CN103771433B - A kind of preparation method of hetero atom SAPO-11 molecular sieve - Google Patents
A kind of preparation method of hetero atom SAPO-11 molecular sieve Download PDFInfo
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- CN103771433B CN103771433B CN201210413481.XA CN201210413481A CN103771433B CN 103771433 B CN103771433 B CN 103771433B CN 201210413481 A CN201210413481 A CN 201210413481A CN 103771433 B CN103771433 B CN 103771433B
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Abstract
The present invention relates to a kind of preparation method of hetero atom SAPO-11 molecular sieve, comprise the following steps: i) by hydrotalcite, phosphorus source, organic formwork agent and the mixing of silicon source, obtain colloidal mixture; Ii) the colloidal mixture crystallization will i) obtained; Iii) the crystallization product washing will ii) obtained, dry, obtain hetero atom SAPO-11 molecular sieve.This hetero atom SAPO-11 molecular sieves is as being hetero atom Mg-SAPO-11 molecular sieve or hetero atom Co-SAPO-11 molecular sieve etc.The present invention is nontoxic, harmless by using in building-up process, and there is the hydrotalcite of special layer structure as aluminium source and hetero atom presoma, improve the performance of hetero atom SAPO-11 molecular sieve, decrease the kind of reaction raw materials, shorten crystallization time, and product degree of crystallinity is high, and crystal size is controlled; In addition, the method mild condition, simple to operate.
Description
Technical field
The present invention relates to a kind of preparation method of hetero atom SAPO-11 molecular sieve.
Background technology
Hetero-atom molecular-sieve is the kind got most of the attention in numerous molecular sieve.Hetero-atom molecular-sieve can be regarded as the special metal complex of a class, by being incorporated in molecular sieve by the transition metal (Ti, V, Gr, Mn, Fe etc.) with oxidisability, thus obtains activated centre that is separated from one another, high degree of dispersion; The special pore passage structure that molecular sieve itself has, then for activated centre provides suitable space, makes hetero-atom molecular-sieve possess the shape selective of oxidation activity and molecular sieve simultaneously, thus can catalyze and synthesize object product by highly selective.
Phosphate aluminium molecular sieve (AlPO
4-n) strictly by AlO
4with PO
4two kinds of tetrahedrons alternately composition, does not have tradable electric charge, does not thus have acidity.Therefore, because it does not have special catalytic capability, so also very limited in the application of catalytic reaction.But, along with the metal heteroatom such as Si and Co, Zn, Mg is introduced AlPO in succession
4in the skeleton of-n molecular sieve, form SAPO, MeAPO and the MeSAPO molecular sieve of substituted type, thus make in the skeleton of molecular sieve, there has been tradable electric charge, and improve its catalytic performance to a great extent.
US Patent No. 4793984 discloses a kind of preparation method of MeAPSO-11 molecular sieve, wherein hetero atom metal M e is selected from Be, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti, V, Zn etc., and template is selected from TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH, di-n-propylamine, Tri-n-Propylamine, diethanol amine, cyclohexylamine etc.; Its concrete preparation method is by the acetate of phosphorus source, water, aluminium source, silicon source, hetero atom metal or sulfate and template mixing, then at 150-200 DEG C, obtains described MeAPSO-11 molecular sieve after crystallization 4-10 days.
Document AppliedCatalystA (1996), 143 (1): 101-110 report containing the synthesis of MgAPO-11, FeASO-11, CoAPO-11, FeMnAPO-11 molecular sieve of transition metal atoms and react at phenol and hydrogen peroxide the application generated in hydroquinones.Wherein, synthesis MgAPO-11 take di-n-propylamine as template, and synthesis FeASO-11, CoAPO-11 take diisopropylamine as template; At 150-200 DEG C, corresponding molecular sieve is obtained through filtering, washing and dry after crystallization 24-168 hour respectively after raw material mixing.
