CN107188194A - A kind of method for preparing high catalytic activity Ti MWW molecular sieves - Google Patents
A kind of method for preparing high catalytic activity Ti MWW molecular sieves Download PDFInfo
- Publication number
- CN107188194A CN107188194A CN201710309386.8A CN201710309386A CN107188194A CN 107188194 A CN107188194 A CN 107188194A CN 201710309386 A CN201710309386 A CN 201710309386A CN 107188194 A CN107188194 A CN 107188194A
- Authority
- CN
- China
- Prior art keywords
- catalytic activity
- molecular sieves
- high catalytic
- gel
- mww
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of method for preparing high catalytic activity Ti MWW molecular sieves, comprises the steps of：At room temperature, butyl titanate, Ludox, boric acid and water are mixed to get to the Gel Precursor of synthesis of molecular sieve；The Gel Precursor that above-mentioned steps are obtained is ground using colloid mill under ultraviolet light, then piperidines is added into the Gel Precursor after grinding to be well mixed, obtain reaction gel, the reaction gel is loaded into hydrothermal crystallizing synthesis reactor, 160~180 DEG C are warming up to, crystallization generated time is 72~120 hours, separation of solid and liquid is carried out after the completion of reaction, gained solid is washed with dust technology, after drying, you can obtain the high catalytic activity Ti MWW molecular sieves with MWW structures.The more conventional method of method for preparing high catalytic activity Ti MWW molecular sieves has the advantages that generated time is short, boron consumption greatly reduces, catalytic activity is significantly improved.
Description
Technical field
The invention belongs to inorganic chemical synthesis technical field, and in particular to one kind prepares high catalytic activity Ti-MWW molecular sieves
Method, butyl titanate, Ludox, boric acid and water are specifically obtained into synthesis of molecular sieve according to certain mixed in molar ratio
Gel Precursor, under ultraviolet light with colloid mill to the Gel Precursor grind certain time, then add have machine aided
Agent prepares high catalytic activity Ti-MWW molecular sieves.
Background technology
Ti-MWW type HTSs are a kind of MWW structure molecular screens containing skeleton titanium atom, because it has MWW points
Son sieve unique sinusoidal 10 yuan of rings reticulated cell system, 12 yuan of rings holes and supercage hole series structure, organic reactant are easier to close to it
Activated centre in duct, but its simultaneous titanium active sites are to H2O2With unique adsorption activation performance, thus a variety of organic
There is very high catalytic oxidation activity, selectivity of product is high, and reaction condition is gentle in compound reaction, and whole catalysis oxidation mistake
Journey non-pollution discharge, has a good application prospect as catalyst, and such as it prepares cyclohexanone oxime in catalysis of pimelinketone oxamidine
Deng all with preferably industrial applications prospect.
Chemistry Letters（Chemistry Letters, 2000：774）A kind of preparation method of Ti-MWW molecular sieves is reported,
It is mainly characterized by introducing boron source as crystallization promoting agent, with titanium source and silicon source formation gel under hydrothermal conditions synthetic crystallization degree compared with
High Ti-MWW structure molecular screens.
CN1466545A discloses a kind of production method of titanosilicate catalyst, and by using this catalyst
The oxidation reaction method that produces oxidized compound, its preparation process and Chemistry Letters（Chemistry Letters, 2000：
774）The method of report is essentially identical.
CN1686795A discloses an a kind of step into the method for composing Ti-MWW molecular sieves, and preparation process is：By silicon source,
Titanium source, boron source, template, Fluorine source and water are uniformly mixed into glue, and hydrothermal crystallizing 5 hours~20 days obtains Ti-MWW molecular screen primary powders,
This synthetic method process is relatively easy, but needs to add Fluorine source.
CN101012062A discloses one kind and surfactant, hydrothermal crystallizing is introduced during Ti-MWW Crystallization of Zeolite
The method for preparing Ti-MWW molecular screen primary powders in 3~10 days.
In summary, the preparation process of Ti-MWW molecular screen primary powders is complicated in the prior art, and generated time is long, because titanium is former
Son is difficult to introduce framework of molecular sieve, generally requires to introduce substantial amounts of boron source as crystallization promoting agent, or adds other organic and inorganic help
Agent, thus cause to prepare cost higher, it is difficult to industrialized production, make itself and excellent catalytic oxidation performance in actual applications by
To a definite limitation.
