CN1195679C - Silicon-aluminium phosphate molecular sieve and its preparing process - Google Patents
Silicon-aluminium phosphate molecular sieve and its preparing process Download PDFInfo
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Abstract
The presents invention discloses a silicon aluminum phosphate molecular sieve and a synthetic method thereof. The molecular sieve is characterized in that X-ray diffraction data before templates are calcined and eliminated at least contains a diffraction peak disclosed in a formula 1, and X-ray diffraction data after the templates are calcined and eliminated at least contains a diffraction peak disclosed in a formula 2. The molar composition is Al2O3, yP2O5 and zSiO2 represented by an anhyrous chemical formula in an oxide mode, wherein the value of y is from 0.01 to 1.5, and the value of z is from 0.05 to 50. The molecular sieve is synthesized by that aluminum sources, phosphorus sources, silicon sources and organic templates are mixed into glue at room temperature to 80 DGE C, 0.1 to 10 weight% of crystal seed measured by dry bases is added, and water thermal crystallisation is carried out for 4 to 500 hours at 120 to 250 DEG C. Catalysts which use the silicon aluminum phosphate molecular sieve provided by the present invention as active components can be used for the conversion reaction of hydrocarbons or compounds containing oxygen.
Description
Technical field
The invention relates to a kind of silicoaluminophosphamolecular molecular sieves and synthetic method thereof.
Background technology
Aluminium phosphate molecular sieve is after al silicate molecular sieve, U.S. UCC company is at the molecular sieve of new generation (USP4310440) of the invention early 1980s, the characteristics of this molecular sieve analog are that its skeleton alternately is formed by connecting by phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron, because framework of molecular sieve is electric neutrality, therefore there are not cation exchange property and catalytic perfomance.Aluminium phosphate molecular sieve is a series of molecular sieves, have unique XRD feature spectrogram and data respectively, wherein existing and existing al silicate molecular sieve has the molecular sieve of same crystal structure, and the molecular sieve of the novel texture that does not have in the existing al silicate molecular sieve is also arranged.
In the aluminium phosphate molecular sieve skeleton, introduce silicon, then become silicoaluminophosphamolecular molecular sieves, it is SAPO series molecular sieve (U.S. UCC company, USP4440871), its framework of molecular sieve is made of phosphorus oxygen tetrahedron, aluminum-oxygen tetrahedron and silicon-oxy tetrahedron, because skeleton is electronegative, skeleton has balance cation to exist outward, therefore has cation exchange property, when the skeleton outer cationic is H
+The time, molecular sieve has acid sites, therefore has the acidic catalyst reactivity worth.Silicoaluminophosphamolecular molecular sieves has been widely used in oil refining and the field of petrochemical industry as the activity of such catalysts constituent element, as the conversion of catalytic cracking, hydrocracking, isomerization, alkylating aromatic hydrocarbon, oxygenatedchemicals etc.
Aluminium phosphate molecular sieve and silicoaluminophosphamolecular molecular sieves since its widely purposes and potential Application Areas obtained development fast, the molecular sieve and the synthetic method of novel texture constantly invent.European patent EP 254075 has been reported the aluminium phosphate molecular sieve AlPO of AFO structure
4-41 and synthetic method.With phosphoric acid, hydrated aluminum oxide (pseudo-boehmite phase), di-n-propylamine is raw material, at first with the aqueous solution of hydrated aluminum oxide and phosphoric acid, after stirring, add di-n-propylamine, mix the back inclosure and have in the stainless steel pressure container of teflon lined, obtain product 150-200 ℃ of crystallization.Preferred feed ratio is 2.0-4.0R: Al in this patent
2O
3: 1.50 ± 0.5P
2O
5: 40-100H
2O, and go forward one by one successively as the method for crystal seed by product, to obtain the AlPO of pure phase
4-41 molecular sieves.
