CN106082261A - A kind of Ti MWW molecular sieve and preparation method thereof - Google Patents
A kind of Ti MWW molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Ti MWW molecular sieve and preparation method thereof, first the water silicon sodium stone of the synthesis two-dimensional structure containing four-coordination Ti, then converts it into three dimensional structure MWW type Ti MWW molecular sieve under hydrothermal synthesizing condition；Reactant mixture preparation process is simple, it is not necessary to introduce boron source as crystallization promoting agent, it is not required that by the step of pickling post-processing approach removing boron, it is not required that carries out respectively mixing plastic, simplifies operating procedure, be easily controlled, reproducible；The method production procedure is short, low cost, beneficially industrialized production and application；The method crystallization time is short, and template consumption can be substantially reduced, and the defect of cell configuration is few and makes have the highest hydrophobicity and oxidation susceptibility.The Ti MWW molecular sieve of synthesis comprises only Si and Ti crystallization, containing minimal amount of non-skeleton Ti, does not contains A1, has relative crystallinity high, and fault of construction is few, and heat stability is high, the highest hydrophobicity and oxidation susceptibility and the feature of nanocrystal yardstick.
Description
Technical field
The present invention relates to a kind of Ti-MWW molecular sieve and preparation method thereof, belong to inorganic chemical synthesis technical field.
Background technology
Ti-MWW molecular sieve is probably maximally effective titanium-silicon molecular sieve catalyst in current epoxidation reaction of olefines, i.e. mistake
Cross Titanium atom and introduce MWW framework of molecular sieve, form Ti-MWW molecular sieve, at first at Chemistry Letters (Chemistry
Letters, 2000,774) open report.Compared with TS-1, the advantage that MWW HTS has following uniqueness: (1) produces
Relative inexpensiveness, preparation method is varied；(2) structure plasticity of stratiform presoma is strong, and multiple method can be used to adjust
Become and modify, there is more open pore passage structure；(3) in the oxidation reaction of various types of olefins or Isosorbide-5-Nitrae-dioxane, Ti-
MWW shows more high catalytic activity, and in ketone Ammoximation reaction, the selectivity of oxime is higher, at benzothiophene or dibenzo
In the oxidation reaction of thiophene, there is more preferable catalytic effect.
Directly the process of Hydrothermal Synthesis Ti-MWW molecular sieve is because the hydrolysis of alkoxide of titanium strongly generates substantial amounts of
The species of non-skeleton Ti, these can directly affect the Ti-MWW molecular sieve catalytic oxidation susceptibility of synthesis, and with dealuminzation MWW zeolite be
The active center of the acidic hydrophilic of the synthetic method member-retaining portion of crystal seed, this also can affect Ti-MWW molecular sieve catalytic oxidisability
Energy.Additionally, there is more cell configuration defect and stability and hydrophobicity are poor, template consumption in the Ti-MWW molecular sieve of synthesis
Excessive and high cost, generating bigger crystal grain is unfavorable for the diffusion of reactant molecule, and these are all direct hydrothermal synthesis method institutes
The problem brought.Comparatively speaking, report Ti-MWW preparation side in Chemistry Letters (Chemistry Letters, 2000,774)
The main feature of method is introduced into boron source as crystallization promoting agent, forms gel synthetic crystallization degree under hydrothermal conditions with titanium source and silicon source
Higher Ti-MWW structure molecular screen.Major part boron atom does not enters into framework of molecular sieve, because the Si/B in product is 11
In the range of 14, and if reduce the consumption of boric acid when feeding intake, Ti-MWW just cannot complete crystallization.This shows to add in gel
The boric acid of excess is requisite, but final boron atom does not enters into framework of molecular sieve, but enters filtrate and leave system.Institute
With, from economic considerations, this is to cause the biggest wastage of material.Although entering the Boron contents of framework of molecular sieve far fewer than crystallization mistake
In journey, but the boron in skeleton can produce weak Bronsted acid, adds the electronegativity of Ti-MWW framework of molecular sieve, finally
The catalytic performance of active center Ti (IV), and the selectivity of reaction principal product will be affected in catalytic reaction.It is thus desirable to will
Ti-MWW molecular screen primary powder processes certain time at a set temperature with finite concentration and a certain amount of acid solution, the most fired
Obtain product Ti-MWW molecular sieve.Said method obtains product Ti-MWW molecular sieve, but the method process is complicated, technological process
Long, production cost is high, is unfavorable for industrialized production and application.
