CN102173437B - Preparation method of controllable metal-doped aluminum phosphate molecular sieve - Google Patents
Preparation method of controllable metal-doped aluminum phosphate molecular sieve Download PDFInfo
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- CN102173437B CN102173437B CN 201110034554 CN201110034554A CN102173437B CN 102173437 B CN102173437 B CN 102173437B CN 201110034554 CN201110034554 CN 201110034554 CN 201110034554 A CN201110034554 A CN 201110034554A CN 102173437 B CN102173437 B CN 102173437B
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- molecular sieve
- phosphate molecular
- aluminium
- aluminum phosphate
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Abstract
The invention belongs to the technical field of preparing heteroatom-substituted aluminum phosphate molecular sieves, in particular relates to a process for preparing an aluminum phosphate molecular sieve doted with a metal such as Fe, Co, Ni or Zn by a fluorine-ion method. According to the invention, a hybrid aluminum phosphate molecular sieve is synthesized by the fluorine-ion method in a hydrothermal system, the substitution amount of transitional metal atoms in the structure of the product is controlled by regulating the amounts of phosphoric acid and hydrofluoric acid, and a series of aluminum phosphate molecular sieves with different heteroatom contents are synthesized to provide useful materials for preparing molecular sieve catalysts. The invention has the benefit and advantage of providing a simple and effective method for preparing the hybrid aluminum phosphate molecular sieve with controllable meal substitution amount.
Description
Technical field
The invention belongs to the preparing technical field that heteroatoms replaces aluminium phosphate molecular sieve, be specifically related to a kind of method of utilizing the metal-doped aluminium phosphate molecular sieve such as fluorion legal system standby Fe, Co, Ni, Cu or Zn.
Background technology
Zeolite molecular sieve has the nano level duct of height rule, adjustable duct characteristic (duct dimension, trend and composition), and higher specific surface area has been widely used in the fields such as catalysis, ion-exchange, separation, absorption.In recent years, along with the development of science and technology, the application of molecular sieve in some emerging fields such as host-guest chemistry, microelectronic device, optics, medical science progressively developed.Therefore, the preparation of zeolite molecular sieve material has become one of current study hotspot.Nineteen eighty-two, the people such as Wilson successfully develop a brand-new molecular sieve family-aluminium phosphate molecular sieve, people are under hydro-thermal and solvent thermal system subsequently, the aluminium phosphate molecular sieve that has different skeleton structures as structure directing agent synthesizes take different organic amines or quaternary ammonium salt cationic.But because the skeleton of aluminium phosphate molecular sieve does not have polarity, its application in fields such as catalysis, electricity, magnetics is greatly limited.In order to break through this limitation, people use heteroatoms that Al or the P atom of part in the skeleton are replaced, and have obtained a series of heteroatomss with special property and have replaced aluminium phosphate molecular sieve.The generation of these special propertys has caused that people replace the synthetic broad interest of aluminum phosphate containing Microporous Compounds to heteroatoms.So far, existing 25 kinds of elements can be doped in the aluminum phosphate skeleton, comprising basic metal, alkaline-earth metal, transition metal and rare earth metal, such as Be, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, Cd, Ga, Eu, As and Si etc.So just can generate five class containing Microporous Compounds, be respectively: SAPO-n, MeAPO-n, MeSAPO-n, EIAPO-n and EISAPO-n (wherein, Me=Mg, Mn, Fe, Co etc.; El=Ga, Ge, As etc.).People have carried out a large amount of research for the synthetic and character that metal replaces aluminium phosphate molecular sieve, and these compounds all belong to first kind heteroatoms and replace aluminium phosphate molecular sieve.Their characteristics are that the content of metallic element is lower, can be synthesized with the synthetic template identical with the aluminium phosphate molecular sieve of its isomorphism.However, this class material still shows extraordinary character, especially catalytic property.
Along with the research to metal tripolyphosphate aluminium deepens continuously, a large amount of more aluminium phosphate molecular sieves of content of heteroatoms are synthesized out.1997, the people such as Stucky successfully synthesized heteroatoms/aluminium greater than (or equaling) 1, even were equivalent to the phosphatic compound of Al substituted metal, had successfully synthesized a series of aluminum phosphate cobalts with molecular sieve structure.
