MATHEMATICAL MODELING OF HIGH-TEMPERATURE GASIFICATION E. S. Golovina, R. A. Kalinenko, A. A. Levitskii, Yu. A. Mirokhin, L. S. Polak, and O. S.

Yusim

COKE

UDC 519.2+518.5:662.749.2:542.993

Development work presently is under way in the Soviet Union and abroad on high-temperature plasma-chemical processes for the gasification of solid fuel with the goal of producing synthesis gas and gaseous power-generating fuel. Some work of this kind has already reached the level of industrial introduction [i]. For this reason, the mathematical modeling of such processes with consideration for hydrodynamics, heat transfer, and kinetics is of considerable importance. This paper presents the results of calculations of the process of high-temperature gasification of coke using a model proposed previously [2]. We examine a version of the process in which a finely divided fuel at a specified temperature (~300 K) is introduced into a stream of oxidant (steam or a steam-oxygen mixture) heated to high temperatures (22000 K). This fuel is then heated, and when a specified temperature is reached it begins to react with the oxidant. A heterogeneous interaction of coke with steam and oxygen can be described in terms of the following overall reactions:
h1

C f + H20 --,- CO + H 2,
h.

(1) (2) (3)

(a)

Cf + C0 2 ---; 2C0,
ha

Cf -I- 0 2 ~ CO 2.
CO --' H~O ---> CO. + lq,~,
h. h4

CO., + H., --; C0 6- H.,0.

(5)

The specifics of the two-phase reactant systems in question is that reactions (1)-(2) occurring in them are strongly endothermic, while reaction (3) is exothermic. For this reason, processes of a change in temperature as a result of the thermal effects of reactions (i)-(3) are superposed on the physical processes of heating of the coke particles by the hot gas flow. This in turn affects the rates of these reactions. One of the goals of computational studies using the effect of the processes of physical and chemical in the case where only endothermic reactions (i) and gate of endothermic and exothermic reactions (i)-(3) in the system. a model is to elucidate the nature of kinetics on the indices of the process (2) (steam gasification) and the aggre(steam-oxygen gasification) take place

The initial velocity of the gaseous-oxidant flow was i0 m/sec, and that of the solid particles was 1 m/sec. In the calculations we varied the following: the initial oxidant temperature T~, the molar ratio G of oxidant to coke, the mass ratio of steam to oxygen in the steam-oxygen mixture, and the size of the coke particles. We determined the changes along the length of the envelope flame in the temperatures and velocities of the gas and coke particles, in the composition of the gasification products, in the rates of reaction (i)-(5), and in the "underfiring" ~ (the ratio of the current mass flow of coke to the initial value). In most of the calculations we assumed that the thermal effects of endothermic reactions (1)-(2) affect only the temperature of a particle. In some calculations specified in Moscow. Translated from Fizika Goreniya i Vzryva, Vol. 25, No. 6, pp. 50-56, NovemberDecember, 1989. Original article submitted April 27, 1988; revision submitted February 20, 1989,

0010-5082/89/2506-0703512.50

9 1990 Plenum Publishing Corporation

703

molel(litersec) I

j/%

u, T,K

.~-~!

10_4!
70-5

i'a

"'

