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Article history: The sorption properties of chars and activated carbons obtained from coffee industry waste materials
Received 29 December 2013 toward hydrogen sulphide are characterised. The effects of pyrolysis temperature and method of activa-
Received in revised form 13 March 2014 tion as well as porous structure, acidbase character of the surface and mineral matter content on the
Accepted 15 March 2014
efciency of H2S removal are checked. Moreover, four different variants of adsorption test are applied,
Available online 24 March 2014
in order to estimate the optimal conditions of hydrogen sulphide capture. Depending on the method
of activation, the adsorbents prepared are characterised by diverse textural parameters, strong basic or
Keywords:
medium-acidic character of the surface and various mineral matter content, varying from 1.2 to
Activated carbon
Coffee industry waste materials
58.4 wt.%. The results obtained in our study have proved that through an appropriate choice of pyrolysis
Pyrolysis conditions and activation procedure for coffee industry waste materials it is possible to obtain adsorbents
Activation with high capacity of hydrogen sulphide, reaching to 281.5 mg H2S/gads. The results of our study have also
Hydrogen sulphide adsorption shown that the adsorption ability of activated carbons prepared depends rst of all on the conditions of
adsorption test, mineral matter content and basicity of the surface and only to a small degree on porous
structure development.
2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2014.03.052
1385-8947/ 2014 Elsevier B.V. All rights reserved.
P. Nowicki et al. / Chemical Engineering Journal 248 (2014) 208215 209
NaOH or KOH, copper(II) ions and by incorporation of nitrogen, using potentiometric titration experiments, according to procedure
sulphur and oxygen functional groups into the carbon structure described earlier [27].
[16,1922]. Important positive inuence on the effectiveness of
H2S removal has the presence of steam in the gas ux during H2S
2.3. Evaluation of hydrogen sulphide sorption capacity
adsorption, the presence of inorganic compounds in the carbon
structure (such as iron oxide, calcium oxide, magnesium) and the
The chars and activated carbons (in the form of grains of 0.75
proper choice of textural parameters [3,16,2326].
1.5 mm in diameter) were packed into a glass column (internal
In our earlier studies on the synthesis of activated carbons from
diameter 9 mm, bed volume 3 cm3). Dry (D) or wet (M, 70% humid-
waste products obtained in production of coffee and their potential
ity) air with 0.1% of H2S was passed through the dry bed of the
use in NO2 adsorption [27], we obtained carbon adsorbents show-
adsorbent at 450 cm3/min. All adsorption tests were performed
ing strongly basic surface, different degrees of surface develop-
at room temperature. Moreover, additional variant of H2S adsorp-
ment, high content of mineral substances (including alkali
tion were used: the samples were wetted before the adsorption
metals) and a considerable content of heteroatoms (mainly nitro-
tests by the air of 70% humidity for 30 min and then the tests were
gen and sulphur) in their structure. As mentioned above all these
performed either in dry (referred as mix-dry MD) or in wet (re-
parameters have signicant inuence on the effectiveness of H2S
ferred as mix-wet MW) conditions. The breakthrough of H2S
adsorption by activated carbons, so the aim of this study was to
were monitored using Multi-Gas Monitor Q-RAE PLUS PGM-
evaluate the adsorbents obtained from the coffee industry waste
2000/2020. The tests were stopped at the breakthrough concentra-
products in adsorption of hydrogen sulphide from the stream of
tion of 100 ppm, because of the electrochemical sensor limit. The
gases and to establish the optimum conditions of this gas removal.
capacities of each material in terms of milligram of hydrogen sul-
phide per gram of adsorbent were calculated by integration of the
area above the breakthrough curves, and from the breakthrough
2. Experimental time, H2S concentration in the inlet gas, ow rate as well as mass
of adsorbent.
