Process Safety and Environmental Protection 140 (2020) 348–355

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Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Oxidation absorption of hydrogen sulfide from gas stream using

vacuum ultraviolet/H2 O2 /urea wet scrubbing system
Yan Wang a,b , Yangxian Liu a,∗ , Yong Wang b,∗
a
School of Energy &Power Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013, China
b
Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013, China

a r t i c l e i n f o a b s t r a c t

Article history: Hydrogen sulfide has serious harm to human body and equipment. Advanced oxidation technology shows
Received 13 February 2020 excellent development prospect for hydrogen sulfide (H2 S) removal due to strong oxidation ability and
Received in revised form 11 April 2020 green process. This article proposed a novel separation process for H2 S from gas stream using vacuum
Accepted 11 May 2020
ultraviolet (VUV)/H2 O2 /urea wet scrubbing system in a VUV-spraying scrubber, and studied the effec-
Available online 17 May 2020
tiveness of H2 S removal and removal pathways using VUV/H2 O2 /urea wet scrubbing system. Results
indicated that the highest H2 S removal efficiency was up to 98.2 % under optimal experimental condi-
Keywords:
tions. Increasing UV-light intensity and solution pH improved the H2 S removal efficiency. Increasing flue
Vacuum ultraviolet/H2 O2 /urea
OH radicals
gas flow rate and H2 S concentration decreased the H2 S removal efficiency. The increase of H2 O2 con-
Gaseous hydrogen sulfide centration, reaction temperature, liquid-gas ratio or urea concentration first increased and then reduced
(H2 S) the H2 S removal efficiency. H2 S was removed by five pathways such as ionization, urea absorption, H2 O2
Photochemical oxidation, photolysis and ·OH oxidation. Photolysis and ·OH oxidation were the two major pathways for
Urea absorption the H2 S removal.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction catalyzer/adsorbent is easily inactivated (Liu and Li, 2019b; and

As an impurity commonly found from natural gas, coal gas and
synthesis gas, H2 S not only can lead to transport equipment and
pipelines corrosion and catalyst poisoning, but also is extremely
harmful for the environment (Bandosz, 2002; Liu and Li, 2019b).
Many measures have been taken to limit H2 S emission. Com-
mon H2 S removal technologies mainly include catalytic/adsorption
removal (Wang et al., 2020 and Liu and Li, 2019b), membrane
separation (Mirfendereski et al., 2019; Cai et al., 2019; Tilahun
et al., 2017 and 2018) biological removal (Pandey et al., 2005;
Malhautier et al., 2003) and wet scrubbing removal (Chen, 2017;
Frare et al., 2010; Jalil et al., 2009; Sharma et al., 1997; Li et al.,
2019; Harasek et al., 2012; Vilmaina et al., 2014; Li and Wei, 2004;
Wang et al., 2019a). The membrane separation is easy to control and
environmental-friendly, which possesses high removal efficiency,
but has poor anti-corrosion ability, high cost and short life (Liu and
Li, 2019b; Wang et al., 2019a). The catalytic/adsorption methods
have the advantages such as simple process and low initial invest-
ment, but its regeneration energy consumption is high, and the
∗ Corresponding authors.
E-mail addresses: liuyx1984@126.com (Y. Liu), wylq@ujs.edu.cn (Y. Wang).
Liu et al., 2019b; Wang et al., 2019a). The biological treatment pos-
sesses mild running conditions and low cost, but is time-consuming
and unable to treat H2 S of high concentration (Wang et al., 2020 and
Liu et al., 2019b; Wang et al., 2019a). Wet scrubbing is the most
widely used and mature method because of its several advantages
such as simple operation, strong adaptability and high efficiency
(Chen, 2017; Wang et al., 2019a). Despite all this, the traditional
absorbers such as alkanolamine and carbonate, have high regen-
eration energy consumption and strong equipment corrosiveness
(Wang et al., 2019a). Some new absorbents such as ionic liquids are
expensive, and are still difficult to obtain application (Wang et al.,
2019a).
On the basis of some advantages such as high oxidation
efficiency and green process, various free radical oxidation tech-
nologies are applied to produce highly active free radicals, ·OH
and SO4 − ·, to oxidize various gaseous pollutants (e.g., SO2 , NOx ,
Hg◦ , CO, VOCs, H2 S, etc. (Wang et al., 2019a, 2019b and 2019c;
Lu et al., 2007; Guo et al., 2011; Liu et al., 2015a; and Liu and
zhou, 2015b; Zhao et al., 2014 and 2015; Wang et al., 2020). These
results show that free radical oxidation technologies have great
development prospect in the field of gas pollutant purification. In
recent years, some new H2 S separation technologies on the basis of
free radical oxidation technologies were developed, which can be