The content of the invention
To overcome above-mentioned the deficiencies in the prior art, Ti-MWW points of high catalytic activity is prepared the invention provides one kind
The method of son sieve, the more conventional method of method for preparing high catalytic activity Ti-MWW molecular sieves has that generated time is short, boron consumption
Greatly reduce, the advantages of catalytic activity is significantly improved.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of method for preparing high catalytic activity Ti-MWW molecular sieves, is comprised the steps of：
（1）At room temperature, butyl titanate, Ludox, boric acid and water are mixed to get to the Gel Precursor of synthesis of molecular sieve；
（2）Using colloid mill to above-mentioned steps under ultraviolet light（1）Obtained Gel Precursor is ground, then to grinding
Piperidines is added in Gel Precursor after mill to be well mixed, reaction gel is obtained, and the reaction gel is loaded into hydrothermal crystallizing closes
Into kettle, 160~180 DEG C are warming up to, crystallization generated time is 72~120 hours, and separation of solid and liquid is carried out after the completion of reaction, dilute nitre is used
Solid obtained by acid elution, after drying, you can obtain the high catalytic activity Ti-MWW molecular sieves with MWW structures.
According to currently preferred, the step（1）In with SiO in molar ratio computing Gel Precursor2∶TiO2∶ B2O3∶H2O
For 1: (0.01 ~ 0.05): (0.01 ~ 0.1): (20 ~ 50)；
According to currently preferred, in the step（2）In ultraviolet light used be the nm of wavelength 180~380 mixed light, it is ultraviolet
Light irradiance is 1000~1 × 106Milliwatt/square metre.
According to currently preferred, in the step（2）Middle colloid mill to the milling time of the Gel Precursor for 2~
12 hours, grinding power was 10~100 watts/kilogram.
According to currently preferred, in step（2）Described in reaction gel with molar ratio computing PD: SiO2 = 0.1~1.0。
According to currently preferred, in step（2）Described in dust technology concentration be 2mol/L, the quality of dust technology used
By 10 times of washing solid masses.
Preparation method of the present invention is improved of both having：On the one hand, ultraviolet light can be to zeolite molecular sieve compound body
System additionally introduces hydroxyl radical free radical, dramatically speeds up the nucleation of zeolite molecular sieve；On the other hand, ultraviolet light may make titanyl
Species are activated, under the synergism that colloid mill is ground, and titanium oxide kind can be made to disperse evenly, to make it in Gel Precursor
It is easier to enter framework of molecular sieve during hydrothermal crystallizing, divides so as to reduce the consumption of the boric acid as crystallization in motion agent, and improve
The catalytic activity of son sieve.
Compared with prior art, beneficial effects of the present invention are：The amount of boric acid used in sieve synthesis procedure is few, institute's score
More preferably, preparation cost is low, and advantageously reduces the waste discharge in industrialized production for son sieve catalytic activity.
Brief description of the drawings
Fig. 1 is the XRD spectrum of molecular sieve prepared by comparative example 1；
Fig. 2 is the XRD spectrum of molecular sieve prepared by comparative example 2；
Fig. 3 is the XRD spectrum of molecular sieve prepared by embodiment 1；
Fig. 4 is the XRD spectrum of molecular sieve prepared by embodiment 2；
Fig. 5 is the XRD spectrum of molecular sieve prepared by embodiment 3；
Fig. 6 is the XRD spectrum of molecular sieve prepared by embodiment 4；
Fig. 7 is the XRD spectrum of molecular sieve prepared by embodiment 5.
Embodiment
With reference to comparative example and embodiment, the present invention is described in further detail.
Ludox used in comparative example and embodiment of the present invention, butyl titanate, boric acid, piperidines, cyclohexanone, hydrogen peroxide,
The raw materials such as ammoniacal liquor, nitric acid are commercially available prod.The mass fraction of ammoniacal liquor used is 25%.
