1. bookTom 30 (2021): Zeszyt 1 (March 2021)
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Analysis of Pyrolysis Characteristics and Kinetics of Cigar Tobacco and Flue-Cured Tobacco by TG-FTIR

Data publikacji: 20 Apr 2021
Tom & Zeszyt: Tom 30 (2021) - Zeszyt 1 (March 2021)
Zakres stron: 29 - 43
Otrzymano: 17 Aug 2020
Przyjęty: 17 Feb 2021
Informacje o czasopiśmie
License
Format
Czasopismo
eISSN
2719-9509
Pierwsze wydanie
01 Jan 1992
Częstotliwość wydawania
4 razy w roku
Języki
Angielski
INTRODUCTION

In recent years, cigars have been accepted by many tobacco consumers because of their special aroma and high nicotine release characteristics. According to a statistic report (1), the global cigar market revenue was US Dollar (USD) 17 billion in 2019 and is expected to increase to USD 19 billion by 2023. Cigars are defined as tobacco rolls wrapped in either tobacco leaf or another tobacco-containing substance (2). A burning cigar can be regarded as a chemical reactor. Smoke is produced through complex chemical and physical reactions during the combustion and pyrolysis processes (3), in which the characteristics of cigar smoke can be further studied.

On the other hand, the production of cigarettes and cigars generates about 20% of tobacco waste (4). These cigar tobacco residues are an abundant biomass resource that is discarded as waste without any treatment. The inappropriate disposal of cigar tobacco residues may waste a renewable biomass resource and could cause serious environmental pollution issues (5). An alternative approach for enhancing the value of this resource is by thermochemical conversion methods. For example, these lignocellulosic bioresources can be converted into valuable products, such as bio-oil, fuel gas and solid carbon, through a pyrolysis process (6). Therefore, the pyrolysis behavior of cigar residues is of great significance for the appropriate utilization.

Many studies have focused on the pyrolysis behavior of plant materials (7,8,9), including tobacco residue (5) via various modern techniques. Among these analytical techniques, thermogravimetric analysis (TG) coupled to Fourier-transform infrared (FTIR) have frequently been used not only in pyrolysis kinetics studies during the thermal decomposition process but were also applied in the characterization of the evolved gas products. With the single-use of TG, Cardoso et al. (10), Guo et al. (11) and Wang et al. (12) performed research on the pyrolysis kinetics of tobacco including the influence of thermal conditions, heating rate, particle size, and data processing. The thermal degradation of tobacco leaves could be divided into three stages: dehydration, main devolatilization, and continuous devolatilization (10,11,12). Gao et al. (6) showed that the pyrolysis of tobacco is a very complicated chemical reaction, which cannot be represented by a single reaction or reaction combination. Valverde et al. (13) found that the global mass loss in tobacco dust pyrolysis can be simulated by four independent parallel mass-loss events. By using TG-FTIR technology, the volatile components in the pyrolysis process of bidi tobacco were identified as H2O, CO2, CO, NH3, HCN, NO, NO2, and some organic volatile compounds (14). However, previous studies have mainly focused on the thermal decomposition of cigarette tobacco. The pyrolysis behavior of cigar tobacco, especially the release of volatiles at different temperatures, has not been fully studied.

Cigar tobacco and cigarette tobacco display different curing methods and chemical compositions, thus their pyrolysis behavior will not be the same. In this study, the pyrolysis behavior of cigar tobacco was comprehensively investigated via thermogravimetric analysis at different heating rates, with the addition of flue-cured tobacco as a contrast. The activation energy was estimated by isoconversional FWO (Flynn-Wall-Ozawa) and Kas (Kissinger-Akahira-Sunose) methods. The mechanism functions were established by Málek and Coats-Redfern methods. Moreover, the release behavior of volatile products during the pyrolysis of cigar tobacco was analyzed dynamically by TG-FTIR. The results can provide theoretical references for the design of cigar products or the processing of cigar residues.

MATERIALS AND METHODS
Material

Three types of tobacco middle leaves were considered in this study: cigar filler tobacco (CFT), cigar wrapper tobacco (CWT) and flue-cured tobacco (FCT). CFT and CWT were cultivated in Hainan Province, China, and collected after air-curing process. FCT was cultivated in Yunnan, China, and collected after flue-curing process. After drying at 40 °C for 5 h, the samples were ground to pass through a 40-mesh sieve and then stored in a sealed container before use. The ultimate analysis of the tobacco was conducted on an Elementar Vario EL cube CHNSO analyzer (Hanau, Germany). Proximate analysis of tobacco was conducted to determine the contents of moisture, volatile matter, fixed carbon and ash by using thermogravimetric method (15). The content of cellulose, hemi-cellulose and lignin in the samples was determined according to a previous work (16). The nicotine content of the samples was determined according to the methods described in ISO 10315 (17).

TG-FTIR analysis

Experiments were performed using a thermogravimetric analyzer (Discovery, TA Instrument, Newcastle, DE, USA) coupled with a FTIR spectrophotometer (Nicolet 8700, Thermo Electron, Waltham, MA, USA) through a transfer line. The mass change of the samples with temperature during the pyrolysis was recorded. Approximately 10 mg of the sample were placed in a platinum crucible. The experiments were performed from 40 °C to 900 °C at different heating rates (5 °C min−1, 10 °C min−1, 15 °C min−1, and 20 °C min−1) under nitrogen atmosphere (99.999% minimum purity) with a flow rate of 30 mL min−1. The stainless-steel transfer pipe and the gas cell in the FTIR were both heated to a constant temperature of 210 °C to minimize secondary reactions. The resolution of the FTIR was set at 4 cm−1, spectrum scan frequency was 8 times per minute, and the spectral region was from 600 cm−1 to 4000 cm−1.

The devolatilization index (Di) is a comprehensive evaluation of volatile release and can reflect the reactivity of the whole pyrolysis process. A greater Di value implies that it is more reactive. Di is determined by the following equation (18,19,20): Di=(RmaxRmean)/(TSTmaxΔT1/2) {D_i} = \left( {{R_{max }} \cdot {R_{mean}}} \right)/\left( {{T_S} \cdot {T_{max }} \cdot \Delta {T_{1/2}}} \right) where Rmax is the maximum devolatilization rate, Rmean the average devolatilization rate, TS the initial volatile release temperature, Tmax is the temperature corresponding to Rmax, and ΔT1/2 is the temperature interval containing the maximum peak where R/Rmax = 1/2. The devolatilization rate, R, is defined as R = dwt/dt, where wt is the mass percentage of the raw sample at time t. Rmax and R can be obtained from the DTG curves.

