Shipei Xuab,
Zhennan Hanc,
Rongcheng Wu*a,
Jiguang Chengc and
Guangwen Xu*ac
aState Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China. E-mail: rwu@ipe.ac.cn; gwxu@ipe.ac.cn
bUniversity of Chinese Academy of Sciences, Beijing 100049, China
cInstitute of Industrial Chemistry and Energy Technology, Shenyang University of Chemical Technology, Shenyang 110142, China
First published on 9th March 2018
This work investigates the evolution of micro/meso pores during a mild thermal treatment of subbituminous coal based on the observation of coal structure changes with the gradual detachment of organic matter from the coal. Pores in coal can be described as super-micropores (d < 1 nm), micropores (1 nm < d < 2 nm) and mesopores (2 nm < d < 50 nm). The decomposition of the carboxyl group at 200 °C decreases the super-micropore volume. A mild and sustained reaction takes place at 300 °C to gradually change the aromaticity and CH2/CH3 ratio of the treated coal. The amount of micropore structure sharply decreases in the early stages of heating, while the amount of mesopore structure continuously decreases during the whole process. A dramatic reaction takes place at 400 °C to sharply change the aromaticity and CH2/CH3 ratio of the treated coal, while the detachment of volatile compounds from the coal matrix caused an evident variation in the mesopore structure of the coal. The aromaticity and CH2/CH3 ratio of coal organics are found to correlate with the volumes of super-micropores and mesopores, respectively. The super-micropores are identified as comprising the inter-layer distance between stacks of aromatic rings, and mesopores are the spaces between macromolecular aromatic rings which are inter-connected via aliphatic chains.
Researchers have performed a lot of studies into the pore and chemical structures of coal during heat treatment.11–14 Several direct characterization tools are also widely used to obtain original structural information.15–19 Zhu et al.20 adopted Raman spectroscopy to characterize the carbon microstructure of char after thermal treatment and found that the char structure evolution behaved differently before and after 800 °C. Increasing the treatment temperature from 500 to 800 °C resulted in a significant decrease in the number of functional groups, a decrease in char yield, and an increase in the number of smaller pores. Structural defects and imperfections of carbon crystallites were gradually eliminated, and the poorly organized structure in the carbon materials gradually became ordered from 800 to 1200 °C. Feng et al.21 found smaller pores of coal samples further developed during the heat treatment above 400 °C, which was mainly due to an enhanced decomposition of surface groups and the release of volatile compounds. The stacking of carbon layers in a graphite-like structure happened during the heat treatment, which was associated with the development of a three-dimensional crystalline structure. These works have indeed studied the chemical and pore structure changes during thermal treatment. However, they mainly focused on the changes of coal at high temperatures at which the original structure of coal had been totally destroyed, making it hard to gain a good insight into the composition and structure of raw coal. There are very few studies investigating the gradual change of coal composition and structure at low temperatures and also for a long treatment time. Furthermore, the clarified relationship between the chemical and physical structures was mainly qualitative, thus requiring further studies for quantitative understanding.
In response to the findings above, this study aims to explore the relationship between the chemical and pore structure of a typical Chinese subbituminous coal under mild conditions. Under such gentle conditions, which are investigated for the first time, functional groups and small molecules gradually escaped from the coal to get slight and continuous changes in coal composition and structure. By investigating the changes, we could gain a deeper understanding of the complex structure in coal. We adopted CO2 and N2 gas adsorption to quantify pore structure changes and to provide a full-range distribution of micro/meso pore sizes. Obtaining two parameters, the aromaticity and ratio of CH2/CH3, by NMR was used to quantify the chemical structure change of coal. Subsequently, linear fitting was adopted to find out the relationship between the chemical and pore structure changes. This would promote our understanding of the chemical and pore structures of this type of coal in thermal conversion.
