CN109850914A - A kind of preparation method of the nanoscale without aluminium Ti-Beta molecular sieve - Google Patents
A kind of preparation method of the nanoscale without aluminium Ti-Beta molecular sieve Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of the nanoscale without aluminium Ti-Beta molecular sieve.Compared with existing synthetic method, which directly synthesizes Ti-Beta molecular sieve by " a step steam auxiliary law ", and the limitation of organic silicon source must be used by breaching traditional " one-step method ", has obtained nanoscale without aluminium Ti-Beta molecular sieve with steam auxiliary law.Compared with the method for existing synthesis Ti-Beta, the amount of template needed for the method is down to half, and silicon source is inorganic silicon source, and synthesis does not need fluoride, and synthesis cost is low；Generated time foreshortens to 48 hours, and step is simple, can effectively reduce energy consumption；Crystallization liquid is seldom, can effectively avoid the pollution problem of a large amount of crystallization waste liquids；Also getting rid of traditional " two-step synthesis method " and " one-step synthesis " containing aluminium simultaneously must use strong acid to pre-process a large amount of spent acid emission problems of bring.
Description
Technical field
The present invention relates to a kind of preparation method of the nanoscale without aluminium Ti-Beta molecular sieve with * BEA structure, specifically
For be it is a kind of using steam booster action one-step synthesis without aluminium nanoscale Ti-Beta molecular sieve preparation method.
Background technique
Beta molecular sieve is unique molecular sieve for intersecting pore canal system with twelve-ring, have unique cellular structure,
Acid and good hydrothermal stability in hydroisomerization, is hydrocracked, shows in the reaction such as alkylating aromatic hydrocarbon, toluene disproportionation
Excellent catalytic performance out.In order to make Beta molecular sieve be more widely used, there will be excellent directional catalyzing oxidation susceptibility
Appraise at the current rate transition metal introduce Beta framework of molecular sieve prepare the hot spot that hetero-atom molecular-sieve is always the research field, as a result,
The various preparation methods of Ti-Beta molecular sieve developed in succession, and in the reaction of the green oxidation of hydrogen peroxide, such as aromatic hydrocarbons
Hydroxylating, oxidation of alcohols, alkene epoxidation, cyclohexanone oxamidinating etc., show splendid catalytic activity.
So far, the preparation method of Ti-Beta molecular sieve mainly has two-step synthesis method, a step hydrothermal synthesis method and a step
Dry gel conversion method.
The process of two-step synthesis method is as follows: pre-synthesis sial system H-Beta molecular sieve being carried out concentrated nitric acid dealuminzation first
Processing, makes its skeleton expose open silicone hydroxyl nest defective bit, then Si-Beta carrier carries out at upper titanium to treated
Reason.The post-processing approach of the one kind " wet impregnation method " such as T.Maschmeyer (Nature, 1995,378,159), by organic gold
Belong to titanium to be introduced into skeleton, but this method needs a large amount of toxic organic solvents, and effective grafting rate of titanium is lower.Later,
Titanium tetrachloride vapors are deposited on by J.Lu (J.Phys.Chem.C, 2009,113,12412) etc. with a kind of chemical vapour deposition technique
On pretreated carrier, to achieve the purpose that titanium introducing skeleton, but this methods experiment process is complicated, to experimental provision
Requirement it is relatively high, and influence of the deposition of titanium source vulnerable to factors.In order to make up the defect of " wet impregnation method ",
B.Tang (Green Chem.2014,16,2281) develops a kind of " dry impregnation method ", by titanium source and through strong acid dealuminzation
Beta carrier roasting direct after mechanical lapping, titanium is successfully introduced into the skeleton of Si-Beta, but this upper titanium method is easy
Generate anatase.In conclusion this " two-step synthesis method " all has following defects that (1) carrier has to pass through strong acid treatment, system
A large amount of spent acid waste liquid can be generated during standby；(2) effective insertion rate of titanium is low, and is highly prone to the influence of extraneous factor.