Kinetic analysis

For the kinetic analysis, the decomposition rate can be described by the following equation: dαdt=k(T)f(α) {{d\alpha } \over {dt}}=k(T)f(\alpha ) where α is the extent of conversion, and α = (m0mt)/(m0m), m0 is the initial mass of the sample, mt is the mass at a given time t, and m is the final mass of the sample, T is the absolute temperature, k(T) is the reaction rate as function of the temperature and f(α) is the reaction model, which is a function of α. The reaction rate constant is typically described in accordance with the Arrhenius equation, which is a function of T and expressed as: k(T)=Aexp(Ea/RT) k(T) = A\,\exp \left( { - {E_a}/RT} \right) where A is the frequency factor, Ea is the activation energy, and R is the universal gas constant (8.3145 J mol−1 K−1).

The heating rate β is defined as dT/dt, which is substituted in Equation [1] to obtain Equation [3]: dαdT=Aβexp(EaRT)f(α) {{d\alpha } \over {dT}} = {A \over \beta }\exp \left( { - {{{E_a}} \over {RT}}} \right)f(\alpha )

The integral form of Equation [3] is expressed as follows, G(α)=0αdαf(α)=Aβ0Texp(EaRT)dT=AEaβRP(u) G\left( \alpha \right) = \int_0^\alpha {{{d\alpha } \over {f\left( \alpha \right)}} = {A \over \beta }} \int_0^T {\exp \left( { - {{{E_a}} \over {RT}}} \right)dT = {{A{E_a}} \over {\beta R}}P\left( u \right)} where G(α) is the integral form of f(α), P(u) is an approximation, and u is defined as the equation of u = Ea/R.

The Flynn-Wall-Ozawa (FWO) method

The FWO method (21) is one of the most widely used model-free methods derived from DOYLE’S approximation (22). With Equation [4], the final form of the FWO equation is expressed as: lg(β)=lg(AEaRG(α))2.3150.457EaRT \lg \left( \beta \right) = \lg \left( {{{A{E_a}} \over {RG\left( \alpha \right)}}} \right) - 2.315 - 0.457{{{E_a}} \over {RT}} where β is the heating rate, and T is the temperature at conversion α. In a plot of lg(β) versus 1/T the slope is −0.457Ea/R, where R is the gas constant, and the activation energy Ea can thus be obtained from the slope.

The Kissinger-Akahira-Sunose (KAS) method

The KAS method (23) is also a model-free method to calculate pyrolysis kinetics, which is based on the following expression: ln(βT2)=ln[AEaRG(α)]EaRT \ln \left( {{\beta \over {{T^2}}}} \right) = \ln \left[ {{{A{E_a}} \over {RG\left( \alpha \right)}}} \right] - {{{E_a}} \over {RT}}

The plot of ln(β/T2) and 1/T data points obtained from the curves recorded for several heating rates is a straight line. The slope is used to calculate the activation energy Ea.

The Málek method

When the activation energy Ea is known, the pyrolysis reaction mechanism of the solid-stage reactions can be obtained by the Málek method (24, 25). The Málek method works by comparing experimental data with a theoretical reference curve. The theoretical curve can be expressed as: y(α)=f(α)G(α)f(0.5)G(0.5) y\left( \alpha \right) = {{f\left( \alpha \right) \cdot G\left( \alpha \right)} \over {f\left( {0.5} \right) \cdot G\left( {0.5} \right)}} where the functions f(α) and G(α) are reaction models. The experimental curve can be expressed as follows: y(α)=(TT0.5)2(dαdt)(dαdt)0.5 y\left( \alpha \right) = {\left( {{T \over {{T_{0.5}}}}} \right)^2}{{\left( {{{d\alpha } \over {dt}}} \right)} \over {{{\left( {{{d\alpha } \over {dt}}} \right)}_{0.5}}}} where T0.5 and (dα/dt)0.5 are the temperature and reaction rate at α = 0.5, respectively. Table 2 lists mathematical expressions of several options for f(α) and G(α). The plot of y(α) versus α produces an experimental curve according to Equation [8]. The pyrolysis reaction model can be obtained by comparing the experimental curves with the theoretical master plots.

The Coats-Redfern method

The Coats-Redfern (26) integration method uses a single model to analyze the characteristics of pyrolysis kinetics. By integrating the temperature approximation of Equation [4], the Coats-Redfern equation is derived as follows: ln[G(α)T2]=ln[ARβEa(12RTEa)]EaRT \ln \left[ {{{G\left( \alpha \right)} \over {{T^2}}}} \right] = \ln \left[ {{{AR} \over {\beta {E_a}}}\left( {1 - {{2RT} \over {{E_a}}}} \right)} \right] - {{{E_a}} \over {RT}}

For the general temperature region and Ea of pyrolysis reaction, Ea2RT, so Equation [9] can be simplified as ln[G(α)T2]=lnARβEEaRT \ln \left[ {{{G\left( \alpha \right)} \over {{T^2}}}} \right] = \ln {{AR} \over {\beta E}} - {{{E_a}} \over {RT}}

The activation energy (Ea) and pre-exponential factor (A) can be obtained from the linear relationship between ln[G(α)/T2] and 1/T.

RESULTS AND DISCUSSION
Composition of tobacco leaves

The composition of different tobacco leaves is summarized in Table 1. The chemical composition of tobacco leaf is affected by factors such as genetics, agricultural practices, soil type, and curing procedures, etc. (27). Cigar tobacco and flue-cured tobacco have significant differences in fixed carbon, ash, nitrogen, oxygen and nicotine content. The nitrogen, nicotine, and ash content of cigar tobacco is higher than that of flue-cured tobacco, while the oxygen and cellulose content is on the contrary. The total content of hemicellulose, cellulose, and lignin in tobacco is from 15% to 20%.

Composition of tobacco leaves.