Adsorption isotherms for N2 at −196 °C and for CO2 at 0 °C were measured in the Quantachrome Autosorb-6B/3B. The N2-adsorption isotherms were obtained for relative pressures (gas pressure against saturated vapor pressure, P/P0) of 0.001 to 0.995, and the CO2-adsorption isotherms were measured in a pressure range of 1 to 760 Torr. The samples were degassed under vacuum at 80 °C for 10 h before the adsorption measurements.22 On the basis of density functional theory (DFT), pore structure parameters were automatically calculated by computer software.23
All NMR spectra were recorded by single pulse excitation/magic angle spinning (SPE/MAS) on a Bruker AV300 spectrometer. The obtained spectra were further processed in Origin Pro 2016 using the Gaussian-curve function. The number of curves adopted is 16 and each one is characterized with its chemical shift at the peak and full width at half maximum of width (FWHM). Table 2 summarizes such parameters of peak assignment for the 16 curves.24
Functional groups | Ketone, aldehyde | Carboxylic acid | Ar–O | Ar–C, H | R–O | –CH2 | –CH3 |
---|---|---|---|---|---|---|---|
Peak center (ppm) | 202 | 187, 178 | 167, 153 | 140, 126, 113, 101 | 96, 76, 56 | 40, 31 | 20, 13 |
FWHM (ppm) | 12–5 | 12–15 | 15–16 | 16–18 | 16–18 | 11–13 | 10–12 |
For all samples their adsorption hysteresis loops belong to the type H3 of the IUPAC classification. The type H3 hysteresis can be caused by the existence of non-rigid aggregates of plate-like particles or assemblages of slit-shaped mesopores.28 The area of the prominent peak in the desorption line reflects the amount of mesopore structure. One can see that it decreased with increasing heating temperature and prolonged heating time. It almost faded away when the temperature reached 400 °C, proving that the slit-shaped mesopores decreased with the increase in heating intensity (higher temperature and longer time). The hysteresis phenomenon of isotherms also existed at low relative pressures to indicate the intercalation, a kind of solid swelling occurring in layered materials. The layer space distance of layered micro-structures in coal expanded with the progress of adsorption so that N2 accessed some spaces that were originally unable to allow N2 to enter. Nitrogen in the expanded layers hardly escapes from the adsorbent, even if the pressure was low. Low pressure hysteresis indicated that the coal had a layered micro-structure, as will be shown later in CO2 adsorption.
For the treatment at 200 °C, the adsorbed N2 quantity first increased in the first hour of the heating process and then decreased with increased heating time. Fig. 1(d) shows that the increase in the adsorbed quantity at the beginning of heating process was caused by the increased mesopore volume. In turn, both micropore and mesopore volumes tended to decrease during the continuous thermal treatment. At 300 °C, the adsorption quantity of N2 at low pressure (p/p0 < 0.05) sharply decreased, corresponding to the sharp decrease in micropore volume. The continuous decrease of the adsorption quantity at high pressure (p/p0 > 0.05) caused a continuous decrease in mesopore volume. For the heat treatment at 400 °C, the adsorption capacity for N2 decreased in the first hour of heating and then increased with heating time. The difference in adsorption capacity was mainly due to micropore adsorption at p/p0 < 0.05. As a result, the mesopore volume diminished first and then remained stable. The micropore volume continuously increased after a sharp decrease in the first hour of heating.
For the treatment at 200 °C, the adsorbed CO2 quantity continuously decreased as the heating time increased. At 300 °C and 400 °C, the adsorption quantity decreased in the first hour of heating and then increased as the heating time was extended. As a summary, Fig. 3 shows the quantitative analysis data. The evolution of the three types of pore varied with heating temperature with a complex nature. Here we observed the continuous change of pore structure during mild thermal treatment, and the data can be used to inter-connect the evolution characteristics of pore structure and chemical composition of coal, as we will do below.
Fig. 4 (a) Solid-state 13C CP/MAS NMR spectra of different samples and (b) the fitting curve of the spectrum for raw coal. |
Fig. 4(b) shows the fitting result for raw coal. Assuming that each carbon has an equal sensitivity to magnetic resonance, the amounts of the assigned carbon functional groups could be determined from the relative peak areas based on their carbon atom number. Table 3 shows the fitting results for all samples, with the aromaticity calculated as aromaticity = A98–220/At, where A98–220 is the area of peaks in the chemical shift region of 98–220 ppm, and At is the total area. The CH2/CH3 ratio (RCH2/CH3) in Table 3 reflects the length of aliphatic chains.
