CN102627297A - Synthetic method for SAPO (Silicoaluminophosphate)-34 molecular sieve - Google Patents
Synthetic method for SAPO (Silicoaluminophosphate)-34 molecular sieve Download PDFInfo
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- CN102627297A CN102627297A CN2012101202980A CN201210120298A CN102627297A CN 102627297 A CN102627297 A CN 102627297A CN 2012101202980 A CN2012101202980 A CN 2012101202980A CN 201210120298 A CN201210120298 A CN 201210120298A CN 102627297 A CN102627297 A CN 102627297A
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Abstract
The invention relates to a synthetic method for an SAPO (Silicoaluminophosphate)-34 molecular sieve and mainly solves the problems of low crystallinity and poor hydrothermal stability of products in the prior art. The technical scheme adopted by the invention is that the synthetic method comprises the following steps of: (a) mixing a silicon source, an aluminum source, a phosphorus source, an organic template agent and water and ageing at room temperature to obtain a crystallized mother solution A; (b) transferring the crystallized mother solution A into a crystallization reactor for carrying out chemical hydrothermal synthesis to obtain a mixed solution B containing the SAPO-34 molecular sieve; and (c) separating a solid product from the mixed solution B by a filtering or centrifuging method. The organic template agent is an organic amine mixer which is formed by two or more of tetraethyl ammonium hydroxide, triethylamine, diethylamine and morpholine. The hydrothermal stability of the SAPO-34 molecular sieve obtained by the invention is improved, so that the problem of poor hydrothermal stability is better solved. The synthetic method can be applied to industrial production of the SAPO-34 molecular sieve.
Description
Technical field
The present invention relates to a kind of compound method of SAPO-34 molecular sieve.
Background technology
1984, U.S. Union Carbide Corp (UCC) developed aluminium silicophosphate series molecular sieve (SAPO-n, n representative structure model).What wherein people attracted attention the most is the SAPO-34 molecular sieve.The SAPO-34 molecular sieve is by PO
4, AlO
4And SiO
4Tetrahedron interconnects and forms; Have oval cage and three-dimensional open-framework that eight Yuans rings of oxygen constitute.The shape of eight Yuans rings of oxygen possibly be oval, circular or wrinkling shape, and the aperture size changes with eight Yuans annular variations of oxygen, but the aperture effective diameter remains between the 0.43-0.50nm.Pore volume is 0.42cm
3/ g, space symmetry group R3m belongs to trigonal system, has the structure similar with chabazite.Because of making it, its particular structure has very big industrial application value.
In more than 20 year of past, researcher both domestic and external was done a large amount of research to the SAPO-34 molecular sieve, and its synthetic carried out deep exploration.European patent EP 0103117 discloses the hydrothermal synthesis method of SAPO-34 molecular sieve, and its technical characterstic is to have added template tetraethyl ammonium hydroxide, Isopropylamine or tetraethyl ammonium hydroxide/di-n-propylamine mixture in the building-up process.On this basis, U.S. Pat 4440871 has reported that again SAPO-34 molecular sieve synthetic improves one's methods, and it has adopted identical template basically.These template prices are generally relatively more expensive, and synthetic cost is high, are unfavorable for the large-scale industrial production popularization.It is the SAPO-34 molecular sieve compound method of template that Chinese patent CN1088483 has invented with triethylamine cheap and easy to get, has significantly reduced the synthetic cost of SAPO-34 sieve catalyst, and has extended in the suitability for industrialized production.Also have patent CN1096496 report to wait to synthesize SAPO-34 molecular sieve catalytic Liu with cheap diethylamine.Chinese patent CN101293660A has reported a kind of through adding the method for crystallization presoma material raising SAPO-34 molecular sieve crystallinity and catalytic performance, and the presoma material is the SAPO-34 crystallization mother liquor of partial crystallization.
SAPO-34 is used as the main active component of preparing light olefins from methanol catalyzer because of its constructional feature and acid matter, and in addition, this molecular screen material also has application in the catalytic reduction process that vehicle exhaust is handled.As a kind of heterogeneous catalyst or support of the catalyst, its catalytic performance and stability are this molecular screen material key in application indexs of decision.All need under the condition of comparatively high temps and steam dividing potential drop, carry out because preparing light olefins from methanol and vehicle exhaust are handled, therefore, it is most important that the hydrothermal stability of catalytic material just becomes.The patent documentation of having reported has carried out a large amount of research to the synthetic and catalytic performance of SAPO-34 molecular sieve, has proposed many improving one's methods, yet it is less to pay close attention to the research of this hydrothermal stability of molecular sieve and percent crystallinity.