Comparative example 1
At room temperature, by a certain amount of Ludox（With SiO2Meter）It is added in a certain amount of water, after stirring, sequentially adds
Butyl titanate（With TiO2Meter）, boric acid（With B2O3Meter）And stir after 12 hours, add a certain amount of piperidines（PD）, it is made anti-
It is 1.0SiO to answer a mole composition in gel, the reaction gel2∶ 0.05TiO2∶1.0B2O3∶1.0PD∶25.0H2O, then will be anti-
Gel is answered to be placed in closed reactor, closed reactor is fixed on the horizontal rotating shaft of homogeneous reactor by connecting rod, regulation turns
Dynamic speed is 30 revs/min, crystallization 120 hours at 180 DEG C, through filtering, washing, dries, obtains Ti-MWW molecular screen primary powders.
It is that 2.0mol/L aqueous solution of nitric acid is to mix at 1: 10 by weight by obtained Ti-MWW molecular screen primary powders and concentration, at 80 DEG C
Gained solid, is calcined 8 hours by agitator treating 10 hours after filtering, drying in 550 DEG C, obtains product for Ti-MWW molecules
Sieve, its XRD spectrum is as shown in Figure 1.
The catalytic activity of synthesized Ti-MWW molecular sieves is evaluated with cyclohexanone oxamidinating reaction, reaction condition is：
As 0.1 gram of the Ti-MWW molecular sieves of catalyst, 6.0 grams of cyclohexanone, 18 grams of water, mass concentration is 27.3% hydrogen peroxide
8.0 grams, 13.9 grams of ammoniacal liquor.Detailed process is：The Ti-MWW molecular sieves using solvent, reactant and as catalyst are added successively
Into flask, under agitation, 80 DEG C are reacted 2 hours, and reaction result is measured after reaction is：Cyclohexanone conversion ratio 65%, ring
Hexanone oxime selectivity 58%, cyclohexanone oxime yield 32%.
Comparative example 2
At room temperature, by a certain amount of Ludox（With SiO2Meter）It is added in a certain amount of water, after stirring, sequentially adds
Butyl titanate（With TiO2Meter）, small amount boric acid（With B2O3Meter）And stir after 12 hours, add a certain amount of piperidines（PD）,
Reaction gel is made, gel mole composition is 1.0SiO2∶0.05TiO2∶0.1B2O3∶1.0PD∶25.0H2O.Then it is reaction is solidifying
Glue is placed in closed reactor, and closed reactor is fixed on the horizontal rotating shaft of homogeneous reactor by connecting rod, and regulation rotates speed
Rate is 30 revs/min, in 180 DEG C of crystallization 120 hours, through filtering, washing, dries, obtains Ti-MWW molecular screen primary powders.It will obtain
Ti-MWW molecular screen primary powders and concentration be that 2.0mol/L aqueous solution of nitric acid is to mix at 1: 10 by weight, in 80 DEG C of agitator treatings
10 hours, gained solid is calcined 8 hours in 550 DEG C after filtering, drying, obtains product for amorphous article, its XRD spectrum is such as
Shown in Fig. 2.
The catalytic activity of gains is evaluated with cyclohexanone oxamidinating reaction, reaction condition is identical with comparative example 1, reaction knot
It is really：Cyclohexanone conversion ratio 21%, cyclohexanone oxime selectivity 0%, cyclohexanone oxime yield 0%.
Embodiment 1
At room temperature, by a certain amount of Ludox（With SiO2Meter）It is added in a certain amount of water, after stirring, sequentially adds
Butyl titanate（With TiO2Meter）, small amount boric acid（With B2O3Meter）After obtain Gel Precursor, in irradiation level 1 × 105Milliwatt/flat
Under square rice, the irradiation of the nm of wavelength 180~380 mixing ultraviolet light, with colloid mill with 100 watt/kilogram gels to gel forerunner
Body is ground 12 hours, is then added a certain amount of to piperidines（PD）, a mole composition in reaction gel, the reaction gel, which is made, is
1.0SiO2∶0.05TiO2∶0.1B2O3∶1.0PD∶25.0H2O.Then reaction gel is placed in closed reactor, confined reaction
Kettle is fixed on the horizontal rotating shaft of homogeneous reactor by connecting rod, and regulation slewing rate is 30 revs/min, in 180 DEG C of crystallization 120
Hour, through filtering, washing, dry, obtain Ti-MWW molecular screen primary powders.It is 2.0mol/L by obtained molecular screen primary powder and concentration
Aqueous solution of nitric acid was by weight for 1: 10 mixing, in 80 DEG C of agitator treatings 10 hours, through filtering, dry after gained solid in 550
DEG C roasting 8 hours, obtains product for Ti-MWW molecular sieves, its XRD spectrum is as shown in Figure 3.
