CN106629762A - Method for rapidly synthesizing TS-1 (Titanium Silicalite-1) molecular sieve by utilizing molecular-sieve hydrothermal-crystallization filter liquor - Google Patents
Method for rapidly synthesizing TS-1 (Titanium Silicalite-1) molecular sieve by utilizing molecular-sieve hydrothermal-crystallization filter liquor Download PDFInfo
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- 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
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Abstract
The invention relates to a titanium silicalite molecular sieve and a synthesis method thereof. According to the method, filtrate after the hydrothermal crystallization in the process of preparing the titanium silicalite molecular sieve is treated, then is used as a substituting or partially substituting template, and is mixed with a silicon source and a titanium source; an obtained first mixture is agitated and hydrolyzed, and then is put in a hydrothermal synthesis kettle to be crystallized; a TS-1 (Titanium Silicalite-1) molecular sieve is obtained through filtration, washing and roasting; the filtrate after the hydrothermal crystallization can be recycled. The titanium silicalite molecular sieve provided by the invention is short in crystallization time and little in waste liquid; the hydrothermal-crystallization filtrate is not obviously decreased in catalytic activity after being recycled for multiple times; the total dosage of the template is reduced by a wide margin; the total yield of the titanium silicalite molecular sieve is improved; the synthesis cost of the titanium silicalite molecular sieve is reduced.
Description
Technical field
The invention belongs to Zeolite synthesis field, specifically a kind of Fast back-projection algorithm of utilization zeolite-water thermal crystallisation filtrate
The method of TS-1 HTSs.
Background technology
HTS (TS-1) is a kind of hetero-atom molecular-sieve with MFI topological structure, with 1981 first by anticipating
The Marco Taramasso of big profit et al. synthesis.Titanium atom is introduced in the silicon skeleton of MFI structure and forms special Ti-O- by it
Si keys, form a kind of catalyst with superior catalytic oxidation activity.It is various with hydrogen peroxide as oxidant that TS-1 is used for catalysis
Organic reaction system in, show good selectivity, its reaction condition is gentle, and by-product is few, with good atom Jing
Ji property and environment friendly, can be widely applied to many fields such as petrochemical industry, show good application potential and good
Development prospect.
The catalysis activity of TS-1 HTSs is closely related with its synthetic method.Classical hydrothermal synthesis method uses metatitanic acid four
Butyl ester is mixed with polyhydric alcohol as template as silicon source, TPAOH aqueous solution as titanium source, tetraethyl orthosilicate
Hydrolysis after even, crystallization liquid is obtained except alcohol, filter, washing, be dried, obtain molecular sieve TS-1 after roasting Jing after hydrothermal crystallizing.It is classical
Hydrothermal synthesis method uses expensive TPAOH as template, and synthesis cost is very high；The TS-1 molecules of synthesis
The former powder of sieve belongs to nanoscale molecular sieve, has many sieve particles in the filtrate after filtration so that under final molecular sieve yield
Drop；The effective group in part containing template in filtrate after hydrothermal crystallizing, in prior synthesizing method as waste liquid not
Have and utilize to greatest extent.
The content of the invention
It is an object of the invention to provide a kind of Fast back-projection algorithm TS-1 titanium silicon molecules of utilization zeolite-water thermal crystallisation filtrate
The method of sieve, filtrate of the method in recycle traditional HTS synthetic method after hydrothermal crystallizing, after reduction
The usage amount of template in continuous synthesis step, reduces synthesis cost；TS-1 sieve particles in filtrate can be used as secondary water
Nucleus during thermal crystallisation, reduces the secondary crystallization time；Due to recycling filtrate, the waste liquid produced in overall process subtracts
Few, so as to improve the utilization rate of titanium source and silicon source on the whole, and the overall yield of HTS is also improved largely.
