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CO2 sorption enhancement of extruded-spheronized CaObased pellets by sacrificial biomass templating technique Jian Sun, Wenqiang Liu, Wenyu Wang, Yingchao Hu, Xinwei Yang, Hongqiang Chen, Yang Peng, and Minghou Xu Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b01859 • Publication Date (Web): 21 Sep 2016 Downloaded from http://pubs.acs.org on September 23, 2016

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CO2 sorption enhancement of extruded-spheronized CaO-based pellets by sacrificial biomass templating technique

Jian Sun, Wenqiang Liu*, Wenyu Wang, Yingchao Hu, Xinwei Yang, Hongqiang Chen, Yang Peng and Minghou Xu* State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China *Corresponding author: Tel: +86 027 87542417-8301; Fax: +86-27-87545526; E-mail: [email protected]; [email protected]; Postal address: State Key Laboratory of Coal Combustion, Huazhong University of Science & Technology, 1037 Luoyu Road, Wuhan 430074, PR CHINA. Abstract The sacrificial biomass templating technique was used to enhance the sorption performance of CaO-based pellets that prepared via an extrusion-spheronization method. Five types of biomass materials were used as the templates: microcrystalline cellulose, corn starch, rice husk, sesbania powder and lycopodium powder. It is found that the addition of biomass templates is effective to improve the cyclic CO2 sorption capacity of the CaO-based pellets. However, two opposite enhancement tendencies of CO2 uptake were observed with the increment of biomass addition. For microcrystalline cellulose, corn starch and rice husk, more addition amounts would result in better improvement of CO2 sorption performance of the CaO-based pellets. It 1

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is attributed to the generated porous microstructure and large amounts of small grains. However, for sesbania powder and lycopodium powder, a decreasing enhancement tendency of the CO2 sorption performance was found with the increasing addition amount. It is probably due to the accelerated sintering of the sorbent because of the presence of excessive amounts of alkali metal elements. Moreover, all biomass-templated CaO-based pellets possess a high anti-attrition capacity. Keywords: CO2 capture, CaO-based pellets, biomass-derived template, enhancement tendency 1. Introduction Nowadays, the use of fossil fuels is facing huge challenges because the combustion process produces a large amount of CO2, which has been considered to be the main cause of global warming.1,

2

Therefore, a range of CO2 capture and

sequestration technologies have been developed to ensure the usage of fossil fuels to be accepted by environment.3, 4 Calcium looping process (CLP) is one of the most promising ones because of its low efficiency penalty and wide range of applicability.5-9 The principle of CLP for CO2 separation is on the basis of the reversible

carbonation/decarbonation

reaction:

CaO+CO2 ↔ CaCO3.

Two

interconnected fluidized-bed (FB) reactors (a carbonation reactor and a calcination reactor) are included in the CLP. CaO-based sorbent is continuously circulated between the two reactors to remove CO2 in the flue gas. Simultaneously, concentrated CO2 gas stream is produced from the calcination reactor under oxy-fuel condition for further utilization and sequestration. 10-12 2


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However, the CaO-based sorbent particles are prone to severe fragmentation and attrition when circulating between the dual FB reactors.13-15 The finely generated powders are easily elutriated from the reactors. It will cause the additional economic efficiency loss because of the need for replenishing more fresh sorbent.16 Therefore, the preparation of CaO-based pellets with good attrition resistance is necessary. Many granulation technologies have been adopted to prepare the CaO-based pellets, and the most

common

methods

extrusion,16-23

include

pelletization,24-29

and

extrusion-spheronization.30 However, the cyclic CO2 capture performance of the CaO-based pellets is inferior to that of the original sorbent powders. It is mainly due to granulation causing the densification of the material and the destruction of porous structure. 25, 30 Therefore, a simple, cost-effective method has been proposed to improve the CO2 uptake of the CaO-based pellets via adding biomass materials.29-33 biomass-based materials have been used, such as rice husk,

29

A range of

microcrystalline

cellulose,30 maple leaves,31 starch32 and flour,33 etc. The CO2 uptake enhancement (based on the last cycle) of the biomass-templated pellets for different biomass types and addition amounts reported in the previous literatures was summarized (Fig. 1). It is found that the biomass-based materials are commonly effective to increase the CO2 uptake of CaO-based pellets, as long as the addition amounts are in the right range. The enhanced CO2 uptake is mainly attributed to the generated porous microstructure within the biomass-templated pellets because of the thermal degradation of biomass materials at high temperature.30, 31 Additionally, the residual biomass ash after thermal 3


