Appl Petrochem Res (2015) 5:207–213

DOI 10.1007/s13203-015-0106-1

KACST-FORUM

A novel process to recover sulfur in aqueous phase under ambient

condition
Yu Huang1 • Haoyi Chen1 • Yongchun Lu1 • Bonan Liu2 • Huahong Shi1 •

Tiancun Xiao1,2

Received: 9 January 2015 / Accepted: 24 March 2015 / Published online: 4 April 2015
Ó The Author(s) 2015. This article is published with open access at Springerlink.com

Abstract Sulfur recovery is an important industrial pro- was filtered out. The sulfur powder has the same laser
cess for fossil fuel clean consumption, in which H2S is Raman spectra with the Claus process, with the main
firstly separated from the gas stream from the structure as S8 with high purity.
hydrodesulfurization process or gasified gas of coal or
biomass. Meanwhile, almost equivalent half amount of SO2 Keywords Sulfur recovery  Claus  Aqueous phase 
is produced from the boiler on-site due to the power and Flue gas  Hydrogen sulfide
steam generation or the fluid catalytic cracking process in a
refinery. Currently, H2S is converted into elemental sulfur
using Claus process, which is being used worldwide, and Introduction
SO2 is removed from the flue gas using lime or lime water.
The two sulfur removal technologies require lots of capital Sulfur is one of the main pollutants from fossil fuel and
investment and operating cost. Here, we have developed a mostly emitted to air in the form of SO2, and 99 % of
novel process for SO2 in flue gas to react with H2S from the which in air comes from human sources. The main source
gasified gas stream, to convert them elemental sulfur by of sulfur dioxide in the air is industrial activity that pro-
washing the flue gas and H2S with liquid catalyst con- cesses materials that contain sulfur, e.g., the generation of
taining water stream, the sulfur in SO2 and H2S is con- electricity from coal, oil, or gas that contains sulfur [1–4].
verted into elemental sulfur and floated in the washed Directly combusting coal gives rise to not only SO2, but
solution pool, which can be filtered out. also dust and heavy metal pollutant. One of the main aims
Here, the pilot test results of the aqueous phase ambient in oil refinery is to remove the sulfur in the crude oil and
temperature sulfur recovery process has been described and convert it into sulfur powder, which is a solid matter. In-
analyzed. The system converted more than 1000 ppm of deed, sulfur recovery process is becoming increasingly
H2S and 500–600 ppm of SO2 in the flue gas into elemental important with the increase of total fossil fuel consumption,
sulfur in aqueous phase at temperature below 100 °C. The thus a cleaner way to make use of fossil fuel and more
flue gas was washed with our acid aqueous media, and the effective way to recover sulfur are urgently needed.
sulfur is formed in the aqueous acid catalyst solution and For example, to make use of coal or bunker oil in a
cleaner and more economical way, gasification has been
developed and used worldwide, which converts the solid
& Tiancun Xiao fuel or the high viscose bunker oil into syngas and the
[email protected]; organic sulfur in it to H2S [5–10]. The H2S gas is highly
http://www.boxenergytech.com toxic and often converted into elemental sulfur through the
1 process on an industrial scale, referred as the Claus process
Guangzhou Boxenergytech Ltd, D-102 International Business
Incubator, Guangzhou Development Zone, Guangzhou, [11–16]. The acid gas stream, consisting mostly of
People’s Republic of China hydrogen sulfide, together with a controlled stoichiometric
2
Inorganic Chemistry Laboratory, Oxford University, South quantity of air is then fed to a furnace so that one-third of
Parks Road, Oxford OX1 3QR, UK the hydrogen sulfide is burned to sulfur dioxide. The

