CN1280012C - Bitransition metal modified molecular sieve and its preparation and use - Google Patents
Bitransition metal modified molecular sieve and its preparation and use Download PDFInfo
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- CN1280012C CN1280012C CNB2004100167523A CN200410016752A CN1280012C CN 1280012 C CN1280012 C CN 1280012C CN B2004100167523 A CNB2004100167523 A CN B2004100167523A CN 200410016752 A CN200410016752 A CN 200410016752A CN 1280012 C CN1280012 C CN 1280012C
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Abstract
The present invention relates to a molecular sieve modified by two transitional metals, a preparing method thereof and an application thereof. The molecular sieve is composed of a molecular sieve and two transitional metals chosen from Fe, Zn, Cu, V and Ti, and the two transitional metals are attached to the surface of the molecular sieve in an oxide mode. The preparing method of the molecular sieve comprises: firstly, dissolving the salt of the first transitional metal, Al(NO3)3.9H2O and phosphoric acid in water; carrying out reflux; then adding ethanol solution containing template agent P123; carrying out reflux; adding TEOS; carrying out reflux; finally, transferring the mixture into a polypropylene kettle for crystallization, filtration, cleaning, baking, calcining and template agent removing to obtain the molecular sieve modified by the first transitional metal; adding the molecular sieve modified by the first transitional metal into the salt solution of the second transitional metal; carrying out reflux, filtration, cleaning, baking and calcining to obtain the molecular sieve modified by two transitional metals. The molecular sieve can be used as a catalyst in the reaction of synthesizing phenol by using liquid molecular oxygen to oxidize benzene in one step. The molecular sieve has the advantages of simple structure, easy preparation and good catalytic performance.
Description
Technical field
The present invention relates to a kind of two transition metal modified molecular sieve and preparation and purposes, definitely say, relate to a kind of two transition metal modified SBA-15 molecular sieve and preparation and purposes, belong to the technical field of modified molecular sieve catalyst and preparation and purposes.
Background technology
Phenol is a kind of crucial industrial chemicals.It is a presoma of producing bisphenol-A, phenolic resins, caprolactam, nylon-6, cleaning agent, adhesive, antioxidant and other many chemical products, and therefore, the market demand of phenol is very big, and in various chemical products, its output occupies top ten.The employed method of industrial production phenol all is an indirect synthesis technique at present, promptly earlier the benzene reaction is generated intermediate product, and then the intermediate product reaction is generated phenol.Cumene method most importantly in these methods: with benzene and propylene is raw material, generates isopropylbenzene under acid catalysis, and isopropylbenzene generates hydrogen phosphide cumene through oxidation, decomposes with sulfuric acid or resin again, obtains equimolar phenol and acetone simultaneously.Because the growth of the market demand of acetone is much smaller than phenol, so the production of phenol is restricted by the market of acetone.The method of multistep synthesizing phenol is because of a large amount of consumption of raw materials, and productive rate is not high, so cost is higher, and causes serious environmental to pollute.
In the background technology, the method for oxidation step benzene synthesizing phenol has two kinds: vapor phase method and liquid phase method.The gas-phase one-step synthetic method uses the ZSM-5 zeolite molecular sieve of modification as catalyst, with N
2O is as oxidant, oxidation step benzene, directly synthesizing phenol.Because the synthetic route temperature of this method is higher than 200 ℃, produces and be subjected to oxidant N
2The restriction of O is very big, so production cost is very high.The liquid phase one-step synthetic method with the molecular sieve of Fenton reagent, heteropoly acid and various transition metal ion-modified as catalyst, with hydrogen peroxide as oxidant, oxidation step benzene, directly synthesizing phenol.Because the activity of phenol is higher than benzene, so can produce a large amount of byproduct benzoquinones and benzenediol with the synthetic route of this method, the selectivity of phenol is relatively poor.The method of report with molecular oxygen oxidation step benzene synthesizing phenol arranged recently: under the catalytic action of the silica of metal ion such as platinum, palladium, vanadium, copper and heteropoly acid modification, aluminium oxide, MCM-41 molecular sieve, with molecular oxygen as oxidant, oxidation step benzene, directly synthesizing phenol.The advantage of this method is that selectivity is very high, and shortcoming is that the productive rate of phenol is still very low.