At Catalysis Letters, 1991, the 11 volumes in the 199-208 page or leaf, have reported with the diethylamine to be synthetic SAPO-4 1 result of template, are raw material with phosphoric acid, pseudo-boehmite, silicon dioxide powder, at feed ratio are: 1.0R: P
2O
5: Al
2O
3: 0.4SiO
2: 55H
2O, 195 ℃ of crystallization obtained molecular sieve product in 48 hours.
It is the result of synthetic SAPO-34 (CHA structure) molecular sieve of template that CN1096496 has reported with diethylamine or based on the organic compounds containing nitrogen group of diethylamine.
Summary of the invention
The inventor finds, under identical organic formwork agent such as diethylamine, triethylamine, di-n-propylamine, Diisopropylamine, tetraethyl ammonium hydroxide existence condition, different raw materials, feed ratio, one-tenth glue and crystallization condition can obtain the not crystallized product of jljl phase, comprise AEL (SAPO-11), AFO (SAPO-41), CHA (SAPO-34), SAPO-43 (GIS) and APC, APD, thing phases such as tridymite, and also the product that obtains often is the mixture of above-mentioned thing phase.And, can obtain a kind of silicoaluminophosphamolecular molecular sieves of novel texture by the control synthesis condition.
Therefore, the purpose of this invention is to provide a kind of silicoaluminophosphamolecular molecular sieves with novel texture (brief note is SRM-2) and its synthetic method is provided.
Silicoaluminophosphamolecular molecular sieves provided by the invention is characterized in that the XRD data before the roasting removed template method contain the diffraction peak shown in the table 1 at least; XRD data behind the roasting removed template method contain the diffraction peak shown in the table 2 at least, and mole is Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2, wherein the value of y is 0.01～1.5, and is preferred 0.1～1.4, more preferably 0.15～1.2; The value of z is 0.05～50, and is preferred 0.1～40, more preferably 0.2～20.Wherein, the condition of said roasting removed template method generally is 300～700 ℃ of following constant temperature 2～10 hours.
Table 1
| 2θ(°) | d(_) | Relative intensity |
| 8.13-8.30 | 10.89-10.65 | VS |
| 11.55-11.72 | 7.66-7.55 | W |
| 14.17-14.35 | 6.25-6.17 | S |
| 16.43-16.61 | 5.39-5.34 | M |
| 18.34-18.52 | 4.84-4.79 | M |
| 20.16-20.34 | 4.40-4.36 | W |
| 21.79-21.99 | 4.08-4.04 | M |
| 23.30-23.50 | 3.82-3.78 | W |
| 24.74-24.94 | 3.60-3.57 | M-S |
| 26.12-26.32 | 3.41-3.39 | M-S |
| 28.69-28.89 | 3.11-3.09 | W-M |
| 29.88-30.08 | 2.99-2.97 | M |
| 32.14-32.44 | 2.78-2.76 | W-M |
| 35.33-35.63 | 2.54-2.52 | W |
*W 0～20%, and M 20～60%, and S 60～80%, and VS 80～100%, down together.
Mole before the molecular sieve provided by the present invention, its roasting removed template method is xR:Al when forming with the anhydrous chemical formulation of oxide form
20
3: yP
2O
5: zSiO
2Wherein R is the organic formwork agent that is present in the molecular sieve crystal duct, comprises the mixture of diethylamine or diethylamine and triethylamine, di-n-propylamine, Diisopropylamine etc., and the value of x is 0.01～5.0, and is preferred 0.03～4.0, and the value of y and z as defined above.
