CN110028078A - A kind of preparation method of Titanium Sieve Molecular Sieve - Google Patents
A kind of preparation method of Titanium Sieve Molecular Sieve 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- 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 discloses a kind of preparation methods for the Titanium Sieve Molecular Sieve for belonging to technical field of zeolite molecular sieve preparation.Including by silicon source, template, alkali source, titanium source mix, hydrolyzed, except alcohol after obtain precursor glue A；The precursor glue A through hydrothermal crystallizing, be centrifugally separating to obtain mother solution C and solid D；The solid D is washed, obtains Titanium Sieve Molecular Sieve after dry, calcining；The crystallization system for carrying out hydrothermal crystallizing includes the pipe reaction device and autoclave high-pressure installation being connected in series；The mother solution C participates in reaction as part or all of raw material sources, circulation.Circulation technology of the present invention is environmentally protective, rapidly and efficiently, it is at low cost, template dosage is reduced to the 15wt.%-25wt.% of traditional handicraft in cyclic process；Titanium-silicon molecular sieve catalyst relative crystallinity produced by the present invention is high, partial size is held in 100-180nm, and skeleton Ti content is high and only exists in the form of framework titania, while catalyst shows similar catalytic activity.
Description
Technical field
The invention belongs to technical field of zeolite molecular sieve preparation, in particular to a kind of preparation method of Titanium Sieve Molecular Sieve.
Background technique
Titanium-silicon molecular sieve TS-1 is the zeolite molecular sieve of MFI structure, is the novel miscellaneous original of last century early eighties exploitation
Sub- molecular sieve.It is to replace part silicon atom by the transition metal titanium atom with redox ability, and be evenly distributed on bone
In frame；Unique cellular structure, the introducing of hetero atom Ti and the hydrophobic ability of skeleton make it have both shape selective catalysis and catalysis
The function of oxidation, especially the selective catalytic oxidation system with hydrogen peroxide composition urge a series of selection of organic matters
Change has the effect of excellent, such as the epoxidation reaction of alkene, the hydroxylating of aromatic hydrocarbons, the oxidation reaction of alkane, alkohol and amine,
And Ammoximation reaction of cyclohexanone etc., in addition, TS-1 can also be used in the synthesis etc. of thioether.With other catalytic oxidation system phases
Than TS-1 and H2O2The catalytic oxidation system atom utilization of composition is high, and principal product selectivity and high income, by-product is water, right
Environmental nonpollution, reaction condition is mild, and technical process is simple, highly-safe；And TS-1 itself has good chemical stabilization
Property and thermal stability.These features all extremely meet the requirement of green chemical industry, show good prospects for commercial application.
There are two types of the synthetic methods of Titanium Sieve Molecular Sieve, one is hydrothermal crystallization method (hydrothermal synthesis method i.e. described below),
The precursor glue that the titanium source of definite composition, silicon source, template and alkali source form is subjected to crystalline substance under certain temperature and pressure
Change reaction, and is obtained by the preparation steps such as separation, washing, dry, calcining.Another kind is to use gas-solid phase isomorphous replacement process,
Due to TS-1 and ZSM-5 cellular structure having the same, removed from the molecular sieve for having obtained MFI topological structure aluminium,
Titanium atom after leaving structural vacancy, is replaced vacancy to enter in the skeleton structure of molecular sieve by boron atom, to be bonded into TS-1
Molecular sieve.For gas-solid phase isomorphous replacement process, synthesis cost is lower, but the molecular sieve prepared still contains certain skeleton
Aluminium, skeleton Ti content is lower, and the disordered state etc. of defect is presented in structure, therefore hydrothermal synthesis is still currently the most important ones TS-1
Synthetic method.
