Advances in Materials Science and Engineering
Volume 2018 (2018), Article ID 5306825, 7 pages
https://doi.org/10.1155/2018/5306825

Research Article

Use of Nanostructured Layered Double Hydroxides as Nanofilters in the Removal of Fe²⁺ and Ca²⁺ Ions from Oil Wells

Emmanuel K. Ephraim,¹ Chinyere A. Anyama,¹ Ayi A. Ayi,1,2 and Jude C. Onwuka²

¹Inorganic Materials Research Laboratory, Department of Pure and Applied Chemistry, University of Calabar, P.M.B. 1115 Calabar, Nigeria
²Department of Chemistry, Federal University Lafia, Lafia, Nasarawa, Nigeria

Correspondence should be addressed to Ayi A. Ayi; ayiayi72@gmail.com

Received 1 February 2018; Accepted 2 April 2018; Published 24 April 2018

Academic Editor: Luca De Stefano

Copyright © 2018 Emmanuel K. Ephraim et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

Four new metal-aluminum layered double hydroxides (LDHs), Mg-Al(OH)₂PO₄ (1), Mg-Al(OH)₂PO₄PF₆ (2), Ca-Al(OH)₂SO₄ (3), and Ca-Al(OH)₂PO₄PF₆ (4), were prepared by the coprecipitation method followed by mild hydrothermal processing at 60°C. Mg²⁺ and Ca²⁺ in solution with Al³⁺ were titrated with NaOH over 3–5 h to yield Mg-Al and Ca-Al layered double hydroxides, respectively, incorporating PO₄³⁻, PO₄³⁻PF₆⁻, and SO₄²⁻ anions in the interlamellar spaces. The isolated compounds were characterized with the help of XRD, IR, and SEM/EDAX, and their ability to remove scale-forming ions from the aqueous system was studied with the help of atomic absorption spectroscopy (AAS). The SEM micrographs of Mg-O-Al-OH and Ca-O-Al-OH layers intercalated with PO₄³⁻ and/or [PO₄PF₆]⁴⁻ anions are similar consisting of uniform nanospheres with an average size of 100 nm, while the M-O-Al-OH layer of compound 3, intercalated with SO₄²⁻ anions, consists of hexagonal nanoplate crystals. In the infrared spectra, the characteristic absorption band for water molecules was observed in all the compounds. The XRD pattern showed that d₀₁₂ and d₁₀₄ peaks of M-Al-PO₄ LDHs corresponding to interplanar spacing of 3.4804 and 2.5504 Å, respectively, shifted to higher 2θ values for the M-Al-PO₄PF₆ system, which indicates a decrease in the interlamellar spacing as PF₆⁻ was incorporated along with PO₄³⁻ anion. The XRD pattern for Ca-Al-SO₄ LDHs was quite different, showing the presence of low-angle peaks at 2θ = 11.68 and 14.72°. The results of the column adsorption studies showed that there was a significant removal of Ca²⁺ by all the compounds under investigation with an efficiency of 84–99%. However, compounds 1 and 2 remove Fe²⁺ effectively with the efficiency of 98.73 and 99.77%, respectively; compounds 3 and 4 were shown to have little or no effect.

1. Introduction

Recently, it has been reported that as gas and oil production progresses, in many oil fields, the ratio of produced brine water to hydrocarbon often increases. These brines are corrosive and tend to produce calcite or sulphate scales [1, 2]. Scaling, which stems from supersaturation of mineral ions in the process fluid, is the deposition of a mineral salt on processing equipment. A natural gas well will, besides producing natural gas, also produce water and carbon dioxide (CO₂). The produced water can come from two sources: water vapor in the gas that condenses into liquid water and formation water containing salts [3]. This water is the source of hydrate formation, and in combination with CO₂, it forms a weak carbonic acid (H₂CO₃), as shown in (1). Scaling is caused by salts and can occur when the produced water contains formation water [4]:

This carbonic acid will continue to dissociate hydrogen, creating new deprotonated species of carbonic acid, as seen in the following equation:

