# Catalytic fast pyrolysis of biomass over hierarchical zeolites: comparison of mordenite, beta and ZSM-5

Ludovic Pinard, Liangyuan Jia, Nathan Pichot, Amir Astafan, Anthony Dufour

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Ludovic Pinard, Liangyuan Jia, Nathan Pichot, Amir Astafan, Anthony Dufour. Catalytic fast pyrolysis of biomass over hierarchical zeolites: comparison of mordenite, beta and ZSM-5. Energy & Fuels, 2024, 38 (15), pp.14351-14364. 10.1021/acs.energyfuels.4c01188. hal-05235191

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Catalytic fast pyrolysis of biomass over hierarchical zeolites:
comparison of mordenite, beta and ZSM-5.

Ludovic Pinard<fnref n="1" />*, Liangyuan Jia<fnref n="2" />, Nathan Pichot<fnref n="1" />,<fnref n="3" />,<fnref n="4" />, Amir Astafan<fnref n="4" />, Anthony Dufour<fnref n="3" />*

For Energy&Fuels

Revised manuscript_Cleaned

<footnote n="1">¹LCS, ENSICAen, CNRS, UMR6506, 6 Boulevard du maréchal Juin, 14000 Caen, France</footnote>

<footnote n="2">² School of Chemistry and Chemical Engineering, Hefei University of Technology, Anhui, Hefei, 230009, China</footnote>

<footnote n="3">³ LRGP, Université de Lorraine, CNRS, ENSIC, 1 rue Grandville 54000 Nancy, France</footnote>

<footnote n="4">⁴ Institut de Chimie des Milieux et Matériaux de Poitiers, UMR 7285 CNRS, 4 Rue Michel Brunet, 86073 Poitiers Cedex9 France</footnote>

<footnote>* ludovic.pinard@ensicaen.fr and anthony.dufour@univ-lorraine.fr</footnote>
Abstract

Biomass catalytic fast pyrolysis (CFP) is a promising process but its development is still hampered by the
formation of coke which reduces the carbon selectivity of the process to the targeted aromatic
hydrocarbons. It is important to better understand the effect of zeolite structure on the mechanisms of coke
deposit and how this coke deposit poison the active sites (Bronsted sites, BAS). Here, we provide a
systematic comparison of various zeolites: mordenite (MOR), beta (*BEA) and ZSM-5 (MFI) with different
hierarchization methods (NaOH, HF, NH4F). The effect of crystal size has been also studied for *BEA.
These zeolites were tested with a constant biomass to catalyst ratio of 0.8 in a double fixed bed reactor
which enables to decouple biomass pyrolysis and ex-situ volatiles conversion. The formation of volatiles
species was monitored on-line by photoionization mass spectrometry. Aromatic hydrocarbons were also
quantified by GC/MS-FID. The spent catalysts were analysed by pyridine probe (for acidity), FTIR (for
coke composition) and N2 sorption (for porous structure). The structure of mordenite with a two
dimensional network of channels and weak connections between the channels leads to a fast deactivation
by pores blocking even after different hierarchization methods. The hierarchical MFI (obtained by mild
desilication with NaOH) was the best selective zeolite towards aromatic hydrocarbons. The selectivity
towards aromatics and coke formation depends on the shape of canals but not on the H+ cage environment.

*BEA promotes the diffusion of species to BAS in larger pores than MFI but it leads to a lower shape-selectivity than MFI, especially after partial deactivation by coke.
# 1. Introduction

Aromatics (benzene, toluene, xylenes, BTX) are key building blocks for the chemistry and they are produced from crude oil by catalytic reforming and fluid catalytic cracking (FCC) units in refineries. The catalytic fast pyrolysis (CFP) of biomass represents an interesting route for producing green aromatics and olefins by mimicking the FCC of crude oil. In this process, the oxygenated volatiles formed by biomass pyrolysis diffuse within the catalyst particles (like zeolites) and contact the catalytic acid sites to form the targeted products (aromatics, olefins) but also coke and gas (mainly CO, CO₂). Zeolites are the main catalysts proposed for biomass CFP.¹,² Various zeolites have been tested and tailored for biomass CFP. The addition of a metal (Co, Mo, Ga, Fe, Ni, etc.), the acidity (mainly silica-to-alumina ratio), the size and shape of pores, binders (etc.) are the main studied parameters.³⁻¹⁸

Despite all the numerous studies on materials synthesis, the catalysts still suffer from deactivation during biomass CFP. Figure 1 presents the main mechanisms of deactivation applied to biomass CFP.

<figure><img src="image_2.png" /><figcaption>Figure 1. Main mechanisms of catalysts deactivation applied to biomass pyrolysis, here displayed with a HZSM-5 (MFI structure) doped with metallic nanoparticles, such as Co, Ga, etc. (figure edited by the authors for this present article)</figcaption></figure>

A first deactivation mechanism is alkali poisoning. It is an irreversible deactivation of the catalysts. Alkali present in ashes can be accumulated in the catalyst after the burn-off of char or even react with active sites (notably potassium and sodium)⁷,¹⁹⁻²². Different process configurations are envisioned in order to reduce catalysts deactivation notably by alkali species. “In-situ” CFP means that biomass (and then char/ashes) are in contact with zeolite in a dual fluidized bed (DFB) reactor. “Ex-situ” means that biomass pyrolysis is conducted in a first reactor and only the vapours are in contact with the zeolite in a second reactor. This second reactor can be a fluidized bed or sequential fixed beds.²³ One potential benefit of fixed bed upgrading over fluidized bed upgrading is catalyst flexibility, providing greater control over chemistry and product composition.²³ Obviously, ex-situ pyrolysis in a fixed bed solves the attrition problem of zeolite particles when operated in fluidized beds. Attrition is another source of zeolites deactivation and loss.²⁴,²⁵ For these reasons, this present study deals with the ex-situ CFP in a fixed bed reactor. Another deactivation phenomenon is the dealumination (Figure 1) of zeolites by steam in the regenerator or stripper zone²⁰.
Metals have been added to improve zeolites performances<sup>2,5,8,26</sup>. The main challenge is to maintain small nanoparticles of reduced metals which are prone to oxidation (during coke/char oxidation) and sintering (Figure 1). Metals can be reduced during the pyrolysis of biomass (by coke and pyrolysis gas) and reduced metallic nanoparticles may enhance some hydrogenation reactions. Co in ZSM-5 (MFI) was suggested to strongly enhance aromatization reactions.<sup>27</sup> Oxidized Ga/ZSM-5 continued to exhibit improved decarbonylation and decarboxylation activities.<sup>28</sup>

