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Fuel Vol. 77, No. 6, pp. 563-569, 1998 0 1998 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0016-2361/98 $19.00+0.043

A study of carbonaceous char oxidation in air by semi-quantitative FTIR spectroscopy

Alain Kochan*, Andrtej Krzton b, Giskle Finqueneisel a, Olivier Heintza, Jean-Victor Webera and Thierry Zimnya
allJT Dhpartement Chimie, rue V. Demange, 57500, Saint-Avold, France b/nstitute of Coal Chemistry, Polish Academy of Science, Sowinskiego 5, 44-700, Gliwice, (Received 6 February 1997; revised 12 May 19971 Poland

The aim of this study was to describe the methodology of semi-quantitative characterization of carbonaceous material oxidized under mild thermal conditions. Infrared spectroscopic analysis was applied to the determination of chemical changes induced by oxidation. A curve fitting model has thus been developed to evidence the evolution of specific chemical groups during treatment. The possibility to follow mechanisms and kinetics of carbonaceous char oxidation through data obtained by this model has been demonstrated. 0 1998 Elsevier Science Ltd. All rights reserved (Keywords: chars; oxidation; FTIR; spectroscopy; curve fitting; modelling)

Carbonaceous materials are of great interest because of their use as filtering media or catalyst support 1-4. Related to this, particular attention is accorded to low cost substances that can be converted into active carbon with specific properties. The applications using these materials require specific features (adsorptive potentialities, specific area...) that underline the need to develop adequate preparation methods and to use selected raw materials 5-11. For the study of active chars preparation methods, a device designed for the treatment of samples in a gas flow has been developed. The parameters that can be controlled on this apparatus are the temperature, the duration of the treatment and the nature of the gas. The present paper focuses on the development of a curve fitting model that will permit the identification of individual chemical functional groups and their evolution during an oxidation process. For this purpose, Fourier transformed infrared spectroscopy (FTIR) in the diffuse reflectance mode was used. On the basis of the spectroscopic data and those obtained in the literature 12- .21-26, it has been possible to deconvolute the area specific to carbonyl vibrations into several bands with the help of mathematical tools for spectral data treatment. Though this method is in its preliminary stage, it has proven its ability to visualize the transformations undergone by chars through variations of individual chemical groups. Thus, the possibility to access an understanding of the mechanisms and kinetics of the oxidation of chars by means of infrared analysis has been shown.

EXPERIMENTAL The samples used were coal chars from the carbonization of a law rank coal in a pilot scale rotary kiln (length: 6 m, diameter: 0.6 m). Carbonization was achieved in air in two stages. In the first, coal was heated from ambient temperature to 700C (coal temperature) in 20 min. In the second, coal was kept at 700C for 4 min. After this, the chars were cooled with water. The main features of the coals and relevant chars are given in Table 1. Chars were also characterized by thermogravimetric analysis (TGA) in the range 20-900C. Before thermal treatment, chars were crushed and sieved to a particle size ranging from 200 to 630 pm. This specific particle size was needed for other experiments. For the thermo-oxidative treatment, the chars were inserted in a glass column enclosed in a vertical tubular oven. The glass column (diameter: 35 mm, length: 500 mm) was designed to permit the sample to be in a gas flow to simulate a moving bed device (see Figure 1 for more details). Because of this treatment in a gas flow, too small a particle size had to be avoided to prevent sample loss. The thermal treatment can be decomposed into three steps. During the first step, the temperature was increased in four ramps until the treatment temperature was attained. Throughout this step, the sample remains in a nitrogen flow. Four ramps with decreasing heating rates were used in order to avoid overstepping the treatment temperature due to inertia in the heating control. When the oxidation temperature was reached, nitrogen was replaced by air. During this second step, the temperature was kept constant for a given duration depending on experimental procedure. After the second step, heating is stopped and nitrogen replaced the air. The

* Corresponding

author.

