CN101612586A - A kind of molecular sieve catalyst and preparation thereof and application - Google Patents
A kind of molecular sieve catalyst and preparation thereof and application Download PDFInfo
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- CN101612586A CN101612586A CN200810012017A CN200810012017A CN101612586A CN 101612586 A CN101612586 A CN 101612586A CN 200810012017 A CN200810012017 A CN 200810012017A CN 200810012017 A CN200810012017 A CN 200810012017A CN 101612586 A CN101612586 A CN 101612586A
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- molecular sieve
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Abstract
The present invention relates to a kind of molecular sieve catalyst and this catalyst and directly make application in the phenol at benzene and hydroperoxidation.This catalyst carrier is the phosphate aluminium molecular sieve catalyst, and catalytic active component is the compound of simple metal vanadium.Its preparation method is the oxide or the vanadic sulfate of vanadium metal, aluminum nitrate, and the template agent, phosphoric acid by a certain percentage, is regulated pH, and the phosphate aluminium molecular sieve of the synthetic monometallic vanadium of hydro-thermal is through oven dry, high-temperature roasting finished product.This catalyst preparation process is simple, in the hydroxylating of benzene direct oxidation system phenol good applicability is arranged.
Description
Technical field
The present invention relates to the phenol preparation, reaction condition and process that the application in benzene direct oxidation system phenol reactant of the molecular sieve catalyst that specifically a kind of list is transition metal modified and this catalyst, this catalyst relate to Preparation of catalysts and use this one step of catalyst synthesizing phenol.
Background technology
Phenol is important Organic Chemicals, is widely used in petrochemical industry, and agricultural and plastics industry are large tonnage products important among the current organic chemical industry, mainly use its novolak resin, bisphenol-A, caprolactam, aniline, and various pharmaceutical intermediate.
The industrial preparation of phenol mainly depends on cumene method at present, i.e. the cumenyl method.This method adopts benzene alkylation to obtain isopropylbenzene, and cumene oxidation obtains hydrogen phosphide cumene, and the cracking under acid catalysis of last hydrogen phosphide cumene generates phenol and acetone.Obviously, this tediously long production method has its unsurmountable shortcoming.From the economic benefit angle, a large amount of generations of co-product acetone make the market demand of acetone restrict the productivity effect of this method to a certain extent.From environmental, the production procedure in three steps is long, the energy consumption height, and the intermediate product explosive, three-waste pollution is serious.Therefore, the research of phenol by directly hydroxylating benzene has more and more shown its superiority and importance.
Domestic and international research mainly is divided three classes: N
2The O oxidizing process, O
2Oxidizing process, H
2O
2Oxidizing process.
Nineteen eighty-three, (J.Physchem .1983 87:903-908) have found that at first benzene is at V to Iwamoto
2O
5/ SiO
2Under the catalysis, utilize N
2O can make the direct hydroxylating of benzene make phenol as oxidant at high temperature.Suzuki (Chem.Let., 1988,198 (6): 953-956) find to utilize the ZSM-5 molecular sieve catalyst can obtain high reaction selectivity after this greater than 99% in lower reaction temperature (300-400K).Panov (Appl.Catal.A:genenal, 1993,98:1-20) reaction mechanism of Fe-ZSM-5 catalyst to be goed deep into, temperature is when 400 spend, and the conversion ratio of benzene reaches 92%, selectivity 97%.
(Science 2,002 295 (5552): 105-107) found by permeability palladium film device O first for Niwa
2And H
2Can generate original position H
2O
2Thereby, Oxybenzene system phenol.Work as H
2/ O
2Be 4.6 o'clock, the conversion ratio of benzene is 25%, and the phenol selectivity is 77%.Document (J.Mol.Catal.A:Chem.208 (2004) 203) has report, polyoxometallate TBA-PW
11Cu is for there being advantages of high catalytic activity.Under the effect of co-conducer ascorbic acid, 323K reacts 12h, and the conversion ratio of benzene reaches 9.2%, and the selectivity of phenol is about 91.8%.