Item CFT CWT FCT
Proximate analysis (wt.%)
Moisture 2.95 3.84 1.89
Volatile 77.31 75.41 76.79
Fixed carbon 12.80 11.19 16.76
Ash 9.89 13.40 6.54
Ultimate analysis (wt.%)
C 43.57 42.95 41.83
H 5.88 6.17 6.32
N 3.63 3.77 1.67
S 0.00 0.18 0.17
O 36.52 37.41 43.28
Biochemical analysis (wt.%)
Hemicellulose 2.25 3.24 2.81
Cellulose 11.35 13.12 14.26
Lignin 2.84 3.65 3.21
Nicotine content (wt.%) 2.20 2.33 2.07

CFT = cigar filler tobacco; CWT = cigar wrapper tobacco; FCT = flue-cured tobacco

Functional expressions of several common response models.

Mechanisms Symbol G(α) f(α)
One-dimensional diffusion D1 α2 12α1 {1 \over 2}{\alpha ^{ - 1}}
Two-dimensional diffusion D2 α + (1 − α)ln(1 − α) [−ln(1 − α)]−1
Three-dimensional diffusion D3 [1(1α)13]2 {\left[ {1 - {{\left( {1 - \alpha } \right)}^{{1 \over 3}}}} \right]^2} 32(1α)23[1(1α)13]1 {3 \over 2}{\left( {1 - \alpha } \right)^{{2 \over 3}}}{\left[ {1 - {{\left( {1 - \alpha } \right)}^{{1 \over 3}}}} \right]^{ - 1}}
Avrami-Erofeev A2 [ln(1α)]12 {\left[ { - \ln \left( {1 - \alpha } \right)} \right]^{{1 \over 2}}} 2(1α)[ln(1α)]12 2\left( {1 - \alpha } \right){\left[ { - \ln \left( {1 - \alpha } \right)} \right]^{{1 \over 2}}}
Avrami-Erofeev A3 [ln(1α)]13 {\left[ { - \ln \left( {1 - \alpha } \right)} \right]^{{1 \over 3}}} 3(1α)[ln(1α)]23 3\left( {1 - \alpha } \right){\left[ { - \ln \left( {1 - \alpha } \right)} \right]^{{2 \over 3}}}
First-order reaction F1 −ln(1 − α) 1 − α
1.5-order reaction F3/2 2[(1α)12]2 2\left[ {{{\left( {1 - \alpha } \right)}^{-{1 \over 2}}}} \right] - 2 (1α)32 {\left( {1 - \alpha } \right)^{{3 \over 2}}}
Second-order reaction F2 (1 − α)−1 − 1 (1 − α)2
Contracting area R2 1(1α)12 1 - {\left( {1 - \alpha } \right)^{{1 \over 2}}} 2(1α)12 2{\left( {1 - \alpha } \right)^{{1 \over 2}}}
3D contracting volume R3 1(1α)13 1 - {\left( {1 - \alpha } \right)^{{1 \over 3}}} 3(1α)23 3{\left( {1 - \alpha } \right)^{{2 \over 3}}}

Figure 1

TG (a) and DTG (b) curves of CFT, CWT and FCT pyrolysis processes at the heating rate of 10 °C min−1.

Figure 2

TG-DTG curves of CFT (a), CWT (b) and FCT (c) pyrolysis processes under different heating rates of 5 °C min−1, 10 °C min−1, 15 °C min−1, and 20 °C min−1.

Thermogravimetric analysis

The TG-DTG curves of CFT, CWT and FCT pyrolysis processes at the heating rate of 10 °C min−1 are shown in Figure 1. The pyrolysis behavior of tobacco is very complicated, in addition to the decomposition of biopolymers such as cellulose, hemicellulose, pectin, and lignin, further comprising a large number of decompositions of non-polymer compounds. Generally, the decomposition of cigar tobacco can be divided into four stages. In stage I, the decrease in mass occurs primarily due to the evaporation of water, which accounts for almost 3% of the sample. In stage II, the thermal decomposition of hemicellulose in tobacco takes place mainly between 220 °C and 285 °C (28, 29), the peak at about 270 °C could be the maximum decomposition rate of hemicellulose. In addition, some low-temperature volatiles are released, partially due to the decomposition of sugars, pectin, and nicotine, that occurs at this stage (30, 31). The mass loss of CFT and CWT at this stage is 23% and 20%, respectively. In stage III, the temperature range and the temperature of the peak of the DTG curve are very close to the decomposition temperature of cellulose (32, 33). This indicates that stage III of the DTG curve may correspond to cellulose pyrolysis of the cigar tobacco leaves. In this stage, the thermal decomposition rate increases compared with that of stage II. In stage IV, a shoulder between 420 °C and 600 °C was observed, which could be related to the decomposition of lignin (34). Mass loss after 600 °C may include dehydrogenization and aromatization of residual carbon (3). Among the three components, hemicellulose is the easiest to be pyrolyzed, followed by cellulose, and lignin is the most difficult one. This may be due to differences in the chemical structures and natures of polymeric materials. Hemicellulose is a mixture of various monosaccharides (xylose, mannose, glucose, galactose, etc.) with a low degree of polymerization. In contrast, the cellulose molecule is a very long polymer of glucose without branches, which results in thermal degradation more difficult than in hemicellulose. Lignin is composed of three kinds of benzene-propane and is heavily cross-linked. Therefore, lignin has high thermal stability and is difficult to decompose (35). The main pyrolysis stages (stage II and stage III) of CFT and CWT contribute to a mass loss of 48.48% and 44.95%, respectively. CWT has been grown under shade treatment conditions that may be unfavorable for the accumulation of organic material in the leaves.

However, it can be seen from the DTG curves that the pyrolysis process of flue-cured tobacco is different from that of cigar tobacco. This may be caused by differences in physical structure and chemical composition. Flue-cured tobacco has an obvious mass loss peak at 200 °C, which corresponds to the decomposition of volatile compounds. The significant difference observed may be due to the difference in sugar content. According to the previous literature (27), flue-cured tobacco has a high sugar content, while in cigars - as air-cured tobacco - their sugars have been virtually depleted via metabolic activities. In addition, flue-cured tobacco has a continuous mass loss peak between 230 °C and 400 °C due to the lower hemicellulose content relative to the cellulose content, while the mass loss peak of cigar tobacco occurs at a slightly lower temperature at this stage. This result shows that the thermal decomposition temperature of biopolymers in cigar tobacco is lower than that of flue-cured tobacco, which may be due to the lower crystallinity and/or the lower degree of polymerization of the biopolymers in the cigar tobacco (36).