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Carbonaceous

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et al.
Initially, eight experiments were realized by gradually varying the temperature of oxidative treatment from 260 to

Table 1

Features of the coal and relevant chars

coal

used as sample
Char 11.9 2.9 143

for the oxidation treatment

Volatile matter (wt%)
Ash content (wt%)

Vitrinite reflectance (%) Specific area (BET N2) (m g- )

42 2.1 0.56 < 20

Ejj
OVEN \

ml-l

fJ=-w~e#
flowmeter

temperature
controller

d Y IAl

Air Nitrogen

330C in 10C steps, each experiment duration being 140 min. A further, six oxidative treatments were carried at 280C with durations varying from 150 to 250 min in steps of 20 min. Infrared spectrometric measurements were achieved on a spectrometer equipped with a high sensitive mercurycadmium-telluride (MCT) detector. Samples were analyzed in diffuse reflectance (DRIFT) mode by using the Graseby Specac Selector accessory in an off-axis optical geometry. Spectra were recorded by co-adding 750 scans in the range 4000-700 cm- at a resolution of 2 cm- . The analysis chamber was purged continuously with dry air and infrared scanning began only 10 min after sample insertion. Potassium bromide (KBr) ground to an average particle size of 10 pm was used as sample matrix and reference material. The sample, ground separately to a particle size ranging from 40 to 100 pm was mixed with potassium bromide in the proportions 5/95 (% by weight) respectively. To linearize the relationship between concentration and spectral response the Kubelka-Munk function flRm) was applied to the spectral data f(R )= (1 -Rc$ m 2R, _ 2.303~ s

Figure 1 Schematic drawing of the laboratory device used for sample oxidation.

during this third step in the column until ambient temperature was reached. During these steps, gas flows were kept constant at a value of 150 ml min- . This flow rate was determined by taking into account that higher values could provoke partial combustion of the sample during treatment with air as was observed with other carbonaceous material. Temperature and duration of the second step (oxidation step) were used to determine the treatment parameters. sample remained

where: R, represents the ratio of the single beam reflectance spectrum of the sample to the single beam reflectance spectrum of a non absorbing standard (here KBr), E is the molar absorptivity, c is the concentration of the sample and s is a scattering coefficient. The Kubelka-Munk function is known to be applicable only if the scattering coefficient remains constant. This implies among other parameters that particle size and packing density of the samples rn:ssJ & kept constant and that an off axis geometry is needed . Hence, attention was paid to standardization of sample preparations and spectra recording. To develop a curve fitting model that could be used to follow the evolution of oxidation, attention was focused on infrared absorption bands specific to carbon-oxygen linkages.

3500

3000

2500
Wavenumber (cm-l)

2000

1500

1000

Figure 2

Example of DRIFT spectrum recorded on an oxidated char. A-raw spectrum, B-smoothed

spectrum.

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Nonetheless, the part of the spectrum corresponding to etheric C-O vibrations could not be used as it was poorly resolved and bands due to mineral matter components that could interfere were present. Therefore, the wavelengths specific to carbonyl C=O domain 1850-1620 cm- , stretching vibrations, was preferred. As carbonaceous samples such as chars give rise to weak infrared signal in absorbance, it is necessary to avoid the presence of bands due to atmospheric water. Such bands are visible even if water is present at very low concentration and can therefore induce errors in the interpretation of spectra especially in the domain 1850-1620 cm- . Thus, the spectra were recorded as single beams at different periods corresponding to different drying steps of the sample chamber. By this means, it was possible to select the spectrum where the rotational-vibrational bands of water vapor were so low and sharp that they could be removed as noise by smoothing. An example of a spectrum before and after smoothing is given Figure 2. Curve fitting was realized for the region 1890-1505 cm- . For this operation, the concerned wavelengths zone was truncated from the spectrum and submitted to a linear baseline correction that could be repeated on each sample by using identical points as baseline models were developed. To determine the number of bands present in the region and evaluate their width at half height, mathematical treatments such as first and second derivatives * were used as well as reports of work with the same objective and data concerning identified vibrations in the infrared 12,15,17,22-26. These parameters could be averaged as fifteen samples representing fifteen different steps in oxidation were used. Once the number, positions and width at half height of the bands determined, curve fittings were achieved with the help of the Bio-Rad Win-IR release 3.01~ program implemented with such a calculation module The algorithm used adjusts iteratively every variable for each peak in an attempt to minimize the statistical variable K* (chi squared)

which is a weighted difference between fitted and measured data.

