CN102627289A - Modification method of titanium-containing molecular sieve - Google Patents
Modification method of titanium-containing molecular sieve Download PDFInfo
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- CN102627289A CN102627289A CN2012100793470A CN201210079347A CN102627289A CN 102627289 A CN102627289 A CN 102627289A CN 2012100793470 A CN2012100793470 A CN 2012100793470A CN 201210079347 A CN201210079347 A CN 201210079347A CN 102627289 A CN102627289 A CN 102627289A
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Abstract
The invention discloses a modification method of a titanium-containing molecular sieve. The method comprises the following steps of: (1) preparing an acidic slurry of the titanium-containing molecular sieve; (2) preparing a silicon-containing alkaline solution; and (3) conducting hydrothermal crystallization so as to obtain a modified titanium-containing molecular sieve. The method of the invention has a simple process and is easy for industrial implementation. After modification, the titanium-containing molecular sieve has obviously enhanced surface hydrophobicity and substantially improved catalytic oxidation activity.
Description
Technical field
The present invention relates to a kind of method of modifying of molecular sieve containing titanium, specifically, relate to a kind of method that forms the pure silicon molecular sieve on the molecular sieve containing titanium surface, belong to inorganic chemical synthesis technical field.
Background technology
Molecular sieve containing titanium is the novel hetero-atom molecular-sieve of the exploitation early 1980s.Because the titaniferous hetero-atom molecular-sieve is introduced framework of molecular sieve to the transition metal titanium atom with the characteristic of appraising at the current rate, given when forming the oxidation-reduction catalysis effect and selected the shape function, thereby it has good directional catalyzing oxidation susceptibility, formed molecular sieve containing titanium/H
2O
2The green chemical industry reaction process of heterogeneous catalytic oxidation.They have shown better industrial application prospect in the oxidation of alkane, the epoxidation of alkene, the oxidation of alcohols, the ammonia oxidation of pimelinketone and the fields such as hydroxylation of aromatic hydrocarbons.
Molecular sieve containing titanium generally is to adopt hydrothermal crystallizing synthetic method to prepare.As; Synthetic (US 4410501) of molecular sieve containing titanium TS-1 molecular sieve; Typical method is that to adopt organo-silicon ester and organic titanium ester respectively be silicon source and titanium source, be template with the TPAOH; It is synthetic under certain temperature and pressure, to carry out hydro-thermal, and obtains product through operations such as conventional separation, washing, drying, roastings.Synthetic (ZL200510025146.2) of molecular sieve containing titanium Ti-MWW molecular sieve; Silicon source, titanium source, boron source, template, fluorine source and water are uniformly mixed into glue; Carry out hydrothermal crystallizing then, get the Ti-MWW molecular screen primary powder, again with Ti-MWW molecular screen primary powder and acidic solution effect; After roasting, the Ti-MWW molecular sieve.Yet direct synthetic molecular sieve containing titanium is because its surface hydrophobicity is relatively poor; Be unfavorable for the performance of its catalytic oxidation performance, therefore, the normal employing of investigators further carried out modification to the synthetic molecular sieve containing titanium; Improve its hydrophobicity, thereby improve the catalytic oxidation performance of molecular sieve containing titanium.
ZL200610116838.2 has reported a kind of compound method of molecular sieve containing titanium of alkali modification; It is characterized in that; Ti-MWW molecular sieve, basic cpd (piperidines, hexamethylene imine or both mixtures) solution are mixed; Carry out the alkali modification processing under 120～200 ℃,, get the Ti-MWW molecular sieve of alkali modification again through filtration, washing, dry, roasting.This method is to improve its surface hydrophobicity through the method to the secondary hydrothermal crystallizing of molecular sieve containing titanium.
