Beruflich Dokumente
Kultur Dokumente
ABSTRACT
Five tropical biomass have been subjected to low temperature conversion and their chars
activated by partial physical gasification to produce active carbons. The biomass are T.
catappa, B. nitida, L.leucophylla, D. regia and O. martiana.
The bulk densities of the samples ranged from 0.32 g.cm3 to 0.52 g.cm3. Out of the
samples T. catappa recorded the highest cullulose content (41.9 g.100g-1), while O.
martiana contained the highest lignin content(40.7 g.100g-1). The ash of the samples were
low (0.5 - 4.4%). The percentage of char obtained after conversion were high (33.7% -
38.6%).
Active carbons obtained from T. catappa, D. regia and O martiana, recorded a high
methylene blue number and iodine. They also displayed good micro- amd mesostructural
characteristics (Vmicro between 0.33cm3.g-1 -0.40cm3.g-1; Vmeso was between 0.05 cm3.g-1 -
0.07 cm3.g-1) and the BET specific surface exceeds 1000 m2.g-1.
All these values compared favourably with high grade commercial active carbons.
KEYWORDS
INTRODUCTION
Active carbons are microcrystalline solids which exhibit high porosity, adsorptive capacity
and enormous surface area. Its internal surface allows for the adsorption of organic materials
as well as non-polar compounds and metals from gas and/or liquid media1-5. For many
decades active carbons have been produced from a number of carbonaceous materials like
coals, lignite, peat and wood. However agricultural by-products still remains the cheap and
renewable source of active carbons. Chemical activation involves the use of chemical
activating agents like ZnCl2, H3PO4, NH4Cl e.t.c, before the carbonisation step. By far the
majority of industrial active carbons used throughout the world is produced by physical
means using steam or other gases as the activating agent. This procedure involves the
carbonisation of the substrates to produce coke followed by the activation with steam or
other agents at elevated temperature. There are some problems associated with the
carbonisation step. Polyaromatic compounds like PCBs are known to be produced during
this process which can result in severe environmental consequences. Apart from this, the oil
contains a junk of compounds which are not useful and are burned off in most cases 6. Low
temperature conversion, a thermocatalytic conversion process developed by Bayer and
Kutubuddin 7-9, offers an extensive recovery of raw materials in the form of oil and char
without any detrimental effect on the environment. This process also referred to as “oil from
sludge”, involves the heating of wastes, sludges and biomass in special converters in the
presence of nitrogen or argon at 320oC – 400oC for 3h. Since the process is operated in the
absence of air, reducing conditions in the reactor system catalytically dehalogenate OCs
according to the Deacon process10. This process is further catalysed by the presence of
heavy metals in the raw material. The chemical and energy feedstocks which are produced
are easy to store and to handle. The oil consists of various saturated and unsaturated
hydrocarbons, fatty acids and a number of other compounds which can be used as fuel 8. The
char can be used as solid fuel or refined by partial gasification to yield active carbon.
In view of the potential of the low temperature conversion and the underutilisation of
the hulls of these biomass, this work therefore considers the conversion of the biomass to oil
and char. The char will be refined by partial gasification with steam. The work will also
involve the determination of the adsorptive properties of the active carbons and the
enumeration of their possible uses.
T. catappa belongs to the Family Combretaceae. It is a native of Malaysia and the Western
Pacific, introduced into West Africa. The tree is used as a shade and avenue tree while the
timber is reddish and elastic, and have found use in the construction of boats and houses 11.
The fleshy pericarp of the fruit is eaten in many parts of West Africa while the husk, which
contains the seed is discarded. The epicarp and mesocarp residue of this fruit have been used
as fertiliser in Spain12. B. nitida belongs to the Family Papilionoideae. It is an economic
agro-forest tree13. Some parts of the plants have been used for ethnomedicinal purposes14.
As far as we know there is no work in literature on the utilisation of the legume fruit
produced by this tree. L leucophylla belongs to the family, Mimosoideae. It is also a tropical
legume tree. Limited work have been reported on the utilisation of the legume fruit. Lye et
al15, have reported feeding studies of the fruit on pigs and some researchers have reported
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the utilisation of the seed flour as plywood glue extender 16. D. regia belongs to the family,
Caesalpiniodeae. It one of the most important tropical hardwoods. Most research have been
directed its use as a timber17,18. Babassu (Orbignya martiana) is a native of North and
Central regions of Brazil. It is now grown extensively in Nigeria and some West African
countries. The O. martiana coconut has an ellipsoidal shape of about 10cm in length and
6cm in diameter. The endocarp which was used for this studies consists of about 58% of the
fruit 19.