In the hydrogen peroxide oxidation system, Thangaraj (Appl.Catal., 1990,57:91～93) passes through research TS-1, Fe-TS-1 and Fe-ZSM-5, and the catalytic activity of ZSM-5, the selectivity of phenol can bring up to 93%.The synthetic vanadium metal of Nomiya (J.Mol.Catal.A.:Chem., 1996,114:181～190) replaces heteropoly acid H
4PMo
11VO
40For the catalyst of finding preferably, to do at acetate under the condition of solvent, phenol yield can reach 26%, selectivity 90%.
With hydrogen peroxide as oxidant, the reaction condition gentleness, therefore selectivity height, accessory substance mainly are water, are eco-friendly synthetic routes.The catalyst that the method is used mainly is a HTS, and it costs an arm and a leg, and only at the catalyst recovery yield height, the value of application is arranged just under the good situation of repetitive rate.Therefore, need the easier preparation of exploitation, cheap catalyst.
Summary of the invention
The object of the present invention is to provide a kind of catalyst, the phosphate aluminium molecular sieve catalyst that it is modified for the filtering metal vanadium, can make the transition metal vanadium of remarkable catalytic effect in solid-phase catalyst, bring into play good catalytic action, reduce content of vanadium in the catalyst, overcome the shortcoming of homogeneous system catalyst costliness.It is oxidant with the hydrogen peroxide that another object of the present invention is to provide a kind of, the catalyst system of phenol by directly hydroxylating benzene.
Catalyst provided by the present invention is a carrier with the phosphate aluminium molecular sieve, and the transition metal vanadium is the activity of such catalysts component, in the catalyst in transition metal vanadium and the molecular sieve mol ratio of aluminium be 0.1～5: 100.In the described catalyst in transition metal vanadium and the molecular sieve mol ratio of aluminium be 4～1: 100.
Compound vanadic sulfate, vanadic anhydride all can be used as the vanadium source, and the preferably sulfuric acid vanadyl is as transition metal source.Its preparation method is: with aluminum nitrate, and phosphoric acid, vanadic sulfate, the template agent adds in the aqueous solution in proportion successively, fully stirs, and after the adjusting acid-base value,, filters oven dry, Muffle furnace roasting, finished product through crystallization.Above-mentioned crystallization, dry and sintering temperature all adopts current techique.The nitrate of vanadium or sulfate, aluminum nitrate, phosphoric acid, template agent soon, their mol ratio is 0.01: 1～1.5: 1～1.5: 1～1.5, regulate the pH=3-4 value, 30-70 ℃ of hydro-thermal is synthetic, reaction time 〉=12 hour, and 150-170 ℃ down through leaving standstill crystallization 〉=24 hour, filter, drying, calcining is prepared into the phosphate aluminium molecular sieve catalyst that the monometallic vanadium is modified.Its calcining heat is at 500～800 ℃, time 4-5 hour.
A kind of benzene direct hydroxylating under the hydrogen peroxide effect prepares the method for phenol, adopts above-mentioned catalyst oxidation synthetic.Its catalytic process is a liquid and solid phase reaction, and with acetonitrile, acetate isopolarity solvent is a solvent, is auxiliary agent with the ascorbic acid, and its addition and substrate mol ratio are 1: 10～100.Hydrogen peroxide with 35%～50% is an oxidant, preferred 30%～35%.With benzene is substrate, and hydrogen peroxide used dropping funel slowly to add in the reaction system, at 30 ℃～70 ℃, and synthesis under normal pressure 2～24 hours.Its preferable reaction temperature is 45 ℃～70 ℃, and the reaction time is 12～24 hours.The mol ratio of hydrogen peroxide and benzene is 0.5～2.5～1, and described polar organic solvent is formic acid, acetate and/or acetonitrile, and its consumption is 4～6g/10mmol benzene.
