Catalytic Pyrolysis of Pine Biomass Over H-Beta Zeolite in a Dual-Fluidized Bed Reactor: Effect of Space Velocity on the Yield and Composition of Pyrolysis Products

Aho, Atte; Tokarev, A. V.; Backman, Peter; Kumar, Narendra; Eränen, Kari; Hupa, Mikko; Holmbom, Bjarne; Salmi, Tapio; Murzin, Dmitry Yu.

doi:10.1007/s11244-011-9716-8

Cited by 47 publications

(37 citation statements)

References 31 publications

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“…Zeolite beta and its modified versions are known to be effective catalysts for several reactions concerning the valorisation of biomass, e.g. corn fiber to Fur [38]; levuglucosan (an intermediate of (hemi)cellulose pyrolysis) to glucose [39] or Fur [40]; saccharides to Fur [41,42], 5-(hydroxymethyl)furfural (HMF) [42][43][44][45][46][47], or LEs [48,49]; cellulose and hemicelluloses to diesel [50]; hemicelluloses to polyols [51]; C-3 sugar to methyl lactate and lactic acid [52]; FA to 2-(ethoxymethyl)furfural (EMF) and ethyl levulinate (EL) [53]; biodegradable surfactants via acetalisation [54] or etherification of HMF [55]; Fur to GVL [4]; pyrolysis of biomass or derived compounds to aromatic/aliphatic 4 hydrocarbons [56][57][58][59][60][61][62][63][64][65][66]; sugarcane bagasse to bio-oil and upgrading to fuel [67]; co-conversion of biogenic waste and vegetable oil [68]; and pyrolysis of organosolv lignin to phenolic compounds [69,70]. The introduction of different elements into zeolite beta widens its catalytic potential.…”

Section: Introductionmentioning

confidence: 99%

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

Antunes

Lima

Neves

et al. 2015

Journal of Catalysis

137

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Aiming at the valorisation of furfural (Fur) via sustainable routes based on process intensification and heterogeneous catalysis, the one-pot conversion of this renewable platform chemical to useful bio-products, namely furfuryl alkyl ethers (FEs), levulinate esters (LEs), levulinic acid (LA), angelica lactones (AnLs) and -valerolactone (GVL), was investigated using a single heterogeneous catalyst, in 2-butanol, at 120 ºC. Various chemical 2 reactions are involved in this process, which requires catalysts with active sites for acid and reduction chemistry. For this purpose, it was explored for the first time the catalytic potentialities of modified versions of zeolite beta containing Al and Sn sites prepared from commercially available nanocrystaline zeolite beta via post-synthesis partial dealumination followed by solid-state ion-exchange. The post-synthesis conditions influenced considerably the catalytic performances of these types of materials. The best-performing catalyst was (Sn) SSIE -beta1 with Si/(Al+Sn)=19 (Sn/Al=27.6), which led to total yield of bio-products of 83% at 86% Fur conversion, and exhibited steady catalytic performance for six consecutive runs. A systematic catalytic study using the prepared catalysts with different bio-products as substrates, together with the molecular level and microstructural characterisation of the materials, helped understand the effects of different material properties on the specific reaction pathways in the overall system. These studies led to mechanistic insights into the reaction network of Fur to the bio-products in alcohol media, upon which a kinetic model was developed for the first time. The superior performance of (Sn) SSIE -beta1 in various steps was related to the dealumination degree, dispersion and amount of Sn-sites, and acid properties.

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Section: Introductionmentioning

confidence: 99%

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

Antunes

Lima

Neves

et al. 2015

Journal of Catalysis

137

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“…So far, ZSM-5 has been shown to be the best catalyst for improving the bio-oil quality in biomass pyrolysis, mainly due to its shape selective pore structure [7][8][9]. Fluidized bed reactors have been extensively studied in biomass pyrolysis due to their scalability, excellent mass and heat transfer properties, good mixing between the solids and suspending fluid, uniform catalyst distribution and so forth [10][11][12]. Catalyst supports have been used and incorporated with zeolites (e.g., Y and ZSM-5 zeolite)…”

Section: Introductionmentioning

confidence: 99%

The effect of ZSM-5 catalyst support in catalytic pyrolysis of biomass and compounds abundant in pyrolysis bio-oils

