selective carbonylation of dimethyl ether to methyl acetate catalyzed by acidic zeolites
DESCRIPTION
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. - PowerPoint PPT PresentationTRANSCRIPT
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Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites
Huimin Zhan
2013.7.19
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Background
CH3OCH3+CO CH3COOCH3
Catalyst:
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CH3OCH3+CO CH3COOCH3400-500K , 1.5MPa
H-MOR
-Mild reaction condition-Non-noble metal catalyst , selectivity > 99%-Highly atom-economic-Less by-product
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Mechanism Study
DME pulsing studies:DME and water were detected in the effluent during subsequent He treatment
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DME–CO mixtures
Pure CO DME–CO mixtures
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DME:CO=1:46.5
Technology Condition
CO/H2/DME=72/18/10
CO/H2/DME=76/19/5
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Catalyst
Undetectable on H-USY (Si/Al=3:1), H-
BEA (Si/Al=12.5:1), and amorphous
SiO2–Al2O3 (Si/Al=3:1)
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inside the 8MR
outside the 8MRmore accessible to 12MRchannel
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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
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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
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The Synthesis of Catalyst
Pyt:吡咯烷; TMA:四甲基铵; HMI:环己亚胺
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Pre-adsorption of Pyridine
HOMR-6 、 Py-HMOR-6 : Si/Al=6 ;HMOR-10 、 Py-HMOR-10 : Si/Al=10
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The Addition of Methyl Acetate or Acetic Acid in Reactant
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Selective Dealumination of Mordenite
The method of dealumination :
H-MOR pyridine Py-HMOR aqueous NaOH solution Py-Na-MOR calcine
H-Na-MOR1023K
a gas stream of 30% H2Oaqueous NaOH
solutionNH4NO3
ion-exchange
NH4-MOR calcine HMOR-1023
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The selective removal of aluminium from the 12-membered ring channels and also from the surface of the zeolite.
(NH4)2SiF6
A : MORB : MOR (NH4)2SiF6
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The selective extraction of silicon from a zeolite framework
NaOH 、 NH4OH:
Selective Extraction of Silicon
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Cu/H-MOR
Cu loading amount : 4.7wt%
The location exchange of proton with Cu2+ after ion-exchange treatment
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Cu loading amount : Catalyst B ——15mol% ; Catalyst E ——59mol%
Reaction condition : 300℃, 70bar , GHSV=4000h-1 , CO/H2/DME=72/18/10
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The Impact of Particle Size and Crystal Size
Particle size : 2-3.5μm
The carbonylation of dimethyl ether
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Crystal size : 0.1-1.5 μm
Crystal size : Catalyst I——0.1-0.5μm ; Catalyst J——3-7 μm
The carbonylation of methanol
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HZSM-35
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序号 ZSM-35 MOR 基质 稀土A 80g 27g拟薄水铝
石B 80g 同上C 64g 16g 同上D C循环五次后得到 D
E 64g 16g 同上 La 1wt%
F E循环五次后得到 F
G 56g 24g 同上 La 1wt%
H 40g 40g 同上 La 0.5wt%
I 64g 16g 50g 硅溶胶 La 1.5wt%
J 56g 14g 75g 硅溶胶 Ce 3wt%
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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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Thanks for Your Attention!Qs & As