https://doi.org/10.1016/j.psep.2020.05.025
0957-5820/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 Y. Wang et al. / Process Safety and Environmental Protection 140 (2020) 348–355
divided into wet type and dry type (Liu et al., 2019b; Wang et al.,
2019a). Some representative dry methods such as photocatalytic
oxidation, plasma degradation, and so on, have been developed
(Yu et al., 2013; Xia et al., 2008; Dang et al., 2012; Wang et al.,
2018a; Zhao et al., 2017), but none of them can be applied because
of several disadvantages such as low equipment reliability, large
energy consumption, or/and easy deactivation of photocatalyst (Liu
et al., 2019b). In comparison with dry H2 S separation technologies
using free radical oxidation, wet H2 S separation technologies using
free radical oxidation have better reliability and higher removal
efficiency (Chen, 2017; Wang et al., 2019a), which shows good
development prospect.
Recently, Wang and Liu (Wang et al., 2019a and c; Wang et al.,
2018b) used Fenton-based oxidation systems to generate ·OH to
remove gaseous H2 S in wet scrubbers, and their results showed
that gaseous H2 S was efficiently removed by Fenton-based oxida-
tion systems. However, Fenton-based oxidation systems possess
various deficiencies such as very narrow pH window, uncontrol-
lable reaction rate and difficult recovery of iron ions (Wang et al.,
2019a,c; Wang et al., 2018b; Babuponnusami and Muthukumar,
2014). Our previous studies indicated that VUV/H2 O2 wet scrub-
bing system possessed very strong oxidation capacity, broad
effective pH window, more controllable reaction rate, and no metal
ion pollution, which has achieved an efficient removal for several
pollutants such as NOx , SO2 , Hg◦ , etc. (Liu and wang, 2016, 2018a,
2018b, 2018c and 2019c). In some industrial gases, NOx , SO2 , Hg◦ ,
CO, H2 S, etc. exist simultaneously (Liu and Li, 2019b; Yang et al.,
2019 and 2020). Therefore, it has important significance to further
study the feasibility of H2 S removal using VUV/H2 O2 wet scrubbing
system, because developing the simultaneous removal technolo-
gies of multi-gaseous pollutants has an important industrial value
(Liu et al., 2016, 2018a and 2020). However, the product of H2 S
removal by free radical oxidation contains sulfuric acid solution,
which may cause system/device corrosion and product recovery
difficulty. According to the results of Wang et al. 2019a and 2018b,
neutral or weak alkaline solution is quite conducive to absorption of
Fig. 1. Experimental device and schematic diagram.
349
H2 S based on free radical oxidation in liquid phase. As we all know,
urea is a kind of weak alkali absorbent, which has been applied suc-
cessfully for SO2 removal from flue gas, and the absorption product
is recyclable ammonium sulfate (Fang and Ceng, 2011). Therefore,
adding urea to the VUV/H2 O2 wet scrubbing system not only can
improve the removal efficiency of H2 S, but also can prevent the
corrosion of the product sulphuric acid to equipment, which has
a good industrial practice value. However, up to present, the rel-
evant research on oxidation absorption of gaseous H2 S removal
using VUV/H2 O2 /urea wet scrubbing system has been not studied
yet.
Moreover, spraying scrubber is the most widely used reactor
in the field of flue gas treatment due to its simple structure and
huge advantages of gas-liquid mass transfer (Liu et al., 2016, 2018a
and 2019c). Hence, we developed a novel absorption process of
H2 S from gas stream using VUV/H2 O2 /urea wet scrubbing system
in a VUV-spraying scrubber. The effects of main process variables
(VUV-light intensity, concentrations of urea and H2 O2 , solution
pH, gas flow rate, reaction temperature, liquid-gas ratio and H2 S
concentration) on H2 S removal were studied. The products and
mechanism of H2 S removal were also measured and revealed. The
results will offer essential theoretical foundation for the develop-
ment of the new H2 S separation technology, and effectively expand
the industry application of photochemical technologies in gaseous
H2 S separation field.
2. Experimental section
2.1. Experimental system
As found from the Fig. 1, an experimental installation con-
tains a gas generation system, a temperature control system, a
VUV-spraying scrubber, and an exhaust gas measurement and
purification system. The gas generation system is made up of H2 S
and N2 high purity gases, a gas mixer (silica glass), flowmeters
and two Teflon gas valves. The VUV-spraying scrubber mainly con-
350 Y. Wang et al. / Process Safety and Environmental Protection 140 (2020) 348–355

