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Fuel 116 (2014) 341–349

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Effects of an environmentally-friendly, inexpensive composite
iron–sodium catalyst on coal gasification
Rodolfo Monterroso a, Maohong Fan a,⇑, Fan Zhang a, Ying Gao a, Tiberiu Popa a, Morris D. Argyle b,
Brian Towler a, Qingyun Sun c
a
University of Wyoming, Department of Chemical and Petroleum Engineering, 1000 E. University Ave., Laramie, WY 82071, United States
b
Department of Chemical Engineering, Brigham Young University, 350 CB, Provo, UT 84602, United States
c
US–China Energy Center, West Virginia University, Morgantown, WV 26506, United States

h i g h l i g h t s g r a p h i c a l a b s t r a c t 

The effects of a composite catalyst on
coal gasification were evaluated. 
The use of the composite can improve
the yields of useful gases. 
The composite catalyst can combine
the advantages of its two component
catalysts.

a r t i c l e i n f o a b s t r a c t

Article history: The objective of this research is to study the effect of the composite catalyst, FeCO3–Na2CO3, on gasifica-
Received 23 May 2013 tion of a low-sulfur sub-bituminous Wyodak coal from the Powder River Basin (PRB) of Wyoming. The
Received in revised form 1 August 2013 catalytic effects of the composite catalysts were evaluated by comparing their effluent gas compositions
Accepted 2 August 2013
and carbon conversion kinetics to those achieved in the presence of either FeCO3 or Na2CO3 catalyst alone
Available online 20 August 2013
or without the presence of any catalyst. All of the evaluation work was conducted in a fixed bed gasifier at
atmospheric pressure. Compared to raw coal with no catalyst, the composite catalyst is efficient in
Keywords:
increasing the carbon conversion rate constant by as much as two times within the 700–800 °C range
Catalytic
Coal
due to its ability to reduce the activation energy of gasification by about 30–40%. Compared to pure
Gasification sodium and iron catalysts, the composite catalyst can increase the yields of desired products H2 and
CO at 800 °C by 15% and 40%, respectively. The composite catalyst can not only synergize the advantages,
but also overcome the challenges of pure iron or pure sodium based catalytic coal gasification processes.
Published by Elsevier Ltd.

1. Introduction integrated gasification combined cycle (IGCC) processes, coal gasi-
fication has recently received increased attention. Since the energy
Coal gasification has been commercially used for over 60 years needed to achieve gasification temperatures is obtained from exo-
in the production of fuels and chemicals [1]. Due to the reduced thermic combustion reactions prior to gasification, the rate at
environmental impacts and the high efficiency obtained from which the pre-gasification step and gasification occur need to be
increased in order to achieve lower operating temperatures to con-
⇑ Corresponding author. Tel.: +1 3077665633. sume less energy. Furthermore, there is a need to increase the ratio
E-mail address: mfan@uwyo.edu (M. Fan). of gases that preserve the highest heat of combustion, e.g., carbon

0016-2361/$ - see front matter Published by Elsevier Ltd.
http://dx.doi.org/10.1016/j.fuel.2013.08.003