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degradation may also influence the texture of the biomass-templated pellets.30, 31, 34 The twofold effects of biomass-based materials can result in the different enhancement tendencies of CO2 uptake for the CaO-based pellets with the increase of biomass addition amounts. However, the researches on enhancing the CO2 uptake of the CaO-based pellets via adding biomass materials are still limited. There are many other biomass-based materials can also effectively enhance the CO2 uptake of the CaO-based pellets. Moreover, it is generally accepted that the resistance to attrition would be lowered due to the addition of biomass, but rarely studied. In this work, five types of biomass materials (i.e. microcrystalline cellulose, corn starch, rice husk, sesbania powder and lycopodium powder) were selected as the templating materials to prepare the biomass-templated CaO-based pellets via an extrusion-spheronization method. After thermal degradation, the composition of the biomass residue was also analyzed, especially the contained alkali metals. The variation of anti-attrition ability of the extruded–spheronized pellets was investigated with the addition of different types and amounts of biomass materials. Moreover, the techniques

of

field

emission

scanning

electron

microscopy

and

N2

absorption/desorption were used to characterize the micromorphology, structure and porosity of the CaO-based pellets. 2. Experimental 2.1. Preparation of the sorbent pellets A calcium hydroxide reagent (>95 wt.%) from Sinopharm Chemical Reagent Co. Ltd., Shanghai, China was selected as the calcium precursor. Five types of biomass 4


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materials: microcrystalline cellulose (MC), corn starch (CS), rice husk (RH), sesbania powder (SP) and lycopodium powder (LP) were sieved into a size fraction of 45-75 um. The preparation principle of structurally improved CaO-based pellets via sacrificial biomass templating is displayed in Fig. 2. It demonstrates that the structurally improved CaO-based pellets could be obtained via calcining the biomass-templated pellets. It is mainly attributed to the template particles are replaced by the micro-sized cavities during high-temperature calcination process, and the release of pyrolysis gas further improves the porosity of the pellets. During the preparation process, weighted amounts of calcium hydroxide reagent and biomass template materials were vigorously blended to obtain the homogeneous mixtures, which were then wetted by spraying moderate amount of deionized water; finally, the pellets with particle size fraction of 0.9-1.25 mm were prepared via a miniature extruder and spheronizer. More detailed description of the pelletization procedure can be found in the Supporting Information. A range of CaO-based pellets with the abovementioned five types of templating materials and three different biomass ratios (5, 10, and 20 wt.%) were prepared. The addition ratio is based on the solid-to-solid ratio, i.e., the biomass-derived templating material to the Ca(OH)2 reagent. The photographs of the biomass-templated pellets containing 20 wt.% of biomass-derived templating materials are displayed in Fig. 3. It is observed that the biomass-templated pellets possess high sphericity, aside from the SP-templated pellets, which is beneficial to enhance their anti-attrition ability. The CaO-based pellets added with the microcrystalline cellulose, corn starch, rice husk, sesbania powder and 5


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lycopodium powder are designated as CH-MCx, CH-CSx, CH-RHx, CH-SPx and CH-LPx, respectively, where x is the ratio of the added biomass material. For instance, the CaO-based pellets containing 10 wt.% of microcrystalline cellulose are designated as CH-MC10. Pure Ca(OH)2 pellets without biomass addition were prepared for comparison purposes, designated as CH. 2.2. Testing and characterization of the sorbent pellets The CO2 uptake of the CaO-based pellets was tested using a Perkin-Elmer thermogravimetric analyzer (TGA, Pyris 1). Before the carbonation/calcination cycle test commenced, the sorbent pellets (~25-35mg) were firstly heated to 850 °C under a N2 flow of 100 ml/min at a heating rate of 20 °C/min. The sorbent pellets were maintained at 850 °C for 10 min in order to ensure the complete calcination, and then the

cyclic

carbonation/calcination

tests

were

performed.

A

complete

carbonation/calcination conditions are as follows: first, the pellets were cooled to 650 °C at a rate of -25 °C/min; once 650 °C was reached, the atmosphere was immediately switched to 15 vol.% CO2 (the total gas flow was 100 ml/min and N2 used as the balance gas), and the pellets were kept for 30 min under this condition for CO2 sorption; then, the temperature of the pellets was raised to 850 °C at a rate of 20 °C/min under an atmosphere of 100 vol.% N2 (a total gas flow of 100 ml/min), and the

temperature

was

kept for

2

min

for

the

calcination.