Another key deactivation presented in Figure 1 is the formation of coke. The zeolite shape selectivity governs the nature and location of coke. For example, many oxygenate volatiles formed during the pyrolysis of biomass (syringyl-aromatics, levoglucosan, etc.)<sup>29-32</sup> cannot enter the micropores of ZSM-5 and produce coke on the crystal surface ("external coke", see Figure 1). Precoking on the surface of zeolites or MgO addition could be an effective way to reduce coke formation.<sup>33</sup>

The light alcohols, acids and furans, etc., formed by biomass pyrolysis have access to active sites located in the micropores and can be converted into aromatics and coke precursors. The latter grows up to be trapped by steric constraints. The coke formation is a genuine shape selectivity reaction. An efficient way to mitigate the internal coke is the shortening of the diffusion path length of molecules in the micropores at few nanometres, which can be achieved through the synthesis of nanocrystal or by the creation of intragranular mesopores connected to the microporous network.<sup>34,35</sup> The formation of mesopores promotes the accessibility of reactants to the active sites and also the outwards diffusion of coke precursors from the zeolite channel network<sup>2,26,36</sup>. Different approaches have been developed for producing additional mesoporosity in zeolites, either by demetallation ("top-down" approach) or by hydrothermal synthesis ("bottom-up" approach)<sup>37</sup>. Zeolite hierarchization through demetallation treatments (acid treatment for dealumination or alkaline for desilication) is an efficient approach to mitigate catalyst deactivation.<sup>37</sup> Desilication by alkaline treatment leads to higher mesoporous surface area and larger amounts of protonic active sites, when compared to dealumination<sup>38</sup>, which can also lead to extra-framework aluminium, partially occupying the channels.

Various types of hierarchical zeolites produced by bottom-up or top-down approaches have been tested for the catalytic pyrolysis of biomass<sup>2,11,26,36,39</sup>. References are reviewed in supplementary material. We summarize hereafter some main findings of these reviewed references.

Hernando et al.<sup>40</sup> have shown that MgO-loaded hierarchical HZSM-5 provided bio-oil with enhanced energy yields and lower oxygen content, probably due to the adequate balance of acid and basic sites. Y. Yu et al.<sup>29</sup> demonstrated that, in terms of aromatics selectivity, ZSM-5 was the best catalyst towards aromatics formation, among those they tested, followed by *BEA (beta), MOR (mordenite), and FAU (faujasite) zeolites. But ZSM-5 presents a fast deactivation by coke<sup>29</sup>. Mihalcik et al.<sup>13</sup> have studied MOR, *BEA, and ZSM-5 zeolites and came to similar conclusions. The Si/Al ratio has also been shown to have its impact through acidity (number and strength of active sites)<sup>13</sup>. ZSM-5 and *BEA hierarchization have been extensively studied by Bi et al.<sup>41</sup>. A significant increase in activity, compared to parent zeolites, was attributed to promoted mass transfers of heavier molecules in mesopores<sup>41</sup>. Furthermore, hierarchization seems very promising to reduce pore blockage and active site deactivation<sup>42-44</sup>. Stefanidis et al.<sup>45</sup> developed mesoporous MOR in order to promote the accessibility to the acid sites in 2D structure of MOR. They found that alkaline treatment of high Si/Al MOR resulted in enhanced catalytic activity and led to a noticeable decrease in oxygenated content in the bio-oils<sup>45</sup>. The present authors have studied a hierarchical MFI zeolite in micro-fluidized bed<sup>46</sup>. We have also analysed heavy products by high resolution mass spectrometry<sup>47</sup>.
Many different zeolites were studied but some results are based on small scale pyrolysis (in micro-pyrolysis reactor combined to GC/MS) with uncontrolled mass transfers of volatiles in the zeolite beds. Furthermore, some conclusions are based on %areas (of GC/MS), which do not quantify the mass yields selectivity in the targeted species (BTX).

To the best of our knowledge, hierarchical MOR, *BEA, and ZSM-5 zeolites have not yet been compared with quantitative analysis of hydrocarbons and with a detailed characterization of the deactivated zeolites after biomass pyrolysis (coke, acidity, pores, etc.).

For these reasons, we compare in this present work a wide range of zeolites (10) with: 1) different frameworks (MOR, *BEA, ZSM-5), 2) various acid site concentrations (Si/Al: 12-40) and 3) textural characteristics (crystal size of 20-800 nm with and without mesopores). We quantify their selectivity to aromatic hydrocarbons and their stability (towards coke formation) in the fast pyrolysis of wood. Our pyrolysis method allows decoupling 1) the primary pyrolysis of biomass and 2) the ex-situ catalytic conversion of vapours. Volatiles are analysed on-line by photo-ionisation mass spectrometry (PI-MS) and also quantified by GC/MS-FID. The coke deposit and the porous structure of zeolites after deactivation are characterized and they are related to products formation.

## 2. Materials and Methods

### 2.1. Zeolites production and characterizations

Table 1 shows the pore volume dimensions for the three zeolite frameworks: MOR, *BEA and MFI. Various post-treatments were carried out on commercial zeolites from Zeolyst or Süd Chemie to create intracrystalline mesopores. Protocols for treatment by leaching with NaOH, HF or NH4F are described in the supplementary information. The catalysts are labelled as follows: the capital letter indicates the origin of the material: C for commercial, S for synthesised and Hx for hierarchical (post-modification), in brackets the IZA (International Zeolite Association) structural code and in subscripts the crystal size: S (50<σ<500 nm), N <50 nm and M >500 nm). H<sub>A</sub> (and H'<sub>A</sub>) H<sub>B</sub>, and H<sub>uB</sub> mean hierarchized through alkaline (NaOH), biased (HF), and unbiased (NH<sub>4</sub>F) treatments, respectively. The detailed hierarchization procedures are reported in the supporting information.
<caption>Table 1. Nomenclature of the zeolites tested in this work.</caption>

In bracket the zeolite framework; the subscript indicates the crystal size; for hierarchization, H<sub>A</sub> and H'<sub>A</sub>: alkaline treatment (NaOH at), H<sub>B</sub> and H<sub>uB</sub>: biased (HF) and unbiased (NH<sub>4</sub>F) fluorine treatments respectively.

