Journal of Environmental Chemical Engineering 7 (2019) 103006

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Journal of Environmental Chemical Engineering

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

Cleaning produced water: A study of cation and anion removal using T

different adsorbents
⁎
Breno Gustavo P. Bezerraa, Anderson Parodiab, Djalma R. da Silvaa, Sibele B.C. Pergherb,
a
Núcleo de Processamento Primário e Reuso de Água Produzida e Resíduo, Centro de Ciências Exatas e da Terra, Universidade Federal do Rio Grande do Norte (UFRN),
Campus de Lagoa Nova, 59078-970, Natal, RN, Brazil
b
LABPEMOL - Laboratório de Peneiras Moleculares, Instituto de Química, Universidade Federal do Rio Grande do Norte (UFRN), Campus de Lagoa Nova, 59078-970,
Natal, RN, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Produced water is the largest volume flow byproduct in oil and gas production and has a negative environmental
Adsorption impact due to its complex composition and high disposal costs. In this sense, it is paramount to development new
Metals technologies for the removal of cations and anions from produced water. In this work, different materials such as
Produced water zeolites (with cation exchange properties), lamellar double hydroxides (that can remove anions) and aluminas
Zeolite
with diferente particles size (9–16 mesh, 16–32 mesh, in pastile and ɣAl2O3) exhibiting amphoteric properties
Alumina
LDH
were evaluated for the adsorption of cations and anions of produced water. Zeolite, ɣAl2O3 and calcined LDH
provided the most satisfactory results with the removal of 60–99% of the cations and anions, reaching values
below the maximum allowed by Resolution 430 of the National Council of the Environment.

1. Introduction Na+, K+, Ca2+, Mg2+, Ba2+, and anions such as Cl−, SO42-, CO32-,
HCO3− and silica (SiO2) [5].
Water and energy consumption are directly related and are essential In the United States, the estimated annual volume of produced
for the conservation of human life. Globally, the energy field has been water was 21 billion barrels with 50 billion barrels produce in the rest
heavily dominated by fossil fuels and this is expected to continue for the of the world throughout 2009 [6]. According to the statistics collected
next several decades [1]. However, despite their advantages, fossil fuels from the groundwater protection council, the oil and gas industry in the
also severely affect the environment during their production, distribu- US generated 21.1 billion barrels of produced water in 2012 [7].
tion and use. The oil and gas raised to the surface are accompanied by a In Brazil, according to the annual report of the National Agency of
significant amount of water that is known as oil-producing water [2]. Petroleum, natural gas and biofuels - ANP, between January and
This oil-producing water is also commonly known as produced water October in 2016, the production of produced water was over 159 mil-
and is formed during production along with the oil and/or wastewater lion m3, where 2.5 million m3 was due to the subsoil discharge, 73.3
gas [3] and is the largest byproduct and has a negative environmental million m3 was due to the surface discharge and 184.7 million m3 was
impact due to its complex composition and high disposal costs. injected for use in the secondary recovery [8]. In 2011, the PETROBRAS
As the largest waste stream of oil and gas refineries, produced water system discarded 188 million m3 of produced water and sanitary ef-
contains a wide variety of pollutants, such as dispersed dissolved oils fluents from operations. On the coast of Rio Grande do Norte, ap-
and greases, production solids, dissolved gases, soluble and insoluble proximately 100,000 m3 of produced water generated by submarine
organic compounds, chemicals involved in the separation and produc- emissions are discarded daily [9].
tion process, and inorganic and dissolved mineral formation products The extracted volumes of produced water are waste products of the
[4]. oil fields. Thus, there are some reuse options, such as in injection,
The main hydrocarbon groups present in the water include alkanes, discharge, reuse in oil and gas operation, and consumption for use with
aromatics, polynuclear aromatics, hydrocarbon compounds containing agriculture and livestock [10].
oxygen, nitrogen, sulfur and unknown hydrocarbons (oil and grease). Consequently, standards related to the rewatering of produced
The produced water also contains metals such as Al, Fe, Cd, Pb, Cu, Zn, waters are essential for preventing the discharge of these large volumes
Ni, Cr and high amounts of salts dissolved predominantly with cations of water into the environment that would give rise to uncontrolled and

