Sulphonated MIL-101(Cr): Microwave responsive catalyst for ...
Transcript of Sulphonated MIL-101(Cr): Microwave responsive catalyst for ...
Sulphonated MIL-101(Cr): Microwave responsive catalyst for fructose dehydration into platform chemicals
Nour Aljammal 1,2, Bert Biesemans1 , Jeroen Lauwaert3, Francis Verpoort2,4,5 , Philippe M. Heynderickx2,5, Joris W. Thybaut1
JICHEC09
1Laboratory for Chemical Technology, Ghent University2 Department of Green Chemistry and Technology, Faculty of Bioscince Engineering , Ghent University3 Industrial Catalysis and Adsorption Technology (INCAT), Department of Materials, Textiles, and Chemical Engineering, Ghent University4 Department of Organometallics, Catalysis, and Ordered Materials, Wuhan University of Technology, Wuhan, China5Center for Environmental and Energy Research (CEER), Ghent University Global Campus, South Korea
Biomass is our only renewable source of carbon-based fuels & chemicals
3/20
ConversionProcesses
– Trees – Agricultural Crops– Agricultural Residues– Forest Residues– Animal Wastes– Municipal Solid Waste
PRODUCTS
Fuels:– Ethanol– Renewable Diesel – Renewable Gasoline– Hydrogen
Power:– Electricity– Heat (co-generation)
Chemicals– Plastics– Solvents– Chemical Intermediates– Phenolics– Adhesives– Furfural– Fatty acids– Acetic Acid– Carbon black– Paints– Dyes, Pigments, and Ink
Food, Feed and Fiber
- Enzymatic Fermentation- Gas/liquid Fermentation- Acid Hydrolysis/Fermentation- Catalytic Dehydration, Hydration, Oxidation,
Reduction, Etherification- Gasification- Pyrolysis- Combustion- Co-firing
BiomassFeedstock
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Moving towards sustainability
4Zakzeski et al Chem. Rev. 2010, 110, 3552-3599.
• Potential catalyst: metal organic framework
• New technology: microwave reactor
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Research objectives
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The goal of this work is to investigate the potential of microwave irradiation in the conversion of renewable
resources to platform chemicals. The following research questions were formulated:
▪ Which MOFs are used for fructose dehydration?
▪ Can microwave irradiation be applied to intensify fructose dehydration process and what are the advantages
of this technology?
▪ Has the microwave radiation an influence on the Arrhenius parameters rather than traditional heating? Or
How does the microwave relate to the laws of thermodynamics?
Outline
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▪ Introduction
▪ Metal organic framework synthesis
▪ Microwave-assisted reactor vs. conventional reactor
▪ Results
▪ Kinetic modelling
▪ Conclusions
Solvothermal synthesis
• sonciate in high boiling solvent (e.g. DMF)
• heat without stirring for hours/days• centrifuge and filter
Optimization
Reproducibility
➢ temperature➢ order of addition➢ metal source
➢ humidity➢ suspension quality➢ purity of metal salt➢ speed of assembly
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12
Reactor
Catalyst3 ml solvent
HPLC, RID detector, Amnix HPX-87H ion-exclusion
column
Aljammal et al., Applied Organometallic Chemistry (2021): e6419
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Power Mode Power [watt] Time [min]Fructose conv.
[%]
Yield [%] J
mmol·(kJ·L)-1
5-HMF FA LA
Fixed Power 100 30 - trace 0.00 0.00 0.020
Fixed Power 150 30 - 0.55 0.00 0.00 0.024
Fixed Power 200 30 - 0.88 0.00 0.00 0.013
Fixed Power 250 30 - 0.60 0.00 0.00 0.842
Standard power 100-150 30 <99 18.94 3.41 4.41 2.693
Standard power 100-150 5 <99 60.60 14.00 12.99 0.342
Dynamic control 200 30 <99 12.32 trace trace 1.924
Dynamic control 50 30 <99 17.32 2.41 3.71 1.075
Dynamic control 100 30 <99 19.35 1.82 2.96 0.342
Dynamic control 200 30 <99 12.32 trace trace 0.020
Efficiency coefficient (j) =5 − HMF
P. time. v
j : efficiency coefficient in mmol·(KJ·L)−1
P: input power of the microwavet: elapsed time (s)v: volume of the reaction solution
Results
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Results
All reactions were performed in DMSO/Acetone (7:3), 5 min reaction time.
