Supporting Information for: Separation in biorefineries by liquid phase adsorption: itaconic acid as case study

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1 Supporting Information for: Separation in biorefineries by liquid phase adsorption: itaconic acid as case study Kai Schute, 1 Chaline Detoni, 1,2 Anna, Kann 1, Oliver Jung 1, Regina Palkovits, 1 * and Marcus Rose 1 * 1 Lehrstuhl für Heterogene Katalyse und Technische Chemie, Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, D Aachen, Germany. 2 Chemistry School, Federal University of Rio de Janeiro, Rio de Janeiro, RJ , Brazil. * Corresponding Author: rose@itmc.rwth-aachen.de, palkovits@itmc.rwth-aachen.de TABLE OF CONTENTS Table S1. Partial pressures (p/p 0 ) values used to calculate micropore and total pore volume and BET specific surface area. Table S2. Composition of fermentation solution of Aspergillus terreus. Table S3. Redlich-Peterson, Langmuir and Freundlich isotherm model constants and correlation coefficients for itaconic acid in single solution. Table S4. Redlich-Peterson, Langmuir and Freundlich isotherm model constants and correlation coefficients for glucose in single solution. Table S5. Redlich-Peterson, Langmuir and Freundlich isotherm model constants and correlation coefficients for itaconic acid in single solution. Table S6. Redlich-Peterson, Langmuir and Freundlich isotherm model constants and correlation coefficients for itaconic acid in multicomponent solution. Table S7. Adsorption values of the continuous study. Figure S1. Adsorption uptakes of a) itaconic acid and b) glucose in competitive adsorption and equilmolar solution (0,25 mmol g sol -1 ) at different temperatures. Figure S2. Coverage of a) HCP and b) A Supra EUR as function of the equilibrium concentration of itaconic acid. Figure S3. Values of R L for the adsorption of glucose in a single solution. S1

2 Figure S4. Coverage of a) HCP and b) A Supra EUR depending on the equilibrium concentration of glucose. Figure S5. Values of R L for the adsorption of itaconic acid to a) HCP and b) A Supra EUR. Figure S6. Coverage of itaconic acid on a) HCP and b) A Supra EUR depending on the equilibrium concentration of itaconic acid. Figure S7. Values of R L for the adsorption of itaconic acid in a multicomponent solution at different temperatures. Figure S8. Coverage of itaconic acid depending on different temperatures. Figure S9. Itaconic acid speciation depending on the ph of the solution.(adapted from [7]). Figure S10. Exemplary chromatogram of a typical itaconic acid/glucose solution S2

3 Table S1. Partial pressure values used and the results of the textural properties. p/p 0 (S BET Rouquerol) p/p 0 (V total ) p/p 0 (V micro ) S BET (m² g -1 ) a V total (cm³ g -1 ) b V micro (cm³ g -1 ) b Supra EUR Darco G SX1G RX3 Extra CBV CBV X NaLSX NaCZF Amberlite HCP a Specific surface area (S BET ) was calculated by the BET isotherm method using Rouquerol plot to determine the accurate relative pressure region. b Total pore volume (V total ) was calculated according to the Gurvich method. The micropore volume (V micro ) was calculated according to the t-plot method. Table S2. Composition of fermentation solution of Aspergillus terreus. ph=2. Compound Concentration (g L -1 ) Glucose 52.7 Potassium 0.03 Phosphate 0.00 Ammonium 0.45 Nitrate 1.60 MgSO 4 7 H 2 O 1.00 CaCl 2 2 H 2 O 5.00 FeCl 3 6 H 2 O ZnSO 4 7 H 2 O CuSO 4 5 H 2 O Itaconic acid S3

4 1. Adsorption models Langmuir adsorption isotherm. The isotherm model of Langmuir based on thermodynamic consideration was originally developed for gas adsorption on activated carbons. This model assumes reversible monolayer adsorption to a defined number of localized surface sites which are all equivalent and have the same affinity. Steric hindrance and lateral interactions between adsorbed molecules are negligible. Constant enthalpy and sorption activation energy for all molecules lead to a homogenous adsorption[3] whereas the energy state of each site is independent of the presence or absence of adsorbed molecules at neighboring sites.[2] The monolayer adsorption is graphically characterized by a plateau which indicates a saturation of the active surface sites as well as the equilibrium.[3] Equation (1) describes the relation between the uptake of adsorbate by the adsorbent and the liquid-phase concentration at equilibrium, where and are the adsorption capacity and the Langmuir constant linking to rate of adsorption, respectively.[3, 4] (1) Equation (2) expresses the characteristic of the Langmuir isotherm model by the dimensionless equilibrium factor, where is liquid-phase initial concentration. Values between zero and one indicate that the adsorption is favorable.[4, 5] (2) As Langmuir predicts monolayer adsorption, the equilibrium coverage describes the degree of adsorption. It is defined as the relation of molecules adsorbed on the surface to the total number of S4

