ISSN 1990 7931, Russian Journal of Physical Chemistry B, 2009, Vol. 3, No. 5, pp. 802806. Pleiades Publishing, Ltd.

., 2009. Original Russian Text A.S. Rozenberg, L.A. Grigoryan, I.Yu. Gudkova, D.B. Lempert, G.B. Manelis, 2009, published in Khimicheskaya Fizika, 2009, Vol. 28, No. 10, pp. 5257.

COMBUSTION, EXPLOSION, AND SHOCK WAVES

Mass Transfer of Zinc Containing Compounds during Filtration Combustion in the Counterflow Regime: 3. Mass Transfer at a Low Content of the Zinc Containing Component in the Initial Stock
A. S. Rozenberg, L. A. Grigoryan, I. Yu. Gudkova, D. B. Lempert, and G. B. Manelis
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia e mail: lempert@icp.ac.ru
Received February 21, 2008

AbstractThe regularities of filtration combustion and of the mass transfer of zinc containing products from model stock compositions with a low content of the zinc containing component were experimentally studied over a range of governing parameters. The parameters of the combustion of stock samples, degree of extrac tion of zinc containing products into sublimate from the condensed sample, and chemical form of the zinc containing compounds released were determined. The results obtained were discussed. DOI: 10.1134/S1990793109050157

In the previous work [1], we studied the filtration combustion in the regime of counterflow of air and a solid phase containing zinc oxide, coal, and an inert component and determined the condition of mass transfer of zinc containing products for model com positions of the stock with relatively high zinc oxide content (1020%). It was demonstrated [14] that variation of governing parameters of the combustion process, such as the fuel content in the stock (10 40%) and the oxidizer flow rate (0.012.0 m3/(m2 s)), makes it possible to change the temperature profile of the combustion wave so as to ensure the predominance of oxidation or reduction zones. For the systems stud ied in [1], the maximum combustion temperature ranged within 6901300C, increasing with both the oxidizer flow rate and fuel content. The degree of extraction of ZnO into sublimate from the stock increased with the temperature in the combustion wave, reaching ~34%. It was assumed that [1] the mass transfer of ZnO from the stock during combustion was likely to be associated with the transport of zinc vapor (product of ZnO reduction by carbon monoxide) in the direction of the gas flow into the cooled region where it was oxi dized by gaseous oxygen containing combustion products (for example, CO2). That the degree of extraction of volatile zinc containing products into sublimate was low was explained by a too short time of their residence in the combustion zone. In light of these findings, one can expect that a decrease in the content of the zinc containing component in the stock may result in an increase in the degree of zinc containing products into sublimate.

The aim of the present work was to experimentally study the characteristics of the combustion process and of the mass transfer of metal containing products in the regime of filtration combustion of various model compositions at a low content of zinc in the initial stock. METHODS Characteristics of the samples. We studied several stock samples with a low content of zinc. The compo sitions of the zinc containing components are pre sented in Table 1. Mixture CZn 3 approximately imi tates the composition of natural pyrite ores. Samples CZn 2.4, CZn 5, and CZn 5.5 contain metallic zinc; in particular, sample CZn 5.5 contained galvanized roof ing iron in the form of chips 1.32.5 mm in diameter and 0.5 mm in thickness. When preparing the zinc containing components of the stock, we used granulated zinc oxide (CZn 3) and zinc dust (CZn 2.4 and CZn 5), which were pre pared as follows. Fine powders of coal and bentonite clay were mixed with analytical grade zinc oxide and analytical grade Fe2O3 to prepare CZn 3 mixture and zinc dust to prepare CZn 2.4 and CZn 5. Next, distilled water was added to obtain a slurry, which was filled into dents in a Plexiglas, after which pieces of mixture were pressed out of the dents and rolled into small balls, which were dried at 150C. The mixture granules thus prepared were 24 mm is size. The fuel was AG 3 coal, the ash content of which was measured to be 10%. The inert components (CIn) were red and chamotte brick and quartz chips. All the

