CN107774331B - Metal-loaded MOFs catalyst, preparation method thereof and application thereof in PMDPTA synthesis - Google Patents
Metal-loaded MOFs catalyst, preparation method thereof and application thereof in PMDPTA synthesis Download PDFInfo
- Publication number
- CN107774331B CN107774331B CN201711015304.5A CN201711015304A CN107774331B CN 107774331 B CN107774331 B CN 107774331B CN 201711015304 A CN201711015304 A CN 201711015304A CN 107774331 B CN107774331 B CN 107774331B
- Authority
- CN
- China
- Prior art keywords
- metal
- catalyst
- methylamine
- bis
- pmdpta
- 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
Classifications
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a metal-loaded MOFs catalyst, a preparation method thereof and application thereof in PMDPTA synthesis, and particularly relates to the technical field of catalysts. The catalyst adopts an excess impregnation method, at least one solution of metal chloride or metal nitrate and MOFs materials are stirred for 24 hours at room temperature, and a catalyst precursor is obtained after suction filtration; and (3) reacting the catalyst precursor with a reducing agent to obtain the metal-loaded MOFs catalyst. The preparation method of the catalyst has the advantages of simple preparation process, stable structure and the like. The catalyst is used for synthesizing PMDPTA, and has the advantages of low cost, high product yield, environmental protection and the like.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a metal-loaded MOFs catalyst, a preparation method thereof and application thereof in PMDPTA synthesis.
Background
Polyurethane (PU) is a high molecular polymer containing urethane groups (-NH-CO-O-) in molecules, and plays an important role in various fields such as ships, buildings, electromechanics, light industry and the like. The most common polyurethane materials are present in the form of foams. The polyurethane foam is prepared by the gradual polymerization reaction of binary or polybasic isocyanate and polyol compound under the action of a catalyst. Wherein, the catalyst not only can accelerate the reaction, but also can control the reaction speed, influence the fluidity of the reaction mixture and the physicochemical property of the product, thereby playing a crucial role in the formation of the polyurethane foam. The catalysts which are more commonly used at present include organometallic compounds and organic amine compounds. The organic metal compound is mainly organic tin compound and is mainly used for catalyzing polyurethane resin industrially; the catalyst has great harm to human body and serious environmental pollution, and does not meet the requirement of environmental protection. Therefore, organic amine catalysts are the main research direction of current polyurethane catalysts.
Organic amine catalysts are usually based on tertiary amine catalysts and are mainly used for catalyzing polyurethane foams. Common tertiary amine catalysts are triethylene diamine (TMDA), diethylene triamine (DMTA) and N, N, N ', N ', N ' -pentamethyl dipropylene triamine (PMDPTA). The traditional synthesis process of PMDPTA is obtained by methylation reaction of 3, 3' -imino-bis (N, N-dimethylallylamine) and formaldehyde solution in the presence of formic acid. The process route has high cost and low yield, and inevitably produces environmental pollution and strong corrosivity. In order to reduce the cost, improve the yield and protect the environment, the improved process takes methylamine solution and acrylonitrile as raw materials, and PMDPTA with high yield is obtained by three steps of Michael addition, hydrogenation and methylation, and the used catalyst is W-3 Raney Ni. The chemical equation is as follows:
however, the W-3 Raney Ni catalyst has the defects of complex synthesis process, easy oxidation, difficult storage and the like. And the metal-supported catalyst can effectively overcome the defects. MOFs are crystalline porous materials with periodic network structures formed by connecting inorganic metal centers (metal ions or metal clusters) and bridged organic ligands with each other through self-assembly. Compared with other inorganic porous materials, the MOFs material has the characteristics of large specific surface area, adjustable structure, easy functionalization and the like. Therefore, the MOFs material is used as an excellent carrier and applied to various reactions.
Therefore, the metal-loaded MOFs catalyst for replacing the W-3 Raney Ni catalyst in the synthesis of PMDPTA and the preparation method thereof are urgently needed.
