Figure 1.
Hybrid catalysis simultaneous process applied to the transformation of glucose to HMF (D-Glc = D-glucose, D-Fru = D-Fructose, HMF = 5-hydroxymethylfurfural).
Figure 1.
Hybrid catalysis simultaneous process applied to the transformation of glucose to HMF (D-Glc = D-glucose, D-Fru = D-Fructose, HMF = 5-hydroxymethylfurfural).
Figure 2.
Methodology from a sequential approach towards an integrated continuous process.
Figure 2.
Methodology from a sequential approach towards an integrated continuous process.
Figure 3.
Relative enzymatic activity of IGI in D-glucose isomerization at pH 7.5 as a function of temperature.
Figure 3.
Relative enzymatic activity of IGI in D-glucose isomerization at pH 7.5 as a function of temperature.
Figure 4.
Relative enzymatic activity of IGI in D-glucose isomerization at 343 K as a function of pH.
Figure 4.
Relative enzymatic activity of IGI in D-glucose isomerization at 343 K as a function of pH.
Figure 5.
D-glucose consumption during the isomerization step as a function of time; (Δ), D-fructose formation (□), D-glucose amount in the blank experiment at pH 8.5 (○). Initial conditions: D-Glucose (100 mM), IGI (0.5 g), Tris-HCl 100 mM, pH 8.5, V = 100 mL, 343 K, 750 rpm.
Figure 5.
D-glucose consumption during the isomerization step as a function of time; (Δ), D-fructose formation (□), D-glucose amount in the blank experiment at pH 8.5 (○). Initial conditions: D-Glucose (100 mM), IGI (0.5 g), Tris-HCl 100 mM, pH 8.5, V = 100 mL, 343 K, 750 rpm.
Figure 6.
Fructoboronate complex formation at the interphase between the first aqueous phase and the organic liquid membrane.
Figure 6.
Fructoboronate complex formation at the interphase between the first aqueous phase and the organic liquid membrane.
Figure 7.
Structures of the arylboronic acids used for extraction of fructose.
Figure 7.
Structures of the arylboronic acids used for extraction of fructose.
Figure 8.
Influence of the arylboronic acid structure on the complexation/transportation process after 45 min. [D-Fructose]i = 100 mM, [Boronic acid] = 100 mM, [Aliquat336®] = 200 mM, Tris HCl 100 mM pH 8.5, MIBK, 343 K, 750 rpm.
Figure 8.
Influence of the arylboronic acid structure on the complexation/transportation process after 45 min. [D-Fructose]i = 100 mM, [Boronic acid] = 100 mM, [Aliquat336®] = 200 mM, Tris HCl 100 mM pH 8.5, MIBK, 343 K, 750 rpm.
Figure 9.
Evolution of [D-fructose] in the aqueous phase as a function of time for different 3,4-DCPBA/Aliquat336® ratios. [D-fructose]i = 100 mM, [3,4-DCPBA] = 100 mM, [Aliquat336®] = X mM (X varies from 0 to 400 mM), Tris-HCl 100 mM pH 8.5, MIBK, 343 K, 750 rpm.
Figure 9.
Evolution of [D-fructose] in the aqueous phase as a function of time for different 3,4-DCPBA/Aliquat336® ratios. [D-fructose]i = 100 mM, [3,4-DCPBA] = 100 mM, [Aliquat336®] = X mM (X varies from 0 to 400 mM), Tris-HCl 100 mM pH 8.5, MIBK, 343 K, 750 rpm.
Figure 10.
Initial extraction rate in aqueous phase (blue rods) and extraction yield (red dots) in function of 3,4-DCPBA:Aliquat336® molar ratio. [D-Fructose]i = 100 mM, [3,4-DCPBA] = 100 mM, [Aliquat336®] = X mM (X varies from 0 to 400 mM), Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Figure 10.
Initial extraction rate in aqueous phase (blue rods) and extraction yield (red dots) in function of 3,4-DCPBA:Aliquat336® molar ratio. [D-Fructose]i = 100 mM, [3,4-DCPBA] = 100 mM, [Aliquat336®] = X mM (X varies from 0 to 400 mM), Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Figure 11.
Evolution of the D-Fructose extraction yield for different 3,4-DCPBA and Aliquat336® concentrations for a 1:2 molar ratio. [D-Fructose]i = 100 mM, [3,4-DCPBA] = Y mM (Y varies from 25 to 300 mM), [Aliquat336®] = Y × 2 mM, Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Figure 11.
Evolution of the D-Fructose extraction yield for different 3,4-DCPBA and Aliquat336® concentrations for a 1:2 molar ratio. [D-Fructose]i = 100 mM, [3,4-DCPBA] = Y mM (Y varies from 25 to 300 mM), [Aliquat336®] = Y × 2 mM, Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Figure 12.
Influence of the initial D-Fructose:3,4-DCPBA molar ratio on the the extraction yield. [D-Fructose]i = X mM, [3,4-DCPBA] = 100 mM, [Aliquat336®] = 200 mM, Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Figure 12.
Influence of the initial D-Fructose:3,4-DCPBA molar ratio on the the extraction yield. [D-Fructose]i = X mM, [3,4-DCPBA] = 100 mM, [Aliquat336®] = 200 mM, Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Figure 13.
Influence of the initial D-Fructose concentration on the amount of D-fructose extracted. [D-Fructose]i = X mM (X varies from 25 to 1000), [3,4-DCPBA] = 100 mM, [Aliquat336®] = 200 mM, Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Figure 13.
Influence of the initial D-Fructose concentration on the amount of D-fructose extracted. [D-Fructose]i = X mM (X varies from 25 to 1000), [3,4-DCPBA] = 100 mM, [Aliquat336®] = 200 mM, Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Figure 14.