For hydrothermal synthesis method, preparing evenly dispersed precursor glue is the TS-1 technology core for synthesizing framework titania structure
The heart, however reaction of the butyl titanate in alkali source is fast response process, the mixed performance of consersion unit seriously affects titanium species and exists
Existence form in framework of molecular sieve, undesirable mixed performance are easy to cause the accumulation of titanium species part excessive concentrations and generate not
It is dissolved in the Detitanium-ore-type TiO of water2, to influence the catalytic performance of TS-1.Also, it is numerous research shows that silicon species hydrolyzed state
The same dispersion performance for influencing titanium species, and traditional stirred autoclave is difficult to control accurately when titanium species enter silicon species glue
Silicon species hydrolyzed state, therefore, it is difficult to match titanium hydrolysis rate and silicon hydrolysis rate, so that titanium is in crystallization process with extra-framework titanium
Form exist, not only promoted the decomposition of hydrogen peroxide, also reduced the selectivity for target product.
Meanwhile conventional hydrothermal synthetic method is long there is also the reaction time, template used dose of additional amount is much larger than mould needed for theory
Plate agent dosage, a large amount of organic liquid wastes lead to the problem of and then seriously pollute environment.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of Titanium Sieve Molecular Sieve, specific technical solution is as follows:
A kind of preparation method of Titanium Sieve Molecular Sieve includes mixing silicon source, template, alkali source, titanium source, is hydrolyzed, except after alcohol
Obtain precursor glue A；The precursor glue A through hydrothermal crystallizing, be centrifugally separating to obtain mother solution C and solid D；The solid D is through washing
Wash, dry, calcine after obtain Titanium Sieve Molecular Sieve；
Further, the hydrolysis process is using the conventional process for being able to achieve silicon source, titanium source hydrolysis in the prior art.
Further, the silicon source, alcohol such as ethyl alcohol, butanol etc., hydrothermal crystallizing reaction can be generated in titanium source hydrolytic process
Before need to do except alcohol processing.
The crystallization system for carrying out hydrothermal crystallizing includes the pipe reaction device and autoclave high-pressure installation being connected in series；Further include
The heating device of controlling crystallizing system temperature.
The mother solution C participates in reaction as part or all of raw material sources, circulation.
The silicon source, template, alkali source, titanium source hybrid mode are as follows: silicon source, template, alkali source mix at normal temperature
After even, add titanium source and be uniformly mixed.
The mother solution C guarantees material ratio as part material source, by additional raw material；
The hybrid mode of the mother solution C and additional raw material are as follows: mother solution C mixes at normal temperature with silicon source, template, alkali source
After even, add titanium source and be uniformly mixed.
The silicon source be one of silicic acid orthocarbonate, tetrabutyl silicate, tetraethyl orthosilicate, silica solution, silicon tetrachloride or
It is several；The template is tetrapropylammonium hydroxide and/or 4-propyl bromide；The alkali source is tetrapropylammonium hydroxide, second
One or more of hydramine, ethylenediamine；The titanium source is butyl titanate and/or titanium tetrachloride.
Each molar ratio of material is
SiO2:TPA+:OH-:TiO2:H2O=1:(0.05-0.5): (0.3-1): (0.02-0.04): (16-35)；
It is further preferred that
SiO2:TPA+:OH-:TiO2:H2O=1:(0.05-0.5): (0.3-0.45): (0.02-0.04): (16-35).
Silicon source is in the present invention with SiO2Note, titanium source is with TiO2Note, alkali source is with OH-Note, template is with TPA+Note.
The temperature of the hydrolysis is 50-60 DEG C, time 3-6h；The temperature except alcohol is 80 DEG C, time 1h；It is described
The temperature of hydrothermal crystallizing is 130-240 DEG C, time 5-60min.
Residence time >=1 second of the precursor glue A in pipe reaction device, the precursor glue A can directly exist
Hydrothermal crystallizing reaction is completed in pipe reaction device.