<table><thead><tr><th>Structure</th><th>Parent</th><th>Post-synthesis treatment</th><th>Crystal size range<sup>a</sup></th><th>Code</th><th>Reference</th></tr></thead><tbody><tr><td rowspan="4">MOR</td><td rowspan="4">C: Commercial (Süd Chemie)</td><td>/</td><td>S</td><td>C-(MOR)<sub>S</sub></td><td>/</td></tr><tr><td>H<sub>A</sub>: Alkaline (NaOH), 343K</td><td>S</td><td>H<sub>A</sub>-(MOR)<sub>S</sub></td><td rowspan="3">Issa et al. (2019)<sup>35</sup></td></tr><tr><td>H'<sub>A</sub>: Alkaline (NaOH), 358K</td><td>S</td><td>H'<sub>A</sub>-(MOR)<sub>S</sub></td></tr><tr><td>H<sub>B</sub>: Biased (HF), 298K</td><td>S</td><td>H<sub>B</sub>-(MOR)<sub>S</sub></td></tr><tr><td></td><td></td><td>H<sub>uB</sub>: Unbiased (NH<sub>4</sub>F), 298K</td><td>S</td><td>H<sub>uB</sub>-(MOR)<sub>S</sub></td><td></td></tr><tr><td rowspan="2">*BEA</td><td rowspan="2">C: Commercial CP814e (Zeolyst)</td><td>/</td><td>N</td><td>C-(*BEA)<sub>N</sub></td><td>/</td></tr><tr><td>H<sub>A</sub>: Alkaline (NaOH), 343K</td><td>N</td><td>H<sub>A</sub>-(*BEA)<sub>N</sub></td><td>Sammoury et al. (2018)<sup>48</sup></td></tr><tr><td></td><td>S: Synthesized</td><td>/</td><td>M</td><td>S-(*BEA)<sub>M</sub></td><td>Borade et al. (1996)<sup>49</sup></td></tr><tr><td>MFI</td><td></td><td>/</td><td>S</td><td>C-(MFI)<sub>S</sub></td><td>/</td></tr><tr><td></td><td>C: Commercial CBV8014 (Zeolyst)</td><td>H<sub>A</sub>: Alkaline (NaOH), 343K</td><td>S</td><td>H<sub>A</sub>-(MFI)<sub>S</sub></td><td>Raad et al. (2018)<sup>34</sup></td></tr></tbody></table>

## 2.2. Characterization of the fresh and spent catalysts

The Si/Al ratio of the samples was assessed via ICP-OES. Samples were dissolved in an acid solution (4 mL HNO<sub>3</sub> >68%, 3 mL HCl 34-37%, 1 mL HF 47-51% and 42 mL Ultra-pure water), with microwave assistance (Anton-Paar Multiwave Pro), and analysed with ICP-OES – 5110 Agilent VDV. The crystal sizes were determined using a scanning electron microscope (SEM) (Philips XL30 FEG).

Nitrogen sorption measurements were carried out at 77 K, from 0 till 100 kPa (absolute pressure) with a *Micromeritics 3Flex* apparatus. Fresh samples were degassed for 15h at 623 K. For spent samples, degassing is performed at ambient temperature (to prevent oxidation and/or thermal desorption). The microporous volume (V<sub>micro</sub>) and the external surface area were calculated from the t-plot curve using the Harkins-Jura method and a thickness range between 4.5 and 5.8 Å. Total porous volume (V<sub>pore</sub>) was calculated with a

<footnote><sup>a</sup> N = Nanometer (ø<50 nm), S = Sub-micrometer (50<ø<500 nm), M = Micrometer (ø>500 nm)</footnote>
single point adsorption method at around P/P₀ = 0.98, and the specific surface area was calculated with the BET method.

Pyridine adsorption (423 K) monitored by infrared (IR) spectroscopy (Nicolet Magna FTIR iS50 spectrometer) was used to quantify acidity (Pyr-FTIR)⁵⁰,⁵¹. Samples were shaped into wafers and activated *in-situ* in the IR cell (under air, ambient to 623 K for 15 h for fresh catalysts, and 423 K for spent samples). The interaction between pyridine and the acid sites of zeolites produces some characteristic bands for pyridine adsorbed on Brønsted and Lewis acid sites in the 1300-1700 cm⁻¹ region: pyridinium ions (1490, 1545, 1640 cm⁻¹) and coordinated pyridine (1455, 1490, 1600-1630 cm⁻¹). Their concentration was calculated using the Beer-Lambert-Bouguer's law:

$$C = \frac{A}{\varepsilon} * \frac{S}{m} * 1000 \qquad (\text{Eq. 1})$$

where C is the acid sites concentration (µmol/g), A the band's area (absorption/cm), S the wafer's surface (2 cm²), m the mass of the wafer (mg), and ε the molar extinction coefficient (cm/µmol).

Molar extinction coefficients were previously determined to be respectively 1.13 cm/µmol and 1.28 cm/µmol for Brønsted and Lewis acid sites⁵¹.

The mass of coke was measured by thermogravimetric analysis (TGA). 20 mg of the spent catalyst were placed in a platinum crucible and in a SDT Q600 TD/TG unit (TA instrument). The sample analyses were carried out under air flow (100 mL.min⁻¹) between 303 K (plateau for 10 min) and 1173 K (10 K.min⁻¹). The final temperature was maintained for 10 min, then the TGA was allowed to cool down.

## 2.3. Catalytic pyrolysis in a double fixed-bed reactor combined with SPI-MS

A double fixed bed micro-reactor was designed at CNRS Nancy to test these various zeolites by ex-situ pyrolysis. It is composed of 2 interconnected U-shape quartz reactors as presented in Figure 2.

<figure><img src="image_3.png" /><figcaption>Figure 2. Scheme of the double fixed-bed reactors developed at CNRS Nancy combined with photo-ionization mass spectrometry (PI-MS) and impingers for GC/MS-FID quantification of volatiles</figcaption></figure>
The first fixed bed is used to perform the pyrolysis of biomass and the 2nd one to convert ex-situ the volatiles over the zeolite. A similar U-shape reactor was introduced in our previous work for biomass primary pyrolysis and it was shown to give a good control of pyrolysis conditions: final temperature, quenching of the solid, mass transfers, etc.<sup>52-54</sup> In this present work, the 2nd fixed bed of zeolites allows for an interesting decoupling between biomass pyrolysis and volatiles conversion, for instance by conducting these 2 reactions at different temperatures, quenching times, solid mass, etc.

