CN1559682A - Bitransition metal modified molecular sieve and its preparation and use - Google Patents
Bitransition metal modified molecular sieve and its preparation and use Download PDFInfo
- Publication number
- CN1559682A CN1559682A CNA2004100167523A CN200410016752A CN1559682A CN 1559682 A CN1559682 A CN 1559682A CN A2004100167523 A CNA2004100167523 A CN A2004100167523A CN 200410016752 A CN200410016752 A CN 200410016752A CN 1559682 A CN1559682 A CN 1559682A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- molecular sieve
- modified molecular
- metal modified
- weight
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A molecular sieve modified by two transition metals is composed of molecular sieve and the oxides of two transition metals chosen from Fe, Zn, Cu, V and Ti. Its preparing process includes such steps as dissolving the salt of the first transition metal, Al(NO3)3.9H2O and phosphoric acid in water, reflux, adding alcohol solution containing template agent P123, reflux, adding TEOS, reflux, crystallizing, filter, washing baking, calcining removing template agent, adding the solution of the second transition metal salt, reflux, filter-washing, baking and calcining. It can be used as the catalyst for synthesizing phenol by using liquid molecular oxygen to oxidize benzene.
Description
Technical field
The present invention relates to a kind of two transition metal modified 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 dihydroxyphenyl propane, resol, hexanolactam, nylon-6, sanitising agent, tackiness agent, antioxidant and other many Chemicals, and therefore, the market demand of phenol is very big, and in various Chemicals, 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 isopropyl benzene under acid catalysis, and isopropyl benzene 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 raw material consumption, 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 process and liquid phase method.The gas-phase one-step synthesis method with the ZSM-5 zeolite molecular sieve of modification as catalyzer, with N20 as oxygenant, oxidation step benzene, directly synthesizing phenol.Because the synthetic route temperature of this method is higher than 200 ℃, the restriction that production is subjected to oxygenant N20 is very big, so production cost is very high.The liquid phase one-step synthesis method with the molecular sieve of Fenton reagent, heteropolyacid and various transition metal ion-modified as catalyzer, with hydrogen peroxide as oxygenant, 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 dihydroxy-benzene 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 katalysis of the silicon-dioxide of metal ion such as platinum, palladium, vanadium, copper and heteropolyacid modification, aluminum oxide, MCM-41 molecular sieve, with molecular oxygen as oxygenant, 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 catalyzer 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 molecular sieve.Technical scheme of the present invention is characterised in that, described molecular sieve is formed by two kinds among 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 compound, and two transition metal modified 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 molecular sieve, it is characterized in that, and prepare the first transition metal modified 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 soln that contains template 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 transition metal modified molecular sieve of winning; The two transition metal modified molecular sieves of refabrication: the first transition metal modified molecular sieve is added the solution that contains second transition metal salt, refluxes, filter, clean, oven dry, roasting, two transition metal modified molecular sieves.
Now describe above-mentioned technical scheme in detail.The concrete operations step:
The first step prepares the first transition metal modified 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 soln 6-11 part weight that contains template P123, template P123: alcoholic acid weight ratio=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 molecular sieve of 0.9-1.5 part weight;
The two transition metal modified 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: water or alcoholic acid weight ratio=and 1: 100,60-90 ℃ was refluxed 24 hours, filtered, and cleaned, oven dry, 550 ℃ of roastings 4 hours, the two transition metal modified molecular sieve of 0.9-1.5 part weight, two transition metal modified 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 molecular sieves in the reaction of molecular oxygen liquid phase one-step oxidation benzene synthesizing phenol as catalyzer.The present invention is characterised in that for realizing the technical scheme that this purpose adopts, and under two transition metal modified molecular sieve catalytics and under the reductive agent participation, is oxygenant 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, reductive agent is an xitix, 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 molecular sieve of 0.5 part of weight as catalyzer, the acetic acid of adding 32-63 part weight and the water of 30-60 part weight are as solvent, the xitix of 5-10 part weight is as reductive agent, the benzene of 4-8 part weight is dissolved in solvent, charges into molecular oxygen to benzole soln, i.e. 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 catalyzer, 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 oxygenant oxidation step benzene, directly synthesizing phenol is saved starting material, reduces and pollutes, and production cost is reduced greatly.