//

Fig. i. Change in Tg (i), T (2), and the reaction rates w I (3), w 2 (4~, w~ (5), ws (6), vg (7), and Vp (8), calculation 1 over the length of the reactor. the text, we varied the fraction 7 of the heat of reaction (3) liberated in the solid phase. The rate constants of reactions (i)-(5) used in the calculations are presented in Table i. The reactivity of cokes of different origin differs significantly; their kinetic rate constants also differ. To determine the effect of the rate constants of a specific reaction on the parameters of the envelope flame, we performed the calculation while varying the values of k I and k 3 (see Table i). Most of the calculations were made by using the values of k@ and k@. A characteristic feature of the process of steam gasification of coke is a monotonic change in temperatures and velocities of particles and gas over the length of the envelope flame (see Fig. i and Table 2). These quantities change most intensively in the initial zone of the envelope flame at a length s < 0.6 m. The maximum values of the particle temperatures T~_ ax are reached at s = 0.1-0.3 m. They depend on both the preheating of the gas T~ and the ~atio G of oxidant to fuel. For example, at G = 0.67, as the initial gas temperature increases from 2000 to 3000 K the value of T~pax increases from 1115 to 1460 K, and for T~ = 3000 K and G = 0.67-3.33 T~pax = 1460-1720 K. The particle temperature increases as a result of heating by the hot gas only up until the start of endothermic reactions (1)-(2). Then Tp decreases as a result of heat absorption by endothermic reactions (see Table 2, calculations i, 4, 8-11). This fact should be underscored: after the commencement of endothermic reactions the particle temperature does not increase even in cases where Tg is greater than Tp by i000 K at the start of the reactions (calculation ii). The rate w~ of reaction (i) has a maximum in the region of the largest values of Tp. The maximum value for the rate w 2 of reaction (2) is observed for large values of s in the reaction zone with an elevated CO 2 concentration. The values of w I exceed wz by approximately two orders of magnitude (see Fig. i). At the root of the envelope flame the rate w 4 of the forward gas-phase reaction is significantly higher than the rate of the reverse reaction ws. Equalization of w4 and ws, i.e., thermodynamic equilibration, is observed only when s = i0 m. In the case of gasification of coke with a stemm-oxygen mixture, we see a sharp increase in the particle temperature at the root of the envelope flame, where the exothermic oxidation reaction (3) proceeds vigorously (Fig. 2). At a length of 0.06 m (over a time of 2.2 10 -2 sec), a particle is heated from 300 to i000 K, and the rate of reaction (3) assumes its maximum value. Oxygen is completely spent at s < 0.i m. The maximum value of

704

TABLE i. Values of Rate Constants Used in the Calculations for Reactions (1)-(5)
fl

Rate constants

ho

E,

Values of k for T-(K)

~OI,)

kJ/mole 87,9 180,0 180,0 t70,4 90,0 83,5 12,6 48,2 3,47.t0 -~ t,6.10 -~ 0,8. lO-t 3,7.t0 -~ 1,7 6,6. i0 -3 615 423 i.2.1(! -2 2.0.!0-~ O.t 22 t

Literature cited
$ [3] [3] N1 [5] [51 [0t

13,2 3,6.i0 a k~ t,8.I05 7.t06 3-10 ~ i,5. I0 ~ k~ 2,8.103

t,4. iOa

6,0.I0-~
1.4 0.7 500 370
1.0

k~

n.p3
10:; 2,9. tt):~

i,3. !t~':~ 7,7.i0:

*The dimension of the rate constants kl, k2, and k 3 is m/sec, and that of k4 and k s is m3/(kmole-sec). % Calculated from the value of k, and the equilibrium constant of reactions (4) and (5), k = 1.6945 + 1855.6/T. According to the data of E. S. Golovina and colleagues. TABLE 2. Changes in the Quantities Tg (K), Tp (K), and Upon Steam Gasification of Coke Over the Length of the Reactor (Calculations Using the Values of k? and k@)
m uc
"~ 0

t=O,11~

l=o,3ti1

l~i,OIi2

o.;, % Tg Tp
i

Tg Tp

fi

Tg

Tp

2 3 4 5 7 8 9 I0
ti

2000 2000 2000 2500 2500 2500 2500 2000 3000 3000

0,76 0,67 0.67 0.67 0167 0167 210 3.3 0,67 3,3

0 20 30 20 30 0 O0 0

14101060 ,99 t270 1i15 14701437 ,8111420[1250 147011540 ,72ii46011310 172511290 ,991t5i51t200 t900 1494 .761i760ti410 /t965 t6'10 ,65 1860 i495 2050 t420 ,961t8801t410 2300 15'15 ,95122001t530 2030 1460 ,94 i750ti380 2750 t720 ,89 2620 i700