One step hydrothermal synthesis method is that titanium source is directly introduced into the method in Gel Precursor and carrying out crystallization by one kind.
T.Blasco (Chem.Commun.1996,20,2367) et al. develops the side of a step hydrothermal synthesis Ti-Beta molecular sieve for the first time
Method.But the synthesis process of this method be unable to do without this highly corrosive of HF, highly toxic mineralizer, preparation process risk is big,
And titanium source is single butyl titanate, needs to be pre-processed for a long time in hydrogen peroxide system in preparation process, no
Only make synthesis cycle too long, also creates the wasting of resources.Later, B.R.Wang (Micropor.Mesopor.Mater.2019,
278,30) limitation for et al. breaking through HF for the first time, goes out Ti-Beta molecular sieve, still, crystallization time using fluorine-containing salts one-step synthesis
Reach 10 days.Above all there is following inevitable defect: (1) crystallization excessive cycle in " one-step synthesis ", generally 7~
10 days；(2) template demand is big, general TEAOH/SiO2>=0.55, and silicon source, titanium source are all organic matter, make entirely to prepare
Cost is significantly increased；(3) crystallization waste liquid discharging amount is big, directly contributes the wasting of resources and environmental pollution, this is also hydro-thermal method synthesis
Not the drawbacks of Ti-Beta molecular sieve not can avoid.
Therefore, the defect for breaking through conventional hydrothermal synthesis, looks for a kind of low template dosage, rapidly and efficiently synthesizes Ti-Beta
The green synthesis method of molecular sieve is necessary.
1998, T.Tatsumi (J.Phys.Chem.B 1998,102,7126) was synthesized with " dry gel conversion method " for the first time
The consumption of template is down to TEAOH/SiO by Ti-Beta2=0.44, greatly reduce industrial cost.But synthesis side
Method has following defects that (1) entire synthesis cycle is long, and crystallization time is longer, needs 5 days time；(2) titanium source is four fourth of metatitanic acid
Ester, it is necessary to be pre-processed in hydrogenperoxide steam generator；(3) template consumption is higher, higher cost；(4) its synthesis process
It must be carried out under the system containing aluminium, in its system, aluminium is the necessary condition of nucleation, but in order to reduce aluminium element to reaction
The influence of system selectivity, needs subsequent sour treatment process, and this processing mode causes environmental pollution and the wasting of resources again.
In order to which adverse effect of the aluminium element to reaction to be preferably minimized, M.Ogura (J.Catal.2001,199,41) etc. exists
Synthesizing Ti-Beta in system without aluminium, but has been the absence of the aluminium element for being conducive to nucleation, the crystallization period reaches 8 days, and
And titanium source and template dosage are not still improved, entire synthesis cost is still higher.
In short, all having following defects that (1) crystallization in the method for above-mentioned " dry gel conversion method " synthesis Ti-Beta molecular sieve
Period is long, the poor repeatability of operation, and with stray crystal；(2) crystal grain is big, generally micron level.(2) silicon source is confined to positive silicic acid
Ethyl ester, titanium source are confined to butyl titanate, lead to synthesis cost height.And utilization one step of steam booster action proposed by the present invention is closed
At the method for Ti-Beta, the above-mentioned harsh problem of hydrothermal synthesis bring can not only be effectively avoided, even more one kind is more advantageous to realization
Ti-Beta molecule sieves industrialized green synthesis method on a large scale.Entire synthesis process step is simple, synthesizes without two steps, closes
Very short at the time, and titanium source and silicon source are inorganic matter, template dosage is only the half of current report amount, make entirely to synthesize at
Originally it is greatly reduced.
Summary of the invention
The object of the present invention is to provide a kind of steps simply, time-consuming is short, template consumption is few, is not necessarily to Fluorine source, silicon source, and a step is closed
At the preparation method of nanoscale Ti-Beta molecular sieve.