The present invention is achieved by the following technical solutions：A kind of Fast back-projection algorithm of utilization zeolite-water thermal crystallisation filtrate
The method of TS-1 HTSs, comprises the steps：
(1) process of hydrothermal crystallizing filtrate
During HTS will be prepared, hydrothermal crystallizing filtrate is cooled to room temperature, and 10～40min of supersound process is filtered
Go out liquid A, it is standby；
(2) prepared by crystallization liquid
At a temperature of 25 DEG C, filter liquor A is mixed with template, pH to 9～12 is adjusted with ammonia and stir 15min, obtained
To mixed liquid B；Under 25 DEG C of constant temperature stirrings, silicon source is slowly added in mixed liquid B, stirs 0.5～3h, obtain mixed liquor
C1；The silicon source available silicon content SiO added in mixed liquor C12It is 1 with filter liquor mass ratio:(2.7～4.2)；
Titanium source is added in polyhydric alcohol, at a temperature of 25 DEG C, constant temperature stirs 0.5～3h, obtains mixed liquor C2, wherein titanium source
TiO2Mol ratio with polyhydric alcohol is 1：(2～10)；Under stirring, mixed liquor C2 is added dropwise in mixed liquor C1, is mixed
40～50 DEG C are gradually heating to after the completion of conjunction, 0.5～1h of insulated and stirred；70～90 DEG C are warming up to again, and 2～4h of alcohol is caught up with insulation,
And continue moisturizing to keep liquid level constant, finally give crystallization liquid；New silicon source SiO for adding in crystallization liquid2：Titanium source TiO2：Template
The mol ratio of agent is 1:(0.010～0.080):(0～0.10)；
(3) hydrothermal crystallizing
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, 16～42h of crystallization at a temperature of 165～190 DEG C, after taking-up through
Filter, washing, be dried, TS-1 HTSs obtained after roasting；Abovementioned steps are iteratively repeated, zeolite-water thermal crystallisation filtrate is realized
Repetition recycle.
The hydrothermal crystallizing filtrate utilized in step (1) of the present invention can be using existing (including classics) HTS synthesis
Method or the filtrate to existing similar method after the hydrothermal crystallizing during Hydrothermal Synthesiss, or step of the present invention (3)
Filtrate after middle hydrothermal crystallizing.The available silicon content SiO of silicon source2As with SiO in silicon source2The quality of calculating.
In the present invention, in crystallization liquid, the new silicon source for adding, titanium source and template only refer only to the middle addition of step (2)
Silicon source, titanium source and template.
Compared with prior art, the technology of the present invention has following remarkable advantage：
1. secondary HTS synthesis, the nanometer in filtrate point are carried out for raw material due to adopting the filtrate after hydrothermal crystallizing
Son sieve as the crystal seed of secondary crystallization, therefore can be minimized the time required to hydrothermal crystallizing, reduces the response time；
2., using hydrothermal crystallizing filtrate as one of template raw material, substitute to a certain extent or part instead of template
The consumption of agent, relative to traditional TS-1 Zeolite synthesis method, the total consumption of template is reduced；
3. hydrothermal crystallizing filtrate is recycled, the generation of experimental waste liquid can be greatly lowered, while not divided in filtrate
From molecular sieve the overall yield of molecular sieve can be improve with secondary utilization；
4. HTS is prepared using the inventive method recycled for multiple times hydrothermal crystallizing filtrate, its molecular sieve catalytic
Can decline not substantially, in phenol hydroxylation experiment, after three circulations prepare molecular sieve, its conversion ratio declines 2.5%.
Description of the drawings
Fig. 1 be embodiment it is 2-in-1 into molecular sieve SEM electron microscopic pictures.
Fig. 2 is the molecular sieve SEM electron microscopic pictures of the synthesis of embodiment 4.
Fig. 3 is the molecular sieve SEM electron microscopic pictures of the synthesis of embodiment 5.
Fig. 4 is the change of molecular sieve phenol conversion in phenol hydroxylation evaluation test of the synthesis of embodiment 0,2,4,5
Trendgram.
Fig. 5 be embodiment it is 2-in-1 into molecular sieve XRD spectra.
Specific embodiment
The invention will be further described for following examples, does not carry out considered critical to the scope of the present invention.
In the present invention, the silicon source is tetraalkyl esters of silicon acis, and the formula of tetraalkyl esters of silicon acis is Si (OR1)4, R1For alkyl,
As preferred R1It is the alkyl with 2～4 carbon atoms.
When being embodied as, the titanium source is tetraalkyl titanate, and its formula is Ti (OR2)4, R2For alkyl, as preferred R2
It is the alkyl with 2～4 carbon atoms.
