<sup>31</sup>P-NMR analysis of bio-oils obtained from the pyrolysis of biomass

David, Kasi; Kosa, Matyas; Williams, Alex C.; Mayor, Rhett; Park, Jongwoo; Muzzy, John D.; Ragauskas, Arthur J.

doi:10.4155/bfs.10.57

Cited by 37 publications

(45 citation statements)

References 28 publications

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“…Fu et al 122 initially adopted quantitative 31 P NMR to understand the nature of pyrolysis oils. 31 P NMR was used by other researchers to track the water content of pyrolysis oil, as well as the chemical transitions of bio-oil that take place during pyrolysis of biomass and the ensuing catalytic upgrading processes [123][124][125][126][127][128] . Following these efforts, a laboratory analytical procedure for the quantification of hydroxyls in bio-oil has been developed by National Renewable Energy Laboratory 129 .…”

Section: Applications Of the 31 P Nmr Protocolmentioning

confidence: 99%

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy

et al. 2019

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The analysis of chemical structural characteristics of biorefinery product streams (such as lignin and tannin) has advanced substantially over the past decade, with traditional wet-chemical techniques being replaced or supplemented by NMR methodologies. Quantitative 31 P NMR spectroscopy is a promising technique for the analysis of hydroxyl groups because of its unique characterization capability and broad potential applicability across the biorefinery research community. This protocol describes procedures for (i) the preparation/solubilization of lignin and tannin, (ii) the phosphitylation of their hydroxyl groups, (iii) NMR acquisition details, and (iv) the ensuing data analyses and means to precisely calculate the content of the different types of hydroxyl groups. Compared with traditional wet-chemical techniques, the technique of quantitative 31 P NMR spectroscopy offers unique advantages in measuring hydroxyl groups in a single spectrum with high signal resolution. The method provides complete quantitative information about the hydroxyl groups with small amounts of sample (~30 mg) within a relatively short experimental time (~30-120 min).

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Section: Applications Of the 31 P Nmr Protocolmentioning

confidence: 99%

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy

et al. 2019

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“…31 P-NMR is an extensively applied analytical technique used to observe the phosphorus-derived hydrogen-bounded oxygen (OH-hydroxyl) moieties in coal processing [24,25], biodiesel [26], and lignin-based biomass=oil. [27,28]. Granata and Argyropoulos [29] derivatized lignin using the phosphitylating agent 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) to determine the various hydroxyl functional groups present in lignin.…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal upgrading of algae paste: Application of ³¹P‐NMR

Patel

Hellgardt

2013

Env Prog and Sustain Energy

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Although already proposed in the 1940s, hydrothermal upgrading of biomass, and specifically algae, to produce biocrude has only recently become a much researched topic. Algae are of special interest as they are capable of much higher biomass accumulation rates than terrestrial plants. To understand the transformation of algal biomass into biocrude, this process needs to be scrutinized in as much detail as possible to identify the most appropriate reaction conditions. It is usually not possible to identify individual transformation steps; however, in this article we demonstrate the use of 31P‐NMR to follow the fate of derivatized (2‐chloro‐4,4,5,5‐tetramethyl‐1,3,2‐dioxaphospholane) hydroxyl groups to start understand, which chemical species are involved in the initial degradation steps. Our data show the occurrence of a very fast degradation of acidic OH groups (derived from the hydrolysis of lipids) and aliphatic OH groups (derived from the fast hydrolysis of carbohydrates). The degradation of proteins leads to polyphenols, which appear to be rather stable even over prolonged treatment periods. Small quantities of aromatic compounds are also formed as secondary degradation products through sugar dehydration and cyclization as well as peptide transformation. It appears that additional deoxygenation routes exist as the deoxygenation rate using 31P‐NMR and that determined by elemental analysis differ. The formed oil (biocrude) is compared with typical North Sea oils using simulated distillation and was found to contain a significant high boiling faction, which would require further treatment (e.g., hydrocracking) to shift the boiling range to a more valuable oil composition. © 2013 American Institute of Chemical Engineers Environ Prog, 32: 1002–1012, 2013

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“…This compound reacts with hydroxyl groups arising from aliphatic, phenolic, and carboxylic groups in the presence of an organic base (such as pyridine) to give phosphitylated products, whose presence can be quantified through 31 P‐NMR spectroscopy . Prior to 31 P‐NMR analysis, bio‐oils were phosphitylated with 150 mL of TMDP and then the spectra were acquired with a Bruker Avance II 250 MHz according to the method reported by David et al . In order to assess the extent of the functionalization of the aromatic structures of the lignin fragments and other phenolic compounds present in the bio‐oil with reactive epoxy groups, 31 P‐NMR was performed again to the reaction product to verify the removal of phenolic hydroxyl groups after chemical reaction with epichlorohydrin in alkaline conditions.…”

Section: Methodsmentioning

confidence: 99%

Fast pyrolysis bio‐oil as precursor of thermosetting epoxy resins

Sibaja

Adhikari²,

Celikbag

et al. 2017

Polymer Engineering & Sci

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Fast pyrolysis bio‐oil was employed as a source of phenolic compounds in the production of a bio‐based polymeric network. The bio‐oil was reacted with epichlorohydrin in alkaline medium using benzyltriethylammonium chloride as a phase transfer catalyst. The amount of free phenolic hydroxyl groups before and after modification was quantified through 31P‐NMR spectroscopy; and the epoxy content of the bio‐oil upon the chemical functionalization was measured by means of a titration using HBr in acetic acid solution. Grafting of epoxy functions onto the monomer`s structure was studied by FTIR. Likewise, α‐resorcylic acid was also modified with reactive epoxy moieties, and used as low molecular weight comonomer. The epoxidized derivatives of the bio‐oil were cured in epoxy polymers with 4‐dimethylaminopyridine. Thermo‐mechanical characterization showed that the obtained materials behave as thermoset amorphous polymers, exhibiting modulus values ranging from approximately 1.5–3.4 GPa at room temperature and glass transition temperatures above 100°C. POLYM. ENG. SCI., 58:1296–1307, 2018. © 2017 Society of Plastics Engineers

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³¹P-NMR analysis of bio-oils obtained from the pyrolysis of biomass

Cited by 37 publications

References 28 publications

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy

Hydrothermal upgrading of algae paste: Application of ³¹P‐NMR

Fast pyrolysis bio‐oil as precursor of thermosetting epoxy resins

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31P-NMR analysis of bio-oils obtained from the pyrolysis of biomass

Cited by 37 publications

References 28 publications

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy

Hydrothermal upgrading of algae paste: Application of 31P‐NMR

Fast pyrolysis bio‐oil as precursor of thermosetting epoxy resins

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Product

Resources

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³¹P-NMR analysis of bio-oils obtained from the pyrolysis of biomass

Hydrothermal upgrading of algae paste: Application of ³¹P‐NMR