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Chemical Engineering Journal 248 (2014) 208215

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Chemical Engineering Journal


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

Hydrogen sulphide removal on carbonaceous adsorbents prepared from


coffee industry waste materials
Piotr Nowicki, Paulina Skibiszewska, Robert Pietrzak
, Umultowska 89b, 61-614 Poznan
Laboratory of Applied Chemistry, Faculty of Chemistry, Adam Mickiewicz University in Poznan , Poland

h i g h l i g h t s

 The alternative method of utilisation of coffee industry waste materials is proposed.


 Very effective H2S adsorbents were prepared from coffee industry waste materials.
 The adsorbents prepared show greater efciency of H2S removal than commercial ones.
 Sorption capacity depends mainly on mineral matter content and adsorption conditions.

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

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.

1. Introduction pollutants from anthropogenic sources. Much attention has been


paid to this problem and it is a subject of studies all over the world.
Everyday huge amounts of toxic gas pollutants are released to Some of the recommendations are to use desulfurized fuels, to im-
the atmosphere. The dominant among them are volatile organic prove efciency of their combustion and use of the energy from
compounds, carbon and nitrogen oxides, ammonia, methane as this combustion, to purify the exhaust gases formed in the process
well as sulphur compounds [1]. Particularly hazardous for human [3].
health and for the natural environment are the inorganic sulphur Sulphur compounds can be effectively removed by many ways,
compounds such as SO2, CS2 or H2S. They originate from the eco- e.g. by wet scrubbing, catalytic oxidation or combustion [45]. An
nomic and industrial activity of man (in particular hydrogen sul- important role in limitation of the emission of sulphur compounds
phide), including electric power plant emission, industrial plants (in particular H2S) to the atmosphere has been played by adsor-
emission, animal farms, septic tanks, waste purication plants as bents [68], especially activated carbons [914]. Thanks to their
well as from natural sources such as volcano eruptions, thermal unique physicochemical properties they can not only be effective
springs and bogs [2]. As the emission from the natural sources is adsorbents, but also as catalysts or their carriers, so the removal
uncontrollable, it is very important to work on limiting the of gases containing sulphur can take place by physical or chemical
adsorption or by catalytic oxidation on the carbon surface [1518].
Corresponding author. Tel.: +48 618291581; fax: +48 618291555. The effectiveness of H2S removal by activated carbons can be
E-mail address: pietrob@amu.edu.pl (R. Pietrzak). improved by their impregnation with caustic materials such as

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.

Scheme 1. Preparation conditions of activated carbons.