posite catalysts contain anions including NO 3 and SO4 .1. 2. The removal of this material is complicated because it combines with 2. catalyst and coal mixture and the composite catalyst and coal mix- ifier [2]. to obtain the following weight ratios of catalyst to dry ash free pensive also exhibit great potential in improving the kinetics of (DAF) basis coal: 0%-Fe + 4%-Na. A 50 mg sample of coal and catalyst. [11] also studied the effect of Fe.9]. Na2CO3 10% (w/w) was reduced. Ca(OH)2 and their combinations. increasing conversion rates. They also observed that the extent of this effect is larger with In this study. Gaseous product compositions . Sigma-Aldrich) with Na2CO3 (99. especially when the chosen catalyst is Na2CO3) on coal gasification. US Weld- conversion of the solid char [8]. These findings were observed more prominently through mixtures were prepared by adding the appropriate amounts of the 600–800 °C temperature range [14]. FeCO3 was found to be 2. FMC Inc. [2] found increases in the 3%-Fe + 1%-Na. Recently. dark colored containers in order to prevent structural oxidized. Ultimate and proximate analyses Co. pure Na2CO3. Cypres and at 250 °C to form a brown powder. Catalytic gasification tests sticky ash and turns into a highly viscous paste [1]. The proximate analyses coking coal from Kuznetsk in Russia. the over- all efficiency of the process is hindered and less desirable in terms The fixed-bed reactor used for pyrolysis and gasification exper- of cost-effectiveness and applicability. Na2CO3. Otto and Shelef showed that.. formed using sodium and iron composite catalysts.200 °C and held at this temperature for another 10 minutes for tion rate of a lignite coal and found considerable improvements isothermal equilibration.2. on a ceramic capped alumina sample holder. including plugging. Liquid tar from coal gasification produces a number of ad. availability. and D4239 methods.1. The pure iron catalyst and coal carbon conversion rates during both pyrolysis and gasification mixture was produced by loading the appropriate amount of FeCO3 steps and a decrease in the activation energy when Na2CO3 was with coal to obtain the desired weight of iron in the mixture.3.8 wt%. moderate in this study are described elsewhere [2]. Nordgreen et al. potentially harmful to gasifier and undesired for production of ing the gasification temperature. Their interests were concentrated on the mate analyses were performed on PRB chars obtained at 700 °C.) in a 10% (w/w) Additionally. and favorable Catalytic coal gasification is one of the main techniques used to results have been achieved [4. one problem that has been encoun.342 R. Catalysts ferent iron compounds have been tested as catalysts for coal gasi- fication with encouraging results. The ulti- coal from Pennsylvania. the iron based catalyst demonstrated its strong abil.2. in many 2. [14].4. Douchanov and ing) at 100 ml/min to a maximum pyrolysis temperature of Angelova [7] studied the effect of 13 metallic salts on the gasifica.1. and Li on different types of activated carbon and other The results of proximate and ultimate analyses of the coal used coal chars using non-coking coal from Uonuki in Japan. Thermo-gravimetric analysis [9]. As a result. SDT Q600 apparatus.16].). 2%-Fe + 2%-Na. washed with ity in significantly alleviating the tar issue often met in gasification. and environmental friendliness [1–4. Coal analysis cases.12–14]. D5016.15]. the gasification [1. Different catalysts have been studied in the past demonstrating such results [1–8]. Zn. pure FeCO3.6.10].8 wt%.7. sub-bituminous coal from the Powder River Basin (PRB) of Wyo- Wang et al. Catalytic coal gasification has 2.2. Moreover. Additionally. the tars were initially in air tight. For example. FeCO3. produced by the addition of iron as a catalyst. and calcined as reported by Popa et al. Monterroso et al. the life span of the corrosive and environmentally acceptable carbonates (FeCO3 and gasifiers can be increased. sodium carbonate and distilled water. the devolatilization rate during pyrolysis of the coal and moisture content changes. The catalyst and coal [14].2. [3. Conversely. non-corrosive. 1%-Fe + 3%-Na. Kasaoka et al. This material (FeCO3) was Soudan–Moinet. such as low price. availability. The resulting FeCO3 precipitate was filtered. 1. Na2CO3 or FeCO3–Na2CO3 to PRB pulverized (200 mesh) coal Sodium based catalysts which are widely available and inex. then used as a catalyst. when comparing these rates to those obtained with non-catalytic coal gasification. / Fuel 116 (2014) 341–349 monoxide (CO) and hydrogen (H2) vs. verse effects throughout the process. After pyro. iments is described elsewhere [2]. energy of the gasification of a subbituminous Wyodak coal [3]. the reported com- 2 improve the gasification process due to its efficiency. Accordingly.. the retention of many of these salts in the char diminishes ad. this reduction results from improved mass transport or dif- fusion affected by the porosity of the catalytically gasified carbons 2. mixing it and subsequently adding water to create a paste which tered with the use of Na2CO3 is the formation of more non-volatile was dried at 90 °C for 72 h prior to gasification. solution. Dif. FMC Inc. Catalysts have the potential to achieve both of these iron based catalysts. Experiments shown substantial decreases in the activation energy associated with the process [1.2. and 4%-Fe + 0%-Na.6. and the composition of the tar remained unchanged solutions were prepared with Na2CO3 (99. Ni. Thermo-gravimetric analyses (TGA) of the Wyodak low-sulfur Li2CO3. Catalyst preparation a promising catalyst for considerable reduction of the activation Aqueous solutions were prepared by mixing FeSO47H2O (99%. played by the inlet gas or mixture of gases [11]. These researchers observed that hematite.2. The pure sodium tars that condense at lower temperatures downstream of the gas. tures were prepared using the same procedure. has a high impact on tar breakdown 2. Iron based catalysts have demonstrated many benefits. this research was designed to enhancing the production of the desired gases by changing the evaluate the effect of new composite catalysts consisting of less selectivity in the process [4. which are and low cost [1–4].1.8. loaded lysis. Catalyst loading on coal [14]. 2. was heated at verse impacts on the gasification operation and enhances the 20 °C/min in flowing Ar or N2 (Ultra High Purity (UHP).6]. carbon dioxide (CO2) and In order to overcome the shortcomings of individual sodium or water (H2O). a few gasification studies have been per- desired effects.1. A few previously studied coal gasification catalysts are K2CO3. catalysts have the capacity of lower. determined that while ferric oxide and ferrous screened on a 125 lm sieve to exclude larger particles and stored oxide did not possess any catalytic activity. dried at 92 °C. However. and strong coking Pittston were performed according to ASTM D5142 and D5016. for example.5]. and FeCO3–Na2CO3 were hematite (Fe2O3) than with magnetite (Fe3O4) or wüstite (FeO) loaded with coal for catalytic gasification. studied the synergistic effect of using Ca(OH)2 in char ming and catalyst samples were performed using a TA Instruments preparation for K2CO3 catalyzed coal gasification [7.2. properties of the non-carbonate ferrous catalyst and on the role 800 °C and 900 °C by ASTM D5373. Popa et al. Thus. and high-quality syngas.

