CN103274430A - Method for synthesizing pure phase SAPO-31 molecular sieve by recycling crystallization mother solution - Google Patents
Method for synthesizing pure phase SAPO-31 molecular sieve by recycling crystallization mother solution Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a pure phase SAPO-31 (silicoaluminophosphate-31) molecular sieve by recycling a crystallization mother solution, and relates to the technical field of molecular sieve synthesis. The method comprises the steps of recovering the crystallization mother solution of hydrothermal synthesis of a silicoaluminophosphate molecular sieve, adding new raw materials according to a matching ratio to prepare a collosol mixture, and synthesizing the SAPO-31 molecular sieve after microwave assisted ageing treatment. According to the method, ingredients, not participating in reaction, in the synthesis mother solution of the silicoaluminophosphate molecular sieve are recycled after the microwave assisted ageing treatment, and a great number of molecular sieve microcrystals exist in the mother solution subjected to the microwave assisted treatment, so that the crystallization time can be shortened greatly, and the generation of stray crystals are avoided. On the one hand, the zero discharge of the crystallization mother solution is realized, and the environmental pollution is reduced; on the other hand, since the mother solution is made full use of, the use level of the synthesis raw materials is greatly lowered, and the raw material cost is saved.
Description
Technical field
The invention belongs to the aluminium silicophosphate molecular sieve synthesis technical field, be specifically related to the method for the synthetic pure phase SAPO-31 molecular sieve of a kind of recycling crystallization mother liquor.
Background technology
Mesopore SAPO-31 molecular sieve is a kind of aluminium silicophosphate molecular sieve of the ATO of having type topological framework, has the one dimension straight hole road structure of the twelve-ring of non-intersection.Because its duct effect of contraction in the normal paraffin hygrogenating isomerization reaction, more is conducive to generate the less single branched chain isomer product of kinetics size.Therefore as the acid carrier of dual-function catalyst, the SAPO-31 molecular sieve shows in the normal paraffin hygrogenating isomerization reaction than SAPO-5 and the higher isomerization selectivity of SAPO-11 equimolecular sieve.
US Patent No. 4310440, US4440871 disclose the synthetic method of aluminium silicophosphate molecular sieve, at first synthesis material are mixed with crystallization liquid, synthesize the aluminium silicophosphate molecular sieve of series structure by hydrothermal synthesis method.Chinese patent CN102275949 discloses the synthetic method of SAPO-31 molecular sieve, and its characteristics are to prepare a kind of nanometer SAPO-31 molecular sieve, makes the acid adjustability of molecular sieve stronger, and acidic site density is higher.
Synthetic SAPO-31 molecular sieve is template with organic amines such as di-n-propylamine, two n-amylamines or two normal hexyl Amines usually in above-mentioned these methods, when wherein being template with the di-n-propylamine, is prone to stray crystals such as SAPO-5 and SAPO-11 in the crystallization product; Two n-amylamines, two normal hexyl Amines and more the aliphatic diamine of long-chain can avoid occurring stray crystal as template, and these long-chain template are expensive.
In general, hydrothermal method synthesis of molecular sieve yield is generally 50%-80%, so can contain a large amount of unreacting material components and molecular sieve crystallite 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 of laboratory, 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 in the prior art the synthetic cost height of SAPO-31 molecular sieve, waste liquid directly discharging cause wastage of material and environmental pollution problems, a kind of method of recycling the synthetic pure phase SAPO-31 molecular sieve of crystallization mother liquor is provided, particularly this method increase microwave-assisted ageing is handled collosol intermixture and is made gel mixture, colloidal sol utilization ratio height, synthetic product degree of crystallinity purity is all higher.