Table 2
| 2θ(°) | d(_) | Relative intensity |
| 8.21-8.31 | 10.77-10.63 | VS |
| 11.68-11.78 | 7.57-7.51 | W-M |
| 14.30-14.40 | 6.19-6.15 | S |
| 16.54-16.64 | 5.36-5.32 | W-M |
| 18.54-18.64 | 4.79-4.76 | W |
| 20.31-20.41 | 4.37-4.35 | W |
| 21.93-22.13 | 4.05-4.01 | W-M |
| 23.44-23.64 | 3.80-3.76 | W |
| 24.96-25.16 | 3.57-3.54 | M |
| 26.36-26.56 | 3.38-3.35 | M-S |
| 28.94-29.14 | 3.09-3.06 | W |
| 30.08-30.38 | 2.97-2.94 | M |
| 32.36-32.66 | 2.76-2.74 | W |
| 35.60-35.90 | 2.52-2.50 | W |
The synthetic method of silicoaluminophosphamolecular molecular sieves provided by the invention comprises: press feed ratio aR: Al under room temperature～80 ℃, preferred 15～75 ℃ of temperature
2O
3: bP
2O
5: cSiO
2: dH
2O, aluminium source, phosphorus source, silicon source and organic formwork agent are mixed into glue, adding in a kind of in the silicoaluminophosphamolecular molecular sieves of the aluminium phosphate molecular sieve that is selected from the AFO structure of butt 0.1～10 weight %, preferred 2～8 heavy %, AFO structure or the silicoaluminophosphamolecular molecular sieves provided by the present invention (SRM-2) or wherein two or three mixture be crystal seed, hydrothermal crystallizing 4～500 hours, preferred 10～200 hours under 120～250 ℃, preferred 150～220 ℃ temperature; Wherein R is an organic formwork agent, and the value of a is 0.5～10.0, and is preferred 0.6～9.0, more preferably 0.7～8.0; The value of b is 0.5～1.5, and is preferred 0.6～1.2, more preferably 0.7～1.1; The value of c is 0.05～50, and is preferred 0.1～40, more preferably 0.15～20; The value of d is 10～150, and is preferred 20～120, more preferably 25～100.
In the synthetic method provided by the invention, said aluminium source is selected from aluminium hydroxide, hydrated aluminum oxide, aluminum isopropylate or aluminum phosphate, wherein preferred hydrated aluminum oxide or aluminum isopropylate; Said silicon source is selected from solid silicone, silicon sol or silicon ester; Said phosphorus source is selected from phosphoric acid or aluminum phosphate, wherein preferably phosphoric acid; Said organic formwork agent is diethylamine or diethylamine and is selected from one or both or two or more mixtures in di-n-propylamine, Diisopropylamine, the triethylamine that wherein preferred diethylamine is a template.
The silicoaluminophosphamolecular molecular sieves of this novel texture provided by the present invention (SRM-2), can pass early work is that crystal seed uses, also can use as crystal seed jointly with the aluminum phosphate and/or the silicon aluminium phosphate of AFO structure, wherein preferred its silicoaluminophosphamolecular molecular sieves with the AFO structure mixes as crystal seed.As the above-mentioned aluminium phosphate molecular sieve or the silicoaluminophosphamolecular molecular sieves of crystal seed, no matter whether the roasting removed template method, all is suitable for using as crystal seed in the synthetic method provided by the invention.
In synthetic method provided by the invention, said one-tenth glue temperature is room temperature～80 ℃, and preferred temperature is 10～75 ℃.Although at preferred feed ratio with preferably become the glue temperature and add under the condition of an amount of crystal seed, to the requirement that becomes the glue order not necessarily, but under general above-mentioned condition, select certain time ordered pair that feeds intake to improve the crystallization velocity of molecular sieve, thereby the shortening crystallization time, the degree of crystallinity that improves product all has significant advantage.Preferably feed intake order at first phosphorus source and aluminium source being mixed with deionized water (or distilled water), after stirring, add template, add silicon source and crystal seed after stirring again; The preferred order that feeds intake adds the solution of phosphoric acid and suitable quantity of water then for the aluminium source is mixed with suitable quantity of water, after stirring, adds template, silicon source and crystal seed more successively.
In the synthetic method provided by the invention, in the said crystallization condition, general crystallization temperature is 140～250 ℃, and preferred crystallization temperature is 150～220 ℃.
Although also can synthesize the silicoaluminophosphamolecular molecular sieves of this novel texture under static conditions, preferred crystallization is dynamically to carry out under autogenous pressure, heats up and thermostatic crystallization under at agitation condition.This agitation condition removes the homogeneity of increase system in the general sense, comprise increase conduct heat and the efficient of mass transfer outside, to suppress AEL, AFI, AFO and CHA thing mutually and other stray crystal thing phase tangible advantage is all arranged.