123
208 Appl Petrochem Res (2015) 5:207–213

hydrogen sulfide and sulfur dioxide are next reacted to- must be removed from the flue gas before it is emitted to air.
gether at elevated temperature in the gas phase to generate The removal of SO2 from flue gas is often through the lime
elemental sulfur and a tail gas [12–15, 17, 18]. The ele- water or dry lime powder treatment of the flue gas, the SO2
mental sulfur is then recovered for sale or disposal and the is converted into calcium sulfate, e.g., gypsum. Figure 1
tail gas either vented or subject to further treatment. gives a typical configuration of desulfurization of flue gas,
Meanwhile, the infrastructure of coal gasification plant where the lime water is spayed to the up-flowing flue gas,
often requires a power plant and steam boiler to provide and the sulfur dioxide reacts with the lime in the lime water
electricity and steam, where almost half amount of the to give calcium sulfate, the gypsum precipitation.
gasified coal is combusted; therefore SO2 is generated and It is known that the Claus process is mainly based on the
reaction of H2S with SO2 to give sulfur powder and water,
which can be expressed by the following chemical reaction:
2H2 S = = = 2H2 O + 3S ð1Þ
H2 S2 O5 + 4H2 S = = = 6S + 3H2 O ð2Þ
H2 SO3 + 2H2 S = = = 3S + 3H2 O ð3Þ
In a heavy oil, petroleum coke, or coal gasification plant,
there are H2S separated from the gasified gas stream [19–
24], and also SO2 from the flue gas from coal combustion
for power generation. Therefore, it is possible to make use
of H2S to react with SO2 without burning the H2S to
generate SO2. However, so far, there has been no such kind
of study. In this work, we firstly introduced the separated
H2S gas into the flue, and replaced the lime water with an
aqueous catalyst system to wash the flue gas containing
H2S, a complete sulfur removal and also sulfur powder
recovery process has been developed.

The process principle consideration

The flue gas stream containing SO2 is mixed with the H2S
Fig. 1 The schematic setup of the flue gas desulfurization, adopted from:
http://en.wikipedia.org/wiki/Flue-gas_desulfurization#mediaviewer/
feeding gas separated from the syngas stream, which
File:Flue_gas_desulfurization_unit_EN.svg should be fully mixed in the flue gas stream. The two

Fig. 2 The relationship

between redox potential (E) and
pH of hydrogen sulfide and
sulfur dioxide in liquid phase
under the condition of room
temperature (25 °C) and normal
pressure. This is calculated
according to the thermodynamic
method, as shown in http://
www.slideshare.net/
RafaelArdila1/atlas-eh-ph

123
Appl Petrochem Res (2015) 5:207–213 209

reactants would interact with the aqueous catalyst con- potential decreases with the increase of pH, which is
taining liquid media, and the sulfur dioxide would form preferably below 7.0 for the high Eh.
various species such as S2O52- or HSO3- which would
further react with H2S to give elemental sulfur, as shown in
reactions of 2 and 3. Experimental
As shown in Fig. 2, the redox potential of H2S reaction
with SO2 in the aqueous system to give sulfur occurs at the The sulfur recovery experimental was carried out in a lab scale
pH of 0–10, and the sulfur content gradually disappears micro-reactor system; the image of the setup is shown in Fig. 3.
with the increase of pH. However, to contain both SO2 and The system can operate at temperature from room tem-
H2S in the aqueous system, the redox potential range perature to 200 °C and the pressure can range from 1 to 20
should be from 0.2 to 0.5. As we know, Eh is a measure of bars. The gas flow is controlled by gas flowing meter. The
the redox (oxidation–reduction) state of a solution. As SO2 content in N2 or mimic flue gas is about 200–1000 ppm,
shown in Fig. 2, the drive for the elemental sulfur forma- and the H2S is fed separately from another gas stream, which
tion is 0.3–0.5 V in the reaction system, and the redox is controlled to be 1.8–2.2 times (vol.) of the SO2. The re-
action pressure is often carried out at ambient pressure.
SO and SO2 and
2
H S in H2S in
2
The chemicals and analysis system

All the chemicals are industrial grade and supplied by

Guangzhou Xinhe Standard Gas Company and China
National Chemical Agent Company. Sulfur compounds in
the gas stream are analyzed using temperature programmed
gas chromatographic procedure employing a fused silica
capillary column connected to a flame photometric detector
(FPD). The FPD has a high selectivity to sulfur compounds
compared to other non-sulfur gases. The sample collection
PLC loop was connected micro sampling valve which was
Control
plumbed into the carrier gas line.
Reactor 1 Reactor 2 Spare The contents of the loop were transferred to the head of
Reactor
the capillary column where the sulfur compounds were
Fig. 3 The setup of the ambient temperature aqueous phase sulfur focused in a narrow band, cryogenically. The detection
recovery test system limit with this system was approximately 1 ppm (wt.) S.

