CN109985658A - The method of modifying of h-mordenite molecular sieve for dimethyl ether carbonylation reaction - Google Patents
The method of modifying of h-mordenite molecular sieve for dimethyl ether carbonylation reaction Download PDFInfo
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- CN109985658A CN109985658A CN201910221033.1A CN201910221033A CN109985658A CN 109985658 A CN109985658 A CN 109985658A CN 201910221033 A CN201910221033 A CN 201910221033A CN 109985658 A CN109985658 A CN 109985658A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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Abstract
The invention discloses a kind of method of modifying of h-mordenite molecular sieve for dimethyl ether carbonylation reaction.By h-mordenite molecular sieve in inert atmosphere or H2Under the conditions of one kind or mixed atmosphere of gas, in 300-600 DEG C of drying；H-mordenite molecular sieve after being dried；By the h-mordenite molecular sieve after drying 250-400 DEG C at a temperature of, be passed through the gaseous mixture of pyridine or picoline and inert atmosphere, enable the pre- Adsorption of Pyridine of mordenite molecular sieve or picoline, until molecular sieve Adsorption of Pyridine or picoline are saturated；The mordenite molecular sieve that Adsorption of Pyridine or picoline are saturated is subjected to desorption by heating processing, is passed through inert atmosphere, under conditions of desorption temperature is higher than 50-250 DEG C of adsorption temp, so that the pyridine of weakly stable or picoline desorption.Methyl acetate is produced for Dimethyl ether carbonylation using catalyst of the invention, has obtained high yield and stable methyl acetate yield.
Description
Technical field
The mordenite molecular sieve preparation method modified the present invention relates to pyridine and pyridine substance and its it is used for dimethyl ether
Carbonylation belongs to mordenite molecular sieve catalysis Dimethyl ether carbonylation technical field.It is particularly used for dimethyl ether carbonyl
Change the method for modifying of the h-mordenite molecular sieve of reaction.
Background technique
Ethyl alcohol is received significant attention as a kind of important clean fuel and chemicals, and there is an urgent need to explore efficient ethyl alcohol
Synthetic method, to meet ever-increasing market demand.It wherein, is the diformazan of Material synthesis by coal, biomass, shale gas etc.
Ether has important by the tandem green ethyl alcohol synthetic route of carbonylation methyl acetate, methyl acetate preparation of ethanol by hydrogenating
Prospects for commercial application.Currently, industrial methyl acetate adds the technique of hydrogen ethanol production quite complete maturation, but diformazan
It is low that the technique that ether carbonylation produces methyl acetate is still faced with dimethyl ether conversion rate, and poor catalyst stability, service life be short, catalyst
The disadvantages of expensive.
The Dimethyl ether carbonylation catalyst of reporting is Volkovad seminar (J.Am.Chem.Soc.131 (2009)
13054-13061) the heteropoly acid Rh/CsxH prepared3-xPW12O40Catalyst.But it is using noble metal Rh etc., catalyst cost
Height, and the stability of this catalyst system is very poor, the serious curtailment service life of catalyst.
Modenite is because of its unique pore structure, the advantages that big specific surface area, high stability and highly acid, two
There is important industrial application value in the carbonylation of dimethyl ether methyl acetate field.However, during Dimethyl ether carbonylation, mercerising
Easy carbon distribution inactivation, hinders its industrial application on zeolite molecular sieve.Patent CN101613274B is changed using organic amines such as pyridines
Sex pilus geolyte molecular sieve catalyst, modified pyridine substance are saturated absorption in the duct of molecular sieve, can poison mercerising
Acidic site in 12 annulus duct of zeolite, inhibits the formation of carbon distribution, and then improve the stability of the catalyst, but can make it simultaneously
Catalytic activity reduces about 40%~50%.
Therefore it provides a kind of high activity, high stability, highly selective Dimethyl ether carbonylation produce the catalysis of methyl acetate
Agent is current researcher's urgent problem to be solved in the art.