The TG-DTG curves of CFT, CWT and FCT pyrolysis processes at different heating rates are shown in Figure 2. The mass loss at different heating rates during the pyrolysis of samples was obtained from TG-DTG curves and is summarized in Table 3. With the rise of the heating rate, the reaction rate accelerates, and the DTG curves move toward the higher temperature. This may be due to the fact that the time required to reach the final temperature is reduced as the heating rate increases. This results in a decrease in the reaction time experienced by the sample, and thermal hysteresis occurrs during the pyrolysis process (37). As shown in Table 3, the mass loss is not strongly dependent upon the heating rate. This suggests that the total mass loss at any stage depends primarily on the basic composition of the sample (38).

Mass loss at different temperature intervals during pyrolysis of tobacco leaf samples.

Sample Stage I Stage II Stage III

Temperature interval (°C) Mass loss (%) Temperature interval (°C) Mass loss (%) Temperature interval (°C) Mass loss (%)
CFT
 5 40–130 2.84 130–283 22.60 283–397 26.43
10 40–134 2.88 134–292 23.26 292–411 26.78
15 40–142 3.03 142–296 23.07 296–415 26.77
20 40–146 3.06 146–299 23.35 299–424 27.34
CWT
 5 40–131 2.81 131–273 20.04 273–407 25.33
10 40–140 2.85 140–284 20.83 284–417 24.65
15 40–144 2.84 144–287 20.94 287–419 24.32
20 40–151 2.96 151–291 21.08 291–426 24.44
FCT
 5 40–101 1.29 101–216 21.09 216–401 38.82
10 40–103 1.10 103–227 22.27 227–405 38.41
15 40–108 1.15 108–232 21.76 232–408 38.19
20 40–115 1.27 115–240 22.12 240–416 37.40

CFT = cigar filler tobacco; CWT = cigar wrapper tobacco; FCT = flue-cured tobacco

The characteristic parameters of pyrolysis (TS, Tmax, Rmax, Rmean, ΔT1/2, and Di) of CFT, CWT and FCT at varying heating rates are summarized in Table 4. At a heating rate of 10 °C min−1, the devolatilization indices Di of CFT, CWT, and FCT are 6.99 × 10−7%2 °C−3 min−2, 10.62 × 10−7%2 °C−3 min−2, and 27.3 × 10−7%2 °C−3 min−2, respectively. In summary, compared with CFT and CWT, FCT has a lower characteristic temperature of volatiles release, and the ΔT1/2 is narrower. This shows that FCT is more reactive than CFT and CWT. As shown in Table 4, Rmax, and Di increase as the heating rate increases. Generally speaking, combustibles with greater Di value imply that they are more reactive. Thus, increasing the heating rate is in favor of the release of volatile substances.

Characteristic parameters of tobacco leaves during pyrolysis.

Sample TS (°C) Tmax (°C) Rmax (% min−1) Rmean (% min−1) ΔT1/2 (°C) Di (10−7%2 °C−3 min−2) Residue (%)
CFT
 5 130 313 −2.01 −0.43 105 2.02 24.46
10 134 323 −3.96 −0.86 112 6.99 24.73
15 142 330 −5.78 −1.27 121 12.91 25.71
20 146 335 −7.65 −1.68 122 21.61 26.11
CWT
 5 131 297 −2.16 −0.43 72 3.30 24.75
10 140 307 −4.21 −0.83 76 10.62 27.56
15 144 310 −6.22 −1.23 79 21.61 28.25
20 151 315 −8.18 −1.62 82 33.94 28.97
FCT
 5 101 188 −1.82 −0.47 60 7.51 18.75
10 103 197 −3.73 −0.92 62 27.30 20.06
15 108 201 −5.60 −1.36 64 54.80 21.38
20 115 206 −7.30 −1.80 65 85.30 21.82
FTIR analysis of gas products

The 3D FTIR spectrum of the gases emitted during tobacco pyrolysis are shown in Figure 3. On the whole, the 3D spectra demonstrate similar gas release behavior with some slight differences. Five characteristic absorbance bands with the maximum absorption at 3565 cm−1, 2357 cm−1, 1749 cm−1, 1504 cm−1, and 667 cm−1 are observed for tobacco samples. This result suggests that the gas products corresponding to these five bands are the pyrolysis products. Moreover, each characteristic FTIR peak exhibits several peaks, and the evolution with temperature corresponds to the DTG curves.

In order to identify the components of the gas products, the 2D FTIR spectra at the peak temperature of the four stages are shown in Figure 4. Based on the FTIR spectra, the result of component identification of the gas products is shown in Table 5. To avoid interference from the pyrolyzed mass, the absorbance has been normalized by dividing it by the initial mass of tobacco.

Identification of gas products during pyrolysis of tobacco based on FTIR spectra.

Wavenumber (cm−1) Functional groups Compounds References
3500–4000 (selected:3566) O-H Symmetrical and asymmetrical stretching H2O (14, 42, 45)
2250–2500 (selected:2359) Asymmetrical stretching in O=C=O CO2 (14, 45)
2850–3030 (selected:3016) C-H Stretching CH4 (43)
2000–2250 (selected:2190) Stretching vibration in CO CO (14, 45)
1710–1800 (selected:1749) C=O Stretching Carbonyl groups (14, 45)
1050–1200 (selected:1180) C-O Stretch Hydroxyl groups (14)
1450–1650 Aromatic C=C-C ring stretch Aromatics (42, 43)
3070–3130 (selected:3076) Aromatic C-H in plane bend
966 NH3 (42)

Figure 3

3D TG/FTIR diagram of pyrolysis products for CFT (a), CWT (b) and FCT (c).

Figure 4

FTIR spectra of volatile products at peak temperature for tobacco samples.

