J. Anal. Appl.

Pyrolysis 85 (2009) 294300

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

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

Jerusalem artichoke pyrolysis: Energetic evaluation

lez b, G. Mart nez a, S. Roma n b J.M. Encinar a,*, J.F. Gonza
a b

Dpto. de Ingeniera Qumica y Qumica Fsica, UEX, Avda de Elvas s/n, 06071 Badajoz, Spain Dpto. de Fsica Aplicada, UEX, Avda de Elvas s/n, 06071 Badajoz, Spain

A R T I C L E I N F O

A B S T R A C T

Article history: Received 28 June 2008 Accepted 17 November 2008 Available online 27 November 2008 Keywords: Pyrolysis Temperature Jerusalem artichoke waste Pyrolysis kinetics Energy evaluation

The pyrolysis process of Jerusalem artichoke (Heliantuhus tuberosus L.) waste was carried out. The objective of this work was to characterize the solid, liquid and gaseous phases, studying the inuence of the operating variables and determining the optimal conditions. Thus, the inuence of temperature (400800 8C), particle size (0.632.00 mm), N2 ow rate (75300 mL min1) and initial sample mass (2.510 g) were investigated. In these series, the yields of the three phases, their higher heating value and the proximate analysis of the solid phase were determined. Under the conditions of this study, an increase in reaction temperature leads to a decrease in the solid and liquid yields and to an increase in the gas phase yield. However, the variation of the initial sample mass and the particle size do not exert a dened inuence in the yield of the three phases. On the other hand, increasing the N2 ow causes a decrease in the liquid and an increase in the gas yields. According to the energetic characterization of the phases generated, different uses were proposed. Finally, as previous step to the design of the industrial equipments, a kinetic study of the process, based on the generation of the principal gases, was accomplished. With this purpose, it was considered that the gases are formed through parallel independent rst-order reactions, with different activation energies. From this model, rate constants for the formation of each gas and their corresponding activation energies were determined. 2008 Elsevier B.V. All rights reserved.

1. Introduction Environmental pollution is becoming more than ever a serious problem associated, among other factors, with the great emissions of CO2, NOx and SOx resulting from the rising use of fossil fuels. For this reason, it is important to be concerned about the use of biomass as a clean and renewable substitute for fossil energy. Biomass residues, including those originated from wood industry, forest and agricultural by-products, paper manufacturing and, more recently, energy crops, are renewable sources and an alternative to fossil combustibles [13]. Conversion of biomass residues to energy and different products of industrial interest (activated carbons, for example) can be carried out by thermochemical methods such as pyrolysis, gasication and liquefaction [46]. These methods are the most appropriate for these applications and the most commercially used [7]. Depending on temperature and heating rate, different types of pyrolysis exist: conventional, fast and ash. Conventional pyrolysis is the most appropriate one if the solid phase, i.e. the char, is the objective. The main applications of chars are domestic fuel, reducing agent and raw material for active carbon production [8,9].

Also, this process generates low/medium high heating value gases and liquids, which are used to recover certain chemicals [6]. The other two types of pyrolysis lead to greater quantities of gases, especially when high temperatures and residence times are employed [10]. Jerusalem artichoke can be considered as an energy crop due to its known advantageous characteristics and, as a consequence, the study of its pyrolysis process is interesting. Taking into account what has been said before, and continuing previous research [1114], we carried out a detailed study of the pyrolysis of Jerusalem artichoke waste, in order to determine the quality of the char obtained and to identify and quantify the gases produced in the process. The inuence of the following variables was studied: temperature, initial sample weight, particle size and N2 ow rate. Additionally, a kinetic study of the process, based on the generation of the main gases, was made. 2. Experimental The experimental set-up, similar to one described elsewhere [1114], is shown in Fig. 1. It basically consisted of a cylindrical stainless steel reactor equipped with a heating system, inlet gas feeding and accessories to collect the liquid and gas phases. It had a heat exchanger at its top, which kept samples at room temperature before the start of the run; a suspension system held the basket,

* Corresponding author. Tel.: +34 924 289672. E-mail address: jencinar@unex.es (J.M. Encinar). 0165-2370/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jaap.2008.11.023

J.M. Encinar et al. / J. Anal. Appl. Pyrolysis 85 (2009) 294300

295

Fig. 1. Experimental set-up.

