and
G. McKay*
Department of Chemical Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, HONG KONG
The uses of active carbons and carbon chars for liquid and gas phase applications has been presented. Their application for decolourising, water treatment, solvent recoveiy, militaly uses, nuclear industry, air purification, domestic uses, precious metal recovery and catalysis, have been outlined. A detailed review of the production and manufacture of activated carbonsfiom a wide range of carbonaceous sources is given. Methods of activation are discussed based on a range of chemicals and how these chemicals influence surface activity, pore size and pore distribution. The
techniques for characterising activated carbons are reviewed in detail and include porosimetry, sorptometry, topography, pore size distnbution, isotherms and suflace area measurements. The specrfic results of some active carbons derived @om
*Authorfor correspondence.
23 1
Introduction
The removal of contaminants out of ,.quids and gases is a process which has received considerable attention throughout the twentieth century. However, the interest in h s topic is not confined to more recent years. As long ago as 1550 BC the Egyptians used charcoal to purify oils and early ocean going ships stored drinking water in wooden barrels, the inside of which had been charred. The earliest date at which the adsorptive powers of carbons and charcoals were d e f ~ t e l yrecognised was in 1773 when Scheele described experiments with gases. In 1786 Lowitz noticed the decolourising effects of charcoal on solutions. A few years later, wood char was employed to purify cane sugar and in 1808, was applied to the developing sugar beet industry. The discovery by Figers in 1811 of the greater decolourising power of bone char, led to its swift adoption by the sugar refiners. At first, pulverised bone char was applied on a single use and discard basis, but limited supplies made regeneration necessary. Active carbon is a generic term referring to highly porous carbonaceous materials. Activated carbon can be from any carbon containing material by thermal decomposition or pyrolysis followed by activation with steam or carbon &oxide at high temperatures (700-1 l0OOC). During the 19th century, many studies were made to develop decolourising carbons from other source materials. Bussy in 1822 heated blood with potash and produced a carbon with 20 to 50 times the decolourising power of bone char. Blood char so produced was used for years in many laboratory studies. In 1865, Hunter reported the gas-adsorbing power of coconut char. In the same year Stenhouse prepared a decolourising char by heating a mixture of flour, tar and magnesium carbonate. In another process Winser and Swindells heated paper mill wastes, and many of these processes are similar to processes now in industrial use, however they were not developed until long after the time of their discovery. Reasons for this are found in manufacturing problems that could not have been dealt with at the time, such as the corrosive nature of most activation con&tions, whch require special structural materials not then available, and the unavailability of precise control instrumentation, which has been developed only relatively recently. AnotheI
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major factor which retarded the development of these special carbons was the absence of apparent needs for a more powefil adsorptive carbon than bone char. However early suggestions for a market, which have now become important, were made by Lipscombe, who, in 1862 prepared a carbon to purify potable water, and Stenhouse in 1854, who described the forerunner to the modem gas mask. The use of carbon molecular sieves in gas separation, in particular oxygen and nitrogen, has grown steadily in the past years (Sircar et al., 1996). These carbons are characterised by a high adsorption capacity and by the size of the micropores which must be of the same order of magnitude as the adsorbate molecules (Stoekli et al., 1996). Depending on the ability of a molecule to diffuse into the micropore volumes dxtates the ability of carbon molecular sieves to effect separations of gas mixtures. The creation of a large sorptive capacity in the micropores is achieved by physical or chemical activation but this also leads to wide micropore openings. The reduction in width of micropore openings can be acheved by the deposition of carbon resulting from the crackmg of hydrocarbons adsorbed in the micropores via heat treatment (Stoekli et al., 1996) or through mild gasification (Verma and Walker, 1993). As a consequence there is a reduction in pore size and pore volume thus decreasing adsorption capacity. As a result, the use of activated carbon fibres as molecular sieves is increasing. These fibres often have a greater adsorption rate and larger capacity than typical granular activated carbons when used in gas filtration (Suzuki, 1994). The key commercial applications of molecular sieve-type activated carbons in the gas separation and purification industry have been reviewed (Sircar et al., 1996).