In the first stage (T1), the main volatile component is H2O, as evidenced by the absorbance band between 3500 cm−1 and 4000 cm−1, which was mainly caused by the evaporation of the sample. In stage II (T2), the bands in the region from 2250 cm−1 to 2500 cm−1 and 580 cm−1 to 700 cm−1 demonstrate the release of CO2. CO2 is the dominant gas during tobacco pyrolysis, and is mainly produced by the cracking and reforming of carbonyl and carboxyl groups (39). Besides, a very small asymmetric absorption peak corresponding to C-O appears in the wavenumber from 1050 cm−1 to 1200 cm−1, indicating the existence of alcohols and phenols (40). The C=O stretching vibration in the range from 1710 cm−1 to 1800 cm−1 is attributed to aldehydes, ketones, and organic acids which contained the carbonyl groups. The bands in the region from 1450 cm−1 to 1650 cm−1 are the C=C stretching vibration and benzene skeleton vibration. The band at 966 cm−1 represents NH3. With the pyrolysis temperature increased to T3, the abovementioned absorbance bands gradually increased in intensity. The band from 2850 cm−1 to 3030 cm−1 is characteristic of hydrocarbon gases such as CH4. The absorption band from 2000 cm−1 to 2250 cm−1 indicates the presence of CO. The spectrum obtained at T4 shows that the main components of the gases released are CO, CO2, and water, which are caused by the carbonates inherent or generated during pyrolysis (41).

According to the widely used Lambert-Beer law, the absorbance at a specific wavenumber is linearly related to the gas concentration (44). Therefore, changes in absorbance during pyrolysis reflect changes in the concentrations of different gases. Figure 5 compares the evolution of gas products with increasing temperatures during the pyrolysis of tobacco samples. As shown, the gas products (except for CH4 and CO) are concentrated within the temperature range from 200 °C to 400 °C. Moreover, the evolution of released CO2 with temperature is consistent with the thermogravimetric analysis. The CO2 released from 200 °C to 400 °C can mainly be attributed to the cracking and reforming of carboxyl groups that CWT exhibit a more intense signal in this stage, whereas above 400 °C, the polymerization reaction of solid phase coking is accompanied by the emission of CO2 as the temperature increases.

Figure 5

Evolution of gas products with increasing temperature in the pyrolysis of tobacco.

Figure 6

Arrhenius plots of FWO method for CFT (a), CWT (b) and FCT (c) at different conversion rates.

Figure 7

Arrhenius plots of KAS method for CFT (a), CWT (b) and FCT (c) at different conversion rates.

The release rate of water varied with the temperature, the band below 200 °C was related to the evaporation of water. The appearance of a maximum at around 320 °C for H2O can be attributed to the decomposition of hemicellulose and cellulose by the cracking of hydroxyl groups in the lateral chains (45). CH4 is formed by the cleavage of methoxyl groups and methylene groups. This band shows a maximum at around 540 °C, which is associated with lignin decomposition. For CO, two peaks appear at around 330 °C and 500 °C, indicating that the formation of CO is related to the decomposition of cellulose and lignin, and the release amount of CO above 600 °C increases significantly. The release of CO is consistent with the results reported by BAKER (46), suggesting that the formation of carbon oxide occurs in two regions, a low-temperature region from 100 °C to 450 °C and a high-temperature region from 500 °C to 900 °C. The total amount of carbon oxides is independent of the heating rate, but the relative proportions of CO2 and CO are strongly dependent on the heating rate. BAKER proposed that CO undergoes some gas phase reactions, and that CO2 undergoes both gas phase reaction and heterogeneous reaction. The release curves of carbonyl and hydroxyl compounds were consistent in the maximum mass loss range, indicating that the formation of aldehydes and ketones from tobacco pyrolysis went along with the formation of alcohols and phenols. Aromatics were formed at temperatures above 500 °C and with a maximum at around 540 °C, suggesting that the production of aromatic compounds was related to lignin decomposition. Compared with CFT and CWT, FCT had lower decomposition intensity on CO2, CH4, CO, and aromatics.

Determination and comparison of activation energy

To determine the activation energy of the pyrolysis of cigar tobacco and flue-cured tobacco, two different model-free isothermal conversion methods (FWO and KAS models) were used. In the FWO method, the activation energy can be determined from the plots of lg(β) versus 1/T. In the KAS method, the activation energy can be determined from the plots of lg(β/T2) versus 1/T. Figures 6 and 7 show the dependence of the activation energy on the conversion (α = 0.1–0.9) for the different tobacco leaves based on the isoconversional FWO and KAS methods, respectively. The corresponding values calculated from the slope and the coefficients of determination R2 at different degrees of conversion (α) are presented in Table 6. The Ea values of CFT range from 207.4 kJ mol−1 to 319.3 kJ mol−1, that of CWT range from 160.4 kJ mol−1 to 260.5 kJ mol−1, and that of FCT range from 100.1 kJ mol−1 to 192.1 kJ mol−1. Importantly, the coefficients of determination R2 of all curves are above 0.98 indicating that all linear plots are statistically relevant. The difference between the two methods is less than 2%, indicating the accuracy and reliability of the calculations of the FWO and KAS methods.

Activation energies of cigar tobacco leaves obtained by the FWO method and KAS method.

Conversion CFT CWT FCT



FWO KAS Difference FWO KAS Difference FWO KAS Difference



Ea (kJ mol−1) Correlation coefficient R2 Ea (kJ mol−1) Correlation coefficient R2 (%) Ea (kJ mol−1) Correlation coefficient R2 Ea (kJ mol−1) Correlation coefficient R2 (%) Ea (kJ mol−1) Correlation coefficient R2 Ea (kJ mol−1) Correlation coefficient R2 (%)
0.1 207.4 0.984 210.3 0.982 1.40 160.4 0.993 161.0 0.993 0.35 102.2 0.999 100.1 0.999 1.02
0.2 249.9 0.995 254.2 0.994 1.72 206.9 0.987 209.1 0.986 1.05 120.4 0.999 118.9 0.999 0.76
0.3 253.5 0.994 257.6 0.994 1.59 229.3 0.990 232.2 0.989 1.26 121.4 0.996 119.6 0.996 0.92
0.4 252.2 0.995 255.9 0.994 1.42 228.8 0.992 231.4 0.991 1.12 155.4 0.994 154.7 0.994 0.35
0.5 222.2 0.995 224.0 0.994 0.77 215.6 0.993 217.2 0.993 0.74 172.3 0.996 172.0 0.996 0.15
0.6 219.3 0.994 220.6 0.993 0.58 221.9 0.994 223.5 0.994 0.74 171.9 0.996 171.2 0.996 0.38
0.7 266.4 0.999 269.7 0.988 1.21 238.0 0.989 240.0 0.988 0.82 173.5 0.998 172.5 0.998 0.52
0.8 301.3 0.992 305.7 0.991 1.43 234.3 0.994 235.2 0.994 0.38 162.6 0.984 160.5 0.982 1.06
0.9 315.2 0.993 319.3 0.993 1.28 259.3 0.994 260.5 0.994 0.45 192.1 0.983 190.4 0.980 0.84
Average 254.2 257.5 221.6 223.3 155.4 151.1

CFT = cigar filler tobacco

CWT = cigar wrapper tobacco

FCT = flue-cured tobacco

FWO = Flynn-Wall-Ozawa method

KAS = Kissinger-Akahira-Sunose method

Figure 8

Changes in Ea versus α obtained by applying the FWO and KAS methods.

