1. Bubbling Reactor Technology for Rapid Synthesis of Uniform, Small MFI-Type Zeolite Crystals Wei Liu*, Yuxiang(Tony) Rao, Haiyin Wan, Abhi Karkamkar, Jun Liu, Liquan Wang Pacific Northwest National Laboratory Richland, Washington, USA Presentation at AIChE 2011 Meeting Minneapolis, MN, USA Oct 19 th , 2011

5. Proposed Zeolite Synthesis Routes Scheme 1 Proposed zeolite synthesis routes (a) desired and b) undesired zeolite growth pathway Homogenous parent solution Formation of uniform nucleus Growth of individual nuclei Stable suspension of small crystals Homogenous parent solution Formation of uniform nucleus Coalescence & growth Agglomerates of different crystal sizes (a) Desired zeolite growth pathway (b) Un-desired zeolite growth pathway

8. Zeolites Characterization(SEM/EDS) Figure 1 Morphology of zeolite crystals prepared in this work (*growth conditions same as sample #2 &3 but without Al precursor in the growth solution ) (a)Sample #2 (Si/Al=30 ) (b)Sample #6 (Si/Al=32) (c)Sample #7 (Si/Al=86) (d)Sample #8 (Si/Al=48) (e)Sample #3 (Si/Al=9) (f) Silicalite* (Si/Al=infinity)

9. Zeolites Characterization(TEM) (b) ZSM-5 growth solution(Si/Al=13) after heated at 140 o C for 1.0 h (a) ZSM-5 growth solution(Si/Al=13) after heated at 140 o C for 0.5 h Figure 2 TEM analysis of particle evolution with growth time (Run condition #3) Zeolite crystal growth rate: ~100nm/hour Literature report*: 1.8~3.8nm/hour * Schoeman, B. J.; Sterte, J.; Otterstedt, J. E. “Analysis of the Crystal-Growth Mechanism of TPA-Silicalite-1”. Zeolites 1994 , 14 , 568.

10. Zeolites Characterization(TEM) Figure 3 Small ZSM-5 crystals of different Si/Al ratio synthesized at 140 o C for 2 h. (a) ZSM-5 crystals of Si/Al=72 (sample#1) (b) ZSM-5 crystals of Si/Al=30 (sample#2) (c) ZSM-5 crystals of Si/Al=9 (sample#3)

11. Zeolites Characterization(BET) Table 2. Surface area of small-crystal ZSM-5 powder prepared with different growth times (Si/Al ratio of 13 in the parent growth solution, 140 o C, 25sccm N 2 flow) a. Surface area calculated with t method from N 2 desorption isotherm. Observation: a. zeolite pores (micro-pore ) b. Void space inside zeolite crystal (meso-pore) c. meso-pore disappeared with increasing reaction time SA P = external surface area of a particle  z = density of ZSM-5 framework, 1.93 g/cc. D p = particle size for a sphere, cube or tablet Cause of meso-porosity: a. TPAOH or gas bubble trapped inside the crystal b. Si precursors (TEOS) incorporated into particles Figure 4 Pore size distribution of small crystal ZSM-5 powder prepared with different growth times. Growth time, h Langmuir surface area m 2 /g Multipoint BET surface area m 2 /g Micro-pore surface area a m 2 /g (T-method) Meso-pore surface area a m 2 /g Estimated particle size nm (Dp) 1 495 352 194 158 20 2 NM 433 266 168 19 4 519 391 251 141 22

12. Zeolites Characterization(XRD) Figure 5 XRD pattern of in-house zeolite (Si/Al=72) fitted with standard HZSM-5 High purity zeolite crystal was obtained!!!

15. Zeolites Characterization(NMR, 1 H) Figure 8 Solid State 1 H MAS NMR of in-house ZSM-5 samples taken at different temperatures. (a) at 25 o C as received, (b) at 250 o C after heating up to 250 o C for 10min, (c) at 25 o C after cooling down from 250 o C.

18. Applications #1(bubbling reactor) CO 2 capture adsorbents Scheme 3 Silicalite crystal layer growth on the surface of 13X beads/ZSM-5 particles Figure 11. SEM images of 13X beads after silicalite coating. (cross section view) Figure 10. Adsorption curves for 13X beads under wet CO 2 gas stream, a) unmodified, b) silicalite coated)

19. Applications #2 (bubbling reactor) HMF adsorption from ionic liquid mixtures Preparation and Testing of Adsorbents for the Separation of Ionic Liquids From HMF Wednesday, October 19, 2011: 1:45 PM 208 D (Minneapolis Convention Center) Yuxiang Rao 1 , Alan Cooper 2 , Heather Brown 2 and Wei Liu 3 , (1)Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, (2)Pacific Northwest National Lab, Richland, WA, (3)Pacific Northwest National Laboratory, Richland, WA HMF is an important chemical product since it has the potential to be used as a feedstock to replace petroleum-derived aromatics for production of a range of specialty chemicals and plastics. In this work, we will demonstrate an economically-viable, ionic liquid catalytic process for conversion of biomass-derived raw sugar to 5-hydroxymethylfurfural(HMF). The experimental work includes preparation of adsorbents materials by membrane coating, catalytic reactions in ionic liquid fluids and separation of reacted products by extraction and adsorption, which includes (i) catalytic reaction tests in both a batch and flow reactor system to develop systematic understandings to critical process operation parameters and establish material balances, and (ii) screening of adsorbents and identification of an effective adsorption process for separation of HMF product from reaction mixtures and for complete recovery of the catalyst and ionic liquid.The adsorbent materials tested for this project were characterized by XRD, SEM/EDS and Nitrogen adsorption/desorption technology .

21. Thank you!