Electronic Supplementary Material
Parametric Catalytic Study on the Production of
Renewable Fuels and Chemicals from Phospholipidcontaining Biomass
Emmanuel D. Revellame, William E. Holmes, Tracy J. Benson, Allison L. Forks, W. Todd French and Rafael
Hernandez
S1. Experimental Procedure for Phospholipid Cracking on Quatra C
The Quatra C is a reactor/analyzer device, which uses small amounts of catalyst, usually 5-25
mg, and ~1 mg reactant for each experimental run. A typical reaction sequence began with the loading
of catalyst into a glass tube using silanized glass wool to hold the catalyst in place. The catalyst tube was
then loaded into the reaction zone of the Quatra C and the temperature was raised to the desired
reaction temperature. Air and water were monitored using the mass spectrometer (MS), and reactions
were not initialized until the air and water were less than 5 amu and 5% (H2O+/H2O amu), respectively.
These parameters were chosen based on typical operating conditions for a mass spectrometer to
prevent damage to the ionizing filament, which also coincided with the prevention of an oxidative
reaction environment. Reactions were performed by injection of the reactant into the injection port.
The Quatra C utilizes a solid-sampling injection port that can be temperature programmed. The reactant
was weighed into glass micro-vial and then loaded into the solid sampler. The injector was then closed
and the temperature was raised to volatize the reactant. Helium carrier gas was used to transport the
volatilized material into the reactor.
The temperature profile for the GC oven started at 0°C for 5 minutes, ramped to 60°C at
5°C/minute, then to 300°C at 8°C/minute and finally held for 12 minutes. Liquid CO2 was used to achieve
the low temperatures inside the GC oven. The segmentation parameters on the MS were set to scan at
10-80 m/z for the first 10 minutes and then scan at 50-400 m/z for the remainder of the
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chromatographic run. Scanning of lower mass ranges during the initial phase of the analysis enabled
maximum sensitivity for early eluting lower molecular weight compounds (see Figure S1).
C16:0 FA
H+ZSM-5
C16 :0 FA
C18:1 FA
C18:1 FA
Aromatics
Aromatics
Figure S1. Typical total ion chromatograms from GC/MS for cracking of phosphatidylglycerol on H+ZSM5.
S2. Minimum Fluidization and Terminal Velocities
The properties of freeze-dried activated sludge and catalysts, which were necessary for
calculations of fluidized-bed operating parameters, were estimated. Bulk density determination was
conducted by measuring the volume of a sample with known mass. Volume measurement was done
using a graduated cylinder. Particle density was determined by water displacement method. For
activated sludge, property estimations were conducted using the sample with lower moisture content
alone. This was due to possible effect of sample moisture content on the properties being estimated.
Since both samples were from the same batch of sludge, it was assumed that their properties are almost
identical. The estimated properties of activated sludge and catalysts used in this study are presented in
Table S1.
Table S1. Estimated properties of activated sludge and catalysts.
Property
Activated
Sludge
H+ZSM5
Average particle diameter, dp (μm)
223
137
Bulk density, ρb (mg/cm3)
304.6
322.8
Particle density, ρp (mg/cm3)
1554.1
2482.5
2
The properties (i.e. density and viscosity) of He at different temperature and pressure were
calculated based on the equations proposed by Petersen [1] and are given in Equations 1 and 2 for
density and viscosity, respectively.
−1
𝜌𝑓 = 0.17623
𝑃
(𝑇⁄𝑇 )
[1 + 0.53 × 10
−3
𝑃
(𝑇⁄𝑇 )
𝑜
1.2
(kg/m3)
]
Equation 1
𝑜
𝑇 0.7
𝜇 = 1.865 × 10−5 (𝑇 )
𝑜
(kg/m-s)
Equation 2
Minimum fluidization velocity, umf for each material was calculated based on Ergun equation
(Equation 3) applied at the minimum or incipient fluidization [2]. Since reactions in this study were
performed at elevated temperature and slightly above atmospheric pressures, the effect of these
conditions were evaluated using a rearrangement of Equation 3 given by Rowe (1984) as cited by Yates
(2003) [3] (Equation 4).