2.1. Sample preparation
The starting material coffee industry waste materials (C) in 3. Results and discussion
the form of pellet was subjected to pyrolysis process (P) followed
by physical activation with CO2 (PA) or chemical activation with 3.1. Sorption properties of chars toward hydrogen sulphide
KOH (CA), according to procedures described in detail in our earlier
work [27] and presented briey in Scheme 1. As follows from the data collected in Table 1, the main compo-
nents of the inorganic substance in the coffee industry waste mate-
rials are the compounds of potassium, calcium, magnesium,
2.2. Analytical procedures sodium and iron, whose presence is known to have benecial inu-
ence on the sorption properties of carbon adsorbents. The presence
The elemental analysis of the all samples under investigation of such compounds suggests that the chars and rst of all activated
was performed on an Elementar Analysensysteme instrument, carbons obtained by chemical or physical activation, will show
model Vario EL III. The contribution of metals in the precursor high sorption capacity not only towards NO2 [27] but also towards
was measured on an emission spectrophotometer Varian ICP-OES H2S. To verify this supposition, each of the materials obtained was
VISTA-MPX. The content of mineral matter for all samples obtained subjected to adsorption tests in four variants. The results, collected
was determined according to the DNS ISO 1171:2002. The textural in Table 2, reveal that the sorption capacity towards H2S signi-
characterisation of the samples was based on the nitrogen-adsorp- cantly depend on the thermal conditions of pyrolysis and the var-
tion isotherms determined at 196 C with a Quantachrome Auto- iant of activation, however, the greatest inuence on the
sorb iQ surface area analyzer. The content of surface oxygen effectiveness of H2S removal from the gas stream have the condi-
functional groups of acidic and basic character was determined tions of adsorption process.
a 100 b 100
CP5 W
CP5 D
CP5 MW
H S concentration [ppm]
CP5 MD
H2S connentration [ppm] CP8 D CP8 W
80 CP8 MD
80 CP8 MW
60 60
40 40
20 20
2
0 0
0 10 20 30 40 50 0 50 100 150 200 250
Time [min] Time [min]
c 100
CP5PA D
d 100
CP5PA W
H S concentration [ppm]
H S concentration [ppm]
CP5PA MD CP5PA MW
CP8PA D CP8PA W
80 CP8PA MD 80 CP8PA MW
60 60
40 40
20 20
2
0 0
0 20 40 60 80 100 120 0 100 200 300 400 500
Time [min] Time [min]
e 100 f 100
H S concentration [ppm]
H S concentration [ppm]
80 80
60 60
40 40
CP5CA W
CP5CA D CP5CA MW
20 20
2
CP5CA MD
2
CP8CA W
CP8CA D CP8CA MW
CP8CA MD
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 8
Time [min] Time [min]
Fig. 1. H2S breakthrough curves obtained for chars and activated carbons during adsorption in various conditions.
from 3 (Fig. 2a) to 14.6 mg H2S/gads depending on the conditions of and carbons obtained by physical activation with carbon dioxide,
the adsorption test (Fig. 2b), while chars and the corresponding mean pore diameter is much greater and close to 9.512.5 nm
carbon samples activated with CO2 having the surface area not for CP5 and CP8 chars and about 14.524.0 nm for CP8PA and
exceeding 20 m2/g adsorb much greater amounts of H2S, e.g. sam- CP5PA samples, respectively. The presence of so large pores in
ple CP5PA even up to 281.5 mg in mix-wet conditions. the structure can improve sorption capacity, especially towards
As indicated by the data given in Fig. 3, much greater inuence H2S in the presence of steam. According to earlier literature re-
on the effectiveness of hydrogen sulphide removal from the ux of ports, large pore size and basic character of adsorbent surface fa-
gases has the type of porous structure. The mean pore diameter of vour oxidation of sulphide ions, formed on dissociation of H2S, to
the carbon samples chemically activated with KOH (CP5CA and elemental sulphur. Sulphur formed as a result of this process gets
CP8CA) is close to 3 nm, and their pore structure is composed deposited in the carbon pores and can block the access to subse-
mainly of micropores, see [27]. A denite prevalence of small size quent particles of the adsorbate to pores and to adsorption centres,
pores may be one of the reasons for so poor sorption properties of thus reducing the sorption capacity. If the pore diameters of the
these carbons as the majority of the pores may be inaccessible to adsorbent are small, the oxidation of HS ions do sulphur oxides
adsorbate molecules. Also, upon adsorption in wet conditions or that can form H2SO4 in subsequent reactions happens more often.