The

above

carbonation/calcination cycle was repeated for 25 times in order to study the pellets’ cyclic CO2 sorption performance. The CO2 capture capacity (Cn, g CO2/g calcined sorbent, g/g), CO2 capture capacity loss rate (Ln, %) and CO2 capture rate (Vn, g/g/min) 6


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are used to evaluate the cyclic CO2 sorption performance of the pellets. They are calculated according to equations. (1), (2) and (3), respectively:30, 35 = = =

(2)

(1)

× 100%

(3)

where m0 and mn are the initial calcination mass and the mass of the sorbent after the nth carbonation, respectively; is the CO2 capture capacity of the pellets vs carbonation time; C1 and Cn refer to the 1st and nth CO2 capture capacity. The attrition propensity of the pellets was tested using a CS-2 friability tester. The specific testing parameters were the same as that reported in our previous work.30 The weighted amounts of pellets (~1.5 g) were placed into the drum when the test was started. After 1000 and 3000 rotations, the particles passed through a sieve with a square aperture of 170 um were regarded as a result of attrition. The attrition propensity of the pellets was directly evaluated by the percentage of their weight loss. The ultimate analysis of the biomass materials were tested using a Vario Micro Cube elemental analyzer. The calorific value of the biomass materials was measured using a Parr 6300 automatic calorimeter. A focused-beam X-ray fluorescence spectrometer (XRF, Model: EAGLE III) was used to analyze the biomass pyrolysis ashes (biomass residues obtained at 850 °C under pure N2). Phase compositions of the sorbent pellets were analyzed in an X’Pert PRO X-ray diffractometer. A Nova NanoSEM 450 field emission scanning electron microscope microscopy (FSEM) was used to observe the surface morphology changes of the CaO-based pellets. The 7


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specific surface area, pore volume and the BJH pore size distribution of sorbent pellets were analyzed via a Micromeritics ASAP 2020 Accelerated Surface Area and Porosimetry System. 3. Results and discussion 3.1. Analysis of biomass-derived templates The ultimate analysis results of different biomass-derived templates are listed in Table 1. The LP has the highest carbon content (64.05 wt.%) and hydrogen content (9.66 wt.%), by contrast the RH has the lowest carbon content (38.81 wt.%) and hydrogen

content

(5.76

wt.%).

However,

the

sulfur

contents

of

theses

biomass-derived templates are low, merely ranging from 0.15 to 0.25 wt.%. In addition, the calorific values of the biomass materials are closely related to their carbon and hydrogen contents. In Table 1, the LP has the highest calorific value of 28.39 MJ/kg which is nearly two times that of the RH, because of the highest carbon and hydrogen contents of the LP. The pyrolysis characteristics of these biomass materials under N2 were also investigated, and the TG and DTG results are depicted in Fig. 4 (a) and (b), respectively. As shown in Fig. 4 (a), obvious weight loss is observed for all the biomass-derived templates with the increasing temperature. Different biomass materials obtain different residual yields. The MC has the lowest residual yield of 3.89%, in comparison with the RH that has the highest residual yield of 29.95%. Two distinct temperature zones (Ⅰand Ⅱ) corresponding to the weight loss peaks of the TG curves can be found from the DTG curves (Fig. 4 (b)). The temperature zoneⅠ (below 146 °C) is caused by the loss of free water contained in 8


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the biomass materials. The pyrolysis gases (mainly including H2, CH4, H2O, CO and CO2)36 releasing in the temperature zone Ⅱ (163-524 °C) is responsible for the sharp drops of the TG curves. The composition of the pyrolysis residues of the biomass-derived templates is given in Table 2, and distinct discrepancy is observed for the residues derived from different biomass materials. 3.2. Characterization of biomass-templated pellets The X-ray diffraction patterns of the calcined biomass-templated pellets are depicted in Fig. 5. It is obvious to find that the major diffraction peaks of all the pellets appear at identical 2θ angles of 32.26o, 37.38o, 53.92o, 64.23o, 67.42o and 79.64o. These peaks are indexed to typical CaO diffractions of (111), (200), (220), (311), (222) and (400) planes (JCPDS, 04-0777).37 It indicates that the addition of biomass materials does not alter the crystalline phases of the products. It is worth noting that there are no diffraction peaks of calcium sulphate, indicating the sulfur within the biomass-derived templates does not cause the deactivation of the CaO. The appearing Ca(OH)2 patterns suggest that the CaO hydration during the preparation of samples for XRD analysis. The porosity characterization of the biomass-templated pellets were performed using the method of N2 absorption/desorption. The specific surface area and pore volume of the pellets are listed in Table 3. It is found that the addition of biomass material is effective to improve the porosity of the CaO-based pellets, aside from the SP-templated pellets. Particularly, the CH-MC20 pellets display the highest specific surface area (19.04 m2/g) and pore volume (0.140 cm3/g), which are nearly 1.5 times 9


