Chemical-Looping Combustion of Kerosene and Gaseous Fuels with

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Cite This: Energy Fuels XXXX, XXX, XXX−XXX

Chemical-Looping Combustion of Kerosene and Gaseous Fuels with a Natural and a Manufactured Mn−Fe-Based Oxygen Carrier P. Moldenhauer,*,† A. Serrano,‡ F. García-Labiano,‡ L. F. de Diego,‡ M. Biermann,† T. Mattisson,† and A. Lyngfelt† †

Department of Space, Earth and Environment, Chalmers University of Technology, 412 96 Gothenburg, Sweden Instituto de Carboquímica (ICB-CSIC), Miguel Luesma Castán 4, 50018 Zaragoza, Spain

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‡

S Supporting Information *

ABSTRACT: Two different oxygen-carrier materials with similar molar ratios of Mn:Fe:Al were tested in continuous chemicallooping combustion operation with different fuels, i.e., syngas (H2/CO), methane, and kerosene. One oxygen carrier was manufactured by spray drying, and the other one was a naturally occurring ore that was crushed. Experiments were conducted in a bench-scale, chemical-looping combustion reactor with continuous fuel addition and continuous circulation of oxygen-carrier particles. In fresh state, i.e., before fuel operation, both materials showed clear CLOU properties. In used state, i.e., after fuel operation, the CLOU properties of the manufactured oxygen carrier were slightly higher than before, whereas those of the natural material decreased significantly. Operation with fuel was conducted for a total of about 47 h between 850 and 950 °C, and clear differences in fuel conversion were observed. At similar oxygen-carrier-to-fuel ratios and temperatures, the manganese ore achieved a clearly higher methane conversion, whereas the manufactured material achieved a higher conversion of H2 and CO. Near-complete conversion of syngas, i.e., >99%, was reached with both materials tested. Particle circulation was indirectly measured and used to estimate solids conversion during continuous operation. The materials were characterized with ICPSFMS, XRD, and SEM/EDX, and rate indices were calculated based on data obtained in TGA tests with different reactants. Thermodynamic equilibrium calculations were made and used to interpret results from oxygen release and TGA tests. Attrition indices and material porosity were determined for fresh and used samples of the materials used. The manganese ore exhibited a clearly lower structural integrity during redox operation compared to the manufactured material. However, the cost of producing an oxygen carrier from an ore is significantly lower than manufacturing an oxygen carrier by spray drying.

1. INTRODUCTION Carbon capture and storage technologies, CCS, are expected to play a key role in reducing greenhouse gas emissions and in achieving the objective of limiting the average global temperature increase to less than 2 °C compared to preindustrial levels. The Intergovernmental Panel on Climate Change, IPCC, has already warned that such a goal can only be achieved if CCS technologies are widely implemented for large-scale applications in power generation.1 Chemical-looping combustion, CLC, has great potential for reducing the costs of CO2 capture in combustion applications, since it may avoid the energy penalty for the separation of CO2.2 In CLC processes, air and fuel are never mixed, and thus, gas separation, which is needed in other CCS technologies, is avoided. CLC is based on oxygen transfer from air to fuel by means of a solid oxygen carrier, which is usually a metal oxide. The oxygen-carrier particles circulate continuously between two interconnected fluidized-bed reactors and transfer oxygen from the air reactor to the fuel in the fuel reactor, where the fuel is oxidized. Chemical looping with oxygen uncoupling, CLOU, is a process closely connected to CLC, wherein the main difference is related to the fuel oxidation mechanism.3 Whereas in CLC the fuel is exclusively burned by a gas−solid reaction between the gaseous fuel components and the metal oxide, in CLOU the fuel additionally reacts with oxygen in the gas phase, which is released by the oxygen carrier in the fuel reactor. The ratio © XXXX American Chemical Society

