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Journal of Molecular Liquids 229 (2017) 555–565

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Journal of Molecular Liquids

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Reviews

A review for coffee adsorbents


Ioannis Anastopoulos a,b,⁎⁎, Mina Karamesouti a,⁎⁎, Athanasios C. Mitropoulos c, George Z. Kyzas c,⁎
a
Laboratory of Soils and Agricultural Chemistry, Department of Natural Resources and Agricultural Engineering, Agricultural University of Athens, Athens GR-11855, Greece
b
Department of Agrobiotechnology, Agricultural Research Institute, P.O. Box 22016, 1516 Nicosia, Cyprus
c
Hephaestus Advanced Laboratory, Eastern Macedonia and Thrace Institute of Technology, Kavala GR-654 04, Greece

a r t i c l e i n f o a b s t r a c t

Article history: This review examines the performance of new highly promising materials in water purification industry. Low-
Received 9 November 2016 cost and effective industrial wastes may have ample applications in water decontamination procedures, the
Received in revised form 16 December 2016 most popular of which is the biosorption, a metabolically passive process. Coffee residues are by-products pro-
Accepted 28 December 2016
duced in considerable quantities worldwide. Recently available researches show an expanding applicability of
Available online 29 December 2016
coffee by-products in the wastewater treatment. The food industry, the agriculture and aquaculture, the medicine
Keywords:
and the cosmetics are indicatively some of the industries that discharge significant quantities of toxic substances
Coffee residues through their wastewaters. Dyes and heavy metals are among the most typical chemicals of aforementioned
Biosorbents wastewaters, with various harmful effects on living organisms. The current work collects information from re-
Heavy metals cently published researches discussing the potential of raw or modified coffee residues for wastewater decon-
Dyes tamination. Important adsorption stages such as (i) equilibrium (isotherms), (ii) kinetic, and (iii) desorption
Adsorption isotherms are also compared. Moreover, crucial factors affecting the adsorption process, such as the effect of solution pH,
Kinetics contact time, temperature and adsorbent's dose, are also mentioned.
© 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 555
2. Isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
2.1. Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
3. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
3.1. Parameters of adsorption processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
3.2. Parameters of characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
3.2.1. FTIR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
3.2.2. BET and pHZPC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
3.2.3. SEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
3.2.4. Composition and functional groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
4. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563

1. Introduction

Water pollution due to industrial activity or hazards has become a


global issue of concern. Toxic substances into the water deter human
use, while they impair the beneficial uses of water. Among the numer-
⁎ Correspondence to: G.Z. Kyzas, Hephaestus Advanced Laboratory, Eastern Macedonia ous chemical pollutants, heavy metals are reported as the most harmful
and Thrace Institute of Technology, Kavala GR-65404, Greece.
⁎⁎ Corresponding authors.
substances for both flora and fauna, while dyes, produced by a plethora
E-mail addresses: ianastopoulos@ari.gov.cy (I. Anastopoulos), of manufactories are extremely toxic. The majority of dyes usually orig-
minakaramesouti@gmail.com (M. Karamesouti), georgekyzas@gmail.com (G.Z. Kyzas). inates from the textile industry, paper and plastic factories, tannery,

http://dx.doi.org/10.1016/j.molliq.2016.12.096
0167-7322/© 2017 Elsevier B.V. All rights reserved.
556 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565

pharmaceutical or food industry etc. [1]. They are organic substances, material with a remarkable adsorptive efficiency. Their researches re-
and are potentially dissolved in water. Based on their solubility and veal how operating conditions such as temperature, contact time, pH,
chemical characteristics, dyes are categorized into acid, basic, direct, initial substance concentration, biosorbent's dose and particle size affect
mordant, vat, reactive, disperse, azo and sulfur dyes. Examples of acid the sorption procedure. Current review article compares the adsorptive
dyes are the acid violet and the acid brilliant blue, while basic dyes are capacity of the various forms of coffee wastes, discussing the most fa-
Rhodamine B and Methylene blue. Contradictorily, the heavy metals vorable conditions for the decontamination process, separately for
are not degradable and have a multiplication effect on the majority of each hazardous substance.
biological species. They are usually disclosed during mining operations,
by agricultural products industries, tanneries, paper industries, etc. [2]. 2. Isotherms
Copper, chromium, cadmium nickel, mercury, lead and zing are the
ones usually contained in untreated industrial waters. It is necessary to form the most appropriate adsorption equilibrium
Among the most common methods for the removal of heavy metals correlation in the attempt to discover innovative adsorbents in gain ac-
from wastewaters include ion-exchange, filtration, chemical precipita- cess to an ideal adsorption system [38], which is vital for consistent pre-
tion, electrochemical treatment, chemical precipitation and adsorption diction of adsorption parameters and quantitative comparison of
[2]. For both types of aforementioned substances, adsorption is the adsorbent behavior for various adsorbent systems (or for varied exper-
most widely used method for water purification, due to the low cost, imental conditions) [39,40]. Adsorption isotherms, which is a common
the effectiveness in a wide range of pollutants and the undemanding ap- name of equilibrium relationships, are essential for optimization of the
plicability [3–27]. Several materials have been tested for their adsorp- adsorption mechanism pathways, expression of the surface properties
tion capacity such as the activated alumina, the silica gel, zeolites and and capacities of adsorbents, and productive design of the adsorption
the most popular the activated carbon [28]. Despite their satisfactory systems since they explain how pollutants interrelate with the adsor-
performance, industries are prohibited to use them extensively, due to bent materials [41,42].
their considerable cost. For this reason, scientific community incessantly Explaining the phenomenon through which the preservation (or re-
investigates for new, low cost, effective and environmentally friendly lease) or mobility of a substance from the aqueous porous media or
materials. aquatic environments to a solid-phase at a persistent temperature and
The agricultural by-products are another cause of environmental pH takes places, in broad-spectrum, an adsorption isotherm is an in-
awareness, since their disposal require careful treatment as well. A liter- valuable curve [43,44]. The mathematical association which establishes
ature survey reveals that coffee was the primary agricultural export for a significant role towards the modeling analysis, operational design and
twelve countries in 2004 and “the second most valuable commodity applicable practice of the adsorption systems is normally represented
exported by developing countries” from 1970 to circa 2000 [29]. More- by plotting a graph between solid-phase and its residual concentration
over, the coffee industry has almost doubled its production during the [45].
last decades skyrocketing the quantity of coffee wastes [30,31]. Based When the concentration of the solute remains unchanged as a result
on the United States Department of Agriculture (USDA), over 150 mil- of zero net transfer of solute adsorbed and desorbed from sorbent sur-
lion of 60 kg bags of coffee were produced during the period 2012–13, face, a condition of equilibrium is achieved. These associations between
while 1 ton of coffee may yield to N600 kg of residues [31]. the equilibrium concentration of the adsorbate in the solid and liquid
The coffee tree or shrub belongs to the family Rubiaceae. The Coffea phase at persistent temperature are defined by the equilibrium sorption
arabica (Arabica) and Coffea canephora (Robusta) plant species are pro- isotherms. Linear, favorable, strongly favorable, irreversible and unfa-
viding the 75 and 25% of the world's production respectively [32,33]. vorable are some of the isotherm shapes that may form. Understanding
With coffee drinks being one of the most popular beverages worldwide, of the mechanism of adsorption, surface properties, along with the ex-
a significant quantity of by-products is generated as well (6 Mt/yr) [31]. tent of affinity of the adsorbents are delivered by the physicochemical
The main coffee industry by-products are the spent coffee grounds parameters accompanied by the fundamental thermodynamic supposi-
(SCG), the coffee silverskin (CS) and the coffee husks (CH). CS is a tegu- tions [46].
ment of coffee beans obtained as a by-product of the roasting process. It In terms of three basic approaches, an extensive diversity of equilib-
is a residue with high concentration of soluble dietary fiber (86% of total rium isotherm models (Langmuir, Freundlich, Langmuir-Freundlich
dietary fiber) and high antioxidant capacity, probably due to the con- Brunauer-Emmett-Teller, Redlich-Peterson, Dubinin-Radushkevich,
centration of phenolic compounds in coffee beans, as well as to the pres- Temkin, Toth, Koble-Corrigan, Sips, Khan, Hill, Flory-Huggins and
ence of other compounds formed by the Maillard reaction during the Radke-Prausnitz isotherm), have been framed in the past [47]. The
roasting process, such as melanoidins [34]. Microscopic examination first approach to be mentioned is kinetic consideration, while thermo-
shows the presence of fibrous tissues from the surface layers of the CS. dynamics being the second one. A state of dynamic equilibrium with
The main components of these fibrous tissues are cellulose and hemicel- both adsorption and desorption rates in a balance is an adsorption equi-
lulose. Glucose, xylose, galactose, mannose, and arabinose are the librium and a framework of deriving numerous forms of adsorption iso-
monosaccharides present in CS; glucose being found in major amounts. therm models are given by thermodynamics [48,49]. The key idea in the
Proteins and extractives are also fractions present in significant generation of characteristic curve is generally given by the third ap-
amounts in this coffee waste. proach which is potential theory [50]. The alteration in the physical in-
SCG is a residue with fine particle size, high humidity (in the range of terpretation of the model parameters compels us to follow an
80 to 85%), organic load, and acidity, obtained during the treatment of interesting trend in the isotherm modeling which is the derivation in
raw coffee powder with hot water or steam for the instant coffee prep- more than a single approach [51]. Nowadays, the most widely used
aration. Almost 50% of the worldwide coffee production is processed for models are Langmuir, Freundlich and Langmuir-Freundlich (Table 1).
soluble coffee preparation [35]. Therefore, SCG is generated in large The amount of pollutant's uptake at equilibrium Qe (mg/g) is calcu-
amounts, with a worldwide annual generation of 6 million tons [36]. lated using the mass balance equation:
Numerically, 1 ton of green coffee generates about 650 kg of SCG, and
about 2 kg of wet SCG are obtained to each 1 kg of soluble coffee pro- ðC0 ‐Ce ÞV
Qe ¼ ð1Þ
duced [37]. m
The coffee companies, in an attempt to reduce their costs and avoid
environmental pollution, focus on alternative and profitable uses for a where C0 and Ce (mg/L) are the initial and equilibrium pollutant's con-
suppositional useless waste. Several researchers have investigated the centration, respectively; V (L) is the volume of adsorbate (solution); m
treated or untreated coffee wastes and have concluded that it is a (g) is the mass of adsorbent.
I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565 557

