Supporting information

Efficient Conversion of Levulinic Acid into γ-Valerolactone over Raney Ni Catalyst Prepared from Melt-quenching Alloy

Zeming Rong*, Zhuohua Sun, Lu Wang, Jinkun Lv, Yong Wang and Yue Wang

State Key Laboratory of Fine Chemicals, School of Chemical Engineering,

Dalian University of Technology, Dalian 116024, P. R. China.

E-mail:

Tel: +86 411 84986242

Experimental section

Catalyst preparation

RQ-Ni was prepared by the quenching method: 46.4 wt.% Ni, 49.3 wt.% Al and 4.3 wt.% Mo were melted and rapidly quenched on a fast-rotating copper roller to form alloy ribbon. After the alloy ribbon was crushed and treated with ball-milling and sieving, the powder fraction of 200-300 mesh was collected and then Al was leached out by using excess amount of 20 wt.% NaOH aqueous solution at 373 K for 2 h.

Activity test and product analysis

The catalytic hydrogenation reaction was conducted in a stainless-steel autoclave (75 ml capacity) heated in oil bath. 500 mg Levulinic Acid (LA), 20 mL solvent (water, methanol, ethanol, isopropanol, 1,4-dixoane) and 200 mg catalyst (RQ-Ni, Raney Ni, Raney Co, Raney Cu, Raney Fe) were directly added into the reactor, which was sealed and then purged with N2 and H2 for 3 times respectively. At the end of the reaction, 2ml of the reaction liquid was taken out and tested by ICP (Perkin Elmer, Optima 2000DV).

The products were quantitatively analyzed by GC-FID (Techcomp 7890F, FID detector, DB-FFAP (30m×250μm×0.25μm) capillary column) with calibrated area normalization method and qualitatively analyzed by GC-MS (Agilent 5979C).

Hot filtration test was carried out as follows: 500 mg LA, 20mL water and 200 mg RQ-Ni were directly added into the reactor, which was sealed and then purged with N2 and H2 for 3 times respectively. Then the reactor was heated to 373K and pressurized to 2MPa with H2. The reaction was performed for 1 h and cooled to room temperature. The product was analyzed by GC-FID. Furthermore, the solid QS-Ni was taken out from the reactor using a magnet. Then the reaction was sequentially performed for another 1h and the product was quantitatively analyzed by GC-FID.

Catalyst characterization

XRD

Powder X-ray diffraction (XRD) patterns were recorded on a Rigaku D/max-2400 diffract meter (Cu Kα/λ=0.1541 nm/40 kV/200 mA). The sample was scanned from 10° to 90° with a rate of 5° min-1.

BET

The N2 adsorption–desorption isotherms were obtained by using a 3H-2000PS1 sorption system (Beishide Instrument-ST (Beijing) Co., Ltd.). Firstly, the sample (about 500mg) was dried in vacuum at 473K for 6 h. The N2 isotherms were carried out at 77 K. The specific surface areas were calculated from the isotherms using the Brunauer-Emmett-Teller (BET) method. The pore distribution and the cumulative volumes of pores were obtained by the Barrett-Joyner-Halenda (BJH) method from the desorption branches of the isotherms.

SEM

The surface morphologies were characterized with scanning electron microscopy (SEM, FEI, QUANTA 450). Firstly, the sample was washed with methanol and THF for 3 times respectively. Then it was dried at room temperature for 24h and transferred into the SEM chamber with good dispersion. Finally, the sample was quickly moved into the vacuum evaporator for test.

ICP

200mg RQ-Ni catalyst was dissolved in aqua regia (9ml HCl and 3ml HNO3 dilute to 100ml) and then test the concentration of Al and Ni respectively.

Table.S1 The effect of solvents for LA hydrogenationa.

Solvent / The first run / The second run / The third run
Con. (%) / Sel. (%) / Con. (%) / Sel. (%) / Con. (%) / Sel. (%)
Water / 99.5 / 99.8 / 55.1 / 99.8 / 33.0 / 99.8
Methanol / 97.8 / 96.0 / 93.3 / 91.2 / 83.2 / 87.5
Ethanol / 95.3 / 93.1 / 89.5 / 91.1 / 91.0 / 89.4
Isopropanol / 98.9 / 95.4 / 98.4 / 95.5 / 96.2 / 93.0
1,4-dioxane / 95.4 / 96.8 / 85.1 / 96.4 / 77.3 / 96.9

a.  Reaction conditions: RQ-Ni 200mg, LA 500mg, solvent 20ml, 393K, 2MPa, 2h.

Table.S2 The study for the catalytic activity of leached species

Run / Cat. / Time/h / Con.% / Sel.%
1 / RQ-Ni / 1 / 46.0 / 99.9
2 / Removal of solid RQ-Ni / 1 / 46.5 / 99.9

a.  Reaction conditions: RQ-Ni 200mg, LA 500 mg, H2O 20ml, 393K, 2MPa.

Fig. S1 GC image of LA hydrogenation.

Fig. S2 MS image of isopropanol solvent.

Fig. S3 MS image of isopropyl levulinate.

Fig. S4 MS image of GVL.

Fig. S5 MS image of PLA.

Fig. S6 MS image of LA.