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

3

Moving towards sustainability

4Zakzeski et al Chem. Rev. 2010, 110, 3552-3599.

• Potential catalyst: metal organic framework

• New technology: microwave reactor

4

Research objectives

5

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

6

▪ Introduction

▪ Metal organic framework synthesis

▪ Microwave-assisted reactor vs. conventional reactor

▪ Results

▪ Kinetic modelling

▪ Conclusions

7

What are metal-organic frameworks?

8

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

9

UiO-66

[Zr6O4(OH)4]

Synthesized MOFs

1,4-benzodicarboxylic acid struts.

10

11

UiO-66-SO3H MOF-5 ZIF-8 MOF-808

MIL-101(Cr)

MIL-101(Cr) -SO3H

12

Reactor

Catalyst3 ml solvent

HPLC, RID detector, Amnix HPX-87H ion-exclusion

column

Aljammal et al., Applied Organometallic Chemistry (2021): e6419

13

Conventional vs. Microwave reactor

14

Reaction Mechanism

15

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

16

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

17

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

18

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

19

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).

20

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

21

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 %.

22

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

23

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

24

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

25

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

27

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

28

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

29

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

30

➢ 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 nour.aljammal@ugent.beT 003293311757

https://www.lct.ugent.be

Noor Aljammal