Catalytic cracking performance of alkaline-treated zeolite Beta in the terms of acid sites properties and their accessibility

The zeolite Beta is considered as a promising additive for FCC catalyst in diesel oil production. In this article, it is shown that hierarchical zeolite Beta obtained by an optimized desilication procedure increases diesel and propylene yields during gas oil cracking reaction. The alkaline treatment of zeolite Beta (Si/Al = 22) by desilication with NaOH and NaOH&TBAOH was investigated. The catalytic performance improvement of desilicated zeolite Beta has been rationalized by deep characterization of the samples including X-ray diffraction, low-temperature adsorption of nitrogen, solid-state 29Si MAS NMR and IR studies of acidity. Finally, the catalytic performance of the zeolites Beta was evaluated in the cracking of n-decane, 1,3,5-tri-iso-propylbenzene, and vacuum gas oil. It was found that desilication with NaOH&TBAOH ensures the more uniform intracrystalline mesoporosity with the formation of narrower mesopores, while preserving full crystallinity resulting in catalysts with the most appropriated acidity and then with better catalytic performance.Also, M.C.I.L., J.M.T. and F.R. thank financial support from the Spanish Ministry of Economy and Competitiveness through the Severo Ochoa program (SEV-2012-0267) as well as operating grants Consolider Ingenio Multicat (CSD-2009-00050) and MAT-2012-3856-0O2-01.Tarach, K.; Gora-Marek, K.; Tekla, J.; Brylewska, K.; Datka, J.; Mlekodaj, K.; Makowski, W.... (2014). Catalytic cracking performance of alkaline-treated zeolite Beta in the terms of acid sites properties and their accessibility. Journal of Catalysis. 312:46-57. https://doi.org/10.1016/j.jcat.2014.01.009S465731

Acidity and accessibility studies of desilicated ZSM-5 zeolites in terms of their effectiveness as catalysts in acid-catalyzed cracking processes

The structural, textural and acidic characteristics of hierarchical ZSM-5 (Si/Al = 18-32), obtained with two desilication approaches, and the effect of these treatments on the reactivity in various cracking reactions of variable feedstock size and severity have been investigated. Emphasis is given to understanding the accessibility of acid sites; this was investigated by textural analysis, FTIR probe molecules (pyridine, trimethylacetonitrile and 2,4,6-trimethylpyridine) and reactions involving n-decane, 1,3,5-triisopropylbenzene (TIPB), and low and high-density polyethylene, LDPE and HDPE, respectively. Higher surface areas and a narrower pore size distribution were obtained for NaOH&TBAOH-treated materials, comparing to NaOH-treated ones. FTIR studies of pivalonitrile and collidine adsorption correlate well with the mesopore surface area. For n-decane cracking activity, the acid strength is a determining factor, revealing that the NaOH&TBAOH treatment gave stronger sites than NaOH, but lower than the native zeolite. In contrast, the TIPB cracking activity was improved by the developed mesoporosity of the alkaline treated zeolites, and this was correlated to the pivalonitrile and collidine accessibility factors. During the n-decane and TIPB cracking, hydrogen transfer reactions were reduced, leading to high olefin production for the NaOH&TBAOH materials due to the shorter microporous paths after desilication. The increased accessibility of the acid sites also leads to an enhanced cracking activity of polyethylenes at low conversions, as determined by a decrease in the T5% and T50%; both parameters are linearly dependent on the pivalonitrile and collidine accessibility factors, for LDPE and HDPE. The T5% for HDPE is more influenced by the accessibility factors than it is for the LDPE. This is interpreted to be the result of the branching degree of HDPE and LDPE; linear HDPE is more sensitive to the enhanced number of pore mouths of ZSM-5 channels on the mesopores. At high conversion, the influence on the T50% of the accessibility factors for HDPE and LDPE is weaker, suggesting that the cracking at this stage involves intermediate molecules of smaller size with fewer diffusional limitations. With respect to our own prior work, the chosen zeolite and the cracking of polyolefins gave more pronounced differences for the hierarchical ZSM-5