As everyone knows, the content of metal and distribution situation have a great impact the catalytic property of this molecular sieve in the aluminium phosphate molecular sieve that replaces of metal.Different from the aluminium phosphate molecular sieve of neutrality, comprising heteroatomic aluminium phosphate molecular sieve is anion frame, needs organic amine ion or protonated water to come balancing charge.In addition, fluorion also can be regulated the electric charge in the skeleton, but also the formation of some special structural motif (such as the two tetra-atomic rings) that can lead.According to host-guest charge matching principle, if can control organic amine in the skeleton and the amount of fluorion, just can mix heteroatomic content in the corresponding adjusting skeleton.
Through exploration for many years, the synthetic of inorganic microporous compound developed multiple synthetic method gradually by traditional Hydrothermal Synthesis, such as the fluorion method, turn brilliant, xerogel method, the methods such as ion heat.Here article fluorion method once.Synthetic hydro-thermal or the solvent process for thermosynthesizing that refers to microporous phosphate in the presence of fluorion of fluorion.Fluorion replaces OH-as mineralizer, and synthesis zeolite makes the crystal that obtains relatively more perfect.Because fluorion replaces OH-, system can be adjusted to acidity by alkalescence, is conducive to the generation that some are not suitable for crystal synthetic under the alkaline condition.In addition and since fluorion can with the complex compound of some Element generation fluorine so that raw material fully dissolves, be beneficial to element and enter skeleton, and finally obtain perfect large single crystal.This synthetic route has characteristic itself, and introduces other complex ion in synthetic or sequestrant has been created a good start for the hydrothermal crystallizing of containing Microporous Compounds.Fluorion mainly plays following three kinds of effects in Zeolite synthesis: mineralizer effect, charge balance effect, and structure-directing effect.
At present, how to control the content of metal in the aluminium phosphate molecular sieve that metal replaces and distribute and still face very large challenge.How to prepare regulatable metal-doped aluminium phosphate molecular sieve and also just become one of key issue that this area needs to be resolved hurrily.
Summary of the invention
The object of the invention is to utilize the fluorion synthetic method to prepare the heteroatoms replacement and measure regulatable hydridization aluminium phosphate molecular sieve, utilize the method can convenient, effectively synthesize the aluminium phosphate molecular sieve that various metals replaces, and control heteroatomic content in the product structure by the modulation proportioning.
The present invention utilizes the fluorion method, and by metal in the modulation reaction system, the amount of phosphoric acid and hydrofluoric acid prepares the hydridization aluminium phosphate molecular sieve of different metal content.
The inventive method step is as follows:
(1) 0.03～0.15g aluminium source being joined volume is that 15mL, tetrafluoroethylene are in the stainless steel still of lining, adds other source metal of 0.2～0.5g again in still; Then add 0～5mL water, 0.5～3.0mL organic amine, 0.07～1.0mL phosphoric acid, 0.02～0.15mL massfraction and be 40% hydrofluoric acid; At last the baking oven of putting into 150～200 ℃ after the reactor sealing was heated 3～8 days;
(2) after question response is finished reactor taken out and be put in naturally cooling under the room temperature, product is shifted out dry under 50～90 ℃ of temperature condition with repeatedly supersound washing 3～7 times of intermediate water afterwards, obtain at last the aluminium phosphate molecular sieve that metal replaces.
The source of aluminium described in the preceding step is aluminum isopropylate, pseudo-boehmite or aluminium hydroxide.
Described other source metal are that metal is the soluble compound of Fe, Co, Ni, Cu or Zn, such as ironic oxalate (C
6Fe
2O
125H
2O), Ferrox (FeC
2O
42H
2O), iron trichloride (FeCl
36H
2O), iron protochloride (FeCl
24H
2O), ferric sulfate (Fe
2(SO
4)
3), iron nitrate (Fe (NO
3)
39H
2O), cobaltous acetate (C
4H
6CoO
44H
2O), cobaltous carbonate (CoCO
3), rose vitriol (CoSO
4), Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO
3)
26H
2O), cobalt chloride (CoCl
26H
2O), nickelous acetate (Ni (CH
3COO)
24H
2O), nickelous nitrate (Ni (NO
3)
26H
2O), nickel oxide (NiO), nickelous chloride (NiCl
26H
2O), cupric chloride (CuCl
2), venus crystals (C
4H
6CuO
4H
2O), cupric nitrate (Cu (NO
3)
23H
2O), zinc acetate ((CH
3COO)
2Zn2H
2O), zinc chloride (ZnCl
2), zinc nitrate (Zn (NO
3)
26H
2O), zinc oxide (ZnO), zinc phosphate (Zn
3(PO
4)
22H
2O) compound.
