The Application of the Nanofiltration Membrane NF270 for Separation of Fermentation Broths
Abstract
:1. Introduction
2. Materials and Methods
2.1. Feed Solution
2.2. NF Set-Up
- (i)
- Sepa-CFII plate membrane module manufactured by GE Osmonics (Minnetonka, MN, USA) with the membrane active area equal to 0.015 m2; the channel in the module was filled with polypropylene net-spacer (50 mesh),
- (ii)
- 3CP Stainless Steel Plunger Pump model 3CP1221 (CAT PUMPS, Hampshire, England),
- (iii)
- feed tank (volume 5 L),
- (iv)
- cooling bath (thermostatic Grundfos valve).
2.3. Experimental Protocol
2.4. Analytical Methods
3. Results and Discussion
3.1. Membrane Performance
3.2. Separation of Organic Compounds
3.2.1. 1,3-Propanediol and Glycerol
3.2.2. Carboxylic Acids and Ethanol
- (i)
- The highest rejection of succinic acid is related to the fact that it is a diprotic acid, hence, its separation was based on much stronger electrostatic interactions than in the cases of monoprotic acid (lactic, acetic, and formic acids).
- (ii)
- The Stokes radius and MW of charged acids ions: formate, acetate, lactate, and succinate are 0.200 nm and 45.01 g/mol, 0.225 nm and 59.04 g/mol, 0.230 nm and 89.07 g/mol, 0.255 nm and 116.07 g/mol, respectively. It indicates that the highest size ions were retained to a greater extent by the membrane, while the ions with the smallest size were characterized by the lowest retention. This finding indicated that the organic acids retention was based not only on the Donnan exclusion but also on the sieve mechanism.
- (iii)
- For anions with a larger radius, the charge center is farther from the surface and consequently, the electrostatic interactions between anions and negatively charged membrane surface are weaker [38].
- (iv)
- The diffusion coefficients of charged acids ions: formate, acetate, lactate, and succinate are 0.99·10−9, 1.06 10−9, 1.38·10−9, and 1.84 10−9 m/s2, respectively. Therefore, it can be indicated that the above-presented order of diffusion coefficients is inversely reflected in the rejection sequence. Indeed, ions characterized by the highest diffusion coefficient more easily flow through the membrane.
3.3. Separation of Ions
3.3.1. Anions
- (i)
- The rejection of divalent SO42− and trivalent PO43− anions was higher than that of monovalent ions Cl− due to the fact that they are characterized by higher charge density. This observation indicates that the Donnan effect was the key mechanism of the separation of anions present in 1,3-PD fermentation broths.
- (ii)
- The Stokes radius and MW of anions: Cl-, NO3−, PO43− and SO42− are 0.332 nm and 35.45 g/mol, 0.335 nm and 62 g/mol, 0.339 nm and 94.97 g/mol, 0.379 nm and 96.06 g/mol, respectively. It indicates that the highest retention was obtained for anions that present the highest both radius and MW. Therefore, it can be concluded that the steric hindrance effects also played a significant role in the anion’s separation. It is confirmed by the fact that for anions Cl−, negative retention has been reported.
- (iii)
- In the case of ions with a larger radius, the charge center is at a greater distance from the surface and consequently, the electrostatic interactions between ions and the negative membrane surface are weaker [38].
- (iv)
- In light of dielectric exclusion theory, ions Cl− have significantly lower hydration-free energy than PO43− and SO42−, hence, they can easily reduce the number of water molecules in the hydration shell:
3.3.2. Cations
- (i)
- The rejection of divalent cation Ca2+ was higher than that of monovalent ones NH4+, K+, and Na+, which can be attributed to the fact that Ca2+ is characterized by higher charge density. This result indicates the key role of the Donnan effect during the separation of cations present in 1,3-PD fermentation broths.
- (ii)
- The Stokes radius of cations: NH4+, K+, Na+, and Ca2+ are 0.331 nm, 0.331 nm, 0.358 nm, and 0.412 nm, respectively. It indicates that the highest retention was obtained for cations characterized by the highest hydrated radius. Therefore, it can be concluded that the steric hindrance effects also played a significant role in the cations separation. It is confirmed by the fact that the same retention degree (59%) has been noted for cations (NH4+ and K+) with the same hydrated radius (0.331 nm). It is necessary to mention that no effect of MW on the retention was recorded, which indicates that with regard to cations separation, the hydrated radius is a more significant parameter.
- (iii)
- The diffusion coefficients of cations: NH4+, K+, Na+, and Ca2+ are equal to 1.95·10−9, 1.96·10−9, 1.33·10−9, and 0.97·10−9 m2/s respectively, thus, they are inversely reflected in the rejection sequence. It confirms the thesis that cations with higher diffusion coefficients easily passed through the membrane.
