Original papers
Materials for energy and environment, next-generation photovoltaics, and green technologies УДК 66.021:66.081.32 DOI: 10.17277/jamt.2024.02.pp.122-131
A study of adsorption characteristics of activated carbon material for typical organic and inorganic pollutants
© Igor N. Shubina^, Oksana A. Ananyevaa
a Tambov State Technical University, Bld. 2, 106/5, Sovetskaya St., Tambov, 392000, Russian Federation
Abstract: The paper presents the results of adsorption studies on the developed activated carbon material (AM), obtained by two activation methods - with one (AM1) and two activators (AM2), respectively, as well as its compacted versions (AMK) using polyvinyl alcohol (РУА), polyvinyl acetate (PVAQ and basalt fiber (BF) as binders, with regard to typical pollutants of aquatic environments - organic dyes and heavy metals. The carbon materials sorption capacity was assessed by the ability to remove dye molecules - "methylene blue" (MB) and "sunset yellow" (SY) using spectrophotometry analysis, as well as by the ability to remove heavy metal salts - lead (Pb2) using X-ray fluorescence spectrometry. As a result of adsorption kinetic studies, the absorption capacity of the starting material, activated and compacted materials was determined. The sorption capacity for lead for the materials carbonisate and AMK1 was 71 and 65 mg-g-1, respectively, the optimal sorption time was 30 minutes; for the materials AM1, AM2, AMK1/PV^ AMK1/PVAС and AMK1/BF 65, 66, 49, 45, 42 mg-g-1 accordingly, the optimal sorption time was 15 min. For MB and SY dyes, the parameters were 1000 - 2010 mg-g-1, 66 - 972 mg-g-1 and 15 min, respectively. To analyze the adsorption mechanisms using kinetic relationships and sorption isotherms, empirical equations of pseudo-first and pseudo-second order, Elovich equation and intraparticle diffusion model were used. The presented results show the possibility of using the developed activated carbon material as an effective sorbent of organic and inorganic pollutants from aqueous solutions.
Keywords: activated carbon material; compaction; adsorption; methylene blue; yellow sunset; lead; kinetics.
For citation: Shubin IN, Ananyeva OA. Studies of adsorption characteristics of activated carbon material for typical organic and inorganic pollutants. Journal of Advanced Materials and Technologies. 2024;9(2):122-131. DOI: 10.17277/jamt.2024.02.pp.122-131
Исследование адсорбционных характеристик активированного углеродного материала по отношению к типовым органическим и неорганическим загрязнителям
© И. Н. ШубинаИ, О. А. Ананьева3
а Тамбовский государственный технический университет, ул. Советская, 106/5, пом. 2, Тамбов, 392000, Российская Федерация
Аннотация: Представлены результаты исследований адсорбционной способности разработанного активированного углеродного материала (АМ), полученного двумя методами активации - с одним (АМ1) и двумя активаторами (АМ2) соответственно, а также его компактированных вариантов (АМК) с использованием в качестве связующих поливинилового спирта (ПВС), поливинилацетата (ПВА) и базальтового волокна (БВ) по отношению к типовым загрязнителям водных сред - органическим красителям и тяжелым металлам. Сорбционная способность углеродных материалов оценивалась по способности удаления молекул красителей - «метиленового синего» (МС) и «желтого «солнечного заката» (СЗ) с помощью спектрофотометрического анализа, а также ионов тяжелых металлов - свинца (РЬ2) с помощью рентгенофлуоресцентной спектрометрии. В результате проведенных адсорбционных кинетических исследований установлена поглотительная способность исходного, активированных
и компактированных материалов. Сорбционная емкость по свинцу для материалов карбонизат и АМК1 составила 71 и 65 мг/г соответственно, оптимальное время сорбции - 30 мин; для материалов АМ1, АМ2, АМК1/ПВС, АМК1/ПВА и АМК1/БВ - 65, 66, 49, 45, 42 мг/г соответственно, оптимальное время сорбции - 15 мин. Для красителей МС и СЗ получены значения емкости: 1000 - 2010 мг/г, 66 - 972 мг/г и 15 мин соответственно. Для анализа механизмов поглощения применялись эмпирические уравнения псевдо-первого и псевдо-второго порядка, Еловича и внутричастичной диффузии. Представленные результаты показывают возможность применения разработанного активированного углеродного материала в качестве эффективного сорбента органических и неорганических поллютантов из водных растворов.