The present invention uses acetate, acetonitrile isopolarity solvent, can increase the intersolubility of benzene and hydrogen peroxide.Add ascorbic acid, can play the effect of co-conducer, reduction high price transition metal vanadium is beneficial to the catalytic action of better performance active sites.Accessory substance mainly is a benzoquinones.
Product analysis of the present invention is to use capillary gas chromatograph to finish.Temperature programming separates at the SE-30 capillary column, adopts the toluene internal standard method, utilizes working curve accurately to obtain the content of phenol in the reactant liquor.
Advantage:
1. the transition metal vanadium is employed as the activated centre of the homogeneous catalyst of benzene direct oxidation system phenol, but it is difficult in repeatedly to reclaim in the reaction and uses as homogeneous catalyst, and itself complex structure, what often obtain in preparation process is the mixture of many structures.The catalyst that the present invention is designed, active component are the transition metal vanadium, as its Stability Analysis of Structures of a kind of molecular sieve catalyst, catalytic activity is higher, and utilize framework of molecular sieve, after heterogeneousization of activated centre in the homogeneous system, can reduce its loss in system.
2. catalyst involved in the present invention, the preparation condition gentleness, easy and simple to handle, molecular sieve catalyst obtains easily.
3. the molecular sieve catalyst that contains the activated centre vanadium involved in the present invention is used for the reaction of benzene direct oxidation system phenol, and catalytic activity preferably can be arranged, and under the interpolation that ascorbic acid is arranged, the yield of reaction is improved a lot.
The specific embodiment
Embodiment 1: Preparation of catalysts
Take by weighing Al (NO successively
3)
39H
2O 37.5g after the water dissolving, drips 85% phosphatase 11 1.6g, mixes in 60 ℃ of water-baths and stirs, and constant pressure funnel drips and contains VOSO
40.082g the aqueous solution, fully stir the back and add template agent triethylamine 2.53g, be about 3.5 with NaOH acid adjustment basicity to pH after, 170 ℃ of following crystallization 12 hours, through washing, filtration, drying is sintered into finished product V-APO-5. at 600 ℃
Embodiment 2: hydrogen peroxide oxidation benzene directly prepares the reaction of phenol
Take by weighing V-APO-5 catalyst 0.2g, add benzene 10mmol.Acetonitrile, acetate all can be as reaction dissolvents, and consumption is 6ml, add co-conducer ascorbic acid 1mmol, electromagnetic agitation, the back Dropwise 35 % hydrogen peroxide (mol ratio of benzene and hydrogen peroxide 1: 1.5) that heats up reacted 8 hours, phenol yield 5.0-6.5%, phenol selectivity 86%.
