1. Introduction
Recent energy policy developments in Korea have been focused on decommissioning nuclear power plants and phasing out coal. The coal phase-outs involve the decommissioning of old power plants and re-powering projects rather than the complete elimination of coal power plants, and investments are being made in regard to fuel conversion technology that will enable the utilization of renewable energy from the perspective of economic base loads. As of 2017, coal-fired power plants in Korea continue to represent the most crucial means of power generation, and these plants contribute to 31.6% (36.9 GW) of the total power generation capacity. Compared to 2015 when coal-fired power plants were responsible for over 40% of the power generation, the enforcement of the Renewable Energy Portfolio Standard (RPS) enacted in 2012 has driven many of the domestic coal-fired power plants to switch to a partially mixed form of coal and biomass for the acquisition of renewable energy certificates (REC), in following the Paris Agreement and its goal of CO
2 emission reductions; presently, the use of biomass in coal-fired power plants is anticipated to increase further [
1,
2]. In other words, it seems inevitable that the use of biomass fuel in coal-fired power plants will expand, and thus, there is a need to investigate the characteristics of biomass fuel.
To illustrate, the Korea South-East Power Co. (KOEN) (Jinju, Korea) replaced YeongDong unit #1 (YD #1) (Yeongdong, Korea), a 200 MW anthracite coal power plant that has been in operation for 44 years since its establishment in May 1973, with a 125 MW biomass-fired boiler. As such, KOEN carried out the replacement of the old facility and the fuel conversion process so as to increase the installed life and be responsive to the RPS system while preparing a response framework for CO
2 emission rights, thereby setting an example for the fuel conversion of coal-fired power plants in Korea. Nonetheless, biomass-fired boilers, including the system at YD #1, inevitably have experienced problems caused by the characteristics of biomass, the most common ones being the low calorific values due to the high inherent moisture of biomass and the low pulverization potential; moreover, considerable difficulty is associated with predicting the combustibility of biomass because of its unique characteristics that differ from carbonaceous solid fuels, exhibiting a high degree of carbonization [
3,
4].
To improve fuels with high inherent moisture, low calorific values, and low pulverization potentials, recent trends in biomass research have focused on torrefaction technology, which may provide a solution to some extent. Torrefaction is also referred to as mild pyrolysis as it takes into account the pyrolysis temperature range for the three main polymers, namely, cellulose, hemicellulose, and lignin, that make up the chemical components of biomass, and it involves carrying out pretreatment steps for each component at its respective pyrolysis temperature to facilitate the production of torrefied fuel. Through torrefaction, the surface of biomass with a pronounced distribution of hydrophilic functional groups turns hydrophobic, thus making it difficult for moisture adsorption to occur, which decreases the inherent moisture. The pretreatment process also assists with biomass pulverization via the destruction of its organic structure for higher effectiveness, and it mediates the devolatilization of a certain amount of volatile gases to increase the fixed carbon, thus resulting in increased calorific values [
5,
6,
7]. Since torrefaction technology fundamentally depends on the pretreatment process under pyrolysis conditions for the production of carbon-rich fuels, it is essential that the basic pyrolysis characteristics of the biomass fuel are thoroughly understood through in-depth analyses of the biomass pyrolysis [
8,
9,
10,
11].
In an ideal pulverization scenario, the pulverized coal takes on a form approximating a sphere with fine porosity. The microporous structure is negligible in graphite with a high degree of carbonization, but as the carbonization degree decreases from anthracite coal to bituminous coal, subbituminous coal, then to lignite, the microporous structure exhibits a more evolved form, and when devolatilization is complete, the microporous structure in char exhibits an even more evolved form that makes a substantial contribution to the specific surface reactivity. As such, in contrast to coal, with a solid fuel with a spherical, porous structure, the biomass fuel is composed of fibers whose characteristics of specific surface development deviate from coal with a high degree of carbonization. Thus, the results of analyses with such fuels may differ greatly from the characteristics of char oxidation obtained with conventional carbon-based solid fuels [
12,
13].