The dimensions of the 2 quartz reactors are: 3.5mm (internal diameter, I.D.), 80mm length (for inlet tubes) and 110mm length (four outlet tubes); the biomass and zeolite are positioned in 10mm I.D., 25mm length quartz (with a sintered plate).

85mg (7%water content, 79mg anhydrous, powder 100-200µm) of oak wood (complete analysis previously presented in ref. 52 and in supplementary material) was pyrolyzed and the mass of zeolite was set at 100mg. The biomass to catalyst ratio (BCR) was kept at 0.8 (wt.). This BCR was selected based on our previous work.<sup>46</sup> because it leads to a significant deactivation of microporous ZSM-5 zeolite (without hierarchization). Indeed, primary pyrolysis products (as the ones formed without a catalyst) were detected from this BCR of 0.8. Concerning the mass of zeolite bed, 100mg of zeolite enables the testing of advanced materials (low mass required), a good control of mass transfers through the fixed bed of zeolite (lower than 10mm height) and extensive characterization of the spent catalyst (acidity, coke, N<sub>2</sub> sorption).

The flow rate of N₂ as carrier gas was set at 120mL/min (measured at atmospheric pressure and 293 K). Therefore, the residence time (at 773 K) of biomass volatiles from the first sintered plate to the inlet of the first impinger was as low as 0.8sec (calculated with an empty 2nd reactor). All the heated lines between the 2 reactors and before the impingers were heated at 623 K.

At the outlet of the heated lined, the analytical method was the same as the one previously presented.<sup>46</sup> Briefly, a heated capillary line transfers a small fraction of the volatiles to a custom photo-ionization mass spectrometer (Photonion, Germany) operated with a laser and a Xenon cell to ionize the volatiles at 10.5eV. This soft ionization method is of tremendous importance to monitor on-line biomass volatiles.<sup>55</sup>

The major part of volatiles was condensed in 3 impingers, filled with 10mL methanol and glass beads in order to break the aerosols. The first impinger was cooled by water ice and the 2 other ones by a mix of isopropanol and liquid nitrogen at 213 K. The last impinger was analysed separately in order to check the efficient trapping of volatiles (no breakthrough). The solution of methanol was analysed by GC/MS-FID and internal calibration. The detailed method is provided in supplementary material.

The pyrolysis procedure was the following: 1) oak and zeolite were positioned in the 2 reactors; 2) the 2nd furnace was moved on the zeolite (flushed by N₂) and heated to 383 K at 5 K/min, then let 1 hour at 383 K and heated from 383 K to 773 K in 10 K/min; 3) during this time the 2nd furnace was preheated at 773 K (wood was dried at 393 K during 10min.); 4) impingers and sampling lines were connected, mass spectrometer acquisition started; 5) then the preheated first furnace was quickly moved up on the dried wood reactor. The pyrolysis products were analysed by our on-line PI-MS. Pyrolysis time was around 90 sec (see supplementary material). The reproducibility of the device and procedure is shown in the supplementary material for 4 different experiments on the HZSM-5 (C-(MFI)₅) (Figure S1).
# 3. Results and Discussion

## 3.1. Characterization of fresh zeolites

Three types of zeolite were used: MOR, \*BEA and MFI, with a wide range of acid and textural properties. The catalysts properties (crystal size, micropore and mesopore volumes, concentrations of Bronsted and Lewis acid sites, Si/Al), which were previously synthesized and characterized in other studies$^{48,49}$ are presented in Table 2.

<table><caption>Table 2. Textural and acidic properties of the fresh catalysts</caption><thead><tr><th>Catalyst code</th><th>Si/Al<sup>a</sup><br>mol/mol</th><th>Crystal size<sup>b</sup><br>(nm)</th><th>V<sub>micro</sub><sup>c</sup><br>cm<sup>3</sup>/g</th><th>V<sub>meso</sub><sup>c</sup><br>cm<sup>3</sup>/g</th><th>DH<br>(V<sub>meso</sub> + V<sub>micro</sub>) / V<sub>micro</sub></th><th>[P<sub>Y</sub>H<sup>+</sup>]<sup>d</sup><br>µmol/g</th><th>[PyL]<sup>d</sup><br>µmol/g</th></tr></thead><tbody><tr><td>C-(MOR)<sub>s</sub></td><td>20</td><td>100-500</td><td>0.18</td><td>0.11</td><td>1.6</td><td>552</td><td>47</td></tr><tr><td>H<sub>A</sub>-(MOR)<sub>s</sub></td><td>19</td><td>100-500</td><td>0.12</td><td>0.36</td><td>4</td><td>382</td><td>118</td></tr><tr><td>H'<sub>A</sub>-(MOR)<sub>s</sub></td><td>18</td><td></td><td>0.09</td><td>0.27</td><td>4</td><td>329</td><td>59</td></tr><tr><td>H<sub>B</sub>-(MOR)<sub>s</sub></td><td>35.6</td><td>100-500</td><td>0.18</td><td>0.14</td><td>1.8</td><td>220</td><td>50</td></tr><tr><td>H<sub>UB</sub>-(MOR)<sub>s</sub></td><td>15</td><td>100-500</td><td>0.17</td><td>0.15</td><td>1.9</td><td>497</td><td>68</td></tr><tr><td>C-(\*BEA)<sub>N</sub></td><td>12</td><td>20</td><td>0.25</td><td>0.75</td><td>4.0</td><td>346</td><td>349</td></tr><tr><td>H<sub>A</sub>-(\*BEA)<sub>N</sub></td><td>8.9</td><td>15</td><td>0.22</td><td>0.44</td><td>3.0</td><td>334</td><td>442</td></tr><tr><td>S-(\*BEA)<sub>M</sub></td><td>36</td><td>780</td><td>0.21</td><td>0.02</td><td>1.1</td><td>523</td><td>100</td></tr><tr><td>C-(MFI)<sub>s</sub></td><td>40</td><td>250</td><td>0.17</td><td>0.07</td><td>1.4</td><td>304</td><td>44</td></tr><tr><td>H<sub>A</sub>-(MFI)<sub>s</sub></td><td>32</td><td>250</td><td>0.15</td><td>0.38</td><td>3.5</td><td>231</td><td>63</td></tr></tbody></table>