210 P. Nowicki et al. / Chemical Engineering Journal 248 (2014) 208215

Table 1 so an extension of time at which the characteristic point


Inorganic components of starting material. corresponding to the so-called breakthrough of the bed is ob-
Main elements wt.% Trace elements ppm served. The farther section of the curves shows a small increase
K 6.021 Sr 92 in H2S concentration to 100 ppm.
Ca 2.613 Rb 50
S 0.124 Zn 46 3.2. Sorption properties of activated carbons toward hydrogen
P 0.291 B 18 sulphide
Na 0.103 Cu 8.2
Fe 0.045 Ti 5.2
Al 0.018 Cr 1.5 Chemical and physical activation of chars leads to adsorbents of
Mn 0.016 Ni 1.3 much different sorption capacities. As follows from the data shown
in Table 2 and in Fig. 2a and b, carbon samples CP5PA and CP8PA
obtained by physical activation have much higher sorption capac-
Table 2 ities than the samples CP5CA and CP8CA obtained by chemical
H2S breakthrough capacity of the activated carbons in different conditions. activation, in spite of the fact that the former are characterised
by much less developed surface area and porous structure [27].
Sample Dry conditions (mg/g) Wet conditions (mg/g)
Moreover, the results obtained for carbon samples activated by
D MD W MW
KOH are much worse than for the corresponding chars, which
CP5 6.2 15.2 13.9 97.3 means that the sorption capacity towards H2S is determined by
CP8 8.2 26.0 146.6 152.5 the chemical structure and acidbase character of the adsorbent
CP5PA 9.3 44.6 216.0 281.5
CP8PA 12.8 64.6 202.4 214.0
surface and the textural parameters are less important. This prob-
CP5CA 3.0 4.6 4.6 5.7 lem will be discussed further on in the text.
CP8CA 3.2 11.1 3.8 14.6 Generally speaking, similarly as for chars, the effectiveness of
hydrogen sulphide removal by activated carbons depends on the
variant of the adsorption process and to a smaller degree on the
Interestingly, already the materials obtained as a result of thermal conditions applied during pyrolysis. The lowest effective-
pyrolysis show good sorption capacity towards hydrogen sulphide, ness of H2S removal from the ux of gases, irrespective of the acti-
in particular sample CP8. As follows from the data given in Table 2, vation variant, is noted during adsorption in dry conditions.
upon adsorption in dry conditions the amount of H2S adsorbed by Particularly ineffective are the chemically activated carbons (CA),
particular chars was small and almost independent of the thermal showing over three times lower sorption capacity than the analo-
conditions of pyrolysis. Of great inuence on the effectiveness of gous samples activated by CO2 (PA), and about twice smaller sorp-
hydrogen sulphide removal in dry conditions has the presence of tion capacity than chars CP5 and CP8 chars from which they were
a water lm (produced as a result of adsorbent bed wetting by obtained. Preliminary wetting of the sample prior to the adsorption
blowing through it humid air prior to the adsorption test) as evi- test brings a signicant improvement in the effectiveness of H2S
denced by about 3 times greater sorption capacity of both chars removal (similarly as for chars), especially for the physically acti-
in mix-dry conditions (MD). When H2S adsorption takes place in vated carbons. Moreover, from among samples CP5PA, CP8PA,
mix-dry conditions, the inuence of temperature of pyrolysis of CP5CA and CP8CA, much higher sorption capacity towards H2S is
the initial material is signicant. An increase in the pyrolysis tem- found for the carbon obtained from char CP8. Much greater sorp-
perature from 500 to 800 C caused almost twice increase in the tion capacities obtained upon adsorption in wet as well as mix-
sorption capacity. wet conditions mean that the presence of steam in the gas ux is
The inuence of temperature on the sorption capacity of chars benecial for H2S removal effectiveness. Particularly good result
obtained from coffee industry waste material is much more pro- was obtained for sample CP5PA, whose maximum sorption capac-
nounced when the process takes place in wet conditions, in which ity in mix-wet conditions is 281.5 mg/gads and is almost 50 times
the difference between the sorption capacity of samples CP5 and greater than for the analogous carbon CP5AC obtained by chemical
CP8 is as much as 138.6 mg/g. In mix-wet conditions (MW) the ef- activation with KOH. Moreover, the results obtained for CP8PA and
fect of temperature is also considerable, but the difference between even more those obtained for CP5PA, are similar to those for com-
the two chars is much smaller. Comparison of the results of mercial carbons chemically activated with H3PO4 [15]. Upon
adsorption in dry (D) and wet (W) conditions reveals the magni- adsorption in wet conditions the effect of the pyrolysis tempera-
tude of the benecial effect of the presence of steam in the gas ux ture on the sorption properties of activation products is different
on the adsorption capacity of chars towards hydrogen sulphide. It than in dry conditions, as evidenced by the higher sorption capac-
is particularly pronounced for sample CP8 which in wet conditions ities of the activated carbons obtained from char CP5. The excep-
adsorbs about 19 times more H2S than in dry conditions. This tion is carbon CP8CA, which shows greater effectiveness of H2S
means that this sample shows much higher sorption capacity than removal from the ux of gases than CP5CA, irrespectively of the
the commercial activated carbon modied with nitrogen which in adsorption conditions.
the same conditions adsorbs only 104 mg H2S/gads [14]. Explanation of such benecial sorption capacities of carbon
Moreover, preliminary wetting of the adsorbent bed (similarly samples activated with carbon dioxide and chars obtained from
as in the adsorption in dry conditions) also signicantly improves coffee industry waste materials needs considering the effect of tex-
sorption capacity, especially for char CP5. Most probable explana- tural parameters, acidbase character and content of mineral
tion is that H2S molecules can dissociate in the lm of water substance.
formed at the carbon surface, and the sulphide ions HS formed
can be oxidised to elemental sulphur. However, on the basis of 3.3. The effect of textural parameters on the H2S sorption capacity
the character of H2S breakthrough curves (Fig. 1a and b), it can
be supposed that the presence of steam has no signicant effect As follows from the data in Fig. 2, the degree of surface area
on the mechanism of hydrogen sulphide sorption by the chars ob- development has no direct inuence on the amount of hydrogen
tained. The curves have similar shape and the introduction of sulphide adsorbed on the carbon materials obtained. The above
steam to the system brings only a broadening of the at section observation is based on the fact that carbon samples CP5CA and
of curve, when the H2S breakthrough curve overlaps the x axis, CP8CA with surface area between 1500 and 2000 m2/g absorb only
P. Nowicki et al. / Chemical Engineering Journal 248 (2014) 208215 211

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

observation is supported by the fact that according to the data


a 2000 surface area
adsortpion in dry conditions
adsortpion in mix-dry conditions shown in Figs. 3 and 4, both chars and carbons obtained by their
60
physical activation have the pore structure with domination of

