The organic distribution constant (f
e), which indicates the distribution of the easily biodegradable volatile solids (VS
e) and persistently biodegradable volatile solids (VS
p), was estimated to be 0.066 for the ADSC. In comparison, the f
e of the ADSC hydrothermal hydrolysate was 0.641, 0.651, 0.669, and 0.540 at the hydrothermal pretreatment reaction temperatures of 160°C, 180°C, 200°C, and 220°C, respectively. The organic matter (VS) contained in the ADSC was characterized as consisting of 11.9% biodegradable volatile solids (VS
B) and 88.1% non-biodegradable volatile solids (VS
NB). More specifically, the VS
B fraction of ADSC was estimated to be composed of VS
e of 5.5% and VS
p of 6.3%. The VS
B fraction of the ADSC hydrothermal hydrolysate increased to 17.9%, 23.3%, 26.7%, and 23.7% at hydrothermal reaction temperatures of 160°C, 180°C, 200°C, and 220°C, respectively, whereas VS
NB decreased to 82.1%, 76.7%, 73.3%, and 76.3%, respectively. Regarding the VS
B fraction of the ADSC hydrothermal hydrolysate, 11.5%, 15.2%, 17.8%, and 12.8% were estimated to be VS
e, and 6.5%, 8.1%, 8.8%, and 10.9% to be VS
p at the hydrothermal reaction temperatures of 160°C, 180°C, 200°C, and 220°C, respectively. As aforementioned, the hydrothermal pretreatment reaction temperature of 200°C yielded the largest amount of methane. However, considering the VS content obtained after the hydrothermal pretreatment, VS obtained from the ADSC of 1ton was 189.5 kg, and VS obtained from ADSC hydrolysate were 181.6, 171.8, 140.1, and 145.9 kg at the hydrothermal reaction temperatures of 160°C, 180°C, 200°C, and 220°C, respectively. Then, the methane of 10.2 Nm
3/ton-ADSC was recovered from ADSC of 1.0 ton, and methane yields of ADSC hydrolysate increased to 15.6, 18.0, 17.4, and 17.2 Nm
3/ton-ADSC (
Figure 3). Therefore, the optimal hydrothermal reaction temperature that yielded the maximum methane yield was 180°C based on mass balance.
Hydrothermal pretreatment was shown to be an efficient method for hydrolyzing cattle manure containing difficult-to-decompose organic matter. However, hydrothermal pretreatment has been reported to lead to different degrees of solubilization of organic substances depending on the constituents of the raw materials, reaction temperature, and reaction time [
21,
23,
24]. In this study, a hydrothermal reaction temperature of 200°C was determined to be the optimal temperature at which the methane yield is maximized. However, as the hydrothermal reaction temperature increased, the VS
e and VS
p fractions increased simultaneously with the VS
p content (persistently biodegradable) changing most significantly at the hydrothermal reaction temperature of 200°C. Marin-Batista et al [
10] reported a methane yield of 0.111 Nm
3/kg-VS
added from the anaerobic digestion of cattle manure and reported yields of 0.294, 0.235, and 0.080 Nm
3/kg-VS
added from the hydrothermal hydrolysates at hydrothermal reaction temperatures of 170°C, 200°C, and 230°C, respectively. In addition, Kim et al [
25] reported methane potentials of 0.197, 0.231, 0.221, and 0.200 Nm
3/kg-VS
added for pig sludge hydrothermally pretreated at 200°C, 220°C, 250°C, and 270°C, respectively. These results are consistent with the results of our study in that the maximum methane yield was obtained at a hydrothermal reaction temperature of 200°C and decreased at hydrothermal reaction temperatures of 220°C or higher. In particular, this decrease in the methane yield was often reported for the high-temperature hydrothermal pretreatment of diverse biomass. Gossett et al [
26] reported that hydrothermal pretreatment could solubilize the cellulose and lignin in the raw material at a hydrothermal reaction temperature of 160°C or higher, but discovered that phenolic substances might be produced, thereby inhibiting the productivity of methanogens. In addition, it has been reported that, as the temperature of the hydrothermal pretreatment increases, the portion of soluble organic matter increases, but the concentration of refractory material in the soluble organic matter also increases [
27,
28]. Furthermore, Oh and Yoon [
29] reported that the methane yields for hydrothermal hydrolysate at 170°C, 180°C, 190°C, 200°C, and 220°C using poultry slaughterhouse wastewater sludge cake were 0.222, 0.242, 0.237, 0.228, and 0.197 Nm
3/kg-COD
added, respectively. The lower methane yield at a reaction temperatures higher than 200°C may be attributable to the Maillard reaction in which carbohydrates react with amino acids at high temperatures to form melanoidine with low biodegradability [
3,
30]. Therefore, the lower methane yield of the ADSC hydrothermal hydrolysate pretreated at the hydrothermal reaction temperature of 220°C in this study may be the effect of recalcitrant substances produced by the cell wall material contained in the sawdust in the ADSC during the high-temperature hydrothermal reaction. Particularly, the ADSC in this study has already undergone anaerobic digestion, and the raw ADSC was composed of difficult-to-decompose organic substances; therefore, the possibility exists that the cellulose, hemicellulose, lignin, etc. contained in the sawdust could be converted into phenolic compounds during the hydrothermal pretreatment. In addition, another possibility is that carbohydrates could react with amino acids at high temperatures according to the Maillard reaction, because ADSC contains large amounts of cellulose and nitrogen sources such as bacterial cells.