Microtubule hydraulic diameter used in the pipe reaction device is 0.05mm-10mm；Autoclave high-pressure installation
Used autoclave is that the outer gallbladder of stainless steel is lined with polytetrafluoroethylene (PTFE), and autoclave is static hydrothermal kettle or Dynamic Hydrothermal kettle, institute
It states the dynamic characteristic of Dynamic Hydrothermal kettle and passes through one of built-in machines stirring, magnetic agitation or external mechanical rotation or a variety of
Mode is realized.
The mother solution C direct circulation, or recycled after normal heating concentration or heating under reduced pressure concentration.
The normal heating temperature is 50-100 DEG C；The vacuum degree of the heating under reduced pressure concentration is -80~-99kPa, heating
Temperature is 30-60 DEG C.
The washing, drying of solid D, calcine technology are identical as the parameter of prior art preparation Titanium Sieve Molecular Sieve in the present invention,
Those skilled in the art according to the prior art it can be learnt that, do not influence those skilled in the art to the reason of technical solution of the present invention
Solution.
The mother solution C is as segment template agent source, and template agent content is template weight in precursor glue A in mother solution C
75wt.%-85wt.%, fixed each molar ratio of material is constant, and additional template agent dosage is original template agent dosage
15wt.%-25wt.%.
The invention has the benefit that
(1) present invention mutually ties the high pressure water heating kettle of the pipe reaction device of flowing chemistry and conventional hydrothermal synthetic method
It closes, the preparation process applied to TS-1；It is distributed using tubular reactor rapid temperature rise and drop and radial temperature, concentration gradient small
Feature greatly accelerates crystallization velocity, and crystallization time is short, and 5-60min can complete crystallization process, reduces process energy consumption；It is short
Crystallization time significantly reduce template decomposition at high temperature and disappearing in alkaline environment in conventional hydrothermal synthesis
Consumption, while avoiding a large amount of pollution problems of the organic liquid waste to environment produced by template decomposes；
(2) present invention mixes the Recycling Mother Solution being centrifugally separating to obtain with additional fresh material, re-starts hydrolysis, hydro-thermal
Crystallization, realizes recycling for 75wt.% template above agent, not only greatly reduces the cost of material of catalyst, also
The discharge for avoiding organic liquid waste reduces the subsequent processing steps of synthesis process；
(3) circulation technology of the present invention it is environmentally protective, rapidly and efficiently, it is at low cost, template dosage is reduced in cyclic process
The 15wt.%-25wt.% of traditional handicraft (i.e. convention stir kettle technique)；Titanium-silicon molecular sieve catalyst produced by the present invention is opposite
Crystallinity can reach 95% or more, and partial size is held in 100-180nm, and skeleton Ti content is high and is only deposited in the form of framework titania
, while catalyst shows similar catalytic activity.
Detailed description of the invention
Attached drawing 1 is the preparation technology flow chart of Titanium Sieve Molecular Sieve of the present invention；
Attached drawing 2 is crystallization system schematic diagram of the present invention；
Label declaration: 1- pipe reaction device；2- autoclave high-pressure installation.
Specific embodiment
The present invention provides a kind of preparation methods of Titanium Sieve Molecular Sieve, with reference to the accompanying drawings and examples to the present invention do into
The explanation of one step.
As shown in Figure 1, the method that the present invention prepares Titanium Sieve Molecular Sieve includes that the preparation of precursor glue, crystallization system and mother liquor follow
Ring；Specifically includes the following steps:
(1) at normal temperature after evenly mixing by silicon source, template, alkali source, it adds titanium source to be uniformly mixed, gained reaction solution
3-6h is hydrolyzed at 50-60 DEG C, is removed alcohol 1h at 80 DEG C, is obtained precursor glue A；
(2) the precursor glue A enters crystallization system, and hydrothermal crystallizing reacts 5-60min at 130-240 DEG C, is hanged
Turbid B；
(3) it is centrifuged after being rapidly cooled to room temperature suspension B, obtains mother solution C and solid D；Solid D is washed, it is dry, forge
The last handling processes such as burning obtain titanium-silicon molecular sieve TS-1 powder；
(4) in cyclic process, fixed each molar ratio of material is constant, and mother solution C is and required as part or all of raw material sources
The fresh feed of supplement mixes, and repeats hydrolysis, except alcohol, prepares precursor glue A；
(5) circulating repetition step (2)~(4) realize that Recycling Mother Solution prepares Titanium Sieve Molecular Sieve.