Figure 8 depicts the relationship between the activation energy Ea calculated by the FWO and KAS methods at different conversions. The kinetic analysis results show that Ea is highly dependent on α, which indicates that the pyrolysis of tobacco leaf is a complex process including parallel, competitive and consecutive reactions. Taking the results of the CFT as an example, the activation energy increased rapidly as the conversion value increased from 0.1 to 0.2, and remained approximately at about 250 kJ mol−1 as α increased from 0.2 to 0.4. At this stage, the pyrolysis temperature was not particularly high, and corresponded to the drying of the cigar tobacco and the partial pyrolysis of hemicellulose. Therefore, a higher energy was required to increase the reactivity. As the pyrolysis proceeded and α increased from 0.4 to 0.6, the activation energy Ea decreased from 253.5 kJ mol−1 to 219.3 kJ mol−1 (FWO), this stage was mainly contributed by the thermal degradation of cellulose. Cellulose was initially pyrolyzed into active cellulose, resulting in a decrease in polymerization degree and molecular chain length. Active cellulose continued to degrade into more components with lower molecular weight and required lower activation energy (37). When α was higher than 0.6, the value of Ea increased significantly. This stage corresponded to the lignin pyrolysis in the DTG curve. Since lignin consists mainly of three forms of highly cross-linked benzene-propane (35), its thermal stability is high and the activation energy required for pyrolysis increases. At this stage, coke is produced at the same time, which also increases the activation energy value.

Generally, there are similar variations in the activation energy of the three types of tobacco. Since the conversion rate of flue-cured tobacco is from 0.1 to 0.3, corresponding to the pyrolysis of volatile components such as sugars, the activation energy gradually increases from 100.1 kJ mol−1 to 121.4 kJ mol−1. Comparing the activation energies during the whole process, the activation energy of FCT is relatively lower than that of CFT and CWT. Because the value of the apparent activation energy represents the minimum energy required for a chemical reaction to occur, greater apparent activation energy indicates lower pyrolytic reactivity. These results indicate that the volatile materials of FCT decomposed more easily than the components of the CFT and CWT.

Determination of reaction mechanism

Heterogeneous reactions usually involve a superposition of several elementary processes such as order-based, the diffusion, the random nucleation and nuclei growth, these reaction mechanisms G(α) are summarized in Table 2. The theoretical curves y(α) versus α were plotted using Equation [7] and are shown in Figure 9. This figure also shows the experimental curves for three types of tobacco leaf, where S1 and S2 are the curves of the sample in stage II and stage III, respectively. As shown in Figure 9, the theoretical curve for G(α) corresponding to the one-dimensional diffusion D1 is consistent with the experimental data of S1 in tobacco. Thus stage II follows one-dimensional diffusion D1, which is in accordance with the results obtained by Gao et al. (6) studying flue-cured tobacco. The experimental curve S2 of FCT matched well with the theoretical master plot of two-dimensional diffusion D2. However, the experimental curve S2 of CFT and CWT did not fit very well to any of the theoretical curves, but it was acceptably close to the theoretical curves of 1.5-order reaction F3/2 and second-order reaction F2. In order to determine the reaction mechanism further, the Coats-Redfern method was used to determine the thermal decomposition mechanism of stage III.

By combining the two mechanism functions, values for Ea, A, and correlation coefficients (R2) were obtained by the Coats-Redfern method, and are shown in Table 7. For the pyrolysis of CFT and CWT in stage III, the second-order reaction F2 had higher correlation coefficients (0.997 and 0.984) compared with the 1.5-order reaction F3/2. Simultaneously, the activation energy Ea obtained by the Coats-Redfern method was close to the activation energy (234.42 kJ mol−1 and 224.65 kJ mol−1) obtained by the FWO and KAS isoconversional methods. Thus, the most likely kinetic mechanism of stage III for cigar tobacco is second-order reaction F2.

Kinetic parameters of tobacco thermal decomposition obtained by Coats-Redfern method.

Sample Stage Reaction Fitted equation A (min−1) Ea (kJ mol−1) Correlation coefficient R2
CFT II D1 Y = −10165.86x + 6.09 4.49 × 104 84.5 0.995
III F3/2 Y = −23551.40x + 26.44 7.12 × 1013 195.8 0.990
F2 Y = −28195.40x + 34.48 2.65 × 1017 234.4 0.997
CWT II D1 Y = −10305.79x + 5.30 7.74 × 104 85.7 0.998
III F3/2 Y = −22403.96x + 25.26 4.17 × 1013 186.2 0.963
F2 Y = −27020.35x + 33.40 1.73 × 1017 224.7 0.984

Figure 9

y(α) versus α curves at 10 °C min−1 calculated by Equation [8] for tobacco leaves, (a) CFT, (b) CWT, (c) FCT.

The pyrolysis of tobacco is a complex and continuous process, which is affected by different reactions. The thermal decomposition of ligno-cellulosic biomass is initially limited by diffusion mechanisms (47). First-order and second-order reactions typically occur during pyrolysis when cellulose content is higher than the lignin content (48). In stage III, the difference of cigar tobacco and flue-cured tobacco is the temperature range, leading to a different reaction mechanism. It also shows that reaction mechanism may be highly related to the degradation behavior of the main components. In addition, the activation energy of cigar tobacco found in our experiments was higher than that reported in a study on tobacco waste (103.94 kJ mol−1) (10) and tobacco dust (43.6 kJ mol−1 – 227.0 kJ mol−1) (13). The difference could be related to the type of species, growth condition, particle size of tobacco and the different kinetic models.