Hydrotalcite (LDH) be a kind of nontoxic, harmless, not containing heavy metal, environment amenable inorganic material.Specifically, hydrotalcite is the novel inorganic functional material that a class has layer structure, its main body laminate chemical composition and its laminate cationic characteristic, laminate charge density or the factor such as anion exchange capacity, supermolecular intercalation structure closely related.In general, as long as metal cation has suitable ionic radius and charge number, all LDH laminate can be formed.Its chemical composition 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 anion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-etc. inorganic and organic ion and complex ion.Interlevel inorganic anion is different, and the interlamellar spacing of hydrotalcite is then different.The special layer structure of hydrotalcite makes it can play favourable, outstanding effect in some field.But the application of current hydrotalcite in molecular sieve, especially hetero atom SAPO-11 molecular sieve still still rarely has report.
Summary of the invention
The object of the present invention is to provide a kind of method using hydrotalcite as aluminium source and hetero atom precursor power hetero atom SAPO-11 molecular sieve.
According to the present invention, provide a kind of preparation method of hetero atom SAPO-11 molecular sieve, comprise the following steps: i) by hydrotalcite, phosphorus source, organic formwork agent and the mixing of silicon source, obtain colloidal mixture; Ii) the colloidal mixture crystallization will i) obtained; Iii) the crystallization product ii) obtained is washed, dry, obtain hetero atom SAPO-11 molecular sieve.
Preferably, in step I) in the colloidal mixture that obtains, with molar basis 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; Preferred a is 0.2-1.6, b be 0.6-1.0, c be 0.05-1.0, d be 4.0-6.0, e is 20-70; Further preferably a is 0.5-1.0, b be 0.8-1.0, c be 0.1-0.6, d be 4.0-5.0, e is 30-60.
In one embodiment, above-mentioned hetero atom SAPO-11 molecular sieve is hetero atom Mg-SAPO-11 molecular sieve or hetero atom Co-SAPO-11 molecular sieve.
Hydrotalcite used in the present invention, its chemical composition 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 anion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-etc. inorganic and organic ion and complex ion, x is M
3+/ (M
2++ M
3+) molar ratio, m is the quantity of the crystallization water.In one embodiment, hydrotalcite elects magnalium hydrotalcite or cobalt aluminum hydrotalcite as.
The silicon source used in the inventive method, phosphorus source and organic formwork agent are conventional.As silicon source, any silicon source for the synthesis of hetero atom SAPO-11 molecular sieve can be used, such as, be selected from one or more in White Carbon black, ethyl orthosilicate, solid silicone and Ludox; Phosphorus source can be one or more in phosphorous compound and phosphoric compound, is preferably phosphoric acid or phosphorous acid; As organic formwork agent, any organic formwork agent for the synthesis of hetero atom SAPO-11 molecular sieve can be used, such as, be 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 magnalium hydrotalcite, and silicon source is Ludox, and organic formwork agent is di-n-propyl amine.
In the present invention, crystallization is carried out preferably by hydrothermal crystallizing, and wherein hydrothermal crystallizing temperature is 100-220 DEG C, and be preferably 180-200 DEG C, be more preferably 180-200 DEG C, pressure is self-generated pressure, and crystallization time is 1-24h.
Particularly preferably be, hydrothermal crystallizing carries out 2-24 hour at the temperature of 180-200 DEG C and self-generated pressure.
For above-mentioned steps iii) in washing, usually can use the washing methods such as filtration washing, centrifuge washing, preferably use centrifuge washing.
For above-mentioned steps iii) in drying, usually carry out at 80-130 DEG C, preferably carry out at 110-130 DEG C; Drying time is generally 2-48 hour, is preferably 2-24 hour.
In a preferred embodiment, step I) comprising: hydrotalcite is dissolved in water the aqueous solution being made into hydrotalcite, then in the described aqueous solution, adds phosphorus source, after stirring, then add organic formwork agent and silicon source successively.