150𝜇𝑢𝑚𝑓 (1−𝜀𝑚𝑓 )
2
𝜙 2 𝑑𝑝
3
𝜀𝑚𝑓
𝑢𝑚𝑓 = 42.9 𝜌
+
2
1.75𝜌𝑓 𝑢𝑚𝑓
1
3
𝜙𝑑𝑝
𝜀𝑚𝑓
= 𝑔(𝜌𝑝 − 𝜌𝑓 )
𝜇
(1 − 𝜀𝑚𝑓 ) {[1 +
𝑓 𝑑𝑝
3.0 × 10−4
Equation 3
3
𝜀𝑚𝑓
1/2
2 𝐺𝑎]
(1−𝜀𝑚𝑓 )
− 1}
Equation 4
where;
𝐺𝑎 =
3 𝜌 (𝜌 −𝜌 )𝑔
𝑑𝑝
𝑓 𝑝
𝑓
𝜇2
Equation 5
Equation 4 is independent of sphericity, ϕ, thus, preliminary fluidization experiment was
conducted to determine the experimental umf at ambient conditions. A glass column with similar
dimensions as the actual reactor was used for this experiment. This was done to estimate the bed
voidage at incipient fluidization, εmf. Using the experimental umf and with the aid of Equation 4, the εmf of
3
the system was calculated to be equal to 0.33. This value, which was thought to have shape factor
associated with it, was taken as the εmf for the binary mixture of activated sludge and H+ZSM5 and was
assumed independent of composition, temperature and pressure.
Terminal velocity, ut for all materials was calculated from the Equation 6, which is a function of
an empirical drag coefficient, CD. Consequently, the empirical drag coefficient is a function of Reynolds
number, Re given in Equation 7. It was initially assumed that the Reynolds number at terminal velocity,
Ret would fall within 0.01 < Re ≤ 20. For this range of Re, CD can be calculated from Equation 8 [4].
𝑢𝑡 = [
𝑅𝑒 =
4𝑑𝑝 (𝜌𝑝 −𝜌𝑓 )𝑔
3𝜌𝑓 𝐶𝐷
1/2
]
𝑑𝑝 𝑢𝜌𝑓
𝜇
24
𝐶𝐷 = 𝑅𝑒 [1 + 0.1315𝑅𝑒 (0.82−0.05𝑙𝑜𝑔10 𝑅𝑒) ]
Equation 6
Equation 7
Equation 8
Calculations of minimum fluidization and terminal velocities at different temperature were
initially conducted at atmospheric pressure (see Figure S2). However, preliminary experiments indicated
that pressure could go up to 3 bar during actual reactions. This pressure could be high enough to
significantly affect the minimum fluidization and terminal velocities. According to Knowlton (1999),
pressure greatly affects umf for particle sizes greater than 100 microns [5]. Thus, umf and ut were
calculated at different pressure at 500°C and the results are presented in Figure S3. Terminal velocities
at 500°C and 1-3 bar pressure were calculated from Equations 6 and 8, simultaneously and a Re range of
0.14 – 1.04 was obtained, confirming the initial assumption. Results of these calculations indicated that
the velocity of He could be set between 6.6 to 618.0 mm/s.
4
20
180
Activated sludge
H+ZSM5
Activated sludge
H+ZSM5
150
Velocity, cm/s
Velocity × 101, cm/s
15
10
5
120
90
60
30
0
0
0
100
200
300
400
500
0
100
200
Temperature, °C
300
400
500
Temperature, °C
(a)
(b)
Figure S2. Effect of temperature on (a) minimum fluidization and (b) terminal velocities at 1 bar for activated
sludge and H+ZSM5.
10
120
Activated sludge
H+ZSM5
Activated sludge
Velocity, cm/s
8
Velocity × 101, cm/s
H+ZSM5
100
6
4
2
80
60
40
20
0
0
1
2
3
4
5
1
2
Pressure, bar
(a)
3
4
5
Pressure, bar
(b)
Figure S3. Effect of pressure on (a) minimum fluidization and (b) terminal velocities at 500°C for activated sludge
and H+ZSM5.
These calculations indicated that the umf for the sludge and catalyst at the reaction condition
were 6.60 and 4.08 mm/s, respectively. However, Cheung et al. (1974) suggested that for binary solid
mixtures, Equation 9 should be used to calculate for umf [6]. Based from this equation, the calculated umf
for the mixture of catalyst and sludge with mass ratios of 5 and 10 (catalyst to sludge), were 6.23 and
5.79 mm/s, respectively. Although the velocity could be set to up to 618.0 mm/s, it was set to just above
the umf for better sampling collection (gaseous products) and analysis.
