RAPID ACTIVATION METHOD, PROCESS, AND APPARATUS FOR MAKING PELLETIZED ACTIVATED CARBON FROM CARBONACEOUS WASTES

Abstract: A method and apparatus for the thermal activation of carbonaceous materials to obtain highly porous, high surface area active carbons in very short processing times, based on the catalytic effect of certain wall materials upon the activating gas, particularly CO2, which is beneficial for rapid generation of micropores during the activation process, yet retards excessive burn-off during oxidation applicable to biomass and processing of ligno-cellulosic and cellulosic waste byproducts, where it has potential economic advantage due to the compact reactor sizes, which can be built feasibly, as well as the reduced energy requirement.

Description: Rapid Activation Method, Process, and Apparatus for Making Pelletized Activated Carbon from Carbonaceous Wastes Background Of The Invention The use of agricultural and industrial waste byproducts for making activated carbon are well documented in the research and patent literature. Particularly, paper mill sludge (or filter cake), waste paper, olive pits, walnut shells, prune pits, sugar-cane bagasse, "biomass" or waste wood and bark from lumber and paper mill processing. These wastes are all generated in many thousands of tons annually, and have been shown to produce good quality activated carbons, usually by chemical activation. The major obstacle to wider use of these waste byproducts as activated carbon feedstock, are the economies inherent in conventional processing plants, which require a large feedstock processing rate in order to justify the high capital costs. Large scale processing is dictated by two main factors: long required processing time, and the relatively low yield of active carbon relative to the aforementioned feedstocks. Conventional activation processing requires relatively large activation apparatus and large feedstock flow rates to run economically. The extended processing time necessitates large processing vessels, which are expensive. This tends to limit the application, for instance, to "biomass" or waste wood, which is one of the few carbonaceous waste byproducts available in one place, generated on the order of several hundred tons/day. Other current applications are coconut shells, again available in large volumes at concentrated processing facilities. However, paper mills typically produce 5-100 dry tons/day of sludge, and despite quite a number of patents on sludge activation, there exists no activation plant anywhere. Three major forms of activated carbon are currently on the market, namely, powder, granular, and pelletized. Of the three, pellets give the lowest pressure drop in a packed filter configuration, and also have additional benefits such as high regeneration recovery. Low pressure drop in filters is very important in liquid phase applications, where it affects the size of and power consumption of pumping machinery. Whereas coal based active carbon pellets are available for gas phase use, the conventional industry has not been successful in producing ligno-cellulosic based active carbon pellets. Activated carbons are highly porous and have very large specific surface area, normally measured by the N 2 BET, between 450 and 1 ,800 m 2 /gram. The accepted International Union of Pure and Applied Chemistry convention distinguishes between three major porosities, present in all activated carbons in various proportions, as follows: Micropores, with an average diameter up to 2 Nm, Mesopores, with diameter between 2 Nm and 50 Nm, and Macropores, with diameter larger than 50 Nm. Most of the surface area inherent in commercial activated carbons comes from micropores. Active carbons have a layered skeletal structure made of joined aromatic (6 member carbon) rings, but far less organized than graphite. The layered structure originates in the parent material. Activated carbons have many characteristics and attributes which are strongly dependent on the parent material and the method of preparation. All methods of preparation involve first a carbonization step, in which disorganized so-called volatile matter is removed from the feedstock, concentrating the aromatic layers or sheets. This carbonized char is then activated. The 2 major modern preparation methods have been patented nearly 100 years ago, and are roughly classified as "chemical activation" and "thermal activation" or "gas-phase activation". The chemical methods involve activation with acids such as H 3 PO 4 , or combinations of H 2 SO 4 and HNO 3 , or mixing with ZnCI 2 , as well as many other compounds. The feedstock material is first ground to sub-millimeter particles, then thoroughly mixed with the activation chemical, sometimes pelletized at this stage, then heated to some elevated temperature, such as 600 °C . The process normally takes several hours, the acids or activation reactant are washed out and re-generated, and the final activated product is crushed to granular form. Practically all commercial activation of ligno-cellulosic materials is done chemically. Thermal activation methods use mostly CO 2 or steam, at temperatures above 850 °C. In some cases air is used for activation, in which case the activation temperature is much lower, e.g., below 400 °C. These methods are usually applied to coal feedstocks, from lignite to bituminous coals, and sometimes to dense ligno-celulosic based chars, like coconut shells. Rotary kilns can be 35 m long and 4 m in diameter, used for steam activation. Other kilns use flue gas for CO 2 activation, in multiple-hearth furnaces and shaft-furnaces. The reaction in these kilns generates hydrogen (in steam activation) and CO (in both CO 2 and steam activation). Processing, including carbonization, can take 6 - 8 hours. The large reactive surface area is believed to be generated by first oxidizing the carbon available in the aromatic structure. The basic chemistry and methods of activated carbon can be found in Yehaskel, Ed. "Activated Carbon- Manufacture and Regeneration" (Noyes data Corp., NJ. 1978). Peparation of Adsorbents pp.161-173. Mattson, H.B. Mark, Jr., Eds. "Activated Carbon", pp. 1-31 (Marcel Dekker, Inc., NY 1971), contains a discussion of the overall chemical mechanism of activation and its apparent kinetics, for thermal activation in steam and CO 2 . It explains the source of the observed diffusion-limited apparent reaction order (with respect to oxygen) of Vz, and its apparent activation energy of 42 kcal/ ol. This can be used to calculate activation reactor cavity for an activation A discussion of industrial activation processing can be found in "Ullman's Encyclopedia of Industrial Chemistry", vol. A5, pp. 126-140 (VCH Verlag, 1985), which also provides a thorough description of ligno-cellulosic carbonization prior to activation, with specific reference to the Degussa fluid bed pyrolyser. Specifically, the rotary kiln, the multiple- hearth furnace, the "shaft furnace" (US patent 2,966,447 issued to Walter on Dec. 27 1960), and the fluidized bed are all used for thermal activation in conventional processing. None of these mention the effect of internal surface/volume ratio, as a means to promote certain reactive gas phase radicals to enhance activation of these processes are all designed to impart heat to a mixture of solid particles and activating gas. Cheremisinoff, and F. Ellerbusch, "Carbon Adsorption Handbook", pages 241-279 ( Ann Arbor Science Publishers, Inc., 1978), discusses the adsorption properties of various carbon surfaces, and its measurement. Prior activation processes are extremely long. Mantell, Ed, "Carbon and Graphite Handbook, pages 183-188 (J. Wiley Interscience 1968), has a discussion of ligno- cellulosic waste materials activation, mostly by steam. It lists "processing times" and burn-off for several materials such as sawdust briquettes, nutshells etc., under steam activation at 900° C to 950°C, starting with 60 minutes. No corresponding BET surface data was reported. Steam activation times listed by Yehaskel (supra) for bituminous coals are much longer, typically 3 -6 hours. Banasal, J.B. Donnet, and F. Stoeckli, Eds. "Active Carbon" Pages 1-26 (Marcel Dekker, Inc., NY, 1988). discusses in detail an example of pine wood activation in steam at 950 C, in laboratory process. The reactor design is not described. Rather high BET surface areas were obtained at 50% to 80% burn-off, however, activation times were not mentioned. The activation of biomass, ligno-cellulosic wastes, and cellulosic wastes has been addressed. al-Khalid, N.M. Haimur, S.A. Sayed, and B.A. Akash "Activation of Olive seed waste residue using C0 2 in a fluidized bed reactor" Fuel Processing Tech. 57 pp. 55-64 (1998) discuss the CO 2 activation of olive pits in a fluid bed comprised of a 46 mm dia. steel pipe, processing 100 g of solids at a time. The material