between gas−solid reaction and fuel oxidation by gaseous oxygen may vary for different oxygen-carrier materials and fuels. When applying CLOU to combustion of solid fuels, the preliminary stage of char gasification can be avoided as the nonvolatile fuel components can react directly with the gaseous oxygen released by the oxygen carrier.3 In fact, CO2 capture efficiencies near 100% with low amounts of unburnt components have been obtained during operation in continuous units.4−7 Due to the versatility of oxygen carriers with CLOU properties, they can also be used with gaseous and liquid fuels. Manganese oxides, copper oxides, and cobalt oxides are materials with potential CLOU properties, i.e., they are thermodynamically capable of releasing oxygen to the gas phase between 800 and 1200 °C in the fuel reactor. However, the CLOU oxide system Mn3O4/Mn2O3 requires temperatures below 800 °C to be possible to oxidize at an oxygen concentration of 5 vol %, which is assumed at the outlet of the air reactor.3 This limitation can be overcome by combining manganese oxides with other metals, such as calcium, copper, iron, magnesium, nickel, or silica, which increase the equilibrium temperature for the oxidation reaction.8 Received: May 7, 2018 Revised: July 24, 2018 Published: July 24, 2018 A

DOI: 10.1021/acs.energyfuels.8b01588 Energy Fuels XXXX, XXX, XXX−XXX

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Energy & Fuels

Table 1. Elemental Composition (without oxygen) of the Materials in the Fresh State, i.e., after Heat Treatment but before Fuel Operation M28FA14-1200 (mass %) Fe Mn Al Si Ca others (K, Mg, P, Ti, Ba, ...) Mn:Fe:Al molar ratio Mn/(Mn + Fe) molar ratio

M28FA14-1200 (atom %)

40.7 20.0 6.3

55.0 27.5 17.5

n/a n/a

1:2:0.64 0.33

Metmin orea (mass %)

Metmin orea (atom %)

35.9 15.2 1.7 5.9 0.6 0.8 n/a n/a

52.5 22.6 5.0 17.2 1.2 1.5 1:2.33:0.22 0.30

a

Determined by ICP-SFMS according to SS-EN ISO 17294-1,2 (mod) and EPA method 200.8 (mod).

focused on the valorization of low-value side products into more value-added materials from the oil industry.55,56 Depending on their configuration, oil refineries can produce large quantities of low-value products, which can be used as fuels in a CLC process to produce heat and steam in furnaces and boilers. Heat and steam production in an oil refinery add up to about 50% of its total CO2 emissions. Therefore, applying CLC technology in oil refineries could bring significant reductions in CO2 emissions.57 Several works have been published in recent years that deal with liquid fuels such as kerosene, bitumen, dodecane, and fuel oil. Moldenhauer et al.55,58−60 demonstrated the feasibility of using kerosene as fuel in a continuous 300 Wth CLC unit working with nickel-, copper-, and ilmenite-based oxygen carriers. The process was scaled up to a 10 kWth CLC unit. There the proof of concept was carried out with a calciummanganite-based oxygen carrier with fuel oil, and long-term experiments were carried out with ilmenite and fuel oil.61 Finally, undiluted vacuum residue, fuel oil, as well as different blends of these two were used as fuel.55 With undiluted vacuum residue as fuel, up to 93% of all carbon leaving the fuel reactor was in the form of CO2 and carbon leakage to the air reactor was below 1%. Serrano et al.62 tested three different liquid fuels, i.e., diesel, mineral lubricant oil, and synthetic lubricant oil, in a 1 kWth CLC continuous unit with an Febased oxygen carrier. Fuel reactivity was found to vary with the type of chemical bond of the hydrocarbon, and reactivity was found to be higher for alkenes (synthetic lubricant oil) than for alkanes (diesel and mineral lubricant oil). In this study two oxygen carriers are compared that have similar ratios of Mn:Fe. One oxygen carrier is manufactured with defined constituents, and the other oxygen-carrier material is based on a Mn−Fe mineral. The latter material has much lower cost of production as compared to the manufactured oxygen carrier. The two materials were assessed using three different fuels, kerosene, methane, and a syngas (CO/H2), and experiments were conducted in a laboratoryscale, circulating fluidized-bed reactor with a nominal fuel input of 300 Wth.