Described organic amine is diethylenetriamine or quadrol.Reaction system is gelling system, and the organic amine in the system both can be used as template, also can serve as solvent, has introduced a small amount of water in the system.
Effect of the present invention and benefit provide a kind of simple and effective method and prepare the metal replacement and measure regulatable hydridization aluminium phosphate molecular sieve.
Description of drawings
Fig. 1: be three-dimensional framework and the pore structure synoptic diagram of resulting hydridization aluminium phosphate molecular sieve among the embodiment 1, it is a kind of ACO molecular sieve structure type that typically has the three dimensional intersection duct, (1) figure be structure along the synoptic diagram of c-axis direction, (2) figure is FeO
4F hexahedron and PO
4Two tetra-atomic ring primitives that tetrahedron consists of, (3) figure is along the axial octatomic ring of a duct.
Fig. 2: for the Al/Fe that obtains among the embodiment 1 than the scanning electron microscope diagram (I) that is 1/3.9 ACO molecular sieve, the Al/Fe that obtains among the embodiment 2 is than the scanning electron microscope diagram (II) that is 1/5 ACO molecular sieve, and the Al/Fe that obtains among the embodiment 3 is than the scanning electron microscope diagram (III) that is 1/9 ACO molecular sieve;
Fig. 3: the thermogravimetic analysis (TGA) figure of the ACO molecular sieve that replaces for the heteroatoms among the embodiment 1, this figure does under air conditions;
Fig. 4: the Mossbauer test spectrogram that the ACO molecular sieve that replaces for the heteroatoms among the embodiment 3 records at ambient temperature, adopt radioactive source to be
57Co/Pd, testing tool model: the MS-500 of England Oxford company type Mossbauer spectrometer; The resolution data parameter is the a-Fe calibration;
Fig. 5: be embodiment 1,2, the x ray powder diffraction of the ACO molecular sieve that heteroatoms replaces in 3 and the contrast of simulating spectrogram, the x ray powder diffraction of molecular sieve among the corresponding embodiment 1 of I, the x ray powder diffraction of molecular sieve among the corresponding embodiment 2 of II, the x ray powder diffraction of molecular sieve among the corresponding embodiment 3 of III;
Fig. 6: be the magnetic test pattern of the ACO molecular sieve of heteroatoms replacement among the embodiment 1, this figure utilizes quantum design MPMS-XL SQUID magnetometer, tests under the 5000Oe field intensity, and Range of measuring temp is 2-300K;
Fig. 7: be 30% hot ellipsoid figure of the ACO molecular sieve of heteroatoms replacement among the embodiment 1;
As shown in Figure 1, the ACO molecular sieve that (1) figure expression heteroatoms replaces is along the structure iron of c-axis direction, and its structure is that the basic structural unit by two tetra-atomic rings interconnects and forms.Show among the figure that it contains the straight hole road of octatomic ring, the diethylenetriamine that adds in the reaction process is decomposed into quadrol, and the quadrol of diproton is present in the octatomic ring duct; (2) structural motif of two tetra-atomic rings in the figure expression ACO structure, fluorine atom is positioned at two tetra-atomic ring centers, phosphorus forms four-coordination with four Sauerstoffatoms and is connected, and iron forms pentacoordinate with the fluorine atom at four Sauerstoffatoms and center and is connected, and iron and phosphorus atom connect and compose the three-dimensional framework structure by bridging oxygen atom; (3) figure expresses the pore size in octatomic ring duct;
As shown in Figure 2, figure I is Al/Fe than the shape characteristic that is 1/3.9 ACO molecular sieve, and crystal is irregular fragment; Figure II is Al/Fe than the shape characteristic that is 1/5 ACO molecular sieve; Figure III is Al/Fe than the shape characteristic that is 1/9 ACO molecular sieve, and crystal is fairly regular dodecahedron structure; We can find out by Electronic Speculum figure, along with the increase of Fe content in the molecular sieve structure, and the gradually regularization of the pattern of crystal;
As shown in Figure 3, embodiment 1 resulting crystal can be stabilized to 300 degree, spends organic formwork agent, water molecules and the fluorion that begins to remove in the structure 300, when arrival 630 is spent, guest molecule removes fully, and weight loss is 21.6%, coincide fine with theoretical weight loss;
