CHEMICALS PRODUCTION FROM BIOMASS AND ORGANIC WASTES WITH HIGHTEMPERATURE WATER–FOR SUSTAINABLE CHAMICALS PRODUCTION SYSTEM–M.Shirai
Research Center for Compact Chemical System, National Institute of Advanced Industrial Science and Technology (AIST)
Sendai, Japane-mail: m.shirai@aist.go.jp, tel +81-22-237-5219, fax +81-22-237-5224

Abstract
Environmentally benign systems to produce valuable chemicals from biomass-derived compounds and organic wastes
using high-temperature water were studied. Three examples, (1) hydrolysis of poly(ethylene terephthalate) toterephthalic acid and ethylene glycol in high-temperature liquid water, (2) dehydration of polyols to the corresponding
cyclic ethers in high-temperature liquid water under high-pressure carbon dioxide, and (3) gasification of lignin oversupported metal catalysts in supercritical water, are shown in this manuscript.

Keywords: Compact chemistry, Supercritical fluids, High-temperature liquid water, Carbonic acid

1. Introduction
To establish sustainable chemicals production, we
have to utilize inexhaustible resources, such as biomass
and organic wastes. Also, the technologies for suchtransformations should be safe and easy. Water is anenvironmentally benign media because of its non-toxic
and non-flammable properties. The dielectric constantvalues of water decrease with an increase in temperature,indicating that solubility of organic compounds increases.
Ion product values of water increase with an increase intemperature to 10-11 at around 523 K. These properties
indicate that high temperature liquid water around 523 K
could be a media for acid- and base-catalyzed reactionsof organic compounds. In this paper, three examples ofchemical reaction using high-temperature water including
supercritical water are reported.

2. Materials and Methods
Catalytic reactions under high-pressure conditions
were studied with a batch reaction system using stainlesssteel tube reactors.

3. Results and Discussion
3.1. Hydrolysis of polyethylene terephthalate
Poly(ethylene terephthalate) (PET), which is apolyester of terephthalic acid (TPA) and ethylene glycol(EG). Hydrolysis behavior of PET resin in water wasstudied with a batch reactor [1]. TPA and EG were
produced at higher than 473 K. The maximum yields ofTPA and EG were both 95 % at 543 K.

3.2. Dehydration of polyols
Five- or six-membered cyclic ethers were obtainedby an intermolecular dehydration reaction of polyalcoholcompounds, which could be obtained by selective
decomposition of cellulose, in high-temperature liquidwater (523-573 K) [2]. The formation rates of the cyclicethers were enhanced by the addition of high-pressure ofcarbon dioxide (17-27 MPa). Carbonic acid is formed in
the mixture of water and carbon dioxide and proton
derived from carbonic acid catalyzes dehydration rates.
3.3. Supercritical gasification of lignin
Lignin is a component woody biomass and highmolecular-weight compound with random structure.
Organosolve-lignin and real biomass containing lignin(sugarcane bagasse) [3] were completely gasified andfuel gases (methane and hydrogen) were obtained overcarbon supported ruthenium catalysts in water at 673 K.
This work was supported by Special Coordination Funds
for Promoting Science and Technology for “Developmentof Sustainable Catalytic Reaction System using Carbon
Dioxide and Water”.

References[1] O.Sato, M.Shirai et al., Chem. Lett. 38 (2009) 268–269.
[2] A. Yamaguchi, M.Shirai et al., Green Chem. 11 (2009)48-52.,A. Yamaguchi, M.Shirai et al., Green Chem. 13(2011) 873-881., A. Yamaguchi, M.Shirai et al., ACS
Catal. 1 (2011) 67-69.
[3] M.Osada, M.Shirai et al., Energy Fuelsl 20 (2006)
930–935., M. Osada, M.Shirai et al., Energy Fuels 26(2012) 3179-3186.

7th International Symposium on Feedstock Recycling of Polymeric Materials (7th ISFR 2013)
New Delhi, India, 23-26 October 2013