which contained the residues samples. The heating system consisted of a ceramic furnace and power source, temperature being controlled to 5 8C automatically by means of computer software. As it can be observed in Fig. 1, the lower part of the reactor is connected to a liquid sample collecting and condensation system. This system was composed of three traps, cooled with ice, that retain the condensed liquids and to collect the small drops of oils swept with the gases. All experiments were carried out isothermally in a fast pyrolysis regime. The operation variables were studied in the following ranges: temperature (400800 8C), initial sample mass (2.510 g), particle size (0.632.00 mm) and N2 ow rate (75300 mL min1). The procedure carried out during the pyrolysis processes is described as follows: the basket was loaded with a certain amount of sample and was placed at the top of the reactor (cooling zone). During the heating, N2 was supplied to provide an inert atmosphere; once the target temperature was reached, the basket was moved down towards the heating zone, and the run was started. From this moment on, gaseous samples were extracted at regular intervals and analyzed chromatographically. After the stipulated dwell time had passed, heating was turned off and the basket was moved back to the refrigeration zone. Finally, once room temperature was reached, the weight of the carbonaceous residue remaining in the basket and the liquids obtained were weighted. Then, the solid, gas and liquid fractions were analyzed. The solid phase was characterized in terms of its proximate analysis, using a standards thermogravimetric method [15]. Also, the higher heating value (HHV) of solids and liquids was determined. The gas phase was analyzed chromatographically with a 4000 HRGC Konik gas chromatograph provided with two thermal conductivity detectors and a double injector connected to two columns: one a 60/80 (mesh range) Carboxen 1000 of 15 ft. 1/8 in. stainless steel (2.1 mm i.d.) and the other a 100/ 120 (mesh range) Porapak Q of 3 m 1/8 in. stainless steal (2 mm i.d.).

3. Results and discussion The dwell time used in the pyrolysis processes was 30 min, in accordance with previous studies, which demonstrated that during such a period of time most gases have been completely removed [1113]. The gas was mainly composed of H2, CO, CH4, CO2 and traces of hydrocarbons such as ethane and ethylene. The total molar production of each component during the run was calculated in accordance with Simmons and Sanchezs method [16]. The fraction yields were obtained by means of a mass balance; quantifying the tars and the solid fractions by weight and the gas fraction from the detected gases. Using this procedure, we achieved experimental errors not greater than 5% with respect to the initial mass. 3.1. Inuence of temperature In Figs. 2 and 3 the effect of temperature on different parameters of the pyrolysis of Jerusalem artichoke waste is shown. As observed, the increase in temperature leads to a decrease in the solid and liquid yields and to an increase in the gas phase yield. The decrease in liquid yield is more notable, which is probably caused by the high cracking suffered by this phase as the temperature increases. This suggests that the observed increase in the gas phase yield is partially due to the decrease of the liquid fraction. This cracking effect has been observed in previous works made by us [1114,17,18] and other authors [19,20] on the pyrolysis of other lignocellulosic materials. With respect of the proximate analyses of the chars, it was found that an increase in temperature led to an increase in the contents of xed carbon and, parallely, a decrease in the percentage of volatile matter, and, consequently, to a slight increment in the ash content. In addition, the production of the gases presents an increase with temperature in all cases.

296

J.M. Encinar et al. / J. Anal. Appl. Pyrolysis 85 (2009) 294300

Fig. 2. Fraction yields and proximate analysis of chars. Inuence of temperature (N2 ow rate: 150 mL min1; particle size: 0.631 mm; initial sample weight: 5 g).

Fig. 4. Evolution of CO concentration with time. Inuence of temperature (N2 ow rate: 150 mL min1; particle size: 0.631 mm; initial sample weight: 5 g).