The system consisting of manganese and iron is among the most interesting combinations due to its advantageous thermodynamic properties and also because a number of minerals contain Mn and Fe in a suitable ratio,9−15 and the use of Mn−Fe-based minerals could be an excellent possibility to significantly reduce the cost of the overall process. Phase transformations occur with changes in temperature, oxygen partial pressure, or ratio of Mn:Fe, x. For the oxygencarrier materials investigated here, the transformation between (MnxFe1−x)2O3 (bixbyite) and (MnxFe1−x)3O4 (spinel) is suitable for CLOU, see reaction R1. This reaction is expected to occur when the partial pressure of oxygen is high, i.e., at a high level of fuel conversion. At much lower oxygen partial pressures, which would occur, for example, in chemical-looping reforming (CLR), the spinel can be reduced to (MnxFe1−x)O (mangano-wüstite), reaction R2. Reaction R2 should be seen as an analogy, because in order to proceed to the right-hand side, a reactant needs to be present, i.e., oxygen cannot be released to the gas phase. 3(MnxFe1 − x)2 O3 ↔ 2(MnxFe1 − x)3 O4 + 0.5O2

(R1)

2(MnxFe1 − x)3 O4 ↔ 6(MnxFe1 − x)O + O2

(R2)

Earlier investigations have studied Mn−Fe-based oxygencarrier materials; however, operational experience from continuous CLC units with Mn−Fe-based materials is still limited. Manufactured Mn−Fe-based oxygen carriers were tested at Chalmers 300 W unit with gaseous fuels8,12,16,17 and at CSIC’s 500 W units using gaseous and solid fuels, respectively.15 In other studies, manufactured Mn−Fe-based materials were studied in batch, fluidized-bed operation9,18,19 as well as in TGA experiments.13,20,21 Mineral Mn- and Febased material, i.e., mostly manganese ores, have been tested at CSIC in a 500 W unit with solid fuel,22 at IFP Lyon in a 10 kW unit with solid fuel,23 at Tsinghua University in a 1 kW unit with gaseous fuel,24 and at VTT Espoo in a 20 kW unit with solid fuel.25 At Chalmers University, manganese ores were investigated in a 300 W unit with gaseous fuels,26 in a 10 kW unit with solid fuels,27−29 and in a 100 kW unit with solid fuels.30−32 Further studies were conducted in TGAs33−39 and batch, fluidized-bed reactors.40−54 Positive results have thus been found with both manufactured and natural materials. The CLOU effect has been seen for most studies using the manufactured Mn−Fe-based materials. Also, manganese ores have shown some oxygen release, although the rate seems to be dependent upon the actual composition. Early chemical-looping combustion investigation has focused on the use of solid and gaseous fuels, but lately there has been growing interest in the use of liquid fuels, particularly

2. EXPERIMENTAL SECTION 2.1. Oxygen Carriers. This work analyzes the performance of two different oxygen carriers based on a combination of manganese and iron, M28FA14-1200 and Metmin ore. M28FA14-1200 is a manufactured oxygen carrier that also contains alumina to increase its mechanical stability. Spherical particles were produced through spray drying by VITO (Flemish Institute for Technological Research in Mol, Belgium) using the following synthesis composition: 58.2 wt % Fe2O3, 27.8 wt % Mn3O4, and 13.9 wt % AlOOH, which corresponds to a molar ratio of Mn:Fe:Al = B