⁎
Corresponding author.
E-mail addresses: [email protected], [email protected] (S.B.C. Pergher).

https://doi.org/10.1016/j.jece.2019.103006
Received 29 December 2018; Received in revised form 4 March 2019; Accepted 5 March 2019
Available online 06 March 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
B.G.P. Bezerra, et al. Journal of Environmental Chemical Engineering 7 (2019) 103006

irreversible pollution of the marine environment. Table 1

Through Resolution No. 430, Brazilian Environmental Law has es- Characteristics of Produced Water from Petroleum ([13]).
tablished the conditions and standards for the discharge of effluents, Parameter value
determining the maximum concentration limits of the pollutants;
treatment of effluents can be difficult and their impact on the en- Salinity 1440 g Kg−1
Total solids 2223 mg L−1
vironment, health and quality of life of the population has motivated
Resistivity 361.0 Ω cm
the investigation and development of new methodologies for their CO3−2 21048 mg L−1
monitoring [11]. pH 6.7
Thus, it is increasingly important to develop new efficient water Conductivity 2.8 mS cm−1
purification technologies. Although, a large number of technologies Sulfite 4.57 mg L−1
Chloride 6200 mg L−1
such as photocatalysis [12], electrochemical treatment ([13] and [1]),
HCO3− 203,288 mg L−1
membrane filtration [6], ozonization [10], and flocculation [4] have Density 0.974 g cm−3
been developed for water treatment, in this study, we have adopted a Suspended solids 836 mg L−1
cost-effective, reliable and efficient adsorption-based technology. The Total dissolved solids 1387 mg L−1
Chemical oxygen demand 4600 mg L−1
adsorption method has long been considered to be an efficient and
simple approach and has been used for water remediation [14].
The use of adsorbent materials in the treatment of effluents has
Aldrich; and aluminas with different grain sizes such as Al1 for γ-alu-
increased due to their high adsorption capacities, and their use as ion
mina (powder) and Al2 (9–16 mesh), Al3 (16–32 mesh), Al4 (Pastille).
exchangers, such as molecular sieves and adsorbents.
Thus, it was observed that cations and anions can be retained by the
adsorbent materials by cation exchange and by chemical adsorption. 2.2. Adsorbent materials characterization techniques
In previous studies, adsorption of the toxic metals in produced water
was examined. For example, the adsorption capacity was measured as a The adsorbents were characterized using a Bruker D2 Phase X-ray
function of the time of contact with the produced water, in periods from diffractometer (XRD) with a Lynxere detector and Cu radiation, by
0 to 24 h. At the end of treatment, the samples were analyzed by ICP- scanning electron microscopy (SEM) using a ZEISS, Auriga model in-
OES for Co, Cd, Cr, Mo, Pb and Zn. It was verified that the optimum strument with an FEG (Field Emission Gun) type emitter, and by ni-
contact time was 4 h, and the values found in this period were smaller trogen sorption at 77 K performed using a Micromeritics brand ASAP
than the maximum amounts allowed by the resolution 430 of 2020 instrument. Data obtained from 77 K nitrogen sorption isotherms
CONAMA, proving that the zeolite A is a capable adsorbent material, were analyzed using the BET (Brunauer, Emmett and Teller) method to
allowing quick and easy removal of these elements present in the determine the surface area (SBET); an αs-plot was used for the de-
complex matrix of produced water [11]. termination of micropore volume (Vo), the Horvath and Kawazoe
In view of this, it is important to evaluate the removal of other method for micropore size distribution (PSD) and the Gurvich rule was
cations and other anionic species present in produced water using a used to determine the total pore volume (VTP).
variety of materials such as zeolites with cation exchange properties,
lamellar double hydroxides (LDH) that can remove anions, aluminas of 2.3. Reagents, standards and reference materials
different particle sizes (9–16 mesh, 16–32 mesh and in Pastille) and
ƔAl2O3 exhibiting amphoteric properties. The petroleum produced water used in this study was provided by
the RN CE Operation Unit – Brazil. In Tables 1 and 2 it is showed the
2. Material and methods
Table 2
Cation and Anion concentrations in Produced Water by
Fig. 1 presents a general scheme of the experimental procedure used petroleum reserves in the world ([4]).
in this work. The adsorbent materials used were characterized by XRD,
SEM and N2 adsorption. After the adsorption test, the PW was analyzed Metal Values (mg L−1)

