CN104556141A - Synthetic method of SAPO-34 molecular sieve - Google Patents
Synthetic method of SAPO-34 molecular sieve Download PDFInfo
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- CN104556141A CN104556141A CN201310512058.XA CN201310512058A CN104556141A CN 104556141 A CN104556141 A CN 104556141A CN 201310512058 A CN201310512058 A CN 201310512058A CN 104556141 A CN104556141 A CN 104556141A
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Abstract
The invention discloses a synthetic method of an SAPO-34 molecular sieve. The synthetic method is characterized by comprising the following steps: uniformly mixing a silicon source, a phosphorus source and an aluminum source according to a feeding proportion that a weight ratio of P2O5 to SiO2 to Al2O3 to H2O is equal to (0.6-1.2):(0.01-0.8):(0.6-1.2):(20-100), drying to obtain a silicon-phosphorus-aluminum dry glue of which the solid content is not less than 60%, and mixing the silicon-phosphorus-aluminum dry glue with a template agent, wherein according to the content of 1mol of Al2O3 in the silicon-phosphorus-aluminum dry glue, the adding amount of the template agent is 1-2.5mol; adding the template agent and part of water to obtain a mixture under the condition that a molar ratio of water in the mixture to the aluminum source calculated based on Al2O3 is not more than 20; and putting the mixture into a sealed reaction kettle, performing segmented crystallization under self-generated pressure, and recycling products. The synthetic method disclosed by the invention is low in water-aluminum ratio, and ensures that the single kettle yield can be improved; meanwhile, the sewage discharge quantity can be greatly reduced, and the cost reduction and environment protection can be facilitated; and an induction period can be greatly shortened when the synthesized molecular sieve is applied to MTO reaction, and the diene selectivity can reach 85.9%.
Description
Technical field
The invention provides a kind of method of low water aluminum ratio synthesis SAPO-34 molecular sieve.
Background technology
SAPO-34 molecular sieve is that connection C.-Chem AG of the U.S. is in a kind of phosphor-silicon-aluminum molecular sieve of exploitation in 1984, belong to octatomic ring chabazite CHA structure, isometric system, octatomic ring aperture is 0.43nm × 0.43nm, the molecular dynamics similar diameters of octatomic ring aperture and ethene and propylene.SAPO-34 molecular sieve has suitable strength of acid, total acid content and good hydrothermal stability, shows excellent catalytic performance in preparing light olefins from methanol (MTO).
In the last thirty years, in the synthesis of SAPO-34 molecular sieve, domestic and international researcher has done a large amount of work.The synthesis of SAPO-34 molecular sieve has a lot of method, such as hydrothermal synthesis method, microwave process for synthesizing, the gentle phase-transfer synthesis method of liquid phase synthesizing method etc., and the most frequently used is hydrothermal synthesis method.Chinese patent CN101121529A, CN101633508A etc. adopt hydrothermal synthesis method.Synthesis step is roughly as follows: (1) prepares crystallization liquid: the add-on calculating raw material according to certain charge ratio relation, 85% ortho-phosphoric acid is mixed with deionized water, this phosphate aqueous solution is labeled as A, then aluminium source is mixed with deionized water and obtain mixture B, A is joined rapid stirring in B even, finally add organic formwork agent, silicon source and residue deionized water, rapid stirring is even, and crystallization liquid is ready; (2) ageing: crystallization liquid is transferred in crystallizing kettle, room temperature ageing; (3) crystallization: by crystallizing kettle temperature programming to 180-250 DEG C of crystallization; Finally sample filtering or centrifugation are obtained SAPO-34 molecular screen primary powder.Document (chemical reaction engineering and technique, 2009,25,523-525) point out that liquid phase crystallization method and gas phase crystallization method are that silicon phosphorus aluminium is prepared into dry glue, then add organic formwork agent and crystal, finally centrifugal, filter and drying obtain SAPO-34 molecular sieve.
Patent (CN101743061A, CN101121529A, CN101830482A) adopted hydrothermal synthesis method to synthesize pure phase SAPO-34 molecular sieve, its n (H
2o)/n (Al
2o
3) than being greater than 30, document (Materials Chemistry and Physics, 123 (2010) 507 – 509) synthesis SAPO-34 molecular sieve n (H
2o)/n (Al
2o
3) than being 77.N (H
2o)/n (Al
2o
3) lower than environmental pollution, cost increase and the single still yield of easily causing bigger than normal.