0,97 0,77 0.67 0~91 0170 0160 0185 0179 0,84 0,66

i140 1320 1385 1300 i565 i690 i645 2050 i450 2430

1050 ii80 i235 iiSO i3i5 1395 1310 1470 1250 i630

0,9i 0,7i 0,63 0,82 0,62 0,52 0,68

I 965: 945 0,82 [1115 107010.62

ttt85

tIo3o i00510,70 li225 ii6010,49 li345 124510,39 Ii270 i16510,44 0,541t86o t44010,2S 0,7t lit05 i070 0,59 0,34 -- 0,0~*

113010155

*The value of ~ is 0.04 at a length of 3 m. Tmax p in this zone of the envelope flame significantly exceeds (by 80-850 K) the temperature of the gas flow. The value of ~p ~max is determined mainly by the 02 concentration in the mixture, i.e., by the exothermic effect of reaction (3). For example, for T~ = 2000 K and a 10% oxygen content in the mixture, T~ ax = 1560 K (T~ = 1470 K), and for a 30% 02 content T~ ax = 2350 K (Tg = 1500 K) (see Fig~ 2). Such an ~xcess of the temperature of a carbon particle over the gas temperature during gasification in oxygen-containing mixtures has been observed in experimental work [7] and theoretical work [8]. The absolute values of T max depend on the particle radius: under identical conditions (T~ = 2000 K, G = 0.67, k@, kl) ~ , as the particle radius decreases from 3 x i0-" to 10 -5 m, ~max -p increases from 219'0 to 2580 K for a 30% oxygen content (by weight) in the original steam-oxygen mixture and from 1470 to 1690 K for a 10% oxygen concentration. The value of T~pax depends on the assumed values of the rate constants For T~ = 2000 K, G = 0.67, R = 10 -4 m, k@, and a 30% oxygen content in the ture,gT~ ax has values of 2350 K (k~), 2240 K (k~), and 1660 K (k~). Thus, creases with decreasing activation energy and decreasing absolute value of stant of reaction (3). of reaction (3). steam--oxygen mixthe value dethe rate con-

It seemed relevant to assess how some basic parameters of the envelope flame such as

705

i_
ca 70 o

%
sel

/
.,~
4-I

,
~ ~.~

~/ t0_,/
I

12! ~

.
\r

I\
\

i0-~
-

.'~" '61
r l ll~ "1 \

9
I X
8-

fo.s

Ill \

~f~
Io-~ Ic~ ' f I / I.Ji
10"5 10 !

76-

~'--.~ \
~

'

0,06' 0~064 O,OS6' 0~072 O,OfS ~,m

Fig. 2. Change over length of reactor in T~ (I) Tp (2), w I (3), w 2 (4), w~ (5), w4 (6), w5 (7)7 [O2i (8), Vg (9), and Vp (i0), calculation 3. T~gax, T~ ax, and underfiring would change if were evolved in the gas phase. Calculations heat y in reaction (3) that goes to heating max decreases from 1 to 0.3, the value of Tp part of the heat of heterogeneous reaction (3) were carried out by varying the fraction of of a particle: 7 = i, 0.7, 0~ and 0.3. As naturally decreases, while the values of Tg and

underfiring in the initial reaction zone (s < i) increase (Table 3). When ~ ~ 1 m, underfiring is approximately the same for all ~. Thus, the specific system in question is not very sensitive to the value of y, since homogeneous reactions (4) and (5) that occur in it are practically thermoneutral, and the additional heat liberated in the gas phase is reconsumed to heat particles. The iiberation of heat at the root of the envelope flame as exothermic reaction (3) proceeds and the significant resultant heating of particles significantly influence the rates of reactions (i), (2), (4), and (5) and the hydrodynamics of the process (the particle and gas velocities). The maximum values of w I and w 2 are observed at the T~pax attained in the coke-combustion zone (see Fig. 2). The absolute values of w I and w 2 during coke gasification by a steam-oxygen mixture exceed by orders of magnitude the values of the same rates in the absence of oxygen. During steam-oxygen gasification, as during steam gasification, the rate w~ of the forward reaction at the root of the envelope flame exceeds by 1.5-2 orders of magnitude the rate w s of the reverse reaction, and when ~ = i0 m w 4 = w 5. 9 The gas-flow velocity Vg at the root of the envelope flame decreases monotonically, and then increases sharply in the coke-combustion zone (see Fig. 2) as a result of the rise in temperature and the increase in the volume of the reaction products due to the intensive course of gasification reactions (1)-(3). The particle velocity Vp increases monotonically. The absolute values Vg and Vp for s = i0 m are approximately twice as high in this case as in the absence of oxygen. This is explained by the higher gas temperature at the outlet and the relatively large increase in the volume of reaction products. The nature of the change in the reaction rates also determines the amount of underfiring. As the 02 concentration increases from 0 to 30%, the underfiring at T~ = 2500 K and s = i m decreases from 0.82 to 0.52. Here most of the conversion of carbonaceous matter occurs in the combustion zone in oxygen (see Table 2, calculations 3-7). Increasing G also leads to an increase in fuel conversion (calculations 4, 8, and 9). Underfiring also decreases with increasing T~ (calculations i, 4, and I0). We see from the data in Fig. 3 that the same de-