Fig. 4 Schematic setup of the

industrial process of the
aqueous phase sulfur recovery
system—the desulfurization
unit, where the reaction of SO2
and H2S occurs at three stages
with acid aqueous catalyst
washing media

123
210 Appl Petrochem Res (2015) 5:207–213

Characterization of the sulfur powder converts into elemental sulfur when passing through from
the tower bottom to tower top.
The crystalline structure and phase component of the re- After the desulfurization unit, the gas enters the washing
sulting sulfur powder were determined using X-ray tank from the top of the tower, the washing process can
diffraction with a Philips X’ PeRT Pro Alpha 1 diffrac- absorb the left residual H2S and SO2 into the liquid phase
tometer with Cu Ka radiation (k = 1.5406Å) operated at a so as to ensure this process can achieve deep desulfuriza-
tube current of 40 mA and a voltage of 40 kV. Data were tion. Thereby the clean gas is obtained. Moreover, the
collected over 2h values from 20° to 70°, at a scan speed of mixed liquor of desulfurizing reaction tower enriches
2° min-1. The Laser Raman spectra of the sulfur sample the elemental sulfur constantly and is discharged from the
were recorded using a Perkin Elmer 400F Ramanstation tower bottom to some extent. Then it is transferred to the
Raman spectrometer, with the sulfur powder. filtration system by the sulfur rich liquid bump (P-101).
The filtering system includes double bag filter (F-101A/
B), poor liquid buffer tank (V-102) and pneumatic di-
Industrial operation flow diagram and operation aphragm additive pump (P-104). The elemental sulfur is
unit separated and the liquid is recycled after the rich liquid
sulfur getting through the double bag filter. The filtrate will
The technological process of the liquid-phase desulfuriza- enter the poor liquid buffer tank. The mixed liquor con-
tion process is showed in Figs. 4 and 5. The whole aqueous taining soluble catalyst is replenished by pneumatic di-
phase sulfur recovery technology composes of desul- aphragm additive pump. The filter liquor after sulfuric acid
furization unit (Fig. 4) and filtering unit (Fig. 5). catalyst top-up will re-enter the desulfurizing reaction
The desulfurization system mainly includes desulfuriz- tower by using the sulfur-poor liquid pump and re-used in a
ing reaction tower (T-101) and washing tower (V-101). closed loop.
After passing the supercharger (C-101), the gas containing By using this liquid-phase desulfurization process at
H2S and flue gas from outside of the device enters the room temperature under atmospheric pressure, we achieved
tower from the bottom of the desulfurizing reaction tower. deep desulfurization in the gas that containing H2S and SO2
At same time, the mixed liquor containing sulfuric acid in the flue gas and the sulfur concentration in tail gas is
catalyst enters the tower from the top of the tower. The gas reduced to\50 ppm, this is due to that the low temperature
and the liquid contact adequately, then the H2S will be operation overcomes the thermodynamic restricts of the
absorbed and then react with SO2 in the flue gas stream in reaction 1, which is strong exothermic reaction, the DH is
the acid catalyst system. Elemental sulfur is generated 233.6 kJ/mol of SO2. Thus aqueous phase operation can
along with the reaction. All the H2S gas almost completely help the heat transfer and control the reaction to occur at

Fig. 5 The schematic diagram

of the sulfur powder filtration
unit

123
Appl Petrochem Res (2015) 5:207–213 211

low temperature. It also produces highly pure elemental flue gas temperature was about 200–300 °C and the acid
sulfur powder, which contains little insoluble impurities catalyst solution media was sprayed to the up-flow gas at
like alumina or iron or the embedded hydrogen sulfide gas, three stages and the sulfur rich solution temperature can be
in contrast to the high temperature Claus process [12, 17]. up to 70 °C.
This sulfur powder product is valuable for chemical and The change of the total sulfur concentration with the
agricultural use. time on stream is shown in Fig. 6. The excess of SO2 in the
gas stream is to ensure the complete conversion of H2S.
There was no H2S detected in the exit gas stream. As
Industrial side stream test results shown in Fig. 6, the total sulfur removal ratio varied from
98 to 100 %, but the overall average sulfur removal ratio is
A side stream test of the aqueous phase ambient tem- more than 99.6 %, and the exit sulfur content varied from
perature sulfur recovery technology has been set up in 10 to 600 ppm, which may be due to the adsorption–des-
Gansu Huating Coal Conversion Company according to the orption in the sulfur saturated washing liquid. The overall
design shown in Figs. 4 and 5. The flue gas was from the average exit sulfur content as SO2 is about 150–170 weight
steam boiler, containing 500–520 ppm of sulfur after dust ppm, which can meet the emission regulations. The system
removal. The diverted gas flowing rate to the reactor was tends to be stable with the time on stream and after 160 h
60 nM3/h, and H2S separated from the gasified gas stream of time on stream, the sulfur removal efficiency and also
has purity of 60–80 vol % balanced with N2, which was fed the exit sulfur concentration all stable, not decay in the
into the flue gas at H2S:SO2 volume ratio of 1.8–2.1:1. The 160 h operation.
Sulfur often easily forms colloid in water solution, and
1000 100
the separation of sulfur from water is difficult in many
cases. To develop the way to separate the sulfur from the
sulfur gas concentration (ppm)