CONCLUSIONS

In this work, the pyrolysis kinetics of cigar tobacco and flue-cured tobacco were investigated at different heating rates. The chemical composition varied with tobacco type, with cigar tobacco having a higher content of nitrogen, nicotine and ash, while flue-cured tobacco had a higher content of oxygen and cellulose. Cigar tobacco pyrolysis could be divided into four stages, consisting of

Stage I: evaporation of water;

Stage II: decomposition of hemicellulose and emission of low-temperature volatiles;

Stage III: decomposition of cellulose;

Stage IV: decomposition of lignin and the formation of char.

Flue-cured tobacco had obvious mass loss at 200 °C due to its high volatile components such as sugars. During the pyrolysis of different types of tobacco, most of the gas species were released in the second and third stage. H2O, CO2, CH4, CO, carbonyls, alcohols, phenols, and aromatic compounds were identified by FTIR spectra. Generally, the total amounts of CO2, CH4, CO, and aromatics released from cigar tobacco pyrolysis are higher than that from flue-cured tobacco pyrolysis. The change tendency of activation energy was quite similar between flue-cured tobacco and cigar tobacco, and the activation energy distribution along with the conversion rate is a comprehensive expression of pyrolysis behaviors of various components. The pyrolysis reaction model for cigar tobacco could be well described by one-dimensional diffusion and a second-order reaction, and the reaction model for flue-cured tobacco could be described by one-dimensional diffusion and two-dimensional diffusion.

Figure 1

TG (a) and DTG (b) curves of CFT, CWT and FCT pyrolysis processes at the heating rate of 10 °C min−1.
TG (a) and DTG (b) curves of CFT, CWT and FCT pyrolysis processes at the heating rate of 10 °C min−1.

Figure 2

TG-DTG curves of CFT (a), CWT (b) and FCT (c) pyrolysis processes under different heating rates of 5 °C min−1, 10 °C min−1, 15 °C min−1, and 20 °C min−1.
TG-DTG curves of CFT (a), CWT (b) and FCT (c) pyrolysis processes under different heating rates of 5 °C min−1, 10 °C min−1, 15 °C min−1, and 20 °C min−1.

Figure 3

3D TG/FTIR diagram of pyrolysis products for CFT (a), CWT (b) and FCT (c).
3D TG/FTIR diagram of pyrolysis products for CFT (a), CWT (b) and FCT (c).

Figure 4

FTIR spectra of volatile products at peak temperature for tobacco samples.
FTIR spectra of volatile products at peak temperature for tobacco samples.

Figure 5

Evolution of gas products with increasing temperature in the pyrolysis of tobacco.
Evolution of gas products with increasing temperature in the pyrolysis of tobacco.

Figure 6

Arrhenius plots of FWO method for CFT (a), CWT (b) and FCT (c) at different conversion rates.
Arrhenius plots of FWO method for CFT (a), CWT (b) and FCT (c) at different conversion rates.

Figure 7

Arrhenius plots of KAS method for CFT (a), CWT (b) and FCT (c) at different conversion rates.
Arrhenius plots of KAS method for CFT (a), CWT (b) and FCT (c) at different conversion rates.

Figure 8

Changes in Ea versus α obtained by applying the FWO and KAS methods.
Changes in Ea versus α obtained by applying the FWO and KAS methods.

Figure 9

y(α) versus α curves at 10 °C min−1 calculated by Equation [8] for tobacco leaves, (a) CFT, (b) CWT, (c) FCT.
y(α) versus α curves at 10 °C min−1 calculated by Equation [8] for tobacco leaves, (a) CFT, (b) CWT, (c) FCT.

Composition of tobacco leaves.

Item CFT CWT FCT
Proximate analysis (wt.%)
Moisture 2.95 3.84 1.89
Volatile 77.31 75.41 76.79
Fixed carbon 12.80 11.19 16.76
Ash 9.89 13.40 6.54
Ultimate analysis (wt.%)
C 43.57 42.95 41.83
H 5.88 6.17 6.32
N 3.63 3.77 1.67
S 0.00 0.18 0.17
O 36.52 37.41 43.28
Biochemical analysis (wt.%)
Hemicellulose 2.25 3.24 2.81
Cellulose 11.35 13.12 14.26
Lignin 2.84 3.65 3.21
Nicotine content (wt.%) 2.20 2.33 2.07

Characteristic parameters of tobacco leaves during pyrolysis.

Sample TS (°C) Tmax (°C) Rmax (% min−1) Rmean (% min−1) ΔT1/2 (°C) Di (10−7%2 °C−3 min−2) Residue (%)
CFT
 5 130 313 −2.01 −0.43 105 2.02 24.46
10 134 323 −3.96 −0.86 112 6.99 24.73
15 142 330 −5.78 −1.27 121 12.91 25.71
20 146 335 −7.65 −1.68 122 21.61 26.11
CWT
 5 131 297 −2.16 −0.43 72 3.30 24.75
10 140 307 −4.21 −0.83 76 10.62 27.56
15 144 310 −6.22 −1.23 79 21.61 28.25
20 151 315 −8.18 −1.62 82 33.94 28.97
FCT
 5 101 188 −1.82 −0.47 60 7.51 18.75
10 103 197 −3.73 −0.92 62 27.30 20.06
15 108 201 −5.60 −1.36 64 54.80 21.38
20 115 206 −7.30 −1.80 65 85.30 21.82

Identification of gas products during pyrolysis of tobacco based on FTIR spectra.

Wavenumber (cm−1) Functional groups Compounds References
3500–4000 (selected:3566) O-H Symmetrical and asymmetrical stretching H2O (14, 42, 45)
2250–2500 (selected:2359) Asymmetrical stretching in O=C=O CO2 (14, 45)
2850–3030 (selected:3016) C-H Stretching CH4 (43)
2000–2250 (selected:2190) Stretching vibration in CO CO (14, 45)
1710–1800 (selected:1749) C=O Stretching Carbonyl groups (14, 45)
1050–1200 (selected:1180) C-O Stretch Hydroxyl groups (14)
1450–1650 Aromatic C=C-C ring stretch Aromatics (42, 43)
3070–3130 (selected:3076) Aromatic C-H in plane bend
966 NH3 (42)

Kinetic parameters of tobacco thermal decomposition obtained by Coats-Redfern method.