As shown in Figure 4, the chemical shift of the iron of embodiment 3 resulting crystal is 1.18mm/s, and electric quadrupole moment is 2.12mm/s, and is corresponding with ferrous iron good, shows that the ferro element in the structure all exists with ferrous form;
As shown in Figure 5, XRD shows that the XRD spectra of the ACO molecular sieve of three kinds of different al preparing/Fe ratio is corresponding fine with the XRD figure spectrum of the aluminum phosphate ACO structure of simulation, shows that the synthetic sample of experiment is pure phase;
As shown in Figure 6, the compound that obtains among the embodiment 1 has stronger antiferromagnetism, meets Curie-Weiss law X
m=C/ (T-θ), X
mThat (unit is cm to molar susceptibility
3/ mol), C is that (unit is cm to Curie constant
3K/mol), θ is Weiss constant (unit is K), and T is the temperature shown in the X-coordinate (unit is K), by 1/X
m-T collection of illustrative plates learns that this molecular sieve all meets Curie-Weiss law in the 2-300K scope, and Curie constant is 3.63cm
3K/mol, Weiss constant be-18.1K, and negative Weiss constant represents between the iron atom in this molecular sieve stronger antiferromagnetic exchange effect is arranged;
As shown in Figure 7, the compound that embodiment 1 obtains, iron (aluminium) position that includes a crystallography non-equivalence in unsymmetrical structure unit, the P of a crystallography non-equivalence, the quadrol molecule of the water molecules of non-protonization and 0.5 diproton; Metal with are connected a Sauerstoffatom and a fluorine atom and connect with pentacoordinate, phosphorus is connected with four-coordination with Sauerstoffatom; Metal links to each other by oxo bridge with phosphorus atom;
Embodiment
The present invention will be further described below by embodiment, but embodiments of the present invention are not limited to this, can not be interpreted as limiting the scope of the invention.
Embodiment 1:
With aluminum isopropylate, ironic oxalate, phosphoric acid, hydrofluoric acid, diethylenetriamine are that the synthetic Al/Fe of template is than the tertiary iron phosphate aluminum molecular screen with ACO molecular sieve structure type that is 1/3.9.
The 0.07g aluminum isopropylate is added in the stainless steel still that the 15mL tetrafluoroethylene is lining, continues in still, to add 0.32g six oxalic acid hydrate iron; In succession in still, add 1.0mL diethylenetriamine and 0.5mL phosphoric acid; The hydrofluoric acid that adds 0.03mL 40%; Whole process does not need to stir, and at last the baking oven of putting into 160 ℃ after the reactor sealing is heated 6 days;
After question response is finished the reactor taking-up is put in naturally cooling under the room temperature; Product is shifted out, with repeatedly supersound washing 6 times of intermediate water, dry under 80 ℃ of temperature condition, obtain at last Al/Fe and be 1/3.9 tertiary iron phosphate aluminum molecular screen, quality is 0.12g, and this molecular sieve is the ACO structure type;
Embodiment 2:
With aluminum isopropylate, ironic oxalate, phosphoric acid, hydrofluoric acid, diethylenetriamine are that the synthetic Al/Fe of template is than the tertiary iron phosphate aluminum molecular screen with ACO molecular sieve structure type that is 1/5.
The 0.07g aluminum isopropylate is added in the stainless steel still that the 15mL tetrafluoroethylene is lining, continues in still, to add 0.32g six oxalic acid hydrate iron; In succession in still, add 1.0mL diethylenetriamine and 0.5mL phosphoric acid; The hydrofluoric acid that adds 0.07mL 40%; Whole process does not need to stir, and at last the baking oven of putting into 160 ℃ after the reactor sealing is heated 6 days;
After question response is finished the reactor taking-up is put in naturally cooling under the room temperature; Product is shifted out, with repeatedly supersound washing 6 times of intermediate water, dry under 80 ℃ of temperature condition, obtain at last Al/Fe than the tertiary iron phosphate aluminum molecular screen with ACO structure that is 1/5, quality is 0.08g;
Embodiment 3:
With aluminum isopropylate, ironic oxalate, phosphoric acid, hydrofluoric acid, diethylenetriamine are that the synthetic Al/Fe of template is than the tertiary iron phosphate aluminum molecular screen with ACO molecular sieve structure type that is 1/9.