Disclosure of Invention
The invention aims to provide a metal-loaded MOFs catalyst, a preparation method thereof and application thereof in PMDPTA synthesis. The catalyst has the advantages of simple preparation method, stable structure, high yield and environmental protection.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a metal-loaded MOFs catalyst comprises a carrier and an active component, wherein the carrier is an MOFs material (metal-organic framework material), and the active component is single metal or composite metal particles.
Preferably, the mass content of the active component in the metal-loaded MOFs catalyst is 0.1-20%.
The preparation method of the metal-loaded MOFs catalyst comprises the following preparation steps:
(1) dissolving at least one of metal chloride or metal nitrate in a certain solvent to obtain a solution;
(2) stirring the solution obtained in the step (1) and MOFs materials for 24 hours at room temperature by an excess impregnation method to obtain a catalyst precursor;
(3) and (3) reacting the catalyst precursor obtained in the step (2) with a reducing agent to obtain the metal-loaded MOFs catalyst.
Preferably, the raw material of the active component in the metal-supported MOFs catalyst is at least one of palladium chloride, nickel chloride, palladium nitrate, copper chloride, copper nitrate, chromium chloride, zinc chloride and ferric chloride. That is, the metal chloride in step (1) of the preparation method of the metal-supported MOFs catalyst comprises palladium chloride, nickel chloride, copper chloride, chromium chloride, zinc chloride or ferric chloride, and the metal nitrate in step (1) comprises palladium nitrate or copper nitrate.
Preferably, the solvent in step (1) of the preparation method of the metal-supported MOFs catalyst is at least one of water, methanol, ethanol or acetone.
Preferably, the support of the catalyst, i.e., the MOFs material, comprises at least one of a zeolitic imidazole framework material, a Laval Hill framework material, UiO-66 or UiO-67.
Preferably, the zeolitic imidazolate framework material comprises ZIF-8 and ZIF-67, and the Laval Hill framework material comprises MIL-101 and MIL-100, i.e. said MOFs material is at least one of ZIF-8, ZIF-67, UiO-66, UiO-67, MIL-101 and MIL-100.
Preferably, the preparation process of the MOFs material is as follows: respectively stirring the methanol solution of zinc nitrate or cobalt nitrate and a certain amount of methanol solution of 2-methylimidazole at room temperature for 24 hours to obtain ZIF-8 or ZIF-67; reacting a certain amount of zirconium chloride and a methanol solution of terephthalic acid or terephthalic acid in a hydrothermal kettle at 120 ℃ for 24 hours to obtain UiO-66 or UiO-67; respectively reacting a certain amount of chromium nitrate or ferric nitrate with a DMF (dimethyl formamide) solution of terephthalic acid in a hydrothermal kettle at 220 ℃ for 8 hours to obtain MIL-101; and respectively reacting a certain amount of chromium nitrate or ferric nitrate with a DMF (dimethyl formamide) solution of trimesic acid in a hydrothermal kettle at the temperature of 150 ℃ for 24 hours to obtain the MIL-100.
Preferably, in the step (3) of the preparation method of the metal-supported MOFs catalyst, the reducing agent is one of hydrazine hydrate, sodium borohydride or hydrogen.
The application of the prepared metal-loaded MOFs catalyst in synthesizing a polyurethane catalyst-PMDPTA comprises the following specific steps:
(1) reacting methyl alcohol solution of methylamine with acrylonitrile at 25 ℃ to obtain N, N-bis (2-cyanoethyl) methylamine;
(2) reacting N, N-bis (2-cyanoethyl) methylamine, ethanol, sodium hydroxide and a metal-loaded MOFs catalyst for 6 hours under the conditions that the hydrogen pressure is 2.0-3.0MPa and the temperature is 80-100 ℃, stopping the reaction, cooling to room temperature, performing suction filtration on the mixture, and concentrating the filtrate to obtain N, N-bis (3-aminopropyl) methylamine, wherein preferably, the volume ratio of the N, N-bis (2-cyanoethyl) methylamine to the solvent is 1: 3-9; the mass ratio of the amount of the catalyst to the N, N-bis (2-cyanoethyl) methylamine is 1: 3-7;
(3) n, N-di (3-aminopropyl) methylamine, methanol and a metal particle-loaded MOFs catalyst, reacting a formaldehyde solution (37 wt%) for 5 hours under the conditions that the hydrogen pressure is 2.5-4.0MPa and the temperature is 90-110 ℃, stopping the reaction, cooling to room temperature, performing suction filtration on the mixture, and concentrating the filtrate to obtain the PMDPTA.
