CN103771433A - Preparation method of heteroatomic SAPO-11 molecular sieve - Google Patents
Preparation method of heteroatomic SAPO-11 molecular sieve Download PDFInfo
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- CN103771433A CN103771433A CN201210413481.XA CN201210413481A CN103771433A CN 103771433 A CN103771433 A CN 103771433A CN 201210413481 A CN201210413481 A CN 201210413481A CN 103771433 A CN103771433 A CN 103771433A
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- molecular sieve
- sapo
- hydrotalcite
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Abstract
The invention relates to a preparation method of a heteroatomic SAPO-11 molecular sieve, which comprises the following steps: i) mixing hydrotalcite, a phosphorus source, an organic template agent and a silicone source to obtain a colloidal mixture; ii) crystallizing the colloidal mixture; iii) washing and drying the crystallization product to obtain the heteroatomic SAPO-11 molecular sieve. The heteroatomic SAPO-11 molecular sieve is a heteroatomic Mg-SAPO-11 molecular sieve or a heteroatomic Co-SAPO-11 molecular sieve. The nontoxic and harmless hydrotalcite with a special layered structure is used during the synthesis process is used as an aluminum source and a heteroatomic precursor, so that the performance of the heteroatomic SAPO-11 molecular sieve is improved, the kinds of reaction raw materials are reduced, the crystallization time is shortened, the crystallinity of the heteroatomic SAPO-11 molecular sieve is high, the crystal size is controllable, and the method is mild in reaction condition, and simple to operate.
Description
Technical field
The present invention relates to a kind of preparation method of heteroatoms SAPO-11 molecular sieve.
Background technology
Hetero-atom molecular-sieve is the kind getting most of the attention in numerous molecular sieves.Hetero-atom molecular-sieve can be regarded as the special metal complexes of a class, by the transition metal (Ti, V, Gr, Mn, Fe etc.) with oxidisability is incorporated in molecular sieve, thereby obtains active centre separated from one another, high dispersing; The special pore passage structure that molecular sieve itself has, for active centre provides suitable space, makes hetero-atom molecular-sieve possess the shape selective of oxidation activity and molecular sieve simultaneously, thereby can catalyze and synthesize object product by highly selective.
Phosphate aluminium molecular sieve (AlPO
4-n) strictly by AlO
4with PO
4alternately composition of two kinds of tetrahedrons, does not have tradable electric charge, thereby does not have acidity.Therefore, because it does not have special catalytic capability, so also very limited in the application of catalyzed reaction.But, along with the metal heteroatoms such as Si and Co, Zn, Mg are introduced AlPO in succession
4in the skeleton of-n molecular sieve, form SAPO, MeAPO and the MeSAPO molecular sieve of substituted type, thereby make there has been tradable electric charge in the skeleton of molecular sieve, and improved to a great extent its catalytic performance.
U.S. Pat 4793984 discloses a kind of preparation method of MeAPSO-11 molecular sieve, wherein heteroatoms metal M e is selected from Be, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti, V, Zn etc., and template is selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, di-n-propylamine, Tri-n-Propylamine, diethanolamine, hexahydroaniline etc.; Its concrete preparation method is by the acetate of phosphorus source, water, aluminium source, silicon source, heteroatoms metal or vitriol and template mixing, then at 150-200 ℃, after crystallization 4-10 days, obtains described MeAPSO-11 molecular sieve.
Document Applied Catalyst A (1996), 143 (1): 101-110 has reported containing the synthetic of MgAPO-11, the FeASO-11 of transition metal atoms, CoAPO-11, FeMnAPO-11 molecular sieve and reacted the application generating in Resorcinol at phenol with hydrogen peroxide.Wherein, synthetic MgAPO-11 is take di-n-propylamine as template, and synthetic FeASO-11, CoAPO-11 are take Diisopropylamine as template; Raw material makes corresponding molecular sieve through filtration, washing and oven dry after crystallization 24-168 hour respectively after mixing at 150-200 ℃.