In the hydrothermal crystallizing filtrate of step (1) of the present invention and step (2) crystallization liquid, the template is tetrapropyl hydrogen-oxygen
Change one or more in ammonium, tetraethyl ammonium hydroxide, TBAH, 4-propyl bromide, diethylamine, carbamide to appoint
The mixture of meaning ratio mixing.For example, mass ratio is 1:1:1 TPAOH, tetraethyl ammonium hydroxide, tetrabutylammonium hydrogen
Amine-oxides；Mass ratio is 1:2 TBAH, 4-propyl bromide；Mass ratio is 3:2 diethylamine, carbamide.
During concrete application, the polyhydric alcohol is selected from normal propyl alcohol, isopropanol, n-butyl alcohol, ethylene glycol.
Embodiment 0
The acquisition of hydrothermal crystallizing liquid：
Using Thangaraj et al. methods prepare conventional HTS (Zeolites, 1992, Vol.12, p943～
950), specific embodiment is as follows：
Template is added in silicon source, 25 DEG C of stirring hydrolysis 1.5h obtain mixed liquor D1；Titanium source is added in polyhydric alcohol,
Mol ratio is 1:5,25 DEG C of stirring 1h, obtain mixed liquor D2；Under stirring, mixed liquor D2 is added dropwise over into mixed liquor D1
In, 50 DEG C are gradually heating to after the completion of mixing, 0.5h is stirred；85 DEG C are warming up to again, are caught up with alcohol 2h, and are continued moisturizing to keep liquid
Face is constant.Settled solution is obtained, wherein each material ratio (mole) silicon source SiO2：Titanium source TiO2：Template：Water is 1:0.070:
0.50:20。
Above-mentioned solution is transferred in Hydrothermal Synthesiss kettle, in 180 DEG C of crystallization 75h, is filtered after taking-up.Filter cake is washed
Wash, be dried, titanium-silicon molecular sieve TS-1 is obtained after roasting implementing sample 0.
Embodiment 1
The filtrate of embodiment 0 is cooled to into room temperature, supersound process 30min obtains filter liquor A, standby.
At a temperature of 25 DEG C, filter liquor A ammonia is adjusted into pH to 12 and 15min is stirred, mixed liquid B is obtained；At 25 DEG C
Under constant temperature stirring, silicon source is slowly added in mixed liquid B, stirs 3h, obtain mixed liquor C1.The silicon added in mixed liquor C1
Source available silicon content SiO2It is 1 with filter liquor mass ratio:4.2, silicon source SiO of addition2It is 1 with the template mol ratio for adding:0.
Titanium source is added in polyhydric alcohol, mol ratio is 1:At a temperature of 3,25 DEG C, constant temperature stirring 0.5h, obtains mixed liquor C2；
Under stirring, mixed liquor C2 is added dropwise in mixed liquor C1, after the completion of mixing, is gradually heating to 40 DEG C, insulated and stirred 1h,
70 DEG C are warming up to again, and alcohol 2h is caught up with insulation, and continues moisturizing to keep liquid level constant；Finally give crystallization liquid.Add in crystallization liquid
Silicon source SiO for entering2：Titanium source TiO2：The mol ratio of template is 1:0.010:0.
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, crystallization 20h at a temperature of 165 DEG C is filtered after taking-up.By filter cake
Titanium-silicon molecular sieve TS-1 is obtained after washing, dry, roasting and implements sample 1.
The silicon source be tetraethyl orthosilicate, the titanium source be butyl titanate, the polyhydric alcohol be isopropanol, the template
Agent is 25% TPAOH aqueous solution.
Embodiment 2
The filtrate of embodiment 0 is cooled to into room temperature, supersound process 10min obtains filter liquor A, standby.
At a temperature of 25 DEG C, filter liquor A is mixed with template, pH to 11 is adjusted with ammonia and stir 15min, mixed
Close liquid B；Under 25 DEG C of constant temperature stirrings, silicon source is slowly added in mixed liquid B, stirs 2h, obtain mixed liquor C1.Mixed liquor
The silicon source available silicon content SiO added in C12It is 1 with filter liquor mass ratio:3.5, silicon source SiO of addition2With the template for adding
Mol ratio is 1:0.05.