As shown in Fig. 2, crystallization system includes concatenated pipe reaction device 1 and autoclave high-pressure installation 2 in the present invention, also wrap
Include the heating system of controlling crystallizing system temperature.Precursor glue A squeezes into crystallization system using conveying device, successively in pipe reaction
Crystallization is carried out in device 1, autoclave high-pressure installation 2.
Embodiment 1
Crystallization system includes concatenated tubular reactor and tank reactor, further includes the heating of controlling crystallizing system temperature
System, wherein tubular reactor hydraulic diameter 0.9mm, tank reactor are the stainless steel high pressure of built-in polytetrafluoroethylliner liner
Kettle, heating system are electric heating cover.
Titanium Sieve Molecular Sieve is prepared referring to the above method, the specific steps are as follows:
(1) using tetraethyl orthosilicate TEOS as silicon source, tetrapropylammonium hydroxide TPAOH is template and alkali source, butyl titanate
TBOT is titanium source, and silicon source, template and alkali source are carried out mixing 0.5h at normal temperature, and titanium source is then added, and mixing is certain
3-6h is hydrolyzed after time at 50-60 DEG C, alcohol 1h is removed at 80 DEG C, obtains precursor glue A；Each molar ratio of material is SiO2:
TPAOH:TiO2:H2O=1:0.35:0.02:25.
(2) precursor glue A is passed through crystallization system, the hydrothermal crystallizing 25min at 175 DEG C obtains suspension B；
(3) it is centrifuged after being rapidly cooled to room temperature suspension B, obtains mother solution C and solid D；Washed, calcining of solid D etc.
Last handling process obtains the TS-1 of fresh template preparation, is MFI structure through analysis product, and titanium only exists in the form of framework titania.
(4) fixed each molar ratio of material is constant, filtered mother solution C as segment template agent and alkali source source, directly with
The fresh template mixing of supplement, repeats to participate in hydrolysis, crystallization process, the TS-1 of mother solution C circulation preparation is obtained, through analyzing product
For MFI structure, titanium only exists in the form of framework titania.
(5) circulating repetition step (2)~(4) realize that Recycling Mother Solution prepares Titanium Sieve Molecular Sieve.
The relative crystallinity 98.7% of titanium-silicon molecular sieve TS-1 obtained by step (3)~step (5), mean particle size exists
120nm；I.e. circulation front and back gained Titanium Sieve Molecular Sieve relative crystallinity, partial size do not change.After mother solution C circulation, embodiment 1
The required fresh TPAOH dosage of supplement is reduced to the 17.5wt.% of initial TPAOH dosage.
Embodiment 2
Crystallization system includes concatenated tubular reactor and tank reactor, further includes the heating of controlling crystallizing system temperature
System, wherein tubular reactor hydraulic diameter 0.9mm, tank reactor are the stainless steel high pressure of built-in polytetrafluoroethylliner liner
Kettle, heating system are oil bath heating.
Select silicon source for tetraethyl orthosilicate TEOS, template and alkali source are tetrapropylammonium hydroxide TPAOH, and titanium source is metatitanic acid
Butyl ester TBOT, each molar ratio of material are SiO2:TPAOH:TiO2:H2O=1:0.35:0.02:25.According to 1 phase of embodiment
Same method, is passed through crystallization system for precursor glue A, the hydrothermal crystallizing 25min at 175 DEG C obtains suspension B；Suspension B is fast
The last handling processes such as speed is centrifuged after being cooled to room temperature, and obtains mother solution C and solid D, and solid D is filtered, washed, is calcined obtain fresh
The TS-1 that template is prepared, is MFI structure through analysis product, and titanium only exists in the form of framework titania.