5
𝑢𝑚𝑓,𝑏
𝑢𝑚𝑓 = 𝑢𝑚𝑓,𝑠 (
𝑢𝑚𝑓,𝑠
)
𝑥𝑏2
Equation 9
S3. FCC Product Analyses
Hydrocarbon Analysis (GC-TCD) (Gaseous Products)
The GC oven was programmed at an initial temperature of 30°C for 2 minutes, then ramped to
250°C at 10°C/minute and held for 6 minutes. The injector and detector were at 200°C and 250°C,
respectively for the duration of the analysis.
Permanent Gases Analysis (GC-TCD)
Permanent gases were analyzed using a GC-TCD configured with isolation valve, valve oven, and
purged-packed inlet to which the column was attached for separation. Analysis was conducted
isothermally at 50°C for 10 minutes. Valve oven was set to 150°C and injector and detector were set at
200°C and 250°C, respectively [7]. Gaseous samples were also analyzed on a GC-MS for compound
identity verifications (see Figure S4). The condition of the GC-MS is discussed below.
Liquid Product Analysis (GC-MS)
The GC oven was programmed at 30°C for 3 minutes, ramped to 150°C at 5°C/minute, then to
300°C at 10°C/minute, then to 320°C at 5°C/minute and finally held for 14 minutes. The injector was at
300°C for the duration of the analysis and was operated in split mode with a ratio of 40:1 with a 5 μL
injection volume. The carrier gas was ultra pure grade He and was set at 1 ml/minute programed to 2
ml/min over the duration of the analysis (see Figure S5).
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Figure S4. GC-MS analysis of gaseous product from fluidized-bed catalytic cracking of activated sludge using H+ZSM5.
7
Figure S5. Typical total ion chromatogram from GC-MS analysis of liquid products from fluidized-bed catalytic cracking of activated sludge using H+ZSM5.
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9
S4. Preliminary FCC of Activated Sludge (Effect of Temperature)
250
mg products/g sludge
500C
600C
200
150
100
50
ar
b
C
C
ar
bo
n
o n Di o
M xi d
on e
ox
M i de
et
ha
E t ne
hy
le
n
Et e
ha
C
ne
3
O
C
3 lefin
Pa
ra
f
C
4 fin
O
C
4 lefin
Pa
ra
f
C
5 fin
O
C
5 lefin
Pa
ra
f
C
6 fin
O
A c le
et fin
on
it
B e ril e
nz
e
To ne
lu
e
X y ne
le
ne
s
0
Figure S6. Profiles of gaseous product obtained from fluidized-bed catalytic cracking of activated sludge using
H+ZSM5 at two different temperatures with air as fluidizing gas. Moisture content = 13% (weight). Catalyst to
sludge mass ratio = 10.
Notations
CD
empirical drag coefficient
dp
particle diameter, m
g
acceleration due to gravity, m/s2
Ga
Galileo number
OD
outside diameter
P
pressure, bar
Re
Reynolds number
Ret
Reynolds number at terminal velocity
T
temperature, K
To
absolute temperature, 273.15 K
umf
minimum fluidization velocity, m/s
umf,b
minimum fluidization velocity of bigger
particle, m/s
umf,s
minimum fluidization velocity of smaller
particle, m/s
ut
terminal velocity, m/s
xb2
mass fraction of bigger particle
Greek Symbols
εmf
voidage at minimum fluidization
μ
viscosity, kg/m-s
ρb
bulk density, kg/m3
ρf
fluid density, kg/m3
10
ρp
particle density, kg/m3
ϕ
sphericity
References
1.
Petersen H (1970) The Properties of Helium: Density, Specific Heats, Viscosity, and Thermal Conductivity at
Pressures from 1 to 100 Bar and from Room Temperature to About 1800 K, Danish Atomic Energy
Commission
2.
McCabe WL, Smith JC, Harriott P (1985) Unit Operations of Chemical Engineering, 4th ed. McGraw-Hill
Publishing Company, New York
3.
Yates J (2003) In: Yang W-C (ed) Handbook of Fluidization and Fluid-Particle Systems. Marcel Dekker, Inc.,
New York, Basel, ch 5 pp 129-154
4.
Clift R, Grace JR, Weber ME (1978) Bubbles, Drops, and Particles. Academic Press, New York
5.
Knowlton TM (1999) In: Yang W-C (ed) Fluidization, Solids Handling and Processing. Noyes Publications,
Westwood, NJ, ch 2 pp 111-152
6.
Cheung L, Nienow AW, Rowe PN (1974) Chem Eng Sci 24:1301
7.
Zhou Y, Wang C, Firor R, Analysis of Permanent Gases and Methane with the Agilent 6820 Gas
Chromatograph Agilent Technologies, Inc. (2003).
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