In the water mixture, there will be a mixture of , , and . Finally, in the presence of calcium and carbonic acid, calcium carbonate will precipitate out [5, 6]:

The composition of the formation water varies greatly with the reservoirs, but the usual constituents are Na⁺, Ca²⁺, K⁺, Mg²⁺, Fe²⁺, Cl⁻, SO₄²⁻, and HCO₃⁻. Long pipelines are constructed of carbon steel [6]. Carbonic acid will corrode the iron in the pipeline wall, producing iron carbonate. This iron carbonate can precipitate in the production fluid and follow the gas and liquid flow, causing problems downstream:

The formation of scale blockage inside oil wells constricts the flow of geothermal fluids in these wells thus significantly reducing their output [7]. Furthermore, fresh water and marine sediments are contaminated by oil spills along with urban runoffs and industrial and domestic effluents. This poses a serious concern as the presence of contaminants affects aquatic organisms. Inorganic nanomaterials with well-defined cavities and surfaces have great potential for remediating today’s environmental and industrial problems [8]. Nanostructured layered double hydroxides (LDHs) are promising materials in wastewater treatment due to their ability to capture organic and inorganic anions [9, 10]. Layered double hydroxides (LDHs) are a class of anionic clays with the structure based on brucite- (Mg(OH)₂−) like layers [11–15]. The lattice structure of LDHs, with the general formula [M²⁺1–xM³⁺x(OH)₂]x+(An–)x/n·yH₂O, has a positively charged brucite-shaped layers, consisting of a divalent metal ion M²⁺ (e.g., Ca²⁺, Zn²⁺, Mg²⁺, and Ni²⁺) octahedrally surrounded by six OH⁻ hydroxyl groups [16–18]. The substitution of the M²⁺ metal with a trivalent M³⁺ cation gives rise to the periodic repetition of positively charged sheets (lamellas) alternating with charge-counter balancing An– ions. These LDHs have found widespread applications in diverse areas as sensors [19, 20], adsorbents in wastewater treatment [21–23], catalytic removal of soot and NOx in vehicle engine exhausts [10], and as drug and gene carriers [24–26].

During the course of our investigation of LDHs as a scale inhibitor, we were interested in using Mg and Ca as divalent metal ions to prepare Mg-Al- and Ca-Al layered double hydroxides intercalated with PO₄³⁻, PO₄³⁻/PF₆⁻, and SO₄²⁻ anions, and we have been successful in synthesizing four new LDHs with nanostructures, namely, Mg-Al(OH)₂PO₄ (1), Mg-Al(OH)₂PO₄PF₆ (2), Ca-Al(OH)₂SO₄ (3), and Ca-Al(OH)₂PO₄PF₆ (4). In this work, the synthesized LDH nanostructures are being investigated as nanofiltration materials to remove scale forming ions like Fe²⁺ and Ca²⁺. The synthesis, characterization, and adsorption properties of these four new compounds have been reported.

2. Materials and Methods

2.1. Materials

Orthophosphoric acid (H₃PO₄), magnesium nitrate (Mg(NO₃)₂), aluminum sulphate (Al₂(SO₄)₃), sodium hydroxide (NaOH), sulphuric acid (H₂SO₄), aluminum hydroxide (Al(OH)₃), calcium nitrate tetrahydrate (Ca(NO₃)₂·4H₂O), and 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF₆) were used. Analytical grades of all the chemicals were obtained from commercial sources and used without further purification.