Sample | Functional groups | Aromaticity | RCH2/CH3 | ||||||
---|---|---|---|---|---|---|---|---|---|
Ketone, aldehyde | Carboxylic acid | Ar–O | Ar–C, H | R–O | –CH2– | –CH3 | |||
Raw coal | 2.55 | 3.50 | 11.53 | 55.96 | 3.98 | 15.44 | 7.04 | 0.73 | 2.19 |
200-1 | 2.34 | 3.34 | 11.66 | 55.53 | 3.63 | 15.99 | 7.51 | 0.73 | 2.13 |
200-40 | 2.21 | 2.94 | 11.65 | 56.21 | 4.35 | 15.51 | 7.13 | 0.73 | 2.17 |
200-80 | 1.63 | 2.82 | 11.1 | 57.76 | 3.63 | 15.78 | 7.28 | 0.73 | 2.17 |
300-1 | 2.26 | 3.32 | 10.94 | 56.16 | 3.67 | 15.99 | 7.66 | 0.74 | 2.09 |
300-40 | 2.16 | 3.16 | 13.02 | 56.04 | 4.45 | 13.71 | 7.46 | 0.74 | 1.84 |
300-80 | 1.84 | 2.64 | 11.48 | 60.20 | 3.51 | 12.99 | 7.34 | 0.76 | 1.77 |
400-1 | 2.23 | 3.30 | 12.41 | 64.55 | 3.31 | 7.41 | 6.79 | 0.82 | 1.09 |
400-20 | 2.20 | 3.29 | 11.78 | 67.56 | 4.53 | 5.27 | 5.37 | 0.85 | 0.98 |
400-40 | 2.11 | 3.10 | 10.55 | 71.10 | 3.92 | 4.55 | 4.67 | 0.87 | 0.97 |
400-60 | 2.01 | 2.91 | 9.63 | 76.01 | 2.28 | 3.84 | 3.32 | 0.91 | 1.16 |
400-80 | 1.80 | 2.66 | 9.04 | 75.82 | 2.21 | 4.30 | 4.17 | 0.89 | 1.03 |
400-100 | 1.76 | 2.24 | 9.09 | 75.51 | 3.26 | 4.04 | 4.10 | 0.89 | 0.99 |
When extending the treatment time at 200 °C, the most significant change in the chemical structure was the continuous decrease of the fitting peak areas for the ketone, aldehyde and carboxylic acid functional groups. The aromaticity and CH2/CH3 ratio are stable. The main chemical variation at 200 °C is thus the decomposition of functional groups such as carboxyl. At 300 °C, the CH2/CH3 ratio decreased from 2.19 to 1.77 when the treatment time was prolonged to 80 hours. The corresponding aromaticity increased from 0.73 to 0.76. In this heating process, the pyrolysis reaction started. However, the supplied energy was insufficient to cause dramatic reactions. At 400 °C, the CH2/CH3 ratio decreased from 2.19 (raw coal) to 0.99 for the sample heated for 100 hours (400-100), but the aromaticity conversely increased from 0.73 to 0.89. Compared to the continuous change at 300 °C, the major chemical variation at 400 °C occurred in the first hour of heating, and then there was little variation.
At 200 °C, some carboxyl groups were decomposed to decrease the carboxylic acid peak area in the 13C-NMR fitting data. The aromaticity and CH2/CH3 ratio did not obviously change when prolonging the heating time, indicating that aliphatic hydrocarbons were stable at this temperature. At 300 °C, there was no acute degradation of the vitrinite structure but only a slight change which caused a continuous increase in aromaticity and a decrease in the CH2/CH3 ratio. When reaching 400 °C, pyrolysis reactions obviously took place to sharply vary the aromaticity and CH2/CH3 ratio of the sample. Aliphatic side chains and small organic groups should escape from the sample to increase the aromaticity and decrease the CH2/CH3 ratio.
These relationships would promote our understanding of structure evolution during thermal conversion. At 200 °C, the super-micropore volume decreased from 0.061 ml g−1 to 0.048 ml g−1 without a change in aromaticity, showing that the decreased interlayer space between the stacking aromatic rings is caused by the fracture of hydrogen bonds in oxhydryl and carboxyl species. The micropore pore volume decreased from 0.004 ml g−1 to 0.001 ml g−1 and the mesopore volume decreased from 0.016 ml g−1 to 0.013 ml g−1 to show the expansion of the structure frame and the dominant action of heat treatment (no reaction). A slight increase in mesopore volume from raw coal to sample 200-1 at the beginning of the heat treatment should be due to dehydration that released some pores.
Furthermore, at 300 °C, the super-micropore volume decreased from 0.061 ml g−1 to 0.047 ml g−1 in the first 40 h, indicating the breakage of hydrogen bonds in oxhydryl and carboxyl species (the same as at 200 °C). This volume further increased to 0.061 ml g−1 in the later 40 h, possibly due to the increase in aromatic structure as shown in Table 3. The micropore completely disappeared from 0.004 ml g−1 in the first hour. In this process the composition of coal slightly changed to decrease the CH2/CH3 ratio from 2.19 to 1.77 when heating for 80 h, showing essentially the decomposition of aliphatic chains. Finally, the mesopore volume decreased from 0.016 ml g−1 to 0.007 ml g−1.
With heating at 400 °C, the super-micropore volume decreased from 0.061 ml g−1 to 0.051 ml g−1 in the first hour, then gradually increased to 0.080 ml g−1 in 80 hours and finally remained stable. The increase in aromatic structure is the main reason for this. The micropore volume dropped to zero from 0.004 ml g−1 in the first hour and gradually rose again to 0.008 ml g−1. At 400 °C there is sufficient energy for volatile compounds to escape from coal to form micropores. The mesopore volume quickly decreased from 0.016 ml g−1 to a stable value of 0.006 ml g−1 in the first hour. This corresponds with the NMR data showing the decomposition of aliphatic chains and the destruction of mesopores in coal.
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