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Specific Heat of Lignin

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Specific Heat of Lignin

f

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Tiffany Fung
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© © All Rights Reserved
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Electronic Supplementary Material (ESI) for Green Chemistry.

This journal is © The Royal Society of Chemistry 2016

A Sustainable Lignocellulosic Biodiesel Production Integrating Solar- and Bio-power Generation

Michael Zanotti, Zhenhua Ruan, Mauricio Bustamente, Yan Liu*, Wei Liao*

Department of Biosystems and Agricultural Engineering, Michigan State University, East

Lansing, MI 48824, USA

*: Corresponding authors

Wei Liao

524 South Shaw Lane, Room 202

East Lansing, MI 48824

Telephone: 1-517-432-7205

Fax: 517-432-2892

E-mail: [email protected]

Yan Liu

524 South Shaw Lane, Room 203

East Lansing, MI 48824

Telephone: 1-517-432-7205

Fax: 517-432-7897

E-mail: [email protected]

1
2
Supplemental Material

The major unit operations in a lignocellulosic biodiesel refinery capable of producing 10

million gallons of biodiesel a year include (1) corn stover collection & transportation to the

biorefinery, (2) corn stover pretreatment and enzymatic hydrolysis, (3) lignin processing, (4)

fungal lipid fermentation, (5) fungal biomass drying, (6) lipid extraction and transesterification,

(7) wastewater treatment, and (8) solar-bio-power generation. The boundary for the process is

shown in Figure 1. The details of individual unit operations are described as follow.

1 Corn stover collection and transportation

The agricultural residue - corn stover is the selected substrate for fungal lipid

fermentation in this study. It should be made clear that we do not view corn stover to be the only

suitable source for fungal lipid production, rather we consider it as a readily available and

attainable resource which can bridge the gap until other dedicated energy crops will be

developed. In our scenario corn stover is treated as an agricultural residue from corn production,

and as such, only energies related to collection, transport, and fertilizer replacement are

examined.

The energy input of corn stover production is summarized from harvesting of the corn

stover, all the way to its delivery at the biorefinery gate 1, 2. The following values were used in

this study: (1) collection/transport to local storage of 196.90 MJ/t, (2) local storage inputs of

30.50 MJ/t, (3) corn stover compaction for transport of 233.70 MJ/t, and (4) transport of

compacted corn stover to end users 62.4 MJ/t. We also assume that harvesting corn stover

likewise removes nutrients that must be replaced by adding additional fertilizer to what is

typically applied during regular corn production. The amount of Nitrogen (N), Phosphorus (P),
3
and Potassium (K) fertilizer replacements assumed for this study are 8.80, 0.60, and 7.20 kg/t dry

matter, respectively 1, 3. Energy inputs for N, P, and K fertilizer production were 47.70, 13.35,

and 8.09 MJ/kg, respectively, which are calculated from GREET 1.8c.

2 Corn stover pretreatment and enzymatic hydrolysis

Corn stover received by the biorefinery must undergo both physical and thermochemical

treatment steps in order to disrupt the macromolecular structure of lignocellulose (cellulose,

hemicellulose, and lignin). This allows hydrolytic enzymes to penetrate and hydrolyze the

carbohydrate polymers to their monomeric sugar constituents, which can readily be metabolized

for fungal lipid production. The composition of corn stover is 36.3% (w/w) cellulose, 22.0%

(w/w) xylan, and 18.6% (w/w) lignin 4.

Physical treatment is the initial size reduction of the biomass. This process is

accomplished using a hammer mill, which has energy inputs of 180 MJ/t of herbaceous biomass
5. A combined hydrolysis process is then used to carry out corn stover pretreatment and

enzymatic saccharification, while process co-products such as lignin are utilized for additional

energy production. Combined hydrolysis refers to two separate steps using dilute sulfuric acid

and dilute sodium hydroxide solutions to first pretreat corn stover, and then directly followed by

enzymatic saccharification on the mixture of acid and alkali treated slurries without

detoxification and liquid–solid separation 4. Our previous study found optimal corn stover

pretreatment conditions to be 10% solid loading (w/w) and 2% acid (w/w) and 2% alkali (w/w)

at 130°C for 1 hr 4. Energy consumption to heat the pretreatment slurry to its desired temperature

is calculated using the following equation.