Summary of the invention
The work that there is high Dimethyl ether carbonylation to produce methyl acetate for current document and result of study discovery modenite
Property, however since the acidic site in 12 membered ring channels of modenite is easy carbon distribution, the inactivation of catalyst can be caused.In order to solve
This problem, some researchers are adsorbed on the acidic site in 12 membered ring channels using pyridine or picoline, inhibit catalyst
Carbon distribution inactivation.Patent CN101613274B is saturated the acidity being adsorbed onto 12 membered ring channels using pyridine and pyridine substance
On position, the stability of catalyst is improved.However, our result of study is found, have at present to the method for modenite modification
Non-selective the characteristics of poisoning acidic site in 12 membered ring channels.Non-selectively poison the acidity in 12 membered ring channel of modenite
Position, will reduce the active sites of Dimethyl ether carbonylation, reduces the activity of catalyst.In order to solve this problem, we are to molecular sieve
Modification process is improved, and during being modified with pyridine and pyridine substance, increases the pyridine under certain condition
Or picoline desorption process, selectively poison the strong adsorption potential of pyridine or picoline, and by the pyridine on weakly stable position
Or picoline desorption.Strong and weak adsorption potential is our structural analyses based on framework of molecular sieve, the pyridine on the sour position in discovery part
Absorption will receive the limitation of framework of molecular sieve steric hindrance, enable the adsorption capacity of this moieties pyridine weaker, so being weakly stable.This portion
The activity for dividing weakly stable position that there is Dimethyl ether carbonylation, therefore our molecular sieve modified technique will significantly improve catalyst and live
Property.In addition, catalyst still can be protected during Dimethyl ether carbonylation after the pyridine or picoline on weakly stable position are desorbed
Hold high stability, it is not easy to the carbon distribution inactivation of catalyst occur.
Technical problem solved by the present invention is proposing a kind of new modenite method of modifying, obtained modification mercerising
Zeolite molecular sieve produces methyl acetate for Dimethyl ether carbonylation, after solving existing pyridines substance modification catalyst, catalyst
The problem of stability increases, but catalytic activity declines to a great extent.
The technical solution adopted by the invention is as follows:
The method of modifying of h-mordenite molecular sieve for dimethyl ether carbonylation reaction；Include the following steps:
1) catalyst pre-processes: by h-mordenite molecular sieve in inert atmosphere or H2One kind or mixed atmosphere item of gas
Under part, in 300-600 DEG C of drying；H-mordenite molecular sieve after being dried；
2) pre- Adsorption of Pyridine processing: by the h-mordenite molecular sieve after drying 250-400 DEG C at a temperature of, be passed through
The gaseous mixture of pyridine or picoline and inert atmosphere enables the pre- Adsorption of Pyridine of mordenite molecular sieve or picoline, until point
Son sieve Adsorption of Pyridine or picoline saturation；
3) desorption by heating pyridine: the mordenite molecular sieve that Adsorption of Pyridine or picoline are saturated is carried out at desorption by heating
Reason, is passed through inert atmosphere, under conditions of desorption temperature is higher than 50-250 DEG C of adsorption temp, so that the pyridine or methyl of weakly stable
Pyridine desorption.
The inert atmosphere is N2, Ar or He.
Drying time 1-96h in the step (1).
The volume content of the gaseous mixture pyridine or picoline of step (2) pyridine or picoline and inert atmosphere is
0.5-5%.
The sial atomic ratio of the h-mordenite molecular sieve catalyst is (5-30): 1.
Modified mordenite produced by the present invention is used for Dimethyl ether carbonylation methyl acetate.
Inert atmosphere used may be the same or different in each step.
Methyl acetate is produced for Dimethyl ether carbonylation using the obtained catalyst of the present invention, has obtained high yield and steady
Fixed methyl acetate yield；High activity of catalyst of the invention is demonstrated, high stability is highly selective.
The invention has the advantages that the mordenite molecular sieve method that prepared pyridine is modified is simple to operation.And it solves
After traditional pyridine modified mordenite, the problem of catalytic activity declines, the present invention, can be with by increasing separating process
Selectively poison strong adsorption potential with pyridine or picoline, restores the catalytic activity of modified catalysts, and keep simultaneously
High catalytic stability and highly selective.The present invention can under mild conditions using such catalyst, and high activity and height are steady
Surely realize that Dimethyl ether carbonylation produces the process of methyl acetate.
Detailed description of the invention
Fig. 1 is the catalysis that MOR-250-300 catalyst prepared by embodiment 1 produces methyl acetate for Dimethyl ether carbonylation
Activity curve.
Fig. 2 is the catalysis that MOR-300-400 catalyst prepared by embodiment 2 produces methyl acetate for Dimethyl ether carbonylation
Activity curve.
Fig. 3 is the catalysis that MOR-350-400 catalyst prepared by embodiment 3 produces methyl acetate for Dimethyl ether carbonylation
Activity curve.
