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Hydrogen sulfide removal in water-based drilling fluid by metal oxide nanoparticle and

ZnO/TiO2 nanocomposite

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2017 Mater. Res. Express 4 075501

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Mater. Res. Express 4 (2017) 075501 https://doi.org/10.1088/2053-1591/aa707b

PAPER

Hydrogen sulfide removal in water-based drilling fluid by metal


oxide nanoparticle and ZnO/TiO2 nanocomposite
RECEIVED
19 December 2016
RE VISED
26 April 2017
ACCEP TED FOR PUBLICATION
M Salehi Morgani1, R Saboori2 and S Sabbaghi2,3
1
2 May 2017 School of Chemical and Petroleum Engineering, Shiraz University, Shiraz, Iran
2
PUBLISHED
Nanotechnology Research Institute, Shiraz University, Shiraz, Iran
3
5 July 2017 Nano Chemical Engineering Department, Shiraz University, Shiraz, Iran
E-mail: Sabbaghi@shirazu.ac.ir

Keywords: hydrogen sulfide, removal, drilling fluid, TiO2 and ZnO nanoparticles, ZnO/TiO2 nanocomposite

Abstract
Advanced approaches to the application of nanomaterials for environmental studies, such as waste-
water treatment and pollution removal/adsorption, have been considered in recent decades. In this
research, hydrogen sulfide removal from water-based drilling fluid by ZnO and TiO2 nanoparticles
and a ZnO/TiO2 nanocomposite was studied experimentally. The ZnO and TiO2 nanoparticles
were synthesized by sedimentation and the sol–gel method. A sol-chemical was employed to
synthesize the ZnO/TiO2 nanocomposite. X-ray diffraction, scanning electron microscopy (SEM),
Brunauer–Emmett–Teller (BET) surface analysis, inductively coupled plasma mass spectrometry
(ICP), dynamic light scattering (DLS) and Fourier transform infrared spectroscopy were used to
characterize the produced ZnO and TiO2 nanoparticles, and the ZnO/TiO2 nanocomposite. The
results showed that the concentration of hydrogen sulfide decreased from 800 ppm to about 250 ppm
(about 70% removal) and less than 150 ppm (more than 80% removal) using the TiO2 and ZnO
nanoparticles with a 0.67 wt% concentration, respectively. Hydrogen sulfide removal using the ZnO/
TiO2 nanocomposite with a 0.67 wt% showed the highest value of removal in comparison with the
TiO2 and ZnO nanoparticles. The hydrogen sulfide level was lowered from 800 ppm to less than
5 ppm (99% removal) by the nanocomposite.

1. Introduction

In the oil industry, drilling fluid is of great importance, and some consider drilling fluid in wells to be like blood
in vessels. Drilling fluid is a smart fluid that is supposed to be able to multi-task (e.g. cooling and lubricating the
drill string and the drill bit, balancing and overcoming formation pressure, cleaning the well, transporting drilled
cuttings and stabilizing well) [1, 2]. So, attempts to make drilling fluid smarter would result in better circumstances
for drilling a well. During drilling operations some interference occurs, such as that caused by formation fluids,
which usually carry corrosive and hazardous components like hydrogen sulfide in both the liquid and gas phase.
Hydrogen sulfide causes a wide range of health problems, environmental issues and metal facility corrosion
[3]. Workers are primarily exposed to hydrogen sulfide by breathing it. The severity of the effects depends on how
much you breathe and for how long. Exposure to very high concentrations can quickly lead to death. As a conse-
quence, rig crew are at risk from this hazardous gas. Due to the fact that H2S gas is present in formations along the
drilling path, it could contribute to a number of tragic disasters. The previous sentences were devoted to clarifying
why we need to be conscious of H2S gas content in the drilling fluid and waste-water produced by rig operation.
Absorption and biological treatment are the main conventional methods for removing H2S in the commercial
process [4]. The absorption method was employed to remove sulfide by using various porous materials such as
activated carbons (ACs) [5], modified ACs [6, 7], activated carbon films [8] and modified clay [9]. The different
advantages and disadvantages of these materials were discussed by Wang et al, and they used mesoporous mat­
erials (e.g. SBA-15) to develop solid catalysts to purify H2S gas [10]. Wu et al explored the role of different forms
of CuOx nanoparticles (Cu, Cu2+, Cu+) in H2S removal at different temperatures and in different atmospheric
conditions [11]. Due to the fact that porosity and the surface of the adsorbents play a significant role in their per-
formance, this has become an interesting route to the utilization of the active phase (e.g. various metal oxides).
© 2017 IOP Publishing Ltd
Mater. Res. Express 4 (2017) 075501 M Salehi Morgani et al

Figure 1.  A flow diagram for the synthesis of a ZnO/TiO2 nanocomposite by the solo-chemical method.