Fig. 4 shows, as example, the evolution of CO concentration with time at the different temperatures studied. As it can be seen, the curves are similar in shape, showing a maximum concentration at a given time. The maximum concentration and corresponding reaction times are both signicantly temperature-dependent. Thus, as the temperature is higher, the maximum concentration is greater and the reaction times needed to reach it are lower. As a consequence, the molar production increases with the temperature. Fig. 5 shows the evolution of CO production with time at the different temperatures. It can be seen that it grows steadily during the rst range of time, then reaching a plateau, which indicates

that by this time (approximately 10 min) most of the CO has been released. It has to be pointed out that the shape of the curves in the case of the other components followed a similar trend. 3.2. Inuence of mass sample and of particle size Table 1 shows the value of different pyrolysis parameters as a function of initial sample weight and particle size. It can be seen that the distribution of pyrolysis products and their composition is scarcely inuenced by these variables. Nevertheless, some slight tendencies can be observed with respect to the inuence of the particle size on the phases yields and

Fig. 3. Inuence of temperature on gas production (N2 ow rate: 150 mL min1; particle size: 0.631 mm; initial sample weight: 5 g).

Fig. 5. Evolution of molar production of CO. Inuence of temperature (N2 ow rate: 150 mL min1; particle size: 0.631 mm; initial sample weight: 5 g).

J.M. Encinar et al. / J. Anal. Appl. Pyrolysis 85 (2009) 294300 Table 1 Inuence of initial sample weight and particle size on yields of different fractions, proximate analysis of chars and gas production (temperature: 600 8C; N2 ow rate: 150 mL min1). Operating conditions 0.631.00a 5b Fraction yields (wt.%) Solids 22.0 Liquids 41.4 Gases 36.6 1.001.60a 5b 1.602.00a 5b 0.631.00a 2.5b 0.631.00a 10b Fraction yields (wt.%) Solids Liquids Gases

297

Table 2 Inuence of nitrogen ow rate on yields of different fractions, proximate analysis of chars and gas production (temperature: 600 8C; particle size: 0.631 mm; initial sample weight: 5 g). Parameter Nitrogen ow rate (mL min1) 75 150 300

21.2 44.0 34.8

20.6 44.8 34.6

21.8 38.6 39.6

21.3 40.4 38.3

23.0 47.8 29.2

22.0 41.4 36.6

21.0 38.4 40.6

Proximate analysis of chars (wt.%) Fixed carbon 53.55 53.84 Volatile matter 39.42 39.52 Ash 7.03 6.57 Gas production (mol/kg residue) H2 2.590 CO 2.250 CH4 0.734 CO2 2.595
a b

53.39 40.36 6.25

53.33 39.45 7.22

54.05 39.44 6.51

Proximate analysis of charcoal (wt.%) Fixed carbon 50.77 Volatile matter 43.58 Ash 5.65 Gas production (mol/kg residue) H2 0.689 CO 1.708 CH4 0.628 CO2 2.066

53.55 39.42 7.03

54.47 37.88 7.65

1.342 3.799 1.230 2.676

1.483 3.108 1.233 3.163

1.387 2.012 0.735 3.144

2.751 1.934 1.045 3.004

2.590 2.250 0.734 2.595

2.296 2.901 0.889 2.653

Particle size (mm). Initial mass (g).

their products distribution. Thus, the solid and gas yields decreased a little, whereas those of the liquids was increased as the particle size was increased. With respect to the proximate analysis, a little decrease in the ashes content of the chars and a slight increase in the volatile matter were observed with increasing particle size. These facts might be due to a slight effect of transfer limitations processes. In these cases, the gases molar production did not seem to vary signicantly, without a dened tendency. In relation to the initial mass of the samples, it can be observed that the correspondent values to the yield of the phases, proximate analysis and production of gases remain basically constant. In consequence, it was found that these parameters are not signicantly inuenced for the initial mass of the samples. According to the aforementioned effects of these variables, it could be concluded that the internal gradients of temperature might be negligible and, therefore, the particle heating is practically homogeneous. 3.3. Inuence of nitrogen ow rate The effect of N2 ow rate on pyrolysis yields is shown in Table 2. As observed, an increase in this variable caused a decrease of the liquid yield and an increase of the gas yield. The solid fraction decreased slightly. These facts can be related to secondary reactions of components of gas and liquid fractions to generate condensable components. If residence time of gases is lower (because N2 ow rate is higher), the mentioned reactions will be produced in a less extent. 3.4. Kinetic study of gas generation In the pyrolytic process, most of gases are generated thermally; concretely, hydrogen and methane are formed from volatile matter cracking and depolymerization reactions, and carbon monoxide and carbon dioxide from descarboxylation and depolymerization reactions [21]. These reactions are favoured by temperature, so that an increase in gas production is expected with rising temperature, as this can be seen from the results shown in Fig. 3. However, nding kinetics that explains the thermal decomposition of biomass residues is not easy due to the complexity of these materials. The principal kinetic models assume that pyrolysis takes place through parallel reactions with the biomass residues decomposing directly to each nal compo-