The zeolite microporous volume (V<sub>micro</sub>) is a “fingerprint” of the framework type. Commercial MFI, MOR, and \*BEA zeolites feature V<sub>micro</sub> of 0.17, 0.18, and 0.25 cm<sup>3</sup>/g, respectively, which are the micropore volumes expected for conventional well-crystallized zeolites for these structures. Commercial MOR and MFI and synthesized \*BEA with micrometre crystal S-(\*BEA)<sub>M</sub> can be assimilated as purely microporous materials. The alkaline treatment causes a local collapse of the zeolite framework through its desilication, creating intracrystalline mesopores, which decreases both V<sub>micro</sub> and the concentration of the Bronsted acid sites (BAS) slightly. Desilication (with NaOH), unlike fluorine treatment, preserves a large part of the microporosity and acidity of the zeolite (Table 2). The commercial \*BEA zeolite (C-(\*BEA)<sub>N</sub>) is already a hierarchical material with a significant mesoporous volume resulting from the aggregation of the nanocrystals (20 nm). After alkaline treatment on MOR and MFI, the mesopores are intracrystals.

It is possible to estimate the degree of hierarchization (DH, Table 2) of all these materials by the ratio:

$$DH = \frac{V_{meso} + V_{micro}}{V_{micro}}$$

It is worth noting that the DH factor is the inverse of the relative micropore volume. A DH value of 1 corresponds to a purely microporous material. An alkaline treatment on MFI and MOR zeolites doubles the degree of hierarchization, while the impact of acid leaching is somewhat limited (an increase of 0.3). DH increases significantly up to 4 by decreasing the zeolite crystal size to the nanometric scale through the aggregation of particles for C-(\*BEA)<sub>N</sub>.<sup>56</sup>

<footnote><sup>a</sup> by ICP-AES, <sup>b</sup> SEM, <sup>c</sup> N<sub>2</sub> physorption, <sup>d</sup> Pyridine adsorption followed by FTIR</footnote>
The BAS concentration depends on both the Si/Al molar ratio and on their accessibility to the pyridine probe. Hence, the rate between the probed acid sites to the theoretical, calculated from the Si/Al ratio the zeolite ([PyH⁺]₄₂₃K/[H⁺]Theoretical), depends strongly on the zeolite framework. On *BEA and MFI zeolites, this ratio is close to 1 (Table 2). It is only 0.8 for MOR due to acid sites located on the sodalite cages and side pockets, which are inaccessible to the basic pyridine probe.

Five catalysts: C-(*BEA)N, H<sub>A</sub>-(*BEA)N, C-(MFI)s, H<sub>A</sub>-(MOR)s, H<sub>A</sub>'-(MOR)s feature a comparable concentration of Brønsted acid sites (ca 300-380 µmol/g). *BEA zeolite has a larger number of defects than MFI and MOR zeolites, leading to higher concentrations of Lewis acid sites.

## 3.2. Dynamics of volatiles formation as studied by on-line SPI-MS

The SPI-MS enables to monitor on-line the formation of volatiles. The SPI-MS profile of some main markers of cellulose, hemicelluloses and lignin and with an empty 2nd reactor is presented in supplementary material (Figure S2). We have previously discussed in details the formation of biomass primary volatiles as analyzed by SPI-MS.<sup>46,57</sup> It is out of the scope of this present work to discuss biomass primary pyrolysis in details. Briefly, the first step is the formation of *m/z* 114 (4-hydroxy-5,6-dihydro-2H-pyran-2-one, a typical marker of hemicelluloses pyrolysis) and furans (*m/z* 96 and 68) furfural. Then, lignin primary markers are formed (like *m/z* 180 4-vinyl-syringol, *m/z* 154 2,6-dimethoxy-phenol, *m/z* 168 4-methyl-syringol). *m/z* 126 can be assigned to 5-hydroxymethyl-furfural and photoionization fragment from levoglucosan (LVG, from cellulose pyrolysis).

When a zeolite catalyst was positioned in the 2nd reactor (at 773K), the composition of volatiles was completely modified and the species can be classified in 3 main families, with some of the most important species being<sup>46,58</sup>: 1) deoxygenated products (*m/z* 78 benzene, *m/z* 106 xylenes, *m/z* 42 propylene and fragment of 2,5-dihydrofuran); 2) partially deoxygenated products (*m/z* 82 furan, *m/z* 94 phenol) and 3) primary biomass-derived compounds formed from a deactivated catalyst (*m/z* 98 LVG fragments, *m/z* 114, etc.).

In the early step of pyrolysis, deoxygenated products (hydrocarbon aromatics) are formed with all zeolites (Figure 3 and other results presented in supplementary material – Figure S4), but only the MFI exhibit xylenes as the major products during the whole conversion of biomass.

Concerning mordenite, C, H<sub>B</sub>, H<sub>uB</sub> exhibit mainly deactivated products. H<sub>A</sub> and H<sub>A</sub>' MOR present a higher peak in hydrocarbon aromatics than the parent MOR but only in the early stage of pyrolysis (Figure 3). The hydrocarbon aromatics may be formed from the conversion of the first hemicelluloses volatiles but the MOR (even after hierarchization) is fastly deactivated. Then, the major contribution comes from furans formed over the partly deactivated zeolites. The alkaline treatment (by NaOH) of these 2 zeolites (H<sub>A</sub> and H<sub>A</sub>' MOR) lead to a higher mesopores volumes and hierarchization degree (Table 2) and therefore a relative better stability compared to the other 3 mordenites. As shown by Chaouati and al.<sup>59</sup>, the generation of mesopores connected to the micropores through alkaline treatment on MOR zeolite mitigates the coke toxicity.

