CN103880894A - Method for directly synthesizing heteropoly acid material with double active centers - Google Patents
Method for directly synthesizing heteropoly acid material with double active centers Download PDFInfo
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- CN103880894A CN103880894A CN201210554700.6A CN201210554700A CN103880894A CN 103880894 A CN103880894 A CN 103880894A CN 201210554700 A CN201210554700 A CN 201210554700A CN 103880894 A CN103880894 A CN 103880894A
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Abstract
The invention provides a method for r directly synthesizing a heteropoly acid material with double active centers, and relates to a preparation method of a vanadium-based catalytic material for catalyzing hydroxylation of benzene to prepare phenol. A target material is synthesized in one step through a hydro-thermal synthesis method at a reaction temperature of 100-240 DEG C, by using phosphorus-molybdenum heteropoly acid, Cu(NO3)2.3H2O, 1,3,5-trimesic acid and tetramethyl ammonium hydroxide as raw materials and by using water as a solvent. The catalytic materials synthesized by the method are applied in hydroxylation of benzene, and high phenol yield is obtained under mild reaction conditions.
Description
Technical field
The present invention relates to a kind of phospho-molybdic acid, Cu (NO
3)
23H
2o, 1,3,5-trimesic acid, Tetramethylammonium hydroxide are raw material, by the method for Hydrothermal Synthesis, under the temperature of reaction of 100 ℃ ~ 240 ℃, make water as solvent, the method for one-step synthesis target material.
Background technology
Phenol is a kind of important chemical intermediate, can be used for producing dihydroxyphenyl propane, resol, dyestuff, antioxidant and medicine etc.At present, phenol whole world demand approaches 1,000 ten thousand tons, and China Pyrogentisinic Acid's demand accounts for 10% of world's aggregate demand.The traditional production method of phenol is cumene method, and 95% phenol is produced by the method in the world at present.In the method, the hydrolysis of isopropyl benzene needs a large amount of mineral acids, brings certain environmental problem; Can be subject to again the restriction in co-product acetone market simultaneously.Especially in overall process, the phenol total recovery based on benzene feedstock only has 5%.Therefore, no matter consider from angle or the Atom economy of Sustainable development, people wish the method being oxidized by green catalysis always, and direct oxidation benzene one step is prepared phenol.But, in benzene hydroxylation reaction, benzene feedstock stable in properties, be difficult to oxidizedly, meanwhile, product phenol character is active, very easily there is further oxidative degradation, therefore, a major challenge that phenol is catalytic chemistry field is always produced in benzene direct oxidation, and especially the research of the benzene direct oxidation phenol processed take molecular oxygen as oxygen source is considered to one of great difficult problem of current catalytic field always.
Molecular oxygen is that benzene one step is prepared the optimal oxygenant of phenol, still, due to molecular oxygen stable in properties, is difficult to activation, thereby has experienced a very long research course.1987, the people such as Hideo Orita used CuCl as catalyzer, and xitix is as co-conducer, and the phenol yield obtaining only has 0.23%.Until nineteen ninety-five, the people such as Shigeru Tsuruya use the zeolite molecular sieve of [10] Cu load just to obtain 1.69% phenol yield.The people such as Tsuruya use CsPMoV
2as catalyzer, use aqueous acetic acid as solvent, obtained 7.2% phenol yield, but the reaction times reaches 1440 minutes.Subsequently, the people such as Wang Jun uses Py
3pMo
10v
2o
40as catalyzer, use equally aqueous acetic acid as solvent, obtain 11.5% phenol yield, will foreshorten to 600 minutes the reaction times simultaneously.But existing benzene hydroxylation reaction system efficiency is very low.The present invention is by introducing the heteropolyacid that contains catalytic activity in metal-organic framework materials, use metal and organism to form metal-organic framework materials, then heteropolyacid is coated, prepares the coated heteropolyacid target catalytic material of metal-organic framework materials.The polyacid that this target material is coated, ordered arrangement is in the cavity of metallic organic framework, and meanwhile, the node metal of skeleton and heteropolyacid only have the spacing of molecular scale, can act synergistically well, can improve greatly the activity of benzene hydroxylation catalyst system.