In this study, a type of lignocellulosic woody biomass that has been widely used, an available form of biomass, and a type of herbaceous biomass whose use has recently soared were selected for further analyses. To help to widen the scope for application of the lignocellulosic woody and herbaceous biomass in the field of power generation, the pyrolysis behaviors of the biomass were analyzed in detail by focusing on the basic physical properties and thermal reaction characteristics of the biomass and applying the multi-Gaussian distributed activation energy model (DAEM). Furthermore, by examining the char oxidation rate, the fundamental characteristics and thermal behaviors of the biomass were comprehensively analyzed with the Kissinger equation.
2. Materials and Methods
2.1. Biomass Sample Preparation
To compare the characteristics of the lignocellulosic woody and herbaceous biomass, wood pellets were selected as the representative woody biomass material, and kenaf was selected as the representative herbaceous biomass material. For wood pellets, the ones produced in Vietnam that account for over 70% of wood pellet imports in Korea were used. Virtually all imported amounts of wood pellets are consumed as fuel in Korean power plants. Kenaf (
Hibiscus cannabinus L.) is a subtropical plant with a large scope of use as an industrial material. It is also the most widely used plant in phytoremediation applications, as it exhibits over 5 times greater CO
2 absorption rates than general crops [
14].
The biomass used in this study was dried and pulverized using a vibratory disc mill (RS 200, Retsch GmbH, Haan, Germany), after which it was separated using a sieve shaker (AS 200, Retsch GmbH, Haan, Germany) for particle sizes of 75–90 μm. The biomass char was prepared under a nitrogen atmosphere and heated up to 950 °C with a 10 °C/min heating rate using a commercial thermogravimetric analyzer (TGA 701, LECO Co., St. Joseph, MI, USA) and maintaining the material under the preparation conditions until the weight loss rate measured at a level below 1%/min.
2.2. Biomass Sample Analysis
Approximately 5 g of sample was analyzed in the proximate analysis carried out with the thermogravimetric analyzer (TGA 701) (LECO Co., St. Joseph, MI, USA) based on the American Society for Testing and Materials (ASTM) D3172 method. The values of the ultimate analysis were obtained using a commercially available device (Leco-TruSpec Micro CHNS, LECO Co., St. Joseph, MI, USA). For the oxide analysis, the biomass ash was measured using an X-ray fluorescence (XRF) spectrometer (S8 TIGER, Bruker, Karlsruhe, Germany) based on the ASTM D4326 method.
The ash fusion temperature (AFT) was measured using the thermomechanical analysis (TMA) device designed and produced by the Pusan Clean Coal Center (PC3) at Pusan National University [
15]. A schematic diagram of the TMA device is given in
Figure 1. The TMA device is composed of a heating chamber and a penetrating rod, as well as a ram, crucible, linear variable differential transformer (LVDT), and thermocouple. An ash sample can be heated up to 1600 °C through the vertical tube heating furnace that controls the specific calorific value. The amount of ash used in each experiment was approximately 200 mg. The 60 g penetrating rod was connected to a weight in order to maintain the weight balance between the rod and the sample weight. In this study, the wood pellet and kenaf ash samples were heated from room temperature up to 1600 °C with a 5 °C/min heating rate. The temperature at which 25% of the total displacement variation occurred was defined as T25, and based on the same logic, T50, T75 and T90 temperatures were also measured.
To detect the elements in the biomass samples, a commercially available analyzer (Optima 8300, Perkin-Elmer, Norwalk, CT, USA) was used in conjunction with an inductively coupled plasma-optical emission spectrometer (ICP-OES; KBSI Gwangju Center). The prepared sample was mixed with 5 mL nitric acid and 5 mL hydrogen peroxide, and then, the mixture was placed in a microwavable container for pretreatment in equipment set at 800 W of power and 180 °C; this involved two consecutive runs of 15 min and 10 min. Next, the mixture was washed with distilled water, and 0.3–0.35 g of sample was mixed with 4 mL hydrogen peroxide and left overnight. Then, 7 mL of 70% nitric acid was added for microwave digestion, followed by pretreatment at 800 W, 200 °C for two consecutive runs of 15 min and 15 min. Next, 50 μL of 49% hydrofluoric acid was added, and lastly, the sample was washed with distilled water to make it ready for the analyses.
