CN109876854B - Naphthalene liquid-phase oxidation catalyst, preparation method and application thereof - Google Patents
Naphthalene liquid-phase oxidation catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN109876854B CN109876854B CN201711282747.0A CN201711282747A CN109876854B CN 109876854 B CN109876854 B CN 109876854B CN 201711282747 A CN201711282747 A CN 201711282747A CN 109876854 B CN109876854 B CN 109876854B
- Authority
- CN
- China
- Prior art keywords
- naphthalene
- catalyst
- transition metal
- molecular sieve
- gel
- 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 application discloses a naphthalene liquid phase oxidation catalyst, which comprises a Beta molecular sieve containing transition metal oxide particles and a preparation method thereof, wherein the preparation method comprises the following steps: a) preparing gel: mixing a structure directing agent, an aluminum source, a silicon source, a transition metal precursor, a fluoride ion source and water, and stirring to form gel, wherein the gel comprises the following components in a molar ratio: SiO 22/Al2O310-1000, and M/Si is 0.01-2, wherein M is a transition metal; b) and (3) crystallization: transferring the gel obtained in the step a) into a synthesis kettle, and crystallizing for 0.5-10 days at the temperature of 110-220 ℃. The application also discloses the application of the catalyst in catalyzing naphthalene oxidation reaction in an organic solvent, the conversion rate of naphthalene and the selectivity of a target product are effectively improved, the reaction condition is mild, the operation is simple, and the catalyst is easy to prepare, pollution-free and recyclable.
Description
Technical Field
The invention relates to a naphthalene liquid-phase oxidation catalyst, a preparation method and application thereof, belonging to the field of chemistry and chemical engineering.
Background
Naphthalene is industrially most important fused ring aromatic hydrocarbon, and oxygen-containing organic chemicals synthesized by oxidation occupy an important position in petrochemicals. Naphthalene can be converted into oxygen-containing compounds such as naphthol, 1, 4-naphthoquinone, phthalic anhydride and the like by using an oxidation reaction, and the oxygen-containing compounds are important organic chemical raw materials and important intermediates and raw materials for organic synthesis, so that the catalytic oxidation of the naphthalene is one of important ways for producing various high-value chemicals by using the naphthalene as a raw material.
Naphthalene can be first oxidized to naphthol in the presence of a catalyst, followed by deep oxidation of naphthol to 1, 4-naphthoquinone and phthalic anhydride, and then deep oxidation to maleic anhydride to water, carbon monoxide and carbon dioxide, among others. In the main product of naphthalene oxidation, naphthol is unstable and can be continuously oxidized under the action of catalyst to obtain 1, 4-naphthoquinone and phthalic anhydride. Thus, the selectivity of naphthol is low, so that the main products of oxidation are 1, 4-naphthoquinone and phthalic anhydride. The 1, 4-naphthoquinone and the phthalic anhydride are easy to separate, and the operation is simple, so the technical route can be used as a green chemical technology for producing the 1, 4-naphthoquinone, and has higher economic value, technical value and environmental protection value.
The synthesis of 1, 4-naphthoquinone has been studied to some extent at home and abroad. Moreover, the 1, 4-naphthoquinone is mainly prepared by using naphthalene as a raw material, and the following ways are mainly adopted:
(1) after the alkyl naphthalene is prepared by alkylation of naphthalene, 1, 4-naphthoquinone is prepared by oxidation.
(2) Naphthalene is sulfonated and hydrolyzed into naphthol, and the naphthol is catalyzed and oxidized by a transition metal complex catalyst to prepare the 1, 4-naphthoquinone.
(3) When naphthalene is directly catalyzed and oxidized by air to prepare phthalic anhydride, a small amount of 1, 4-naphthoquinone by-product is obtained.
(4) Naphthalene liquid phase oxidation method, namely indirect electrolytic oxidation of high-valence heavy metal salt and oxidation preparation of 1, 4-naphthoquinone by nitric acid, hydrogen peroxide and the like.
In the early days, the naphthoquinone is mostly produced by the oxidation of alkyl hydrocarbon of naphthalene and naphthol, the process is complex, and the cost of the naphthoquinone is high. The method is gradually replaced by new production processes. In the late fifties, due to the development of electrochemical methods in organic synthesis, the indirect electrolytic oxidation by high-valence heavy metal salts and the use of HNO3、H2O2、IO4 -、S2O4 2-The naphthoquinone prepared by the oxidation of the non-metallic oxide can obtain better effect. Therefore, the technology of preparing 1, 4-naphthoquinone by liquid phase oxidation method is rapidly developed.