5 available surface sites.[6] Equation (3) is obtained as Langmuir constant relates to the coverage and is the concentration of adsorbate at equilibrium. (3) Freundlich adsorption isotherm. According to experimental variances from the Langmuir isotherm model, the ideal adsorption of monolayering and equal active sites cannot be applied for all adsorptions. Consequently, Freundlich proposes a new model characterized by reversible multilayer adsorption. The surface sites have a wide distribution of adsorption enthalpy and activation energy leading to a heterogeneous surface. The adsorption to the surface sites starts with the occupation of the strongest bonding sites, followed by an exponential decrease and concluding in the completion of adsorption process. Freundlich isotherms are significant for heterogeneous systems especially for organic compounds or strongly interacting species on activated carbons and molecular sieves.[3] Equation (4) illustrates the correlation of and, where and are Freundlich constants. is the Freundlich constant related to adsorption capacity whereas indicates how favorable the adsorption process is. Increasing values of relate to a more heterogeneous system.[4] (4) Redlich-Peterson adsorption isotherm. Redlich-Peterson isotherm model combines the advantages of Langmuir and Freundlich isotherms and is characterized by three parameters. Equation (5) expresses the isotherm model, where, and are Redlich-Peterson constants; values lies between zero and one.[4] In order to determine the adsorption equilibrium for a wide concentration range, the equation has a linear dependence on S5

6 concentration in the numerator and an exponential in the denominator. As a result, the model can be executed for homogenous and heterogeneous systems.[3] (5) In the limit of low concentrations, tends to one and Redlich-Peterson approaches Langmuir isotherm. In terms of high concentrations, Redlich-Peterson isotherm model converge to Freundlich while approximates zero.[3] If is zero, the isotherm is described by Henry s law equation which describes a linear dependence of the uptake and the equilibrium concentration.[4] Thomas-Model for continuous adsorption To model breakthrough curves for the determination of adsorption capacities and macrokinetic information, depending on the flow rate and adsorbent amount, the Thomas-Model is a widely used and broad applicable model. It s mathematical description is given below: (6) The kinetic coefficient K th and the column capacitiy q th can hereby be calculated by plotting c t /c 0 against t and using a non linear regression fit. S6

7 2. Single- solute adsorption isotherms Table S3. Redlich-Peterson, Langmuir and Freundlich isotherm model constants and correlation coefficients for itaconic acid in single solution. HCP A Supra EUR Redlich-Peterson R² [g g ads -1 ] [g mmol -1 ] β Langmuir R² [mmol g -1 ads ] [g mmol -1 ] Freundlich R² [g g -1 ads ] n S7

8 Figure S1. Values of R L for the adsorption of itaconic acid in a single solution. (a) (b) Figure S2: Coverage of a) HCP and b) A Supra EUR as function of the equilibrium concentration of itaconic acid. S8

9 Table S4. Redlich-Peterson, Langmuir and Freundlich isotherm model constants and correlation coefficients for glucose in single solution. HCP A Supra EUR Langmuir R² [mmol g -1 ads ] [g mmol -1 ] Freundlich R² [g g -1 ads ] n [ ] Figure S3. Values of R L for the adsorption of glucose in a single solution. S9

10 (a) (b) Figure S4. Coverage of a) HCP and b) A Supra EUR depending on the equilibrium concentration of glucose. 3. Multicomponent adsorption isotherm for itaconic acid and glucose Table S5. Redlich-Peterson, Langmuir and Freundlich isotherm model constants and correlation coefficients for itaconic acid in single solution. HCP IA A Supra EUR IA HCP G A Supra EUR G Redlich-Peterson R² [g g -1 ads ] [g mmol -1 ] β [ ] Langmuir R² [mmol g -1 ads ] [g mmol -1 ] Freundlich R² [g g -1 ads ] n [ ] S10

11 (a) (b) Figure S5. Values of R L for the adsorption of itaconic acid to a) HCP and b) A Supra EUR. Figure S6. Coverage of itaconic acid on a) HCP and b) A Supra EUR depending on the equilibrium concentration. S11

12 3.1 Influence of temperature on multicomponent isotherm of HCP Table S6. Redlich-Peterson, Langmuir and Freundlich isotherm model constants and correlation coefficients for itaconic acid in multicomponent solution at different temperatures. 20 C 50 C 80 C Redlich-Peterson R² [g g -1 ads ] [g mmol -1 ] β [ ] Langmuir R² [mmol g -1 ads ] [g mmol -1 ] Freundlich R² [g g -1 ads ] n [ ] S12

13 Figure S7. Values of R L for the adsorption of itaconic acid in a multicomponent solution at different temperatures. Figure S8. Coverage of itaconic acid on HCP depending on different temperatures. S13

14 Figure S9. Itaconic acid speciation depending on the ph of the solution.(adapted from [7]). Table S6. Adsorption values of the continuous study. Solute q Th [g/g] k Th [L g -1 min -1 ] q des [g/g] % Desorbed Single Solute Itaconic Acid Competitive Itaconic Acid Glucose Figure S10. Exemplary chromatogramm of a typical itaconic acid/glucose solution. S14

15 4. References [1] M. León, T. D. Swift, V. Nikolakis, D. G. Vlachos, Adsorption of the Compounds Encountered in Monosaccharide Dehydration in Zeolite Beta, Langmuir 2013, 29, [2] R. C. Bansal, M. Goyal, Activated Carbon Adsorption, CRC Press, [3] K. Y. Foo, B. H. Hameed, Adsorption isotherm, kinetic modeling and mechanism of 2,4,6- trichlorophenol on coconut husk-based activated carbon, Chem. Eng. J. 2010, 159, [4] I. A. W. Tan, A. L. Ahmad, B. H. Hameed, Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon, J. Hazardous Mater. 2009, 164, [5] T. W. Weber, R. K. Chakravorti, Pore and Solid Diffusion Models for Fixed-Bed Adsorbers, AIChE Journal 1974, 20, [6] P. W. Atkins, J. de Paula, Physikalische Chemie, Vol. 4, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, [7] J. Stodollick, R. Femmer, M. Gloede, T. Melin, M. Wessling, J. Membr. Sci. 2014, 453, S15