Table 1
Lists of adsorption isotherms mostly discussed in the present study.

Isotherm Non-linear form Ref

Langmuir Qe ¼ Q m KL C e [52]
1þKL Ce
Freundlich Qe = KF(Ce)1/n [53]
Langmuir-Freundlich Q e ¼ Q m KLF C1=n
e
1=n
[54]
1þKLF Ce

Table 2
Lists of kinetic equations.

Equation Equation form Ref

Pseudo-first order (non-linear) Qt¼ Q e ð1‐e−k l t Þ [58]


Pseudo-first order (linear) 1n(Qe‐Qt) = 1n(Qe)‐K1t [58]
Pseudo-second order (non-linear) k Q2t
Q t ¼ 1þk2 2 Qe e t [59]

Pseudo-second order (linear) t


¼ 1
þ ðQ1e Þt [60]
Qt k2 Q 2e

2.1. Kinetics The physicochemical properties of the adsorbent basically corre-


spond to particle diameter, the cation exchange capacity the zeta poten-
Kinetic studies are important for the prediction of optimum condi- tial, the pH value at the point of zero change (pHPZC) and the functional
tions in full-scale batch adsorption processes [55]. Kinetic modeling groups (verified by FTIR spectra), which affect the adsorptive efficiency
gives information about adsorption mechanisms and possible rate-con- of solids. Generally, low particle diameter suggests greater surface area,
trolling steps such as mass transport or chemical reaction processes which in turn enhances adsorption. Moreover, cation exchange capacity
[55–57]. Several kinetic models as pseudo-first and pseudo-second as well as higher zeta potential measurements also increase adsorptive
order (linear or non-linear forms), intraparticle diffusion and Elovich capacity of solids.
are available. The most prevalent are the pseudo-first and the pseudo- Among the most significant chemical characteristics of adsorbates
second order kinetic equations. The linear and non-linear forms of pseu- affecting adsorption, the pKa, the ionic radius, the electronegativity
do-first and pseudo-second order kinetic models are presented in Table and the free energy of dehydration can also be considered. In the case
2. of ions, the greater the atomic weight, the electronegativity and the
ionic size, the greater the affinity for the sorption. On the contrary, the
3. Discussion higher the values of the free energy of hydration, the more ion metals
tend to remain to the solute phase, instead of being adsorbed. Addition-
3.1. Parameters of adsorption processes ally, the lower the pKa value, the higher the adsorption.
But, the prevailing experimental conditions are very important for
Adsorption is a process occurring on the surface of almost all solids. the adsorption evaluation. The critical experimental conditions affecting
However, the adsorption capacity of solid materials is dependent on the adsorption capacity of a solid are the initial concentration, the pH of
several highly interrelated factors, which can be classified into four the aqueous solution, the contact time, the temperature, the biomass
main categories/domains: (i) the physicochemical properties of the ad- dosage and the co-existence of other pollutants.
sorbent, (ii) the chemical characteristics of the adsorbates, (iii) the pre- The initial concentration and the adsorption capacity are generally
vailing experimental conditions and d) the affinity between adsorbent positively correlated, however in cases of extreme increase of the initial
and the adsorbate. concentration, the aforementioned assumption is not valid [61].

250
Synthetic sample
225 250

200
175 200
Q e (mg/g)

150
Q e (mg/g)

150
125
100
100
75
50 o o
25 C - pH=2 o o
25 C - pH=10 50 BB - 25 C RB - 25 C
o o
25 45 C - pH=10 45 C - pH=2 o
BB - 45 C
o
RB - 45 C
o o
65 C - pH=10 65 C - pH=2 o
BB - 65 C
o
RB - 65 C
0 0
0 100 200 300 400 500 600 700 800 900 0 100 200 300 400 500 600 700 800 900
Ce (mg/L)
Ce (mg/L)

(a) (b)
Fig. 1. Effect of temperature in dyes removal ((a) synthetic mixtures; (b) single-component dye solutions) after adsorption onto coffee wastes. Reprinted with permission [66,67].
558 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565

Table 3
Adsorption parameters (experimental conditions) for the removal of heavy metals.