The present invention is characterized in that for a kind of method of recycling the synthetic pure phase SAPO-31 molecular sieve of mother liquor, comprises the steps:
1) the SAPO-31 molecular sieve solid product that will synthesize for the first time filters or centrifugation, then mother liquor is reclaimed;
2) analyze each component concentration in the recovery mother liquor; According to each components contents in the mother liquor, add aluminium source, silicon source, phosphorus source, template and water in proportion, be mixed with the synthetic collosol intermixture of synthesis of molecular sieve, the mol ratio of described synthetic each material of collosol intermixture is: aR:Al
2O
3: bP
2O
5: cSiO
2: dH
2O, wherein R is template, the value of a is that the value of 0.1～1.5, b is that the value of 0.1～2, c is that the value of 0.1～1, d is 30～90;
3) with step 2) described collosol intermixture is through microwave-assisted ageing processing, and treatment temp is 40～140 ℃, and the treatment time is 0.1～24h, forms gel mixture;
4) gel mixture after the microwave-assisted processing is placed crystallizing kettle, behind 140 ℃～200 ℃ following hydrothermal crystallizing 6h～20h, the product furnace cooling after-filtration behind the hydrothermal crystallizing is obtained filter cake and filtrate;
5) filter cake is placed on deionized water wash and dries the aluminium silicophosphate SAPO-31 molecular screen primary powder that obtains pure phase in the baking oven;
6) filtrate described in the step 4) is reclaimed, repeats above 1 as crystallization mother liquor), 2), 3), 4), 5) step, it is synthetic to carry out the SAPO-31 molecular sieve.
In technique scheme, step 2) the aluminium source described in be in Tai-Ace S 150, aluminum chloride, aluminum isopropylate, pseudo-boehmite and the aluminum oxide 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, two n-amylamines and two normal hexyl Amines.
The optimization process temperature that microwave-assisted ageing described in the step 3) is handled is 60～120 ℃, and the treatment time is 0.5～12h.
The crystallization temperature of the optimization of crystallizing kettle described in the step 4) is under 150 ℃～190 ℃, and the crystallization time of optimization is 16h～30h.
Template in the molecular sieve crystallization mother liquor that reclaims is preferably 0.1～0.8 with the template integral molar quantity ratio in the molecular sieve crystallization liquid.
The method of the synthetic pure phase SAPO-31 molecular sieve of recycle mother liquor of the present invention compared with prior art, its following unusual effect: 1) synthesis mother liquid of Hui Shouliyonging need not through any processing, can directly it be fed intake to carry out molecular sieve and synthesize; 2) the inventive method can repeatedly reclaim mother liquor, can realize recycling, and effectively reduces environmental pollution; 3) the inventive method has taken full advantage of unreacted species in the mother liquor, cuts down the consumption of raw materials, and has saved synthetic cost; 4) existence of molecular sieve crystallite can be played the effect of crystal seed in the mother liquor, can shorten crystallization time, improves the relative crystallinity of synthesis of molecular sieve; 5) adopt the inventive method by the microwave heating ageing, avoided the generation thermograde, more even to the heating of the material in the medium, can synthesize high-crystallinity pure phase SAPO-31 molecular sieve.
Embodiment
The present invention will be further described below in conjunction with embodiment, but the present invention is unrestricted in following specific embodiment.：
Embodiment 1
With 300g(massfraction 85%) phosphoric acid be dissolved in the 750g deionized water, add the 510g aluminum isopropylate lentamente and the 75g silicon sol makes it to stir, add organic amine template two normal hexyl Amine 210g then, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.3
P
2O
5/Al2O
3=1.04
R/Al
2O
3=0.9
H
2O/Al
2O
3=37.7
The colloidal sol that stirs is moved in the stainless steel crystallizing kettle, stirred crystallization 36 hours at 170 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 12 hours under 120 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 10 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, test result is as shown in table 1, diffraction data shows the characteristic peak that product that the inventive method obtains has the SAPO-31 molecular sieve, diffraction angle 2 θ (°)=the assorted peak of SAPO-11 molecular sieve appears in 8.1,9.57,21.23,22.22,22.95,23.31 places.
