CN110054198A - A kind of preparation method of Ti-MWW molecular sieve - Google Patents
A kind of preparation method of Ti-MWW molecular sieve Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of Ti-MWW molecular sieve, comprising the following steps: (1) silicon source, boric acid, organic amine template, crystal seed and water is mixed to get mixture A；(2) titanium source, organic alcoholic solution are mixed to get solution B；(3) the mixture A in step (1) and step (2) is sufficiently mixed with solution B, is evaporated, grinds and obtain dry powder；(4) dry powder obtained in step (3) is vacantly placed in constant temperature static crystallization in the pressure vessel for filling water and organic amine template, the solid obtained after crystallization passes through washing, drying, pickling, roasting, obtains Ti-MWW molecular sieve.Compared with prior art, Ti-MWW molecular sieve prepared by the present invention improves the dispersibility of titanium, reduce crystallite dimension, substantially increase catalytic performance, and preparation method is efficiently simple, crystallization time is shortened, while reducing 60% boric acid dosage and 15% template dosage, reduces wastewater discharge.
Description
Technical field
The present invention relates to a kind of preparation fields of zeolite molecular sieve, belong to Inorganic synthese field.
Background technique
The preparation method of Ti-MWW molecular sieve includes classical hydro-thermal method and traditional dry gum method.Classical hydro-thermal method includes a step water
Thermal method and secondary hydro-thermal method.One step hydro thermal method needs a large amount of templates and boric acid when synthesizing Ti-MWW molecular sieve, and most of
Starting boronic acid does not simultaneously enter skeleton, but is lost in washing, causes the waste of raw material.Meanwhile one step hydro thermal method is not sloughed
Boron in skeleton increases the electronegativity of framework of molecular sieve, therefore catalytic activity will receive certain influence.Secondary hydro-thermal method synthesis
Ti-MWW molecular sieve preparation method is complicated, needs a large amount of acid to slough the boron in skeleton, generates a large amount of spent acid waste water, seriously affect
Ecological environment.And the Ti-MWW molecular sieve that traditional dry glue method is prepared out, it is asked since the dispersibility of titanium is lower, crystallite dimension is larger etc.
Topic is so that the catalyst of this method preparation only shows 4.2% catalytic activity (Catalysis in n-hexylene epoxidation reaction
Today,2005,99(1):233-240)。
Ti species are introduced by Corma et al. (Cheminform, 1999,30 (34): 779-780) by the way of grafting
In MCM-22 framework of molecular sieve by layer removing, Ti/ITQ-2 molecular sieve is prepared, this method belongs to the model of secondary synthesis
Farmland.But the titanium sieve molecular sieve activity center Ti species that this method is prepared are easy to be lost, it is active poor in the reaction.
Wu et al. (Journal of Physical Chemistry B, 2001,105 (15): 2897-2905) is by boric acid
As structural promoter, synthesize Ti-MWW molecule using piperidines or hexamethylene imine as structure directing agent success one step hydro thermal method
Sieve.But since there are a large amount of boric acid for system, keep catalytic performance poor, simultaneously because the use of a large amount of boric acid and template,
Result in serious problem of environmental pollution.
However, up to the present, the high activity of Ti-MWW molecular sieve, little crystal grain and efficiently synthesizes problem and never have
To solution.The dispersibility that titanium in Ti-MWW molecular sieve can be improved using this method reduces the crystallite dimension of molecular sieve, thus greatly
The catalytic performance of molecular sieve is improved greatly, and preparation method is efficiently simple, reduces 60% boric acid and 15% template
Dosage shortens the manufacturing cycle of molecular sieve to reduce wastewater discharge, has significant industrial prospect and economic effect
Benefit.