In these figures. a 15% increase. At this temperature.0012 53.6 4%. Despite these differences. respectively.0004 and iron on these reactions is almost negligible [2–7]. consistent carried out using approximately 5. All the tests were performed three times at the same con. has an inverse effect on the yield of H2 (see Fig.8 3%.1. again catalysts. / Fuel 116 (2014) 341–349 343 were measured by gas chromatography [2]. and coal mixture to 1. The reported data are the average values of these triplicate increased from 1. therefore. which were obtained from the TGA and ulti. The coal process. R.7 tained with the use of pure iron catalyst (0. the effect of higher loadings of iron and lower T(°C) 0 loadings of sodium was a decreased production of CO.4% increase in the production of CO compared to the one ob- 0. Effect of catalyst on pyrolysis catalysts per mole of carbon in the char.Fe+0%-Na composite catalyst.Fe+0% -Na -0. which leads to the decrease in hydrogen of carbon in the char. This is partially due to the presence of sodium Methane (CH4) was not studied in detail in this research because ions during gasification.2) as observed for ments due to the coal used and the gasification conditions chosen non-catalyzed and catalyzed coal gasification [3. The resulting chars were then gasified by introduc. Δg/Δ° C the reported molar yields of CO were almost identical for the three Mass fraction 1%. the mass fraction of iron was directly correlated to hydrogen tion of our laboratory).0 g DAF coal samples. Fig. For the com- 1 posite catalysts. On the other hand.Fe+1%-Na Fe + 1%-Na catalyst). catalysts is lower than that of the coal with the pure iron catalyst ification process. and 900 °C 3. step was obtained from H2O through the water-associated reac- Fe + 1%-Na catalyst was the most effective in increasing the rate tions. Mass balances were performed to obtain the cation temperature increases.0008 2%.25 mol H2/mol C with raw coal to 1.45 mol H2/mol C with 4%-Fe + 0%-Na had the least mass loss between about 500 and the 4%-Fe + 0%-Na catalyst and coal mixture. did at a given temperature. with the exception of the 3%-Fe + 1%-Na composite catalyst. and iron carbides and iron oxides become the pyrolysis up to the gasification test temperature and the amount only iron species present. The 750 °C. In these reactions.Fe+3%-Na 2%. This effect is apparently related to the higher rate of conversion of the 3%-Fe + 1%-Na mix- Fig. including the water gas shift (WGS) reaction. This fact has been studied in the past and can be related to the temperature dependence of the equilibrium constants of the water gas shift and the Boudouard reactions [3. The coals loaded with 4%-Fe + 0%-Na and the 2%-Fe + 2%. all of the coal samples reached 2%-Fe + 2%-Na and 1%-Fe + 3%-Na catalysts led to higher yields of approximately the same mass at temperatures higher than hydrogen than the 3%-Fe + 1%-Na and the pure sodium catalysts 750 °C. 1.Fe+2% -Na 0. The experiments were and oxygen with increasing pyrolysis temperatures. the production ditions. As the gasifi- for the research.2. Figs. Fig.14]. the H2/CO ratio increases as well. as indicated in Fig. 3. the catalytic effect of both sodium 0. Monterroso et al.Fe+1% -Na catalysts.83 mol CO/mol C with the 3%- 3%. tion. were initially pyrolized by heating at 20 °C/min to the desired gas- ification temperatures of 700 °C. (4%-Fe + 0%-Na). carbon in the char) as a function of iron loading and pyrolysis tem- respectively. a 16% increase. 750 °C.54 mol CO/mol C with 1%. Higher loadings of iron generally produce higher yields of H2.32 mol H2/mol C with the 2%-Fe + 2%-Na cat- alyst and coal mixture. TGA data for pyrolysis of coals loaded with different amount of composite the iron loading increases. However.7].9 -0. 2 shows the hydrogen molar yield (normalized per mole of ing H2O and N2 with flow rates of 0. at 800 °C the use of composite catalysts led to a 4%. The gasification experiments were performed at perature. also affects the gasification of the PRB coal [4]. loaded with the 4%-Fe + 0%-Na catalyst produced the highest Na catalysts displayed the lowest pyrolysis rates. which can lower H2 [2–5].2. with 2%. CO2 and H2 is reported to be the major driving force for hydrogen production [5]. which with the formation of more refractory chars. 800 °C.1. the 0 200 400 600 800 1000 catalytic effect of iron on the reactions involved in the production T(°C) of CO has been shown to be less extensive [4. the composition of CO in the mixture yields of CO and H2 based on the remaining mass of char after starts to increase. mate analyses. as one component of the 0. production [3]. Factors affecting yields of CO. which . Furthermore. 2. 850 °C. as Fig. 3 and 4 show the molar yields of CO and CO2 normalized ples generated from the coal loaded with various amounts of the per mole of carbon in the gasified char. the situation is complex for the coal gasifica- tion with FeCO3–Na2CO3 composite catalysts.1 ml/min. the equilibrium favors the production of 0. Results and discussion with the exception of the 3%-Fe + 1%-Na catalyst and coal mixture.4]. while from 1. For example at 800 °C. which was also ob- Wyoming Powder River (PBR) loaded with different composite served during pyrolysis (see the previous discussion associated catalysts. 1). The pyrolysis results of the coal with the 0%-Fe + 4%-Na with Fig. Sodium carbonate.Fe+3% -Na -0. 1 shows that the 3%.4. However.5. which produced the least amount of hydrogen among the studied 3. Metallic iron in the ash layer 3.15 mol H2/mol C with the 0%-Fe + 4%-Na catalyst experiments. The hydrogen production at 800 °C increased Fe + 2%-Na lagging initially at temperatures below 375 °C. except at 0 200 400 600 800 1000 900 °C. The composition of the generated syngas is important since it is The production of hydrogen with the Fe2CO3–Na2CO3 composite not only one of the indicators of the overall performance of the gas.5 CO as the temperature increases [2. tion of CO and the CO/CO2 ratio increase as the temperature in- The carbon content generally increased at the expense of hydrogen creases.Fe+2%-Na the 4%-Fe + 0%Na catalyst and 0. but also affects the potential uses of the syngas. 1 shows the pyrolysis results of four Wyodak coals from ture compared to the other composite ones. In our previous study of pure iron catalyzed coal gasifica- ambient atmospheric pressure (approximately 75 kPa at the eleva. the produc- composite catalysts at different temperatures are listed in Table 1.5]. Table 2 shows of pyrolysis because it led to the highest mass loss during pyrolysis the moles of H2 per mole of C generated only from water. yields [3].04 g/min and 4. The ultimate analyses of the char sam. amount of hydrogen. Temperature of low (<1% of the gaseous product) yields obtained in all experi. Composition of the catalysts and pyrolysis temperature in flowing N2. Much of the hydrogen formed during the gasification catalyst was published elsewhere [2].

