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Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites. Huimin Zhan 2013.7.19. Background. CH 3 OCH 3 +CO CH 3 COOCH 3. Catalyst :. 400-500K , 1.5MPa. CH 3 OCH 3 +CO CH 3 COOCH 3. H-MOR.
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Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites Huimin Zhan 2013.7.19
Background CH3OCH3+CO CH3COOCH3 Catalyst:
400-500K,1.5MPa CH3OCH3+CO CH3COOCH3 H-MOR -Mild reaction condition -Non-noble metal catalyst,selectivity>99% -Highly atom-economic -Less by-product
Mechanism Study DME pulsing studies: DME and water were detected in the effluent during subsequent He treatment
DME–CO mixtures DME–CO mixtures Pure CO
Technology Condition CO/H2/DME=72/18/10 DME:CO=1:46.5 CO/H2/DME=76/19/5
Catalyst Undetectable on H-USY (Si/Al=3:1), H-BEA (Si/Al=12.5:1), and amorphous SiO2–Al2O3 (Si/Al=3:1)
outside the 8MR more accessible to 12MRchannel inside the 8MR
Distribution of H+ Sites in MOR Propane : absorbed on sites located only within 8-MR channels n-Hexane : absorbed on sites located only within 12-MR channels ~3610cm : H+ in 12-MR channels ~3590cm : H+ in 8-MR channels
Distribution of H+ Sites in Cation-Exchanged MOR Samples Na + exchange occurred selectively by replacement of H+ within 8-MR side pockets Co2+ replaced H+ with similar probability in 8-MR and 12-MR channels
The Synthesis of Catalyst Pyt:吡咯烷;TMA:四甲基铵;HMI:环己亚胺
Pre-adsorption of Pyridine HOMR-6、Py-HMOR-6:Si/Al=6 ;HMOR-10、Py-HMOR-10:Si/Al=10
Selective Dealumination of Mordenite The method of dealumination : pyridine aqueous NaOH solution calcine Py-Na-MOR H-MOR Py-HMOR aqueous NaOH solution NH4NO3 ion-exchange 1023K H-Na-MOR a gas stream of 30% H2O calcine HMOR-1023 NH4-MOR
(NH4)2SiF6 The selective removal of aluminium from the 12-membered ring channels and also from the surface of the zeolite. A:MOR B:MOR (NH4)2SiF6
Selective Extraction of Silicon NaOH、NH4OH: The selective extraction of silicon from a zeolite framework
Cu/H-MOR Cu loading amount : 4.7wt% The location exchange of proton with Cu2+ after ion-exchange treatment
Cu loading amount:Catalyst B ——15mol%;Catalyst E——59mol% Reaction condition:300℃,70bar,GHSV=4000h-1,CO/H2/DME=72/18/10
The Impact of Particle Size and Crystal Size The carbonylation of dimethyl ether Particle size :2-3.5μm
The carbonylation of methanol Crystal size:Catalyst I——0.1-0.5μm ;Catalyst J——3-7 μm Crystal size :0.1-1.5 μm
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
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