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Energy & Fuels 1:2:0.64. This material was calcined at 1200 °C for 4 h and sieved to the size range 90−250 μm. A different batch of this oxygen carrier, i.e., with the same composition and procedure of manufacture, was previously tested by Azimi et al.19 in an investigation of Mn−Fe-based oxygen carriers stabilized with alumina. They conducted experiments in a bench-scale, batch fluidized-bed reactor made of quartz glass and studied the reactivity of the oxygen-carrier materials with different fuels, i.e., wood char, methane, and a syngas, as well as their CLOU properties. Metmin is a mineral which mainly contains Fe, Mn, Si, Al, and Ca (molar fraction from high to low excluding oxygen), see Table 1. This material was heat treated for 24 h at 950 °C and then crushed and sieved to the desired particle size range, i.e., 90−250 μm. The elemental composition of the mineral was determined by inductive coupled plasma-sector field mass spectrometry (ICP-SFMS). This ore was previously tested by Sundqvist et al.48 as part of a screening study with 11 different manganese ores that were tested in batch fluidizedbed operation with a syngas (50 vol % H2 in CO) and methane. There Metmin ore had the highest release of oxygen to the gas phase, i.e., the highest CLOU effect, but also a high attrition index and low to intermediate reactivity toward CO and CH4. Both oxygen carriers are mainly composed of iron and manganese, though the fraction of manganese was larger in M28FA14-1200, see Table 1. After the experimental campaign, both oxygen carriers were physically and chemically characterized to detect possible changes in their properties, see Table 5. Bulk density was measured based on ISO standard 3923-1. Particle porosity was determined by mercury intrusion porosimetry in a Quantachrome PoreMaster 33 with particles between 90 and 250 μm. The crushing strength was measured by a digital force gauge, Shimpo FGN-5, with particles in the range 180−250 μm. The attrition rate was measured by means of a customized jet-cup attrition rig with particles in the range 125−180 μm, which simulates the effect of grid-jet attrition and cyclone attrition in a circulating fluidized-bed reactor. The attrition index, Ai, is defined as the rate of fines production during the second half of an attrition test.63 Attrition was also determined during redox operation in the 300 W unit. Here, a so-called redox attrition is determined based on fines captured in filters and fines in the reactor divided by the fuel operation time. Crystalline phases were determined by X-ray powder diffraction with a Bruker AXS D8 ADVANCE equipped with an X-ray source working at 40 kV and 40 mA and an energy-dispersive one-dimensional detector. In addition, samples of particles before and after operation were characterized by scanning electron microscopy, SEM, in an ISI DS-130 coupled to an ultrathin window PGT Prism detector for energy-dispersive X-ray, EDX, analysis with the aim of examining the microstructure of the particles and to detect possible structural transformations. Thermodynamic equilibrium calculations were done using FactSage 7.0 with the databases FToxid and FTmisc.64 2.2. Fuels. A liquid fuel, kerosene, and two gaseous fuels, a syngas (50 vol % H2 in CO) and methane, were tested. Kerosene, which was provided by Preem AB in Gothenburg, Sweden, is composed of a combination of hydrocarbons, mostly alkanes. Its main characteristics are shown in Table 2. The boiling range distribution of kerosene was measured in a gas chromatograph (GC), and it was found that 95 wt % of the fuel content had an evaporation point below 225 °C and 5 wt

% below 139 °C. The gaseous fuels were tested as a reference, since a significant number of oxygen carriers have previously been tested with these fuels in this reactor system. 2.3. 300 W CLC Reactor. The experimental campaign was carried out in a bench-scale, 300 Wth chemical-looping reactor with continuous circulation of oxygen carrier. A detailed description of the reactor can be found elsewhere.59 Figure 1 shows a layout of the

Figure 1. Layout of the 300 W chemical-looping reactor. reactor system. The fuel reactor, FR, has a square cross-section of 25 × 25 mm, whereas the air reactor, AR, has a rectangular cross-section in the bottom, 25 × 42 mm, which tapers down to 25 × 25 mm higher up in the reactor. The inlet flows, fuel and air, are never mixed, and they are fed to the reactor through two different windboxes located in the bottom part of the reactor. In the air reactor there is a circulating fluidized-bed regime, where the solids are oxidized and lifted to the upper part of the reactor. There the mixture of particles and the exhaust flow of air are separated in a gravitational separator. Finally, the particles reach the bubbling bed in the fuel reactor, where they are reduced before flowing back into the air reactor, via the lower loop seal, where a new cycle begins. This reactor was originally designed for gaseous fuels; thus, it was necessary to design and construct a fuel injection system for liquid fuels. In the injection system, shown in Figure 2, the fuel is first evaporated and then mixed with superheated steam. A steam generator provides the required flow of steam, and a heating band is used to superheat the steam to the desired temperature. A

