CN104556091B - A kind of preparation method of SAPO-34 molecular sieve - Google Patents
A kind of preparation method of SAPO-34 molecular sieve Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of SAPO-34 molecular sieve, it is characterized in that comprising the steps: (1) by He Lv source, phosphorus source according to (0.6～1.2) P2O5:Al2O3:(20～60)H2A mole proportioning of O mixes, and dry obtain solid content and is not less than 60% the dry glue A of phosphorus aluminium; (2) dry 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 aluminium2O3Meter, the addition of said template is 1～2.5 mole, said silicon source addition is with SiO2Count 0.1～1 mole; (3) mixture B be placed under closed reactor self-generated pressure to segmentation crystallization and reclaim product.
Description
Technical field
The invention relates to a kind of preparation method of SAPO-34 molecular sieve, more specifically say about oneThe hydro-thermal synthetic preparation method of SAPO-34 molecular sieve.
Background technology
SAPO-34 molecular sieve is a kind of phosphor-silicon-aluminum molecular sieve that connection C.-Chem AG of the U.S. developed in 1984,For the chabasie CHA structure of octatomic ring, belong to cubic system, aperture is in 0.43nm left and right, with ethene and thirdThe molecular diameter of alkene is close, and SAPO-34 molecular sieve has suitable acid strength, pore passage structure and good waterHeat endurance has shown excellent catalytic performance in preparing light olefins from methanol (MTO).
SAPO-34 molecular sieve synthetic has a lot of methods, such as hydrothermal synthesis method, microwave process for synthesizing, liquid phaseSynthetic method, gas phase shift synthetic method etc. Wherein the most frequently used is hydrothermal synthesis method, as CN101121529A,CN101633508A etc. are disclosed is all the method that adopts Hydrothermal Synthesis SAPO-34 molecular sieve. Hydrothermal Synthesis sideThe step of method roughly comprises: (1) is prepared crystallization liquid, (2) ageing and (3) crystallization and reclaimed. Traditional hydro-thermal is closedThe shortcomings such as poor repeatability after becoming the method for SAPO-34 molecular sieve to exist to amplify, single still yield are low.
CN102372288A is by silicon source, phosphorus source, aluminium source, fluoride and organic formwork agent are prepared into dry glue,Adopt the synthetic SAPO-34 molecular sieve of gas phase crystallization method, the SAPO-34 molecular sieve that synthesized obtains is at MTOIn reaction, diene selective is 81.9%. CN101125665A generates dry glue to the pretreatment of silicon phosphorus aluminium source and becomesSAPO-34 molecular sieve, has mainly solved the sticky wall problem that crystallizing kettle exists. CN101633508A discloses oneThe synthetic method of planting SAPO-34 molecular sieve, the method is by rate of charge (a1R1+a2R2)：Al2O3：bP2O5：cSiO2：dH2O, mixes plastic, water at 100-250 DEG C by aluminium source, phosphorus source, silicon source and organic formwork agentAfter thermal crystallisation 4-500 hour, reclaim product, it is characterized in that said organic formwork agent is R1 and R2,R1 adds in mixing plastic process, and R2 adds at hydrothermal crystallization process, and R1 and R2 are identical or different.
Summary of the invention
The object of the invention is the problem existing for prior art, the SAPO-34 molecular sieve of easy repetition is providedPreparation method, gained molecular sieve has less crystal grain, is more suitable in pilot scale and industrial production.