Adsorbent Metal Experimental conditions Isotherm Kinetic Qm or removal (%) Ref

Coffee grounds Cu(II) (1) 0.5–3.0 mg/L – – 97%a [71]


(2) b200 μm, N200 μm
(3) 5 g/L
(5) 120–130 rpm
(7) 60 min
Coffee residues (1) 0–150 mg/L LF PS1 70 mg/g [72]
(7) 5–1440 min
(2) 475–525 μm
(4) 2–8
Exhausted coffee grounds (1) 124.7 mg/L – – 16.4% [73]
(2) 0.25–0.45 mm
(4) pH 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 18% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 23.7% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 20.8% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 40.3% [73]
(4) 5
(7) 60 min
Spent coffee grains (1) 0.08–4.72 mmol/L L PS2 0.19 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 2–12
(7) 0–1440 min
Spent coffee grains (1) 0.08–4.72 mmol/L L PS2 0.45 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 4–5
(7) 7200 min
Spent coffee grains (1) 0.08–4.72 mmol/L L PS2 1.53 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 2–12
(7) 7200 min
Coffee grounds Pb(II) (1) 0.5–3.0 mg/L – – 96%a [71]
(2) b200 μm, N200 μm
(3) 5 g/L
(5) 120–130 rpm
(7) 60 min
Spent coffee grains (1) 0.01–1.2 mmol/L L PS2 0.42 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 3, 4
(7) 7200 min
Spent coffee grains (1) 0.01–1.2 mmol/L L PS2 0.45 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 2–12
(7) 7200 min
Spent coffee grains (1) 0.01–1.2 mmol/L L PS2 0.77 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 2–12
(7) 7200 min
Coffee husks (1) 25 mg/L L PS2 7.2 mg/g [75]
(3) 0–9 g/L
(4) 0.5–9
(6) 0–150 °C
(7) 0–240 min
Coffee husks (1) 25 mg/L L PS2 230 mg/g [76]
(3) 0–9 g/L
(4) 0.5–9
(6) 0–150 °C
(7) 0–240 min
Coffee residues (1) 20, 80 mg/L – PS2 9.7 mg/g [77]
(2) 0.149 mm
(3) 1, 2 g/L
(4) 3, 5
(7) 0–180 min
Exhausted coffee grounds (1) 19–291 μmol/L L – 18.5–72.4 μmol/ga [78]
(2) 1 mm
(3) 0.388–8.738 g/L
Coffee husks (1) 0–120 mg/L L, F PS2 50.8 mg/g [79]
(3) 0.5–12 g
(4) 2–9
I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565 559

Table 3 (continued)

Adsorbent Metal Experimental conditions Isotherm Kinetic Qm or removal (%) Ref

(5) 50–300 rpm


(7) 30–240 min
Exhausted coffee grounds Cr(VI) (1) 98.1, 304.9 mg/L – – 87.93, 88.54%a [73]
(2) 0.25–0.45 mm
(4) pH 2
(5) 40 rpm
(7) 4 days
Exhausted coffee grounds (1) 98.1, 304.9 mg/L – – 88.95, 90.38%a [73]
(4) pH 2
(5) 40 rpm
(7) 4 days
Exhausted coffee grounds (1) 98.1, 304.9 mg/L – – 90.21, 91.22%a [73]
(4) pH 2
(5) 40 rpm
(7) 4 days
Exhausted coffee grounds (1) 98.1, 304.9 mg/L – – 90.18, 91.21%a [73]
(4) pH 2
(5) 40 rpm
(7) 4 days
Exhausted coffee grounds (1) 98.1, 304.9 mg/L – – 84.5, 86.63%a [73]
(4) pH 2
(5) 40 rpm
(7) 4 days
Coffee husks (1) 25 mg/L L PS2 5.9 mg/g [75]
(3) 0–9 g/L
(4) 0.5–9
(6) 0–150 °C
(7) 0–240 min
Coffee husks (1) 25 mg/L L PS2 220 mg/g [76]
(3) 0–9 g/L
(4) 0.5–9
(6) 0–150 °C
(7) 0–240 min
Coffee husks (1) 20–100 mg/L L PS2 59.54 mg/g [80]
(3) 0.5–5 g
(4) 2–8
(6) 25–55 °C
(7) 30–240 min
Exhausted coffee grounds Ni(II) (1) 124.7 mg/L – – 0% [73]
(2) 0.25–0.45 mm
(4) pH 5
(7) 60 min
Exhausted coffee grounds (1) 124.7 mg/L – – 7.7% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1) 124.7 mg/L – – 6.9% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 7.7% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 24.3% [73]
(4) 5
(7) 60 min
Coffee residues Zn(II) (1) 20, 80 mg/L – PS2 4.4 mg/g [77]
(2) 0.149 mm
(3) 1, 2 g/L
(4) 3, 5
(7) 0–180 min

(1) Initial concentration, (2) particle size, (3) adsorbent dosage, (4) effect of pH, (5) agitation speed, (6) effect of temperature, (7) effect of contact time, (8) effect of solution's volume, (9)
effect of ionic strength.
L: Langmuir, F: Freundlich, L-F: Langmuir-Freundlich, PS1: Pseudo-first order, PS2: Pseudo-second order.
a
Calculated from initial concentration study.

The solution pH plays an important role in controlling the surface first stage, the sorption process is accelerated due to the high availability
charge of the adsorbent, the degree of ionization of the adsorbate in of active sites on the biosorbent, while, in the second stage, the process
the solution as well as in the dissociation of various functional groups is decelerated until an equilibrium is reached [63].
on the active sites of the adsorbent [62]. Temperature is also critical to the adsorption process. The reported
Concerning the contact time, there are always identified two main positive correlation between the temperature and adsorption is mainly
stages during sorption process: (i) the rapid and quantitatively predom- attributed to the increased numbers of active surface sites and the in-
inant and (ii) the slower and quantitatively insignificant. During the crease in the porosity, which consequently increases the pore volume
560 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565

Table 4
Adsorption parameters (experimental conditions) for the removal of dyes.

Adsorbent Dye Experimental conditions Isotherm Kinetic Qm or removal (%) Ref

Biochar from coffee grounds Rhodamine B (2) 0.3 mm – – 45%a [81]


(3) 0.3–5 g
(4) 1–10
Biochar from coffee grounds (2) 0.3 mm – – 18%a [81]
(3) 0.3–5 g
(4) 1–10
Biochar from coffee grounds (2) 0.3 mm – – 38%a [81]
(3) 0.3–5 g
(4) 1–10
Coffee ground powder (1) 7.18 mg/L L PS1, PS2 2.52 mg/g [82]
(3)1 g/L
(6) 5–19 °C
(7) 0–120 min
(8) 10–200 mL
(9) 0.001–0.1 M K2SO4
Coffee ground powder Rhodamine 6G (1) 6.65 mg/L L PS1, PS2 7.7 mg/g [82]
(3) 1 g/L
(6) 5–19 °C
(7) 0–120 min
(8) 10–200 mL
(9) 0.001–0.1 M K2SO4
Coffee wastes Crystal violet (1) 80–400 mg/L L PS2 125 mg/g [83]
(3) 0.1–10 g/L
(4) 2.3–10.5
(6) 20–50 °C
(7) 0–180 min
(9) 0–30 g/L NaCl
Polyphenol coffee grounds (1) 50, 150, 250 mg/L F PS2 36.82 mg/g [84]
(3) 5, 15, 25 g/L
(4) 3, 6, 9
(5) 200 rpm
(6) 27 °C
(7) 0.5, 5.25, 10 min
Coffee wastes Toluidine blue (1) 80–400 mg/L L PS2 142.5 mg/g [83]
(3) 0.1–10 g/L
(4) 2.3–10.5
(6) 20–50 °C
(7) 0–180 min
(9) 0–30 g/L NaCl
Coffee wastes Methyl orange (1) 20–120 mg/L L PS2 58.82 mg/g [85]
(3) 0.2–20 g/L
(4) 2.7–10.5
(5) 120 rpm
(6) 25–55 °C
(7) 0–240 min
(9) 0–10 g/L NaCl
Coffee wastes (1) 20–120 mg/L L PS2 62.5 mg/g [85]
(3) 0.2–20 g/L
(4) 2.7–10.5
(5) 120 rpm
(6) 25–55 °C
(7) 0–240 min
(9) 0–10 g/L NaCl
Coffee residues Methyl red (1) 5–50 mg/L L, F – 98%a [86]
(2) 0.05–0.25 g/L
(4) 3–10
(7) 10–60 min
Coffee residues (1) 5–50 mg/L L, F – 93.5%a [86]
(2) 0.05–0.25 g/L
(4) 3–10
(7) 10–60 min
Coffee residues (1) 5–50 mg/L L, F – 86.3%a [86]
(2) 0.05–0.25 g/L
(4) 3–10
(7) 10–60 min
Magnetic coffee silverskin Methylene blue (1) 25–1000 mg/L L PS2 556 mg/g [87]
(7) 30–300 min
Magnetic green coffee (1) 50 mg/L – PS2 66.2 mg/gb [88]
(2) b500 μm
(3) 0.5 g/L
(4) 5.5
(6) 20 °C
(7) 30–300 min
Magnetic coffee silverskin (1) 50 mg/L – PS2 99 mg/gb [88]
(2) b500 μm
I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565 561