the overall yield of hydrogen with this catalyst is the lowest.12 81.40 0. the effect of sodium in the composite catalysts is not terms of efficiency and total yield in production of hydrogen when completely undesirable. Time production.33 0. when the reaction is com. (b) average molar yield of CO with error bars [numbers 1.47 0.33 0.27 1.1 a 1.55 T (°C) 1%-Fe + 3%-Na 2%-Fe + 2%-Na 3%-Fe + 1%-Na 4%-Fe + 0%-Na 3%-Fe+1%-Na 700 1. 5 shows the trend of H2 production as a function of time at rates than pure iron catalysts do.38 850 1. / Fuel 116 (2014) 341–349 Table 1 Ultimate analysis of the chars with composite catalysts.3 1.11 0. Sample ID Pyrolysis temperature Ash (wt%) C (wt%) H (wt%) N (wt%) S (wt%) 4%-Fe + 0%-Na 700 18.47 3%-Fe + 1%-Na 800 15. 3. loadings of Fe and 0.21 0.90 84. In this case.47 2%-Fe + 2%-Na 900 13.16 1. the 2%- observable value corresponds to the 0%-Fe + 4%-Na catalyst. this Fe + 2%-Na catalyst demonstrates considerable advantages.40 700 720 740 760 780 800 820 840 860 880 900 800 1.10 0.30 0.95 0.4 1.31 82.36 4%-Fe + 0%-Na 900 16. between the production rate of hydrogen and the overall yield is lysts and coal mixtures evaluated.15 0.21 1.51 4%-Fe + 0%-Na 800 16. 2 and Table 2. 3.25 1%-Fe + 3%-Na 800 13. an interesting balance different temperatures for the two pure and three composite cata. respectively].26 85.08 1.09 1. since at 900 °C (Fig.32 2%-Fe + 2%-Na 800 15. 3 and 4 in the Fe loading axis represent 1%- Fe + 3%-Na.09 1.09 1.30 1.2.2.38 3%-Fe + 1%-Na 900 13.73 3%-Fe + 1%-Na 700 16. 2.85 mol CO/mol C gasification temperatures [Numbers 1.83 0.29 1.97 0.14 0. duced yield of hydrogen compared to the other composite cata- plete. Therefore. 2%-Fe+2%-Na 0.08 0. the 3%-Fe + 1%-Na catalyst.344 R. discussed previously in association with Fig.39 1.94 1.57 81.78 83.33 T( °C) 900 1.62 1.18 1. lysts. 3%-Fe + 1%-Na.5 mo l H 2/mol C 1. the effect of composite catalysts is superior in Nonetheless.94 1.82 0. lysts. Molar yields of H2 per mole of carbon in the char vs.26 0. the overall pro.17 Fig.48 750 1.03 0. as it is an aid in accelerating hydrogen compared to pure iron or pure sodium catalysts.6 900 850 800 4 T( °C 3 ) 750 2 ing b 1.44 2%-Fe + 2%-Na 700 16. .52 84. and 3%-Fe + 1%-Na.79 82.32 1. since as the time proceeds.2 1. while being slower than the pure sodium catalyst only during duction of H2 is lower than that of the composite catalysts and a few stages of the reaction at different temperatures. Molar yield of CO per mole of carbon in the char vs.56 1. the results demonstrate again a re- ture increases.23 1.00 load 700 1 % Fe Fig. 2 and 3 in the Fe loading axis represent 1%-Fe + 3%-Na.05 0.07 1.19 0.79 80.75 82. Monterroso et al.93 0. and 4%-Fe + 0%-Na.13 1. 5c). respectively]. as it is only due to the initially increased reaction rate with pure sodium produces hydrogen at a faster rate than the other composite cata- catalyst loaded coals.67 1%-Fe + 3%-Na 900 13.00 1. different loadings of Fe and temperatures. 2%-Fe + 2%-Na. In the case of the pure iron catalyst. In general. 0. Although at 700 °C the highest obtained when using composite catalysts.22 1.91 0.09 81.19 79. 2.70 Table 2 1%-Fe+3-%Na Molar yield of H2 (H2/mol C in char) that originated from H2O.22 1.22 1. (a) average molar yield of CO. These catalysts lead to faster hydrogen generation Fig. 2%- is related to the decreased production of H2 with this catalyst as Fe + 2%-Na.12 1.23 1.44 0. This effect is more evident as the tempera.65 0.58 1%-Fe + 3%-Na 700 15.22 0.76 1.33 1.43 0.03 0.