For a long time, the liquid phase oxidation method of naphthalene requires the participation of a stoichiometric amount of heavy metal-based catalysts such as chromium oxide and the like, so a large amount of heavy metal-containing industrial wastewater is generated in industrial production, the treatment process of the wastewater is difficult and complicated, and very serious pollution is caused to the environment. Since the seventies of the twentieth century, researchers attempted to develop novel catalysts to solve the problem of chromium-containing wastewater, and although such studies achieved some visible results in terms of pollution, the conversion of naphthalene and the selectivity of 1, 4-naphthoquinone were low.
In general, the naphthalene liquid phase oxidation method avoids the use of catalysts such as chromium salts which pollute the environment, but still cannot avoid the use of catalysts or oxidants which are not environmentally friendly in order to improve the yield and selectivity of the target product. Therefore, the research of the liquid phase catalytic oxidation method of naphthalene still lies in developing a suitable catalyst to improve the conversion rate of naphthalene and the selectivity of the target oxidation product.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a naphthalene liquid-phase oxidation catalyst and a preparation method and application thereof. The activity of the naphthalene oxidation catalyst prepared by the method and the selectivity of main oxidation products are both improved.
According to one aspect of the present invention, there is provided a catalyst for liquid phase oxidation of naphthalene, the catalyst comprising a Beta molecular sieve containing transition metal oxide particles.
According to another aspect of the present invention, there is provided a method for preparing a Beta molecular sieve containing transition metal oxide particles by in-situ loading synthesis, comprising the steps of:
a) preparing gel: mixing a structure directing agent, an aluminum source, a silicon source, a transition metal precursor, a fluoride ion source and water, and stirring to form gel;
b) and (3) crystallization: transferring the gel obtained in the step a) into a synthesis kettle, and crystallizing for 0.5-10 days at the temperature of 110-220 ℃;
c) and (3) product separation: and c) centrifugally separating and washing the product obtained in the step b), drying the product in an oven at the temperature of 80-120 ℃ under air atmosphere, and roasting the product at the temperature of 500-600 ℃ to obtain the Beta molecular sieve containing the transition metal oxide particles.
Preferably, the crystallization time in the step b) is 2 to 7 days.
Preferably, the structure directing agent is at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium hydroxide.
Preferably, the aluminum source is at least one of aluminum sulfate, sodium aluminate and pseudo-boehmite.
Preferably, the silicon source is at least one of silica sol, white carbon black and tetraethoxysilane.
Preferably, the transition metal precursor is a nitrate of a transition metal element M having a valence-change property.
Further preferably, the transition metal element M is at least one selected from titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu).
Preferably, said fluoride ion (F)-) The source is selected from HF, NaF, NH4F.
Preferably, the molar ratio of each component in the gel composition in the step a) satisfies:
SiO2/Al2O310-1000, and M/Si is 0.01-2, wherein M is a transition metal.
Further preferably, SiO in step a)2/Al2O3＝200～500，M/Si＝0.01～0.02。
Preferably, the crystallization reaction temperature in the step b) is 120-180 ℃; the crystallization time is 2-7 days.
According to another aspect of the present invention, there is provided a method for preparing a catalyst for liquid phase oxidation of naphthalene, comprising the steps of: naphthalene, the catalyst and an organic solvent are added into a reaction vessel, hydrogen peroxide is used as an oxidant, and the catalyst oxidizes the naphthalene.
Preferably, the reaction temperature is 40-150 ℃, and the reaction time is 2-10 hours.
Preferably, the organic solvent is at least one selected from acetone, acetic acid, acetonitrile, dimethyl sulfoxide and dichloromethane.
The beneficial effects of the invention include:
the Beta molecular sieve containing the transition metal oxide particles prepared by the invention is used for a naphthalene liquid phase oxidation catalyst, and the conversion rate of naphthalene and the selectivity of 1, 4-naphthoquinone are effectively improved.
Drawings
Figure 1 is an XRD spectrum of a sample of molecular sieve prepared in one embodiment of the present application.