Fig. 4 is the catalysis that MOR-300-500 catalyst prepared by embodiment 4 produces methyl acetate for Dimethyl ether carbonylation
Activity curve.
Fig. 5 is the catalysis that MOR-250-500 catalyst prepared by embodiment 5 produces methyl acetate for Dimethyl ether carbonylation
Activity curve.
Fig. 6 is MOR-400-500-Py-CH prepared by embodiment 63Catalyst produces acetic acid first for Dimethyl ether carbonylation
The catalytic activity curve of ester.
Specific embodiment
Explanation of the invention, the substance that embodiment obtains specifically are named for convenience are as follows: when modified material is pyridine, are urged
The naming method of agent is MOR-x-y, and x is the adsorption temp of pyridine, and y is the desorption temperature of pyridine.When modified material is methyl
When pyridine, the naming method of catalyst are as follows: MOR-x-y-Py-CH3, x is the adsorption temp of picoline, and y is picoline
Desorption temperature.
Embodiment 1
1) the H-MOR modenite that silica alumina ratio is 5:1 is packed into reactor, 300 DEG C of dry 1h under Ar gas；
2) dried cooling catalyst is passed through 0.5% pyridine/He gaseous mixture, until Catalyst Adsorption pyridine to 250 DEG C
Saturation；
3) after Adsorption of Pyridine saturation, it is passed through N2Gas is warming up to 300 DEG C；At 300 DEG C, N2Pyridine 1h is desorbed under gas, obtains pyridine
The mordenite molecular sieve MOR-250-300 of selective modification.
Catalyst is used for Dimethyl ether carbonylation and produces methyl acetate, reaction condition are as follows: reaction pressure 1.5MPa, reaction
Gas group is divided into 3.0%DME/95.5%CO/1.5%N2, air speed is 5280mL (gh)-1.Prepared MOR-250-300 catalyst
The catalytic activity curve of methyl acetate is produced for Dimethyl ether carbonylation as shown in Figure 1, as can be seen from the figure after reacting 5h
The conversion ratio of dimethyl ether reaches maximum value 30%, then begins to decline, and to after 40h, the conversion ratio of dimethyl ether is 20%.
Embodiment 2
1) the H-MOR modenite that silica alumina ratio is 6:1 is packed into reactor, in N2Lower 500 DEG C of gas dry 72h；
2) by dried cooling catalyst to 300 DEG C, it is passed through 2% pyridine/N2/ Ar gaseous mixture, until Catalyst Adsorption
Pyridine saturation；
3) after Adsorption of Pyridine saturation, it is passed through N2Gas is warming up to 400 DEG C；At 400 DEG C, N2Pyridine 1h is desorbed under gas, obtains pyridine
The mordenite molecular sieve MOR-300-400 of selective modification.
Catalyst produces methyl acetate, reaction condition for Dimethyl ether carbonylation are as follows: reaction pressure 1.5MPa, reaction gas
Group is divided into 3.0%DME/95.5%CO/1.5%N2, air speed is 5280mL (gh)-1.Prepared MOR-300-400 catalyst is used
The catalytic activity curve of methyl acetate is produced in Dimethyl ether carbonylation as shown in Fig. 2, as can be seen from the figure two after reacting 5h
The conversion ratio of methyl ether reaches maximum value 41% or so, then begins to slowly decline, and to after 40h, the conversion ratio of dimethyl ether is 35%
Left and right.
Embodiment 3
1) the H-MOR modenite that silica alumina ratio is 16:1 is packed into reactor, 400 DEG C of dry 96h under He gas；
2) dried cooling catalyst is passed through 2% pyridine/He gaseous mixture to 350 DEG C, until Catalyst Adsorption pyridine is full
With；
3) it after Adsorption of Pyridine saturation, is passed through Ar gas and is warming up to 400 DEG C；Pyridine 1h is desorbed under 400 DEG C, Ar gas, obtains pyrrole
The mordenite molecular sieve MOR-350-400 of pyridine selective modification.
Catalyst produces methyl acetate, reaction condition for Dimethyl ether carbonylation are as follows: reaction pressure 1.5MPa, reaction gas
Group is divided into 3.0%DME/95.5%CO/1.5%N2, air speed is 5280mL (gh)-1.Prepared MOR-350-400 catalyst is used
The catalytic activity curve of methyl acetate is produced in Dimethyl ether carbonylation as shown in figure 3, as can be seen from the figure two after reacting 5h
The conversion ratio of methyl ether reaches maximum value 20%, then keeps stablizing, and to after 30h, the conversion ratio of dimethyl ether is 20%.