Regardless of the crystal size, the 3 *BEA present a similar pattern which is very different than MOR. The hydrocarbons (notably m/z 42) are the major contribution all along biomass conversion, then furans and phenols are formed (notably during cellulose and lignin main devolatilisation steps). The hierarchization of
*BEA ($H_A$-(*BEA)$_N$) or a larger crystal size ($S$-(*BEA)$_M$) does not significantly impact the profile in products formation. As indicated by the large number of Lewis sites probed (Table 2), the *BEA zeolites contain a large number of extra framework aluminium species (EFAL) species. Thus, the higher cracking activity on these three zeolites could be attributed to an enhancement of the BAS strength by EFAL species<sup>60</sup>. Indeed, a study combining MAS NMR with DFT calculations<sup>61</sup> showed the existence of a clear interaction between the Brønsted and Lewis acid sites (LAS) leading to an increase in the acid site strength in the zeolite framework.

The MFI is the only zeolite to present 2 peaks of deoxygenated products (hydrocarbon aromatics like xylenes) as the major products. The 2 peaks correspond to the conversion of hemicelluloses and cellulose volatiles (cf. the time profile shown in the supplementary material without catalyst – Figure S2). The profile is always dominated by hydrocarbons all along the pyrolysis time. MFI converts primary volatiles to hydrocarbons more efficiently than *BEA zeolite, not because of the strength of the BAS acid site and the length of diffusion paths, but mostly because of the shape of canals around the acid sites.<sup>4,11,29</sup> Phenols and furans are also formed at the final stage of the pyrolysis by the partial conversion of methoxy-phenols from lignin pyrolysis and of cellulose primary vapours.<sup>29,46</sup>

<figure><img src="image_4.png" /></figure>

Figure 3. Evolution of some important markers for MOR, *BEA and MFI zeolites: m/z 106 (xylenes), 82 (2-methyl furan), 42 (propylene and fragments of 2,5-dihydrofuran), 94 (phenol), 98 (levoglucosan fragments and 1,2 cyclopentanedione) as a function of time (analyzed by on-line SPI-MS). The time "0 sec." corresponds to when the furnace (preheated) is in its final position (after its lift out) on the biomass bed.
### 3.3. Comparison of the zeolites based on SPI mass spectra and statistical analysis

The accumulated mass spectra of SPI-MS during the whole conversion of biomass are presented in Figure 4 (and in supplementary material – Figure S5).

For all mordenites, the major contributions are *m/z* corresponding to oxygenated products (furans, primary pyrolysis products as levoglucosan markers, etc.). For all *BEA*, the major contribution is *m/z* 42 (propylene and dihydrofuran fragments) and aromatic hydrocarbons. For the 2 MFI, the major peaks are the contributions of aromatics hydrocarbons.

<figure><img src="image_5.png" /><figcaption>Figure 4. SPI total mass spectra (averaged along the whole pyrolysis time) of the catalytic products for MOR, *BEA* and MFI zeolites (other zeolites presented in supplementary materials – Figure S5)</figcaption></figure>

We have previously shown the interest to treat the mass spectra by statistical analysis in order to better unravel the significant differences between the pyrolysis conditions.<sup>46,57</sup> Figure 5 presents the principal component analysis (PCA) of all the mass spectra (accumulated during the whole pyrolysis time) obtained with the various tested catalysts. PC1 and PC2 explain 91% of the variance. Figure 5 displays a very clear separation between the 3 types of zeolites, despite the high variability in crystal size, texture and acidity within each zeolite type.

Xylenes and ethylbenzene are clear MFI markers. The 3 *BEA* zeolites are clearly differentiated from the other type of zeolites by *m/z* 42 (propylene and dihydrofuran fragments).
Furan and methyl furan (m/ζ̄68, 82) are marker for hierarchical mordenites produced by alkaline treatment (H<sub>A</sub>-(MOR)<sub>s</sub> and H<sub>A</sub>'-(MOR)<sub>s</sub>). The higher mesoporosity and added connectivity between channels (2D to ~3D) induced by this treatment when compared to commercial and fluorine treatments (see DH in Table 2) promote some partial deoxygenation of *primary biomass-derived compounds*. It reduces the deactivation rate of MOR. Desilication is the method of choice for the development of intracrystalline mesoporosity. The formation of mesoporosity leads to an improved resistance to coking through a reduction in the diffusion path length of coke precursors.<sup>35</sup> Primary products from oak pyrolysis (m/ζ̄114, 98, 126) are markers for the 3 other mordenites, which present a very weak deoxygenation activity.

<figure><img src="image_6.png" /><figcaption>Figure 5. PCA of SPI-MS analysis of the volatiles produced by the various zeolites: groups per type of catalysts are clearly evidenced highlighting typical markers in volatiles</figcaption></figure>

**3.4. Comparison of the zeolites based on GC/MS quantification of aromatic hydrocarbons**

SPI-MS is an interesting method to monitor in real time the volatiles, but it is semi-quantitative. Therefore, it is required to compare the zeolites by quantitative GC/MS analysis. Figure 6 displays the mass yields (based on anhydrous biomass) of the targeted aromatic hydrocarbons.
<figure><img src="image_7.png" /><figcaption>Figure 6. Mass yields (% mass of product/mass of anhydrous wood) as quantified by GC/FID-MS for MFI and *BEA zeolites.</figcaption></figure>

The mass yields of BTX were too small for mordenite-types zeolites (not presented). Figure 6 clearly shows that MFI presents a much higher yield in aromatic hydrocarbons compared to the 3 *BEA zeolites in agreement with previous work<sup>40,62,63</sup> (conducted under different pyrolysis conditions). Aromatics yields are higher with MFI zeolites than with *BEA zeolites* whatever the degree of hierarchization. This result highlights the key role of the shape and aperture of the pores (Table 1). Steric constraints within the MFI zeolite prevent alkylation reactions. In the case of BEA zeolites, alkylation reactions promote the formation of polyaromatic compounds and hence of coke, therefore reducing the selectivity to mono-aromatics formation whatever the hierarchization methods used (Figure 7a). Despite the numerous studies on biomass CFP, the quantitative data (mass yields) comparing MFI and *BEA on wood pyrolysis are scarce (see our table of literature analysis in supplementary material – Table S1). The hierarchization of *BEA does not improve the mass yield in aromatic hydrocarbons whereas the hierarchization of MFI (by NaOH) increases the mass yields in aromatic hydrocarbons, in agreement with our previous work in fluidized bed conditions<sup>46</sup>. Therefore, the hierarchization of MFI improves the selectivity in aromatics for both reactor configurations (ex-situ fixed bed or in-situ fluidized bed). The improvement in aromatic hydrocarbons after the hierarchization of ZSM-5 is in agreement with the work of Eschenbacher et al.<sup>64</sup> who studied the same zeolite (CBV8014 from Zeolyst Int. with a similar hierarchization by NaOH) but with higher biomass to catalyst ratio in a fixed bed downstream a continuous ablative pyrolysis reactor. These authors especially notice the increase in GC-identifiable molecules and a decrease in the molecular weight of the bio-oil with the mesoporous CBV8014 zeolite. This result is explained by the enhanced conversion of heavy oligomers in the mesopores.<sup>64</sup> We have also evidenced this effect of mesopores on oligomers by high resolution mass spectrometry.<sup>47</sup>