Titanium source is added in polyhydric alcohol, mol ratio is 1:At a temperature of 5,25 DEG C, constant temperature stirring 1h, obtains mixed liquor C2；Stirring
Mix under state, mixed liquor C2 is added dropwise in mixed liquor C1, after the completion of mixing, be gradually heating to 45 DEG C, insulated and stirred 0.5h,
80 DEG C are warming up to again, and alcohol 3h is caught up with insulation, and continues moisturizing to keep liquid level constant；Finally give crystallization liquid.Add in crystallization liquid
Silicon source SiO for entering2：Titanium source TiO2：The mol ratio of template is 1:0.070:0.05.
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, crystallization 24h at a temperature of 170 DEG C is filtered after taking-up.By filter cake
Titanium-silicon molecular sieve TS-1 is obtained after washing, dry, roasting and implements sample 2.
The silicon source be tetraethyl orthosilicate, the titanium source be butyl titanate, the polyhydric alcohol be isopropanol, the template
Agent is 25% TPAOH aqueous solution.
Embodiment 3
The filtrate of embodiment 0 is cooled to into room temperature, supersound process 40min obtains filter liquor A, standby.
At a temperature of 25 DEG C, filter liquor A is mixed with template, pH to 9 is adjusted with ammonia and stir 15min, mixed
Close liquid B；Under 25 DEG C of constant temperature stirrings, silicon source is slowly added in mixed liquid B, stirs 1h, obtain mixed liquor C1.Mixed liquor
The silicon source available silicon content SiO added in C12It is 1 with filter liquor mass ratio:2.7, silicon source SiO of addition2With the template for adding
Mol ratio is 1:0.10.
Titanium source is added in polyhydric alcohol, mol ratio is 1:At a temperature of 10,25 DEG C, constant temperature stirring 3h, obtains mixed liquor C2；
Under stirring, mixed liquor C2 is added dropwise in mixed liquor C1, after the completion of mixing, is gradually heating to 50 DEG C, insulated and stirred 1h,
90 DEG C are warming up to again, and alcohol 4h is caught up with insulation, and continues moisturizing to keep liquid level constant；Finally give crystallization liquid.Add in crystallization liquid
Silicon source SiO for entering2：Titanium source TiO2：The mol ratio of template is 1:0.040:0.10.
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, crystallization 42h at a temperature of 180 DEG C is filtered after taking-up.By filter cake
Titanium-silicon molecular sieve TS-1 is obtained after washing, dry, roasting and implements sample 3.
The silicon source be tetraethyl orthosilicate, the titanium source be butyl titanate, the polyhydric alcohol be isopropanol, the template
Agent is 25% TPAOH aqueous solution.
Embodiment 4
The filtrate of embodiment 2 is cooled to into room temperature, supersound process 30min obtains filter liquor A, standby.
At a temperature of 25 DEG C, filter liquor A is mixed with template, pH to 11 is adjusted with ammonia and stir 15min, mixed
Close liquid B；Under 25 DEG C of constant temperature stirrings, silicon source is slowly added in mixed liquid B, stirs 2h, obtain mixed liquor C1.Mixed liquor
The silicon source available silicon content SiO added in C12It is 1 with filter liquor mass ratio:3.5, silicon source SiO of addition2With the template for adding
Mol ratio is 1:0.05.
Titanium source is added in polyhydric alcohol, mol ratio is 1:At a temperature of 5,25 DEG C, constant temperature stirring 1h, obtains mixed liquor C2；Stirring
Mix under state, mixed liquor C2 is added dropwise in mixed liquor C1, after the completion of mixing, be gradually heating to 45 DEG C, insulated and stirred 0.5h,
80 DEG C are warming up to again, and alcohol 3h is caught up with insulation, and continues moisturizing to keep liquid level constant；Finally give crystallization liquid.Add in crystallization liquid
Silicon source SiO for entering2：Titanium source TiO2：The mol ratio of template is 1:0.070:0.05.
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, crystallization 24h at a temperature of 170 DEG C is filtered after taking-up.By filter cake
Titanium-silicon molecular sieve TS-1 is obtained after washing, dry, roasting and implements sample 4.
The silicon source be tetraethyl orthosilicate, the titanium source be butyl titanate, the polyhydric alcohol be isopropanol, the template
Agent is 25% TPAOH aqueous solution.
Embodiment 5
The filtrate of embodiment 4 is cooled to into room temperature, supersound process 30min obtains filter liquor A, standby.