tains a reactor lid, a pH meter, a peristaltic pump, a pH reagent

tank, a gas distributor, a pump, a silicate round glass container (10
cm in diameter and 60 cm in length), a quartz glass tube, a VUV
lamp (wavelength of 185 nm), and three Teflon nozzles (the size
of spraying droplet is about 80−120 ␮m). The operating temper-
ature control system is composed of a thermometer and a digital
thermostatic water bath. The exhaust gas measurement and purifi-
cation system has a H2 S analyzer and an exhaust gas absorption
bottle. Three Teflon nozzles are maintained 120 degree each other
on the basis of a level. The spacing between the top of reactor and
the nozzles is 15 cm. The distance between the bottom of reactor
and the gas distributor is 20 cm.

2.2. Experimental procedures

The simulated gas was prepared using H2 S and N2 high purity

gases. The H2 S inlet concentration was regulated based on adjust-
Fig. 2. Effect of H2 O2 concentration on H2 S removal efficiency. Experimental con-
ment of H2 S and N2 flowmeters. The H2 S analyzer (less than ditions: Urea concentration of 0.5 mol/L, H2 S concentration of 1000 ppm, VUV-light
2% repeatability error and measurement limit is 0.1 ppm; PULI intensity of 132 ␮W/cm2 , gas flow rate of 1.5 L/min, solution pH of 7.61, temperature
Technology Co., Ltd.) was applied for the measurement of H2 S of 40◦ C, and liquid-gas ratio of 2.0.
concentration before and after each test. De-ionized water and
30 % H2 O2 solution (it was purchased from Sinopharm Chemical through the VUV-spraying scrubber outlet. Removal efficiency of
Reagent Co., Ltd., China) were used to prepare 500 ml H2 O2 /urea H2 S was obtained by the Eq. (1):
mixed solution (all reagents are analytically pure). The pH value
of H2 O2 /urea solution was regulated by adding HCl and/or NaOH Cin − Cout
Removal efficiency = × 100% (1)
solutions. The thermostatic water bath and thermometer were used Cin
to control the temperatures. Peristaltic pump and containing−HCl In Eq. (1),Cin is H2 S inlet concentration and Cout is H2 S outlet
and/or NaOH solution tanks were applied to control the pH value of concentration.
H2 O2 /urea solution (a digital pH meter was applied to monitor pH).
The containing-H2 S simulated gas entered the VUV-spraying scrub- 3. Results and discussions
ber after the temperature and the pH value of H2 O2 /urea mixed
solution were successfully adjusted to the required data. A photo- 3.1. Effect of H2 O2 concentration on H2 S removal
chemical oxidation reaction was carried out in the VUV-spraying
scrubber when the VUV lamp was activated. The H2 S concentra- The effect of H2 O2 concentration on H2 S removal efficiency was
tion was analyzed in the outlet of the VUV-spraying scrubber via the investigated, which is shown in Fig. 2. As the H2 O2 concentration
H2 S analyzer, which was defined as the outlet concentration of H2 S. increases from 0 to 0.2 mol/L, H2 S removal efficiency increases at
Every experiment time had been controlled at 20 min, and the mean first (38.7%–98.2%), and then reduces (98.2%–90.1%). The results
value of all data (the H2 S outlet concentration was recorded once from the previous scholars (Liu et al., 2016; Hao et al., 2017, and