Figure 2 is an XRD spectrum of a sample of molecular sieve prepared in one embodiment of the present application.
FIG. 3 is an SEM photograph of a molecular sieve sample prepared in one embodiment of the present application.
FIG. 4 is an SEM photograph of a molecular sieve sample prepared in one embodiment of the present application.
FIG. 5 is an SEM photograph of a molecular sieve sample prepared in one embodiment of the present application.
FIG. 6 is an SEM photograph of a molecular sieve sample prepared in one embodiment of the present application.
FIG. 7 is an SEM photograph of a molecular sieve sample prepared in one embodiment of the present application.
FIG. 8 is an SEM photograph of a molecular sieve sample prepared in one embodiment of the present application.
FIG. 9 is an SEM photograph of a molecular sieve sample prepared in one embodiment of the present application.
Detailed Description
The following examples are merely illustrative of the present invention and the present invention is not limited to these examples. All the similar structures and similar changes of the invention are included in the protection scope of the invention.
Example 1
Mixing the TEAOH solution with 10g of deionized water, adding hydrofluoric acid, uniformly stirring the mixture by using a magnetic stirrer, and adding ferric nitrate, ethyl orthosilicate and aluminum sulfate. The mixture was stirred for 4h at 60 ℃ in a thermostatic waterbath to give a composition ratio of 0.5 TEAOH: 1.0SiO2：0.005Al2O3：0.01Fe2O3：0.65HF：5H2A solution of O. The solution was transferred to a stainless steel synthesis kettle equipped with a polytetrafluoroethylene liner and crystallized in an oven at 110 ℃ for 10 days. And after crystallization, carrying out suction filtration and drying on the product in the kettle, and roasting the product in a muffle furnace at 550 ℃ for 5 hours to obtain the Beta molecular sieve catalyst containing the transition metal oxide particles. The XRD pattern of the Beta molecular sieve catalyst prepared in this example is shown as pattern No. 1 in FIG. 1, and the electron micrograph is shown in FIG. 3.
The catalyst prepared by the method is used for naphthalene liquid-phase oxidation reaction. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 60 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 25.3%, the selectivity for naphthol was 5.3%, the selectivity for 1, 4-naphthoquinone was 74.2%, and the selectivity for phthalic anhydride was 15.3%.
Example 2
The TEAOH solution was mixed with 10g of deionized water and hydrofluoric acid was added. After the mixture was stirred uniformly with a magnetic stirrer, ferric nitrate, ethyl orthosilicate, and aluminum sulfate were added. The mixture was stirred for 4h at 60 ℃ in a thermostatic waterbath to give a composition ratio of 0.5 TEAOH: 1.0SiO2：0.002Al2O3：0.05Fe2O3：0.65HF：5H2A solution of O. The solution was transferred to a stainless steel synthesis kettle equipped with a polytetrafluoroethylene liner and crystallized in an oven at 120 ℃ for 7 days. And after crystallization, carrying out suction filtration and drying on the product in the kettle, and roasting the product in a muffle furnace at 550 ℃ for 5 hours to obtain the Beta molecular sieve catalyst containing the transition metal oxide particles. The XRD pattern of the Beta molecular sieve catalyst prepared in this example is shown in figure 1, number 2, and the electron micrograph is shown in figure 4.
The catalyst prepared by the method is used for naphthalene liquid-phase oxidation reaction. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 80 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 45.3%, the selectivity for naphthol was 4.3%, the selectivity for 1, 4-naphthoquinone was 70.2%, and the selectivity for phthalic anhydride was 18.1%.
Example 3
Mixing the TEAOH solution with 10g of deionized water, adding hydrofluoric acid, uniformly stirring the mixture by using a magnetic stirrer, and adding ferric nitrate, ethyl orthosilicate and aluminum sulfate. The mixture was stirred for 4h at 60 ℃ in a thermostatic waterbath to give a composition ratio of 0.5 TEAOH: 1.0SiO2：0.003Al2O3：0.01Fe2O3：0.65HF：5H2A solution of O. The solution was transferred to a stainless steel synthesis kettle equipped with a teflon liner and crystallized in an oven at 140 ℃ for 7 days. After crystallization is finished, the product in the kettle is filtered and dried, and is roasted for 5 hours in a muffle furnace at 550 ℃, and the oxide containing transition metal is obtainedParticulate Beta molecular sieve catalyst. The XRD pattern of the Beta molecular sieve catalyst prepared in this example is shown as pattern No. 3 in FIG. 1, and the electron micrograph is shown as FIG. 5.
