Experimental studies on the pyrolysis of humins from the acid-catalysed dehydration of C6-sugars

Rasrendra, Carolus Borromeus; Windt, Michael; Wang, Y.; Adisasmito, Sanggono; Makertihartha, Igbn; Eck, Ernst R. H. van; Meier, Dietrich; Heeres, Hero J.

doi:10.1016/j.jaap.2013.07.003

Cited by 76 publications

(87 citation statements)

References 55 publications

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“…One of the pathways investigated to date is the conversion of the cellulose and hemicellulose fraction into bio-based platform chemicals like 5-hydroxymethylfurfural (HMF) and levulinic acid (LA) [7,8] . 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].…”

Section: Introductionmentioning

confidence: 99%

“…In our previous work we have reported the thermal pyrolysis, a mature and commercially available technology [20][21][22][23][24][25], as a potential route to convert humins into a pyrolysis oil enriched with low molecular weight compounds [7] . The aim of this approach is to convert a solid, low energy density feed into an easily transportable fuel with a high energy density.…”

Section: Introductionmentioning

confidence: 99%

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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: 99%

Section: Introductionmentioning

confidence: 99%

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

Agarwal

Heeres

2017

Journal of Analytical and Applied Pyrolysis

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“…Rasrendra et al [47] have reported high values of residues as well during pyrolysis experiments. Although they measure at a constant temperature increase, the observed formation of polyaromatic hydrocarbons might be an explanation for the high values reported in this work.…”

Section: Carbon Residuementioning

confidence: 95%

“…The structure and properties of humins have been studied extensively by Van Zandvoort et al [29,[43][44][45], Constant et al [42] and others [46][47][48][49][50]. In the former two sets of studies, the molecular structure was estimated with techniques including elemental analysis, IR and various 1D and 2D NMR methods.…”

Section: Introductionmentioning

confidence: 99%

Spray Combustion Analysis of Humins

Feijen¹,

Klink

Jong

et al. 2017

SAE Technical Paper Series

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Second generation biomass is an attractive renewable feedstock for transport fuels. Its sulfur content is generally negligible and the carbon cycle is reduced from millions to tens of years. One hitherto non-valorized feedstock are so-called humins, a residual product formed in the conversion of sugars to platform chemicals, such as hydroxymethylfurfural and methoxymethylfurfural, intermediates in the production of FDCA, a building block used to produce the polyethylene furanoate (PEF) bottle by Avantium.The focus of this study is to investigate the spray combustion behavior of humins as a renewable alternative for heavy fuel oil (HFO) under large two-stroke engine-like conditions in an optically accessible constant volume chamber. To reduce the viscosity to HFO levels of the otherwise crystalline humins, methyl levulinate (ML), another side-stream from the same sugar dehydration process, is blended to the former compound at 25 wt.-%; a ratio comparable to that actually produced in many dehydration processes.Various fuel properties of interest, including elemental composition, heating value, density, ignition quality, acid number, flash point, pour point, carbon residue, sediment, water and ash content are measured for the resulting humins-ML blend.The blend is injected into an optically accessible constant volume chamber, the dimensions, injector characteristics and prevailing ambient conditions of which are representative of those found in large two-stroke marine engines. Commercial HFO is used as a benchmark.The combustion process is evaluated by means of shadow imaging and OH*-chemiluminescence. The former and latter optical techniques are used to determine the phasing and overall magnitude of the heat release event, and ignition delay/location and flame lift off length, respectively.From the results becomes clear that the average ignition delay is comparable to that of HFO, albeit at a higher cycle-to-cycle variation. Notwithstanding a longer lift off length and more downstream ignition kernels, the overall results suggest that the proposed bioblend is a feasible renewable alternative for HFO in terms of technical feasibility.

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“…However, the upgrading of glucose to HMF is much more challenging than that of fructose [14][15][16]. While mineral acids such as HCl and H 2 SO 4 can be used as catalysts for the conversion of either sugar to HMF in aqueous solution at elevated temperatures, especially glucose suffers from severe degradation to humins under these conditions [17][18][19]. Also, HMF can be rehydrated to levulinic acid in water of low pH [15,18].…”

Section: Introductionmentioning

confidence: 99%

Early Transition Metal Doped Tungstite as an Effective Catalyst for Glucose Upgrading to 5-Hydroxymethylfurfural

2018

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Glucose valorization to 5-hydroxymethylfurfural (HMF) remains challenging in the transition towards renewable chemistry. Lewis acidic tungstite is a viable, moderately active catalyst for glucose dehydration to HMF. Literature reports a multistep mechanism involving Lewis acid catalyzed isomerization to fructose, which is then dehydrated to HMF by Brønsted acid sites. Doping tungstite with titanium and niobium improves activity by optimizing the ratio between Lewis and Brønsted acid sites. Graphical AbstractKeywords Biomass · Glucose · 5-Hydroxymethylfurfural · Tungsten oxide · Doping

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Experimental studies on the pyrolysis of humins from the acid-catalysed dehydration of C6-sugars

Cited by 76 publications

References 55 publications

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

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

Spray Combustion Analysis of Humins

Early Transition Metal Doped Tungstite as an Effective Catalyst for Glucose Upgrading to 5-Hydroxymethylfurfural

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