Reforming of Poly(3-hydroxybutyrate) to Oils and Propylene over Cerium Oxide

Kang, Shimin; Zhang, Xiquan; Zhang, Weijie; Li, Wenshan; Chen, Huigan; Yang, Pingju; Tang, Panpan; Cheng, Ke-Ke; Xu, Yongjun

doi:10.1021/acs.energyfuels.8b03226

Cited by 8 publications

(6 citation statements)

References 17 publications

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“…The formation of aliphatic olefins should involve olefin (mainly propylene) polymerization, and the formation of aromatics probably involved a series of reactions including ketonization and alkylation, etc. according the former reports . In addition, the C, H, O, N in the oils were 79.1 wt%, 12.3 wt%, 8.5 wt%, and 0.1 wt%, respectively.…”

Section: Figuresupporting

confidence: 66%

One‐Pot Catalytic Conversion of Poly(3‐hydroxybutyrate) to Propylene at 240 °C

et al. 2019

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Poly(3-hydroxybutyrate) (PHB), a renewable feedstock from microorganisms, was a good resource for propylene production by a simple one-pot reaction. The reaction was catalyzed by triruthenium dodecacarbonyl (TD) at relatively mild temperature (240°C), and the yield and selectivity of propylene reached 22.9 wt% and 46.8%, respectively. A small part of hydrocarbon oils reached 9 wt% was also obtained, which contained 79.1 wt% of carbon and 12.3 wt% of hydrogen, with a theoretical high heating value of 41.2 MJ/kg. Poly(3-hydroxybutyrate) (PHB) [(C 4 H 6 O 2 ) n ], a material accumulated in a variety of microorganisms, is one kind of renewable aliphatic biomass. [1,2] PHB has been regarded as a potential material for the production of valuable compounds, e. g., crotonic acid (CA) and propylene, due to its special structural property and renewability. [3,4] Propylene, the second most important starting product in petrochemical industry, has been widely used for production of valuable chemicals, including polypropylene, propylene oxide, acrylonitrile, etc. [5][6][7] Recently, propylene from biomass has attained much more attention for the production of gasoline through oligomerization of olefins. [8,9] The conventional pathways of PHB conversion usually require high temperature (see Figure 1). The direct production of propylene from PHB by a conventional non-catalytic pyrolysis is not advocated, due to a low yield even at high temperature (> 300°C, Figure 1-1). [10][11][12] Propylene with a yield of 23.4 wt% can be also obtained from PHB through hydrothermal reforming. However, the temperature of the hydrothermal reforming was still high (370°C, Figure 1-2), [13] and heating the huge reaction solvent water to high temperature also increased the energy input. Catalytic pyrolysis at mild temperature is a promising way to save energy input, and the key is to develop an effective catalyst. Triruthenium dodecacarbonyl (TD) is an environmental-friendly catalyst, owing to its acid-free, non-corrosive and non-toxic characteristics, [14,15] and it was found that TD is active in the catalytic decarboxylation of long-chain fatty acid from plant oil. [16,17] In this work, TD was applied for the catalytic depolymerization of PHB, with the aim to obtain propylene at relatively mild temperature (240°C).Since no former information was reported on what is the lowest temperature or temperature range that the TD can catalytically depolymerize PHB, comprehensive thermal analysis (TG, DTG and DSC) of PHB, TD, and PHB-TD mixture were conducted (see Figure 2). Both the TG and DTG curves showed that the decomposition of TD begins at about 245°C, and therefore the highest catalytic pyrolysis temperature should be less than 245°C. PHB is a polyester with high crystallinity, which melted at around 180°C, according to the endothermic peak by the DSC curve at Figure 2B. This means that the reaction was changed from solid-solid contacting reaction to liquidphase involved reaction (solid-liquid or homogeneous phase) when the temperature was above 18...

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Section: Figuresupporting

confidence: 66%

One‐Pot Catalytic Conversion of Poly(3‐hydroxybutyrate) to Propylene at 240 °C

et al. 2019

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“…The yields of bio‐oils (HHV 33.3 MJ kg −1 ) and propylene can reach 35 and 17 wt %, respectively, through a one‐step reaction under mild reaction conditions (e.g. 240°C) 61 . CeO 2 also exhibited excellent reusability and a few solid residues were formed after the reactions, making it a potential candidate for commercial‐scale production owing to its good catalytic activity, reusability and environment‐friendly and low‐cost characteristics 61 .…”