4
𝐸𝑠𝑙𝑢𝑟𝑟𝑦 = 𝑀𝑠𝑙𝑢𝑟𝑟𝑦 × 𝐶𝑝 ‒ 𝑠𝑙𝑢𝑟𝑟𝑦 × Δ𝑇 (1)

where Eslurry (kJ) is the energy consumption for heating the pretreatment slurry, Mslurry is the total

mass of the slurry (kg), Cp-slurry, is the specific heat capacity of the slurry (3.96 kJ/kg°C), and ΔT

is the temperature difference between the initial slurry temperature (15°C) and final desired

temperature (130°C) 6. Latent heat of vaporization is not factored into the equation due to the

fact that the reaction occurs in a pressurized reactor.

After thermochemical pretreatment is complete, the hydrolysate is cooled to 50°C.

Regenerative heat exchange is assumed to occur between the hot pretreatment slurry at 130°C

and the incoming water used for the next pretreatment batch. Thus, total heat recovered is

calculated using equation 1, with the exception of ΔT being 80°C. The recovered heat is used to

maintain the enzymatic reaction temperature of 50°C. Hydrolytic enzymes are then added to the

cooled slurry at 50°C to cleave the hydrolytic bonds in the remaining cellulose and hemicellulose

chains. An enzyme loading of 47 kg-protein/t-biomass was used in our previous study resulting

in a total sugar yield of 74.2% 4. The lignin solubility of 13% at our pretreatment conditions is

consistent with a previous study 7.

Both pretreatment and hydrolysis reactors are assumed to be 200 m3 in effective size (5.0

meter in diameter and 10.0 meter in height) with continuous agitation through the reaction

solution. The agitation times for pretreatment and hydrolysis are 1 hours and 72 hours,

respectively. The parameters for agitating both reactors are listed in Table S1. The electricity use

for the agitation is calculated as follows:

5
𝑃𝑔
𝑃=
𝜂𝑔 (2)

where Pg and P are agitation power (W) and total electrical power (W), respectively. ηg is the

global efficiency for agitation. Pg is described by equation 3 8.

𝑃𝑔 = 𝑁𝑃𝜌𝑁3𝐷5 (3)

Here Np is the power number for propeller, ρ is the fluid density (kg/m3), N is the agitation speed

(revolutions/s), and D is the agitator diameter (m). Values for each parameter are listed in Table

2.

The hydrolysis slurry has a relatively high viscosity due to the alkali pretreatment. Our

experiments indicate that vacuum filtration does not work for such a high viscosity slurry. A

pressure filter is thus selected as the liquid-solid separation unit to obtain the enzymatic

hydrolysate in this study. The filtration operates under 50°C, and is able to recover 99% of the

sugars in the hydrolysis slurry 9. The energy consumption of the pressure filter is 309.64 kJ/kg

dry biomass residue.

Since the fermentation temperature is 25°C, the enzymatic hydrolysate must be cooled

down before inoculating the fungal seed. Considering the location of the studied biorefinery, the

average groundwater temperature is 15°C. Therefore, the incoming water for the process is used

to cool down the enzymatic hydrolysate as well to recover the heat and prepare the hydrolysate

for the fermentation. The heat recovery is calculated by equation 1 again, with the ΔT being

25°C and Cp-solution being 4.18 kJ/kg°C,


6
3 Lignin processing

The biomass residues remaining after enzymatic hydrolysis consist primarily of the

insoluble lignin fraction at 80% (w/w) of the dry residue. Considering the fact that lignin is the

second most abundant terrestrial polymer on our planet after cellulose, the amount of lignin

produced will be significantly increased along with the implementation of lignocellulosic

biorefineries to generate biofuels. Lignin valorization then becomes vital to improving the

economic performance of the second-generation biofuel product and enhancing the sustainability

of lignocellulosic biorefining 10, 11. Potential paths to valorize the residual lignin include carbon

fiber composites for structural materials, solid fuels for energy generation, and low-molecular-

weight aromatic compounds for value-added chemical production 11-13. Compared to lignin solid

fuel for power generation, carbon fiber composites and value-added aromatic compound

production are still in the research and development stage. Therefore, our study utilizes lignin as

solid fuels to generate energy for the process uses.

The wet biomass residue from the pressure filter are dried to further reduce its moisture

content for combustion. The energy required for lignin drying must consider not only the total

lignin mass, but also its water content to account for the heat of vaporization, as shown by the

following equation.

