1. Hydrothermal Conversion of Biomass Waste for Bio-based Chemicals
and Hydrochar
Shicheng Zhang
Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP3), Department of Environmental Science and Engineering, Fudan University, Shanghai

2. Content 1
Introduction 2
Hydrothermal liquefaction of biomass waste 3
Separation of liquefaction products for chemicals 4
Hydrochar and its application

3. 1. Introduction
Environmental problem & Resource recovery from biomass waste
Water pollution (eutrophication)
air pollution
Enteromorpha
Water hyacinth
Biomass burning
Algae Bloom in Lake Tai
Ecological invasion

4. Components of Biomass Waste
Biomass waste is composed of cellulose, hemicellulose, lignin, lipids, proteins, pectin, organic acids, chlorophyll, polyphenols and so on.

5. Resource Recovery from Biomass Wastes @Fudan Bio-based Chemicals
Biooil
Biofuels
Hydrothermal liquefaction
Green pesticide
Waster Soluble Products
Catalytic liquefaction
Liquid Fertilizer
BT 2014, 2015
ES&T 2014
Carbon 2014, 2016
Energ. Fuel. 2010, 2012, 2015
ACS Sus Chem Eng 2014, 2015
sand willow
Porous Carbon
Soil Amendment
Water
hyacinth
Alternanthera
philoxeroides
Livestock
manure
Straw
Solid Products
hydrochar
Biogas upgrading
Enteromorpha
Biogas
Anaerobic Digestion
Syngas biomethanation
ES&T 2013, 2014
Water Res 2014
Biotechnol Bioeng 2012
BT 2016
Biotechnol Biofuel 2015, 2016
Hydrogen

6. 2. Hydrothermal liquefaction of biomass waste
Hydrothermal liquefaction of macroalgae
Enteromorpha Prolifera
The maximum yield of bio-oil is 23.0 wt % obtained at 300℃, 30min, algae to water ratio of 1:7.5, with 5% Na2CO3, with HHVs around 30 MJ/kg.
The bio-oil is a mixture of various compounds, and fatty acids are found the main compounds.
Dong Zhou, Shicheng Zhang*, Jianmin Chen, et al. Energy & Fuels. 2010, 24, 4054–4061. (ESI paper)

7. 2. Hydrothermal liquefaction of biomass waste
Liquefaction of macroalgae in alcohols
methanol
Ester compounds
ethanol
Low-Lipid Macroalgae
Enteromorpha Prolifera
White: methanol Gray: ethanol
Dong Zhou, Shicheng Zhang*, Jianmin Chen, et al. Energy & Fuels. 2012, 26 (4),

8. 2. Hydrothermal liquefaction of biomass waste
Catalytic liquefaction of rice straw to lactic acid
NiO
Rafia Younas, Shicheng Zhang*, Liwu Zhang*, et al. Catalysis Today. Accepted.

9. 2. Hydrothermal liquefaction of biomass waste
Hydrothermal liquefaction of desert shrub Salix Psammophila
The bio-oil is mainly composed of phenolic compounds.
Changjun Li, Shicheng Zhang*, et al. BioResources. 2013, 8(2),
Shicheng Zhang, et al. Chinese patent, ZL X; Chinese patent application number:

10. 3. Products separation Two- stage nano-filtration and reverse osmosis
Monophenols separation
Hang Lyu, Shicheng Zhang*, et al. Journal of Membrane Science. 2016, 504, 141.