Section: Liquid Fuelsmentioning

confidence: 99%

“…240°C) 61 . CeO 2 also exhibited excellent reusability and a few solid residues were formed after the reactions, making it a potential candidate for commercial‐scale production owing to its good catalytic activity, reusability and environment‐friendly and low‐cost characteristics 61 . The co‐production of high‐quality oil and propylene over CeO 2 via PHB reforming is expected to be a promising route when the cost of PHB feedstock is lowered.…”

Section: Liquid Fuelsmentioning

confidence: 99%

Tailored recycling chemicals and fuels from poly‐3‐hydroxybutyrate: A review

Kang

Liang

Yuan

et al. 2022

Biofuels Bioprod Bioref

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With the threat of ‘white pollution’, the large‐scale production and application of biodegradable plastics have become crucial. Poly‐3‐hydroxybutyrate (PHB) is the simplest and most used member of the polyhydroxyalkanoate family, with a uniform C4 structural unit (C4H6O2). To reduce the impact of PHB on waste treatment, various recycling strategies have been developed for the tailored conversion of PHB to targeted chemicals and fuels. Given the special structural unit, PHB and its plastic forms have the potential to serve as a sustainable feedstock for producing a series of value‐added chemicals and fuels, including (i) crotonic acid via pyrolysis, (ii) (R)‐β‐hydroxybutyric acid via hydrolysis, (iii) propylene via depolymerization and decarboxylation, (iv) liquid fuels via deoxygenation and oligomerization, (v) n‐biobutanol via catalytic hydrogenolysis, (vi) methyl crotonate via thermolysis and esterification, (vii) (R)‐3‐hydroxybutyrate methyl ester via catalytic methanolysis, and (viii) β‐aminobutyric acid via ammonolysis. This review article provides a systematic review focusing on the reaction pathways, primary applications and market potential of the target products, and the pros and cons of current bio‐refineries in comparison with conventional petroleum refineries. The thermochemical processes developed for PHB degradation and polypropylene (a typical petroleum‐derived plastic to be replaced by PHB) are also comprehensively evaluated to reveal the future opportunities and challenges of PHB's broad‐scale production and utilization. PHB‐derived chemicals and fuels have a mature market already, and it is confirmed that the tailored valorization of PHB is a promising pathway to expand the market and gain more environmental and energy benefits. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.

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“…This results in an activation energy that is lower in the presence of oxygen and may explain how cell wall degradation occurs in oak products at temperatures below what would be expected. Fast pyrolysis occurs when wood is exposed to a high temperature with a very quick ramp rate in the absence of oxygen or in the presence of a low quantity of oxygen that is consumed very quickly ( 127–131 ) . This process generates vapours, charcoal‐like char and brown liquid condensate that has many of compounds of interest to both whiskey and biofuel producers ( 65, 85, 132, 133 ) .…”

Section: Thermolysis and Pyrolysis: Mechanisms On How Cell Walls Contribute Flavourmentioning

confidence: 99%

Sources of variation in bourbon whiskey barrels: a review

2021

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Oak barrels serve two purposes in the production of distilled spirits: storage containers and reaction vessels. It is the latter function which bestows barrel aged spirits with their unique and highly sought after flavour profiles. However, achieving consistent flavour profiles between barrels is notoriously difficult as no two barrels are comprised of the same source of oak. Source variation is due to a range of factors, beginning with the genetic and topographical background of the oak tree from which the barrel staves originate, the spatial region of the tree from which the stave was taken and continuing through each step of the barrel production process. In this review, we detail each source of variation and highlight how this variation affects the reactants present in the barrel staves. The effect of pyrolysis on biomass is explored and how this knowledge relates to barrels that undergo the practices of toasting and charring is discussed. We also detail the significance of variation in the availability of reactants during the maturation process. The goal of writing this review is to identify areas of needed research, stimulate research and encourage investigation into the possibility of creating barrels with more consistent properties. © 2021 The Authors. Journal of the Institute of Brewing published by John Wiley & Sons Ltd on behalf of The Institute of Brewing & Distilling.

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Reforming of Poly(3-hydroxybutyrate) to Oils and Propylene over Cerium Oxide

Cited by 8 publications

References 17 publications

One‐Pot Catalytic Conversion of Poly(3‐hydroxybutyrate) to Propylene at 240 °C

One‐Pot Catalytic Conversion of Poly(3‐hydroxybutyrate) to Propylene at 240 °C

Tailored recycling chemicals and fuels from poly‐3‐hydroxybutyrate: A review

Sources of variation in bourbon whiskey barrels: a review

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