Summary of the invention
To be solved by this invention is the low problem with the hydrothermal stability difference of product percent crystallinity in the prior art, and a kind of new SAPO-34 molecular sieve compound method is provided.This method synthetic zeolite product has good crystallinity, and after high-temperature water thermal treatment, the percent crystallinity loss is very little.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: the compound method of SAPO-34 molecular sieve may further comprise the steps:
1) silicon source, aluminium source, phosphorus source, organic formwork agent and water are mixed, at room temperature wear out, obtain crystallization mother liquor A;
2) crystallization mother liquor A is transferred to carry out the chemical water thermal synthesis in the crystallizing kettle, obtain containing the mixed liquid B of product;
3) through filtering or centrifugation method, from mixed liquid B, isolate solid SAPO-34 zeolite product.
In the technique scheme, the organic formwork agent that uses is the organic amine mixture, and this organic amine mixture is selected from tetraethyl ammonium hydroxide, triethylamine, diethylamine and the morphine quinoline two or more and mixes; Crystallization mother liquor A in forming in oxide compound mole proportioning is: SiO
2: Al
2O
3: P
2O
5: H
2O=0.1～2.0: 1.0: 0.6～1.4: 20～200; The silicon source is selected from one or more in silicon sol, positive tetraethyl orthosilicate and the WHITE CARBON BLACK; The aluminium source is selected from one or more in aluminum isopropylate, pseudo-boehmite and the white lake; The phosphorus source is selected from one or more in phosphoric acid and the phosphorous acid; Organic amine mixture and P in the crystallization mother liquor
2O
5The mole proportioning be 0.5～5.0: 1; For shortening the hydro-thermal synthetic time, can in crystallization mother liquor, add crystal seed, crystal seed is the SAPO-34 molecular sieve, crystal seed shared weight ratio in the SAPO-34 zeolite product is 0.1wt%～10wt%; At room temperature carrying out digestion time in the step (1) is 1～200 hour, is preferably 2～80 hours; The chemical water thermal synthesis is carried out under following condition in the step (2): 130～220 ℃ of temperature of reaction, 2～120 hours reaction times, 1～1000 rev/min of stirring velocity.
In the compound method of above-mentioned SAPO-34 molecular sieve, become the aging of glue process can make the higher aluminium source of the polymerization degree obtain better activation, and make crystallization mother liquor form more even distribution, help to obtain the product that structure is formed homogeneous; Use the mixing organic formwork agent then can through coordinating molecular sieve crystal nucleation and growth process, obtain the product that grain size distribution is moderate, percent crystallinity is high, lattice imperfection is few to the greatest extent with its length.The integrity that this composition is evenly distributed, the zeolite product of good crystallinity can keep crystalline structure for more time in the thermal and hydric environment of harshness.
Use Rigaku (Neo-Confucianism) Geigerflex diffractometer to measure the percent crystallinity of product, percent crystallinity is calculated according to 12.8 °, 15.9 °, 17.9 ° and 20.4 ° of peak heights of locating in the XRD figure, is 100% with the percent crystallinity of the best sample of crystallization.The hydrothermal stability condition for surveys is that sample was handled 5 hours under 850 ℃, 5% water vapor with tube furnace, and the percent crystallinity of sample compares before and after will handling then, calculating crystal reservation degree:
Embodiment
Through embodiment the present invention is described further below.But embodiment does not limit the scope of the present invention.
Comparative example 1
10g pseudo-boehmite (Al
2O
3: 70wt%) with 5.5g silicon sol (SiO
2: 30wt%) be added in the 37g deionized water, stir and form solution, add 17.6g ortho-phosphoric acid (P again
2O
5: 61.6wt%), stir to make in 2 hours and mix, keep whipped state, add 21g triethylamine (TEA) again, stirs 2 hours formation homogeneous solutions, the mol ratio of its composition is 0.4SiO
2: 1Al
2O
3: 1.1P
2O
5: 3TEA: 40H
2O adds the 0.4gSAPO-34 crystal seed again, makes crystallization liquid.Crystallization liquid is aging after 12 hours, and 185 ℃ of following dynamic crystallizations 24 hours, stirring velocity was 120 rev/mins with crystallization liquid.Product obtains solid phase prod after spinning, with it 120 ℃ of oven dry in baking oven, 600 ℃ of roastings are 5 hours then, remove template, the former powder of SAPO-34 (numbering SP34-1), percent crystallinity is as shown in table 1.