Figure 2.  A schematic of the setup for H2S removal from the drilling fluid.

Because metal oxides such as ZnO and Zn-based sorbents have a high equilibrium constant and thermal stability,
they are attractive materials for removing H2S. Garces et al [12] conducted experiments on commercially avail-
able ZnO at low temperatures (60 °C –400 °C) and found that adsorption capacity increased with temperature,
reaching 87% desulfurization at 400 °C. In another study, a different Zn/Ti-based sorbent was prepared by the
sol–gel method and H2S was separated from the industrial mixture of gases [13]. In another study, the effect of
CdO/polyacrylamide (AM) and vinylacetate (VA) nanocomposites (CdO/AMVA nanocomposites) on scaveng-
ing H2S in the oil industry was discussed by Nassar et al [14]. Graphene/ZnO nanostructured composites formed
in situ were employed to measure the effect on H2S removal by Lonkar et al [15]. Nanocomposites based on cop-
per, zinc and nickel loaded onto activated carbon (Cu–Zn–Ni/AC), and cobalt and nickel nanoparticles loaded
onto γ-alumina (Ni–CO/γAl2O3) were applied to the adsorption of hydrogen sulfide (H2S) from natural gas by
Daneshyar et al [16].
Nanoscale materials have a sufficient active surface, so they are the best candidates for combating the afore-
mentioned issue. Nanomaterials are also able to perform extremely quickly. Evidence for the applications of nano-
structured materials over a wide range of fields and industries is crystal clear, and the strong potential of nanoscale
materials convinced our group to focus on an approach that uses them. A number of nanomaterials have been
used to remove hydrogen sulfide. Wang et al [10] studied the use of SBA-15 and ZnO nanoparticles for removing
H2S from the gas stream, for example.
In this study, the effect of ZnO and TiO2 nanoparticles, and a ZnO/TiO2 nanocomposite on removing the
sulfide from water-based drilling fluid was investigated. The nanoparticles and nanocomposite were synthesized
and characterized by XRD and FTIR analysis. These nanomaterials were added to water-based drilling fluid which
was rich in sulfide content to evaluate their effect on hydrogen sulfide removal. The effects of the nanomaterial
concentration and time on H2S removal from the water-based drilling fluid were also investigated.

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Mater. Res. Express 4 (2017) 075501 M Salehi Morgani et al

Figure 3.  The XRD pattern of the ZnO nanoparticles.

Figure 4.  The XRD pattern of the TiO2 nanoparticles.

2.  Materials and methods

2.1. Materials
Zinc acetate dihydrate (Zn(CH3COO)2 · 2H2O), ammonium hydroxide (NH4OH), titanium(IV) isopropoxide
(TTIP), isopropanol, sodium hydroxide (NaOH), ethanol, methanol, citric acid, hydrochloric acid (HCl, 37%)
and sodium sulfide hydrate (Na2S · H2O) were purchased from Merck Co. The bentonite was supplied by NIOC
Co., and the sulfide reagent 1 and 2 was supplied by the Hach company.

2.2.  Synthesis of ZnO nanoparticles


ZnO nanoparticles were synthesized by the precipitation method. Isopropanol (10 ml) and zinc acetate (0.1 g)
were mixed at 65 °C for 15 min. The mixture was then added to isopropanol (12 ml) in a water bath at 0 °C. The
amount of NaOH (0.05 M) in the water bath (0 °C) was added drop wise into the final solution and stirred. The
produced solution was kept at 65 °C for 5 min. Finally, it was washed with ethanol, methanol and water three times
and then cooled.
2.3.  Synthesis of TiO2 nanoparticles
The TiO2 nanoparticles were synthesized by the sol–gel method. TTIP (2 ml) was added to isopropanol (50 ml) and
stirred for 30 min using a magnetic stirrer. At this stage, diluted HCl was combined with the solution and mixed
for 5 min. The final solution changed into a gel and was aged for 48 h at room temperature. Finally, the dry powder
was calcined at 400 °C.