This effect can be directly ex- 3.2 and gasification temperatures. especially of the 3%-Fe + 1%-Na catalyst during the layer. Effects of catalysts on carbon conversion kinetics ification. and 3%-Fe + 1%-Na. 6 shows the trend of CO production as a function of time at Raw coal 0%-Fe+4%-Na different temperatures for the tested catalyst and coal mixtures. R.50 b 1. 800 °C. 2%-Fe+2%-Na 3%-Fe+1%-Na tion of either the pure catalysts or the composite catalysts. the bon in raw coal is considerably slower than that of the catalyzed 0%-Fe + 4%-Na catalyst presents higher conversions rates at all coals.3.20 2%-Fe+2%-Na 3%-Fe+1%-Na 4%-Fe+0%-Na 0. which was different composite and pure catalysts. 0 0 50 100 150 200 tion of CO include the oxidation step of carbon through Na2O and Time (min) a subsequent reduction of CO2 by metallic sodium [6. as the gasification temperature increases. (a) average molar yield of CO2 (b) average molar yield of CO2 with error bars [numbers 1. 7b and c.3 3%-Fe+1%-Na 4%-Fe+0%-Na 0 0 40 80 120 160 200 Time (min) b 0.3 0. the catalytic effect disappears since iron carbides are in- gasification. The mechanisms through which Na2CO3 enhances the rate and the overall produc. use of the catalysts can reduce the gasification temperatures.40 Mol H2 /mol C 1%-Fe+3%-Na mol CO 2 /mol C 0. slower by creating mass transfer resistance [3. Monterroso et al. furthermore.4]. Effect of time on H2 production at (a) 700 °C.2 0. 7 shows the coal conversion plots at 700 °C. in which raw coal displays a higher slope during this portion.6 Raw coal 0%-Fe+4%-Na 1%-Fe+3%-Na 2%-Fe+2%-Na 0. as observed in Fig. Molar yield of CO2 per mole of carbon in the char vs. Conversion plained by the proposed iron-catalyzed coal gasification mecha- Fig.9 Mol H2 /mol C Fig.30 2%-Fe+2%-Na Raw coal 3%-Fe+1%-Na 0%-Fe+4%-Na 0.00 0 700 750 800 850 900 0 50 100 150 200 T(°C) Time (min) Fig.6 1%-Fe+3%-Na The rates and overall yields of CO increase with sodium concentra. The effect of the catalysts is particularly pronounced ert species and will only make the overall gasification process at the lower reaction temperatures. [18. temperature.21] who found that alkali phenolates and oxygen deficient alkali oxides were carbon oxidiz- ers. where the conversion of car. nevertheless. respectively].1. 700 °C. The composite catalysts show the previously . the improvement is hindered.17. and nism in which metallic iron in the form of c-Fe can be present. in which the enhanced carbon conversion rates for all of but has no catalytic effect due to its lack in mobility in the ash the catalysts. 0.20.6 1%-Fe+3%-Na 0.9 0. / Fuel 116 (2014) 341–349 345 a a 1. Saber and Falconer noticed that other carbon oxidizers could also exist Fig. different loadings of Fe c 1. 2%-Fe + 2%-Na. 5. Obviously. (b) 800 °C.3.9 0. 900 °C.18]. 0. if cementite (Fe3C) is still present at such tem- gasification process. while the primacy in terms of the overall efficiency was obtained with the pure sodium catalyst (0%-Fe + 4%-Na). and thus iron catalysts have less positive mance in terms of conversion rate compared to the raw coal at impact on CO production than sodium. These types of complexes might not exist when iron-based cat. 2 and 3 in the Fe loading axis represent 1%- Fe + 3%-Na. confirmed by Certofontain et al.3 production rates over the pure iron catalyst (4%-Fe + 0%-Na). and (c) 900 °C for during sodium-based catalytic coal gasification [19]. 4. especially in the later period of gas- 3.2 Mol H2 /mol C 0. The 4%-Fe + 0%-Na catalyst shows better perfor- alysts are being used. are evident relative to the uncatalyzed peratures.10 0. The 4%-Fe+0%-Na composite catalysts showed a notable advantage in terms of CO 0. Conversely.

4 2%-Fe+2%-Na 3%-Fe+1%-Na 4%-Fe+0%-Na 0 0. conversion appears to be fairly insensitive to the composition of the iron and present. Hematite and a-Fe.4 Raw coal Conversion (X) 0%-Fe+4%-Na 1%-Fe+3%-Na 0. / Fuel 116 (2014) 341–349 a 0.3.8 Mol CO/mol C 2%-Fe+2%-Na 3%-Fe+1%-Na 4%-Fe+0%-Na Conversion (X) 0.6 Raw coal 0. pure catalysts and raw temperature increases. at 800 °C.8 Mol CO/mol C 0.4 2%-Fe+2%-Na 0 50 100 150 200 1%-Fe+3%-Na Time (min) 4%-Fe+0%-Na 0.4 1%-Fe+3%-Na Conversion (X) 2%-Fe+2%-Na 3%-Fe+1%-Na 4%-Fe+0%-Na 0.3] when using different compositions of so- lished in a different study.8 c1 Mol CO/mol C 0.6 0. (b) 800 °C and (c) 900 °C. Current studies are being conducted to investigate this sodium catalysts for gasification at this lower temperature.6].2 Raw coal 0%-Fe+4%-Na 3%-Fe+1%-Na 0 0.2 3%-Fe+1%-Na Raw Coal 4%-Fe+0%-Na 0%-Fe+4%-Na 0.6 a1 Raw coal 0%-Fe+4%-Na 0. tained by Popa et al. At 800 °C and 900 °C. Shrinking core model gasification. has previously been described in the devolatilization rates ob- the carbon conversion is faster than those obtained with the other served during the pyrolysis stage shown in Fig. the effect of 3%. dium or iron as single catalysts. (b) 800 °C. so the claim.2 0 50 100 150 200 Time (min) b 1 0 0 150 300 450 600 Time (min) b1 0.8 0%-Fe+4%-Na 0. due to the presence of metallic sodium ions [4.3 0. 0 0 50 100 150 200 discussed trend. time for different composite catalysts.6 Raw Coal 0%-Fe+4%-Na 1%-Fe+3%-Na 0. 6.2 Fig. the effect of this catalyst is fairly coal at (a) 700 °C. Some results in terms of tar alle. two composite catalysts.45 1%-Fe+3%-Na 0.8 0. however with the reaction rate constants discussed next and the results ob- the data and analysis of the mitigation mechanism will be pub. [2. the conversion rate is bet- ter than even that of 0%-Fe + 4%-Na during the earlier period of 3. At 700 °C.4 1%-Fe+3%-Na 0 2%-Fe+2%-Na 0 50 100 150 200 3%-Fe+1%-Na 4%-Fe+0%-Na Time (min) 0. 1. similar to those of the other composite catalysts. Monterroso et al. It ishypothesized that this behavior is related to an The gasification kinetics were quantified in the 700–900 °C enhanced mobility of the catalytic iron species when sodium is temperature range.6 0.346 R.2. which play an important role during optimal Fe to Na ratio should be selected to achieve desired gas the latter stages of the gasification process [3]. Thus.6 2%-Fe+2%-Na 0. and at 900 °C. in which the 3%-Fe + 1%-Na catalyst demonstrates Time (min) a higher carbon conversion rate that is even more evident as the Fig. is considerably more pronounced.15 0.2 c 1 0 0 100 200 300 400 Time (min) 0. The shrinking core model was used to . 7. and (c) 900 °C for different composite and pure catalysts. could be activated yields or tar mitigation capability. Effect of time on CO production at (a) 700 °C. This is consistent viation capabilities by composite catalysts were observed. Further evidence of these effects Fe + 1%-Na catalyst. Conversion vs.

