CN107537550B - Molecular sieve catalyst containing eight-membered ring channels and preparation method and application thereof - Google Patents
Molecular sieve catalyst containing eight-membered ring channels and preparation method and application thereof Download PDFInfo
- Publication number
- CN107537550B CN107537550B CN201710736254.3A CN201710736254A CN107537550B CN 107537550 B CN107537550 B CN 107537550B CN 201710736254 A CN201710736254 A CN 201710736254A CN 107537550 B CN107537550 B CN 107537550B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- membered ring
- precursor
- catalyst containing
- sieve catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a molecular sieve catalyst containing eight-membered ring channels and a preparation method and application thereof, belonging to the technical field of chemical catalysis. The preparation method of the molecular sieve catalyst containing the eight-membered ring channel comprises the following steps: 1) carrying out catalytic reaction on the activated hydrogen type molecular sieve and a small molecular organic substance at 300-600 ℃ to obtain a precursor A; the molecular dynamics diameter of the small molecular organic matter is 0.4-0.7 nm; 2) under the protection of inert gas, carbonizing the precursor A obtained in the step 1) at 700-900 ℃ for 1-10 h to obtain a precursor B; 3) and mixing the precursor B with a dispersant, performing ball milling to obtain mixed slurry, performing solid-liquid separation, washing and drying to obtain the catalyst, wherein the dispersant is any one or more of water, methanol and ethanol. The molecular sieve catalyst containing the eight-membered ring channel obtained by the method has high selectivity and long service life in the process of preparing methyl acetate.
Description
Technical Field
The invention relates to a molecular sieve catalyst containing eight-membered ring channels and a preparation method and application thereof, belonging to the technical field of chemical catalysis.
Background
Methyl acetate (methyl acetate) is widely used in the industries of textile, spice, medicine and the like, is an important organic raw material intermediate, and downstream products mainly comprise acetic acid, acetic anhydride, methyl acrylate, vinyl acetate, acetamide and the like. In China, the production of methyl acetate is mainly a traditional esterification method. The method has the problems of complicated product and catalyst separation, expensive and short-lived noble metal rhodium and serious corrosion of equipment caused by iodide. The solid acid is used for catalyzing the carbonylation of dimethyl ether to prepare methyl acetate, the catalyst used in the process is a solid catalyst, the catalyst is free of corrosion and easy to separate, and the problem of excess DME productivity can be solved.
At present, the catalyst which is researched more and has better catalytic effect is mainly a mordenite molecular sieve. The framework structure of mordenite has 12-membered ring and 8-membered ring straight channels along [001], the 8-membered ring channel is located between the 12-membered ring channels, and the 8-membered ring straight channel is also present along [010 ]. The 12-membered ring orifice is elliptical, and has a size of 0.65nm × 0.70nm, the [001] direction 8-membered ring orifice is 0.26nm × 0.57nm, and the [010] direction side pocket 8-membered ring orifice is 0.34nm × 0.48 nm. Research shows that for the dimethyl ether carbonylation reaction catalyzed by the molecular sieve, the activity of the acid site in the 8-membered ring channel is higher, and the acid site in the 12-membered ring channel is closely related to the inactivation of the molecular sieve catalyst. Therefore, in order to improve the stability of the catalyst and the selectivity of methyl acetate, it is necessary to selectively weaken or eliminate the role of the acidic site in the 12-membered ring in the reaction system.
To this end, various approaches have been taken to achieve this goal. Two methods of pyridine adsorption and dealumination are mainly used. The method for pre-adsorbing pyridine has the problem of slow desorption of the pyridine adsorbent in the using process, and the product quality is difficult to avoid influence. In the dealumination by acid treatment or steam treatment, there are problems that the dealumination selectivity is poor and the molecular sieve structure is liable to collapse. The molecular sieve pre-carbon deposition technology is a method for effectively modifying the acid site of a catalyst.