Hydrotalcite (LDH) be a kind of nontoxic, harmless, containing heavy metal, environment amenable inorganic materials.Specifically, hydrotalcite is the novel inorganic functional materials that a class has laminate structure, and the factors such as its main body laminate chemical constitution and its laminate cationic characteristic, laminate electric density or anion exchange capacity, supermolecular intercalation structure are closely related.In general, as long as metallic cation has suitable ionic radius and charge number, all can form LDH laminate.Its chemical constitution can be expressed as [M
iI 1-xm
iII x(OH)
2]
x+(A
n-)
x/nmH
2o, wherein M
iIfor Mg
2+, Ni
2+, Co
2+deng divalent metal; M
iIIfor Al
3+, Cr
3+, Fe
3+deng trivalent metal cation; A
n-for negatively charged ion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-etc. inorganic and organic ion and complexing ion.Interlayer inorganic anion difference, the interlamellar spacing of hydrotalcite is different.The special laminate structure of hydrotalcite makes it can bring into play favourable, outstanding effect in some field.But the application of hydrotalcite in molecular sieve, especially heteroatoms SAPO-11 molecular sieve at present still still rarely has report.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing heteroatoms SAPO-11 molecular sieve using hydrotalcite as aluminium source and heteroatoms presoma.
According to the present invention, a kind of preparation method of heteroatoms SAPO-11 molecular sieve is provided, comprise the following steps: i) hydrotalcite, phosphorus source, organic formwork agent and silicon source are mixed, obtain colloidal mixture; Ii) by colloidal mixture crystallization i) obtaining; Iii) the crystallization product ii) obtaining is washed, dry, obtain heteroatoms SAPO-11 molecular sieve.
Preferably, in step I) in the colloidal mixture that obtains, in mole number R:Al
2o
3: P
2o
5: SiO
2: MO:H
2o=a:1:b:c:d:e; Wherein, R is organic formwork agent, and M is the transition metals such as Mg, Co, Mn or Ni, and a is 0.1-2.0, and b is 0.5-1.2, and c is 0.01-1.2, and d is 4.0-8.0, and e is 15-80; Preferably a is 0.2-1.6, and b is 0.6-1.0, and c is 0.05-1.0, and d is 4.0-6.0, and e is 20-70; Further preferably a is 0.5-1.0, and b is 0.8-1.0, and c is 0.1-0.6, and d is 4.0-5.0, and e is 30-60.
In one embodiment, above-mentioned heteroatoms SAPO-11 molecular sieve is heteroatoms Mg-SAPO-11 molecular sieve or heteroatoms Co-SAPO-11 molecular sieve.
Hydrotalcite used in the present invention, its chemical constitution general formula can be expressed as [M
2+ 1-xm
3+ x(OH)
2]
x+(A
n-)
x/nmH
2o, wherein M
2+for Mg
2+, Ni
2+, Co
2+, Mn
2+deng divalent metal, M
3+for Al
3+, Cr
3+, Fe
3+deng trivalent metal cation, A
n-for negatively charged ion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-etc. inorganic and organic ion and complexing ion, x is M
3+/ (M
2++ M
3+) molar ratio, the quantity that m is crystal water.In one embodiment, hydrotalcite is elected magnesium aluminum-hydrotalcite or cobalt aluminum hydrotalcite as.
The silicon source, phosphorus source and the organic formwork agent that in the inventive method, use are conventional.As silicon source, can use any silicon source for the synthesis of heteroatoms SAPO-11 molecular sieve, be for example selected from one or more in White Carbon black, tetraethoxy, solid silicone and silicon sol; Phosphorus source can be one or more in phosphorous compound and phosphoric compound, is preferably phosphoric acid or phosphorous acid; As organic formwork agent, can use any organic formwork agent for the synthesis of heteroatoms SAPO-11 molecular sieve, be for example selected from one or more in di-n-propyl amine, diisopropylamine and diethylamide.
In a preferred embodiment of the inventive method, phosphorus source used is phosphoric acid, and hydrotalcite is magnesium aluminum-hydrotalcite, and silicon source is silicon sol, and organic formwork agent is di-n-propyl amine.