per minute) was adopted as the H2 S outlet concentrations. This 2019) showed that 1 mol H2 O2 could be decomposed to 2 mol ·OH
study adopted a single factor research method for process param- on the basis of the Eq. (2).
eter optimization, that was, when a process parameter or factor
was studied, all other parameters or factors remained unchanged. H2 O2 + hv → ·OH + ·OH (2)
The benchmark experimental conditions are listed under the title
The ·OH produced from the Eq. (2) can oxidize H2 S to SO4 2−
of each Figure.
through the following a series of reactions (3)-(10) (Wang et al.,
2018b, 2019a and 2019c) because of its strong oxidizing property.
2.3. Measurement methods and conditions
H2 O
H2 S −→H+ + HS− (3)
A UV spectrophotometric method (UV-2450 from Shimadzu)
− −
was applied to determine NH4 + . An electron spin resonance (ESR) HS + ·OH → HSOH· (4)
spectrometer (ESP-300, Bruker) was applied to determine free rad- H2 S + ·OH → HS · +H2 O (5)
icals (·OH), and 5,5-dimethyl-1-pyrrolidine N-oxide (DMPO) was
applied as spin trap agent. A SO2 analyzer (resolution of 1 ppm, KM- H2 O2 + HS· → H2 SO2 · + H· (6)
950, Kane of UK) was applied to determine SO2 from gas stream
HSOH·− + H2 O2 → H2 + H2 SO3 (7)
(the byproduct SO2 may be produced). An ion chromatography
(Dionex: ICS1600) was applied to determine SO3 2− /SO4 2− . A HPLC H2 O2 + H2 SO2 · → H2 + H2 SO4 (8)
(high performance liquid chromatography) (Agilent1260 of USA)
was applied to determine elemental sulfur (S◦ ), and the determined H2 O2 + H2 SO3 → H2 O + H2 SO4 (9)
methods reference the literatures (Sun et al., 2015; Lin et al., 2012; H2 SO3 + ·OH → H2 SO4 + ·H (10)
Liu et al., 2017a; and 2017b).
In addition, relevant research (Wang et al., 2018b, 2019a and
2.4. H2 S removal efficiency 2019c) also showed that H2 O2 could directly oxidize H2 S to gener-
ate S◦ through the following reactions (11) and (12).
The inlet concentrations of H2 S were obtained by determining H2 O2 + H2 S → 2H2 O + S0 ↓ (11)
the H2 S concentrations through the bypass. The outlet concentra-
− 0 −
tions of H2 S were obtained by determining the H2 S concentrations H2 O2 + HS → H2 O + S ↓ +OH (12)
 Y. Wang et al. / Process Safety and Environmental Protection 140 (2020) 348–355
Fig. 3. Effect of urea concentration on H2 S removal efficiency. Experimental condi-
tions: H2 O2 concentration of 0.2 mol/L, VUV-light intensity of 132 ␮W/cm2 , solution
pH of 7.61, temperature of 40◦ C, gas flow rate of 1.5 L/min, liquid-gas ratio of 2.0,
and H2 S concentration of 1000 ppm.
On the basis of the Eqs. (2)–(12), with increasing the H2 O2 con-
centration, the photochemical removal system can generate more
·OH, which will promote the H2 S removal.
However, a large number of results (Liu et al., 2016; Hao and
Zhao, 2016 and 2019; Adewuyi and Khan, 2013 and 2015; Wang
et al., 2019d) also indicated that under high H2 O2 concentrations,
several self-consumption reactions of ·OH (e.q.s 13–16) might occur
in the liquid phase. Thus H2 O2 with high concentrations caused a
lower removal efficiency of H2 S. Many similar results were also
obtained by some other scholars (Liu et al., 2016 and 2019d; Hao
and Zhao, 2016 and 2019; Adewuyi and Sakyi, 2013 and 2015;
Wang et al., 2019d).
·OH + ·OH → H2 O2 k = 5.0 × 109 M−1 s−1