The Chinese patent with publication number CN 101475432A discloses a method for selectivity of butene double bond isomerization reaction, which adopts a method of pre-depositing carbon to prepare an aluminosilicate catalyst of the pre-depositing carbon to improve the selectivity of butene double bond isomerization, but the starting point of the patent is that the pre-depositing carbon covers strong acid sites in pore channels, but does not cover weak acid sites which play a role in isomerization, and the pore openings of a molecular sieve are easy to block in the preparation method of the pre-depositing carbon catalyst, which is unfavorable for the reaction activity of the subsequent butene isomerization reaction.
Disclosure of Invention
The invention aims to provide a preparation method of a molecular sieve catalyst containing eight-membered ring channels.
The second purpose of the invention is to provide a molecular sieve catalyst containing eight-membered ring channels, so as to improve the service life and selectivity of the molecular sieve catalyst in the dimethyl ether carbonylation reaction.
The third purpose of the invention is to provide the application of the molecular sieve catalyst containing eight-membered ring channels in the dimethyl ether carbonylation reaction.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a molecular sieve catalyst containing eight-membered ring channels comprises the following steps:
1) carrying out catalytic reaction on the activated hydrogen type molecular sieve and the small molecular organic matter at 300-600 ℃, and stopping the reaction when the conversion rate of the small molecular organic matter is lower than 5% to obtain a precursor A; the molecular dynamics diameter of the small molecular organic matter is 0.4-0.7 nm;
2) under the protection of inert gas, carbonizing the precursor A obtained in the step 1) at 700-900 ℃ for 1-10 h to obtain a precursor B;
3) and mixing the precursor B with a dispersant, performing ball milling to obtain mixed slurry, performing solid-liquid separation, washing and drying to obtain the catalyst, wherein the dispersant is any one or more of water, methanol and ethanol.
The hydrogen type molecular sieve in the step 1) is hydrogen type mordenite or hydrogen type ZSM-35 molecular sieve. The mordenite has the MOR structure. The ZSM-35 molecular sieve has a FER structure.
The activation method of the hydrogen type molecular sieve in the step 1) comprises the following steps: activating the hydrogen type molecular sieve for 0.5-4 h at 350-600 ℃ in an activating atmosphere.
The activating atmosphere is any one of nitrogen, air, oxygen and helium.
The molecular dynamics diameter of the small molecular organic matters in the step 1) is preferably 0.5-0.7 nm.
The micromolecular organic matter in the step 1) is any one or more of 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, propylene, butylene, butadiene, pentene, toluene and xylene. The molecular diameter of the small molecular organic matter is between twelve-membered ring/ten-membered ring and eight-membered ring of the molecular sieve, so that the small molecular organic matter can selectively enter a twelve-membered ring/ten-membered ring channel and selectively cover an acid site in the twelve-membered ring/ten-membered ring channel by adopting a pre-carbon deposition method, and the acid site of the eight-membered ring is basically not influenced.
The four molecular formulas of the butylene are C4H8Any one or more of the isomers of (a).
The above-mentioned amylenes are of six molecular formulae C5H10Any one or more of the isomers of (a).
The xylene is one or more of o-xylene, p-xylene and m-xylene.
The catalytic reaction in step 1) is carried out in a reactor. The reactor is any one of a fixed bed, a fluidized bed and a moving bed reactor.
In the step 2), the heating rate of heating to 700-900 ℃ is 50-200 ℃/min. In the step 2), soft carbon deposition (such as polycyclic aromatic hydrocarbon and the like) generated in the molecular sieve macropore in the catalytic reaction in the step 1) can be further converted into graphite carbon through high-temperature carbonization, and the graphite carbon is more stable and is not easy to desorb in the subsequent use process, so that the service life of the catalyst is prolonged.
And (3) introducing inert gas for cooling after the reaction is stopped in the step 1). The inert gas is nitrogen or helium.
The inert gas in the step 2) is nitrogen or helium.
The mass ratio of the dispersing agent to the precursor B in the step 3) is 1-50: 1.
The water in the step 3) is deionized water.
The ball milling in the step 3) is performed for 1-12 h at a rotating speed of 250-600 rmp.