Influence of the pH of the aqueous receiving phase on the D-fructose complex transportation. Extraction process: Tris-HCl 100 mM pH 8.5, [D-Fru]i = 100 mM, [3,4-DCPBA] = 100 mM, [Aliquat336®] = 200 mM, MIBK, 343 K. Receiving phase: Citrate buffer 100 mM pH 3 and 5, Tri-HCl pH 8, H2SO4 for pH 1.
Figure 14.
Influence of the pH of the aqueous receiving phase on the D-fructose complex transportation. Extraction process: Tris-HCl 100 mM pH 8.5, [D-Fru]i = 100 mM, [3,4-DCPBA] = 100 mM, [Aliquat336®] = 200 mM, MIBK, 343 K. Receiving phase: Citrate buffer 100 mM pH 3 and 5, Tri-HCl pH 8, H2SO4 for pH 1.
Figure 15.
Illustration of the sequential process with isomerization and complexation/transportation step, hydrolysis/release step and dehydration step.
Figure 15.
Illustration of the sequential process with isomerization and complexation/transportation step, hydrolysis/release step and dehydration step.
Figure 16.
Illustration of the continuous process.
Figure 16.
Illustration of the continuous process.
Table 1.
Influence of the boronic acid structure on the extraction yield and rate.
Table 1.
Influence of the boronic acid structure on the extraction yield and rate.
Boronic Acid | pKa | Extraction Yield % | Extraction Rate μmol/min |
---|
4-TBPBA | 9.3 | 8.3 | ± 5.6 | 0.52 | ± 0.08 |
PBA | 9.1 | 32.4 | ± 0.3 | 1.27 | ± 0.39 |
2,4-DCPBA | 8.9 | 43.3 | ± 1.6 | 1.56 | ± 0.34 |
3,4-DCPBA | 7.4 | 46.5 | ± 4.9 | 1.48 | ± 0.23 |
2,3-DCPBA | 7.4 | 49,2 | ± 1.6 | 1.99 | ± 0.17 |
4-TFMPBA | 9.1 | 50.3 | ± 2.2 | 1.26 | ± 0.12 |
3,5-DCPBA | 7.4 | 55.3 | ± 0.9 | 1.94 | ± 0.20 |
Table 2.
Initial extraction rates for various concentrations in the system. [D-Fructose]i = 100 mM, [3,4-DCPBA] = Y mM (Y varies from 25 to 300 mM), [Aliquat336®] = Yx2 mM, Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
Table 2.
Initial extraction rates for various concentrations in the system. [D-Fructose]i = 100 mM, [3,4-DCPBA] = Y mM (Y varies from 25 to 300 mM), [Aliquat336®] = Yx2 mM, Tris-HCl 100 mM, pH 8.5, MIBK, 343 K, 750 rpm.
[3,4-DCPBA] | Extraction Rate |
(mM) | (μmol/min) |
25 | 0.89 | ±0.15 |
50 | 1.37 | ±0.41 |
150 | 1.45 | ±0.05 |
100 | 1.22 | ±0.15 |
200 | 1.40 | ±0.21 |
300 | 1.33 | ±0.14 |
Table 3.
D-fructose extraction yield and initial extraction rate for different concentrations.
Table 3.
D-fructose extraction yield and initial extraction rate for different concentrations.
[D-Fru] | [3,4-DCPBA] | [Aliquat336®] | Extraction Yield |
---|
mM | mM | mM | % |
---|
100 | 100 | 200 | 43.3 | ± 4.22 |
200 | 200 | 400 | 32.6 | ± 1.22 |
300 | 300 | 600 | 27.3 | ± 4.6 |
Table 4.
Transport yield and extraction rate of D-fructoboronate hydrolysis to D-fructose and D-fructose release in the aqueous phase as a function of its pH.
Table 4.
Transport yield and extraction rate of D-fructoboronate hydrolysis to D-fructose and D-fructose release in the aqueous phase as a function of its pH.
pH | Transport Yield | Extraction Rate |
---|
| (%) | (μmol/min) |
---|
5 | 100 | ± 4.2 | 1.58 | ± 0.14 |
3 | 91.5 | ± 6.3 | 1.53 | ± 0.13 |
1 | 54.5 | ± 3.7 | 1.84 | ± 0.09 |
8 | 22.7 | ± 5.2 | 0.63 | ± 0.14 |
Table 5.
Results obtained from sequential process. The D-Fructose released yield was calculated using the amount of D-Fructose in the organic phase at the end of the 1st transport. The fructose conversion yield was calculated using the amount of fructose in the aqueous receiving phase at the end of the 2nd transport. The HMF total amount was calculated using the initial amount of glucose in the aqueous donor phase.
Table 5.
Results obtained from sequential process. The D-Fructose released yield was calculated using the amount of D-Fructose in the organic phase at the end of the 1st transport. The fructose conversion yield was calculated using the amount of fructose in the aqueous receiving phase at the end of the 2nd transport. The HMF total amount was calculated using the initial amount of glucose in the aqueous donor phase.
| | 1st step | 2nd step | 3rd step | |
---|
| Isomerization | D-Fructose Extracted | D-Glucose Extracted | D-Fructose Released | Fructose Conversion | HMF Yield | HMF Total |
% | 74.5 | 56.5 | 1.56 | 57.4 | 52 | 21.9 | 5.3 |
time | 3 h | 3 h | 35 h | 41 h |
Table 6.
Results obtained by continuous process.
Table 6.
Results obtained by continuous process.
| Isomerization | Fructose Extraction | HMF | Selectivity |
---|
Yield (%) | 70.1 | 50.2 | 4.1 | 70.4 |