2.3. Thermogravimetric Analysis
To investigate the pyrolysis behaviors of the biomass, a commercially available thermogravimetric analysis (TGA) system (SDT Q600, TA Instruments, New Castle, DE, USA) was used, and the mass reduction curves for biomass pyrolysis were obtained. This experiment used approximately 15 mg of biomass, and by introducing nitrogen at a 100 mL/min flow rate, an inert atmosphere was created. The temperature was raised up to 950 °C with a 10 °C/min heating rate to complete the experiment. The biomass pyrolysis domains were divided into separate intervals to reflect the characteristics of each biomass sample, and for estimating the simple kinetics for each interval, a single first-order reaction model was used to deduce the activation energy and frequency factor [
16]. Under non-isothermal conditions, the equation for estimating the solid fuel pyrolysis kinetics can be expressed as:
where
T is the absolute temperature,
α is the extent of biomass conversion,
β is the heating rate,
R is the universal gas constant,
E is the activation energy, and
A is the frequency factor.
The conversion extent
α of the biomass fuel can be determined based on:
where
is the initial weight of the biomass sample,
is the weight of the biomass sample at time
t, and
is the final weight at the end of the reaction.
The differential conversion function is expressed as:
where
n is the reaction order;
n = 1 was assumed in this study.
By using the simplifying temperature integral function with the Doyle integral approximate, Equation (1) can be rewritten as Equation (4) [
17]:
The linear regression form of Equation (4) is given as:
By using the above linear regression form, the activation energy and the frequency factor can each be deduced based on the gradient and the intercept of Y axis.
2.4. Multi-Gaussian Distributed Activation Energy Model
The DAEM involves a multiple parallel reaction process based on the assumption that the pyrolysis mechanism of solid fuels comprises a myriad of independent and parallel first-order reactions, each with its own activation energy. The components deduced from the pyrolysis behaviors were expressed by the parallel Gaussian distribution model, and the DAEM equation suggested in the work of Miura and coauthors is as shown below [
18,
19].
Here,
α is the extent of conversion,
T is the absolute temperature,
is the pre-frequency factor,
β is the heating rate,
E is the activation energy, and
f(
E) is a function of the activation energy distribution.
To estimate the kinetic parameters, the activation energy distribution was calculated using the equation for the Gaussian distribution based on the mean activation energy
and standard deviation
σ.
The derivative of Equation (1) obtained by applying Equation (7) is as shown below.
To deduce the optimal values for the kinetic parameters (
,
, etc.), an objective function was defined as shown in Equations (9) and (10) below. By using the algorithm given in
Figure 2, the DAEM of each biomass parameter was calculated.
2.5. Char Oxidation Kinetics
To deduce the reaction rate for biomass char, the non-isothermal mass reduction curve was obtained according to the combustion reaction of biomass char up to 950 °C while changing the heating rate from 5, 10, 20 and 30 °C/min in the air. Here, the reaction rate of char oxidation was taken into account by using the Kissinger equation that assumes the activation energy can be obtained regardless of the reaction order when an appropriate linearity emerges during TGA while changing the heating rate [
20].
In Equation (11), x is the carbon conversion and is the activation energy for char oxidation. In Equation (12), q is the heating rate and is the temperature at which the reaction rate is the highest. Thus, the Kissinger equation produces a result from which a valid analysis can be drawn if the graph of against displays appropriate linearity. Thus, the Kissinger analysis allows for the estimation of the mean activation energy for the overall reaction process regardless of the reaction order when for each different heating rate is known.