Table 4 (continued)

Adsorbent Dye Experimental conditions Isotherm Kinetic Qm or removal (%) Ref

(3) 0.5 g/L


(4) 5.5
(6) 20 °C
(7) 30–300 min
Magnetic spent coffee grounds (1) 50 mg/L – PS2 78.1 mg/gb [88]
(2) b500 μm
(3) 0.5 g/L
(4) 5.5
(6) 20 °C
(7) 30–300 min
Coffee residues (1) 10–100 mg/L L – 4.68 mg/g [89]
(2) b0.595 mm
(3) 20–60 g/L
(4) 3–10
(5) 100 rpm
(6) 30 °C
(7) 0–20 min
Coffee residues (3) 0.5–1 g/L L PS2 112 mg/g [1]
(4) 7.5
(6) 25 °C
(7) 0–1440 min
Pyrolized coffee residues (3) 0.5–1 g/L L PS2 132 mg/g [1]
(4) 7.5
(6) 25 °C
(7) 0–1440 min
Coffee residues (1) 5–60 mg/L F PS2 6.69 mg/gb [90]
(2) b0.5 mm
(3) 7 g/L
(5) 120 rpm
(6) 27 °C
(7) 10–180 min
Coffee husks Brilliant yellow 3G-P (1) 15–550 mg/L L – 24.04–35.04 mg/g [91]
(4) 2–12
(6) 20, 30, 40 °C
Coffee wastes Remazol red 3BS (1) 0–1000 mg/L L, L-F PS1 179–241 mg/g [92]
Remazol yellow 3RS (2) 475–525 μm PS2
Remazol blue RN (3) 0–15 g/L PS3
(4) 2–12
(5) 60–180 rpm
(6) 25–65 °C
(7) 0–1440 min
Coffee husks Fast green (3) 0.5 to 5 mg/L L, F PS1 96.6 mg/g [93]
(4) 2–5
(5) 120 rpm

(1) Initial concentration, (2) particle size, (3) adsorbent dosage, (4) effect of pH, (5) agitation speed, (6) effect of temperature, (7) effect of contact time, (8) effect of solution's volume, (9)
effect of ionic strength.
L: Langmuir, F: Freundlich, L-F: Langmuir-Freundlich, PS1: Pseudo-first order, PS2: Pseudo-second order, PS3: Pseudo-third order.
a
Calculated from initial concentration study.
b
Calculated from kinetic study.

of the adsorbent. Aksu reported an increase of the activated carbon's ca- other bio-materials, the temperature increase affects the texture of bio-
pacity, by increasing the temperature from 25 to 45 °C [64]. Additional- mass, reducing the sorption capacity. Based on Qaiser et al. [69], the
ly, the increase of temperature decreases the thickness of the boundary overall metal uptake by biomass is significantly affected by the temper-
layer surrounding the sorbent, enhancing the adsorption as well. More- ature, due to the high variability of potential binding sites.
over, higher temperature increases the kinetic energy of the dye mole- The biomass dosage is positively correlated to the adsorptive capac-
cules, enhancing the rate of intraparticle diffusion of the sorbate. Alpat ity due to the fact that the greater the surface area the greater the avail-
et al. [65] reported an increase in the Ni(II) biosorption within the tem- ability of the adsorption sites [70]. However, after a certain point, it is
peratures 20 to 40 °C, while in temperatures from 40 to 60 °C a decrease found that the uptake capacity drops, due to the aggregation/agglomer-
was reported. This decrease is possibly attributed to the deactivation of ation of adsorbent particles, leading to a decrease in the available sur-
the biosorbent surface or the destruction of some active sites on the face area [70]. Table 3 indicates the initial experimental conditions
biosorbent's surface. Contrary results were presented by Kyzas, who from the biosorption experiments of heavy metals using coffee resi-
found that the increase of temperature caused an increase in adsorption dues/wastes as biosorbent material, while the respective Table 4 is for
capacity for dyes removal [66,67] (Fig. 1a, b). dyes removal.
Horsfall and Spiff [68] concluded that at high temperatures there is
noted a decrease in the thickness of the boundary layer due to the in- 3.2. Parameters of characterization
creased tendency of the metal ion to escape from the biomass surface,
while the metal is in solution phase, limiting the adsorption process. 3.2.1. FTIR
The decrease in the adsorption, resulting from the increasing tempera- There are many analytical techniques to characterize the coffee res-
ture, occurs due to the weak interaction between the biomass surface idues. Fourier transform analysis is a useful tool, which reveals the pos-
and the metal ion, implying that a physisorption process take place. In sible functional groups which are able to interact with target pollutant.
562 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565