Use the coated heteropolyacid material of metallic organic framework to there is no at present bibliographical information in benzene hydroxylation field.
Summary of the invention
The object of the invention is to develop the method that a class is suitable for the coated heteropoly acid catalysis material of the metal-organic framework materials of catalysis benzene hydroxylation phenol processed.
The preparation method of the coated heteropoly acid catalysis material of the metal-organic framework materials of catalysis benzene hydroxylation provided by the invention phenol processed, with Cu (NO
3)
23H
2o, 1,3,5-trimesic acid, Tetramethylammonium hydroxide are raw material, by the method for Hydrothermal Synthesis, under the temperature of reaction of 100 ℃ ~ 240 ℃, make water as solvent, the method for the coated heteropllyacids material of one-step synthesis metal-organic framework materials.
Be suitable for cationic part of the present invention and have 1,3,5-trimesic acid, EDTA, sulphosalicylic acid, Isosorbide-5-Nitrae-terephthalic acid, 4-toluene sulfonic acide, 2, the nitrogenous class of the form such as dipicolimic acid 2,4-HBA or carboxylic-acid part, these raw materials can be bought on market.
In the present invention, the organic backbone mol ratio of the metal of metal-organic framework materials and metal-organic framework materials is between 1:50 ~ 50:1, and preferably between 1:5-5:1.
Being applicable to reaction medium of the present invention is the aqueous solution.
Be suitable for temperature of reaction of the present invention between 100 ℃ ~ 240 ℃, and preferably between 120 ℃ ~ 180 ℃.
The preparation method of the vanadium base catalytic material of catalysis benzene hydroxylation of the present invention phenol processed, uses common phospho-molybdic acid, Cu (NO
3) 23H
2o, 1,3,5-trimesic acid, Tetramethylammonium hydroxide are raw material, reaction conditions gentleness, reaction yield is high, simple synthetic method.
Accompanying drawing explanation
Molecular structure heteropolyacid anions [the PMo of Fig. 1 resulting materials
11vO
40]
4-, be coated in the cavity of framework material, use in the drawings 1 expression; Counter cation Tetramethylammonium hydroxide lack of alignment in crystal, more clear in order to observe, from figure, left out; The copper oxygen octahedra that center C u atom and ortho position Sauerstoffatom thereof form bunch forms the basic structural unit of metallic organic framework, uses in the drawings 2 expressions.
The infrared spectrum of Fig. 2 embodiment 1 resulting materials: metallic organic framework uses 1 to represent, the target material of the coated heteropolyacid anions of metallic organic framework uses 2 to represent, and heteropolyacid anions is used 3 to represent.As can be seen from the figure, target material 2 contains and lays respectively at 951,868,798cm
-1v
as(Mo-O
t), v
as(Mo-O
b-Mo) and v
as(Mo-O
c-Mo) vibration absorption peak, and be positioned at 1071,1055cm
-1ν (P-O) vibration absorption peak.Target compound 2 contains the characteristic peak of polyacid and the characteristic peak of skeleton simultaneously.The XRD powdery diffractometry of Fig. 3 embodiment 1 resulting materials: metallic organic framework uses 1 to represent, the target material of the coated heteropolyacid anions of metallic organic framework uses 2 to represent, and heteropolyacid anions is used 3 to represent.XRD powder data presentation, target material is all obvious with the framework material characteristic peak that is not coated polyacid, illustrates that the ordered structure of skeleton is not subject to the impact of coated polyacid, the target material that resulting materials is homogeneous.
Embodiment
Following embodiment will describe more comprehensively to the present invention.