𝐸𝑙𝑖𝑔𝑛𝑖𝑛 = 𝑀𝑤𝑙 × 𝑊 × [(𝐶𝑝 ‒ 𝑤𝑎𝑡𝑒𝑟 × Δ𝑇) + Δ𝐻𝑣] + [𝑀𝑤𝑙 × (1 – 𝑊)] × (𝐶𝑝 ‒ 𝑙𝑖𝑔𝑛𝑖𝑛 × Δ𝑇) (4)

Here, Elignin is the total energy to dry the dewatered lignin, Mwl is the total mass of wet lignin

after dewatering (kg), W is the percentage of water in lignin, ΔHv is the latent heat of water at
7
75°C (2321.37 kJ/kg), Cp-water is the specific heat capacity of water (4.19 kJ/kg-°C), Cp-lignin is the

specific heat capacity of solid lignin (1.10 kJ/kg-°C) 14, and ΔT is the temperature difference

between the initial biomass residue temperature (50°C ) and the drying temperature (75°C).

4 Fungal lipid fermentation

Our previous experimental data of the M. isabellina from the flask and fermentor cultures

on the combined hydrolysate were used to carry out the mass and energy balance for the fungal

lipid fermentation 4. A fungal cell mass concentration of 17.2 g/L, comprised of 29.7% lipid was

reported under a carbon:nitrogen ratio (mol:mol) of 65.3 from a 96-hour batch culture. This

equates to a lipid yield of 0.069 g-lipid/g-corn stover.

Energy consumption is a major consideration in aerobic fermentation systems. Many

components can affect the final power consumption such as agitation, air compression, and

refrigeration. Identifying the operating conditions and unit operations is a key step towards

accurately accounting for all energy inputs. Due to the fact that the M. isabellina fermentation is

exothermic, the reaction heat needs to be removed to maintain the fermentation temperature

(25°C). The oxygen uptake rate for the fungus is 1.0 mol oxygen/kg dry fungal biomass/hr. Since

the amount of energy released from the consumption of one mole oxygen for aerobic cultures is

460 kJ/mol oxygen consumed 8, the reaction heat generated during the fermentation can be

calculated by multiplying oxygen uptake and energy release per mol oxygen consumption.

Centrifugal water-cooled chillers are selected to cool the fermentation broth.

Considering the fact that industrial fermenters for aerobic cultivation are typically in the

range of 100 to 250 m3 15, 200 m3 in effective volume (5.0 meter in diameter and 10.0 meter in

height) is selected as the fermenter size for fungal lipid accumulation. The fermenters are
8
continuously stirred with air sparged through the fermentation broth. The aeration rate is 1 m3

air/m3 broth/minute. The culture time is 96 hours. Energy input for the fermentation, largely

electricity for agitation, air compression, and cooling, is calculated as follows 16.

𝑃𝑔 𝑃𝑐
𝑃= + + 𝑃𝑟
𝜂𝑔 𝜂𝐶 (5)

Where Pg, Pc, Pr and P are required agitation energy (W), compressed energy (W), cooling

energy (W) and total electrical power (W), respectively. ηg and ηC are the global efficiencies for

agitation and compression, respectively. Compressed power is described by the following

equations.

𝑃𝑐 = 𝛼1𝑄 (6)

𝛾‒1
𝑃1
𝛼1 =
𝛾
𝛾‒1
𝑃0 [
𝑃0 () 𝛾
‒ 1]
(7)

Where Q is the air volumetric flow (m3/s), α1 is the coefficient described by equation 7, P0 is the

atmospheric pressure (N/m2), P1 is the compressor outlet pressure (N/m2), and γ = 1.4 for air

compression. Agitation power (Pg) is described by equation 8 below.

7.32𝑄𝑃0

(
𝑃𝑔 = 0.90 + 2.1 𝑒
𝑃2
) 𝑁𝑃𝜌𝑁3𝐷5
(8)

9
Where Np is the un-aerated power number, ρ is the fluid density (kg/m3), N is the agitation speed

(revolutions/s), P2 is the pressure at the bottom of the vessel (N/m2), and D is the agitator

diameter (m) 16.

The chiller efficiency is assumed at 0.6 kW/ton (defined as kW electricity needed to

remove a ton of cooling water that is equivalent to 12,661 kJ per hour). The electricity demand

for cooling the fermenters can then be calculated using heat of the fermentation reaction and

chiller efficiency (Supplemental material). Values for each parameter are listed in Table S1.

After the fermentation, the fungal biomass is harvested and dewatered by a pressure filter

again. The unit energy consumption of the pressure filter is also set at 309.64 kJ/kg dry fungal

biomass residue.