233
characterisation have been established according to, for example pore classification, surface area or surface topography, in order to compare carbons and assess their adsorptive potential. The use of activated carbon for wastewater treatment and potable water purification has been the topic of a number of papers in the Advances in Chemistry Series (ACS) between 1960 and 1997; a particularly relevant volume was on the application of granular activated carbon (McGuire and Suffet, 1983) to water treatment.
(ii) Topography
Topographical stumes of the external surface of activated carbon gives an indication of the porous nature of the carbon's exterior. The external pores are generally large pores, normally mesopores and macropores depending on the parent material, and are important in terms of adsorption as they are transport pores allowing the passage of the adsorbing species, from the adsorptive, to the adsorbents internal porous structure. Scanning electron microscopy (SEM) is a very effective and accurate method often used for surface investigations. SEM gives a three-dimensional picture of the surface structure. Zulkamain et al. (1993) found that activated carbons from mangrove wood have surface pores of 20-40pm diameter whereas cross-sectioned samples showed internal pore distributions of 80-100pm, 10-20pm and 1-2pm. Stoeckli (1989) reported on using High-Resolution Transmission Electron Microscopy (HRTEM) to confirm findings in adsorption experiments regarding the hsorganised nature of microporous carbons. Using a selective technique developed by O b e r h known as "dark-field", the carbons' interplaner spacings were determined from the micrographs. Figure 1 shows SEM pictures of new peat and of the peat char based on
234
Figure I. Scanning electron micrographs of raw peat, and of peat char - after charringfor 30 mintues.
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(iii) Porosimehy
Porosimetry is a study related to the structure of a medium. Mercury porosimetry is used extensively as a means of characterising porous media and powders. By far the most important aspect of mercury porosimetry is its use for determining pore size dmibution. The concept of using mercury penetration was fust suggested by
Smetana in 1842 to show the porous nature of wood. Then Washbum in 1921, and independently in 1941 by Loisy, proposed a method by which pore size distribution could be determined from pressure-volume data for mercury penetration. However, it was not until a paper was published in 1945 by Ritter and Drake that experimental methods and data were described for this procedure. Mercury porosimetry works on the principle that, as mercury is a non-wetting liquid towards most substances (having a contact angle with mercury greater than 90"), it will not penetrate into openings without pressure being applied. If the solid to be investigated is placed in a container with a tapered capillary end, evacuated and filled to a predetermined level with mercury, when pressure is applied the mercury level will fall as it is pushed into the pores. The decrease in the mercury level is directly related to the pressure exerted and from this the volume-pressure porosimetric curve can be constructed. Winslow (1978) raised the issue that intrusion could be destructive to the pore structure. For accuracy and to study microporous structures, increasingly higher pressures are being used. He concluded that little or no damage was incurred with strong materials however, weaker structures were susceptible at high pressure to pore redistribution. Van Brake1 et al. (1981) also raised the question of mechanical deformation of the sample being tested. From the findings of Moscou and Lub (1981), Dees and Polderman (1981), and Spitzer (1981), they concluded that additional porosity creation or mechanical deformation depends on the sample preparation. Ritter and Drake showed that, with a mercury pressure-volume relationshlp, on retraction by a reduction in pressure a proportion of mercury remains in the pores resulting in a &splay of hysteresis. Hysteresis has been attributed to two causes;
236
(a) contact angle hysteresis in wluch the advancing contact angle is different to the receeding angle and (b) structural hysteresis or ink-bottle hysteresis arising from the non-cylindrical nature of pores in real porous bodies (cylindrical capillaries do not display hysteresis). Due to structural hysteresis, surface areas obtained from
porosimetry will never be accurate. Although there are problems linked with the accuracy of porosimetry data, the method provides a characteristic of pore space geometry, h s information combined with a comparative method can be used as a means of sorbent characterisation. The standard methods used today are still based on Washburns original theory and have been described in detail (Bradley et al., 1989). Porosimetry is used frequently and accurately as a characterisation tool in the catalysis industry.
