1. Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites Huimin Zhan 2013.7.19

2. Background CH 3 OCH 3 +CO CH 3 COOCH 3 Catalyst ： Costly noble metal Halide promoter Homogeneous Rh/Cs Catalyst Costly noble metal Halide-free Rh/Cs 2 HPW 12 O 40 Zeolite Halide-free MOR

3. CH 3 OCH 3 +CO CH 3 COOCH 3 400-500K ， 1.5MPa H-MOR -Mild reaction condition -Non-noble metal catalyst ， selectivity ＞ 99% -Highly atom-economic -Less by-product

4. Mechanism Study DME pulsing studies ： DME and water were detected in the effluent during subsequent He treatment

5. DME–CO mixtures Pure CO DME–CO mixtures

7. DME:CO=1:46.5 Technology Condition CO/H2/DME=72/18/10 CO/H2/DME=76/19/5

8. Catalyst Undetectable on H-USY (Si/Al=3:1), H- BEA (Si/Al=12.5:1), and amorphous SiO 2 –Al 2 O 3 (Si/Al=3:1)

9. inside the 8MR outside the 8MR more accessible to 12MRchannel

10. Distribution of H + Sites in MOR ~3610cm : H + in 12-MR channels ~3590cm : H + in 8-MR channels Propane : absorbed on sites located only within 8-MR channels n-Hexane : absorbed on sites located only within 12-MR channels

11. Distribution of H + Sites in Cation- Exchanged MOR Samples Na + exchange occurred selectively by replacement of H + within 8-MR side pockets Co 2+ replaced H + with similar probability in 8-MR and 12-MR channels

13. The Synthesis of Catalyst Pyt ：吡咯烷； TMA ：四甲基铵； HMI ：环己亚胺

14. Pre-adsorption of Pyridine HOMR-6 、 Py-HMOR-6 ： Si/Al=6 ;HMOR-10 、 Py-HMOR-10 ： Si/Al=10

15. The Addition of Methyl Acetate or Acetic Acid in Reactant

16. Selective Dealumination of Mordenite The method of dealumination : H-MOR pyridine Py-HMOR aqueous NaOH solution Py-Na-MOR calcine H-Na-MOR 1023K a gas stream of 30% H 2 O aqueous NaOH solution NH 4 NO 3 ion-exchange NH 4 -MOR calcine HMOR-1023

18. The selective removal of aluminium from the 12- membered ring channels and also from the surface of the zeolite. (NH 4 ) 2 SiF 6 A ： MOR B ： MOR (NH 4 ) 2 SiF 6

19. The selective extraction of silicon from a zeolite framework NaOH 、 NH 4 OH ： Selective Extraction of Silicon

20. Cu/H-MOR Cu loading amount : 4.7wt% The location exchange of proton with Cu 2+ after ion-exchange treatment

22. Cu loading amount ： Catalyst B ——15mol% ； Catalyst E ——59mol% Reaction condition ： 300 ℃， 70bar ， GHSV=4000h -1 ， CO/H 2 /DME=72/18/10

23. The Impact of Particle Size and Crystal Size Particle size ： 2-3.5μm The carbonylation of dimethyl ether

24. Crystal size ： 0.1-1.5 μm Crystal size ： Catalyst I——0.1-0.5μm ； Catalyst J——3-7 μm The carbonylation of methanol

25. HZSM-35

26. 序号 ZSM-35MOR 基质稀土 A80g 27g 拟薄水铝 石 B80g 同上 C64g16g 同上 D C 循环五次后得到 D E64g16g 同上 La 1wt% F E 循环五次后得到 F G56g24g 同上 La 1wt% H40g 同上 La 0.5wt% I64g16g 50g 硅溶胶 La 1.5wt% J56g14g 75g 硅溶胶 Ce 3wt%

27. Work Plan 研究内容： 硅铝比，比表面积和孔分布，酸性及酸量，晶粒大小和颗粒尺寸等对 羰基化的影响 工作计划： 1 、尝试合成丝光沸石，实现不同硅铝比、酸量、晶粒尺寸等丝光沸 石的可控制备 2 、寻找合适的丝光沸石处理方法，对工业丝光沸石进行改性，制备 性能更优良的催化剂 3 、调试设备，考察反应工艺条件

28. Thanks for Your Attention! Q s & A s