706

TABLE 3. D e p e n d e n c e firing on 7
Tg ,K I4

of

Tmax _g , Tmax ~p , and Underl,N 0, i 0,3 1,0

1,0 0,7 0,5 0,3

t510 t930 2t90 2450

I .

2340 2040 1840 t6t0

0.72 0.74 0,78 0,83

0,67 0.68 0,71 0,74

0.63 0.6i 0.63 0,64

f2 ~,0

-~

-3

-2

-7

Fig. 3. Change over length of reactor in underfiring in calculations 2 (solid circles), 5 (open boxes), and i0 (open triangles). grees of carbon conversion can be obtained by reducing the initial temperature of the steamoxygen mixture from 3000 to 2000 K but raising the oxygen content from 0 to 30%. This combination of conditions leads to an identical particle-temperature distribution over the length of the envelope flame (see Table 2). The data obtained in the calculation make possible an evaluation of the relations between the kinetic constants k i and the mass-transfer coefficients ~i = Di/2Rp Nudif, where D i is the diffusion coefficient of the i-th component and Nudi f is the Nusselt diffusion number. According to [9], the following regimes of reactions (i)-(3) were determined from the relations: the kinetic regime for ~i/ki > 9, the transitional regime for 9 > ~i/ki > 0.i, and the diffusional regime for ~i/ki < 0.1. For the values of k~ used in the calculations, reaction (i) proceeds in the kinetic regime in all cases examined, but in the calculation with k~ the transitional regime for this reaction occurs when Tp > 1800 K. These regimes are realized in the system only when there are additions of 30% oxygen to the narrow zone of the solution where reaction (3) proceeds vigorously. For reaction !2~ the transitional regime is observed when Tp > 1800 K, Rp = 10 -4 m, and Tp > 1670 K if Rp i0 -s m, which values are realized in the coke-combustion zone. For reaction (3) the transitional regimes obtain when:
T

R m p'

<t150 < 1325 <930 <1860

t0 -~ t0-~
10 -4

ka ~.a
kb

10-~

k~

The diffusional regimes for this reaction occur when Tp > 1800 K (Rp = i0 -4 m, k~) and Tp > 1600 K (Rp = 10 -4 m, k~).

3 i0 -s m,

The following patterns can be traced in the change in composition of the gasification products. For a constant G = 0.67 and T~ = 2000-3000 K, the H20 content in the products decreases, CO and H20 increases, and when Z ~ 5 C02 decreases (Table 4, calculations i, 4, i0).
707

TABLE 4. Change in Composition of Reaction Products (vol. %) Over Length

/=o,5m l=l,O m
tt: I{20

1=5 m
Ha HI:O

l=iO
He

~.r~ = 0 -.o ;O aa ~"

H~_O[COz

CO

(:o~

CO

co~

go

H=O

COz

CO

tie

1 2 3

I; 7 IO i1

83.0 2.0 6.0 9.0 74.0 4 0 5O .01 5,7 2611 i81244,0 8,0 40,O 4.3 37 ,O 18.7 35,0 6.4 63.6 / 3,4 13,t 19.9 50.7 5.7 50,81 4:4 22,5 22.2 42,7 6,1 4"2 31 316 [32.4121.7135,51 5,0 35 ~2 2.6 4t .6120,3129,8J 3,7 74.7 117 It0 .Oil3.5J66.4J 3.i 81161 1.3 7,3 9,8 74.7 2 4 48,2 / 3,2 21,1127,5 38,7 4,9 174.2l 112 [tl ,0~13,5166,91 2,1