Embodiment 3: the evaluating catalyst that the loading of vanadium metal is different
Press the preparation method who describes in the example 1, the molecular sieve catalyst of preparation different metal content of vanadium is that with example 2 differences just the ratio of loading is different.In with example 2, under the identical application conditions, investigate of the influence of the content of vanadium metal to the catalytic reaction effect.The vanadium loading is investigated analysis result such as following table 1 with the mol ratio of vanadium metal and aluminium oxide (aluminum nitrate conversion):
By table 1 as seen, at Al
2O
3: VOSO
4At 100: 4 o'clock, phenol had higher yield and selectivity.The influence of the loading of table 1 vanadium
| Al 2O 3∶VOSO 4 | Phenol yield (%) | Phenol selectivity (%) |
| 400∶1 | ???3.4 | ??85.2 |
| 200∶1 | ???3.5 | ??84.7 |
| 100∶1 | ???4.6 | ??86.6 |
| ????100∶2 | ????5.7 | ????85.7 |
| ????100∶3 | ????6.0 | ????86.4 |
| ????100∶4 | ????6.5 | ????86.8 |
Embodiment 4: the temperature influence that direct oxidation prepares phenol reactant to benzene
Press example 2 described reaction methods, add substrate, behind catalyst and the ascorbic acid, the heating reaction system drips hydrogen peroxide (mol ratio of benzene and hydrogen peroxide 1: 1.5) to different reaction temperatures, reacts analysis result such as table 28 hours:
By table 2 as seen: when temperature greater than 40 ℃, phenol yield is significantly improved, when reaction temperature is increased to more than 50 ℃, phenol yield is stabilized in 5～5.5%, so optimal reaction temperature is 45 ℃～70 ℃.Table 2 Temperature Influence
| Reaction temperature ℃ | Phenol yield (%) |
| ??30 | ??1.2 |
| ??40 | ??4.3 |
| ??50 | ??5.1 |
| ??55 | ??5.4 |
| ??60 | ??5.5 |
| ??70 | ??5.3 |
Embodiment 5: benzene and hydrogen peroxide different mol ratio are to the influence of reaction
Press example 2 described reaction methods,, reacted analysis result such as table 38 hours at 50 ℃ of hydrogen peroxide (benzene is also different with the mol ratio of hydrogen peroxide) that drip variable concentrations:
By to variable concentrations, the hydrogen peroxide of different proportion is investigated, and the ratio of finding hydrogen peroxide and benzene was at 1.5: 1 o'clock, and taking one thing with another all is a more satisfactory rate of charge.
Table 3 benzene and hydrogen peroxide different mol ratio are to the influence of reaction
Embodiment 6: add the influence of the amount of reducing agent ascorbic acid to reaction
Press example 2 described methods, in 60 ℃ of water-baths, reacted 12 hours, benzene and hydrogen peroxide mol ratio are 1: 1.5, add the influence of the co-conducer ascorbic acid investigation of different amounts to reaction result.Analysis result such as table 4
By investigating, find that reacting has result preferably when ratio that ascorbic acid adds quality and catalyst is 0.6: 1～1.2: 1 left and right sides.
Table 4 ascorbic acid consumption is to the influence of reaction
| Ascorbic acid and catalyst quality ratio | 0∶1 | ?0.2∶1 | ?0.4∶1 | ?0.6∶1 | ?0.8∶1 | ?1∶1 | ?1.2∶1 | ?1.4∶1 |
| Yield (%) | 1.1 | ??2.7 | ??3.2 | ??7.9 | ??8.2 | ??8.4 | ??10.3 | ??10.5 |
Embodiment 7: the reaction time is to the influence of phenol by directly hydroxylating benzene
Press example 2 described methods, when 50 ℃ of water-baths, the hydrogen peroxide of Dropwise 35 % (mol ratio of benzene and hydrogen peroxide is 1: 1.5), investigate of the influence of differential responses time, analysis result such as table 5 to reaction:
By investigating, prolong reaction time Pyrogentisinic Acid yield and be significantly improved, and undue prolongation can cause that the aggravation of deep oxidation causes yield and selectivity slightly to descend, so the reaction time be controlled at 16～24 hours preferable.
The influence in table 5 reaction time
| Reaction time | 8 | ?12 | ?16 | ?20 | ?24 | ?28 | ?32 |
| Phenol yield (%) | 5.0 | ?10.1 | ?13.2 | ?13.3 | ?14.2 | ?14.0 | ?13.8 |
| Phenol selectivity (%) | 85.4 | ?85.3 | ?86.3 | ?86.7 | ?86.7 | ?86.2 | ?84.9 |
Embodiment 8: catalyst amount is to the influence of reaction
Press example 2 described methods, take by weighing different molecular sieve catalyst V-APO-5, be heated to 50 ℃, the hydrogen peroxide of Dropwise 35 % (mol ratio of benzene and hydrogen peroxide is 1: 1.5), reacted analysis result such as table 6 12 hours:
By investigating the mass ratio that catalyst adds quality and substrate benzene (0.8g), find that phenol has yield and selectivity preferably when catalyst 0.15g-0.3g.