The 0.07g aluminum isopropylate is added in the stainless steel still that the 15mL tetrafluoroethylene is lining, continues in still, to add 0.32g six oxalic acid hydrate iron; In succession in still, add 1.0mL diethylenetriamine and 0.12mL phosphoric acid; The hydrofluoric acid that adds 0.1mL 40%; Whole process does not need to stir, and at last the baking oven of putting into 160 ℃ after the reactor sealing is heated 6 days;
After question response is finished the reactor taking-up is put in naturally cooling under the room temperature; Product is shifted out, with repeatedly supersound washing 6 times of intermediate water, dry under 80 ℃ of temperature condition, obtain at last Al/Fe than the tertiary iron phosphate aluminum molecular screen with ACO structure that is 1/9, quality is 0.09g.
Claims (3)
1. the preparation method of the aluminium phosphate molecular sieve of a controllable metal-doped, its step is as follows:
(1) 0.03～0.15g aluminium source being joined volume is that 15mL, tetrafluoroethylene are in the stainless steel still of lining, adds the soluble compound of Fe, Co, Ni, Cu or the Zn of 0.2～0.5g in the still again; Then add 0～5mL water, 0.5～3.0mL organic amine, 0.07～1.0mL phosphoric acid, 0.02～0.15mL massfraction and be 40% hydrofluoric acid; At last the baking oven of putting into 150～200 ℃ after the reactor sealing was heated 3～8 days; Organic amine is diethylenetriamine;
(2) after question response is finished reactor taken out and be put in naturally cooling under the room temperature, product is shifted out dry under 50～90 ℃ of temperature condition with repeatedly supersound washing 3～7 times of intermediate water afterwards, obtain at last metal-doped aluminium phosphate molecular sieve.
2. the preparation method of the aluminium phosphate molecular sieve of a kind of controllable metal-doped as claimed in claim 1, it is characterized in that: there are aluminum isopropylate, pseudo-boehmite or aluminium hydroxide in the aluminium source.
3. the preparation method of the aluminium phosphate molecular sieve of a kind of controllable metal-doped as claimed in claim 1, it is characterized in that: the soluble compound of Fe, Co, Ni, Cu or Zn is ironic oxalate C
6Fe
2O
125H
2O, Ferrox FeC
2O
42H
2O, iron trichloride FeCl
36H
2O, iron protochloride FeCl
24H
2O, ferric sulfate Fe
2(SO
4)
3, iron nitrate Fe (NO
3)
39H
2O, cobaltous acetate C
4H
6CoO
44H
2O, rose vitriol CoSO
4, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES Co (NO
3)
26H
2O, cobalt chloride CoCl
26H
2O, acetic acid nickel (CH
3COO)
24H
2O, nitric acid nickel (NO
3)
26H
2O, nickelous chloride NiCl
26H
2O, cupric chloride CuCl
2, venus crystals C
4H
6CuO
4H
2O, cupric nitrate Cu (NO
3)
23H
2O, zinc acetate Zn (CH
3COO)
22H
2O, zinc chloride ZnCl
2, zinc nitrate Zn (NO
3)
26H
2O or zinc phosphate Zn
3(PO
4)
22H
2O.
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| CN104340992B (en) * | 2013-08-02 | 2016-08-24 | 中国科学院大连化学物理研究所 | A kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve with-CLO structure and preparation method thereof |
| CN105776238A (en) * | 2014-12-17 | 2016-07-20 | 中国科学院大连化学物理研究所 | Ionothermal synthesis method of LAU type metal aluminum phosphate molecular sieve |
| CN106809860B (en) * | 2015-11-27 | 2019-03-19 | 中国科学院大连化学物理研究所 | A kind of ion process for thermosynthesizing of ATS type Metal-aluminophosphate Molecular Siever |
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| CN1467155A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing aluminium silicophosphate molecular sieve |
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| CN1467155A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing aluminium silicophosphate molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| 段淑娥.NiAPO-11分子筛的合成与结构研究.《西安工业学院学报》.2000,第20卷(第1期), * |
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