Gamliel

Valla

et al. 2016

Journal of Analytical and Applied Pyrolysis

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Supported ZSM-5 is commonly used for in-situ biomass pyrolysis vapor upgrading in fluidized bed reactors. In this work, we investigate the effects of catalyst support on the pyrolysis product distribution by studying pyrolysis of woody biomass and bio-oil derived model compounds. Specifically, miscanthus, toluene and furan are catalytically pyrolyzed over bulk ZSM-5, supported ZSM-5 and a commercial Al2O3 support. The pyrolysis product distributions of biomass and each model compound are presented and discussed. The coke formed on the catalysts and support, which is also responsible for catalyst deactivation, is analyzed using temperature programmed oxidation (TPO). It is shown that pyrolysis of miscanthus, toluene and furan over supported ZSM-5 produces less liquid products, particularly mono-aromatic hydrocarbons, than over bulk ZSM-5, mainly due to the dilution of Brønsted acid sites by the catalyst support. The Lewis acidity of the Al2O3 support promotes alkylation and cyclization of propylene leading to enhanced benzene production. The Lewis acidity of the support also enhances coke production with a less condensed structure, while selectivity to poly-aromatics is deteriorated.

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“…In order to decrease the content of oxygenated compounds in the bio-oil, zeolites and mesoporous catalysts can be used [13,14]. Numerous researchers [15][16][17][18][19] studied the catalytic pyrolysis of lignocellulose biomass using ZSM-5 and found that ZSM-5 promoted the deoxygenation forming aromatic hydrocarbons [12].…”

Section: Introductionmentioning

confidence: 99%

The thermal degradation of lignocellulose biomass with an acid leaching pre-treatment using a H-ZSM-5/Al-MCM-41 catalyst mixture

Ratnasari

Horn

Brunner

et al. 2019

Fuel

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Improvements on the pyrolysis process of biomass fuels are needed to obtain a high-quality of bio-oil. Pretreatment by acid leaching prior to the pyrolysis process is considered to remove Alkali and Alkaline Earth Metal (AAEM) from the biomass, since AAEM adversely affect the catalytic pyrolysis process. Therefore, the main objective of the present work was to determine and compare the effect of mixed-catalysts consisting of H-ZSM-5 and Al-MCM-41, which are used at different ratios in lignocellulose biomass pyrolysis via Thermal Gravimetric Analysis (TGA) for both, un-leached and leached biomass. In addition, the activation energies have been determined based on the solid-state reaction mechanism. The results from the acid leaching treatment showed that the optimum leaching process was set to 30 min, 30°C and 5 wt% acetic acid in the leaching liquid. This resulted in 59%, 95%, 99%, and 96% reduction degree of Calcium (Ca), Magnesium (Mg), Potassium or Kalium (K), and Natrium (Na), respectively. The Higher Heating Values (HHVs) for un-leached and leached biomass were 19.42 and 19.14 MJ/kg, respectively, calculated by using the Milne formula. The HHV value is not significantly influenced by the acid-leaching pre-treatment. Thermogravimetric analysis showed similar trends for the mass loss as a function of temperature and four stages could be determined from the thermal degradation of biomass. There was no significant shift in the temperature profiles between un-leached and leached biomass degradations. However, the removal of AAEM significantly affected the degradation of hemicellulose, cellulose, and lignin. A 12.4-18.2% increase of mass losses could be found in Phase 2 for leached biomass, compared to un-leached biomass. The mass losses in Phase 2 also increased with increased heating rates. From the un-leached biomass experiments using a catalyst mixture, the percentage of mass loss increased from 64.95 wt% at 10 K min −1 to 68.33 wt% at 50 K min −1 . Moreover, for the leached biomass, it rose from 65.71 wt% at 10 K min −1 to 66.73 wt % at 30 K min −1 , before decreasing to 62.44 wt% at 50 K min −1 . A lower mass loss in Phase 4 for leached biomass compared to un-leached biomass showed the influence of an AAEM removal. The second order (F2) mechanism was able to illustrate the catalytic pyrolysis process, proven by the result that the coefficient of determination (R 2 ) was higher than 0.99, which was high compared to other mechanisms. An acid leaching pretreatment led to a reduction in the activation energies. The activation energies for the un-leached biomass were 26.94 and 25.56 kJ mol −1 at a heating rate of 10 K min −1 for a process without and with a catalyst mixture, respectively. The activation energies for leached biomass were 24.05 and 21.80 kJ mol −1 . The results also showed that the use of the acid leaching process as a treatment prior to catalytic pyrolysis is positive, since it resulted in high devolatilization and reaction rate.

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Catalytic Pyrolysis of Pine Biomass Over H-Beta Zeolite in a Dual-Fluidized Bed Reactor: Effect of Space Velocity on the Yield and Composition of Pyrolysis Products

Cited by 47 publications

References 31 publications

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

The effect of ZSM-5 catalyst support in catalytic pyrolysis of biomass and compounds abundant in pyrolysis bio-oils

The thermal degradation of lignocellulose biomass with an acid leaching pre-treatment using a H-ZSM-5/Al-MCM-41 catalyst mixture

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