Short

Communications

Coal

gasification

by microwave

plasma

in water

vapour

Djamal

Djebabra,

Odile

Dessaux

and

Pierre

Goudmand
des Sciences et Techniques

Laboratoire de PhysicoChimie de IEnergstique et des Plasmas, Universitb de Lille, Flandres-Artois 59655 Villeneuve d*Ascq cedex, France (Received 9 July 1990; revised 24 April 1991)

The influence of several parameters on the H, and CO yields from gasification of a coal (Blanzy) by microwave plasma in water vapour, in a static system, is discussed. The yields of H, and CO significantly increase for low coal weights placed in the discharge illustrating that the gasification occurs on the surface of the coal layer. The time necessary for complete gasification and the gasification yields are measured for several initial weights of coal. The relative yields of H, and CO depend on the initial water vapour pressure and are independent of coal granulometry. The reactivity of a coal which was pre-reacted in the discharge is similar to that of an original coal, so a possible recycling of the solid can be envisaged.
(Keywords: coal; gasification; microwave techniques)

A microwave plasma in water vapour creates radicals or ions in thermodynamical non-equilibrium, which react with coal so that the activation energy of C + H,O + H, + CO, is the reaction: greatly lowered. In a static system, previous studies, were essentially concerned with the effect of the type of coal on the gasification yield in the presence of different plasma gases (Ar+H,O, Ar). The main reaction products were H,, CO, CO,, CH, and C,H, with H, and CO being the most important. The highest yields were obtained for lignite and kerogen (33.5 and 31.8 wt%, respectively). In the present work, only the H, and CO yields are studied. EXPERIMENTAL A known weight of coal, m,, is placed in a quartz tube so that all the coal powder is in the discharge zone. In a vacuum (~0.10 hPa), a water vapour pressure, P,, is introduced in the reactor. The discharge was then produced over z min. After the discharge, the pressure in the reactor is P. The reaction products are then trapped at liquid nitrogen temperature; the measured pressure is P. Helium is added to the products which are not condensed at liquid nitrogen temperature (HZ and CO) up to a pressure of 1200 hPa. The H, and CO are quantitatively analysed by gas chromatography (g.c.)3 with a molecular sieve column. The discharge tube which contains the coal is weighed before and after reaction to determine the loss in weight of coal during the reaction, m.
001&2361/91/121473~3 0 1991 Butterworth-Heinemann

STUDY CONDITIONS AND PARAMETERS ILLUSTRATING THE EXPERIMENTAL RESULTS The conditions which affect the H, and CO yields are: weight of coal which is placed in the discharge zone, m,; discharge time, r; initial water vapour pressure, P,; granulometry, d; incident microwave power, w; the gas surrounding the coal in the discharge, and the type of carbonaceous material used. In this study, we have used the coal Blanzy, the analysis of which is given in Table I. The incident microwave power is kept constant (100 W). Three parameters illustrate the evolution from the gasification reaction: the number of H, and CO moles: nH2 and nco; the pressure, P=P,,+P,-o which is proportional to n = nH2+ nc,; the ratio P/n must satisfy the equation for an ideal gas; the loss in weight during the reaction process, m.
Table 1

The experimental results are given as the arithmetic mean of results of three to five experiments4. To study the effect of one parameter, the values of all other parameters are kept constant: 5 = 6 min, P, = 21.33 hPa and 0.063 <d(mm) < 0.100.

RESULTS
EfSecr of initial weight of coal

The effect of m, on H, and CO yields and on the loss in weight m is studied for m, values between 1 mg and 120 mg. The results are given in Table 2. The consistent relatively low maximal value of H, and CO yields which is observed for m, > 80 mg can be explained in two ways: the products of the reaction are not eliminated; and by the depletion of reactive species coming from the discharge in the outer layer of the coal deposition.

Analyses of coal Blanzy-original Elemental analysis (%) Original coal

and pre-reacted Proximate analysis (wt%) of original coal

Pre-reacted coal
78.6 3.5

H N 0 (by diff.) S Ash

79.2 3.3

1.4 4.0 1.4 9.0

1.6 3.5 1.6 11.2

Moisture 1.91 Volatile matter (dry basis) 9.12 Ash (dry basis) 11.25 Fixed C (dry basis) 79.63