Summary of the invention
The purpose of the present invention is in view of the deficiencies of the prior art and provide a kind of Ti-MWW molecular sieve preparation method.For
Reach above-mentioned purpose using following technical scheme: the preparation of dry powder and the steam-transfer crystallization method preparation Ti-MWW molecule of dry powder
Sieve.Mixed emulsion is evaporated first to obtain dry glue at a certain temperature, obtained dry glue is vacantly placed in and fills water and has
The solid obtained after crystallization is passed through washing, drying, pickling, roasting by constant temperature static crystallization in the pressure vessel of machine amine template
Obtain Ti-MWW molecular sieve.This method shortens the synthesis cycle of molecular sieve, improves the preparation efficiency of molecular sieve, can be used as alkene
Hydrocarbon ring oxidation catalyst.
The technical solution of the present invention is as follows:
A kind of preparation method of Ti-MWW molecular sieve, comprising the following steps:
(1) silicon source, boric acid, organic amine template, crystal seed and suitable quantity of water the preparation of dry powder: are mixed to get mixture first
A, then titanium source dissolution is obtained into solution B in organic solvent, it is evaporated after then mixing mixture A with solution B, grinds and done
Powder.The wherein molar ratio of the Si in silicon source, the Ti in titanium source, boric acid, organic amine template, organic solvent and water are as follows: Si:Ti:
B2O3: organic amine template: organic solvent: H2O=1:(0.02~0.10): (0.03~0.12): (0.06~0.18): (0.78
~3.92): (60~120)；Wherein crystal seed with SiO2The mass ratio of the silicon source of meter are as follows: crystal seed: SiO2=0.05~0.25.
(2) above-mentioned dry powder vacantly the preparation of Ti-MWW molecular sieve: is placed in the pressure appearance for filling water and organic amine template
Constant temperature static crystallization in device.The solid obtained after crystallization is passed through into washing, drying, pickling, roasting, obtains Ti-MWW molecular sieve.
The wherein molar ratio of the Si in dry powder, organic amine template and water are as follows: dry powder: organic amine template: H2O=1:(0.21~
1.25): (0.98~5.89).
In step (1), silicon source is one of white carbon black, silica solution, tetraethyl orthosilicate or a variety of；Crystal seed is Ti-
One or more of MWW, B-MWW and the B-MWW molecular sieve of boron removal；Titanium source is butyl titanate, fluotitanic acid, isopropyl titanate
One of or it is a variety of；Organic amine template is one of piperidines, hexamethylene imine, ethylenediamine or a variety of；Organic solvent
For one of ethyl alcohol, isopropanol, n-butanol or a variety of；Evaporated temperature is 50~100 DEG C simultaneously, and being evaporated the time is 5~20h.
In step (2), static crystallization temperature is 160~190 DEG C, and crystallization time is 2~7d；Pickling concentration is 1~4mol/
L, pickling time are 10~20h, and pickling temperature is 50~120 DEG C；Maturing temperature be 500~600 DEG C, calcining time be 6~
10h；Organic amine template is one of piperidines, hexamethylene imine, ethylenediamine or a variety of.
Compared with prior art, the present invention has following remarkable advantage:
1. one step dry gum method preparation process of Ti-MWW molecular sieve proposed by the present invention is simple, raw material availability is high, can reduce
The dosage of template and boric acid reduces the discharge amount of waste water, meets green chemistry theory.
2. one step dry gum method preparation process of Ti-MWW molecular sieve proposed by the present invention is substantially shorter the synthesis week of molecular sieve
Phase improves the preparation efficiency of molecular sieve.
3. dispersibility of the titanium in framework of molecular sieve can be improved in preparation method proposed by the present invention, while using organic alcohols
The crystallite dimension that molecular sieve can be reduced as solvent substantially increases the epoxidised catalytic activity of n-hexylene.
Detailed description of the invention
Fig. 1 is the XRD spectra for the Ti-MWW molecular sieve that embodiment 1 obtains.
Specific embodiment
The operating procedure of all embodiments according to the above technical scheme carries out.Each embodiment is only enumerated in each step
Technical data.