The total volume of the precursor B and the dispersing agent is less than 3/4 of the volume of the ball milling tank. The molecular sieve sample is crushed by adopting a ball milling method, and the connectivity between the eight-membered ring channel and the outside is fully released, so that the dimethyl ether carbonylation activity is improved.
A molecular sieve catalyst containing eight-membered ring channels is prepared by the preparation method of the molecular sieve catalyst containing eight-membered ring channels. The molecular sieve catalyst containing eight-membered ring channels has high selectivity in the reaction of preparing methyl acetate by carbonylation of dimethyl ether.
The molecular sieve catalyst containing eight-membered ring channels is applied to the dimethyl ether carbonylation reaction.
According to the preparation method of the molecular sieve catalyst containing the eight-membered ring channel, the acid sites in the 12-membered ring/10-membered ring channels of the molecular sieve are covered by hard carbon by adopting a pre-carbon deposition method, and the connectivity between the 8-membered ring channel and the outside is fully released by adopting a ball milling method, so that the activity and the stability of dimethyl ether carbonylation are improved. The molecular sieve catalyst containing the eight-membered ring channel obtained by the method has high selectivity and long service life in the process of preparing methyl acetate.
Drawings
FIG. 1 is a schematic process flow diagram of a method for preparing the molecular sieve catalyst containing eight-membered ring channels of example 1.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
Example 1
The preparation method of the molecular sieve catalyst containing eight-membered ring channels of this embodiment, as shown in fig. 1, includes the following steps:
1) converting the mordenite molecular sieve into hydrogen-type mordenite by adopting an ammonia exchange method, filling the hydrogen-type mordenite into a fixed bed reactor, and heating to 400 ℃ in a nitrogen atmosphere to activate for 2 h;
2) after activation, cooling to 300 ℃, introducing 1-propanol into the catalyst bed layer for catalytic reaction, stopping substrate feeding when the conversion rate of the 1-propanol is lower than 5%, and purging the catalyst bed layer by nitrogen to cool to obtain a precursor A;
3) placing the precursor A in a high-temperature furnace, heating to 900 ℃ at a heating rate of 200 ℃/min under the protection of nitrogen, and carbonizing for 1h to obtain a precursor B;
4) mixing the precursor B obtained in the step 3) with a dispersant methanol, placing the mixture in a planetary ball mill to perform ball milling for 12 hours at the rotating speed of 300rpm, and then filtering, washing and drying the mixture to obtain the catalyst, wherein the mass ratio of the methanol to the precursor B is 10: 1.
Example 2
The preparation method of the molecular sieve catalyst containing eight-membered ring channels of the embodiment comprises the following steps:
1) converting the mordenite molecular sieve into hydrogen-type mordenite by adopting an ammonia exchange method, filling the hydrogen-type mordenite into a fluidized bed reactor, and heating to 400 ℃ in a nitrogen atmosphere to activate for 1 h;
2) after activation, keeping the temperature at 400 ℃, introducing 1-butanol into the catalyst bed layer for catalytic reaction, stopping substrate feeding when the conversion rate of the 1-butanol is lower than 5%, and purging the catalyst bed layer by helium to cool to obtain a precursor A;
3) placing the precursor A in a high-temperature furnace, heating to 700 ℃ at a heating rate of 150 ℃/min under the protection of nitrogen, and carbonizing for 4h to obtain a precursor B;
4) mixing the precursor B obtained in the step 3) with a dispersant methanol and deionized water, placing the mixture in a planetary ball mill, carrying out ball milling for 8 hours at the rotating speed of 300rpm, and then filtering, washing and drying the mixture to obtain the catalyst, wherein the mass ratio of the methanol to the deionized water is 1:1, and the mass ratio of the total mass of the methanol and the deionized water to the precursor B is 25: 1.