to quantify the cations and anions removed, using ion chromatography Calcium 13–25800
and ICP-OES. Sodium 132–97000
Potassium 24-4300
Magnesium 8–6000
2.1. Adsorbent materials Iron < 0.1–100
Aluminum 310–410
Zeolites A and NaX were obtained from Diatom Mineração, Ltda., Boron 5–95
Barium 1.3–650
the lamellar double hydroxide (LDH) were obtained from Sigma-
Cadmium < 0.005–0.2
Chromium 0.02–1.1
Copper < 0.002–1.5
Lithium 3–50
Manganese < 0.004–175
Lead 0.002–8.8
Strontium 0.02–1000
Titanium < 0.01–0.7
Zinc 0.01–35
Arsenic < 0.005–0.3
Mercury < 0.001–0.002
Silver < 0.001–0.15
Beryllium < 0.001–0.004
Cloreto 80-200.000
Bicarbonato 77–3990
Sulfato < 2–1650
Azoto amoniacal 10 a 300
Sulfito 10
Fig. 1. Scheme of experimental procedure.

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B.G.P. Bezerra, et al. Journal of Environmental Chemical Engineering 7 (2019) 103006

Fig. 2. Diffractograms and micrographs of: zeolite A; zeolite NaX; LDH; Al1; Al2; Al3 and Al4.

characteristics of this produced water and the range of concentrations 2.4. Produced water characterization
of cations and anions normally found in produced water in the world.
All aqueous solutions were prepared with high purity water with the For determination of Cl−, Br−, SO42- and HCOO− (formate) anions,
resistivity of 18.2 MΩ cm that was obtained using an Elga Purelab Ultra a Dionex ICS-2000 Ion Chromatograph was used as well as method
system (Elga Labwater, UK). 9056 A - Determination of Inorganic Anions by Ion Chromatography
In the preparation of the calibration curves for the Anion and [15].
Cations Chromatographic System, DIONEX-Thermo Fisher Scientific In the determination of K +, Ca 2+, Mg 2+, Sr 2+, Ba 2+ and NH 4 +
multi-element standards of 1000 mg L−1 of K +, Ca2 +, Mg2 +, Sr2 +, cations, a Dionex ICS-3000-D 6919-03 Standard Test Method for
Ba2 +, NH4 +, Cl-, Br-, SO42-, NH4+ and formate in water were used. Determination of Dissolved Alkali and Alkaline Earth Cations and
For the preparation of the ICP-OES calibration curve, reference so- Ammonium in Water and Wastewater by Ion Chromatography [16] was
lutions (SpecSol, São Paulo) of 1000 mg L−1 of Ag, B, Be, Co, Mn, Cd, used.
Cr, Ni, Zn, Mo, P, Pb, Fe, K, Ca, Mg, Sr and Ba in 5% (v/v) HNO3 were In the determination of the metals, an ICP-OES (Thermo Fisher
used. Scientific, Bremen, Germany), model iCAP 6300 Duo was used, with
axial and radial view, with a simultaneous detector CID (Charge

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B.G.P. Bezerra, et al. Journal of Environmental Chemical Engineering 7 (2019) 103006

Injection Device). A gas with commercial purity of 99.996% (White

Martins-Praxair) was used to purge the optics for plasma generation and
was also used as the nebulization and auxiliary gas. A Burgener Mira
Mist nebulizer and cyclonic nebulization chamber were used in the
sample introduction system. In this system, the sample was pumped
into the plasma with a peristaltic pump coupled to the equipment and
its flow was controlled by the computer program (iTeva - Thermo
Scientific). A dismountable type quartz torch was used. The instrument
parameters were optimized as a function of the robustness of the plasma
for acidified aqueous solutions. These optimized parameters were:
power source RF, 1350 W; nebulizer gas flow rate, 0.75 L/min; auxiliary
gas flow, 0.5 L/min; stabilization time, 15 s. The wavelengths used were
Ag (243,779 nm), B (249,773 nm), Be (313,042 nm), Co (228,616 nm),
Mn (257,610 nm), Cd (214,438 nm), Cr(357,869 nm), Ni (221.647 nm),
Zn (213.856 nm), Mo (281.615 nm), P (213.618 nm), Pb (220.353) and
Fe (259.640 nm).