Hierarchically structured ZSM-5 obtained by optimized mesotemplate-free method as active catalyst for methanol to DME conversion

In the presented studies, a new method for the synthesis of hierarchical porous materials with ZSM-5 zeolite properties was applied. The proposed method is based on the acidification of the zeolite seeds slurry using HCl solution, followed by hydrothermal treatment, enabling the aggregation of zeolite nanoseeds with the formation of the interparticle mesoporous structure. The influence of the duration of zeolite parent mixture aging before and after acidification on the resulting properties of the samples was investigated. The physicochemical properties of the obtained micro-mesoporous samples were analyzed using techniques such as N-2-sorption measurements, X-ray diffraction, TG analysis, NH3-TPD and electron microscopy. In the second part of the studies, the influence of the modified zeolite sample parameters (such as porosity, acidity and crystallinity) on their catalytic activity for dimethyl ether (DME) synthesis from methanol was studied. DME is considered as a future clean alternative to diesel fuel and the development of methods for its synthesis is currently of high scientific interest. It was shown that modification of the porous structure and acidity of the zeolitic samples strongly influences their catalytic activity, selectivity and stability for the DME synthesis process. The micro-mesoporous samples, despite their significantly lower acidity, exhibited high catalytic activity (similar to conventional ZSM-5 zeolite) and enhanced selectivity towards DME, as well as higher stability in a long term catalytic test (higher resistance to the formation of coke deposits) in comparison to standard MFI-type zeolites.This work was supported by the National Science Center under grant no. 2011/03/N/ST5/04820. Part of the research was carried out with equipment purchased thanks to the financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program (contract no. POIG.02.01.00-12-023/08). U. D. gives thanks to Spanish Government by the funding (project MAT2014-52085-C2-1-P).Rutkowska, M.; Macina, D.; Piwowarska, Z.; Gajewska, M.; Díaz Morales, UM.; Chmielarz, L. (2016). Hierarchically structured ZSM-5 obtained by optimized mesotemplate-free method as active catalyst for methanol to DME conversion. Catalysis Science and Technology. 6(13):4849-4862. https://doi.org/10.1039/c6cy00040aS4849486261

Desilication of highly siliceous zeolite ZSM-5 with NaOH and NaOH/tetrabutylamine hydroxide

The results of both chemical and XPS analysis pointed out that desilication of highly siliceous ZSM-5 of Si/Al = 164 was more effective in the surface zone than in the bulk, contrary to zeolite ZSM-5 of Si/Al = 31.6. According to the IR studies in parent zeolite the concentration of protonic sites was very close to the concentration of Al indicating that all Al atoms can form Si-OH-Al. The results of our quantitative IR studies strongly support the realumination thesis, i.e. some Al atoms extracted in basic solutions are subsequently reinserted forming new acidic hydroxyls. In desilicated zeolites all Al atoms were able to form protonic sites, however part of them dehydroxylated during the activation of zeolite producing Lewis acid sites according to the stoichiometry: one protonic site was transformed into one Lewis site. Low temperature nitrogen adsorption revealed that the alkaline treatment of highly siliceous zeolite with 0.2 M NaOH/TBAOH mixture produced mesopores of smaller diameter and narrower pore size distribution than in the case of zeolite of medium Si/Al ratio. This result can be explained by low concentration of Al which similarly as TBA(+) cations plays the role of pore directing agents (PDA). Contrary to TEA(+), the presence of Al in desilication mixture, led to the formation of larger pores. Therefore, in highly siliceous zeolite TBA(+) played dominant role as PDA producing narrower pores. Highly siliceous zeolite with uniform distribution of relatively narrow pores may be useful catalyst or catalyst support. The influence of desilication temperature on porosity development was also investigated. The increase of desilication temperature from 338 to 353 K resulted in both more extensive demetalation (more Si and Al is extracted) and the distinct increase of the volume and surface of mesopores. Both lower concentration of protonic sites and higher concentration of Lewis sites confirmed partial zeolite destruction upon desilication at elevated temperature. The experiments of pivalonitrile sorption followed by IR spectroscopy showed a significant increase of accessibility of acid sites to bulky pivalonitrile molecules. (C) 2012 Elsevier Inc. All rights reserved.The research was partially carried out with the equipment purchased thanks to the financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program (Contract No. POIG.02.01.00-12-023/08).Sadowska, K.; Góra-Marek, K.; Drozdek, M.; Kustrowski, P.; Datka, J.; Martínez-Triguero, J.; Rey Garcia, F. (2013). Desilication of highly siliceous zeolite ZSM-5 with NaOH and NaOH/tetrabutylamine hydroxide. Microporous and Mesoporous Materials. 168:195-205. https://doi.org/10.1016/j.micromeso.2012.09.033S19520516