Method includes the following steps:
1. basic step
1) silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source is with OH?Meter, according to silicon source: titanium source: alkali source: template: water=
1:0.001~0.05:0.01~0.8:0.05~0.5:20~80 molar ratio is sufficiently mixed, and is then added and is equivalent to silicon source matter
The pure silicon crystal seed of amount 0.001%~10%, aging 0.5~2 hour under conditions of temperature is 20~80 DEG C, by the water after aging
Gel evaporates 12~48 hours in 50~100 DEG C of oil bath, obtains the xerogel of templating and seeding；
2) the resulting xerogel of step 1) is ground, according to water: dry powder quality is than being respectively placed in kettle for 0.05~1 ratio
In small liner, in 130~160 DEG C crystallization 20~96 hours, products therefrom 0.2~3mol/L ammonium salt solution intermediate ion hand over
It changes 3~12 hours, washs to neutrality and after drying, calcined 4~12 hours at 510~580 DEG C, obtain Ti-Beta molecular sieve.
2. wherein, silicon source, titanium source, alkali source, template, water molar ratio be silicon source: titanium source: alkali source: template: water=1:
0.005~0.015:0.01~0.16:0.05~0.15:30~60, the additional amount of crystal seed be silicon source quality 0.05%~
5%.
3. wherein, the aging temperature is 20~60 DEG C, the time is 0.5~1 hour, and the evaporated temperature is 60~90
DEG C, the time is 20~40 hours.
4. wherein, the mass ratio 0.1~0.5 of crystallization water and dry powder.
5. wherein, crystallization temperature is 140~160 DEG C, crystallization time is 36~72 hours.
6. wherein, the silicon source is one or more of white carbon black, silica gel, waterglass, silica solution.
7. wherein, the titanium source is one or both of ammonium titanium fluoride, titanium sulfate.
8. wherein, the organic quaternary ammonium alkaloids are tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl hydrogen
One or more of amine-oxides.
9. wherein, the alkali source is one or both of sodium hydroxide, potassium hydroxide.
10. wherein, the ammonium salt is one or more of ammonium nitrate, ammonium chloride, ammonium fluoride, ammonium phosphate.
Compared with existing synthesis Ti-Beta sieve technology, this method has following remarkable advantage: (1) one-step method is direct
Synthesis, simple process.Compared to traditional " two-step synthesis method ", the method can directly pass through " one-step synthesis " synthesize it is highly crystalline
Ti-Beta molecular sieve is spent, and synthesis process can be directly added into titanium source, not need to carry out titanium source additional processing；(2) when synthesizing
Between be greatly reduced.The method crystallization time of synthesis Ti-Beta molecular sieve provided by the invention only needs two days, when the preparation of presoma
Between only need one day, far fewer than synthesis cycle needed for current report, there is absolute predominance on time cost；(3) synthesis cost
It is greatly reduced.The half for the minimum flow that the consumption of this method template is only reported so far, and the silicon source and titanium source that use are equal
For inorganic matter, Material Cost is greatly reduced；(4) product has nano-scale dimension.It is, in general, that Ti-Beta in hydrothermal system
The partial size of molecular sieve is micron order, and the partial size that the present invention synthesizes Ti-Beta molecular sieve is nanoscale, is conducive to diffusion mass transfer；
(5) entire presence of the synthesis process without aluminium, eliminates aluminium element to the adverse effect of reaction；(6) product yield is high.Conventional hydrothermal
The crystallization process of synthesis needs a large amount of solvents, and after the completion of crystallization, there are still silicon species, titanium species, fluoride, templates in solvent
Deng part " nutriment ", therefore product yield is relatively low, and still, " steam auxiliary law " proposed by the present invention can be by all moulds
" nutriment " of plate is completely used for synthesis Ti-Beta molecular sieve, with nearly 100% product yield；(7) low pollution.It is logical
Often, the residual substance dissolved under hydrothermal condition in a solvent falls directly as pollutant emission, and almost without remnants in the present invention
Crystallization discharging of waste liquid, and synthesis process is without using hydrofluoric acid, the fluoride etc. of highly corrosive.(8) method provided by the invention
Not only it had been not necessarily to carry out carrier strong acid pretreatment, but also without carrying out strong acid dealumination treatment to crystallization product, had reduced to the maximum extent
The wasting of resources and environmental pollution.