0020 0. 8a because This movement is assumed to occur uniformly. They are lower our previous finding that pure iron catalysts enhance the rate of than those with pure sodium catalysts in the temperature range the reaction only through a portion of the process as conversion of 700–850 °C. Tem.0014 0. According to the literature. At 800 °C. alyzed coal gasification when sodium is present in composite cat- alysts is reflected in the corresponding ksc values.0032 0. Therefore. the use of the exhibited by raw coal. Subsequently.0018 0. which is a confirmation of PRB coal) but also those with pure iron catalysts.0022 0. a reduction during the first stage of the reaction through which the shrinking of the char particle radius must take place as gasification advances. most of the lysts is trivial.0029 min1 obtained for raw coal).0057 0. layer of ash and catalyst. The kinetics improvement of iron is about 42% higher than that with the 4%-Fe + 0%-Na. the ksc value for the 4%-Fe + 0%-Na catalyst is only A decrease in the activation energies with the use of any of the 0.27].5 times for equation: this catalyst (0. Another possibility. The constant from 0. E1 was only applied to fit the data collected during the position of an intermediate carbon oxygen surface species. raw coal is superior to the gaseous products are formed. namely Na2O and Fe3O4. The in- and low mobility of some of the catalytic agents such as Fe0 [3]. The ever. while the catalyzed gasification.0009 750 0. R.0027 0. The improvement of the kinetics of iron cat.3. and con.0012 min1 with raw coal to 0.0052 0.0037 900 0. The rate constants increase as a result of the use of the com. At higher temperatures. the 2%-Fe + 2%-Na catalyst is not fully evident in Fig.3.0064 0.0047 0.0052 0.0049 0. metals based catalytic coal gasification mechanism is the decom- fore.0028 0.0072 0. For the coal gasification may be enhanced by its coexistence with sodium composite catalytic coal gasification. obtained with 3%-Fe + 1%-Na are always higher than those with ble 3. The reaction rate decreases when the pure-iron catalyst (4%-Fe + 0%-Na) (Fig. composition of reaction products including CO. to the interface of the shrinking. For example. diffusion resistances similar complexes at particular compositions of the catalysts. Activation energies 800 °C. core model is applicable. species such as Fe3O4 and due to the function of the latter in improving the mobility of iron. Na2CO3 are predominantly present on the carbon surface and thus This study is being conducted separately by the research group and influence the reaction between carbon and water vapor [3. T (°C) 0%-Fe + 4%-Na 1%-Fe + 3%-Na 2%-Fe + 2%-Na 3%-Fe + 1%-Na 4%-Fe + 0%-Na Raw coal 700 0.0029 850 0. 8c). such as the decrease of reactants near the iron fer from the metal oxide species. Fig. [18] stated that the rate determining step of the alkali not accurately represent the gasification kinetics [26. 8 shows the Arrhenius plots for the carbon conversions centrations of the catalytic species such as FeO and Na2O play accelerated by the composite catalysts. fontain et al. 0.0071 0. unre. the improvement is 1. the results will be published separately. the rates of reaction are considerably higher in the case dX  ¼ ksc ð1  XÞ2=3 ðE1Þ of the pure sodium catalyst and coal mixture (0%-Fe + 4%-Na) com- dt pared to those of raw coal. the rate determining step is the oxygen trans- end of the reaction. There.0058 0. while pure sodium based catalysts increase the reac. How- during the linear portion of the conversion vs. Certo- char particle become less available and shrinking core model can.27]. The for gasification products (CO and H2) are negligible [26. difference is about 30% at 900oC. Suzuki et al. Moreover. conversion reaction rate constants indicate that the 3%-Fe + 1%-Na the reaction moves from the surface into the particle through a catalyst is better than the 2%-Fe + 2%-Na and 1%-Fe + 3%-Na ones. the coal particle has a film boundary layer through was previously mentioned.0033 0. while the diffusivity rate constant through the possible formation of sodium ferrites (NaxFeyOz) or can be neglected. creased oxygen transfer in the case of Fe3O4 could be a result of and therefore it cannot be applied to the nonlinear part of the the enhanced mobility created by the presence of metallic sodium. at 3.0045 0. while that for the 3%-Fe + 1%-Na catalyst is studied catalysts was observed when compared to the result 0.0022 min1. At 700 °C. is that the catalytic effect of iron on which steam diffuses to the surface to react with carbon. and ksc is the the pure iron catalyst and coal mixture (4%-Fe + 0%-Na) are lower specific carbon conversion rate constant.0060 .0041 0.0015 800 0. The activation Table 3 Carbon conversion reaction rate constants (min1) obtained from the shrinking core model. sodium increases the The values of the reaction rate constant (ksc) derived from E1 gasification rate more significantly than ironbecause the ksc values under different catalytic gasification conditions are listed in Ta.0044 0. the difference between these two cata- since at this point of the catalytic gasification reaction. They do not necessarily change linearly with the catalysts are not only higher than those without catalysts (the raw concentrations of sodium and iron.0022 min1.4. In the synergy may exist in different ways.0032 0. whereas some of the reaction rates of where X is the carbon conversion fraction. perature.3. than those of raw coal. when iron and sodium are pres- The model assumes that the overall rate is essentially equal to ent together during gasification. Thus. a 100% improvement.0028 0. The rate constants achieved with all the composite posite catalysts. conversion. [4.83 times. The comparisons of carbon important roles at the beginning of gasification [6]. The superiority of the 3%-Fe + 1%-Na catalyst when compared to acted core that progresses toward the center of coal particle [26]. which is also being gasification nears completion at the core because active sites on investigated in the previously mentioned ongoing research.6] demonstrated that when using this type of shrinking core model does not account for conditions near the composite catalyst. / Fuel 116 (2014) 341–349 347 represent the coal gasification kinetics studied in this research. 4%-Fe + 0%-Na. Rate constants Based on the results shown in Table 3.0022 0.0044 min1.4].0049 0. which initial stages of the gasification process. an in- shrinking core model [22–25] is based upon the following crease of 1.0044 min1 vs. time curves. which analytically was refers to R6 for the case of the sodium catalyzed gasification.0046 0. but this relative difference decreases with temper- progresses. Monterroso et al. at 700 °C. 3. The composite catalysts reduce the activa- 3%-Fe + 1%-Na composite catalyst increased the conversion rate tion energy of carbon conversion by 30–40%. consequently an improvement in the reaction rates of R6 through R9 is expected. they may function synergistically the observed rate of reaction. as it first stage. ature. the rate constant with 2%-Fe + 2%-Na tion rate over the entire range. For example. t is time.