Table 5 cationic species while at pH values lower than pHPZC, the solid surface
Interactions of functional groups of coffee adsorbents and their shifts in FTIR spectra. has a positive charge and could interact with ionic species [98]. Τhe
Adsorbent Wavenumber Assignment Ref knowledge of pHPZC could be useful to understand the protonation/de-
(cm−1) (functional groups) protonation behavior of sorbent materials for explaining the adsorption
Coffee wastes 3446 Bonded O\ \H [83] mechanism [97]. Besides the pHPZC, adsorption also depends on the sur-
2924 C\\H face area. The amount of material adsorbed is directly proportional to
2852 CH2 the specific surface. The more the surface area the more adsorbed
1728 C_O stretching vibration
amount [99].
1658 COO
1535 N\\H
1454 C_O 3.2.3. SEM
1382 COO\ \ The morphology of coffee adsorbents varies due to the treatment of
1165 C\\O\\C stretching vibration them (washing etc.) before adsorption use. Azouaou et al. showed the
1029 C\\O stretching vibration
Spent coffee 3473 Bonded O\ \H, N\\H [94,95]
structure of coffee grounds indicating that the coffee grounds had a po-
grounds 2925 Aliphatic\\CH rous and homogenous structure with deep pores [100] (Fig. 2a, b). On
2854 Aliphatic\\CH the other hand, in the case of untreated coffee materials the surface
1741 C_O stretching was not smooth, but scraggy with a variety of cavities [67,101] (Fig.
1641 C_O stretching, N\ \H, secondary
2c, d). These cavities can be characterized as channels onto the surface
amine
1543 Secondary amine group of untreated coffee materials instead of pores, given the small surface
1462 Symmetric banding of CH3 area calculated from BET analysis.
1377 N\\H,\\OH stretching
1246 Symmetric banding of CH3 3.2.4. Composition and functional groups
1165 C\\O\\C vibration
The most usual way to determine the surface functional groups onto
1088 Stretching vibration of C\
\OH
613 Stretching vibration of\\CN coffee adsorbents is based on the Boehm titration method [102]. Aque-
Coffee residues 3390 Stretching vibration of bonded O\\H [96] ous solutions of NaHCO3 (0.10 mol/L), Na2CO3 (0.05 mol/L), NaOH
2924 Asymmetrical stretch vibration\ \CH3 (0.10 mol/L), and HCl (0.10 mol/L) were prepared. 50 mL of these solu-
2854 Symmetrical stretch vibration\\CH2
tions were added to vials containing 1 g of dry coffee samples, let to be
1651 Stretching vibration of C_O
1463 Symmetric bending of\ \CH3 shaken (~140 rpm) until equilibrium (24 h), and then filtered. Five so-
1377 Asymmetrical bending vibration of lution blanks (without the adsorbent) were also prepared. In this way,
\\CH3,\ \CH2 the number of the basic sites was calculated from the amount of HCl
that reacted with the coffee adsorbents. The various free acidic groups
were derived using the assumption that NaOH neutralizes carboxyl, lac-
Many researchers applied this technique before (pure) and after (load- tone and phenolic groups, Na2CO3 neutralizes carboxyl and lactone and
ed material) adsorption to find changes in absorption of different bands. NaHCO3 neutralizes only carboxyl groups. The excess of base or acid was
Α detailed description about different functional groups is listed in Table then determined by back titration using NaOH (0.10 mol/L) and HCl
5. Imessaoudene et al. [94] observed that after cobalt by spent coffee the (0.10 mol/L) solutions [103]. Based on the above, Kyzas found that the
infrared bands 3473, 1641, 1543, 1377, 1088 and 613 cm−1 were slight- composition of coffee residues was 44% water, 12% protein, 14% lipids,
ly shifted to 3465, 1635, 1520, 1379, 1068 and 609 cm−1, respectively, 25% carbohydrates and 5% ash [72]. According to Boehm method
suggested that\\OH, C_O and amino groups may be participate in ad- [102], the functional groups at the surface of adsorbents were carboxylic
sorption process. Nitayaphata et al. [89] concluded that after methylene 0.97 mmol/g and basic 0.93 mmol/g, followed by phenolic 0.14 mmol/g
blue adsorption by coffee residues the bands shifted from 3390 and and 0.11 lactonic mmol/g. In another study [67], the respective compo-
1651 cm−1 to 3396 and 1627 cm−1, respectively demonstrated that sition was determined as 41% water, 9% protein, 20% lipids, 27% carbo-
carbonyl and hydroxyls group could be ideal actives sites for methylene hydrates and 3% ash, while the results from Boehm method showed
blue adsorption. Based on another study, before and after adsorption of that the coffee surface was carboxylic 0.94 mmol/g and basic
crystal violet cationic dye by polyphenol-extracted coffee grounds, the 0.91 mmol/g, followed by phenolic 0.16 mmol/g and 0.12 lactonic
bands went from 2924 to 2920 cm−1 attributed to C\\H asymmetric mmol/g. Franca et al. [104] found different results for the composition
and symmetric stretch of methyl and methylene groups get involved (47% water, 7% protein, 17% lipids, 28% carbohydrates and 1% ash),while
in adsorption. the results from Boehm method showed that the coffee surface was ap-
proximately neutral (carboxylic 0.80 mmol/g and basic 0.78 mmol/g,
3.2.2. BET and pHZPC followed by phenolic 0.12 mmol/g and 0.07 lactonic mmol/g). Oliveira
Another significant material characteristics of that governed the ad- et al. found different results [105]; the proximate composition of the
sorption phenomenon are the pH and surface area (Table 6). In sorption coffee husks employed was 10% water, 11% protein, 2% lipids, 70% car-
processes, the pH plays a significant role due to the fact that it affects the bohydrates and 7% ash. The functional groups at the surface of the
ionization of active sites and it influences the surface charge. The pH at husks were predominantly phenolic (2.24 mmol/g), followed by lacton-
which the sorbent surface charge takes a zero value is defined as point ic (1.05 mmol/g), carboxylic (0.60 mmol/g) and basic (0.49 mmol/g)
of zero charge (pHPZC) [97]. For pH values higher than pHPZC, the sor- groups. All above clearly indicate the differentiation of surface chemis-
bent has a negative sorbent surface charge and could interact with try of coffees which is directly related with the treatment before the ad-
sorption use.

Table 6 4. Concluding remarks


BET and pHPZC parameters of various coffee adsorbents.

Adsorbent BET surface area (m2/g) pHPZC Ref Current work reviews the most recent researches on wastewater pu-
Coffee residues 0.19 3.9 [77] rification using the widely available coffee by-products. Scientists main-
Coffee husks 0.41 5.2 [91] ly focus on the adsorption of heavy metals and dyes, since they are
Coffee wastes ~2.3 3.3–3.5 [92] considered as the most common chemical pollutants, threatening
Coffee residues 187 – [89] water resources and the ecosystem. The researchers applied the tech-
Coffee wastes – 5.5 ± 2 [83]
nique of the adsorption, since it is acknowledged as the most effective
I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565 563

Fig. 2. SEM images for different coffee adsorbents. Reprinted with permission by Elsevier [67,100,101].