In summary it analyzes, the method for " a step steam auxiliary law " proposed by the present invention synthesis Ti-Beta molecular sieve has
It the characteristics of making Ti-Beta molecular sieve realize heavy industrialization, synthesis cost and carrying capacity of environment is substantially reduced, greatly improves
The application field of Ti-Beta molecular sieve.
Detailed description of the invention
Fig. 1 is the XRD diagram for the Ti-Beta molecular sieve that the present invention synthesizes.
Fig. 2 is the UV-vis figure for the Ti-Beta molecular sieve that the present invention synthesizes.
Fig. 3 is the SEM figure for the Ti-Beta molecular sieve that the present invention synthesizes.
Specific embodiment
The present invention provides a kind of preparation method of nanoscale Ti-Beta molecular sieve, which is characterized in that this method includes following
Step:
1) silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source is with OH?Meter, according to silicon source: titanium source: alkali source: template: water=
1:0.001~0.05:0.01~0.8:0.05~0.5:20~80 molar ratio is sufficiently mixed, and is then added and is equivalent to silicon source matter
The pure silicon crystal seed of amount 0.001%~10%, aging 0.5~2 hour under conditions of temperature is 20~80 DEG C, by the water after aging
Gel evaporates 12~48 hours in 50~100 DEG C of oil bath, obtains the xerogel of templating and seeding；
2) the resulting xerogel of step 1) is ground, according to water: dry powder quality is than being respectively placed in kettle for 0.05~1 ratio
In small liner, in 130~160 DEG C crystallization 20~96 hours, ammonium salt solution intermediate ion exchange of the products therefrom in 1mol/L is 5 small
When, it washs to neutrality and after drying, is calcined 6 hours at 550 DEG C, obtain Ti-Beta molecular sieve.
According to the method for the present invention, in step 1) be preferably silicon source, titanium source, alkali source, template, water molar ratio be silicon
Source: titanium source: alkali source: template: water=1:0.005~0.015:0.01~0.16:0.05~0.15:30~60, crystal seed add
Enter 0.05%~5% that amount is silicon source quality.
According to the method for the present invention, what inorganic silicon source compound described in step 1) can be well known in the art is various
The solid silicon source or liquid silicon source of high quality purity.It specifically, can be one of white carbon black, silica gel, waterglass, silica solution
Or it is several, it can express good relative crystallinity.Preferably white carbon black and silica solution.
According to the method for the present invention, the various high quality that inorganic ti sources described in step 1) can be well known in the art
The solid titanium source of purity.Specifically, it can be one or both of ammonium titanium fluoride, titanium sulfate, can express good phase
To crystallinity.Preferably ammonium titanium fluoride.
According to the method for the present invention, alkali source described in step 1) is preferably sodium hydroxide.
According to the method for the present invention, the quaternary ammonium base that template described in step 1) can be well known in the art
Class.It specifically, can be one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropyl hydrogen-oxygen ammonium salt solution or several
Kind.Preferably tetraethyl ammonium hydroxide solution.
According to the method for the present invention, ammonium salt described in step 2) is ammonium nitrate, in ammonium chloride, ammonium fluoride, ammonium phosphate
It is one or more of.Preferably ammonium nitrate.
According to the method for the present invention, aging temperature described in step 1) is preferably 20~60 DEG C, and the time is preferably 0.5~1
Hour.
According to the method for the present invention, evaporated temperature described in step 1) is preferably 60~90 DEG C, and the time is preferably 20~40
Hour.
According to the method for the present invention, the method known to those skilled in the art of aging method described in step 1).
According to the method for the present invention, method method known to those skilled in the art is evaporated described in step 1).
