Valorization of Humin‐Based Byproducts from Biomass Processing—A Route to Sustainable Hydrogen

Hoang, Thi Minh Chau; Lefferts, Leon; Seshan, Kulathuiyer

doi:10.1002/cssc.201300446

Cited by 95 publications

(109 citation statements)

References 32 publications

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“…HMF is considered a versatile chemical building block for C-6 compounds, such as alkoxymethylfuranics, 2,5-furandicarboxylic acid, 2,5-dimethylfuran, adipic acid, 1,6-hexanediol and caprolactam [8][9][10]. The demand for HMF as a platform chemical has already lead to the opening of a pilot plant by the Dutch company Avantium with the aim to produce 40 tonnes/year of HMF, which may subsequently be used to make have already been suggested in literature, including thermal and catalytic gasification as well as humin introduction in PFA (polyfurfuryl alcohol) to make an elaborate composite with enhanced properties [12,17].…”

Section: Introductionmentioning

confidence: 98%

Catalytic pyrolysis of recalcitrant, insoluble humin byproducts from C6 sugar biorefineries

Agarwal

Heeres

2017

Journal of Analytical and Applied Pyrolysis

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a b s t r a c tHumins are solid by-products formed during the acid-catalysed conversions of C-6 sugars to platform chemicals like hydroxymethylfurfural and levulinic acid. We here report an experimental study on the liquefaction/depolymerisation of humins using catalytic pyrolysis. Synthetic humins (SH) and crude industrial humins (CIH, including purified industrial (PIH) samples) from the acid-catalysed conversion of C-6 sugars to HMF/LA were tested. Thermal degradation patterns of both humin types vary significantly. Major thermal decomposition of the industrial humins was observed between 50 and 650 • C (weight loss approx. 66 wt%), whereas, major weight loss was observed between 200 and 800 • C for the synthetic humins (47 wt%). A series of catalytic pyrolysis tests with synthetic humins and different zeolites were performed using a PTV-GC/MS (humin to catalyst wt ratio of 0.2, 550 • C). Best results were obtained using HZSM-5 (SiO 2 /Al 2 O 3 = 50). For quantitative analysis, a gram scale pyrolysis unit was used, giving a product oil (9-11 wt% on humin intake) with approximately 1.5 and 10 wt% aromatics from synthetic and crude industrial humins, respectively. GPC data on the product oils clearly shows the breakdown of the humin structure into low molecular weight species. The HHV value of the liquid products (up to 41 MJ kg −1 ) is considerably higher than that of the crude industrial humin feed (21-24 MJ kg −1 ).

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Section: Introductionmentioning

confidence: 98%

Catalytic pyrolysis of recalcitrant, insoluble humin byproducts from C6 sugar biorefineries

Agarwal

Heeres

2017

Journal of Analytical and Applied Pyrolysis

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“…Catalytic pyrolysis was used to transform AHRs from miscanthus obtained at different hydrolysis conditions into bio-oil [3]. In later studies, Hoang et al investigated the catalytic gasification of humins to produce hydrogen [4] and syngas [5].…”

Section: Introductionmentioning

confidence: 99%

Kinetic study of the pyrolysis of miscanthus and its acid hydrolysis residue by thermogravimetric analysis

Cortes

Bridgwater

2015

Fuel Processing Technology

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The kinetic parameters of the pyrolysis of miscanthus and its acid hydrolysis residue (AHR) were determined using thermogravimetric analysis (TGA). The AHR was produced at the University of Limerick by treating miscanthus with 5 wt.% sulphuric acid at 175°C as representative of a lignocellulosic acid hydrolysis product. For the TGA experiments, 3 to 6 g of sample, milled and sieved to a particle size below 250 μm, were placed in the TGA ceramic crucible. The experiments were carried out under non-isothermal conditions heating the samples from 50 to 900°C at heating rates of 2.5, 5, 10, 17 and 25°C/min. The activation energy (E A ) of the decomposition process was determined from the TGA data by differential analysis (Friedman) and three isoconversional methods of integral analysis (Kissinger-Akahira-Sunose, Ozawa-Flynn-Wall, Vyazovkin). The activation energy ranged from 129 to 156 kJ/mol for miscanthus and from 200 to 376 kJ/mol for AHR increasing with increasing conversion. The reaction model was selected using the non-linear least squares method and the preexponential factor was calculated from the Arrhenius approximation. The results showed that the best fitting reaction model was the third order reaction for both feedstocks. The pre-exponential factor was in the range of 5.6 × 10 10 to 3.9 × 10 +13 min −1 for miscanthus and 2.1 × 10 16 to 7.7 × 10 25 min −1 for AHR.

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“…21 We had briefly discussed the nature of the humin residue at elevated temperatures required for the reforming reaction. Humin in this state mainly consists of an aromatic/graphitised carbon structure.…”

Section: Introductionmentioning

confidence: 99%

Humin based by-products from biomass processing as a potential carbonaceous source for synthesis gas production

et al. 2015

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Lignocellulosic biomass is addressed as potential sustainable feedstock for green fuels and chemicals.(Hemi)cellulose is the largest constituent of the material. Conversion of these polysaccharides to biobased platform chemicals is important in green chemical/fuel production and biorefinery. Hydroxymethyl furfural, furfural and levulinic acid are substantial building blocks from ( poly)saccharides. Synthesis of these molecules involves acid catalysed hydrolysis/dehydration reactions which leads large formation of insoluble by-products, called humins. Humin obtained from dehydration of glucose is used in this study.Fractionisation of humin was investigated using various solvents (e.g., acetone, H 2 O, and NaOH 1%).Characterisation of humin using various techniques including ATR-IR, HR-SEM, solid state NMR, elemental analysis, Raman spectroscopy, pyrolysis, etc. confirms its furan rich structure with aliphatic oxygenate linkages. The influence of thermal treatment on humin was investigated. Humin undergoes a lot of changes both in morphology and structure. Humin loses ca. 45 wt% when preheated to 700°C ( prior to the gasification temperature) and contains above 92 wt% C in mainly aromatic/graphitic structures. Valorisation of humin via dry reforming was studied. Non-catalytic dry reforming of humin is very difficult; however, alkali catalysts (e.g. Na 2 CO 3 ) can enhance the reaction rate tremendously.

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Valorization of Humin‐Based Byproducts from Biomass Processing—A Route to Sustainable Hydrogen

Cited by 95 publications

References 32 publications

Catalytic pyrolysis of recalcitrant, insoluble humin byproducts from C6 sugar biorefineries

Catalytic pyrolysis of recalcitrant, insoluble humin byproducts from C6 sugar biorefineries

Kinetic study of the pyrolysis of miscanthus and its acid hydrolysis residue by thermogravimetric analysis

Humin based by-products from biomass processing as a potential carbonaceous source for synthesis gas production

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