0
20
40
60
80
100
140 150 160 140 150 160 140 150 160 140 150 160 140 150 160 140 150 160 140 150 160
MIL-101 SO₃H MIL-101- NH₂ UiO-66 ZIF-8 (SP) ZIF-8 (MW) ZIF-8 (RT) MOF-5
HMF Yield % FA yield % LA yield%
Efficiency coefficient
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0
0.5
1
1.5
2
2.5
3
3.5
Eff
icie
ny
co
eff
ice
nt
J,m
mo
l·(k
J·L
)−1
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 =5 − 𝐻𝑀𝐹
𝑃. 𝑡𝑖𝑚𝑒. 𝑣
All reactions were performed in DMSO/Acetone (7:3), 5 min reaction time at 160°C.
Effect of – grafting rate of So3H
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Catalyst typeS content (mmol g-1)
Grafting rate
FruConv.(%)
5-HMF yield (%)
FA yield (%)
LA yield (%)
J
mmol·(kJ·L)-1
MIL-101(Cr) - - 98.23 8.89 0.0 0.0 0.026
MIL-101(Cr)-SO3Hb 0.23 2.91 95.63 38.40 0.20 0.56 0.114
MIL-101(Cr)-SO3Hb 0.56 15.32 98.39 54.44 1.72 0.89 0.161
MIL-101(Cr)-SO3Ha 0.91 19.63 < 99 60.60 14.00 12.99 0.228
Conditions: 100 mg fructose, 3ml solvent, (7:3) DMSO/acetone , 5 min at 160 °C
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Solvent Selection
0 20 40 60 80 100
DMSO/Acetone 7:3Water/GVL 9:1
DMSOEthanol
Water
DMSO/Acetone 7:3Water/GVL 9:1
DMSOEthanol
Water
DMSO/Acetone 7:3DMSO
ZIF-
8 M
WM
IL-1
01 S
O₃H
MOF
-5
Fructose conversion % HMF Yield %
Reaction conditions: 100 mg fructose, 30 mg catalyst, and 160 °C.
➢ Environmentally benign solvent such as water and ethanol
➢ High boiling point polar aprotic organic solvents such as dimethyl sulfoxide (DMSO), (DMSO/acetone)
➢ Biphasic systems (γ-valerolactone(GVL)/water).
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Formation of 5-HMF in DMSO solvent system
➢ The ability of DMSO to restrain thehydrolysis of HMF into levulinic and formicacid by bonding with water moleculesproduced from the reaction
Reaction time
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0
20
40
60
80
100
5 10 20 30 40 50
Reaction Time (min)
Reaction time effect on product distribution by MW for fructose dehydration reaction.
All reactions were performed in 3 ml DMSO/Acetone (7:3), R = 0.3, and the results reported are after 5 min, at 160 °C.
■ fructose conversion %■ 5-HMF yield %■ FA yield %■ LA yield %.
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Method of heating
Temp timeFructose conv. %
HMF yield %
MW 160 5 min 95.42 60.7
MW 160 10 min 99.85 95.2
CH 160 5 hr 100 95.3
Reaction conditions: 500 mg fructose, 5 mL DMSO/acetone (7:3) at 160 ⁰C over 30 mg MIL-101 SO₃H
Time reduction
Conventionally heated reactions that once took hours conventionally, can be completed in minutes with laboratory microwave reactors!
Effect of temperature and cat/substrate ratio
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0
10
20
30
40
50
60
70
140 150 160 170 140 150 160 170 140 150 160 170
0.1 cat/sub (mw) 0.03 cat/sub (mw) 0.01 cat/sub (mw)
Yiel
d%
0
10
20
30
40
50
60
70
140 150 160 140 150 160 140 150 160
0.1 cat/sub (CH) 0.03 cat/sub (CH) 0.01 cat/sub (CH)
Yiel
d %
3 ml DMSO/acetone medium (70:30 w/w)
■ 5-HMF, ■ FA ■ LAMW and 5 minutes CH and 60 minutes
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HMF
Sol’n
140
⁰C
150
⁰C
160
⁰C
Reaction conditions: 100 mg fructose, 10 mg catalyst, 3mL DMSO/acetone (7:3)
Humin
Effect of temperature and cat/substrate ratio
Kinetic model construction
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There are four key steps in our kinetic model:
▪ fructose dehydration to form 5-HMF;▪ fructose and 5-HMF reaction to form degradation
products;▪ the reaction of fructose to HMF is pseudo irreversible
and of first order▪ humins can be formed from 5-HMF, fructose and are
soluble in DMOS/Ac
Humins & unidentified decomposition product
C6H12O6 Int. C6H6O3 C5H8O3+ CH2O2
k1 k2 k3
k4
Fructose Intermediate
5-HMF
LA FA
𝑑𝐶𝑓𝑟𝑢
𝑑𝑡= −𝑘1𝐶𝑓𝑟𝑢
𝑑𝐶𝐼𝑛𝑡.𝑑𝑡
= 𝑘1𝐶𝑓𝑟𝑢 − 𝑘2𝐶𝐼𝑛𝑡.