2.4.  Synthesis of ZnO/TiO2 nanocomposite


The ZnO/TiO2 nanocomposite was synthesized by the solo-chemical method. Zinc sulfite dihydrate (1.5 g) was
mixed to deionized water (30 ml) for 30 min. Ammonium hydroxide solution was added to the solution gradually
while stirring. The color of the solution turned white because of the production of white precipitation by the zinc

3
Mater. Res. Express 4 (2017) 075501 M Salehi Morgani et al

Figure 5.  XRD analysis of the ZnO/TiO2 nanocomposite.

Figure 6.  The FTIR spectrum of (a) the ZnO nanoparticles, (b) the TiO2 nanoparticles and (c) the ZnO/TiO2 nanocomposite.

hydroxide Zn(OH)2. Stirring was then continued until the white color had vanished completely (solution A).
TTIP (2 ml) was mixed with isopropanol (25 ml) and then stirred for 1 h. Diluted citric acid was combined
with the solution and stirred for 2 h (solution B). Solutions A and B were mixed for 1 h using a magnetic stirrer
(1000 rpm), and the final mixture was sonicated in a homogeneous ultrasonic bath for 45 min. The obtained
mixture was brought to room temperature to ensure a precipitated, dried powder and then calcined at 400 °C. The
nanocomposite of ZnO/TiO2 was synthesized, and the flow diagram of nanocomposite preparation is shown in
figure 1. To obtain the ratio of Zn to Ti, ICP mass spectroscopy was used.

2.5.  Drilling fluid preparation and H2S removal


To obtain a drilling fluid, 3 wt% of bentonite was mixed in deionized water using a Hamilton batch mixer (HBM)
for 20 min. Sodium sulfide hydrate (0.35 g/150 ml) was added to the water-based drilling fluid (equivalent to
800 ppm hydrogen sulfide). Then nanoparticles with specific concentrations of 0.1, 0.2, 0.5, 0.75 and 1 g per 150 ml,
were added to the prepared drilling fluid. The solutions were mixed for 10, 20 and 30 min, and finally, the samples
were filtered and centrifuged. The final solution was then prepared to investigate the amount of remaining sulfide.
To measure the residual concentration of sulfide in the solution, a Hach DR-2800 was used. The sulfide reagents 1

4
Mater. Res. Express 4 (2017) 075501 M Salehi Morgani et al

(a)

(b)

(c)

Figure 7.  SEM images of (a) the ZnO nanoparticle, (b) the TiO2 nanoparticle and (c) the ZnO/TiO2 nanocomposite.

Table 1.  BET surface area analysis results.

BJH average pore


Nanoscale scavenger Surface area (m2 g−1) BJH average pore volume (cm3 g−1) diameter (A°)

TiO2 nanoparticles 23.62 0.1269 282.305


ZnO nanoparticles 37.24 0.1327 445.091
ZnO/TiO2 nanocomposite 54.52 0.1412 507.260

and 2 were supplied by Hach Co., and the tests were based on the standard method. A schematic of the H2S removal
from the drilling fluid setup is shown in figure 2.

3. Characterization

To determine the characteristics of the TiO2, the ZnO nanoparticles and the TiO2/ZnO nanocomposite,
x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), inductively coupled plasma mass
spectrometry (ICP), a scanning electron microscope (SEM), Brunauer–Emmett–Teller (BET) surface analysis,
and dynamic light scattering (DLS) were used. The composition blend of the sample was examined via a Unisantis
XMD 300, x-ray diffractometer and systematic Xpert PRO XRD (λ  =  0.178 90 nm). A 2θ confine was used starting
at 30–75 in stages of 0.02 with an enumeration time of 1 s. The FTIR of the nanoparticles and nanocomposite in

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Mater. Res. Express 4 (2017) 075501 M Salehi Morgani et al

Figure 8.  H2S removal (ppm and %) in water-based drilling fluid after (a) 10 min, (b) 20 min and (c) 30 min.

the KBr pellets was recorded on a PerkinElmer FTIR (model: spectrum RXI). To measure the exact ratio of Zn
and Ti, ICP analysis (Varian-Vista Pro) was employed for the ZnO/TiO2 nanocomposite scavenger. To determine
the morphology of the nanomaterials, an SEM was used. To obtain the surface area and pore volume of the
nanomaterials, BET surface analysis (Micromeritics) was used. The average particle size of the nanomaterial was
recorded on a Horiba LB-360 (0.001–6 µm).