was first ground to dia. < 1 mm. The material was then activated at 900°C for over 60 minutes, after 30 minutes of carbonization to 600°C. Interestingly, the weight loss reported at 60 minutes for T max =700 o C - 850°C was 80% - 90%, while the iodine numbers reported were between 100 and 400 mg/g, quite low for this extent of burn-off, and indicative of low BET surface; however, BET surface area was not reported. It appears that this steel reactor, which has a surface/volume ratio of 4/D = 4/0.046 = 87 1/m is causing excessive burn-off without significant pore surface development. Heschel, and E. Klose "On the suitability of agricultural by-products for the manufacture of granular activated carbon" Fuel, Vol. 74, No.12, pp. 1786-1791 (1995) have investigated 17 different samples of wood and agricultural-waste for a study of suitability for activation. Following charring at 5 - 100 deg.C/min (then soaking for 30 minutes) under N 2 to T =750°C - 950°C, activation under a mixture of steam (35%) and N 2 (65%) was performed in a fixed bed , in the same temperature range as above, for 20 minutes to 2 hours. Burn-off (XB) between 20% and 80% was observed, and BET surface area values plotted vs XB were provided for some of the samples, i.e., plum stones, peach stones, and coconut shells. Burn-off, BET values in the range of 980 - 1300 m2/g were obtained (similar to the values we have measured at much faster activation times and under CO 2 ). Tancredi has investigated eucalyptus wood activation, using a 75 mm quartz tube. Following carbonization at 10 deg. C/min for 2 hours (probably reaching Tmax=800 °C, then soak). Tancredi, T. Cordero, J. Rodriguez Mirasol, and J.J. Rordiguez "Activated carbon from Uruguayan eucalyptus wood" Fuel Vol.75, No. 15, pp. 1701-1706 (1996); see also, Tancredi, T. Cordero, J. Rodriguez Mirasol, and J.J. Rordiguez "CO 2 gasification of eucalyptus wood chars" Fuel Vol.75, No.13, pp. 1505-1508 (1996). Their quartz tube had a ratio of surface/volume = 4/D = 4/0.075 = 53. Gas flow rate for CO 2 was 200 CC/min. Their results were summarized in the following table. Aαvation Method Tmax Activation Burn-Off BET Surf deg.C Time, mm XB, % m2/g Steam 800 60 0 42 1,030 800 90 0 58 1,190 C02 800 180 0 35 - 800 240 0 47 1,240 While good quality powdered active carbons were generated by the foregoing process; the times for activation are one order of magnitude longer than the process of the present invention. Kannan noted the subtle effect of catalysis by metals inherent in the wood or biomass, during CO 2 gasification. Kannan and G.N. Richards, "Gasification of Biomass chars in CO 2 : dependence of gasification rate on indigenous metal content", Fuel Vol.69, No. 6, pp. 747-751 (1990). The gasification rate, dXB/dt, under CO 2 at Tmax = 700° C was studied in particular, and was found to correlate reasonably with the K concentration for 6 out of 8 agricultural biomass samples. Such relative acceleration effects were retarded when silica was added, which indicates an inhibiting role for the silica, such as in chain- termination. In silica rich biomass such as rice straw, the effect of K was retarded. The rates reported overall were still one order of magnitude below those found in the process of the present invention. Toles, et al., have compared chemical activation and CO 2 activation of pecan and almond shells. CO 2 activation was preceded with carbonization to 700°C fci over 60 minutes, under N 2 flow. A CO 2 (13%) and N 2 (87%) volumetric mixture at a flow rate of 1 ,670 CC/min. was used to activate, at Tmax = 700°C - 800 °C for 5-8 hours. The samples were powdered prior to charring and activation. Toles, W.E. Marshall and M.M. Jones, "Granular activated carbons from nutshells for the uptake of metals and organic compounds", Carbon (35) No. 9, pp. 1407-1414 (1997). The results are summarized as follows, Acivation Conditions Tmax Activation Burn-Off BET Surf deg C Time, mm XB, % m2/g Almond Shells, C02 800 360 83% 349 800 480 86% 202 Pecan Shells, C02 800 300 78% 430 800 480 77% 464 The results are quite low in terms of the BET obtained, which were consistently much lower than the acid-activation results they have reported, with BET in the range 1 ,000 - 1 ,200 m2/g. It appears that a steel tube was used as a furnace, which may explain the need for dilute CO 2 and the rather poor results. Bernardo, R. Egashira, and J. Kawasaki "Decolorization of Molasses' wastewater using activated carbon prepared from cane bagasse" Carbon Vol.35, No.9, pp. 1217-1221 (1997), have prepared samples of active carbon by steam activation of bagasse from two sources, Thailand and Brazil, which behaved very differently. In summary the graphs of Figures 1 a, 1 b, and 1c were prepared, using their data. Carbonization was done to 300°C for 60 min. followed by steam activation (3 CC/min flow rate) for 30 to 120 minutes. The reactor wall was steel, and its diameter was 35 mm (S/A = 114 1/m). Acceptable results were obtained, although burn-off rates are one order of magnitude below those of the present invention as shown in Fig. 1c. However, the high BET values are likely made by a single-point correlation, as indicated by the low iodine numbers reported (676, and 741 mg/g). For a general discussion of chemical activation see, e.g., Jagtoyen and F. Derbyshire "Activated carbons from yellow poplar and white oak by H 3 PO 4 activation" Carbon Vol.36, No.7-8 pp. 1085-1097 (1998); Bernaddi, D. Legras, J.N. Rouzaud, and F. Beguin "Influence of the atmosphere in the chemical activation of wood by phosphoric acid" Carbon (36) No. 7-8, pp. 306-309 (1998); Namasivayam and K. Kadrivelu "Uptake of mercury (II) from wastewater by activated carbon from coirpith" Carbon 37 pp.79-84 (1999); US Patent 5,162,286 "Method of Producing granular activated carbon" issued Nov.10 1992 to MacDowall (Olive pits; H 3 PO 4 ); US Patent 4,937,223 "Process for preparing activated carbon" issued Jun 26 1990 (papermill waste lignin; adding KOH, etc); US Patent 5,614,459 "Process for making activated carbon" (biomass or any carbonaceous precursor; use ZnCI 2 and even SnCI 2 ); and, Bernardo, R. Egashira, and J. Kawasaki "Decolorization of Molasses' wastewater using activated carbon prepared from cane bagasse" Carbon Vol.35, No.9, 1997, pp. 1217-1221 ; Henning, and J. Degel "Activated carbon for solvent recovery", paper presented at the Meeting of the European Rotogravure Assoc. Engineering Group, Mulhouse, France, March 20-21 , 1990 [ Available from Carbon Link, Ltd, Wigan, UK website]; DeLiso, K.E. Zaun, "Activated Carbon bodies having clay binder and method of making same" US Patent 5,488,021 Jan.30,1996, is a patent in which active carbon and attapulgite clay are mixed and molded into filter bodies. A number of references have addressed the activation of coal based materials or pitch, using CO 2 or steam, as well as chemical activation. Regarding chemical activation, very high BET surface can indeed be attained with relatively low burn-off. However, regeneration of the chemicals, as well as problems with toxicity and by-product handling are quite serious deterrents to the process. In all coal based coke activation processes, the activation rates are lower by one to several orders of magnitude than those of the present invention. See, e.g., Otowa, Y. Nojima, and T. Miyazaki "Development of KOH activated high surface area carbon and its application to drinking water purification" Carbon (35) No.9 (1997) pp. 1315-1319; Bessant and P.L. Walker, Jr. "Acivation of Anthracite: Using carbon dioxide vs. Air" Carbon Vol.32, No.6, 1994 pp.1171-1176; Finqueneisel, T. Zimny, A. Albiniak, T. Siemieniewska, D. Vogt, and J.V. Weber "Cheap Adsorbent Part 1 : Active cokes from lignites and improvement of their adsorptive properties by mild oxidation" Fuel Vol.77, No.6, 1998, pp. 549-556; Shchipko, and B.N. Kuznetsov "Influence of the origin of chars, produced from lignite by different methods, on features of their activation process" Fuel Vol.77, No.6, 1998, pp. 527-532; Siemieniewska, A. Albiniak, E. Broniek, E. Kaczmarczyk, A. Jankowska, B. McEnaney, X.S. Chen, E. Alain, G.Furdin, and D. Begin "Porosity development in steam activated chars from mixtures of coal tar pitch with graphite-FeCI3 intercalation compounds" Fuel Vol.77, No.6, 1998, pp. 509-517; Pis, Mahamud, J.A. Pajares, J.B. Parra, and R.C. Banasal "Preparation of active carbons from coal part III: Activation of Char" Fuel Process Tech. Vol.57 (1998) 149-161 ; Pis, J.B. Parra, Gema de la Puente, Fernando Rubiera, and J.A. Pajares "Development of macroporosity in activated carbons by effect of coal peroxidation and burn-off" Fuel Vol.77, No.6, 1998, pp. 625-630; Alcaniz-Monge, D. Xcarzola-Amoros, A. Linares-Solano, S. Yoshida and A. Oya "Effect of the activation gas on tesile strength and pore structure of pitch-based carbon fibres" Carbon Vol.32, No.7, 