RESULTS

AND DISCUSSION analysis of the non treated chars

Thermogravimetric

Three weight losses of different magnitude were found (Figure 3). The first, at a temperature of about lOOC, corresponds to the water loss due to moisture. The second one, very weak (approximately 2% of the total weight), appeared in the temperature range situated between 220 and 420C. In this latter temperature range, oxidations were carried out. The last weight loss had its maximum (12% of total weight) at a temperature of 700C. Infrared spectrometric measurements

The 1890-1505 cm- region of the spectra obtained after truncation and baseline correction are represented in Figure 4A for samples treated at 280C with different durations and in Figure 4B for samples treated for 140 min at different temperatures. Care must be taken because scaling of Figure 4A and B are different and traces were drawn to prevent spectrum parts being hidden. Because of this, the ascending order of temperatures is not respected on Figure 4B and semi-quantitative comparison of data cannot be done here. These figures show that a normalization of these spectra by a convenient quantity is necessary for the semi-quantitative evolution of bands and thereby the influence of oxidation parameters. As shown in Figure 5 (example of a sample treated at 260C for 140 min), 12 bands have been identified with the help of the minima of second derivative curves in the zone 1890-1505 cm- applied to the fifteen spectra recorded. In this example, the position of the band at 1748 cm- was determined on other spectra and, for non treated chars, the bands at 1846 and 1809 cm- were not present. To obtain

Temperature (C) - 1000

( DTG(%/min) -

- -

. . . . . TG (%) .
I

2.5 0.0

.
-800 ?? ... .

-2.5

Figure 3

Data obtained by thermogravimetric analysis (TGA) of the non treated chars.

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l&O

do0

I{50

do0

Id50 (cm-l)

Id00

Id50

1850

Ii00

1750

I?00

l&50

do0

Ii50

Wavenumber

Wavenumber

(cm-l)

Figure 4 DRIFT spectra of the region 1890-1505 cm- after truncation and baseline correction. A-sample oxidated at 280C with increasing durations (expressed in minutes), B-sample oxidated during 140 min with increasing temperatures (expressed in C).

Table 2 Imposed intervals for positions and widths at half height of the bandset used for the curve fitting model in the region 18901505 cm-
Wavenumber intervals (cm- ) 1842-1848 1809-1816 1773-1781 1742-1750 1708-1716 1682-1690 1655-1663 1629-1636 1601-1608 1572-1580 1545-1552 1526-1530 Maximum width at half height (cm- ) 26 33 37 40 45 32 41 35 47 40 35 22

these 12 bands, the most representative ones, which were also common to all spectra, were selected. They have been chosen by taking into account that most of the sharp peaks arising in a second derivative curve were related to remaining water bands. It is also to be noted that adding supplementary bands should result during fitting in multiple solutions in terms of band height and width for adjacent band groups in a same spectrum. For this reason and in order to avoid aleatory variations, the minimal band number necessary to obtain a satisfactory fit was selected. For the development of the curve fitting model, band positions and widths at half height were forced to vary in specific intervals that were determined through the analysis of second derivative curves (see Table 2). Band shapes were set to pure Gaussian or to a mix between Gaussian and Lorentzian (usually very weak percentage of lorentzian; mostly 1 X 10e6%). Only band heights could vary freely.

After each spectrum was split into an elementary bandset by applying the curve fitting model, normalization of the 1890-1505 cm- region was achieved by dividing the intensity of each point (calculated through the KubelkaMunk relation) by the area of the band in the 1601-1608 cm-i zone. This important band, is assi ned in this case to 8*25.This reference aromatic ring stretching vibrations 13*2 choice can be justified by referring to the structure of the samples. Chars issued from a pyrolysis up to 700C can be considered as essentially constituted of large polyaromatic layers. Thus, ring stretching vibrations can only be observed at the edges and at the level of intraplanar defects due to the presence of heteroatoms or aliphatic bridges. In addition, the reactive sites of polynuclear structures are known to be situated at the layer edges 27328. Taking this into account, it is assumed that the amount of aromatic ring stretching vibrations can be connected with the number of reactive sites likely to be oxidized. Thus, after normalization, it is possible to show the evolutions of individual carbonyl groups in the 1890-1580 cm- region by examination of the fitted curves.
Band assignement The individual bands resulting from the curve fitting of the 1890-1505 cm- zone were attributed to specific infrared stretching vibrations as follows (refer to Figure 5):