The catalyst prepared by the method is used for naphthalene liquid-phase oxidation reaction. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 100 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 4h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 35.3%, the selectivity for naphthol was 21.4%, the selectivity for 1, 4-naphthoquinone was 54.2%, and the selectivity for phthalic anhydride was 16.1%.
Example 4
Mixing the TEAOH solution with 10g of deionized water, adding hydrofluoric acid, uniformly stirring the mixture by using a magnetic stirrer, and adding ferric nitrate, ethyl orthosilicate and aluminum sulfate. The mixture was stirred for 4h at 60 ℃ in a thermostatic waterbath to give a composition ratio of 0.5 TEAOH: 1.0SiO2：0.10Al2O3：0.02Fe2O3：0.65HF：5H2A solution of O. The solution was transferred to a stainless steel synthesis kettle equipped with a polytetrafluoroethylene liner and crystallized in an oven at 150 ℃ for 7 days. And after crystallization, carrying out suction filtration and drying on the product in the kettle, and roasting the product in a muffle furnace at 550 ℃ for 5 hours to obtain the Beta molecular sieve catalyst containing the transition metal oxide particles. The XRD pattern of the Beta molecular sieve catalyst prepared in this example is shown in figure 1, number 4, and the electron micrograph is shown in figure 6.
The catalyst prepared by the method is used for naphthalene liquid-phase oxidation reaction. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 120 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 2h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 25.3%, the selectivity for naphthol was 4.4%, the selectivity for 1, 4-naphthoquinone was 73.2%, and the selectivity for phthalic anhydride was 16.5%.
Example 5
Mixing TEAOH solution with 10g of deionized water, adding hydrofluoric acid, stirring the mixture uniformly by using a magnetic stirrer,adding ferric nitrate, ethyl orthosilicate and aluminum sulfate. The mixture was stirred for 4h at 60 ℃ in a thermostatic waterbath to give a composition ratio of 0.5 TEAOH: 1.0SiO2：0.002Al2O3：0.02Fe2O3：0.65HF：5H2A solution of O. The solution was transferred to a stainless steel synthesis kettle equipped with a polytetrafluoroethylene liner and crystallized in an oven at 180 ℃ for 5 days. And after crystallization, carrying out suction filtration and drying on the product in the kettle, and roasting the product in a muffle furnace at 550 ℃ for 5 hours to obtain the Beta molecular sieve catalyst containing the transition metal oxide particles. The XRD pattern of the Beta molecular sieve catalyst prepared in this example is shown in figure 2, number 5, and the electron micrograph is shown in figure 7.
The catalyst prepared by the method is used for naphthalene liquid-phase oxidation reaction. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 40 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting at constant temperature for 10 h. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 25.8%, the selectivity for naphthol was 10.4%, the selectivity for 1, 4-naphthoquinone was 70.9%, and the selectivity for phthalic anhydride was 13.7%.
Example 6
Mixing the TEAOH solution with 10g of deionized water, adding hydrofluoric acid, uniformly stirring the mixture by using a magnetic stirrer, and adding cobalt nitrate, ethyl orthosilicate and aluminum sulfate. The mixture was stirred for 4h at 60 ℃ in a thermostatic waterbath to give a composition ratio of 0.5 TEAOH: 1.0SiO2：0.005Al2O3：0.01CoO2：0.65HF：5H2A solution of O. The solution was transferred to a stainless steel synthesis kettle equipped with a teflon liner and crystallized in an oven at 220 ℃ for 1 day. And after crystallization, carrying out suction filtration and drying on the product in the kettle, and roasting the product in a muffle furnace at 550 ℃ for 5 hours to obtain the Beta molecular sieve catalyst containing the transition metal oxide particles. The XRD pattern of the Beta molecular sieve catalyst prepared in this example is shown in figure 2, number 6, and the electron micrograph is shown in figure 8.
The catalyst prepared by the method is used for naphthalene liquid-phase oxidation reaction. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 80 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 18.7%, the selectivity for naphthol was 11.2%, the selectivity for 1, 4-naphthoquinone was 24.2%, and the selectivity for phthalic anhydride was 45.3%.