and inexpensive methodology in water purification, while it proves to [3] I. Anastopoulos, G.Z. Kyzas, Agricultural peels for dye adsorption: a review of re-
cent literature, J. Mol. Liq. 200 (2014) 277–285.
be suitable for the vast majority of pollutants. [4] I. Anastopoulos, G.Z. Kyzas, Progress in batch biosorption of heavy metals onto
Despite the significant amount of available literature, comparative algae, J. Mol. Liq. 209 (2015) 77–86.
analysis between studies is intricate due to the absence of a process pro- [5] I. Anastopoulos, G.Z. Kyzas, Composts as biosorbents for decontamination of vari-
ous pollutants: a review, Water Air Soil Pollut. 226 (2015), Article ID 61. .
tocol. Harmonization of experimental processes can be significantly [6] I. Anastopoulos, I. Massas, C. Ehaliotis, Use of residues and by-products of the olive-oil
useful during the juxtaposition of the performance of variable adsor- production chain for the removal of pollutants from environmental media. A review
bents for variable pollutants. The study of adsorption mechanism is a of batch biosorption approaches, J. Environ. Sci. Health., Part A 50 (2015) 677–718.
[7] G.Z. Kyzas, D.N. Bikiaris, Recent modifications of chitosan for adsorption applica-
complex issue and it is usually poorly discussed, mainly based only on tions: a critical and systematic review, Mar. Drugs 13 (2015) 312–337.
model implementation, (i.e. kinetics, thermodynamics etc.). Although [8] G.Z. Kyzas, J. Fu, N.K. Lazaridis, D.N. Bikiaris, K.A. Matis, New approaches on the re-
many researchers use batch experiments, column studies are necessary moval of pharmaceuticals from wastewaters with adsorbent materials, J. Mol. Liq.
209 (2015) 87–93.
for better understanding coffee waste practical applicability in pilot-,
[9] G.Z. Kyzas, K.A. Matis, Nanoadsorbents for pollutants removal: a review, J. Mol. Liq.
and full-scale operations. Evidently, the chemical modification of natu- 203 (2015) 159–168.
ral by-products improves their sorptive ability, however, the sorptive [10] I. Anastopoulos, I. Massas, C. Ehaliotis, Composting improves biosorption of Pb2+
capacity of raw materials should be included in the study, as a reference and Ni2+ by renewable lignocellulosic materials. Characteristics and mechanisms
involved, Chem. Eng. J. 231 (2013) 245–254.
base point, as well. Moreover, testing repetitive adsorption – desorption [11] I. Anastopoulos, M. Panagiotou, C. Ehaliotis, P.A. Tarantilis, I. Massas, NaOH pre-
cycles is critical for material reusability assessment, while testing the treatment of compost derived from olive tree pruning waste biomass greatly im-
material in real wastewaters is necessary for estimating its the actual ef- proves biosorbent characteristics for the removal of Pb2+ and Ni2+ from
aqueous solutions, Chem. Ecol. 31 (2015) 724–740.
ficiency. Finally, apart from the material FTIR analysis and BET surface [12] Y. Zhang, L. Yan, W. Xu, X. Guo, L. Cui, L. Gao, Q. Wei, B. Du, Adsorption of Pb(II) and
area estimation, the initial presence of heavy metals in the original Hg(II) from aqueous solution using magnetic CoFe2O4-reduced graphene oxide, J.
raw materials is another very important information for the scientist. Mol. Liq. 191 (2014) 177–182.
[13] B. Yahyaei, S. Azizian, Rapid adsorption of binary dye pollutants onto the
Future work should focus on the estimate of the potential cost of the nanostructred mesoporous alumina, J. Mol. Liq. 199 (2014) 88–95.
adsorption process. Alternative techniques for the improvement of the [14] X. Tang, Q. Zhang, Z. Liu, K. Pan, Y. Dong, Y. Li, Removal of Cu(II) by loofah fibers as
materials' adsorptive capacity, such as composting, should be consid- a natural and low-cost adsorbent from aqueous solutions, J. Mol. Liq. 191 (2014)
73–78.
ered. Finally, adsorption generates large amount of wastes and conse-
[15] A. Shamsizadeh, M. Ghaedi, A. Ansari, S. Azizian, M.K. Purkait, Tin oxide nanoparti-
quently their disposal suggests a crucial environmental issue. cle loaded on activated carbon as new adsorbent for efficient removal of malachite
green-oxalate: non-linear kinetics and isotherm study, J. Mol. Liq. 195 (2014)
212–218.
[16] T.A. Saleh, A.A. Al-Saadi, V.K. Gupta, Carbonaceous adsorbent prepared from waste
References tires: experimental and computational evaluations of organic dye methyl orange, J.
Mol. Liq. 191 (2014) 85–91.
[1] A. Orfanos, I.D. Manariotis, H.K. Karapanagioti, Sorption of methylene blue onto [17] L. Qian, M. Ma, D. Cheng, The effect of water chemistry on adsorption and desorp-
food industry byproducts, Int. Biochar Initiat (2015), Article ID 7046. . tion of U(VI) on nano-alumina, J. Mol. Liq. 197 (2014) 295–300.
[2] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters: a review, J. Envi- [18] P. Li, Z. Du, X. Ma, G. Wang, G. Li, Synthesis, adsorption and aggregation properties
ron. Manage. 92 (2011) 407–418. of trisiloxane room-temperature ionic liquids, J. Mol. Liq. 192 (2014) 38–43.
564 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565