Summary of the invention
The method of last a kind of oxidation step benzene synthesizing phenol of background technology introduction is the most promising method, if can find the better catalyst of performance, and the productive rate of phenol is expected and can improves so.
First purpose of the present invention is to propose a kind of two transition metal modified SBA-15 molecular sieve.Technical scheme of the present invention is characterised in that, described molecular sieve is formed by two kinds among SBA-15 molecular sieve and five kinds of transition metal: Fe, Zn, Cu, V, the Ti, two kinds of transition metal are attached to the surface of molecular sieve with the form of oxide, and two transition metal modified SBA-15 molecular sieves: first transition metal: the weight ratio of second transition metal is 100: (10-30): (5-10).
Second purpose of the present invention provides the preparation method of described molecular sieve.The present invention for realizing the technical scheme that this purpose adopts is: the preparation method of a kind of pair of transition metal modified SBA-15 molecular sieve, it is characterized in that, and prepare the first transition metal modified SBA-15 molecular sieve earlier: with first transition metal salt, Al (NO
3)
39H
2O and phosphoric acid are water-soluble, reflux, and then add the ethanolic solution that contains template agent P123, reflux, and add TEOS then, reflux, and are transferred to polypropylene still crystallization at last, filter, and clean oven dry, roasting, template agent removing, the SBA-15 molecular sieve of winning transition metal modified; Two transition metal modified SBA-15 molecular sieves of preparation again: the first transition metal modified SBA-15 molecular sieve is added the solution that contains second transition metal salt, refluxes, filter, clean, oven dry, roasting, two transition metal modified SBA-15 molecular sieves.
Now describe above-mentioned technical scheme in detail.The concrete operations step:
The first step prepares the first transition metal modified SBA-15 molecular sieve
With the first modified metal salt of 0.5-2.0 part weight, the Al (NO of 7.5 parts of weight
3)
39H
2O, 85% phosphoric acid of 6.8 parts of weight is dissolved in the water of 30 parts of weight, and 50-80 ℃ was refluxed 24 hours, add the ethanolic solution 6-11 part weight that contains template agent P123, template agent P123: the weight ratio of ethanol=1: 10, continue to reflux 24 hours, add the TEOS of 2.08 parts of weight, refluxed three days, be transferred to polypropylene still crystallization 3 days, filter, clean oven dry, 550 ℃ of roastings 6 hours with distilled water, template agent removing, the first transition metal modified SBA-15 molecular sieve of 0.9-1.5 part weight;
The two transition metal modified SBA-15 molecular sieves of second step preparation
Get 1 part of weight of molecular sieve that the first step makes, the solution that contains second transition metal salt that adds 10 parts of weight, the prescription of this solution is second transition metal salt: the weight ratio of water or ethanol=1: 100,60-90 ℃ was refluxed 24 hours, filter, clean, oven dry, 550 ℃ of roastings 4 hours, get the two transition metal modified SBA-15 molecular sieve of 0.9-1.5 part weight, two transition metal modified SBA-15 molecular sieves: first transition metal: the weight ratio of second transition metal is 100: (10-30): (5-10).
The 3rd purpose of the present invention provides the purposes of described molecular sieve: two transition metal modified SBA-15 molecular sieves in the reaction of molecular oxygen liquid phase one-step oxidation benzene synthesizing phenol as the usage of catalyst.The present invention is characterised in that for realizing the technical scheme that this purpose adopts, and under two transition metal modified molecular sieve SBA-15 catalysis and under the reducing agent participation, is oxidant with the molecular oxygen, and oxidation step is dissolved in the benzene of solvent, directly synthesizing phenol.This technical scheme is further characterized in that, reducing agent is an ascorbic acid, solvent is acetic acid and water, molecular oxygen is oxygen or air, concrete operations step: in stainless steel autoclave, add the two transition metal modified SBA-15 molecular sieve of 0.5 part of weight as catalyst, the acetic acid of adding 32-63 part weight and the water of 30-60 part weight are as solvent, the ascorbic acid of 5-10 part weight is as reducing agent, the benzene of 4-8 part weight is dissolved in solvent, charge into molecular oxygen to benzole soln, be oxygen or air, the pressure of oxygen or air is between 2-8.5Mpa, at 70-90 ℃ of following stirring reaction 12-24 hour, molecular oxygen liquid phase one-step oxidation benzene, the directly phenol of synthetic 1.7-3.5 part weight.