(iv) Sorptometry
Gas sorption analysis and the interpretation of its physical and chemical frndings is by far the most widely used and investigated method of sorbent characterisation. In general, physisorption is used to determine the surface area, pore hstribution and pore volume of a sorbent whereas chemisorption is used to assess the area of any active surface component. Initially the physical adsorption (and desorption) isotherm is determined for the sorbent to be characterised. Thls is generally determined by nitrogen adsorption at the liquid nitrogen temperature of 77K, however, other small molecule adsorptivities
r have also been used, A (77K), Kr (77K), Xe (77K), alkanes (298K), CO, (195K) and
0, (90K). The shape of the isotherm provides an indication of the nature of the pore
structures in the sorbent make-up. Table 1 presents a comparison of pore characteristics for different models for an activated carbon treated with 50% ammonium molybdate and charred at 6OO0C for 30 minutes.
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Table 1.
Adsorption Model
Monolayer Volume
cm3g-'
Surface Area
Micropore Volume
cm3g-'
m2gl
BET
0.094
Langmuir D-R
0.112
raw lignite with a lignite-based activated carbon using steam activation. Nitrogen adsorption data is a good source of information which can be used to yield information regarding the pore size distributions of the carbons. The application of these methods by Brunnauer et al. (1940)yield information on pore radii and pore size distributions. For an industrial application of a carbon to be successful, the value of h s type of physical characterisation cannot be understated. The monolayer capacity of the adsorbent will give an accurate and reproducible value for the surface area of the carbon in question. Langmuir values for monolayer capacity are found to be slightly hgher than those obtained using BET. The micropore volume as determined by the
G,
and D-R
models are generally in good agreement. Surface areas are similar for Langmuir and D-R models whilst BET and from the results in Table 1.
238
239
240
(v) Isotherms
An isotherm is a pictorial representation of the equilibrium adsorptioddesorption
process. It shows the equilibrium relationship, at constant temperature or pressure, and the adsorbed quantity. Brunauer et al. (1940) noted that although isotherms were dfferent for all sorbents and sorbates investigated, common shapes of isotherms were observed. Six isotherm types are generally used as a basis for classification, and these are shown in Figure 4. Type I reversible isotherms are characteristic of microporous solids as seen for example in activated carbons or zeolites. Uptake reaches a limiting value as p/p, tends to 1, indicating that uptake is dependent on micropore volume accessibility rather than surface area. Typical systems include nitrogen on charcoal at -1 8 O and 3C many dyes on activated carbon at 2OOC. Type 1 isotherms are common to non-porous or macroporous solids. They 1 indicate unrestricted monolayer-multilayer adsorption, such as the sorption of nitrogen on iron catalysts at - 195'C. Type I11 isotherms are uncommon and are usually associated with water vapour adsorption. Generally in this type of adsorption, the adsorbent-adsorbate interactions are weak as compared with the adsorbate-adsorbate interactions. An example is bromine on silica gel at 79'C. Type I isotherms are recognised by the presence of a hysteresis loop. This type V of adsorption is observed frequently with many mesoporous industrial adsorbents. The adsorption of n-decane on vycor has been used to study isotherm hysteresis.
1 Type V is related to the Type 1 1isotherm and is very uncommon. Type VI isotherms
are seen with uniform non-porous surfaces and represent stepwise multilayer adsorption.
241
A,(BET) = n. L.a, ,a
and
a, (BET) = A, (BET) / m
where A,(BET) and a,(BET) are the total and specific surface areas respectively, m is the mass of adsorbent, and L is the Avogadro constant. To form a monolayer the adsorbate molecules must be physically adsorbed, however, it is known that physical adsorption generally involves multilayer adsorption. Multilayer adsorption commences at pressures below those required to complete the monolayer formation thus preventing an exact determination of the monolayer capacity from the experimental data. Brunnauer, Emmett and Teller (BET, 1940) proposed a simple model to account for multilayer physical adsorption and hence to determine the monolayer capacity for surface calculation. The BET equation is written:
where V is the volume of gas adsorbed at pressure p; po is the saturated vapour pressure of the liquid at the temperature of the experiment; V,,, is the volume equivalent to an adsorbed monolayer; and C is the BET constant equal to
, exp (H,-H,)/RT; H, is the molar enthalpy of adsorption in the first layer; and H is the
molar enthalpy of condensation. In h s form, a linear plot can be achieved and C and
V, easily determined from the linear slope and intercept.