Improved THETA-1 for light olefins oligomerization to diesel: Influence of textural and acidic properties

The increase in diesel demand, especially in Europe, and the need for high fuel quality requirements are forcing refiners to move into additional processes for production of high cetane diesel in order to meet the present market trends. Oligomerization of light olefins into middle distillate range products is a viable option. The fuel produced through this technology is environmentally friendly, free of sulfur and aromatics, and the adequate choice of the heterogeneous catalyst will direct the selectivity towards low branched oligomers, which will result in a high quality product. In this work we show the benefits of combining basic desilication treatments for generation of additional mesoporosity in mono-directional Theta-1 zeolite, with selective acid dealumination steps that restore not only the microporosity to values close to those of the parent samples, but also the total and strong Bronsted acidity. These modified Theta-1 zeolites present an outstanding catalytic behavior for oligomerization of propene, with a largely increased initial activity, a much higher resistance to deactivation with time on stream, and an improved selectivity to products in the diesel fraction, as compared to the original microporous Theta-1.The authors thank BP Products of North America for their financial support and permission to publish this work, and Consolider Ingenio 2010-Multicat, the "Severo Ochoa Program", and MAT2012-31657 for financial support. R. Sanchis is acknowledged for technical support.Martínez, C.; Doskocil, EJ.; Corma Canós, A. (2014). Improved THETA-1 for light olefins oligomerization to diesel: Influence of textural and acidic properties. Topics in Catalysis. 57(6-9):668-682. https://doi.org/10.1007/s11244-013-0224-xS668682576-9Bellussi G, Mizia F, Calemma V, Pollesel P, Millini R (2012) Microporous Mesoporous Mater 164:127–134Bellussi G, Carati A, Millini R (2010) In: Cejka J, Corma A, Zones S (eds) Zeolites and Catalysis. Wiley-VCH Verlag GmbH & Co., Weinheim, pp 449–491Martinez C, Corma A (2011) Coord Chem Rev 255:1558–1580de Klerk A (2005) Ind Eng Chem Res 44:3887–3893de Klerk A (2006) Energy Fuels 20:439–445de Klerk A (2006) Energy Fuels 20:1799–1805Egloff G (1936) Ind Eng Chem Res 28:1461–1467Degnan TF Jr, Smith CM, Venkat CR (2001) Appl Catal A Gen 221:283–294Apelian MR, Boulton JR, Fung AS (1994) US5284989, to Mobil OilQuann RJ, Green LA, Tabak SA, Krambeck FJ (1988) Ind Eng Chem Res 27:565–570Tabak SA, Krambeck FJ, Garwood WE (1986) AIChE J 32:1526–1531Corma A, Martínez C, Doskocil EJ (2013) J Catal 300:183–196Martens JA, Ravishankar R, Mishin IE, Jacobs PE (2000) Angew Chem Int Ed Engl 39:4376–4379Martens JA, Verrelst WH, Mathys GM, Brown SH, Jacobs PA (2005) Angew Chem Int Ed Engl 117(5833–583):6Pater JPG, Jacobs PA, Martens JA (1998) J Catal 179:477–482Tabak SA (1981) US4254295, to Mobil OilOccelli ML, Hsu JT, Galya LG (1985) J Mol Catal A: Chem 32:377–390Tabak SA (1984) US4504693, to Mobil Oil CorpKholer E, Schmidt F, Wernicke HJ, Pontes MD, Roberts HL (1995, Summer) Hydrocarbon Technology InternationalMartens JA, Verduijn JP (1995) WO95/19945, to Exxon Chemical Patents Inc.Verrelst WH (1995) Martens LRM, WO95/22516, to Exxon Chemical Patents Inc.Verrelst WH, Martens LRM (2000) US6143942, to Exxon Chemical Patents Inc.Verrelst WH, Martens LRM, Verduijn JP (2006) US6013851, to Exxon Chemical Patents Inc.Dakka JM, Mathys GMK, Puttemans MPH (2003) WO03/035583 to Exxon-Mobil Chemical LimitedMatias P, Sa CC, Graca I, Lopes JM, Carvalho AP, Ramoa RF, Guisnet M (2011) Appl Catal A 399:100–109Chal R, Gérardin C, Bulut M, van Donk S (2011) ChemCatChem 3:67–81Perez-Ramirez J, Christensen CH, Egeblad K, Groen JC (2008) Chem Soc Rev 37:2530–2542Verboekend D, Perez-Ramirez J (2011) Catal Sci Technol 1:879–890Serrano DP, Escola JM, Pizarro P (2013) Chem Soc Rev 42:4004–4035Verboekend D, Chabaneix AM, Thomas K, Gilson JP, Perez-Ramirez J (2011) Cryst Eng Comm 13:3408–3416Emeis CA (1993) J Catal 141:347–354Perego C, Peratello S (1999) Catal Today 52:133–145Abello S, Bonilla A, Perez-Ramirez J (2009) Appl Catal A Gen 364:191–198Corma A, Martinez C, Doskocil EJ, Yaluris G (2011) WO2011002631A2, to BP Oil International Limited. BP Corporation North America Inc., UKCorma A, Martinez C, Doskocil EJ, Yaluris G (2011) WO2011002630A2, to BP Oil International Limited. BP Corporation North America Inc, UKHan S, Heck RH, DiGuiseppi FT (1993) US5234875, to Mobil Oil CorporationPeratello S, Molinari M, Bellussi G, Perego C (1999) Catal Today 52:271–27

