CN100579905C - Preparation method of Ti-MWW molecular sieve - Google Patents
Preparation method of Ti-MWW molecular sieve Download PDFInfo
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- CN100579905C CN100579905C CN200710037012A CN200710037012A CN100579905C CN 100579905 C CN100579905 C CN 100579905C CN 200710037012 A CN200710037012 A CN 200710037012A CN 200710037012 A CN200710037012 A CN 200710037012A CN 100579905 C CN100579905 C CN 100579905C
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Abstract
The invention discloses a making method of Ti-MWW molecular sieve in the inorganic chemical synthetic technical domain, which comprises the following steps: introducing surface activator in the crystallizing course of Ti-MWW molecular sieve; making raw powder of Ti-MWW molecular sieve; proceeding acid disposal; sintering; obtaining the product.
Description
Technical field
The present invention relates to a kind of preparation method of Ti-MWW molecular sieve, belong to inorganic chemical synthesis technical field.
Background technology
The MWW structure molecular screen be the molecular sieve of a class with sinusoidal 10 yuan of ring reticulated cell systems, 12 yuan of annular distance caves and supercage hole series structure (Science, 1994,264:1910).The aluminium atom that will have catalytic activity is introduced the MWW framework of molecular sieve, forms MCM-22 molecular sieve (US4,954,325).Because special pore passage structure, as the acidic catalyst active ingredient, the MCM-22 molecular sieve shows catalytic performances such as excellent catalytic cracking (US 4,983,276), alkene and benzene alkylation (US4,992,606, US 4,992,615, US 5,334,795).The MWW structure molecular screen is used for the technology industrialization of alkene and benzene alkylation reaction as the acidic catalyst active ingredient.
The transition metal titanium atom is introduced the MWW framework of molecular sieve, form the Ti-MWW molecular sieve.2000 at first at chemical wall bulletin (Chemistry Letters, 2000:774) open report.Its preparation process is that the first step according to metering, prepares the mixing solutions of template and water, and is divided into 2 parts; Second step, according to metering, titanium source and boron source are joined respectively in the mixing solutions of dividing equally, form the mixed system of titanium source and template and water and the mixed system of boron source and template and water respectively, the silicon source that in the mixed system that forms, adds identical weight then respectively, after obtaining homogeneous gel, two kinds of gels that form are mixed; The 3rd step, the mixed gel that obtains is carried out the hydrothermal crystallizing certain hour under the certain temperature condition, obtain the Ti-MWW molecular screen primary powder; In the 4th step, Ti-MWW molecular screen primary powder and finite concentration and a certain amount of acid solution are handled certain hour at a certain temperature, after roasting obtains product Ti-MWW molecular sieve.
CN1466545A discloses a kind of MWW type titanosilicate, its preparation and the application in producing epoxide.Its preparation process is basic, and (Chemistry Letters, 2000:774) preparation process of open report is identical with chemical wall bulletin.
WO03/074421A1 discloses a kind of titanosilicate, its preparation and the application in the oxidation operation reaction.Its preparation process is, the first step, that hydrothermal crystallizing prepares is siliceous, the MWW structured forerunner of boron, second step, the MWW structured forerunner that the acid treatment the first step obtains, the 3rd step, to carry out hydrothermal crystallizing with the titanium source and the template aqueous solution through the MWW structured forerunner that second step handled handles, in the 4th step, the product that the 3rd step of roasting obtains obtains the product titanosilicate.
CN1686795 discloses a kind of being mixed into by a step and has composed Ti-MWW molecular sieve simple method.
CN1638866 discloses a kind of the processing by silylation and has had the HTS of MWW structure to improve the method for its catalytic performance.
To sum up, up to now, also there is not bibliographical information by in the HTS crystallization process of MWW structure, introducing the method that tensio-active agent improves its catalytic activity.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of Ti-MWW molecular sieve.For achieving the above object, the present invention by the following technical solutions: in Ti-MWW molecular sieve crystallization process, introduce tensio-active agent,, make the Ti-MWW molecular sieve by preparation Ti-MWW molecular screen primary powder and two steps of roasting.
Now describe technical scheme of the present invention in detail.