Example 7
Mixing the TEAOH solution with 10g of deionized water, adding hydrofluoric acid, uniformly stirring the mixture by using a magnetic stirrer, and adding cobalt nitrate, ethyl orthosilicate and aluminum sulfate. The mixture was stirred for 4h at 60 ℃ in a thermostatic waterbath to give a composition ratio of 0.5 TEAOH: 1.0SiO2：0.0001Al2O3：0.02CoO2：0.65HF：5H2A solution of O. The solution was transferred to a stainless steel synthesis kettle equipped with a teflon liner and crystallized in an oven at 140 ℃ for 7 days. And after crystallization, carrying out suction filtration and drying on the product in the kettle, and roasting the product in a muffle furnace at 550 ℃ for 5 hours to obtain the Beta molecular sieve catalyst containing the transition metal oxide particles. The XRD pattern of the Beta molecular sieve catalyst prepared in this example is shown in figure 2, number 7, and the electron micrograph is shown in figure 9.
The catalyst prepared by the method is used for naphthalene liquid-phase oxidation reaction. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 150 ℃, dripping 2mL of 30% hydrogen peroxide, and reacting for 2h under heat preservation. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 28.6%, the selectivity for naphthol was 15.3%, the selectivity for 1, 4-naphthoquinone was 30.2%, and the selectivity for phthalic anhydride was 40.6%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (8)
1. A naphthalene liquid phase oxidation catalyst, characterized in that the catalyst comprises a Beta molecular sieve containing transition metal oxide particles, said catalyst being useful for the highly selective production of 1, 4-naphthoquinone; the synthesis method of the Beta molecular sieve containing the transition metal oxide particles at least comprises the following steps:
a) preparing gel: mixing a structure directing agent, an aluminum source, a silicon source, a transition metal precursor, a fluoride ion source and water, and stirring to form gel, wherein the gel comprises the following components in a molar ratio:
SiO2/Al2O3= 10-1000, M/Si = 0.01-2, wherein M is a transition metal;
the transition metal is iron;
b) and (3) crystallization: transferring the gel obtained in the step a) into a synthesis kettle, and crystallizing for 0.5-10 days at the temperature of 110-220 ℃;
c) and (3) product separation: and c) centrifugally separating and washing the product obtained in the step b), drying the product in an oven at the temperature of 80-120 ℃ under air atmosphere, and roasting the product at the temperature of 500-600 ℃ to obtain the Beta molecular sieve containing the transition metal oxide particles.
2. The liquid phase naphthalene oxidation catalyst of claim 1, wherein the structure directing agent is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide.
3. The liquid phase naphthalene oxidation catalyst of claim 1, wherein the aluminum source is at least one selected from the group consisting of aluminum sulfate, sodium aluminate, and pseudoboehmite.
4. The liquid phase naphthalene oxidation catalyst according to claim 1, wherein the silicon source is at least one selected from the group consisting of silica sol, silica white, and tetraethoxysilane.
5. The liquid phase naphthalene oxidation catalyst of claim 1, wherein the fluoride ion source is selected from the group consisting of HF, NaF, NH4F.
6. The application of the catalyst of any one of claims 1 to 5 as a catalyst for liquid-phase catalytic oxidation reaction of naphthalene, which is characterized in that naphthalene, the catalyst and an organic solvent are added into a reaction vessel, and hydrogen peroxide is used as an oxidant to catalytically oxidize the naphthalene.
7. The use according to claim 6, wherein the reaction temperature is in the range of 40 to 150%oAnd C, the reaction time ranges from 2 to 10 hours.