5 Fungal biomass drying

The moisture content of the wet fungal biomass after the dewatering is 75%. Fungal

biomass needs to be dried for the following process steps. The drying temperature is 100°C,

corresponding to similar conditions used in yeast spray drying, while the incoming biomass

temperature is 25°C. Energy to dry the wet fungal biomass can similarly be calculated using

equation 4 with the following changes. Mwl is replaced by the total weight of wet fungal mass

(Mf), Cp-lignin is replaced with specific heat capacity of dry fungal cells (Cp-f), Hv is 2,244 kJ/kg at

100°C, and ΔT is 75°C. The specific heat capacity for fungal biomass (Cp-f) was calculated based

on the composition of the dry cell mass shown in equation 9 17.

10
𝐶𝑝 ‒ = 1.424 × 𝑋ℎ + 1.549 × 𝑋𝑝 + 1.675 × 𝑋𝑓 + 0.837 × 𝑋𝑎
𝑓 (9)

Here X is the mass fraction, and the subscripts h, p, f, and a, represent carbohydrate (0.43),

protein (0.22), fat (0.30), and ash (0.05), respectively. The coefficients represent the specific heat

capacity for each mass fraction and are expressed in units of kJ/kg-°C 17. Therefore, the

calculated Cp-f is 1.50 kJ/kg-°C.

6 Lipid extraction and transesterification

Different from other oleaginous microbes (i.e., yeasts), our experiments demonstrate that

the lipids in M. isabellina can be extracted without mechanical disruption of its cell membrane.

Hexane has shown to be an effective method to extract fungal lipids directly from dried fungal

cells. Therefore, lipid extraction is modeled using a soybean oil extraction processes without

additional or specialized equipment 18. Mass and energy data regarding fungal lipid extraction

and transesterification were based on the U.S. Soybean Board’s 2010 life cycle analysis study 19.

Consistent with industry-wide practices for soybean biodiesel production, extracted oil is

converted to biodiesel through an alkali catalyzed transesterification process. 0.12 kg of glycerol

co-product is produced for every 1 kg of biodiesel processed. Glycerol possesses a relatively

large LHV of 16 MJ/kg, and therefore it is assumed to be combusted to produce heat in this

study.

11
7 Wastewater treatment

Fermentation effluent after fungal cell harvest is treated by a combined anaerobic

digestion, aerobic treatment, and reverse osmosis (RO) process to extract more energy out of the

remaining organic matter, and recycle the water back to the process. Anaerobic digestion (AD)

first utilizes the organic matter in the effluent to produce methane biogas as an energy by-

product and prepare the effluent with less nutrient content for the following aerobic treatment. A

continuously stirred digester operating at 35°C is assumed to carry out the anaerobic digestion.

The fermentation effluent has a chemical oxygen demand (COD) of 35 g/L. The COD reduction

of 80% is set for the digestion. Energy usage by the AD system includes electricity for mixing

the digestate, as well as heat necessary for raising the fermentation effluent to the desired

temperature. The electricity energy is assumed at 2% of the thermal energy produced by methane

combustion, and the heat demand for heating the reactor will follow equation 1, with Cp of 4.187

kJ/kg-°C and ΔT of 10°C. Total methane production is based on a measured yield of 0.25 kg-

CH4/kg-COD destroyed. The effluent after being treated anaerobically with a COD of 7 g/L then

undergoes an aerobic treatment. The required energy input is calculated based on an energy

consumption of 0.317 kWh/m3 for the effluent with a COD concentration of 500 mg/L 20. The

effluent from aerobic wastewater treatment process still has 1.7% Na2SO4. A RO and hydrated

lime treatment are then implemented to simultaneously produce reclaimed water and

concentrated NaOH solution for the pretreatment uses, and improve the process efficiency. The

RO unit with 80% recovery of the feed water can convert 1 kg reclaimed water into 0.8 kg pure

water and 0.2 kg brine solution. The hydrated lime is then applied on the brine solution to

generate CaSO4 and concentrated NaOH solution. CaSO4 is settled and removed from the

12
solution. The concentrated NaOH could be re-used as alkali in the pretreatment. The energy

consumption for the RO and lime treatment is 3.35 kwh/m3 reclaimed water 21.

8 Combined solar and biological power generation

Two solar technologies, photovoltaics (PV) and concentrated solar power (CSP), were

investigated to be combined with lignin, glycerol, and methane combustion to generate the

power to satisfy the energy needs of the system. Since the power generation principles of PV and

CSP are different, PV-biological power and CSP-biological power were compared to delineate

the effects of different solar technologies on the energy balance of the sustainable lignocellulosic

biodiesel production system.

