Production of Value Added Co-Products from the

Hydrothermal Liquefaction of Unhydrolyzed Solids

Vinod S. Amar1, Bharat Maddipudi1, Anuj Thakkar2, Katelyn Shell3, Dylan Rodene3, Tylor
Westover4, Sergio Harnandez4, Sandeep Kumar2, Ram B. Gupta3, Rajesh Shende1
1Department of Chemical and Biological Engineering
South Dakota School of Mines & Technology, Rapid City, SD
Email: rajesh.shende@sdsmt.edu
Phone: 605-394-1231; Fax: 605-394-1231
2Civil and Environmental Engineering, Old Dominion University, Norfolk, VA
3Chemical and Life Science Engineering, Virginia Commonwealth University, Richmond, VA
4Idaho National Laboratory, Idaho Falls, ID

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 Outline

Fuels and Value Added Co-Products

Hydrothermal liquefaction (HTL) of UHS to bio-oil and other valuable products

 Background Feedstock – corn stover
 Goals
 Experimental
 TOC, HPLC, GC-MS, elemental analysis
 Specific capacitance
 Results
• Reactors – batch and semi-continuous
• Effect of temperature, residence time, initial N2 pressure, catalyst
• Mass balance
• Bio-oil – HHV
• Co-products: lactic acid, phenol, char to battery grade carbon and
nanofibers
Summary

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 Biochemical Residue Co-products
Common problems Proposed solution

 Lignin/solid residue and acids  If wastes are converted into high

land up in waste stream during
biochemical processing
 Phenols and organics acids also  Novel approach of integrated
found in waste stream of
thermochemical processing
 Valuable carbon resource is
wasted in solids and aqueous
wastes
 Recovery and treatment of
wastes do not contribute to
offset the fuel costs
value products, it will offset the
fuel cost
technologies for solid waste
conversion into biocarbon and
carbon nanofibers, and aqueous
waste conversion into lactic acid
and phenols
 Reduce solid waste, utilize
aqueous phase carbon, generates
products that will reduce fuel cost

6 Bioenergy Technology Office

 Technical Approach
1. Develop integrated technology platform to effectively process wastes derived
from corn stover processing into solid and liquid products
2. Characterize the products yield and quality
3. Perform TEA and LCA and estimate fuel costs in terms of $/gge

Bench scale
• Physical tests
• Characterization
• Mass/energy
balance

Pilot scale
• 1 tpd throughput
• Characterization
• Mass/energy
balance
• TEA and LCA

8 Bioenergy Technology Office

 Goal Statement
 Demonstrate production of high value products from waste
streams, as given below, generated during conventional
biochemical processing at a pilot scale level with 1 tpd throughput.
 Aqueous waste stream (I) from alkaline pretreatment of corn stover
 Solid waste residue (I), unhydrolyzed solids (UHS)
 Aqueous waste stream (II) from hydrothermal processing
 Biochar waste (II)

 Outcomes: i) Four products from solid waste and aqueous waste,

which include biocarbon, carbon nanofibers, lactic acid/PLA and
phenols and ii) inclusion of revenues derived from these products
into TEA and LCA demonstrating BETO’s 2022 cost target of $3/gge
with >50% reduction in GHGs emission.

2 Bioenergy Technology Office

 Hydrothermal Liquefaction of Different Wastes
Typical Output
Composition by H2, CO, CO2, CH4 &
Kitchen Weight % light hydrocarbons
58 Gases
Waste 37
Gases %5%%Biocrude
Char

Food Waste

Biocrude

Hydrothermal Liquefaction LBO HB

O
Catalysts: Ni(NO3)2 , Ca(NO3)2

Pinewood Temperature：250°C -300°C

Operating P：800-1600 psig

Reaction Time: 30-90 min Extraction

Char
35 MJ/kg, viscous but highly
miscible with ethanol

CardbCardboard
oard
HBO
Tungal and Shende, Applied Energy, 2014; Energy & Fuels, 2013, Wei et al, Energy & Fuels 2016; Jaswal et al. Energy & Fuels, 2019

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 Bio-oil, char, and char products

18 Bioenergy Technology Office

 Semi-Continuous HTL Reactor System

Lab#202, CBE, SDSMT

Previously funded by US AFCEC(2014-18)
Funded by US AFCEC
US AFCEC EAR−EST#FA4819-14-C-0004

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 Feedstock – corn stover
Feedstock (corn stover) characterization
Table 1. Proximate, ultimate, and HHVs for densified corn stover

Proximate Analysis (wt. %) Ultimate Analysis (wt. %)

Fixed HHV
Feedstock Moisture Volatile Ash H C N O S
Carbon (MJ/kg)
Corn Stover 7.67% 77.18 6.75 16.07 5.69 46.25 0.42 40.51 0.09 18.34

Measurements acquired using ASTM D7582, ASTM D5373, ASTM D4239, and ASTM 5865.

