Carbon, Vol. 32, No. 8, pp.

1493-1498, 1994 Copyright 0 1994 Elsevier Science Ltd

Printed in Great Britain. All rights reserved 0008.6223/94 $6.00 + .OO

0008-6223(94)00103-O

ACTIVATED

CARBON FROM CHERRY STONES

MICHAEL G. LUSSIER,JEFFREY SHULL, and DENNIS J. MILLER* C.

Department of Chemical Engineering, Michigan State University, East Lansing, MI 48824-1226, U.S.A.

(Received 4 November 1993; accepted in revised form 31 May 1994)

Abstract-Fruit stones constitute a significant waste disposal problem for the fruit-processing industry. High-quality activated carbon can be produced from waste cherry stones: the activated carbon is low in impurities and has an adsorption capacity that compares favorably with commercial activated carbons. Activation at 800C in steam for 2-3 hours, following initial carbonization, produces an activated carbon in about 10% yield (by weight) of the initial cherry stone. The activated carbons produced have surface areas (CO* adsorption) as high as 1200 m*/g and Ccl, numbers of 70-80. Activation in carbon dioxide requires higher temperatures (9OOOC) and gives a carbon of slightly lower activity. Carbon from the hull, or hard outer portion of the fruit stone, provides essentially all of the adsorption capacity; the inner kernel does not form a microporous material. The hull structure is dominated by 0.4-micron pores which facilitate access to internal microporosity. This structure requires that the carbon be ground to less than 75 micron particles to achieve reasonable adsorption rates. Key Words-Activated carbon, cherry stones.

1. INTRODUCTION Activated carbon is seeing increased utilization world-

wide for environmental applications and water purification, with the estimated 300 million kg annual production increasing at about 7% annually[ 1,2]. Approximately 60% of activated carbon used in the U.S.A. is produced from coal, 20% from coconut shells, and the remaining 20% from wood and other biomass sources[3]. These other sources include almond shells[4-61, olive stones[7], grape seeds[b], and apricot and peach stones[5,6]. The hardness of fruit stones and nut shells, along with their low ash and heteroatom content, makes them good candidates as feedstocks for activated carbon production. Fruit stones constitute a major source of waste in food processing, and their disposal is becoming an increasing economic burden to fruit growers and processors. Combined stone production from cherry, peach, apricot, and plum processing is estimated to exceed 70 million kg/yr in the U.S.A.[S]. Traditionally, this waste material is incinerated or crushed and used as mulch, but environmental concern may necessitate more costly disposal methods, such as landfilling. In this paper, we focus on formation of activated carbon from cherry stones. This work is part of a larger study aimed at enhancing the economic viability of fruit growers in Michigan and other fruit-producing states.
2. EXPERIMENTAL METHODS

2.1 Activated carbon preparation

Whole, dried stones and cracked morency sour cherries were obtained hulls of Montfrom the Mich-

*Author to whom correspondence

should

be addressed.

igan Cherry Growers Association. The hull (the stony pericarp or hard outer portion of the stone) makes up about 75% of the stone weight; the kernel (seed or embryo) constitutes the other 25% of stone weight. Typical stone moisture content following air drying is about 10%. Stones were cracked in a hand grinder to 3-mm nominal diameter pieces and then carbonized without further treatment. Cracked hulls (-3 mm) were carbonized without treatment. Carbonization was conducted in a horizontal quartz tube placed in a tube furnace. Samples (15-20 grams) were placed in shallow ceramic boats and heated in nitrogen (AGA, 99.99%) from 25C to the carbonization temperature at lOC/minute, soaked for 30 minutes, and then cooled at lOC/minute. Char yield was 26+ 1% by weight (dry basis) from hulls and 25+ 1% by weight (dry basis) from pits. Char yield and char properties were essentially independent of carbonization temperature over the range of 700C to 900C; all carbons discussed in this paper were carbonized at 750C. Hulls and kernels retained their original shape following carbonization, although a size reduction of about one third was observed. Properties of the char are given in the Results. Activation was conducted in a vertical quartz tube furnace using steam or carbon dioxide (AGA, 99.99%) as the activating agent. Carbonized char (6-8 g) was supported on a metal screen in the quartz tube during activation; the vertical configuration forced reactant gas directly through the char bed, thus minimizing the influence of film mass transfer resistances during activation. Samples were heated at lOC/min to the activation temperature, held there for the desired activation time, and then purged with N, and cooled. Activation temperatures ranged from 750C to 900C with activation times of 0.5 to 12 hours.