Dried fruits of the materials (Terminalia Catappa, Bauhania nitida, Leucemia
leucophylla, Delonix regia and Orbignya martiana) were collected from the Botanical
gardens of the University of Ibadan and identified at the Forestry Research Institute of
Nigeria FRIN, Jericho, Ibadan. They were further dried at 105oC for 24h. The samples were
stored in plastic containers prior to analysis and conversion.
Methods
Low temperature conversion was carried out batchwise in triplicate on 250-500g samples in
a laboratory reactor(Fig. 1) in the presence of nitrogen at 380oC for 3h. The samples (2)
were fixed in the tube by glasswool(3), transferred into the furnace(1), and heated under
nitrogen(5). The heating rate was maintained at the rate of 10 K min-1 by the controller(4).
The volatile compounds were condensed by a condenser (6) into a separating funnel (7) with
an exhaust for non condensable gases(8). The yields of the conversion oil, water and char
were determined gravimetrically, while the gas yield was determined by difference (100-
total yield of char, water and oil). The standard deviation of the yields obtained from this
process is usually below 1% 20.
1
2
3 5
6
1 furnace 5 nitrogen supply
2 sample 6 condenser
8
3 glaswool 7 sep. funnel
4 controller 8 exhaust gas outlet
7
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The bulk densities and the proximate chemical composition of the samples are presented in
Table 1.The bulk densities range from 0.32 g.cm3 to 0.52 g.cm3. O martiana recorded the
highest bulk density. During activation, it has been established that the bulk density
determines the rate of volatilisation of the carbons as well as affects the hardness, strength
and porosity of the active carbon produced. A more dense biomass will produce a more
compact and harder active carbon29. L. leucophylla recorded the lowest bulk density(0.32
g.cm3). T. catappa has the highest cellulose content (41.9 g.100g-1) while O. martiana
contained the highest lignin content (40.7 g.100g-1).
Table 1. Bulk density and proximate composition of some tropical biomass
a
Based on a particle size of 0.85 – 2.00mm
b
Determined on dry weight basis
It is known that the lignocellulosic composition of the precursors determines the char
yield, and porosity of the active carbons due to the difference in the thermal stability of the
components(Lignin, cellulose and hemicellulose)20,30. The ash content of the samples range
from 0.5 to 4.4%. They are relatively low compared to other biomass31. Inorganics (ash)
contribute little or nothing to the adsorptive capacity of carbons. Instead they block existing
micropores in active carbons thereby reducing the surface area. The yield of conversion
products and the elemental analysis of the chars are presented in Table 2. Percentage char in
all the samples are high(33.7% to 38.6%. Except for T. catappa, which recorded a
percentage of 12.5%, the percentage conversion oil in all the other samples studied was
below 9%. Elemental analysis indicated that the carbon content of the samples were
high(68.5% and 76.5%). The characteristics of active carbons produced from the various
chars is presented in Tables 3 -7. The chars were activated at times between 0 and 50 min.
except for O martiana in which the activation time was extended till 150min. The higher
activation time might be due to the dense nature of the sample reflected by the highest bulk
density which reduces the rate gasification of the sample. The high carbon content of the
sample might also contribute to the slower rate of depletion of the carbon compared to other
samples.
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Table 2. Yield of conversion products and elemental analysis of the chars of some tropical biomass
T. catappa B. nitida L. leucophylla D. regia O. martiana
Yield of conversion products
Char % 38.6 33.7 35.9 34.0 34.0
Oil % 12.9 7.5 8.6 8.6 4.4
Water % 28.5 30.2 29.1 33.7 40.8
Gas % 19.9 28.7 26.5 23.7 20.8
Analysis of conversion products
C% 76.5 74.9 68.5 75.9 76.9
H% 5.4 4.3 4.8 4.8 6.2
N% 0.6 0.7 2.8 1.3 0.5
S% nd* 0.02 0.05 0.2 nd*
Burn off (%) percentage of carbon gasified during activation ; Vmicro, Vmeso (cm3.g-1) pore volume
by haxane adsorption ; MB (mg.g-1) adsorption of methylene blue per gram active carbon - methylene blue
number ; Iod. (mg.g-1) adsorption of iodine per gram active carbon - iodine number.
Iodine and methylene blue number were used to selection of optimised active carbons (best active
carbons at optimal conditions).
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Burn off (%) percentage of carbon gasified during activation ; Vmicro, Vmeso (cm3.g-1) pore volume by haxane
adsorption ; MB (mg.g-1) adsorption of methylene blue per gram active carbon - methylene blue number ; Iod.