[19] C. Li, Y. Dong, J. Yang, Y. Li, C. Huang, Modified nano-graphite/Fe3O4 composite as [52] I. Langmuir, The constitution and fundamental properties of solids and liquids. Part
efficient adsorbent for the removal of methyl violet from aqueous solution, J. I. Solids, J. Am. Chem. Soc. 38 (1916) 2221–2295.
Mol. Liq. 196 (2014) 348–356. [53] H. Freundlich, Over the adsorption in solution, Z. Phys. Chem. 57 (1906) 385–470.
[20] E.G. Lemraski, E. Kargar, Standard Gibbs energy of adsorption and surface proper- [54] C. Tien, Adsorption Calculations and Modeling, Butterworth-Heinemann, Boston,
ties for ionic liquids binary mixtures, J. Mol. Liq. 195 (2014) 17–21. U.S.A., 1994
[21] R. Hosseini Nia, M. Ghaedi, A.M. Ghaedi, Modeling of reactive orange 12 (RO 12) [55] J. Febrianto, A.N. Kosasih, J. Sunarso, Y.-H. Ju, N. Indraswati, S. Ismadji, Equilibrium
adsorption onto gold nanoparticle-activated carbon using artificial neural network and kinetic studies in adsorption of heavy metals using biosorbent: a summary of
optimization based on an imperialist competitive algorithm, J. Mol. Liq. 195 (2014) recent studies, J. Hazard. Mater. 162 (2009) 616–645.
219–229. [56] D. Park, Y.S. Yun, J.M. Park, The past, present, and future trends of biosorption,
[22] Y.F. Hao, L.G. Yan, H.Q. Yu, K. Yang, S.J. Yu, R.R. Shan, B. Du, Comparative study on Biotechnol. Bioprocess Eng. 15 (2010) 86–102.
adsorption of basic and acid dyes by hydroxy-aluminum pillared bentonite, J. Mol. [57] G.Z. Kyzas, J. Fu, K.A. Matis, New biosorbent materials: selectivity and bioengineer-
Liq. 199 (2014) 202–207. ing insights, Processes 2 (2014) 419–440.
[23] D. Gusain, F. Bux, Y.C. Sharma, Abatement of chromium by adsorption on nanocrys- [58] S. Lagergren, About the theory of so-called adsorption of soluble substances,
talline zirconia using response surface methodology, J. Mol. Liq. 197 (2014) Handlingar 24 (1898) 1–39.
131–141. [59] G. Blanchard, M. Maunaye, G. Martin, Removal of heavy metals from waters by
[24] A.A. El-Bindary, M.A. Hussien, M.A. Diab, A.M. Eessa, Adsorption of Acid Yellow 99 means of natural zeolites, Water Res. 18 (1984) 1501–1507.
by polyacrylonitrile/activated carbon composite: kinetics, thermodynamics and [60] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process
isotherm studies, J. Mol. Liq. 197 (2014) 236–242. Biochem. 34 (1999) 451–465.
[25] A.A. El-Bindary, A.Z. El-Sonbati, A.A. Al-Sarawy, K.S. Mohamed, M.A. Farid, Adsorp- [61] R.P.S. Jeyakumar, V. Chandrasekaran, Adsorption of lead(II) ions by activated car-
tion and thermodynamic studies of hazardous azocoumarin dye from an aqueous bons prepared from marine green algae: equilibrium and kinetics studies, Int. J.
solution onto low cost rice straw based carbons, J. Mol. Liq. 199 (2014) 71–78. Ind. Chem. 5 (2014) 1–9.
[26] L. Cui, W. Xu, X. Guo, Y. Zhang, Q. Wei, B. Du, Synthesis of strontium hydroxyapatite [62] S. Banerjee, M.C. Chattopadhyaya, Adsorption characteristics for the removal of a
embedding ferroferric oxide nano-composite and its application in Pb2+ adsorp- toxic dye, tartrazine from aqueous solutions by a low cost agricultural by-product,
tion, J. Mol. Liq. 197 (2014) 40–47. Arab. J. Chem. (2016) (in press) http://dx.doi.org/10.1016/j.arabjc.2013.1006.1005.
[27] S. Azizian, M. Bagheri, Enhanced adsorption of Cu2+ from aqueous solution by Ag [63] M. Zaheer Aslam, N. Ramzan, S. Naveed, N. Feroze, Ni(II) removal by biosorption
doped nano-structured ZnO, J. Mol. Liq. 196 (2014) 198–203. using Ficus religiosa (Peepal) leaves, J. Chil. Chem. Soc. 55 (2010) 81–84.
[28] A. Bhatnagar, M. Sillanpää, Utilization of agro-industrial and municipal waste ma- [64] Z. Aksu, A. Tatlı, Ö. Tunç, A comparative adsorption/biosorption study of Acid Blue
terials as potential adsorbents for water treatment - a review, Chem. Eng. J. 157 161: effect of temperature on equilibrium and kinetic parameters, Chem. Eng. J.
(2010) 277–296. 142 (2008) 23–39.
[29] S. Ponte, The ‘Latte Revolution’? Regulation, markets and consumption in the glob- [65] S. Alpat, S.K. Alpat, B.H. Çadirci, Ö. Özbayrak, İ. Yasa, Effects of biosorption param-
al coffee chain, World Dev. 30 (2002) 1099–1122. eter: kinetics, isotherm and thermodynamics for Ni(II) biosorption from aqueous
[30] J.M.V. Nabais, P. Nunes, P.J.M. Carrott, M.M.L. Ribeiro Carrott, A.M. García, M.A. solution by Circinella sp, Electron. J. Biotechnol. 13 (2010) 4–5.
Díaz-Díez, Production of activated carbons from coffee endocarp by CO2 and [66] G. Kyzas, A decolorization technique with spent “Greek Coffee” grounds as zero-
steam activation, Fuel Process. Technol. 89 (2008) 262–268. cost adsorbents for industrial textile wastewaters, Materials 5 (2012) 2069–2087.
[31] S.I. Mussatto, E.M.S. Machado, S. Martins, J.A. Teixeira, Production, composition, [67] G.Z. Kyzas, N.K. Lazaridis, A.C. Mitropoulos, Removal of dyes from aqueous solu-
and application of coffee and its industrial residues, Food Bioproc. Tech. 4 (2011) tions with untreated coffee residues as potential low-cost adsorbents: equilibrium,
661–672. reuse and thermodynamic approach, Chem. Eng. J. 189-190 (2012) 148–159.
[32] H.D. Belitz, W. Grosch, P. Schieberle, Coffee, tea, cocoa, Food Chem. 938-951 [68] M. Horsfall Jnr., A.I. Spiff, Effects of temperature on the sorption of Pb2+ and Cd2+
(2009). from aqueous solution by Caladium bicolor (Wild cocoyam) biomass, Electron. J.
[33] H. Etienne, Somatic embryogenesis protocol: coffee (Coffea arabica L. and C. Biotechnol. 8 (2005) 43–50.
canephora P.), Protoc. Somatic Embryogenesis Woody Plants 77 (2005) 167–179. [69] S. Qaiser, A.R. Saleemi, M.M. Ahmad, Heavy metal uptake by agro based waste ma-
[34] R.C. Borrelli, F. Esposito, A. Napolitano, A. Ritieni, V. Fogliano, Characterization of a terials, Electron. J. Biotechnol. 10 (2007) 409–416.
new potential functional ingredient: coffee silverskin, J. Agric. Food Chem. 52 [70] K. Belay, A. Hayelom, Removal of methyl orange from aqueous solutions using
(2004) 1338–1343. thermally treated egg shell (locally available and low cost biosorbent), Chem.
[35] K. Ramalakshmi, L.J.M. Rao, Y. Takano-Ishikawa, M. Goto, Bioactivities of low-grade Mater. Res. 6 (2014) 31–39.
green coffee and spent coffee in different in vitro model systems, Food Chem. 115 [71] J. Seniūnaitė, R. Vaiškunait, V. Bolutien, Coffee grounds as an adsorbent for copper
(2009) 79–85. and lead removal form aqueous solutions, In: The 9th International Conference
[36] T. Tokimoto, N. Kawasaki, T. Nakamura, J. Akutagawa, S. Tanada, Removal of lead “ENVIRONMENTAL ENGINEERING”, VGTU Press, 2014 (22–23 May 2014, Vilnius,
ions in drinking water by coffee grounds as vegetable biomass, J. Colloid Interface Lithuania).
Sci. 281 (2005) 56–61. [72] G.Z. Kyzas, Commercial coffee wastes as materials for adsorption of heavy metals
[37] R.A. Pfluger, Soluble coffee processing, Solid Wastes: Origin, Collection, Processing, from aqueous solutions, Materials 5 (2012) 1826–1840.
and Disposal, 1975. [73] C. Liu, D. Pujol, M.À. Olivella, F. De La Torre, N. Fiol, J. Poch, I. Villaescusa, The role of
[38] V.C. Srivastava, M.M. Swamy, I.D. Mall, B. Prasad, I.M. Mishra, Adsorptive removal exhausted coffee compounds on metal ions sorption, Water Air Soil Pollut. 226
of phenol by bagasse fly ash and activated carbon: equilibrium, kinetics and ther- (2015), Article ID 289. .
modynamics, Colloids Surf., A 272 (2006) 89–104. [74] F.J. Cerino-Córdova, P.E. Díaz-Flores, R.B. García-Reyes, E. Soto-Regalado, R. Gómez-
[39] F. Gimbert, N. Morin-Crini, F. Renault, P.M. Badot, G. Crini, Adsorption isotherm González, M.T. Garza-González, E. Bustamante-Alcántara, Biosorption of Cu(II) and
models for dye removal by cationized starch-based material in a single component Pb(II) from aqueous solutions by chemically modified spent coffee grains, Int. J. En-
system: error analysis, J. Hazard. Mater. 157 (2008) 34–46. viron. Sci. Technol. 10 (2013) 611–622.
[40] Y.S. Ho, J.F. Porter, G. McKay, Equilibrium isotherm studies for the sorption of diva- [75] H.G. Alemayehu, A.K. Burkute, A.G. Ede, Adsorptive removal of Pb(II) and Cr(VI)
lent metal ions onto peat: copper, nickel and lead single component systems, from wastewater using acid untreated coffee husk, Interlink Continental J. Environ.
Water Air Soil Pollut. 141 (2002) 1–33. Sci. Toxicol. 1 (2014) 9–16.
[41] M.I. El-Khaiary, Least-squares regression of adsorption equilibrium data: compar- [76] A.G. Ede, H.G. Alemayehu, A.K. Burkute, Adsorptive removal of Pb(II) and Cr(VI)
ing the options, J. Hazard. Mater. 158 (2008) 73–87. from wastewater using acid untreated and acid treated coffee husks: comparative
[42] G. Thompson, J. Swain, M. Kay, C.F. Forster, The treatment of pulp and paper mill study, Int. J. Res. Chem. Environ. 4 (2014) 26–31.
effluent: a review, Bioresour. Technol. 77 (2001) 275–286. [77] C.-H. Wu, C.-Y. Kuo, S.-S. Guan, Adsorption kinetics of lead and zinc ions by coffee
[43] S.J. Allen, G. McKay, J.F. Porter, Adsorption isotherm models for basic dye adsorp- residues, Pol. J. Environ. Stud. 24 (2015) 761–767.
tion by peat in single and binary component systems, J. Colloid Interface Sci. 280 [78] H.D. Utomo, Lead adsorption onto various solid surfaces, Nat. Resour. 6 (2015) 152.
(2004) 322–333. [79] S. Berhe, D. Ayele, A. Tadesse, A. Mulu, Adsorption efficiency of coffee husk for re-
[44] G. Limousin, J.P. Gaudet, L. Charlet, S. Szenknect, V. Barthès, M. Krimissa, Sorption moval of lead(II) from industrial effluents: equilibrium and kinetic study, Int. J. Sci.
isotherms: a review on physical bases, modeling and measurement, Appl. Res. Publ. 5 (2015) 1–8.
Geochem. 22 (2007) 249–275. [80] A.G. Ede, Adsorptive removal of Cr (VI) ion from wastewater by activated coffee
[45] M.C. Ncibi, Applicability of some statistical tools to predict optimum adsorption husk and banana peel: comparative study, World J. Pharm. Res. 4 (2014) 212–225.
isotherm after linear and non-linear regression analysis, J. Hazard. Mater. 153 [81] K. Chinmai, B.C. Hamsa, K.D. D'souza, B.R. Mahesh Chandra, B.S. Shilpa, Feasibility
(2008) 207–212. studies on spent coffee grounds biochar as an adsorbent for color removal, Int. J.
[46] E. Bulut, M. Özacar, I.A. Şengil, Adsorption of malachite green onto bentonite: equi- Appl. Innov. Eng. Manag. 3 (2014), Article ID 10. .
librium and kinetic studies and process design, Microporous Mesoporous Mater. [82] K. Shen, M.A. Gondal, Removal of hazardous Rhodamine dye from water by ad-
115 (2008) 234–246. sorption onto exhausted coffee ground, J. Saudi Chem. Soc., (in press), DOI: 10.
[47] A. Malek, S. Farooq, Comparison of isotherm models for hydrocarbon adsorption 1016/j.jscs.2013.1011.1005.
on activated carbon, AICHE J. 42 (1996) 3191–3201. [83] R. Lafi, A.B. Fradj, A. Hafiane, B.H. Hameed, Coffee waste as potential adsorbent for
[48] J.H. De Boer, The Dynamical Character of Adsorption, 1953. the removal of basic dyes from aqueous solution, Korean J. Chem. Eng. 31 (2014)
[49] A.L. Myers, J.M. Prausnitz, Thermodynamics of mixed-gas adsorption, AICHE J. 11 2198–2206.
(1965) 121–127. [84] M.D. Pavlović, A.V. Buntić, K.R. Mihajlovski, S.S. Šiler-Marinković, D.G. Antonović, Z.
[50] M.M. Dubinin, The potential theory of adsorption of gases and vapors for adsor- Radovanović, S.I. Dimitrijević-Branković, Rapid cationic dye adsorption on poly-
bents with energetically nonuniform surfaces, Chem. Rev. 60 (1960) 235–241. phenol-extracted coffee grounds-a response surface methodology approach, J. Tai-
[51] D.M. Ruthven, Principles of Adsorption and Adsorption Processes, 1984. wan Inst. Chem. Eng. (2014).
I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565 565