1860-l 750 cm- : 4 bands attributed to lactones and anhydrides

1750-1680 esters 1680-1620 quinones l620-15IO cm- : 2 bands due to ketones, carboxyls and cm- : 2 bands due to conjugated ketones and

cm- : 4 bands that were attributed to aromatic ring stretching modes 13V23.

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1850

1800

1750

1700 Wavenumber (cm-l)

1650

1600

1550

Figure 5

Example of a bandset issued from the curve fitting of a DRIFT spectrum in rhe region 1890-1505 cm- . Upper trace corresponds

to the second derivative of the initial spectrum (thick line).

tempe

re ( C)

ki
7

sa3Fpr
t-

wavenumber (cm- l)

Figure 6

Three dimensionalrepresentationof the evolution of carbonyl bands versus the duration of the oxidative treatment.

Evolution of carbonyl bands versus oxidation parameters For the visualization of evolutions undergone by the carbonyl bandset issued from the curve fitting of this zone, graphical constructions were elaborated for the parameters temperature and time. On these constructions, aromatic ring stretching modes are not represented in order to clarify the drawings. Samples oxidized for 140 min with increasing temperatures On the three dimensional representation of Figure 6 (value 20C for non oxidized char), it appears that areas of lactones and anhydrides bands (numbered 1-4) as well as those of the ketones, carboxyls and esters band (5) increase

with temperature and this in a way that can be considered as continuous. The parallel variations of these carbonyl groups suggests the existence of an equilibrium between anhydrides and carboxyls. For conjugated ketones and quinone bands (6, 7) evolutions are not clearly shown. The area of band 7 (quinones) varies around a value appreciably higher than that of the non treated chars. Band 6 (conjugated ketones) shows variations intermediate between band 7 and the bands l-5. This latter observation suggests that band 6 is a mixed band in which several carbonyl groups participate. Variations of bands 6 and 7 seem to occur by jumps as if the formation of the relevant chemical groups would be dependent of energy quanta. This is suggested by

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time (n

Figure 7

Three dimensional

representation

of the evolution of carbonyl bands versus the temperature

of the oxidative treatment.

the fact that band areas fall to values that are approximately equal to the initial one and that during the heating ramp, samples were under an inert nitrogen atmosphere.
Samples oxidized at 280C with increasing duration

ACKNOWLEDGEMENTS The authors would like to thank the Agence Nationale pour la Valorization de la Recherche (ANVAR-Lorraine) and the EUREKA program EU 1436 Cheap Adsorbents for financial support.

As seen with variable oxidation temperature, results given in Figure 7 (value 0 for non oxidized char) show three distinct evolution trends. For lactones, anhydrides, ketones, carboxyls and esters (bands l-5), after a strong increase due to temperature, areas seem to be stabilized around a constant value. All variations for these 5 bands are quasi parallel. The band attributed to conjugated ketones (6) follows approximately the evolution of bands l-5. This confirms the observations made previously about its mixed nature. For the quinones band (7), an increase that can be considered as continuous is observed. This trend is not well understood yet. A relation between increasing duration and enhancement of reactive sites cannot be invoked here. Such a relation would be valuable only if an increase in the area of other bands could be observed. CONCLUSION For the study of chars and especially for investigating chemical transformations undergone by superficial chemical groups during oxidation, infrared spectroscopy can be considered as a well adapted tool. The present study has shown that the access to kinetics and mechanisms of oxidation reactions is made possible with the help of adequate mathematical treatments such as curve fitting. Being in a preliminary stage, this work has nonetheless pointed out that complex regions of spectra obtained in the infrared DRIFT mode can be decomposed into individual bands which evolution is a key to the understanding of oxidation. Thereby, the influence of treatment parameters can be followed and results can be used for optimization of processes.

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