upon wetting of the bed prior to adsorption, small size pores can In the carbon materials studied the more probable seems the
be partly of fully lled with water molecules from steam. In chars mechanism involving the formation of elemental sulphur. This
212 P. Nowicki et al. / Chemical Engineering Journal 248 (2014) 208215
1500
2
300
b 2000 surface area
adsortpion in wet conditions a 14
1500
10
150 8 40
1000
100 6
500
50 4 20
2
0 0
CP5 CP8 CP5CA CP8CA CP5PA CP8PA 0
0
CP5 CP8 CP5CA CP8CA CP5PA CP8PA
Fig. 2. Dependence of H2S sorption capacity on surface area of materials obtained.
b 14 300
Basic oxygen groups content [mmol/g]
20
8
H2S adsorption [mgl/g]
150
16 6
40
100
12 4
50
8 2
20
0 0
4 CP5 CP8 CP5CA CP8CA CP5PA CP8PA
20 250 conditions
after adsorption in mix-
H2S adsorption [mgl/g]
10 dry conditions
200 after adsorption in wet
16 conditions
8 after adsorption in mix-
pH
wet conditions
12 150
6
8 100 4
4 50 2
0
0 0 CP5 CP8 CP5CA CP8CA CP5PA CP8PA
CP5 CP8 CP5CA CP8CA CP5PA CP8PA
Fig. 5. pH value of chars and activated carbons before and after H2S adsorption in
Fig. 3. Dependence of H2S sorption capacity on average pore diameter. various conditions.
P. Nowicki et al. / Chemical Engineering Journal 248 (2014) 208215 213
3.4. The effect of surface groups of basic character on the H2S sorption
a 60
mineral matter content
capacity
55 adsortpion in dry conditions
adsortpion in mix-dry conditions
Mineral matter content [wt.%]
60
50
The above-mentioned strongly basic character of the adsor-
50 250 smaller and notable only upon adsorption in mix-dry and mix-
60
H2S adsorption in MW [mg/g]
300
50
250
40
200
30
150
20
100
10
50
0
0
CP5PA CP5PA DEM CP5PA CP5PA DEM
Basic groups content [mmol/g]
12
12
10
8 10
6
pH
8
4
6
2
0 4
Fig. 7. Comparison of physico-chemical and sorption properties of CP5PA sample, before and after demineralisation process.
214 P. Nowicki et al. / Chemical Engineering Journal 248 (2014) 208215
CP5PA MW after demineralisation adsorbent surface on sorption capacity towards H2S is much great-
80
er than the type of porous structure and degree of surface area
development.
60 The results obtained in this study also suggest that many other
waste materials containing large amounts of mineral matter and
40 carbon in organic complexes could be successfully applied for pro-
duction of activated carbon. This application may be an attractive
way of utilisation of such waste products.
20
2
0 Acknowledgements
0 50 100 150 200 250 300 350
Time [min]
Financial support received from the Polish Ministry of Higher
Fig. 8. Comparison of H2S breakthrough curves obtained for CP5PA sample in mix- Education and Science (Project Iuventus Plus No. IP2012 004072)
wet conditions, before and after demineralisation process. is gratefully acknowledged.
matter in the structure of these samples can be another reason for References
their much worse sorption capacity towards hydrogen sulphide.
The results collected in Fig. 6a also imply that increasing con- [1] R.CH. Bansal, M. Goyal, Activated Carbon Adsorption, Taylor & Francis Group,
tent of mineral matter in chars and in particular in samples CP5PA Boca Raton, 2005.