Example 3
The preparation method of the molecular sieve catalyst containing eight-membered ring channels of the embodiment comprises the following steps:
1) converting the mordenite molecular sieve into hydrogen-type mordenite by adopting an ammonia exchange method, filling the hydrogen-type mordenite into a moving bed reactor, and heating to 450 ℃ in a nitrogen atmosphere to activate for 1 h;
2) after activation, keeping 450 ℃ and introducing 2-butanol into the catalyst bed layer for catalytic reaction, stopping substrate feeding when the conversion rate of the 2-butanol is lower than 5%, and purging the catalyst bed layer by helium to cool to obtain a precursor A;
3) placing the precursor A in a high-temperature furnace, heating to 800 ℃ at a heating rate of 100 ℃/min under the protection of nitrogen, and carbonizing for 2h to obtain a precursor B;
4) mixing the precursor B obtained in the step 3) with a dispersant methanol, placing the mixture in a planetary ball mill to perform ball milling for 10 hours at the rotating speed of 250rpm, and then filtering, washing and drying the mixture to obtain the catalyst, wherein the mass ratio of the methanol to the precursor B is 1: 1.
Example 4
The preparation method of the molecular sieve catalyst containing eight-membered ring channels of the embodiment comprises the following steps:
1) converting the mordenite molecular sieve into hydrogen-type mordenite by adopting an ammonia exchange method, filling the hydrogen-type mordenite into a moving bed reactor, and heating to 500 ℃ in a nitrogen atmosphere to activate for 1.5 h;
2) after activation, keeping 500 ℃, introducing 2-propanol and toluene into the catalyst bed layer for catalytic reaction, wherein the molar ratio of the 2-propanol to the toluene is 2:1, stopping feeding the substrate when the conversion rate of the toluene is lower than 5%, and purging the catalyst bed layer by using nitrogen to reduce the temperature to obtain a precursor A;
3) placing the precursor A in a high-temperature furnace, heating to 800 ℃ at a heating rate of 80 ℃/min under the protection of helium, and carbonizing for 2h to obtain a precursor B;
4) mixing the precursor B obtained in the step 3) with dispersant deionized water, placing the mixture in a planetary ball mill to perform ball milling for 5 hours at the rotating speed of 400rpm, and then filtering, washing and drying the mixture to obtain the catalyst, wherein the mass ratio of the deionized water to the precursor B is 50: 1.
Example 5
The preparation method of the molecular sieve catalyst containing eight-membered ring channels of the embodiment comprises the following steps:
1) converting the mordenite molecular sieve into hydrogen-type mordenite by adopting an ammonia exchange method, filling the hydrogen-type mordenite into a moving bed reactor, and heating to 350 ℃ in an oxygen atmosphere for activation for 4 h;
2) after activation, keeping 350 ℃, introducing 2-butene and p-xylene into a catalyst bed layer for catalytic reaction, wherein the molar ratio of the 2-butene to the p-xylene is 2:1, stopping feeding a substrate when the conversion rate of the p-xylene is lower than 5%, and purging the catalyst bed layer by nitrogen to reduce the temperature to obtain a precursor A;
3) placing the precursor A in a high-temperature furnace, heating to 750 ℃ at a heating rate of 200 ℃/min under nitrogen, and carbonizing for 3h to obtain a precursor B;
4) mixing the precursor B obtained in the step 3) with a dispersant ethanol, placing the mixture in a planetary ball mill to perform ball milling for 5 hours at the rotating speed of 450rpm, and then filtering, washing and drying the mixture to obtain the catalyst, wherein the mass ratio of the ethanol to the precursor B is 12: 1.
