Catalytic

Hydrothermal Anuj Thakkar1, Katelyn Shell2, Martino Bertosin3,

Dylan Rodene2, Vinod Amar4, Bharat Maddipudi4,
Treatment Tylor Westover5, Alberto Bertucco3, Ram Gupta2,
Rajesh Shende4 and Sandeep Kumar1
(CHT) of 1Old Dominion University, 2 Virginia Commonwealth University, 3
University of Padova, Italy, 4 South Dakota School of Mines and

Lignocellulosic
Technology and 5 Idaho National Laboratory

Biomass Email: skumar@odu.edu (Dr. Sandeep Kumar)

1
 Part I – Pretreatment of Biomass and
Production of Levulinic and Lactic Acid
Anuj Thakkar
Department of Civil and Environmental Engineering
Old Dominion University

Corn Stover, cropwatch.edu

 Introduction
• Lignocellulosic biomass: Renewable, abundant, and inexpensive

• Alternative process for lignocellulosic bioethanol: High enzyme

cost, deactivation of enzymes and inefficient fermentation

• Integrated biorefinery: Multi product process that includes

Levulinic acid, Lactic acid and Biocarbon electrode

• Levulinic acid is identified as one of several key sugar-derived

platform chemicals that can be produced from biomass

• Lactic acid can be polymerized further to produce degradable

bioplastic i.e., Polylactic acid (PLA)

3
Process flow diagram

Product 3

Product 1

Product 2

4
 Hydrothermal pretreatment
Reaction parameters
• Biomass loading: 11 g
• Raw corn stover: Milled to size between 0.23 and
2.68 mm
• Catalyst: 0.45 % (w/v) K2CO3
• Flow rate: 2.5 ml/min for heating and reaction
• Heating, reaction and cooling time: 20 mins each
• Reaction temperature: 190 ℃
• Reaction pressure: 500 psi
• Mode of operation: Semi-continuous, flow
through

5
 Results

Liquid hydrolyzate: TOC (mg/ml)

Preheating Reaction Cooling
15276 20215.7 2718.2
Biochemical analysis
% % % % % % %
Total
Ash Lignin Glucan Xylan Galactan Arabinan Mannan
Raw corn stover 6.51 26.95 28.15 21.61 0 2.53 0 85.75
Pretreated corn stover 9.43 17.98 62.01 8.74 0 0.29 0 98.45
• Cellulose rich/pretreated corn: 37.59 % of initial loading
• 84.7 % of xylan and 76 % of lignin was solubilized in liquid hydrolysate
• 82.77 % of glucan is retained in the biomass

6
Product 1: Levulinic acid

7
Levulinic acid production

Levulinic acid, a member of the gamma-ketoacids, can be

produced through acid-catalyzed dehydration and hydrolysis of
hexose sugars
Reaction parameters
• H2SO4 concentration: 0, 1, 2 & 4 % (w/w) for 5 minutes
reaction time Reactors
• Reaction time: 5, 15, 45, 105 and 165 minutes with 2 % H2SO4
concentration Sand bath

• Reactor volume: 54.2 ml (Reaction mixture: 47.56 ml)

• Reaction temperature: 190 ℃
• Pressure: Autogenous (above vapor pressure)
• Feed: 0.95 g dry raw corn stover or pretreated corn stover, 2 %
(w/v) loading

8
 Results

• Levulinic acid yield is based on cellulose content in the biomass

• 2 % sulfuric acid was found to be optimum concentration for Levulinic acid yield in both raw and
pretreated corn stover

9
 Results

Levulinic acid yield (% of Elemental Analysis Nitrogen Carbon Hydrogen Sulphur

2 % H2SO4 cellulose) (%) (%) (%) (%)
Reaction Raw Corn Pretreated Corn Raw corn stover 0.5 44.0 5.5 0
time (min) Stover Stover (RCS)
5 35.78 30.06 Solid residue 0.4 42.9 3.9 0
15 36.21 31.52 generated from
45 36.19 31.25 RCS
105 37.41 30.94
Pretreated corn 0.2 39.5 5.1 0
165 36.60 30.13
stover (PCS)
Solid residue 0.3 33.0 3.9 0
generated from
PCS

• Slightly higher yield from raw biomass could be due to presence of higher
hemicellulose which up to certain extent is converted to Levulinic acid
• Reaction time has very less or no impact on Levulinic acid yield over a wide range of
reaction time

10
 Results
Simplified acid catalyzed decomposition of lignocellulosic biomass
(Darryn W. Rackemann and William O. S. Doherty, 2010, The conversion of lignocellulosics to levulinic acid.)

Liquid stream: Contribution of C in TOC (%)

Lactic acid Formic acid Acetic acid Levulinic acid HMF Furfural Total
Raw corn stover 2.74% 5.29% 5.45% 20.44% 0.78% 10.24% 44.95%
Pretreated corn stover 0.65% 7.37% 0.43% 33.87% 0.67% 3.51% 46.50%
• Removal of hemicellulose from corn stover helped in reduced production of furfural and
acetic acid from pretreated corn stover
• Higher carbon percentage of Levulinic acid in TOC in pretreated corn stover is due to higher
concentration of cellulose and lower concentration of hemicellulose and lignin

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Product 2: Lactic acid

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Lactic acid production

Lactic Acid
(mg/L)

Before WO 1831

After WO 1955

After RotaVap 3293

6.7 % increase in Lactic acid conc.
after WO

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Part II – Conversion of Solid Waste Residue
for Energy Storage
Katelyn Shell
Department of Chemical and Life Science Engineering
Virginia Commonwealth University

14

Corn Stover, cropwatch.edu

Product 3: Biocarbon

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Biomass for Energy Storage
Where can biocarbon be implemented?
• Li-ion Batteries
• Supercapacitors
• Capacitors
• Fuel Cells