1994, pp.1277-1287; Alcaniz-Monge, D. Xcarzola-Amoros, A. Linares-Solano, "Production of activated carbons: use of CO 2 vs. H 2 O as activating agent. A reply to letter from P.L. Walker, Jr." Carbon Vol.35, No.10-11 , 1997, pp.1665-1668. This is illustrated by the data taken from Alcaniz-Monge, et al., (from their figure.2). For comparison, we have overplotted olive pits activation data, using the process of the present invention in Figure 2a. Alcaniz-Monge, et al., have reported micropore volumes, but not the corresponding BET surface area values. The authors have discussed in detail the role of CO and H 2 in inhibition of the oxidation and burn-off, which are quite relevant in our processing as well. Refs. [28 - 41] deal with catalysis. The paper by the Pfefferies discusses catalysis in combustion, but makes no reference to activation or gasification. Pfefferle, and W.C. Pfefferle "Catalysis in Combustion" Cat. Rev. -Sci. Eng., 29 (2&3) pp. 219-267 (1987). The mechanism of gas phase catalysis by vibrational transfer at the wall is discussed, and data presented for quartz wall surfaces which suggests a catalytic effect. Specifically, probing of the boundary layer over quartz walls, show a significant concentration of O and OH radicals, with the concentration peak is distended from the wall on the order of 10 mm. Coated Pt plates show similar behavior, but the peak is considerably closer to the wall. The Radical concentration's peak position distends further when the temperature is increased between 800 C and 950 C, and also as the distance downstream from the leading edge is increased, although in the latter case the peak is also somewhat lowered. Similar effects with pure uncoated alumina were mentioned as well. V. Guterl, J. Lahaye, and P. Ehrburger "The catalytic reduction of nitric oxide by carbon monoxide over silica", Fuel Vol.76 No. 6, pp. 517-520 (1997) further supports the observation that silica can act as catalytic surface in gas phase processes akin of combustion. Other references cited deal with additives to the char being activated to enhance its activation at lower temperatures than normally used for CO 2 or steam activation. Such additives are K 2 CO 3 , and CaO, as well as other materials, and must be thoroughly mixed with the carbon being activated to become effective. ShuFen Li and Y. Cheng have compared catalytic gasification of a "gas-coal char" (possibly bituminous coal coke), by K 2 CO 3 and Na 2 CO 3 . Li, ShuFen and Y. Cheng "Catalytic gasification of gas-coal char in CO 2 " Fuel, Vol.74, No.3, pp. 456-458 (1995). Coking was done by pyrolysis under N2 for 1 hour to 900 °C. Carbon content was 56% of the coke, along with 33% ash and the rest H, O, S, and N. Interestingly, the ash contained 52% SiO 2 , 37% AI 2 O 3 and 4% CaO. The authors found that gasification rate has increased appreciably for CO 2 gasification, when the catalysts were added in the range of up to 25% for Na 2 CO 2 , and up to 20% K 2 CO 3 . The maximal values given are at saturation. The catalysts were introduced by impregnation. The activation temperature range was 790 to 1020 °C. Samples of 15 g were placed in a fixed bed reactor made of a stainless steel pipe, 20 mm ID, with a CO 2 flow of 800 CC/min. The authors found K 2 CO 3 to be a more effective catalyst than the sodium based one. We have extracted and plotted their observed burn-off vs time rates with data using the present invention (MBR) for Southern pine char activation, illustrated in Figure 2b. The comparison indicates that MBR's catalytic reactor XB vs time slopes are remarkably similar to the catalysed gasification reported by Li and Cheng, while still being consistently faster. Salinas-Martinez de Lecea, M. Almela-Alarcon, and A. Linares-Solano "Calcium catalysed carbon gasification in CO 2 and Steam", Fuel Vol.69, No.1 , January 1990, pp.21-27, have used Ca in the carbon matrix obtained by charring a polymer, to show catalytic effect. They have observed saturation at 4% Ca loading, with the excess Ca assumed in low dispersion. Ca was loaded from a solution of Ca-acetate, by ion exchange, and also by impregnation. The mechanism seems to catalyse both the CO 2 and steam gasification, the former much more appreciably. The overall catalytic mechanism for CO 2 activation was stated as CO 2 + M * = CO + M*O C + M * O = CO + M* where M * denotes a catalytic active site. The reported burn-off rates for CO 2 were 0.01 1/min for zero catalyst, and 0.067 1/min for 4% (maximal) catalyst. We have observed activation burn-off rates of 0.08 to 0.12 1/min in the initial stages of activation. The authors did not report the final BET surface values obtained. Neeft et al have studied catalytic carbon-black (soot) oxidation with a variety of catalytic compounds added to the carbon; altogether 18 such materials were tested, including Ni, Bi, Cu, Mo, Mn, Li, Fe, Ca, Cr, Pb, Sb, V, Cs, K, Na and Ag - based oxides, mixed with the soot at a 1 :1 weight ratio. Neeft, M. Makkee, J.A. Moulijn "Catalytic oxidation of carbon black- 1. Activity of catalysts and classification of oxidation profiles" Fuel, Vol.77, No.3, (1998) pp. 11 1-119. The oxidation was done in a TGA apparatus with proper oxidative gas flow control, using a mixture of 10% O 2 by volume in Ar, at a flow rate of 200 CC/min. Typical experiments lasted 5-200 hours. In all cases the carbon black was mixed intimately with the catalytic compounds. The burn-off extent vs time was measured from the CO and CO 2 gas profiles detected downstream of the test cell. In all cases reported, the initial burn-off reaction rate was high, gradually decreasing in a manner not different from that observed dXB/dt with the present invention, however at a considerably lower rate. For instance, a few of the peak rates reported are 0.003 1/min. for Bi 2 O 3 at 20% conversion, 0.006 1/min for CuO at 40% conversion, and 0.015 1/min for Ca 2 CO 3 , at 40% conversion. Gokarn et al. reported a series of catalytic experiments with Ca and Na lignosulfonates as catalysts, added at 10% to 20% weight to the coke. Shchipko, and B.N. Kuznetsov "Catalytic pyrolysis of Kansk-Achinsk lignite for production of porous carbon materials" Fuel Vol.74, No.5, pp. 751-755 (1995). These were applied to a coke generated from bituminous coal, and oxidized using a TGA apparatus with steam flow at 3 grams/min, superheated to 700 °C and 800 °C. The rate data measured are summarized as follows: Gasification Method Tmax Catalyst dXB/dt BET Surf. TGA Apparatus deg.C Used, % 1/min m2/g Steam - All 700 0 0.0010 - 700 10%A+10%B 0.0086 - B=Na-lignosulfunate 800 10%A+20%B 0.0283 - The rates shown in the art are at least one to two orders of magnitude lower than obtained using the present invention. Others have also dealt with catalysis, but none has a fast thermal activation method which derives from the presence of a catalytic surface forming the reactor wall Summary Of The Invention The current invention provides a method and apparatus to accomplish rapid activation of carbonaceous materials, within minutes. The method utilizes particular materials which provide special catalytic effects in the so-called thermal activation of chars by C0 2 , or steam. Such materials are, for example, quartz, near-pure high-density alumina ceramic, and mullite (a ceramic combination of about 63.5% alumina and 36.5% Si0 2 ). These materials are observed to promote rapid micropore development in pelletized chars, while in the meantime suppressing exterior burn-off. The catalytic materials remain unaffected through the activation process, with virtually zero or negligible attrition or contamination over extended use. The materials form the activating reactor wall linings, and are used as well as to channel and preheat the inflow of activating gas. Commonly used catalytic materials, such as K 2 C0 3 , Na 2 C0 3 , and CaO, used in activation processes in admixture with the carbonaceous chars being activated, affect an ion transfer with the carbon basal structure, and require intimate contact with the char. Their activity is proportional to their mass ratio in the mixture with the char, and the spent and residual material has to be removed after activation. In contrast, the materials in this invention act on the activating gas, affecting a vibrational transfer and causing production of reactive radicals, e.g., O (oxygen) which are swept away from the catalyst surface by the convective motions of the activating gas, and diffuse into, and react within, the aromatic carbon basal structure to form surface complexes - C(O), which are subsequently broken-off, to form the porous structure. Because the life span of such radicals, which are formed at the catalytic wall in the flow, is limited by their respective recombination reactions, and their concentration will be reduced by mixing downstream, it is important for the char pellets to be present