Upgrading biomass pyrolysis vapors over β-zeolites: role of silica-to-alumina ratio

Mukarakate, Calvin; Watson, Michael J.; Dam, Jeroen ten; Baucherel, Xavier; Budhi, Sridhar; Yung, Matthew M.; Ben, Haoxi; Iisa, Kristiina; Baldwin, R.M.; Nimlos, Mark R.

doi:10.1039/c4gc01425a

Cited by 99 publications

(118 citation statements)

References 40 publications

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“…Consequently, the total product yield was increased greatly even at low catalyst quantities. However, when a large amount of catalyst was added, the large amount of acid sites would promote charring reactions [2,11,59], resulting in a decreased total product yield. Figure 5 shows that both the yield and concentration of the LGO were increased gradually at the catalyst-to-biomass ratio lower than 1 and then decreased at higher catalyst quantities.…”

Section: Effects Of the Catalyst-to-biomass Ratiomentioning

confidence: 98%

Selective Production of Levoglucosenone from Catalytic Fast Pyrolysis of Biomass Mechanically Mixed with Solid Phosphoric Acid Catalysts

Zhang

Lü

et al. 2015

Bioenerg. Res.

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Solid phosphoric acid (SPA) catalysts with different carriers were prepared and used for catalytic fast pyrolysis of poplar wood to produce levoglucosenone (LGO), a valuable anhydrosugar derivative that can be used in various organic synthesis applications. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were performed to evaluate the catalytic capabilities of these catalysts under different reaction conditions. The results indicated that SPA catalyst prepared with the SBA-15 carrier exhibited the best catalytic capability for selectively producing LGO. Both the catalytic pyrolysis temperature and catalyst-to-biomass ratio affected the pyrolytic products greatly. The maximal LGO yield reached as high as 8.2 wt% from poplar wood, obtained at the pyrolysis temperature of 300°C and the catalyst-to-biomass ratio of 1. The by-products during the catalytic pyrolysis process were mainly acetic acid (AA) and furfural (FF). In addition, the SPA catalyst possessed better catalytic capability than the liquid phosphoric acid (H 3 PO 4 ) catalyst to produce LGO.

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Section: Effects Of the Catalyst-to-biomass Ratiomentioning

confidence: 98%

Selective Production of Levoglucosenone from Catalytic Fast Pyrolysis of Biomass Mechanically Mixed with Solid Phosphoric Acid Catalysts

Zhang

Lü

et al. 2015

Bioenerg. Res.

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“…7,60 Briefly, powdered samples of biomass were pyrolyzed in the inner tube of an annular reactor and the evolved vapors were entrained and transported in helium carrier gas through a fixed catalyst bed. 7,60 Briefly, powdered samples of biomass were pyrolyzed in the inner tube of an annular reactor and the evolved vapors were entrained and transported in helium carrier gas through a fixed catalyst bed.…”

Section: Horizontal Reactor-mbmsmentioning

confidence: 99%

“…7 Briefly, the micropyrolyzer (Rx-3050TR, Frontier Laboratories, Japan) has a pyrolysis zone and a catalytic upgrading zone, with the catalytic upgrading zone located downstream of the pyrolysis zone. A detailed description of the tandem micropyrolyzer-GCMS can be found elsewhere.…”

Section: Tandem Micropyrolyzer-gcms/fidmentioning

confidence: 99%

Catalytic fast pyrolysis of biomass: the reactions of water and aromatic intermediates produces phenols

et al. 2015

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During catalytic upgrading over HZSM-5 of vapors from fast pyrolysis of biomass (ex situ CFP), water reacts with aromatic intermediates to form phenols that are then desorbed from the catalyst micropores and produced as products. We observe this reaction using real time measurement of products from neat CFP and with added steam. The reaction is confirmed when 18 O-labeled water is used as the steam source and the labeled oxygen is identified in the phenol products. Furthermore, phenols are observed when cellulose pyrolysis vapors are reacted over the HZSM-5 catalyst in steam. This suggests that the phenols do not only arise from phenolic products formed during the pyrolysis of the lignin component of biomass; phenols are also formed by reaction of water molecules with aromatic intermediates formed during the transformation of all of the pyrolysis products. Water formation during biomass pyrolysis is involved in this reaction and leads to the common observation of phenols in products from neat CFP. Steam also reduces the formation of non-reactive carbon in the zeolite catalysts and decreases the rate of deactivation and the amount of measured "coke" on the catalyst. These CFP results were obtained in a flow microreactor coupled to a molecular beam mass spectrometer (MBMS), which allowed for real-time measurement of products and facilitated determination of the impact of steam during catalytic upgrading, complemented by a tandem micropyrolyzer connected to a GCMS for identification of the products.

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“…Commercial zeolite MFI ZSM-5 (30) was used. The layered zeolite structure, MCM-22 and the delaminated aluminosilicate, ITQ-2, at Si/Al ratio of 35 were synthesized from layered zeolite precursor, MCM-22 (P), using the similar method described in the literature [12]. The proximate analysis was performed to measure the moisture content, ash content, and volatile matter of solid biomass using the ASTM standards.…”

Section: Biomass and Catalystmentioning

confidence: 99%

“…The recent studies studied catalytic pyrolysis of biomass using commercial zeolites [10][11][12][13][14]. They reported the use zeolites and zeolite-like materials as an efficient and effective medium in catalytic fast pyrolysis.…”

Section: Introductionmentioning

confidence: 99%

The Role of Zeolite Structure and Acidity in Catalytic Deoxygenation of Biomass Pyrolysis Vapors

et al. 2015

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Catalytic upgrading of paddy husk was performed over 10-MR zeolites (MCM-22, ITQ-2 and ZSM-5) in a drop type fixed-bed reactor. This work investigated the role of structure and acidity of zeolites on pyrolysis-oil yield and degree of deoxygenation. Catalytic pyrolysis experiments were carried out at the catalyst/biomass ratio (0.05 -0.5) at temperature of 450 °C. The oil yield decreased by using catalyst and this decrease oil yield is attributed to catalytic cracking of bio-oil vapor on the catalyst. The route for deoxygenation of pyrolysis vapors was identified to be dehydration, decarboxylation and decarboxylation. ITQ-2 showed high degree of deoxygenation as compare to MCM-22 which is due to more accessible external active sites of ITQ-2.The organics yield in pyrolysis oil was highest with ZSM-5 in comparison with other zeolites.

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Upgrading biomass pyrolysis vapors over β-zeolites: role of silica-to-alumina ratio

Abstract: This study investigates the role of β-zeolite acid site density on hydrocarbon and coke yields.

Cited by 99 publications

References 40 publications

Selective Production of Levoglucosenone from Catalytic Fast Pyrolysis of Biomass Mechanically Mixed with Solid Phosphoric Acid Catalysts

Selective Production of Levoglucosenone from Catalytic Fast Pyrolysis of Biomass Mechanically Mixed with Solid Phosphoric Acid Catalysts

Catalytic fast pyrolysis of biomass: the reactions of water and aromatic intermediates produces phenols

The Role of Zeolite Structure and Acidity in Catalytic Deoxygenation of Biomass Pyrolysis Vapors

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