Supplementary Information for: Xylose Isomerization to ... AWS
Supplementary Information for: Xylose Isomerization to Xylulose and its Dehydration to Furfural in Aqueous Media Vinit Choudhary, Ana B. Pinar, Stanley I. Sandler, Dionisios G. Vlachos*, and Raul F. Lobo* Center for Catalytic Science and Technology and Catalysis Center for Energy Innovation Department of Chemical Engineering, University of Delaware, Newark, DE 19716 *E-mail: [email protected], [email protected] Table of contents Material synthesis and experimental methods Material characterization Catalysis
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S1
Experimental Methods Material Synthesis:
Sn-containing zeolite beta was synthesized in fluoride medium, following
the procedure described by Corma and co-workers.1 The molar composition of the synthesis gel was: 1 SiO2 : 0.01 SnO2 : 0.54 HF : 7.5 H2O. The organic structure directing agent (SDA) molecules were removed by calcination of the solid samples in air (heating up to 550 ºC at 3 ºC/min and then keeping this temperature for 6 h). The structure of the crystalline phases obtained was determined by X-ray diffraction (XRD, PANalytical X’Pert PRO-MPD diffractometer, Cu Kα radiation), while the organic content was characterized by thermogravimetric analysis (TGA, Mettler Toledo TGA/DSC 1 STARe System, heating rate 20 °C/min, air flow 80 mL/min, temperature range 30–900 °C). The chemical composition was determined by inductively coupled plasma (ICP) analysis performed by Galbraith Laboratories (Knoxville, TN), and the crystal morphology was studied by scanning electron microscopy (SEM) on a JEOL JSM 7400F. N2 adsorption measurements were carried out in a Micromeritics ASAP 2020 instrument. The catalytic experiments were carried out in 10 ml thick-walled glass vials (Sigma-Aldrich) heated in a temperature-controlled oil bath, which was placed on top of a digital stirring hotplate (Fisher Scientific). All the chemicals (DMSO, HCl, glucose, xylose, xylulose, lyxose and Amberlyst-15 (dry form)) were purchased from Sigma-Aldrich. In a typical experiment, 1 ml of an aqueous solution of xylose (10% wt) and the corresponding catalyst amount (to achieve a 1:50 metal to xylose molar ratio) were added to the reactor and sealed. A magnetic stirrer was used for mixing during reaction. The kinetics experiments were carried out using multiple such vial reactors, which were taken out at specific times and quenched in water at room temperature.
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The liquid samples were analyzed using high performance liquid chromatography (HPLC) using a Waters alliance system (e2695) equipped with refractive index detector. Sugars were detected with a Biorad HPX87C (300 x 7.8) column, using pure water (pH=7) as the mobile phase at a flow rate of 0.60 ml/min and a column temperature of 65 ⁰C. Xylose, xylulose and lyxose elute at 11.6, 13.9, 14.4 minutes, respectively. During reaction sample analysis, xylulose and lyxose peaks overlap, and lyxose appears as a bump on the right arm of the xylulose peak. We used the symmetry of the peak and quantified xylulose using the left half of the peak. Since all these isomers have a similar response factor, we could further quantify lyxose by subtracting the calculated xylulose peak area from the total peak area. Furfural was detected with a Biorad HPX87H (300 x 7.8) column, using water (0.005 molar sulphuric acid) as the mobile phase at a flow rate of 0.65 ml/min and a column temperature of 65 ⁰C. Conversion of xylose, yield and selectivity of the products are defined as follows (the change in the number of moles during dehydration is neglected): %
Here Ci is the molar concentration of species i.
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Material Characterization
Figure S1. XRD patterns of as-prepared (bottom) and calcined (top) Sn-beta sample. The peak highlighted with an asterisk (*) corresponds to the sample holder.
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1 m
Figure S2. SEM micrograph of calcined zeolite Sn-beta synthesized in the presence of fluoride anions.
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Catalysis Tables Table S1: Glucose isomerization into fructose and mannose using Sn-beta zeolite. Reaction conditions: initial glucose 10% wt, glucose to Sn molar ratio of 1:50, at 110 ºC, reactor volume of 1 ml. Time
Conversion
Yield (%)
Entry
(min)
(%)
Fructose
Mannose
1
30
69.8
29.2
8.6
This work
2
45
71.1
29.8
8.5
This work
3
30
55
32
9
Moliner et al.2
4
45
60
32.7
9.7
Moliner et al.2
Reference
Table S2: Effect of DMSO on xylose conversion. Reaction conditions: initial xylose 10% wt., xylose to Sn molar ratio of 1:50, reactor volume of 1 ml. DMSO (% wt) in
Xylose
Xylulose
Lyxose
water
Conversion (%)
yield (%)
yield (%)
0
84.0
17.7
6.3
1
76.4
28.8
8.6
5
69.4
32.4
10.5
50
0.5
-
-
S6
References (1) S. Valencia, A. Corma (UOP LCC), Stannosilicate molecular sieves, U.S. Patent 5,968,473,
Oct 19, 1999. (2) Moliner, M.; Roman-Leshkov, Y.; Davis, M. E., Proceedings of the National Academy of Sciences of the United States of America 2010, 107, 6164-6168.