99 aqueous phase catalyst system, we have taken 1000 ml of

Total sulfur removal rate %

800
the sulfur rich catalyst solution and left it in the beaker
exit gas content 98 statically in air (as shown in Fig. 7). It is shown that after
600 average exit gas concentration
total sulfur removal rate 1 h placement, the sulfur powder settle down to the bottom
average sulfur removal rate 97 of the beaker, which can be separated easily through de-
400 canting the top water layer. This suggests that the sulfur
96
could be easily filtered from the aqueous phase catalyst
200 system. This also lays the foundation for the elemental
95
sulfur filtration technology development.
0 94
The sulfur powders from the aqueous phase catalyst
0 20 40 60 80 100 120 140 160 system and also from the high temperature Claus process
Time on stream (h) have been collected and characterized using laser Raman,
the results are shown in Fig. 8. It is shown that there are
Fig. 6 The sulfur removal efficiency with the time on stream in the four main distinct Raman bands seen in all the samples,
flue gas and H2S conversion, the operation conditions: feeding rate:
Lflue gas = 60 nM3/h, H2S feeding concentration 800–1000 ppm; flue corresponding to the frequencies of 82, 154, 218, and
gas containing 500–520 ppm vol SO2 pressure: R1: 0.14 MPa 474 cm-1. The bands at the frequencies 82, 154, 218, and

Fig. 7 The images of the sulfur

containing aqueous catalyst
media and after settling down;
a the as-received sulfur-catalyst
liquid solution, b after 1 h
setting down

123
212 Appl Petrochem Res (2015) 5:207–213

Acknowledgments We would like to thank Huating Coal Conver-

sion Plant for their help in running the side stream test of the tech-
nology in their plant. Great thanks are due to Guangdong Provincial
Science Parks Hi-Tech Program (Project No: 2012B010900045).

Open Access This article is distributed under the terms of the

Creative Commons Attribution 4.0 International License (http://
creativecommons.org/licenses/by/4.0/), which permits unrestricted
use, distribution, and reproduction in any medium, provided you give
appropriate credit to the original author(s) and the source, provide a
link to the Creative Commons license, and indicate if changes were
made.