At a temperature of 25 DEG C, filter liquor A is mixed with template, pH to 11 is adjusted with ammonia and stir 15min, mixed
Close liquid B；Under 25 DEG C of constant temperature stirrings, silicon source is slowly added in mixed liquid B, stirs 2h, obtain mixed liquor C1.Mixed liquor
The silicon source available silicon content SiO added in C12It is 1 with filter liquor mass ratio:3.5, silicon source SiO of addition2With the template for adding
Mol ratio is 1:0.05.
Titanium source is added in polyhydric alcohol, mol ratio is 1:At a temperature of 5,25 DEG C, constant temperature stirring 1h, obtains mixed liquor C2；Stirring
Mix under state, mixed liquor C2 is added dropwise in mixed liquor C1, after the completion of mixing, be gradually heating to 45 DEG C, insulated and stirred 0.5h,
80 DEG C are warming up to again, and alcohol 3h is caught up with insulation, and continues moisturizing to keep liquid level constant；Finally give crystallization liquid.Add in crystallization liquid
Silicon source SiO for entering2：Titanium source TiO2：The mol ratio of template is 1:0.070:0.05.
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, crystallization 24h at a temperature of 170 DEG C is filtered after taking-up.By filter cake
Titanium-silicon molecular sieve TS-1 is obtained after washing, dry, roasting and implements sample 5.
The silicon source be tetraethyl orthosilicate, the titanium source be butyl titanate, the polyhydric alcohol be isopropanol, the template
Agent is 25% TPAOH aqueous solution.
Embodiment 6
The filtrate of embodiment 0 is cooled to into room temperature, supersound process 30min obtains filter liquor A, standby.
At a temperature of 25 DEG C, filter liquor A is mixed with template, pH to 11 is adjusted with ammonia and stir 15min, mixed
Close liquid B；Under 25 DEG C of constant temperature stirrings, silicon source is slowly added in mixed liquid B, stirs 2h, obtain mixed liquor C1.Mixed liquor
The silicon source available silicon content SiO added in C12It is 1 with filter liquor mass ratio:3.5, silicon source SiO of addition2With the template for adding
Mol ratio is 1:0.05.
Titanium source is added in polyhydric alcohol, mol ratio is 1:At a temperature of 8,25 DEG C, constant temperature stirring 1h, obtains mixed liquor C2；Stirring
Mix under state, mixed liquor C2 is added dropwise in mixed liquor C1, after the completion of mixing, be gradually heating to 50 DEG C, insulated and stirred 1h, then
Secondary to be warming up to 80 DEG C, alcohol 2.5h is caught up with insulation, and continues moisturizing to keep liquid level constant；Finally give crystallization liquid.Add in crystallization liquid
Silicon source SiO for entering2：Titanium source TiO2：The mol ratio of template is 1:0.030:0.05.
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, crystallization 16h at a temperature of 190 DEG C is filtered after taking-up.By filter cake
Titanium-silicon molecular sieve TS-1 is obtained after washing, dry, roasting and implements sample 6.
The silicon source be tetraethyl orthosilicate, the titanium source be butyl titanate, the polyhydric alcohol be isopropanol, the template
Agent is diethylamine.
Embodiment 7
The filtrate of embodiment 0 is cooled to into room temperature, supersound process 30min obtains filter liquor A, standby.
At a temperature of 25 DEG C, filter liquor A is mixed with template, pH to 12 is adjusted with ammonia and stir 15min, mixed
Close liquid B；Under 25 DEG C of constant temperature stirrings, silicon source is slowly added in mixed liquid B, stirs 0.5h, obtain mixed liquor C1.Mixing
The silicon source available silicon content SiO added in liquid C12It is 1 with filter liquor mass ratio:3.5, silicon source SiO of addition2With the template for adding
Agent mol ratio is 1:0.05.
Titanium source is added in polyhydric alcohol, mol ratio is 1:At a temperature of 2,25 DEG C, constant temperature stirring 1h, obtains mixed liquor C2；Stirring
Mix under state, mixed liquor C2 is added dropwise in mixed liquor C1, after the completion of mixing, be gradually heating to 45 DEG C, insulated and stirred 0.5h,
80 DEG C are warming up to again, and alcohol 3.0h is caught up with insulation, and continues moisturizing to keep liquid level constant；Finally give crystallization liquid.In crystallization liquid
Silicon source SiO of addition2：Titanium source TiO2：The mol ratio of template is 1:0.080:0.05.