Ключевые слова: активированный углеродный материал; компактирование; адсорбция; метиленовый синий; желтый солнечный закат; свинец; кинетика.
Для цитирования: Shubin IN, Ananyeva OA. Studies of adsorption characteristics of activated carbon material for typical organic and inorganic pollutants. Journal of Advanced Materials and Technologies. 2024;9(2):122-131. DOI: 10.17277/jamt.2024.02.pp.122-131
1. Introduction
Nowadays, many regions of Russia, especially the industrialized ones, are facing the problem of environmental pollution, especially water pollution. The development of industrial complexes, technologies and materials is directly related to the emergence of new chemical production facilities, which, as a rule, produce large volumes of wastewater that require proper and high quality recycling or treatment. Failure to comply with disposal requirements has serious consequences for the environment and the ecological situation in general. The most typical representatives of toxic pollutants of water resources are various organic dyes
and heavy metals (e.g. methylene blue (MB) and
2+
sunset yellow (SY) dyes or heavy metals - Pb ). They are widely used in a variety of industries and, when present in wastewater, have a detrimental effect on flora and fauna, including humans. Therefore, water needs to be treated to remove these pollutants and research in this direction is relevant [1-3].
One of the most popular methods of water treatment is sorption, which is technologically proven, economically justified and in many cases the most effective [1, 3-5].
The most widely used modern adsorption materials are activated carbons [6-9], silica gels and zeolites [10-14]. These form the basis of industrial sorption materials, but do not always fully meet the ever-increasing demands on their efficiency [1, 7].
The solution to this problem - the creation of an effective sorbent - is seen in the development and research of promising activated carbon materials (AMs), which combine a high specific surface area and significant porosity with a predominance of micro- and mesopores, the presence of sufficiently large transport pores, ensuring rapid diffusion of sorbent substances, chemical inertness and stability in real application conditions. This is confirmed by a number of publications on this subject [1, 6, 9, 15-16].
To obtain such carbon materials, different pre-carbonized carbon sources, such as furfural, hydroquinone, dextrin, urotropine, natural carbons, carbon nanotubes, graphene or their combinations, are activated by various gas- or liquid-phase reagents: different acids or alkalis, steam, etc. [17-24].
In practice, the resulting activated highly porous
carbon materials can be used in the form of powders,
granules or fibers, which often places additional high
requirements on the possibility of their molding for
convenience of further use in finished products and
improvement of sorption properties. They should also
have a high specific surface area and large pore
volume, have a hierarchical porous structure, be
environmentally safe, economical and highly
selective, which makes them promising and in
demand materials for use in adsorption of organic and
inorganic pollutants from aqueous media, including
various heavy metals and dyes, i.e. these materials
should have a specific surface area of 2 —1
500-3000 m -g and a porosity of more than 1 cm3-g-1 [1, 6, 8, 9, 25, 26].
The influence of the technological parameters of activation of the initial carbon raw material and the modes of its subsequent compaction on the sorption properties is studied in [27-31], where the authors note their relationship, as well as the possibility of using the results of laboratory studies in real production conditions.
The relationship between adsorption and structural properties of highly porous carbon materials is assessed in [15, 32, 33], where the importance of research in this direction is pointed out.
The analysis of the literature sources shows the undoubted interest in the research of the adsorption activity of sorbents on typical pollutants, which in various works was in the following ranges: on MB dye - 61-1190 mg-g-1 [34-39], on SY dye -44-333 mg-g-1 [40-43] and on lead - 40-413 mg-g-1 [41-46].