Summary of the invention
The object of the invention is the H existed for prior art
2o/Al
2o
3the problem higher, environmental pollution is serious and single still yield is on the low side, proposes a kind of at low H
2o/Al
2o
3than under condition, silicon phosphorus aluminium precursor Hydrothermal Synthesis is adopted to go out the method for the SAPO34 molecular sieve of high-crystallinity pure phase.
The synthetic method of SAPO-34 molecular sieve provided by the invention, is characterized in that according to charge ratio: (0.6 ~ 1.2) P
2o
5: (0.01 ~ 0.8) SiO
2: (0.6 ~ 1.2) Al
2o
3: (20 ~ 100) H
2o, mixes silicon source, phosphorus source and aluminium source, and drying obtains the dry glue of silicon phosphorus aluminium that solid content is not less than 60%, is mixed by the dry glue of silicon phosphorus aluminium with template, with 1 mole of Al in the dry glue of silicon phosphorus aluminium
2o
3meter, the add-on of said template is 1-2.5 mole, adds template and part water obtains mixture, gained mixture Zhong Shui with Al
2o
3the mol ratio in the aluminium source of meter is not more than 20, mixture be placed in crystallization under closed reactor autogenous pressure and reclaim product, wherein, said crystallization in temperature range from low to high, sequentially divides three sections carry out, the crystallization temperature of adjacent two sections is not identical and rear one section of crystallization temperature is no less than 40 DEG C higher than temperature crystallization the last period, and said three sections of crystallization temperatures are respectively 20 ~ 90 DEG C, 90 ~ 150 DEG C and 150 ~ 250 DEG C.
Method provided by the invention; phosphorus source, silicon source, aluminium source and portions of de-ionized water mixing is adopted to generate silicon phosphorus aluminium glue precursor; water aluminum ratio is not more than 20; and crystallization process adopts segmentation crystallization; obtain low silicon SAPO-34 molecular sieve, amplify reproducible, relative crystallinity reaches more than 100%, improve single still yield, MTO decomposition induction time significantly shortens and diene selective reaches 85.9%; quantity of wastewater effluent significantly reduces simultaneously, is conducive to reducing costs and protection of the environment.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope shape appearance figure of comparative example 1 synthetic sample.。
Fig. 2 is the scanning electron microscope shape appearance figure of the 2-in-1 one-tenth sample of comparative example.。
Fig. 3 is the XRD spectra of embodiment 1 synthetic sample.
Fig. 4 is the scanning electron microscope shape appearance figure of embodiment 1 synthetic sample.
Fig. 5 is the XRD spectra of the 2-in-1 one-tenth sample of embodiment.
Fig. 6 is the scanning electron microscope shape appearance figure of the 2-in-1 one-tenth sample of embodiment.
Fig. 7 is the XRD spectra of embodiment 3 synthetic sample.
Fig. 8 is the scanning electron microscope shape appearance figure of embodiment 4 synthetic sample.
Embodiment
The synthetic method of SAPO-34 molecular sieve provided by the invention, is characterized in that according to charge ratio: (0.6 ~ 1.2) P
2o
5: (0.01 ~ 0.8) SiO
2: (0.6 ~ 1.2) Al
2o
3: (20 ~ 100) H
2o, mixes silicon source, phosphorus source and aluminium source, and drying obtains the dry glue of silicon phosphorus aluminium that solid content is not less than 60%, is mixed by the dry glue of silicon phosphorus aluminium with template, with 1 mole of Al in the dry glue of silicon phosphorus aluminium
2o
3meter, the add-on of said template is 1 ~ 2.5 mole, adds template and part water obtains mixture, gained mixture Zhong Shui with Al
2o
3the mol ratio in the aluminium source of meter is not more than 20, mixture be placed in crystallization under closed reactor autogenous pressure and reclaim product, wherein, said crystallization in temperature range from low to high, sequentially divides three sections carry out, the crystallization temperature of adjacent two sections is not identical and rear one section of crystallization temperature is no less than 40 DEG C higher than temperature crystallization the last period, and said three sections of crystallization temperatures are respectively 20 ~ 90 DEG C, 90 ~ 150 DEG C and 150 ~ 250 DEG C.