The catalytic activity of Ti-MWW molecular sieves is evaluated with cyclohexanone oxamidinating reaction, reaction condition is identical with comparative example 1,
Reaction result is：Cyclohexanone conversion ratio 95%, cyclohexanone oxime selectivity 96%, cyclohexanone oxime yield 91%.
Embodiment 2
At room temperature, by a certain amount of Ludox（With SiO2Meter）It is added in a certain amount of water, after stirring, sequentially adds
Butyl titanate（With TiO2Meter）, small amount boric acid（With B2O3Meter）After obtain Gel Precursor, in irradiation level 1 × 104Milliwatt/flat
Under square rice, the irradiation of the nm of wavelength 180~380 mixing ultraviolet light, with colloid mill with 100 watt/kilogram gels to gel forerunner
Body is ground 12 hours, is then added a certain amount of to piperidines（PD）, reaction gel is made, gel mole composition is 1.0SiO2∶
0.05TiO2∶0.1B2O3∶1.0PD∶25.0H2O.Then reaction gel is placed in closed reactor, closed reactor passes through even
Bar is fixed on the horizontal rotating shaft of homogeneous reactor, and regulation slewing rate is 30 revs/min, in 160 DEG C of crystallization 120 hours, warp
Filter, wash, dry, obtain Ti-MWW molecular screen primary powders.It is 2.0mol/L nitric acid aqueous solutions by obtained molecular screen primary powder and concentration
Solution was by weight for 1: 10 mixing, in 80 DEG C of agitator treatings 10 hours, through filtering, dry after gained solid be calcined 8 in 550 DEG C
Hour, product is obtained for Ti-MWW molecular sieves, and its XRD spectrum is as shown in Figure 4.
The catalytic activity of Ti-MWW molecular sieves is evaluated with cyclohexanone oxamidinating reaction, reaction condition is identical with comparative example 1,
Reaction result is：Cyclohexanone conversion ratio 83%, cyclohexanone oxime selectivity 78%, cyclohexanone oxime yield 65%.
Embodiment 3
At room temperature, by a certain amount of Ludox（With SiO2Meter）It is added in a certain amount of water, after stirring, sequentially adds
Butyl titanate（With TiO2Meter）, small amount boric acid（With B2O3Meter）After obtain Gel Precursor, in the milliwatt of irradiation level 1 × 105/flat
Under square rice, the irradiation of the nm of wavelength 180~380 mixing ultraviolet light, with colloid mill with 10 watt/kilogram gels to gel forerunner
Body is ground 2 hours, is then added a certain amount of to piperidines（PD）, reaction gel is made, gel mole composition is 1.0SiO2∶
0.05TiO2∶0.1B2O3∶0.3PD∶25.0H2O.Then reaction gel is placed in closed reactor, closed reactor passes through even
Bar is fixed on the horizontal rotating shaft of homogeneous reactor, and regulation slewing rate is 30 revs/min, in 180 DEG C of crystallization 72 hours, is passed through
Filter, wash, dry, obtain Ti-MWW molecular screen primary powders.It is that 2.0mol/L nitric acid is water-soluble by obtained molecular screen primary powder and concentration
Liquid was by weight for 1: 10 mixing, in 80 DEG C of agitator treatings 10 hours, through filtering, dry after gained solid it is small in 550 DEG C of roastings 8
When, product is obtained for Ti-MWW molecular sieves, and its XRD spectrum is as shown in Figure 5.
The catalytic activity of Ti-MWW molecular sieves is evaluated with cyclohexanone oxamidinating reaction, reaction condition is identical with comparative example 1,
Reaction result is：Cyclohexanone conversion ratio 79%, cyclohexanone oxime selectivity 75%, cyclohexanone oxime yield 59%.