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Mater. Res. Express 4 (2017) 075501 M Salehi Morgani et al

Table 2.  A comparison between the performance of the ZnO nanoparticles and the Zn/TiO2 nanocomposite for H2S removal.

Nanoparticle concentration
Time (min) (g/150 ml) Removal by ZnO/TiO2 (%) Removal by ZnO (%) Removal enhancement (%)

10 0.10 47.50 39.00 21.79


0.20 68.87 61.25 12.44
0.50 87.00 73.13 18.96
0.75 96.38 76.25 26.40
1.00 97.50 81.50 19.63

20 0.10 50.50 43.75 15.42


0.20 70.00 61.87 13.14
0.50 88.50 75.25 17.60
0.75 96.62 77.37 24.88
1.00 99.50 83.50 19.16

30 0.10 52.50 44.00 19.32


0.20 69.50 62.50 11.20
0.50 86.12 77.50 11.12
0.75 98.75 78.12 26.40
1.00 99.75 84.75 17.70

Table 3.  Comparison between the performance of the TiO2 nanoparticles and the ZnO/TiO2 nanocomposite for H2S removal.

Nanoparticle concentration
Time (min) (g/150 ml) Removal by ZnO/TiO2 (%) Removal by TiO2 (%) Removal enhancement (%)

10 0.10 47.50 32.50 46.15


0.20 68.87 53.12 29.65
0.50 87.00 60.00 45.00
0.75 96.37 66.50 44.92
1.00 97.50 68.62 42.08

20 0.10 50.50 33.37 51.31


0.20 70.00 54.00 29.63
0.50 88.50 60.37 46.58
0.75 96.62 66.25 45.85
1.00 99.50 69.00 44.20
30 0.10 52.50 35.00 50.00
0.20 69.50 60.00 15.83
0.50 86.12 62.50 37.80
0.75 98.75 66.37 48.78
1.00 99.75 70.37 41.74

4.  Results and discussion

Figures 3–5 depict the XRD patterns of the ZnO and TiO2 nanoparticles and the ZnO/TiO2 nanocomposite in
powdered form, respectively. The diffraction peaks represent the origin of the ZnO nanoparticles, and are 2θ  =  32,
34.5, 36.5, 47.5, 57, 63, 66, 68, 69, 72.5 and 77 for the ZnO nanoparticles in figure 3; 2θ  =  25.5, 37.5, 48, 53 and 55
indicate the TiO2 nanoparticles in figure 4 [17–19]. In figure 5 it is evident that the mentioned peaks present for
the ZnO/TiO2 nanocomposite are 2θ  =  25.5, 29.5, 35.5, 41.5 and 57.
Figure 6 shows an FTIR analysis of the ZnO and TiO2 nanoparticles and the ZnO/TiO2 nanocomposite. An
O–H asymmetrical stretching vibration caused a broad adsorption peak from 3600 cm−1 to 2500 cm−1, which is
due to structural H–O. The peak at 1600 cm−1 is dedicated to the H–OH bending vibration of H2O. C–H stretching
and deformation cause a band between 2980 and 2905 cm−1 [20]. At 1450 cm−1 there seems to be a peak which is
allocated to the C–H bending vibration [21]. A C–O stretching peak is also revealed at 1278 cm−1 [22]. The peaks
at 433 and 536 cm−1 correspond to Zn–O (figure 6(a)) [10, 17, 23–25]. The Ti–O and Ti–O–Ti bond peaks emerge
at 500 and 1000 cm−1 (figures 6(b) and (c)) [26, 27]. The peak at 616 cm−1 corresponds to Ti–Zn (figure 6(c)).
The results of ICP mass spectroscopy show that the percentages of Zn and Ti particles in the ZnO/TiO2 nano-
composite are 37% and 63%, respectively.

