## 2 Materials and Methods
### Pyrolysis Experiments  
The pyrolysis and catalytic pyrolysis were carried out in a horizontal tubular furnace with integrated control systems provided by Nabertherm with a length of 450 mm and an inner diameter of 50 mm. The schematic layout of the experimental setup is shown in Figure 2.  
First, 15.0 g of sample cut into 10-20 mm pieces was used in an inert N\({}_{2}\) atmosphere. It is important to underline that only layers and ear straps were chosen for pyrolysis tests. The nose bridge was separated from the samples. Once the sample has been weighed, the reactor is started, and the nitrogen flow rate is regulated to 50 L/h. The sample is introduced when no oxygen is left in the oven, and it starts heating with a heating rate of 10 \({}^{\circ}\)C/min until the test temperature (450-550 \({}^{\circ}\)C) is reached. Once the temperature is arrived at, a residence time in the furnace of 60 min is programmed. To collect the liquids (bioils) generated, two glass traps, submerged in a bath of water, ice, and salt, are placed at the outlet of the tubular reactor. The volatiles that do not condense pass through the pipe and end up filling a hermetic gasbag to constitute the gaseous fraction. Each bag is filled for 15 min, for a total of four bags. After the experiment has been completed, the biooil is weighed, and biooil yield is calculated using Equation (1). The biochar is weighted when the reactor is cooled to room temperature, and biochar yield is obtained using Equation (2). Syngas yield is determined by applying the mass balance to the system (Equation (3)). Equations (1)-(3)are as follows:  
\[Oil\ Yield\ (\%)=\frac{M_{\mathrm{O}}}{M_{\mathrm{S}}}\cdot 100 \tag{1}\]  
Figure 2: Pyrolysis experimental installation.  
\[Biochar\ Yield\ (\%)=\frac{M_{\rm C}}{M_{\rm S}}.100 \tag{2}\]  
\[Syngas\ Yield\ (\%)=100-(Oil\ Yield\ (\%)+Char\ Yield\ (\%)) \tag{3}\]  
where \(M_{\rm S}\) is the mass of the sample; \(M_{\rm O}\) is the mass of biooil; \(M_{\rm C}\) is the mass of biochar.  
In the catalytic pyrolysis experiments, the catalyst was placed ex situ with 5% of the sample mass. Catalyst was mixed with glass balls to prevent clogging. The catalyst was placed at the outlet of the furnace so that the volatiles were in contact with the catalyst. From this point, the catalytic pyrolysis operating procedure was the same as the standard pyrolysis experiment performed at 500 \({}^{\circ}\)C (the temperature that provided higher liquid product yields). Once the experiment was over and the reactor reached room temperature, the catalyst was recovered. Fractions yields were obtained using Equations (1)-(3). Finally, the catalyst was calcined at 550 \({}^{\circ}\)C for 3.5 h in air atmosphere to regenerate the catalyst and then it was kept free of moisture until the next run.  
Three tests were carried out with the catalyst, and after each use the catalyst was treated as indicated above. In addition, the surface properties of the catalyst after each use were determined using N\({}_{2}\) adsorption at 196 \({}^{\circ}\)C on a Micromeritics ASAP 2020, and we determined the infrared spectrum using a Perkin-Elmer spectrophotometer, model Spectrum 65.  
In addition, all test were performed in triplicate and mean values have been shown.