Fixed each molar ratio of material is constant, and filtered mother solution C is concentrated into 1.8mol/L in 75 DEG C of normal heating 8h, then
It is used as template and alkali source after mixing with fresh template, repeats hydrolysis, crystallization process, obtains the TS-1 of mother solution C circulation preparation,
It is MFI structure through analysis product, titanium only exists in the form of framework titania.
Mother liquid obtained C constantly recycles participation reaction, realizes that Recycling Mother Solution prepares Titanium Sieve Molecular Sieve.
The relative crystallinity 96.5% of 2 mother solution C of embodiment circulation front and back gained titanium-silicon molecular sieve TS-1, catalyst granules are flat
Equal partial size is in 120nm.After mother solution C circulation, the fresh TPAOH dosage of supplement needed for embodiment 2 is reduced to initial TPAOH dosage
19wt.%.
Embodiment 3
Crystallization system includes concatenated tubular reactor and tank reactor, further includes the heating of controlling crystallizing system temperature
System, wherein tubular reactor hydraulic diameter 0.9mm, tank reactor are the stainless steel high pressure of built-in polytetrafluoroethylliner liner
Kettle, heating system are oil bath heating.
Select silicon source for tetraethyl orthosilicate TEOS, template and alkali source are tetrapropylammonium hydroxide TPAOH, and titanium source is metatitanic acid
Butyl ester TBOT, each molar ratio of material are SiO2:TPAOH:TiO2:H2O=1:0.35:0.02:25.According to 1 phase of embodiment
Same method, is passed through crystallization system for precursor glue A, the crystallization 25min at 175 DEG C obtains suspension B；The fast quickly cooling of suspension B
But mother solution C and solid D are obtained to being centrifuged after room temperature, solid D is filtered, washed, is calcined etc., and last handling processes obtain fresh template
The TS-1 that agent is prepared, is MFI structure through analysis product, and titanium only exists in the form of framework titania.
Fixed each molar ratio of material is constant, and filtered mother solution C is evaporated under reduced pressure at 45 DEG C, adds when vacuum degree is -95kPa
Hot 3h is concentrated into 2.05mol/L, then is used as template and alkali source after mixing with fresh template, repeats hydrolysis, crystallization process,
The TS-1 of mother solution C circulation preparation is obtained, is MFI structure through analysis product, titanium only exists in the form of framework titania.
Mother liquid obtained C constantly recycles participation reaction, realizes that Recycling Mother Solution prepares Titanium Sieve Molecular Sieve.
The relative crystallinity 97.3% of 3 mother solution C of embodiment circulation front and back gained titanium-silicon molecular sieve TS-1, catalyst granules are flat
Equal partial size is in 120nm.After mother solution C circulation, the fresh TPAOH dosage of supplement needed for embodiment 3 is reduced to initial TPAOH dosage
18wt.%.
Embodiment 4
Crystallization system includes concatenated tubular reactor and tank reactor, further includes the heating of controlling crystallizing system temperature
System, wherein tubular reactor hydraulic diameter 1.7mm, tank reactor are the stainless steel high pressure of built-in polytetrafluoroethylliner liner
Kettle, while built-in rotor keeps magnetic agitation in crystallization process, heating system is electric heating cover heating.
Select silicon source for tetraethyl orthosilicate TEOS, template and alkali source are tetrapropylammonium hydroxide TPAOH, and titanium source is metatitanic acid
Butyl ester TBOT, each molar ratio of material are SiO2:TPAOH:TiO2:H2O=1:0.45:0.03:25.According to 1 phase of embodiment
Same method, is passed through crystallization system for precursor glue A, the crystallization 25min at 175 DEG C obtains suspension B；The fast quickly cooling of suspension B
But mother solution C and solid D are obtained to being centrifuged after room temperature, solid D is filtered, washed, is calcined etc., and last handling processes obtain fresh template
The TS-1 that agent is prepared, is MFI structure through analysis product, and titanium only exists in the form of framework titania.
