CN102351214A - Method for synthesizing AlPO4-34 aluminum phosphate molecular sieve - Google Patents

Method for synthesizing AlPO4-34 aluminum phosphate molecular sieve Download PDF

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Publication number
CN102351214A
CN102351214A CN2011101906594A CN201110190659A CN102351214A CN 102351214 A CN102351214 A CN 102351214A CN 2011101906594 A CN2011101906594 A CN 2011101906594A CN 201110190659 A CN201110190659 A CN 201110190659A CN 102351214 A CN102351214 A CN 102351214A
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source
crystal seed
organic formwork
formwork agent
molecular sieve
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CN2011101906594A
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李牛
王晨光
项寿鹤
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Nankai University
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Nankai University
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Abstract

The invention provides a method for synthesizing an AlPO4-34 aluminum phosphate molecular sieve. Phosphoric acid is used as a phosphoric source, pseudo boehmite is used as an aluminum source, AlPO4-34 crystals are used as seed crystals, morpholine is used as template agents, the phosphoric source, the aluminum source, the organic template agents, the seed crystals and water are added according to the molar ratio of Al2O3/H3PO4/drewamine/H2O being 0.5/1.0/1.0 to 3.0/25 to 100, 0.02 to 0.1g/1 mol aluminum raw material is added into the seed crystals, the synthesized colloid is prepared, then, the colloid is subjected to hydrothermal crystallization at 160 to 200 DEG C and self-generated pressure for 36 to 180h, is washed by water and separated and is baked at room temperature to 80 DEG C, and the product is obtained. When the method is adopted, the AlPO4-34 aluminum phosphate molecular sieve product is prepared in an environment-friendly process.

