CN104556091A - Preparation method of SAPO-34 molecular sieve - Google Patents
Preparation method of SAPO-34 molecular sieve Download PDFInfo
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- CN104556091A CN104556091A CN201310512056.0A CN201310512056A CN104556091A CN 104556091 A CN104556091 A CN 104556091A CN 201310512056 A CN201310512056 A CN 201310512056A CN 104556091 A CN104556091 A CN 104556091A
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Abstract
The invention discloses a preparation method of a SAPO-34 molecular sieve, which is characterized by comprising the following steps: (1) uniformly mixing a phosphorus source and an aluminum source according to the mol ratio of (0.6-1.2)P2O5:Al2O3:(20-60)H2O, and drying to obtain phosphorus aluminum dry glue A with the solid content of not lower than 60%; (2) uniformly contacting and mixing the phosphorus aluminum dry glue A with a template and a silicon source to obtain a mixture B, wherein the addition amount of the template agent is 1-2.5 mol on the basis of 1 mol of Al2O3 in the phosphorus aluminum dry glue A, and the addition amount of the silicon source is 0.1-1 mol on the basis of SiO2; and (3) putting the mixture B in a closed reaction kettle, sectionally crystallizing under autogenous pressure, and recovering the product.
Description
Technical field
The invention relates to a kind of preparation method of SAPO-34 molecular sieve, is more particularly the hydro-thermal synthetic preparation method about a kind of 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, for the chabazite CHA structure of octatomic ring, belong to isometric system, aperture is at about 0.43nm, close with the molecular diameter of ethene and propylene, SAPO-34 molecular sieve has suitable strength of acid, pore passage structure and good hydrothermal stability, shows excellent catalytic performance in preparing light olefins from methanol (MTO).
The synthesis of SAPO-34 molecular sieve has a lot of method, such as hydrothermal synthesis method, microwave process for synthesizing, liquid phase synthesizing method, gas phase transfer synthesis method etc.Wherein the most frequently used is hydrothermal synthesis method, is all the method adopting Hydrothermal Synthesis SAPO-34 molecular sieve disclosed in CN101121529A, CN101633508A etc.The step of hydrothermal synthesis method roughly comprises: (1) is prepared crystallization liquid, (2) ageing and (3) crystallization and reclaimed.The method of traditional Hydrothermal Synthesis SAPO-34 molecular sieve deposits the shortcomings such as poor repeatability, single still yield be after amplification low.
CN102372288A, by silicon source, phosphorus source, aluminium source, fluorochemical and organic formwork agent are prepared into dry glue, adopts gas phase crystallization method synthesis SAPO-34 molecular sieve, synthesized by SAPO-34 molecular sieve diene selective in MTO reaction of obtaining be 81.9%.CN101125665A generates dry glue to the pre-treatment of silicon phosphorus aluminium source and becomes SAPO-34 molecular sieve, mainly solves the sticky wall problem that crystallizing kettle exists.CN101633508A discloses a kind of synthetic method of SAPO-34 molecular sieve, and the method is by feed ratio (a
1r1+a
2r2): Al
2o
3: bP
2o
5: cSiO
2: dH
2o, by aluminium source, phosphorus source, silicon source and organic formwork agent mixing plastic, at 100-250 DEG C after hydrothermal crystallizing 4-500 hour, reclaim product, it is characterized in that said organic formwork agent is that R1 and R2, R1 add in mixing plastic process, R2 adds at hydrothermal crystallization process, and R1 and R2 is identical or different.
Summary of the invention
The object of the invention is for prior art Problems existing, provide the preparation method of the SAPO-34 molecular sieve easily repeated, gained molecular sieve has less crystal grain, is more suitable in pilot scale and industrial production.
The present inventor is unexpected on the basis of a large amount of preparation SAPO-34 molecular sieve test to be found, the preparation process of dry for phosphorus aluminium glue is combined with special segmentation crystallization process, can obtain the SAPO-34 molecular sieve that crystal grain is little, and when it reacts for MTO, catalytic effect is better.Based on this, form the present invention.