sufficiently close to the reactor wall surface during the activation processing. The catalytic materials of the present invention enhance the activation process, through their effect on the activation gas. To increase efficiency, the reactor catalytic walls preferably have a high surface- area/volume ratio in the reactor, far higher than in common activation kilns. Further, the char pellets being activated must be kept at close proximity to the nearest wall surface, again unlike common activation kilns, in which material may be stacked or layered at appreciable distance from the nearest reactor wall. The novel reactors comprise (1) a high, catalytic surface-area/volume ratio, (2) a low, internal catalytic wall-surface proximity, and (3) a proper activation gas flow and distribution pattern, coupled to the catalytic wall surfaces. A superior, unexpected result of this invention is, that the activation stage can be completed within minutes, which is quite uncommon for known thermal activation processes, especially using C0 2 . There is no need for intimate grinding and mixing of the catalyst with the char prior to activation, and certainly no need to separate or wash out any unwanted process by-product or toxic or corrosive additive, as in the case of chemical activation. Two substantial benefits result from this innovation. First, short activation kiln residence times imply a compact reactor for reasonable solid material flow-rates. The ability to build compact activation kilns economically, especially for processing biomass and waste agricultural by-products is a major benefit. Second, the short activation processing times also result in less energy waste. These two benefits address two of the major drawbacks of the activated carbon industry, namely, very high capital investment requirement, and high energy costs. Examples of activation reactor designs are described herein, with appropriate high inner surface-area/volume ratio, and with appropriate distributed activation gas inflow and product gas exhaust. One is a straight-cylindrical or straight- prismatic cavity, with an L/D > 1 , through which the char pellets may move axially under the gravitational force while being activated. This reactor can be used in batch mode or in a continuous process. The second is an Archimedes screw, used to move the material through the reactor; both the cylindrical shell and screw surface materials are catalytic. Compared with the straight-cavity reactor, the screw reactor can attain a higher material processing rates for the same cross section; however, it is more complex mechanically. In cases where the parent feedstock for the char is ligno-cellulosic (e.g., wood or biomass) or cellulosic (e.g., paper waste, or paper mill sludge or filter cake), as well as carbon extracted from coal-burning boiler ash, it is important that the carbonaceous material used as feedstock is sufficiently densified, in pellet form. In these cases, in particular, the manner of char preparation and carbonization is very important for the final activation results. A unique aspect of the present invention is in using the heavy fraction of pyrolytic oils or "tar" generated during the feedstock charring process, as plasticizer/binder for the char pellet formation. The char pellets thus formed by mixing the ground char with the pyrolytic oils, at high pressure, e.g., by extrusion, are first dried and then carbonized under inert atmosphere by gradual heating to elevated temperatures before final activation. Otherwise, (e.g., if the use of pyrolytic oils for energy becomes necessary, or that insufficient quantities are generated during pyrolysis), sugar-wastes or molasses can be used for this purpose. A further innovation of the present invention involves the coating of the char pellets with a coating of graphite powder. For this purpose, the char pellets, upon exit from the extruder (or any other pelletization or agglomeration device) in a moist or tacky-surface state, drop through a fine flake of e.g., 200 mesh graphite, which adheres to the pellet exterior to provide a uniform thin coating. This immediately serves to deter inter-pellet adherence, or sticking. This layer remains intact during the next pellet carbonization process. It later serves two more important purposes, without any interference with the activation process itself, as follows: (1) to allow smooth passage through the reactors, particularly through the straight-cavity reactor where pellet transfer is driven by the gravitational force, and where "bridging" or formation of inter-locked pellet clusters must be avoided, and where lateral friction between the pellets and the wall surface should be reduced; and (2) as the coating remains on the final product activate., pellets as well, it allows denser packing in any filter arrangement, which allows for a higher adsorbent capacity per unit filter volume, (compared with uncoated pellets). Brief Description of the Drawings Figures 1 a - 1c are graphs of data from the bagasse steam activation of Bernardo, et al. Figure 2a is a graph of data from a Pitch Activation of Alcaniz-Monge. Figure 2b is graph of data comparing the SouthPine char activation of Li & Cheng with the present invention. Figure 3 is an illustration of one embodiment of the present process. Figure 4a is an illustration of a cross-sectional view of a 5-layer activation reactor. Figure 4b is a detailed view of a equalateral triansle of rods from Figure 4a. Figure 5 is a cross-sectional view of a 7-tube cylindrical reactor shell. Figure 6 is a schematic of a 7-tube reactor. Figure 7 is a schematic view of an activation reactor with an Archimedes screw. Figure 8a-8d are graphs from Example 1 showing the effects of the catalyst. Figure 9a-9d are graphs from Example 1 showing the effect of activation temperature. Figure 10a-10d are graphs from Example 1 showing the effect of CO 2 flow. Figure 11a-11d are graphs of results from Example 2 Figure 12a-12d are graphs from Example 3 comparing alumina and quartz tubes. Figure 13a-13d are graphs of results from Example 4. Figure 14a-14d are graphs of results from Example 5. Figure 15a-15d are graphs of results from Example 6. Figure 16a-16d are graphs of results from Example 7. Figure 17a-17d are graphs of results from Example 8. Detailed Description Of The Invention The invention provides a method to accomplish rapid activation of carbonaceous materials, within minutes. This is done by utilization of particular materials which provide special catalytic effects in the so-called thermal activation of chars by C0 2 , or steam. Such materials include, for example, quartz, near-pure high- density alumina ceramic, mullite (a ceramic combination of about 63.5% alumina and 36.5% Si0 2 ). The materials are present on the inner walls and surfaces of the activation reactor chamber, not in mixture with the carbonaceous char being activated. These materials promote rapid micropore development in pelletized chars, while in the meantime suppressing exterior burn-off. The catalytic materials remain unaffected through the activation process, with virtually zero or negligible attrition or contamination over extended use. The materials form the activating reactor wall linings, and are used as well to channel and preheat the inflow of activating gas. Commonly used catalytic activation materials, such as K 2 C0 3 , Na 2 C0 3 , and CaO, used in activation processes in admixture with the carbonaceous chars being activated, affect an ion transfer with the carbon basal structure, and require intimate contact with the char. Their activity is proportional to their mass ratio in the mixture with the char, and the spent and residual material has to be removed after activation. In contrast, in the present invention the catalytic materials act on the activating gas, affecting at elevated temperatures typical to activation, (from, about 850 ° C to about 1000 ° C) a vibrational transfer and causing production of reactive radicals, e.g., for C0 2 and steam activation, respectively, C0 2 + M ► M + CO + O* (1) H 2 0 + M ► M + OH + O * (2) where M represents the catalytic (wall) effect, and O * is the oxygen radical which is swept away from the catalyst surface by the activating gas. These radicals diffuse into, and react within, the aromatic carbon basal structure, to form surface complexes - C(O), which are subsequently broken-off, thus forming the active porous structure. The general reactions for thermal activation can be found, e.g., in the texts by Ullman's, Banasal et al, and Mattson and Mark., and are illustrated by the following formulas: R - C + O * + N ► R - C(O) + N (3) R - C(O) + N *R * + CO + N (4) N in the foregoing two reactions represents any neutral body, and R * denotes the activated carbon product. Because the life span of such O* radicals, which are formed at the catalytic materials in the