·OH + HO2 · → H2 O + O2 k = 1.0 × 1010 M−1 s−1
·OH + H2 O2 → H2 O + HO2 · k = 2.7 × 107 M−1 s−1
HO2 · +HO2 · → H2 O2 + O2 k = 3.4 × 107 M−1 s−1
3.2. Effect of urea concentration on H2 S removal
The effect of urea concentration on H2 S removal efficiency was
tested, which is shown in Fig. 3. As the urea concentration increases
from 0 to 1.5 mol/L, H2 S removal first increases and then reduces
(the optimum value is 0.5 mol/L). The results from Wang et al.
2018b, 2019a and 2019c showed that neutral and weak alkaline
conditions could enhance the removal of H2 S by free radical oxida-
tion in the liquid phase. It is well known that urea is a weak alkali
absorbent, which can ionize to produce OH− through the following
reaction Eq.s (17) and (18).
+
(NH2 )2 CO + H2 O → NH2 COONH4 + H2 O → CO2-
3 + 2NH4
− −
CO2-
3 + H2 O → HCO3 + OH
So appropriately adding urea to the system can increase the H2 S
removal efficiency. However, the previous studies (Hao and Zhao,
2016, 2017 and 2019) had shown that carbonate was a kind of scav-
enger for ·OH. Adding urea of high concentration to the system can
inhibit the H2 S removal because the product CO3 2− is a typical free
radical scavenger, and can consume ·OH in solution. Therefore, urea
concentration causes dual effects on the removal process of H2 S.
351
Fig. 4. Effect of temperature on removal efficiency of H2 S. Experimental con-
ditions: Urea concentration of 0.5 mol/L, H2 S concentration of 1000 ppm, H2 O2
concentration of 0.2 mol/L, gas flow rate of 1.5 L/min, VUV-light intensity of 132
␮W/cm2 , solution pH of 7.61, and liquid-gas ratio of 2.0.
(13)
(14)
Fig. 5. Effect of VUV-light intensity on removal efficiency of H2 S. Experimental
(15) conditions: Urea concentration of 0.5 mol/L, H2 S concentration of 1000 ppm, H2 O2
concentration of 0.2 mol/L, gas flow rate of 1.5 L/min, solution pH of 7.61, tempera-
(16) tures of 40◦ C, and liquid-gas ratio of 2.0.
3.3. Effect of temperature on H2 S removal
On the basis of common wet scrubbing desulfurization tem-
peratures (2019b; Wang et al., 2019c), 20 to 70◦ C is selected as
the studied range of reaction temperature. As exhibited in Fig. 4,
within the range of 20–40 ◦ C, with increasing the reaction temper-
ature, H2 S removal efficiency increases slightly. However, within
the range of 40 ◦ C to 70 ◦ C, increasing the reaction tempera-
ture reduces H2 S removal efficiency. The results of many scholars
(Wang et al., 2019c and 2018b; Hao and Zhao, 2016 and 2019)
showed that increasing temperature could promote chemical reac-
tions, strengthening the H2 S removal. However, Wang et al., 2018b,
(17) 2019b and 2019c indicated that increasing temperature would
cause a decrease in solubility coefficient of H2 S. This would inhibit
(18) the removal rate of H2 S due to the increasing of the mass transfer
resistance between gas and solution. Based on the above positive
and negative factors, changing the reaction temperature causes a
double effect on the H2 S removal process.
3.4. Effects of VUV-light intensity on H2 S removal
Effects of VUV-light intensity on H2 S removal efficiency were
investigated, which are displayed in Fig. 5. It is found that as
352 Y. Wang et al. / Process Safety and Environmental Protection 140 (2020) 348–355

