CN101417238A - Modifying process for titanium-silicon molecular sieve - Google Patents
Modifying process for titanium-silicon molecular sieve Download PDFInfo
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- CN101417238A CN101417238A CNA2008102041496A CN200810204149A CN101417238A CN 101417238 A CN101417238 A CN 101417238A CN A2008102041496 A CNA2008102041496 A CN A2008102041496A CN 200810204149 A CN200810204149 A CN 200810204149A CN 101417238 A CN101417238 A CN 101417238A
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- molecular sieve
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Abstract
The invention discloses a modification method of Ti-Si molecular sieve, belonging to the field of inorganic chemical synthesis technique. The method uniformly mixes the Ti-Si molecular sieve and complexing agent compound solution and carries out the modification disposal at the temperature ranging from room temperature to 100 DEG C; subsequently, the modified Ti-Si molecular sieve is obtained by the normal operations of filtration, washing, drying and baking. The obtained modified Ti-Si molecular sieve has higher catalytic oxidation activity.
Description
Technical field
The present invention relates to inorganic chemical synthesis technical field, specifically a kind of method of modifying of HTS.
Background technology
HTS promptly is that the transition metal titanium atom is incorporated in the framework of molecular sieve with certain topological structure, forms the porous crystalline material with catalytic oxidation activity.It with the HTS catalyst and with rare H
2O
2Gentle reaction system for oxidant formation, showing high activity, selectivity aspect the oxidation operation reactions such as oxidation of alkene epoxidation, aromatic hydrocarbons hydroxylating, ketone oxamidinating, alkane oxidation and alcohol, form accessory substance and only be the eco-friendly Green Chemistry process of water, caused people's extensive attention.At present industrialization and HTS with wide application prospect have TS-1 and Ti-MWW.TS-1 is a kind of HTS of the MFI of having topological structure, and nineteen eighty-three is at first at US4,410,501 reports, Ti-MWW is a kind of HTS of the MWW of having topological structure, and 2000 at first at chemical wall bulletin (ChemistryLetters, 2000:774) open report.Research is at present thought, the activated centre of HTS is the isolated Ti species that are in framework of molecular sieve, but not the existence of skeleton Ti species directly influences its catalytic oxidation performance, and it is extremely important for giving full play to its catalytic performance therefore to develop the method that effectively removes non-skeleton Ti species in the HTS.
Lu etc. (Catal.Today, 93～95 (2004) p353～357) adopt certain density KAc, NaAc, NH respectively
4Ac, NH
4Cl and HNO
3Solution is handled the TS-1 behind the roasting removed template method under 80 ℃ of conditions, but found that and have only the non-skeleton Ti of part species to be removed, also have non-skeleton Ti species in the product, and the phenol hydroxylation activity of treated TS-1 product only improves less than 1%.
ZL98117503.1 discloses the method for modifying of a kind of HTS (TS-1), it is characterized in that TS-1 molecular sieve, acid compound and the water that will synthesize earlier mix, and reacts 5 minutes～6 hours down at 5～95 ℃, obtains acid-treated TS-1 molecular sieve; Gained is mixed through acid-treated TS-1 molecular sieve, organic base (fatty amine, alcamines or quaternary ammonium base compounds) and water, and in sealed reactor, reacted 2 hours～8 days down in 120～200 ℃.This method can make the non-skeleton Ti species of gained TS-1 molecular sieve reduce, thereby has improved the catalytic oxidation activity of TS-1 molecular sieve.
CN1657168 discloses a kind of method that adopts acid solution that the TS-1 molecular screen primary powder of not roasting is handled, and can effectively improve the catalytic activity of TS-1 molecular sieve.
Also there is not at present the complexing agent of employing that HTS is carried out the report that modification effectively improves the titanium molecular sieve catalysis activity.
Summary of the invention
The method of modifying that the purpose of this invention is to provide a kind of HTS, this method has following advantage: non-skeleton Ti species in the selectively removing HTS effectively, the HTS of the modification that obtains has higher catalytic oxidation activity.
The present invention achieves the above object by the following technical solutions:
HTS, complexing agent compound solution are mixed, carry out modification under room temperature～100 ℃ and handle, again through filtration, washing, drying, the roasting of routine, the HTS of modification.
Now describe technical scheme of the present invention in detail:
A kind of method of modifying of HTS prepares HTS by conventional method, and the complexing agent compound solution is to contain the compound that can form complex compound with the Ti species: at least a solution in oxalic acid, EDTA, the acetylacetone,2,4-pentanedione, and operating procedure:
The preparation of first step reactant mixture
HTS and complexing agent compound solution are mixed, form reactant mixture, HTS: complexing agent: water weight ratio=1: (0.05～0.5): (8～50);
The second step modification is handled
The reactant mixture that the first step is made is ℃ down reaction 0.5～20 hour in room temperature～100, more after filtration, washing, drying and roasting, the HTS of modification.