In method of the present invention, described silicon source is any one or several mixture in acidic silicasol, white carbon black, particulate silica gel, positive silicon ester, preferred acidic silicon sol and white carbon black; Aluminium source is any one or several mixture in dry glue powder, pseudo-boehmite, SB powder, aluminum alkoxide, preferred dry glue powder and SB powder; Phosphorus source is preferably 85% ortho-phosphoric acid; Template is any one or several mixture in tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine, is wherein preferably the tetraethyl ammonium hydroxide of 25% and the triethylamine of 100%.The mixture of the preferred tetraethyl ammonium hydroxide of said template and triethylamine, further preferably, in the mixture of said tetraethyl ammonium hydroxide and triethylamine, the molar ratio of tetraethyl ammonium hydroxide and triethylamine is (0.1 ~ 2): 1.
Preferably, said mixture Zhong Shui with Al
2o
3the mol ratio in aluminium source of meter is less than 16, more preferably mixture Zhong Shui with Al
2o
3the mol ratio in the aluminium source of meter is 10-16.
In method of the present invention, saidly mixture is placed in crystallization under closed reactor autogenous pressure, adopts the mode of segmentation crystallization to carry out, comprise 20-90 DEG C of aging, 90-150 DEG C nucleus and generate and 150-250 DEG C of nucleus production process.The crystallization temperature of adjacent two sections is not identical and rear one section of crystallization temperature is no less than 40 DEG C, preferably 60 ~ 70 DEG C higher than temperature crystallization the last period.Said three sections of crystallization temperatures are respectively 20 ~ 90 DEG C, 90 ~ 150 DEG C and 150 ~ 250 DEG C, are preferably 20 ~ 60 DEG C, 110 ~ 130 DEG C and 180 ~ 210 DEG C.Preferably total crystallization time controls at 30-90 hour further.Such as, in a concrete embodiment of the present invention, crystallization process be 25-35 DEG C crystallization 5-10 hour, 100-150 DEG C crystallization 10-20 hour, 150-200 DEG C crystallization 10-45 hour.
The process of said recovery product is familiar with by those skilled in the art, such as, comprise filtration, washing, dry and roasting etc.Said drying can be carry out at 100-110 DEG C, and said roasting can be carry out under 400-600 DEG C of constant temperature.
The invention will be further described by the following examples, but content not thereby limiting the invention.
In embodiment, XRD spectra is measured by Rigaku D/MAX-III A type diffractometer; The Quanta200F type scanning electron microscope that scanning electron microscope shape appearance figure is produced by FEI Co. measures.
Comparative example 1
This comparative example illustrates process and the product of preparing SAPO-34 molecular sieve according to CN101633508A.
Joined in 10g deionized water by 85% ortho-phosphoric acid (analytical pure) 11g, rapid stirring evenly obtains solution A; Separately take 7g dry glue powder to be dissolved in 10g deionized water, stir and add template 6g tetraethyl ammonium hydroxide again, stir, more above-mentioned solution A is added, stir and obtain uniform colloidal sol in 2 hours.By massfraction be 30% 3g acidic silicasol join respectively in above-mentioned colloidal sol, stirring and obtaining molar ratio is 0.1SiO
2: 1Al
2o
3: 1P
2o
5: 0.2TEAOH:1.4TEA:60H
2the initial crystallization colloidal sol of O, is then placed in 100 milliliters of stainless steel closed reactors by initial crystallization colloidal sol, 120 DEG C of crystallization 5h; 7g triethylamine is added after still temperature drop to room temperature, be warming up to 190 DEG C again and continue crystallization 8 hours, crystallization product is taken out to during room temperature until still temperature drop, filtration or centrifugal deionized water are washed till neutrality, the thermostatic drying chamber being placed in 100-110 DEG C is dry, finally puts into retort furnace and is warming up to 550 DEG C of constant temperature calcinings and within 4 hours, obtains the former powder of product.
This comparative sample scanning electron microscope shape appearance figure (SEM) is shown in Fig. 1, and show that grain morphology is cubes, crystal grain is greater than 2 microns.