flow, is limited by their respective recombination reactions, and their concentration will be reduced by mixing downstream with the activation product gases (CO and other gases), it is important for the char pellets to be present sufficiently close to the reactor wall surface during the activation processing. The present invention utilizes the unique, unexpected attributes of this family of catalytic materials which enhance the activation process, through their effect on the activation gas. To be effective, the reactor catalytic walls preferably have a high surface- area/volume ratio, far higher than in common activation kilns. Further, the char pellets being activated must be kept at close proximity to the nearest wall surface, coupled with the activating gas flow, again unlike common activation kilns, in which material may be stacked or layered at appreciable distance from the nearest reactor wall, and the activation gas is injected without any regard to the reactor wall surface. Based on the novel activation method of the present invention, a novel reactor design is used. Its innovative features include, (1) the use of high, catalytic surface-area/volume ratio, (2) low, internal catalytic wall- surface proximity, and (3) proper activation gas flow and distribution pattern, coupled to the catalytic wall surfaces. The overall process, inclusive of all preparation steps prior to activation is shown schematically in Fig. 3 where, as an example, the subject is processing of olive pits into active carbon. The process shown in Fig. 3 can be applied to all ligno-cellulosic or biomass use as feedstock for activation. We note that the process as shown is self-sufficient regarding energy, and may even export excess energy; this includes cases where drying of the feedstock is necessary prior to pyrolysis, to the extent of removal of 60% moisture or more. Energy is available from the producer gas generated in the activation process, and from the extra pyrolysis oil produced in the charring step. In cases where the parent feedstock for the char is ligno-cellulosic (e.g., wood or biomass) or cellulosic (e.g., paper waste, or paper mill sludge or filter cake), as well as carbon extracted from coal-burning boiler ash, it is important that the carbonaceous material used as feedstock is sufficiently densified, preferably in pellet form. In these cases, in particular, the manner of char preparation and carbonization is very important for the final activation results. The innovation herein is in using the heavy fraction of pyrolytic oils or "tar" generated during the feedstock charring process, as plasticizer/binder for the char pellet formation. The char pellets thus formed by mixing the ground char with the pyrolytic oils, at high pressure, e.g., by extrusion, are first dried and then carbonized under inert atmosphere by gradual heating to elevated temperatures before final activation. Otherwise, (e.g., if the use of pyrolytic oils for energy becomes necessary, or that insufficient quantities are generated during pyrolysis), sugar-wastes or molasses can be used for this purpose. Additional steps in the process include coating the char pellets with graphite powder. For this purpose, the char pellets, upon exit from the extruder (or any other pelletization or agglomeration device) in moist or tacky-surface state, drop through a fine flake of e.g., 200 mesh graphite, which would adhere to the pellet exterior to provide a uniform thin coating. This would immediately serve to deter inter-pellet adherence, or sticking. This layer remains intact during the next pellet carbonization process. It later serves two more important purposes, without any interference with the activation process itself, as follows: (1) to allow smooth passage through the reactors, particularly through the straight-cavity reactor where pellet transfer is driven by the gravitational force, and where "bridging" or formation of inter-locked pellet clusters must be avoided, and where lateral friction between the pellets and the wall surface should be reduced; and (2) as the coating remains on the final product activated pellets as well, it allows denser packing in any filter arrangement, which allows for a higher adsorbent capacity per unit filter volume, (compared with uncoated pellets). A number of activation reactor designs are described herein, having appropriate high inner surface-area/volume ratio, and with appropriate distributed activation gas inflow and product gas exhaust. One is a straight-cylindrical or straight- prismatic cavity, with an L/D > 1 , through which the char pellets may move axially under the gravitational force while being activated. This reactor can be used in batch mode or in a continuous process. Another incorporates an Archimedes screw, used to move the material through the reactor; both the cylindrical shell and screw surface materials are catalytic. Compared with the straight-cavity reactor, the screw reactor can attain higher material processing rates for the same cross section; however, it is more complex mechanically. Straight-Cylindrical Cavity Apparatus This is comprised of a shell having a cavity, preferably cylindrical, with an Length/Diameter > 1 , which has a set of tubes within, running the whole length of the cavity, and arranged at equal distance from each other as well as from the walls. The cross sectional arrangement is based on repeating the basic equilateral triangle formed by three adjacent tube axes, to form a hexagonal tube array, which has the shell surrounding it. The example illustrated in Fig. 2a has a 5 tube-layer arrangement. The design shown keeps the char pellets which are being activated between the tubes and against the shell wall, at a distance not larger than "a" from any tube or shell surface; the value of "a" is imposed by the design, as well as the tube diameter. Activation heat is provided by both tubes and through the shell, by radiation, in proportion to their ratio of peripheries in the cross section, as shown in the last column of Table 1. The activation gas is to be injected through the shell and the tube walls, through injection ports and/or porous wall sections. This gas is super-heated by the heaters positioned outside the shell and within the tubes, where it is forced over the catalytic surfaces at the elevated activation temperature. The objective is to provide uniform activation conditions (temperature and activating gas flow) throughout the reactor cavity; although axial variations, of both heating flux and activating gas flow rate, are possible, and may, under certain conditions, be desirable. The same cavity can be utilized for batch process (in which the full reactor is charged at once, the char pellet batch is activated, then the full activated pellet batch is discharged promptly. If the cavity axis is kept vertical, filling from above and discharge at the bottom would be affected through proper openable closures. The bottom then opens into a quench compartment, where the discharged pellets are cooled under inert gas injection to near room temperature. The top is provided with a char pellet feed port (air-locked), and a gas discharge port. The differences between the foregoing batch process and a continuous process, using the same prismatic cavity, are the top and bottom closures, which are here continuously operating, and the pellet charge, which is non-uniform, as the char is gradually activated as it moves through the reactor axially. The axial pellet motion is at rates in the range of 0.01 to 1.0 meters/min, preferably about 0.10 meters/min, which is rather slow, and may be affected by gravity. It is noted that considerable pellet volumetric shrinkage occurs upon activation and burn-off, which need to be taken into account with any particular discharge metering design. Figure 4a shows one quarter of the activation apparatus in cross section, in the quadrant formed by its orthogonal symmetry lines. Fig. 4b is a section from Figure 4a cross section showing the basic equilateral triangle tube ensemble. The pellets pass between the tubes, made of, or coated with, catalytic material. The formulation for the cross sectional surface area, A, and the periphery, S, has been derived as follows: A = F1( a, d, N(n) ) = 6 [ n (2a+d) 2 3 /4 + n(2a+d) (2a+d/2) + (2a+d/2) 2 π /6 ] - (πd 2 /4 ) * N(n) (5) S = F2( a, d, N(n) ) = 6 [ n (2a+d) + 2(2a+d/2) π /6 ] + πd * N(n) (6) where the total number of tubes, N is expressed as function of the number of "layers", n, as shown in Fig. 4a, namely, N(n) = 1 + 6n [1 + (n-1)/2 ] (7) Now the ratio of periphery/cross-sectional area can be expressed as S / A = F2 (a, d, N(n) ) / F1 (a, d, N(n) ) (8) For a right-prismatic cavity, the above is the ratio of catalytic surface/volume in the reactor. The total available surface can be evaluated by multiplying S by L, the reactor effective length. The