nent through one reaction of rst-order [2225]. In this work, we take a similar approach by considering each gas to be formed in a single rst-order parallel reaction with different activation energies. The rate of generation of a gas component in a batch reactor can be expressed as r dm dt (1)

where m represents the number of gas moles generated. At given time t, m is given by Z t m C F dt (2)
0

where C is the concentration of a given gas component and F is the total gas ow rate. Since the reaction is rst-order, the rate of thermal decomposition for Jerusalem artichoke waste is given by dM kM dt (3)

where M is the residue mass. In Eq. (2), m can be related to the loss of residue mass (M0 M) by introducing a coefcient a: Z t c F dt aM 0 M (4) m
0

where M0 is the initial mass of residue to be pyrolysed. Differentiation Eq. (4), and using Eq. (3), yields: dm dM m aM0 a akM ak km0 m dt dt a (5)

where m0 = aM0 represents the total moles of gas generated when the whole pyrolysis of the residue has been completed, i.e. when the residue is exhausted. This value can be obtained from pyrolysis experiments carried out at high temperatures and extended reaction times when no more gas is released [26]. In this work, this value has been obtained with experiments at 900 8C and a time of 120 min. After separation of variables and integration, Eq. (5) becomes:   m0 ln kt (6) m m0 A plot of the left-hand side of Eq. (6) vs. time should therefore yield a straight line whose slope is k, the rate constant of gas formation. The values of k were obtained from least-squares t of

298

J.M. Encinar et al. / J. Anal. Appl. Pyrolysis 85 (2009) 294300

the experimental data corresponding to Jerusalem artichoke waste. As example, in Fig. 6, a plot of Eq. (6) for all gases is shown. Also, in Fig. 7, a plot for the hydrogen in experiments carried out at different temperature is shown. In addition, Table 3 presents the rate constant obtained for all gases in experiments carried out at different temperatures. The experimental points t favourably to the kinetic model chosen, with values of R2 = 0.98 0.99 in all cases. One can see that the value of k increases with increasing temperature. From the values of k at the different temperatures, by means of an Arrhenius function (Eq. (7)) it is possible to obtain the activation energies for the formation of each gas and the Arrhenius preexponential factors. ln k ln k0 Ea 1 R T (7)

Fig. 8 shows the Arrhenius plots for H2, CO, CH4 and CO2 formation. It can be observed the behaviour expected, that is an increase in constant kinetics with an increase in reaction temperature. Nevertheless, this increment is not observed in the same way for all of the series. Hydrogen, carbon monoxide and methane present an increase faster than carbon dioxide. On the other hand, in the case of the CO2, the adjustment is only valid for the values corresponding at low temperatures. Table 4 presents the activation energies and the Arrhenius preexponential factors for the formation of each gas and correlation coefcients of the least-squares analysis. Finally, Table 5 gives the activation energies from individual gases obtained in other works reported in the literature using different raw materials and operating conditions. Although it is difcult to compare those data with the ones obtained here, one observes that the activation energies determined in this work are within the intervals found in Table 5. 3.5. Energy evaluation In a background view, the pyrolysis of Jerusalem artichoke waste originates three phases: solid, liquid and gas. The latter two ones contain a wide variety of components. As far as energy

Fig. 7. Verication of the kinetic model for hydrogen. Temperature inuence (N2 ow rate: 150 mL min1; particle size: 0.631 mm; initial sample weight: 5 g).

