## Materials & Methods
### Mass and Energy Balance  
Product yields (\(Y\)) were determined on an as-received basis and were defined as the ratio of the pyrolysis product \(i\) (i.e., char, gas, or bio-oil) to the mass of the feedstock. \[Y_{i}=\frac{m_{i}}{m_{feed}} \tag{1}\]  
Products carbon yield (\(Cy\)) was obtained as the ratio of the carbon concentration (%\(C_{\textit{real}}\)) in the feed to that recovered in pyrolysis products \(i\). \[Cy_{i}=\frac{m_{i}\%C_{i}}{m_{feed}\%C_{feed}} \tag{2}\]  
According to [PERSON] et al. [49], a rough estimation of the heat of pyrolysis (\(Q_{py}\)) can be calculated closing the energy balance on the pyrolyzer:  
\[\Delta H_{t,\ N_{2}}+\Delta H_{t,\ \textit{bm}}+Q_{heat}=\Delta H_{t,\ \textit{pyragas}}+ \Delta H_{t,\ \textit{char}}+Q_{\textit{PJoss}} \tag{3}\]  
\[Q_{py}=Q_{heat}-Q_{p,loss}=\Delta H_{t,\ \textit{pyragas}}+\Delta H_{t,\ \textit{char}}- \Delta H_{t,\ N_{2}}-\Delta H_{t,\ \textit{bm}} \tag{4}\]  
where \(\Delta H_{t,k}\) is the total enthalpy of the element \(k\) (e.g., biomass, nitrogen, char, and pyrogas), \(Q_{\textit{heat}}\) is the heat provided to the pyrolyzer by the electrical heaters, and \(Q_{p,loss}\) is the heat losses through the reactor wall. The total enthalpy \(\Delta H_{t,k}\) was calculated by the following equation as the sum of the standard enthalpy of formation (\(\Delta H_{\textit{f}k}\)) at reference conditions (25 \({}^{\circ}\)C, 1 atm) and the sensible enthalpy (\(\Delta H_{(T)s,k}\)) required to certain temperature \(T\):  
\[\Delta H_{t,k}=\Delta H_{f,k}+\Delta H_{(T)s,k} \tag{5}\]  
\[\Delta H_{f,k}=\sum_{j=1}^{N}n_{rj}\overline{n}_{f,j}^{0} \tag{6}\]  
\[\Delta H_{(T)s,k}=(T-T_{0})\cdot\sum_{j=1}^{N}n_{rj}Cp_{j} \tag{7}\]where \(n_{r,i}\), \(h^{0}_{f,j}\), and \(cp_{j}\) are the molar flow rate, the standard enthalpy of formation, and the heat capacity of component \(i\), respectively. The standard enthalpy of formation (\(h^{0}_{f}\)) of the element \(k\) (e.g., pyrolysis products and biomass) is defined as the change of energy that is related to the formation of a substance from its elements at standard pressure and temperature. Furthermore, the standard enthalpy of formation of a fuel can be estimated based on its stoichiometric combustion balance and the fuel's higher heating value:  
\[\sum_{w=1}^{N}m_{re,w}\overline{h}^{0}_{f,re,w}=\sum_{w=1}^{M}m_{pr,w} \overline{h}^{0}_{f,pr,w}+HHV_{re}\sum_{w=1}^{N}m_{re,w} \tag{8}\]  
where \(m_{re,w}\) and \(m_{pr,w}\) are the mass flow rate of the component \(w\) of the reactants and the products, respectively. The higher heating values (\(HHV\), MJ kg\({}^{-1}\)) of the raw biomass, char, and bio-oil fractions were determined by the Channiwala and Parik unified correlation [50]. \[HHV=0.3491\cdot C+1.783\cdot H+0.100\cdot S-0.103\cdot O-0.0151\cdot N-0.0211 \cdot Ash \tag{9}\]  
where \(C\), \(H\), \(O\), \(N\), \(S\), and \(Ash\) represent the carbon, hydrogen, oxygen, nitrogen, sulfur, and ash content of the sample expressed in mass percentages on a dry basis, respectively. Oxygen is calculated by difference. The higher heating value (\(HHV\), MJ\(\cdot\)Nm\({}^{-3}\)) of the non-condensable gas can be calculated using the following equation [51]:  
\[HHV=(12.776\cdot H_{2}+12.644\cdot CO+39.847\cdot CH_{4}+63.438\cdot C_{2}H_{4} )/100 \tag{10}\]  
where the gas content is given in vol% (or mol%) on a nitrogen-free basis. Heat losses \(Q_{p,loss}\) is the sum of heat transfer by natural convection and radiation. These have been evaluated by taking into account a mean room temperature of 25 \({}^{\circ}\)C and a wall temperature of 60 \({}^{\circ}\)C.  
The energy recovered in the pyrolysis products (\(\epsilon\)) was determined as the ratio of the chemical energy retained by pyrolysis products \(i\) to biomass chemical energy:  
\[Cy_{i}=\frac{m_{i}\%C_{i}}{m_{feed}\%C_{feed}} \tag{2}\]0  
The performed elemental analysis of the bio-crude allowed assessing the distribution of carbon among the different condensed fractions. The initial carbon input constitutes up to 46.58% of the woody biomass feedstock.