The operating procedure that is further characterized in that of the present invention: in the first step, HTS: complexing agent: the weight ratio of water=1: (0.15～0.3): (15～25); In second step, the reactant mixture that the first step makes reacted 2～10 hours down in 50～80 ℃.
Compared with prior art, method of the present invention has following remarkable advantage:
(1), operation is simple, process is controlled easily.
(2), non-skeleton Ti species in the selectively removing HTS effectively.
(3), the catalytic activity of the modifying titanium-silicon molecular sieve that makes of the present invention obviously improves.
The specific embodiment
All embodiment all operate by the operating procedure of technique scheme.
Embodiment 1
According to document (Chemistry Letters, 2000:774) synthesis of titanium silicon molecular sieve Ti-MWW.
In the first step, HTS Ti-MWW: complexing agent: the weight ratio of water=1: 0.3: 25, form reactant mixture, complexing agent is ethylenediamine tetra-acetic acid (EDTA); In second step, the reactant mixture that the first step makes is in 100 ℃ of down reactions 20 hours, obtains the Ti-MWW zeolite product after the modification.
Embodiment 2
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, HTS Ti-MWW: complexing agent: the weight ratio of water=1: 0.5: 50; In second step, the reactant mixture that the first step makes is in 80 ℃ of down reactions 10 hours, obtains the Ti-MWW zeolite product after the modification.
Embodiment 3
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, HTS Ti-MWW: complexing agent: the weight ratio of water=1: 0.05: 8; In second step, the reactant mixture that the first step makes is in 100 ℃ of down reactions 10 hours, obtains the Ti-MWW zeolite product after the modification.
Embodiment 4
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, HTS Ti-MWW: complexing agent: the weight ratio of water=1: 0.25: 15, complexing agent are acetylacetone,2,4-pentanedione; In second step, the reactant mixture that the first step makes reacted under room temperature 10 hours, obtained the Ti-MWW zeolite product after the modification.
Embodiment 5
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, HTS Ti-MWW: complexing agent: the weight ratio of water=1: 0.25: 15; In second step, the reactant mixture that the first step makes reacted under room temperature 10 hours, obtained the Ti-MWW zeolite product after the modification.
Embodiment 6
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, HTS Ti-MWW: complexing agent: the weight ratio of water=1: 0.3: 15, complexing agent are oxalic acid; In second step, the reactant mixture that the first step makes is in 100 ℃ of down reactions 0.5 hour, obtains the Ti-MWW zeolite product after the modification.
Embodiment 7
According to document (ZL200510025146.2) synthesis of titanium silicon molecular sieve Ti-MWW.
Implementation process is with embodiment 1, obtains the Ti-MWW zeolite product after the modification.
Embodiment 8
According to document (US4,410,501) synthesizing titanium-silicon molecular sieve TS-1.
In the first step, titanium-silicon molecular sieve TS-1: complexing agent: the weight ratio of water=1: 0.3: 25, form reactant mixture, complexing agent is EDTA; In second step, the reactant mixture that the first step makes is in 100 ℃ of down reactions 20 hours, obtains the TS-1 zeolite product after the modification.
Embodiment 9
According to document (Zeolites, 1992 (12): 943) synthesizing titanium-silicon molecular sieve TS-1.
Implementation process is with embodiment 8, obtains the TS-1 zeolite product after the modification.
Embodiment 10
Epoxy with the 1-n-hexylene turns to the catalytic activity that probe reaction is estimated modification front and back HTS.Detailed process is, solvent is acetonitrile (catalyst is Ti-MWW) or methyl alcohol (catalyst is TS-1), oxidant is the hydrogen peroxide of concentration 30.1%, successively catalyst, solvent, reactant and oxidant are added in the reactor, stir, reactant: catalyst: the weight ratio of solvent is 1: 0.05: 5, reactant: the mol ratio of oxidant is 1: 1, and 60 ℃ were reacted 2 hours.It is as shown in the table for the result.
| HTS | 1-n-hexylene conversion ratio |
| Embodiment 1 | 71％ |
| Comparative Examples 1 | 55％ |
| Embodiment 2 | 69％ |
| Embodiment 3 | 70％ |
| Embodiment 4 | 67％ |
| Embodiment 5 | 68％ |
| Embodiment 6 | 65％ |
| Embodiment 7 | 72％ |
| Comparative Examples 7 | 57％ |
| Embodiment 8 | 32％ |
| Comparative Examples 8 | 26％ |
| Embodiment 9 | 35％ |
| Comparative Examples 9 | 28％ |
All Comparative Examples catalyst system therefors are the HTS of non-modified among the embodiment in the table.As can be known, behind existing method synthetic HTS Ti-MWW and TS-1 process the inventive method modification processing, its catalytic oxidation activity obviously improves.
Claims (5)
1, a kind of method of modifying of HTS is characterized in that this method comprises following concrete steps:
(1), the preparation of reactant mixture
HTS, complexing agent and water are mixed, and form reactant mixture, wherein HTS: complexing agent: water=1: (0.05～0.5): (8～50) are weight ratio;
(2), modification is handled
The reactant mixture that step (1) is made is ℃ down reaction 0.5～20 hour in room temperature～100, again through filtration, washing, drying and the roasting of routine, the HTS of modification.