2.2. Methods

The standard procedure of coprecipitating a divalent with trivalent metal ions in the presence of a base was followed in the present studies [27–30]. The coprecipitation was carried out at room temperature, and the gel was continuously and magnetically stirred. The mixture was kept under magnetic stirring for 3 h. The precipitate was heated in the mother liquor for 18 h at 60°C, and then it was washed with distilled water and separated by centrifugation. The resulting material was dried overnight at 70°C in the incubator. For compound 1, orthophoshoric acid was used as the source of the PO₄³⁻ anion. For compounds 2 and 4, 1-ethyl-3-methylimidazolium hexafluorophosphate and orthophosphoric acid were used to introduce PF₆⁻ and PO₄³⁻ anions, respectively. For compound 3, the source of the SO₄²⁻ anion was H₂SO₄. In a typical synthesis of 1, a 250 mL solution containing Mg(NO₃)₂ (0.0375 mmol), Al(OH)₃ (0.0125 mmol) (with the Mg-Al ratio of 3 : 1), and H₃PO₄ (0.5 mmol) was added dropwise from burette into a 15 mL solution of NaOH (2 M) under constant stirring at room temperature for 3 h. The mixture with a pH of 10 was heated at 60°C for 18 h, and the resulting slurry was collected via centrifugation (10 min, 500 min⁻¹). The product was washed thrice with deionized water before drying. A similar procedure was used for compounds 2–4, the difference being in the metal and SO₄²⁻ ions for compounds 3 and 4.

2.3. Characterization

The samples were analyzed by the Rigaku MiniFlex II X-ray diffractometer using monochromatic Cu κα radiation (λ = 0.1541 nm) at the speed of 3 s in 2θ range between 5 and 75° and step size of 0.03°.

The scanning electron microscopy (SEM) studies of the LDHs were made with a field emission electron microscope (FESEM JSM-6700 F), coupled with an energy dispersion analyzer (EDX). The specimens were Au coated (sputtering) to make them conductive. The SEM acceleration voltage was 10 kV.

The Fourier transform infrared (FTIR) spectra for the synthesized LDHs were recorded over the wave number range of 400–4000 cm⁻¹ using the Perkin Elmer FTIR spectrometer. The powdered samples were mixed with KBr (in a 1 : 200 ratio of their weight) and pressed in the form of pellets for measurement.

2.4. Adsorption Column Experiments

Aqueous solutions of Fe²⁺ and Ca²⁺ prepared from their salts FeSO₄·7H₂O and CaCl₂, respectively, were analyzed by atomic absorption spectroscopy. The column was set up by packing 5 g of LDHs in 20 mL syringes, and the metal ion solution was poured through the packed samples as filter (Scheme 1). The metal ion solutions were collected at the outlet of the LDH column, and the eluded portion (i.e., the filtrate) was also analyzed by AAS. The degree of surface covered (θ) by the ions was computed using the following equation:

Scheme 1: The experimental setup for the column adsorption studies.

The effectiveness of the LDHs as adsorbent was calculated with the help of the following equation:

where is the partition coefficient, is the concentration of Fe²⁺ or Ca²⁺ ions in solution, and is the concentration of the ions adsorbed in the LDHs.

The removal efficiency of Fe²⁺ and Ca²⁺ by the LDHs in percentage was calculated using the following equation:

where is the initial concentration of the ions and is the concentration of the ions adsorbed in LDHs.

3. Results and Discussion

All the metal-aluminum layered double hydroxides were prepared by the coprecipitation method followed by mild hydrothermal treatment at 60°C. Divalent metal ions (Mg and Ca) in solution with Al³⁺ titrated with NaOH over 3–5 h yielded Mg-Al and Ca-Al layered double hydroxides, respectively. In the present studies, SO₄²⁻, PO₄³⁻, and PF₆⁻ anions were used in the interlamellar space to balance the layer positive charge. The conditions chosen for the synthesis provided an aqueous solution of Al³⁺ and M²⁺ (molar fraction Al³⁺/(Al³⁺ + M²⁺) = 0.25 and M²⁺/Al³⁺ = 3 molar ratio), prepared by dissolving metal salts in distilled water to give M²⁺-Al-LDH with x = 0.25 (i.e., the composition is more likely represented by M²⁺0.75Al0.25(OH)₂An−x/n·yH₂O. Where x/n for PO₄³⁻, [PO₄PF₆]⁴⁻, and SO₄²⁻).

