CN103303936A - Method for synthesizing pure-phase SAPO-41 molecular sieve by use of crystallization mother liquid - Google Patents
Method for synthesizing pure-phase SAPO-41 molecular sieve by use of crystallization mother liquid Download PDFInfo
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- CN103303936A CN103303936A CN2013102693185A CN201310269318A CN103303936A CN 103303936 A CN103303936 A CN 103303936A CN 2013102693185 A CN2013102693185 A CN 2013102693185A CN 201310269318 A CN201310269318 A CN 201310269318A CN 103303936 A CN103303936 A CN 103303936A
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Abstract
The invention discloses a method for synthesizing a pure-phase SAPO-41 molecular sieve by use of crystallization mother liquid, relating to the technical field of molecular sieve synthesis. The mother liquid obtained by filtration after the crystallization of an SAPO-41 molecular sieve is used as one part of the raw material for the synthesis of the same type of molecular sieve, and a corresponding new raw material is supplemented proportionally to prepare a sol mixture for synthesizing a molecular sieve. The method disclosed by the invention can make full use of the microcrystal and the component not involved in reaction in the SAPO-41 molecular sieve synthesis mother liquid; on one hand, the heating is assisted by microwaves, thus the generation of a hybrid crystal phase in the molecular sieve is eliminated, and the crystallinity and purity of the SAPO-41 molecular sieve are improved; and on the other hand, by use of the mother liquid and microcrystal seed therein, the crystallization time is shortened, the grain size of the molecular sieve is reduced, zero emission of the crystallization mother liquid is realized, environmental pollution is reduced, and the synthesis cost of the molecular sieve is lowered.
Description
Technical field
The invention belongs to the aluminium silicophosphate molecular sieve synthesis technical field, be specifically related to a kind of method of utilizing the synthetic SAPO-41 molecular sieve of crystallization mother liquor of microwave-assisted.
Background technology
Mesopore SAPO-41 molecular sieve is the aluminium silicophosphate mesoporous molecular sieve with AFO structure, and the one dimension ellipse hole road of being made up of ten-ring is of a size of 0.43mm * 0.70mm.The SAPO-41 framework of molecular sieve is made of Si, P, Al and O element, belongs to rhombic system, and unit cell dimension is a=0.97nm, b=2.55nm, c=0.84nm.Its typical structure parameter is: aperture 0.60nm, pore volume 0.22mLg
-1Because suitable pore passage structure and the acidity of medium tenacity make it show higher activity and isomery selectivity in the reaction of normal alkane isomerizations such as isomerization dewaxing.
US Patent No. 4859312 has reported that the SAPO-11 of Pt or Pd load and SAPO-41 catalyzer can make heavy oil carry out hydrocracking and isomerization reaction simultaneously, thereby reduces viscosity and the pour point of oil product, the oil product that obtains having better flowability.U.S. US5135638 has reported is combined SAPO-11, SAPO-31 and SAPO-41 with hydrogenation activity component Pt or Pd, content of wax component can be isomerizated into the lubricating oil component of low pour point and high viscosity index (HVI).
US Patent No. 4310440 discloses the synthetic method of aluminium silicophosphate molecular sieve, at first synthesis material is mixed with crystallization liquid, successfully synthesizes a brand-new molecular sieve family-aluminium silicophosphate molecular sieve AlPO by hydrothermal synthesis method
4US Patent No. 4440871 brings into use tetrabutylammonium hydroxide amine as template, and Si is incorporated into AlPO
4Synthesize the SAPO-41 molecular sieve in-41.Chinese patent CN1448336 and CN1923688 disclose a kind of synthetic method of SAPO-41 molecular sieve, are characterized in needing in the building-up process to use the template of high dosage.
The method of these synthetic SAPO-41 molecular sieves need perhaps adopt the synthetic SAPO-41 of method of conventional high template dosage with expensive quaternary amine as template, synthetic cost costliness, and product is prone to stray crystal.
In general, hydrothermal method synthesis of molecular sieve yield is generally 50%-80%, so can contain the unreacting material component in the crystallization mother liquor after molecular sieve synthesizes.These components all are dissolved in the mother liquor behind the molecular sieving, and behind the synthesis of molecular sieve, mother liquor is often directly outwelled, and for industrial production, the discharging of mother liquor causes wastage of material on the one hand; Can pollute environment on the other hand.
Summary of the invention
The objective of the invention is to overcome has stray crystal, the direct discharging of waste liquid to cause wastage of material and environmental pollution problems in the synthetic cost height of SAPO-41 molecular sieve, the product in the prior art, a kind of method of utilizing the synthetic SAPO-41 molecular sieve of crystallization mother liquor of microwave-assisted is provided.
The present invention is a kind of method of utilizing the synthetic SAPO-41 molecular sieve of crystallization mother liquor, it is characterized in that, recovery contains the crystallization mother liquor of SAPO-41 molecular sieve crystallite crystal seed and unreacted components, again described crystallization mother liquor is replenished new raw material, gel mixture is carried out the microwave-assisted ageing handle, synthetic SAPO-41 molecular sieve; Concrete steps comprise:
1) will be for the first time synthetic SAPO-41 molecular sieve solid product membrane pore size be that the filter membrane of 0.1 μ m carries out vacuum filtration and separates, recovery filtrate obtains containing the crystallization mother liquor of crystallite crystal seed;
2) analyze the crystallization mother liquor component concentration, add aluminium source, silicon source, phosphorus source, template and water, be mixed with the collosol intermixture of synthesis of molecular sieve, the mol ratio of each material is aR:Al in the wherein said collosol intermixture
2O
3: bP
2O
5: cSiO
2: dH
2O, wherein R is template, the value of a is that the value of 0.5 ~ 2, b is that the value of 0.1 ~ 3, c is that the value of 0.1 ~ 2, d is 20 ~ 80;
3) with step 2) in described collosol intermixture obtain initial gel mixture at 15～65 ℃ of following heated by microwave ageing 2～10h;
4) initial gel mixture described in the step 3) is placed crystallizing kettle, at 150 ℃ ~ 200 ℃ following hydrothermal crystallizing 10 ~ 40h, the product furnace cooling after-filtration behind the hydrothermal crystallizing is obtained filter cake and filtrate;
5) filter cake described in the step 4) is placed in the baking oven 100 ℃ ~ 120 ℃ oven dry down with deionized water wash; Filter cake after the oven dry is placed retort furnace roasting 5 ~ 20h, obtain the SAPO-41 molecular screen primary powder after the cooling;
6) filtrate described in the step 4) is reclaimed, as the crystallization mother liquor recycle.
In technique scheme, step 2) the template molar weight in the described molecular sieve crystallization mother liquor is 0.1～0.9 with template integral molar quantity ratio in the molecular sieve crystallization liquid.
Step 2) source of aluminium described in is one or more in aluminum oxide, Tai-Ace S 150, aluminum isopropylate and the pseudo-boehmite; The silicon source is selected from one or more in silicon sol, solid oxidation silicon, tetraethoxy and the silica gel; The phosphorus source is phosphoric acid or phosphorous acid; Template is one or more in di-n-propylamine, Diisopropylamine and the diethylamine.
The inventive method beneficial effect compared with prior art is: 1) method of the synthetic SAPO-41 of the present invention is recycled the crystallization mother liquor that contains crystallite repeatedly and is come synthesis of molecular sieve, can effectively reduce discharging of waste liquid, reduce environmental pollution; 2) in the crystallization mother liquor unreacted component be used to again molecular sieve synthetic in, saved raw material, reduced synthetic cost; 3) contained crystallite makes the inventive method can synthesize the SAPO-41 molecular sieve of high-crystallinity fast in the mother liquor; 4) by the microwave heating ageing, avoided the generation thermograde, more even to the heating of the material in the medium, the molecular sieve mother liquor is reused, can greatly improve nucleation rate and the quantity of crystallization process nucleus inductive phase, avoid the generation of stray crystal phase in the product.
Embodiment
The present invention will be further described with subordinate list with the following Examples, implements process of the present invention, condition, test method etc., is universal knowledege and the common practise of this area, and it is commercially available that agents useful for same is, except the following content of mentioning specially.
Embodiment 1
The 156g pseudo-boehmite is joined in the 600g deionized water, stir 30min.Under the vigorous stirring, slowly drip the solution that 272.1g phosphoric acid (85wt%) and 401.1g deionized water form then, (chemical pure, 97wt%) 357.2g then add silicon sol (30wt% SiO to drip di-n-propylamine again
2) 24g, form collosol intermixture, the collosol intermixture that obtains is moved in the stainless steel crystallizing kettle, at 185 ℃, the spontaneous crystallization 38h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 17h under 100 ℃, namely obtains molecular screen primary powder.Molecular screen primary powder is 550 ℃ of roasting 10h under air atmosphere, remove template, get the SAPO-41 molecular sieve.The X-ray diffractometer test result is as shown in table 1.
Gained sample of the present invention adopts Japanese D/MAX-2500 type X-ray diffraction of science (XRD) instrument to carry out diffraction experiment, and the characteristic feature peak with SAPO-41 molecular sieve is identified in contrast, is the crystalline phase of SAPO-41 molecular sieve, and the stray crystal phase is arranged, 2 θ (
oThe stray crystal peak of SAPO-11 molecular sieve appears in)=8.10,9.57,21.23,22.22,22.95,23.31 places.Condition determination: the Cu target, the K alpha-ray (λ=0.15418nm), Ni filtering, operating voltage 40kV, working current 200mA, sweep limit 5 ~ 55
o, sweep velocity 10
o/ min.The intensity of diffraction peak is got by the peak height of diffraction peak and the percentage calculation of highest peak peak height.Relative crystallinity calculates the ratio get 6 highest peak peak height sums and 6 highest peak peak heights of embodiment 1 sample sum, and to be designated as 100%, embodiment, 1 sample degree of crystallinity be 100%.Because the silicon oxide of different samples is different with the ratio of aluminum oxide, and the influence of grain-size and laboratory apparatus error, the deviation of measuring value of diffraction angle 2 θ is estimated as ± 0.20 degree.
The X ray diffracting data (embodiment 1 gained sample) of the SAPO-41 molecular sieve that table 1 is synthetic
Embodiment 2
The crystallization mother liquor that reclaims among the embodiment 1 as synthesis material, is mixed into collosol intermixture with a certain amount of pseudo-boehmite, phosphoric acid, di-n-propylamine, silicon sol, deionized water after analyzing component concentration, and it is synthetic to carry out the SAPO-41 molecular sieve, and it is as follows specifically to feed intake:
The 78g pseudo-boehmite is joined in the 200g deionized water, stir 30min.Under the vigorous stirring, slowly drip the solution that 136g phosphoric acid (85%) and 321g deionized water form then, drip the crystallization mother liquor that di-n-propylamine (chemical pure, 97 %) 178.6g and 529.4g contain di-n-propylamine 178.4g again, then add silicon sol (30wt% SiO
2) 24g, form collosol intermixture, the collosol intermixture that obtains is moved in the stainless steel crystallizing kettle, at 185 ℃, the spontaneous crystallization 36h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 15h under 120 ℃, namely obtains molecular screen primary powder.Former powder is 550 ℃ of roasting 10h under air atmosphere, obtain molecular sieve after the removal template.The molecular sieve that obtains is tested with X-ray diffractometer, and test result is as shown in table 2, and diffraction data shows that product is the SAPO-41 molecular sieve, 2 θ (
oThe stray crystal peak of SAPO-11 molecular sieve appears in)=8.10,9.57,21.23,22.22,22.95,23.31 places.
The X ray diffracting data (embodiment 2 gained samples) of the SAPO-41 molecular sieve that table 2 is synthetic
Embodiment 3
With the crystallization mother liquor that reclaims among the embodiment 2 as synthesis material, be mixed into collosol intermixture with a certain amount of pseudo-boehmite, phosphoric acid, di-n-propylamine, silicon sol, deionized water after analyzing component concentration, after the colloidal sol process microwave-assisted heat treated, it is synthetic to carry out the SAPO-41 molecular sieve, specifically feeds intake, operates as follows:
The 49.9g pseudo-boehmite is joined in the 300g deionized water, stir 30min.Under the vigorous stirring, slowly drip the solution that 87g phosphoric acid (85%) and 48.1g deionized water form then, drip the crystallization mother liquor that di-n-propylamine (chemical pure, 97%) 114.3g and 720g contain di-n-propylamine 242.6g again, then add silicon sol (30wt% SiO
2) 24g, forming collosol intermixture, colloidal sol obtains initial gel mixture behind the stirring ageing 5h under the condition of microwave-assisted heating (55 ℃ of Heating temperatures).The gel mixture that obtains is moved in the stainless steel crystallizing kettle, at 190 ℃, the spontaneous crystallization 26h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 16h under 100 ℃, namely obtains molecular screen primary powder.Former powder is 550 ℃ of roasting 11h under air atmosphere, obtain molecular sieve after the removal template, and the X-ray diffractometer test result is as shown in table 3, and the test shows product is pure phase SAPO-41 molecular sieve.
The X ray diffracting data (embodiment 3 gained samples) of the SAPO-41 molecular sieve that table 3 is synthetic
Embodiment 4
With the crystallization mother liquor that reclaims among the embodiment 3 as synthesis material, be mixed into collosol intermixture with a certain amount of pseudo-boehmite, phosphoric acid, di-n-propylamine, silicon sol, deionized water after analyzing component concentration, after the colloidal sol process microwave-assisted heat treated, it is synthetic to carry out the SAPO-41 molecular sieve, specifically feeds intake, operates as follows:
The 38.1g pseudo-boehmite is joined in the 200g deionized water, stir 30min.Under the vigorous stirring, slowly drip the solution that 68g phosphoric acid (85%) and 80g deionized water form then, drip the crystallization mother liquor that di-n-propylamine (chemical pure, 97%) 89.3g and 794.1g contain di-n-propylamine 267.6g again, then add silicon sol (30wt% SiO
2) 24g, forming collosol intermixture, colloidal sol obtains initial gel mixture behind the stirring ageing 3h under the condition of microwave-assisted heating (60 ℃ of Heating temperatures).The gel mixture that obtains is moved in the stainless steel crystallizing kettle, at 180 ℃, the spontaneous crystallization 26h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 13h under 110 ℃, namely obtains molecular screen primary powder.Former powder is 550 ℃ of roasting 11h under air atmosphere, obtains after the removal template, and be that pure phase does not have stray crystal SAPO-41 molecular sieve by X-ray diffractometer test shows product, test data repeats no more.
Embodiment 5
468.6g Tai-Ace S 150 is joined in the 500g deionized water, stir 30min.Then under the vigorous stirring, slowly drip the solution that 145g phosphorous acid and 272g deionized water form, drip diethylamine (chemical pure again, 97wt%) 350g, then add solid oxidation silica flour 60g, form collosol intermixture, the collosol intermixture that obtains is moved in the stainless steel crystallizing kettle, at 185 ℃, the spontaneous crystallization 40h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 12h under 120 ℃, namely obtains molecular screen primary powder.Molecular screen primary powder is 550 ℃ of roasting 4h under air atmosphere, remove template, get the SAPO-41 molecular sieve.The X-ray diffractometer test result is as shown in table 4, has SAPO-41 molecular sieve characteristic peak, but 2 θ (
oThe stray crystal peak of SAPO-11 molecular sieve appears in)=8.10,9.57,21.23,22.22,22.95,23.31 places.
The X ray diffracting data (embodiment 5 gained samples) of the SAPO-41 molecular sieve that table 4 is synthetic
Embodiment 6
With the crystallization mother liquor that reclaims among the embodiment 5 as synthesis material, be mixed into collosol intermixture with a certain amount of Tai-Ace S 150, phosphorous acid, diethylamine, solid oxidation silica flour, deionized water after analyzing component concentration, it is synthetic to carry out the SAPO-41 molecular sieve, and it is as follows specifically to feed intake:
344.8g Tai-Ace S 150 is joined in the 300g deionized water, stir 30min.Then under the vigorous stirring, slowly drip the solution that 106.6g phosphorous acid and 207.5g deionized water form, drip diethylamine (chemical pure again, 97%) 257.4g and 480g contain the crystallization mother liquor of diethylamine 92.6g, then add solid oxidation silica flour 60g, form collosol intermixture, the collosol intermixture that obtains is moved in the stainless steel crystallizing kettle, at 180 ℃, the spontaneous crystallization 35h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 15h under 110 ℃, namely obtains molecular screen primary powder.Former powder is 550 ℃ of roasting 5h under air atmosphere, obtain molecular sieve after the removal template.The X-ray diffractometer test result is as shown in table 5, and the product molecular sieve has SAPO-41 molecular sieve characteristic peak.
The X ray diffracting data (embodiment 6 gained samples) of the SAPO-41 molecular sieve that table 5 is synthetic
Embodiment 7
With the crystallization mother liquor that reclaims among the embodiment 6 as synthesis material, be mixed into initial gel with a certain amount of Tai-Ace S 150, phosphorous acid, diethylamine, solid oxidation silica flour, deionized water after analyzing component concentration, after the gel process microwave-assisted heat treated, it is synthetic to carry out the SAPO-41 molecular sieve, specifically feeds intake, operates as follows:
344.8g Tai-Ace S 150 is joined in the 300g deionized water, stir 30min.Then under the vigorous stirring, slowly drip the solution that 106.6g phosphorous acid and 207.5g deionized water form, drip diethylamine (chemical pure again, 97%) 257.4g and 480g contain the crystallization mother liquor of diethylamine 92.6g, then add solid oxidation silica flour 60g, form collosol intermixture, collosol intermixture obtains initial gel mixture behind the stirring ageing 6h under the condition of microwave-assisted heating (55 ℃ of Heating temperatures).The gel mixture that obtains is moved in the stainless steel crystallizing kettle, at 180 ℃, the spontaneous crystallization 23h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 10h under 120 ℃, namely obtains molecular screen primary powder.Former powder is 550 ℃ of roasting 5h under air atmosphere, obtain molecular sieve after the removal template.The X-ray diffractometer test result is as shown in table 6, and the product molecular sieve is that pure phase does not have stray crystal SAPO-41 molecular sieve.
The X ray diffracting data (embodiment 7 gained samples) of the SAPO-41 molecular sieve that table 6 is synthetic
Embodiment 8
The 287.4g aluminum isopropylate is joined in the 500g deionized water, stir 30min.Then under the vigorous stirring, slowly drip the solution that 145g phosphorous acid and 500g deionized water form, drip Diisopropylamine (chemical pure again, 97wt%) 339g, then add tetraethoxy 150g, form collosol intermixture, the collosol intermixture that obtains is moved in the stainless steel crystallizing kettle, at 185 ℃, the spontaneous crystallization 37h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 18h under 100 ℃, namely obtains molecular screen primary powder.Molecular screen primary powder is 550 ℃ of roasting 6h under air atmosphere, remove template, get the SAPO-41 molecular sieve.The X-ray diffractometer test result is as shown in table 7, has SAPO-41 molecular sieve characteristic peak, but 2 θ (
oThe stray crystal peak of SAPO-11 molecular sieve appears in)=8.10,9.57,21.23,22.22 places.
The X ray diffracting data (embodiment 8 gained samples) of the SAPO-41 molecular sieve that table 7 is synthetic
Embodiment 9
The crystallization mother liquor that reclaims among the embodiment 8 as synthesis material, is mixed into collosol intermixture with a certain amount of aluminum isopropylate, phosphorous acid, Diisopropylamine, tetraethoxy, deionized water behind the molecular components content, and it is synthetic to carry out the SAPO-41 molecular sieve.It is as follows specifically to feed intake:
The 231.8g aluminum isopropylate is joined in the 500g deionized water, stir 30min.Then under the vigorous stirring, slowly drip the solution that 117.2g phosphoric acid and 307.6g deionized water form, drip Diisopropylamine (chemical pure again, 97%) 273.7g and 370.6g contain the crystallization mother liquor of Diisopropylamine 65.2g, then add tetraethoxy 150g, form collosol intermixture, the collosol intermixture that obtains is moved in the stainless steel crystallizing kettle, at 190 ℃, the spontaneous crystallization 35h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 14h under 110 ℃, namely obtains molecular screen primary powder.Former powder is 550 ℃ of roasting 6h under air atmosphere, obtain molecular sieve after the removal template.The X-ray diffractometer test result is as shown in table 6, and the product molecular sieve has SAPO-41 molecular sieve characteristic peak, but 2 θ (
oThe stray crystal peak of SAPO-11 molecular sieve appears in)=8.10,9.57,21.23,22.22 places.
The X ray diffracting data (embodiment 9 gained samples) of the SAPO-41 molecular sieve that table 8 is synthetic
Embodiment 10
With the crystallization mother liquor that reclaims among the embodiment 9 as synthesis material, be mixed into collosol intermixture with a certain amount of aluminum isopropylate, phosphorous acid, Diisopropylamine, tetraethoxy, deionized water after analyzing component concentration, after the collosol intermixture process microwave-assisted heat treated, it is synthetic to carry out the SAPO-41 molecular sieve, specifically feeds intake, operates as follows:
The 199.2g aluminum isopropylate is joined in the 400g deionized water, stir 30min.Then under the vigorous stirring, slowly drip the solution that 100.9g phosphorous acid and 294.3g deionized water form, drip Diisopropylamine (chemical pure again, 97%) 235.5g and 587.9g contain the crystallization mother liquor of Diisopropylamine 103.5g, then add tetraethoxy 150g, form collosol intermixture, colloidal sol obtains initial gel mixture behind the stirring ageing 4h under the condition of microwave-assisted heating (50 ℃ of Heating temperatures).The gel mixture that obtains is moved in the stainless steel crystallizing kettle, at 180 ℃, the spontaneous crystallization 30h that depresses.Crystallization finishes the back cooling, and the film of cooled solidliquid mixture by 0.1 μ m filtered, and the mother liquor that wherein will contain crystallite is recycled, and solid product continues to be washed to neutrality, and solid product is dry 12h under 120 ℃, namely obtains molecular screen primary powder.Former powder is 550 ℃ of roasting 4h under air atmosphere, obtain molecular sieve after the removal template.Be that pure phase does not have stray crystal SAPO-41 molecular sieve by X-ray diffractometer test shows product molecular sieve.
The X ray diffracting data (embodiment 10 gained samples) of the SAPO-41 molecular sieve that table 9 is synthetic
Claims (1)
1. method of utilizing the synthetic pure phase SAPO-41 molecular sieve of crystallization mother liquor, it is characterized in that, recovery contains the crystallization mother liquor of SAPO-41 molecular sieve crystallite crystal seed and unreacted components, again the synthesis material of described crystallization mother liquor as the SAPO-41 molecular sieve is continued to use; Concrete steps comprise:
1) will be for the first time synthetic SAPO-41 molecular sieve solid product membrane pore size be that the filter membrane of 0.1 μ m carries out vacuum filtration and separates, recovery filtrate obtains containing the crystallization mother liquor of crystallite crystal seed;
2) analyze the crystallization mother liquor component concentration, add aluminium source, silicon source, phosphorus source, template and water, be mixed with the collosol intermixture of synthesis of molecular sieve, the mol ratio of each material is aR:Al in the wherein said collosol intermixture
2O
3: bP
2O
5: cSiO
2: dH
2O, wherein R is template, the value of a is that the value of 0.5 ~ 2, b is that the value of 0.1 ~ 3, c is that the value of 0.01 ~ 2, d is 20 ~ 80;
3) with step 2) in described collosol intermixture obtain initial gel mixture at 15～65 ℃ of following heated by microwave ageing 5～10h;
4) initial gel mixture described in the step 3) is placed crystallizing kettle, at 150 ℃ ~ 200 ℃ following hydrothermal crystallizing 15 ~ 40h, the product furnace cooling after-filtration behind the hydrothermal crystallizing is obtained filter cake and filtrate;
5) filter cake described in the step 4) is placed in the baking oven 100 ℃ ~ 120 ℃ oven dry down with deionized water wash; Filter cake after the oven dry is placed retort furnace roasting 5 ~ 20h, obtain the SAPO-41 molecular screen primary powder after the cooling;
6) filtrate described in the step 4) is reclaimed, as the crystallization mother liquor recycle.
2. method according to claim 1 is characterized in that step 2) described in template molar weight in the molecular sieve crystallization mother liquor be 0. 1 ~ 0.9 with template integral molar quantity ratio in the molecular sieve crystallization liquid.
3. method according to claim 1 is characterized in that step 2) described in the aluminium source be in aluminum oxide, Tai-Ace S 150, aluminum chloride, aluminum isopropylate and the boehmite one or more; The silicon source is selected from one or more in silicon sol, solid oxidation silicon, tetraethoxy and the silica gel; The phosphorus source is phosphoric acid or phosphorous acid; Template is one or more in di-n-propylamine, Diisopropylamine, tetrabutylammonium hydroxide amine and the diethylamine.
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| CN103979569A (en) * | 2014-06-04 | 2014-08-13 | 陕西省煤化工工程技术研究中心 | Preparation method of silicoaluminophosphate molecular sieve with hierarchical pore structure |
| CN105753014A (en) * | 2014-12-17 | 2016-07-13 | 中国科学院大连化学物理研究所 | AFO structure multistage pore silicoaluminophosphate zeolite and preparation thereof |
| CN109694082A (en) * | 2018-12-30 | 2019-04-30 | 山东齐鲁华信高科有限公司 | The preparation method of ZSM-23 molecular screen |
| CN112619448A (en) * | 2020-11-11 | 2021-04-09 | 宁波大学 | Roasting-assisted molecular sieve membrane successive transfer synthesis method |
| CN114477209A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Silicon-aluminum molecular sieve and preparation method and application thereof |
| CN114477210A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method thereof |
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| CN105753014A (en) * | 2014-12-17 | 2016-07-13 | 中国科学院大连化学物理研究所 | AFO structure multistage pore silicoaluminophosphate zeolite and preparation thereof |
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