According to the method for the present invention, the ratio of crystallization water and dry powder is preferably crystallization water: the mass ratio of dry powder in step 2)
It is 0.1~0.5.
According to the method for the present invention, crystallization temperature is preferably 140~160 DEG C in step 2), and crystallization time is preferably 36~
72 hours, and the product after ion exchange is washed to neutrality and after drying, it is calcined 6 hours at 550 DEG C.
According to the method for the present invention, washing described in step 2), drying, method of roasting by those skilled in the art public affairs
The method known.It is 2~10 hours dry at 110 DEG C after washing 3 soluble ions for example, by using deionized water.
According to the method for the present invention, crystallization process in step 2) crystallization process well known in the art, the crystallization mistake
Journey is static crystallization process.
Below by way of specific embodiment, the present invention will be described in detail, but the present invention is not restricted to following implementations
Example.
Reagent in following embodiment, various silicon sources are purchased from Shanghai Shan Bo Industrial Co., Ltd., titanium source and organic formwork
Agent is purchased from West Asia reagent Co., Ltd, remaining reagent is purchased from Sinopharm Chemical Reagent Co., Ltd..
The mole of silicon source in following embodiment is with SiO2It counts, the mole of titanium source is with TiO2The mole of meter, template
With TEA+Meter, the quality of silicon source is with contained SiO2Meter.
Embodiment 1
The present embodiment is used to illustrate a kind of preparation method of nanoscale Ti-Beta molecular sieve.
First by silicon source, titanium source, alkali source, template, water according to white carbon black: ammonium titanium fluoride: NaOH:TEAOH:H2O=1:
The molar ratio of 0.015:0.1:0.15:50 is sufficiently mixed, and the crystal seed for being equivalent to silicon source quality 5% is then added, and is 30 in temperature
Aging 0.5 hour under conditions of DEG C.Hydrogel after aging is evaporated 24 hours in 60 DEG C of oil bath, obtains templating and crystalline substance
The xerogel of kindization.Resulting xerogel is ground to no granular sensation, takes 10g to be put in small liner, then put it into and fill 1g
In the crystallizing kettle of the 50ml of water, kettle is sealed, in 145 DEG C crystallization 60 hours, products therefrom is in 0.5mol/L ammonium nitrate solution
It ion exchange 12 hours, washs to neutrality and after drying, is calcined 8 hours at 510 DEG C, obtain product S1.Its XRD as shown in Figure 1,
UV-vis is as shown in Fig. 2, SEM is as shown in Figure 3.Wherein in Fig. 1, a is the original powder spectrogram before roasting, and b is the sample spectra after roasting
Figure.
Embodiment 2
The present embodiment is used to illustrate a kind of preparation method of nanoscale Ti-Beta molecular sieve.
First by silicon source, titanium source, alkali source, template, water according to white carbon black: titanium sulfate: NaOH:TEAOH:H2O=1:
The molar ratio of 0.01:0.16:0.05:40 is sufficiently mixed, and the crystal seed for being equivalent to silicon source quality 1% is then added, and is 30 in temperature
Aging 0.5 hour under conditions of DEG C.Hydrogel after aging is evaporated 36 hours in 50 DEG C of oil bath, obtains templating and crystalline substance
The xerogel of kindization.Resulting xerogel is ground to no granular sensation, takes 10g to be put in small liner, then put it into and fill 5g
In the 50ml crystallizing kettle of water, kettle is sealed, in 135 DEG C crystallization 72 hours, products therefrom in 2.5mol/L ammonium nitrate solution from
Son exchange 5 hours, is washed to neutrality and after drying, and is calcined 12 hours at 550 DEG C, is obtained product S2.Its characterization result and implementation
Example 1 it is consistent.
Embodiment 3
The present embodiment is used to illustrate a kind of preparation method of nanoscale Ti-Beta molecular sieve.
