Solvent-free Synthesis of Zeolites from Solid Raw Materials

Transcription

1 Solvent-free Synthesis of Zeolites from Solid Raw Materials Limin Ren, Qinming Wu, Chengguang Yang, Longfeng Zhu, Caijin Li, Pengling Zhang, Haiyan Zhang, Xiangju Meng,*, Feng-Shou Xiao*, Department of Chemistry, Zhejiang University, Hangzhou , China. Department of Chemistry, Jilin University, Changchun , China. Reagents Na 2 SiO 3 9H 2 O (SiO 2 of 20 wt.%, Tianjin Guangfu Chemical Reagent Co, Ltd.), Fumed silica (SiO 2 of 100 wt.%, Shenyang Chemical Reagent Co, Ltd.), Tetrapropylammonium bromide (TPABr, 98%, Tianjin Guangfu Chemical Reagent Co, Ltd.), NH 4 Cl (Tianjin Fuchen Chemical Reagent Co, Ltd.), Boehmite (Al 2 O 3 of 70 wt.%, Liaoning hydratight science and technology development Co., LTD), Fe(NO 3 ) 3 9H 2 O (Beijing Chemical Works), H 3 BO 3 (Beijing Chemical Works), Ga 2 O 3 (Beijing Chemical Works), CaCO 3 nanocrystals with average size of 100 nm (Jilin University), HCl acid (37 wt.%, Beijing Chemical Works), N,N'-Diaminoguanidine monohydrochloride (purity of 90 wt.%, Qingdao Xinyu chemical science and technology Co., Ltd.), NaOH (Beijing Chemical Works), NaAlO 2 (Sinopharm Chemical Reagent Co, Ltd.), and SiO 2 2H 2 O (produced in our lab). Syntheses of samples S-Si-ZSM g of Na 2 SiO 3 9H 2 O, g of fumed silica, 0.24 g of TPABr, and g of NH 4 Cl were mixed together one by one. After grinding for S1

2 10-20 min, the mixture was transformed to an autoclave and heated at 180 C for h. After filtration at room temperature and drying at 80 C, a crystalline product of S-Si-ZSM-5 was obtained. S-M-ZSM-5 (M=Al, Fe, B, or Ga) g of Na 2 SiO 3 9H 2 O, g of fumed silica, 0.24 g of TPABr, g of NH 4 Cl, and a certain amount of heteroatom source were mixed together one by one. The heteroatom source could be g of boehmite, g of Fe(NO 3 ) 3 9H 2 O, g of H 3 BO 3, or g of Ga 2 O 3, respectively. After grinding for min, the mixture was transformed to an autoclave and heated at 180 C for h. After filtration at room temperature and drying at 80 C overnight, a crystalline product of S-M-ZSM-5 was obtained. Hierarchically porous S-Si-ZSM g of Na 2 SiO 3 9H 2 O, g of fumed silica, 0.24 g of TPABr, g of nano CaCO 3 and g of NH 4 Cl were mixed together one by one. After grinding for min, the mixture was transformed to an autoclave and heated at 180 C for h. After filtration at room temperature and drying at 80 C, a crystalline product of S-Si-ZSM-5 was obtained. After treatment by 1M HCl acid solution, hierarchically porous S-Si-ZSM-5 with macroporosity was obtained. S-ZSM-39 zeolite. As a typical run, 0.27 g of SiO 2, 1.35 g of Na 2 SiO 3 9H 2 O, 0.18 g of NH 4 Cl, and g of N,N'-Diaminoguanidine monohydrochloride were mixed together one by one. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 180 C for 4 days. S-SOD zeolite. As a typical run, g of Na 2 SiO 3 9H 2 O were mixed with 1.18 g of NaAlO 2. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 80 C for 4 h. S2

3 S-MOR zeolite. As a typical run, 2.67 g of SiO 2 2H 2 O were mixed with g of NaAlO 2 and g of NaOH one by one. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 160 C for 84 h. S-Beta zeolite. As a typical run, 6.5 g of SiO 2 3H 2 O were mixed with 1.09 g of NaAlO 2 and 0.19 g of NaOH one by one. After grinding for 15 min and addition of 0.4 g of Beta zeolite as seeds, the mixture was transferred to an autoclave and heated at 140 C for 72 h. The S-Beta sample contains a small amount of MOR zeolite. S-FAU zeolite. As a typical run, 3.17 g of SiO 2 3H 2 O were mixed with 1.64 g of NaAlO 2. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 100 C for 24 h. Characterization X-ray diffraction (XRD) patterns were obtained with a Rigaku D/MAX 2550 diffractometer with Cu Kα radiation. Scanning electron microscopy (SEM) images were collected by JEOL electron microscopes (FE-JSM 6700, Japan). UV/Vis spectra were measured on a PERKIN ELMER Lambda 20 spectrophotometer. NMR spectra were recorded on a Varian Infinityplus-400 spectrometer. The sample composition was determined by inductively coupled plasma (ICP) with a Perkin-Elmer plasma 40 emission spectrometer. The power of the laser at the sample was about 3.0 mw. Mercury method was taken by an Autopore IV 9500 mercury porosimeter (Micromeritics Co.). A contact angle of 130 was assumed in the pore size calculation. The nitrogen isotherms at -196 C were measured using a Micromeritics ASAP 2020M system. The samples were outgassed for 10 h at 200 C before the measurements. The pore-size distribution for micropores was calculated using HK model. UV Raman spectra were measured with a Jobin-Yvon T64000 triple-stage spectrometer with spectral resolution of 2 cm -1. The laser line at 325 nm was used as an exciting source with an output of 50 mw. S3