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MASS TRANSFER OF ZINC CONTAINING COMPOUNDS Table 1. Composition of the initial zinc containing components of the stock Initial mixture CZn 3 CZn 2.4 CZn 5 CZn 5.5 Content of Zn in galvanized iron, % 5.5 Content, wt % zinc dust 2.4 5 ZnO 3 bentonite clay 55 85.6 83 Fe2O3 30 coal 12 12 12

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solid components were in the form of particles with a size of 1.3 to 2.5 mm. The stock contained the following ingredients: CZn 3fuel (coal)CIn (mixture with zinc oxide); CZn 2.4fuel(coal)CIn and CZn 5fuel(coal) CIn (mixtures with zinc dust); CZn 5.5fuel(coal)CIn (mixture with galvanized iron). The content of the zinc containing component in the first three mixtures ranged within 1.52.0% Zn and within 24% Zn for the fourth composition. Organization of the combustion process. As in [1], the compositions were burned in a vertical quartz reac tor, which was described in [3]. The oxidizer flow rate, measured with a rotameter, was varied from 0.01 to 1.8 m3/(m2 s). The combustion process was organized as follows. After a steady oxidizer flow was established, an exter nal heater with an external (with respect to the reac tor) temperature control was switched on to initiate the ignitor (a mixture of sawdust and coal). The ignitor was placed ahead of the stock in the direction of the flow. Its initiation occurred 57 min after the heater temperature reached 550600C. After ignition of the stock, the external heater was switched off, and com bustion occurred in the self sustained mode. The burning velocity U (mm/min) was calculated by the formula U = h m / ( m ing ) , where hm is the height at which the thermocouple was positioned above the ignitor, m is the time it took to reach the maximum temperature Tmax in the combus tion zone, and ing is the ignition delay time. Chemical analysis of the samples. To determine how zinc is distributed over the filtration combustion zones in the reactor, a quantitative chemical analysis of the initial stock and of various fractions of the com bustion products at different heights along the stock bed (fractions 1 3) and sublimated products (0) deposited on the internal walls of the reactor was per formed as described in [1]. The probes were decom posed with hydrochloric acid. The zinc content was determined by titration with the use of complexone III [5, 6]. In parallel, the content of metallic zinc in the presence of zinc oxide was measured as described in
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[1]. The degree of extraction nZnO of zinc containing products after combustion was calculated by the for mula nZnO = (MZnO, i MZnO)/MZnO, i 100%, where MZnO is the total content of ZnO in the stock after combustion and MZnO, i is the initial content of ZnO in the stock. Microscopic observations were performed in reflected and transmitted light on an MBS 1 instru ment at magnifications within 1656. Mass spectrometric measurements were per formed on an MX 1307 instrument. EXPERIMENTAL RESULTS AND DISCUSSION Specifics of the combustion of the CZn 3 coal CInair system (system S1). Racall that the CZnO 3 mixture imitates the composition of pyrite ores. We used small stock samples and, correspondingly, a small reactor, 10 mm in diameter, without an external ther mal reflective shield. The ignitor began to burn at 500C, 56 min after the heater was switched on. The combustion occurred rapidly, featuring a bright and wide (3040 mm) luminescent zone; the temperature in the combustion zone was ~1300. The burning velocity and temperature in the combustion zone increased with the oxidizer flow rate: at a fixed fuel content (40% carbon) and oxidizer flow rate of v = 0.22 m3/(m2 s), the burning velocity was 4.4 mm/min and Tmax = 1200, whereas at v = 0.48 m3/(m2 s), Tmax > 1300 and U = 14.0 mm/min. Analysis of the combustion products of system S1. During stock combustion, a white deposit was formed at the reactor walls opposite and above the stock bed (yellowish when collected). The granules themselves were also coated with a white deposit. Around the thermocouple, the stock material was sintered because of a high temperature in the reaction zone. Microscopic observations of the burnt stock revealed fritted dark grey inclusions, probably pro duced by high temperatures in the combustion wave. A chemical analysis of the burnt stock showed that the degree of extraction of zinc containing products into sublimate was rather high. It increased with the oxidizer flow rate. For example, at a fixed fuel content (40% carbon) and an oxidizer flow rate of v =
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804 Table 2. System CZn 2.4coalCInair Run no. 1 2 3 4 5 6 7 8 v, m3/(m2 s) 0.26 0.38 0.54 0.38 0.26 0.21 0.22 0.22 m gr , % 60 60 80 80 80 60 60 60
0

