CN106542549A - A kind of fluorine richness titanium phosphate aluminum molecular screen F TAPO 5 and preparation method thereof - Google Patents
A kind of fluorine richness titanium phosphate aluminum molecular screen F TAPO 5 and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of fluorine richness titanium phosphate aluminum molecular screen F TAPO 5 and preparation method thereof, preparation process：(1) be stirred vigorously it is lower by phosphorus source, silicon source, fluorine-containing titanium source, template and deionized water according to mol ratio 0.96:1.5:0.04‑0.3:0.8:50 mix homogeneously, 25 35 DEG C stirring 20 40 minutes after obtain molecular sieve precursor colloidal sol；Precursor sol is proceeded in the water heating kettle with PTFE linings, in 160～185 DEG C of 18～30h of Crystallizing treatment；After crystallization terminates, centrifugation goes out solid, and distilled water cleans solid and obtains fluorine-containing titanium phosphate aluminum molecular screen original powder after 90 110 DEG C of 10 15h of drying to neutrality；(2) molecular screen primary powder that step (1) is obtained is put into into tube furnace constant temperature zone, template is removed in 500～650 DEG C of 4～8h of roasting under oxygen atmosphere, obtain fluorine richness titanium phosphate aluminum molecular screen F TAPO 5.Fluorine richness titanium phosphate aluminum molecular screen obtained by the inventive method has stronger Lewis acid and surface hydrophobic, can apply in catalysis of pimelinketone oxamidine reaction.
Description
Technical field
The present invention relates to aluminium phosphate molecular sieve, and in particular to a kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 and its system
Preparation Method and application.
Background technology
Early 1980s, Italian Enichem companies develop titanium-silicon molecular sieve TS-1.TS-1 and low concentration dioxygen
The catalyst system and catalyzing of water composition can realize the selective oxidation of the organic compound such as alcohols, phenol, alkene in a mild condition, its
Middle phenol hydroxylation, cyclohexanone oxamidinating and epoxidation of propylene have been achieved with industrialization so that TS-1 becomes molecular sieve art
Milestone.Subsequently, researcher is incorporated into titanium in each molecular sieve analog, prepares different structure new containing titanium molecule with composition
Sieve.Two big class can be divided into according to these molecular sieves are constituted：(1) HTS, such as TS-2, Ti- β, Ti-MWW, Ti-MOR and
Ti-MCM-41 etc.；(2) titanium phosphate aluminum molecular screen, such as TAPO-5, TAPO-36, TAPO-31 and TPASO-5 etc..
Compared with HTS, titanium phosphate aluminum molecular screen have the advantages that structure diversity, easily adulterate, prepare it is simple,
By the extensive concern of researcher.Existing document (J.Chem.Soc., Chem.Commun., 1995,373；Journal of
Catalysis177,(1998)231–239；J.Am.Chem.Soc.2011,133,7340–7343；Catalysis Today
213 (2013) 211-218) titanium phosphate aluminum molecular screen preparation method disclosed in is realized by hydrothermal crystallization method：By phosphorus source (phosphorus
Acid), silicon source (boehmite or aluminium hydroxide), template, titanium source (butyl titanate, isopropyl titanate, tetraethyl titanate) and go
Ionized water makes gel according to a certain percentage, and template agent removing is removed in then aged, roasting.Titanium phosphate aluminum molecule obtained by this method
Sieve shows certain catalysis activity in the reaction such as cyclohexane oxidation, epoxidation of propylene, phenol hydroxylation and ammonia hydroxylating.
However, as titanium phosphate aluminum molecular screen surface obtained by this method has abundant hydroxyl, showing stronger parent
Aqueouss, are unfavorable for reactant and product adsorption and desorption on a catalyst；And the Lewis acid strengths of active center titanium are weaker,
Activating hydrogen peroxide ability is weak.This directly results in titanium phosphate aluminum molecular screen and shows in the catalytic oxidation of phenols, ketone etc.
Poor catalytic performance, limits application of the titanium phosphate aluminum molecular screen in catalysis oxidation field.Therefore, strengthen titanium phosphate aluminum molecule
The Lewis acidity of sieve surface hydrophobic and active center titanium is to improve the key of its catalytic oxidation performance.F-In crystallization process
Middle removing mineralizer acts on the effect of outer, Shang Nengqi certain structure directing and backbone element, and F- may replace surface A l-OH
And P-OH, surface hydrophobic is improve, the strong electronegativity of fluorine may improve the electropositive of active center titanium, so as to improve
Lewis is acid.Research work with regard to this aspect is there is not yet document report.
