Chromium adsorption studies using brewer’s spent grain biochar: kinetics, isotherm and thermodynamics

Geremias, Rodrigo; Pelissari, Catiane; Libardi, Nelson; Carpiné, Danielle; Ribani, Rosemary Hoffmann

doi:10.1590/0103-8478cr20210914

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SOIL SCIENCE • Cienc. Rural 53 (10) • 2023 • https://doi.org/10.1590/0103-8478cr20210914 copy

Chromium adsorption studies using brewer’s spent grain biochar: kinetics, isotherm and thermodynamics

Estudo da adsorção de cromo usando biochar proveniente de bagaço de malte: cinética e termodinâmica

Authorship SCIMAGO INSTITUTIONS RANKINGS

ABSTRACT:

Brewer’s spent grain (BSG) is a residue from brewery production, that can be reused as adsorbent of heavy metals like Chromium (Cr). In this study, BSG was used as a biochar for Cr adsorption in batch adsorption experiments. The biochar pyrolysis temperature (500, 600 and 700ºC), pyrolysis time (30, 105 and 180 minutes) and zinc chloride concentration (5, 12.5 and 20%) were evaluated and optimized from a fractional factorial design. An equilibrium adsorption capacity of 78.13 mg.g^-1 and a yield of 26.42% were achieved using 700ºC, 30 min, 12.5%. This biochar was applied to the adsorption of Cr in aqueous solution, under different stirring speeds (100, 150 and 200 rpm). The higher agitation speed reduced the adsorption capacity of the coal from 90 to 72 mg.L^-1. In addition, the Cr adsorption equilibrium was reached before 100 min. The pseudo-first order model best described the Cr adsorption kinetics. The Redlich-Peterson isothermal model best fitted the experimental data, with the parameter g (close to 1) suggesting Langmuir’s assumptions as the most appropriate to describe the adsorption of Cr on the optimized activated carbon.

Key words:
biosorption; chromium removal; activated carbon; brewer’s waste

Universidade Federal de Santa Maria Universidade Federal de Santa Maria, Centro de Ciências Rurais , 97105-900 Santa Maria RS Brazil , Tel.: +55 55 3220-8698 , Fax: +55 55 3220-8695 - Santa Maria - RS - Brazil
E-mail: cienciarural@mail.ufsm.br

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[1] E-mail: catiane.pelissari@unoesc.edu.br. ^*Corresponding author

Run	Pirolysis temperatura (⁰C)	Pirolysis time (min)	ZnCl₂ (%)	Surface area (m².g^-1)	Yield (%)	Adsorption capacity (mg.g^-1)
1	-1 (500)	-1 (30)	0 (12.5)	393	18.43	38.33
2	+1 (700)	-1 (30)	0 (12.5)	412	26.42	78.13
3	-1 (500)	+1 (180)	0 (12.5)	392	17.34	27.33
4	+1 (700)	+1 (180)	0 (12.5)	284	16.53	28.13
5	-1 (500)	0 (105)	-1 (5)	298	18.52	30.12
6	+1 (700)	0 (105)	-1 (5)	285	16.2	21.2
7	-1 (500)	0 (105)	+1 (20)	288	19.32	20.12
8	+1 (700)	0 (105)	+1 (20)	399	20.43	68.9
9	0 (600)	-1 (30)	-1 (5)	287	16.54	29.4
10	0 (600)	+1 (180)	-1 (5)	312	15.44	26.5
11	0 (600)	-1 (30)	+1 (20)	401	18.12	72.2
12	0 (600)	+1 (180)	+1 (20)	292	16.44	23.15
13	0 (600)	0 (105)	0 (12.5)	320	16.16	30.2
14	0 (600)	0 (105)	0 (12.5)	302	18.12	31.3
15	0 (600)	0 (105)	0 (12.5)	312	17.2	29.8