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2.2 Activated carbon characterization 2.2.1 Micropore volume and surface area.
Adsorption of COz at 298 K was used as a generally accepted[9] measure of the micropore volume and surface area of the activated carbons. The isotherms, obtained in a Sartorius high pressure microbalance (P/P, = 0.0005 to 0.2), were analyzed by the DubininRadushkevich method[lO], and a surface area was assigned from the value of W, and a CO2 molecular area of 0.26 nm2[ll]. Nitrogen (BET) surface area measurements were conducted in a Micromeritics 2700 flow sorptometer at 78 K and relative pressures (P/P,) of 0.05-0.3. Significant time (about 1 hour) was required to achieve adsorption equilibrium in the activated carbons. Micropore volume was also characterized by CC& adsorption according to the ASTM Standard Method[l2]. The method involves passing an air stream saturated in Ccl, over a bed of activated carbon. Total CC& uptake, which is determined by weight gain of the carbon over time, is reported in g CCL, per 100 g carbon. 2.2.2 Mesopore volume. Adsorption of methylene blue dye (Aldrich Chemical Co., MW = 320) from aqueous solution was used to characterize both mesopore capacity (pore diameters greater than 1.3 nm) and kinetic uptake rates of the activated carbons. Methylene blue also serves as a model compound for adsorption of organic contaminants from aqueous solutions. The ASTM Standard Method[ 13) was used as the basis for the measurements. Kinetic uptake rates were measured by withdrawing l-ml aliquots at predetermined time intervals from a lOO-ml solution initially containing 100 mg/liter methylene blue and 20 mg carbon. Analysis was conducted colorimetritally at 661 nm on a UV/VIS spectrophotometer. Total uptakes for methylene blue were determined by adsorption over a 24-hour period. Only a single initial concentration of methylene blue was used: the uptakes reported are thus at different final solution concentrations, but nevertheless give a relative measure of mesopore capacity. 2.2.3 Macropore volume. Carbon macropore volume and size distribution were characterized by mercury porosimetry using a Micromeritics 33 10 Poresizer at a pressure range of l-30,000 psia. Pore size distribution is reported for pores between 6 nm and 200 micron in diameter. Scanning electron microscopy (SEM) was also used to gain perspective of the stone structure.

found that hulls form a high-quality activated carbon while kernels form a non-active material with a surface area of -100 m2/g. Thus, the hull provides about 98% of the adsorption capacity, yet constitutes only 90 wt% of an activated carbon made from the entire stone. Because hulls alone produce a superior carbon, they were used as the starting material in many experiments. Carbonization of the hulls gives 0.2+_0.01 g carbonized char/g initial stone. Char burn-off represents the percentage of carbonized material that is gasified during activation.

3.2 Ultimate analyses

Ultimate analyses of the char and two typical activated carbons produced from hulls are given in Table 1. Activated carbon CH-23 was activated in steam (2 hours, SOOC)to 50% burn-off, and CH-36SV was activated in CO2 (2 hours, 9OOC) to 68% burn-off. The high oxygen content and low hydrogen content for CH-36SV is typical of carbons gasified in CO,. These ultimate analyses were conducted at a commercial analytical laboratory, and gave lower-thanexpected ash contents for the activated carbons. The ash contents in parentheses in Table 1 were determined via burn-off studies (12 hours in air at 9OOC) in our laboratory, and are in agreement with the ultimate analyses. The decreased ash content following activation cannot be attributed to different starting materials, as different batches of cherry hulls had almost identical ash contents. We therefore suspect that the ash is undergoing decomposition during extended exposure to high temperatures and reactant gases during activation. The exact reason for low ash content in the activated carbons is not fully understood, but further study of ash composition and behavior is beyond the scope of this work.