The productive rate of phenol reaches 18-36%, and the selectivity of phenol is higher than 97%.
Compare with background technology, the present invention has the following advantages:
1. the related two transition metal modified molecular sieve structure of the present invention is simple, is easy to preparation.
2. the catalytic performance of the related two transition metal modified molecular sieve of the present invention is good, and during as catalyst, the productive rate height of phenol can reach 15-36% to this molecular sieve in the reaction of molecular oxygen liquid phase one-step oxidation benzene synthesizing phenol; The selectivity of phenol reaches more than 97%, and product is single; Use molecular oxygen as oxidant oxidation step benzene, directly synthesizing phenol is saved raw material, reduces and pollutes, and production cost is reduced greatly.
The specific embodiment
Two transition metal modified molecular sieve: the Ti-Fe-SBA-15 of embodiment one preparation
First, second transition metal is respectively Fe, Ti, is two kinds among five kinds of transition metal: Fe, Zn, Cu, V, the Ti, the concrete operations step:
The first step prepares first transition metal modified molecular sieve: the Fe-SBA-15
With 0.5 gram, the first transition metal salt Fe (NO
3)
36H
2O, 7.5 gram Al (NO
3)
39H
2O, the phosphoric acid of 6.8 gram 85wt% are dissolved in 30 gram water, and 50 ℃ were refluxed 24 hours, add ethanolic solution 6 grams that contain template agent P123, template agent P123: the weight ratio of ethanol=1: 10 adds 2.08 TEOS that restrain after continuing to reflux 24 hours again, refluxed three days, be transferred to polypropylene still crystallization three days, and filtered, clean, oven dry, 550 ℃ of roastings 6 hours, template agent removing, the transition metal modified molecular sieve Fe-SBA-15 of 0.9 gram first;
Two transition metal modified molecular sieve: the Ti-Fe-SBA-15 of second step preparation
Get 1 and restrain the first transition metal modified molecular sieve, add the ethanolic solution of 10 gram butyl titanates, butyl titanate: the weight ratio of ethanol=1: 100,60 ℃ were refluxed 24 hours, filtered, and cleaned, oven dry, 550 ℃ of roastings 4 hours, the two transition metal modified molecular sieve Ti-Fe-SBA-15 of 0.9 gram.
Two transition metal modified molecular sieve: the Cu-Fe-SBA-15 of embodiment two preparations
First, second transition metal is respectively Fe, Cu, is two kinds among five kinds of transition metal: Fe, Zn, Cu, V, the Ti, the concrete operations step:
The first step prepares first transition metal modified molecular sieve: the Fe-SBA-15
With 1.5 grams, the first transition metal salt Fe (NO
3)
36H
2O, 7.5 gram Al (NO
3)
39H
2O, the phosphoric acid of 6.8 gram 85wt% are dissolved in 30 gram water, and 80 ℃ were refluxed 24 hours, add ethanolic solution 11 grams that contain template agent P123, template agent P123: the weight ratio of ethanol=1: 10 adds 2.08 TEOS that restrain after continuing to reflux 24 hours again, refluxed three days, be transferred to polypropylene still crystallization 3 days, and filtered, clean, oven dry, 550 ℃ of roastings 6 hours, template agent removing, the transition metal modified molecular sieve Fe-SBA-15 of 1.5 grams first;
Two transition metal modified molecular sieve: the Cu-Fe-SBA-15 of second step preparation
Get 1 and restrain the first transition metal modified molecular sieve, add 10 gram CuSO
4The aqueous solution, CuSO
45H
2O: the weight ratio of water=1: 100,60 ℃ were refluxed 24 hours, filtered, clean, oven dry, 550 ℃ of roastings 4 hours, the two transition metal modified molecular sieve Cu-Fe-SBA-15 of 1.5 grams.