Embodiment 4
At room temperature, by a certain amount of Ludox（With SiO2Meter）It is added in a certain amount of water, after stirring, sequentially adds
Butyl titanate（With TiO2Meter）, small amount boric acid（With B2O3Meter）After obtain Gel Precursor, in irradiation level 1 × 105Milliwatt/flat
Under square rice, the irradiation of the nm of wavelength 180~380 mixing ultraviolet light, with colloid mill with 100 watt/kilogram gels to gel forerunner
Body is ground 12 hours, is then added a certain amount of to piperidines（PD）, reaction gel is made, gel mole composition is 1.0SiO2∶
0.04TiO2∶0.1B2O3∶1.0PD∶25.0H2O.Then reaction gel is placed in closed reactor, closed reactor passes through even
Bar is fixed on the horizontal rotating shaft of homogeneous reactor, and regulation slewing rate is 30 revs/min, in 160 DEG C of crystallization 120 hours, warp
Filter, wash, dry, obtain Ti-MWW molecular screen primary powders.It is 2.0mol/L nitric acid aqueous solutions by obtained molecular screen primary powder and concentration
Solution was by weight for 1: 10 mixing, in 80 DEG C of agitator treatings 10 hours, through filtering, dry after gained solid be calcined 8 in 550 DEG C
Hour, product is obtained for Ti-MWW molecular sieves, and its XRD spectrum is as shown in Figure 6.
The catalytic activity of Ti-MWW molecular sieves is evaluated with cyclohexanone oxamidinating reaction, reaction condition is identical with comparative example 1,
Reaction result is：Cyclohexanone conversion ratio 92%, cyclohexanone oxime selectivity 90%, cyclohexanone oxime yield 83%.
Embodiment 5
At room temperature, by a certain amount of Ludox（With SiO2Meter）It is added in a certain amount of water, after stirring, sequentially adds
Small amount butyl titanate（With TiO2Meter）, less amount boric acid（With B2O3Meter）After obtain Gel Precursor, in irradiation level 1 × 105In the least
It is solidifying to this with 100 watt/kilogram gels with colloid mill under watt/square metre, the irradiation of the nm of wavelength 180~380 mixing ultraviolet light
Glue presoma is ground 12 hours, is then added a certain amount of to piperidines（PD）, reaction gel is made, gel mole composition is
1.0SiO2∶0.01TiO2∶0.02B2O3∶1.0PD∶25.0H2O.Then reaction gel is placed in closed reactor, confined reaction
Kettle is fixed on the horizontal rotating shaft of homogeneous reactor by connecting rod, and regulation slewing rate is 30 revs/min, in 180 DEG C of crystallization 120
Hour, through filtering, washing, dry, obtain Ti-MWW molecular screen primary powders.It is 2.0mol/L by obtained molecular screen primary powder and concentration
Aqueous solution of nitric acid was by weight for 1: 10 mixing, in 80 DEG C of agitator treatings 10 hours, through filtering, dry after gained solid in 550
DEG C roasting 8 hours, obtains product for Ti-MWW molecular sieves, its XRD spectrum is as shown in Figure 7.
The catalytic activity of Ti-MWW molecular sieves is evaluated with cyclohexanone oxamidinating reaction, reaction condition is identical with comparative example 1,
Reaction result is：Cyclohexanone conversion ratio 73%, cyclohexanone oxime selectivity 69%, cyclohexanone oxime yield 50%.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of changes, modification can be carried out to these embodiments, replace without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of method for preparing high catalytic activity Ti-MWW molecular sieves, it is characterised in that comprise the steps of：
（1）At room temperature, butyl titanate, Ludox, boric acid and water are mixed to get to the Gel Precursor of synthesis of molecular sieve；
（2）Using colloid mill to above-mentioned steps under ultraviolet light（1）Obtained Gel Precursor is ground, then to grinding
Piperidines is added in Gel Precursor after mill to be well mixed, reaction gel is obtained, and the reaction gel is loaded into hydrothermal crystallizing closes
Into kettle, 160~180 DEG C are warming up to, crystallization generated time is 72~120 hours, and separation of solid and liquid is carried out after the completion of reaction, dilute nitre is used
Solid obtained by acid elution, after drying, you can obtain the high catalytic activity Ti-MWW molecular sieves with MWW structures.