3.3 Dependence on activation conditions

The dependence of hull char burn-off on activation temperature and activation time is given in Fig. 1 for both steam and CO, activation. (Solid lines represent curve fits of the data.) Figure 2 gives CC& adsorption capacity versus char burn-off for all experiments performed with hulls; it is seen from Fig. 2 that adsorption capacity is higher for steam activation than for

Table 1. Ultimate analysis of char and activated carbons from cherry hulls (wtYo, dry basis) Activated Carbons

3. RESULTS AND DISCUSSION

Char C H N S Ash 0 (by diff) 91.2 1.2 1.2 0.03 4.5 (4.3) 1.87 100.00

(CH-23) 95.4 1.0 1.0 0.01 0.9 (0.8) 1.69 100.00

(CH-36SV) 82.5 0.3 1.2 0.05 1.8 14.15 100.00

3.1 Starting materials

One objective of this study was to determine the relative contribution of the kernel and hull to the overall adsorption capacity of the activated carbon produced from cherry stones. Upon carbonizing and activating separate samples of hulls and kernels, we

Activated carbon from cherry stones

90 t

1495

?y ;I : ,:
b 5

80 70 60 50
40 30 20 10 OJ 0.0 0.5 1 .o Activation 1.5 Time 2.0 (hr) 2.5 3.0 .

.
f

; . i.

..,

Fig. 1, Char burn-off at different activation conditions: (A) 800C in steam; (Cl) 825C in steam; (+) 850C in steam;

(V) 900C in C02.

COz activation. To achieve desired adsorption capacities (CCL, number above 60), char burn-off must be greater than 40% in steam activation and above 60% in CO2 activation. Carbons produced at very high burn-offs (>80%) have very high activities (Ccl4 number of -lOO), but are produced in such small quantities that they are impractical. The highest adsorption capacity per unit weight starting material [(Ccl4 number in Fig. 2) x (1 - fraction char burn-off)] is at 40%-50% burn-off (yield of 0.1-0.12 g carbon/g stone) for both steam and CO2 activation; this represents the optimum extent of burn-off for activated carbon preparation. The data in Fig. 2 include carbons produced at all combinations of temperature and activation times, indicating that extent of burn-off, instead of activation conditions, dictates the adsorption capacity of carbons produced from cherry hulls. Activation times at temperatures below 800C in steam or below 900C in COz were excessively long (for instance, 12 hours at 800C in CO* to achieve 50% burn-off) and gave activities no higher than those for carbons activated at higher temperatures. The activation times in Fig. 1 (1-3 hours) correspond to those in commercial carbon manufacturing processes, and are much shorter than the corresponding times (3060 hours) reported by Rodriguez-Reinoso and Molina-

Sabio[S] to achieve the same burnoff at the same temperature. Either cherry hull ash catalyzes gasification or the experiments reported in ref. [5] were influenced by mass transfer resistances. Table 2 gives a summary of activation conditions and adsorption properties for representative activated carbons produced from cherry hulls (CH-) and entire stones (CP-). Table 2 also includes adsorption properties of two reference carbons and of the char prior to activation which, surprisingly, showed a relatively high surface area (420 m2/g) based on CO, adsorption. Nitrogen adsorption on the unactivated char gave a much smaller (BET) area of about 80 m2/g; N? uptake was exceptionally slow and never certain to be complete, so that the reported BET area is an estimate. This very slow, limited Nz adsorption has been previously reported[5,9] to result from the formation of ultramicroporosity: such small pores are kinetically excluded by activated diffusion of N2 at 77 K and are too small for Ccl, to access, but are readily accessed by CO2 at 298 K. Ultramicroporosity in carbonized biomass materials has been attributed to pore-mouth deposition of secondary carbon formed via volatile decomposition during carbonization[5]. It is noteworthy that activated carbons do not exhibit such ultramicroporosity, as the surface areas determined from CO2 adsorption and from N2 adsorption are similar in trend and magnitude for the activated carbons. Activated carbon yield per unit weight stone is reported in Table 2 to illustrate the higher yields obtained when using the entire stone. The carbon formed from the entire stone, however, shows relatively lower specific adsorption capacity than the corresponding carbons produced from the hulls only. This is because of the presence of kernel residues, constituting lo%13% of the carbon weight, which contribute little to adsorption capacity. Carbons produced from cherry stones have adsorption capacities comparable to the coconut-derived activated carbon and the coal-based decolorizing carbon that were analyzed. 3.4