Description

A kind of AlPO 4The compound method of-34 aluminium phosphate molecular sieves
Technical field
The present invention relates to the compound method of aluminium phosphate molecular sieve, specifically is aluminium phosphate molecular sieve AlPO 4-34 floride-free compound method.Through adding fluorine-containing AlPO 4-34 crystal seeds, building-up process is fluoridize not, thereby obtains the extremely low AlPO of fluorine content 4-34 products reach the purpose of environmental protection, have potential to be worth to its suitability for industrialized production.
Background technology
Bibliographical information, aluminium phosphate molecular sieve AlPO 4-34 skeleton is made up 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 break off about 350 ℃, and whole skeleton is converted into the CHA structure.Present compound method all will add hydrogen fluoride in building-up process, utilize the very strong coordination ability of F ion, makes Al and F form coordination, with firm AlPO 4-34 skeleton structure.Hydrofluoric acid is volatile, and equipment is had intensive corrodibility, so use the synthetic AlPO of hydrofluoric acid 4-34 molecular sieves are both dangerous also not environmental protection in suitability for industrialized production, had hindered AlPO significantly 4The extension production of-34 molecular sieves.
Summary of the invention
The objective of the invention is to optimize AlPO 4The compound method of-34 aluminium phosphate molecular sieves is through adding fluorine-containing AlPO 4-34 crystal seeds change synthesis condition, thereby in building-up process, do not use hydrogen fluoride and obtain AlPO 4-34 zeolite products.
The present invention is through following step: aluminium source, phosphorus source, organic formwork agent, crystal seed and water or aluminium source, phosphorus source, crystal seed, organic formwork agent and water are mixed process synthetic colloid earlier, the temperature when becoming glue is 15～35 ℃.Should synthesize then colloid 160～200 ℃ with autogenous pressure under hydrothermal crystallizing 36～180 hours, 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: H 2O=0.5: 1.0: 1.0～3.0: 25～100, preferred Al 2O 3: H 3PO 4: R: H 2O=0.5: 1.0: 1.5～3.0: 25～75; The crystal seed quality is 0.02～0.1 gram/1 a moles, of aluminum per mole of titanium metal raw material, preferred 0.05～0.07 gram/1 moles, of aluminum per mole of titanium metal raw material.
In the inventive method, said phosphorus source is a phosphoric acid; The aluminium source is the salt of pseudo-boehmite, aluminum isopropylate, white lake, aluminum oxide and aluminium; Organic formwork agent is morpholine, piperidines and pyridine; Crystal seed is with hydrogen fluoride synthetic AlPO 4-34 crystal, or the lower AlPO of the fluorine content that obtains with the present invention 4-34 crystal.
In the inventive method, preferably phosphoric acid is the phosphorus source, and pseudo-boehmite is the aluminium source, and morpholine is a template, and crystal seed is with hydrogen fluoride synthetic AlPO 4-34 crystal.
In the inventive method; The addition sequence of said phosphorus source, aluminium source, crystal seed and organic formwork agent is the order according to aluminium source, phosphorus source, crystal seed, organic formwork agent; Or the order of aluminium source, phosphorus source, organic formwork agent, crystal seed, or the order of phosphorus source, aluminium source, organic formwork agent, crystal seed, or the order of phosphorus source, aluminium source, crystal seed, organic formwork agent; Or the order in crystal seed, organic formwork agent, aluminium source, phosphorus source, or the order in aluminium source, crystal seed, organic formwork agent, phosphorus source adds.
In the inventive method, preferably will synthesize colloid 180～200 ℃ with autogenous pressure under hydrothermal crystallizing 48～120 hours, collect, wash and be drying to obtain product then.
The invention has the beneficial effects as follows: at AlPO provided by the present invention 4In the compound method of-34 molecular sieves, do not use hydrofluoric acid, the zeolite product that synthesizes with hydrofluoric acid synthetic AlPO 4-34 crystalline structure are identical.
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Description of drawings
Fig. 1 is the embodiment of the invention 1 described product A lPO 4-34 SEM photo
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 2 described product A lPO 4-34 x-ray diffractogram of powder (XRD).
Fig. 4 is the embodiment of the invention 3 described product A lPO 4-34 x-ray diffractogram of powder (XRD).
Embodiment
Embodiment 1
At 20 ℃; With 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, pour 0.87 gram pseudo-boehmite pressed powder into and stir, add 0.05 gram crystal seed again; Drip 3.0 milliliters of morpholines while stirring; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 200 ℃ of crystallization 48 hours.
Embodiment 2
At 20 ℃; With 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, pour 0.87 gram pseudo-boehmite pressed powder into and stir, drip 3.0 milliliters of morpholines while stirring; Add 0.05 gram crystal seed again; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 185 ℃ of crystallization 108 hours.
Embodiment 3
At 20 ℃; With 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, pour 0.87 gram pseudo-boehmite pressed powder into and stir, drip 2.0 milliliters of morpholines while stirring; Add 0.06 gram crystal seed again; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 185 ℃ of crystallization 96 hours.
Embodiment 4
At 20 ℃; In 10 ml waters, add 0.05 gram crystal seed, and drip 3.0 milliliters of morpholines stirrings, pour 0.87 gram pseudo-boehmite pressed powder again into; Drip 0.76 milliliter of phosphoric acid while stirring; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 200 ℃ of crystallization 96 hours.
Embodiment 5
At 20 ℃; In 10 ml waters, add 0.05 gram crystal seed, and drip 3.0 milliliters of morpholines stirrings, pour 0.58 gram pseudo-boehmite pressed powder again into; Drip 0.51 milliliter of phosphoric acid while stirring; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 190 ℃ of crystallization 54 hours.
Embodiment 6
At 20 ℃; With 0.51 milliliter of phosphoric acid of 10 ml waters dissolving, pour 0.58 gram pseudo-boehmite pressed powder into and stir, add 0.05 gram crystal seed again; Drip 3.0 milliliters of morpholines while stirring; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 185 ℃ of crystallization 72 hours.
Embodiment 7
At 20 ℃; With 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, to pour 0.87 gram pseudo-boehmite pressed powder into and stir, the limit adds 0.06 gram crystal seed again; Stir the limit and drip 2.0 milliliters of morpholines; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 190 ℃ of crystallization 72 hours.
Embodiment 8
At 20 ℃; With 0.76 milliliter of phosphoric acid of 10 ml waters dissolving, pour 0.87 gram pseudo-boehmite pressed powder into and stir, drip 1.5 milliliters of morpholines while stirring; Add 0.07 gram crystal seed again; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 200 ℃ of crystallization 72 hours.
Embodiment 9
At 20 ℃; With 0.51 milliliter of phosphoric acid of 10 ml waters dissolving, pour 0.58 gram pseudo-boehmite pressed powder into and stir, drip 1.5 milliliters of morpholines while stirring; Add 0.07 gram crystal seed again; Be stirred to even back and move in 20 milliliters of stainless steel cauldrons, then by the post-treating method of the molecular sieve of routine, collect, washing and 80 ℃ of dryings in 200 ℃ of crystallization 96 hours.