Two transition metal modified molecular sieve: the V-Zn-SBA-15 of embodiment three preparations
First, second transition metal is respectively Zn, V, is two kinds among five kinds of transition metal: Fe, Zn, Cu, V, the Ti, the concrete operations step:
The first step prepares first transition metal modified molecular sieve: the Zn-SBA-15
With 1.0 grams, the first transition metal salt Zn (NO
3)
26H
2O, 7.5 gram Al (NO
3)
39H
2O, the phosphoric acid of 6.8 gram 85wt% are dissolved in 30 gram water, and 70 ℃ were refluxed 24 hours, add ethanolic solution 10 grams that contain template agent P123, template agent P123: the weight ratio of ethanol=1: 10 adds 2.08 TEOS that restrain after continuing to reflux 24 hours again, refluxed three days, be transferred to polypropylene still crystallization 3 days, and filtered, clean, oven dry, 550 ℃ of roastings 6 hours, template agent removing, the transition metal modified molecular sieve Zn-SBA-15 of 1.2 grams first;
Two transition metal modified molecular sieve: the V-Zn-SBA-15 of second step preparation
Get 1 and restrain the first transition metal modified molecular sieve, add 10 gram NH
4VO
3The aqueous solution, NH
4VO
3: the weight ratio of water=1: 100,70 ℃ were refluxed 24 hours, filtered, clean, oven dry, 550 ℃ of roastings 4 hours, the two transition metal modified molecular sieve catalyst V-Zn-SBA-15 of 1.2 grams.
Two transition metal modified molecular sieve: the V-Cu-SBA-15 of embodiment four preparations
First, second transition metal is respectively Cu, V, is two kinds among five kinds of transition metal: Fe, Zn, Cu, V, the Ti, the concrete operations step:
The first step prepares first transition metal modified molecular sieve: the Cu-SBA-15
With 2.0 grams, the first transition metal salt CuSO
45H
2O, 7.5 gram Al (NO
3)
39H
2O, the phosphoric acid of 6.8 gram 85wt% are dissolved in 30 gram water, and 60 ℃ were refluxed 24 hours, add ethanolic solution 11 grams that contain template agent P123, template agent P123: the weight ratio of ethanol=1: 10 adds 2.08 TEOS that restrain after continuing to reflux 24 hours again, refluxed three days, be transferred to polypropylene still crystallization 3 days, and filtered, clean, oven dry, 550 ℃ of roastings 6 hours, template agent removing, the transition metal modified molecular sieve Cu-SBA-15 of 1 gram first;
Two transition metal modified molecular sieve: the V-Cu-SBA-15 of second step preparation
Get 1 and restrain the first transition metal modified molecular sieve, add 10 gram NaVO
3The aqueous solution, NaVO
3: the weight ratio of water=1: 100,90 ℃ were refluxed 24 hours, filtered, clean, oven dry, 550 ℃ of roastings 4 hours, the two transition metal modified molecular sieve catalyst V-Cu-SBA-15 of 1 gram.
Two transition metal modified molecular sieve: the Ti-Zn-SBA-15 of embodiment five preparations
First, second transition metal is respectively Cu, V, is two kinds among five kinds of transition metal: Fe, Zn, Cu, V, the Ti, the concrete operations step:
The first step prepares first transition metal modified molecular sieve: the Zn-SBA-15
With 1.0 grams, the first transition metal salt Zn (NO
3)
26H
2O, 7.5 gram Al (NO
3)
39H
2O, the phosphoric acid of 6.8 gram 85wt% are dissolved in 30 gram water, and 50 ℃ were refluxed 24 hours, add ethanolic solution 7 grams that contain template agent P123, template agent P123: the weight ratio of ethanol=1: 10 adds 2.08 TEOS that restrain after continuing to reflux 24 hours again, refluxed three days, be transferred to polypropylene still crystallization 3 days, and filtered, clean, oven dry, 550 ℃ of roastings 6 hours, template agent removing, the transition metal modified molecular sieve Zn-SBA-15 of 1.1 grams first;
Two transition metal modified molecular sieve: the Ti-Zn-SBA-15 of second step preparation
Get 1 and restrain the first transition metal modified molecular sieve, add the ethanolic solution of 10 gram butyl titanates, butyl titanate: the weight ratio of ethanol=1: 100,60 ℃ were refluxed 24 hours, filtered, and cleaned, oven dry, 550 ℃ of roastings 4 hours, the two transition metal modified molecular sieve Ti-Zn-SBA-15 of 1.1 grams.