In a particularly preferred embodiment of the method for the invention, comprise the steps:
A: hydrotalcite is dissolved in water the aqueous solution being made into hydrotalcite, stirs 0.5-2h;
B: be incorporated into by phosphoric acid in the aqueous solution of the hydrotalcite obtained in steps A, stirs 0.5-2h, then adds di-n-propyl amine and Ludox successively wherein again, and stir 1-4h, obtaining having with molar basis is 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 as the present invention above define;
C: by the colloidal mixture of step B gained hydrothermal crystallizing 2-24 hour at 150-200 DEG C;
D: leach step C gained crystallization product, washing, then dry 2-24 hour at 80-130 DEG C, obtains hetero atom SAPO-11 molecular sieve.According to the method preparing hetero atom SAPO-11 molecular sieve of the present invention, nontoxic, harmless by using in building-up process, and the hydrotalcite with special layer structure, as aluminium source and hetero atom presoma, decreases the kind of reaction raw materials, shortens crystallization time; The product degree of crystallinity prepared is high, and is easy to the granularity controlling crystalline product; 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 end product that embodiment 1 obtains.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but scope of invention is not limited to these embodiments.
In the examples below, identify whether the end product obtained by the inventive method is hetero atom Mg-SAPO-11 molecular sieve by X-ray diffraction spectrum figure.The instrument adopted is power & light company of U.S. ARLX ' TRA type diffractometer, and be specifically 35kV at x-ray tube voltage, electric current is 30mA, and sweep limits is 3-40 °, and sweep speed is carry out qualitative analysis to sample under the condition of 2 °/min.
Embodiment 1
Take 32.76g(0.14mol) magnalium hydrotalcite, be dissolved in 10g deionized water and be made into the magnalium hydrotalcite aqueous solution, stir 0.5h.Then 16.14g(0.14mol is instilled wherein with vigorous stirring) H
3pO
4(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 10.08g(0.042mol is taken again) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, wherein with molar basis R:Al
2o
3: P
2o
5: SiO
2: MgO:H
2o=0.5:1:1:0.6:4:50, R are di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 180 DEG C under air-tight state, at autogenous pressures hydrothermal crystallizing 3h.
Leached by crystallization product, cooling, centrifuge washing, then dry 12h at 120 DEG C, obtain hetero atom Mg-SAPO-11 molecular sieve product, and its X-ray powder diffraction figure as shown in Figure 1.
Embodiment 2
Take 32.76g(0.14mol) magnalium hydrotalcite, be dissolved in 10g deionized water and be made into the magnalium hydrotalcite aqueous solution, stir 0.5h.Then 16.14g(0.14mol is instilled wherein with vigorous stirring) H
3pO
4(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 10.08g(0.042mol is taken again) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, wherein with molar basis R:Al
2o
3: P
2o
5: SiO
2: MgO:H
2o=0.4:1:1:0.6:4:50, R are di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 190 DEG C under air-tight state, at autogenous pressures hydrothermal crystallizing 4h.
Leached by crystallization product, cooling, centrifuge washing, then in 120 DEG C of dry 6h, obtain hetero atom Mg-SAPO-11 molecular sieve product, its X-ray powder diffraction figure (not shown) is substantially identical with Fig. 1.
Embodiment 3
Take 32.76g(0.14mol) magnalium hydrotalcite, be dissolved in 10g deionized water and be made into the magnalium hydrotalcite aqueous solution, stir 0.5h.Then 16.14g(0.14mol is instilled wherein with vigorous stirring) H
3pO
4(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 10.08g(0.042mol is taken again) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, wherein with molar basis R:Al
2o
3: P
2o
5: SiO
2: MgO:H
2o=0.3:1:1:0.6:4:50, R are di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 200 DEG C under air-tight state, at autogenous pressures hydrothermal crystallizing 2h.
Leached by crystallization product, cooling, centrifuge washing, then in 110 DEG C of dry 12h, obtain hetero atom Mg-SAPO-11 molecular sieve product, its X-ray powder diffraction figure (not shown) is substantially identical with Fig. 1.
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 16.14g(0.14mol is instilled wherein with vigorous stirring) H
3pO
4(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 10.08g(0.042mol is taken again) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, wherein with molar basis R:Al
2o
3: P
2o
5: SiO
2: CoO:H
2o=0.4:1:1:0.6:4:50, R are di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 200 DEG C under air-tight state, at autogenous pressures hydrothermal crystallizing 2h.