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that of the CH pellets. It is mainly attributed to the MC possesses the greatest weight loss (3.89 % residual), leading to the generation of more abundant micro-sized pores and cavities to replace the MC particles. Additionally, the CH-CS20 pellets also display a relatively high specific surface (18.36 m2/g) while displaying a higher residual of 17.59 %. The reason for their high specific surface is probably owing to the rapid weight loss rate of the CS, as shown in Fig. 4 (b). The rapid weight loss leads to the fast release of the pyrolysis gas, easily forming the porous structure in the interior of the CS-templated pellets. Moreover, higher specific surface area and pore volume can be obtained when more amounts of biomass materials are added to the pellets (Table 3). The N2 adsorption-desorption isotherms and pore size distributions of the calcined sorbent pellets are depicted in Fig. 6. The physisorption isotherms of the calcined pellets belong to the Type II isotherm (Fig. 6 (a)), which represents unrestricted monolayer-multilayer adsorption.38 Point B is the turning point that indicates the completion of monolayer coverage and the beginning of multilayer adsorption. In addition, clear adsorption hysteresis loops (Type H3) are observed in the physisorption isotherms at high relative pressure (P/P0 is higher than 0.8). The appearing of hysteresis loop is usually associated with capillary condensation in mesopore structures,38 which could be substantiated by the pore size distributions (Fig. 6 (b)). The unimodal pore size distributions are observed, and the pore volume peaks centered in the mesopore range (20-50 nm). 3.3. Performance of biomass-templated pellets 10


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The cyclic CO2 capture capacity of the biomass-templated pellets was tested in the TGA, and the results are depicted in Fig. 7. The CH pellets entirely composed of Ca(OH)2 reagent were also tested for comparison purposes. It is found that the CO2 capture capacity of all the pellets gradually decreases with an increasing number of carbonation/calcination cycles. Particularly, the CH pellet displays a lowest CO2 capture capacity of 0.168 g/g in the 25th cycle, which is merely 30 % of their initial CO2 capture capacity. The rapid loss-in-capacity is commonly occurred for CaO-based sorbent because of the sintering of sorbent during high temperature carbonation/calcination process.39-41 The addition of biomass materials can effectively enhance the cyclic CO2 capture performance of the CaO-based pellets. Although the biomass-templated pellets do not exhibit better CO2 uptake than the CH pellets in the initial cycle, their superiorities for CO2 capture are highlighted in the last few cycles (Fig. 7). The improved CO2 capture performance of the biomass-templated pellets is mainly attributed to their modified inner structure. The alteration of the inner structure is brought by the thermal degradation of the biomass particles which results in large amounts of cavity and pores in the interior of the pellets.30, 31, 42 However, the effectiveness of CO2 sorption enhancement varies with the biomass type and the addition amount. To intuitively evaluate the superiorities of the biomass-templated pellets, the CO2 capture capacities of all the tested pellets in the 1st, 10th and 25th cycle are plotted in Fig. 8. Two opposite enhancement trends of CO2 sorption capacity for the biomass-templated pellets can be observed with the increment of biomass addition. The MC-templated, CS-templated and RH-templated 11


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pellets display an ‘increasing tendency’ on the CO2 uptake with the addition amount of the corresponding biomass increasing from 5 to 20 wt.%. Particularly, the CO2 capture capacity of the CH-MC20 pellet in the 25th cycle is 0.360 g/g, which is nearly 1.4 times that of the CH-MC5 pellet. In contrast, the CO2 capture capacity of the SP-templated and LP-templated pellets displays a ‘decreasing tendency’ with the increase of biomass addition. For instance, the CO2 capture capacity of CH-LP5 pellet is 0.345g/g in the 25th cycle, while that of CH-LP20 pellet reduces to 0.250 g/g. Similar decreasing trend for the leaf-templated pellets was reported by Ridha31, who found that the addition of 20 wt.% of leaf was inferior to the addition of 10 wt.% of leaf. Further analysis on the CO2 capture capacity data depicted in Fig. 8 was performed. The CH pellet displays the highest CO2 capture capacity loss rate (Ln) of 69.59 % in comparison with the biomass-templated pellets. It indicates that the biomass addition is also beneficial to improve the CO2 sorption stability of the CaO-based pellets. It is worth noting that the effect of the addition of biomass materials on the CO2 uptake of the CaO-based pellets appears to be twofold. First, it is shown that the thermal degradation of the biomass materials would improve the pore structure of the pellets, promoting the diffusion of CO2 to react with the interior, free CaO.30 Therefore, more small grains and micro-sized cavities are observed on the surface of the cycled MC-templated pellets compared to the cycled CH pellets, as shown in Fig. 9 (d-e). It is also shown that the pyrolysis residues of the biomass materials within the pellets affect their CO2 sorption capacity. Whether the effect is positive or negative 12