Models	Non-linear equations	Reference
Pseudo-first order (PFO)	$q_{t} = q_{e} (1 - e^{{- K}_{1} t})$	(LAGERGREN, 1898LAGERGREN, S. Zur theorie der sogenannten adsorption gelõster stoffe, Kungliga Svenska Vetenskapsakademiens. Handlingar, v 24, p.1-39, 1898.)
Pseudo-second order (PSO)	$q_{t} = \frac{K_{2} q_{e}^{2} t}{1 + K_{2} q_{e} t}$	(HO & MCKAY, 1999HO, Y.S; MCKAY, G. A. kinetic study of dye sorption by biosorbent waste product pith. Resources, Conservation And Recycling, [S.L.], v.25, n.3-4, p.171-193, mar. 1999. Elsevier BV. Available from: <Available from: http://dx.doi.org/10.1016/s0921-3449(98)00053-6 >. Acessed: Oct. 10, 2021. http://dx.doi.org/10.1016/s0921-3449(98)... )
Elovich	$q_{t} = \frac{1}{β} l n (1 + α β t)$	(ROGINSKY & ZELDOVICH, 1934ROGINSKY, S,Z.; ZELDOVICH, J. The catalytic oxidation of carbon monoxide on manganese dioxide. Chemcatchem.v.1, p.554, 1934. Acessed: Apr. 18, 2021.)
Langmuir	$q_{e} = \frac{q_{m} K_{L} C_{e}}{1 + K_{L} C_{e}}$	(LANGMUIR, 1918LANGMUIR, I. THE ADSORPTION OF GASES ON PLANE SURFACES OF GLASS, MICA AND PLATINUM. Journal Of The American Chemical Society, [S.L.], v.40, n.9, p.1361-1403, 1918. American Chemical Society (ACS). Available from: <Available from: http://dx.doi.org/10.1021/ja02242a004 >. Acessed: Sept. 30, 2021. http://dx.doi.org/10.1021/ja02242a004... )
Freundlich	$q_{e} = K_{F} C_{e^{\frac{1}{n}}}$	(FREUNDLICH, 1906FREUNDLICH, H. Over the adsorption in the solution. The Journal of Physical Chemistry, v.57, p.385-47, 1906. Acessed: Feb. 10, 2021.)
Redlich-Peterson	$q_{e} = \frac{K_{R} C_{e}}{1 + a_{R} C_{e}^{b}}$	(REDLICH & PETERSON, 1959REDLICH, O.; PETERSON, D L. A Useful Adsorption Isotherm. The Journal Of Physical Chemistry, [S.L.], v.63, n.6, p.1024-1024, 1 jun. 1959. American Chemical Society (ACS). Available from: <Available from: http://dx.doi.org/10.1021/j150576a611 >. Acessed: Apr. 18, 2021. http://dx.doi.org/10.1021/j150576a611... )
Temkin	$q e = \frac{R T}{b_{t}} l n (K_{t} ∙ C_{e})$	(TEMKIN & PYZHev, 1939TEMKIN, M.; PYZHEV, V. Kinetics of the synthesis of ammonia on promoted iron catalysts. The Journal of Physical Chemistry, v.13, p.851-867, 1939. Acessed: Jan. 18, 2021.)

Agitation (rpm)	q_e,exp (mg.g^-1)	Pseudo-first order	Pseudo-second order	Elovich
100	87.6	q_e= 80.95 ± 1.88	q_e= 93.35 ± 1.84	α = 10.82 ± 0.52
		k₁ = 0.039 ± 0.004 R² _adjust = 0.932	k₂ = 5.42 x 10^-4 ± 5.51 x 10^-5	β = 0.05 ± 8.93 x 10^-4
		∆q= 10.5	R² _adjust=0.978	R² _adjust =0.998
			∆q= 8.56	∆q = 3.37
150	90.3	q_e= 84.59 ± 2.01	q_e= 93.62 ± 1.86	α = 38.82 ± 3.73
		k₁ = 0.058 ± 0.007	k₂ = 9.32×10^-4 ± 1.78×10^-4	β = 0.064 ± 0.002
		R² _adjust = 0.961	R² _adjust=0.961	R² _adjust= 0.993
		∆q= 9.32	∆q= 5.67	∆q= 4.85
200	72.4	q_e = 64.08 ± 1.60	q_e = 68.71 ± 1.52	α = 349.7 ± 142.8
		k₁ = 0.163 ± 0.03	k₂ = 0.003 ± 7.279 x 10^-4	β = 0.127 ± 0.007
		R² _adjust = 0.797	R² _adjust = 0.907	R² _adjust = 0.980
		∆q= 12.49	∆q= 7.09	∆q= 4.13