The above-mentioned sample of gained of the present invention adopts Japanese D/MAX-2500 type X-ray diffraction of science (XRD) instrument to carry out diffraction experiment, and contrast identifies whether be the crystalline phase of SAPO-31 molecular sieve.Condition determination: the Cu target, the K alpha-ray (λ=0.15418nm), Ni filtering, operating voltage 40kV, working current 200mA, 5～55 ° of sweep limits, 10 °/min of sweep velocity.The intensity of diffraction peak is got by the peak height of diffraction peak and the percentage calculation of highest peak peak height.The X ray diffracting data by the SAPO-31 sieve sample that the embodiment of the invention 1 makes is listed in table 1, 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 SAPO-31 molecular sieve X ray diffracting data that table 1 embodiment 1 synthesizes
Embodiment 2
The crystallization mother liquor that reclaims among the embodiment 1 as synthesis material, is analyzed behind the component concentration and to be mixed into collosol intermixture with a certain amount of phosphoric acid, aluminum isopropylate, two normal hexyl Amines, silicon sol, deionized water to carry out the SAPO-31 molecular sieve synthetic, and it is as follows specifically to feed intake:
With 205.4g(massfraction 85%) phosphoric acid be dissolved in the 641.4g water, add the 408.1g aluminum isopropylate lentamente and the 75g silicon sol makes it to stir, add organic amine template two normal hexyl Amine 153.5g and 169.4g then and contain the crystallization mother liquor of two normal hexyl Amine 42g, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.3
P
2O
5/Al
2O
3=0.8
R/Al
2O
3=1
H
2O/Al
2O
3=40
The colloidal sol that stirs is moved in the stainless steel crystallizing kettle, stirred crystallization 30 hours at 175 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 12 hours under 120 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 10 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, test result is as shown in table 2, diffraction data shows that the product that the inventive method obtains has SAPO-31 molecular sieve characteristic peak, diffraction angle 2 θ (°)=the assorted peak of SAPO-11 molecular sieve appears in 8.1,9.57,21.23,22.22,22.95,23.31 places.
The SAPO-31 molecular sieve X ray diffracting data that table 2 embodiment 2 synthesizes
Embodiment 3
The crystallization mother liquor that reclaims among the embodiment 2 as synthesis material, is analyzed behind the component concentration and to be mixed into collosol intermixture with a certain amount of phosphoric acid, aluminum isopropylate, two normal hexyl Amines, silicon sol, deionized water to carry out the SAPO-31 molecular sieve synthetic, and it is as follows specifically to feed intake:
With 147.6g(massfraction 85%) phosphoric acid be dissolved in the 545.2g water, add the 275.4g aluminum isopropylate lentamente and the 75g silicon sol makes it to stir, add organic amine template two normal hexyl Amine 113.4g and 389.9g then and contain the crystallization mother liquor of two normal hexyl Amine 96.6g, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.3
P
2O
5/Al
2O
3=0.9
R/Al
2O
3=0.9
H
2O/Al
2O
3=45
Reactant stirs ageing and obtains gel mixture after 6 hours under the condition of microwave-assisted heating (75 ℃ of Heating temperatures), and gel mixture is moved in the stainless steel crystallizing kettle, stirs crystallization 20 hours at 180 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 10 hours under 120 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 15 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, and test result is as shown in table 3, and diffraction data shows that the product that the inventive method obtains is pure phase SAPO-31 molecular sieve.
The SAPO-31 molecular sieve X ray diffracting data that table 3 embodiment 3 synthesizes
Embodiment 4
The crystallization mother liquor that reclaims among the embodiment 3 as synthesis material, is analyzed behind the component concentration and to be mixed into collosol intermixture with a certain amount of phosphoric acid, aluminum isopropylate, two normal hexyl Amines, silicon sol, deionized water to carry out the SAPO-31 molecular sieve synthetic, and it is as follows specifically to feed intake:
With 126.6g(massfraction 85%) phosphoric acid be dissolved in the 111.1g water, add the 214.2g aluminum isopropylate lentamente and the 75g silicon sol makes it to stir, add organic amine template two normal hexyl Amine 72.6g and 491.6g then and contain the crystallization mother liquor of two normal hexyl Amine 122.9g, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.3
P
2O
5/Al
2O
3=1
R/Al
2O
3=1
H
2O/Al
2O
3=30
Reactant stirs ageing and obtains gel mixture after 9 hours under the condition of microwave-assisted heating (60 ℃ of Heating temperatures), and gel mixture is moved in the stainless steel crystallizing kettle, stirs crystallization 36 hours at 165 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 20 hours under 120 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 13 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, and diffraction data shows that the product that the inventive method obtains is pure phase SAPO-31 molecular sieve, and test result repeats no more.
Embodiment 5
The crystallization mother liquor that reclaims among the embodiment 3 as synthesis material, is analyzed behind the component concentration and to be mixed into collosol intermixture with a certain amount of phosphoric acid, aluminum isopropylate, two normal hexyl Amines, silicon sol, deionized water to carry out the SAPO-31 molecular sieve synthetic, and it is as follows specifically to feed intake:
With 1O4.2g(massfraction 85%) phosphoric acid be dissolved in the 185g water, add the 174.4g aluminum isopropylate lentamente and the 125g silicon sol makes it to stir, add organic amine template two normal hexyl Amine 70.2g and 559.4g then and contain the crystallization mother liquor of two normal hexyl Amine 139.8g, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.5
P
2O
5/Al
2O
3=1.04
R/Al
2O
3=0.9
H
2O/Al
2O
3=37.7
Reactant stirs ageing and obtains gel mixture after 10 hours under the condition of microwave-assisted heating (65 ℃ of Heating temperatures), and gel mixture is moved in the stainless steel crystallizing kettle, stirs crystallization 38 hours at 170 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 20 hours under 120 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 13 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, and diffraction data shows that the product that the inventive method obtains is pure phase SAPO-31 molecular sieve, and test result repeats no more.
Embodiment 6
92.1g phosphorous acid is dissolved in the 486g water, add the 72.86g pseudo-boehmite lentamente and the 78.13g tetraethoxy makes it to stir, add organic amine template di-n-propylamine 101.2g then, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.7
P
2O
5/Al
2O
3=1.04
R/Al
2O
3=1.1
H
2O/Al
2O
3=50
The colloidal sol that stirs is moved in the stainless steel crystallizing kettle, stirred crystallization 24 hours at 180 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 14 hours under 110 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 23 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, test result is as shown in table 4, diffraction data shows that the product that the inventive method obtains has SAPO-31 molecular sieve characteristic peak, diffraction angle 2 θ (°)=the assorted peak of SAPO-11 molecular sieve appears in 8.1,9.57,21.23,22.22,22.95,23.31 places.
The SAPO-31 molecular sieve X ray diffracting data that table 4 embodiment 6 synthesizes
Embodiment 7
With the crystallization mother liquor that reclaims among the embodiment 6 as synthesis material, analyze behind the component concentration and to be mixed into collosol intermixture with a certain amount of phosphorous acid, pseudo-boehmite, di-n-propylamine, tetraethoxy, deionized water to carry out the SAPO-31 molecular sieve synthetic, it is as follows specifically to feed intake:
37.4g phosphorous acid is dissolved in the 255.6g water, add the 65.1g pseudo-boehmite lentamente and the 69.8g tetraethoxy makes it to stir, add organic amine template di-n-propylamine 16.72g and 300g then and contain the crystallization mother liquor of di-n-propylamine 36.6g, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.7
P
2O
5/Al
2O
3=1.04
R/Al
2O
3=1.1
H
2O/Al
2O
3=50
The colloidal sol that stirs is moved in the stainless steel crystallizing kettle, stirred crystallization 40 hours at 170 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 11 hours under 110 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 21 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, test result is as shown in table 5, diffraction data shows that the product that the inventive method obtains has SAPO-31 molecular sieve characteristic peak, diffraction angle 2 θ (°)=the assorted peak of SAPO-11 molecular sieve appears in 8.1,9.57,21.23,22.22,22.95,23.31 places.