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mainly depends on the yield and composition of the pyrolysis residues. Therefore, it is speculated that the ‘decreasing tendency’ of the SP-templated and LP-templated pellets is due to the accelerated sintering of the sorbent as a result of the contained excessive amounts of alkali metal elements (Table 2), when adding more biomass materials.34 As shown in Fig. 9 (g-i), severe sintering and a lot of larger grains are observed on the surface of the cycled LP-templated pellets, when increasing the addition amount of LP templating materials from 5 to 20 wt.%. CO2 capture rate is used to distinguish the different reaction stages between the CO2 and CaO during the carbonation process. The CO2 capture rates of the MC-templated and LP-templated pellets (representing abovementioned two types of biomass-templated pellets) were investigated in this work, and the results are shown in Fig. 10. It is found that the curve of CO2 capture rate includes three segments, a steep rising segment, a rapid declining segment and a horizontal segment, respectively corresponding to the chemical reaction controlled stage, the transition stage and the product layer diffusion controlled stage.43 The principle for the identification of the three carbonation stages is illustrated in Figure S2. The chemical reaction controlled stage and the transition stage both can be defined as the fast CO2 sorption stage in this work. The fast CO2 sorption stage contributes to most of the CO2 uptake of the sorbent. The beginning of the horizontal segment in the CO2 capture rate curve is regarded as the termination of the fast CO2 sorption stage. It is obvious to find that the addition of MC and LP templating materials can effectively enhance the CO2 capture rate of the CaO-based sorbent. After multiple carbonation/calcination cycles, the 13


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terminal time of the fast CO2 sorption stage are delayed for both the MC-templated and LP-templated pellets. In the 25th cycle, the terminal time of the fast CO2 sorption stage is significantly delayed when adding 20 wt. % of MC (Fig. 10 (b)), much superior to the addition of 5 wt.% of MC. On the contrast, less addition of LP is found to be more effective for the delay of the terminal time of the fast CO2 sorption stage, as depicted in Fig. 10 (d). The capability to resist the thermal shock and attrition is important for the CaO-based pellets to be used in the CLP.44, 45

As shown in Fig. 9 (a-c), it is observed

that no apparent cracks appearing on the surface of cycled pellets. It indicates that the pellets have a high capability to resist the thermal shock caused by the temperature difference between the carbonation and calcination stages.29,

43

The abrasion test

results of the biomass-templated and CH pellets are listed in Table 4 in the form of weight loss. Although the weight loss of biomass-templated pellets is higher than that of the CH pellets, the maximum one is still low than 3 % after 3000 rotations, indicating a high anti-attrition ability. The anti-attrition ability of the pellets prepared in this work via extrusion-spheronization is even higher than that of the cement-bounded particles produced merely via extrusion. It is mainly attributed to the adoption of the extrusion-spheronization method here that can directly produce the spherical particles. Generally, the spherical particles are superior to cylindrical particles (via extrusion method) on resisting attrition.21 Moreover, the preparation of biomass-templated sorbent pellets for CO2 capture via an extrusion-spheronization method mainly includes two advantages. First, 14


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extrusion-spheronization is a very mature granulation technology for the preparation of pellets from powdered materials, being easy to be scaled up. In addition, the biomass-derived materials are readily available and very cheaper in comparison with other synthetic organic materials,31 so the preparation cost of biomass-templated pellets is relatively very low. Therefore, no matter considering the feasibility and cost of the granulation technology, large-scale production of biomass-templated pellets is highly potential to achieve. 4. Conclusions Efforts were made to enhance the CO2 uptake of the extruded–spheronized CaO-based pellets via sacrificial biomass templating. This work used five types of biomass templates including microcrystalline cellulose, corn starch, rice husk, sesbania powder and lycopodium powder. It is found that higher enhancement of the CO2 sorption performance of the sorbent pellets is achieved, when adding more microcrystalline cellulose, corn starch or rice husk. On the contrary, the addition of more sesbania powder or lycopodium powder results in inferior CO2 sorption performance enhancement. Moreover, the biomass-templated pellets also display a relatively high resistance to thermal shock and attrition. It is concluded that promising sorbent pellets can be produced by combining the extrusion-spheronization and sacrificial biomass templating technique. Supporting Information Preparation process of biomass-templated pellets (Fig. S1) and schematic for the