Embodiment 1:
Step 1: the preparation of dry powder
Silicon source, boric acid, organic amine template, crystal seed and suitable quantity of water are mixed to get mixture A first, then titanium source is dissolved
Solution B is obtained in organic solvent, is evaporated 20h after then mixing mixture A with solution B at 50 DEG C, grinding obtains dry powder.
Wherein silicon source is silica solution (three nation's chemical industry of Fujian, 27.0wt%), and crystal seed Ti-MWW, titanium source is fluotitanic acid, Organic amine template
Agent is hexamethylene imine, and organic solvent is ethyl alcohol.It is the Ti in Si, titanium source, boric acid, organic amine template in silicon source, organic
The molar ratio of solvent and water are as follows: Si:Ti:B2O3: organic amine template: organic solvent: H2O=1:0.10:0.04:0.06:
0.78:60；Wherein crystal seed with SiO2The silicon source mass ratio of meter are as follows: crystal seed: SiO2=0.05.
Step 2: the preparation of Ti-MWW molecular sieve
Above-mentioned dry powder is vacantly placed in constant temperature static crystallization in the pressure vessel for filling water and organic amine template.Finally will
The solid obtained after crystallization passes through washing, drying, pickling, roasting, obtains Ti-MWW molecular sieve.Wherein Si, organic amine in dry powder
The molar ratio of template and water are as follows: dry powder: organic amine template: H2O=1:0.21:0.98；Organic amine template is six methylenes
Base imines；Static crystallization temperature is 160 DEG C, crystallization time 7d；Pickling solution is the HNO of 2mol/L3Solution, pickling time are
10h, pickling temperature are 50 DEG C；Maturing temperature is 500 DEG C, calcining time 20h.
Embodiment 2~6
Implementation process is in addition to having following difference, remaining step is with embodiment 1:
Embodiment 2: silicon source is tetraethyl orthosilicate in the first step, and crystal seed B-MWW, titanium source is isopropyl titanate, organic amine
Template is piperidines, and organic solvent is isopropanol.It is evaporated condition are as follows: 60 DEG C, 16h；Wherein the Si in silicon source, the Ti in titanium source,
Boric acid, organic amine template, the molar ratio of organic solvent and water are as follows: Si:Ti:B2O3: organic amine template: organic solvent: H2O
=1:0.07:0.05:0.08:0.85:70；Wherein crystal seed with SiO2The mass ratio of the silicon source of meter are as follows: crystal seed: SiO2=0.1.
The molar ratio of Si, organic amine template and water in second step in dry powder are as follows: dry powder: organic amine template: H2O=1:0.42:
1.96；Organic amine template is piperidines；Crystallization temperature is 170 DEG C, crystallization time 5d；Pickling solution is the HNO of 1.0mol/L3It is molten
Liquid, pickling time 12h, pickling temperature are 70 DEG C；Roasting condition is 540 DEG C, 7h.
Embodiment 3: silicon source is white carbon black (German Degussa A200) in the first step, and crystal seed is boron removal B-MWW, and titanium source is titanium
Sour four butyl esters, organic amine template is ethylenediamine, and organic solvent is n-butanol.It is evaporated condition are as follows: 70 DEG C, 12h；Wherein in silicon source
Si, the Ti of titanium source, boric acid, organic amine template, the molar ratio of organic solvent and water are as follows: Si:Ti:B2O3: Organic amine template
Agent: organic solvent: H2O=1:0.05:0.06:0.1:1.5:80；Wherein crystal seed with SiO2The mass ratio of the silicon source of meter are as follows: brilliant
Kind: SiO2=0.15.The molar ratio of Si in dry powder in second step, organic amine template and water are as follows: dry powder: organic amine template:
H2O=1:0.62:2.95；Organic amine template is ethylenediamine；Crystallization temperature is 170 DEG C, crystallization time 4d；Pickling solution is
The HNO of 3mol/L3Solution, pickling time 14h, pickling temperature are 80 DEG C；Roasting condition is 560 DEG C, 8h.