Comparative example 2
This comparative example illustrates the process preparing SAPO-34 molecular sieve according to CN101633508A.
With comparative example 1, difference is that water aluminum ratio wherein becomes 50
Fig. 2 is shown in by the SEM photo of this comparative sample, and show that grain morphology is cubes, grain-size is 800nm.
Embodiment 1
According to 0.3SiO
2: 1Al
2o
3: 1P
2o
5: 30H
2o adds ratio, by 30% acidic silicasol, 85% phosphoric acid, pseudo-boehmite and water fully mix, be placed in 80 DEG C of dry 24h of moisture eliminator and obtain the dry glue of silicon phosphorus aluminium that solid content is 80%.Take silicon phosphorus aluminium glue 180g, join 1L crystallizing kettle.Add 171gTEAOH and 122gTEA, mix, then add 40g water, stir.The additional proportion of each component: 0.3SiO
2: 1Al
2o
3: 1P
2o
5: 0.5TEAOH:2TEA:13H
2o.
Mixture is placed in 1L stainless steel autoclave, segmentation crystallization: aged at room temperature 10h, 100 DEG C of crystallization 10h and 180 DEG C crystallization 40h, crystallization product is taken out when autoclave temperature is down to room temperature, sample after filtration or centrifugal deionized water be washed till neutrality, the thermostatic drying chamber being placed in 120 DEG C is dry, finally puts into stoving oven and is warming up to 550 DEG C of constant temperature calcining 5h and obtains molecular screen primary powder.
XRD diffraction spectrogram and the SEM photo of gained sample are shown in Fig. 3 and Fig. 4 respectively, and XRD diffraction spectrogram shows that sample is SAPO-34 molecular sieve, and without stray crystal phase, SEM photo shows that crystal grain is tabular cubes, and grain-size is 500nm, and thickness is 200nm.
Embodiment 2
Identical with the method that embodiment 1 prepares the dry glue of silicon phosphorus aluminium, take the silicon phosphorus aluminium glue 76g prepared, join 300mL crystallizing kettle, then add 164gTEAOH and 6gTEA, mix, then add 26g water, stir, the additional proportion of each component: 0.15SiO
2: 1Al
2o
3: 1P
2o
5: 0.8TEAOH:0.5TEA:20H
2o.
Mixture is placed in 300mL stainless steel autoclave, segmentation crystallization: aged at room temperature 10h, 100 DEG C of crystallization 10h and 180 DEG C crystallization 40h, crystallization product is taken out when autoclave temperature is down to room temperature, sample after filtration or centrifugal deionized water be washed till neutrality, the thermostatic drying chamber being placed in 80-120 DEG C is dry, finally puts into stoving oven and is warming up to 550 DEG C of constant temperature calcining 5h and obtains SAPO-34 molecular screen primary powder.
XRD diffraction spectrogram and the SEM photo of gained sample are shown in Fig. 5 and Fig. 6 respectively, and XRD diffraction spectrogram interpret sample is SAPO-34, and without stray crystal phase, SEM photo shows that crystal grain is cubes, and grain-size is 600nm.
Embodiment 3
Identical with the method that embodiment 1 prepares the dry glue of silicon phosphorus aluminium, take the silicon phosphorus aluminium glue 80g prepared, join 600mL crystallizing kettle, then add 320gTEAOH and 12gTEA, mix.The additional proportion of each component: 0.6SiO
2: 1Al
2o
3: 1P
2o
5: 1.6TEAOH:1TEA:13H
2o.
Mixture is placed in 600mL closed reactor, segmentation crystallization: aged at room temperature 10h, 100 DEG C of crystallization 10h and 180 DEG C crystallization 40h, crystallization product is taken out when autoclave temperature is down to room temperature, sample after filtration or centrifugal deionized water be washed till neutrality, the thermostatic drying chamber being placed in 80-120 DEG C is dry, finally puts into stoving oven and is warming up to 550 DEG C of constant temperature calcining 5h and obtains molecular screen primary powder.
The XRD diffraction spectrogram of sample is shown in Fig. 7, shows that sample is SAPO-34.