2.5. Adsorption tests

The treatment of the petroleum produced water was performed

using 50 mL ( ± 0.01 mL) of the solution in contact with a mass of
0.30 g ( ± 0.001 g) of the different adsorbents. The samples were
placed in 150 mL Erlenmeyer flasks and subjected to a stirring in an
orbital shaker table at a speed of 200 rpm ( ± 5 rpm) at room tem-
perature (25 ± 0.5 °C). The optimum time of 4 h was used based on the
findings of the previous studies [11]. At the end of this time period, the
samples were filtered, recovering some of the adsorbents and the su-
pernatants and were analyzed by ICP-OES and ion chromatography
(using the procedure specified on 2.4 item)
The pH values of the solutions of the supernatants after the ad-
sorption processes were measured and were less than 2.0 ( ± 0.1),
which is an adequate value. The pH not only influences the adsorption
of the chemical species in the solution but also affects the interfacial
chemistry of the adsorbents [17].
The tests were carried out in triplicate, and the blank was con-
sidered as zero time, i.e., with no contact with the adsorbents.

3. Results and discussion

3.1. Adsorbent materials

Zeolites, aluminas and LDH were used as the absorbent materials.

The results of X-ray and SEM analysis are shown in Fig. 2. It is observed
that the results for the commercial zeolite samples are consistent with
the standard zeolite data, showing that the samples were pure zeolite
phases [18]. For the alumina samples, it is observed that the different
granulometry does not alter the crystalline structure of the material. In
the LDH diffractogram, we observe fine reflections, resulting from a
well-defined basal spacing, probably because this material only con-
tains chloride in the interlamellar domain [19].
The zeolite isotherm is shown in Fig. 3a, and it is found that zeolite
A shows a low adsorption of N2 and consequently low specific area, due Fig. 3. Nitrogen adsorption and desorption isotherms at 77 K for: a) zeolite A
to the size of its micropores [20,21]. In addition, the adsorption of the and NaX; b) Al1, Al2, Al3 and Al4; c) LDH.
zeolite (type I) is high at low pressures, indicating the presence of mi-
cropores [21,22]. Table 3
The isotherms of the alumina samples (Fig. 3b) have the same Structural properties of the materials.
profile (type IV) and hysteresis (type H3) that are characteristic of Material SBET [m2/g] VTP [cm3/g] /0,98
mesoporous materials, indicating that the differences in the particle
sizes have little influence on the porous structure of these materials LTA 5 0.01
NaX 547 0.22
[23].
LDH 12 0.03
For the LDH (Fig. 3c), the isotherm presented the type II format Al1 220 0.63
characteristic of nonporous materials, because the dimensions of the Al2 287 0.63
lamellae are larger than the relative size of the nitrogen molecule [12]. Al3 253 0.59
According to Table 3, the material with the highest specific area was Al4 276 0.63

NaX zeolite (547 m2/g), followed by the aluminas that presented a

specific surface area of approximately 250 m2/g, and finally LDH and

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B.G.P. Bezerra, et al. Journal of Environmental Chemical Engineering 7 (2019) 103006

Table 4 Table 5
Figures of merit obtained for the determination of K+, Ca2+, Mg2+, Sr2+, Ba2+, Figures of merit obtained for the determination of Ag, B, Be, Co, Mn, Cd, Cr, Fe,
NH4+, Cl−, Br−, SO42- and formate in the samples of produced water by ionic Ni, Mo, P, Pb, Zn in samples of water produced by ICP-OES after treatment by
liquid chromatography after adsorption treatment in different adsorbents; adsorption in different adsorbents; LD = detection limit; R = linear correlation
LD = detection limit; R = linear correlation coefficient. coefficient.
Parameter Linear range (mg L−1) R LD Parameters Linear Range/μg L−1 LD/μg L−1 R Slope