[85] R. Lafi, A. Hafiane, Removal of methyl orange (MO) from aqueous solution using [95] D. Imessaoudene, S. Hanini, A. Bouzidi, Biosorption of strontium from aqueous so-
cationic surfactants modified coffee waste (MCWs), J. Taiwan Inst. Chem. Eng. 58 lutions onto spent coffee grounds, J. Radioanal. Nucl. Chem. 298 (2013) 893–902.
(2016) 424–433. [96] W. Nitayaphat, T. Jintakosol, K. Engkaseth, Y. Wanrakakit, Removal of methylene
[86] H.S. Jahin, Adsorption of methyl red from aqueous solutions using activated carbon blue from aqueous solution by coffee residues, Chiang Mai J. Sci. 42 (2015)
prepared from coffee residue, Int. J. Environ. Pollut. 3 (2014) 126–132. 407–416.
[87] A. Zuorro, A.D. Battista, R. Lavecchia, Magnetically modified coffee silverskin for the [97] N. Fiol, I. Villaescusa, Determination of sorbent point zero charge: usefulness in
removal of xenobiotics from wastewater, Chem. Eng. Trans. 35 (2013) 1375–1380. sorption studies, Environ. Chem. Lett. 7 (2009) 79–84.
[88] A. Zuorro, R. Lavecchia, S. Natali, Magnetically modified agro-industrial wastes as [98] V. Dulman, S.M. Cucu-Man, Wood sawdust, tree bark and wood chips: waste ligno-
efficient and easily recoverable adsorbents for water treatment, Chem. Eng. cellulosic materials for dye removal, in: G. Crini, P.M. Badot (Eds.), Sorption Pro-
Trans. 38 (2014) 349–354. cesses and Pollution: Conventional and Non-conventional Sorbents for Pollutant
[89] W. Nitayaphat, T. Jintakosol, K. Engkaseth, Y. Wanrakakit, Removal of methylene Removal from Wastewaters, Presses Univ. Franche-Comté, Paris, France 2010,
blue from aqueous solution by coffee residues, Chiang Mai J. Sci. 42 (2015) pp. 233–267.
407–416. [99] K.H. Tan, Principles of Soil Chemistry, Taylor & Francis, CRC press, Boca Raton, Flor-
[90] M.D. Pavlović, I.R. Nikolić, M.D. Milutinović, S.I. Dimitrijević-Branković, S.S. Šiler- ida, USA, 2010.
Marinković, D.G. Antonović, Plant waste materials from restaurants as the adsor- [100] N. Azouaou, Z. Sadaoui, A. Djaafri, H. Mokaddem, Adsorption of cadmium from
bents for dyes, Chem. Ind. 69 (2015) 667–677. aqueous solution onto untreated coffee grounds: equilibrium, kinetics and ther-
[91] I.I. Fasfous, N.A. Farha, Removal of Cibacron Brilliant Yellow 3G-P dye from aqueous modynamics, J. Hazard. Mater. 184 (2010) 126–134.
solutions using coffee husks as non-conventional low-cost sorbent, World Acade- [101] W.E. Oliveira, A.S. Franca, L.S. Oliveira, S.D. Rocha, Untreated coffee husks as
my of Science, Engineering and Technology, International Journal of Chemical, Mo- biosorbents for the removal of heavy metals from aqueous solutions, J. Hazard.
lecular, Nuclear, Materials and Metallurgical Engineering, 6, 2012, pp. 908–914. Mater. 152 (2008) 1073–1081.
[92] G.Z. Kyzas, N.K. Lazaridis, A.C. Mitropoulos, Optimization of batch conditions and [102] H.P. Boehm, Chemical identification of surface groups, Adv. Catal. 16 (1966)
application to fixed-bed columns for a sequential technique of total color removal 179–274.
using “greek coffee” residues as materials for real dyeing effluents, J. Eng. Sci. [103] H. Valdés, M. Sánchez-Polo, J. Rivera-Utrilla, C.A. Zaror, Effect of ozone treatment
Technol. Rev. 5 (2012) 66–75. on surface properties of activated carbon, Langmuir 18 (2002) 2111–2116.
[93] N. Ahalya, M.N. Chandraprabha, R.D. Kanamadi, T.V. Ramachandra, Adsorption of [104] A.S. Franca, L.S. Oliveira, M.E. Ferreira, Kinetics and equilibrium studies of methy-
fast green onto coffee husk, J. Chem. Eng. Res. 2 (2014) 201–207. lene blue adsorption by spent coffee grounds, Desalination 249 (2009) 267–272.
[94] D. Imessaoudene, S. Hanini, A. Bouzidi, A. Ararem, Kinetic and thermodynamic [105] L.S. Oliveira, A.S. Franca, T.M. Alves, S.D.F. Rocha, Evaluation of untreated coffee
study of cobalt adsorption by spent coffee, Desalin. Water Treat. 57 (2016) husks as potential biosorbents for treatment of dye contaminated waters, J. Haz-
6116–6123. ard. Mater. 155 (2008) 507–512.