Fixed each molar ratio of material is constant, and filtered mother solution C is evaporated under reduced pressure at 45 DEG C, adds when vacuum degree is -93kPa
Hot 3.6h is concentrated into 1.95mol/L, then is used as template and alkali source after mixing with fresh template, repeats hydrolysis, crystallization mistake
Journey obtains the TS-1 of Recycling Mother Solution preparation, is MFI structure through analysis product, and titanium only exists in the form of framework titania.
Mother liquid obtained C constantly recycles participation reaction, realizes that Recycling Mother Solution prepares Titanium Sieve Molecular Sieve.
The relative crystallinity 99.2% of 4 mother solution C of embodiment circulation front and back gained titanium-silicon molecular sieve TS-1, catalyst granules are flat
Equal partial size is in 120nm.After mother solution C circulation, the fresh TPAOH dosage of supplement needed for embodiment 4 is reduced to initial TPAOH dosage
18wt.%.
Embodiment 5
Crystallization system includes concatenated tubular reactor and tank reactor, further includes the heating of controlling crystallizing system temperature
System, wherein tubular reactor hydraulic diameter 0.8mm, tank reactor are the stainless steel high pressure of built-in polytetrafluoroethylliner liner
Kettle, heating system are oil bath heating.
Select silicon source for tetraethyl orthosilicate TEOS, template is tetrapropylammonium hydroxide TPAOH, and alkali source is ethanol amine, titanium
Source is butyl titanate TBOT, and each molar ratio of material is SiO2: TPAOH: ethanol amine: TiO2:H2O=1:0.25:0.5:
0.03:25.In the same manner as shown in Example 1, precursor glue A is passed through crystallization system, crystallization 25min, obtains at 175 DEG C
To suspension B；Suspension B is centrifuged after being rapidly cooled to room temperature, and obtains mother solution C and solid D, and solid D is filtered, washed, is calcined
Equal last handling processes obtain the TS-1 that fresh template is prepared, and are MFI structure through analysis product, titanium is only in the form of framework titania
In the presence of.
Fixed each molar ratio of material is constant, and filtered mother solution C is evaporated under reduced pressure at 45 DEG C, adds when vacuum degree is -93kPa
Hot 5h, then it is used as template and alkali source after mixing with fresh template, hydrolysis, crystallization process are repeated, Recycling Mother Solution preparation is obtained
TS-1, through analysis product be MFI structure, titanium only in the form of framework titania exist.
Mother liquid obtained C constantly recycles participation reaction, realizes that Recycling Mother Solution prepares Titanium Sieve Molecular Sieve.
5 mother solution C of embodiment recycles the relative crystallinity 95.2% of forward and backward gained titanium-silicon molecular sieve TS-1, catalyst granules
Average grain diameter is in 180nm.After mother solution C circulation, the fresh TPAOH dosage of supplement needed for embodiment 5 is reduced to initial TPAOH dosage
25wt.%.
Comparative example
Titanium-silicon molecular sieve TS-1 is prepared using traditional stirred tank technique as comparative example 1-5: right unlike embodiment 1-5
Crystallization system is convention stir kettle in ratio 1-5, the time in hydrothermal crystallizing time reference traditional handicraft.Analysis is found, is compared
Effectively template agent content is essentially 0 in mother liquor in example 1-5, i.e. template decomposes completely；Even if carrying out Recycling Mother Solution, required benefit
Filling fresh template dosage does not also reduce.