Therefore, SAPO-34 molecular sieve preparation method provided by the invention, is characterized in that comprising the steps:
(1) by phosphorus source and aluminium source according to (0.6 ~ 1.2) P
2o
5: Al
2o
3: (20 ~ 60) H
2the mol ratio of O mixes, and drying obtains the dry glue A of phosphorus aluminium that solid content is not less than 60%;
(2) dry for phosphorus aluminium glue A is contacted to mix with template, silicon source obtain mixture B, wherein, with 1 mole of Al in the dry glue A of phosphorus aluminium
2o
3meter, the add-on of said template is 1 ~ 2.5 mole, and said silicon source add-on is with SiO
2count 0.1 ~ 1 mole;
(3) mixture B 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.
The preparation method of SAPO-34 molecular sieve provided by the invention, first generate the dry glue of phosphorus aluminium with phosphorus source, aluminium source and portions of de-ionized water mixing, the dry glue of phosphorus aluminium is conducive to the generation of primary structure units, shorten the inductive phase that primary structure units is formed, be conducive to Zeolite synthesis and set up running balance faster; Further combined with the segmentation crystallization adopting special temperature range, make brilliant caryogenic speed be greater than the speed of nucleus growth, contribute to the generation of nucleus, be conducive to the formation of fine grain SAPO-34 molecular sieve.In addition, the SAPO-34 molecular sieve that the inventive method prepares is the even grained of 300-500nm, and degree of crystallinity is more than 100%, MTO diene selective can reach 83.59%.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope shape appearance figure of the comparative sample of comparative example 1.
Fig. 2 is the XRD spectra of the comparative sample of comparative example 2.
Fig. 3 is the stereoscan photograph of the comparative sample of comparative example 3.
Fig. 4 is the XRD spectra of the comparative sample of comparative example 4.
Fig. 5 is the XRD spectra of embodiment 1 sample.
Fig. 6 is the scanning electron microscope shape appearance figure of embodiment 1 sample.
Fig. 7 is the XRD spectra of embodiment 2 sample.
Fig. 8 is the scanning electron microscope shape appearance figure of embodiment 3 sample.
Embodiment
The preparation method of SAPO-34 molecular sieve provided by the invention, is characterized in that comprising the steps:
(1) by phosphorus source and aluminium source according to (0.6 ~ 1.2) P
2o
5: Al
2o
3: (20 ~ 60) H
2the mol ratio of O mixes, and drying obtains the dry glue A of phosphorus aluminium that solid content is not less than 60%;
(2) dry for phosphorus aluminium glue A is contacted to mix with template, silicon source obtain mixture B, wherein, with 1 mole of Al in the dry glue A of phosphorus aluminium
2o
3meter, the add-on of said template is (1 ~ 2.5) mole, and said silicon source add-on is with SiO
2count 0.1 ~ 1 mole;
(3) mixture B 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 preparation method of the present invention, described phosphorus source can be ammonium hydrogen phosphate, phosphoric acid and primary ammonium phosphate, and preferred 50%-85% phosphoric acid, is more preferably 85% ortho-phosphoric acid.Described aluminium source can be selected from dry glue powder, pseudo-boehmite, SB powder, aluminum alkoxide any one or several mixtures, wherein preferably dry glue powder, SB powder and pseudo-boehmite, more preferably Al
2o
3content is the dry glue powder of 75%.Described template can be selected from tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine any one or several mixtures, wherein preferred tetraethyl ammonium hydroxide, triethylamine and morpholine, more preferably the mixture of tetraethyl ammonium hydroxide and triethylamine, preferably the mol ratio of tetraethyl ammonium hydroxide and triethylamine is (0.05 ~ 2.5) further: the mixture of 1.Described silicon source can be selected from acidic silicasol, white carbon black, particulate silica gel, positive silicon ester any one or several mixtures, wherein preferred acidic silicon sol and white carbon black, the more preferably acidic silicasol of 30%.