The values determined for Sieve10,

Sieve50, and Sieve90 are 0.23, 0.88 and
2.68 mm, respectively. These values are
within the target values (Sieve10 > 0.1
mm and Sieve90 < 3 mm) the project.

9
 Experimental – TOC, HPLC and GC/MS

◦ Feedstock: UHS Glydia biotech AFEX pretreated corn

stover (batch 1, SKU: AFEXCSUH500G-B1/1)
◦ Reactor: 300 mL PARR SS316
◦ Reaction parameters- Temp: 250-300oC, N2 purge: 40-150
psi, Total pressure: 1100-1800 psi, reaction time: 30-120
min, Biomass: solvent: 1:06-1:30, Stirring speed: 1500 rpm

Agilent GC–MS/7890 GC system/5975C MSD

Column: HP-5 ms capillary
(5% phenyl, 95% dimethylpolysiloxane)
30 m x 250 mm x 0.25 mm)
Carrier fluid: He, flow rate 2 mL/min
Oven temp: 40oC to 250oC, no-isothermal
Injector temp: 230oC
Detector Temp: 250oC
NIST Library 2008, ver 2.0f
NDIR CO2 detector Column: Phenomenex Rezex ROA H+
Phosphoric acid: 6M (300 mm x 7.8 mm)
Potassium persulfate 30% Detector: SPD-10A (UV-vis) 210 nm
(w/v) Mobile phase: 0.005 M H2SO4 10
Oven Temp: 60oC
Injection volume: 10 microliter
 Experimental – Elemental Analysis and HHV
Analysis of HBO and char
𝑊𝑡.𝑜𝑓 𝑐ℎ𝑎𝑟
𝑊𝑡. %𝐶ℎ𝑎𝑟 = 𝑊𝑡.𝑜𝑓 𝑑𝑟𝑦 𝑏𝑖𝑜𝑚𝑎𝑠𝑠 x 100
Tungal and Shende, Applied Energy, 2014; Energy & Fuels,
2013, Wei et al, Energy & Fuels 2016; Jaswal et al. Energy &
Fuels, 2019
𝑊𝑡.𝑜𝑓 𝐻𝐵𝑂
𝑊𝑡. %𝐻𝐵𝑂 = 𝑊𝑡.𝑜𝑓 𝑑𝑟𝑦 𝑏𝑖𝑜𝑚𝑎𝑠𝑠 x 100

Dulong formula Friedl et al

HHV (MJ/kg) = 0.338C + 1.428(H - O/8) + 0.095S

Treatment time: 2 hours
UHS supplied by Glydia biotech AFEX pretreated corn stover

Sergiy et al, Biofuels,

2014

11
 Effect of HTL Temp and Initial PNitrogen

Biomass to solvent ratio – 1:10, Biomass to solvent ratio – 1:10,

Reaction time : 1-hour, Initial reactor Reaction time : 1-hour,
pressure: 40 psi, N2 Temperature : 275oC

12
 Effect of B:S and HTL Reaction Time
Effect of biomass to solvent ratio Effect of HTL reaction time

HTL temperature : 275oC, Reaction Biomass to solvent ratio – 1:10,

time : 1-hour, Initial reactor pressure: Temperature : 275oC, initial reactor
100 psi, N2 pressure : 100 psi, N2