CN1466545A discloses the production method of a kind of titanosilicate catalyst, and by using this catalyst
Oxidation reaction produce oxidized compound method, the most same Chemistry Letters of preparation process (Chemistry Letters, 2000:
7740), there is similar defect in method.Document (Catalysis Surveys from Asia, 2004,8 (2): 137) is reported
Road, Ti-MWW molecular sieve is maximally effective titanium-silicon molecular sieve catalyst in current epoxidation reaction of olefines, but need to develop simpler
Single preparation method is beneficial to the application of this molecular sieve.CN1686795A discloses an a kind of step and becomes to compose Ti-MWW molecular sieve
Method, preparation process is: silicon source, titanium source, boron source, template, fluorine source and water are uniformly mixed into glue, hydrothermal crystallizing 5 hours
～20 days, obtain Ti-MWW molecular screen primary powder；This synthetic method process is relatively easy, but needs to add fluorine source, has both added cost,
Add again the corrosivity to equipment.CN101012062A discloses a kind of introducing surface during Ti-MWW Crystallization of Zeolite
Activating agent, hydrothermal crystallizing 3～the method preparing Ti-MWW molecular screen primary powder in 10 days；The addition of surfactant improves catalyst
Activity, but too increase production cost, crystallization time length adds energy resource consumption and production cost simultaneously.W003/
074421A1 discloses a kind of titan silicate, and composition structural formula is: xTiO2 (1-x) SiO2, has the X-of MWW structure molecular screen
X ray diffraction spectrogram；Its preparation process: first hydrothermal crystallizing prepares siliceous, the MWW structured forerunner of boron, and then, acid treatment obtains
MWW structured forerunner, then the product upper step obtained carries out hydrothermal crystallizing process together with titanium source and template aqueous solution,
After the fired titan silicate product obtaining crystal structure of product that upper step is obtained；The synthetic method of this patent has been carried out twice
Hydrothermal crystallization process, technological process is long, and cost is high.CN104944436A provides the side of a kind of Fast back-projection algorithm Ti-MWW molecular sieve
Method, the method is characterized mainly in that by a mole composition, organic amine, water, titanium source, boron source and silicon source are uniformly mixed and made into gel puts
Enter closed reactor to carry out rotating ageing and rotating crystallization around horizontal rotating shaft, obtain molecular sieve crystalline flour, through the post processing of some
Finally give Ti-MWW zeolite product；This patent synthetic method is difficult to crystallization and obtains the high-crystallinity of high skeleton Ti content completely
Zeolite product, substantial amounts of Ti is in outside skeleton, reduces the density in Ti-MWW molecular sieve active center, additionally, this synthesis
Method is higher for equipment requirements, it is difficult to synthesis is amplified in industry, and integrated cost is higher.
Knowable to synthetic method presented above, need introducing boron source as crystallization promoting agent, acid treatment is used in rear synthesis
Removing boron is to guarantee the activity of Ti-MWW molecular sieve, and Ti-MWW Zeolite synthesis is complex, causes technological process long, produces into
This height, is unfavorable for industrialized production and the application of this molecular sieve.
Summary of the invention
The technical problem to be solved is for the deficiencies in the prior art, and provides a kind of Ti-MWW to divide
Son sieve, this molecular sieve has MWW framing structure, comprises only Si and Ti crystallization, is substantially free of Al, containing minimal amount of non-skeleton
Ti。
The two of the purpose of the present invention are to provide the preparation method of a kind of above-mentioned Ti-MWW molecular sieve, first synthesis Ti Han four-coordination
Water silicon sodium stone (kanemite) of two-dimensional structure, under hydrothermal synthesizing condition, then convert it into three dimensional structure MWW type Ti-
MWW molecular sieve；Need not introduce boron source during synthesis Ti-MWW molecular sieve, crystallization time is short, and template consumption can be significantly
Reduce, and the defect of cell configuration is few and make to have the highest hydrophobicity and oxidation susceptibility, can be as relatively macromole body
The epoxidation catalyst that long-pending alkene is excellent.