Figure 1 shows the FTIR spectra of the isolated layered double hydroxides. The characteristic absorption band for the water molecules was observed in all the compounds. The band observed in the region 3402–3455 cm⁻¹ corresponds to the OH stretching vibration, while the band at 1640 cm⁻¹ is attributed to the bending mode of the lattice water. The stretching vibrational modes of PO₄³⁻ or SO₄²⁻ units were observed in the region 1057–1130 cm⁻¹. The bands in the region 600–430 cm⁻¹ are attributable to the M–O vibrations. The various assignments are in good agreement with similar compounds in the literature [29–36].

Figure 1: FTIR spectra of the as-synthesized layered double hydroxides: (a) Mg-Al(OH)₂PO₄ (1), (b) Mg-Al(OH)₂PO₄PF₆ (2), (c) Ca-Al(OH)₂SO₄ (3), and (d) Ca-Al(OH)₂PO₄PF₆ (4).

Figure 2 shows the representative XRD patterns of the M-Al-LDHs. The X-ray powder diffraction lines of Mg-Al(OH)₂PO₄ (1) were preliminarily indexed in the rhombohedral system space group R-3c (167) with the unit cell data: a = b = 4.7602 and c = 12.9930 Å (Ref. Code = 01-075-1862). The d₀₁₂ and d₁₀₄ peaks of M-Al-PO₄-LDHs corresponding to interplanar spacing of 3.4804 and 2.5504 Å, respectively, shifted to higher 2θ angles for Mg-Al(OH)₂PO₄PF₆ (2), which indicates a decrease in the interlamellar spacing as PF₆⁻ was incorporated along with PO₄³⁻ anion. The XRD pattern for Ca-Al(OH)₂SO₄ (3) was quite different, showing the presence of low-angle peaks at 2θ = 11.68 and 14.72°, which are indicative of carbonate anions being incorporated into the interlamellar space of LDH. The presence of the carbonate is due to the fact that the synthesis was carried out in air at a pH value of 10. The result obtained is in agreement with similar compounds in the literature [28–30, 36]. Compound 3 crystallizes in monoclinic space group (Ref. Code = 00-047-0964) with the following cell parameters: a = 12.6700, b = 6.9270, and c = 12.0280 Å and volume = 1055.63 Å³. The d₁₁₀ peak has a d-spacing of 6.027 Å, whereas the d-spacing for the d₀₁₃ and d₀₀₄ peaks are 4.474 and 3.005 Å, respectively.

Figure 2: XRD pattern of as-synthesized compounds: (a) Mg-Al(OH)₂PO₄ (1), (b) Mg-Al(OH)₂PO₄PF₆ (2), (c) Ca-Al(OH)₂SO₄ (3), and (d) Ca-Al(OH)₂PO₄PF₆ (4).

The surface structure and morphology of the metal-aluminum LDHs were studied with the help of scanning electron microscope (SEM). The representative SEM images of the as-synthesized layered double hydroxides are presented in Figure 3. The representative SEM micrographs of Mg-O-Al-OH and Ca-O-Al-OH layers intercalated with PO₄³⁻ and/or [PO₄PF₆]⁴⁻ anions are similar consisting of uniform nanospheres of M-Al layered double hydroxides, while the Ca-O-Al-OH layer of compound 3, intercalated with SO₄²⁻ anions, consists of hexagonal nanoplates.

(a)

(b)

(c)

(d)

Figure 3: SEM images of as-synthesized compounds: (a) Mg-Al(OH)₂PO₄ (1), (b) Mg-Al(OH)₂PO₄PF₆ (2), (c) Ca-Al(OH)₂SO₄ (3), and (d) Ca-Al(OH)₂PO₄PF₆ (4).