In example, material is by washing, dry obtaining, and productive rate calculates based on Mo.
Embodiment 1
By 0.1062gH
4pMo
11vO
4019H
2o (0.05mmol), 0.240g Cu (NO
3)
23H
2o (1mmol), 0.105g1,3,5-Benzenetricarboxylic acid (0.5mmol), 0.09g (CH3) 4NOH (1mmol) is dissolved in 10mL deionized water, uses 2MNaOH to regulate pH2.5.This solution is transferred in 23 mL autoclaves, and 5 ℃/h of temperature programming, rises to 160 ° of C and keeps 48h, and slow cooling is to room temperature, and target material is lenticular and separates out from reaction solution.Resulting materials is washed, used XRD single crystal diffraction to determine its structure (concrete structure as shown in Figure 1), obtaining double activity center's heteropllyacids quality of materials yield by calculated mass is 35%.
The catalytic material that use obtains reacts for benzene hydroxylation, by 0.025mmol catalyzer, and 0.78g benzene (10mmol), 6.8mL acetonitrile, 0.9g xitix, 2MPaO
2add in 50mL autoclave and react, magnetic agitation, temperature of reaction is 80 ℃, keeps 0.5h, obtaining phenol yield is 7.5%.
By 0.2123gH
4pMo
11vO
4019H
2o (0.1mmol), 0.120g Cu (NO
3)
23H
2o (0.5mmol), 0.105g1,3,5-Benzenetricarboxylic acid (0.5mmol), 0.045g (CH
3)
4nOH (0.5mmol) is dissolved in 10mL deionized water, uses 2MNaOH to regulate pH7.8.This solution is transferred in 23mL autoclave, and 50 ℃/h of temperature programming, rises to 120 ° of C and keeps 72h, and slow cooling is to room temperature, and target material is lenticular and separates out from reaction solution.Resulting materials is washed, used XRD single crystal diffraction to determine its structure (concrete structure as shown in Figure 1), obtaining double activity center's heteropllyacids quality of materials yield by calculated mass is 25%.
The catalytic material that use obtains reacts for benzene hydroxylation, by 0.025mmol catalyzer, and 0.78g benzene (10mmol), 6.8mL acetonitrile, 0.9g xitix, 2MPaO
2add in 50mL autoclave and react, magnetic agitation, temperature of reaction is 80 ℃, keeps 2h, obtaining phenol yield is 7.8%.
By 0.2123g H
4pMo
11vO
4019H
2o (0.1mmol), 0.240g Cu (NO
3)
23H
2o (1mmol), 0.105g 1,3,5-Benzenetricarboxylic acid (0.5mmol), 0.18g (CH
3)
4nOH (2mmol) is dissolved in 10mL deionized water, uses 2MNaOH to regulate pH7.8.This solution is transferred in 23mL autoclave, and 25 ℃/h of temperature programming, rises to 240 ° of C and keeps 16h, and slow cooling is to room temperature, and target material is lenticular and separates out from reaction solution.Resulting materials is washed, used XRD single crystal diffraction to determine its structure (concrete structure as shown in Figure 1), obtaining double activity center's heteropllyacids quality of materials yield by calculated mass is 42%.
The catalytic material that use obtains reacts for benzene hydroxylation, by 0.025mmol catalyzer, and 0.78g benzene (10mmol), 6.8mL acetonitrile, 0.9g xitix, 2MPaO
2add in 50mL autoclave and react, magnetic agitation, temperature of reaction is 80 ℃, keeps 20min, obtaining phenol yield is 7.2%.