ZL01140182.6 has reported a kind of method of modifying of HTS of the MFI of having structure; It is characterized in that; TS-l molecular sieve and silicon-containing compound, organic gel and the water that will synthesize by the method for prior art mix according to a certain percentage; Then the gained mixture is put into sealed reactor, 80 ~ 190 ℃ temperature and autogenous pressure held 0.1-150 hour, molecular sieve is carried out modification with silicon.CN10160213A has reported a kind of method of modifying of TS-1 titanium-silicon molecular sieve catalyst; It is characterized in that; With TS-1 titanium-silicon molecular sieve catalyst parent in nitrogen atmosphere; Under 50 ~ 300 ℃ temperature condition, feed the silylating reagent reaction after 0.5 ~ 10 hour, can obtain the TS-1 titanium-silicon molecular sieve catalyst of modification.Above method is to adopt silicon to improve the hydrophobicity on surface attached to molecular sieve outer surface.Can know that from embodiment silicon should be that the form with silicon-dioxide exists.Yet the concrete structure of silicon-dioxide is not confirmed explanation, and above method is difficult to control deposition and the distribution of silicon-dioxide on the molecular sieve surface.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of process
,The molecular sieve containing titanium surface hydrophobicity is strong after the modification, the method for modifying of the molecular sieve containing titanium that catalytic oxidation activity is high.
The present invention adopts following technical scheme to achieve the above object: a kind of method of modifying of molecular sieve containing titanium is characterized in that: comprise the steps:
The preparation of the acid slurries of
molecular sieve containing titanium: according to the weight ratio molecular sieve containing titanium: water is 1: (3～20); Molecular sieve containing titanium, acidic cpd and water are mixed; The pH value of the slurries that form is between 1～5; The consumption of acidic cpd is confirmed according to the span of control of slurry pH value; Molecular sieve containing titanium is the micropore molecular sieve containing titanium with crystalline structure, and acidic cpd is at least a in organic acid, mineral acid or the strong acid weak base salt;
Molecular sieve containing titanium in the step of the present invention
: water is preferably 1: (5～10); The pH value of slurries is preferably 2 ~ 3; Molecular sieve containing titanium is a kind of among TS-1, TS-2, Ti-MWW, Ti-MOR, the Ti-Beta.Organic acid is a kind of in oxalic acid, oxalic acid, the phenylformic acid; Mineral acid is a kind of in nitric acid, hydrochloric acid, the sulfuric acid; Strong acid weak base salt is (NH
4)
2SO
4, NH
4Cl, NH
4NO
3, NH
4H
2PO
4In a kind of.
Step of the present invention
Middle SiO
2: organic formwork agent: water is preferably 1: (0.05 ~ 0.5): (15 ~ 20).
Step of the present invention
Middle SiO
2Weight be in the acid slurries of molecular sieve containing titanium molecular sieve containing titanium weight 2% ~ 5%.The hydrothermal crystallizing temperature is preferably 140～180 ℃, and the hydrothermal crystallizing time is 24～72 hours.
Pure silicon molecular sieve (Silicalite-1) has the characteristic of strong-hydrophobicity; Its hydrophobicity is higher than conventional crystalline silicon dioxide or amorphous silica; Be usually used in modification is carried out on the surface of Si-Al molecular sieve with acid catalysis performance, reach the purpose in the acid site of the hydrophobicity that strengthens the molecular sieve surface and shielded surfaces.The present invention is based on molecular sieve containing titanium particle surface and silica sol granule surface electric charge matching principle; Make silica sol granule in the enrichment of molecular sieve containing titanium particle surface earlier; Carry out hydrothermal crystallizing afterwards again; Reach the purpose that forms pure silicon molecular sieve (Silicalite-1) at the molecular sieve containing titanium particle surface, be about to the acid slurries of molecular sieve containing titanium and siliceous basic soln and mix, carry out hydrothermal crystallization process then; Through conventional filtration, drying and other steps, promptly obtain the modified titanium-containing molecular sieve again.
Compared with prior art, the present invention has following remarkable advantage:
(1) process is simple, is easy to industrializing implementation;
(2) the molecular sieve containing titanium surface hydrophobicity obviously strengthens after the modification, and its catalytic oxidation activity significantly improves.