The derivation of the BET equation results from many over simplifications and idealisations and in fact its linear form is only linear in the relative pressure range of
0.05-0.35.In spite of its limitations, the BET method is still the most widely used
method for surface determination in sorbent characterisation. Some indication of the applicability of the BET model as a method for surface determination may be
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obtained from a comparison of data obtained with different sorbates on the same porous material.
2. Liquid-Phase Applications
Activated carbons for use i liquid-phase applications differ from gas-phase carbons n primarily in pore size &sttibution. Liquid-phase carbons have significantly more pore volume in the macropore range, whlch permits liquids to d f h s e more rapidly into the mesopores and micropores. The larger pores also promote greater adsorption of large molecules, either impurities or products, in many liquid-phase applications. Liquid-phase activated carbon can be applied either in a powder, granular or shaped form. The average size of powdered carbon particles is 15-25 pm, and they are most often used in batch applications. Granular or shaped-carbon particle size is usually 0.3-3.0 mm, and these carbons are more suitable for use in continuous flow systems.
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3. Gas-Phase Applications
Gas-phase applications of activated carbon include separation, gas storage, and catalysis. Although only about 20% of activated carbon production is used for gasphase applications, these products are generally more expensive than liquid-phase carbons and account for about 40% of the total value of shpments. Most of the activated carbon used in gas-phase applications is granular or shaped. Separation processes comprise the m i gas-phase applications of activated an carbon. These usually exploit the differences in the adsorptive behaviour of gases and vapours on activated carbon, on the basis of molecular weight and size. For example, organic molecules with a molecular weight greater than about 40 are readily removed from air by activated carbon. Recent uses include odour removal and gas purification; also the use of carbon molecular sieves for gas separation processes.
4. Water Treatment
A major use of activated carbon is in the treatment of both potable and effluent water.
244
treatment, but it may be left with an undesirable taste or odour (Cheremisinoff, 1993). Activated carbons can be used as a fmal polishmg treatment to remove such tastes or odours. Activated carbon is never a primary treatment, but is normally used in conjunction with a suitable chemical treatment. Industrial effluent containing toxic or harmful contaminants can be treated with activated carbon to avoid sea or river pollution. Also effluents from detergent manufacturers, refiners, electroplating and chemical manufacturers, and from manufacturers of insecticides, herbicides and fungicides, can effectively be treated with activated carbon. Activated carbon is also a very effective dechlorinator, and therefore is used by manufacturers of soft drinks and beers where water has been superchlorinated to render it sterile.
5. Decolourising
Activated carbon developed out of the decolourising industry where it was first used in decolourising sugar. It is still extensively used for this application. It is also used as a decolouriser in the purification of edible oil, foodstuffs, pharmaceutical intermediates and chemicals such as esters, surfactants and alcohols. The wine and spirit industry uses activated carbon to ensure that whte wine, vodka and bacardi, etc., reach the consumer with the correct appearance and flavour.
6. Solvent Recovery
Industries such as paints, adhesives, transparent film, printing, rubber, plastics, dry cleaning, chemicals and textiles, increasingly use hydrocarbon solvents during the manufacture of their products. These solvents must be recovered for both For this purpose activated carbons are
particularly effective, and adsorb most solvents for any concentration above 1000 ppm. The method involves passing solvent-laden air through a bed of carbon until
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the bed is saturated. At this point the air stream is redirected to another bed and the first bed is stripped of the solvent by passing steam at 105'C through the bed in the reverse direction to air flow. The solvent is then separated from the aqueous phase, and the carbon bed goes into a drylng cycle to prepare it again for the solvent-laden air stream. Solvents recovered by this method include chloroform, carbon
tetrachloride, acetone, pentane, methyl ethyl ketone, tetrahydrofuran, white spirit, benzene, toluene, xylene, petroleum and ether.