The content of the invention
It is an object of the invention to provide a kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 and preparation method thereof.
To reach above-mentioned purpose, the present invention is employed the following technical solutions：
Phosphorus source, silicon source, fluorine-containing titanium source, template and deionized water are mixed, then crystallization, last separated, dry, roasting
Burn and obtain fluorine richness titanium phosphate aluminum molecular screen.
Technical scheme is described in detail now：
A kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 and preparation method thereof, its feature are the fluorine-containing titanium phosphate
Aluminum molecular screen F-TAPO-5 is prepared by following steps：
(1) be stirred vigorously it is lower by phosphorus source, silicon source, fluorine-containing titanium source, template and deionized water according to mol ratio 0.96:1.5:
0.04-0.3:0.8:50 mix homogeneously, obtain molecular sieve precursor colloidal sol after 25-35 DEG C of stirring 20-40 minute；Precursor sol is turned
Enter in the water heating kettle with PTFE linings, in 160～185 DEG C of 18～30h of Crystallizing treatment；After crystallization terminates, centrifugation goes out solid
Body, distilled water cleaning solid to neutrality are dried 10-15h and obtain fluorine-containing titanium phosphate aluminum molecular screen original powder after 90-110 DEG C；
(2) molecular screen primary powder that step (1) is obtained is put into into tube furnace constant temperature zone, in 500～650 under oxygen atmosphere
DEG C 4～8h of roasting removes template, obtains fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5.
In the step (1), phosphorus source is phosphoric acid (H3PO4), silicon source is aluminium hydroxide (Al (OH)3), fluorine-containing titanium source is hexafluoro
Titanium acid ammonium (NH4TiF6), template is N- methyldicyclohexyl amine (MCHA).
In the step (1), 25-35 DEG C of stirring 20-40 minute is preferably 30 DEG C and stirs 30 minutes.
Baking temperature in the step (1) is preferably 110 DEG C, and drying time is preferably 12h.
In the step (1), crystallization temperature is preferably 180 DEG C, and crystallization time is preferably 24h.
In the step (2), sintering temperature is preferably 575 DEG C, and roasting time is preferably 6h.
Fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 prepared by the present invention has higher Lewis acid and surface hydrophobicity
Property, can apply in catalysis of pimelinketone oxamidine.
Beneficial effects of the present invention compared with prior art：
1st, the ammonium hexa-fluorotitanate used by the present invention is not only cheap, and provides modified required while titanium source is provided
Fluorine source, realize the one-step synthesis that fluorine richness titanium phosphate aluminium powder sieves F-TAPO-5, simple to operate, process is easy to control, time-consuming few,
With universality.
2nd, present invention gained fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 has higher Lewis acid and surface hydrophobicity
Property, excellent catalytic performance is shown in cyclohexanone oxamidinating reaction.
Description of the drawings
XRD figure of the Fig. 1 for embodiment 1-4 sample；
XPS spectrum figures of the Fig. 2 for 3 sample of embodiment；
Fig. 3 is the pyridine infrared spectrum of comparative example 1 and embodiment 1-4.
Specific embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
In comparative example and embodiment, reagent used is commercially available chemical reagent.
Embodiment using method and instrument being listed below, but should not be construed as restricted.
Using the D8 Advance type x-ray diffractometers of Bruker, with reference to the description of manufacturer, carry out X-ray and spread out
Penetrate；
Using the 27 type infrared spectrometers of Tensor of Bruker, with reference to the description of manufacturer, infrared point of pyridine is carried out
Analysis；
Using Kratos AXIS ULTRA DLD multifunctional light electronics energy disperse spectroscopies, with reference to manufacturer specification, XPS is carried out
Analysis.
Ketohexamethylene, the concentration of cyclohexanone-oxime carry out quantitative analyses using gas chromatography.Gas chromatograph used is
6890 type gas chromatograpies of Agilent companies；Analysis chromatographic column used is HP-5 posts.