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Short Communications
E#ect qf discharge time The effect of t is studied for mO= 1, 5, 10 and 60 mg. Among the parameters described, the total pressure P can be continuously measured. It is the sum of the partial pressures of all gaseous products and of the pressure of nondecomposed water vapour. A plot of P as a function of t (Figure I) allows the determination of the time T* from which the gasification can be considered as complete. It is defined as the time from which the variation of P, during 10 min, is equal to 1.33 hPa. The study of the influence of the discharge time, for T values <T*, on the H, and CO yields (Table 3) leads to the following: for a given value of m, (Figure I) the rate of gasification decreases with time and the initial rate of gasification is higher with higher m, values. The rate of gasification by defect is defined by: R = am where z = 104/91m,. (The ratio of 100/91 is from the presence of 9% ash in the coal studied.) With our operating conditions, for mO= 1 mg, gasification can be considered as complete after 15minandR=71~10%.Form0=60mg, the values of T* and R are, respectively, 50 min and 8.5+ 1%. Whatever the m, and T values, H, is mainly produced rather than CO. For a given value of m,, conthe ratio nH2/nC0 is approximately stant when T varies and increases when m, decreases. Indeed, the spatial extent of the plasma is more important for low values of m,, so the dissociation rate of the water vapour and H, concentration increases. Effect of the values qf the initial water vapour pressure and qf granulometry The effect of the P, value is studied for three P, values: 6.67, 13.33 and 21.33 hPa, with the last value being the highest under our experimental conditions. The value of m, is kept constant at 5 mg. Tab/e 4 shows that nH2, n,, (to a smaller extent) and m increase with P,. This observation can be explained by an increase in the H and OH concentrations in the discharge zone. Four ranges of granulometry have been used: d(mm) < 0.063, 0.063 < d(mm)<0.100,0.250<d(mm)<0.500and 0.500<d(mm) ~0.800. The m, value is 10 mg. The results show an independence of the rate of gasification in H, and CO with granulometry, giving evidence that the process is little influenced by diffusion into the coal particles. Complementary experiments Three types of complementary experiments are carried out: the first is to specify the influence of an argon adjunction to coal; the second is a previous thermal processing in order to look at the possible influence of the dehydration of coal; and the third is the study of coal which was pre-reacted in the discharge. Iizfluence of an urgon adjunction to coal in a microwave discharge In this study, the m, value is 60 mg. For a discharge time of 6 min, the pressure remains constant after discharge in coal without plasma gas. With an Ar pressure of 49.33 hPa and 5 = 20 min, an increase in total pressure of 2.66 hPa is observed. The analysis of reaction products by g.c. shows the formation of a small amount of CO (nco= 1.3 x 10e5 mol); H, is not detected. For lower values of Ar pressure and T, no increase in total pressure is observed. These results contradict those of Fu et al.*. Perhaps, this discrepancy originates from, on the one hand, the difference between the amounts of volatile material in various coals, and on the other, from the Ar pressure used. Previous thermal processing qf coal. The granulometry which is used is 0.250<d(mm)<0.500 and m,=5 and 10 mg. The coal is heated at 373 K for 1 h before reacting in the microwave discharge. The results obtained do not show that thermal processing under these conditions influences the H, and CO yields. Study, of the reactivity of a coal which was pre-reucted in the dischurge. The values of the pressure P and of the weight m of gasified coal obtained from the same initial weight of coal, either which has

T (min)

Figure 1 Plot of P versus z. Values of M, (mg): A, 1; B, 5; C, 10; D, 60

Table 2

Effect of initial weight of coal m,

hI (x 105) (mol)

nco
2.6 4.7 5.5 11.1 13.2 14.6 15.0 15.2

(x 105) (mol)

P (hPa) 13 18 22 37 42 47 49 49

(W
0.39 0.57

1 5 10 30 60 80 100 120

4.3 6.1 6.5 13.1 14.8 16.6 16.9 16.5

I .o
1.83 2.5 3.4 3.3 4.0

Table 3

Effect of discharge time T

nI12

mo
(mg) 1

nco

r (min) 6 10 15 3 6 10 20 30 2 6 20 40 6 17 30 50

(x 105) (mol) 4.3 6.9 7.4 3.5 6.1 8.0 12.4 13.1 5.1 6.5 14.2 16.9 14.8 19.9 25.8 28.9

(x IO') (mol)

p (hPa) 13 18 20 12 18 21 35 37 15 22 42 52 42 60 74 85

(w)
0.39 0.56 0.65 0.54 0.57 0.83 1.2 1.4 0.71 1.o

2.6 4.4 4.6 3.3 4.7 5.4 9.4 10.5 3.8 5.5 12.2 14.4 13.2 18.3 23.5 26.2

10

1.95
2.5 2.5 3.35 3.8 4.7

60

Table 4 2Pa) 6.67 13.33 21.33

Etfect of initial pressure of water vapour P,

4,

nco
3.8 4.5 4.7

(x 105) (mol) 3.6 4.9 6.1

( x 10) (mol)

P (hPa) 11.5 15.5 18.0

WI (m8) 0.44 0.51 0.57

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Short Communications previously reacted (p.r.) or which has not previously reacted (n.p.r.) in the discharge, are compared. The m, value is 52 mg. After reaction, a manual separation of the ashes is carried out. The coal which is recovered (37.50 mg) reacts in the discharge for 6 min. The values of PL and %. are, respectively, 38 + 1 hPa and 2.9f0.2 mg. These values are compared with those (Ph,+r, = 39 + 2 hPa and mn.p.r. = 3.6kO.3 mg) obtained from 37.5 mg of coal which was not previously reacted. There is no considerable decrease in the Hz and CO yields of the pre-reacted coal. The analysis of the coal shows (Table 1) that the composition of this coal is not modified in comparison with that of the coal which was not previously reacted. This result confirms the hypothesis of the gasification of the surface of the coal layer. Two observations provide evidence that H, coming from the reaction coal + water vapour plasma essentially originates from the decomposition of the water vapour: the first is that the amount of H, is the same in the recuperated coal as in the coal which has not reacted; and the second is by comparison of the values of H, yield of coal gasification by plasma of water vapour and the initial H, content of the coal. REFERENCES

1 Vastola, F. J., Walker, P. L. and Wightman,

2 J. P. Carbon 1963,1, 11; Chrm. Eng. 1962. 44, 2 Fu, Y. C. and Blaustein, B. D. Chem. Ind. 1967, 1257; Fuel 1968, 47, 463; Ind. Eng.
Chem. Proc. Design Dewlop. 1969, 8, 257;

Fu, Y. C.. Blaustein, B. D. and Wender, I. Chem. Eng. Progr. Svmp. Ser. 1971, 67.
47 3

Djebabra, D. PhD Thesis University of Lille, 1990 Lacroix, Y. Analyse chimique. InterprCtation des rksultats par le calcul statistique, Masson, Paris, 1973

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