7. Military Uses
Activated carbon was first used in World War I to protect against chlorine gas. Most of the world's armed forces now use activated carbon to protect against attack by toxic gases, such as mustard gas, during conflicts. Other such gases include hydrogen cyanide, cyanogen chloride, phosphine and arsine. These carbons are put to use in personal gas masks, shelter filters and inlet filters for tanks and armowed cars. A further use is in m l t r suiting where combat uniforms contain a layer of carboniiay impregnated material under the outer cover. This protects the wearer from splashmg of liquid gas after a toxic gas canister has exploded.
8. Nuclear Reactors
In the western world, all nuclear power reactors have activated carbon ventilators installed as a precaution against radioactive iodine leaks f o the core or heat rm exchanger systems. Special carbons impregnated with potassium iodide or potassium tri-iodide are commonly used for the purpose. Also a potential problem with radioactive krypton and xenon was highlighted as a result of the Three Mile Island accident in 1979. To cope with this, special off-gas delay beds were designed so that passage of radioactive krypton and xenon through the bed could be delayed, u t l ni such time as the radiation hazard could have decayed to an acceptable level. These types of bed are now being fitted to many nuclear reactors.
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9. Air Treatment
There are a large number of applications in which activated carbon is used to remove noxious contaminants f o air streams. The commonest include the ventilation of rm areas where large numbers of people congregate, such as airports, hospitals, submarines, office blocks and theatres. It is essential that toxic contaminants, which result from industrial activity, such as mercury vapour, sulphur dioxide and hydrogen sulphde, must be removed with maximum efficiency. In these instances a highly efficient impregnated carbon is usually employed.
12. Catalysis
Many chemical reactions require a catalyst to improve efficiency, accordingly, in many cases activated carbon's large surface area is used as a support for such catalysts, thus further improving efficiency. Examples of its use include the production of chloro-fluoro carbons, terephthalic acid, vinyl chloride and sulphuryl chloride.
247
expandmg. Some of the source materials that have been investigated are outlined in Table 2.
248
Cras eel
Coal Coconut shells Coffee beans Corncobs and corn stalks Cottonseed hulls Distillery waste Fish Blue Dust Fruit piths Gmphite
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process is usually carried out in a fxed bed, however, in recent years fluidised beds have also been utilised. The second method of chemical activation involves the incorporation of inorganic additives or metallic chlorides into the precursor before carbonisation. The action of these additives degrades and dehydrates the cellulosic materials present during carbonisation at 250-650C. L i e , usually the raw material that is blended with activators such as sulphuric acid, phosphoric acid, zinc chloride or potassium duocyanate or other vegetable matter, is carbonised at temperatures up to 900OC. The activated carbons produced have a unique surface property.
Cheremisinoff and Ellerbusch (1978) noted that the high specific area of activated carbon (typically in the order of 1000m2/g; De John, 1976) is nonpolar or only slightly polar due to surface oxide groups and inorganic impurities.