Example 6
The preparation method of the molecular sieve catalyst containing eight-membered ring channels of the embodiment comprises the following steps:
1) converting the mordenite molecular sieve into hydrogen-type mordenite by adopting an ammonia exchange method, filling the hydrogen-type mordenite into a moving bed reactor, and heating to 450 ℃ in an air atmosphere to activate for 0.5 h;
2) after activation, keeping 450 ℃ and introducing micromolecular organic matters with the molecular dynamics diameter smaller than 0.7nm into the catalyst bed layer to perform catalytic reaction on the dimethylbenzene, stopping feeding the substrate when the conversion rate of the dimethylbenzene is lower than 5%, and purging the catalyst bed layer by adopting nitrogen to reduce the temperature to obtain a precursor A;
3) placing the precursor A in a high-temperature furnace, heating to 700 ℃ at a heating rate of 100 ℃/min under the protection of helium, and carbonizing for 2h to obtain a precursor B;
4) mixing the precursor B obtained in the step 3) with water and ethanol serving as a dispersing agent, placing the mixture in a planetary ball mill, carrying out ball milling for 4 hours at the rotating speed of 550rpm, and then filtering, washing and drying the mixture to obtain the catalyst, wherein the mass ratio of the water to the ethanol is 1:1, and the mass ratio of the total mass of the water and the ethanol to the precursor B is 40: 1.
Example 7
The preparation method of the molecular sieve catalyst containing eight-membered ring channels of the embodiment comprises the following steps:
1) converting the mordenite molecular sieve into hydrogen-type mordenite by adopting an ammonia exchange method, filling the hydrogen-type mordenite into a moving bed reactor, and heating to 490 ℃ in an air atmosphere to activate for 0.5 h;
2) after activation, keeping 490 ℃, introducing micromolecular organic matters 1, 3-butadiene with the molecular kinetic diameter less than 0.7nm and cis-2-butene into a catalyst bed layer for catalytic reaction, wherein the molar ratio of the 1, 3-butadiene to the cis-2-butene is 1: 1; stopping feeding the substrate when the conversion rates of the 1, 3-butadiene and the cis-2-butene are lower than 5%, and purging the catalyst bed layer by adopting nitrogen to reduce the temperature to obtain a precursor A;
3) placing the precursor A in a high-temperature furnace, heating to 800 ℃ at a heating rate of 50 ℃/min under nitrogen, and carbonizing for 6h to obtain a precursor B;
4) mixing the precursor B obtained in the step 3) with deionized water of a dispersing agent, placing the mixture in a planetary ball mill for ball milling for 1h at the rotating speed of 600rpm, and then filtering, washing and drying the mixture to obtain the catalyst, wherein the mass ratio of deionized water to the precursor B is 45: 1.
Example 8
The preparation method of the molecular sieve catalyst containing eight-membered ring channels of the embodiment comprises the following steps:
1) converting the mordenite molecular sieve into hydrogen-type mordenite by adopting an ammonia exchange method, filling the hydrogen-type mordenite into a moving bed reactor, and heating to 600 ℃ in an air atmosphere for activation for 0.5 h;
2) after activation, keeping 600 ℃ and introducing 1-pentene into the catalyst bed layer for catalytic reaction, stopping substrate feeding when the conversion rate of the 1-pentene is lower than 5%, and purging the catalyst bed layer by nitrogen to reduce the temperature to obtain a precursor A;
3) placing the precursor A in a high-temperature furnace, heating to 700 ℃ at a heating rate of 50 ℃/min under nitrogen, and carbonizing for 10h to obtain a precursor B;
4) mixing the precursor B obtained in the step 3) with dispersant deionized water, placing the mixture in a planetary ball mill to perform ball milling for 1h at the rotating speed of 600rpm, and then filtering, washing and drying the mixture to obtain the catalyst, wherein the mass ratio of the deionized water to the precursor B is 45: 1.
Examples of the experiments
The activity evaluation of the catalyst is carried out on a continuous flowing pressurized stainless steel fixed bed reactor (the inner diameter is 8mm), and the catalyst powder obtained in the examples 1-7 is tableted and sieved to obtain particles of 40-60 meshes for the reaction performance evaluation of the dimethyl ether carbonylation for producing methyl acetate. The control was mordenite in the hydrogen form without any treatment. 1.0g of each catalyst is respectively loaded into a reactor, the temperature is reduced to 200 ℃ after the activation of inert atmosphere, and after the temperature is stable, the mixed gas of dimethyl ether, hydrogen and carbon monoxide is fed and reacted under the conditions that the pressure is 2.0MPa and the gas volume flow rate is 1500 ml/g/h. Wherein the total flow of hydrogen and dimethyl ether is 16.4ml/min, and the ratio of dimethyl ether: carbon monoxide: the hydrogen was 5:35:60 (by volume) and the results of the catalyst reaction are shown in Table 1.