Models	-------------------------------------------------------Temperature-------------------------------------------------------
	25 °C	35 °C	45 °C
-----------------------------------------------------------------------Langmuir-----------------------------------------------------------------------
q_m	31.88 ± 3.39	48.58 ± 7.35	64.60 ± 11.73
K_L	1.13 ± 0.60	0.32 ± 0.15	0.04 ± 0.012
R²	0.927	0.927	0.986
∆q_e	4.39	4.75	3.70
----------------------------------------------------------------------Freundlich--------------------------------------------------------------------------
K_F	19.78 ± 3.92	18.56 ± 4.82	22.12 ± 8.855
n_F	6.36 ± 3.95	3.47 ± 1.45	4.78 ± 2.86
R²	0.861	0.888	0.798
∆q_e	6.04	5.65	9.15
-------------------------------------------------------------------Redlich-Peterson------------------------------------------------------------------
K_RP	17.64 ± 4.21	7.18 ± 0.66	1.999 ± 0.23
a_RP	0.206 ± 0.14	0.004 ± 0.004	4.59x10^-4 ± 0.001
g	0.89 ± 0.18	0.87 ± 0.40	0.88 ± 0.95
R²	0.971	0.984	0.991
∆q_e	3.48	2.64	1.66
-------------------------------------------------------------------------Temkin------------------------------------------------------------------------
b	603.4 ± 310.14	253.0 ± 86.7	224 ± 8.08
A	70.531 ± 211.69	3.338 ± 3.60	0.551 ± 0.37
R²	0.876	0.907	0.995
∆q_e	6.78	5.45	2.12