**3.5. Characterization of the spent zeolites**

The catalytic transformation of volatiles at 773 K leads to high coke content (> 7.5 wt. %) whatever the zeolite framework, as well as the hierarchization degree of the material **(Figure 7a)**. The high reaction temperature favours the kinetic rate of coke formation much more than the diffusion of coke precursors, even after enhancing the diffusion in crystals, by reducing the crystals size or by hierarchization, by mesopores formation in crystals (see Table 2).
<figure><img src="image_8.png" /><figcaption>Figure 7. Coke content (a, after deactivation, for spent catalysts) and concentration of Brønsted acid sites (b), micropores (c) and mesopores (d) volumes for fresh and spent catalysts</figcaption></figure>

However, the medium-pore zeolite (MFI) is more resistant to coking than the large pore pseudo-mono - (MOR)- and tri-dimensional-(*BEA) zeolites. This result means that steric constraints also limit coke formation: the large pore zeolites promote the growth of coke contrariwise to medium pores ones (MFI). The higher content of coke in the *BEA than in the MFI could also be related to a higher acid strength of *BEA.

<figure><img src="image_9.png" /><figcaption>Figure 8. Bands of coke molecules in regions 3200-2700 cm⁻¹ (a) and 1800-1300 cm⁻¹ (b). Weight fractions of coke based on catalyst initial mass are also recalled.</figcaption></figure>
The coked zeolites were analyzed by FTIR (Figure 8). The bands of carbonaceous compounds deposited on commercial zeolites are observed on two IR spectra domains: i) 2700-3200 cm⁻¹: CH stretching modes of aromatic and paraffinic groups, ii) 1400-1800 cm⁻¹: C=C stretching modes of unsaturated (olefin, polyenyl, aromatic and polyaromatic) groups and CH bending of paraffinic groups. The band at 3062 cm⁻¹ corresponds to aromatic CH stretching modes, 2972 and 2925 cm⁻¹ to the asymmetric stretching mode of CH₃ and CH₂ groups, respectively and 2972 and 2866 cm⁻¹ are related to symmetric stretching mode of CH₃ in hydrocarbons chains⁶⁵. Attribution of bands in region between 1300-1800 cm⁻¹ is more complex, because it could be attributed to different stretching modes of C=C condensed and non-condensed aromatics and also bending vibrations of CH. Bands at 1600, 1575, 1510, are usually assigned to polyaromatic coke with a number of aromatic rings superior to 3 (NAR>3)⁶⁶. The band at 1710 cm⁻¹ (vCO) indicated the presence of a low content of oxygenated compounds. The coke bands are almost identical regardless of the zeolite framework. Indeed, the transformation of hydrocarbons at high temperature leads to the formation of polyaromatic compounds replicating the shape of micropores.⁶⁷

About the pseudo mono-dimensional zeolite (MOR), even on those with intracrystalline mesopores (Figure 7d), the coke completely neutralizes the Brønsted acid sites (Figure 7b), which indicates a pore blocking by molecules having a size similar to pyridine. The IR spectra of the OH region on the spent catalysts confirms the inaccessibility of the bridged OH groups to organic molecules (see supplementary material – Figure S6). Alkaline and fluorine treatments have created connections between the main channel and the mesopores as evidenced by the presence of residual micropore volumes after deactivation (Figure 7c). Yet, the opening generated by post-treatments are too small to allow the diffusion of organic molecules in the main channels. The structure of mordenite with 2D channels lead to a fast deactivation, plugging by coke even after different hierarchization methods.

Concerning the three-dimensional zeolites (MFI and \*BEA), the losses of BAS and microporosity are partial (Figure 7 b and c) which means that deactivation occurs mainly by poisoning rather than pores blockage. The loss of mesoporous volumes in all the samples suggests that a part of the coke is retained on the mesopores, regardless of whether they are intergranular (\*BEA samples) or intracrystalline (MOR and MFI zeolites)-(Figure 7d).

Figure 9 presents relations between coke content and BAS and degree of hierarchization.
<figure><img src="image_10.png" /></figure>

<figure><img src="image_11.png" /></figure>

<figure><img src="image_12.png" /><figcaption>Figure 9. Coke content as a function of the initial concentration of Brønsted acid sites (a), degree of hierarchization (DH) of zeolite (b) and the multiplication of these two parameters (c). Commercial microporous zeolites are represented with full points.</figcaption></figure>

The coke content is not well related to the concentration of initial BAS present in fresh zeolites (Figure 9a). On the larger pore zeolites (*BEA, MOR), the coke content increases with the degree of hierarchization (Figure 9b) and the trend is clearer when taking into account the acidity (Figure 9c). Mesopores opening in the 2D channels structure of mordenites do not promote the diffusion of coke precursors in the main channels. Therefore coke content increases with DH for MOR and *BEA. The hierarchization of large pore zeolites promote the accumulation of coke contrariwise to medium pores ones (MFI). For MFI, coke content seems independent of DH and BAS*DH. This fact can be explained by the steric constraints which limit coke formation in the MFI crystals even after its hierarchization. It is interesting to notice that the reduction in mesopores due to coke deposit is much lower in the hierarchical MFI than in the hierarchical *BEA zeolites (Figure 7d). NaOH leached zeolites and nanometric zeolites present the highest coke
contents. This result may be explained by the increased number of silanols and Lewis acid sites (as for *BEA samples) because they are prone to trap desorbed products³⁸,⁶⁸,⁶⁹.

### 3.6. Relation between aromatics' selectivity, coke deposit and zeolite structures

Figure 10a presents the mass yields in monoaromatic hydrocarbons as a function of coke deposit. It highlights a much higher total yield in monoaromatic hydrocarbons for MFI and notably for the hierarchical MFI with a lower coke content than all the *BEA and MOR zeolites. The HZSM-5 presents a better compromise to monoaromatic hydrocarbons selectivity and stability towards coke.