15


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identification of three carbonation stages (Fig. S2) Acknowledgements The research is supported by the National Natural Science Foundation of China (51306063) and the Foundation of State Key Laboratory of Coal Combustion (FSKLCCB1602). The Analytical and Testing Center at the Huazhong University of Science and Technology is also being appreciated.

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calcination behaviour of a uniformly-distributed CuO/CaCO3 particle in Ca–Cu chemical looping. Appl Energ 2016, 164, 400-410. 12. Li, Z.; Wang, Y.; Li, Z.; Luo, G.; Lin, S.; Yao, H., Steam gasification behavior during coal combustion and CaO regeneration in O2/CO2/steam atmosphere. Fuel 2016, 184, 409-417. 13. Scala, F.; Salatino, P.; Boerefijn, R.; Ghadiri, M., Attrition of sorbents during fluidized bed calcination and sulphation. Powder Technol 2000, 107, (1), 153-167. 14. Li, Z.; Wang, Y.; Yao, H.; Lin, S., Novel CO2 sorbent: Ca (OH)2 with high strength. Fuel Process Technol 2015, 131, 437-442. 15. Yao, X.; Zhang, H.; Yang, H.; Liu, Q.; Wang, J.; Yue, G., An experimental study on the primary fragmentation and attrition of limestones in a fluidized bed. Fuel Process Technol 2010, 91, (9), 1119-1124. 16. Manovic, V.; Anthony, E. J., CaO-based pellets supported by calcium aluminate cements for high-temperature CO2 capture. Environ Sci Technol 2009, 43, (18), 7117-7122. 17. Manovic, V.; Anthony, E. J., Screening of binders for pelletization of CaO-based sorbents for CO2 capture. Energ Fuel 2009, 23, (10), 4797-4804. 18. Manovic, V.; Anthony, E. J., Long-term behavior of CaO-based pellets supported by calcium aluminate cements in a long series of CO2 capture cycles. Ind Eng Chem Res 2009, 48, (19), 8906-8912. 19. Manovic, V.; Anthony, E. J., CO2 carrying behavior of calcium aluminate pellets under high-temperature/high-CO2 concentration calcination conditions. Ind Eng Chem Res 2010, 49, (15), 6916-6922. 20. Manovic, V.; Anthony, E. J., Reactivation and remaking of calcium aluminate pellets for CO2 capture. Fuel 2011, 90, (1), 233-239. 21. Qin, C.; Yin, J.; An, H.; Liu, W.; Feng, B., Performance of extruded particles from calcium hydroxide and cement for CO2 capture. Energ Fuel 2011, 26, (1), 154-161. 22. Qin, C.; Du, H.; Liu, L.; Yin, J.; Feng, B., CO2 Capture Performance and Attrition Property of CaO-Based Pellets Manufactured from Organometallic Calcium Precursors by Extrusion. Energ Fuel 2013, 28, (1), 329-339. 23. Derevschikov, V. S.; Lysikov, A. I.; Okunev, A. G., CaO/Y2O3 pellets for reversible CO2 capture in sorption enhanced reforming process. Catal. Sustainable Energy 2012, 1, 53-59. 24. Wu, Y.; Manovic, V.; He, I.; Anthony, E. J., Modified lime-based pellet sorbents for high-temperature CO2 capture: reactivity and attrition behavior. Fuel 2012, 96, 454-461. 25. Broda, M.; Manovic, V.; Anthony, E. J.; Müller, C. R., Effect of pelletization and addition of steam on the cyclic performance of carbon-templated, CaO-based CO2 sorbents. Environ Sci Technol 2014, 48, (9), 5322-5328. 26. Manovic, V.; Wu, Y.; He, I.; Anthony, E. J., Spray water reactivation/pelletization of spent CaO-based sorbent from calcium looping cycles. Environ Sci Technol 2012, 46, (22), 12720-12725. 27. Manovic, V.; Fennell, P. S.; Al-Jeboori, M. J.; Anthony, E. J., Steam-enhanced 17