Adsorbent	q_m (mg.g^-1)	Experimental conditions	Reference
Actived carbon	199.7	55 ^oC; pH 3.0; d = 1.0 g L^-1	LOPES et al., (2021LOPES, G.K. P.et al Steam-activated carbon from malt bagasse: optimization of preparation conditions and adsorption studies of sunset yellow food dye. Arabian Journal Of Chemistry, [S.L.], v.14, n.3, p.103001, mar. 2021. Elsevier BV. Available from: <Available from: http://dx.doi.org/10.1016/j.arabjc.2021.103001 >. Acessed: Oct. 10, 2021. http://dx.doi.org/10.1016/j.arabjc.2021.... )
Fe₃O₄-activated carbon	22.31	25 ^oC; pH 5.88; d = 1.0 g L^-1	CAZETTA et al. (2016CAZETTA, L.A. et al. Magnetic Activated Carbon Derived from Biomass Waste by Concurrent Synthesis: efficient adsorbent for toxic dyes. Acs Sustainable Chemistry & Engineering, v.4, n.3, p.1058-1068, 2016. American Chemical Society (ACS). Available from: <Available from: http://dx.doi.org/10.1021/acssuschemeng.5b01141 >. Accessed: Nov. 18, 2021. http://dx.doi.org/10.1021/acssuschemeng.... )
Cu:ZnS-NPs-Actived carbon	85.4	25 ^oC; pH 6.0	AGARWAL et al. (2016AGARWAL, S. et al. Ultrasound-assisted adsorption of Sunset Yellow CFC dye onto Cu doped ZnS nanoparticles loaded on activated carbon using response surface methodology based on central composite design. Journal of Molecular Liquids, [S.L.], v.219, p.332-340, 2016. Elsevier BV. Available from: <Available from: http://dx.doi.org/10.1016/j.molliq.2016.02.100 >. Accessed: May. 02, 2021. http://dx.doi.org/10.1016/j.molliq.2016.... )
Modified chitin	93.3	55 ^oC; pH 4.0	LIMA et al., (2009)LIMA, E. C. et al. A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. Wrong use of equilibrium constant in the Van’t Hoof equation for calculation of thermodynamic parameters of adsorption. Journal Of Molecular Liquids, [S.L.], v.273, p.425-434, jan. 2019. Elsevier BV. Available from: <Available from: http://dx.doi.org/10.1016/j.molliq.2018.10.048 >. Acessed: Nov. 18, 2021. http://dx.doi.org/10.1016/j.molliq.2018....
Carboxylated-functionallized sugarcane bagasse	69.40	25 ^oC; pH 5.5 d = 1.0 g L^-1	RAMOS et al., (2016RAMOS, S. N.C et al. Removal of cobalt(II), copper(II), and nickel(II) ions from aqueous solutions using phthalate-functionalized sugarcane bagasse: mono- and multicomponent adsorption in batch mode. Industrial Crops And Products, [S.L.], v.79, p.116-130, jan. 2016. Elsevier BV. Available from: <Available from: http://dx.doi.org/10.1016/j.indcrop.2015.10.035 >. Acessed: Dec. 18, 2021. http://dx.doi.org/10.1016/j.indcrop.2015... )
Zinc-modified sugarcane bagasse	>200	25 ^oC; pH 5.5 d = 2.0 g L^-1	GAO et al., (2015GAO, F. et al. Removal of aqueous ammonium by biochars derived from agricultural residuals at different pyrolysis temperatures. Chemical Speciation & Bioavailability, [S.L.], v.27, n.2, p.92-97, 3 abr. 2015. Informa UK Limited. Available from: <Available from: http://dx.doi.org/10.1080/09542299.2015.1087162 >. Acessed: Oct. 10, 2021. http://dx.doi.org/10.1080/09542299.2015.... )
Steam activated macroalgae biomass	137	25 ^oC; pH 5.5 d = 0.1 g L^-1	KIM et al., (2016)KIM, B et al. Removal of Cu2+ by biochars derived from green macroalgae. Environmental Science And Pollution Research, [S.L.], v.23, n.2, p.985-994, 28 mar. 2015. Springer Science and Business Media LLC. Available from: <Available from: http://dx.doi.org/10.1007/s11356-015-4368-z >. Acessed: Oct. 24, 2021. http://dx.doi.org/10.1007/s11356-015-436...

Parameters	SQ	DF	MS	F-value	P-value
(1)Pirolysis temperature(L)	1198.775	1	1198.775	1986.919	0.000503
Pirolysis temperature(Q)	0.239	1	0.239	0.396	0.593555
(2)Pirolysis time (min)(L)	2045.375	1	2045.375	3390.125	0.000295
Pirolysis time (min)(Q)	383.571	1	383.571	635.754	0.001569
(3)ZnCl2 (%)(L)	269.197	1	269.197	446.183	0.002234
ZnCl2 (%)(Q)	214.650	1	214.650	355.773	0.002799
1L by 2L	380.250	1	380.250	630.249	0.001583
1L by 2Q	288.331	1	288.331	477.897	0.002086
1Q by 2L	162.140	1	162.140	268.740	0.003700
1L by 3L	832.323	1	832.323	1379.540	0.000724
1Q by 3L	47.274	1	47.274	78.354	0.012523
2L by 3L	532.456	1	532.456	882.523	0.001131
Error	1.207	2	0.603
Total SS	5194.590	14
R²	0.9983

Temperature	------------------------------------------------------Parameters----------------------------------------------------
	∆G (kJ.mol^-1)	∆H (kJ.mol^-1)	∆S (J.mol^-1.K^-1)
30	-52.84	3.07	123.58
40	-54.91
50	-56.12