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 soln 6 grams that contain template P123, template P123: alcoholic acid weight ratio=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 soln of 10 gram butyl (tetra) titanates, butyl (tetra) titanate: alcoholic acid weight ratio=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 soln 11 grams that contain template P123, template P123: alcoholic acid weight ratio=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 soln 10 grams that contain template P123, template P123: alcoholic acid weight ratio=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 soln 11 grams that contain template P123, template P123: alcoholic acid weight ratio=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 soln 7 grams that contain template P123, template P123: alcoholic acid weight ratio=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 soln of 10 gram butyl (tetra) titanates, butyl (tetra) titanate: alcoholic acid weight ratio=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 xitix, 8 gram benzene, 60 gram water, the 32 gram acetic acid that in autoclave, add 0.5 gram embodiment, one preparation, 80 ℃ of controlled temperature, charge into oxygen, oxygen pressure is 4Mpa, 12 hours reaction times, 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 xitix, 4 gram benzene, 30 gram water, the 63 gram acetic acid that in autoclave, add 0.5 gram embodiment, two preparations, 70 ℃ of controlled temperature, charge into oxygen, oxygen pressure is 2Mpa, 16 hours reaction times, 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 xitix, 8 gram benzene, 30 gram water, the 32 gram acetic acid that in autoclave, add 1 gram embodiment, three preparations, 70 ℃ of controlled temperature, charge into oxygen, oxygen pressure is 2Mpa, 24 hours reaction times, 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 xitix, 8 gram benzene, 30 gram water, the 63 gram acetic acid that in autoclave, add 0.5 gram embodiment, one preparation, 90 ℃ of controlled temperature, charge into oxygen, oxygen pressure is 4Mpa, 16 hours reaction times, 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 xitix, 8 gram benzene, 60 gram water, the 63 gram acetic acid that in autoclave, add 1 gram embodiment, five preparations, 80 ℃ of controlled temperature, charge into air, air pressure is 8.5Mpa, 8 hours reaction times, molecular oxygen liquid phase one-step oxidation benzene, directly synthetic 1.7 gram phenol, productive rate 18%.
Claims (5)
1, a kind of two transition metal modified molecular sieve, it is characterized in that, described molecular sieve is formed by two kinds among 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 compound, and two transition metal modified 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 two transition metal modified molecular sieves of claim 1 is characterized in that, prepares the first transition metal modified 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 soln that contains template 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 transition metal modified molecular sieve of winning; The two transition metal modified molecular sieves of refabrication: the first transition metal modified molecular sieve is added the solution that contains second transition metal salt, refluxes, filter, clean, oven dry, roasting, two transition metal modified molecular sieves.
3, the preparation method of two transition metal modified molecular sieves according to claim 2 is characterized in that the concrete operations step:
The first step prepares the first transition metal modified 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 soln 6-11 part weight that contains template P123, template P123: alcoholic acid weight ratio=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 molecular sieve of 0.9-1.5 part weight;
The two transition metal modified 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: water or alcoholic acid weight ratio=and 1: 100,60-90 ℃ was refluxed 24 hours, filtered, and cleaned, oven dry, 550 ℃ of roastings 4 hours, the two transition metal modified molecular sieve of 0.9-1.5 part weight, two transition metal modified molecular sieves: first transition metal: the weight ratio of second transition metal is 100: (10-30): (5-10).
4, the purposes of the described two transition metal modified molecular sieves of claim 1, it is characterized in that, two transition metal modified molecular sieves in the reaction of molecular oxygen liquid phase one-step oxidation benzene synthesizing phenol as catalyzer, under two transition metal modified molecular sieve catalytics and under the reductive agent participation, with the molecular oxygen is oxygenant, oxidation step is dissolved in the benzene of solvent, directly synthesizing phenol.