In embodiment, the conversion ratio of Ketohexamethylene, the selectivity of cyclohexanone-oxime are to calculate according to the following equation respectively：
Comparative example 1
The method synthesis titanium phosphate aluminum of this comparative example reference literature (J.Am.Chem.Soc.2011,133,7340-7343)
Molecular sieve TAPO-5：
By phosphoric acid, aluminium hydroxide, isopropyl titanate, triethylamine and deionized water according to mol ratio be 0.2Ti:1TEA:
1Al:1P:40H2The amount mixing of O, prepares gel.System is transferred to into band teflon-lined rustless steel crystallization subsequently
In kettle, it is put into after sealing and is placed in crystallization 24h in 175 DEG C of baking ovens.After crystallization terminates, crystallizing kettle is taken out, room temperature is naturally cooled to.From
The heart is separated and is washed with deionized powder for several times, is then dried 12h at 110 DEG C and is obtained TAPO-5 molecular screen primary powders.By TAPO-5
Former powder is placed in tube furnace, after being heated to 550 DEG C under nitrogen atmosphere, is switched to oxygen atmosphere and is kept 12h, obtain TAPO-5 molecules
Sieve.
TAPO-5 is applied in catalysis of pimelinketone oxamidine：By 0.5g TAPO-5 molecular sieves, 1.0g Ketohexamethylene, uncle 1.7g
Butanol and 1.7g water are added in there-necked flask, are heated up and are kept to 80 DEG C.Under stirring, using constant pressure funnel by 3.6g
It is added drop-wise in said mixture in strong aqua ammonia and 3.9g hydrogen peroxide, time for adding is 2 hours, and after hydrogen peroxide is added, constant temperature is anti-again
Answer 30 minutes, reaction terminates.With toluene as internal standard, gas chromatographic analysiss product, evaluating data are shown in Table 1.
Embodiment 1
By 4.151g H3PO4With 10.0g H2O stirs mixing at 30 DEG C, weighs 2.7648g Al (OH)3Powder is added
To in above-mentioned system, after continuing stirring 0.5h, by 0.191g N2H8TiF6Powder is added in system.Again by 3.751g MCHA
It is slowly dropped in above-mentioned suspension, is eventually adding 10.0g water, the mol ratio of raw material is Al (OH)3:H3PO4:N2H8TiF6:
MCHA:H2O=0.96:1.5:0.04:0.8:50, the stainless of inner liner polytetrafluoroethylene is transferred into after continuing to be stirred vigorously 1h
In steel crystallizing kettle, in 180 DEG C of crystallization 24h.After the completion of crystallization, centrifugation is simultaneously washed with distilled water to neutrality, 110 DEG C of dryings
12h, obtains F-TAPO-5 original powder.By the F-TAPO-5 for obtaining originals powder, in tube furnace, under oxygen atmosphere, 575 DEG C of roasting 6h take off
Except structure directing agent, molecular sieve is obtained, be labeled as：F-TAPO-5(0.04).
Embodiment 2
By 4.151g H3PO4With 10.0g H2O stirs mixing at 30 DEG C, weighs 2.7648g Al (OH)3Powder is added
To in above-mentioned system, after continuing stirring 0.5h, by 0.764g N2H8TiF6Powder is added in system.Again by 3.751g MCHA
It is slowly dropped in above-mentioned suspension, is eventually adding 10.0g water, the mol ratio of raw material is Al (OH)3:H3PO4:N2H8TiF6:
MCHA:H2O=0.96:1.5:0.1:0.8:50, the stainless of inner liner polytetrafluoroethylene is transferred into after continuing to be stirred vigorously 1h
In steel crystallizing kettle, crystallization 24h at 180 DEG C.After the completion of crystallization, centrifugation is simultaneously washed with distilled water to neutrality, 110 DEG C of dryings
12h, obtains F-TAPO-5 original powder.By the F-TAPO-5 for obtaining originals powder, in tube furnace, under oxygen atmosphere, 575 DEG C of roasting 6h take off
Except structure directing agent, molecular sieve is obtained, be labeled as：F-TAPO-5(0.1).
Embodiment 3
By 4.151g H3PO4With 10.0g H2O stirs mixing at 30 DEG C, weighs 2.7648g Al (OH)3Powder is added
To in above-mentioned system, after continuing stirring 0.5h, by 1.528g N2H8TiF6Powder is added in system.Again by 3.751g MCHA
It is slowly dropped in above-mentioned suspension, is eventually adding 10.0g water, the mol ratio of raw material is Al (OH)3:H3PO4:N2H8TiF6:
MCHA:H2O=0.96:1.5:0.2:0.8:50, the stainless of inner liner polytetrafluoroethylene is transferred into after continuing to be stirred vigorously 1h
In steel crystallizing kettle, crystallization 24h at 180 DEG C.After the completion of crystallization, centrifugation is simultaneously washed with distilled water to neutrality, 110 DEG C of dryings
12h, obtains F-TAPO-5 original powder.By the F-TAPO-5 for obtaining original powder, at 575 DEG C of air atmosphere, roasting 6h takes off in the Muffle furnace
Except structure directing agent, molecular sieve is obtained, be labeled as：F-TAPO-5(0.2).