Fig. 6. Effect of solution pH on H2 S removal efficiency. Experimental conditions: Fig. 7. Effect of gas flow rate on H2 S removal efficiency. Experimental condi-
Urea concentration of 0.5 mol/L, H2 S concentration of 1000 ppm, H2 O2 concentra- tions: Urea concentration of 0.5 mol/L, H2 O2 concentration of 0.2 mol/L, VUV-light
tion of 0.2 mol/L, VUV-light intensity of 132 ␮W/cm2 , gas flow rate of 1.5 L/min, intensity of 132 ␮W/cm2 , solution pH of 7.61, reaction temperatures of 40◦ C, H2 S
temperature of 40◦ C, and liquid-gas ratio of 2.0. concentration of 1000 ppm, and liquid-gas ratio of 2.0.

VUV-light intensity increases from 0 to 243 ␮W/cm2 , the removal

efficiency of H2 S greatly increases from 33.3%–99.8%. As seen from
the Eqs. (2)–(10), based on the increase of VUV-light intensity, more
effective photon (hv) will be generated in solution (correspond-
ingly, hv will lead to the generation of more ·OH in solution), which
will enhance the H2 S removal. Several results (Yu et al., 2013; Xia
et al., 2008) also indicated that ultraviolet light could directly lead
to the photolysis of H2 S to produce S◦ on the basis of the Eq. (19):
UV
H2 S + hv−→ S0 + H2 (19)

So increasing the VUV-light intensity can promote the H2 S

removal. However, it is seen that with increasing the VUV-light
intensity from 132 to 243 ␮W/cm2 , the H2 S removal efficiency
only increases from 98.2%–99.8%. So 132 ␮W/cm2 was set as the
optimized VUV-light intensity.

3.5. Effects of solution pH on H2 S removal

Some results (Liu and wang, 2016 and Liu and wang, 2019c)
showed that solution pH usually had significant effect on redox
reaction. So the effect of solution pH on H2 S removal also was
researched, and the result can be seen from Fig. 6. It is seen that
as the solution pH increases from 1.51 to 9.82, the H2 S removal
efficiency obviously increases. The effect of solution pH on H2 S
removal efficiency mainly involves several reasons. The enhance-
ment of alkalinity (solution pH) will improve the ionization process
(E.q. 3). The reaction between the ionization product HS− with the
oxidants belongs to a homogeneous reaction (Wang et al., 2018b
and 2019a), and can be achieved more easily in comparison with
gas-liquid heterogeneous reaction. A high solution pH is helpful to
the H2 S removal, but when the solution pH is increased to 9.82, the
self-decomposition of H2 O2 greatly accelerates (a lot of O2 was pro-
duced). This will result in poor utilization for reagent. In addition,
many studies (Liu et al., 2015a; Wang and Liu, 2019b; Zhao et al.,
2014; Adewuyi and Sakyi, 2013 and 2015) have shown that under
the condition of strong alkalinity, the ·OH will be consumed through
H2 O2 , which is not conducive to the removal of H2 S. On the basis
of the comprehensive consideration of H2 S removal efficiency and
H2 O2 /·OH utilization efficiency, 7.61 is set as the optimum value.
3.6. Effects of gas flow rate on H2 S removal
The gas flow rate is an important parameter for the design of
the scrubber. Hence, studying the effect of gas flow rate on H2 S
Fig. 8. Effect of H2 S concentration on H2 S removal efficiency. Experimental condi-
tions: Urea concentration of 0.5 mol/L, gas flow rate of 1.5 L/min, H2 O2 concentration
of 0.2 mol/L, temperatures of 40◦ C, VUV-light intensity of 132 ␮W/cm2 , solution pH
of 7.61, and liquid-gas ratio of 2.0.
removal is necessary. From the Fig. 7, with the increase of the gas
flow rate from 0.5 to 2.8 L/min, the H2 S removal efficiency signif-
icantly decreases. When the diameter of the scrubber is constant,
an increase in the gas flow rate will increase the velocity of the gas
passing the scrubber. Based on the rising of the gas flow velocity,
the time of H2 S residence in reaction zone will reduce, which is
deleterious to the H2 S removal.
3.7. Effect of H2 S concentration on H2 S removal
Depending on operating parameters or different gas sources,
the concentration of H2 S will vary greatly (concentration often
ranges from hundreds to tens of thousands of ppm). Several tests
were done to investigative the effect of H2 S concentration on H2 S
removal efficiency. As seen from Fig. 8, when H2 S concentration
increases from 500 to 2500 ppm, there is a obvious decline in H2 S
removal efficiency. As seen from the above Eq.s (2)–(12) and (19)
that H2 S can consume hv, H2 O2 and ·OH from the solution. When
the other conditions were remained constant, the concentrations
of hv, H2 O2 and ·OH also would keep constant (Liu et al., 2018d). But
with increasing H2 S concentration, the number of H2 S molecules
that passes the scrubber is greatly increased, which increases the
 Y. Wang et al. / Process Safety and Environmental Protection 140 (2020) 348–355 353

(the removal efficiency of H2 S increases from 42.3%–98.2% greatly).