To achieve these goals, the present invention adopts the following technical scheme that
The preparation method of a kind of Ti-MWW molecular sieve, comprises the following steps:
(1) by esters of silicon acis, titanate esters and butanol mix homogeneously, then it is added thereto to NaOH and H2O, then in room temperature～
It is sufficiently stirred for being prepared as mixed solution at 120 DEG C；By described mixed solution at 650～750 DEG C in closed pressure vessel
Reaction 3～6h, product is through filtering, wash, obtaining water silicon sodium stone (kanemite) containing Ti after drying after completion of the reaction；
Described esters of silicon acis is with SiO2Meter, titanate esters are with TiO2Meter, NaOH are with Na2O counts, SiO2: TiO2: butanol: Na2O:
H2Mol ratio=1:0.01～0.05:4.0 of O～15.0:0.015～0.15:4.5～35.0；
(2) by the water silicon sodium stone obtained in step (1) and template and H2After O mix homogeneously, in reactor, 120
～crystallization 2～15 days at 170 DEG C, obtain the former powder of HTS with MWW framing structure；
Described water silicon sodium stone is with SiO2Meter, SiO2: template: H2Mol ratio=1:0.1～1.0:2.0～8.0 of O；
(3) the former powder of HTS obtained in step (2) is mixed according to the weight ratio of 1:5～100 with aqueous acid
Uniformly being prepared as reactant mixture, reactant mixture reacts 0.5～24h at room temperature～100 DEG C, and product passes through after completion of the reaction
Filter, wash, obtain acid-treated product after drying；
(4) acid-treated product that step (3) obtains in 500～600 DEG C of roastings 2～is obtained Ti-MWW molecule for l0 hour
Sieve.
In technique scheme, in step (1), described esters of silicon acis is tetraethyl orthosilicate, quanmethyl silicate, silicic acid four fourth
Any one in ester, preferably any one in quanmethyl silicate, tetraethyl orthosilicate.
In technique scheme, in step (1), described titanate esters is tetraethyl titanate, tetraisopropyl titanate or metatitanic acid
Any one in four butyl esters, preferably butyl titanate.
In technique scheme, in step (1), described butanol is any one in the tert-butyl alcohol or n-butyl alcohol, or
The two mixture mixed with arbitrary proportion.
In technique scheme, in step (1), described SiO2: TiO2: butanol: Na2O:H2The mol ratio of O is preferably 1:
0.0125～0.033:4.0～8.0:0.026～0.052:6.5～13.5.
In technique scheme, in step (2), described template is hexamethylene imine, piperidines, N, N, N-front three
In base-1-diamantane (obsolete) ammonium hydroxide any one, two kinds and the above mixture mixed with arbitrary proportion.
In technique scheme, in step (3), in described aqueous acid, the concentration of acid is 0.1～1.0mo1/L.
In technique scheme, in step (3), described aqueous acid is mineral acid or organic aqueous acid, its
In, described mineral acid is any one in hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid, described organic acid be formic acid, acetic acid, third
Acid or tartaric acid in any one.
In technique scheme, in step (3), described aqueous acid is preferably mineral acid or organic aqueous acid
The product obtained after heat treatment 5～24h at 70～100 DEG C.
In technique scheme, in step (3), the former powder of described HTS is preferably with the weight ratio of aqueous acid
1:10～50.
The present invention also provides for a kind of Ti-MWW molecular sieve being prepared from through said method, and this molecular sieve belongs to typical
MWW structure, XRD figure is as shown in Figure 1.
Compared with prior art, the present invention has a following remarkable advantage:
(1) during preparing Ti-MWW molecular screen primary powder, reactant mixture preparation process is simple, it is not necessary to introduces boron source and makees
For crystallization promoting agent, it is not required that by the step of pickling post-processing approach removing boron, it is not required that carry out respectively mixing plastic, simplify
Operating procedure, is easily controlled, reproducible；
(2) production procedure is short, low cost, beneficially industrialized production and application.
Accompanying drawing illustrates:
The XRD figure spectrum of the Ti-MWW molecular sieve that Fig. 1: the embodiment of the present invention 1 obtains.