Molecular sieve provided by the present invention can be used for the conversion reaction of hydro carbons, acidic components as catalyzer such as catalytic cracking, hydrocracking, isomerization, catalytic dewaxings, also can be used for the conversion reaction of oxygen-containing organic compound, as the conversion reaction of methyl alcohol, ethanol, dme etc.Can be prepared into dual-function catalyst behind this molecular sieve carried transition metal such as VA, VIA, VIIA, VIIIA, IB and the IIB family metal, can behind loaded metal, use by the hydrogen conversion catalyst that faces as hydro carbons.For molecular sieve being prepared into metallic dual-function catalyst, can be with molecular sieve elder generation roasting removed template method, impregnating metal again; Perhaps earlier with roasting removed template method again behind the molecular sieve impregnating metal.
Embodiment
The following examples will be further described the present invention.
The X-ray powder diffraction of molecular sieve is measured used instrument and is produced Bruker D5005 for Germany in each embodiment and the Comparative Examples, adopts the CuK alpha-ray; Molecular sieve composition x-ray fluorescence spectrometry.
Aluminum phosphate as the used AFO structure of crystal seed among the embodiment is to adopt EP254075 disclosed method synthetic, and the silicoaluminophosphamolecular molecular sieves of AFO structure is according to Catalysis Letters, 1991, the 11 volumes, the process synthetic of narrating in the 199-208 page or leaf.
Raw materials used except that specifying among the embodiment, be chemically pure reagent.
Embodiment 1
With 288.2 gram phosphoric acid (85% phosphoric acid, chemically pure reagent, down with) and 905.2 gram deionized waters join the colloid generating kettle that places 45 ℃ of water-baths and mix and stir, stir after 30 minutes to wherein adding 178.1 and restrain hydrated aluminum oxides and (contain Al
2O
372%, Chang Ling catalyst plant product, down together), mixed 2 hours.Then, 145.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 288.5 gram silicon sol, the back that stirs adds 15.8 gram AFO structure aluminium phosphate molecular sieves, fully stirs 2 hours, makes reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 80 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Getting this crystallization product of part makes the X-ray powder diffraction and measures (sweep limit be 2 θ=5 °-35 °), its result data such as table 3.
Get the above-mentioned molecular screen primary powder of part, in stoving oven under the air atmosphere, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then with the temperature rise rate of 2 ℃ of per minutes.Sample after the roasting is measured its result data such as table 4 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.53P
2O
5: 1.1SiO
2
Table 3
| 2θ(°) | d(_) | Relative intensity |
| 8.181 | 10.799 | 100.0 |
| 11.600 | 7.623 | 12.3 |
| 14.216 | 6.225 | 73.4 |
| 16.482 | 5.374 | 26.0 |
| 18.394 | 4.819 | 27.2 |
| 20.207 | 4.391 | 8.2 |
| 21.893 | 4.056 | 34.8 |
| 23.400 | 3.798 | 14.8 |
| 24.844 | 3.581 | 49.4 |
| 26.221 | 3.396 | 59.0 |
| 28.788 | 3.099 | 19.6 |
| 29.982 | 2.978 | 32.2 |
| 32.243 | 2.774 | 22.5 |
| 33.306 | 2.693 | 3.2 |
| 35.418 | 2.534 | 18.2 |
| 40.283 | 2.238 | 3.2 |
| 42.085 | 2.146 | 5.1 |
| 43.830 | 2.065 | 7.4 |
| 47.143 | 1.927 | 8.1 |
| 47.925 | 1.898 | 8.0 |
| 48.726 | 1.868 | 5.4 |
| 49.534 | 1.840 | 3.2 |
Table 4
| 2θ(°) | d(_) | Relative intensity |
| 8.264 | 10.696 | 100.0 |
| 11.727 | 7.544 | 34.1 |
| 14.346 | 6.172 | 79.5 |
| 16.593 | 5.341 | 21.6 |
| 18.591 | 4.771 | 21.0 |
| 20.357 | 4.361 | 1.1 |
| 22.029 | 4.034 | 21.4 |
| 23.544 | 3.778 | 15.9 |
| 25.058 | 3.553 | 45.7 |
| 26.463 | 3.367 | 61.4 |
| 29.042 | 3.074 | 16.6 |
| 30.234 | 2.955 | 33.5 |
| 32.505 | 2.754 | 20.5 |
| 33.585 | 2.668 | 3.6 |
| 35.710 | 2.514 | 16.0 |
Embodiment 2