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p. S2-S3
p. S4-S5
p. S6
S1
Experimental Methods Material Synthesis:
Sn-containing zeolite beta was synthesized in fluoride medium, following
the procedure described by Corma and co-workers.1 The molar composition of the synthesis gel was: 1 SiO2 : 0.01 SnO2 : 0.54 HF : 7.5 H2O. The organic structure directing agent (SDA) molecules were removed by calcination of the solid samples in air (heating up to 550 ºC at 3 ºC/min and then keeping this temperature for 6 h). The structure of the crystalline phases obtained was determined by X-ray diffraction (XRD, PANalytical X’Pert PRO-MPD diffractometer, Cu Kα radiation), while the organic content was characterized by thermogravimetric analysis (TGA, Mettler Toledo TGA/DSC 1 STARe System, heating rate 20 °C/min, air flow 80 mL/min, temperature range 30–900 °C). The chemical composition was determined by inductively coupled plasma (ICP) analysis performed by Galbraith Laboratories (Knoxville, TN), and the crystal morphology was studied by scanning electron microscopy (SEM) on a JEOL JSM 7400F. N2 adsorption measurements were carried out in a Micromeritics ASAP 2020 instrument. The catalytic experiments were carried out in 10 ml thick-walled glass vials (Sigma-Aldrich) heated in a temperature-controlled oil bath, which was placed on top of a digital stirring hotplate (Fisher Scientific). All the chemicals (DMSO, HCl, glucose, xylose, xylulose, lyxose and Amberlyst-15 (dry form)) were purchased from Sigma-Aldrich. In a typical experiment, 1 ml of an aqueous solution of xylose (10% wt) and the corresponding catalyst amount (to achieve a 1:50 metal to xylose molar ratio) were added to the reactor and sealed. A magnetic stirrer was used for mixing during reaction. The kinetics experiments were carried out using multiple such vial reactors, which were taken out at specific times and quenched in water at room temperature.
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The liquid samples were analyzed using high performance liquid chromatography (HPLC) using a Waters alliance system (e2695) equipped with refractive index detector. Sugars were detected with a Biorad HPX87C (300 x 7.8) column, using pure water (pH=7) as the mobile phase at a flow rate of 0.60 ml/min and a column temperature of 65 ⁰C. Xylose, xylulose and lyxose elute at 11.6, 13.9, 14.4 minutes, respectively. During reaction sample analysis, xylulose and lyxose peaks overlap, and lyxose appears as a bump on the right arm of the xylulose peak. We used the symmetry of the peak and quantified xylulose using the left half of the peak. Since all these isomers have a similar response factor, we could further quantify lyxose by subtracting the calculated xylulose peak area from the total peak area. Furfural was detected with a Biorad HPX87H (300 x 7.8) column, using water (0.005 molar sulphuric acid) as the mobile phase at a flow rate of 0.65 ml/min and a column temperature of 65 ⁰C. Conversion of xylose, yield and selectivity of the products are defined as follows (the change in the number of moles during dehydration is neglected): %
Here Ci is the molar concentration of species i.
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Material Characterization
Figure S1. XRD patterns of as-prepared (bottom) and calcined (top) Sn-beta sample. The peak highlighted with an asterisk (*) corresponds to the sample holder.
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1 m
Figure S2. SEM micrograph of calcined zeolite Sn-beta synthesized in the presence of fluoride anions.
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Catalysis Tables Table S1: Glucose isomerization into fructose and mannose using Sn-beta zeolite. Reaction conditions: initial glucose 10% wt, glucose to Sn molar ratio of 1:50, at 110 ºC, reactor volume of 1 ml. Time
Conversion
Yield (%)
Entry
(min)
(%)
Fructose
Mannose
1
30
69.8
29.2
8.6
This work
2
45
71.1
29.8
8.5
This work
3
30
55
32
9
Moliner et al.2
4
45
60
32.7
9.7
Moliner et al.2
Reference
Table S2: Effect of DMSO on xylose conversion. Reaction conditions: initial xylose 10% wt., xylose to Sn molar ratio of 1:50, reactor volume of 1 ml. DMSO (% wt) in
Xylose
Xylulose
Lyxose
water
Conversion (%)
yield (%)
yield (%)
0
84.0
17.7
6.3
1
76.4
28.8
8.6
5
69.4
32.4
10.5
50
0.5
-
-
S6
References (1) S. Valencia, A. Corma (UOP LCC), Stannosilicate molecular sieves, U.S. Patent 5,968,473,
Oct 19, 1999. (2) Moliner, M.; Roman-Leshkov, Y.; Davis, M. E., Proceedings of the National Academy of Sciences of the United States of America 2010, 107, 6164-6168.
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