CN102285663A - Synthesis method of low-fluorine AlPO4-34 aluminum phosphate molecular sieve - Google Patents
Synthesis method of low-fluorine AlPO4-34 aluminum phosphate molecular sieve Download PDFInfo
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- CN102285663A CN102285663A CN2011101906575A CN201110190657A CN102285663A CN 102285663 A CN102285663 A CN 102285663A CN 2011101906575 A CN2011101906575 A CN 2011101906575A CN 201110190657 A CN201110190657 A CN 201110190657A CN 102285663 A CN102285663 A CN 102285663A
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- molecular sieve
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Abstract
The invention provides a synthesis method of low-fluorine AlPO4-34 aluminum phosphate molecular sieve. The method comprises: mixing pseudoboehmite (Al2O3) serving as an aluminum source, phosphoric acid (H3PO4) serving as a phosphorus source, morpholine serving as an organic template agent, hydrofluoric acid (HF) and water (H2O) according to a molar ratio of 0.5:1.0:(1.0-3.0):(0.05-0.33):(25-100) to prepare a synthetic colloid; and hydrothermally crystallizing the colloid for 36 to 120 hours at 160 to 200 DEG C and under a self-generated pressure; washing with water, separating and drying at a temperature between room temperature and 80 DEG C; and thus, obtaining the product. When the method provided by the invention is used, the AlPO4-34 molecular sieve product can be prepared by an environment-friendly process.
Description
Technical field
The present invention relates to the synthetic method of aluminium phosphate molecular sieve, specifically is low hexafluorophosphoric acid aluminum molecular screen AlPO
4-34 synthetic method.By changing aluminium phosphate molecular sieve AlPO
4The consumption of organic formwork agent and synthesis condition in-34 building-up processes can synthesize partly alternative F of O and Al formation coordinate aluminium phosphate molecular sieve AlPO in the skeleton
4-34 products, thus hydrofluoric acid consumption in the building-up process reduced, reach the purpose of environmental protection.
Background technology
Aluminium phosphate molecular sieve AlPO
4-34 skeleton is made of P, Al, O, F element, and part A l and F form coordination, belong to triclinic(crystalline)system, unit cell dimension is the a=0.90 nanometer, b=0.93 nanometer, c=0.95 nanometer, the CHA structure of its similar international zeolite association name has the cage type channel system of octatomic ring opening.AlPO
4In-34 the skeleton, part A l and F form hexa-coordinate, and the Al-F key can disconnect about 350 ℃, and whole skeleton is converted into the CHA structure.But analyze the synthetic method and the AlPO of bibliographical information
4Find in the comparison of-34 monocrystalline data that the aluminium fluorine is than the numerical value that all provides less than monocrystalline 1: 0.33, the i.e. AlPO of bibliographical information in synthetic the feeding intake
4-34 synthetic in the F ions excessive, and crystalline framework all is the F ion with part A l formation coordinate.
The AlPO of document Microporous and Mesoporous Materials 30 (1999) 145-153 report
4-34 the synthetic aluminium fluorine ratio that feeds intake is 1: 0.35; Document J.Phys.Chem.B 2000,104, the AlPO of 5697-5705 report
4-34 the synthetic aluminium fluorine ratio that feeds intake is 1: 0.5.Hydrofluoric acid has intensive corrodibility to equipment, also can pollute environment, so reduce the hydrofluoric acid amount for AlPO
4-34 molecular sieve suitability for industrialized production have the potential meaning.
Summary of the invention
The object of the present invention is to provide AlPO
4The synthetic method of-34 aluminium phosphate molecular sieves by changing the consumption of hydrofluoric acid and organic formwork agent, can synthesize the aluminium fluorine with F in shortage than the AlPO that is higher than bibliographical information
4The zeolite product of-34 monocrystalline, wherein partly replacing F and Al formation coordinate part central atom is O.