Table 3 Rate constants of H2, CO, CH4 and CO2 formation in the pyrolysis of Jerusalem artichoke waste. Inuence of temperature (N2 ow rate: 150 mL min1; particle size: 0.631 mm; initial sample weight: 5 g). Temperature (8C) k 103 min1 H2 400 500 600 700 800 0.02 3.49 13.94 51.80 163.30 CO 9.01 18.02 48.70 107.90 236.65 CH4 3.10 13.10 42.05 138.40 337.91 CO2 42.93 63.40 101.40 132.60 276.74

recovery is concerned, the most appropriate phases would be solid and gas. The liquid phase (HHV of 9.7 MJ kg1 at 400 8C, decreasing at higher temperatures), once separation problems are overcome, could be useful for the recovery of certain important chemicals. The energy value of the solid phase is based on the carbon content. Another possibility would be to carry out gasication processes to obtain activated carbon or gases. The energy value of the gases is effectively their heating power. Table 6 shows the highest heating values of gases and solid yields based on their heat of combustion and Tillmans expression, respectively [34]. As seen in Table 6, the highest heating value of the gases increases with temperature, as a consequence of the greater gas yield (see Fig. 2). The gas mixture generated may be classied as
Table 4 Activation energy and Arrhenius pre-exponential factors of H2, CO, CH4 and CO2 formation in the pyrolysis of Jerusalem artichoke waste (N2 ow rate: 150 mL min1; particle size: 0.631 mm; initial sample weight: 5 g). Gas Activation energy (Ea) (kJ mol1) 86.5 45.4 68.1 26.20 Arrhenius pre-exponential factor (k0) (min1) 2249.3 26.2 561.7 4.1 Correlation coefcient (R2)

Fig. 6. Kinetic model verication (N2 ow rate: 150 mL min1; particle size: 0.63 1 mm; initial sample weight: 5 g; temperature: 600 8C).

H2 CO CH4 CO2

0.99 0.98 0.99 0.94

J.M. Encinar et al. / J. Anal. Appl. Pyrolysis 85 (2009) 294300 Table 5 Activation energies for individual gases reported by different authors. Raw material T (8C) Ea (kJ mol1) H2 Sweet gum Penicum maxima Cellulose Holm-oak sawdust Cellulose Wood our Wood tars Wheat straw Pinedust Sunower Grape Tobacco Maize C. cardunculus L. Jerusalem artichoke 3001100 200300 292328 300900 3001100 3001100 500800 600750 600750 400700 400700 400700 400700 300800 400800 86 17 114 129 36 57 76 84 45 88 92 86 CO 61 37 14 220 48 88 30 56 20 21 23 19 48 45 CH4 69 120 19 250 94 20 83 62 72 80 77 16 68 CO2 18 98 49 16 32 21 Workers

299

Nunn et al. [27] Ekwenchi et al. [28] Bilbao et al. [29] Figuereido et al. [30] Hajaligol et al. [31] Simmons and Sanchez [16] Boroson et al. [26] Bilbao et al. [32] Bilbao et al. [32] Encinar et al. [33] Encinar et al. [33] Encinar et al. [33] Encinar et al. [33] Encinar et al. [11] This work

Table 6 Highest heating values of gases and solids. HHV Temperature (8C) 400 Gases (MJ kg of raw material) Solids (MJ kg1 of solid)
1

800 8C, where charcoals with the highest heating value are obtained with satisfactory xed carbon and volatile matter contents. Also, the HHV of the gases is high.
600 2.03 26.07 700 4.04 26.34 800 10.97 26.67