05 0. is defined as ksc ¼ AeEa=RT ðE2Þ Ni.75 Time (s) c c -4. mixture (a: CO. In this research. the activation 3.0024 Mol CH4 ln K -6 0. including composite ones. However.348 R.009 4%-Fe+0%-Na ln K 0. Ea3%-Fe+1%-Na = 53.85 0. Application of the shrinking core model to the yields of energies generally increased with increasing iron content and individual carbonaceous products decreasing sodium content.0008 -6. which was reduced to 52 kJ/mol with the use of the 2%-Fe + 2%-Na catalyst.3.75 CO2 experimental data 0.0 kJ/mol.006 -5. Analysis of this equation where Ni. Arrhenius plots: (a) 3 composite catalysts and raw coal. as follows: Ea0%-Fe+4%-Na = 42.t refers to the moles of carbonaceous gas. Xi (i = CO.15 Raw coal 1%-Fe+3%-Na 0.75 Shrinking core model for CH4 0 0 1000 2000 3000 4000 -7.95 1 1.05 0.0032 Raw coal 0%-Fe+4%-Na 4%-Fe+0%-Na -5.85 0. For the other catalysts.f refers the total moles of carbonaceous gas fects of the catalysts on the PRB coal gasification are positive at generated or the total moles of carbon converted to produce the . Monterroso et al.5 1/T×10-3(K-1) 0.95 1 1.5. the net ef. The Arrhenius equation is panded to also model the yield of each carbon-containing gas spe- cies as follows. at small decreases in the pre-exponential factor. 8.95 1 1.9 0. leads to moles of carbon converted to produce the carbonaceous gas. b: CO2.015 0. R is the ideal gas constant.06 CO experimental data Shrinking core model for 0. this use was ex- 59. CO2.4 kJ/mol and Ea4%-Fe+0%-Na = associated reaction kinetics. (b) Iron and sodium pure catalysts and raw coal and (c) Pure iron and sodium catalysts and composite Fig.25 0. c: CH4) with extended shrinking core model at 800 °C. and T is the absolute reaction temperature.25 0 0 1000 2000 3000 4000 -6.75 0%-Fe+4%-Na 1%-Fe+3%-Na 0.09 ln K -6 0. / Fuel 116 (2014) 341–349 a -4 1/T×10-3(K-1) a 0.003 Shrinking core model for CO2 -6.0 kJ/mol. most of the tested temperatures due to their roles in significant energy obtained with non-catalytic coal gasification was reductions of the activation energy. The shrinking core model is typically used to derive particle Ea1%-Fe+3%-Na = kJ/mol 53. generated or indicates that use of catalysts. i.6 kJ/mol. 9.03 CO -7 0 0 1000 2000 3000 4000 -8 Time (s) 1/T×10-3(K-1) b b 0.12 -5 2%-Fe+2%-Na Mol CO 3%-Fe+1%-Na 0.012 2%-Fe+2%-Na 3%-Fe+1%-Na Mol CO2 -5. 89. any time and N i.25 0.9 0.3. CH4).t Xi ¼ ðE3Þ Ni. Conversion. Carbonaceous gas yielding data fitting for a 2%-Fe + 2%-Na catalyst and coal catalysts.5 Time (s) Fig.05 -4.0016 CH4 experimental data 0.85 0.9 0. i.f where A is the pre-exponential factor.