H2S adsorption [mgl/g]


large pores (Fig. 3) and have surfaces of strongly basic character
Surface area [m /g]

1500
2

of the surface (Fig. 4). Moreover, the electrochemical sensor used


40 did not detect SO2 molecules in the exhaust gases, which suggests
1000 that SH ions formed chiey undergo oxidation to elemental sul-
phur. However, it cannot be excluded that SO2 formed during mea-
surements could be oxidised to SO3, and then as a result of reaction
20
500 with steam, could form H2SO4. This thesis is to some degree sup-
ported by the decrease in pH of chars and activated carbons ob-
served after the process of adsorption (Fig. 5). The same data,
0 0 Figs. 3 and 4, also imply that for the majority of adsorbents
CP5 CP8 CP5CA CP8CA CP5PA CP8PA

300
b 2000 surface area
adsortpion in wet conditions a 14

Basic oxygen groups content [mmol/g]


adsortpion in mix-wet conditions basic groups content
250 adsortpion in dry conditions
adsortpion in mix-dry conditions

H2S adsorption [mgl/g]


12 60
surface area [m /g]

1500

H2S adsorption [mgl/g]


200
2

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]

basic groups content


adsortpion in wet conditions
adsortpion in mix-wet conditions
12 250
a 24

H2S adsorption [mgl/g]


average pore diameter
adsortpion in dry conditions 10
adsortpion in mix-dry conditions
60 200
Average pore diameter [nm]

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

0 0 Fig. 4. Dependence of H2S sorption capacity on basic surface groups content.


CP5 CP8 CP5CA CP8CA CP5PA CP8PA

b 24 average pore diameter


300 14 before adsorption
adsortpion in wet conditions
adsortpion in mix-wet conditions after adsorption in dry
12
Average pore diameter [nm]

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-

H2S adsorption [mgl/g]


45
bents surfaces also has important inuence on their sorption
40
capacity towards H2S. As follows from the data in Fig. 4, for the
35 40 majority of the samples studied there is a clear correlation be-
30 tween the content of groups of basic character and the efciency
25 of hydrogen sulphide removal. For chars an increase in the number
20 of basis surface groups, irrespectively of the adsorption test condi-
20
15 tions, is strongly positively correlated with increasing sorption
10 capacity towards H2S. The most dramatic difference is observed
5 between the results for samples CP5 and CP8 upon adsorption in
0 0 wet conditions (Fig. 4b). Upon adsorption in dry and mix-dry con-
CP5 CP8 CP5CA CP8CA CP5PA CP8PA ditions (Fig. 4a) a similar relation is noted for the samples activated
with CO2, but in wet, and in particular in mix-wet conditions, the
b 60 mineral matter content
300 opposite tendency appears. For CP5CA and CP8CA, the effect of
55 adsortpion in wet conditions the content of surface basic groups on sorption capacity is much
adsortpion in mix-wet conditions
Mineral matter content [wt.%]

50 250 smaller and notable only upon adsorption in mix-dry and mix-

H2S adsorption [mgl/g]


45 wet conditions.
40 200
35
30 150 3.5. The effect of mineral substance content on the H2S sorption
25 capacity
20 100
15
It should be stressed that the number of surface basic groups on
50 the adsorbents studied also depends on the content of the mineral
10
substance in their structure. As mentioned above, the initial mate-
5
rial contains a large number of complexes of such metals as potas-
0 0
CP5 CP8 CP5CA CP8CA CP5PA CP8PA
sium, calcium, magnesium, sodium and iron, whose contribution
can vary signicantly upon the applied thermo-chemical treat-
Fig. 6. Dependence of H2S sorption capacity on mineral matter content. ment. The data from Fig. 6 illustrate that the process of pyrolysis,
and in particular the process of physical activation, lead to a great
increase in the content of mineral matter relative to that in the raw
produced, greater amounts of sulphuric acid are formed upon coffee industry waste material (16 wt.% [27]). For the carbon sam-
adsorption in wet or mix-wet conditions, as indicated by greater ples activated with KOH (CP5CA and CP8CA), the content of min-
pH changes relative to their initial values than those in dry or eral matter is much smaller and does not exceed 2 wt.%, so is 8
mix-dry conditions. times smaller than in the raw material. This low content of mineral
Mineral matter content [wt. %]

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

CP5PA CP5PA DEM CP5PA CP5PA DEM

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

100 preliminary wetting of the adsorbent. Moreover, the inuence of


CP5PA MW the content of mineral matter and acidbase character of the
H S concentration [ppm]

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
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