Detailed description of the invention
Hereinafter the detailed description of the invention of technical solution of the present invention is described in detail, but the present invention is not limited in following description
Hold:
Embodiment 1:
(1) by 212.58g silester (with SiO2Meter), 17.19g butyl titanate is (with TiO2Meter) and the tertiary fourth of 229.47g
Alcohol mix homogeneously, is then slowly added dropwise 3.58g NaOH solid (with Na under the situation being stirred continuously wherein2O counts) and
118.0gH2O, is the most at room temperature sufficiently stirred for being prepared as mixed solution；By mixed solution in 700 DEG C of closed pressure vessel
Reaction 4h, filters serosity after completion of the reaction, washs and 120 DEG C of two-dimensional layer water silicon sodium stone powders dried containing four-coordination Ti；
SiO2: TiO2: butanol: Na2O:H2Mol ratio=the 1:0.05:4.0:0.043:6.6 of O；
(2) by the water silicon sodium stone that obtains in step (1) (with SiO2Meter) with 22.54g hexamethylene imine (HMI) and
39.60g H2After O mix homogeneously, crystallization 4 days in reactor, at 140 DEG C, obtain Ti-MWW molecular screen primary powder；
SiO2: hexamethylene imine: the mol ratio=1:0.16:2.2 of water；
(3) by the acetic acid aqueous solution of the former powder of HTS that obtains in step (2) and 0.4mol/L according to the weight of 1:50
Amount ratio is prepared as reactant mixture, processes 2 hours at 90 DEG C, after completion of the reaction product again through filtering, washing, 120 DEG C dry
Dry obtain acid-treated product；
(4) acid-treated product that step (3) obtains is obtained Ti-MWW sieve sample 1# for 3 hours in 550 DEG C of roastings, its
XRD figure is composed as shown in Figure 1: in figure, and this molecular sieve has characteristic peak 2 θ=7.22 °, 7.90 °, 9.54 °, 14.42 °, 16.14 °,
22.64 °, 23.72 °, 26.14 °, belong to typical MWW structure.
Measure mean diameter and the relative crystallinity of the sample that embodiment 1 obtains；And calculating crystallization reservation degree, crystallization retains
Degree is relative crystallinity after roasting Template removal and initial sample relative crystallinity ground ratio；Measure single-autoclave yield rate, use ICP's
Al content in methods analyst molecular sieve, obtain the results are shown in Table 1.
Embodiment 2:
(1) by 155.33g methyl silicate (with SiO2Meter), 8.59g butyl titanate is (with TiO2Meter) and the tertiary fourth of 449.21g
Alcohol mix homogeneously, is then slowly added dropwise 2.17g NaOH solid (with Na under the situation being stirred continuously wherein2O counts) and
142.2g H2O, is the most at room temperature sufficiently stirred for being prepared as mixed solution；By mixed solution in 650 DEG C of closed pressure vessel
Reaction 5h, filters serosity after completion of the reaction, washs and 120 DEG C of two-dimensional layer water silicon sodium stone powders dried containing four-coordination Ti；
SiO2: TiO2: butanol: Na2O:H2Mol ratio=the 1:0.025:6.0:0.026:7.9 of O；
(2) by the water silicon sodium stone that obtains in step (1) (with SiO2Meter) with 45.08g hexamethylene imine (HMI) and
64.80g H2After O mix homogeneously, crystallization 5 days in reactor, at 150 DEG C, obtain Ti-MWW molecular screen primary powder；
SiO2: hexamethylene imine: the mol ratio=1:0.32:3.6 of water；
(3) by the aqueous hydrochloric acid solution of the former powder of HTS that obtains in step (2) and 0.2mol/L according to the weight of 1:70
Amount ratio is prepared as reactant mixture, processes 3 hours at 95 DEG C, after completion of the reaction product again through filtering, washing, 115 DEG C dry
Dry obtain acid-treated product；
(4) acid-treated product that step (3) obtains is obtained Ti-MWW sieve sample 2# for 4 hours in 540 DEG C of roastings.
According to described in embodiment 1 method measure embodiment 2 obtain the mean diameter of sample, relative crystallinity, crystallization protect
Office Copy, single-autoclave yield rate and Al content, the results are shown in Table 1.