The present invention is through following step: aluminium source, phosphorus source, organic formwork agent, hydrofluoric acid and water or aluminium source, phosphorus source, organic formwork agent, hydrofluoric acid and water are mixed make synthetic colloid earlier, the temperature when becoming glue is 15～35 ℃.Should synthesize colloid hydrothermal crystallizing 36～120 hours under 160～200 ℃ and autogenous pressure then, collect, wash and be drying to obtain product.
Aluminium of the present invention source is with Al
2O
3Meter, the phosphorus source is H
3PO
4Meter, organic formwork agent is represented with R.Reaction mass is according to synthetic colloid: the Al of following mole proportioning
2O
3: H
3PO
4: R: HF: H
2O=0.5: 1.0: 1.0～3.0: 0.05～0.33: 25～100, preferred Al
2O
3: H
3PO
4: R: HF: H
2O=0.5: 1.0: 1.0～2.0: 0.1～0.2: 25～75.
In the inventive method, said phosphorus source is a phosphoric acid; The aluminium source is the salt of pseudo-boehmite, aluminum isopropylate, aluminium hydroxide, aluminum oxide and aluminium; Organic formwork agent is morpholine, piperidines and pyridine.
In the inventive method, preferably phosphoric acid is the phosphorus source, and pseudo-boehmite is the aluminium source, and morpholine is a template.
In the inventive method, said phosphorus source, aluminium source, organic formwork agent and hydrofluoric addition sequence are the order addings according to phosphorus source, aluminium source, hydrofluoric acid, organic formwork agent.
In the inventive method, preferably will synthesize colloid hydrothermal crystallizing 48～96 hours under 180～200 ℃ and autogenous pressure, collect, wash and be drying to obtain product then.
The invention has the beneficial effects as follows: at AlPO provided by the present invention
4The consumption of hydrofluoric acid can be reduced significantly in the synthetic method of-34 molecular sieves, and zeolite product that synthesizes and skeleton part all are the AlPO of fluorion
4-34 crystalline structure are identical, and character such as thermogravimetric are variant.
The present invention is further described below in conjunction with accompanying drawing and embodiment.
Description of drawings
Fig. 1 is with excessive F synthetic AlPO
4-34 x-ray diffractogram of powder (XRD).
Fig. 2 is the embodiment of the invention 1 described product A lPO
4-34 x-ray diffractogram of powder (XRD).
Fig. 3 is the embodiment of the invention 1 described product A lPO
4-34 SEM photo.
Fig. 4 is the embodiment of the invention 1 described product A lPO
4-34 with AlPO shown in Figure 1
4Thermogravimetric result's contrast of-34.
Embodiment
Embodiment 1
At 20 ℃, with 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, pouring 0.87 gram pseudo-boehmite pressed powder into stirs, the hydrofluoric acid that adds 0.09 milliliter again, drip 1.9 milliliters of morpholines while stirring, be stirred to even back and move in 20 milliliters of stainless steel cauldrons in 200 ℃ of crystallization 48 hours, the post-treating method of molecular sieve is routinely then collected, washing and 80 ℃ of dryings.
Embodiment 2
At 20 ℃, with 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, pouring 0.87 gram pseudo-boehmite pressed powder into stirs, the hydrofluoric acid that adds 0.05 milliliter again, drip 1.9 milliliters of morpholines while stirring, be stirred to even back and move in 20 milliliters of stainless steel cauldrons in 200 ℃ of crystallization 96 hours, the post-treating method of molecular sieve is routinely then collected, washing and 80 ℃ of dryings.
Embodiment 3
At 20 ℃, with 0.51 milliliter of phosphoric acid of 10 ml waters dissolving, pouring 0.58 gram pseudo-boehmite pressed powder into stirs, the hydrofluoric acid that adds 0.05 milliliter again, drip 1.9 milliliters of morpholines while stirring, be stirred to even back and move in 20 milliliters of stainless steel cauldrons in 180 ℃ of crystallization 72 hours, the post-treating method of molecular sieve is routinely then collected, washing and 80 ℃ of dryings.