Sodium (Na ) +
20 0,9998 0,0349 Ag 3.5 – 896.0 0.0004 0.99997 0.160217
Potassium (K+) 0.5 - 25 0.9991 0.5845 B 10.0 – 2560 0.0004 0.99989 7.285092
Calcium (Ca2+) 0.5-25 0.9995 0.7351 Be 3.5 – 896.0 0.0001 0.99978 621.295532
Magnesium (Mg2+) 0.25-12,5 0.9997 0.2653 Co 3.5 – 896.0 0.0004 0.99,970 2.153137
Strontium (Sr2+) 0.2 - 10 0.9991 0.2193 Mn 10.0 – 2560 0.0001 0.99963 71.193191
Barium (Ba2+) 0.2 - 10 0.9997 0.2336 Cd 3.5 – 896.0 0.0001 0.99991 7.518802
Ammonium (NH4+) 0.5 - 25 0.9995 0.3447 Cr 3.5 – 896.0 0.0007 0.99990 12.51198
Chloride (Cl−) 0.2 - 100 0.9995 0.5545 Fe 10.0 – 2560 0.0034 0.99991 0.654014
Bromide (Br−) 0.01 - 20 0.9997 0.0072 Ni 3.5 – 896.0 0.0004 0.99981 1.242035
Sulfate (SO42−) 0.2 - 20 0.9996 0.0812 Mo 10.0 – 2560 0.0009 0.99978 2.391468
Formate (HCOO−) 0.2 - 20 0.9992 0.1949 P 10.0 – 2560 0.0042 0.99978 0.286798
Pb 3.5 – 896.0 0.0019 0.99940 0.614260
Zn 10.0 – 2560 0.0001 0.99998 8.404282
zeolite A (12 and 5 m2/g respectively). For zeolite A, the low specific
area is due to the fact that its small pores block the entrance of the
nitrogen molecules, so that the measured specific area is due only to the figures of merit obtained using the calibration curves are presented in
external area of the material. the Table 4.
The initial concentration of the Cl− ion was 2571.3097 mg L-1
without the presence or action of adsorbents, and after the treatment of
3.2. Evaluation of the ability to remove cations and anions
the effluent, approximately 50% removal was obtained relative to all of
the used materials, with approximately 56% removal for Al1 and Al2;
In this work, three different samples of produced water with dif-
the obtained results were extremely satisfactory for all of the adsorbents
ferent concentrations of cations, anions and different salinities were
used, thus, demonstrating good removal performance (Fig. 4a). It was
used for performing the treatments; the adsorbent materials mentioned
expected that LHD materials can remove more anions than the other
above were used in this effluent.
materials in study, due its high anion exchange capacity. The LDH
The quantifications of the analytes were performed by liquid chro-
material used in this study, have CO3-2 compensating the layer charge,
matography for certain cations and anions and by ICP-OES and the

Fig. 4. Concentration of ions in produced water. a) Cl−, b) Na+, c) HCOO-, Br-, SO42- d) NH4+, K+, Ca2+, Mg2+, Sr2+ and Ba2+.

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B.G.P. Bezerra, et al. Journal of Environmental Chemical Engineering 7 (2019) 103006

Fig. 5. Concentration of ions in produced water. a) Fe; b) Cd, Cr, Mn, Ni, Zn; c) Ag, B, Be, Co and d) P, Pb.

Fig. 6. Scheme of the cation and anion removal (a) A Zeolite, (b) LDH and (c) Alumina.

and it can be exchanged by Cl- and others anions. It was well knew that were equal to 7.8123 mg L−1 and 10.5616 mg L−1, corresponding to
the stability the layer with the following anions are: CO32- > OH- > F- 80% and 94% removal, respectively, in the presence of zeolite A and
> Cl- > SO42- > Br- > NO3- > I− [19]. So CO3-2 has more tendency to calcined LDH (Fig. 4b). As expected LDH has the mayor anion remove
stay in the interlayer than Cl-. Because this, LDH remove similar capacity followed by aluminas (anphoteric properties) and then the
quantities of all other materials. zeolites. It may seem strange that zeolites can remove anions, but it can
The initial concentration of the formate ion was approximately occur due to the high cations content (compensating the framework
5.2651 mg L−1 without the presence or action of adsorbents. After the charge) that attract the anions., this phenomena is well known on
treatment of the effluent, the results obtained for all the adsorbents Cancrenite zeolite [24].
used were approximately the same, with the best removal of approxi- The initial concentration of the sodium ion was approximately
mately 80% obtained for LDH; this is due to the positive charge present 2971.77 mg L−1 without the presence or action of adsorbents, and the
in their lamellae that requires a negative charge for stabilization. For values obtained after treatment of the effluent with the different ad-
bromide and sulfate, with initial concentrations of 38.1651 mg L−1 and sorbents were close to each other, with the removal of approximately
170.0594 mg L−1 respectively, after the treatment, their concentrations 55% obtained for Al1 (Fig. 4c). It was expected that zeolite materials