TABLE 1 results of catalytic reactions of catalysts obtained in examples 1 to 7 and a control catalyst
Note: a: the highest conversion rate in the reaction process; b: selectivity of methyl acetate at the highest conversion during the reaction; c: the time taken for the conversion to decrease to half of the maximum conversion.
Claims (8)
1. A preparation method of a molecular sieve catalyst containing eight-membered ring channels is characterized by comprising the following steps:
1) carrying out catalytic reaction on the activated hydrogen type molecular sieve and the small molecular organic matter at 300-600 ℃, and stopping the reaction when the conversion rate of the small molecular organic matter is lower than 5% to obtain a precursor A; the molecular dynamics diameter of the small molecular organic matter is 0.4-0.7 nm; the micromolecular organic matter in the step 1) is any one or more of 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, propylene, butylene, butadiene, pentene, toluene and xylene; the hydrogen type molecular sieve is hydrogen type mordenite or hydrogen type ZSM-35 molecular sieve;
2) under the protection of inert gas, carbonizing the precursor A obtained in the step 1) at 700-900 ℃ for 1-10 h to obtain a precursor B;
3) and mixing the precursor B with a dispersant, performing ball milling to obtain mixed slurry, performing solid-liquid separation, washing and drying to obtain the catalyst, wherein the dispersant is any one or more of water, methanol and ethanol.
2. The method of claim 1, wherein the activation of the hydrogen form of the molecular sieve in step 1) comprises: activating the hydrogen type molecular sieve at 350-600 ℃ for 0.5-2 h in an activating atmosphere.
3. The method of claim 2 wherein the activating atmosphere is any one of nitrogen, air, oxygen, and helium.
4. The method for preparing the molecular sieve catalyst containing eight-membered ring channels according to claim 1, wherein the temperature rise rate of the step 2) to 700-900 ℃ is 50-200 ℃/min.
5. The preparation method of the molecular sieve catalyst containing the eight-membered ring channel according to claim 1, wherein the mass ratio of the dispersing agent to the precursor B in the step 3) is 1-50: 1.
6. The method for preparing the molecular sieve catalyst containing eight-membered ring channels according to claim 1, wherein the ball milling in the step 3) is performed at a rotating speed of 250 to 600rmp for 1 to 12 hours.
7. A molecular sieve catalyst containing eight-membered ring channels, prepared by the process of claim 1.
8. The use of a molecular sieve catalyst containing eight-membered ring channels according to claim 7 in the carbonylation of dimethyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710736254.3A CN107537550B (en) | 2017-08-24 | 2017-08-24 | Molecular sieve catalyst containing eight-membered ring channels and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710736254.3A CN107537550B (en) | 2017-08-24 | 2017-08-24 | Molecular sieve catalyst containing eight-membered ring channels and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107537550A CN107537550A (en) | 2018-01-05 |
| CN107537550B true CN107537550B (en) | 2020-05-08 |
Family
ID=60958359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710736254.3A Active CN107537550B (en) | 2017-08-24 | 2017-08-24 | Molecular sieve catalyst containing eight-membered ring channels and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107537550B (en) |
Citations (5)
| 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 |
| CN103203248A (en) * | 2012-01-13 | 2013-07-17 | 中国科学院大连化学物理研究所 | Preparation method for ZSM-35 molecular sieve carbonylation catalyst |
| CN103896769A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing methyl acetate via carbonylation of dimethyl ether |
| CN104689845A (en) * | 2013-12-05 | 2015-06-10 | 中国科学院大连化学物理研究所 | Catalyst used for preparing methyl acetate through dimethyl ether carbonylation, preparation method and application thereof |
| CN105618112A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Hydro-cracking catalyst containing Y molecular sieve, and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2174713A1 (en) * | 2008-10-13 | 2010-04-14 | BP Chemicals Limited | Dealumination process |