177.1 gram hydrated aluminum oxides and 630.2g deionized waters are joined after the colloid generating kettle that places 50 ℃ of water-baths mixes 30 minutes, add by 288.0 gram phosphoric acid and 275.0 and restrain the solution that deionized waters are configured to and mixed 2 hours.Then, 135.8 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 144.0 gram silicon sol, the back that stirs adds synthetic molecular screen primary powder in 15.0 gram the foregoing descriptions 1, fully stirs 2 hours, makes reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 65 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result data meets the feature of table 2.The mole of the sample after the roasting consists of: Al
2O
3: 0.61P
2O
5: 0.55SiO
2
Embodiment 3
288.2 gram phosphoric acid and 905.4 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths mix and stir, stirs after 30 minutes to wherein adding 177.1 and restrain hydrated aluminum oxides and mixed 2 hours.Then, 135.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 173.5 gram silicon sol, fully stirred 2 hours, add the molecular sieve of 16 gram embodiment, 1 preparation, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 65 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result data meets the feature of table 2.The mole of sample consists of after the roasting: Al
2O
3: 0.50P
2O
5: 0.71SiO
2
Embodiment 4
178.0 gram hydrated aluminum oxides and 562.0 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 286.0 gram phosphoric acid and 340.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.108.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 115.4 gram silicon sol, the back that stirs adds synthetic molecular screen primary powder among the 15.0 gram embodiment 1, fully stirs 2 hours, makes reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 185 ℃ and autogenous pressure, stirred crystallization 70 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.61P
2O
5: 0.43SiO
2
Embodiment 5
178.0 gram hydrated aluminum oxides and 620.0 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 288.0 gram phosphoric acid and 311.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.144.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 288.5 gram silicon sol, add synthetic molecular sieve among the 15 gram embodiment 1, fully stirred 2 hours, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 60 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets 1 feature.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.50P
2O
5: 1.10SiO
2
Embodiment 6
178.0 gram hydrated aluminum oxides and 630.0 gram deionized waters are joined the colloid generating kettle that places 40 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 288.0 gram phosphoric acid and 239.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.185.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 433.0 gram silicon sol, add the aluminium phosphate molecular sieve of 10 gram AFO structures, fully stirred 2 hours, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 65 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.54P
2O
5: 1.70SiO
2
Embodiment 7
178.0 gram hydrated aluminum oxides and 620.0 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 288.0 gram phosphoric acid and 255.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.243.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 576.9 gram silicon sol, add synthetic molecular sieve among the 5 gram embodiment 1, fully stirred 2 hours, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 60 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.45P
2O
5: 2.30SiO
2
Embodiment 8
178.0 gram hydrated aluminum oxides and 600.0 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 288.0 gram phosphoric acid and 281.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.315.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 721.0 gram silicon sol, add synthetic molecular sieve among the 10 gram embodiment 1, fully stirred 2 hours, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 60 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.39P
2O
5: 2.80SiO
2
Embodiment 9
178.0 gram hydrated aluminum oxides and 630.0 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 288.0 gram phosphoric acid and 256.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.360.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 866.0 gram silicon sol, add synthetic molecular sieve among the 20 gram embodiment 1, fully stirred 2 hours, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 65 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.40P