Thus, taking into account the need and relevance of this research direction - development and research of effective sorbents - the aim of this work was to study the sorption activity of the developed activated carbon material in relation to organic dyes and heavy metals.
2. Materials and Methods
2.1. Reagents and techniques for the preparation of activated and compacted carbon materials
Based on preliminary studies, the authors of the paper developed and studied an activated carbon material obtained by two activation methods and its compacted variants with different binders. The work consisted of several stages.
In the first stage, samples of activated carbon material were obtained using one activator -potassium hydroxide (KOH) and two activators -KOH + H2O. In general, this process was a high temperature chemical activation of the initial carbonisate with the activator(s) at a temperature of 400-7500 °C for two hours in an inert environment [18]. At this stage, AM was obtained with a specific surface area greater than 2700 m2-g-1 and a pore volume greater than 1.3 cm3-g-1 [27].
The second stage of work involved obtaining compacted samples using such binders as polyvinyl alcohol (PVA), polyvinyl acetate (PVAC) and basalt fiber (BF), the main technological and process parameters for obtaining which are considered in [29]. Moreover, at this stage, only carbon material activated with one activator (AMK1) was used for compacting. The binder content in different compacted samples was as follows: basalt fibre (LLC 'Kamenny Vek', Dubna, Russia) in the amount of 5 % (AMK1/BF), polyvinyl alcohol (TC Spektr-Chem, Moscow, Russia) - 20 % (AMK1/PVA), polyvinyl acetate (JSC 'Pigment', Tambov, Russia) -20 % (AMK1/PVAC).
As a result, a number of samples were prepared for the next (third) stage of the research, including: initial carbonisate, carbon materials activated with one AM1 and two AM2 activators, and carbon materials AMK1/PVA, AMK1/PVAC and AMK1/BF compacted with different binders.
2.2. Adsorption studies
The third stage of the research consisted in
determining the adsorption activity of the previously
2+
obtained samples on Pb , for which batch experiments were carried out in a limited volume. The sorbent weighing 0.01 g was placed in 30 mL of
Pb2+ solution with Co = 100 mg-L1 according to Russian Standard 4453-74 at pH = 6. Each tube containing purified solutions and sorbent was shaken continuously for 5, 15, 30 and 60 min on a Multi Bio RS-24 programmable rotator (Biosan, Riga, Latvia). The equilibrium concentration of lead ions was determined by energy dispersive X-ray fluorescence spectrometry (ARLQuant Thermo Scientific spectrometer, ThermoScientific, USA).
To study sorption to organic dyes, 30 mL of MB, SY solution with an initial concentration of 1500 mg-L-1 at pH = 6 was taken and 0.01 g of sorbent was added. Tubes containing the tested solution and sorbent suspension were placed in a programmable multi-rotator Multi Bio RS-24 (Biosan, Riga, Latvia) and stirred continuously for 5, 15, 30 and 60 min. The optical density of the filtered dye solution was then measured on a PE-5400VI spectrophotometer (Ekroskhim Co., Ltd, St. Petersburg, Russia) at a wavelength of X = 815 nm for MB and X = 513 nm for SY.
The static sorption capacity of the sorbents, Qe, mg/g, was calculated using the formula
Qe =
(Co - Ce)V
(1)
m
final
1
where Q and Ce are the initial and concentrations of the substances in solution, mg-L V is the volume of the solution, L; m is the sorbent weight, g.
3. Results and Discussion
Figure 1 shows the time dependence of lead ion adsorption on the starting material (carbonisate) and the activated materials AM1 and AM2.
Qt, mg 80 -70 ■ 60 -50 -40 -30 -20 -10 ■
g
■Carbonisate
AMI
-AM2
10
20
30
40
50 t, min
+2
Fig. 1. Kinetic dependence of adsorption of Pb ions on carbonisate and the activated materials AM1, AM2
As a result of kinetic studies, carbonisate was found to have an adsorption capacity for the removal of lead ions equal to 71 mg-g-1, with the optimal sorption time being 30 min. The adsorption capacity on lead for activated materials AMI and AM2 is 65 and 66 mg-g-1, respectively, the optimal sorption time is 15 min.
In order to describe the ongoing processes of lead ion sorption, namely the mechanisms involved in the transfer of sorbent to the surface and inside the structure of sorbents, the equations of known kinetic models (pseudo-first and pseudo-second order, Elovich equation and intraparticle diffusion model) [47] were applied to the obtained experimental data. Table 1 and Figure 2 show the kinetic data for lead and the results of the mathematical processing of the kinetic data for carbonisate, AM1 and AM2 materials.
As a result of the experimental data processing, it was found that the mechanism of the sorption process in the removal of lead ions is well described by the pseudo-first order equation and the pseudosecond order equation. It can be noted that the pseudo-second order model has the highest
determination coefficients R2 for the removal of lead ions (for AM2 R2 = 0.9977; for AM1 R2 = 0.9994; for carbonisate R = 0.9998). Based on this, it can be assumed that diffusion limitation (internal and external diffusion) and 'sorbate-sorbate' interaction contribute to the rate of the sorption process. It should also be noted that the Elovich model for AM1 material has a high coefficient of determination - R2 = 0.9983.
Kinetic studies of the compacted carbon materials - AMK1, AMK1/PVA, AMK1/BF, AMK1/PVAC - have also been carried out.
As a result of kinetic studies of sorption capacity of compacted carbon materials (Fig. 3), it was found that the initial AMK1 has an adsorption capacity for removal of lead ions equal to 65 mg-g-1, optimum time of sorption 30 min. With the addition of a binder, the highest sorption capacity is shown by the AMK1/PVA compacted carbon sorbent -49 mg-g-1, optimum sorption time 15 min. When basalt fibre (AMK1/BF) and polyvinyl acetate (AMK1/PVAC) were used, the adsorption capacity was 45 and 42 mg-g-1, respectively, optimum sorption time 15 min.
Table 1. Parameters of lead ion sorption kinetics on carbonisate, AM1 and AM2 materials
Pseudo-first order Pseudo-second order
log(Qe - Qt ) = log Qe' - k' t 2.303 t 1 1 Qt k2Qe2 Qe
Qe k1 R2 Qe k2 R2
Carbonisate 43.511 0.0523 0.995 84.7458 0.00224 0.9998
AM1 16.319 0.0385 0.995 69.93007 0.0078 0.9994
AM2 28.138 0.0435 0.991 76.3359 0.00399 0.9977
Elovich equation Intraparticle diffusion model
Qt - 1 1 = - ln(ap)+- P P ln t Qt = kdt05 + C
a P R2 kid C R2
Carbonisate 62.4998 0.0699 0.9841 6.1843 33.644 0.9041
AM1 80493.4 0.2025 0.9983 2.1906 52.052 0.9664
AM2 1552.34 0.1307 0.9853 3.4665 46.643 0.9953
* Qe - amount of adsorbed contaminant on the adsorbent surface at the moment of equilibrium, mg-g-1 ; Qt - amount of adsorbed contaminant on the adsorbent surface at time t, mg-g- ; k1 - pseudo-first order adsorption rate constant, min-1; k2 - pseudo-second-order adsorption rate constant, g-(mg-min)1; a - adsorption constant, 1-(min-mg/g)-1; p - surface coverage and chemisorption activation energy, g-mg-1; kid - internal diffusion coefficient, 1-(mg/g-min)-1; C - boundary layer thickness, mg-g1._
l0g(Qe 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2
- Qt)
Carbonisate R2 = 0.995 R2 = 0.995 R2 = 0.991
t/Qt
0.80.6. 0.40.2-
0 10 20 30 40 50 60 i, min 0
(a)
Carbonisate R2 = 0.9998 R2 = 0.9994 R2 = 0.9977
10 20 30 40 50 60 t, min (b)
Qt, mg-g 80 -70 -60 -50 ■
40 -30 .