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mC , % 40 40 20 20 20 20 20 20

Tmax, 1200 >1300 >1300 >1300 1350 1110 1130

m, % 46.3 48 9.6 30 31 17 28 29

U, mm/min 5 17.5 16.7 12 5.3 8.3 6

Note: Tmax is the maximum temperature in the combustion zone, m0 is the initial content of the components, and m is the mass loss of the stock after combustion; the subscripts gr and C stand for granules and coal.

0.22 m3/(m2 s), nZnO= 38%, changing to nZnO = 79% at v = 0.48 m3/(m2 s). No metallic zinc was observed in the combustion products. Specifics of the burning of the CZn 2.4coalCIn air system (system S2). This system was studied to explore the possibility of formation of metallic zinc in the combustion products. The ignitor began to burn at about 500, 56 min after the switch on of the exter nal heater. Moisture appeared at the reactor walls. The combustion zone was bright and wide (~30 mm), about half the stock bed height. Combustion occurred at high temperatures, 11101350. The results are summarized in Table 2. As the oxidizer flow rate increases, so depends on the temperature in the combustion zone and the burn ing rate (at a given content of coal in the stock). The figure shows the dependence of the velocity of com bustion wave propagation on the oxidizer flow rate at
U, mm/min 18 16 14 12 10 8 6 4 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 v, m3/(m2 s)

Effect of oxidizer flow rate on the combustion wave veloc ity at a constant carbon content (20%) in the stock for the CZn 2.4coalCInair system.

fixed carbon content (20%) for system S2. As can be seen, the burning velocity increases linearly with the oxidizer flow rate. Analysis of the combustion products of system S2. During stock combustion, a white yellowish deposit was formed at the reactor walls opposite the stock bed and grey brown one (composed of resin and soot). Granules of burnt stock were also covered with a white deposit of zinc oxide. Microscopic observations revealed the presence of fritted inclusions with metal lic luster. No Zn containing products were revealed in the burnt stock. This suggests that the degree of sublima tion is 100%. No metallic zinc in the combustion products outside the stock was detected. Specifics of the burning of the CZn 5coal CIn(quartz)air system (system S3). A reactor with a diameter of 20 mm was used. The ignitor began to burn at about 550 5 min after the switch on of external heating; the external heater was switched off immediately after that. The combustion zone was bright and wide (~30 mm). The results are listed in Table 3. Note that run 4 was performed under condi tions of an additional heating of the reactor wall oppo site the stock bed, with the heater being switched on at the moment of ignition. The temperature of external heating was close to the ignitor temperature (600 700). The temperature and burning velocity increased with the coal content in the stock (at a fixed oxidizer flow rate) (run nos. 1 and 3 in Table 3). The maximum temperature in the combustion zone and burning velocity increased with the oxidizer flow rate at a given content of coal (run nos. 2 and 3). Analysis of the combustion products of system S3. Before the ignitor began to burn, white smoke was observed in the reactor and moisture droplets on its walls. During stock combustion, a white yellowish deposit was formed at the reactor walls opposite. Igni tion occurred at 550, 56 min after the switch on of the external heater. The burnt stock was separated into
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MASS TRANSFER OF ZINC CONTAINING COMPOUNDS Table 3. System CZnO 5coalCIn(quartz)air Run no. 1 2 3 4 v, m3/(m2 s) 0.22 0.43 0.22 0.06 m gr , % 60 60 60 40
0

805

mC , % 20 10 10 60

Tmax, 1133 1230 1020 935

m, % 6 16.7 23 51

U, mm/min 10 9 5.6 1.4

Chemical analysis, % 1.9 1.9 1.5 2.4

nZnO, %* 36.6 41.5 58.5 35.7

Notes: For notations, see Table 2. * With consideration given to 10% ash content.