𝑑𝐶5−𝐻𝑀𝐹𝑑𝑡
= 𝑘2𝐶𝐼𝑛𝑡. − 𝑘3𝐶5−𝐻𝑀𝐹 − 𝑘4𝐶5−𝐻𝑀𝐹
𝑑𝐶4𝑑𝑡
= 𝑘3𝐶5−𝐻𝑀𝐹
Parameter Estimation
➢ Estimating all 8/10 parameters at once is viable with 3
responses, fructose dehydration, 5-HMF and LA+FA
formation
➢ Regression is performed in 2 steps
• isothermal regression
• Arrhenius plots → initial estimates for k Tavg
• non-isothermal regression
• two estimation methods were used in succession,
namely, non-linear least squares and Bayesian
estimation.26
Too many parameters (8/10) for the used responses (3)
Multiple local minimum
Difficult to get good initial estimates
𝑘𝑛 = 𝑒∆𝑆𝑛𝑅 × 𝑒
−𝐸
𝑅×
1
𝑇−
1
𝑇𝑎𝑣𝑔 …eq.1
𝑘𝑛 = 𝑒∆𝑆𝑛−∆𝑆𝑚𝑤
𝑅×𝑒
−(𝐸−∆𝐻𝑚𝑤)×
𝑅(1
𝑇−
1
𝑇𝑎𝑣𝑔)…eq.2
Performance profile, 10mgcat, 3ml solvent @160°C
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0
0.1
0.2
0.3
0.4
0.5
0.6
0 10 20 30 40 50 60
Conc
. (m
mol
)Time (min)
MW
fructose
5-HMF
LA+FA
side product
k1,mw 0.80±0.013 s-1
k2,mw 0.25±0.022 s-1
k4,mw 0.07±0.0043 s-1
k3,mw 0.004±0.0074 s-1
■ fructose ■ intermediate ■ 5-HMF ■ LA+FA ■ Humins
0
0.1
0.2
0.3
0.4
0.5
0.6
0 50 100 150 200 250 300
Conc
. (m
mol
)Time (min)
Performance profile, 10mgcat, 3ml solvent @160°C
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CHfructose
5-HMF
LA+FA
side product
k1,CH 0.10±0.013 s-1
k2,CH 0.036±0.0026 s-1
k4,CH 0.0093±0.00036 s-1
k3,CH 0.0005±0.00008 s-1
■ fructose ■ intermediate ■ 5-HMF ■ LA+FA ■ Humins
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𝑘𝑛 = 𝑒∆𝑆𝑛−∆𝑆𝑚𝑤
𝑅×𝑒
ቇ−(𝐸−∆𝐻𝑚𝑤)×
𝑅(1𝑇−
1𝑇𝑎𝑣𝑔
𝑘𝑛 = 𝑒∆𝑆𝑛𝑅 × 𝑒
ቇ−𝐸𝑅×(1𝑇−
1𝑇𝑎𝑣𝑔
Parameter Optimal
estimates
t-values Deviation 95% marginal HPD
intervals∆S1 -18.76∆S2 -28.17 -46.47 0.61 ± 1.20∆S3 -63.78 -43.57 1.46 ± 2.89∆S4 -38.86 -122.43 0.32 ± 0.63
∆SMW -16.77 -42.49 0.39 ± 0.78∆HMW 6.60×105 5.87 1.12×105 ± 2.22×105
∆Hmw is so large that the Ea, app for the MW model become almost zero. Hence, the microwave data appears to be almost independent of the temperature, which isn’t weird as MW reactor able to deliver all necessary energy via the radiation.
Quantification of microwave effect in terms of ∆Smw and ∆Hmw
Conclusion
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➢ Highly acidic MOFs such as MIL-101 and UiO-66 are found to be suitable candidates for fructose dehydration under microwave-assisted reaction conditions in solvents such as DMSO and DMSO/acetone.
➢ MW irradiation can enhance the catalytic performance of an intrinsic catalyst (transition metal oxides). However, MW-responsive catalysts is still at a development stage because few of them can be used effectively.
➢ The catalytic efficiency is positively correlated with the MW radiation time, MW power and catalyst- polar functional group grafting-rate.
➢ The use of microwave energy instead of conventional heating often results in good yields in a short time as compared with reaction by classical synthetic methods
➢ Evidently, the presence of the microwaves makes the entropy more positive by 16.7 J/mol. The high
disposal efficiency and low activation energy suggested that microwave heating would be more promising
than conventional heating for biomass conversion
Thank YouLABORATORY FOR CHEMICAL TECHNOLOGY
Technology 125, 9052 Ghent, Belgium
E [email protected] 003293311757
https://www.lct.ugent.be
Noor Aljammal