foregoing formulation was used to generate several examples, as shown in Table 1. As shown, S/A will increase with the number of layers (and tubes). Table 1 shows that, while the overall shell diameter, and the S/A ratio increase moderately with addition of layers, the number of tubes increases appreciably, which imply an increase in the complexity of the reactor construction. We also note that, with the parameters selected, a 7-tube (1 tube-layer) reactor would be sufficient, and the simplest to construct. It would have about 1.1 square meters of catalytic surface per 1 meter axial length. Table 1 Total Total Total Area Total Layers Tubes Diameter A Periphery, S S/A Stu es/ S REC Pellets I N meter m2 meter 1 /meter % kg/meter 1 7 0.220 0.0374 1.114 29.78 39.5% 9.4 2 19 0.340 0.0685 2.228 32.51 53.6% 17.1 3 37 0.460 0.1015 3.719 36.63 62.5% 25.4 4 61 0.580 0.1364 5.587 40.95 68.6% 34.1 5 91 0.700 0.1732 7.832 45.22 73.0% 43.3 An actual example is worked out, for the parameters a = 20 mm and d = 20 mm. For a reactor length of 1 meters, a 7-tube reactor (1 tube layer) configuration will process 9.5 kg of char pellets (intrinsic density of 0.50 g/CC and aggregate void fraction of 0.5), in about 10 minutes. It would have a shell diameter of 220 mm, and surface/volume ratio of 30 1/m, with all tubes and the shell made of special ceramic material, e.g., high-density and high purity alumina, Al 2 0 3 . In a typical activation of biomass char, where the char burn-off is 65%, the overall mean power consumption would be 100 kWatt. Of this power, the 7 tubes provide 39.5 kW by radiation, (see last column in Table 2), or 5.7 kW/Tube. The shell would provide 60.5 kW of the power, by radiation. The energy can be provided to the aforementioned elements by gas heat or electric heaters or other suitable means. The activation process would consume 18 kg of C0 2 . The activation gas must be provided in excess, so that our example requires 2.5 the consumed amount, or (on average) 4.5 kg/min of C0 2 , injected uniformly (or otherwise) through the shell and the tubes, as described earlier. The activation process in our example will generate 22.6 kg of CO (and other gases), which can be burned for energy. With the burn-off mentioned, 3.3 kg of activated carbon pellets would be produced per each 10 minutes, or about 20 kg/hour. The foregoing example illustrates the necessity to use a cavity-array for any industrial-scale processing, which is entirely intentional. For instance, to process 200 tonnes/day dry biomass, assuming a char/feedstock ratio of 35%, 3 tonnes/hr of char pellets are to be processed; if one reactor cavity unit can process 60 kg/hour, then an array of 50 tubes should be used. A somewhat easier to manufacture variant of the foregoing device is shown in Fig. 3, which has the same 7-tube ensemble, yet with a cylindrical shell. To overcome the salient regions where the shell wall is distended from the interior, a set of 8 fins with width 2a have been added, which would run axially through the length of the cavity, and add considerable surface area. With this addition, the configuration shown in Fig. 5 (with D=220 mm, a = d = 20 mm and 6 fins attached to the shell and 2 to the center tubes with a width of 40mm each) would have a ratio of S/A =51 , and could accommodate 11 kg of char pellets for processing within a charge length of L=1m. The foregoing design's schematic cut-away side view is shown in Fig. 6. The char pellets enter at top and move gradually downward along the axis to the bottom, where processing is complete the pellet motion velocity is about 10 cm/min. The total cavity length (of about 1 meter) is filled with pellets. Helical Screw Apparatus This is a cylindrical shell with interior shaft and screw, where both shell and screw are built of, or coated with, the catalytic materials discussed in the foregoing sections. A cutaway side view schematic is provided in Fig. 7. Heating and activating gas flow are provided through the shell and the screw shaft, by properly installed injection ports. The cell unit (one full turn of the screw) shown in Fig.7 can be built with a pitch such that the interior surface area to volume ratio is 50 or so, and the full pitch length is 2a, a constraint discussed in the foregoing section. The ratio of surface/volume for this reactor is calculated for one full turn of the screw, where the material has moved a distance of 2a axially. This is, 2AH + 2π { Ro [2a - c/cos(B2)] + Ri [2a - c/cos(B1)] } A / V = 2π a (Ro 2 - Ri 2 ) - AH * c (9) where AH is the surface of the helical blade, c denotes the blade thickness, Ri is the shaft radius, and Ro is the shell inner radius. The expression for the helical surface area has been derived, AH ≡ ( a2 / π ) { [cot(B1)/sin(B1) - cot(B2)/sin(B2)] + log | tan(B1/2) / tan(B2/2) | } where B1 ≡ arctan( a / π Ri ) , and B2 ≡ arctan( a / π Ro ). (10) The examples described below indicate how the individual constituents of the preferred process, methods and apparatus and the conditions for using them function to provide the desired result. The examples will serve to further typify the nature of this invention, but should not be construed as a limitation in the scope thereof, which scope is defined solely in the appended claims. EXAMPLES Several specific cases of successful application of the rapid activation methods herein are described in this section. A brief introduction in which the experimental setup is discussed is first, followed by the particular activation results. Pyrolysis Apparatus The pyrolysis apparatus used in the examples consists of a cylindrical Pyrex glass reactor of 25-mm nominal diameter. The reactor is placed inside an electric tube furnace (Omega, CRFC-12512/120-C-A, 600 Watts). Pyrolysis gas (N2, 99.99% pure) enters from one end of the tube and is heated by flowing through a center section of porous plug. A desired rate of temperature rise in the pyrolysis chamber is maintained by an Omega PID temperature controller. Feedstock pellets are placed directly downstream of the plug and are pyrolyzed by the combined convective heating of the gas and radiative heat from the furnace. The feedstock pellets are heated from the room temperature to 400°C in 20 minutes and held at 400°C for another 10 minutes. The gaseous pyrolysates exit from the other end of the tube (aided by a vacuum pump) and consist of condensible fractions and a mixture of non-condensible permanent gases. The stream is passed through a series of two condensers. The first condenser is kept at 100°C by boiling water, capturing all the heavy fraction above 100°C. The second condenser is kept at below 0°C by an ice/water mixture (with CaCI 2 solution), and captures water and pyrolysate fractions with boiling point below 0°C. Each condenser is made of a 13-mm copper tube coil, housed in a stainless steel container which can be filled with boiling water (maintained by a 1.5 kW electric heater) or ice/water mixture. Condensate from each condenser is collected in Pyrex glass vessel, which is filled with ceramic beads to increase condensation surface area. Char Pelletization. Solid char residue is removed at the end of a batch run for mass measurement and for further processing. Prior to activation, the char is pelletized. This process follows common procedures, using a sugar type plasticizer / binder, such as molasses or Dextran™ a form of dextrose with very high molecular weight for example. Heavy pyrolytic oils (tar from pyrolysis) from the charring process is also an excellent plasticizer, as was found in our experiments, using tar from Ensyn Tech., Inc., and from our own pyrolysis of ligno-cellulosic feedstock. In all Examples, molasses have been used successfully, at a ratio of about 1 :2 by mass relative to the char. The char is ground to a 100-200 mesh, and mixed thoroughly with the plasticizer, then extruded using a mechanical benchtop press, at pressures of about 00 atm. For the industrial process, pressure in the range of about 100 - about 1 ,000 atm can be used. The pellets are first dried in air, and sometimes coated with fine graphite flake, by rolling the near-dry pellets in graphite powder. This coating adds about 0.1 % to the pellet mass. The "green" pellets are then carbonized or re-charred under N 2 atmosphere. This is done by gradual heating to 400 C or higher over a period of 30 minutes to 60 minutes, then soaking at the maximal temperature for about 10 - 20 minutes. The same apparatus described above for charring is used for this purpose. Re-charred pellets are ready for activation without cooling. Activation apparatus. The activation apparatus used in the Examples consisted of a set of tubes having a 25-mm nominal diameter, made of materials whose wall effects on the activation are to be investigated. Specifically they are: quartz (Vycor brand of Corning, Inc., 96% silica), alumina (99.7% alumina, l-COR 995 from Ipsen Ceramics), mullite (63.5% alumina and 34.2% silica, l-MUL 900 from Ipsen ceramics), and 316 stainless steel. A tube of a given material is placed in an electric tube furnace (the same as used for the pyrolysis process), and the temperature in the center section of the tube is maintained to within ±2°C. Activation gas (C0 2 , anaerobic grade, 99.99% pure) is injected from one end of the tube and is heated to the desired activation temperature by passing first through a packed bed of alumina beads (3mm mean diameter, W.R. Grace) retained between two porous plugs, located in the center section of the tube. Initially, the tube is purged with high- purity grade N2 (99.99% pure), while it is heated to attain a desired activation temperature. Prior to placing the char pellets for activation, C0 2 flow is started at a desired rate, while the N 2 is shut off. Once a pure C0 2 atmosphere is attained inside the tube, char pellets are inserted quickly from the opposite end of the tube and are placed downstream of the heated plug. A ceramic- sheathed K-type thermocouple is inserted from the other end of the tube for the temperature measurement adjacent to the char pellets being activated. The thermocouple is located downstream of the char so as to keep it isolated from the activation process. A load of 15 grams or even several pellets can be activated in this method. The nominal S/A = 160 1/m for the tubes used. At the end of the activation period, the activation reactions are quenched by switching the gas flow back to N 2 while shutting the CO 2 off. Once the pellets are cooled off, they are removed for the mass measurement and the surface area analysis. The same apparatus is used for activation by CO 2 + N 2 mixtures, as well as for steam activation. Surface area analysis Surface area analysis for the activated carbon pellets was done in a Micromeritics Gemini 2375 surface area analyzer, equipped with the Stardriver data acquisition, control, and analysis software. Standardized sample preparation procedures are followed, which include degassing of the sample under N 2 at 150°C for 1 hour in a Micromeritics FiowPrep 060 apparatus, prior to analysis. A comprehensive 30- point measurement is made for a micropore volume analysis (BJH adsorption) and a multipoint BET surface area analysis is carried out (typically for 4 points). The data for activation is normally represented in all Examples by a group of 4 diagrams: (a) shows burn-off vs time, in which burn-off, XB, is the percent of char consumed or gasified in the activation process, as a percent of the starting char mass; (b) is a plot of BET specific surface area, and micropore (BJH) surface area, (m 2 /gram), plotted against the corresponding char burn-off, which serves as reaction progress coordinate; (c) is a plot of gasification rate, dXB/dt, vs extent of burn-off, XB, which indicates the rate of the process; and, (d) is a plot of the gradient of BET surface area relative to burn-off, d(BET)/dXB, which indicates the extent of pore development for the gasification observed. The last two diagrams indicate, in all cases, a very high rate of gasification in the beginning, which then becomes moderate, and a rather complex dependence of pore development on burn-off. Gasification rates are at least one order of magnitude, or more, higher than any published data on steam or C0 2 activation. Example No.1 Southern Pine (cured 20 years). Figures 8 through 10 illustrate the results of this material's processing and analysis. We have used the char to demonstrate the effect of wall material, maximal temperature, and gas flow. Figure β demonstrates the effect of the catalytic materials tested. Quartz, alumina and mullite show similar behavior in Figs.8a and 8c regarding burn-off vs time and burn-off rate. Interestingly, the steel tube we have used (Fe is a known catalyst) indeed accelerates the burn-off appreciably, yet, as shown in Fig. 8b, its BET surface development is poor, and the tendency at higher XB extent is to lose porosity, or burn-off the basal carbon exterior instead of further pore development. All of the ligno-celluosic and cellulosic materials tested herein have a cellular or fibrous macro-structure, with charred plant cell wall thickness on the order of 2 micrometers, as shown with the scanning electron micrographs enclosed. It is therefore easy to realize why activation competes with total gasification of the char. Thus it is important to penetrate and oxidize the basal aromatic structure, yet equally important is to retard excessive oxidation which invariably leads to material loss without appreciable micro-pore development. The set of Figs. 9(a)-(d) illustrate the effect of activating temperature, where the results systematically vary for Tmaχ=850°C, 900°C, and 950°C to faster activation and higher porosity, although the burn-off can be excessive at high Tmax. In all cases a low flow rate of CO 2 was used, 57 CC/min, and all tests were made in the alumina tube. We note, nevertheless, that a BET surface of 1 ,037 m2/g is obtained for activation at 950°C for 10 minutes, at moderate burn-off of 66%. The set of Figs. 10(a)-(d) illustrate the effect of flow rate of CO 2 , which was varied through 3 orders of magnitude (Tmax=850°C, and all testing done in the alumina tube). Due to the small mass of char pellets being activated, in all cases the CO 2 concentration was nearly 100%. However the forced convective effects, which vary with the flow rate, of delivering oxygen radicals to the surface (thus promoting inward diffusion and pore development), as well as enhancing oxidation of external surfaces (thus promoting burn-off) are competing, and one or another may become prevalent at different flow regimes. In summary, the effect was far smaller than that of Tmax, discussed earlier. Example No.2 Creosoted Wood (20 year old telephone pole). The results are shown in Figs. 11 (a)-(d). Creosote is a mixture of aromatic petroleum and coal by products, and forms an appreciable percentage of the structure mass (over 50% even in 20 year old treated wood). The char is therefore soaked with a high proportion of H/C and the C-H bonds in the char are quite difficult to break during activation. The charring of this feedstock material has taken nearly 2 hours of gradual heating to Tmax=400°C, and re-charring of the cured char pellets was done by gradual heating to Tmax=400°C over 1 hour. The activation was all carried out at 850°C, and CO 2 flow rate of 2,465 CC/g, in alumina tube. Here we observe a near linear burn-off vs, time in Fig. 5.4(a), extending however to 25 minutes where about 72% burn-off occurs, and a BET of 883 m 2 /g is obtained. The BET pore development vs XB accelerates at higher burn-off, probably after the C-H surface groups were finally oxidized. Example No. 3, Pyrovac Char. This is a char obtained from a mixture of wood waste in Canada. The Pyrovac process is a vacuum charring which endeavors to maximize the pyrolytic oil yield. The particular char obtained was generated by their process at 495 °C, and considered relatively low-volatility char. We have pelletized it by using molasses as binder, and re-charred by gradual heating to 500 °C in 30 minutes. In Figs 12.a-d we have compared activation in the alumina and quartz tubes, using T=850 °C, and C0 2 flow rate of 2,465 CC/min, activating up to 10 minutes. Alumina has resulted in this case in faster burn-off, yet for lower XB values, quartz has yielded better BET, while alumina performed better for higher XB values. Quartz has obtained BET of 978 m 2 /g at XB=63.3%. Example No. 4, Olive Pits. This feedstock is very dense and very hard. We have charred the whole pellets, which resulted in considerable amount of pyrolytic oil generated, some of which is seen in the enclosed SEMs to have solidified in the char. The coarse granular char obtained (following the normal pyrolysis procedure described above, Tmax=400 °C) was then milled to fine powder (100-200 mesh) and pelletized with molasses, then re-charred in the same process. The carbonized pellets were then activated in a quartz tube. The results are summarized in Figs. 13.a-d. Although an extended activation to 45 min. was attempted, the results were negative, showing more burn off and less BET surface than for 30 minute activation. The same quartz attribute was noted earlier with the Pyrovac char activation above. All activation was carried out with Tmax=850 C and CO2 flow rate of 2,465 CC/min. Here a peak value of 1 ,285 m2/g was observed, at 66.3% burn-off. SEMs for olive pits char and activated carbon are enclosed, Figs 5.12a,b,c,d. Fig. 5.12. a, b show the char at different magnifications, with clear solidified tar at the surface. Figs 5.12.c,d show the resultant activated carbon (5 min. activation at 850 °C); the activated surface shows fissures of sub-micron width, indicating