-
2017
- 2017-08-24 CN CN201710736254.3A patent/CN107537550B/en active Active
Patent Citations (5)
| 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 |
| CN103203248A (en) * | 2012-01-13 | 2013-07-17 | 中国科学院大连化学物理研究所 | Preparation method for ZSM-35 molecular sieve carbonylation catalyst |
| CN103896769A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing methyl acetate via carbonylation of dimethyl ether |
| CN104689845A (en) * | 2013-12-05 | 2015-06-10 | 中国科学院大连化学物理研究所 | Catalyst used for preparing methyl acetate through dimethyl ether carbonylation, preparation method and application thereof |
| CN105618112A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Hydro-cracking catalyst containing Y molecular sieve, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Stability Enhancement of H-Mordenite in Dimethyl Ether Carbonylation to Methyl Acetate by Pre-adsorption of Pyridine;Junlong LIU等;《Chinese Journal of Catalysis》;20100731;第31卷(第7期);第730页左栏第2段，第1.1节，Fig.1，第733页第2段，第3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107537550A (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107537548B (en) | Carbon-containing molecular sieve catalyst and preparation method and application thereof | |
| CN109569686B (en) | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of halogenated nitrobenzene | |
| CN107537549B (en) | Zeolite molecular sieve catalyst and application thereof | |
| CN101885662B (en) | Toluene methanol alkylation method | |
| CN110975806B (en) | Adsorbent, application of adsorbent in co-oxidation method for co-production of refining dimethyl benzyl alcohol hydrogenolysis raw material and method | |
| CN107519929B (en) | Molecular sieve catalyst and application thereof | |
| CN111151287B (en) | Alkaline oxide modified boron nitride catalyst and preparation method and application thereof | |
| CN107285342B (en) | The method of solid acid post-processing synthesis multi-stage porous SAPO-34 molecular sieve | |
| KR101742360B1 (en) | Bismuth molybdate catalyst having zeolite coating layer, preparation method thereof and method of preparing 1,3-butadiene using the same | |
| CN101947444B (en) | Attapulgite load nano Pd catalyst and method for preparing chloroaniline by catalyzing and deoxidating attapulgite load nano Pd catalyst | |
| CN109759109B (en) | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of nitrobenzene compounds | |
| CN107445831B (en) | Process for producing glyoxylic acid esters | |
| CN108014777B (en) | Carbon carrier for hydrogenation catalyst, preparation method of carbon carrier, palladium-based supported hydrogenation catalyst and application of palladium-based supported hydrogenation catalyst | |
| CN104971758B (en) | A kind of azepine of high activity activated carbon supported palladium catalyst, its preparation method and application | |
| CN107519916B (en) | Molecular sieve catalyst, and preparation method and application thereof | |
| CN107537550B (en) | Molecular sieve catalyst containing eight-membered ring channels and preparation method and application thereof | |
| US11292761B2 (en) | Method for directly producing methyl acetate and/or acetic acid from syngas | |
| US20210162381A1 (en) | Catalyst for preparing pyridine base from syngas, and preparation method and application thereof | |
| CN109701574B (en) | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of pyridine ring compounds | |
| CN107519915B (en) | Catalyst for dimethyl ether carbonylation and preparation method and application thereof | |
| CN107537547B (en) | Catalyst for dimethyl ether carbonylation and preparation method and application thereof | |
| CN107537551B (en) | Molecular sieve catalyst for carbonylation reaction and preparation method and application thereof | |
| CN107519914B (en) | Molecular sieve catalyst for carbonylation reaction and preparation method and application thereof | |
| CN101302141B (en) | Method for directly synthesizing phenyl hydrate by catalyzing dioxygen and liquid-phase oxidation benzene | |
| CN104419453B (en) | A kind of method of many unsaturated hydrocarbon selective hydrogenations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |