Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites
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Transcript of Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites
Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites
Huimin Zhan
2013.7.19
Background
CH3OCH3+CO CH3COOCH3
Catalyst:
CH3OCH3+CO CH3COOCH3400-500K , 1.5MPa
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
Pure CO DME–CO mixtures
DME:CO=1:46.5
Technology Condition
CO/H2/DME=72/18/10
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)
inside the 8MR
outside the 8MRmore accessible to 12MRchannel
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
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
The Addition of Methyl Acetate or Acetic Acid in Reactant
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
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
The selective extraction of silicon from a zeolite framework
NaOH 、 NH4OH:
Selective Extraction of Silicon
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
Particle size : 2-3.5μm
The carbonylation of dimethyl ether
Crystal size : 0.1-1.5 μm
Crystal size : Catalyst I——0.1-0.5μm ; Catalyst J——3-7 μm
The carbonylation of methanol
HZSM-35
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%
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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