In the present invention, crystallization is preferably undertaken by hydrothermal crystallizing, and wherein hydrothermal crystallizing temperature is 100-220 ℃, is preferably 180-200 ℃, more preferably 180-200 ℃, and pressure is autogenous pressure, crystallization time is 1-24h.
Particularly preferably be, hydrothermal crystallizing carries out 2-24 hour under the temperature of 180-200 ℃ and autogenous pressure.
Washing for above-mentioned steps in iii), can be used the washing methods such as filtration washing, centrifuge washing conventionally, preferably uses centrifuge washing.
Dry for above-mentioned steps in iii) carries out conventionally at 80-130 ℃, preferably at 110-130 ℃, carries out; Be generally 2-48 hour time of drying, be preferably 2-24 hour.
In a preferred embodiment, step I) comprising: hydrotalcite is dissolved in to the aqueous solution that is made into hydrotalcite in water, then in the described aqueous solution, adds phosphorus source, after stirring, then add successively organic formwork agent and silicon source.
In a particularly preferred embodiment of the method for the invention, comprise the steps:
A: hydrotalcite is dissolved in to the aqueous solution that is made into hydrotalcite in water, stirs 0.5-2h;
B: phosphoric acid is incorporated in the aqueous solution of the hydrotalcite obtaining in steps A, stirs 0.5-2h, then add successively wherein again di-n-propyl amine and silicon sol, stir 1-4h, obtain having with mole number and count R:Al
2o
3: P
2o
5: SiO
2: MO:H
2the colloidal mixture of O=a:1:b:c:d:e, wherein R is di-n-propyl amine, M, a, b, c, d and e above define as the present invention;
C: by the colloidal mixture of step B gained hydrothermal crystallizing 2-24 hour at 150-200 ℃;
D: leach step C gained crystallization product, washing, then dry 2-24 hour at 80-130 ℃, obtains heteroatoms SAPO-11 molecular sieve.According to the method for preparing heteroatoms SAPO-11 molecular sieve of the present invention, nontoxic, harmless by using in building-up process, and there is the hydrotalcite of special laminate structure as aluminium source and heteroatoms presoma, reduced the kind of reaction raw materials, shortened crystallization time; The product degree of crystallinity of preparing is high, and is easy to control the granularity of product crystal; In addition, methods experiment of the present invention is simple to operate, easily completes.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the final product that obtains of embodiment 1.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but scope of invention is not limited to these embodiment.
In following examples, identify by X-ray diffraction spectrum figure whether the final product obtaining by the inventive method is heteroatoms Mg-SAPO-11 molecular sieve.The instrument adopting is the ARL X ' TRA of power & light company of U.S. type diffractometer, is specifically 35kV at x-ray tube voltage, and electric current is 30mA, and sweep limit is 3-40 °, and sweep velocity is, under the condition of 2 °/min, sample is carried out to qualitative analysis.
Embodiment 1
Take 32.76g(0.14mol) magnesium aluminum-hydrotalcite, be dissolved in 10g deionized water and be made into the magnesium aluminum-hydrotalcite aqueous solution, stir 0.5h.Then under vigorous stirring, splash into wherein 16.14g(0.14mol) H
3pO
4(the 85 % by weight aqueous solution), then stir 1h.Measuring 4.78ml(0.035mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then taking again 10.08g(0.042mol) silicon sol joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, wherein in mole number R:Al
2o
3: P
2o
5: SiO
2: MgO:H
2o=0.5:1:1:0.6:4:50, R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 180 ℃ under air-tight state, hydrothermal crystallizing 3h under autogenous pressure.
Crystallization product is leached, cooling, centrifuge washing, then dry 12h at 120 ℃, obtains heteroatoms Mg-SAPO-11 molecular sieve product, and its X-ray powder diffraction figure is as shown in Figure 1.