8. Use according to claim 6, wherein the organic solvent is selected from at least one of acetone, acetic acid, acetonitrile, dimethyl sulfoxide, dichloromethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711282747.0A CN109876854B (en) | 2017-12-06 | 2017-12-06 | Naphthalene liquid-phase oxidation catalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711282747.0A CN109876854B (en) | 2017-12-06 | 2017-12-06 | Naphthalene liquid-phase oxidation catalyst, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109876854A CN109876854A (en) | 2019-06-14 |
| CN109876854B true CN109876854B (en) | 2020-10-09 |
Family
ID=66924595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711282747.0A Active CN109876854B (en) | 2017-12-06 | 2017-12-06 | Naphthalene liquid-phase oxidation catalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109876854B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63501288A (en) * | 1985-09-20 | 1988-05-19 | ジ・アップジョン・カンパニ− | 1,4-naphthalene diol and 1,4-hydroquinone derivatives |
| US6500972B2 (en) * | 2001-01-03 | 2002-12-31 | Chinese Petroleim Corp. | Synthesis of TMBQ with transition metal-containing molecular sieve as catalysts |
| CN1335258A (en) * | 2001-02-28 | 2002-02-13 | 刘希尧 | Synthesis of nanometer size beta-zeolite |
| CN102249887A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Preparation method of 2-menaquinone |
| CN102516054A (en) * | 2011-12-15 | 2012-06-27 | 东南大学 | Method for synthesizing 2-methyl-1, 4-naphthoquinone |
| CN102921456B (en) * | 2012-11-07 | 2014-09-10 | 中国科学院上海硅酸盐研究所 | Heterogeneous catalyst, preparation method of heterogeneous catalyst and application of heterogeneous catalyst |
| CN105294377B (en) * | 2014-07-03 | 2018-01-09 | 中国石油化工股份有限公司 | The method of decalin base |
| CN107262140B (en) * | 2016-12-04 | 2020-11-03 | 中国科学院大连化学物理研究所 | 2, 6-dimethylnaphthalene catalyst prepared from 2-methylnaphthalene, preparation and application thereof |
-
2017
- 2017-12-06 CN CN201711282747.0A patent/CN109876854B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109876854A (en) | 2019-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106964396B (en) | RTH type topological structure molecular sieve catalyst and its preparation method and application for dimethyl ether carbonylation reaction | |
| Dapurkar et al. | Novel mesoporous (Cr) MCM-48 molecular sieves: Promising heterogeneous catalysts for selective oxidation reactions | |
| CN106693981A (en) | Iron-molybdenum catalyst for formaldehyde synthesis through methanol oxidation as well as preparation method and application | |
| JP2006175436A (en) | Catalyst for oxidation of methanol to formaldehyde | |
| CN108821306B (en) | Preparation method of metal modified hierarchical pore HZSM-5 molecular sieve | |
| TWI605030B (en) | Composite oxide and its manufacturing method and use | |
| CN113231102B (en) | Glutaric acid selective polyacid catalyst based on micro-mesoporous Zr-MOF material and preparation method and application thereof | |
| CN107572585A (en) | A kind of bismuth oxybromide visible light catalyst and preparation method thereof | |
| CN108285151B (en) | Ce isomorphous substituted LTL molecular sieve and preparation method thereof | |
| JP4743620B2 (en) | Improved catalyst | |
| CN109876854B (en) | Naphthalene liquid-phase oxidation catalyst, preparation method and application thereof | |
| CN108722455B (en) | Preparation method of vanadium phosphorus oxide catalyst | |
| CN108440262A (en) | A kind of method that solid-liquid biphasic catalysis oxidation of beta-isophorone prepares 4- ketoisophorones | |
| JP2001233608A (en) | Method for synthesizing vpo catalyst | |
| JP4242842B2 (en) | Method for producing vanadyl pyrophosphate catalyst | |
| CN107790191A (en) | The preparation method of the solid acid catalyst reacted for cyclohexanone and ethylene ketal | |
| CN112138673B (en) | Preparation method of bimetallic oxide material and application of bimetallic oxide material in cyclohexyl hydroperoxide decomposition reaction | |
| CN108586202B (en) | Synthesis method of intermediate 4-phenylbutanol | |
| CN108610250B (en) | Method for preparing anthraquinone by anthracene oxidation method | |
| CN111822032B (en) | Catalyst for synthesizing 2,5-dichlorophenol and in-situ synthesis method of 2,5-dichlorophenol | |
| CN114832830B (en) | MOF-derived B/A/B structure oxide heterojunction and preparation method and application thereof | |
| CN117943114A (en) | Modified ETS-10 molecular sieve, preparation method, catalyst for preparing aromatic aldehyde by oxidizing methyl-substituted aromatic hydrocarbon and application | |
| US6774081B1 (en) | Process for preparing vanadyl pyrophosphate catalyst | |
| CN115970748B (en) | Catalyst for heterogeneous synthesis of piperidine nitroxide free radical | |
| CN108706607B (en) | Zeolite molecular sieve, preparation method and application thereof |
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 |