The PV-biological power generation includes an amorphous silicon (a-Si:H) thin film PV

unit and lignin/methane/glycerol combustion unit (Fig 2a). The PV module is for the electricity

generation only. The a-Si:H thin film PV is selected because of its low temperature coefficient

(0.1% /°C) that allows the PV unit to be operated at a wide range of temperatures without

substantial power loss 22. The electricity generated from the PV module is used to mainly power

the unit operations in the lignocellulosic biodiesel production. The lignin/methane/glycerol

combustion unit (boilers) is dedicated to generate thermal energy for the heat demand of the

lignocellulosic biodiesel production. The PV-biological power generation has advantages of

direct electricity generation and high utilization efficiencies of electricity and heat. The PV

panels need to be 37⁰ tilted at Meade County, Kansas to obtain maximal solar collection. The

average solar radiation available to be extracted by PV is 18 MJ/m2/day at Meade County 23, 24.

The electricity conversion efficiency (from solar radiation to alternative current) of the thin film

PV is 12%. The thermal efficiencies of boilers for lignin/methane combustion are set at 95%.
13
The parasitic load for the PV-biological power generation was set at 5% of the energy output of

the power generation, which refers to the energy used to power pumps and fans for the

lignin/methane/glycerol combustion of thermal energy production 25. The parasitic load is

assumed 100% from the PV.

Parabolic trough technology is currently a proven commercial CSP technology on the

market 26. The parabolic trough solar system is capable of concentrating solar energy to generate

steam up to 400°C 26. The CSP-biological power generation uses a parabolic solar trough power

technology to integrate with lignin/glycerol/methane combustion to generate power (electricity

and heat) for the process uses (Fig. 2b). The CSP-biological power generation includes parabolic

solar trough receiver, boilers, and steam turbine cogeneration. Combining solar thermal energy

with lignin/glycerol/methane combustion has advantages of solving unsteady energy flow issues

of solar radiation (using lignin/methane/glycerol combustion during the period without solar

radiation) and alleviating the demand of large solar thermal storage. Meade, KS was again the

location for the studied system. The parabolic trough receivers were one-axis tracing parabolic

troughs with horizontal north-south axis. The mirror facet uses aluminum skins with a cardboard

honeycomb core and 3M’s EPC-305+ polymeric reflector 26. The average solar radiation

available to be extracted by the parabolic trough receiver is 18 MJ/m2/day at Meade County,

Kansas 23. Solar-radiation-to-steam thermal efficiency (considering radiation and convection

receiver losses, piping and storage thermal losses, and heat-medium to steam thermal losses) was

assumed to be 70%. The thermal efficiency of the boilers was set at 95%. The electricity and

thermal efficiency of the steam turbine cogeneration were 25% and 60%, respectively. The

parasitic load for the CSP-biological power generation was set at 10% of the energy output of the

power generation, which refers to the energy used by pumps, fans, and the positioning of the
14
parabolic troughs for both CSP and biological power generation 27. The parasitic load is also

100% from the CSP.

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16
Table S1. Parameters of reactors for pretreatment, enzymatic hydrolysis, and aerobic fungal
fermentation at an industrial scale of 200 m3
Parameters Value Unit
Pretreatment reactor (200 m ) 3 a

Np (power number for propeller) 0.35 -


D (Agitator diameter) 1.65 m
ρ (liquid density) 1000 kg/m3
N (agitation speed) b
1.50 rotation/s
ηg (Global efficiency for agitation) 0.70 -
Hydrolysis reactor (200 m ) 3 a

Np (power number for propeller) 0.35 -


D (Agitator diameter) 1.65 m
ρ (liquid density) 1000 kg/m3
N (agitation speed) b
1.50 rotation/s
ηg (Global efficiency for agitation) 0.70 -
Fermentor (200 m ) 3 a

P0 (atmospheric pressure) 1.0 x 105 N/m2


P1 (Compressor exit pressure) 3.0 x 105 N/m2
P2 (Pressure at the bottom of the fermentor) 2.5 x 105 N/m2
Np (power number for propeller) 0.35 -
D (Agitator diameter) 1.65 m
ρ (liquid density) 1000 kg/m3
N (agitation speed)c 3 rotation/s
Q (air flow) d 3.34 m3/s
ηg (Global efficiency for agitation) 0.70 -
ηc (Global efficiency for compressor) 0.50 -
Chiller efficiency 0.60 kW/ton
Heat released per mole oxygen consumed during the kJ/mol O2
460
fungal fermentation consumed
a. The geometry of the reactors is 5 meter in diameter and 12 meter in height. The height for 200 m3
effective volume is at 10 meter. The impeller is propeller.
b. The agitation speed for pretreatment and hydrolysis reactors is 90 rpm.
c. The agitation speed for fermenters is 180 rpm.
d. The air flow is 1 vvm.

17

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