13
 HTL Derived Co-Products (Non-catalytic)

No catalyst
Temperature, oC Char % HBO % LA % Phenol % HBO HHV (MJ/Kg)
B:S 1:10, 1 h, 250 42.25 21.55 23.72 10.55 30.40
40 psi N2 275 38.74 20.19 21.14 20.19 27.09
300 35.80 18.83 17.39 18.8 30.43
Initial Pressure, psi Char % HBO % LA % Phenol % HBO HHV (MJ/Kg)
0 37.67 21.48 25.95 12.45 30.01
B:S 1:10, 1 h,
40 38.74 20.19 21.14 13.27 27.09
275oC 100 38.60 20.12 25.10 13.28 29.25
150 38.60 19.55 26.63 12.85 30.04
Time, min Char % HBO % LA % Phenol % HBO HHV (MJ/Kg)
B:S 1:10, 275oC 30 37.52 21.91 28.71 11.62 29.38
100 psi N2 60 38.60 20.12 25.10 12.73 29.25
120 39.46 16.40 26.53 14.03 30.49
UHS/DI-water ratio Char % HBO % LA % Phenol % HBO HHV (MJ/Kg)
275oC, 1h 1:30 29.00 22.56 25.06 6.33 28.95
100 psi N2 1:10 38.60 20.12 25.10 13.39 29.25
1:06 40.99 20.92 23.23 12.75 29.42

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 HTL Derived Co-Products (Catalytic)

Effect of catalyst
Initial HTL operating
Sample Purge Pressure, conditions Lactic acid Phenol HBO Char
gas psi Temperature Pressure, (wt.%) (wt.%) (wt.%) (wt.%)
, oC psi
UHS-5wt.% N2 40 300 1475 19.61 15.21 20 32.4
Ni(OH)2
UHS-5wt.% N2 40 300 1500 14.05 9.32 24.3 25.7
K2CO3
UHS-5wt.% CO2 40 300 1650 13.72 11.29 20.2 34
Ni(NO3)2

15
 Proposed Pathways – Compounds Observed

Market
5-HMF 2019 $56 million, $61 million 2024
Phenol 2018 $20 billion, $28 billion 2024
Lactic acid $8 billion, PLA $10 billion 2024
Vanillin $725 million 2024
Nan et al. Energy Fuels (2016); Tungal and Shende, Applied Energy (2014); Jaswal et. al (2019)

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 GC/MS characterization of Bio-oil

a C4-C11
Oxygenated
Hydrocarbons

C17-C22
b Oxygenated
Hydrocarbons

Nan et al. Energy & Fuels, 2016, 30 (6), pp 4933-4944; Jaswal et al., Energy & Fuels, 2019

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 Reduction of Water Consumption and
Higher Bio-Oil Production
Biocrude

Bio-oil • Heavy bio-oil production increase from

12 wt% in cycle 1 to 37 wt% in cycle 5.
• Bio-oil, biochar production and pH of
biocrude reached to a stationary level at
cycle 6.
• This technique is addressing both high
water consumption and low bio-oil
production issues.

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 Burning behavior of bio-oils recovered

LBO from Cardboard HBO from Cardboard Directly Biomass burning

US AFCEC EAR−EST#FA4819-14-C-0004
 Fuel blends with ethanol and biodiesel

Funded by
US AFCEC
(2014-18)

US AFCEC EAR−EST#FA4819-14-C-0004
 Electrospun Polyacrylonitrile/Biochar Carbon
Nanofiber Mats

Sonication for 24 h

Capacitance: 37.6 F.g-1

W. Nan, Y. Zhao, Y. Ding, A. R. Shende, H. Fong, and R. V. Shende, Materials Letters 205, 206-210 (2017)
Char to Biocarbon (Battery grade) – SEM images

Standard Catalytic

Demir et al. I&EC Res, 2015

Specific capacitance of biocarbon from char

𝑉2
𝑉1 𝐼𝑑𝑉
Specific Capacitance 𝐶 =
𝑚υΔ𝑉
 Conclusions

 We have demonstrated production of lactic acid, phenol, biocarbon and carbon

Nanofibers from corn stover derived UHS using HTL under non-catalytic and
catalytic conditions

 Yield of different products was found to vary based on temperature, B:S ratio,
and time

 The aqueous crude could be recycled many times and after 6th cycle, it reached
35 wt% bio-oil production.

 The bio-oil was found to have HHV of 35 MJ/kg and it could form a blend with
biodiesel and ethanol

 The blended fuels could be used in an electric generator for power generation
without upgradation

 Carbon nanofiber based supercapacitors showed specific capacitance of 37 F/g

whereas graphitized carbon indicated specific capacitance of 125-269 F/g.

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 Acknowledgements

Award DE-EE0008252

Pilot scale biochemical and Hydrothermal integrated biorefinery (IBR)

For fuels and value added products

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