Upgrading of bio-oil via acid-catalyzed reactions in alcohols — A mini review

Hu, Xun; Gunawan, Richard; Mourant, Daniel; Hasan, Mahmudul; Wu, Liping; Song, Yao; Lievens, Caroline; Li, Chun‐Zhu

doi:10.1016/j.fuproc.2016.08.020

Cited by 102 publications

(48 citation statements)

References 117 publications

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“…Over the past decade, a number of acid catalysts have been developed to efficiently catalyze the various acid‐catalyzed reactions . Homogeneous acid catalysts (HCl, H 2 SO 4 , etc.)…”

Section: Introductionmentioning

confidence: 99%

Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5‐Hydroxymethylfurfural

Shao

Sun

et al. 2019

Energy Tech

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Distinct crystal phases of an oxide affect the configuration of surface atoms, which might further affect coordination with sulfate during sulfonation for the preparation of SO42−/MxOy type of acid catalyst. Herein, such an effect is investigated with zirconia of the tetragonal or monoclinic phase as the model catalysts. The results show that sulfonation inhibits the transformation of zirconia from the tetragonal phase to the monoclinic phase, whereas the varied phase of zirconia also affects the bonding patterns of sulfate species with zirconia in sulfonation. The sulfated zirconia of monoclinic phase contains more abundant acidic sites and more Brønsted acid sites than that of sulfated zirconia of tetragonal phase. Consequently, the sulfated zirconia of monoclinic phase is more active than the sulfated zirconia of tetragonal phase for the conversion of furfuryl alcohol in ethanol and conversion of fructose in dimethyl sulfoxide, achieving the yield of ethyl levulinate of 96.4% and a high yield of 5‐hydroxymethylfurfural. The sulfated zirconia is not stable in protic solvent due to the leaching of sulfur species and the change in configurations of the sulfate species and the zirconium species, but in the aprotic solvent, they show good stability and recyclability.

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“…Over the past decade, a number of acid catalysts have been developed to efficiently catalyze the various acid‐catalyzed reactions . Homogeneous acid catalysts (HCl, H 2 SO 4 , etc.)…”

Section: Introductionmentioning

confidence: 99%

Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5‐Hydroxymethylfurfural

Shao

Sun

et al. 2019

Energy Tech

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“…Nevertheless, the conversion of glucose or HMF involves polymerization reactions, which lead to the formation of coke and the deactivation of solid acid catalysts. 13,14 For carbon-based catalysts such as solid acidic resin catalysts or sulfonated activated carbon, their regeneration via combustion is an issue. The development of robust catalyst systems is still a key research focus in biorefinery.…”

Section: Introductionmentioning

confidence: 99%

Conversion of monosaccharides into levulinic acid/esters: impacts of metal sulfate addition and the reaction medium

Sun

Zhang

Shao

et al. 2019

J of Chemical Tech & Biotech

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BACKGROUND: Inorganic salts could be used as catalysts for the effective conversion of sugars. In this study, the impacts of various metal sulfates (Na 2 SO 4 , K 2 SO 4 , MnSO 4 , CoSO 4 , NiSO 4 , ZnSO 4 , CuSO 4 , Fe 2 (SO 4 ) 3 , La 2 (SO 4 ) 3 and Ce(SO 4 ) 2 ) on the conversion of glucose/fructose to levulinic acid in varied reaction media were evaluated. RESULTS:The sulfates strongly chelated with the sugars, preventing their dehydration reactions in the presence of sulfuric acid and leading to polymerization of the sugars. The sulfates themselves showed varied activity and selectivity for the conversion of the sugars to levulinic acid/esters or 5-hydroxymethylfurfural (HMF), depending on the coordination with the reaction medium. K 2 SO 4 or Na 2 SO 4 could catalyze the production of HMF from glucose/fructose in water, while in DMSO the yield of HMF was substantially higher. In THF, nevertheless, almost no HMF was formed, while other sulfates such as NiSO 4 in THF could effectively catalyze the conversion of fructose to HMF. In alcohols, Fe 2 (SO 4 ) 3 was the most effective sulfate for the conversion of the sugars to levulinic acid/esters, and the alcohols could effectively suppress the polymerization of the sugars. CONCLUSION:The distinct catalytic performances of the sulfates in the varied reaction media originated from their different coordination or chelation with the sugars and the reaction medium.

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“…The effluent stream from the pyrolysis process is composed of a fraction of permanent gases (CO2, CO, CH4, H2, and light hydrocarbons), water and condensable organic compounds. After condensation, the resulting product, which is often referred to as "bio-oil" [2] or "pyrolysis oil" [3,4], consists of a mixture of water and oxygen-containing organic compounds (e.g., carboxylic acids, phenols, alcohols, aldehydes, ketones and furans [5-7]) derived from the thermal decomposition of major biomass components. Despite the fact that pyrolysis oil can be upgraded to liquid fuel by means of complex deoxygenation and hydrogenation processes [8], a practical approach to avoid undesirable condensation of volatiles (which causes operational issues in the downstream applications of the pyrolysis gas)…”

Section: Introductionmentioning

confidence: 99%

Physically activated wheat straw-derived biochar for biomass pyrolysis vapors upgrading with high resistance against coke deactivation

Alvira

Greco

González

et al. 2019

Fuel

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Wheat straw-derived biochars (produced through slow pyrolysis at 500 °C and 0.1 MPa) were physically (with CO2) and chemically (with K2CO3) activated to assess their performance as renewable and low-cost catalysts for biomass pyrolysis vapors upgrading. Preliminary cracking experiments, which were carried out at 700 °C using a mixture of four representative model compounds, revealed a clear correlation between the volume of micropores of the catalyst and the total gas production, suggesting that physical activation up to a degree of burn-off of 40% was the most interesting activation route. Next, steam reforming experiments were conducted using the most microporous material to analyze the effect of both the bed temperature and gas hourly space velocity (GHSV) on the total gas production. The results showed a strong dependence between the bed temperature and the total gas production, with the best result obtained at the highest temperature (750 °C). On the other hand, the change in GHSV led to minor changes in the total gas yield, with a maximum achieved at 14500 h-1. Under the best operating conditions deduced in the previous stages, the addition of CO2 into the feed gas stream (partial pressure of 20 kPa) resulted in a total gas production of 98% with a H2/CO molar ratio of 2.16. This good result, which was also observed during the upgrading of the aqueous phase of a real biomass pyrolysis oil, was ascribed to the relatively high coke gasification rate, which refresh the active surface area preventing deactivation by coke deposition.

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Upgrading of bio-oil via acid-catalyzed reactions in alcohols — A mini review

Cited by 102 publications

References 117 publications

Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5‐Hydroxymethylfurfural

Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5‐Hydroxymethylfurfural

Conversion of monosaccharides into levulinic acid/esters: impacts of metal sulfate addition and the reaction medium

Physically activated wheat straw-derived biochar for biomass pyrolysis vapors upgrading with high resistance against coke deactivation

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