2. a kind of method for preparing high catalytic activity Ti-MWW molecular sieves according to claim 1, it is characterised in that described
Step（1）In with SiO in molar ratio computing Gel Precursor2∶TiO2∶ B2O3∶H2O is 1: (0.01 ~ 0.05): (0.01 ~ 0.1)
∶(20~50)。
3. a kind of method for preparing high catalytic activity Ti-MWW molecular sieves according to claim 1, it is characterised in that in institute
State step（2）In ultraviolet light used be the nm of wavelength 180~380 mixed light, ultraviolet light irradiation degree is 1000~1 × 106In the least
Watt/square metre.
4. a kind of method for preparing high catalytic activity Ti-MWW molecular sieves according to claim 1, it is characterised in that in institute
State step（2）Middle colloid mill is 2~12 hours to the milling time of the Gel Precursor, and grinding power is 10~100 watts/thousand
Gram.
5. a kind of method for preparing high catalytic activity Ti-MWW molecular sieves according to claim 1, it is characterised in that in step
Suddenly（2）Described in reaction gel with molar ratio computing PD: SiO2 = 0.1~1.0。
6. a kind of method for preparing high catalytic activity Ti-MWW molecular sieves according to claim 1, it is characterised in that in step
Suddenly（2）Described in the concentration of dust technology be 2mol/L, the quality of dust technology used by 10 times of washing solid masses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710309386.8A CN107188194B (en) | 2017-05-04 | 2017-05-04 | A method of preparing high catalytic activity Ti-MWW molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710309386.8A CN107188194B (en) | 2017-05-04 | 2017-05-04 | A method of preparing high catalytic activity Ti-MWW molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107188194A true CN107188194A (en) | 2017-09-22 |
| CN107188194B CN107188194B (en) | 2019-07-23 |
Family
ID=59874068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710309386.8A Active CN107188194B (en) | 2017-05-04 | 2017-05-04 | A method of preparing high catalytic activity Ti-MWW molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107188194B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126860A (en) * | 2018-08-20 | 2019-01-04 | 青岛科技大学 | A kind of application for the method and acid mesopore molecular sieve preparing acid mesopore molecular sieve using hydrogen peroxide |
| 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 |
| CN112158856A (en) * | 2020-08-25 | 2021-01-01 | 郑州大学 | Method for preparing Ti-MWW molecular sieve |
| US10968110B2 (en) * | 2019-04-26 | 2021-04-06 | China University Of Petroleum (East China) | Method for preparing titanium silicon molecular sieve |
| CN113368884A (en) * | 2021-06-15 | 2021-09-10 | 南京工程学院 | Limited-area catalyst for catalytic oxidation of carbon monoxide and preparation method thereof |
| CN115650249A (en) * | 2022-09-19 | 2023-01-31 | 中建安装集团有限公司 | Method for preparing high-performance TS-1 titanium silicalite molecular sieve at low cost |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686795A (en) * | 2005-04-18 | 2005-10-26 | 华东师范大学 | Method of synthesizing Ti-MWW molecular sieve |
| JP2008308388A (en) * | 2007-06-18 | 2008-12-25 | Sumitomo Chemical Co Ltd | Method for producing titanosilicate and method for producing oxime |
| CN104437616A (en) * | 2014-11-21 | 2015-03-25 | 武汉工程大学 | Lamellar catalyst containing mesoporous titanium-silicate molecular sieves and preparation method and application of lamellar catalyst |
| CN104876238A (en) * | 2015-04-20 | 2015-09-02 | 吉林大学 | Method for assisted synthesis of molecular sieve by means of ultraviolet radiation |
| 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 |
| CN105645430A (en) * | 2016-02-25 | 2016-06-08 | 湖北大学 | Crystal-seed method for rapidly synthesizing Ti-MWW molecular sieves through rotation |
| 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 |
-
2017
- 2017-05-04 CN CN201710309386.8A patent/CN107188194B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686795A (en) * | 2005-04-18 | 2005-10-26 | 华东师范大学 | Method of synthesizing Ti-MWW molecular sieve |
| JP2008308388A (en) * | 2007-06-18 | 2008-12-25 | Sumitomo Chemical Co Ltd | Method for producing titanosilicate and method for producing oxime |