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calcium looping cycles with calcium aluminate pellets doped with bromides. Ind Eng Chem Res 2013, 52, (23), 7677-7683. 28. Liu, F.; Chou, K.; Huang, Y., A novel method to make regenerable core-shell calcium-based sorbents. J Environ Manage 2006, 79, (1), 51-56. 29. Sun, J.; Liu, W.; Hu, Y.; Li, M.; Yang, X.; Zhang, Y.; Xu, M., Structurally Improved, Core-in-Shell, CaO-Based Sorbent Pellets for CO2 Capture. Energ Fuel 2015, 29, (10), 6636-6644. 30. Sun, J.; Liu, W.; Hu, Y.; Wu, J.; Li, M.; Yang, X.; Wang, W.; Xu, M., Enhanced performance of extruded–spheronized carbide slag pellets for high temperature CO2 capture. Chem Eng J 2016, 285, 293-303. 31. Ridha, F. N.; Wu, Y.; Manovic, V.; Macchi, A.; Anthony, E. J., Enhanced CO2 capture by biomass-templated Ca (OH)2-based pellets. Chem Eng J 2015, 274, 69-75. 32. Chen, H.; Zhao, C.; Yang, Y., Enhancement of attrition resistance and cyclic CO2 capture of calcium-based sorbent pellets. Fuel Process Technol 2013, 116, 116-122. 33. Erans, M.; Beisheim, T.; Manovic, V.; Jeremias, M.; Patchigolla, K.; Dieter, H.; Duan, L.; Anthony, E., Effect of SO2 and steam on CO2 capture performance of biomass-templated calcium aluminate pellets. Faraday Discuss 2016. 34. Li, Y.; Zhao, C.; Ren, Q.; Duan, L.; Chen, H.; Chen, X., Effect of rice husk ash addition on CO2 capture behavior of calcium-based sorbent during calcium looping cycle. Fuel Process Technol 2009, 90, (6), 825-834. 35. Li, Y.; Su, M.; Xie, X.; Wu, S.; Liu, C., CO2 capture performance of synthetic sorbent prepared from carbide slag and aluminum nitrate hydrate by combustion synthesis. Appl Energ 2015, 145, 60-68. 36. Worasuwannarak, N.; Sonobe, T.; Tanthapanichakoon, W., Pyrolysis behaviors of rice straw, rice husk, and corncob by TG-MS technique. J Anal Appl Pyrol 2007, 78, (2), 265-271. 37. Akgsornpeak, A.; Witoon, T.; Mungcharoen, T.; Limtrakul, J., Development of synthetic CaO sorbents via CTAB-assisted sol–gel method for CO2 capture at high temperature. Chem Eng J 2014, 237, 189-198. 38. Sing, K. S., Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure Appl Chem 1985, 57, (4), 603-619. 39. Sun, J.; Liu, W.; Wang, W.; Hu, Y.; Yang, X.; Chen, H.; Zhang, Y.; Li, X.; Xu, M., Optimizing Synergy between Phosphogypsum Disposal and Cement Plant CO2 Capture by Calcium Looping Process. Energ Fuel 2016, 30, (2), 1256-1265. 40. Hu, Y.; Liu, W.; Sun, J.; Li, M.; Yang, X.; Zhang, Y.; Xu, M., Incorporation of CaO into novel Nd2O3 inert solid support for high temperature CO2 capture. Chem Eng J 2015, 273, 333-343. 41. Li, Z.; Liu, Y.; Cai, N., Understanding the enhancement effect of high-temperature steam on the carbonation reaction of CaO with CO2. Fuel 2014, 127, 88-93. 42. Puccini, M.; Seggiani, M.; Vitolo, S., Lithium silicate pellets for CO2 capture at high temperature. Chem. Eng. Trans 2003, 35, 373-378. 43. Sun, J.; Liu, W.; Li, M.; Yang, X.; Wang, W.; Hu, Y.; Chen, H.; Li, X.; Xu, M., 18


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Mechanical Modification of Naturally Occurring Limestone for High Temperature CO2 Capture. Energ Fuel 2016, 30, (8), 6597-6605. 44. Xu, Y.; Luo, C.; Zheng, Y.; Ding, H.; Zhang, L., Macropore Stabilized Limestone Sorbents Prepared by Simultaneous Hydration–Impregnation Method for High Temperature CO2 Capture. Energ Fuel 2016, 30, (4), 3219-3226. 45. Zhang, W.; Li, Y.; Duan, L.; Ma, X.; Wang, Z.; Lu, C., Attrition behavior of calcium-based waste during CO2 capture cycles using calcium looping in a fluidized bed reactor. Chem Eng Res Des 2016, 109, 806-815.

