilute acid on ammonia gas to purification absorption. Absorbent solution is dilute
119


sulfuric acid solution, and after cleaning the tail gas to the high-altitude discharge, the absorption of sulfuric
acid solution can be made semi-finished products, which can also be applied to the monosodium glutamate
plant area of green trees. The pH value of the secondary stripping tower is 11, and the stripping efficiency is
about 90% at room temperature. After the secondary stripping, the concentration of ammonia can reach the
biochemical pool for the treatment.
6. Conclusion
The effect of blowing time, waste water pH, stripping temperature and gas-liquid volume ratio on ammonia
removal rate was investigated by using stripping method to treat high concentration ammonia wastewater
produced in industrial production. At 50 °C and strongly alkaline condition, the gas-liquid ratio is linear with the
stripping efficiency. And it can be deduced that the effect of different air flow rates below 1000 on the blowout
efficiency is not significant. The maximum air flow rate of this experiment is 2L/min, and the maximum reaction
time (stripping time) is 120min, so the maximum gas-liquid ratio is only 800. At the same time, this paper also
explores the reaction mechanism of ammonia removal in stripping method and the application of ammonia in
industrial wastewater produced by monosodium glutamate.
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