Claims (10)
1. a kind of preparation method of Titanium Sieve Molecular Sieve, which is characterized in that including silicon source, template, alkali source, titanium source are mixed, warp
Hydrolysis, except obtaining precursor glue A after alcohol；The precursor glue A through hydrothermal crystallizing, be centrifugally separating to obtain mother solution C and solid D；Institute
State solid D it is washed, it is dry, calcining after obtain Titanium Sieve Molecular Sieve；
The crystallization system for carrying out hydrothermal crystallizing includes the pipe reaction device and autoclave high-pressure installation being connected in series；
The mother solution C participates in reaction as part or all of raw material sources, circulation.
2. preparation method according to claim 1, which is characterized in that the mixing of the silicon source, template, alkali source, titanium source
Mode are as follows: silicon source, template, alkali source after mixing, add titanium source and are uniformly mixed at normal temperature.
3. preparation method according to claim 1, which is characterized in that the mother solution C is as part material source, by outer
Raw material is added to guarantee material ratio；
The hybrid mode of the mother solution C and additional raw material are as follows: mother solution C is uniformly mixed at normal temperature with silicon source, template, alkali source
Afterwards, titanium source is added to be uniformly mixed.
4. preparation method according to claim 1, which is characterized in that the silicon source be silicic acid orthocarbonate, tetrabutyl silicate,
One or more of tetraethyl orthosilicate, silica solution, silicon tetrachloride；The template is tetrapropylammonium hydroxide and/or 4 third
Base ammonium bromide；The alkali source is one or more of tetrapropylammonium hydroxide, ethanol amine, ethylenediamine；The titanium source is metatitanic acid
Butyl ester and/or titanium tetrachloride.
5. preparation method according to claim 1, which is characterized in that each molar ratio of material is SiO2:TPA+:OH-:
TiO2:H2O=1:(0.05-0.5): (0.3-1): (0.02-0.04): (16-35).
6. preparation method according to claim 1, which is characterized in that the temperature of the hydrolysis is 50-60 DEG C, time 3-
6h；The temperature except alcohol is 80 DEG C, time 1h；The temperature of the hydrothermal crystallizing is 130-240 DEG C, time 5-60min.
7. preparation method according to claim 1, which is characterized in that the precursor glue A is in pipe reaction device
Residence time >=1 second；Microtubule hydraulic diameter used in the pipe reaction device is 0.05mm-10mm；Autoclave is high
Autoclave used in pressure device is that the outer gallbladder of stainless steel is lined with polytetrafluoroethylene (PTFE), and autoclave is static hydrothermal kettle or Dynamic Hydrothermal
The dynamic characteristic of kettle, the Dynamic Hydrothermal kettle passes through one of built-in machines stirring, magnetic agitation or external mechanical rotation
Or various ways are realized.
8. preparation method according to claim 1, which is characterized in that the mother solution C direct circulation, or it is dense through normal heating
It is recycled after contracting or heating under reduced pressure concentration.
9. preparation method according to claim 8, which is characterized in that the normal heating temperature is 50-100 DEG C；It is described
The vacuum degree of heating under reduced pressure concentration is -80~-99kPa, and heating temperature is 30-60 DEG C.
10. preparation method according to claim 1, which is characterized in that the mother solution C is female as segment template agent source
Template agent content is the 75wt.%-85wt.% of template weight in precursor glue A in liquid C, and fixed each molar ratio of material is constant,
Additional template agent dosage is the 15wt.%-25wt.% of original template agent dosage.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112429747A (en) * | 2020-11-30 | 2021-03-02 | 大连理工大学 | Preparation method for rapidly synthesizing titanium silicalite TS-1 with high titanium content under normal pressure by circularly using crystallization mother liquor |
| WO2021123227A1 (en) | 2019-12-19 | 2021-06-24 | Basf Se | Continuous synthesis of a titanosilicate zeolitic material, said zeolitic material, molding prepared thereof, and their use |
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| CN115215351A (en) * | 2022-06-12 | 2022-10-21 | 中海油天津化工研究设计院有限公司 | Method and device for continuously producing molecular sieve in tubular reactor |
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