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, crystallization 16h at a temperature of 190 DEG C is filtered after taking-up.By filter cake
Titanium-silicon molecular sieve TS-1 is obtained after washing, dry, roasting and implements sample 7.
The silicon source be tetraethyl orthosilicate, the titanium source be butyl titanate, the polyhydric alcohol be isopropanol, the template
Agent is diethylamine.
Test
The catalytic performance that probe reaction evaluates TS-1 molecular screen primary powders of the present invention is turned to phenolic hydroxy.Implementation steps are：
20.00g phenol, 20.00g acetone, 1.200g molecular sieves are added in reaction there-necked flask, top backflow, side is
Thermometer and charge door, oil bath heating add 9.000g hydrogen peroxide, 75 DEG C of reaction 2h to 75 DEG C.Determine product neighbour's benzene
Conversion ratio of the gross production rate of diphenol and hydroquinone as phenol.As a result it is as shown in table 1.
1 embodiment phenol conversion of table
| Sample number into spectrum | Phenol conversion (%) |
| Implement sample 0 | 24.69 |
| Implement sample 1 | 18.67 |
| Implement sample 2 | 24.56 |
| Implement sample 3 | 22.65 |
| Implement sample 4 | 24.32 |
| Implement sample 5 | 24.08 |
| Implement sample 6 | 21.34 |
| Implement sample 7 | 23.89 |
In comparison sheet 1, each group embodiment understands, is substituted using hydrothermal crystallizing filtrate or part alternate template agent carries out TS-1
In HTS original powder method, the new amount for adding titanium source affects maximum to the catalytic performance of molecular sieve, adds when titanium source is improved
During amount, phenol conversion increases.Contrast is implemented sample 0,2,4,5 and is understood, recycles filtrate using the inventive method and prepares TS-1
HTS original powder can keep its catalysis activity substantially, can relative to traditional TS-1 HTSs original powder, preparation method thereof
To save substantial amounts of template.
Claims (5)
1. a kind of method of the Fast back-projection algorithm TS-1 HTSs of utilization zeolite-water thermal crystallisation filtrate, it is characterised in that bag
Include following steps：
（1）The process of hydrothermal crystallizing filtrate
During HTS will be prepared, hydrothermal crystallizing filtrate is cooled to room temperature, and 10 ~ 40min of supersound process obtains filter liquor
A, it is standby；
（2）It is prepared by crystallization liquid
At a temperature of 25 DEG C, filter liquor A is mixed with template, pH to 9 ~ 12 is adjusted with ammonia and stir 15min, mixed
Liquid B；Under 25 DEG C of constant temperature stirrings, silicon source is slowly added in mixed liquid B, stirs 0.5 ~ 3h, obtain mixed liquor C1；Mixing
The silicon source available silicon content SiO added in liquid C12It is 1 with filter liquor mass ratio:（2.7~4.2）；
Titanium source is added in polyhydric alcohol, at a temperature of 25 DEG C, constant temperature stirs 0.5 ~ 3h, obtains mixed liquor C2, wherein titanium source TiO2With it is many
The mol ratio of first alcohol is 1：（2~10）；Under stirring, mixed liquor C2 is added dropwise in mixed liquor C1, after the completion of mixing by
40 ~ 50 DEG C are warming up to gradually, 0.5 ~ 1h of insulated and stirred；70 ~ 90 DEG C are warming up to again, and 2 ~ 4h of alcohol is caught up with insulation, and continues moisturizing to protect
Hold liquid level constant, finally give crystallization liquid；New silicon source SiO for adding in crystallization liquid2：Titanium source TiO2：The mol ratio of template is 1:
（0.010~0.080）:（0~0.10）；
（3）Hydrothermal crystallizing
Crystallization liquid is transferred in Hydrothermal Synthesiss kettle, 16 ~ 42h of crystallization at a temperature of 165 ~ 190 DEG C, after taking-up Jing filter, washing,
TS-1 HTSs are obtained after dry, roasting；Abovementioned steps are iteratively repeated, the repetition of zeolite-water thermal crystallisation filtrate is realized again
Utilize.