A kind of preparation method of Ti-MWW molecular sieve is characterized in that, introduces tensio-active agent, operation steps in Ti-MWW molecular sieve crystallization process:
The first step prepares the Ti-MWW molecular screen primary powder
TiO in the titanium source in molar ratio
2: the SiO in the silicon source
2: the B in the boron source
2O
3: the F in the fluorine source
-: organic formwork agent: H
2O is (0.001～0.2): 1: (0.1～5): (0～2.0): (0.1～5): (5～150) and by weight tensio-active agent: the SiO in the silicon source
2Be (0.01～0.1): 1 prepares raw material, described titanium source is a tetralkyl titanate, halogenated titanium or titanium oxide, described silicon source is a silicic acid, silica gel, silicon sol or silicic acid tetraalkyl ester, described boron source is boric acid or borate, described fluorine source is a Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, silicofluoric acid or silicofluoride, described organic formwork agent is a piperidines, hexamethylene imine or both mixtures, described tensio-active agent is alkyl quaternaries cation surface active agent or nonionogenic tenside, earlier that organic formwork agent is water-soluble, add the titanium source to the organic formwork agent aqueous solution, stir, add boron source and fluorine source, stir, add silicon source and tensio-active agent, obtain mixture, described mixture was in 130～200 ℃ of hydrothermal crystallizings 3～10 days, after filtration, washing, drying obtains the Ti-MWW molecular screen primary powder;
Second one-step baking
The product that previous step is obtained obtains product Ti-MWW molecular sieve in 500～600 ℃ of roastings 3～10 hours.
Technical scheme of the present invention is further characterized in that, in the first step, and the TiO in the titanium source
2: the SiO in the silicon source
2: the B in the boron source
2O
3: the F in the fluorine source
-: organic formwork agent: H
2The mol ratio of O is (0.005～0.1): 1: (0.15～2): (0～1.0): (0.5～3): (15～50), 150～190 ℃ of following hydrothermal crystallizings 5～8 days.
Technical scheme of the present invention is further characterized in that, in the first step with between second step, is added with the first step ':
The first step ' acid treatment
The Ti-MWW molecular screen primary powder that the first step is obtained is that 0.1～18mol/l acidic solution is 1 according to weight ratio with concentration: mix (5～100), stir, get reaction mixture, described acidic solution is mineral acid or organic acid, mineral acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and organic acid is formic acid, acetate, propionic acid or tartrate, and reaction mixture was handled 10 minutes～3 days down at 50～200 ℃, after filtration, washing, drying, obtain acid-treated product.
Technical scheme of the present invention is further characterized in that, in the first step ' in, Ti-MWW molecular screen primary powder that the first step makes and concentration are that the weight ratio of 0.5～6mol/l acidic solution is 1: (10～65), reaction mixture was handled 5～36 hours down at 70～130 ℃.
Compared with prior art, the present invention has following remarkable advantage:
(1) catalytic activity of Zhi Bei Ti-MWW molecular sieve obviously improves;
(2) Production Flow Chart is short, and cost is low, is beneficial to suitability for industrialized production and application.
Description of drawings
The XRD spectra of the product Ti-MWW molecular sieve that Fig. 1 obtains for embodiment 1.Among the figure, this molecular sieve has characteristic peak 2 θ=7.22 °, 7.90 °, 9.54 °, 14.42 °, 16.14 °, 22.64 °, 23.72 °, 26.14 °.This molecular sieve belongs to typical MWW structure.
Embodiment
All embodiment all operate by the operation steps of technique scheme.Each embodiment is only enumerated the technical data in each step.
Embodiment 1
In the first step, the TiO in the titanium source
2: the SiO in the silicon source
2: the B in the boron source
2O
3: the F in the fluorine source
-: organic formwork agent: H
2The mol ratio of O is 0.033: 1: 0.67: 1: 1.4: 19, and tensio-active agent: the SiO in the silicon source
2Weight ratio be 0.015: 1, the titanium source is a tetrabutyl titanate, the silicon source is a silica gel, the boron source is a boric acid, and the fluorine source is HF, and organic formwork agent is a piperidines, tensio-active agent is the alkyl quaternaries cation surface active agent cetyl trimethylammonium bromide, mixture is in 170 ℃ of hydrothermal crystallizings 7 days, after filtration, washing, drying, obtains the Ti-MWW molecular screen primary powder; The first step ' in, Ti-MWW molecular screen primary powder that the first step obtains and concentration are that the 2mol/l salpeter solution is 1: 50 according to weight ratio, reaction mixture was handled 20 hours down in 100 ℃, after filtration, washing, drying, obtained acid-treated product; In second step, the product that previous step obtains was in 550 ℃ of roastings 7 hours.
The XRD spectra of the product Ti-MWW molecular sieve that embodiment 1 obtains as shown in Figure 1.
Embodiment 2～8
Implementation process except for the following differences, all the other are all with embodiment 1:
In embodiment 2 the first steps, mol ratio: 0.10TiO
2: SiO
2: 0.67B
2O
3: 0F
-: 1.4 organic formwork agents: 19H
2O, weight ratio: tensio-active agent: the SiO in the silicon source
2Be 0.005: 1, mixture was in 130 ℃ of hydrothermal crystallizings 10 days; In second step, the product that previous step obtains was in 600 ℃ of roastings 3 hours.