The SAPO-31 molecular sieve X ray diffracting data that table 5 embodiment 7 synthesizes
Embodiment 8
With the crystallization mother liquor that reclaims among the embodiment 7 as synthesis material, analyze behind the component concentration and to be mixed into collosol intermixture with a certain amount of phosphorous acid, pseudo-boehmite, di-n-propylamine, tetraethoxy, deionized water to carry out the SAPO-31 molecular sieve synthetic, it is as follows specifically to feed intake:
82.13g phosphorous acid is dissolved in the 537.3g water, add the 116.57g pseudo-boehmite lentamente and the 125g tetraethoxy makes it to stir, add organic amine template di-n-propylamine 46.6g and 400g then and contain the crystallization mother liquor of di-n-propylamine 48.8g, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.7
P
2O
5/Al
2O
3=1.04
R/Al
2O
3=1.1
H
2O/Al
2O
3=50
Reactant stirs ageing and obtains gel mixture after 8 hours under the condition of microwave-assisted heating (70 ℃ of Heating temperatures), and gel mixture is moved in the stainless steel crystallizing kettle, stirs crystallization 35 hours at 175 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 20 hours under 120 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 13 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, and test result is as shown in table 6, and diffraction data shows that the product that the inventive method obtains is pure phase SAPO-31 molecular sieve.
The SAPO-31 molecular sieve X ray diffracting data that table 6 embodiment 8 synthesizes
Embodiment 9
With the crystallization mother liquor that reclaims among the embodiment 8 as synthesis material, analyze behind the component concentration and to be mixed into collosol intermixture with a certain amount of phosphorous acid, pseudo-boehmite, di-n-propylamine, tetraethoxy, deionized water to carry out the SAPO-31 molecular sieve synthetic, it is as follows specifically to feed intake:
255.72g phosphorous acid is dissolved in the 1225.94g water, add the 285.6g pseudo-boehmite lentamente and the 219g tetraethoxy makes it to stir, add organic amine template di-n-propylamine 46.6g and 489g then and contain the crystallization mother liquor of di-n-propylamine 48.8g, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.5
P
2O
5/Al
2O
3=1.04
R/Al
2O
3=1.1
SiO
2/Al
2O
3=40
Reactant stirs ageing and obtains gel mixture after 12 hours under the condition of microwave-assisted heating (65 ℃ of Heating temperatures), and gel mixture is moved in the stainless steel crystallizing kettle, stirs crystallization 30 hours at 170 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 18 hours under 120 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 12 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, and diffraction data shows that the product that the inventive method obtains is pure phase SAPO-31 molecular sieve, and test result repeats no more.
Embodiment 10
With the crystallization mother liquor that reclaims among the embodiment 9 as synthesis material, analyze behind the component concentration and to be mixed into collosol intermixture with a certain amount of phosphorous acid, pseudo-boehmite, di-n-propylamine, tetraethoxy, deionized water to carry out the SAPO-31 molecular sieve synthetic, it is as follows specifically to feed intake:
205.39g phosphorous acid is dissolved in the 983.28g water, add the 232.83g pseudo-boehmite lentamente and the 107g tetraethoxy makes it to stir, add organic amine template di-n-propylamine 121.35g and 423.8g then and contain the crystallization mother liquor of di-n-propylamine 51.7g, after waiting to stir, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3=0.3
P
2O
5/Al
2O
3=1.04
R/Al
2O
3=1
SiO
2/Al
2O
3=40
Reactant stirs ageing and obtains gel mixture after 7 hours under the condition of microwave-assisted heating (65 ℃ of Heating temperatures), and gel mixture is moved in the stainless steel crystallizing kettle, stirs crystallization 30 hours at 170 ℃, spontaneous depressing.Cooled solidliquid mixture is filtered in cooling after the crystallization end, obtains filter cake and crystallization mother liquor, and the mother liquor that wherein will contain crystallite is recycled, and filter cake continues to be washed to neutrality, and drying is 18 hours under 120 ℃, namely obtains molecular screen primary powder.Template is removed in the 550 ℃ of roastings 12 hours under air atmosphere of former powder, obtains molecular sieve.The molecular sieve that obtains is tested with X-ray diffractometer, and diffraction data shows that the product that the inventive method obtains is pure phase SAPO-31 molecular sieve, and test result repeats no more.