Cao J. David Bell and Dr.i 1  : ðE4Þ gasification of a powder river basin coal. H2 and COx The integral form of E4 is generation from coal gasification catalyzed by a cost-effective iron catalyst. Appl Catal A 2013. Fan M.f  Ni. alyzed PRB coal gasification process at 800 °C. 9. The authors sincerely thank Mr. . Moulijin JA. J Chem Soc 1987. Kim S. Koga J. The composite catalyst appears to combine [20] Hashimoto K. Comparison of kinetic and diffusional models for solid–gas reactions. are r2CO ¼ 0:9469.85:689–94. Moulijn JA. Falconer J. The results of the [10] Wang J. Angelova G. The overshoot. Comparison of zone-reaction model and unreacted- The research was supported by Wyoming Clean Coal Program. Brown L. [14] Cypres R. fluidized bed gasification of biomass. 1st N d N i. [8] Song B. Carbon 1987. Role of surface salt complexes in alkali catalyzed carbon gasification. Shimbori T. Inoue K. Wen CY.464:207–17.72:797–803. Eutectic salt catalysts for graphite and 4.62:231–3. Slimane R. Walker P. New York: Wiley. Na. Catalytic activity of alkali and iron salt mixtures for steam-char gasification. Fuel 1985. Argyle MD. i. Fuel 2010. and Dr. Rh.62:849–56.56  104 s1. Lamby E.25:351–9. thank Dr.82:176–9. Gas–solid reaction model for a shrinking spherical particle with unreacted shrinking core. and r 2CH4 ¼ 0:9782. Catalytic steam gasification of graphite: effects of intercalated to model the yields of CO. Liliedahl T. where ksc.64:805–9. / Fuel 116 (2014) 341–349 349 carbonaceous gas at the end of the gasification. we gasification of coal chars. Comparison of zone-reaction model and unreacted-core Acknowledgements shrinking model in solid—gas reactions—I isothermal analysis. R. " 3 # [4] Suzuki T. r 2CO2 ¼ 0:9999. Bell D. Towler BF. Miura K. Bill Fuerst. Ni:t ¼ 1   þ1  Ni.f Ni. FeCO3–Na2CO3 compos. FMC Inc. use of the composite catalyst FeCO3–Na2CO3 during coal gasifica. Kosky P. Yao Y. Towler BF. Sjöström K.15:317–25. Fuel coefficients of the three plots. Pyrolysis of coal and iron oxides mixtures. evaluation of the so-called CO to those obtained from raw coal or the pure iron catalyst. Director of Technol. by using the composite catalyst (FeCO3–Na2CO3) when compared [18] Certofontain M.14: their individual shortcomings. Ogata S. Wen CY. including hydrogen gasification of carbon. hydrogen produced comes from water instead of coal or char. Jiang M. Watanabe Y.103:626–30. Cao J. Xu J. CO2. Chem Eng Sci 1971. Influence of iron oxides on the pyrolysis of coal. AIChE J 1986. [23] Ishida M. Mechanism of to model hydrogen production data because the majority of the woody biomass pyrolysis and gasification in a fluidized bed of porous alumina particles. Fan M. Fuel 1983. 1999. Importance of carbon active sites in the Minerals. Energy  1 Fuels 1988. Energy Fuels 2006. [26] Homma S. AIChE J 1968.26:1031–41. Hatano H. Porre H. Tang J.2:673–9. Yao Y. [15] McKee D. 555–6. Speicher EA. Conclusions coal char gasification.32:691–5. In addition. Coal gasification and its applications. Watanabe Y. E6 was not used [13] Matsuoka K. Soudan–Moinet C. 2011.89:310–7. [21] Mims CA. Isotope exchange and the sodium-catalyzed CO2 tion can improve the yields of useful gases. Kammen D.6:445–7. Chemical reaction engineering. Pd and Pt. Jiang M.i [7] Douchanov D. 2005. Steam pulsed gasification of Na2CO3 or ksc. Carbon 1977. Dyar MD.103:161–70. Chem the US Department of Energy. Fuel 1983. Shirai T.57 . Metallic iron as a tar breakdown catalyst related to atmospheric. Monterroso et al. Aaron Reichl.63  105 s1. ite catalysts are promising materials for catalytic coal gasification.f 3 Fuel 1986. and SIDCO Minerals Inc. President of SIDCO [27] Radovic L. Effects of coal carbonization conditions on ksc.  106 s1. Oxford: Elsevier. CO2 Gasification of activated carbon catalyzed PRB coal were considerably improved under different conditions by earth alkaline elements. Jenkins R. [25] Ishida M. E6 was used [9] Otto K. becomes a reality. Shelef M. Effect of catalysis and inlet gas on coal gasification. Aileen Halverson at FMC and Mr. Enhanced catalysis of K2CO3 for steam model for each of the three gases compared with the experimental gasification of coal char by using Ca(OH)2 in char preparation. although more work needs to be performed before the feasibility [22] Levenspiel O.26:1043–8. Yusaku S. Chem Eng Sci ogy and Business Development Alkali Chemicals Division. Shimada M. H2S AND COS. dt Ni:f [3] Popa T. Steam gasification of coal char catalyzed 3 by K2CO3 for enhanced production of hydrogen without formation of methane. Walker P. [24] Ishida M. and CH4 from the 2%-Fe + 2%-Na cat.t [2] Popa T. 1. Eng Sci 1971. Inoue K. or [6] Suzuki T. Relation between the gasification rate and the amount of oxygen on carbon surface during the gasification of the advantages of its two component catalysts and to overcome a carbon supporting several alkaline metal salts. Fuel 1980. Watanabe A. Fuel 2009.t  2=3 ed. Suzuki Y. and carbon monoxide. Therefore. andksc. The model fits are reasonable based on the regression [12] Nordgreen T. and externally added Ru. Gao Y. Fuel 2013.66:697–701.24:277–85. 3rd ed. Matsumoto S. Yulong Zhang for their suggestions. Zhang Y. Combining E1 and References E3 leads to:   [1] Bell D. ksc.i is the generation rate constant of species i. Ni.f ðE5Þ [5] Wang J. [19] Saber JM. Fuel 1989. Fuel 1993.t 3 ksc. The rates of carbon conversion during gasification of Wyodak [17] Kapteijin F. data are shown in Fig.59:48–54. [16] Matsumoto S. ¼ tþ1 ðE6Þ Ni.60:4971–80. Catalytic coal  ¼ ksc. Fan M.CH4 = 3.CO = 1. Agalianos D. as the coefficients of determination 2006.i t Fe(NO3)3 loaded Yallourn coal char. Carbon 1986. Chem Soc Jpn 1985. Char gasification in steam at 1123 K catalyzed by K. core shrinking model in solid—gas reactions—II non-isothermal analysis.88:1572–9. Ca and Fe–effect of H2. CO2 step-response experiments during alkali catalyzed carbon gasification. Temperature–programmed desorption and CO2–pulsed gasification of sodium or iron-loaded Yallourn coal char. Spiro CL. Pabstl J. Fuel 1987.14:311–7. The resulting generation rate constants are [11] Kasaoka S. Kuramoto K. for their valuable input to the research.CO2 = 1. rate of steam gasification of char..20:2727–31. Wen CY.