The purposes of the molecular sieve Ti-Fe-SBA-15 of embodiment six embodiment one preparation
Concrete operations step: the molecular sieve Ti-Fe-SBA-15,5 gram ascorbic acid, 8 gram benzene, 60 gram water, the 32 gram acetic acid that in autoclave, add 0.5 gram embodiment, one preparation, 80 ℃ of control temperature, charge into oxygen, oxygen pressure is 4Mpa, 12 hours reaction time, molecular oxygen liquid phase one-step oxidation benzene, directly Synthetic 2 .7 restrains phenol, productive rate 28%.
The purposes of the molecular sieve Cu-Fe-SBA-15 of embodiment seven embodiment two preparations
Concrete operations step: the molecular sieve Cu-Fe-SBA-15,7 gram ascorbic acid, 4 gram benzene, 30 gram water, the 63 gram acetic acid that in autoclave, add 0.5 gram embodiment, two preparations, 70 ℃ of control temperature, charge into oxygen, oxygen pressure is 2Mpa, 16 hours reaction time, molecular oxygen liquid phase one-step oxidation benzene, directly synthetic 1.7 gram phenol, productive rate 36%.
The purposes of the molecular sieve V-Zn-SBA-15 of embodiment eight embodiment three preparations
Concrete operations step: the molecular sieve V-Zn-SBA-15,10 gram ascorbic acid, 8 gram benzene, 30 gram water, the 32 gram acetic acid that in autoclave, add 1 gram embodiment, three preparations, 70 ℃ of control temperature, charge into oxygen, oxygen pressure is 2Mpa, 24 hours reaction time, molecular oxygen liquid phase one-step oxidation benzene, directly synthetic 3.1 gram phenol, productive rate 32%.
The purposes of the molecular sieve V-Cu-SBA-15 of embodiment nine embodiment four preparations
Concrete operations step: the molecular sieve V-Cu-SBA-15,7 gram ascorbic acid, 8 gram benzene, 30 gram water, the 63 gram acetic acid that in autoclave, add 0.5 gram embodiment, one preparation, 90 ℃ of control temperature, charge into oxygen, oxygen pressure is 4Mpa, 16 hours reaction time, molecular oxygen liquid phase one-step oxidation benzene, directly synthetic 3.5 gram phenol, productive rate 36%.
The purposes of the molecular sieve Ti-Zn-SBA-15 of embodiment ten embodiment five preparations
Concrete operations step: the molecular sieve Ti-Zn-SBA-15,7 gram ascorbic acid, 8 gram benzene, 60 gram water, the 63 gram acetic acid that in autoclave, add 1 gram embodiment, five preparations, 80 ℃ of control temperature, charge into air, air pressure is 8.5Mpa, 8 hours reaction time, molecular oxygen liquid phase one-step oxidation benzene, directly synthetic 1.7 gram phenol, productive rate 18%.
Claims (3)
1, a kind of two transition metal modified SBA-15 molecular sieve that is used for the reaction of catalytic one-stage Oxybenzene synthesizing phenol, it is characterized in that, described molecular sieve is formed by two kinds among SBA-15 molecular sieve and five kinds of transition metal: Fe, Zn, Cu, V, the Ti, two kinds of transition metal are attached to the surface of SBA-15 molecular sieve with the form of oxide, and two transition metal modified SBA-15 molecular sieves: first transition metal: the weight ratio of second transition metal is 100: (10-30): (5-10).