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List of Table Captions Table 1. Ultimate analysis and calorific value of biomass-derived templates (air-dried basis). Table 2. XRF elemental analysis of the biomass pyrolysis residue. Table 3. The specific surface area and pore volume of the CaO-based pellets. Table 4. Weight loss of sorbent pellets during attrition tests.

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Table 1.

a

Sample

N

C

H

S

Oa

Qb (MJ/kg)

MC

0

43.49

6.51

0.25

49.76

15.35

RH

0.93

38.81

5.76

0.21

54.30

14.90

SP

1.9

41.07

6.68

0.20

50.15

16.00

CS

0

39.26

6.70

0.15

53.89

15.24

LP

1.24

64.05

9.66

0.17

24.88

28.39

Oxygen content was calculated by subtraction of C, H, N and S contents from 100

wt.%. b

Q refers to the calorific value of the sample.

21


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Table 2. Component

MC

CS

RH

SP

LP

MgO

1.02

2.63

Al2O3

2.13

9.03

SiO2

8.78

P2O5

2.92

64.46

0.77

2.87

32.12 11.20 24.10 43.12

SO3

56.69 18.29

K2O

23.23 38.68 16.75 24.77 36.87

CaO

7.99

1.01

2.16

2.66

44.13

0.66

4.23

TiO2

0.07

0.18

MnO

0.62

0.40

Fe2O3

11.30

0.57

3.57

22


2.76

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Energy & Fuels

Table 3. Specific surface

Pore volume

area, BET, m2/g

(cm3/g)

CH

12.82

0.094

CH-MC20

19.04

0.140

CH-MC5

16.59

0.129

CH-CS20

18.36

0.136

CH-RH20

13.92

0.102

CH-SP20

9.46

0.071

CH-LP20

16.45

0.110

CH-LP5

13.78

0.099

Sample

23


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Table 4. Sorbent CH CH -MC5 CH -MC10 CH -MC20 CH -CS5 CH -CS10 CH -CS20 CH -RH5 CH -RH10 CH -RH20 CH -SP5 CH -SP10 CH -SP20 CH -LP5 CH -LP10 CH -LP20

Weight loss (%) after 1000 rotations after 3000 rotations 0.11 0.15 0.15 0.39 0.08 0.15 0.60 0.99 0.60 1.12 0.89 1.61 0.64 1.38 0.11 0.17 0.30 1.19 0.29 0.79 0.52 1.50 1.65 2.93 0.49 0.94 0.36 0.69 0.59 1.16 0.78 1.40

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Energy & Fuels

List of Figure Captions Fig. 1. Summary of the CO2 sorption enhancement in the last cycle of the biomass-modified pellets. The enhancement was calculated based on the elevated ratio of CO2 sorption capacity owing to the addition of biomass. Fig. 2. The preparation principle of structurally improved CaO-based pellets via sacrificial biomass templating. Fig. 3. Photographs of the biomass-templated pellets with 20 wt.% of biomass-derived templates. Fig. 4. (a) TG and (b) DTG curves of different biomass-derived templates pyrolysis in N2 . Fig. 5. X-ray diffraction patterns of calcined CaO-based pellets. Fig. 6. (a) N2 adsorption-desorption isotherms and (b) pore size distributions of calcined pellets. The hollow symbols represent the adsorption isotherms and the solid symbols represent the desorption isotherms in Fig. 6 (a). Fig. 7. Cyclic CO2 capture capacity of biomass-templated pellets with the addition of 5, 10 and 20 wt.% of the biomass materials. Calcination at 850 °C under 100 vol.% N2 for 2 min and carbonation at 650 °C under 15 vol.% CO2 for 30 min. Fig. 8. The CO2 capture capacity of different biomass-templated pellets in the 1st, 10th and 25th cycle. Fig. 9. The surface morphology images of cycled sorbent pellets. Fig. 10. The CO2 capture capacity and CO2 capture rate of the MC-templated and LP-templated pellets, (a) and (c) the 1st cycle, (b) and (d) the 25th cycle. 25


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Fig. 1

26


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Fig. 2

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Fig. 3

28


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Fig. 4

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Fig. 5

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Fig. 6

31


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Fig. 7

32


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Fig. 8

33


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Fig. 9

34


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Fig. 10

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CO2 Sorption Enhancement of Extruded ... - ACS Publications

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