The adsorption efficiency of the LDHs in the removal of Fe²⁺ and Ca²⁺ scale-forming ions from aqueous solutions is presented in Tables 1 and 2, respectively. The analyses of the results are shown in Figure 4. The results present in Table 1 show that there was a significant removal of Fe²⁺ by compounds 1 and 2 with the efficiency of 98.73 and 99.77%, respectively, while compounds 3 and 4 have little or no effect in removing Fe²⁺. The reduction in the adsorption efficiency of compound 3 for Fe²⁺ is due to the presence of SO₄²⁻ in the interlamellar space. The literature reports have shown that the presence of SO₄²⁻ in the interlamellar space reduces the adsorption efficiency. When both SO₄²⁻ and CO₃²⁻ coexist, they had a significant effect upon the adsorption efficiency [31]. It has also been demonstrated that the interlayer CO₃²⁻ ions in LDHs are difficult to be exchanged by other anions [32–37]. Furthermore, the reduction in the removal efficiency of Fe²⁺ by compounds 3 and 4 can be attributed to the larger size of Ca²⁺ (100 pm) over Mg²⁺ (72 pm), in addition to the plate-like morphology of 3 with 1 m average size. The results for Ca²⁺ removal present in Table 2 and Figure 4 show that all the synthesized LDHs under investigation were effective in the cleanup with 84–99% removal efficiency. The effectiveness of compound 3 in removing Ca²⁺ is attributed to its affinity for both SO₄²⁻ and CO₃²⁻ anions, which are both intercalated in the interlamellar space.

Table 1: Results of the adsorption study of Fe²⁺.

LDHs
Actual amount, (ppm)
Eluded amount, (ppm)
Absorbed amount, (ppm)
Degree of surface coverage, θ
Distribution partition coefficient,
Absorption efficiency (%)

1
9.8526
0.1247
9.7279
0.99
1.01
98.73

2
9.8526
0.0222
9.8304
1.00
1.00
99.77

3
9.8526
8.0994
1.7532
0.18
5.62
17.79

4
9.8526
7.1938
2.6588
0.27
3.71
26.99

Table 2: Results of the adsorption study of Ca²⁺.

LDHs
Actual amount, (ppm)
Eluded amount, (ppm)
Absorbed amount, (ppm)
Degree of surface coverage, θ
Distribution partition coefficient,
Absorption efficiency (%)

1
7.7780
0.7165
7.7064
0.99
1.01
99.08

2
7.7780
0.7563
7.0217
0.90
1.11
90.28

3
7.7780
0.7937
6.9843
0.90
1.11
89.80

4
7.7780
1.2238
6.5542
0.84
1.19
84.27

Figure 4: Results for the removal of Fe²⁺ and Ca²⁺ ions by compounds 1–4.

4. Conclusion

In conclusion, four metal-aluminum layered double hydroxides were prepared by coprecipitating Mg or Ca and Al metal salts with a base under controlled conditions. The SEM revealed that compounds 1, 2, and 4 consist of nanoparticles with an average size of 100 nm, whereas compound 3 consists of hexagonal plates with an average size of 1 m. The XRD studies showed the crystalline nature of the nano-LDHs. The results of the column adsorption studies have shown that there is significant potential for using nanostructured LDHs as nanofilters to remove ions responsible for scale formation in oil wells. However, compounds 1 and 2 can remove Fe²⁺ with greater efficiency, and all the synthesized LDHs nanostructures have been demonstrated to effectively remove Ca²⁺ from the oil wells. However, in moving from laboratory conditions to the complicated conditions of high salinity, low permeability, and heterogeneous rock properties in oilfield core materials [38], the transport and retention properties of the nanostructured LDHs should be investigated.

Conflicts of Interest

The authors declare that there are no conflicts of interest in publishing this article.

Acknowledgments

This work was supported by The World Academy of Sciences for the Advancement of Science in Developing Countries (TWAS) under Research Grant no. 12-169 RG/CHE/AF/AC-G-UNESCO FR: 3240271320 for which grateful acknowledgment is made. Ayi A. Ayi is also grateful to the Royal Society of Chemistry for Personal Research Grant. The assistance of Professor J.-G. Mao of Fujian Institute of Research on the Structure of Matter, Fujian Institute of Research, in the XRD and SEM analyses is gratefully acknowledged.

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