-1
Carbonisate R2 = 0.9941
•AM1 •AM2
R2 = 0.9983 R2 = 0.9853
1.0 1.5 2.0 2.5 3.0 3.5 4.0 ln(t) (c)
Qt, mg-g 8070-1 6050 -40 -30-
Carbonisate- R2 = 0.9041 R2 = 0.9664 ' AM2 R2 = 0.9953
1
8 t0.
(d )
Fig. 2. Results of mathematical processing of the experimental kinetic dependencies using pseudo-first order models (a); pseudo-second order models (b); Elovich equation (c); intraparticle diffusion model (d)
Qt, mg-g-1 80 -70 -60 -50 -40 -30 -20 -10 -
0
AMK1 AMK1/PVA AMK1/BF AMK1/PVAC
10
20
30
40
50 t, min
Fig. 3. Kinetic dependences of the adsorption of lead ions on the compacted carbon sorbents AMK1, AMK1/PVA, AMK1/BF, AMK1/PVA
The experimental data obtained for AMK1, AMK1/PVA, AMK1/BF and AMK1/PVAC samples were also processed by the equations of known kinetic models (Table 2, Fig. 4).
The pseudo-second-order model had the highest determination coefficients R for the removal of lead ions (for AMK1 R2 = 0.9948; for AMK1/PVA R2 = 0.9988; for AMK1/BF R2 = 1; for AMK1/PVAC R = 0.9997). Accordingly, it can be concluded that the reaction between adsorbate and sorbent functional groups is strictly stoichiometric (one molecule
occupies one position on the sorbent), i.e. there is a
+2
chemical interaction between Pb ions and sorbent functional groups. For the kinetic data for the AM1 material, high coefficients of determination are also observed for the Elovich (R = 0.9936) and pseudofirst order (R2 = 0.9926) models.
2
3
4
5
6
7
Table 2. Parameters of lead ion sorption kinetics on the materials AMK1, AMK1/PVA, AMK1/BF, AMK1/PVAC
Pseudo-first order Pseudo-second order
Qe k1 R2 Qe k2 R2
АМК1 38.318 0.0495 0.9926 78.125 0.00259 0.9948
AMK1/PVA 10.416 0.0299 0.9741 55.56 0.00964 0.9988
AMK1/BF 9.667 0.038 0.9169 49.02 0.01378 1
AMK1/PVAC 25.067 0.0504 0.9656 54.054 0.00475 0.9997
Elovich equation Intraparticle diffusion model
a ß R2 kid C R2
АМК1 178.749 0.0959 0.9936 4.6843 37.938 0.9866
AMK1/PVA 139636 0.2716 0.9741 1.6489 41.861 0.9605
AMK1/BF 14111.3 0.2520 0.9238 1.6675 36.221 0.8022
AMK1/PVAC 86.5644 0.1245 0.9725 3.4523 26.252 0.8829
log(Qe - Qt) 1.6
AMK1 R2 = 0.9926 AMK1/PVA R2 = 0.9656 AMK1/BF R2 = 0.9169 AMK1/PVAC R2 = 0.9741
t/Qt 1.21.00.80.60.40.2-
10 20 30 40 50 60 t, min 0
(a)
R2 = 0.997
2
R2 = 0.9988
•AMK1 ^ AMK1/PVA ■AMK1/BF • AMK1/PVAC R2 = 0.9997
10 20 30 40 50 60 t. min
(b)
0
Qt, mg-g-7060 -50 -4030 -20
• AMK1 R2 = 0.9936 ■AMK1/PVA R2 = 0.9741 'AMK1/BF R2 = 0.9238 ■AMK1/PVAC R2 = 0.9725
1.0 1.5
2.0
2.5 3.0 3.5
(c)
4.0 ln(i)
Qt, mg-g 70 -605040 -
30" 20-
AMK1
R = 0.9866
AMK1/PVA r2 = 0.9605 AMK1/BF R2 = 0.8022 AMK1/PVAC R1 = 0.8829
5 6 (d)
8 t°.