Chars are formed when the precursor material is carbonised or pyrolysed usually in the absence of air. Pyrolysis of lignocellulosic materials liberates most of the volatile non-carbon elements, normally hydrogen, oxygen and nitrogen, from the precursor matrix resulting in a non-graphitisable char with a rigid carbon skeleton, made up of aromatic sheets and strips. Chars can be produced over a range of temperatures and charring times, each carbonisation condition resulting in a sorbent with unique adsorption properties. Zulkamain et al. (1993) investigated the effects of heating times and temperatures on carbons prepared from mangrove wood. They noted optimum conditions of preparation at 5OO0C for 3 hours, producing a carbon which had a high iodine number of 503 m2/g,greater than that of a coconut carbon produced under the same conditions. The pore sizes of the resultant carbon were larger than those of coconut shell (40pm). Drozhalina et al. (1984) reported on the influence of brown coal being added to peat in variable fractions prior to carbonisation at 800-
900OC. They found that the strength of the carbon was improved by the inclusion of
brown coal, porosity developed, and as temperature increased a parallel increase in micropore and macropore volume was observed. Chars prepared under specific carbonisation conditions can be utilised successfully, without further processing,
250
however, their adsorptive potential, i.e. surface area, porosity and surface oxide groups, can be greatly enhanced by chemical modification or physical activation. Chaney (1919, 1923) suggested that chars to be used in physical activation should be prepared at temperatures below 6OO0C, however, McBain (1936) produced an activated carbon from a sugar char carbonised at 900C.
llOOC. Initially the active oxygen in the activating agent bums away the tany
pyrolysis off-products trapped within the pores, initialising the porosity development, then the microporous structure is developed as the oxi&sing agent bums away the more reactive areas of the carbon skeleton. It is desirable that the burning-out of the carbon skeleton, to create new pores, initiates and occurs within the particle interior and not from the exterior surface as t h ~ s would result in an overall loss of porosity and surface area. The chemical and physical nature of physically activated carbons is very dependent on the precursor, the oxidising agent employed, the temperature of activation and the degree of activation. The activating agent employed, in physical processes, has been investigated by many authors. Steam is preferable to carbon dioxide and much better than air for activating many chars. Utilising steam for activation requires a high temperature of activation to provide rapid oxidation, however, temperatures above 1OOOC impair adsorptive power. Work conducted by
251
Gamer and Packer (1980) showed that activation with steam at 850C for up to 2% hours produced activated carbons with significantly increased activity, although, the yield of product was seen to decrease with increasing time. Gergova et al. (1994) prepared a range of steam activated-carbons, between 600-700C for 1-3 hours, from a range of agrrcultural by-products. They reported common trends within the carbons produced such as surface area and porosity increase with increasing temperature and time. They also noted that the resultant carbon propemes were very dependent on the precursor material. Activation is performed to open up a porous structure within the adsorbent. Gergova et al. (1994) along with other authors Garner and Packer (1980), Kaloc et al. (1996) and McDougall(l991) have shown that porosity development is
CO, activation on carbon containing wastes, nearly 2 times less than that of steam.
The resultant pore structure is also dependent on the activator employed. Zietek et al.
252
(1996) showed that pore volumes increased with both activators but that steam activation resulted in microporous structures and C02 resulted in larger micropores and mesoporous structures. When air or oxygen as used as the activating agent problems are encountered due to the exothermic nature of the reaction of carbon with a& (oxygen). The rapidity of
this reaction makes it difficult to control, resulting in excessive bum-off and reducing
the product yield. Despite the operational difficulties several authors have published their findings on air activation. Buczek et al. (1995) investigated air as an activator and also 10% oxygen in nitrogen for carbons f o hard coal. Their results showed rm that texturally little changed and very little increase in surface area or micropore volume was observed, as compared to a steam activated carbon. Gomez-Corzo et al. (1996) prepared air activated carbons from cherry stones. From their experiments it was observed that carbon yield and pore volume decreased with increased activation time, however, the pore structure remained greater than for carbons produced by N, treatments. Work conducted by Jankowska (1996) prepared a carbon from Polish anthracite at 5OO0C in 21% oxygen, and showed that oxygen activation produced carbons with low surface areas and pore volumes. He concluded that activity decreases in the order of steam > carbon dioxide > oxygen. It is interesting to note that Lu and Chung (1996) used O3 activation prior to heat treatment and CO, activation, to enhance the chemical and physical properties of the fmal product. They observed a slight decrease in surface area, due to the removal of surface microcracks, but also noted an increase in mesopore size.