[2] G.W. van Loon, S.J. Duffy, Environmental Chemistry: a Global Perspective,
and CP8PA obtained by their physical activation, is accompanied second ed., Oxford University Press, 2005.
by clear improvement in the effectiveness of hydrogen sulphide re- [3] E.J. Bottani, J.M. Tascon, Adsorption by Carbons, rst ed., Elsevier, Amsterdam,
moval from the ux of gases. On the other hand, for chemically 2008.
[4] T.J. Bandosz, Activated Carbon Surfaces in Environmental Remediation,
activated samples, practically no correlation is observed between Elsevier, Oxford, 2006.
the content of mineral matter and sorption capacity. Similar rela- [5] V. Meeyoo, J.H. Lee, D.L. Trimm, N.W. Cant, Hydrogen sulphide emission
tions were observed for the carbon samples in the process of control by combined adsorption and catalytic combustion, Catal. Today 44
(1998) 6772.
adsorption in wet and mix-wet conditions (Fig. 6b). For CP5 and [6] T.K. Tseng, H.C. Chang, H. Chu, H.T. Chen, Hydrogen sulde removal from coal
CP8 chars, increased content of mineral matter brings even more gas by the metalferrite sorbents made from the heavy metal waste water
spectacular improvement in the sorption capacity, especially in sludge, J. Hazard. Mater. 160 (2008) 482488.
[7] J. Wang, Y. Zhang, L. Han, L. Chang, W. Bao, Simultaneous removal of hydrogen
adsorption in wet conditions. Unfortunately, in the same condi-
sulde and mercury from simulated syngas by iron-based sorbents, Fuel 103
tions no benecial effect of increased content of mineral matter (2013) 7379.
on sorption capacity towards H2S is observed for the samples acti- [8] W. Yuan, T.J. Bandosz, Removal of hydrogen sulde from biogas on sludge-
derived adsorbents, Fuel 86 (2007) 27362746.
vated with CO2 (PA). This observation may indicate that in the
[9] Y. Xiao, S. Wang, D. Wu, Q. Yuan, Experimental and simulation study of
presence of steam in the ux of gases, especially after preliminary hydrogen sulde adsorption on impregnated activated carbon under anaerobic
wetting of the adsorbent bed, too high content of mineral matter conditions, J. Hazard. Mater. 153 (2008) 11931200.
can be a ballast deteriorating the sorption capacity. [10] M.P. Cal, B.W. Strickler, A.A. Lizzio, S.K. Gangwal, High temperature hydrogen
sulde adsorption on activated carbon II. Effects of gas temperature, gas
To verify our thesis saying that the exceptionally good sorption pressure and sorbent regeneration, Carbon 38 (2000) 17671774.
capacity of chars and in particular the carbon samples activated by [11] J. Masuda, J. Fukuyama, S. Fujii, Inuence of concurrent substances on removal
physical method, are related rst of all to a high content of mineral of hydrogen sulde by activated carbon, Chemosphere 39 (1999) 16111616.
[12] Y. Duan, Y. Xiang, D. Xia, Removal of hydrogen sulde from light oil with solid
matter in their structure, we used the most effective adsorbent base, Fuel Process. Technol. 86 (2004) 237244.
CP5PA but with mineral matter removed in reaction with concen- [13] Y. Elsayed, M. Seredych, A. Dallas, T.J. Bandosz, Desulfurization of air at high
trated HCl. As follows from the results of adsorbing performance of and low H2S concentrations, Chem. Eng. J. 155 (2009) 594602.
[14] K. Kante, C. Nieto-Delgado, J.R. Rangel-Mendez, T.J. Bandosz, Spent coffee-
this sample, presented in Figs. 7 and 8, the demineralisation led not based activated carbon: specic surface features and their importance for H2S
only to a drastic decrease in the content of mineral matter (from separation process, J. Hazard. Mater. 201202 (2012) 141147.