Fig. 4. Results of the mathematical processing of experimental kinetic dependencies using pseudo-first order models (a); pseudo-second order (b); Elovich equation (c); intraparticle diffusion (d)
1
2
3
4
7
Carbon material
(a)
2500
934
Carbon material ib) 972_
Carbon material
(c)
Fig. 5. Comparative results of studies on the adsorption activity of activated carbon materials: a - on the sorption of lead ions Pb2+; b - MB molecules; c - SY molecules
Summarising the studies on the determination of the sorption activity of the developed activated carbon material on typical organic [29, 30] and inorganic pollutants from aqueous solutions (including its compacted variants) (Fig. 5), it can be concluded that the developed material shows comparable or higher adsorption capacities on typical pollutants [34-46].
However, a number of peculiarities can be noted in the course of this study. The activated material obtained shows a rather low sorption activity towards inorganic substances (lead), but in general it is comparable with the results obtained by other authors [42-46]. Moreover, the compacted samples showed slightly worse results, which is explained by the presence of a binder, which is an inert ballast, as well as the formation of a new structure of the material when it is compacted with another.
Analysing the results obtained for dye MB (a typical representative of cationic dyes), it can be seen that the developed activated material, including its compacted variants, shows higher activity in comparison with analogues [34-39] and can be of real practical interest for application in industrial production.
The results for dye SY, an anionic type dye, show a higher efficiency in comparison with the studies of other authors [40, 41], but it can be noted that the sorption activity of the compacted samples also decreases several times with respect to the initial ones.
Thus, the results of the studies on organic dyes MB and SY may indicate a significant influence of the adsorption capacity of the binder used, which can be traced for all the samples studied. At the same time, it should be noted that at this stage of the research, the preferred binder is PVA. Further studies are needed to determine the mechanisms of influence of the technology of obtaining the materials.
4. Conclusion
The paper presents the results of studies of the adsorption activity of the developed carbon material and its compacted variants using different binders. The adsorption capacity of the original, activated and compacted materials was determined. The sorption capacity for lead for carbonisate and AMK1 materials was 71 and 65 mg-g-1, respectively, the optimum sorption time was 30 min; for AM1, AM2, AMK1/PVA, AMK1/PVAC and AMK1/BF materials 65, 66, 49, 45, 42 mg-g-1, respectively, the optimum sorption time was 15 min. For organic dyes - MB and SY, the capacity was 1000 - 2010 mg-g-1,
66 - 972 mg-g-1, respectively, at a sorption time
of 15 min. The obtained experimental kinetic data
were described using known equations of kinetic
models (pseudo-first and pseudo-second order,
Elovich equation and intraparticle diffusion model).
According to the results of the studies, it is possible
to note a high sorption activity of the developed
carbon material for the extraction of cationic and
anionic dyes, as well as similar activity with respect 2+
to Pb ions, which is comparable with analogues. This may open up prospects for its use in solving a number of environmental problems.
5. Funding
This work was financially supported by the Russian Science Foundation (grant agreement No. 22-13-20074), https://rscf.ru/project/22-13-20074.
6. Conflict of interests
The authors declare no conflict of interests.
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Information about the authors / Информация об авторах
Igor N. Shubin, Cand. Sc. (Eng.), Associate Professor, Associate Professor, TSTU, Tambov, Russian Federation; 0RCID 0009-0007-3235-5702; e-mail: [email protected]
Oksana A. Ananyeva, Postgraduate Student, TSTU, Tambov, Russian Federation; 0RCID 0000-0002-11889402; e-mail: [email protected]
Шубин Игорь Николаевич, кандидат технических наук, доцент, ТГТУ, Тамбов, Российская Федерация; ORCID 0009-0007-3235-5702; e-mail:
Ананьева Оксана Альбертовна, аспирант, ТГТУ, Тамбов, Российская Федерация; ORCID 0000-00021188-9402; e-mail: [email protected]
Received 15 April 2024; Accepted 08 May 2024; Published 04 July 2024
Copyright: © Shubin IN, Ananyeva OA, 2024. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/ licenses/by/4.0/).