2. the Fast back-projection algorithm TS-1 HTSs of a kind of utilization zeolite-water thermal crystallisation filtrate according to claim 1
Method, it is characterised in that the silicon source is tetraalkyl esters of silicon acis, and the formula of tetraalkyl esters of silicon acis is Si（OR1）4, R1For alkyl.
3. the Fast back-projection algorithm TS-1 HTSs of a kind of utilization zeolite-water thermal crystallisation filtrate according to claim 1
Method, it is characterised in that the titanium source is tetraalkyl titanate, and its formula is Ti（OR2）4, R2For alkyl.
4. the Fast back-projection algorithm TS-1 HTSs of a kind of utilization zeolite-water thermal crystallisation filtrate according to claim 1
Method, it is characterised in that the template be TPAOH, tetraethyl ammonium hydroxide, TBAH, 4 third
The mixture that one or more in base ammonium bromide, diethylamine, carbamide is mixed with arbitrary proportion.
5. the Fast back-projection algorithm TS-1 HTSs of a kind of utilization zeolite-water thermal crystallisation filtrate according to claim 1
Method, it is characterised in that the polyhydric alcohol is selected from normal propyl alcohol, isopropanol, n-butyl alcohol, ethylene glycol.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107500309A (en) * | 2017-08-18 | 2017-12-22 | 鲁西催化剂有限公司 | A kind of preparation method of HTS |
| CN109721065A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method |
| CN110028078A (en) * | 2019-04-24 | 2019-07-19 | 清华大学 | A kind of preparation method of Titanium Sieve Molecular Sieve |
| CN111186845A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing hierarchical pore TS-1 molecular sieve |
| CN112758951A (en) * | 2020-12-31 | 2021-05-07 | 中海油天津化工研究设计院有限公司 | Method for preparing nano titanium silicalite molecular sieve at low cost |
| CN113086987A (en) * | 2021-03-26 | 2021-07-09 | 聊城市鲁西化工工程设计有限责任公司 | Molecular sieve production wastewater recovery method and recovery system |
| CN114225961A (en) * | 2021-09-09 | 2022-03-25 | 浙江吉瑞通新材料有限公司 | Catalyst for synthesizing propylene oxide and preparation method and application thereof |
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| CN101134575A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Method for preparing TS-1 molecular sieve |
| CN105597818A (en) * | 2016-01-26 | 2016-05-25 | 中国石油大学(北京) | Hydro-thermal synthesis method for TS-1 molecular sieve and obtained product |
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| CN101134575A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Method for preparing TS-1 molecular sieve |
| CN105597818A (en) * | 2016-01-26 | 2016-05-25 | 中国石油大学(北京) | Hydro-thermal synthesis method for TS-1 molecular sieve and obtained product |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500309A (en) * | 2017-08-18 | 2017-12-22 | 鲁西催化剂有限公司 | A kind of preparation method of HTS |
| CN107500309B (en) * | 2017-08-18 | 2019-11-19 | 鲁西催化剂有限公司 | A kind of preparation method of Titanium Sieve Molecular Sieve |
| CN109721065A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method |
| CN111186845A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing hierarchical pore TS-1 molecular sieve |
| CN111186845B (en) * | 2018-11-15 | 2021-09-28 | 中国科学院大连化学物理研究所 | Method for preparing hierarchical pore TS-1 molecular sieve |
| CN110028078A (en) * | 2019-04-24 | 2019-07-19 | 清华大学 | A kind of preparation method of Titanium Sieve Molecular Sieve |
| CN112758951A (en) * | 2020-12-31 | 2021-05-07 | 中海油天津化工研究设计院有限公司 | Method for preparing nano titanium silicalite molecular sieve at low cost |
| CN113086987A (en) * | 2021-03-26 | 2021-07-09 | 聊城市鲁西化工工程设计有限责任公司 | Molecular sieve production wastewater recovery method and recovery system |
| CN114225961A (en) * | 2021-09-09 | 2022-03-25 | 浙江吉瑞通新材料有限公司 | Catalyst for synthesizing propylene oxide and preparation method and application thereof |
| CN114225961B (en) * | 2021-09-09 | 2023-10-31 | 浙江吉瑞通新材料有限公司 | Catalyst for synthesizing epoxypropane and preparation method and application thereof |
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