- (iv)
- (The lowest energy hydration, equal to −326 and −295 kJ/mol, have been reported for NH4+ and K+, respectively, hence, they can easily reduce the number of water molecules in the hydration shell (Equation (14)) and consequently, flow easily through the membrane. In turn, multivalent cations such as Ca2+ require more energy to lose their hydration shells, so their flow through the membrane was difficult [38].
4. Conclusions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Name | Formula | Molecular Weight MW [Da] | Concentration [g/L] | Dissociation Constant pKa [-] | Charge at pH = 7 | Diffusion Coefficient D [10−9 m2/s] | Stokes Radius rS/Hydrated Radius rH [nm] | Hydration Free Energy Eh [kJ/mol] | Shape |
---|---|---|---|---|---|---|---|---|---|
glycerol | C3H8O3 | 92.09 | 0.25–0.28 | 14.40 | neutral | 0.95 [67,68] | rS = 0.258 [67,68] | NI | tetrahedral |
1,3-propanediol | C3H8O2 | 76.09 | 12.21–13.45 | 14.46 | neutral | NI | NI | NI | NI |
formic acid | CH2O2 | 46.05 | 2.10–2.31 | 3.84 | negative | formate: 1.84 [69] | formate: rS = 0.200 [69] | formate: −347.95 [17] | trigonal and tetrahedral |
acetic acid | C2H4O2 | 60.05 | 4.25–4.67 | 4.76 | negative | acetate: 1.38 [69] | acetate: rS = 0.225 [70] | acetate: −328.94 [17] | tetrahedral |
lactic acid | C3H6O3 | 90.08 | 0.59–1.41 | 3.08 | negative | lactate: 1.06 [71] | lactate: rS = 0.230 [71] | lactate: NI | tetrahedral |
succinic acid | C4H6O4 | 118.08 | 1.14–1.39 | 4.21 and 5.64 | negative | succinate: 0.99 [69] | succinate: rS = 0.252 | succinate: NI | NI |
ethanol | C2H6O | 46.10 | 0.89–1.26 | 15.90 | neutral | 1.24 [67] | rS = 0.198 [67] | NI | tetrahedral |
chloride | Cl− | 35.45 | 0.026–0.041 | - | negative | 2.03 [72,73,74] | rH = 0.332 [75] | −340 [76] | spherical |
nitrate | NO3− | 62.00 | 0.002 | - | negative | 1.90 [73,74] | rH = 0.335 [75] | −300 [76] | trigonal |
phosphate | PO43− | 94.97 | 1.926–2.268 | - | negative | 0.61 [74] | rH = 0.339 [77] | −2765 [76] | tetrahedral |
sulfate | SO42− | 96.06 | 1.333–1.536 | - | negative | 1.07 [72,73,74] | rH = 0.379 [75] | −1080 [76] | tetrahedral |
ammonium | NH4+ | 18.04 | 0.448–0.545 | - | positive | 1.95 [73] | rH = 0.331 [75] | −326 [36] | tetrahedral |
sodium | Na+ | 22.99 | 4.451–4.527 | - | positive | 1.33 [72,73,74] | rH = 0.358 [75] | −365 [76] | spherical |
magnesium | Mg2+ | 24.31 | 0.003–0.010 | - | positive | 0.71 [72,73,74] | rH = 0.428 [75] | −1830 [76] | spherical |
potassium | K+ | 39.10 | 1.117–1.499 | - | positive | 1.96 [72,73] | rH = 0.331 [75] | −295 [76] | spherical |
calcium | Ca2+ | 40.08 | 0.011–0.047 | - | positive | 0.79 [72,74] | rH = 0.412 [75] | −1505 [76] | spherical |
Parameter | Unit | Value |
---|---|---|
Manufacturer | [-] | DOW-Filmtec |
Skin-layer material | [-] | polyamide |
Molecular weight cut-off | [Da] | 200–300 |
Average pore radius | [nm] | 0.43 |
MgSO4 rejection | [%] | 97 |
NaCl rejection | [%] | 50 |
Contact angle | [°] | 54.8 |
Maximal pressure | [MPa] | 4.1 |
Maximal temperature | [°C] | 45 |
pH range | [-] | 2–11 |
Isoelectric point | [-] | 4 |
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Tomczak, W. The Application of the Nanofiltration Membrane NF270 for Separation of Fermentation Broths. Membranes 2022, 12, 1263. https://doi.org/10.3390/membranes12121263
Tomczak W. The Application of the Nanofiltration Membrane NF270 for Separation of Fermentation Broths. Membranes. 2022; 12(12):1263. https://doi.org/10.3390/membranes12121263
Chicago/Turabian StyleTomczak, Wirginia. 2022. "The Application of the Nanofiltration Membrane NF270 for Separation of Fermentation Broths" Membranes 12, no. 12: 1263. https://doi.org/10.3390/membranes12121263