good mesopore development; the high magnifications of Fig. 5.12.d are typical to a high porosity microporous carbon. Example No. 5, Ensyn Tech., Inc. RTP™ Char. The Ensyn rapid thermal processing (RTP™) is a commercial flash pyrolysis process, done in a flowing hot sand bed, where the material is first ground to 1 mm size or lower. Here too the pyrolytic oils are the main objective, while solid char is a pesky by product. The char from this process has a high static charge, and is quite difficult to handle. We have pelletized it with molasses as well as with its own pyrolytic oil, both successfully. The results presented herein are for pellets made with molasses. Re-charring was done by gradual heating to 400 °C under N 2 , for 30 minutes. In addition, one set of pellets made with a mixture of coal tar and petroleum pitch was provided by Ensyn (green pellets), which were re- charred by gradual heating over 2 hours to 500 °C. A third set of pellets was made by mixing the Ensyn char with OCC char at 2:1 ratio by mass. All activation was made by Tmax=850 C, and CO 2 flow rate of 2,465 CC/min, using the quartz tube. The results are summarized in Figs. 14.a-d. In Figs 14. a, b it is clear that the fastest burn-off and the highest BET surface areas are obtained with our OCC mixed pellets, and with the plain char pellets. The OCC mix has obtained a BET value of 830 m2/g at 71.6% char burn-off. Figs 14.c,d were plotted for the petrol, based char pellets only. A set of SEMs is provided for this char activation, Figs 5.13 a-d. The char particles in this case, shown in Figs. 5.13.a,b resemble the parent wood cellular structure. The activated carbons developed from it show considerable embrittlement and shrinkage, extensive macropore structure, and the development of mesopores as well. Example No. 6, Paper Mill Sludge (US tissue mill). This sludge is of very low ash content, and highly usable in our process. The material was obtained at 60% moisture and first pelletized by punch and die process to form cylindrical pellets. The pellets were dried in air and charred as described above, by gradual heating to 400 °C under N 2 , for 30 minutes. The char obtained was milled to fine powder (100-200 mesh) and pelletized with molasses, then re-charred in the same process. The carbonized pellets were then activated in an alumina tube, with a C0 2 flow rate of 57 CC/min, at 3 different activation temperatures. The results are summarized in Figs. 15. a-d. Clearly the highest temperature tested, Tmax=950 °C, has a clear advantage, obtaining high rate of burn-off and the highest BET values in the group, namely 575 m2/g at 54% burn-off, in 10 minute activation. The resultant low micropore surface fraction (69%) indicates high utility for water purification. Example No. 7, OCC Sludge (US recycled cardboard liner mill). The material coming from corrugated containers has a high fiber content and relatively low ash, and was found to carbonize readily and activate excellently. The material was obtained at 75% moisture and first pelletized by punch and die process to form cylindrical pellets. The pellets were dried in air and charred as described above, by gradual heating to 400 °C under N 2 , for 30 minutes. The char obtained was ground to fine powder (100-200 mesh) and pelletized with molasses, then re-charred in the same process. The carbonized pellets were then activated in a quartz tube, with a C0 2 flow rate of 2,465 CC/min, at 850 °C . The results are summarized in Figs. 5.9. a-d. Activation between 5 and 15 minutes has resulted in burn-off between 33% and 55%, and quite linear BET surface development vs XB. The maximal BET obtained was 942 m2/g, while its micropore surface area fraction was 78%, again a potential candidate for water purification. SEM photographs are attached, Figs 16.a,b,c, showing the fibrous feedstock, the brittle char and the final activated carbon pellet, which retains the original fiber structures (with shrinkage) with highly mesoporous surface shown. Example No. 8, Boiler Ash Carbon. The material originated in a northeastern power plant burning Venezuelan coal. The ash was sieved once by a Hosokawa, Inc. process, then sieved again at the laboratory by a 100-mesh sieve; material remaining in the sieve was taken as carbonaceous feedstock, and was found to contain less than 8% ash. The material was pelletized with molasses. The pellets were charred as described above, by gradual heating to 500 °C under N 2 , for 30 minutes. The carbonized pellets were then activated in an alumina tube. Two groups of tests were made, (1) with Tmax=850 °C and C0 2 flow rate of 2,465 CC/min, and (2) with Tmax=900 °C, and CO2 flow rate of 57 CC/min. The results for activation between 5 and 25 minutes are summarized in Figs. 17.a-b. The 900 °C activation seems clearly better, although BET is declining after 15 min. activation. The maximal BET obtained is 453 m /g at 48% burn-off, but with just 40% micropore surface fraction, which gives a highly mesoporous activated carbon. Figs. 17 c,d show variation of activated carbon yield vs. CO 2 flow rate, and the corresponding BET surface variation. A 20% BET variation is shown, and in Fig. 17c clearly yield peaks for the 57 CC/min flow rate.

Claims: What is claimed is: Claim 1. A process for the thermal activation of chars comprising heating the char to an activation temperature greater than 800°C and exposing said char to an activation gas containing reactive radicals. Claim 2. The process of claim 1 wherein said activation gas is selected from CO 2 or steam. Claim 3. The process of claim 1 wherein the reactive radicals are produced upon the contact of said activation gas with a catalytic reactive radical producer. Claim 4. The process of claim 3 wherein said catalytic radical producer is selected from quartz, alumina ceramic, or mullite. Claim 5. The process of claim 1 wherein said reactive radicals are oxygen radicals.. Claim 6. The process of claim 1 wherein said char is in the form of pellets. Claim 7. The process of claim 1 wherein said thermal activation is completed in less than 30 minutes. Claim 8. A method for the rapid thermal activation of carbonaceous materials with an activation gas, wherein the carbonaceous materials is exposed to reactive radicals within said activation gas, wherein said radicals react with exposed surface area of the carbonaceous materials to form surface complexes, wherein said complexes break off thereby creating a porous structure in the carbonaceous materials. Claim 9. The method of claim 8 wherein the thermal activation occurs at temperatures above about 800°C. Claim 10. The method of claim 8 wherein the activation gas is CO 2 or steam. Claim 11. The method of claim 8 wherein the source of said reactive radicals is quartz, alumina ceramic, or mullite. Claim 12. The method of claim 8 wherein said chard is in the form of pellets. Claim 13. The method of claim 8 wherein said thermal activation is completed in less than 30 minutes. Claim 14. Porous activated carbon made by the process comprising heating a carbonaceous char to an activation temperature greater than 800°C and exposing said char to an activation gas containing reactive radicals Claim 15. Porous activated carbon made by the thermal activation of chars with an activation gas, wherein the char is exposed to reactive radicals within said activation gas, wherein said radicals react with the char to form surface complexes and said surface complexes break away from the char creating a porous structure in the char. Claim 16. A reactor for a thermal activation process comprising a reaction chamber having an interior surfaces, a heating means for heating the interior of the reaction chamber, and one or more activation gas inlets, wherein said interior surface of the of the reaction chamber is capable of producing reactive radicals upon contact with an activation gas. Claim 17. The reactor of claim 16 wherein said radical producing surface is a coating of quartz, alumina ceramic or mullite. Claim 18. The reactor of claim 16 wherein said radical producing surface is the exposed surface of the reaction chamber which is composed of quartz, alumina ceramic or mullite. Claim 19. The reactor of claim 16, further comprising a plurality of tubes having an outer surface capable of producing reactive radicals upon contact with an activation gas. Claim 20. The reactor of claim 16, further comprising an Archimedes screw element within said reaction chamber for propelling contents of said reaction chamber through said reaction chamber, and a means for rotating said screw.

Inventors: BEN-REUVEN MOSHE, TEWARI SANT S, BEN-REUVEN, MOSHE, TEWARI, SANT, S.
Applicants: BEN REUVEN MOSHE, MBR TECHNOLOGIES INC, TEWARI SANT S, BEN-REUVEN, MOSHE, MBR TECHNOLOGIES, INC., TEWARI, SANT, S.
Application year: 2000
Main classification: F23K3
IPC codes: B01J20, C01B31