,915,146,013,01 7,5 33.5 25 .0 23,0!24,3 13,7 26,2 35:8 36 ,3122.3j17 .Sill ,3t36, t[ 34,8 "14,6126.0 27.8 t2 4]!7,4 42,4 23 ,8127.3j20.7127,4-d ,2J 14.9 33 ,4t2610J16.1] 8,4 36,9 3815 42 ,4124.0J12 8J 6.3t45,7J 3511 ;t118,314O.Ol 7,3 19,01 33,6 ,013 852.0 5.9t15,2 26,9 2~ ,016:9 f 8,9J28AI46.0 t2,0 13 ,4 17,6 49,9 4,518,1 27,3

16.0 713 [3,3 !0.9 L1.7 [0,9 8,2 I2.t i719 916

15.2 17.8 14,4 2712 2tlt 37.3 t3.9 1817 28.6 44.7 9.0 38.3 6.5 47.2 8.5 2t.2 6,5 t6.2 29.6 48.8

40.0 4t,0 37,3 46.5 10,7 41.6 38.0 38,t 29.3 33,0

*The numbers of the calculations coincide with those of of Table 2. The CO 2 concentration in the products is quite high: it increases with decreasing temperature in the envelope-flame zone, since the rate of the CO 2 reduction reaction decreases. For the same reasons the ratio CO/CO2 decreases from 6.6 to 3.0 (~ = 0.5 m) as T$ decreases from 3000 to 2000 K. At 5-10 m this ratio decreases to 1.2-3 (see Table 4). The increase in CO 2 content with decreasing temperature is explained by the decrease in the rate of reaction (2) and by the shift in the equilibrium of reactions (4) and (5) toward CO= formation. The H2/CO ratio in the products ranges from 1.3 to 2.5; it decreases somewhat with increasing T~ and increases with the length of the envelope flame. The calculated patterns of the change in the CO/CO= ratio in the gasification products of coke agree with the experimental values for high-temperature gasification of slags from coal hydrogenation [I0]: CO/CO= = 6 when G = 1.35 and an average-mass temperature of approximately 4000 K. During high-temperature coal gasification, the CO/CO 2 ratio in the products increases from 3-4 at an average temperature of 1300 K in the reaction zone for a reaction time of 1.4 sec to approximately 20 at 1800 K for a reaction time of 0.17 sec [ii]. The calculated H=/CO ratios also are close to the experimental values [i0]. When oxygen is introduced into the reaction mixture, the H=O and CO z concentrations decrease, and the CO concentration increases (see Table 4, calculations 4-7). The H= concentrations either change slightly or decrease. The decrease in CO= concentration with increasing oxygen content in the original mixture is explained by the fact that higher temperatures develop in such mixtures and reaction (2) proceeds more vigorously. The results of the calculation largely hinge on the assumed values of the constants characterizing the physical and chemical mechanism of the process. In this paper we have examined the effect on the calculated results of rate constants and the assumed mechanism of heat liberation in an exothermic reaction. For complex systems one possible method of evaluating the representativeness of the calculations is to compare the calculated and experimental data. Studies in this area have demonstrated satisfactory agreement of the data obtained [i0, ii]. Mathematical analysis of the process of coke gasification by steam and a steam--oxygen mixture has made it possible to determine the dependence of the basic indices of the process (carbon and steam conversion, product composition) on the initial parameters: the initial temperatures, supply rates of particles and gas, the ratio of coke to steam-oxygen mixture, particle size, and kinetic rate constants. We know that an accurate physical and chemical picture of gasification cannot be constructed without taking into account the mutual influence of chemical kinetics and phenomena of heat and mass transfer. Since the experimental elucidation of the relation among phenomena of chemical and physical kinetics in such systems is complex and not always within reach, using mathematical modeling for these purposes is a convenient method of solving the problem.