In embodiment 3 the first steps, mol ratio: 0.05TiO
2: SiO
2: 0.67B
2O
3: 1.5F
-: 1.4 organic formwork agents: 19H
2O, weight ratio: tensio-active agent: the SiO in the silicon source
2Be 0.05: 1, mixture was in 200 ℃ of hydrothermal crystallizings 3 days; In second step, the product that previous step obtains was in 500 ℃ of roastings 10 hours.
In embodiment 4 the first steps, mol ratio: 0.005TiO
2: SiO
2: 0.67B
2O
3: 0.1F
-: 1.4 organic formwork agents: 19H
2O, weight ratio: tensio-active agent: the SiO in the silicon source
2It is 0.01: 1.
In embodiment 5 the first steps, mol ratio: 0.033TiO
2: SiO
2: 0.5B
2O
3: 0.5F
-: 1.4 organic formwork agents: 12H
2O; Tensio-active agent is the alkyl quaternaries cation surface active agent Trimethyllaurylammonium bromide.
In embodiment 6 the first steps, mol ratio: 0.015TiO
2: SiO
2: 2.0B
2O
3: 0F
-: 1.4 organic formwork agents: 12H
2O, tensio-active agent are the nonionogenic tenside polyoxyethylene glycol.
In embodiment 7 the first steps, mol ratio: 0.033TiO
2: SiO
2: 0.67B
2O
3: 0F
-: 1.0 organic formwork agents: 10H
2O.
In embodiment 8 the first steps, mol ratio: 0.033TiO
2: SiO
2: 0.67B
2O
3: 0F
-: 3.0 organic formwork agents: 40H
2O.
The product Ti-MWW molecular sieve that embodiment 2～8 obtains, its XRD spectra and Fig. 1 are similar.
Embodiment 9～12
Implementation process except for the following differences, all the other are all with embodiment 1:
The first step ' acid treatment
Reaction mixture weight proportion and treatment condition:
Embodiment 9Ti-MWW molecular screen primary powder: 6mol/l nitric acid=1: 20, room temperature treatment 10 hours;
Embodiment 10Ti-MWW molecular screen primary powder: 0.5mol/l phosphoric acid=1: 90, handled 36 hours for 120 ℃;
Embodiment 11Ti-MWW molecular screen primary powder: 2mol/l hydrochloric acid=1: 50, handled 18 hours for 100 ℃;
Embodiment 12Ti-MWW molecular screen primary powder: 4mol/l acetate=1: 30, handled 36 hours for 100 ℃.
Embodiment 13
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, the silicon source is a silicon sol, and the titanium source is a titanium tetrachloride, and the boron source is a Sodium Tetraborate, and organic formwork agent is a hexamethylene imine.
The product Ti-MWW molecular sieve that embodiment 9～13 obtains, its XRD spectra and Fig. 1 are similar.
Embodiment 14
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, the fluorine source is an ammonium fluoride, and organic formwork agent is the mixture of piperidines and hexamethylene imine, weight ratio: tensio-active agent: the SiO in the silicon source
2It is 0.05: 1.
The product Ti-MWW molecular sieve that embodiment 14 obtains, its XRD spectra and Fig. 1 are similar.
Except not containing the first step ', the first step of embodiment 15～28 and second step are identical with the first step and second step of embodiment 1～14 respectively.
The product Ti-MWW molecular sieve that embodiment 15～28 obtains, its XRD spectra and Fig. 1 are similar.
Embodiment 29
Epoxy with the 1-n-hexylene turns to the catalytic activity that probe reaction is estimated the Ti-MWW molecular sieve.Detailed process is, solvent is an acetonitrile, oxygenant is that concentration is 30.1% hydrogen peroxide, successively catalyzer, solvent, reactant and oxygenant are added in the reactor, 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.The Ti-MWW building-up process of Comparative Examples 1～6 is except that adding the tensio-active agent in the table, and is identical with the Ti-MWW building-up process of respective embodiments 1～6 respectively.