In preparation method of the present invention, in step (1), the dry glue A of said phosphorus aluminium, solid content is not less than 60%, is preferably 70 ~ 90%.The mol ratio in phosphorus source and aluminium source is preferably (0.9-1.1) P
2o
5: Al
2o
3; In step (2), with 1 mole of Al in the dry glue A of phosphorus aluminium
2o
3meter, the add-on of said template is for being preferably (1.5-2) mole; Said silicon source add-on is with SiO
2meter is preferably (0.2-0.8) mole, is more preferably (0.30-0.45) mole
In preparation method of the present invention, step (3) is said is placed in crystallization under closed reactor autogenous pressure by mixture B, adopt the mode of segmentation crystallization to carry out, and comprises 20-90 DEG C of aging, 90-150 DEG C nucleus and generates 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.
Below by embodiment, the invention will be further described, 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% 1g acidic silicasol join respectively in above-mentioned colloidal sol, stirring and obtaining molar ratio is 0.1SiO
2: 1Al
2o
3: 1P
20
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 accompanying drawing 1, and crystal grain is cubes, and crystal grain is greater than 2 microns.
Comparative example 2
This comparative example illustrates process and the product of preparing SAPO-34 molecular sieve according to CN101633508A.
With the proportioning raw materials of comparative example 1 and to reclaim the process of product identical, difference is that the crystallization condition of said initial crystallization colloidal sol in closed reactor is different: 180 DEG C of crystallization 50h, after still temperature drop to room temperature, take out crystallization product.
The XRD spectra of this comparative sample is shown in Fig. 2, and this figure goes out peak and shows this sample and have α-low temperature tridymite stray crystal to produce at a ° place, 2 θ=26.6.
Comparative example 3
This comparative example illustrates the process and product that adopt the conventional crystallization of phosphorus aluminium glue, non-segmentation crystallization.
85% analytical pure ortho-phosphoric acid 9.2g is joined 30g deionized water for stirring even, be dissolved in the uniform mixture of 25g deionized water for stirring with 7gSB powder to mix, the mixture that rapid stirring obtains for 2 hours is placed in the phosphorus aluminium glue that 120 DEG C of thermostatic drier dryings obtain solid content 85%, the acidic silicasol being 30% by 30g tetraethyl ammonium hydroxide and 3g massfraction adds in above-mentioned phosphorus aluminium glue, the mixture obtained that stirs is placed in 100 milliliters of closed reactors, 170 DEG C of crystallization 80h; Crystallization product is taken out after still temperature drop to room temperature, filtration or centrifugal deionized water are washed till neutrality, it is dry that solid product is placed in the thermostatic drying chamber of 100-110 DEG C, and finally put into retort furnace and be warming up to 550 DEG C of constant temperature calcinings and within 4 hours, obtain the former powder of product, each component ratio is 1Al
2o
3: 0.8P
20
5: 0.30SiO
2: TEAOH:50H
2o.
The stereoscan photograph (SEM) of gained sample is shown in Fig. 3, although show that this sample crystallization is complete, grain-size is greater than 1 micron.
Comparative example 4
With comparative example 1, difference is that in this comparative example, crystal pattern adopts the mode of segmentation crystallization, and crystallization condition carries out according to the segmentation of aged at room temperature 10h, 150 DEG C of crystallization 10h and 200 DEG C crystallization 40h.
Gained sample XRD spectra is shown in Fig. 4, and this figure goes out peak and shows this sample and have AEI structure stray crystal to produce in 2 θ=16.02 °.
Embodiment 1
Taking 7g dry glue powder is dissolved in 10g deionized water, after stirring, joins the solution that 10g deionized water for stirring evenly obtains mix with 85% analytical pure ortho-phosphoric acid 11g, the dry phosphorus aluminium glue obtaining 85% solid content at 80 DEG C.
Phosphorus aluminium glue is moved in 100 milliliters of crystallizing kettles, add 30g tetraethyl ammonium hydroxide, 5.2g triethylamine, the acidic silicasol of 3g massfraction 30% and 17g water, stir, closed reactor, crystallization condition is according to the staging treating of aged at room temperature 10h, 150 DEG C of crystallization 10h and 200 DEG C crystallization 40h, crystallization product is taken out after still temperature drop to room temperature, 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 obtains sample in 4 hours.
The XRD diffraction spectrogram of gained sample and stereoscan photograph are shown in Fig. 5 and Fig. 6 respectively, and the spectrum peak-to-peak type of XRD diffraction spectrogram display is sharp-pointed, without stray crystal phase, shows that product is the SAPO-34 molecular sieve of pure phase; Stereoscan photograph SEM pattern shows that crystal grain is the cubes of lamellar superposition, and crystal grain is at 300nm-500nm.
Embodiment 2
Taking 7gSB powder is dissolved in 25g deionized water, rapid stirring 1 hour, joins the solution that 30g deionized water for stirring evenly obtains mix with 85% analytical pure ortho-phosphoric acid 9.2g, the dry phosphorus aluminium glue obtaining solid content 85% in 120 DEG C of thermostatic driers.
Phosphorus aluminium glue is moved in 100 milliliters of crystallizing kettles, add 30g tetraethyl ammonium hydroxide and 3g massfraction is the acidic silicasol of 30%, stir, closed reactor, crystallization condition is according to the staging treating of aged at room temperature 10h, 140 DEG C of crystallization 10h and 170 DEG C crystallization 70h.After still temperature drop to room temperature, take out crystallization product, to filter or centrifugal deionized water is washed till neutrality, it is dry that product is placed in the thermostatic drying chamber of 100-110 DEG C, finally puts into retort furnace and be warming up to 550 DEG C of constant temperature calcinings and within 4 hours, obtain the former powder of product.
The XRD diffraction spectrogram of gained sample is shown in Fig. 7, and the spectrum peak-to-peak type of XRD diffraction spectrogram display is sharp-pointed, shows that product is the SAPO-34 molecular sieve of pure phase.
Embodiment 3
Taking 27gSB powder is dissolved in 70g deionized water, rapid stirring 1 hour, joins the solution that 60g deionized water for stirring evenly obtains mix with 85% analytical pure ortho-phosphoric acid 55g, dryly in 80 DEG C of thermostatic driers obtains the phosphorus aluminium glue that solid content is 80%.
Phosphorus aluminium glue is moved in 100 milliliters of crystallizing kettles, add the acidic silicasol of 140g tetraethyl ammonium hydroxide and 3g massfraction 30%, stir, airtight crystallizing kettle, crystallization condition is aged at room temperature 10h, 150 DEG C of crystallization 10h and 180 DEG C of crystallization 50h staging treating, crystallization product is taken out after still temperature drop to room temperature, 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.
The stereoscan photograph of gained sample is shown in Fig. 8, and SEM pattern shows that crystal grain is little, and grain morphology is the cubes of sheet superposition, and grain-size is 300nm-500nm.
Comparative example 5-6
This comparative example illustrates that the SAPO-34 product of comparative example 1 and 2 is in the catalytic performance result 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 0.1Mpa, and reaction product is with ethene and propylene for target product, and reaction product is by gas-chromatography on-line analysis, and catalyzed reaction the results are shown in Table 1.
Comparative example 7-8
This comparative example illustrates that the SAPO-34 product of comparative example 3 and comparative example 4 is in the catalytic performance result 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-3 and C-4.Evaluating apparatus is fixed-bed reactor, and appreciation condition is: loaded catalyst is 3g, and reactant is methyl alcohol, mass space velocity 1h
-1carrier gas is nitrogen, nitrogen flow is 350ml/min, temperature of reaction 450 DEG C, reaction pressure is 0.1Mpa, and reaction product is with ethene and propylene for target product, and reaction product is by gas-chromatography on-line analysis, catalyzed reaction the results are shown in Table 1 evaluation method and condition with comparative example 5-6, and catalyzed reaction the results are shown in Table 1.
Embodiment 4-6
Embodiment 1-3 illustrates the catalytic performance effect of embodiment 1-3 gained SAPO-34 sample in methanol to olefins reaction.Embodiment 1-3 gained sample is sieved through compressing tablet, gets 20-40 order sample, be labeled as C-5, C-6, C-7.Evaluation method and condition are with comparative example 3-4, and catalyzed reaction the results are shown in Table 1.
