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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