Embodiment 2
Take 32.76g(0.14mol) magnesium aluminum-hydrotalcite, be dissolved in 10g deionized water and be made into the magnesium aluminum-hydrotalcite aqueous solution, stir 0.5h.Then under vigorous stirring, splash into wherein 16.14g(0.14mol) H
3pO
4(the 85 % by weight aqueous solution), then stir 1h.Measuring 3.82ml(0.028mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then taking again 10.08g(0.042mol) silicon sol joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, wherein in mole number R:Al
2o
3: P
2o
5: SiO
2: MgO:H
2o=0.4:1:1:0.6:4:50, R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 190 ℃ under air-tight state, hydrothermal crystallizing 4h under autogenous pressure.
Crystallization product is leached, and cooling, centrifuge washing, then in 120 ℃ of dry 6h, obtains heteroatoms Mg-SAPO-11 molecular sieve product, and its X-ray powder diffraction figure (not shown) and Fig. 1 are basic identical.
Embodiment 3
Take 32.76g(0.14mol) magnesium aluminum-hydrotalcite, be dissolved in 10g deionized water and be made into the magnesium aluminum-hydrotalcite aqueous solution, stir 0.5h.Then under vigorous stirring, splash into wherein 16.14g(0.14mol) H
3pO
4(the 85 % by weight aqueous solution), then stir 1h.Measuring 2.86ml(0.021mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then taking again 10.08g(0.042mol) silicon sol joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, wherein in mole number R:Al
2o
3: P
2o
5: SiO
2: MgO:H
2o=0.3:1:1:0.6:4:50, R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 200 ℃ under air-tight state, hydrothermal crystallizing 2h under autogenous pressure.
Crystallization product is leached, and cooling, centrifuge washing, then in 110 ℃ of dry 12h, obtains heteroatoms Mg-SAPO-11 molecular sieve product, and its X-ray powder diffraction figure (not shown) and Fig. 1 are basic identical.
Embodiment 4
Take 42.54g(0.14mol) cobalt aluminum hydrotalcite, be dissolved in 10g deionized water and be made into the cobalt aluminum hydrotalcite aqueous solution, stir 0.5h.Then under vigorous stirring, splash into wherein 16.14g(0.14mol) H
3pO
4(the 85 % by weight aqueous solution), then stir 1h.Measuring 3.82ml(0.028mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then taking again 10.08g(0.042mol) silicon sol joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, wherein in mole number R:Al
2o
3: P
2o
5: SiO
2: CoO:H
2o=0.4:1:1:0.6:4:50, R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 200 ℃ under air-tight state, hydrothermal crystallizing 2h under autogenous pressure.
Crystallization product is leached, and cooling, centrifuge washing, then in 110 ℃ of dry 12h, obtains heteroatoms Co-SAPO-11 molecular sieve product, and its X-ray powder diffraction figure (not shown) and Fig. 1 are basic identical.
As can be seen from Figure 1, be the characteristic peak that 8.15 °, 9.40 °, 13.20 ° and 15.57 ° etc. have located all to occur heteroatoms SAPO-11 at 2 θ, show that final product that embodiment 1 obtains has the structure of SAPO-11 molecular sieve.The final product that the final product of embodiment 2-3 obtains with embodiment 1 has identical structure.
Claims (10)
1. a preparation method for heteroatoms SAPO-11 molecular sieve, comprises the following steps:
I) hydrotalcite, phosphorus source, organic formwork agent and silicon source are mixed, obtain colloidal mixture;
Ii) by colloidal mixture crystallization i) obtaining; And
Iii) the crystallization product ii) obtaining is washed, dry, obtain heteroatoms SAPO-11 molecular sieve.
2. method according to claim 1, is characterized in that, in step I) in the colloidal mixture that obtains, in mole number R:Al
2o
3: P
2o
5: SiO
2: MO:H
2o=a:1:b:c:d:e; Wherein, R is organic formwork agent, and M is Mg, Co, Mn or Ni, and a is 0.1-2.0, and b is 0.5-1.2, and c is 0.01-1.2, and d is 4.0-8.0, and e is 15-80.
3. method according to claim 2, is characterized in that, a is 0.2-1.6, and b is 0.6-1.0, and c is 0.05-1.0, and d is 4.0-6.0, and e is 20-70.
4. method according to claim 3, is characterized in that, a is 0.5-1.0, and b is 0.8-1.0, and c is 0.1-0.6, and d is 4.0-5.0, and e is 30-60.