2, method according to claim 1, wherein the described complexing agent of step (1) is at least a in oxalic acid, ethylenediamine tetra-acetic acid (EDTA), the acetylacetone,2,4-pentanedione.
3, method according to claim 1, wherein the described HTS of step (1) is synthetic HTS Ti-MWW and TS-1 of the whole bag of tricks of the prior art.
4, method according to claim 1, wherein the weight ratio of the described HTS of step (1), complexing agent and water is a HTS: complexing agent: water=1: (0.15～0.3): (15～25).
5, method according to claim 1, wherein the described reactant mixture that step (1) is made of step (2) reacted 2～10 hours down in 50～80 ℃.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675249A (en) * | 2012-05-07 | 2012-09-19 | 华东师范大学 | Method for synthesizing epoxide by catalysis of titanium-silicon molecular sieve |
| CN102872909A (en) * | 2011-07-13 | 2013-01-16 | 华东师范大学 | Molecular sieve aggregate and its preparation method |
| CN103143390A (en) * | 2013-03-15 | 2013-06-12 | 华东师范大学 | Modification method of microsphere titanium silicon molecular sieve catalyst |
| CN103157508A (en) * | 2013-03-25 | 2013-06-19 | 浙江圣安化工有限公司 | Modification method for catalytic oxime synthesis catalyst |
| CN103539149A (en) * | 2013-09-25 | 2014-01-29 | 大连理工大学 | Modification method for titanium silicate molecular sieve |
| CN103769201A (en) * | 2014-01-16 | 2014-05-07 | 东南大学 | Anti-coking modification method for biomass catalytic pyrolysis catalyst ZSM-5 molecular sieve |
| CN104512904A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | Mesoporous titanium-silicon material preparation method |
| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
| CN106082259A (en) * | 2016-06-17 | 2016-11-09 | 齐鲁工业大学 | There is overlength catalytic life HTS and low cost preparation method thereof |
| CN106517236A (en) * | 2015-09-15 | 2017-03-22 | 中国石油化工股份有限公司 | Preparation method of titanium silicalite molecular sieve |
| CN106861753A (en) * | 2017-03-20 | 2017-06-20 | 临沭县华盛化工有限公司 | The preparation method of titanium-silicon molecular sieve catalyst and its application in methyl ethyl ketoxime is synthesized |
| CN110548539A (en) * | 2019-08-23 | 2019-12-10 | 江苏扬农化工集团有限公司 | Modification method of titanium silicalite molecular sieve catalyst for HPPO |
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2008
- 2008-12-08 CN CNA2008102041496A patent/CN101417238A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872909B (en) * | 2011-07-13 | 2015-01-14 | 华东师范大学 | Molecular sieve aggregate and its preparation method |
| CN102872909A (en) * | 2011-07-13 | 2013-01-16 | 华东师范大学 | Molecular sieve aggregate and its preparation method |
| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
| CN102675249A (en) * | 2012-05-07 | 2012-09-19 | 华东师范大学 | Method for synthesizing epoxide by catalysis of titanium-silicon molecular sieve |
| CN103143390A (en) * | 2013-03-15 | 2013-06-12 | 华东师范大学 | Modification method of microsphere titanium silicon molecular sieve catalyst |
| CN103157508A (en) * | 2013-03-25 | 2013-06-19 | 浙江圣安化工有限公司 | Modification method for catalytic oxime synthesis catalyst |
| CN103539149B (en) * | 2013-09-25 | 2015-07-22 | 大连理工大学 | Modification method for titanium silicate molecular sieve |
| CN103539149A (en) * | 2013-09-25 | 2014-01-29 | 大连理工大学 | Modification method for titanium silicate molecular sieve |
| CN104512904A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | Mesoporous titanium-silicon material preparation method |
| CN104512904B (en) * | 2013-09-29 | 2016-08-10 | 中国石油化工股份有限公司 | A kind of method preparing mesoporous titanium-silicon material |
| CN103769201A (en) * | 2014-01-16 | 2014-05-07 | 东南大学 | Anti-coking modification method for biomass catalytic pyrolysis catalyst ZSM-5 molecular sieve |
| CN106517236A (en) * | 2015-09-15 | 2017-03-22 | 中国石油化工股份有限公司 | Preparation method of titanium silicalite molecular sieve |
| CN106082259A (en) * | 2016-06-17 | 2016-11-09 | 齐鲁工业大学 | There is overlength catalytic life HTS and low cost preparation method thereof |
| CN106861753A (en) * | 2017-03-20 | 2017-06-20 | 临沭县华盛化工有限公司 | The preparation method of titanium-silicon molecular sieve catalyst and its application in methyl ethyl ketoxime is synthesized |
| CN110548539A (en) * | 2019-08-23 | 2019-12-10 | 江苏扬农化工集团有限公司 | Modification method of titanium silicalite molecular sieve catalyst for HPPO |
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Open date: 20090429 |