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Mater. Res. Express 4 (2017) 075501 M Salehi Morgani et al

SEM images of the ZnO and TiO2 nanoparticles and the ZnO/TiO2 nanocomposite are illustrated in figure 7.
The ZnO and TiO2 nanoparticles and the ZnO/TiO2 nanocomposite shape are spherical. The average particle sizes
of the nanoparticles and nanocomposite are 22 nm, 30 nm and 40 nm for the ZnO and TiO2 nanoparticles and the
ZnO/TiO2 nanocomposite, respectively.
Using the BET method, the surface area of the nanomaterials was measured, and the results of this analysis
are provided in table 1. The highest surface area is for the ZnO/TiO2 nanocomposite. The BET surface area of the
scavenger is 54.52 m2 g−1 and the cumulative volume of the BJH adsorption of the pores is 0.1412 cm3 g−1. The
BET surface area of the ZnO and TiO2 nanoparticles is 37.24 m2 g−1 and 23.62 m2 g−1, respectively.
The removal results are provided in the line graphs, and the effect of the TiO2, the ZnO nanoparticles and the
ZnO/TiO2 nanocomposite in removing the sulfide from the water-based drilling fluid is depicted in figure 8. In
figure 8 it is clear that the removal of H2S is increased by adding ZnO nanoparticles. For instance, the sulfide con-
centration is decreased from 800 ppm to less than 150 ppm with 1 g of the material per 150 ml drilling fluid. This
means that more than 80% of the sulfide has been removed from the drilling fluid. For the TiO2 nanoparticles, the
H2S concentration is decreased from 800 ppm to about 250 ppm (about 70% removal).
It is worth saying that at the same concentration, slightly more H2S is removed by the ZnO nanoparticles in
comparison with the TiO2 nanoparticles. However, the effect of the ZnO/TiO2 nanocomposite is even more con-
siderable. The synthesized nanocomposite causes a noticeable decline in H2S concentration of more than 99%,
which is equivalent to less than 5 ppm by 1 g of the material per 150 ml drilling fluid. This reveals the efficiency of
the ZnO/TiO2 nanocomposite compared to the ZnO and TiO2 nanoparticles, and the difference is illustrated in
figure 8.
The effect of the amount of time in which nanomaterials are in contract with the drilling fluid is surveyed in
figure 8. The results show a marginal improvement in performance to a maximum of 2%. This is due to the fact
that most of the removal occurs in the first 10 min of the performance because of the high specific surface area of
nanoscale materials.
In table 2, a comparison of H2S removal between the ZnO nanoparticles and ZnO/TiO2 nanocomposite is
represented. On average, the percentage of sulfide removal is enhanced by about 18% in the same nanomaterial
concentrations. This trend is also reported in table 3, which shows a comparison between the TiO2 nanoparticles
and the ZnO/TiO2 nanocomposite. The productivity refinement of the ZnO/TiO2 nanocomposite is shown to be
more than 40% on average. As reported in the BET results (table 1), the reason that the ZnO/TiO2 nanocomposite
has the highest H2S removal efficiency of all the scavengers is related to its high surface area.

5. Conclusion

In this work, ZnO and TiO2 nanoparticles and a ZnO/TiO2 nanocomposite were synthesized and characterized by
XRD and FTIR. The synthesized nanomaterials were added to the water-based drilling fluid and hydrogen sulfide
removal was investigated. The results indicate that:

• Hydrogen sulfide decreased from 800 ppm to about 250 ppm (about 70%) using TiO2 nanoparticles with a
0.67 wt% (1 g/150 ml) concentration.
• Hydrogen sulfide decreased from 800 ppm to less than 150 ppm (more than 80%) using ZnO nanoparticles
with 0.67 wt% concentration.
• Hydrogen sulfide using the ZnO/TiO2 nanocomposite showed the highest value of removal in comparison
with the TiO2 and ZnO nanoparticles.
• The hydrogen sulfide decreased from 800 ppm to less than 5 ppm (99%) using the ZnO/TiO2 nanocomposite.

Acknowledgments

Special thanks to the Drilling NanoFluid Laboratory, Faculty of Advanced Technologies, Shiraz University for
providing equipment for the research.

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