253
wide variety of chemicals have been suggested for activation including phosphoric acid (the most popular agent), chloride salts of magnesium, femc iron and aluminium, s o d i m carbonate, and sodium and calcium hydroxide. The only
common trait between all these chemicals is their strength as dehydrating agents.
As mentioned, ZnClz is a popular activator and is employed regularly on an
industrial scale in Europe and Japan. Rodriguez-Reinoso and Molina-Sabio (1992) conducted extensive work into the mechamsm of ZnC1, activation and the physical and chemical nature of the resultant carbons. They reported that during
impregnation, the chemical activator reaches the interior of the precursor and causes hydrolysis reactions to occur. These are noted by weight loss, exit of volatiles, weakening of the structure, and increased elasticity. Accompanying the hydrolysis, particle swelling is observed. During carbonisation the incorporated ZnC1, prevents pyrolysis products, such as tars, forming and thus increases the yield of the product. Further explanation for the increased yield of product comes f o considering the rm action of the chloride on the elemental make-up of the precursor and its derived carbon. ZnC1, tends to cause hydrogen and oxygen atoms to be stripped away as water, rather than as hydrocarbons or as oxygenated organic compounds, leaving the carbon skeleton largely untouched. On the physical and chemical characteristics, Rodriguez-Reinoso and Molina-Sabio ( 1992) concluded that carbons with a well developed porous structure, mainly meso and microporous, can be produced by ZnC1, incorporation. The nature of the carbon is dependent on the amount of chemical incorporated.
As the percentage increases its distribution within the particles
KOH activation has been shown to successfully increase the surface area and pore
volume of active carbons according to the relative amount of KOH incorporated into the precursor. Otowa et al. (1995) showed that an active carbon, with a surface area in excess of 3000m2/g, could be prepared by mixing petroleum coke with excess
254
on the soak times and impregnation ratios utilised. Interesting results were reported
by Gonzalez et al. (1996) who compared preparing carbons from olive stones, firstly by pre-treating with KOH and secondly by treating pre-carbonised olive stones with KOH followed by further heat treatment to activate them. They found that in the original olive stone there is a high increase in pore volume as a consequence of hydrolysis during impregnation, the increase being much smaller in the carbons from the carbonised stones. Use of potassium carbonate dates back to early carbons produced from blood, where 8 parts of dried blood was mixed with 1 part of K,C03 and carbonised at 8OO0C to form blood char. More recently Hayashi et al. (1996) compared the activation potential of K,CO, to Na,CO, and NaOH when producing carbons from bean curd refuse. They found that K2C03works effectively as an activator yielding high surface areas in two temperature ranges, below 4OO0C and above 80OoC. Results for Na,CO, were promising with increased surface areas being observed, however, NaOH was seen to be a very intense activator, in some instances resulting in zero product yield. Butuzova and Krzton (1996) showed that brown coal is a better receptor to NaOH activation than bean-curd refuse, wt enhanced adsorption characteristics observed ih without any mass loss. Many other chemicals have been forwarded as potential activation agents, the
main ones are: ammonium salts, borates, boric acid, calcium oxide, cyanides, ferric
and ferrous compounds, hydrochloric acid, manganese dioxide, nickel salts, nitric acid and sulphur. Allen and Balasundaram (1995) reported on chemically activating Northern Ireland lignite with ZnC1, and iron nitrate and sulphate. On chemical activation alone, they concluded that iron nitrate gave the best performance with the reactivity decreasing in the sequence iron nitrate > zinc chloride > iron sulphate. Some results from this work are shown in Table 3. The type and amount of chemical used in the pre-treatment of peat has a substantial effect on the extent of the development of the pore structure within the carbon. Begin et al. (1996) investigated the influence of Feel, graphite intercalation
255
compound (GIC) on the pyrolysis of coal tar pitch. Results showed that Lewis acid FeC1, released out of the graphite layer during heating promotes polycondensation and dehydration reactions enhancing carbon yield, also catalytic activity was noted on the mesopore growth. US patent number 4,149,994 (1979) describes a chemical process in which no carbonisation occurs. Activation is performed by addmg polar compounds to coal powders, containing non-polar groups bonded with polar groups, and drying at a temperature of 120'C. These carbons perform well in wastewater treatment.