On the influence of Si:Al ratio and hierarchical porosity of FAU zeolites in solid acid catalysed esterification pretreatment of bio-oil

A family of faujasite (FAU) zeolites with different Si:Al ratio, and/or hierarchical porosity introduced via post-synthetic alkaline desilication treatment, have been evaluated as solid acid catalysts for esterification pretreatments of pyrolysis bio-oil components. Acetic acid esterification with aliphatic and aromatic alcohols including methanol, anisyl alcohol, benzyl alcohol, p-cresol and n-butanol was first selected as a model reaction to identify the optimum zeolite properties. Materials were fully characterised using N2 porosimetry, ICP, XRD, XPS, FT-IR, pyridine adsorption, NH3 TPD, In-situ ATR and inverse gas chromatography (IGC). IGC demonstrates that the surface polarity and hence hydrophobicity of FAU decreases with increased Si:Al ratio. Despite possessing a higher acid site loading and acetic acid adsorption capacity, high Al-content FAU possess weaker acidity than more siliceous catalysts. Esterification activity increases with acid strength and decreasing surface polarity following the order FAU30>FAU6>FAU2.6. The introduction of mesoporosity through synthesis of a hierarchical HFAU30 material further enhances esterification activity through improved acid site accessibility and hydrophobicity. Methanol was the most reactive alcohol for esterification, and evaluated with HFAU30 for the pretreatment of a real pyrolysis bio-oil, reducing the acid content by 76% under mild conditions

Catalytic upgrading of bio-oils by esterification

Biomass is the term given to naturally-produced organic matter resulting from photosynthesis, and represents the most abundant organic polymers on Earth. Consequently, there has been great interest in the potential exploitation of lignocellulosic biomass as a renewable feedstock for energy, materials and chemicals production. The energy sector has largely focused on the direct thermochemical processing of lignocellulose via pyrolysis/gasification for heat generation, and the co-production of bio-oils and bio-gas which may be upgraded to produce drop-in transportation fuels. This mini-review describes recent advances in the design and application of solid acid catalysts for the energy efficient upgrading of pyrolysis biofuels