| CN104437616A (en) * | 2014-11-21 | 2015-03-25 | 武汉工程大学 | Lamellar catalyst containing mesoporous titanium-silicate molecular sieves and preparation method and application of lamellar catalyst |
| CN104876238A (en) * | 2015-04-20 | 2015-09-02 | 吉林大学 | Method for assisted synthesis of molecular sieve by means of ultraviolet radiation |
| 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 |
| CN105645430A (en) * | 2016-02-25 | 2016-06-08 | 湖北大学 | Crystal-seed method for rapidly synthesizing Ti-MWW molecular sieves through rotation |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 阳辉: "钛硅分子筛的表征及其催化丙烯环氧化连续反应的研究", 《石油炼制与化工》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126860A (en) * | 2018-08-20 | 2019-01-04 | 青岛科技大学 | A kind of application for the method and acid mesopore molecular sieve preparing acid mesopore molecular sieve using hydrogen peroxide |
| CN109126860B (en) * | 2018-08-20 | 2021-09-10 | 青岛科技大学 | Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve |
| 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 |
| CN109231233B (en) * | 2018-10-23 | 2022-09-09 | 福州大学 | Green synthesis method and application of Ti-MWW molecular sieve |
| US10968110B2 (en) * | 2019-04-26 | 2021-04-06 | China University Of Petroleum (East China) | Method for preparing titanium silicon molecular sieve |
| CN112158856A (en) * | 2020-08-25 | 2021-01-01 | 郑州大学 | Method for preparing Ti-MWW molecular sieve |
| CN113368884A (en) * | 2021-06-15 | 2021-09-10 | 南京工程学院 | Limited-area catalyst for catalytic oxidation of carbon monoxide and preparation method thereof |
| CN115650249A (en) * | 2022-09-19 | 2023-01-31 | 中建安装集团有限公司 | Method for preparing high-performance TS-1 titanium silicalite molecular sieve at low cost |
| CN115650249B (en) * | 2022-09-19 | 2024-01-05 | 中建安装集团有限公司 | Method for preparing high-performance TS-1 titanium silicalite molecular sieve at low cost |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107188194B (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107188194B (en) | A method of preparing high catalytic activity Ti-MWW molecular sieve | |
| CN101643219B (en) | Preparation method of nano-ZSM-5 molecular sieve | |
| CN101786638B (en) | Titanium silicate molecular sieve modification method | |
| CN112158856B (en) | Method for preparing Ti-MWW molecular sieve | |
| CN104495867B (en) | The preparation method of big particle diameter HTS | |
| CN108793181A (en) | A kind of Titanium Sieve Molecular Sieve and preparation and application | |
| CN106082261B (en) | A kind of Ti MWW molecular sieves and preparation method thereof | |
| CN106044793A (en) | Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate | |
| CN104709920A (en) | Tin-containing heteroatomic functional molecular sieve and synthesis and application thereof | |
| CN105645430B (en) | A kind of method of crystal seed method rotation rapid synthesis Ti-MWW molecular sieve | |
| CN106348310A (en) | Preparation method and application of titanium-silicalite-molecular-sieve polymer | |
| CN105329909A (en) | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area | |
| CN107032366A (en) | A kind of method for preparing the HTS TS 1 with high skeleton Ti content | |
| CN109231233A (en) | A kind of green synthesis method of Ti-MWW molecular sieve and application | |
| CN104944436A (en) | Method for quickly synthesizing Ti-MWW molecular sieve | |
| CN106986351B (en) | A kind of synthetic method of titanium-silicon molecular sieve TS-1 and its application in propylene ring oxidation reaction | |
| CN109264782A (en) | A kind of method that low pressure doping prepares pucherite | |
| Zhang et al. | Green synthesis of submicron-sized Ti-rich MWW zeolite powders via a novel mechanochemical dry gel conversion in mixed steam environment | |
| CN108408737A (en) | A method of quickly preparing Y type molecular sieve | |
| CN102627292B (en) | Preparation method of TS-1 molecular sieve | |
| CN107601520A (en) | A kind of preparation method of the molecular sieves of ETS 10 | |
| CN110451522A (en) | A method of preparing TS-1 microspherical catalyst | |
| CN110436479A (en) | A kind of Titanium Sieve Molecular Sieve and its preparation method and application | |
| CN106745038B (en) | A kind of synthetic method of Ti-MWW molecular sieves | |
| CN102424398B (en) | Method for rapid synthesis of titanium silicate molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |