CN1834015A - Synthetic process of SAPO-11 Molecular sieve - Google Patents
Synthetic process of SAPO-11 Molecular sieve Download PDFInfo
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- CN1834015A CN1834015A CN 200510056346 CN200510056346A CN1834015A CN 1834015 A CN1834015 A CN 1834015A CN 200510056346 CN200510056346 CN 200510056346 CN 200510056346 A CN200510056346 A CN 200510056346A CN 1834015 A CN1834015 A CN 1834015A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 52
- 239000000843 powder Substances 0.000 claims description 42
- 239000011541 reaction mixture Substances 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 238000010189 synthetic method Methods 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 quaternary ammonium alkyl ion Chemical class 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 229910014307 bSiO Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 16
- 230000031709 bromination Effects 0.000 description 10
- 238000005893 bromination reaction Methods 0.000 description 10
- 150000002460 imidazoles Chemical class 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009415 formwork Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
This invention relates to a method to synthesize SAPO-11 molecular sieves, which conquers the disadvantages of hydrothermal high-pressure procedure, expensive organic reagents adopted and acid and alkali waste liquid discharge in conventional methods. It has the characteristics that during the synthesis, ionic liquid with a low vapor pressure is adopted as solvent and template and thus the crystallization can be carried out under normal pressure. And as the ionic liquid can be recycled, no expensive organic template is necessary, which greatly cuts down the cost. Besides, no acid or alkali waste liquid is discharged and this method is environmentally friendly.
Description
Technical field
The present invention relates to a kind of synthetic method of molecular sieve, relate to a kind of synthetic method of SAPO-11 molecular sieve particularly.
Background technology
The SAPO-11 molecular sieve is a kind of siliceous aluminophosphate molecular sieve of the AEL of having type topological framework.The type molecular sieve contains one dimension ten-ring straight hole structure, and the duct is oval, and size is 0.39 * 0.63nm, has tradable positively charged ion.Not siliceous AEL type aluminophosphate molecular sieve is not because the skeleton charge balance that aluminum-oxygen tetrahedron and phosphorus oxygen tetrahedron are formed has acidic site.Therefore the SAPO-11 molecular sieve produces acidic site owing to silicon species is introduced framework of molecular sieve, has expanded the purposes of this molecular sieve analog, especially aspect the reaction of alkane hydroisomerizing, but has excellent catalytic performance at the SAPO-11 of precious metal molecular sieve.
The SAPO-11 molecular sieve is at first at first reported be synthesized (US4,440,871) by U.S. UCC company, thereafter have many pieces of reports to occur about the synthetic method or the improved synthetic method of SAPO-11 molecular sieve again, comprising: US 4,701,485, US 5,208,005, US 4,943, and 424, CN1155519C, CN 1174919C.The common feature of these methods is synthesis of molecular sieve products under hydrothermal condition.General hydro-thermal building-up process is: silicon source, aluminium source, phosphorus source, organic formwork agent and water are mixed into glue, some process also will add tensio-active agent and organic alcohols, colloid admixture passes through after the weathering process or directly enters crystallization process, after crystallization finishes, to product filter, wash, drying.The shortcoming of these hydro-thermal building-up processes is that the molecular sieve crystallization process under high pressure carries out, and the conversion unit investment is big, complex process, operational difficulty; The molecular sieve crystallization process need use organic formwork agent, costs an arm and a leg, and can not reclaim, synthetic cost height; Crystallization needs the filtration washing zeolite product after finishing, and the waste reaction solution of phosphoric acid and organic formwork agent, tensio-active agent and organic alcohol etc. can't reclaim, and directly can pollute environment after the discharging.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of SAPO-11 molecular sieve makes synthesizing under normal pressure of SAPO-11 molecular sieve carry out, and need not to use organic formwork agent, and building-up process does not have the acid-base waste fluid discharging.
The synthetic method of a kind of SAPO-11 molecular sieve provided by the present invention comprises: phosphorus source, aluminium source, silicon source, ionic liquid are made homogeneous reaction mixture, progressively heat up then, reaction mixture is carried out ion thermal crystallisation certain hour under certain temperature and pressure, filter then, wash, drying.
Concrete synthesis condition is:
1) in 80-150 ℃ of temperature range, in ionic liquid, add phosphorus source, aluminium source and silicon source, stir, form reaction mixture aP
2O
5: Al
2O
3: bSiO
2: the c ionic liquid, count in molar ratio, a wherein is 0.5-10, and b is 0.05-0.5, and c is 20-100; Then add mineralizer, add-on is 0.001-0.01;
Preferable reaction raw materials mixing temperature is 90-110 ℃; The reaction raw materials mixing temperature is 100 ℃ best;
A was 0.5-5 during preferably the reaction mixture mole was formed, and b is 0.05-0.5, and c is 10-70; A was 1-4 during the reaction mixture mole was formed best, and b is 0.05-0.5, and c is 30-50.
2) reaction mixture is heated to 140-220 ℃, under normal pressure or the autogenous pressure, crystallization time 20-90 hour;
Preferably crystallization condition is 150-200 ℃, under normal pressure or the autogenous pressure, and crystallization time 20-80 hour; Crystallization condition is 150-170 ℃ best, under the normal pressure, and crystallization time 20-80 hour.
3) after crystallization finishes, with the reaction mixture cool to room temperature, add water, filter, water or organic solvent wash powdered samples, and room temperature-110 ℃ drying obtains SAPO-11 molecular sieve powder shape product.
4) collect waste reaction solution, in Rotary Evaporators, moisture content is wherein steamed with the solvent that washs molecular sieve, reclaim ionic liquid.
Employed ionic liquid is for containing following positively charged ion in the above-mentioned synthetic method: quaternary ammonium alkyl ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion [Rim] that replaces of base
+, the pyridinium ion brief note that replaces of base is [Rpy]
+In the ionic liquid of one or more miscellanys.The preferable ionic liquid of effect is to contain the imidazol ion [Rim] that alkyl replaces
+Ionic liquid.
Employed phosphorus source comprises phosphoric acid or aluminum phosphate etc. in the above-mentioned synthetic method, and the aluminium source comprises pseudo-boehmite, hydrated aluminum oxide, Tai-Ace S 150, aluminum nitrate or aluminum isopropylate, and the silicon source comprises silicon sol, water glass or tetraethoxy.The preferable phosphorus source of effect is a phosphoric acid, and the aluminium source is an aluminum isopropylate, and the silicon source is a tetraethoxy.
The mineralizer that adds in the above-mentioned synthetic method is HF, NH
4F or NaF etc.
The invention has the beneficial effects as follows:
It is solvent and template that the building-up process of SAPO-11 molecular sieve adopts ionic liquid, and ion liquid steam forces down, so crystallization process can carry out under normal pressure, and reaction unit need not the applying pressure container, and process economy is strong, and easy-to-operate; Do not use expensive organic template in the building-up process of SAPO-11 molecular sieve, ionic liquid can reclaim repeated use, and synthetic cost is low; No acid-base waste fluid discharging in the building-up process of SAPO-11 molecular sieve, environmental friendliness.
Description of drawings
Fig. 1 is the synthetic SAPO-11 of an institute molecular sieve XRD spectra of the present invention.
Fig. 2 is the synthetic SAPO-11 of an institute molecular sieve stereoscan photograph of the present invention.
Embodiment
Embodiment 1.
80g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 100 ℃, adding 3.2g concentration is the phosphoric acid of 85wt%, stir, add the 2.1g aluminum isopropylate again, stir, add the 0.5g tetraethoxy again, stir, then add the hydrofluoric acid that 0.3g concentration is 40wt%, stir, be warming up to 150 ℃, kept 68 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, this powder 100ml washing with acetone, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.The solvent of moisture content in the filtrate after will washing in Rotary Evaporators and washing molecular sieve steams, and reclaims ionic liquid.
Embodiment 2.
200g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 80 ℃, adding 3.2g concentration is the phosphoric acid of 85wt%, stir, add the 2.1g aluminum isopropylate again, stir, add the 0.5g tetraethoxy again, stir, then add the hydrofluoric acid that 0.3g concentration is 40wt%, stir, be warming up to 150 ℃, kept 68 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, this powder 100ml washing with acetone, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.
Embodiment 3.
40g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 150 ℃, adding 3.2g concentration is the phosphoric acid of 85wt%, stir, add the 2.1g aluminum isopropylate again, stir, add the 0.5g tetraethoxy again, stir, then add the hydrofluoric acid that 0.3g concentration is 40wt%, stir, be warming up to 150 ℃, kept 68 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, this powder 100ml washing with acetone, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.
Embodiment 4.
80g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 100 ℃, adding 9.5g concentration is the phosphoric acid of 85wt%, stir, add the 2.1g aluminum isopropylate again, stir, add the 0.1g tetraethoxy again, stir, then add the hydrofluoric acid that 0.3g concentration is 40wt%, stir, be warming up to 150 ℃, kept 68 hours, the reaction mixture cool to room temperature adds 150ml water then, stirs, then reaction mixture is filtered, obtain brown powder,, obtain white powder this powder 100ml washing with acetone, through the XRD test, this white powder is the SAPO-11 molecular sieve.
Embodiment 5.
80g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 100 ℃, adding 0.5g concentration is the phosphoric acid of 85wt%, stir, add the 2.1g aluminum isopropylate again, stir, add the 0.5g tetraethoxy again, stir, then add the hydrofluoric acid that 0.3g concentration is 40wt%, stir, be warming up to 160 ℃, kept 68 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, this powder 100ml washing with acetone, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.
Embodiment 6.
80g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 100 ℃, adding 3.2g concentration is the phosphoric acid of 85wt%, stir, add the 2.1g aluminum isopropylate again, stir, add the 0.5g tetraethoxy again, stir, then add the hydrofluoric acid that 0.3g concentration is 40wt%, stir, be warming up to 140 ℃, kept 100 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, this powder 100ml washing with acetone, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.
Embodiment 7.
80g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 100 ℃, adding 3.2g concentration is the phosphoric acid of 85wt%, stir, add the 1.1g aluminum isopropylate again, stir, add the 0.2g tetraethoxy again, stir, then add the hydrofluoric acid that 0.3g concentration is 40wt%, stir, be warming up to 220 ℃, kept 20 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, this powder 100ml washing with acetone, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.
Embodiment 8.
80g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 100 ℃, adding 3.2g concentration is the phosphoric acid of 85wt%, stir, add the 4.1g aluminum isopropylate again, stir, add the 0.2g tetraethoxy again, stir, then add the hydrofluoric acid that 0.3g concentration is 40wt%, stir, be warming up to 150 ℃, kept 68 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, this powder 100ml washing with acetone, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.
Embodiment 9.
80g 1-ethyl-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 100 ℃, adding 3.2g concentration is the phosphoric acid of 85wt%, stir, add the 2.1g aluminum isopropylate again, stir, add the 0.5g tetraethoxy again, stir, then add the 0.3g ammonium fluoride, stir, be warming up to 150 ℃, kept 60 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, this powder 100ml washing with acetone, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.
90g 1-propyl group-3-methyl bromination imidazoles is added in the there-necked flask, be warming up to 100 ℃, adding 3.2g concentration is the phosphoric acid of 85wt%, stir, add the 2.1g aluminum isopropylate again, stir, add the 0.5g tetraethoxy again, stir, then add the 0.3g Sodium Fluoride, stir, be warming up to 150 ℃, kept 70 hours, the reaction mixture cool to room temperature adds 150ml water then, stir, then reaction mixture is filtered, obtain brown powder, the 100ml water washing of this powder, obtain white powder, through the XRD test, this white powder is the SAPO-11 molecular sieve, and contains a small amount of unknown stray crystal.
Claims (10)
1, a kind of synthetic method of SAPO-11 molecular sieve, key step is:
A) in 80-150 ℃ of temperature range, in ionic liquid, add phosphorus source, aluminium source and silicon source, stir, form reaction mixture aP
2O
5: Al
2O
3: bSiO
2: the c ionic liquid, in molar ratio, a is 0.5-10, and b is 0.05-0.5, and c is 20-100; Then add mineralizer, the mineralizer add-on is mol ratio 0.001-0.01;
Described ionic liquid comprises and contains following positively charged ion: quaternary ammonium alkyl ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion [Rim] that alkyl replaces
+, the pyridinium ion brief note that alkyl replaces is [Rpy]
+In the ionic liquid of one or more miscellanys;
Described phosphorus source comprises phosphoric acid or aluminum phosphate;
Described aluminium source comprises pseudo-boehmite, hydrated aluminum oxide, Tai-Ace S 150, aluminum nitrate or aluminum isopropylate;
Described silicon source comprises silicon sol, water glass or tetraethoxy;
Described mineralizer comprises HF, NH
4F or NaF;
B) reaction mixture with step a preparation is heated to 140-220 ℃, under normal pressure or the autogenous pressure, and crystallization time 20-100 hour;
C) after crystallization finishes, with the reaction mixture cool to room temperature, filter, water or organic solvent wash powdered samples, and room temperature-110 ℃ drying obtains SAPO-11 molecular sieve powder shape product.
2. the synthetic method of claim 1 is characterized in that, the reaction raw materials mixing temperature of step a is 90-110 ℃.
3. claim 1 or 2 synthetic method is characterized in that the reaction raw materials mixing temperature of step a is 100 ℃.
4, the synthetic method of claim 1 is characterized in that, the ionic liquid of step a is to contain the imidazol ion [Rim] that alkyl replaces
+Ionic liquid.
5. the synthetic method of claim 1 is characterized in that, the phosphorus source of step a is a phosphoric acid; The aluminium source is an aluminum isopropylate; The silicon source is a tetraethoxy.
6. the synthetic method of claim 1 is characterized in that, a was 0.5-5 during the reaction mixture mole of step a was formed, and b is 0.05-0.5, and c is 30-70.
7. claim 1 or 6 synthetic method is characterized in that, a was 1-4 during the reaction mixture mole of step a was formed, and b is 0.05-0.5, and c is 30-50.
8. the synthetic method of claim 1 is characterized in that, the crystallization condition of step b is: 150-200 ℃, and under normal pressure or the autogenous pressure, crystallization time 20-80 hour.
9. claim 1 or 8 synthetic method is characterized in that the crystallization condition of step b is: 150-170 ℃, and under the normal pressure, crystallization time 20-80 hour.
10. the synthetic method of claim 1 is characterized in that, collects the washings of step c, and wherein moisture content or solvent steamed, and reclaims ionic liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913621A (en) * | 2010-08-25 | 2010-12-15 | 中国石油大学(北京) | Method for synthesizing SAPO-11 molecular sieve by using long chain alkyl silane as silicon source |
| CN101913622A (en) * | 2010-08-25 | 2010-12-15 | 中国石油大学(北京) | Preparation method of multistage pore canal SAPO-11 (silicoaluminophosphate-11) molecular sieve and application thereof in gasoline modification |
| CN102188999A (en) * | 2011-03-23 | 2011-09-21 | 天津大学 | Preparation method and application of ionic liquid functionalized Al-MCM-41 mesoporous material |
| CN102139888B (en) * | 2010-01-29 | 2012-11-07 | 中国科学院大连化学物理研究所 | Synthesis method of silicoaluminophosphate molecular sieve with AFO structure |
| CN102786063A (en) * | 2012-08-10 | 2012-11-21 | 中国海洋石油总公司 | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure |
| CN103318916A (en) * | 2012-03-21 | 2013-09-25 | 中国科学院大连化学物理研究所 | Preparation of LTA structure aluminophosphate molecular sieve membrane supported by porous alumina carrier |
| CN103539146A (en) * | 2013-10-28 | 2014-01-29 | 中国海洋石油总公司 | Ion hot method for continuously synthesizing SAPO-11 molecular sieves |
| CN103553074A (en) * | 2013-10-28 | 2014-02-05 | 中国海洋石油总公司 | Method for continuously synthesizing SAPO-42 molecular sieve by ionothermal process |
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| CN1174919C (en) * | 2000-12-01 | 2004-11-10 | 中国石化集团齐鲁石油化工公司 | Process for preparing low-granularity high-crystallinity SAPO-11 molecular sieve |
| CN1176848C (en) * | 2002-05-30 | 2004-11-24 | 复旦大学 | SAPO-11 molecular sieve catalyst and its preparation method |
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