Preferably, the volume ratio of the N, N-bis (3-aminopropyl) methylamine to the solvent is 1: 6-12; the molar ratio of the N, N-di (3-aminopropyl) methylamine to the formaldehyde solution is 1: 4-8; the mass ratio of the amount of the catalyst to the N, N-bis (3-aminopropyl) methylamine is 1: 4-12.
The invention has the beneficial effects that: the preparation method has the advantages of simple preparation method and stable structure. The catalyst is used for synthesizing PMDPTA, and has the advantages of low cost, high yield, environmental friendliness and the like.
Detailed Description
A metal-loaded MOFs catalyst comprises a carrier and an active component, wherein the carrier is an MOFs material (metal-organic framework material), and the active component is single metal or composite metal particles.
The preparation method of the metal-loaded MOFs catalyst and the application of the metal-loaded MOFs catalyst in the synthesis of PMDPTA are as follows:
example 1
0.016g of palladium chloride is dissolved in 5mL of acetone to prepare a homogeneous palladium chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2After 2h of reduction in the atmosphere, 0.1% Pd/MIL-101 catalyst was obtained.
Example 2
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 1 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at 90 ℃ for 6 hours under a pressure of 2.0MPa at a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 13.5g N, N-bis (3-aminopropyl) methylamine in 45.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 1 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at 90 ℃ for 5 hours at a pressure of 3.0MPa and a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture was filtered off with suction and the filtrate was concentrated to give 7.3g of the product PMDPTA in 55.0% yield.
Example 3
0.16 palladium nitrate is dissolved in 25mL of acetone to prepare a homogeneous palladium nitrate acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 1 percent Pd/MIL-101 catalyst.
Example 4
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 3 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at 90 ℃ for 6 hours under a pressure of 2.0MPa at a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 27.3g N, N-bis (3-aminopropyl) methylamine in 91.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 3 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at 90 ℃ for 5 hours at a pressure of 3.0MPa and a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 14.8g of the product PMDPTA in 89.0% yield.
Example 5
0.22g of palladium chloride is dissolved in 25mL of acetone to prepare a homogeneous palladium chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 1 percent Pd/MIL-101 catalyst.
Example 6
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 5 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at 90 ℃ for 6 hours under a pressure of 2.0MPa at a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 26.4g N, N-bis (3-aminopropyl) methylamine in 88.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 5 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at 90 ℃ for 5 hours at a pressure of 3.0MPa and a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture was filtered off with suction and the filtrate was concentrated to give 17.5g of the product PMDPTA, yield 87.0%.
Example 7
0.22g of palladium chloride is dissolved in 25mL of acetone to prepare a homogeneous palladium chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, adding 0.18g of sodium borohydride, continuing stirring for 6h, performing suction filtration, and drying to obtain the 1% Pd/MIL-101 catalyst.
Example 8
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 7 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at 90 ℃ for 6 hours under a pressure of 2.0MPa at a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 27.0g N, N-bis (3-aminopropyl) methylamine in 90.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst prepared in example 7 (3g) were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at 90 ℃ for 5 hours at a pressure of 3.0MPa and a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 17.7g of the product PMDPTA in 88.0% yield.
Example 9
0.22g of palladium chloride is dissolved in 25mL of ethanol to prepare a homogeneous palladium chloride ethanol solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of ethanol, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 1 percent Pd/MIL-101 catalyst.
Example 10
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 9 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at 90 ℃ for 6 hours under a pressure of 2.0MPa at a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 27.3g N, N-bis (3-aminopropyl) methylamine in 91.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 9 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at 90 ℃ for 5 hours at a pressure of 3.0MPa and a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 14.8g of the product PMDPTA in 89.0% yield.
Example 11
0.80g of palladium chloride is dissolved in 50mL of acetone to prepare a homogeneous palladium chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 5 percent Pd/MIL-101 catalyst.
Example 12
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 11 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at 90 ℃ for 6 hours under a pressure of 2.0MPa at a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 27.4g N, N-bis (3-aminopropyl) methylamine in 91.2% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 11 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at 90 ℃ for 5 hours at a pressure of 3.0MPa and a rotation speed of 500rpm, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 18.1g of the product PMDPTA, yield 90.0%.
Example 13
0.41g of nickel chloride is dissolved in 25mL of acetone to prepare a homogeneous nickel chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 1 percent Ni/MIL-101 catalyst.
Example 14
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 13 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction, and the filtrate was concentrated to give 18.0g N, N-bis (3-aminopropyl) methylamine in 60.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 13 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 14.3g of the product PMDPTA, in 71.0% yield.
Example 15
2.05g of nickel chloride is dissolved in 25mL of acetone to prepare a homogeneous nickel chloride acetone solution; the solution was added dropwise to 10g of activated MIL-101 dispersed in 50mL of acetoneStirring for 24h at room temperature, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 5 percent Ni/MIL-101 catalyst.
Example 16
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 15 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 26.3g N, N-bis (3-aminopropyl) methylamine in 87.5% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst prepared in example 15 (3g) were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 16.3g of the product PMDPTA, yield 81.0%.
Example 17
8.20g of nickel chloride is dissolved in 100mL of acetone to prepare a homogeneous nickel chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 20 percent Ni/MIL-101 catalyst.
Example 18
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 17 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 26.4g N, N-bis (3-aminopropyl) methylamine in 88.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst prepared in example 17 (3g) were placed in a 300mL autoclave, which was closed, and the atmosphere in the autoclave was replaced with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 16.5g of the product PMDPTA in 82.0% yield.
Example 19
2.05g of nickel chloride is dissolved in 25mL of acetone to prepare a homogeneous nickel chloride acetone solution; dropwise adding the solution into 10g of activated UiO-66, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 5 percent Ni/UiO-66 catalyst.
Example 20
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 19 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 27.0g N, N-bis (3-aminopropyl) methylamine in 85.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 19 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 14.3g of the product PMDPTA, in 71.0% yield.
Example 21
2.05g of nickel chloride is dissolved in 25mL of acetone to prepare a homogeneous nickel chloride acetone solution; dropwise adding the solution into 10g of activated UiO-67, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 5 percent Ni/UiO-67 catalyst.
Example 22
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 21 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 24.6g N, N-bis (3-aminopropyl) methylamine in 82.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 21 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 14.1g of the product PMDPTA in 70.0% yield.
Example 23
2.05g of nickel chloride is dissolved in 25mL of acetone to prepare a homogeneous nickel chloride acetone solution; dropwise adding the solution into 10g of activated MIL-100, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 5 percent Ni/MIL-100 catalyst.
Example 24
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 23 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 24.0g N, N-bis (3-aminopropyl) methylamine in 80.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 23 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered off with suction and the filtrate was concentrated to give 13.1g of the product PMDPTA in 65.0% yield.
Example 25
2.05g of copper chloride is dissolved in 25mL of acetone to prepare a homogeneous copper chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 5 percent Cu/MIL-101 catalyst.
Example 26
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 25 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 24.6g N, N-bis (3-aminopropyl) methylamine in 82.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 25 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 15.3g of the product PMDPTA in 76.0% yield.
Example 27
2.56g of chromium chloride was dissolved in 100mL of acetone to prepare a homogeneous chromium chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h in the atmosphere to obtain the 5% Cr/MIL-101 catalyst.
Example 28
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 27 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 21.6g N, N-bis (3-aminopropyl) methylamine in 72.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 27 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 14.1g of the product PMDPTA in 70.0% yield.
Example 29
2.05g of zinc chloride is dissolved in 100mL of acetone to prepare a homogeneous zinc chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 5 percent Zn/MIL-101 catalyst.
Example 30
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 29 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction, and the filtrate was concentrated to give 21.0g N, N-bis (3-aminopropyl) methylamine in 70.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 29 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 9.3g of the product PMDPTA, in 46.0% yield.