Embodiment 4: silicon source is silica solution in the first step, and crystal seed Ti-MWW, titanium source is isopropyl titanate, organic amine template
For piperidines, organic solvent is isopropanol.It is evaporated condition are as follows: 80 DEG C, 10h；Wherein the Si in silicon source, the Ti in titanium source, boric acid, have
The molar ratio of machine amine template, organic solvent and water are as follows: Si:Ti:B2O3: organic amine template: organic solvent: H2O=1:
0.03:0.07:0.12:2.0:90；Wherein crystal seed with SiO2The mass ratio of the silicon source of meter are as follows: crystal seed: SiO2=0.2.Second step
The molar ratio of Si, organic amine template and water in middle dry powder are as follows: dry powder: organic amine template: H2O=1:0.83:3.93；Have
Machine amine template is piperidines；Crystallization temperature is 180 DEG C, crystallization time 3d；Pickling solution is the HNO of 4mol/L3Solution, pickling time
For 16h, pickling temperature is 90 DEG C；Roasting condition is 580 DEG C, 9h.
Embodiment 5: silicon source is white carbon black (German Degussa A200) in the first step, and crystal seed B-MWW, titanium source is metatitanic acid four
Butyl ester, organic amine template are piperidines, and organic solvent is isopropanol.It is evaporated condition are as follows: 90 DEG C, 8h；Wherein silicon source, titanium source, boron
Acid, organic amine template, the molar ratio of organic solvent and water are as follows: Si:Ti:B2O3: organic amine template: organic solvent: H2O=
1:0.025:0.08:0.14:2.5:100；The wherein SiO in crystal seed and silicon source2Mass ratio are as follows: crystal seed: SiO2=0.25.Second
The molar ratio of Si, organic amine template and water in step in dry powder are as follows: dry powder: organic amine template: H2O=1:1.04:4.91；
Organic amine template is piperidines；Crystallization temperature is 170 DEG C, crystallization time 2d；Pickling solution is the HNO of 2mol/L3Solution, when pickling
Between be 18h, pickling temperature be 100 DEG C；Roasting condition is 550 DEG C, 6h.
Embodiment 6: silicon source is tetraethyl orthosilicate in the first step, and crystal seed is boron removal B-MWW, and titanium source is butyl titanate,
Organic amine template is ethylenediamine, and organic solvent is n-butanol.It is evaporated condition are as follows: 100 DEG C, 6h；Wherein the Si of silicon source, in titanium source
Ti, boric acid, organic amine template, the molar ratio of organic solvent and water are as follows: Si:Ti:B2O3: organic amine template: You Jirong
Agent: H2O=1:0.02:0.1:0.17:3.5:120；Wherein crystal seed with SiO2The mass ratio of the silicon source of meter are as follows: crystal seed: SiO2=
0.3.In second step, the molar ratio of Si, organic amine template and water in dry powder are as follows: dry powder: organic amine template: H2O=1:
1.25:5.89；Organic amine template is ethylenediamine；Crystallization temperature is 190 DEG C, crystallization time 2d；Pickling solution is 3mol/L's
HNO3Solution, pickling time 20h, pickling temperature are 120 DEG C；Roasting condition is 600 DEG C, 7h.
Comparative example: this comparative example explanation is proposed according to Wu et al. (Catalysis Today, 2005,99 (1): 233-240)
Classical dry gum method synthesize Ti-MWW molecular sieve.This method is that a step dry gum method prepares Ti-MWW, first that butyl titanate is molten
Solution obtains solution A into hydrogenperoxide steam generator；Later by white carbon black (German Degussa, A200), boric acid and crystal seed and Na2O
Mixing is added deionized water and forms mixture B, then two kinds of mixtures of A, B mixed, stirring；Then it is evaporated 12h at 80 DEG C,
Obtain dry glue；Dry glue is placed in again in the steam of piperidines and water, the crystallization 168h at 170 DEG C；To the solid obtained after crystallization into
Row washing, drying, then use the HNO of 2mol/L3Solution pickling 12h at 80 DEG C；Finally, roasting 6h at 550 DEG C, obtain
Ti-MWW molecular sieve.Wherein, crystal seed is the B-MWW of boron removal, the molar ratio of each substance are as follows: Si/Ti=30, Si/B=2, Si/Na
=37, SiO2:H2O:PI=1:2.56:0.71；The quality of crystal seed is with SiO2The 10% of the silicon source quality of meter.