Embodiment 4
By 4.151g H3PO4With 10.0g H2O stirs mixing at 30 DEG C, weighs 2.7648g Al (OH)3Powder is added
To in above-mentioned system, after continuing stirring 0.5h, by 2.292g N2H8TiF6Powder is added in system.Again by 3.751g MCHA
It is slowly dropped in above-mentioned suspension, is eventually adding 10.0g water, the mol ratio of raw material is Al (OH)3:H3PO4:N2H8TiF6:
MCHA:H2O=0.96:1.5:0.3:0.8:50, the stainless of inner liner polytetrafluoroethylene is transferred into after continuing to be stirred vigorously 1h
In steel crystallizing kettle, crystallization 24h at 180 DEG C.After the completion of crystallization, centrifugation is simultaneously washed with distilled water to neutrality, 110 DEG C of dryings
12h, obtains F-TAPO-5 original powder.By the F-TAPO-5 for obtaining original powder, at 575 DEG C of air atmosphere, roasting 6h takes off in the Muffle furnace
Except structure directing agent, molecular sieve is obtained, be labeled as：F-TAPO-5(0.3).
Embodiment 5
For illustrating the crystal structure of embodiment sample.
Fig. 1 is the XRD figure of 1～4 sample of enforcement, each sample 2 θ=7.4,12.9,14.9,19.8,20.8,22.4,
24.6th, 26.0,29.1,30.2,34.7,37.5 ° of characteristic diffraction peaks for AFI structure occur, illustrate that all samples are respectively provided with AFI knots
Structure.
Embodiment 6
The present embodiment is used for presence and the content for illustrating F in 3 gained sample of embodiment.Using xps energy spectrum instrument to embodiment 3
Sample is analyzed, as a result as shown in Figure 2.In Fig. 2, the peak at 685.67eV is F1S fluorine Photoelectron peaks, is contained in illustrating sample
Fluorine, and the atom content of fluorine is about 0.27%.
Embodiment 7
This is tested for illustrating the Lewis acid strengths of comparative example 1 and each embodiment sample.According to list of references (Journal
Of Catalysis 329 (2015) 107-118) described in method (pyridine infrared method) carry out the Lewis acid strengths of determination sample：
To be placed in In-situ Infrared pond after 40mg sample tablettings, after being heated to 500 DEG C evacuation 3h with remove sample surfaces absorption it is miscellaneous
Matter, is then cooled to room temperature, is then passed through pyrido in sample cell and maintains 30min, then sample is heated to 200 DEG C and is maintained
30min, finally gathers infrared spectrum after sample is cooled to room temperature.The pyridine interacted with Lewis acid is in 1448cm-1Near
There is absworption peak, the presence at the peak and its intensity can be used to judgement sample with the presence or absence of Lewis acid and its power.Such as Fig. 3 institutes
Show, comparative example 1 and embodiment sample are in 1448cm-1There is absworption peak in place, illustrates that all samples are respectively provided with Lewis sour.From figure
In it can also be seen that each embodiment sample in 1448cm-1The absorption peak strength at place is above comparative example 1, and identical in Ti content
When, by obtained by this method, sample has higher Lewis sour compared with sample obtained by traditional method.
Embodiment 8
The present embodiment is used for the catalysis of pimelinketone oxamidine performance for illustrating sample obtained by embodiment 1-4, and concrete grammar is as follows：
0.5g embodiment samples, 1.0g Ketohexamethylene, the 1.7g tert-butyl alcohols and 1.7g water are added in there-necked flask, are heated up and is kept to 80
℃.Under stirring, will be added drop-wise in said mixture in 3.6g strong aqua ammonia and 3.9g hydrogen peroxide using constant pressure funnel, dripped
It is 2 hours between the added-time, isothermal reaction 30 minutes again after hydrogen peroxide is added, reaction terminates.With toluene as internal standard, gas chromatogram point
Division thing, evaluating data are listed in table 1.