Table 6 catalyst amount is to the influence of reaction
| Catalyst amount (g) | Phenol yield (%) | Phenol selectivity (%) |
| 0 | ??- | - |
| 0.05 | ??4.9 | 86.2 |
| 0.1 | ??6.6 | 85.9 |
| 0.15 | ??10.5 | 86.4 |
| 0.2 | ??10.2 | 86.5 |
| 0.25 | ??10.8 | 86.7 |
| 0.3 | ??10.7 | 86.7 |
Claims (9)
1. molecular sieve catalyst, it is characterized in that: be carrier with the phosphate aluminium molecular sieve, the transition metal vanadium is the activity of such catalysts component, in the catalyst in transition metal vanadium and the molecular sieve mol ratio of aluminium be 0.1～5: 100.
2. according to the described catalyst of claim 1, it is characterized in that: in the described catalyst in transition metal vanadium and the molecular sieve mol ratio of aluminium be 4～1: 100.
3. described Preparation of catalysts method of claim 1, it is characterized in that: with the nitrate of vanadium or sulfate, aluminum nitrate, phosphoric acid, template agent, their mol ratio is 0.01: 1～1.5: 1～1.5: 1～1.5, regulates the pH=3-4 value, and 30-70 ℃ of hydro-thermal is synthetic, reaction time 〉=12 hour, 150-170 ℃ down through leaving standstill crystallization 〉=24 hour, filters drying, calcining is prepared into the phosphate aluminium molecular sieve catalyst that the monometallic vanadium is modified.
4. according to the described preparation method of claim 3, it is characterized in that: its calcining heat is at 500～800 ℃, time 4-5 hour.
5. according to the described preparation method of claim 3, it is characterized in that: the sulfate of described vanadium is vanadic sulfate.
6. the application of the described catalyst of claim 1 in phenol by directly hydroxylating benzene.
7. according to the described application of claim 6, it is characterized in that: as oxidant, is substrate with benzene with mass concentration 30～50% hydrogen peroxide, in polar organic solvent the benzene direct oxidation is generated phenol, under the normal pressure, reaction temperature is 30 ℃～70 ℃, 2～24 hours reaction time.
8. according to the described application of claim 7, it is characterized in that: be added with the auxiliary agent ascorbic acid in reaction system, its addition and substrate mol ratio are 1: 10～100.
9. according to the described application of claim 7, it is characterized in that: the mol ratio of hydrogen peroxide and benzene is 0.5～2.5～1, and described polar organic solvent is formic acid, acetate and/or acetonitrile, and its consumption is 4～6g/10mmol benzene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228833A (en) * | 2011-05-09 | 2011-11-02 | 南京工业大学 | Cobalt-containing porous material and application thereof in reaction for preparing phenol by benzene hydroxylation |
| CN108435247A (en) * | 2012-02-17 | 2018-08-24 | 罗地亚运作公司 | For the method for hydroxylation of aromatic compound, hydroxylation catalysts and the method for being used to prepare hydroxylation catalysts |
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| CN100443172C (en) * | 2002-09-11 | 2008-12-17 | 中国科学院大连化学物理研究所 | Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228833A (en) * | 2011-05-09 | 2011-11-02 | 南京工业大学 | Cobalt-containing porous material and application thereof in reaction for preparing phenol by benzene hydroxylation |
| CN102228833B (en) * | 2011-05-09 | 2012-12-19 | 南京工业大学 | Cobalt-containing porous material and application thereof in reaction for preparing phenol by benzene hydroxylation |
| CN108435247A (en) * | 2012-02-17 | 2018-08-24 | 罗地亚运作公司 | For the method for hydroxylation of aromatic compound, hydroxylation catalysts and the method for being used to prepare hydroxylation catalysts |
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