500 1.07 25.59

Acknowledgments The authors express their gratitude to the Junta de Extremaa de Econom a, Comercio e Innovacio n for the dura-Consejer nancial support through projects 2PRO4B016/PRI07A088 and n and G. Mart nez thank the Junta de 2PR01A034. S. Roma Extremadura for their research grants. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] L.L. Wright, Biomass Bioenergy 6 (1994) 191. W.G. Hohenstein, L.L. Wright, Biomass Bioenergy 6 (1994) 161. ksel, Appl. Therm. Eng. 24 (2004) 933. K. Comakli, B. Yu A. Derribas, J. Anal. Appl. Pyrolysis 72 (2004) 243. T. Fisher, M. Hajaligol, B. Waymack, D. Kellogg, J. Anal. Appl. Pyrolysis 62 (2002) 331. Z. Luo, S. Wang, K. Cen, Renewable Energy 30 (2005) 377. stro m, E. Bjo rnborn, Biomass Bioenergy 23 (2002) 357. R. Zunzi, K. Sjo D.M. Mackay, P.V. Roberts, Carbon 20 (1984) 95. J.R. Dacey, in: E. Alison Flood (Ed.), The SolidGas Interface, vol. 2, Marcel Dekker, New York, 1967, p. 995. M.J. Antal, Ind. Eng. Chem. Process Des. Dev. 22 (1983) 366. lez, J. Gonza lez, Fuel Process. Technol. 68 (2000) 209. J.M. Encinar, J.F. Gonza lez, J.M. Encinar, J.L. Canito, E. Sabio, M. Chaco n, J. Anal. Appl. Pyrolysis J.F. Gonza 67 (2003) 165. lez, A. Ramiro, C.M. Gonza lez, J. Gan n, J.M. Encinar, E. Sabio, J. Rubiales, a J.F. Gonza Ind. Eng. Chem. Res. 44 (2005) 3003. lez, J.M. Encinar, J.L. Canito, J.J. Rodr guez, J. Anal. Appl. Pyrolysis 5859 J.F. Gonza (2001) 667. C. Valenzuela, A. Bernalte, Bol. Geol. Minero 96 (1985) 58. nchez, J. Anal. Appl. Pyrolysis 3 (1981) 161. G. Simmons, M.J. Sa n, A. Bernalte, A. Ramiro, J.F. Gonza lez, Biomass Bioenergy J.M. Encinar, F.J. Beltra 11 (1996) 397. n, A. Ramiro, J.F. Gonza lez, Fuel Process. Technol. 55 (1998) J.M. Encinar, F.J. Beltra 219. P.T. Williams, S. Besler, Fuel 72 (1993) 151. M.J. Antal Jr., G. Varhegyi, Ind. Eng. Chem. Res. 34 (1995) 703. F. Shazadeh, in: M.L. Wolfrom, R.S. Tipson (Eds.), Advances in Carbohydrate Chemistry, Academic Press, New York, 1968, p. 419. F. Shazadeh, J. Anal. Appl. Pyrolysis 3 (1982) 283. H. Reidelbach, M. Summereld, Papers of The American Chemical Society Division Fuel Chemistry 20, 1975, 161. E.M. Sunberg, W.A. Peters, J.B. Howard, Ind. Eng. Chem. Process Des. Dev. 17 (1978) 37. L.H. Chem, C.Y. Wen, Papers of The American Chemical Society Division Fuel Chemistry, 24, 1979, 141. M.L. Boroson, J.B. Howard, J.P. Longwel, W.A. Peter, AIChE J. 35 (1989) 120. T.R. Nunn, J.B. Howard, J.P. Longwel, W.A. Peters, Ind. Eng. Chem. Process Des. Dev. 24 (1985) 836. M.M. Ekwenchi, B.E. Araka, K.L. Ekpenyoung, Ind. Eng. Chem. Res. 27 (1988) 2169. R. Bilbao, J. Aranzo, M.L. Salvador, Ind. Eng. Chem. Res. 34 (1995) 786.

0.37 24.95

medium-low heating power (0.3710.97 MJ kg1 of raw material). On the other hand, the highest heating value of the obtained solids remains almost constant, because the prot in xed carbon resists the loss of volatile, so that, both contributions compensate in the total HHV. Taking these factors into account, the most appropriate operating temperatures would probably lie between 700 and

Fig. 8. Arrhenius plot for H2, CO, CH4 and CO2 formation in pyrolysis of Jerusalem artichoke waste (N2 ow rate: 150 mL min1; particle size: 0.631 mm; initial sample weight: 5 g).

[28] [29]

300

J.M. Encinar et al. / J. Anal. Appl. Pyrolysis 85 (2009) 294300 n, J.F. Gonza lez, M.J. Moreno, J. Chem. Technol. Biotechnol. [33] J.M. Encinar, F.J. Beltra 70 (1997) 400. [34] D.A. Tillman, 3rd ed., KirkOthemer Encyclopedia of Chemical Technology, vol.11, Wiley, New York, 1980.

[30] J.L. Figuereido, C. Valenzuela, A. Bernalte, J.M. Encinar, Fuel 68 (1989) 1012. [31] M.R. Hajaligol, J.B. Howard, J.P. Longwel, W.A. Peters, Ind. Eng. Chem. Process Des. Dev. 21 (1982) 457. [32] W.A. Bilbao, A. Millera, J. Aranzo, Anidad XLVI 422 (1989) 275.