The ratio of catalytic result of the 1 fluorine-containing titanium phosphate aluminum molecular screen of table with titanium phosphate aluminum molecular screen in Ketohexamethylene oximation reaction
Compared with
| Sample | Ketohexamethylene conversion ratio (%) | Cyclohexanone-oxime selectivity (%) |
| Comparative example 1 | 61.18 | 59.47 |
| Embodiment 1 | 63.83 | 80.62 |
| Embodiment 2 | 67.76 | 85.35 |
| Embodiment 3 | 71.92 | 90.03 |
| Embodiment 4 | 74.66 | 86.43 |
As shown in Table 1, it is used to be catalyzed ring using the fluorine-containing titanium phosphate aluminum molecular screen F-TAPO-5 prepared by the inventive method
Hexanone Ammoximation reaction, its Ketohexamethylene conversion ratio and cyclohexanone-oxime selectivity are above TAPO-5 obtained by traditional method.This be by
After fluorine richness, the hydrophobicity of catalyst surface is improved, and the acid enhancings of Lewis in active center, improves catalyst
Activation capacity to hydrogen peroxide, the final cyclohexanone oxamidinating performance for improving catalyst.Fluorine richness prepared by this explanation this method
The oximes performance of catalysis of titanium phosphate aluminum molecular screen F-TAPO-5 is higher than TAPO-5 molecular sieves obtained by traditional method.
Claims (6)
1. a kind of preparation method of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5, it is characterised in that comprise the following steps：
(1) be stirred vigorously it is lower by phosphorus source, silicon source, fluorine-containing titanium source, template and deionized water according to mol ratio 0.96:1.5:
0.04-0.3:0.8:50 mix homogeneously, obtain molecular sieve precursor colloidal sol after 25-35 DEG C of stirring 20-40 minute；Precursor sol is turned
Enter in the water heating kettle with PTFE linings, in 160～185 DEG C of 18～30h of Crystallizing treatment；After crystallization terminates, centrifugation goes out solid
Body, distilled water cleaning solid to neutrality are dried 10-15h and obtain fluorine-containing titanium phosphate aluminum molecular screen original powder after 90-110 DEG C；
(2) molecular screen primary powder that step (1) is obtained is put into into tube furnace constant temperature zone, is roasted in 500～650 DEG C under oxygen atmosphere
Burn 4～8h and remove template, obtain fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5；
The fluorine-containing titanium source is ammonium hexa-fluorotitanate.
2. the preparation method of a kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 according to claim 1, its feature exist
In：In the step (1), phosphorus source is phosphoric acid, and silicon source is aluminium hydroxide, and template is N- methyldicyclohexyl amine.
3. the preparation method of a kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 according to claim 1, its feature exist
In：In the step (1), 25-35 DEG C of stirring 20-40 minute is replaced by 30 DEG C and stirs 30 minutes.
4. the preparation method of a kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 according to claim 1, its feature exist
In：Baking temperature in the step (1) is 110 DEG C, and drying time is 12h.
5. the preparation method of a kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 according to claim 1, its feature exist
In：In the step (1), crystallization temperature is 180 DEG C, and crystallization time is 24h.
6. the preparation method of a kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 according to claim 1, its feature exist
In：In the step (2), sintering temperature is 575 DEG C, and roasting time is 6h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932512A (en) * | 1997-08-19 | 1999-08-03 | Exxon Chemical Patents, Inc. | Fluorination of synthesized molecular sieve catalysts for increased selectivity to ethylene during conversion of oxygenates to olefins |
| CN1362363A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Mesoporous aluminium phosphotitanate molecular sieve and its prepn |
| CN102616806A (en) * | 2012-04-20 | 2012-08-01 | 上海卓悦化工科技有限公司 | Method for preparing high-performance titanium and silicon molecular sieve |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932512A (en) * | 1997-08-19 | 1999-08-03 | Exxon Chemical Patents, Inc. | Fluorination of synthesized molecular sieve catalysts for increased selectivity to ethylene during conversion of oxygenates to olefins |
| CN1362363A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Mesoporous aluminium phosphotitanate molecular sieve and its prepn |
| CN102616806A (en) * | 2012-04-20 | 2012-08-01 | 上海卓悦化工科技有限公司 | Method for preparing high-performance titanium and silicon molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| ALMUDENA ALFAYATE ET AL.: "Enhanced catalytic activity of TAPO-5 in the oxidation of cyclohexene with hydrogen peroxide under anhydrous conditions", 《CATALYSIS TODAY》 * |
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