2, the preparation method of the described molecular sieve of claim 1 is characterized in that, the concrete operations step:
The first step prepares the first transition metal modified SBA-15 molecular sieve
With the first modified metal salt of 0.5-2.0 part weight, the Al (NO of 7.5 parts of weight
3)
39H
2O, 85% phosphoric acid of 6.8 parts of weight is dissolved in the water of 30 parts of weight, and 50-80 ℃ was refluxed 24 hours, add the ethanolic solution 6-11 part weight that contains template agent P123, template agent P123: the weight ratio of ethanol=1: 10, continue to reflux 24 hours, add the TEOS of 2.08 parts of weight, refluxed three days, be transferred to polypropylene still crystallization 3 days, filter, clean oven dry, 550 ℃ of roastings 6 hours with distilled water, template agent removing, the first transition metal modified SBA-15 molecular sieve of 0.9-1.5 part weight;
The two transition metal modified SBA-15 molecular sieves of second step preparation
Get 1 part of weight of molecular sieve that the first step makes, the solution that contains second transition metal salt that adds 10 parts of weight, the prescription of this solution is second transition metal salt: the weight ratio of water or ethanol=1: 100,60-90 ℃ was refluxed 24 hours, filter, clean, oven dry, 550 ℃ of roastings 4 hours, get the two transition metal modified SBA-15 molecular sieve of 0.9-1.5 part weight, two transition metal modified SBA-15 molecular sieves: first transition metal: the weight ratio of second transition metal is 100: (10-30): (5-10).
3, the described molecular sieve of claim 1 in the reaction of molecular oxygen liquid phase one-step oxidation benzene synthesizing phenol as the usage of catalyst, it is characterized in that, reducing agent is an ascorbic acid, solvent is acetic acid and water, molecular oxygen is oxygen or air, concrete operations step: in stainless steel autoclave, add the two transition metal modified SBA-15 molecular sieve of 0.5 part of weight as catalyst, the acetic acid of adding 32-63 part weight and the water of 30-60 part weight are as solvent, the ascorbic acid of 5-10 part weight is as reducing agent, the benzene of 4-8 part weight is dissolved in solvent, charge into molecular oxygen to benzole soln, be oxygen or air, the pressure of oxygen or air is between 2-8.5Mpa, at 70-90 ℃ of following stirring reaction 12-24 hour, molecular oxygen liquid phase one-step oxidation benzene, the directly phenol of synthetic 1.7-3.5 part weight.
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|---|---|---|---|
| CNB2004100167523A CN1280012C (en) | 2004-03-05 | 2004-03-05 | Bitransition metal modified molecular sieve and its preparation and use |
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|---|---|---|---|
| CNB2004100167523A CN1280012C (en) | 2004-03-05 | 2004-03-05 | Bitransition metal modified molecular sieve and its preparation and use |
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| CN1280012C true CN1280012C (en) | 2006-10-18 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396376C (en) * | 2006-07-17 | 2008-06-25 | 中国石油化工集团公司 | Catalyst for modifying faulty gasoline, preparing method and application thereof |
| CN101569857B (en) * | 2008-04-30 | 2011-09-07 | 中国石油天然气股份有限公司 | Preparation method of molecular sieve adsorbent |
| CN102125867B (en) * | 2011-02-17 | 2013-01-02 | 上海兖矿能源科技研发有限公司 | Synthesis method for directly modifying carbinol to produce propylene catalyst by high silica-alumina-ratio metal |
| CN103566969B (en) * | 2012-07-31 | 2015-08-26 | 中国科学院大连化学物理研究所 | A kind of preparation method of vanadium base catalytic material of catalysis benzene hydroxylation phenol |
| CN104549414B (en) * | 2013-10-28 | 2017-02-08 | 中国石油化工股份有限公司 | Catalyst for hydroxylating aromatics directly and preparation method of catalyst |
| CN109876849B (en) * | 2017-12-06 | 2020-08-11 | 中国科学院大连化学物理研究所 | 1, 4-naphthoquinone catalyst prepared by liquid-phase oxidation of naphthalene and preparation method and application thereof |
| CN112939006B (en) * | 2019-12-10 | 2023-04-25 | 中国科学院大连化学物理研究所 | Modification method of framework silicon-rich zeolite molecular sieve |
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