First by silicon source, titanium source, alkali source, template, water according to silica gel: titanium sulfate: NaOH:TEAOH:H2O=1:
The molar ratio of 0.015:0.09:0.0.1:40 is sufficiently mixed, and the crystal seed for being equivalent to silicon source quality 3% is then added, is in temperature
Aging 2 hours under conditions of 30 DEG C.Hydrogel after aging is evaporated 15 hours in 100 DEG C of oil bath, obtain templating and
The xerogel of seeding.Resulting xerogel is ground to no granular sensation, takes 10g to be put in small liner, then put it into and fill
In the crystallizing kettle of the 50ml of 1.5g water, kettle is sealed, in 160 DEG C crystallization 48 hours, products therefrom is in 3mol/L ammonium nitrate solution
Intermediate ion exchanges 5 hours, washs to neutrality and after drying, and calcines 6 hours at 580 DEG C, obtains product S3.Its characterization result and reality
Apply the consistent of example 1.
Embodiment 4
The present embodiment is used to illustrate a kind of preparation method of nanoscale Ti-Beta molecular sieve.
First by silicon source, titanium source, alkali source, template: water is according to silica solution: ammonium titanium fluoride: NaOH:TEAOH:H2O=1:
The molar ratio of 0.008:0.16:0.06:50 is sufficiently mixed, and the crystal seed for being equivalent to silicon source quality 1% is then added, and is 30 in temperature
Aging 1.5 hours under conditions of DEG C.Hydrogel after aging is evaporated 40 hours in 70 DEG C of oil bath, obtains templating and crystalline substance
The xerogel of kindization.Resulting xerogel is ground to no granular sensation, takes 10g to be put in small liner, then put it into and fill 4g
In the crystallizing kettle of water, kettle is sealed, in 160 DEG C crystallization 72 hours, products therefrom 1.5mol/L ammonium nitrate solution intermediate ion hand over
It changes 7 hours, washs to neutrality and after drying, calcined 6 hours at 560 DEG C, obtain product S4.Its characterization result and embodiment 1
Unanimously.
Embodiment 5
The present embodiment is used to illustrate a kind of preparation method of nanoscale Ti-Beta molecular sieve.
First by silicon source, titanium source, alkali source, template, water according to white carbon black: ammonium titanium fluoride: NaOH:TEAOH:H2O=1:
The molar ratio of 0.009:0.05:0.15:50 is sufficiently mixed, and the crystal seed for being equivalent to silicon source quality 5% is then added, and is 40 in temperature
Aging 0.5 hour under conditions of DEG C.Hydrogel after aging is evaporated 24 hours in 60 DEG C of oil bath, obtains templating and crystalline substance
The xerogel of kindization.Resulting xerogel is ground to no granular sensation, takes 10g to be put in small liner, then put it into and fill
In the crystallizing kettle of 2.5g water, kettle is sealed, in 150 DEG C crystallization 60 hours, products therefrom is in 1mol/L ammonium nitrate solution intermediate ion
Exchange 4 hours is washed to neutrality and after drying, and is calcined 8 hours at 550 DEG C, is obtained product S5.Its characterization result and embodiment 1
It is consistent.
By above data it is found that the Ti-Beta molecular sieve synthesized with " a step steam auxiliary law " provided by the invention
Having high crystallinity and purity, crystal grain is nanoscale.In summary it analyzes, " a step steam auxiliary law " proposed by the present invention synthesis
The method of nanoscale Ti-Beta molecular sieve have make Ti-Beta molecular sieve realize heavy industrialization the characteristics of, make synthesis at
This and carrying capacity of environment substantially reduce, and the application field of Beta molecular sieve greatly improved.