Example 31
1.45g of chlorineDissolving ferric chloride in 100mL of acetone to prepare a homogeneous ferric chloride acetone solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain the 5 percent Fe/MIL-101 catalyst.
Example 32
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 31 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 22.8g N, N-bis (3-aminopropyl) methylamine in 76.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 31 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture is filtered with suction and the filtrate is concentrated to give 14.7g of the product PMDPTA, yield 73.0%.
Example 33
1.02g of nickel chloride and 1.02g of copper chloride were dissolved in 100mL of acetone to prepare a homogeneous solution; dropwise adding the solution into 10g of activated MIL-101, dispersing into 50mL of acetone, stirring at room temperature for 24h, and filtering to obtain a precursor; the precursor was placed in a quartz boat at H2Reducing for 2h under the atmosphere to obtain 5 percent NiCu/MIL-101 catalyst.
Example 34
N, N-bis (2-cyanoethyl) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the catalyst prepared in example 33 (6g) were placed in a 300mL autoclave, which was closed, purged with nitrogen and then with hydrogen three times. The reaction mixture was reacted at a pressure of 2.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 6 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered with suction and the filtrate was concentrated to give 24.3g N, N-bis (3-aminopropyl) methylamine in 81.0% yield.
N, N-bis (3-aminopropyl) methylamine (14.5g), methanol (150mL), a formaldehyde solution (40.6g) and the catalyst (3g) prepared in example 33 were placed in a 300mL autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen, and the air was replaced with hydrogen three times after three times. The reaction mixture was reacted at a pressure of 3.5MPa, a rotation speed of 500rpm and a temperature of 100 ℃ for 5 hours, and the reaction was stopped. After cooling to room temperature, the mixture was filtered off with suction and the filtrate was concentrated to give 15.7g of the product PMDPTA in 78.0% yield.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The application of the metal-loaded MOFs catalyst in the synthesis of PMDPTA is characterized in that the metal-loaded MOFs catalyst comprises a carrier and an active component, wherein the carrier is MOFs material, the active component is single metal or composite metal particles, the mass content of the active component is 0.1-20%, and the application of the metal-loaded MOFs catalyst in the synthesis of PMDPTA comprises the following steps:
(1) reacting methyl alcohol solution of methylamine with acrylonitrile at 25 ℃ to obtain N, N-bis (2-cyanoethyl) methylamine;
(2) reacting the N, N-bis (2-cyanoethyl) methylamine obtained in the step (1) with ethanol, sodium hydroxide and a metal-loaded MOFs catalyst for 6 hours under the conditions that the hydrogen pressure is 2.0-3.0MPa and the temperature is 80-100 ℃, stopping the reaction, cooling to room temperature, carrying out suction filtration on the mixture, and concentrating the filtrate to obtain the N, N-bis (3-aminopropyl) methylamine, wherein the MOFs material is at least one of ZIF-8, ZIF-67, UiO-66, UiO-67, MIL-101 and MIL-100, and the active component in the metal-loaded MOFs catalyst is at least one of palladium chloride, nickel chloride, palladium nitrate, copper chloride, copper nitrate, chromium chloride, zinc chloride and iron chloride;
(3) and (3) reacting the N, N-bis (3-aminopropyl) methylamine obtained in the step (2) with methanol, a metal-loaded MOFs catalyst and 37 wt% formaldehyde solution for 5 hours under the conditions that the hydrogen pressure is 2.5-4.0MPa and the temperature is 90-110 ℃, stopping the reaction, cooling to room temperature, carrying out suction filtration on the mixture, and concentrating the filtrate to obtain the PMDPTA.
2. The use of the metal-supported MOFs catalyst according to claim 1 in PMDPTA synthesis, characterized in that the preparation method of said metal-supported MOFs catalyst comprises the following preparation steps:
(1) dissolving at least one of metal chloride or metal nitrate in a certain solvent to obtain a solution;
(2) stirring the solution obtained in the step (1) and MOFs materials for 24 hours at room temperature by an excess impregnation method to obtain a catalyst precursor;
(3) and (3) reacting the catalyst precursor obtained in the step (2) with a reducing agent to obtain the metal-loaded MOFs catalyst.