Table
| Ti-MWW | 1-n-hexylene transformation efficiency |
| Embodiment 1 | 68％ |
| Comparative Examples 1 | 55％ |
| Embodiment 2 | 64％ |
| Comparative Examples 2 | 53％ |
| Embodiment 3 | 67％ |
| Comparative Examples 3 | 55％ |
| Embodiment 4 | 16％ |
| Comparative Examples 4 | 12 |
| Embodiment | |
| 5 | 67％ |
| Comparative Examples 5 | 55％ |
| Embodiment 6 | 26％ |
| Comparative Examples 6 | 20％ |
Claims (6)
1, a kind of preparation method of Ti-MWW molecular sieve is characterized in that, introduces tensio-active agent, operation steps in Ti-MWW molecular sieve crystallization process:
The first step prepares the Ti-MWW molecular screen primary powder
TiO in the titanium source in molar ratio
2: the SiO in the silicon source
2: the B in the boron source
2O
3: the F in the fluorine source
-: organic formwork agent: H
2O is (0.001～0.2): 1: (0.1～5): (0～2.0): (0.1～5): (5～150) and by weight tensio-active agent: the SiO in the silicon source
2Be (0.01～0.1): 1 prepares raw material, described titanium source is a tetralkyl titanate, halogenated titanium or titanium oxide, described silicon source is a silicic acid, silica gel, silicon sol or silicic acid tetraalkyl ester, described boron source is boric acid or borate, described fluorine source is a Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, silicofluoric acid or silicofluoride, described organic formwork agent is a piperidines, hexamethylene imine or both mixtures, described tensio-active agent is alkyl quaternaries cation surface active agent or nonionogenic tenside, earlier that organic formwork agent is water-soluble, add the titanium source to the organic formwork agent aqueous solution, stir, add boron source and fluorine source, stir, add silicon source and tensio-active agent, obtain mixture, described mixture was in 130～200 ℃ of hydrothermal crystallizings 3～10 days, after filtration, washing, drying obtains the Ti-MWW molecular screen primary powder;
Second one-step baking
The product that previous step is obtained obtains product Ti-MWW molecular sieve in 500～600 ℃ of roastings 3～10 hours.
2, the preparation method of Ti-MWW molecular sieve according to claim 1 is characterized in that, in the first step, and the TiO in the titanium source
2: the SiO in the silicon source
2: the B in the boron source
2O
3: the F in the fluorine source
-: organic formwork agent: H
2The mol ratio of O is (0.005～0.1): 1: (0.15～2): (0～1.0): (0.5～3): (15～50), 150～190 ℃ of following hydrothermal crystallizings 3～8 days.
3, the preparation method of Ti-MWW molecular sieve according to claim 1 is characterized in that, in the first step with between second step, is added with the first step ':
The first step ' acid treatment
The Ti-MWW molecular screen primary powder that the first step is obtained is that 0.1～18mol/l acidic solution is 1 according to weight ratio with concentration: mix (5～100), stir, get reaction mixture, described acidic solution is mineral acid or organic acid, mineral acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and organic acid is formic acid, acetate, propionic acid or tartrate, and reaction mixture was handled 10 minutes～3 days down at 50～200 ℃, after filtration, washing, drying, obtain acid-treated product.
4, the preparation method of Ti-MWW molecular sieve according to claim 3 is characterized in that, in the first step, and the TiO in the titanium source
2: the SiO in the silicon source
2: the B in the boron source
2O
3: the F in the fluorine source
-: organic formwork agent: H
2The mol ratio of O is (0.005～0.1): 1: (0.15～2): (0～1.0): (0.5～3): (15～50), 150～190 ℃ of following hydrothermal crystallizings 3～8 days.
5, the preparation method of Ti-MWW molecular sieve according to claim 3, it is characterized in that, in the first step ' in, Ti-MWW molecular screen primary powder that the first step makes and concentration are that the weight ratio of 0.5～6mol/l acidic solution is 1: (10～65), reaction mixture was handled 5～36 hours down at 70～130 ℃.
6, the preparation method of Ti-MWW molecular sieve according to claim 3 is characterized in that, in the first step, and the TiO in the titanium source
2: the SiO in the silicon source
2: the B in the boron source
2O
3: the F in the fluorine source
-: organic formwork agent: H
2The mol ratio of O is (0.005～0.1): 1: (0.15～2): (0～1.0): (0.5～3): (15～50), 150～190 ℃ of following hydrothermal crystallizings 3～8 days; In the first step ' in, Ti-MWW molecular screen primary powder that the first step makes and concentration are that the weight ratio of 0.5～6mol/l acidic solution is 1: (10～65), reaction mixture was handled 5～36 hours down at 70～130 ℃.
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| US9359216B2 (en) | 2010-11-23 | 2016-06-07 | Reliance Industries Limited | Method for the preparation of MWW type zeolite |
| CN104528757B (en) * | 2014-12-16 | 2017-08-29 | 上海华谊（集团）公司 | The molecular sieve preparation methods of nanoscale MCM 22 |
| CN105329909A (en) * | 2015-11-30 | 2016-02-17 | 湖北大学 | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area |
| CN114455601B (en) * | 2022-02-24 | 2023-06-06 | 江苏扬农化工集团有限公司 | Preparation method and application of molecular sieve |
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Non-Patent Citations (2)
| Title |
|---|
| MWW结构分子筛的研究进展. 傅军等.石油化工，第31卷第7期. 2002 |
| MWW结构分子筛的研究进展. 傅军等.石油化工，第31卷第7期. 2002 * |
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