When the other parameters remained constant, the numbers of
hv, H2 O2 and ·OH that passes the scrubber will have great increas-
ing with the increasing the liquid-gas ratio, which is beneficial for
the H2 S removal. In addition, based on the increasing of liquid-gas
ratio, the mass transfer conditions may be improved by stronger
gas-liquid impact (Liu et al., 2018e), which is also helpful for the
H2 S removal. However, when the liquid-gas ratio is more 2.0, the
H2 S removal efficiency decreases. This phenomenon is likely to be
explained as follows: VUV-light has a limited penetration capac-
ity in solution. When the density of the atomized solution is too
high, its penetration distance will reduce, being deleterious to the
photolysis reactions. Hence, 2.0 is an optimized liquid-gas ratio.

3.9. Mechanism and products of H2 S removal

Fig. 9. Effect of liquid-gas ratio on H2 S removal efficiency. Experimental condi-
tions: Urea concentration of 0.5 mol/L, gas flow rate of 1.5 L/min, H2 O2 concentration
of 0.2 mol/L, VUV-light intensity of 132 ␮W/cm2 , solution pH of 7.61, temperatures
of 40◦ C, and H2 S concentration of 1000 ppm.
equivalent ratio between H2 S and hv/H2 O2 /·OH, thereby being
adverse for the H2 S removal.
3.8. Effects of liquid-gas ratio on H2 S removal
Fig. 9 demonstrates the effect of liquid-gas ratio on the H2 S
removal efficiency. It is found that with increasing the liquid-gas
ratio from 0.53 to 3.3, the H2 S removal efficiency has a large increase
From the Fig. 10 (a), the H2 S removal efficiencies in H2 O, Urea,
H2 O2 , VUV/H2 O, VUV/H2 O2 , VUV/ H2 O2 /urea six removal systems
reach 2.9 %, 11.3 %, 14.6 %, 39.2 %, 76.4 %, 98.2 %, respectively. As seen
from Fig. 10(b)–(d), ESR spectrometer fails to measure free radicals
signals from H2 O, Urea and H2 O2 three removal systems, but suc-
cessfully measures free radicals signals from VUV/H2 O, VUV/H2 O2 ,
VUV/H2 O2 /urea three removal systems. The hyperfine splitting
parameters of free radicals were obtained by fitting the curves. The
free radical which has hyperfine splitting parameters such as aN =
15.0 G and aN = 14.8 G is widely recognized as ·OH (Liu et al., 2017c
and 2018b; Wang et al., 2019d; Hao et al., 2019b). The results show
that ·OH is generated in the VUV/H2 O, VUV/H2 O2 , VUV/H2 O2 /urea