Leached by crystallization product, cooling, centrifuge washing, then in 110 DEG C of dry 12h, obtain hetero atom Co-SAPO-11 molecular sieve product, its X-ray powder diffraction figure (not shown) is substantially identical with Fig. 1.
As can be seen from Figure 1, be the characteristic peak that hetero atom SAPO-11 has all appearred in the places such as 8.15 °, 9.40 °, 13.20 ° and 15.57 ° at 2 θ, indicate the structure that end product that embodiment 1 obtains has SAPO-11 molecular sieve.The end product of embodiment 2-3 has identical structure with the end product that embodiment 1 obtains.
Claims (14)
1. a preparation method for hetero atom SAPO-11 molecular sieve, comprises the following steps:
I) by hydrotalcite, phosphorus source, organic formwork agent and the mixing of silicon source, colloidal mixture is obtained;
Ii) the colloidal mixture crystallization will i) obtained; And
Iii) by ii) crystallization product that obtains washs, dry, obtains hetero atom SAPO-11 molecular sieve;
Wherein, in step I) in the colloidal mixture that obtains, with molar basis 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, b be 0.5-1.2, c be 0.01-1.2, d be 4.0-8.0, e is 15-80.
2. method according to claim 1, is characterized in that, a is 0.2-1.6, b be 0.6-1.0, c be 0.05-1.0, d be 4.0-6.0, e is 20-70.
3. method according to claim 2, is characterized in that, a is 0.5-1.0, b be 0.8-1.0, c be 0.1-0.6, d be 4.0-5.0, e is 30-60.
4. method according to claim 1, is characterized in that, described hetero atom SAPO-11 molecular sieve is hetero atom Mg-SAPO-11 molecular sieve or hetero atom Co-SAPO-11 molecular sieve.
5. method according to claim 1, is characterized in that, the chemical composition 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; M
3+for trivalent metal cation; A
n-for anion; X is M
3+/ (M
2++ M
3+) molar ratio; M is the quantity of the crystallization water.
6. method according to claim 5, is characterized in that, wherein M
2+for Mg
2+, Ni
2+, Co
2+or Mn
2+.
7. method according to claim 5, is characterized in that, wherein M
3+for Al
3+, Cr
3+or Fe
3+.
8. method according to claim 5, is characterized in that, wherein A
n-for CO
3 2-, NO
3 -, Cl
-, OH
-or SO
4 2-.
9. method according to claim 5, is characterized in that, described hydrotalcite is magnalium hydrotalcite or cobalt aluminum hydrotalcite.
10. the method according to any one of claim 1-9, is characterized in that, described silicon source be selected from White Carbon black, ethyl orthosilicate, solid silicone and Ludox one or more; Described phosphorus source is phosphoric acid or phosphorous acid; Described organic formwork agent be selected from di-n-propyl amine, diisopropylamine and diethylamide one or more.
11. methods according to claim 1, is characterized in that, described crystallization is undertaken by hydrothermal crystallizing, and wherein hydrothermal crystallizing temperature is 100-220 DEG C, and pressure is self-generated pressure, and crystallization time is 1-24h.
12. according to method described in claim 11, it is characterized in that, hydrothermal crystallizing temperature is 180-200 DEG C.
13. methods according to claim 1, is characterized in that, step I ii) washing select filtration washing or centrifuge washing; Baking temperature is 80-130 DEG C, and drying time is 2-48 hour.
14. methods according to claim 10, is characterized in that, step I) comprising: hydrotalcite is dissolved in water the aqueous solution being made into hydrotalcite, then in the described aqueous solution, adds phosphorus source, after stirring, then add organic formwork agent and silicon source successively.
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| 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 |
| CN113353954B (en) * | 2021-06-30 | 2022-10-04 | 福州大学 | Green synthetic stepped pore SAPO-11 molecular sieve based on natural minerals 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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