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B.G.P. Bezerra, et al. Journal of Environmental Chemical Engineering 7 (2019) 103006

remove more cations than the others materials, but in the case of so- achieve 50–95% of removal, but anyone works with produced water
dium that not occurs because cations is the compensating cation on and study more than four cations or anions simultaneously.
zeolite framework structure. So all materials remove similar quantities.
The initial concentrations of ammonium, potassium, calcium, 4. Conclusion
magnesium, strontium and barium ions without the presence or action
of adsorbents were 10,228 mg L−1, 99.955 mg L−1, 58.158 mg L−1, In this study different adsorbents (zeolite, LDH and aluminas) were
60,265 mg L−1, 32,083 mg L−1 and 24,020 mg L−1, and the removals used for produced water treatment. It was expected that LDH materials
obtained after treatment of the effluent with the different adsorbents remove preferably anions, zeolites cations and the alumina both cations
were 90%, 61%, 50%, 50%, 65% and 65%, respectively, with the best and anions. It was showed that all materials have good remove capa-
removal obtained for Al1 (Fig. 4d). cities of cations and anions. The removal occurs due to exchange ca-
It is observed that the removals were higher for the aluminas be- pacity of materials and electrostatic interactions. The Zeolite A,
cause they have amphoteric properties; although the lamellar double Al1(ɣAl2O3) and the calcined LDH presenting the best results with
hydroxides have characteristics conducive to anion removal by com- 50–99% removal and with the values below the maximum allowed
pensating the positive charge present in their lamellae, the LDH was values established by Resolution No. 430 of the National Environment
able to remove the ions successfully due to having sufficient spaces Council. In the case of aluminas, the Al1 (that was in powder) has the
between the layers. best capacity of removal than the others with higher particle sizes, due
Table 5 shows the merit figures obtained for the determination of probably of external superficial area. A zeolite removes more cations
the chromium, silver, boron, beryllium, cobalt, manganese, chromium, than NaX zeolite because A zeolite has higher Al content in the fra-
iron, nickel, molybdenum, phosphorus, lead and zinc ions present in a meworks and consequently more cation exchange capacity.
sample of produced water obtained from petroleum as measured by These adsorbents proved to be very capable adsorbent materials,
ICP-OES. allowing simple, quick and easy extraction of the cations and anions in
Fig. 5a shows the variation of the iron ion concentration in pro- the complex matrix of petroleum produced water. It should be noted
duced water after the treatment with different adsorbents as analyzed that the removal becomes more difficult for very low concentrations of
by ICP-OES. The initial iron concentration was 13.417 mg L−1 without cations and anions due to the presence of dissolved inorganic minerals,
the presence or action of adsorbents, and after treatment of the effluent polyaromatic hydrocarbons, BTEX, and the chemical additives used in
in the presence of the calcined LDH, the removal was 99.8%. the drilling, fracturing and oil/water separation.
The initial concentrations of Cd, Cr, Mn, Ni, Zn ions without the
presence or action of the adsorbents were 0.928 mg L−1, 0.909 mg L−1, Acknowledgment
0.949 mg L−1, 0.904 mg L−1 and 1.138 mg L−1, and the removals of
90%, 61%, 50%, 50%, 65% and 65%, were obtained respectively for the The authors thank the Laboratory of Molecular Sieves - LABPEMOL
treatment of the effluent with the different adsorbents; the best removal and the Nucleus of Primary Processing of Reuse of Produced Water and
obtained was by the Al1 material (Fig. 5b). Waste - NUPRAR for the support and development of this work.
The initial concentrations of Ag, B, Be, Co without the presence or
action of adsorbents were 0.863 mg L−1, 2.737 mg L−1, 0.573 mg L−1, References
and 0.835 mg L−1, and the removals of 40%, 30%, 99.7%, and 80%,
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