Figure 10b clearly shows an increase in aromatic yields as a function of the hierarchization for MFI. The increase is much weaker for *BEA and MOR upon hierarchization, whatever the hierarchization methods used.

Figure 10c presents the aromatic yields as a function of the consumed BAS. It confirms a more efficient utilization of BAS in MFI to produce aromatics than in *BEA and MOR. BAS are present in a similar cage-like voids with a diameter of 7.0 Å for the 3 types of zeolites (see Table 1 for zeolites structure). Therefore, the selectivity towards aromatics and coke formation depends on the shape of canals but not on the H⁺ cage environment. *BEA promotes the diffusion of species in larger pores than MFI, but it leads to a lower shape-selectivity than MFI.

Figure 10d presents another information about the initial activity of the zeolites and not after the complete wood pyrolysis. The signal of m/z 106 obtained by SPI-MS has been integrated during the first 60 seconds (and divided by the total ionic current TIC). This is a relative information about the abundance of C8 aromatic hydrocarbons vs. the other ions. This data is only semi-quantitative, but it presents a high interest to assess the activity of fresh zeolites. This first 60 seconds of experiments represent mostly the catalytic products formed from hemicellulose primary species (see supplementary data on SPI-MS results without catalyst). This relative signal of C8 abundance is plotted as a function of the initial BAS and hierarchization degree. Based on Figure 10d, *BEA competes with MFI during these early stages of volatiles conversion. This point may explain some conflicting results obtained in the literature when comparing different zeolites (see table S1 in supplementary material). The performance of zeolites depends on the amount of coke deposit and of the biomass to catalyst ratio (bcr) studied. The composition of primary volatiles is also a concern: the volatiles from hemicelluloses are easier to be converted to aromatic hydrocarbons than lignin primary products. For instance, *BEA zeolites present better selectivity to aromatic hydrocarbons on lignin vapours than ZSM-5.²⁹ Consequently, this work may be extended to a dual fluidized bed configuration where the bcr is much lower than in a fixed bed and where biomass volatiles are in contact with a regenerated zeolite (although potentially deactivated by alkali species).
<figure><img src="image_13.png" /></figure>

<figure><img src="image_14.png" /></figure>

<figure><img src="image_15.png" /></figure>

<figure><img src="image_16.png" /></figure>

Figure 10. Relations between monoaromatic hydrocarbons (wt.%) and a) coke deposit, b) zeolite initial acidity (BAS * degree of hierarchization), c) consumed BAS and d) relative signal of C8 hydrocarbons (m/z 106) obtained by SPI-MS during the first 60sec. as a function of the initial acidity (BAS * degree of hierarchization). Commercial microporous zeolites are represented with full points.
4. Conclusions

This work presents 2 methodologies of potential interest for studying biomass catalytic pyrolysis:

1) A double fixed bed reactor where biomass pyrolysis is decoupled from ex-situ conversion of volatiles;

2) A combination of on-line SPI-MS with GC/MS and advanced characterization of the coked zeolites.

This methodology has been applied to various zeolites presenting complementary porous structures: mordenite, *BEA and MFI. Furthermore, these zeolites have been hierarchized with different methods (NaOH, HF, $NH_4F$, etc.). The effect of crystal size has been also studied for *BEA. The spent catalysts were analysed by pyridine probe (acidity), coke composition by FTIR (without pyridine) and porous structure by $N_2$ sorption.

Our main findings are summarized in Figure 11.

<figure><img src="image_17.png" /><figcaption>Figure 11. Main species produced by the 3 type of zeolites and effect of coke deposit on their deactivation mechanism (fixed bed, biomass to catalyst ratio of 0.8)</figcaption></figure>

The hierarchical MFI (obtained by mild desilication with NaOH) is the best zeolites among the ones tested under our studied bcr ratio (0.8). BAS were present in a similar cage-like voids with a diameter of 7.0 Å for the 3 types of zeolites. Therefore, the selectivity towards aromatics and coke formation depends on the shape of canals but not on the $H^+$ cage environment. *BEA promotes the diffusion of species to BAS in larger pores than MFI but it leads to a lower shape-selectivity than MFI after partial deactivation by coke. For the three-dimensional zeolites (MFI and *BEA), the losses of BAS and microporosity are partial which means that the deactivation by coke molecules occurs mainly by poisoning (Figure 11) rather than pores blockage. The structure of mordenite with 2D channels and small interconnectivity lead to a fast deactivation. The coke completely neutralizes the Bronsted acid sites (analyzed by pyridine) and the deactivation occurs by pores plugging even after different hierarchization methods. We did not succeed to improve the selectivity and stability of MOR zeolites by hierarchization.

Therefore, hierarchical MFI seems the most promising zeolites for scaling-up the process. Other catalysts based on this type of zeolite and formulated (with binders, additives, metals, etc.) may be tested by following
the same methodology and under different configurations, as for instance in a dual fluidized bed or in
sequential fixed beds fed by a continuous pyrolysis reactor. Experiments should be conducted at pilot scale
with long-time on stream experiments (for dual fluidized bed reactors with continuous regeneration) or with
many deactivation/regeneration cycles (for parallel fixed bed reactors). For this purpose, the production of
formulated and shaped hierarchical MFI particles (at kilograms-scale) is a next important step for scaling up
catalytic pyrolysis. The formulation should promote the mechanical strength of particles for long-term
operations and intraparticle gas-phase mass transfers.

**5. Supporting information**

A table reviewing previous studies on catalytic fast pyrolysis with a special emphasize on the comparison
between zeolites and hierarchical zeolites; synthesis protocol of the zeolites; composition of wood oak;
GC/MS method; reproducibility of the pyrolysis protocole; SPI-MS results; N₂ physisorption isotherms;
FTIR spectra of coked MOR zeolites.

**6. Acknowledgements**

Nathan Pichot, Ludovic Pinard and Anthony Dufour would like to thank the French “Agence Nationale de la Recherche (ANR)” and Région Nouvelle-Aquitaine for their financial support, through the PYCASSO and SHAPING projects. Ludovic Pinard thanks the Région Normandie for their financial support, through the Bio/DNH project. The authors thank the Xylofutur cluster for its support.
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