3. Use of the metal-supported MOFs catalyst according to claim 2 in PMDPTA synthesis, wherein the solvent in step (1) is at least one of water, methanol, ethanol or acetone.
4. The use of the metal-supported MOFs catalyst according to claim 3 in PMDPTA synthesis, wherein said MOFs material is prepared by the following method:
the ZIF-8 and ZIF-67 materials are obtained by respectively stirring a methanol solution of zinc nitrate or cobalt nitrate and a certain amount of methanol solution of 2-methylimidazole at room temperature for 24 hours;
MIL-101 is obtained by reacting a certain amount of chromium nitrate or ferric nitrate with DMF solution of terephthalic acid respectively in a hydrothermal kettle at 220 ℃ for 8 h;
the MIL-100 is obtained by reacting a certain amount of chromium nitrate or ferric nitrate with DMF (dimethyl formamide) solution of trimesic acid respectively at 150 ℃ in a hydrothermal kettle for 24 hours;
the UiO-66 and UiO-67 are obtained by reacting a certain amount of zirconium chloride with a methanol solution of terephthalic acid or terephthalic acid in a hydrothermal kettle at 120 ℃ for 24 hours.
5. The use of the metal-supported MOFs catalyst according to claim 2 in PMDPTA synthesis, wherein the reducing agent in step (3) is one of hydrazine hydrate, sodium borohydride or hydrogen gas.
6. The use of the metal-supported MOFs catalyst according to claim 1 in PMDPTA synthesis, wherein the volume ratio of N, N-bis (2-cyanoethyl) methylamine to ethanol in step (2) is 1: 3-9; the mass ratio of the amount of the metal-loaded MOFs catalyst in the step (2) to the N, N-bis (2-cyanoethyl) methylamine in the step (2) is 1: 3-7.
7. The use of the metal-supported MOFs catalyst according to claim 1 in PMDPTA synthesis, wherein the volume ratio of N, N-bis (3-aminopropyl) methylamine and methanol in step (3) is 1: 6-12; the molar ratio of the N, N-bis (3-aminopropyl) methylamine to the formaldehyde solution in the step (3) is 1: 4-8; the mass ratio of the amount of the metal-loaded MOFs catalyst in the step (3) to the N, N-bis (3-aminopropyl) methylamine in the step (3) is 1: 4-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711015304.5A CN107774331B (en) | 2017-10-25 | 2017-10-25 | Metal-loaded MOFs catalyst, preparation method thereof and application thereof in PMDPTA synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711015304.5A CN107774331B (en) | 2017-10-25 | 2017-10-25 | Metal-loaded MOFs catalyst, preparation method thereof and application thereof in PMDPTA synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107774331A CN107774331A (en) | 2018-03-09 |
| CN107774331B true CN107774331B (en) | 2020-05-15 |
Family
ID=61435384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711015304.5A Active CN107774331B (en) | 2017-10-25 | 2017-10-25 | Metal-loaded MOFs catalyst, preparation method thereof and application thereof in PMDPTA synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107774331B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109562952B (en) | 2016-08-10 | 2022-11-01 | 研究三角协会 | Solid-state crystallization method of metal organic framework in mesoporous material and hybrid material thereof |
| AU2019242630B2 (en) * | 2018-03-26 | 2024-05-23 | Research Triangle Institute | Method of making confined nanocatalysts within mesoporous materials and uses thereof |
| CN108636453B (en) * | 2018-04-08 | 2020-11-13 | 浙江工业大学 | Nano noble metal catalyst packaged by metal organic framework material and preparation method and application thereof |
| CN108786921B (en) * | 2018-04-26 | 2021-09-24 | 上海理工大学 | Monoatomic Pd @ UiO-66 catalyst and preparation method and application thereof |