(mg.g-1) adsorption of iodine per gram active carbon - iodine number
Burn off (%) percentage of carbon gasified during activation ; Vmicro, Vmeso (cm3.g-1) pore volume by haxane
adsorption ; MB (mg.g-1) adsorption of methylene blue per gram active carbon - methylene blue number ; Iod.
(mg.g-1) adsorption of iodine per gram active carbon - iodine number
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Burn off (%) percentage of carbon gasified during activation ; Vmicro, Vmeso (cm3.g-1) pore volume by haxane
adsorption ; MB (mg.g-1) adsorption of methylene blue per gram active carbon - methylene blue number ; Iod.
(mg.g-1) adsorption of iodine per gram active carbon - iodine number
Burn off (%) percentage of carbon gasified during activation ; Vmicro, Vmeso (cm3.g-1) pore volume by haxane
adsorption ; MB (mg.g-1) adsorption of methylene blue per gram active carbon - methylene blue number ; Iod.
(mg.g-1) adsorption of iodine per gram active carbon - iodine number
The results of the characteristics of the optimised active carbons in comparison with
the commercial high grade active carbons are depicted in Fig. 3 and 4. The iodine values of
T. catappa, D. regia and O. martiana is almost twice as large as the commercial D/10 and
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higher than all the three high grade active carbons displayed in this work. The values
obtained from this study also compared favourable with similar biomass employed by other
workers for the production of active carbons.
Fig. 3: Characteristics of the optimised active carbons from conversion chars in comparison with
commercial active carbons (Vmicro, Vmeso: pore volume by hexane adsorption; Norit D10 made from
peat for liquid phase use, Carbotech D47/4 made from bituminous coal for gas phase use and Merck
activated carbon made for gas adsorption)
Figure 4: Characteristics of the optimised active carbons from conversion chars in comparison with
commercial active carbons ( MB (mg.g-1) adsorption of methylene blue per gram active carbon ; Iod.
(mg.g-1) adsorption of iodine per gram active carbon ; BET (m2.g-1 ) surface of active carbon by nitrogen
isotherms ; Norit D10 made from peat for liquid phase use ; Carbotech D47/4 made from bituminous
coal for gas phase use ; Merck activated carbon made for gas adsorption).
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Constales et al32, reported a methylene blue number of 275 mg.g-1 and 1180 mg.g-1
iodine number and BET surface of 1035 m2.g-1 for Cuban molasses and results reported by
Ahmedna et al33 for various grades of treated pecan shells. The active carbons were further
characterised by the estimation of their pore volume and pore size distribution using n-
hexane adsorption method. Dubinin34 have proposed three main types of pores namely
macropores, mesopores and micropores. Macropores which have sizes greater than 100nm
have little application in adsorption processes because the surface area is too low to generate
any interest. Mesopores on the other hand have sizes between 2-100nm, have surface area in
the range 20-100 m2.g-1 with pore volume between 20-100 m2.g-1. Micropores (< 2nm) have
highest absorption capacity and higher adsorption energy. Average active carbon is known
to have volumes between 0.2-0.5 cm3.g-1 and areas up to 1000 m2.g-1 35. T. catappa, D. regia
and O. martiana active carbons exhibited a highly developed micopore and mesopore
structure and compares favourably with highly adsorptive materials like Carbotech D47/4
and Merck activated carbon (Fig. 3 and 4). This results also compared favourably with
active carbons produced from similar precursors [English walnut and macadiama
nuts36(Vmicro-0.31cm3.g-1, Vmeso-0.20cm3.g-1) ;pecan shell activated carbon37(total pore
volume 0.868 cm3.g-1, BET surface 1149 m2.g-1) ; olive mill solid residue38 (iodine number
1270 mg.g-1, BET 1500 m2.g-1) ; palm shell39(total pore volume 0.38 cm3.g-1). All the chars
displayed a developed microporous volume except L. leucophylla which produced almost
the same degree of development of micro- and mesoporous volume (0.14cm3.g-1 and
0.10cm3.g-1 micropore and mesopore volume respectively).
In view of the high BET values as well as a highly developed pore volume exhibited
by all the substrates except L. leucophylla, it is suggested that the active carbons could be
applied in solving a wide range of adsorption problems from gas adsorption and
deodorisation to the treatment of waters and wastes waters and adsorption of inorganics.
CONCLUSIONS
Five tropical biomass hulls have been converted to char and activated by partial gasification
to produce active carbons. Conditions for activation have been optimised.
All the substrates show good activity and are comparable to high-grade active
carbons. However T. catappa, D. regia and O martiana displayed exceptionally high
adsorptive capacity and offer the greatest promise for use as high grade active carbons.
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