Embodiment 4
1) the H-MOR modenite that silica alumina ratio is 6:1 is packed into reactor, 500 DEG C of dryings are for 24 hours under Ar gas；
2) dried cooling catalyst is passed through 2% pyridine/Ar gaseous mixture to 300 DEG C, until Catalyst Adsorption pyridine is full
With；
3) it after Adsorption of Pyridine saturation, is passed through Ar gas and is warming up to 500 DEG C；Pyridine 1h is desorbed under 500 DEG C, Ar gas, obtains pyrrole
The mordenite molecular sieve MOR-300-500 of pyridine selective modification.
Catalyst produces methyl acetate, reaction condition for Dimethyl ether carbonylation are as follows: reaction pressure 1.5MPa, reaction gas
Group is divided into 3.0%DME/95.5%CO/1.5%N2, air speed is 5280mL (gh)-1.Prepared MOR-300-500 catalyst is used
The catalytic activity curve of methyl acetate is produced in Dimethyl ether carbonylation as shown in figure 4, as can be seen from the figure two after reacting 2h
The conversion ratio of methyl ether reaches maximum value 28%, then begins to decline, and to after 40h, the conversion ratio of dimethyl ether is 10%.
Embodiment 5
1) the H-MOR modenite that silica alumina ratio is 30:1 is packed into reactor, in H2Lower 600 DEG C of gas dry 2h；
2) dried cooling catalyst is passed through 5% pyridine/N to 250 DEG C2Gaseous mixture, until Catalyst Adsorption pyridine is full
With；
3) after Adsorption of Pyridine saturation, it is passed through N2Gas is warming up to 500 DEG C；At 500 DEG C, N2Pyridine 1h is desorbed under gas, obtains pyridine
The mordenite molecular sieve MOR-250-500 of selective modification.
Catalyst produces methyl acetate, reaction condition for Dimethyl ether carbonylation are as follows: reaction pressure 1.5MPa, reaction gas
Group is divided into 3.0%DME/95.5%CO/1.5%N2, air speed is 5280mL (gh)-1.Prepared MOR-250-500 catalyst is used
The catalytic activity curve of methyl acetate is produced in Dimethyl ether carbonylation as shown in Figure 1, as can be seen from the figure two after reacting 3h
The conversion ratio of methyl ether reaches maximum value 16%, then keeps stablizing, and to after 30h, the conversion ratio of dimethyl ether is 15%.
Embodiment 6
1) the H-MOR modenite that silica alumina ratio is 6:1 is packed into reactor, 350 DEG C of dry 48h under Ar/He atmosphere；
2) dried catalyst drop is warming up to 400 DEG C, is passed through 2% picoline/N2Gaseous mixture, until Catalyst Adsorption
Pyridine saturation；
3) after Adsorption of Pyridine saturation, it is passed through N2Gas is warming up to 500 DEG C；At 500 DEG C, N21h is desorbed under gas, obtains picoline
The mordenite molecular sieve MOR-400-500-Py-CH of selective modification3。
Catalyst produces methyl acetate, reaction condition for Dimethyl ether carbonylation are as follows: reaction pressure 1.5MPa, reaction gas
Group is divided into 3.0%DME/95.5%CO/1.5%N2, air speed is 5280mL (gh)-1.Prepared MOR-400-500-Py-CH3
Catalyst produces the catalytic activity curve of methyl acetate as shown in fig. 6, as can be seen from the figure anti-for Dimethyl ether carbonylation
It answers the conversion ratio of dimethyl ether after 3h to reach maximum value 20%, then begins to decline, to after 40h, the conversion ratio of dimethyl ether is 10%.
The invention proposes the method for modifying of the h-mordenite molecular sieve for dimethyl ether carbonylation reaction；Pass through
Live preferred embodiment is described, related technical personnel obviously can not depart from the content of present invention, in spirit and scope it is right
Method described herein is modified or appropriate changes and combinations, Lai Shixian the technology of the present invention.In particular, it should be pointed out that all
Similar replacement and change is apparent to those skilled in the art, they are considered as being included in essence of the invention
In mind, range and content.