4 Intensity/a.u. Supporting Figures e d c b a Theta/degree Figure S1. XRD patterns of (a) S-Si-ZSM-5, (b) S-Al-ZSM-5 with a Si/Al ratio of 109, (c) S-Fe-ZSM-5 with a Si/Fe ratio of 38, (d) S-B-ZSM-5 with a Si/B ratio of 53, and (e) S-Ga-ZSM-5 with a Si/Ga ratio of 23. S4

5 a b Figure S2. SEM images of (a) S-B-ZSM-5 with a Si/B ratio of 33 and (b) S-Ga-ZSM- 5 with a Si/Ga ratio of 67. S5

6 Figure S3. SEM image of CaCO 3 nanocrystals, which were used as hard templates for synthesizing hierarchically porous S-Si-ZSM-5 zeolite. S6

7 Intensity/a.u Theta/degree Figure S4. XRD pattern of hierarchically porous calcined and acid-treated S-Si-ZSM- 5 zeolite synthesized from using CaCO 3 nanocrystals as hard templates [Calcination at 550 C for 6 h and acidic treating (HCl, 1M) for 24 h at room temperature]. S7

8 225 Volume adsorbed( cm 3 /g) p/p 0 Figure S5. N 2 sorption isotherms of hierarchically porous calcined and acid-treated S- Si-ZSM-5 synthesized from using CaCO 3 nanocrystals as hard templates. [Calcination at 550 C for 6 h and acidic treating (HCl, 1M) for 24 h at room temperature].the steep increase at relative pressure of is attributed to the presence of macroporosity in the sample. S8

9 Cumulative Intrusion(mL/g) Log Differential Intrusion(mL/g) a b intrusion extrusion Intrusion Pore size Pressure/Pa Pore size/nm Figure S6. Mercury method characterization of hierarchically porous calcined and acid-treated S-Si-ZSM-5 synthesized from using CaCO 3 nanocrystals as hard templates. [Calcination at 550 C for 6 h and acidic treating (HCl, 1M) for 24 h at room temperature]. (a) cumulative intrusion and extrusion curves, and (b) intrusion pore size distribution. The macropore volume was 1.2 cm 3 /g. S9

10 Intensity/a.u. d c b a Theta/degree Figure S7. XRD patterns of (a) Na 2 SiO 3 9H 2 O, (b) NH 4 Cl, (c) TPABr, and (d) the mixture of these raw solid materials. The appearance of about 31 associated with NaBr in Fig. S7d is due to the solid reaction between Na 2 SiO 3 9H 2 O with TPABr. S10

11 Volume adsorbed(cm 3 /g) dv/dlog(w) a P/P b Pore width/nm Figure S8. (a) N 2 sorption isotherms and (b) HK pore size distribution of the sample crystallized at 2 h for synthesizing S-Si-ZSM-5 zeolite from solvent-free route. S11

12 Crystallinity/% a b Time/h Figure S9. Crystallization curves of (a) S-Si-ZSM-5 zeolite synthesized from solvent-free route and (b) silicalite-1 zeolite synthesized from hydrothermal route. S12

13 Volume adsorbed (cm 3 /g) Volume adsorbed (cm 3 /g) Volume adsorbed (cm 3 /g) Volume adsorbed (cm 3 /g) a b c p/p d p/p p/p 0 p/p 0 Figure S10. N 2 sorption isotherms of the samples crystallized at (a) 0.5, (b) 1.0, (c) 2.0, and (d) 2.5 h for synthesizing silicalite-1 zeolite from hydrothermal route. S13

14 TG/% DTA/(uV/mg) Temp/ C Figure S11. TG-DTA curves of as-synthesized S-Si-ZSM-5 zeolite. S14

15 Intensity/a.u Theta/degree Figure S12. XRD pattern and SEM image of as-synthesized S-ZSM-39 zeolite from solvent-free synthesis. S15

16 Intensity/a.u Theta/degree Figure S13. XRD pattern and SEM image of as-synthesized S-SOD zeolite from solvent-free synthesis. S16

17 Intensity/a.u Theta/degree Figure S14. XRD pattern and SEM image of as-synthesized S-MOR zeolite from solvent-free synthesis. S17

18 Intensity/a.u Theta/degree Figure S15. XRD pattern and SEM image of as-synthesized S-Beta zeolite from solvent-free synthesis. The S-Beta sample contains a small amount of MOR zeolite. S18

19 Intensity/a.u Theta/degree Figure S16. XRD pattern and SEM image of as-synthesized S-FAU zeolite from solvent-free synthesis. S19

20 Table S1. The starting raw solids for synthesizing zeolites with MFI structure. Run Starting raw solids, g Crystallization time, h Si/M ratios in products (M=Al, Fe, Ga, or B) Sample name Na 2 SiO 3 9H 2 O, fumed silica, 0.24 TPABr, of NH 4 Cl Na 2 SiO 3 9H 2 O, fumed silica, 0.24 TPABr, boehmite, NH 4 Cl Na 2 SiO 3 9H 2 O, g fumed silica, 0.24 TPABr, NH 4 Cl, Fe(NO 3 ) 3 9H 2 O Na 2 SiO 3 9H 2 O, g fumed silica, 0.24 TPABr, NH 4 Cl, Pure silica S-Si-ZSM S-Al-ZSM S-Fe-ZSM S-Ga-ZSM-5 Ga 2 O Na 2 SiO 3 9H 2 O, g fumed silica, 0.24 TPABr, NH 4 Cl, S-B-ZSM-5 H 3 BO Na 2 SiO 3 9H 2 O, g fumed silica, 0.24 TPABr, NH 4 Cl, Pure silica S-Si-ZSM-5 with macropore CaCO 3 S20