Claims (5)
1. recycle the method that crystallization mother liquor synthesizes pure phase SAPO-31 molecular sieve for one kind, it is characterized in that operation steps comprises:
1) the SAPO-31 molecular sieve solid product that will synthesize for the first time filters or centrifugation, then mother liquor is reclaimed;
2) analyze each component concentration in the recovery mother liquor; According to each components contents in the mother liquor, add aluminium source, silicon source, phosphorus source, template and water in proportion, be mixed with the synthetic collosol intermixture of synthesis of molecular sieve, the mol ratio of described synthetic each material of collosol intermixture is: aR:Al
2O
3: bP
2O
5: cSiO
2: dH
2O, wherein R is template, the value of a is that the value of 0.1～1.5, b is that the value of 0.1～2, c is that the value of 0.1～1, d is 30～90;
3) with step 2) described collosol intermixture is through microwave-assisted ageing processing, and treatment temp is 40～140 ℃, and the treatment time is 0.1～24h, forms gel mixture;
4) gel mixture after the microwave-assisted processing is placed crystallizing kettle, behind 140 ℃～200 ℃ following hydrothermal crystallizing 6h～40h, the product furnace cooling after-filtration behind the hydrothermal crystallizing is obtained filter cake and filtrate;
5) filter cake is placed on deionized water wash and dries the aluminium silicophosphate SAPO-31 molecular screen primary powder that obtains pure phase in the baking oven;
6) filtrate described in the step 4) is reclaimed, repeats above 1 as crystallization mother liquor), 2), 3), 4), 5) step, it is synthetic to carry out the SAPO-31 molecular sieve.
2. method according to claim 1 is characterized in that step 2) described in the aluminium source be in Tai-Ace S 150, aluminum chloride, aluminum isopropylate, pseudo-boehmite and the aluminum oxide 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, two n-amylamines and two normal hexyl Amines.
3. method according to claim 1 is characterized in that, the treatment temp that described microwave-assisted ageing is handled is 60～120 ℃, and the treatment time is 0.5～12h.
4. method according to claim 1 is characterized in that, the crystallization temperature of crystallizing kettle described in the step 4) is for being under 150 ℃～190 ℃, and crystallization time is 16h～40h.
5. method according to claim 1 is characterized in that, the template in the recovery mother liquor is 0.1～0.8 with the template integral molar quantity ratio in the molecular sieve crystallization liquid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105293522A (en) * | 2015-11-20 | 2016-02-03 | 陕西延长石油（集团）有限责任公司 | Preparation method of narrow-distribution small-crystal ZSM-5 molecular sieve |
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| CN108314055A (en) * | 2018-03-19 | 2018-07-24 | 深圳科冠华太新材料技术有限公司 | A kind of synthetic method of flake SAPO-34 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105293522A (en) * | 2015-11-20 | 2016-02-03 | 陕西延长石油（集团）有限责任公司 | Preparation method of narrow-distribution small-crystal ZSM-5 molecular sieve |
| CN105800647A (en) * | 2016-02-23 | 2016-07-27 | 山东齐鲁华信高科有限公司 | Method for restoring crystallinity of degenerated filter cake of molecular sieve for preparing low-carbon olefin from methanol |
| CN108314055A (en) * | 2018-03-19 | 2018-07-24 | 深圳科冠华太新材料技术有限公司 | A kind of synthetic method of flake SAPO-34 |
| CN108314055B (en) * | 2018-03-19 | 2021-12-07 | 深圳科冠华太新材料技术有限公司 | Method for synthesizing sheet-shaped SAPO-34 |
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