Embodiment 4
Identical with the method that embodiment 1 prepares the dry glue of silicon phosphorus aluminium, take the silicon phosphorus aluminium glue 180g prepared, join 1L crystallizing kettle.Then add 171gTEAOH and 140gTEA, mix, then add 40g water, stir all with.The additional proportion of each component: 0.3SiO
2: 1Al
2o
3: 1P
2o
5: 0.6TEAOH:3TEA:13H
2o.
Mixture is placed in 1L stainless steel autoclave, segmentation crystallization: aged at room temperature 10h, 100 DEG C of crystallization 10h and 180 DEG C crystallization 40h, crystallization product is taken out when autoclave temperature is down to room temperature, sample after filtration or centrifugal deionized water be washed till neutrality, the thermostatic drying chamber being placed in 120 DEG C is dry, finally puts into stoving oven and is warming up to 550 DEG C of constant temperature calcining 5h and obtains molecular screen primary powder.
The scanning electron microscope shape appearance figure of gained sample is shown in Fig. 8, and show that crystal grain is cubes, grain-size is 800nm.
Comparative example 3-4
This comparative example illustrates the catalytic performance result of comparative example 1 and 2 in methanol to olefins reaction.
The sample compressing tablet of the comparative example 1 and 2 after roasting is sieved, chooses 20-40 object sample, be labeled as C-1 and C-2.Evaluating apparatus is fixed-bed reactor, and appreciation condition is: loaded catalyst is 3g, and reactant is methyl alcohol, mass space velocity 1h
-1, carrier gas is nitrogen, and nitrogen flow is 350mL/min, temperature of reaction 450 DEG C, and reaction pressure is 0.25Mpa, and reaction product is with ethene and propylene for target product, and reaction product is by gas-chromatography on-line analysis, and reaction result is as shown in table 1.
Embodiment 5-8
The present embodiment illustrates the catalytic performance effect of embodiment 1-3 gained sample in methanol to olefins reaction.
Embodiment 1-4 gained roasting sample sieves through compressing tablet, gets 20-40 order sample, is labeled as C-3, C-4, C-5 and C-6.Evaluation method and condition identical with comparative example 3-4, MTO catalytic performance result is as shown in table 1.
Table 1
As can be seen from Table 1, the SAPO-34 sieve sample of low water aluminum ratio method synthesis provided by the invention, in MTO reaction, single pass life and diene selective is all better than comparative sample, diene (C
2 =+ C
3 =) selectivity reaches as high as 85.94%, MTO single pass life and can reach 10h, shows that the SAPO-34 molecular sieve that low water aluminum ratio synthesizes has excellent MTO catalytic performance.
Claims (14)
1. a synthetic method for SAPO-34 molecular sieve, is characterized in that according to charge ratio: (0.6 ~ 1.2) P
2o
5: (0.01 ~ 0.8) SiO
2: (0.6 ~ 1.2) Al
2o
3: (20 ~ 100) H
2o, mixes silicon source, phosphorus source and aluminium source, and drying obtains the dry glue of silicon phosphorus aluminium that solid content is not less than 60%, is mixed by the dry glue of silicon phosphorus aluminium with template, with 1 mole of Al in the dry glue of silicon phosphorus aluminium
2o
3meter, the add-on of said template is 1 ~ 2.5 mole, adds template and part water obtains mixture, gained mixture Zhong Shui with Al
2o
3the mol ratio in the aluminium source of meter is not more than 20, mixture be placed in crystallization under closed reactor autogenous pressure and reclaim product, wherein, said crystallization in temperature range from low to high, sequentially divides three sections carry out, the crystallization temperature of adjacent two sections is not identical and rear one section of crystallization temperature is no less than 40 DEG C higher than temperature crystallization the last period, and said three sections of crystallization temperatures are respectively 20 ~ 90 DEG C, 90 ~ 150 DEG C and 150 ~ 250 DEG C.
2., according to the process of claim 1 wherein, described silicon source is the mixture of one or more in acidic silicasol, white carbon black, particulate silica gel, positive silicon ester.
3., according to the process of claim 1 wherein, said phosphorus source is one or more in ammonium hydrogen phosphate, phosphoric acid and primary ammonium phosphate.