Comparative example 2
With white lake is the aluminium source, takes by weighing 10g white lake (Al
2O
3: 70wt%) with 1.4g silicon sol (SiO
2: 30wt%), the adjustment amount of water is 39g, and all the other operation stepss and composition of raw materials are all with comparative example 1, and the mol ratio that the crystallization liquid of formation is formed is 0.1SiO
2: 1Al
2O
3: 1.1P
2O
5: 3TEA: 40H
2O, products obtained therefrom is denoted as SP34-2.
Comparative example 3
With WHITE CARBON BLACK (SiO
2: 98wt%) replace silicon sol, the WHITE CARBON BLACK add-on is 1.5g, and the adjustment amount of water is 40g, and all with comparative example 1, products obtained therefrom is denoted as SP34-3 for all the other operation stepss and composition of raw materials.
Comparative example 4
Replace triethylamine with diethylamine (DEA), the diethylamine add-on is 10.2g, and the adjustment amount of water is 49g, and all the other operation stepss and composition of raw materials are all with comparative example 1, and the mol ratio that the crystallization liquid of formation is formed is 0.4SiO
2: 1Al
2O
3: 1.1P
2O
5: 2DEA: 50H
2O, products obtained therefrom is denoted as SP34-4.
Comparative example 5
Replace triethylamine with morphine quinoline (Mor), morphine quinoline add-on is 13.5g, and adjustment silicon sol add-on is 1.6g; The phosphoric acid add-on is 16g; The water add-on is 65g, and all the other operation stepss and composition of raw materials are all with comparative example 1, and the mol ratio that the crystallization liquid of formation is formed is 0.1SiO
2: 1Al
2O
3: 1P
2O
5: 2.2Mor: 60H
2O, products obtained therefrom is denoted as SP34-5.
Comparative example 6
Replace triethylamine with the tetraethyl ammonium hydroxide aqueous solution (TEAOH:25wt%), the tetraethyl ammonium hydroxide add-on is 74g, and the adjustment amount of water is 57g, and all the other operation stepss and composition of raw materials are all with comparative example 1, and the mol ratio that the crystallization liquid of formation is formed is 0.4SiO
2: 1Al
2O
3: 1.1P
2O
5: 7.2TEAOH: 100H
2O, products obtained therefrom is denoted as SP34-6.
Embodiment 1
Mixture with triethylamine and tetraethyl ammonium hydroxide is a template.Removing the triethylamine add-on is 21g, and the tetraethyl ammonium hydroxide aqueous solution (TEAOH:25wt%) add-on is 5g, and adjustment water add-on is outside the 33g, and all the other operation stepss and composition of raw materials are all with comparative example 1, and the ratio mol ratio of the crystallization liquid of formation composition is 0.4SiO
2: 1Al
2O
3: 1.1P
2O
5: 3TEA: 0.5TEAOH: 40H
2O, products obtained therefrom is denoted as SP34-7, and this product X RD spectrogram is as shown in Figure 1, is typical SAPO-34 molecular sieve.
Mixture with morphine quinoline and tetraethyl ammonium hydroxide is a template.Removing morphine quinoline add-on is 13.5g, and the tetraethyl ammonium hydroxide aqueous solution (TEAOH:25wt%) add-on is 5g, and adjustment water add-on is outside the 62g, and all the other operation stepss and composition of raw materials are all with comparative example 5, and the mol ratio of the crystallization liquid of formation composition is 0.1SiO
2: 1Al
2O
3: 1P
2O
5: 2.2Mor: 0.5TEAOH: 60H
2O, products obtained therefrom is denoted as SP34-8.
Embodiment 3
Mixture with triethylamine and diethylamine is a template.Take by weighing 10g pseudo-boehmite (Al
2O
3: 70wt%) with 1.6g silicon sol (SiO
2: 30wt%) be added in the 40g deionized water, stir and form solution, add 16g ortho-phosphoric acid (P again
2O
5: 61.6wt%), stir to make in 2 hours and mix, keep whipped state, add 17.5g triethylamine and 2.6g diethylamine again, stir 2 hours formation homogeneous solutions, the mol ratio of its composition is 0.1SiO
2: 1Al
2O
3: 1P
2O
5: 2.5TEA: 0.5DEA: 40H
2O, products obtained therefrom is denoted as SP34-9.
Embodiment 4
Replacing pseudo-boehmite with white lake is 10g as aluminium source white lake add-on, and all with embodiment 3, products obtained therefrom is denoted as SP34-10 for all the other operation stepss and composition of raw materials.
Replace silicon sol as the silicon source with WHITE CARBON BLACK, the WHITE CARBON BLACK add-on is 0.4g, and the adjustment amount of water is 41g, and all with embodiment 3, products obtained therefrom is denoted as SP34-11 for all the other operation stepss and composition of raw materials.
Embodiment 6
Replace pseudo-boehmite as the aluminium source with white lake, WHITE CARBON BLACK replaces silicon sol as the silicon source, and the white lake add-on is 10g; The WHITE CARBON BLACK add-on is 0.4g; And adjustment water add-on is 41g, and all with embodiment 3, products obtained therefrom is denoted as SP34-12 for all the other operation stepss and composition of raw materials.
Embodiment 7
Adjustment silicon sol add-on is 5.5g, and the water add-on is 37g, and all the other operation stepss and composition of raw materials are all with embodiment 3, and the mol ratio that the crystallization liquid of formation is formed is 0.4SiO
2: 1Al
2O
3: 1P
2O
5: 2.5TEA: 0.5DEA: 40H
2O, products obtained therefrom is denoted as SP34-13.
Embodiment 8
Replace pseudo-boehmite as the aluminium source with white lake, WHITE CARBON BLACK replaces silicon sol as the silicon source, and the white lake add-on is 10g; The WHITE CARBON BLACK add-on is 1.5g; And adjustment water add-on is 41g, and all with embodiment 7, products obtained therefrom is denoted as SP34-14 for all the other operation stepss and composition of raw materials.
Embodiment 9
Replace silicon sol as the silicon source with WHITE CARBON BLACK, the WHITE CARBON BLACK add-on is 1.5g, and adjustment water add-on is 41g, and all with embodiment 7, products obtained therefrom is denoted as SP34-15 for all the other operation stepss and composition of raw materials.
Operation steps and proportioning raw materials be all with embodiment 3, but digestion time, crystallization temperature, crystallization time and dynamic agitation rotating speed are adjusted, and actual crystallization condition is listed in table 1 with corresponding sample number into spectrum; Products obtained therefrom is denoted as SP34-16, SP34-17, SP34-18, SP34-19, SP34-20, SP34-21.
Table 1
Embodiment 16
The foregoing description gained SAPO-34 product is carried out the hydrothermally stable property testing.The result is as shown in table 2.
Table 2
2 column data of comparison sheet can be known; Adopt organic amine mixture as SAPO-34 molecular sieve synthetic template, the hydrothermal stability of product is improved, after 850 ℃ of hydrothermal treatment consists; The crystal reservation degree of overwhelming majority products is more than 70%, sample segment even near 90%; The crystallization mother liquor aged at room temperature also can be improved the hydrothermal stability of its product, and digestion time is long more, and product structure stability is high more.
Claims (9)
1. the compound method of a SAPO-34 molecular sieve is characterized in that this method may further comprise the steps:
(1) silicon source, aluminium source, phosphorus source, organic formwork agent and water are mixed, at room temperature wear out, obtain crystallization mother liquor A;
(2) crystallization mother liquor A is transferred to carry out the chemical water thermal synthesis in the crystallizing kettle, obtain containing the mixed liquid B of SAPO-34 zeolite product;
(3) through filtering or centrifugation method, from mixed liquid B, isolate solid SAPO-34 zeolite product;
Described organic formwork agent is the organic amine mixture; The organic amine mixture is selected from tetraethyl ammonium hydroxide, triethylamine, diethylamine and the morphine quinoline two or more and mixes; Described crystallization mother liquor A in forming in oxide compound mole proportioning is: SiO
2: Al
2O
3: P
2O
5: H
2O=0.1～2.0: 1.0: 0.6～1.4: 20～200.
2. the compound method of SAPO-34 molecular sieve according to claim 1 is characterized in that described silicon source is selected from one or more in silicon sol, positive tetraethyl orthosilicate and the WHITE CARBON BLACK.
3. the compound method of SAPO-34 molecular sieve according to claim 1 is characterized in that described aluminium source is selected from one or more in aluminum isopropylate, pseudo-boehmite and the white lake.
4. the compound method of SAPO-34 molecular sieve according to claim 1 is characterized in that described phosphorus source is selected from one or more in phosphoric acid and the phosphorous acid.