Table 2. Main Characteristics of Kerosene lower heating value (MJ/kg) density (kg/dm3) distribution points in distillation curve [T5, T95] (°C) elementary analysis (mass %) C H N S

43.34 0.79 139, 225 86.2 13.5 H2 > CO > CH4. This corroborates the results shown in Figure 6, where both materials exhibited the lowest conversion when CH4 was used as fuel. The calculated rate indices indicate that the material M28FA14-1200 should achieve a higher conversion of CO and CH4 than Metmin ore, while conversion of H2 should be lower. This matches the observations in the 300 W reactor only partly, cf. Figure 5, where the synthesized oxygen carrier M28FA14-1200 achieved higher conversions of CO and H2 but a lower conversion of CH4 than Metmin ore. Figure 10 shows a comparison of the normalized rate indices of the oxygen carriers used here with values reported in the literature for Fe-, Mn-, and Mn−Fe-based oxygen-carrier materials.13,15,33,34,69−71 The normalized rate indices determined here were similar to the reference values, even though the former were obtained at 900 °C and the latter at 950 °C. All materials exhibited higher reactivity during reduction with H2 and during oxidation with air than during reduction with CH4 and CO. However, no clear conclusions can be

Table 6. Theoretical and Measured Oxygen Carrying Capacities for the Oxygen-Carrier Materials M28FA14-1200 and Metmin Ore theoretical maximum valuea

normalized rate index (wt %/min)

a

To establish a maximum, it was assumed that all material consists of Mn and Fe at a ratio of 1:2−1:2.33; values in square brackets, [], indicate the ratio of measured value to theoretic value. J


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Figure 10. Comparison of normalized rate indices for several Fe-, Mn-, and Mn−Fe-based oxygen-carrier materials with gaseous reactants CH4, CO, H2, and O2. Normalized rate indices for M28FA14-1200 and Metmin ore were determined at 900 °C, whereas the normalized rate indices for the reference materials were obtained at 950 °C. Column “Fuel” indicates whether a material was previously used with a fuel (“solid” or “gaseous”) or not (“none”). Exact Mn/(Mn + Fe) ratio of material 16 is unknown and was guessed according to the description in ref 69.

Metmin ore could be a suitable oxygen carrier for processes where (a) the regeneration of bed material in the boiler is high (manganese minerals have a high attrition but are relatively cheap) and (b) a fuel is used that contains methane and light hydrocarbons (compared to the manufactured oxygen carrier M28FA14-1200, Metmin ore achieved a clearly higher methane conversion). A possible application for this material could be a chemical-looping combustion (or reforming) process with biomass. Dried biomass consists mostly of volatiles, with a high fraction of methane, and may contain significant amounts of alkaline compounds in the ash. The presence of SiO2 in Metmin ore might be an additional benefit, as SiO2 absorbs alkali,72 which, in turn, might improve CO conversion.73 Using synthesized oxygen-carrier materials, such as M28FA14-1200, which usually have a high purity, seems more suitable for cleaner fuels, such as, for example, syngas or refinery gas.

drawn regarding the influence of the ratio of Mn:Fe on reactivity. It should be mentioned that changes in reactivity from fresh to used state were observed here as well as for several other Mn-based ores.26,34

4. DISCUSSION Some clear differences between the two oxygen-carrier materials tested were observed with respect to fuel conversion. The mineral oxygen-carrier Metmin ore achieved a clearly higher conversion of methane. This might be a result of one or a combination of the following: (1) a higher porosity, i.e., more reaction sites are available, (2) a more heterogeneous phase/ elemental composition, out of which some phases might catalyze methane decomposition, (3) a higher average reactivity in the fuel reactor due to a different level of reduction as a result of higher solids circulation. High heterogeneity was determined in SEM/EDX analysis. XRD analysis, however, was not able to show a clear difference between the materials. The higher oxygen-carrying capacity of Metmin ore compared to that of the material M28FA14-1200 is unlikely to have an impact on fuel conversion as fuel conversion, and consequently, oxygen partial pressure were high. Solids conversion during fuel operation was usually clearly below 1 wt % for both materials tested, which is far less than the measured maxima of 3.6 and 4.4 wt %. Further, the slightly higher CLOU effect that was measured with Metmin ore, see Figure 4, is believed to play a minor role for the overall gas conversion. While the oxygen release kinetics with fuel were not quantified here, Azimi et al.19 found that for a series of materials similar to M28FA14-1200 oxygen release (CLOU) was much slower than gas−solid reactions (CLC). Therefore, for gaseous fuels as were used here (kerosene was vaporized prior to injection), the main mechanism is believed to be gas− solid reactions, i.e., CLC. The manufactured material M28FA14-1200 achieved a somewhat higher conversion of syngas, i.e., CO and H2, and kerosene, see Figure 6. During experiments with kerosene as fuel, significant fractions of CO and H2 were detected in the gas phase. This is partly a result of steam reforming, see reaction R3, but also suggests that kerosene decomposition and conversion, at least in part, proceed via CO and H2.