Chemical Additives
10% ZnC1,
198
1.1
20% ZnC1,
557
2.3
10% Fe,(SO,),
70
5.4
20% Fe2(S0,),
243
1.8
10% FeSO,
89
5.2
20% FeSO,
412
2.8
256
m is a s
result of the
r e s ~ c t i o nof formation of graphte zones due to the low temperatures used in chemical processes. Another significant difference relates to the pore-size distribution. RodnguezReinoso and Molina-Sabio (1 992) reported that chemical activation of lignocellulosic precursors with ZnC1, resulted in the same micropore volume as CO, activation but with a higher yield. They found that as a consequence of chemical activation the porosity is more developed, and the result is that it leads to carbons having similar micropore volumes but with larger mesopore volumes. Physical activation with CO, was reported to open and widen the microporosity, but at high temperatures there was
an ablation of the exterior of the particle resulting in low carbon yields. Lopez et al.
(1996) investigated the variable effects of CO, and ZnC1, activation on carbons from
wood monolith. In contrast to chemical activation, physical activation resulted in smaller surface areas, smaller yields and significant pore differences. Pore investigations implied that micropore and mesopore size distributions were closer in
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chemical activation as opposed to the physical activation. They concluded that pores can be classified and attributed to the particular activation used, wide micropores and narrow mesopores being associated with chemical activation and narrow micropores and wide mesopores being characteristic of physical activation. Chemical activation has great potential for providing a flexible method for preparing activated carbons with effective control of pore distribution. However, the ramifications and possibilities are fiuther heightened when gasification of these carbons, with steam or CO,, etc., is considered. Low-temperature chemical
modification by HClO, and high-temperature physical activation were combined by Lynubchik et al. (1996) to produce activated carbons f o anthracite. They proposed rm that the chemical modification step lays the foundations of the primary pore structure. Allen and Balasundaram (1995) reported similar findings when producing activated carbons from lignite. Although inconclusive, evidence suggests that chemical
treatment alone determines the pore structure and that gasification merely cleans these pores out. Baranchrkova et al. (1984) steam activated a peat char in the presence of AlCl,. They showed that incorporating 5% AlCl, into the peat resulted in a good microporous carbon after bum-off with steam. Leboda et al. (1996) showed that calcium incorporated into a variety of precursors, by ionic exchange or in solution as calcium acetate, acts as a catalyst in porosity development. It was found that in the presence of CaCO, steam activation caused changes in both the micro and mesoporous structure. The extent to how successful a precursor will be for producing activated carbon is often gauged by its ash content. Flynn et al. (1988) stated that, due to its high ash content, Northern Ireland lignite was unsuitable for producing activated carbon. This problem can be overcome by demineralising, with mineral acids, to remove the majority of inorganic matter which ashes on carbonisation. Demineralisation is a chemical modification process and is often performed in industrial processes prior to pyrolysis and gasification. US patents 4,149,994 and 4,149,995 by Murty (1979 a, b) describe the demineralisation of brown coal by both concentrated and dilute H,SO,, H,PO, and HC1 to reduce the volatile content and thereby increasing the futed carbon
258
content, prior to steam activation. Recent studies by Kaczmarczuk et al. (1996) showed that HC1 could be used successfully to demineralise brown coal prior to carbonisation at 800C and steam activation at 700OC. It was observed that activated carbons derived from the demineralised parent coal possessed greater mechanical strength and nearly double the surface area of those produced without demineralisation. Also, whilst mesopores were dominating in the activated carbons
from the parent coal, micropores dominated the activated carbons f o the rm
demineralised parent coal.
Conclusions
Lignocellulosic materials, in particular peat and ligmte, have considerable potential in the future production of hgh-value-added activated carbons. Recent research is concentrating on understanding the effects of chemical additives and pre-treatment on the quality (sorption capacity, activity, porosity and mechanical strength) of activated
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