1000 Capacitor

Lignin structure. Demir, M. et al., Ind. Eng. Chem. Res. (2017)

Specific Power (W/kg)

100
Renewable carbon replacements for Supercapacitor

petroleum-derived anodes in
batteries and capacitors
10 Li-ion Batteries

Focus herein has been towards

Fuel Cells
increasing surface area, increasing
carbon content and crosslinking 1
10 100 1000 10000
Specific Energy (Wh/kg) 16
Energy Storage and Materials
Supercapacitor – A type of capacitor that can hold up to Supercapacitor Depiction:
100 times more energy than a standard electrolytic
capacitor. Separator

Advantages + -
• High specific power
• Robust - + - +
• Long cycle stability - + - +
• Rapid charging - + - +
Disadvantages - + - +
• Low specific energy - + - +
• Operates at lower voltages - + - +
• High cost per watt http://www.english.grinyov.com.ua

Capacitor Type Rating Scale

Electrostatic pF, μF Good charge capacity
Electrolyte Soaked Electrodes
Electrolytic μF and cycle performance
Supercapacitor F
17
Process Flow Diagram (Activation)
Process 1: Process 2:
HCl washing of HCl washing of
given material given material

Neutralization Neutralization
and drying and drying

Low temperature
annealing (300-
400C, 3 hrs)
Carbonization at
high temperatures
(700-1000C, 3 hrs) Carbonization at high
temperatures (700-
1000C, 3 hrs)

Energy Storage:
Anodes
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Process Flow Diagram (Energy Storage)
Counter Working

Process 1. Process 2. Reference

Conversion of material
into electrode ink
(8:1:1, wt%)

Apply ink to pre- Epoxy

Electrochemical
washed Ni-foam electrodes,
Testing
electrode, dry cure overnight

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Microscopic Carbon after Activation
Process 1: Process 2:

20
Cyclic Voltammetry
Processed by low temperature annealing then high temperature carbonization
– Process 2
𝑉𝑉 0.020
∫𝑉𝑉 2 𝐼𝐼𝐼𝐼𝐼𝐼
Specific Capacitance 𝐶𝐶 = 1
𝑚𝑚υΔ𝑉𝑉 0.015

0.010

Where I is current in amps (A), V is 0.005

voltage, m is mass of active material
0.000
in grams (g), υ is scan rate in V𝑠𝑠 −1 Current (A)
-0.005

-0.010

-0.015
100 mV/s

-0.020 50 mV/s

20 mV/s
-0.025
5 mV/s
-0.030
-1 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0
Potential (V)

Average specific capacitance – 120 F/g at 5 mV/s SWR-ODU080619 A2

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Charge Discharge Comparison
Process 1 Process 2
0.0
SWR-ODU080619 A2

-0.1 SWR-ODU080619 C1

𝐼𝐼𝐼𝐼 -0.2
Specific Capacitance 𝐶𝐶 =
𝑚𝑚Δ𝑉𝑉
-0.3

Where I is current in amps (A), t -0.4

Voltage (V)
is time to charge in seconds (s), -0.5

m is mass of active material in

-0.6
grams (g), and V is voltage (V).
-0.7

-0.8

-0.9

-1.0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
SWR-ODU080619 A2 – 115 F/g at 0.5 A/g Time (s)

SWR-ODU080619 C1 – 58 F/g at 0.5 A/g

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BET
Process Surface Area (𝒎𝒎𝟐𝟐 𝒈𝒈−𝟏𝟏 ) Pore Volume (𝒄𝒄𝒄𝒄𝒈𝒈−𝟏𝟏 )

High Temp Only 327 0.19

Low and High Temp 466 0.24

180

160

140

120
Volume at STP (cc/g)

100 0.25
Pore Volume (a.u.)

80 0.20

0.15
60
0.10
40
0.05

0.00 Adsorption
20
0 5 10 15 20 25 30 35 40 Desorption
Pore Width (nm)
0
0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/P0)

Hysteresis plot of material from process 2 23

Summary of Results
Our Work
Max Max
Surface Area Percent yield
Material Material ID Method Capacitance Capacitance
(𝒎𝒎𝟐𝟐 𝒈𝒈−𝟏𝟏 ) (%)
(𝑭𝑭𝒈𝒈−𝟏𝟏 ) (CV) (𝑭𝑭𝒈𝒈−𝟏𝟏 ) (CD)
Corn SWR- High Temperature
77 58 327 43
Stover ODU080619 Only
Corn SWR- Low Temperature
Stover ODU080619 Then High 120 115 466 41
Temperature
Literature
Max Capacitance
Corn Part Literature References
(F/g)
Karnan, M. et. al. (2017), Wang, L. et. al.
Corncob 390, 385, 328.4, (2017), Wang, D. et. al. (2015)

Stem 232 Lee, M. et. al. (2017)

Husk 356 Song, S. et. al. (2015)

Stalk 213, 323 Wang, L. et. al. (2013), Cao, Y. et. al. (2016)

Corn Stover 246 Jin, H. et. al. (2014)

Corn Starch 162 Pang, L. et. al. (2016)

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Corn Silk 160 Mitravinda, T. et. al. (2018)
 Conclusions

• All the major components of lignocellulosic biomass (corn

stover) can be sufficiently converted into value added products
like Levulinic acid, Lactic acid and Biochar
• Pretreatment of corn stover helps in separating lignin and
hemi-cellulose from rest of the biomass
• Levulinic acid yield from cellulose in pretreated biomass is ~30
% (w/w)
• Solid residue generated is a viable candidate for energy storage
materials
• Simple activation of biochar has produced a max average
capacitance of 120.9 F/g

25
Questions & Acknowledgements

Department of Energy
Award No. DE-EE0008252

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