2O
5: 3.20SiO
2
Embodiment 10
178.0 gram hydrated aluminum oxides and 630.0 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 288.0 gram phosphoric acid and 246.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.360.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 1154.0 gram silicon sol, add synthetic molecular sieve among the 15 gram embodiment 1, fully stirred 2 hours, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 70 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.40P
2O
5: 4.20SiO
2
Embodiment 11
178.0 gram hydrated aluminum oxides and 600.0 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 288.0 gram phosphoric acid and 287.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.405.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 1442.0 gram silicon sol, the back that stirs adds the former powder of 15.0 gram the foregoing description 1 synthesis of molecular sieve, fully stirs 2 hours, makes reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 65 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.35P
2O
5: 5.30SiO
2
Embodiment 12
85.0 gram hydrated aluminum oxides, 51.5 gram deionized waters and 1008.0 gram silicon sol are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 138.4 gram phosphoric acid and 120.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.153.6 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, the back that stirs adds synthetic molecular screen primary powder in 15.0 gram the foregoing descriptions 11, fully stirs 2 hours, makes reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 70 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured its data fit table 2 feature through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.35P
2O
5: 6.90SiO
2
Embodiment 13
85.0 gram hydrated aluminum oxides, 51.5 gram deionized waters and 1386.0 gram silicon sol are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes, 138.4 gram phosphoric acid and 120.0 gram deionized waters are mixed in another container, phosphate aqueous solution is added mix 2 hours in the colloid generating kettle then.175.0 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, the back that stirs adds synthetic molecular screen primary powder in 15.0 gram the foregoing descriptions 11, fully stirs 2 hours, makes reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure, stirred crystallization 70 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result meets the feature of table 1.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured the feature of its data fit table 2 through the X-ray powder diffraction.The mole of sample consists of after the roasting: Al
2O
3: 0.31:P
2O
5: 9.0SiO
2
Claims (25)
1, a kind of silicoaluminophosphamolecular molecular sieves is characterized in that the X-ray diffraction data before the roasting removed template method contain the diffraction peak shown in the table 1 at least; X-ray diffraction data behind the roasting removed template method contain the diffraction peak shown in the table 2 at least, and the anhydrous chemical formulation that mole is formed with oxide form is Al
2O
3: yP
2O
5: zSiO
2, wherein the value of y is 0.01～1.5, the value of z is 0.05～50.
Table 1
2θ(°) d(_) Relative intensity
8.13-8.30 10.89-10.65 VS
11.55-11.72 7.66-7.55 W
14.17-14.35 6.25-6.17 S
16.43-16.61 5.39-5.34 M
18.34-18.52 4.84-4.79 M
20.16-20.34 4.40-4.36 W
21.79-21.99 4.08-4.04 M
23.30-23.50 3.82-3.78 W
24.74-24.94 3.60-3.57 M-S
26.12-26.32 3.41-3.39 M-S
28.69-28.89 3.11-3.09 W-M
29.88-30.08 2.99-2.97 M
32.14-32.44 2.78-2.76 W-M
35.33-35.63 2.54-2.52 W
Table 2
2θ(°) d(_) Relative intensity
8.21-8.31 10.77-10.63 VS
11.68-11.78 7.57-7.51 W-M
14.30-14.40 6.19-6.15 S
16.54-16.64 5.36-5.32 W-M
18.54-18.64 4.79-4.76 W
20.31-20.41 4.37-4.35 W
21.93-22.13 4.05-4.01 W-M
23.44-23.64 3.80-3.76 W
24.96-25.16 3.57-3.54 M
26.36-26.56 3.38-3.35 M-S
28.94-29.14 3.09-3.06 W
30.08-30.38 2.97-2.94 M
32.36-32.66 2.76-2.74 W
35.60-35.90 2.52-2.50 W
2, according to the molecular sieve of claim 1, wherein the value of y is 0.1～1.4; The value of z is 0.1～40.
3, according to the molecular sieve of claim 2, wherein the value of y is 0.15～1.2; The value of z is 0.2～20.