Embodiment 4-10
Be similar to embodiment 1, be with its difference: the organic backbone of metal-organic framework materials, polyoxoanion mass concentration, temperature of reaction, crystallization time, the following result (table one) after reaction finishes:
Table one
Embodiment 11-15
Be similar to embodiment 1, be with its difference: adopt the mol ratio of the organic backbone of organic backbone, heteropolyacid mass concentration, heteropolyacid and the metal-organic framework materials of different metal organic framework material, obtain following result (table two):
Table two
Claims (10)
1. one kind is directly synthesized the method for double activity center's heteropllyacids material, it is characterized in that: take water as reaction medium, using heteropolyacid anions, the metallic compound that metal-organic framework materials is provided, the organic backbone compound of metal-organic framework materials, Tetramethylammonium hydroxide is raw material, by the method one-step synthesis target material of Hydrothermal Synthesis; Described temperature of reaction is between 100 ° of C～240 ℃.
2. method according to claim 1, is characterized in that: the filling ratio of reaction medium in reactor is between 30% ~ 90%.
3. method according to claim 1, is characterized in that: the heteropolyacid that heteropolyacid anions is provided used is the one in a kind of in titanium, vanadium, cadmium, manganese, iron, cobalt, nickel, copper, zinc, silver, platinum, cerium etc. or two kinds of metal-doped phosphorus heteropoly tungstic acids, phosphato-molybdic heteropolyacid, silicotungstic heteropolyacid, silicon-molybdenum heteropoly acid, germanium heteropoly tungstic acid, germanomolybdate, arsenic heteropoly tungstic acid, arsenic molybdenum heteropolyacid; Wherein, the doping of metal is phosphorus, silicon, germanium or arsenic heteroatoms quantity 0.5 ~ 4.5 times.
4. method according to claim 1, it is characterized in that: the organic backbone compound of described metal-organic framework materials is 1,3,5-trimesic acid, EDTA, sulphosalicylic acid, 1,4-terephthalic acid, 4-toluene sulfonic acide, 2, one or two or more kinds in dipicolimic acid 2,4-HBA; The metallic compound that metal-organic framework materials is provided is one or two or more kinds in one or two or more kinds nitrate, vitriol or the muriate in molybdenum, vanadium, tungsten, iron, copper, manganese, cobalt, nickel metal.
5. according to the method described in claim 1,2,3 or 4, it is characterized in that: provide the organic backbone compound mol ratio of metal in the metallic compound of metal-organic framework materials and metal-organic framework materials between 1:50 ~ 50:1.
6. according to the method described in claim 1,2,3 or 4, it is characterized in that: when reaction starts, it is temperature required that the temperature of reaction system is warming up to reaction from room temperature start program 5 ℃ of temperature rise rates/h ~ 50 ℃/h.
7. according to the method described in claim 1,2,3 or 4, it is characterized in that: it is between 20:1 ~ 1:50 that metal and heteropolyacid anions mol ratio in the metallic compound of metal-organic framework materials are provided.
8. according to the method described in claim 1,2,3 or 4, it is characterized in that: Tetramethylammonium hydroxide and heteropolyacid anions mol ratio are between 1:1 ~ 6:1.
9. according to the method described in claim 1,2,3 or 4, it is characterized in that: in reaction system, the heteropolyacid of heteropolyacid anions, the metallic compound that metal-organic framework materials is provided, the organic backbone compound of metal-organic framework materials, Tetramethylammonium hydroxide are provided, and four kinds of reaction mass total mass concentrations are between 2% ~ 50%.
10. method according to claim 1, is characterized in that: reaction starts when front, uses NaOH regulation system pH2-8;
After reaction finishes, reclaim product by washing, yield is 15% ~ 85%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406848A (en) * | 2008-11-24 | 2009-04-15 | 东北师范大学 | Method for preparing high-dispersion solid-carrying Keggin type polyoxometallate crystalline-state catalyst |
-
2012
- 2012-12-19 CN CN201210554700.6A patent/CN103880894A/en active Pending
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|---|---|---|---|---|
| CN101406848A (en) * | 2008-11-24 | 2009-04-15 | 东北师范大学 | Method for preparing high-dispersion solid-carrying Keggin type polyoxometallate crystalline-state catalyst |
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