11. 3. Products separation Fine separation of bio-oil
Shicheng Zhang, et al. Chinese Patent Application number:

12. 3. Products separation
phenol
Separation of phenolic compounds from the aqueous phase product
Aqueous phase product
2-methoxy phenol
phenol
Modified Resin
(DCX modified resin XAD4)
2-methoxy phenol
The adsorption capacity of the modified resin was 1.5 times higher than that of the unmodified resin.
other substances
Kaifei Chen, Shicheng Zhang*, et al. Bioresource Technology 2015, 182,

13. N2 Porous carbon Hydrochar Properties Tetracycline adsorption
4. Hydrochar and its application
Preparation of porous carbon by pyrolysis
Hydrochar
Porous carbon N2
Tetracycline
adsorption
Relationship
Properties
disadvantage：limited pore volume and adsorption ability, and hard collection
Xiangdong Zhu, Shicheng Zhang*, et al. Carbon, 2014, 77,

14. 4. Hydrochar and its application
Detailed results
Porosity affected by activation temperature
Adsorption performances
Surface area and pore volume was
increased after pyrolysis under N2.
500 ℃ is sufficient for activation of hydrochar.
Adsorption capacity is closely related to porosity of porous carbon.
However, the adsorption capacity is
limited.

15. The link between hydrochar properties and porosity of activated carbon
decreases in surface area, pore volume
strong correlations
hydrochar-based activated carbon
increases in stability, recalcitrance, aromaticity
HTC peak temperature & retention time
Activated carbon with high porosity is produced from low HTC temperature and time.
Importantly, strong correlations between hydrochar properties and porosity of hydrochar based activated carbon was obtained.
Xiangdong Zhu, Shicheng Zhang*, et al. ACS Sustainable Chem. Eng. 2015, 3, 833−840

16. Strong positive correlations
Detailed results
Strong positive correlations
Correlations between properties (mass loss, H/C, O/C) of hydrochar with surface area
of activated carbon
Xiangdong Zhu, Shicheng Zhang*, et al. ACS Sustainable Chem. Eng. 2015, 3, 833−840

17. 4. Hydrochar and its application
Preparation of magnetic carbon composite by chemical co-precipitation
advantage：high porosity and adsorption capacity
disadvantage：weak acid resistance of magnetic particle
There are big spaces to improve the porosity of magnetic composite
Porosity of hydrochar, activated carbon and magnetic composite
Xiangdong Zhu, Shicheng Zhang*, et al. ACS Sustainable Chemistry & Engineering, , (4),

18. 4. Hydrochar and its application
Preparation of magnetic carbon composite by simultaneous activation and magnetization
The as-prepared magnetic
carbon composite have high
porosity and high acid
resistance.
Xiangdong Zhu, Shicheng Zhang*, et al. Environmental Science & Technology, 2014; Bioresource Technology

19. The link between performances of magnetic carbon composite and hydrochar properties
strong correlations
decreases in
ID/IG
acid resistance
surface area & pore volume
roxarsone adsorption
HTC
160
200
240
270
300
Hydrochar
increases in
R50 index
H/C, O/C, (O+N)/C
Environmental performance of magnetic carbon composite is controlled by hydrochar properties.
A magnetic carbon composite with strong acid resistance and low graphization degree is produced from low temperature hydrochar.
Xiangdong Zhu, Shicheng Zhang*, et al. Energy & Fuels. 2015, Carbon 2016

20. Detailed results Correlations between R50 index
positive correlation
negative correlation
Correlations between R50 index
of hydrochar with performances
of magnetic carbon composite
negative correlation

21. Detailed results Correlations between aromaticity
negative correlation
positive correlation
positive correlation
Correlations between aromaticity
(H/C atomic ratio) of hydrochar
with performances of magnetic
carbon composite

22. Summary
Hydrothermal conversion of biomass waste for chemicals and materials is beneficial to the sustainable development of energy, resources and environment.
The specific chemicals and carbon materials could be obtained by hydrothermal and catalytic conversion of biomass.
Membrane separation and chromatography separation are efficent techniques for high purity chemicals.
The properties of carbon materials could be easyly controlled by the properties of hydrochar and the activation conditions.
In further researches and applications, it is essential to explore the directional conversion of biomass waste through catalytic methods or conbined technologies, as well as design continous process and scale-up for commercialization.