Embodiment
All embodiment all operate by the operation steps of technique scheme.
Embodiment 1
The preparation of the acid slurries of the first step molecular sieve containing titanium
According to the weight ratio molecular sieve containing titanium: water is 1:5, and molecular sieve containing titanium, acidic cpd and water are mixed, and the pH value of the slurries of formation is 2.5, and acidic cpd is a nitric acid, and molecular sieve containing titanium is Ti-MWW;
The preparation of siliceous basic soln of second step
According to the SiO in the mol ratio silicon source
2: organic formwork agent: water is 1:0.05:20, and silicon source, organic formwork agent and water are mixed, and forms uniform siliceous basic soln, and the silicon source is a tetraethyl orthosilicate, and organic formwork agent is a TPAOH;
The 3rd step hydrothermal crystallizing
According to SiO in the siliceous basic soln
2Weight be in the acid slurries of molecular sieve containing titanium molecular sieve containing titanium weight 5% carry out the mixed solution batching; Siliceous basic soln is joined in the acid slurries of molecular sieve containing titanium; Mix; Afterwards in 150 ℃ of hydrothermal crystallizings 24 hours, again through filter, washing, dry, roasting, obtain product modified titanium-containing molecular sieve Ti-MWW.
Embodiment 2
Implementation process is except that following difference, and all the other are all with embodiment 1:
The preparation of the acid slurries of the first step molecular sieve containing titanium
The pH value of the slurries that form is 2.0, and acidic cpd is a sulfuric acid, and molecular sieve containing titanium is TS-1;
The preparation of siliceous basic soln of second step
The silicon source is a silicon sol;
The 3rd step hydrothermal crystallizing
In 170 ℃ of hydrothermal crystallizings 24 hours, obtain product modified titanium-containing molecular sieve TS-1.
Embodiment 3
Implementation process is except that following difference, and all the other are all with embodiment 1:
The preparation of the acid slurries of the first step molecular sieve containing titanium
The pH value of the slurries that form is 3.5, and molecular sieve containing titanium is Ti-Beta;
The 3rd step hydrothermal crystallizing
In 150 ℃ of hydrothermal crystallizings 48 hours, obtain product modified titanium-containing molecular sieve Ti-Beta.
Embodiment 4
Implementation process is except that following difference, and all the other are all with embodiment 1:
The preparation of the acid slurries of the first step molecular sieve containing titanium
Molecular sieve containing titanium is TS-2;
The preparation of siliceous basic soln of second step
According to the SiO in the mol ratio silicon source
2: organic formwork agent: water is 1:0.1:40, and organic formwork agent is a tetraethyl ammonium hydroxide;
The 3rd step hydrothermal crystallizing
In 170 ℃ of hydrothermal crystallizings 24 hours, obtain product modified titanium-containing molecular sieve TS-2.
Embodiment 5
Implementation process is except that following difference, and all the other are all with embodiment 1:
The preparation of the acid slurries of the first step molecular sieve containing titanium
Molecular sieve containing titanium is Ti-MOR;
The preparation of siliceous basic soln of second step
According to the SiO in the mol ratio silicon source
2: organic formwork agent: water is 1:0.5:50, and organic formwork agent is the mixture of TPAOH and n-Butyl Amine 99, and its weight ratio is 1:1;
The 3rd step hydrothermal crystallizing
In 130 ℃ of hydrothermal crystallizings 72 hours, obtain product modified titanium-containing molecular sieve Ti-MOR.