Macropore structure

. .
. . -

.
n

I.

.
. 5

.
-9

10

20

30
Char

40

50
Burnoff

60
()

70

80

90

Fig. 2. Carbon tetrachloride adsorption capacity versus char burn-off during activation: (V) steam activation; (0) CO, activation.

Macropore distribution of the activated carbons produced, as characterized by mercury porosimetry, is reported in Fig. 3. The macropore structure is clearly dominated by pores of 0.4-micron diameter. During carbonization and up to 20% char burn-off, the pore size distribution changes little, although the total macropore volume increases from 0.19 to 0.49 cm7/g. Again, this increase in total volume likely arises from burn-off of secondary carbon that initially blocks pore entrances. Above 20% burn-off, the 0.4-micron pores are seen to widen as carbon is consumed (see Fig. 4c below), and the total macropore volume increases to 0.66 cm3/g at 50% burn-off. For reference, the macropore volumes of the reference activated carbons were 0.85 cm3/g for the decolorizing carbon and 0.94 cm3/g for the coconut carbon. Macropore structure was further elucidated by

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Table 2. Results of representative activation experiments

co2
Sample Activation conditions Yield (g/g stone) 0.2 0.062 0.100 0.052 0.156 surface areaa (m2/g) 420 1180 1600 1050 890 1220

N, BET surface area (m/g) 80 920 920 1340 930 960 1120

Ccl, number (g/PC x 100) <5 71 77 _ 58 65

Me blue uptakeb (mg/g C) _ 390 490 280 180 350

Char from hull carbonization H-l none Activated carbon CH-36SV CH-9 CH-24 from hulls 9OOC, 2 hr, CO2 8OOC, 2 hr, steam 825C, 2 hr, steam

Activated carbon from entire stones CP-17 800C 2 hr, steam

Reference carbons Darco decolorizing carbon -325 mesh (Aldrich) Coconut-activated carbon -100+200 mesh (Fisher)

CO, adsorption at 298 K, 0.26 nm*/molecule CO,. b24-hour uptake by 20 mg carbon from 100 mg/ml methylene blue solution.

electron microscopy (SEM) of carbonized hulls (Fig. 4). The inner and outer surfaces of the hull are impervious (according to the hulls function of protecting the embryo[l4]); access to internal porosity only exists along the fracture surfaces that expose the inner hull structure. Figures 4a and 4b show the carbonized hull; remains of the stone structure, with thick, lignified cell walls and individual cell cavities of dimensions ranging from 5 microns to 70 microns, are visible. In Fig. 4b, pores (0.4 micron) in the cell walls, formed during stone growth to facilitate intercellular transport[l4], are seen. For the carbonized hull activated to 50% burn-off (Fig. 4c), a widening of the pores, corresponding to the broadening of the pore size distribution seen in Fig. 3, is seen, along with the consumption of the cellular structure. The interconnecting pore-cavity structure of the carbon is similar to the ink-bottle structure commonly used to describe adsorption behavior in porous solids, and explains the observed monodisperse pore size distribution from mercury porosimetry. Because scanning