Embodiment 3:
(1) by 212.58g silester (with SiO2Meter), 3.84g tetraethyl titanate is (with TiO2Meter) and the tertiary fourth of 598.95g
Alcohol mix homogeneously, is then slowly added dropwise 2.75g NaOH solid (with Na under the situation being stirred continuously wherein2O counts) and
212.40g H2O, is the most at room temperature sufficiently stirred for being prepared as mixed solution；By mixed solution at 750 DEG C of closed pressure vessel
Middle reaction 4h, filters serosity after completion of the reaction, washs and 120 DEG C of two-dimensional layer water silicon sodium stone powders dried containing four-coordination Ti
End；
SiO2: TiO2: butanol: Na2O:H2Mol ratio=the 1:0.0167:8.0:0.033:11.8 of O；
(2) by the water silicon sodium stone that obtains in step (1) (with SiO2Meter) (PI, mass concentration is with the piperidines of 100.29g
45%) and 95.40g H2After O mix homogeneously, crystallization 3 days in reactor, at 170 DEG C, obtain Ti-MWW molecular screen primary powder；
SiO2: piperidines: the mol ratio=1:0.53:8.0 of water；
(3) by the aqueous solution of nitric acid of the former powder of HTS that obtains in step (2) and 0.7mol/L according to the weight of 1:30
Amount ratio is prepared as reactant mixture, processes 5 hours at 85 DEG C, after completion of the reaction product again through filtering, washing, 120 DEG C dry
Dry obtain acid-treated product；
(4) acid-treated product that step (3) obtains is obtained Ti-MWW sieve sample 3# for 4 hours in 550 DEG C of roastings.
According to described in embodiment 1 method measure embodiment 3 obtain the mean diameter of sample, relative crystallinity, crystallization protect
Office Copy, single-autoclave yield rate and Al content, the results are shown in Table 1.
Embodiment 4
(1) by 155.33g methyl silicate (with SiO2Meter), 2.87g tetraisopropyl titanate is (with TiO2Meter) and uncle 973.29g
Butanol mix homogeneously, is then slowly added dropwise 4.33g NaOH solid (with Na under the situation being stirred continuously wherein2O counts) and
464.40g H2O, is the most at room temperature sufficiently stirred for being prepared as mixed solution；By mixed solution at 700 DEG C of closed pressure vessel
Middle reaction 5h, filters serosity after completion of the reaction, washs and 120 DEG C of two-dimensional layer water silicon sodium stone powders dried containing four-coordination Ti
End；
SiO2: TiO2: butanol: Na2O:H2Mol ratio=the 1:0.01:13.0:0.052:25.8 of O；
(2) by the water silicon sodium stone that obtains in step (1) (with SiO2Meter) and 769.31g N, N, N-trimethyl-1-diamantane (obsolete)
Ammonium hydroxide (TMDadOH, 25% mass concentration) and 142.20g H2After O mix homogeneously, brilliant in reactor, at 140 DEG C
Change 7 days, obtain Ti-MWW molecular screen primary powder；
SiO2: N, N, N-trimethyl-1-diamantane (obsolete) ammonium hydroxide: the mol ratio=1:0.91:7.9 of water；
(3) by the aqueous tartaric acid solution of the former powder of HTS obtained in step (2) and 0.6mol/L according to 1:20's
Weight ratio is prepared as reactant mixture, at 90 DEG C process 3 hours, after completion of the reaction product again through filtration, washing, 120 DEG C
It is dried to obtain acid-treated product；
(4) acid-treated product step (3) obtained obtains Ti-MWW sieve sample 4# in 5 hours in 540 DEG C of roastings.
According to described in embodiment 1 method measure embodiment 4 obtain the mean diameter of sample, relative crystallinity, crystallization protect
Office Copy, single-autoclave yield rate and Al content, the results are shown in Table 1.
Comparative example
At room temperature, a certain amount of hexamethylene imine (HMI) is joined in a certain amount of water, after stirring half an hour, then depend on
Secondary addition butyl titanate is (with TiO2Meter), boric acid is (with B2O3Meter) and add a certain amount of white carbon (with SiO after stirring2
Meter), prepare reaction gel, gel mole consists of SiO2: 0.04TiO2:0.67B2O3:1.5HMI:25.0H2O.
