Catalysis 2023 Issue

Conventional

Mesoporous

Mesoporous with metal

Cloud point improvement , ˚C 10 0 30 20

225

Reactor temperature , ˚C 245 285 265

305

Figure 6 The benefits of Zeopore’s metal mesoporisation process in dewaxing

changing the exchangeable charge-balancing cation inside the zeolite crystal to other elements, yielding unique multi- metallic materials. For example, a combination of copper inside the zeolite and cerium (oxide) on the external surface may enhance low-temperature deNOx performance. Catalytic benefits warrant change Obviously, the ‘proof in the pudding’ is in catalytic perfor- mance. The potential of these types of metal-containing zeolites is actively being explored in several applications and has already attained noticeable results in dewaxing (see Figure 6 ) and methanol-to-olefins (see Figure 7 ). In dewaxing, the potential of traditional noble metal- loaded mesoporous zeolites is clear. 4 However, the inclu- sion of a metal enhancer applied via Zeopore’s technology proved the presence of even more potential compared to metal-free mesoporous zeolites. Not only did the die- sel losses as a function of cloud point improvement (CPI) reduce by a factor of 2, also large benefits in activity were obtained, requiring about 20°C less for a fixed cloud point improvement. Finally, the saturation of aromatics enhanced significantly and proved more stable as a function of CPI. In the conversion of methanol-to-olefins, mesoporous zeolites have been established to yield a prolonged life- time based on a higher resistance to coking. Yet, gaining selectivity benefits is harder and can be achieved using additives. 5 Figure 7 shows a conventional ZSM-5 and a Zeopore material, both containing metal additives. The

metal mesoporised ZSM-5 displayed a remarkable increase in propylene and butylene selectivity at the expense of undesired alkanes and heavies (C 5 +). Outlook Based on the process, material and catalytic potential iden- tified, metal mesoporisation is of significant value in cur - rent applications in the refining and petrochemical industry. Its potential is further being explored, and the impact on the catalyst level is being investigated, such as assessing in-depth the stability of the formed metal species. Also, its potential in other catalytic reaction applications is currently being explored, such as in the hydrocracking of VGO, which has resulted in ca. 4 wt% of extra middle distillates at fixed conversion and a lower temperature to do so. The latter efforts easily represent benefits in the order of multi-million dollars per converter per year, which will be discussed in another article under development. References 1 K. Du Mong, D. Verboekend, Low-cost mesoporous zeolites deliver catalytic benefits, PTQ Catalysis, 2022, 45-49. 2 J. Zecevic, G. Vanbutsele, K. P. de Jong, J. A. Martens, Nanoscale in- timacy in bifunctional catalysts for selective conversion of hydrocar- bons, Nature , 528, 2015, 245-248. 3 O. Sanahuja-Parejo et al. , Insights into the production of upgrad- ed biofuels using Mg-loaded mesoporous ZSM-5 zeolites, Chem- CatChem , 12, 2020, 5236-5249. 4 J. A. Martens et al. , Hydroisomerization and hydrocracking of linear and multibranched long model alkanes on hierarchical Pt/ZSM-22 zeo- lite, Catalysis Today , 218-219, 2013, 135-142. 5 I. Yarulina et al ., Suppression of the aromatic cycle in methanol-to- olefins reaction over ZSM-5 by post-synthetic modification using cal - cium, ChemCatChem, 8, 2016, 3057-3063. Danny Verboekend is a founder and CTO of Zeopore Technologies and is responsible for technology development and product innova- tion. He has been working and publishing on the synthesis of superior accessible zeolites for over a decade and holds a PhD from the ETH Zurich (Switzerland). Martin d’Halluin is a founder and development engineer of Zeopore Technologies, focusing on catalyst technology development and cata- lytic validation. He holds a degree in chemistry from the University of Bordeaux and a PhD from the University of Nantes (both in France).

50%

Mg/mesoporous

Species Delta , wt% C1 -0.1 C2- -0.1 C2= -1.7 C3- -1.2

40%

Mg/conventional

30%

20%

C4- -1.4 C4= +3.1 C5+ -1.8 C3= +3.4

10%

Time , days

Figure 7 The benefits of Zeopore’s metal mesoporisation in methanol-to-olefins

Catalysis 2023