Table 4. System CZn 5.5coalCInair Run no. 1 2 3 4 5 6 7 8 9 10 11 14 v, m3/(m2 s) 0.22 0.22 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.16 0.06 m gr , % 60 60 60 30 40 40 40 40 40 60 60 60
0

mC , % 20 20 20 60 60 60 60 60 60 40 40 40

Tmax, >1300 >1300 890 1000 895 1160 >1200 855 630 790 940 980

m, % 14 15.7 15 59 42 45 40 53 48 38 36 37.6

Chemical analysis results ZnO, % U, mm/min 0 1 2 6.7 7.5 1.5 1.4 1.7 1.4 0.7 0.7 1.9 4.9 2.7 6.8 6.8 6.8 6.8 6.8 6.8 6.8 6.8 6.8 6.8 6.8 6.8 40.2 0.04 0 4.83 3.18

nZnO, %* 0.06 3.75 5.84

Notes: For notations, see Table 2; for runs 10 and 14, 1 and 2 denote Zn coated Fe plates and the rest of the stock, respectively. * With consideration given to 10% ash content.

fractions, which was subjected to chemical analysis. Note that, in the burnt stock, the shape of the initial zinc containing component remained unchanged, a feature that made it possible to isolate it mechanically. For example, an analysis of granules isolated from the burnt stock after run 1 (Table 3) showed that they contained no zinc, whereas in the rest of the burnt stock the ZnO content was 1.86%. An analysis of gran ules isolated from the burnt stock after run 2 showed that they contained 1.9% ZnO, markedly below its ini tial content (5%). Thus, chemical analysis suggests that the degree of sublimation was 100% in run 1 and 63% in run 2. In run 3, the entire burnt stock was found to con tain 1.5% ZnO. The transport of zinc containing products from the stock into sublimate was 58% at a low oxidizer filtration (v = 0.22 m3/(m2 s)) and a car bon content of 10%. Specifics of the burning of the CZn 5.5coalCIn air system (system S4). This system was studied to explore the possibility of mass transfer of metallic zinc from galvanized iron. The experiments were per
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formed at low oxidizer flow rates; the results are sum marized in Table 4. Note that, in run nos. 14, the inert component was red brick (20% in runs 13 and 10 in run 4). In runs 514, no inert component was added. In runs 68, 10, 11, and 14, the reactor wall were additionally heated to decrease heat losses from the stock (the temperature of the external heater of the stock was close to that of the ignitor heater, 700). As can be seen, the maximum temperature in the combustion zone increases with the air flow rate. For example, at a fixed content of fuel in the stock (20% carbon), an increase in the oxidizer flow rate from 0.06 to 0.22 m3/(m2 s) results in increases in Tmax from 890 to 1300 and in U from 1.5 to 7.5 mm/min. Analysis of the combustion products of system S4. For this system, the mole ratio in runs 410 was [C]/[O2] 1.8. Mass spectrometric analysis of the gaseous combustion products sampled at the reactor outlet (run 9) revealed 12.4% CO2, 3.05% CO, and 83.56% N2, with the [CO2]/[CO] ratio being 4.07. Under the specified conditions, no oxygen in the com bustion products was detected; i.e., it is completely
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consumed in the stock bed. The degree of extraction of zinc containing products into sublimate attains 93 99%; it increases with decreasing oxidizer flow rate and increasing fuel content (runs 1 and 5). The combustion products of run 11 were examined in more detail. The burnt stock was divided in three fractions: 1, 2, and 3. Three subfractions of burnt FeZn plates were isolated from each fraction. Each probe was analyzed for zinc content. In addition, the content of zinc in the remaining stock after sampling of each fraction and in the wash off from the reactor walls was determined. This made it possible to minimize zinc losses during analysis and draw up the balance of zinc content in the burnt stock. The degree of sublimation obtained with consideration given to the data collected for all fractions and subfractions of the stock burning products suggests that the zinc content remaining in the stock fractions after burning increases in the direction of oxidizer flow. This observation is indicative of mass transfer of ZnO from the stock bed. To conclude, we would like to emphasize that, under conditions of inverse combustion wave and tem peratures of 8001300, when the process is con trolled by the reaction C + CO2 = 2CO, the zone after the temperature maximum is reductive. In this zone, at temperatures above 800, ZnO can be reduced to metallic zinc due to the reaction ZnO(s) + CO(g) = Zn(g) + O2(g). Metallic zinc vapor can be carried by the flow in the direction of unreacted stock, where it is oxidized by oxygen containing combustion products (O2) in the cool zone. When studying the extraction of zinc containing combustion products into sublimate, one should take into account two important factors considered in [1]. The first is associated with the kinetics of the processes occurring during filtration combustion, being charac terized by the ratio of the times of residence in the heating (reduction) zone h (h is proportional to the reciprocal of the normalized rate of the process) and the characteristic time of mass transfer mt (mt is the reciprocal of the normalized sublimation rate). At h mt, zinc vapor formed can be practically com pletely transported into the cool zone, and, therefore, the degree of enrichment in zinc will increase with the degree of sublimation. This conclusion follows from the observation that the degree of extraction of zinc containing products increases with decreasing oxi dizer flow rate. At h mt, the mass transfer of zinc vapor formed has no time to occur completely, and, therefore, the degree of sublimation will be lower. Another important factor is a high reactivity metallic zinc formedit is readily oxidized to oxide. Addi tional studies in this direction are needed to elucidate the remaining issues. CONCLUSIONS (1) Filtration combustion and the mass transfer of zinc containing products under these conditions was