Then reaction gel being placed in closed reactor, closed reactor is fixed on the water of homogeneous reactor by connecting rod
On flat turn axle, regulation slewing rate is 10 revs/min.First it is aged 12 hours at 80 DEG C, then to regulate slewing rate be 30 revs/min
Clock, is aged 12 hours at 120 DEG C, then to regulate slewing rate is 40 revs/min, and 170 DEG C of crystallization 30 hours, then regulation rotated speed
Rate is 60 revs/min, 170 DEG C of crystallization 30 hours, through filtering, washing, is dried, obtains Ti-MWW molecular screen primary powder.To obtain
Molecular screen primary powder and concentration be 1.0mol/L aqueous solution of nitric acid by weight mix for 1:50, at 80 DEG C of backflows 20 hours, warp
Filter, wash, be dried, obtain acid-treated product；Again by acid-treated product in 550 DEG C of roastings 8 hours, obtain product Ti-MWW and divide
Son sieve.
The performance of Ti-MWW molecular sieve prepared by the different embodiment of table 1
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| Relative crystallinity/% | 98.1 | 95.9 | 95.4 | 99.8 | 78.3 |
| Average grain size/nm | 46 | 55 | 58 | 49 | 109 |
| Single-autoclave yield rate/% | 78.9 | 76.8 | 72.5 | 77.4 | 46.6 |
| Crystallization reservation degree/% | 91.2 | 90.8 | 91.4 | 92.2 | 73.3 |
| Al content (ICP mensuration) | <1ppm | <2ppm | <1ppm | <2ppm | >10ppm |
| B content (ICP mensuration) | <1ppm | <1ppm | <1ppm | <1ppm | >100ppm |
| Infrared spectrum 960cm<sup>-1</sup>Place's characteristic peak intensity | By force | By force | By force | By force | Weak |
As shown in Table 1: infrared spectrum 960cm-1Place's characteristic peak is the characteristic absorption of four-coordination Ti in sieve sample skeleton
Peak, the power at this feature peak illustrates the relative prevalence of skeleton Ti content, if peak intensity is high, illustrates that skeleton Ti content is more,
And non-skeleton Ti is less.From table 1, molecular sieve infrared spectrum 960cm prepared by the method using the present invention to provide-1Place's feature
The intensity at peak is higher, and the content of its skeleton Ti is higher.Al content, below Monitoring lower-cut, illustrates to be substantially free of in sintetics
Al.Contrastingly, use the Ti-MWW molecular sieve of comparative example's synthesis, more Al impurity may be introduced, can not have simultaneously
Effect removing B element, skeleton Ti content is relatively fewer, and the relative crystallinity obtained and reservation degree of crystallinity all ratios are relatively low, and each side refers to
Mark is worse than the physical and chemical performance of embodiment of the present invention product.
Examples detailed above simply for technology design and the technical characterstic of the present invention are described, can not limit the present invention's with this
Protection domain.All equivalent transformations done according to the essence of the present invention or modification, all should contain in protection scope of the present invention
Within.
Claims (10)
1. the preparation method of a Ti-MWW molecular sieve, it is characterised in that comprise the following steps:
(1) by esters of silicon acis, titanate esters and butanol mix homogeneously, then it is added thereto to NaOH and H2O, then at room temperature～120 DEG C
It is sufficiently stirred for being prepared as mixed solution；Described mixed solution is reacted in closed pressure vessel at 650～750 DEG C 3～6h,
Product is through filtering, wash, obtaining the water silicon sodium stone containing Ti after drying after completion of the reaction；
Described esters of silicon acis is with SiO2Meter, titanate esters are with TiO2Meter, NaOH are with Na2O counts, SiO2: TiO2: butanol: Na2O:H2O rubs
You are ratio=1:0.01～0.05:4.0～15.0:0.015～0.15:4.5～35.0；
(2) by the water silicon sodium stone obtained in step (1) and template and H2After O mix homogeneously, in reactor, 120～170
Crystallization 2～15 days at DEG C, obtain the former powder of HTS with MWW framing structure；
Described water silicon sodium stone is with SiO2Meter, SiO2: template: H2Mol ratio=1:0.1～1.0:2.0～8.0 of O；
(3) the former powder of HTS obtained in step (2) is mixed homogeneously according to the weight ratio of 1:5～100 with aqueous acid
Being prepared as reactant mixture, reactant mixture reacts 0.5～24h at room temperature～100 DEG C, after completion of the reaction product through filtering,
Wash, obtain acid-treated product after drying；
(4) acid-treated product that step (3) obtains in 500～600 DEG C of roastings 2～is obtained Ti-MWW molecular sieve for l0 hour.