5, the purposes of two transition metal modified molecular sieves according to claim 4, it is characterized in that, reductive agent is an xitix, 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 molecular sieve of 0.5 part of weight as catalyzer, the acetic acid of adding 32-63 part weight and the water of 30-60 part weight are as solvent, the xitix of 5-10 part weight is as reductive 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100167523A CN1280012C (en) | 2004-03-05 | 2004-03-05 | Bitransition metal modified molecular sieve and its preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100167523A CN1280012C (en) | 2004-03-05 | 2004-03-05 | Bitransition metal modified molecular sieve and its preparation and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1559682A true CN1559682A (en) | 2005-01-05 |
| CN1280012C CN1280012C (en) | 2006-10-18 |
Family
ID=34440632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100167523A Expired - Fee Related CN1280012C (en) | 2004-03-05 | 2004-03-05 | Bitransition metal modified molecular sieve and its preparation and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1280012C (en) |
Cited By (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 |
| CN102125867A (en) * | 2011-02-17 | 2011-07-20 | 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 |
| 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 |
| CN103566969A (en) * | 2012-07-31 | 2014-02-12 | 中国科学院大连化学物理研究所 | Preparation method of vanadium-base catalytic material for catalyzing benzene hydroxylation to prepare phenol |
| CN104549414A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for hydroxylating aromatics directly and preparation method of catalyst |
| CN109876849A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of naphthalene liquid phase oxidation preparation 1,4- naphthoquinones catalyst and its preparation method and application |
| CN112939006A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Modification method of framework silicon-rich zeolite molecular sieve |
-
2004
- 2004-03-05 CN CNB2004100167523A patent/CN1280012C/en not_active Expired - Fee Related
Cited By (10)
| 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 |
| CN102125867A (en) * | 2011-02-17 | 2011-07-20 | 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 |
| 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 |
| CN103566969A (en) * | 2012-07-31 | 2014-02-12 | 中国科学院大连化学物理研究所 | Preparation method of vanadium-base catalytic material for catalyzing benzene hydroxylation to prepare phenol |
| CN104549414A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for hydroxylating aromatics directly and preparation method of catalyst |
| 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 |
| CN109876849A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of naphthalene liquid phase oxidation preparation 1,4- naphthoquinones catalyst and its preparation method and application |
| 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 |
| CN112939006A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Modification method of framework silicon-rich zeolite molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1280012C (en) | 2006-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1115298C (en) | Y-type molecular sieve and its prepn. | |
| CN1657168A (en) | Preparation method of acid modified titanium-containing molecular sieve | |
| CN1280012C (en) | Bitransition metal modified molecular sieve and its preparation and use | |
| CN111036290A (en) | Preparation method of titanium silicalite molecular sieve for inhibiting byproduct generation in propylene epoxidation process | |
| CN1281494C (en) | Process for preparing small crystal ZSM-5 zeolite | |
| CN101045673A (en) | Method for producing cycloalkanol and/or cycloalkanone | |
| CN1212195C (en) | Method for regeneration of titaniferous catalyst | |
| CN101591024A (en) | A kind of method of modifying of HTS | |
| CN1064072C (en) | Catalyst containing modified kaoling for cracking hydrocarbons | |
| CN1526476A (en) | Catalyst for direct synthesis of methyl carbonate and its prepn | |
| EP0822179A2 (en) | Process for the preparation of amines from olefines using zeolites with nes-structure | |
| CN1053388C (en) | Catalyst for preparation of high purity para-diethylbenzene by using ethylbenzene disproportionation and its technology | |
| CN100553772C (en) | Be used to produce alkylbenzene Preparation of catalysts method | |
| CN1566049A (en) | Solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration | |
| CN1110629A (en) | Catalyzer for preparation fatty amine and technology | |
| CN100553773C (en) | The catalyst that is used for the diisopropylbenzene (DIPB) transalkylation | |
| CN1600757A (en) | Method for preparing propylene/ethane from catalytic cracking C4-C6 | |
| CN111939966B (en) | Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide | |
| CN100453178C (en) | Catalyst for synthesizing iso-propylbenzene | |
| CN111744540A (en) | Solid acid catalyst and application thereof in esterification reaction | |
| CN1843914A (en) | Silicon-aluminium molecular sieve with MWW structure and preparation method thereof | |
| CN1323769A (en) | Transalkylation catalyst and its prepn. | |
| CN1324326A (en) | Method for producing titanium silicate with PUT-structure | |
| CN1224615C (en) | Process for preparation of collidine and 2,3,5,6-tetramethylpyridine | |
| CN1238311C (en) | New aromatic compound hydrogen peroxide hydroxylation synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061018 Termination date: 20100305 |