Claims (10)
1. a kind of preparation method of nanoscale Ti-Beta molecular sieve, which is characterized in that method includes the following steps:
1) silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source is with OH?Meter, according to silicon source: titanium source: alkali source: template: water=1:
0.001~0.05:0.01~0.8:0.05~0.5:20~80 molar ratio is sufficiently mixed, and is then added and is equivalent to silicon source quality
0.001%~10% pure silicon crystal seed, aging 0.5~2 hour under conditions of temperature is 20~80 DEG C；By the water-setting after aging
Glue evaporates 12~48 hours at 50~100 DEG C, obtains the xerogel of templating and seeding；
2) the resulting xerogel of step 1) is ground, according to water: dry powder quality is respectively placed in kettle and small than the ratio for 0.05~1
In liner, in 130~160 DEG C crystallization 20~96 hours, products therefrom 0.2~3mol/L ammonium salt solution intermediate ion exchange 3
It~12 hours, washs to neutrality and after drying, is calcined 4~12 hours at 510~580 DEG C, obtain Ti-Beta molecular sieve.
2. according to the method described in claim 1, wherein, in step 1), silicon source, titanium source, the molar ratio of alkali source, template, water
For silicon source: titanium source: alkali source: template: water=1:0.005~0.015:0.01~0.16:0.05~0.15:30~60, crystal seed
Additional amount be silicon source quality 0.05%~5%.
3. in step 1), the aging temperature is 20~60 DEG C according to the method described in claim 1, wherein, the time 0.5
~1 hour；The evaporated temperature is 60~90 DEG C, and the time is 20~40 hours.
4. according to the method described in claim 1, wherein, in step 2), the mass ratio 0.1~0.5 of crystallization Shi Shuiyu dry powder.
5. according to the method described in claim 1, wherein, in step 2), crystallization temperature is 140~160 DEG C, crystallization time 36
~72 hours.
6. method according to claim 1 or 2, wherein the silicon source is white carbon black, in silica gel, waterglass, silica solution
One or more.
7. method according to claim 1 or 2, wherein the titanium source is one of ammonium titanium fluoride, titanium sulfate or two
Kind.
8. method according to claim 1 or 2, wherein the organic quaternary ammonium alkaloids be tetramethylammonium hydroxide,
One or more of tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide.
9. method according to claim 1 or 2, wherein the alkali source be one of sodium hydroxide, potassium hydroxide or
Two kinds.
10. according to the method described in claim 2, wherein, the ammonium salt is ammonium nitrate, in ammonium chloride, ammonium fluoride, ammonium phosphate
One or more.
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| CN110422854A (en) * | 2019-07-25 | 2019-11-08 | 东北大学 | A kind of preparation method that pure silicon beta molecular sieve is nanocrystalline |
| CN111439756A (en) * | 2020-04-07 | 2020-07-24 | 福州大学 | Preparation method of cascade pore heteroatom M-Beta molecular sieve |
| CN112624142A (en) * | 2021-01-19 | 2021-04-09 | 吉林大学 | Preparation method of nano hierarchical pore Beta molecular sieve |
| CN112742453A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of titanium-containing molecular sieve, catalyst and selective oxidation method |
| CN113443635A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | Titanium-containing Beta molecular sieve and synthesis method thereof |
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| CN110422855A (en) * | 2019-07-25 | 2019-11-08 | 东北大学 | A kind of preparation method that Ti-beta molecular sieve is nanocrystalline |
| CN110422854A (en) * | 2019-07-25 | 2019-11-08 | 东北大学 | A kind of preparation method that pure silicon beta molecular sieve is nanocrystalline |
| CN112742453A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of titanium-containing molecular sieve, catalyst and selective oxidation method |
| CN113443635A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | Titanium-containing Beta molecular sieve and synthesis method thereof |
| CN113443635B (en) * | 2020-03-26 | 2023-02-10 | 中国石油天然气股份有限公司 | Titanium-containing Beta molecular sieve and synthesis method thereof |
| CN111439756A (en) * | 2020-04-07 | 2020-07-24 | 福州大学 | Preparation method of cascade pore heteroatom M-Beta molecular sieve |
| CN112624142A (en) * | 2021-01-19 | 2021-04-09 | 吉林大学 | Preparation method of nano hierarchical pore Beta molecular sieve |
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