Sample Stage Reaction Fitted equation A (min−1) Ea (kJ mol−1) Correlation coefficient R2
CFT II D1 Y = −10165.86x + 6.09 4.49 × 104 84.5 0.995
III F3/2 Y = −23551.40x + 26.44 7.12 × 1013 195.8 0.990
F2 Y = −28195.40x + 34.48 2.65 × 1017 234.4 0.997
CWT II D1 Y = −10305.79x + 5.30 7.74 × 104 85.7 0.998
III F3/2 Y = −22403.96x + 25.26 4.17 × 1013 186.2 0.963
F2 Y = −27020.35x + 33.40 1.73 × 1017 224.7 0.984

Mass loss at different temperature intervals during pyrolysis of tobacco leaf samples.

Sample Stage I Stage II Stage III

Temperature interval (°C) Mass loss (%) Temperature interval (°C) Mass loss (%) Temperature interval (°C) Mass loss (%)
CFT
 5 40–130 2.84 130–283 22.60 283–397 26.43
10 40–134 2.88 134–292 23.26 292–411 26.78
15 40–142 3.03 142–296 23.07 296–415 26.77
20 40–146 3.06 146–299 23.35 299–424 27.34
CWT
 5 40–131 2.81 131–273 20.04 273–407 25.33
10 40–140 2.85 140–284 20.83 284–417 24.65
15 40–144 2.84 144–287 20.94 287–419 24.32
20 40–151 2.96 151–291 21.08 291–426 24.44
FCT
 5 40–101 1.29 101–216 21.09 216–401 38.82
10 40–103 1.10 103–227 22.27 227–405 38.41
15 40–108 1.15 108–232 21.76 232–408 38.19
20 40–115 1.27 115–240 22.12 240–416 37.40

Activation energies of cigar tobacco leaves obtained by the FWO method and KAS method.

Conversion CFT CWT FCT



FWO KAS Difference FWO KAS Difference FWO KAS Difference



Ea (kJ mol−1) Correlation coefficient R2 Ea (kJ mol−1) Correlation coefficient R2 (%) Ea (kJ mol−1) Correlation coefficient R2 Ea (kJ mol−1) Correlation coefficient R2 (%) Ea (kJ mol−1) Correlation coefficient R2 Ea (kJ mol−1) Correlation coefficient R2 (%)
0.1 207.4 0.984 210.3 0.982 1.40 160.4 0.993 161.0 0.993 0.35 102.2 0.999 100.1 0.999 1.02
0.2 249.9 0.995 254.2 0.994 1.72 206.9 0.987 209.1 0.986 1.05 120.4 0.999 118.9 0.999 0.76
0.3 253.5 0.994 257.6 0.994 1.59 229.3 0.990 232.2 0.989 1.26 121.4 0.996 119.6 0.996 0.92
0.4 252.2 0.995 255.9 0.994 1.42 228.8 0.992 231.4 0.991 1.12 155.4 0.994 154.7 0.994 0.35
0.5 222.2 0.995 224.0 0.994 0.77 215.6 0.993 217.2 0.993 0.74 172.3 0.996 172.0 0.996 0.15
0.6 219.3 0.994 220.6 0.993 0.58 221.9 0.994 223.5 0.994 0.74 171.9 0.996 171.2 0.996 0.38
0.7 266.4 0.999 269.7 0.988 1.21 238.0 0.989 240.0 0.988 0.82 173.5 0.998 172.5 0.998 0.52
0.8 301.3 0.992 305.7 0.991 1.43 234.3 0.994 235.2 0.994 0.38 162.6 0.984 160.5 0.982 1.06
0.9 315.2 0.993 319.3 0.993 1.28 259.3 0.994 260.5 0.994 0.45 192.1 0.983 190.4 0.980 0.84
Average 254.2 257.5 221.6 223.3 155.4 151.1

Functional expressions of several common response models.

Mechanisms Symbol G(α) f(α)
One-dimensional diffusion D1 α2 12α1 {1 \over 2}{\alpha ^{ - 1}}
Two-dimensional diffusion D2 α + (1 − α)ln(1 − α) [−ln(1 − α)]−1
Three-dimensional diffusion D3 [1(1α)13]2 {\left[ {1 - {{\left( {1 - \alpha } \right)}^{{1 \over 3}}}} \right]^2} 32(1α)23[1(1α)13]1 {3 \over 2}{\left( {1 - \alpha } \right)^{{2 \over 3}}}{\left[ {1 - {{\left( {1 - \alpha } \right)}^{{1 \over 3}}}} \right]^{ - 1}}
Avrami-Erofeev A2 [ln(1α)]12 {\left[ { - \ln \left( {1 - \alpha } \right)} \right]^{{1 \over 2}}} 2(1α)[ln(1α)]12 2\left( {1 - \alpha } \right){\left[ { - \ln \left( {1 - \alpha } \right)} \right]^{{1 \over 2}}}
Avrami-Erofeev A3 [ln(1α)]13 {\left[ { - \ln \left( {1 - \alpha } \right)} \right]^{{1 \over 3}}} 3(1α)[ln(1α)]23 3\left( {1 - \alpha } \right){\left[ { - \ln \left( {1 - \alpha } \right)} \right]^{{2 \over 3}}}
First-order reaction F1 −ln(1 − α) 1 − α
1.5-order reaction F3/2 2[(1α)12]2 2\left[ {{{\left( {1 - \alpha } \right)}^{-{1 \over 2}}}} \right] - 2 (1α)32 {\left( {1 - \alpha } \right)^{{3 \over 2}}}
Second-order reaction F2 (1 − α)−1 − 1 (1 − α)2
Contracting area R2 1(1α)12 1 - {\left( {1 - \alpha } \right)^{{1 \over 2}}} 2(1α)12 2{\left( {1 - \alpha } \right)^{{1 \over 2}}}
3D contracting volume R3 1(1α)13 1 - {\left( {1 - \alpha } \right)^{{1 \over 3}}} 3(1α)23 3{\left( {1 - \alpha } \right)^{{2 \over 3}}}

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