Method the most according to claim 1, it is characterised in that in step (1), described esters of silicon acis be tetraethyl orthosilicate,
Any one in quanmethyl silicate, silicic acid four butyl ester；Described titanate esters is tetraethyl titanate, tetraisopropyl titanate or metatitanic acid
Any one in four butyl esters；Described butanol is any one in the tert-butyl alcohol or n-butyl alcohol, or the two is with arbitrary proportion
The mixture mixed.
Method the most according to claim 2, it is characterised in that described esters of silicon acis is quanmethyl silicate, tetraethyl orthosilicate
In any one, described titanate esters is butyl titanate.
Method the most according to claim 1, it is characterised in that in step (1), described SiO2: TiO2: butanol: Na2O:
H2The mol ratio of O is 1:0.0125～0.033:4.0～8.0:0.026～0.052:6.5～13.5.
Method the most according to claim 1, it is characterised in that in step (2), described template is that hexa-methylene is sub-
Amine, piperidines, N, in N, N-trimethyl-1-diamantane (obsolete) ammonium hydroxide any one, two kinds and above with arbitrary proportion mixing and
The mixture become.
Method the most according to claim 1, it is characterised in that in step (3), described aqueous acid be mineral acid or
Organic aqueous acid, in aqueous acid, the concentration of acid is 0.1～1.0mo1/L.
Method the most according to claim 6, it is characterised in that described mineral acid is in hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid
Any one, described organic acid is any one in formic acid, acetic acid, propanoic acid or tartaric acid.
Method the most according to claim 6, it is characterised in that described aqueous acid is the water of mineral acid or organic acid
The product that solution obtains after heat treatment 5～24h at 70～100 DEG C.
Method the most according to claim 1, it is characterised in that in step (3), the former powder of described HTS and sour water
The weight ratio of solution is 1:10～50.
10. a Ti-MWW molecular sieve, it is characterised in that be to be prepared from through method described in any one of claim 1～9
's.
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Cited By (5)
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| CN107188194A (en) * | 2017-05-04 | 2017-09-22 | 郑州大学 | A kind of method for preparing high catalytic activity Ti MWW molecular sieves |
| CN107311194A (en) * | 2017-08-01 | 2017-11-03 | 中触媒新材料股份有限公司 | A kind of preparation method and application of Ti MWW molecular sieves |
| CN108212206A (en) * | 2017-12-29 | 2018-06-29 | 中触媒新材料股份有限公司 | A kind of magnetic coupling Ti-MWW microsphere zeolite catalyst preparation methods |
| CN109821570A (en) * | 2019-04-01 | 2019-05-31 | 江西师范大学 | A kind of method that Prepared By Dual-template Method prepares Ti-MWW molecular screen membrane |
| CN110054198A (en) * | 2019-05-26 | 2019-07-26 | 福州大学 | A kind of preparation method of Ti-MWW molecular sieve |
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| CN101148260A (en) * | 2007-08-20 | 2008-03-26 | 华东师范大学 | Titanium-silicon molecular screen with MWW structure and its synthesis and application |
| CN101353169A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Synthetic method of Ti-beta molecular sieve |
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| CN101353169A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Synthetic method of Ti-beta molecular sieve |
| CN101148260A (en) * | 2007-08-20 | 2008-03-26 | 华东师范大学 | Titanium-silicon molecular screen with MWW structure and its synthesis and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107188194A (en) * | 2017-05-04 | 2017-09-22 | 郑州大学 | A kind of method for preparing high catalytic activity Ti MWW molecular sieves |
| CN107311194A (en) * | 2017-08-01 | 2017-11-03 | 中触媒新材料股份有限公司 | A kind of preparation method and application of Ti MWW molecular sieves |
| CN107311194B (en) * | 2017-08-01 | 2019-08-06 | 中触媒新材料股份有限公司 | A kind of preparation method and application of Ti-MWW molecular sieve |
| CN108212206A (en) * | 2017-12-29 | 2018-06-29 | 中触媒新材料股份有限公司 | A kind of magnetic coupling Ti-MWW microsphere zeolite catalyst preparation methods |
| CN109821570A (en) * | 2019-04-01 | 2019-05-31 | 江西师范大学 | A kind of method that Prepared By Dual-template Method prepares Ti-MWW molecular screen membrane |
| CN110054198A (en) * | 2019-05-26 | 2019-07-26 | 福州大学 | A kind of preparation method of Ti-MWW molecular sieve |
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