Embodiment 6
Implementation process is except that following difference, and all the other are all with embodiment 1:
The preparation of the acid slurries of the first step molecular sieve containing titanium
According to the weight ratio molecular sieve containing titanium: water is 1:20, and the pH value of the slurries of formation is 4.5, and acidic cpd is an oxalic acid;
The preparation of siliceous basic soln of second step
According to the SiO in the mol ratio silicon source
2: organic formwork agent: water is 1:0.5:35, and the silicon source is the mixture of tetraethyl orthosilicate and silicic acid four butyl esters, and its weight ratio is 5:5, and organic formwork agent is the mixture of Isopropylamine and TPAOH, and its weight ratio is 9:1;
The 3rd step hydrothermal crystallizing
According to SiO in the siliceous basic soln
2Weight be in the acid slurries of molecular sieve containing titanium molecular sieve containing titanium weight 10% carry out the mixed solution batching, in 190 ℃ of hydrothermal crystallizings 15 hours, obtain product modified titanium-containing molecular sieve Ti-MWW.
Embodiment 7
Implementation process is except that following difference, and all the other are all with embodiment 2:
The preparation of the acid slurries of the first step molecular sieve containing titanium
The pH value of the slurries that form is 1.0, and acidic cpd is sulfuric acid and (NH
4)
2SO
4Mixture, its weight ratio is 1:1;
The preparation of siliceous basic soln of second step
According to SiO in the siliceous basic soln
2Weight be in the acid slurries of molecular sieve containing titanium molecular sieve containing titanium weight 10% carry out the mixed solution batching, the silicon source is the mixture of silicon sol and tetraethyl orthosilicate, its weight ratio is 1:1;
The 3rd step hydrothermal crystallizing
In 150 ℃ of hydrothermal crystallizings 100 hours, obtain product modified titanium-containing molecular sieve TS-1.
Embodiment 8
Implementation process is except that following difference, and all the other are all with embodiment 1:
The preparation of the acid slurries of the first step molecular sieve containing titanium
The pH value of the slurries that form is 4.0, and acidic cpd is NH
4Cl and NH
4H
2PO
4Mixture, its weight ratio is 6:4;
The preparation of siliceous basic soln of second step
According to the SiO in the mol ratio silicon source
2: organic formwork agent: water is 1:0.02:20, and organic formwork agent is the mixture of tetraethyl ammonium hydroxide and TPAOH, and its weight ratio is 8:2;
The 3rd step hydrothermal crystallizing
According to SiO in the siliceous basic soln
2Weight be in the acid slurries of molecular sieve containing titanium molecular sieve containing titanium weight 1.5% carry out the mixed solution batching, in 120 ℃ of hydrothermal crystallizings 72 hours, obtain product modified titanium-containing molecular sieve Ti-MWW.
Embodiment 9
The preparation of the acid slurries of the first step molecular sieve containing titanium
The pH value of the slurries that form is 2.0, and acidic cpd is hydrochloric acid and NH
4NO
3Mixture, its weight ratio is 5:5;
The preparation of siliceous basic soln of second step
According to the SiO in the mol ratio silicon source
2: organic formwork agent: water is 1:1:10, and the silicon source is silicic acid four butyl esters, and organic formwork agent is the mixture of n-Butyl Amine 99 and ethamine, and its weight ratio is 5:5;
The 3rd step hydrothermal crystallizing
According to SiO in the siliceous basic soln
2Weight be in the acid slurries of molecular sieve containing titanium molecular sieve containing titanium weight 8% carry out the mixed solution batching, in 140 ℃ of hydrothermal crystallizings 48 hours, obtain product modified titanium-containing molecular sieve Ti-MWW.
Embodiment 9
Epoxy with n-hexylene turns to the catalytic activity that probe reaction is estimated the modified titanium-containing molecular sieve.Detailed process does; Solvent is acetonitrile (Ti-MWW) or methyl alcohol (TS-1), and oxygenant is that concentration is 30.1% hydrogen peroxide, successively catalyzer, solvent, reactant and oxygenant is added in the reactor drum; Stir; Reactant: catalyzer: the weight ratio of solvent is 1:0.05:5, reactant: the mol ratio of oxygenant is 1:1, and 60 ℃ were reacted 2 hours.The result is as shown in the table.
Evaluation result shows that the catalytic oxidation performance of molecular sieve containing titanium all increases substantially than before unmodified after the modification in the table.