Table 1
As can be seen from Table 1, compared with traditional hydrothermal synthesis method, adopt the dry glue of phosphorus aluminium as phosphorus aluminium source and segmentation crystallization, the SAPO-34 molecular sieve that preparation method provided by the invention obtains diene selective in MTO reaction can reach 83.59%, has more excellent MTO catalytic performance.
Claims (14)
1. a preparation method for SAPO-34 molecular sieve, is characterized in that comprising the steps:
(1) by phosphorus source and aluminium source according to (0.6 ~ 1.2) P
2o
5: Al
2o
3: (20 ~ 60) H
2the mol ratio of O mixes, and drying obtains the dry glue A of phosphorus aluminium that solid content is not less than 60%;
(2) dry for phosphorus aluminium glue A is contacted to mix with template, silicon source obtain mixture B, wherein, with 1 mole of Al in the dry glue A of phosphorus aluminium
2o
3meter, the add-on of said template is 1 ~ 2.5 mole, and said silicon source add-on is with SiO
2count 0.1 ~ 1 mole;
(3) mixture B 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, said phosphorus source is one or more in ammonium hydrogen phosphate, phosphoric acid and primary ammonium phosphate.
3., according to the process of claim 1 wherein, said aluminium source is one or several the mixture in dry glue powder, pseudo-boehmite, SB powder, aluminum alkoxide.
4., according to the process of claim 1 wherein, the mol ratio in said phosphorus source and aluminium source is (0.9-1.1) P
2o
5: Al
2o
3.
5., according to the process of claim 1 wherein, the solid content of the dry glue A of said phosphorus aluminium is 70 ~ 90%.
6., according to the process of claim 1 wherein, said template is selected from one or several the mixture in tetraethyl ammonium hydroxide, triethylamine, diethylamine and morpholine.
7., according to the process of claim 1 wherein, said template is the mixture of tetraethyl ammonium hydroxide and triethylamine.
8., 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 (0.05 ~ 2.5): 1.
9., according to the process of claim 1 wherein, said silicon source is any one or several mixture in acidic silicasol, white carbon black, particulate silica gel and positive silicon ester.
10., according to the process of claim 1 wherein, said silicon source add-on is with SiO
2count 0.2 ~ 0.8 mole.
11. according to the method for claim 10, and wherein, said silicon source add-on is with SiO
2count 0.3 ~ 0.45 mole.
12. according to the process of claim 1 wherein, said crystallization, and its total time controls at 30-90 hour.
13. 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.
14. according to the method for claim 1,12 or 13, said crystallization 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.
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| CN106542547A (en) * | 2016-08-03 | 2017-03-29 | 刘希尧 | A kind of preparation method of 34 molecular sieves of SAPO of high activity low silicon content |
| CN108928836A (en) * | 2018-08-22 | 2018-12-04 | 江西西林科新材料有限公司 | A kind of synthetic method of nanometer of SAPO-34 molecular sieve |
| 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 |
| CN111056562A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve, synthetic method and application thereof, and method for preparing olefin from methanol |
| CN115286035A (en) * | 2022-08-26 | 2022-11-04 | 陕西师范大学 | Preparation method of hollow barium titanate nano-microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106542547A (en) * | 2016-08-03 | 2017-03-29 | 刘希尧 | A kind of preparation method of 34 molecular sieves of SAPO of high activity low silicon content |
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| 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 |
| CN108928836A (en) * | 2018-08-22 | 2018-12-04 | 江西西林科新材料有限公司 | A kind of synthetic method of nanometer of SAPO-34 molecular sieve |
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| CN111056562A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve, synthetic method and application thereof, and method for preparing olefin from methanol |
| CN111056562B (en) * | 2018-10-17 | 2021-10-08 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve, synthetic method and application thereof, and method for preparing olefin from methanol |
| CN115286035A (en) * | 2022-08-26 | 2022-11-04 | 陕西师范大学 | Preparation method of hollow barium titanate nano-microspheres |
| CN115286035B (en) * | 2022-08-26 | 2024-01-16 | 陕西师范大学 | Preparation method of hollow barium titanate nano microsphere |
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