54.1 to 7.4 wt.%), much smaller content of surface basic groups [15] T.J. Bandosz, On the adsorption/oxidation of hydrogen sulde on activated
carbons at ambient temperatures, J. Colloid Interface Sci. 246 (2002) 120.
and much lower pH, but most importantly over 8 times smaller
[16] A. Bagreev, T.J. Bandosz, A role of sodium hydroxide in the process of hydrogen
sorption capacity towards H2S (only 33.3 mg/g). These results illus- sulde adsorption/oxidation on caustic impregnated activated carbons, Ind.
trate the signicant effect of the mineral matter content on the Eng. Chem. Res. 41 (2002) 672679.
[17] W. Feng, S. Kwon, E. Borguet, R. Vidic, R, Adsorption of hydrogen sulde onto
effectiveness of H2S removal by the adsorbents studied.
activated carbon bers: effect of pore structure and surface chemistry,
Environ. Sci. Technol. 39 (2005) 97449749.
[18] A. Ansari, A. Bagreev, T.J. Bandosz, Effect of adsorbent composition on H2S
removal on sewage sludge-based materials enriched with carbonaceous phase,
4. Conclusions Carbon 43 (2005) 10391048.
[19] C.C. Huang, C.H. Chen, S.M. Chu, Effect of moisture on H2S adsorption by
The above presented and discussed results have shown that cof- copper impregnated activated carbon, J. Hazard. Mater. 136 (2006) 866873.
[20] J.P. Boudou, M. Chehimi, E. Broniek, T. Siemieniewska, J. Bimer, Adsorption of
fee industry waste materials can be successfully used for produc- H2S or SO2 on an activated carbon cloth modied by ammonia treatment,
tion of cheap and effective carbon adsorbents. The adsorption Carbon 41 (2003) 19992007.
tests have proved that chars, and in particular carbon materials ob- [21] A. Bagreev, J.A. Menendez, I. Dukhno, I.Y. Tarasenko, T.J. Bandosz, Bituminous
coal-based activated carbons modied with nitrogen as adsorbents of
tained by their physical activation with carbon dioxide, have very
hydrogen sulde, Carbon 42 (2004) 469476.
large sorption capacity towards hydrogen sulphide, similar to [22] M. Stejns, F. Derks, A. Verloop, P. Mars, The mechanism of the catalytic
those of the commercial products available on the market. The oxidation of hydrogen sulphide. II. Kinetics and mechanism of hydrogen
greatest inuence on the effectiveness of H2S removal from the ux sulphide oxidation catalyzed by sulfur, J. Catal. 42 (1976) 8795.
[23] T. Nakamura, S. Tanada, N. Kawasaki, T. Hara, J. Fujisawa, K. Shibata, Hydrogen
of gases have the conditions of adsorption. The best adsorption was sulde removal by iron containing activated carbon, Toxicol. Environ. Chem.
obtained for adsorption in wet conditions, especially after 55 (1996) 279283.
P. Nowicki et al. / Chemical Engineering Journal 248 (2014) 208215 215
[24] V. Meeyoo, D.L. Trimm, N.W. Cant, Adsorption-reaction processes for the [26] A. Bagreev, T.J. Bandosz, On the mechanism of hydrogen sulde removal from
removal of hydrogen sulphide from gas streams, J. Chem. Technol. Biotechnol. moist air on catalytic carbonaceous adsorbents, Ind. Eng. Chem. Res. 44 (2005)
68 (1997) 411416. 530538.
[25] A. Bagreev, T.J. Bandosz, H2S adsorption/oxidation on unmodied activated [27] P. Nowicki, P. Skibiszewska, R. Pietrzak, NO2 removal on adsorbents prepared
carbons: importance of prehumidication, Carbon 39 (2001) 23032311. from coffee industry waste material, Adsorption 19 (2013) 521528.