Probe reaction is turned to the epoxy of n-hexylene: 0.05g catalyst, the n-hexylene of 10mmol, the peroxidating of 10mmol
Hydrogen (mass fraction 30%), 0.50g internal standard cyclohexanone, the solvent of 10mL, reaction temperature are 60 DEG C, reaction time 2h.
Chromatogram analysis method: chromatography model: 6890. chromatographic column of Agilent；Capillary column model: Agilent
19091J-413, HP-5MS.Gas condition: hydrogen flowing quantity: 40mL/min；Air mass flow: 450mL/L；Split ratio is 3.Using
50 DEG C of temperature programming initial temperature, residence time 2min, 5 DEG C/min of heating rate, 250 DEG C of final temperature, residence time 1min.
Catalytic result of the Ti-MWW molecular sieve of Examples 1 to 6 and comparative example in n-hexylene epoxidation reaction such as 1 institute of table
Show.
XRD diagram of the Fig. 1 for 1 gained sieve sample of embodiment, 2 θ=7.22 ° of figure characteristic peak, 7.90 °, 9.54 °,
14.42 °, 16.14 °, 22.64 °, 23.72 °, 26.14 °, belong to typical MWW structure.X-ray powder diffraction instrument (XRD,
PANalytical Axios Petro diffractometer) use Cu-K α for radiographic source instrument, test condition are as follows: voltage
45kV, electric current 40mA, scanning range are 5 °~45 °, and sweep speed is 0.1641 °/s.
The XRD diagram of embodiment 2~6 is consistent with Fig. 1.
Above embodiments combination attached drawing describes the prefered embodiments of the present invention in detail, still, the present invention is not limited to
Detail in above embodiment can carry out technical solution of the present invention within the scope of the technical concept of the present invention
A variety of simple variants, these simple variants all belong to the scope of protection of the present invention.It is further to note that in above-mentioned specific reality
Each particular technique feature described in mode is applied, in the case of no contradiction, can be carried out by any suitable means
Combination, in order to avoid unnecessary repetition, the invention will not be further described in various possible combinations.In addition, of the invention
A variety of different embodiments between can also carry out any combination and equally answer as long as it does not violate the idea of the present invention
When being considered as content disclosed in this invention.
Table 1
Claims (9)
1. a kind of preparation method of Ti-MWW molecular sieve, comprising the following steps:
(1) preparation of dry powder: being mixed to get mixture A for silicon source, boric acid, organic amine template, crystal seed and suitable quantity of water first, then
Titanium source dissolution is obtained into solution B in organic solvent, is evaporated after then mixing mixture A with solution B, ground and obtain dry powder；
The wherein molar ratio of the Si in silicon source, the Ti in titanium source, boric acid, organic amine template, organic solvent and water are as follows: Si:Ti:B2O3:
Organic amine template: organic solvent: H2O=1:(0.02~0.10): (0.03~0.12): (0.06~0.18): (0.78~
3.92): (60~120)；Wherein crystal seed with SiO2The mass ratio of the silicon source of meter are as follows: crystal seed: SiO2=0.05~0.25；
(2) dry powder in step (1) vacantly the preparation of Ti-MWW molecular sieve: is placed in the pressure for filling water and organic amine template
Constant temperature static crystallization in container；The solid obtained after crystallization is finally passed through into washing, drying, pickling, roasting, obtains Ti-MWW points
Son sieve；The wherein molar ratio of the Si in dry powder, organic amine template and water are as follows: dry powder: organic amine template: H2O=1:(0.21
~1.25): (0.98~5.89).