5. SUMMARY AND CONCLUSIONS Two similar materials based on mostly Fe, Mn, and Al were tested as oxygen carrier for chemical-looping combustion. One material, M28FA14-1200, was synthesized and consisted of spray-dried and heat-treated spheres, whereas the other material was a manganese ore that was crushed and heat treated. In total, the materials were tested for about 800−1000 redox cycles with three different fuels: syngas, methane, and kerosene. Clear differences were observed with respect to fuel conversion and particle integrity during fuel operation. While the material M28FA14-1200 achieved a somewhat higher conversion of kerosene and syngas and produced less fines during operation, the manganese ore Metmin was superior with respect to methane conversion. Very high conversion of syngas, i.e., more than 99%, was achieved with both materials; with M28FA14-1200 at 850 °C and a specific fuel-reactor bed mass of 370 kg/MWth and with Metmin ore at 900 °C and 540 kg/MWth. An extensive number of different characterization tests was performed to help explain the differences observed. The reason for the higher reactivity toward methane could not be resolved, but the higher porosity and possibly catalytic effects of Metmin ore seem more likely than the higher oxygen partial pressure via CLOU in an inert atmosphere. However, the oxygen release kinetics with fuel were not measured. The K


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cost of production for the mineral-based oxygen carrier is far lower than for the manufactured material. The following conclusions can be drawn. • With both materials tested, syngas conversion of more than 99% could be achieved, though the specific fuelreactor bed mass necessary was much lower with the manufactured material M28FA14-1200. • Both materials investigated exhibited clear CLOU properties. For the manufactured material M28FA141200, the CLOU properties appear to have remained nearly constant during fuel operation. The CLOU properties of the material based on Metmin ore, however, changed significantly during fuel operation. Measurements with used Metmin ore-based oxygen carrier suggest that CLOU properties at temperatures above 900 °C are limited by oxidation. • For materials with an Mn:Fe ratio similar to the ratio of the materials used here, i.e., about 1:2, full oxidation should be possible as long as the oxygen concentration at the outlet of the air reactor is well above 1.2 vol % at 900 °C or well above 3.7 vol % at 950 °C. However, here it was found that the used Mn ore-based material could not be oxidized fully at 950 °C and a molar fraction of oxygen of 19 vol %. • The main phases detected are (Mn,Fe)2O3 (bixbyite) and (Mn,Fe)3O4 (spinel). Other phases might have important catalytic effects but could not be clearly identified. • Both oxygen-carrier materials have worked well during relatively long test periods with respect to the reactor system used. Conversion was relatively high for both materials investigated, out of which one is available at a very low cost.

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REFERENCES

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S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.energyfuels.8b01588. Content and normalized rate index data (XLSX)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

P. Moldenhauer: 0000-0002-9390-6455 M. Biermann: 0000-0001-8731-267X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was partially supported by the Spanish Ministry of Science and Innovation (MICINN Project ENE2011-26354) and the European Regional Development Fund (ERDF). A.S. also thanks the Spanish Ministry of Economy and Competitiveness for the F.P.I. fellowship. Additional funding was received from the European Research Council (ERC) under the European Union’s Seventh Framework Programme (FP7/ 2007-2013) (grant agreement no. 291235). L


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