| CN108947757B (en) * | 2018-08-07 | 2021-05-25 | 崔九香 | Method for preparing isopropylbenzene by catalytic hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol |
| CN109225144A (en) * | 2018-11-20 | 2019-01-18 | 河南师范大学 | A kind of preparation method of fluoroquinolone antibiotics adsorbent |
| CN109364942B (en) * | 2018-12-10 | 2021-05-28 | 广州立白企业集团有限公司 | Mn-Cu-Ce highly-dispersed supported carbonized PEI @ MOF catalyst and preparation method thereof |
| CN109627475B (en) * | 2018-12-24 | 2021-07-09 | 天津世起科技发展有限公司 | Pd-MOF metal organic framework film and preparation method thereof |
| CN109912809B (en) * | 2019-02-26 | 2022-03-22 | 中国科学院福建物质结构研究所 | Non-noble metal-metal organic framework composite material, preparation method and application thereof |
| CN111111784B (en) * | 2019-12-12 | 2022-09-13 | 广东省石油与精细化工研究院 | UiO-67 coated Co catalyst and preparation method and application thereof |
| CN111195531B (en) * | 2020-01-20 | 2022-08-02 | 安徽师范大学 | Hybrid material of multi-pyridine zinc complex modified MIL-101, preparation method and application of hybrid material in catalyzing degradation of organic phosphorus |
| CN113354825B (en) * | 2020-03-06 | 2022-09-20 | 同济大学 | Zirconium-based metal organic framework material UiO-66(Zr) and room-temperature rapid preparation method and application thereof |
| CN111871466B (en) * | 2020-08-24 | 2023-04-18 | 国家纳米科学中心 | Node-supported metal cluster catalyst in metal organic framework structure and preparation method and application thereof |
| CN112121863B (en) * | 2020-10-26 | 2022-10-04 | 广州大学 | Catalyst for catalytic transfer hydrogenation and preparation method and application thereof |
| CN115282938B (en) * | 2022-07-04 | 2023-11-10 | 浙江理工大学 | Application of bi-metal MOFs-polydopamine-non-woven fabric in heavy metal ion adsorption |
| CN115920975B (en) * | 2022-12-29 | 2024-06-07 | 浙江工业大学 | Preparation method and application of defect MOFs material encapsulated noble metal Pt catalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269317A (en) * | 2007-03-23 | 2008-09-24 | 中国科学院大连化学物理研究所 | Load type stephanoporate metal organic compound hydrogen storing material |
| EP2423241A1 (en) * | 2010-07-24 | 2012-02-29 | Blücher GmbH | Unit with porous organic polymers and use of same |
| CN103923292A (en) * | 2014-04-23 | 2014-07-16 | 胡志刚 | Preparation method of intermediate for polyurethane sponge |
| CN105233872A (en) * | 2015-10-22 | 2016-01-13 | 辽宁大学 | Pd @MIL-101 composite and preparation method and application thereof |
| CN105521766A (en) * | 2015-08-28 | 2016-04-27 | 浙江理工大学 | Gold-palladium-modified MIL-101 and preparation method thereof |
| CN106378194A (en) * | 2016-08-25 | 2017-02-08 | 山东师范大学 | Transition metal copper loaded UiO-66-NH2 composite catalyst, preparation method and application thereof |
-
2017
- 2017-10-25 CN CN201711015304.5A patent/CN107774331B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269317A (en) * | 2007-03-23 | 2008-09-24 | 中国科学院大连化学物理研究所 | Load type stephanoporate metal organic compound hydrogen storing material |
| EP2423241A1 (en) * | 2010-07-24 | 2012-02-29 | Blücher GmbH | Unit with porous organic polymers and use of same |
| CN103923292A (en) * | 2014-04-23 | 2014-07-16 | 胡志刚 | Preparation method of intermediate for polyurethane sponge |
| CN105521766A (en) * | 2015-08-28 | 2016-04-27 | 浙江理工大学 | Gold-palladium-modified MIL-101 and preparation method thereof |
| CN105233872A (en) * | 2015-10-22 | 2016-01-13 | 辽宁大学 | Pd @MIL-101 composite and preparation method and application thereof |
| CN106378194A (en) * | 2016-08-25 | 2017-02-08 | 山东师范大学 | Transition metal copper loaded UiO-66-NH2 composite catalyst, preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| " Pd nanoparticles supported on ZIF-8 as an efficient heterogeneous catalyst for the selective hydrogenation of cinnamaldehyde ";Yuan Zhao et al;《Catalysis Communications》;20140817;第57卷;第119–123页 * |