2. the preparation method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: silicon source is white in step (1)
One of carbon black, silica solution, tetraethyl orthosilicate are a variety of；Crystal seed is the molecule of the B-MWW of Ti-MWW, B-MWW and boron removal
One or more of sieve；Titanium source is one of butyl titanate, fluotitanic acid, isopropyl titanate or a variety of.
3. the preparation method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: organic amine mould in step (1)
Plate agent is one of piperidines, hexamethylene imine, ethylenediamine or a variety of.
4. the preparation method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: organic solvent in step (1)
For one of ethyl alcohol, isopropanol, n-butanol or a variety of.
5. the preparation method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: in step (1), evaporated temperature
It is 50~100 DEG C, being evaporated the time is 5~20h.
6. the preparation method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: static crystallization in step (2)
Temperature is 160~190 DEG C, and crystallization time is 2~7d.
7. the preparation method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: pickling solution in step (2)
For the nitric acid solution of 1~4mol/L, pickling time is 10~20h, and pickling temperature is 50~120 DEG C.
8. the preparation method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: maturing temperature in step (2)
It is 500~600 DEG C, calcining time is 6~20h.
9. the preparation method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: organic amine mould in step (2)
Plate agent is one of piperidines, hexamethylene imine, ethylenediamine or a variety of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111453742A (en) * | 2020-04-07 | 2020-07-28 | 福州大学 | Preparation method and application of Ti-MWW molecular sieve |
| CN115504482A (en) * | 2022-08-12 | 2022-12-23 | 浙江师范大学 | Titanium-silicon molecular sieve, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110190517A1 (en) * | 2010-02-01 | 2011-08-04 | Mandimutsira Beaven S | Process for making titanium-MWW zeolite |
| CN104709918A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院大连化学物理研究所 | Titanium silicon molecular sieve with MWW topological structure and preparation and application thereof |
| CN106082261A (en) * | 2016-06-21 | 2016-11-09 | 中触媒新材料股份有限公司 | A kind of Ti MWW molecular sieve and preparation method thereof |
| CN109231233A (en) * | 2018-10-23 | 2019-01-18 | 福州大学 | A kind of green synthesis method of Ti-MWW molecular sieve and application |
-
2019
- 2019-05-26 CN CN201910443778.2A patent/CN110054198A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110190517A1 (en) * | 2010-02-01 | 2011-08-04 | Mandimutsira Beaven S | Process for making titanium-MWW zeolite |
| CN104709918A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院大连化学物理研究所 | Titanium silicon molecular sieve with MWW topological structure and preparation and application thereof |
| CN106082261A (en) * | 2016-06-21 | 2016-11-09 | 中触媒新材料股份有限公司 | A kind of Ti MWW molecular sieve and preparation method thereof |
| CN109231233A (en) * | 2018-10-23 | 2019-01-18 | 福州大学 | A kind of green synthesis method of Ti-MWW molecular sieve and application |
Non-Patent Citations (2)
| Title |
|---|
| A.THANGARAJ等: ""AN IMPROVED METHOD FOR TS-1 SYNTHESIS：29SI NMR-STUDIES"", 《JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS》 * |
| PENGWU等: ""Synthesis of Ti-MWW by a dry-gel conversion method"", 《CATALYSIS TODAY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111453742A (en) * | 2020-04-07 | 2020-07-28 | 福州大学 | Preparation method and application of Ti-MWW molecular sieve |
| CN115504482A (en) * | 2022-08-12 | 2022-12-23 | 浙江师范大学 | Titanium-silicon molecular sieve, preparation method and application thereof |
| CN115504482B (en) * | 2022-08-12 | 2023-08-11 | 浙江师范大学 | Titanium-silicon molecular sieve, preparation method and application thereof |
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