5. the compound method of SAPO-34 molecular sieve according to claim 1 is characterized in that organic amine and P in the described crystallization mother liquor
2O
5The mole proportioning be 0.5～5.0: 1.
6. the compound method of SAPO-34 molecular sieve according to claim 1 is characterized in that in crystallization mother liquor A, adding crystal seed, and crystal seed is the SAPO-34 molecular sieve, and crystal seed shared weight ratio in the SAPO-34 zeolite product is 0.1wt%～10wt%.
7. the compound method of SAPO-34 molecular sieve according to claim 1 is characterized in that at room temperature carrying out digestion time in the step (1) is 1～200 hour.
8. the compound method of SAPO-34 molecular sieve according to claim 7 is characterized in that at room temperature carrying out digestion time in the step (1) is 2～80 hours.
9. the compound method of SAPO-34 molecular sieve according to claim 1 is characterized in that the chemical water thermal synthesis is carried out in the step (2): 130～220 ℃ of temperature of reaction, 2～120 hours reaction times, 1～1000 rev/min of stirring velocity under following condition.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874833A (en) * | 2012-09-18 | 2013-01-16 | 大连理工大学 | Synthesis method of ZSM-48 molecular sieve |
| CN103121698A (en) * | 2013-02-01 | 2013-05-29 | 浙江大学 | Method for synthesizing SAPO (silicoaluminophosphate)-34 by solid-phase grinding |
| CN103706394A (en) * | 2014-01-06 | 2014-04-09 | 神华集团有限责任公司 | Submicron SAPO-5/SAPO-18 composite molecular sieve and preparation method thereof |
| CN105129815A (en) * | 2015-07-10 | 2015-12-09 | 上海卓悦化工科技有限公司 | Preparation method of crystalline-state silico-aluminum-phosphate material |
| CN105312083A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | CHA-type silicon-aluminum-phosphorous molecular sieves, and preparation methods and applications thereof |
| CN106082269A (en) * | 2016-06-22 | 2016-11-09 | 华微科技（苏州）有限公司 | The method being template synthesis SAPO 34 molecular sieve with triethylamine and diethylamine |
| CN108002403A (en) * | 2017-12-13 | 2018-05-08 | 卓悦环保新材料（上海）有限公司 | A kind of synthetic method of CHA molecular sieves |
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| EP0103117A1 (en) * | 1982-07-26 | 1984-03-21 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN101767800A (en) * | 2009-01-06 | 2010-07-07 | 神华集团有限责任公司 | Method for preparing SAPO-34 molecular sieve |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874833A (en) * | 2012-09-18 | 2013-01-16 | 大连理工大学 | Synthesis method of ZSM-48 molecular sieve |
| CN103121698A (en) * | 2013-02-01 | 2013-05-29 | 浙江大学 | Method for synthesizing SAPO (silicoaluminophosphate)-34 by solid-phase grinding |
| CN103121698B (en) * | 2013-02-01 | 2014-11-05 | 浙江大学 | Method for synthesizing SAPO (silicoaluminophosphate)-34 by solid-phase grinding |
| CN103706394A (en) * | 2014-01-06 | 2014-04-09 | 神华集团有限责任公司 | Submicron SAPO-5/SAPO-18 composite molecular sieve and preparation method thereof |
| CN103706394B (en) * | 2014-01-06 | 2015-08-05 | 神华集团有限责任公司 | Submicron SAPO-5/SAPO-18 composite molecular sieve and preparation method thereof |
| CN105312083A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | CHA-type silicon-aluminum-phosphorous molecular sieves, and preparation methods and applications thereof |
| CN105129815A (en) * | 2015-07-10 | 2015-12-09 | 上海卓悦化工科技有限公司 | Preparation method of crystalline-state silico-aluminum-phosphate material |
| CN105129815B (en) * | 2015-07-10 | 2017-03-08 | 上海卓悦化工科技有限公司 | A kind of preparation method of crystalline state SAPO material |
| CN106082269A (en) * | 2016-06-22 | 2016-11-09 | 华微科技（苏州）有限公司 | The method being template synthesis SAPO 34 molecular sieve with triethylamine and diethylamine |
| CN108002403A (en) * | 2017-12-13 | 2018-05-08 | 卓悦环保新材料（上海）有限公司 | A kind of synthetic method of CHA molecular sieves |
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Application publication date: 20120808 |