708

LITERATURE CITED i. 2. 3. 4. 5. 6. 7. 8. 9. i0. 11. H. Herlits and S. Santen, Chemia Stosowana, 28, 3, 49-56 (1984). E. S. Golovina, R. A. Kalinenko, A. A. Levitskii; et al., Fizo Goreniya Vzryva, 24, 5 (1988). E. S. Purtova, Author's Abstract of a Dissertation for Candidate of Technical Sciences [in Russian], Moscow D. I. Mendeleev Chemical Engineering Institute, Moscow (1982). V. I. Babii and Yu. F. Kuvaev, Combustion of Coal Dust and the Calculation of a CoalDust Jet [in Russian], Energoatomizdat, Moscow (1986). T. V. Vilenskii and D. M. Khzmaly@n, Dynamics of the Combustion of Pulverized Fuel (Computer Studies) [in Russian], Energiya, Moscow (1978). V. Biba, T. Macak, E. Kloss, et al., Ind. Eng. Chem. Process Des. Dev., 17, i, 92-98 (1978). B. C. Young, D. P. McCollor, B. G. Weber, et a l . , Ref. Zh. Khim., 19 (1987). S. N. Veselov, L. A. Zaklyazmenskii, and Yu. E. Markachev, Fiz. Goreniya Vzryva, 22, 3, 38-44 (1986). Z. F. Chukhanov, Coke-Gasification Processes and Problems of Underground Gasification of Fuels [in Russian], Publishing House Academy of Sciences, USSR, Moscow (1957). V. K. Krukovskii, E. A. Kolobova, V. V. Lebedev, et al., Tr. IGI, Moscow (1980). V. K. Krukovskii and E. A. Kolobova, Tr. IGI, Moscow (1981).

MECHANISM AND KINETICS OF THE THERMAL DECOMPOSITION OF COMPOSITE SYSTEMS BASED ON AMMONIUM PERCHLORATE V. N. Orlov, O. P. Korobeinichev, and N. N. Maksimov UDC 536.46

For the understanding of the processes taking place during the combustion of condensed systems and a mathematical description of the reaction kinetics in the surface layer of the condensed phase (c-phase), the investigation of the thermal decomposition of these systems plays a major role. The knowledge of the kinetic parameters for the thermal decomposition of the c-system makes it possible to proceed with a calculation of the combustion rate. Thus, with this in mind, in [i] for composite systems only the kinetic parameters of solidphase processes were used, however the computed combustion rate values were found to be in good agreement with the experimentally measured values. Yet, the experimental thermal decomposition data do not always correlate with the results obtained during combustion [2]. In the opinion of the authors of [2], the lack of correlation between the combustion tests and the thermal decomposition of the corresponding systems is related to the fact that in the thermal decomposition experiments it was not possible to create pressure and temperature conditions, this would be close to those realized in the combustion wave. The measurement of the thermal decomposition rate at such high temperatures requires the application of quick-response methods for the recording of parameters, describing the process rate. However, the use of quick-response methods only partially reduces the difficulties in the investigation of high-temperature kinetics of the thermal decomposition of condensed systems, since in carrying out of isothermal measurements the thermal inertia of the heater and the sample lead to a significant transformation of the material even prior to the emergence of the steady temperature regime. The indicated considerations explain the fact that the experimental thermal decomposition data for composite systems based on ammonium perchlorate (APC) and the APC itself, were obtained at temperatures, that are lower than the characteristic temperatures of the c-phase reacting layer. The upper bounds of the temperature intervals, in which the thermal decomposition of APC and its mixtures with polymers were investigated, were 450 ~ [3] and 400~ [4] respectively. The experimental thermal decomposition data [i, 4-7] for composite systems based on APC are inconsistent and are characterized by a scatter of the effective activation

Cheboksary, Novosibirsk. Translated from Fizika Goreniya i Vzryva, Vol. 25, No. 5, pp. 57-64, November-December, 1989. Original article submitted April i, 1988; revision submitted November 14, 1988. 0010-5082/89/2506-0709512.50 9 1990 Plenum Publishing Corporation 709