most of the pore volume in the hull is reached through 0.4-micron pores, very little mercury is intruded into the carbon until the pressure exceeds that necessary to fill the O.Cmicron diameter pores. At that time, essentially all of the hull cavities fill with mercury. The observed uniformity of these O.Cmicron pores is unusual; similar pores are found in other fruit stones and nut shells[ 151. 3.5 Adsorption rates In addition to equilibrium capacity, the adsorption rate of activated carbon is an important parameter in process design. Adsorption rates in activated carbons have been modelled[ 161, but in this study an empirical approach was taken. We initially observed that COz adsorption by carbon formed from cracked hulls gave high surface area but was unusually slow. Methylene blue adsorption from aqueous solution required several days to approach equilibrium, indicating substantial mass transfer resistances during adsorption. The impervious surfaces of the hull, as observed via SEM, suggest that mass transfer in the hull takes place tangentially from the fracture surface inward, resulting in a long diffusion path. The activated hulls were therefore ground and sieved to different particle sizes and the methylene blue uptake rates again measured. Results are given in Fig. 5 as fractional uptake vs time for four carbons and two reference carbons. (Trend lines are omitted for the reference carbons for clarity.) Equilibrium uptake was reached for all carbons within 24 hours; the equilibrium capacity of each carbon is given in Table 2. Small particle sizes (-100 + 200 mesh, or 75-150 micron) are required to obtain uptake rates similar to the commercial carbons; particle sizes above 75 micron adsorb too slowly to be considered practical. It is interesting to compare uptake rates and ultimate capacities of CP-17 and CH-24 (both 75-150 micron). The CH-24 carbon, from hulls, was activated to 74% burn-off (yield = 0.052 g/g stone)

0.01

0.1 Pore

1 Diameter

10
(micron)

100

Fig. 3. Macropore size distribution at various stages of activated carbon preparation. (-) hulls; (- - -) charred hulls following carbonization; (---) activated to 20% char burn-off; (. . . . .) activated to 50% char burn-off.

Activated carbon from cherry stones

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0.0 0 I

3
Time (hr)

(a)

Fig. 5. Fractional uptake rate of methylene blue from aqueous solution versus activated carbon particle size: (0) CP-17, -16 + 30 mesh; (0) CP-17, -60 + 100 mesh; (a) CP-17, - 100 + 200 mesh; (V) CH-24, - 100 + 200 mesh; (0) Darco carbon, -325 mesh; (m) Coconut carbon, -100 + 200 mesh.

4. CONCLUSIONS Activated carbon can be produced from cherry hulls with activities and yields similar to that reported for other fruit stones and nut shells[S-71. Char yields from carbonization of 2.5%-28% and burn-offs on the order of 40%-60% are typically used to achieve the desired activity. The large weight loss in going from feedstock to final product is one drawback of using biomass materials for activated carbon production. Based on the hull carbon content (-45%), activated carbon yields from this biomass source approach one third of theoretical, at best. Higher carbon yields can be achieved using chemical activation methods[S], but additional processing steps required make chemical activation less attractive economically. Activated carbon produced from cherry hulls has high activity, potentially very low ash, and is a durable, non-dusting material. It can be produced at reasonable temperatures (SOOC) and activation times (2-3 hours) and, when used in pulverized form, compares favorably to commercial activated carbons in both uptake rate and overall capacity.

(b)

Fig. 4. Scanning electron micrographs of the fracture surface of activated carbon from cherry hulls: (a) carbonized hull (x750); (b) carbonized hull (~5000); (c) carbonized hull activated to 50% burn-off (x5000).

Acknowledgements-The support of the Cherry Marketing Institute is gratefully acknowledged. Zhang Zhigang conducted the N2 BET surface area measurements and the ash determinations on the activated carbons.

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as opposed to CP-17 from the entire stone, which was activated to about 40% burn-off (yield = 0.156 g/g stone). More extensive burn-off opens up the pore structure significantly, reducing mass transfer resistances into the interior of the pit material, as well as increasing the total adsorption capacity. Because of the exceedingly long uptake times for unaltered activated hulls, it appears that activated carbon from cherry stones will be best used as a powder or pelletized material.

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