Embodiment 4
At 20 ℃, with 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, pouring 0.87 gram pseudo-boehmite pressed powder into stirs, the hydrofluoric acid that adds 0.08 milliliter again, drip 1.5 milliliters of morpholines while stirring, be stirred to even back and move in 20 milliliters of stainless steel cauldrons in 190 ℃ of crystallization 80 hours, the post-treating method of molecular sieve is routinely then collected, washing and 80 ℃ of dryings.
At 20 ℃, with 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, pouring 0.87 gram pseudo-boehmite pressed powder into stirs, the hydrofluoric acid that adds 0.1 milliliter again, drip 1.0 milliliters of morpholines while stirring, be stirred to even back and move in 20 milliliters of stainless steel cauldrons in 190 ℃ of crystallization 96 hours, the post-treating method of molecular sieve is routinely then collected, washing and 80 ℃ of dryings.
Embodiment 6
At 20 ℃, with 1.52 milliliters of phosphoric acid of 10 ml waters dissolving, pouring 1.74 gram pseudo-boehmite pressed powders into stirs, the hydrofluoric acid that adds 0.1 milliliter again, drip 1.0 milliliters of morpholines while stirring, be stirred to even back and move in 20 milliliters of stainless steel cauldrons in 180 ℃ of crystallization 96 hours, the post-treating method of molecular sieve is routinely then collected, washing and 80 ℃ of dryings.
Claims (8)
1. low fluorine AlPO
4The synthetic method of-34 aluminium phosphate molecular sieves is characterized in that through following step:
Aluminium source, phosphorus source, organic formwork agent, hydrofluoric acid and water mixed make synthetic colloid, temperature when becoming glue is 15～35 ℃, should synthesize colloid hydrothermal crystallizing 36～120 hours under 160～200 ℃ and autogenous pressure then, and collect then, wash and dry, promptly get product;
Wherein, the addition sequence of described phosphorus source, aluminium source, organic formwork agent and hydrofluoric acid is the order adding according to aluminium source, phosphorus source, hydrofluoric acid, organic formwork agent, and synthetic colloidal material mole proportioning is Al
2O
3: H
3PO
4: organic formwork agent: HF: H
2O=0.5: 1.0: 1.0～3.0: 0.05～0.33: 25～100.
2. according to the synthetic method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that described mole proportion optimization is Al
2O
3: H
3PO
4: organic formwork agent: HF: H
2O=0.5: 1.0: 1.0～2.0: 0.1～0.2: 25～75.
3. according to the synthetic method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that described aluminium source is a pseudo-boehmite.
4. according to the synthetic method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that described organic formwork agent is a morpholine.
5. according to the synthetic method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that the described fluorine aluminum ratio that feeds intake was less than 1: 3.
6. according to the synthetic method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that described synthetic colloid hydrothermal crystallizing 48～96 hours under 180～200 ℃ and autogenous pressure, collect then, wash and 60～80 ℃ of oven dry, obtain product.
7. according to the synthetic method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that products obtained therefrom structure and fluorine aluminum ratio were greater than 1: 3 AlPO
4-34 aluminium phosphate molecular sieves are basic identical, and character is different.
8. according to the synthetic method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that products obtained therefrom partly substitutes F and Al by O and forms coordination.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445244A (en) * | 2014-11-28 | 2015-03-25 | 天津神能科技有限公司 | Aluminophosphate molecular sieve AlPO4-34 and fluoride-free preparation method thereof |
| CN104941679A (en) * | 2015-06-29 | 2015-09-30 | 李梦燕 | Method for preparing nano-modified composite molecular sieve |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092737A (en) * | 2011-01-20 | 2011-06-15 | 南开大学 | Synthetic method of AlPO4-34 aluminum phosphate molecular sieve |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092737A (en) * | 2011-01-20 | 2011-06-15 | 南开大学 | Synthetic method of AlPO4-34 aluminum phosphate molecular sieve |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445244A (en) * | 2014-11-28 | 2015-03-25 | 天津神能科技有限公司 | Aluminophosphate molecular sieve AlPO4-34 and fluoride-free preparation method thereof |
| CN104941679A (en) * | 2015-06-29 | 2015-09-30 | 李梦燕 | Method for preparing nano-modified composite molecular sieve |
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