Fig. 10. (a) H2 S removal efficiencies from several studied systems; (b)-(d) ESR spectrums for ·OH radical adducts in H2 O, Urea, H2 O2 , VUV/H2 O, VUV/H2 O2 , VUV/H2 O2 /urea
six removal systems (based on the same conditions). Benchmark experimental conditions: Urea concentration of 0.5 mol/L, temperature of 40◦ C, H2 O2 concentration of
0.2 mol/L, H2 S concentration of 1000 ppm, VUV-light intensity of 132 ␮W/cm2 , solution pH of 7.61, gas flow rate of 1.5 L/min, and liquid-gas ratio of 2.0. (when a process
parameter was studied, all other parameters remained unchanged, and only the studied parameter was changed).
354 Y. Wang et al. / Process Safety and Environmental Protection 140 (2020) 348–355
Table 1
Products of H2 S removal using VUV/H2 O2 /urea oxidation system.
Operating cycle (10 min) NH4 +
Measured concentration (mg/L) 1.66 × 103
Operating cycle (20 min ) NH4 +
Measured concentration (mg/L) 1.71 × 103
Fig. 11. Routes of gaseous H2 S removal using VUV/H2 O2 /urea removal system.
systems, which can offer a direct support for revealing the removal
pathways of H2 S.
Besides, the concentrations of H2 S removal products in the
VUV/H2 O2 /urea were also determined by UV spectrophotometric
method, high efficiency liquid chromatography, ion chromatogra-
phy and gas analyzer, and Table 1 lists the results. It indicates that
S◦ , SO4 2− and NH4 + are produced in the residual solution. SO4 2−
may be produced by oxidation of H2 S, which can be explained based
on the above Eqs. (8)–(10). NH4 + may be produced from the hydrol-
ysis of urea, which can be explained through the Eqs. (17). S◦ may be
produced on the basis of the Eqs. (11),(12) and (19). The by-product
SO2 could be not found from discharge gas.
Through the above analysis of removal products and free radi-
cals, and the comparison of H2 S removal efficiencies in the above
several systems, it can be inferred that several H2 S removal routes
may occur in the VUV/H2 O2 /urea removal system: (A) Urea can
absorb part of H2 S by the OH− produced from the Eq. (17); (B) VUV
can remove part of H2 S through the photolysis Eq. (19); (C) H2 O can
absorb part of H2 S through the above ionization Eq. (3); (D) H2 O2
can oxidize H2 S based on the Eq.s (11) and (12); (E) ·OH produced
from VUV photolysis of H2 O2 and H2 O can oxidize H2 S based on
the Eq.s (4)–(10). It can be also inferred based on comparison of
H2 S removal efficiencies that H2 S removals by ·OH oxidation and
photolysis play leading roles in the total removal share of H2 S. The
other pathways play supplemental roles. The removal pathways of
H2 S can also be described more simply using the following Fig. 11.
The post-treatment of products is a very important problem for
a new pollutant removal technology. In this removal system, S◦ is a
kind of precipitate, which thus is able to be separated easily on the
basis of precipitation process. The residual H2 SO4 will be recovered
based on adding NH3 to form the valuable fertilizer (NH4 )2 SO4 . The
waste heat from some industrial processes can be used to convert
the liquid (NH4 )2 SO4 to the solid (NH4 )2 SO4 on the basis of the basic
principle of evaporation and crystallization (Hao and Zhao, 2016;
SO4 2− SO3 2− S0 SO2
54.4 0 18.7 0
SO4 2− SO3 2− S0 SO2
117.6 0 36.9 0
Hao et al., 2019). In China, the total waste heat resources in 2018
will reach 3095 million tons of standard coal. These waste heat can
provide enough free heat. So the new H2 S separation technology
has a good developmental potential.
4. Conclusions
This article proposed a novel gaseous H2 S removal process
using vacuum ultraviolet (VUV)/H2 O2 /urea wet scrubbing system
based on a VUV-spraying scrubber, and studied the effectiveness of
H2 S removal and the removal pathways using VUV/H2 O2 /urea wet
scrubbing system. Research indicated that the highest H2 S removal
efficiency was up to 98.2 % under optimal experimental conditions.
Increasing UV-light intensity and solution pH led to an increase in
H2 S removal efficiency. Increasing gas flow rate and H2 S concen-
tration resulted in a decrease in H2 S removal efficiency. An increase
in H2 O2 concentration, reaction temperature, liquid-gas ratio and
urea concentration first increased, and then reduced H2 S removal
efficiency. H2 S was removed by five pathways such as ionization,
urea absorption, H2 O2 oxidation, photolysis and ·OH oxidation.
Photolysis and ·OH oxidation were the two major pathways in the
H2 S removal. Sulphur and sulfate were the main removal products
in solution.
Declaration of Competing Interest
All authors declare that we have no financial and personal rela-
tionships with other people, organizations or company that can
inappropriately influence our work. The authors also state that the
processing of this manuscript will not receive any organizational
or personal interference.
All authors declare that the copyright of this manuscript is
entirely determined by the submitting publisher and/or the journal.
The authors have no interest disputes about this publishing rights
or future commercial interests.
All authors agree to the corresponding author’s submission deci-
sion and ensure that there are no disputes of interest.
Acknowledgements
This work is funded through National Nat. Sci. Foundation of
China (Nos. U1710108), and ‘‘Six Personnel Peak” Talent-Funded
Projects of Jiangsu Province(GDZB-014).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.psep.2020.05.
025.
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