Fig. 8 Laser Raman spectra of the recovered sulfur products from

References
various sulfur recovering technologies
1. Nuhu AA (2013) Bio-catalytic desulfurization of fossil fuels: a
mini review. Rev Environ Sci Bio/Technol 12(1):9–23
474 cm-1 correspond to the internal modes of the crown- 2. Shah SN (2014) Sulfur compounds significance in fossil fuels and
like S8 ring and we ascribed them to the E2 torsion mode, their impact on the environment. Adv Chem Res 22:203–216
E2 bond-bending mode, A1, bond-bending mode and A1, 3. Srinivasan T et al (2014) Environment threat: impact on acid rain
formation on soil. Pollut Res 33(1):191–193
bond-stretching mode of the S8 ring, respectively [25, 26].
4. Yuan X et al (2013) Strategic route map of sulfur dioxide re-
The strongest Raman band at 480 cm-1 has two shoulders. duction in China. Energy Policy 60:844–851
The shoulder on the low-frequency side of the band is 5. Anderson GL, Hill AH, Fleming DK (1979) Environmental
assigned to the E2 bond-stretching mode of S8. quality and energy conservation in coal conversion processes.
Energy Environ 6:346–353
The Raman bands of the sulfur from the aqueous phase
6. Netzer D (1979) Fuel gas by Fluor-combination coal gasification.
ambient temperature system are identical to the Raman Coal Technol (Houston) 2nd(3):93–111
spectrum of the sulfur from high temperature Claus pro- 7. Stasa FL, Osterle F (1981) The thermodynamic performance of
cess, suggesting that the sulfur has similar structure. No two combined cycle power plants integrated with two coal
gasification systems. J Eng Power 103(3):572–581
other Raman bands are seen in the sulfur sample from
8. Fermoso J et al (2010) Co-gasification of different rank coals with
aqueous catalyst system, suggesting its surface has no biomass and petroleum coke in a high-pressure reactor for H2-
Laser Raman detectable impurities. rich gas production. Bioresour Technol 101(9):3230–3235
9. Marin-Sanchez JE, Rodriguez-Toral MA (2011) Model for
gasification of residual fuels from petroleum refineries using the
equation oriented (EO) approach. Ind Eng Chem Res
Conclusion 50(5):2628–2640
10. Murthy BN et al (2014) Petroleum coke gasification: a review.
1. Aqueous phase ambient temperature sulfur recovery Can J Chem Eng 92(3):441–468
11. Barnhart JH (1978) Energy analysis of a Claus plant. Chem Eng
has been developed and tested in side stream of a coal
Prog 74(5):58–59
gasification plant; it can convert H2S from the gasified 12. George ZM (1978) Poisoning and regeneration of Claus alumina
syngas and SO2 in the flue gas into sulfur powder catalysts. Can J Chem Eng 56(6):711–715
through a 3-stage acid solution washing techniques. 13. Hicks M (1999) Improved Claus SRU control and emissions
tracking using PLC control. In: Proc—Laurance Reid gas cond
This enables a complete reaction of H2S and SO2 to
conf, pp 199–229
convert into sulfur powder, which makes it possible to 14. Li J, Huang L, He J (2014) The study of the influence of sulfur on
fully recover the sulfur from coal gasification. the catalyst structure in low temperature Claus processes. Adv
2. Aqueous phase reaction helps the heat transfer and Mater Res (Durnten-Zurich, Switz) (Biotechnology, Chemical
and Materials Engineering III) 884–885:182–185
enables the reaction to occur at lower temperature
15. Li Q et al (2013) Economics of acid gas injection with com-
(\100 °C). The sulfur formation in the aqueous phase parison to sulfur recovery in China. Energy Procedia
has big aggregate, which can easily settle down to the 37:2505–2510
aqueous bottom and can be separated from the catalyst 16. Sinha S et al (2014) Toluene destruction in the Claus process by
sulfur dioxide: a reaction kinetics study. Ind Eng Chem Res
through filtration.
53(42):16293–16308
3. The recovered sulfur has high purity and similar purity 17. McHugh T, Luinstra E (1998) The Claus sulfur recovery process.
as the one from high temperature Claus process. The Int J Hydrocarbon Eng 3(9):47–48 (50–52)
simultaneously removing H2S and SO2 from the gas 18. Savin S et al (1998) New developments in sulfur recovery process
technology. Int J Hydrocarbon Eng 3(4):54–56
streams makes it possible to purify the flue gas and
19. Alexander SR, Winnick J (1994) Electrochemical polishing of
H2S process gases in one unit, which would save hydrogen sulfide from coal synthesis gas. J Appl Electrochem
significant capital and operation cost. 24(11):1092–1101

123
Appl Petrochem Res (2015) 5:207–213 213

20. Cormos C-C (2014) Techno-economic and environmental eval- 24. Shannon MS et al (2012) Evaluation of alkylimidazoles as phy-
uations of large scale gasification-based CCS project in Romania. sical solvents for CO2/CH4 separation. Ind Eng Chem Res
Int J Hydrogen Energy 39(1):13–27 51(1):515–522
21. Ma X, Wang X, Song C (2009) ‘‘Molecular basket’’ sorbents for 25. Anderson A, Loh YT (1969) Low temperature Raman spectrum
separation of CO2 and H2S from various gas streams. J Am Chem of rhombic sulfur. Can J Chem 47(6):879–884
Soc 131(16):5777–5783 26. Poborchii VV (1998) Raman spectra of sulfur, selenium or tel-
22. Niswander RH et al (1993) A more energy efficient product for lurium clusters confined in nano-cavities of zeolite A. Solid State
carbon dioxide separation. Sep Sci Technol 28(1–3):565–578 Commun 107(9):513–518
23. Rolker J, Lenormant T, Seiler M (2012) A new chemical system
solution for acid gas removal. Chem Ing Tech 84(6):849–858

123