Claims (10)
1. the method for modifying of a molecular sieve containing titanium is characterized in that: comprise the steps:
The preparation of the acid slurries of
molecular sieve containing titanium: according to the weight ratio molecular sieve containing titanium: water is 1: (3～20); Molecular sieve containing titanium, acidic cpd and water are mixed; The pH value of the slurries that form is between 1～5; The consumption of acidic cpd is confirmed according to the span of control of slurry pH value; Molecular sieve containing titanium is the micropore molecular sieve containing titanium with crystalline structure, and acidic cpd is at least a in organic acid, mineral acid or the strong acid weak base salt;
2. method of modifying according to claim 1 is characterized in that: molecular sieve containing titanium in the step
: water is 1: (5～10).
3. method of modifying according to claim 1 is characterized in that: the pH value of slurries is 2 ~ 3 in the step
.
4. method of modifying according to claim 1 is characterized in that: said molecular sieve containing titanium is a kind of among TS-1, TS-2, Ti-MWW, Ti-MOR, the Ti-Beta.
5. method of modifying according to claim 1 is characterized in that: said organic acid is a kind of in oxalic acid, oxalic acid, the phenylformic acid.
6. method of modifying according to claim 1 is characterized in that: said mineral acid is a kind of in nitric acid, hydrochloric acid, the sulfuric acid.
7. method of modifying according to claim 1 is characterized in that: said strong acid weak base salt is (NH
4)
2SO
4, NH
4Cl, NH
4NO
3, NH
4H
2PO
4In a kind of.
8. method of modifying according to claim 1 is characterized in that: step
Middle SiO
2: organic formwork agent: water is 1: (0.05 ~ 0.5): (15 ~ 20).
9. method of modifying according to claim 1 is characterized in that: step
Middle SiO
2Weight be in the acid slurries of molecular sieve containing titanium molecular sieve containing titanium weight 2% ~ 5%.
10. method of modifying according to claim 1 is characterized in that: in the step
in 140～180 ℃ of hydrothermal crystallizings 24～72 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109746041A (en) * | 2017-11-07 | 2019-05-14 | 万华化学集团股份有限公司 | A kind of method of modifying of Ti-MWW molecular sieve and the preparation method of cyclododecanone oxime |
| CN110668463A (en) * | 2019-11-06 | 2020-01-10 | 中国天辰工程有限公司 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
| CN115557840A (en) * | 2022-11-04 | 2023-01-03 | 浙江新化化工股份有限公司 | Preparation method of 2-nitropropane and catalyst used in preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109746041A (en) * | 2017-11-07 | 2019-05-14 | 万华化学集团股份有限公司 | A kind of method of modifying of Ti-MWW molecular sieve and the preparation method of cyclododecanone oxime |
| CN109746041B (en) * | 2017-11-07 | 2022-07-12 | 万华化学集团股份有限公司 | Modification method of Ti-MWW molecular sieve and preparation method of cyclododecanone oxime |
| CN110668463A (en) * | 2019-11-06 | 2020-01-10 | 中国天辰工程有限公司 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
| CN110668463B (en) * | 2019-11-06 | 2021-04-02 | 中国天辰工程有限公司 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
| CN115557840A (en) * | 2022-11-04 | 2023-01-03 | 浙江新化化工股份有限公司 | Preparation method of 2-nitropropane and catalyst used in preparation method |
| CN115557840B (en) * | 2022-11-04 | 2023-11-10 | 浙江新化化工股份有限公司 | Preparation method of 2-nitropropane and catalyst used in preparation method |
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Application publication date: 20120808 Assignee: ZHEJIANG SUOKE CHEMICAL CO., LTD. Assignor: Yueyang Yutai Chemical Technology Development Co.,Ltd. Contract record no.: 2015330000277 Denomination of invention: Modification method of titanium-containing molecular sieve Granted publication date: 20130925 License type: Common License Record date: 20151218 |
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