experimentally studied for model compositions with a low zinc content over a wide range of governing parameters of the combustion process, with the oxi dizer flow rate and carbon content ranging within 0.060.54 m3/(m2 s) and 1060%, respectively. (2) For the systems studied, the maximum temper ature in the combustion zone was as high as 630 1350, increasing with both the fuel content and oxi dizer flow rate. (3) The burning velocity of all the samples tested increased with the oxidizer flow rate (at a fixed fuel content) within the interval 0.717 mm/min. (4) At a low oxidizer flow rate (0.06 m3/(m2 s)) and a fuel to oxidizer mole ratio higher than 1.8, no oxy gen was detected in the combustion products at the reactor outlet, with the main oxygen containing com ponents being CO and CO2. (5) The ZnO content in the stock fractions was observed to change in the direction of oxidizer flow, a behavior indicative of the mass transfer of zinc con taining combustion products. The zinc contained in the initial granules was experimentally shown to subli mate from there during filtration combustion, almost completely at low oxidizer flow rates. At low zinc con tent, the degree of extraction of zinc containing com bustion products into sublimate depends on the oxi dizer flow rate and fuel content, attaining in some cases 100% at low oxidizer flow rate. ACKNOWLEDGMENTS The authors are grateful to A.F. Zholudev for per forming mass spectrometric analysis of gaseous com bustion products. This work was supported by the Russian Foundation for Basic Research (project no. 06 08 00453 a) and the Department of Chemistry and Materials Science of the Russian Academy of Sciences within the framework of the program Fundamentals of the Rational Use of Nat ural Technogenic Resources (project no. 6). REFERENCES
1. A. S. Rozenberg, L. A. Grigoryan, I. Yu. Gudkova, D. B. Lempert, and G. B. Manelis, Khim. Fiz. 28 (9), 62 (2009) [Russ. J. Phys. Chem. B 3 (5), 782 (2009)]. 2. A. S. Rozenberg, D. B. Lempert, L. A. Grigoryan, A. S. Medvedev, and G. B. Manelis, Dokl. Akad. Nauk 405, 493 (2005). 3. A. S. Rozenberg, L. A. Grigoryan, I. Yu. Gudkova, L. G. Zemlyakova, D. B. Lempert, A. S. Medvedev, and G. B. Manelis, Khim. Fiz. 25 (2), 50 (2006). 4. A. S. Rozenberg, L. A. Grigoryan, I. Yu. Gudkova, L. G. Zemlyakova, D. B. Lempert, A. S. Medvedev, and G. B. Manelis, Khim. Fiz. 25 (5), 39 (2006). 5. P. R. Prishibil, Complexones in Analytic Chemistry (Inostrannaya Literatura, Moscow, 1960) [in Russian]. 6. G. Schwarzenbach and H. Flashka, Complexometric Titration (Ferdinand Enke, Stuttgard, 1965; Nauka, Moscow, 1965).
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