4, according to the molecular sieve of claim 1, the mole before its roasting removed template method is xR:Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2, wherein, R is the organic formwork agent that is present in the molecular sieve crystal duct; The value of x is 0.01～5.0, the value of y and z such as claim 1 definition.
5, according to the molecular sieve of claim 4, organic formwork agent wherein is a kind of in diethylamine or diethylamine and di-n-propylamine, Diisopropylamine, the triethylamine or both or both above mixtures, and the value of x is 0.03～4.0.
6, according to the molecular sieve of claim 1, the condition of wherein said roasting removed template method is 300～700 ℃ of following constant temperature 2～10 hours.
7, the synthetic method of the described molecular sieve of claim 1 is characterized in that under room temperature～80 ℃ by feed ratio aR: Al
2O
3: bP
2O
5: cSiO
2: dH
2O was mixed into glue with aluminium source, phosphorus source, silicon source and organic formwork agent, adds the crystal seed in butt 0.1～10 weight %, 120～250 ℃ of following hydrothermal crystallizings 4～500 hours; Wherein R is an organic formwork agent, the value of a is 0.5～10, the value of b is 0.5～1.5, the value of c is 0.05～50, the value of d is 10～150, and crystal seed is selected from a kind of in the molecular sieve of the silicoaluminophosphamolecular molecular sieves of aluminium phosphate molecular sieve, AFO structure of AFO structure or claim 1 or two or three mixture wherein.
8, the synthetic method of the described molecular sieve of claim 7, said crystal seed are the molecular sieve of claim 1 and/or the silicoaluminophosphamolecular molecular sieves of AFO structure.
9, according to the method for claim 7, wherein said aluminium source is selected from aluminium hydroxide, hydrated aluminum oxide, aluminum isopropylate or aluminum phosphate, said silicon source is selected from solid silicone, silicon sol or silicon ester, said phosphorus source is selected from phosphoric acid or aluminum phosphate, said organic formwork agent be diethylamine or for diethylamine be selected from a kind of in di-n-propylamine, Diisopropylamine, the triethylamine or both or both above mixtures.
10, according to the method for claim 9, wherein said aluminium source is hydrated aluminum oxide or aluminum isopropylate, and said phosphorus source is a phosphoric acid, and said organic formwork agent is a diethylamine.
11, according to the method for claim 7, wherein said crystal seed add-on is 2～8 heavy %.
12, according to the method for claim 7, the temperature during wherein said one-tenth glue is 15～75 ℃.
13, according to the method for claim 7, wherein said crystallization temperature is 150～220 ℃.
14, according to the method for claim 7, wherein said crystallization time is 10～200 hours.
15, according to the method for claim 7, wherein the value of a is 0.6～9.0.
16, according to the method for claim 15, wherein the value of a is 0.7～8.0.
17, according to the method for claim 7, wherein the value of b is 0.6～1.2.
18, according to the method for claim 17, wherein the value of b is 0.7～1.1.
19, according to the method for claim 7, wherein the value of c is 0.1～40.
20, according to the method for claim 19, wherein the value of c is 0.15～20.
21, according to the method for claim 7, wherein the value of d is 20～120.
22, according to the method for claim 21, wherein the value of d is 25～100.
23, according to the method for claim 7, wherein the order that feeds intake of said raw material at first mixes phosphorus source and aluminium source with water, after stirring, adds template, adds silicon source and crystal seed after stirring again.
24, according to the method for claim 7, wherein the order that feeds intake of said raw material adds the solution of phosphoric acid and water then for the aluminium source is mixed with water, after stirring, adds template, silicon source and crystal seed more successively.
25, according to the method for claim 7, wherein said hydrothermal crystallization process is static or dynamically carry out under the autogenous pressure.
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| CN101935048B (en) * | 2009-06-30 | 2013-01-09 | 中国石油化工股份有限公司 | Titanium-contained silicon-aluminum phosphate molecular sieve and synthesis thereof |
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| CN106800300B (en) * | 2015-11-26 | 2018-09-28 | 中国科学院大连化学物理研究所 | A kind of silicoaluminophosphate composite molecular screen and preparation method thereof |
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