| "Pd /MIL-101在温和条件下高选择性催化苯乙酮加氢";简思平等;《广州化工》;20150630;第43卷(第11期);第89–153页 * |
| Comparison of Pd-UiO-66 and Pd-UiO-66-NH2 catalysts performance for phenol hydrogenation in aqueous medium";Qingqing Guan et al;《 Fuel》;20170530;第205卷;第130–141页 * |
| Qingqing Guan et al.Comparison of Pd-UiO-66 and Pd-UiO-66-NH2 catalysts performance for phenol hydrogenation in aqueous medium".《 Fuel》.2017,第205卷第130–141页. * |
| Yuan Zhao et al." Pd nanoparticles supported on ZIF-8 as an efficient heterogeneous catalyst for the selective hydrogenation of cinnamaldehyde ".《Catalysis Communications》.2014,第57卷第119–123页. * |
| 简思平等."Pd /MIL-101在温和条件下高选择性催化苯乙酮加氢".《广州化工》.2015,第43卷(第11期),第89–153页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107774331A (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107774331B (en) | Metal-loaded MOFs catalyst, preparation method thereof and application thereof in PMDPTA synthesis | |
| CN111013576B (en) | Monoatomic catalyst prepared based on surface immobilization method | |
| CN113019414B (en) | Hydrogenation catalyst, preparation method and application thereof | |
| CN110756225B (en) | Metal/MOFs nano catalyst and preparation method and application thereof | |
| CN112495417B (en) | Iron single-atom catalyst and preparation method and application thereof | |
| CN102941093B (en) | Catalyst for decahydronaphthalene preparation by naphthalene hydrogenation, preparation and application thereof | |
| US3328465A (en) | Process for the hydrogenation of nitro compounds | |
| CN107398301B (en) | Catalyst for converting ethyl levulinate into gamma-valerolactone and preparation method thereof | |
| CN111250158B (en) | Carbon-supported alkaline ionic liquid-metal catalyst and preparation and application thereof | |
| CN109876801B (en) | Nano carbon supported high-dispersion platinum catalyst, preparation method thereof and application thereof in hydrogenation reaction of aromatic nitro compound | |
| CN112371189A (en) | Hydroxide-coated ZIF (zinc-oxygen-doped organic framework) MOFs (metal-organic frameworks) heterogeneous catalyst and preparation and application thereof | |
| CN111286024B (en) | Imidazole functionalized covalent triazine framework material and preparation method and application thereof | |
| CN112774707A (en) | Ru-N-C monatomic catalyst and preparation method and application thereof | |
| JP2023153810A (en) | Carbon-based, precious metal-transition metal composite catalyst and preparation method therefor | |
| CN114682303B (en) | Preparation method for synthesizing noble metal@MOF core-shell catalyst by in-situ one-step method | |
| CN109529912B (en) | Composite nano-structure copper catalyst for preparing furfuryl alcohol by furfural hydrogenation and preparation method thereof | |
| CN109880111B (en) | Catalyst for synthesizing polyether amine and preparation method thereof | |
| CN108906101B (en) | Catalyst for hydrogenation synthesis of 4, 4' -diaminodiphenyl ether, and preparation method and application thereof | |
| CN112742422B (en) | Supported catalyst and application thereof in selective hydrogenation of quinoline compounds | |
| CN105107496A (en) | Ruthenium aluminium oxide catalyst and preparation method thereof | |
| CN112246240B (en) | Preparation and application of dimethyl carbonate catalyst | |
| CN112316960B (en) | Method for catalyzing carbon dioxide to generate formaldehyde | |
| CN1740129A (en) | Prepn process of hydroquinone and phenol | |
| EP2402081A1 (en) | Ammonia decomposition catalyst | |
| CN114797991B (en) | Rubber hydrogenation catalyst, preparation method, recovery 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 |