Claims (7)

1. auxiliary AlPO of crystal seed 4The compound method of-34 aluminium phosphate molecular sieves is characterized in that through following step:
Aluminium source, phosphorus source, organic formwork agent, crystal seed and water mixed process synthetic colloid; Temperature when becoming glue is 15～35 ℃; Should synthesize then colloid 160～200 ℃ with autogenous pressure under hydrothermal crystallizing 36～180 hours, collect then, wash and dry, promptly get product;
Wherein, The addition sequence of described phosphorus source, aluminium source, organic formwork agent and crystal seed is the order according to aluminium source, phosphorus source, crystal seed, organic formwork agent; Or the order of aluminium source, phosphorus source, organic formwork agent, crystal seed; Or the order of phosphorus source, aluminium source, organic formwork agent, crystal seed, or the order of phosphorus source, aluminium source, crystal seed, organic formwork agent, or the order of aluminium source, organic formwork agent, phosphorus source, crystal seed; Or the order in aluminium source, crystal seed, organic formwork agent, phosphorus source adds, and synthetic colloidal material mole proportioning is Al 2O 3: H 3PO 4: organic formwork agent: H 2O=0.5: 1.0: 1.0～3.0: 25～100, the add-on of crystal seed is 0.02～0.1 gram/1 a moles, of aluminum per mole of titanium metal raw material.
2. according to the compound 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 20=0.5: 1.0: 1.0～2.0: 0.1～0.2: 25～75, the add-on of crystal seed is 0.05～0.07 gram/1 a moles, of aluminum per mole of titanium metal raw material.
3. according to the compound 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 compound 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 compound method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that described crystal seed is with hydrogen fluoride synthetic AlP0 4-34 crystal, or the lower AlP0 of the fluorine content that obtains with the present invention 4-34 crystal.
6. according to the compound method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that described building-up process do not use fluorine-containing raw materials such as hydrofluoric acid.
7. according to the compound method of the described aluminium phosphate molecular sieve of claim 1, it is characterized in that described synthetic colloid 180～200 ℃ with autogenous pressure under hydrothermal crystallizing 48～120 hours, collect then, wash and 60～80 ℃ of oven dry, obtain product.
CN2011101906594A 2011-07-08 2011-07-08 Method for synthesizing AlPO4-34 aluminum phosphate molecular sieve Pending CN102351214A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106115735A (en) * 2016-06-15 2016-11-16 南开大学 AlPO434 with SAPO 34 composite molecular sieves and synthetic method thereof
CN109081363A (en) * 2018-09-25 2018-12-25 南开大学 A kind of floride-free synthesis AlPO of crystal seed guiding4- 34 method
CN109775715A (en) * 2019-03-18 2019-05-21 正大能源材料(大连)有限公司 A kind of AlPO of floride-free synthesis even grain size4The method of -34 molecular sieves

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CN102092737A (en) * 2011-01-20 2011-06-15 南开大学 Synthetic method of AlPO4-34 aluminum phosphate molecular sieve
CN102092738A (en) * 2011-03-30 2011-06-15 南开大学 Hydrothermal fluorine-free synthesis method of AlPO4-34

Patent Citations (3)

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CN101031511A (en) * 2004-10-01 2007-09-05 埃克森美孚化学专利公司 Aluminophosphate molecular sieve, its synthesis and use
CN102092737A (en) * 2011-01-20 2011-06-15 南开大学 Synthetic method of AlPO4-34 aluminum phosphate molecular sieve
CN102092738A (en) * 2011-03-30 2011-06-15 南开大学 Hydrothermal fluorine-free synthesis method of AlPO4-34

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106115735A (en) * 2016-06-15 2016-11-16 南开大学 AlPO434 with SAPO 34 composite molecular sieves and synthetic method thereof
CN109081363A (en) * 2018-09-25 2018-12-25 南开大学 A kind of floride-free synthesis AlPO of crystal seed guiding4- 34 method
CN109081363B (en) * 2018-09-25 2022-02-22 南开大学 Crystal guiding fluorine-free synthesis AlPO4Method of (2) to (34)
CN109775715A (en) * 2019-03-18 2019-05-21 正大能源材料(大连)有限公司 A kind of AlPO of floride-free synthesis even grain size4The method of -34 molecular sieves
CN109775715B (en) * 2019-03-18 2022-09-09 正大能源材料(大连)有限公司 Fluorine-free AlPO with uniform synthetic grain size 4 Process for producing (E) -34 molecular sieve

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Application publication date: 20120215