4., according to the process of claim 1 wherein, said phosphorus source is 85% ortho-phosphoric acid.
5., according to the process of claim 1 wherein, said aluminium source is one or several the mixture in dry glue powder, SB powder and aluminum alkoxide.
6. according to the process of claim 1 wherein, to be alumina content be in said aluminium source 75% dry glue powder and SB powder.
7., according to the process of claim 1 wherein, said template is the mixture of one or more in tetraethyl ammonium hydroxide, triethylamine, diethylamine and morpholine.
8., according to the process of claim 1 wherein, said template is the mixture of tetraethyl ammonium hydroxide and triethylamine.
9., according to the process of claim 1 wherein, in the mixture of said tetraethyl ammonium hydroxide and triethylamine, the molar ratio of tetraethyl ammonium hydroxide and triethylamine is (0.1 ~ 0.2): 1.
10. according to the process of claim 1 wherein, mixture Zhong Shui with Al
2o
3the mol ratio in the aluminium source of meter is less than 16.
11. according to the process of claim 1 wherein, mixture Zhong Shui with Al
2o
3the mol ratio in the aluminium source of meter is 10-16.
12. according to the process of claim 1 wherein, said crystallization temperature is respectively 20 ~ 60 DEG C, 110 ~ 130 DEG C and 180 ~ 210 DEG C.
13. according to the method for claim 1, said crystallization process be 25-35 DEG C crystallization 5-10 hour, 100-150 DEG C crystallization 10-20 hour, 150-200 DEG C crystallization 10-45 hour.
14. according to the method for claim 1,12 or 13, and wherein, said crystallization, its total time controls at 30-90 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105936511B (en) * | 2016-02-22 | 2018-06-12 | 山东齐鲁华信高科有限公司 | A kind of preparation method of high activity SAPO-34 molecular sieves |
| CN109467100A (en) * | 2017-09-07 | 2019-03-15 | 中国石油化工股份有限公司 | The synthetic method and application of SAPO-34 molecular sieve |
| CN112624150A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Synthetic method of SAPO-34 molecular sieve, synthetic molecular sieve and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125665A (en) * | 2007-08-08 | 2008-02-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN101481121A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Silicoaluminophosphate molecular sieve composition and synthesizing method thereof |
| CN102336413A (en) * | 2010-11-29 | 2012-02-01 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| KR101142350B1 (en) * | 2006-08-08 | 2012-05-18 | 달리안 인스티튜트 오브 케미컬 피직스 | SAPO-34 Molecular Sieve having both Micropores and Mesopores and Synthesis Method thereof |
| CN102530989A (en) * | 2011-12-15 | 2012-07-04 | 神华集团有限责任公司 | Method for preparing large-crystal SAPO-34 molecular sieve, product obtained by the method and application of the product |
-
2013
- 2013-10-25 CN CN201310512058.XA patent/CN104556141B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101142350B1 (en) * | 2006-08-08 | 2012-05-18 | 달리안 인스티튜트 오브 케미컬 피직스 | SAPO-34 Molecular Sieve having both Micropores and Mesopores and Synthesis Method thereof |
| CN101125665A (en) * | 2007-08-08 | 2008-02-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN101481121A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Silicoaluminophosphate molecular sieve composition and synthesizing method thereof |
| CN102336413A (en) * | 2010-11-29 | 2012-02-01 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| CN102530989A (en) * | 2011-12-15 | 2012-07-04 | 神华集团有限责任公司 | Method for preparing large-crystal SAPO-34 molecular sieve, product obtained by the method and application of the product |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105936511B (en) * | 2016-02-22 | 2018-06-12 | 山东齐鲁华信高科有限公司 | A kind of preparation method of high activity SAPO-34 molecular sieves |
| CN109467100A (en) * | 2017-09-07 | 2019-03-15 | 中国石油化工股份有限公司 | The synthetic method and application of SAPO-34 molecular sieve |
| CN109467100B (en) * | 2017-09-07 | 2020-11-13 | 中国石油化工股份有限公司 | Synthesis method and application of SAPO-34 molecular sieve |
| CN112624150A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Synthetic method of SAPO-34 molecular sieve, synthetic molecular sieve and application thereof |
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| CN104556141B (en) | 2017-02-08 |
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