Claims (6)
1. the method for modifying of the h-mordenite molecular sieve for dimethyl ether carbonylation reaction；It is characterized in that including following step
It is rapid:
1) catalyst pre-processes: by h-mordenite molecular sieve in inert atmosphere or H2Under the conditions of one kind or mixed atmosphere of gas,
In 300-600 DEG C of drying；H-mordenite molecular sieve after being dried；
2) pre- Adsorption of Pyridine processing: by the h-mordenite molecular sieve after drying 250-400 DEG C at a temperature of, be passed through pyridine
Or the gaseous mixture of picoline and inert atmosphere, the pre- Adsorption of Pyridine of mordenite molecular sieve or picoline are enabled, until molecular sieve
Adsorption of Pyridine or picoline saturation；
3) desorption by heating pyridine: carrying out desorption by heating processing for the mordenite molecular sieve that Adsorption of Pyridine or picoline are saturated,
It is passed through inert atmosphere, under conditions of desorption temperature is higher than 50-250 DEG C of adsorption temp, so that the pyridine of weakly stable or methyl pyrrole
Pyridine desorption.
2. the method as described in claim 1, it is characterized in that the inert atmosphere is N2, Ar or He.
3. the method as described in claim 1, it is characterized in that drying time 1-96h in the step (1).
4. the method as described in claim 1, it is characterized in that the gaseous mixture pyridine or first of pyridine or picoline and inert atmosphere
The volume content of yl pyridines is 0.5-5%.
5. the method as described in claim 1, it is characterized in that the sial atomic ratio of the h-mordenite molecular sieve catalyst
For (5-30): 1.
6. being used for Dimethyl ether carbonylation second using modified mordenite made from method of modifying described in claim 1
Sour methyl esters.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112495433A (en) * | 2020-12-22 | 2021-03-16 | 华南理工大学 | Pyrazole salt modified hydrogen-type mordenite catalyst, and preparation method and application thereof |
| CN112588312A (en) * | 2020-12-28 | 2021-04-02 | 延长中科（大连）能源科技股份有限公司 | Activation method of catalyst in methyl acetate preparation process |
| WO2021092794A1 (en) * | 2019-11-13 | 2021-05-20 | 中国科学院大连化学物理研究所 | Catalyst for carbonylation of dimethyl ether to produce methyl acetate, preparation method therefor, and use thereof |
| CN112978750A (en) * | 2021-01-26 | 2021-06-18 | 青岛科技大学 | Molecular sieve modification post-treatment method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| CN107537549A (en) * | 2017-08-24 | 2018-01-05 | 中国烟草总公司郑州烟草研究院 | A kind of zeolite molecular sieve catalyst and its application |
-
2019
- 2019-03-22 CN CN201910221033.1A patent/CN109985658B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| CN107537549A (en) * | 2017-08-24 | 2018-01-05 | 中国烟草总公司郑州烟草研究院 | A kind of zeolite molecular sieve catalyst and its application |
Non-Patent Citations (3)
| Title |
|---|
| HUIFU XUE等: "Selective dealumination of mordenite for enhancing its stability in dimethyl ether carbonylation", 《CATALYSIS COMMUNICATIONS》 * |
| LIU JUNLONG等: "Stability Enhancement of H-Mordenite in Dimethyl Ether Carbonylation to Methyl Acetate by Pre-adsorption of Pyridine", 《CHINESE JOURNAL OF CATALYSIS》 * |
| 韩海波 等: "超声波碱处理改性对丝光沸石结构、酸性质及其催化性能的影响", 《化工学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021092794A1 (en) * | 2019-11-13 | 2021-05-20 | 中国科学院大连化学物理研究所 | Catalyst for carbonylation of dimethyl ether to produce methyl acetate, preparation method therefor, and use thereof |
| CN112495433A (en) * | 2020-12-22 | 2021-03-16 | 华南理工大学 | Pyrazole salt modified hydrogen-type mordenite catalyst, and preparation method and application thereof |
| CN112495433B (en) * | 2020-12-22 | 2021-10-22 | 华南理工大学 | Pyrazole salt modified hydrogen-type mordenite catalyst, and preparation method and application thereof |
| CN112588312A (en) * | 2020-12-28 | 2021-04-02 | 延长中科（大连）能源科技股份有限公司 | Activation method of catalyst in methyl acetate preparation process |
| CN112978750A (en) * | 2021-01-26 | 2021-06-18 | 青岛科技大学 | Molecular sieve modification post-treatment method |
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