5. method according to claim 1, is characterized in that, described heteroatoms SAPO-11 molecular sieve is heteroatoms Mg-SAPO-11 molecular sieve or heteroatoms Co-SAPO-11 molecular sieve.
6. method according to claim 1, is characterized in that, the chemical constitution general formula of described hydrotalcite is [M
2+ 1-xm
3+ x(OH)
2]
x+(A
n-)
x/nmH
2o, wherein M
2+for divalent metal, be preferably Mg
2+, Ni
2+, Co
2+, Mn
2+; M
3+for trivalent metal cation, be preferably Al
3+, Cr
3+, Fe
3+; A
n-for negatively charged ion, be preferably CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-; X is M
3+/ (M
2++ M
3+) molar ratio; M is the quantity of crystal water; Described hydrotalcite is preferably magnesium aluminum-hydrotalcite or cobalt aluminum hydrotalcite.
7. according to the method described in any one in claim 1-6, it is characterized in that, described silicon source is selected from one or more in White Carbon black, tetraethoxy, solid silicone and silicon sol; Described phosphorus source is phosphoric acid or phosphorous acid; Described organic formwork agent is selected from one or more in di-n-propyl amine, diisopropylamine and diethylamide.
8. according to the method described in any one in claim 1-7, it is characterized in that, described crystallization is undertaken by hydrothermal crystallizing, and wherein hydrothermal crystallizing temperature is 100-220 ℃, is preferably 180-200 ℃, and pressure is autogenous pressure, and crystallization time is 1-24h.
9. according to the method described in any one in claim 1-7, it is characterized in that, filtration washing or centrifuge washing are selected in step I washing ii); Drying temperature is 80-130 ℃, and be 2-48 hour time of drying.
10. method according to claim 7, is characterized in that, step I) comprising: hydrotalcite is dissolved in to the aqueous solution that is made into hydrotalcite in water, then in the described aqueous solution, adds phosphorus source, after stirring, then add successively organic formwork agent and silicon source.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030315A (en) * | 2014-06-25 | 2014-09-10 | 常州大学 | Method for synthesizing heteroatom aluminophosphate molecular sieve by utilizing natural ore |
| CN113353954A (en) * | 2021-06-30 | 2021-09-07 | 福州大学 | Green synthetic step pore SAPO-11 molecular sieve based on natural minerals and preparation method thereof |
| CN114956115A (en) * | 2021-02-24 | 2022-08-30 | 中国石油天然气股份有限公司 | Metal modified Y-type molecular sieve and preparation method thereof |
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| CN1304874A (en) * | 2000-06-13 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Si-Zn molecular sieve and its synthesizing process |
| CN1724356A (en) * | 2004-07-19 | 2006-01-25 | 中国石油化工股份有限公司 | Molecular sieve with AWo structure containing heteroatom and its synthesizing process |
| CN102744092A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Phosphor and rare earth modified molecular sieve |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1304874A (en) * | 2000-06-13 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Si-Zn molecular sieve and its synthesizing process |
| CN1724356A (en) * | 2004-07-19 | 2006-01-25 | 中国石油化工股份有限公司 | Molecular sieve with AWo structure containing heteroatom and its synthesizing process |
| CN102744092A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Phosphor and rare earth modified molecular sieve |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030315A (en) * | 2014-06-25 | 2014-09-10 | 常州大学 | Method for synthesizing heteroatom aluminophosphate molecular sieve by utilizing natural ore |
| CN104030315B (en) * | 2014-06-25 | 2015-12-02 | 常州大学 | A kind of method utilizing natural ore soil to synthesize heteroatoms aluminium phosphate molecular sieve |
| CN114956115A (en) * | 2021-02-24 | 2022-08-30 | 中国石油天然气股份有限公司 | Metal modified Y-type molecular sieve and preparation method thereof |
| CN113353954A (en) * | 2021-06-30 | 2021-09-07 | 福州大学 | Green synthetic step pore SAPO-11 molecular sieve based on natural minerals and preparation method thereof |
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