The present inventor is unexpected discovery on the basis of a large amount of preparation SAPO-34 molecular sieve test, by phosphorusThe preparation process of the dry glue of aluminium is combined with special segmentation crystallization process, can obtain the SAPO-34 that crystal grain is little and divideSon sieve, and it is while reacting for MTO, and 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 He Lv source, phosphorus source according to (0.6～1.2) P2O5:Al2O3:(20～60)H2Mole proportioning of O is mixedEvenly, dryly obtain solid content and be not less than 60% the dry glue A of phosphorus aluminium;
(2) dry phosphorus aluminium glue A is contacted to mix with template, silicon source obtain mixture B, wherein, with1 mole of Al in the dry glue A of phosphorus aluminium2O3Meter, the addition of said template is 1～2.5 mole, saidSilicon source addition is with SiO2Count 0.1～1 mole;
(3) mixture B be placed under closed reactor self-generated pressure to crystallization and reclaim product, wherein, instituteThe crystallization of saying is in temperature range from low to high, sequentially to divide three sections to carry out, and the crystallization temperature of adjacent two sections is notIdentical and rear one section of crystallization temperature higher than the last period temperature crystallization be no less than 40 DEG C, said three sections of crystallization temperaturesBe 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 with phosphorus source, aluminium source and part deionizationWater mixes the dry glue of generation phosphorus aluminium, and the dry glue of phosphorus aluminium is conducive to the generation of primary structure units, has shortened primary structureThe induction period that unit forms, be conducive to Zeolite synthesis and set up faster dynamic equilibrium; Further combined with adoptingBy the segmentation crystallization of special temperature range, make brilliant caryogenic speed be greater than the speed of nucleus growth, helpIn the generation of nucleus, be conducive to the formation of fine grain SAPO-34 molecular sieve. In addition, the inventive method preparationThe even grained that the SAPO-34 molecular sieve obtaining is 300-500nm, degree of crystallinity is more than 100%, MTO is twoAlkene selectively can reach 83.59%.
Brief description of the drawings
Fig. 1 is the ESEM 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 ESEM shape appearance figure of embodiment 1 sample.
Fig. 7 is the XRD spectra of embodiment 2 samples.
Fig. 8 is the ESEM shape appearance figure of embodiment 3 samples.
Detailed description of the invention
The preparation method of SAPO-34 molecular sieve provided by the invention, is characterized in that comprising the steps:
(1) by He Lv source, phosphorus source according to (0.6～1.2) P2O5:Al2O3:(20～60)H2Mole proportioning of O is mixedEvenly, dryly obtain solid content and be not less than 60% the dry glue A of phosphorus aluminium;
(2) dry phosphorus aluminium glue A is contacted to mix with template, silicon source obtain mixture B, wherein, with1 mole of Al in the dry glue A of phosphorus aluminium2O3Meter, the addition of said template is (1～2.5) mole, instituteThe silicon source addition of saying is with SiO2Count 0.1～1 mole;
(3) mixture B be placed under closed reactor self-generated pressure to crystallization and reclaim product, wherein, instituteThe crystallization of saying is in temperature range from low to high, sequentially to divide three sections to carry out, and the crystallization temperature of adjacent two sections is notIdentical and rear one section of crystallization temperature higher than the last period temperature crystallization be no less than 40 DEG C, said three sections of crystallization temperaturesBe 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 ammonium dihydrogen phosphate (ADP),Preferably 50%-85% phosphoric acid, more preferably 85% orthophosphoric acid. Described aluminium source can be selected from dry glue powder, intend thin water aluminiumAny one or several mixtures in stone, SB powder, aluminum alkoxide, wherein preferably dry glue powder, SB powder andBoehmite, more preferably Al2O3Content is 75% dry glue powder. Described template can be selected from tetraethyl hydrogenAny one or several mixtures in amine-oxides, triethylamine, diethylamine, morpholine, wherein preferred tetremBase ammonium hydroxide, triethylamine and morpholine, more preferably the mixture of tetraethyl ammonium hydroxide and triethylamine, enters oneMole proportioning that walks preferred tetraethyl ammonium hydroxide and triethylamine is (0.05～2.5): 1 mixture. InstituteState silicon source can be selected from acidic silicasol, white carbon, particulate silica gel, positive esters of silicon acis any one or severalThe mixture of planting, wherein preferred acidic Ludox and white carbon, more preferably 30% acidic silicasol.
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%,Be preferably 70～90%. Mole proportion optimization in He Lv source, phosphorus source is (0.9-1.1) P2O5:Al2O3; Step (2)In, with 1 mole of Al in the dry glue A of phosphorus aluminium2O3Meter, the addition of said template is for being preferably (1.5-2)Mole; Said silicon source addition is with SiO2Meter is preferably (0.2-0.8) mole, more preferably(0.30-0.45) mole
In preparation method of the present invention, step (3) is said, and that mixture B is placed in to closed reactor is spontaneousCrystallization under pressure, adopts the mode of segmentation crystallization to carry out, and comprises that 20-90 DEG C aging, 90-150 DEG C nucleus is rawBecome and 150-250 DEG C of nucleus production process. The not identical and rear one section of crystallization temperature of the crystallization temperature of adjacent two sectionsHigher than the last period temperature crystallization be no less than 40 DEG C, preferably 60～70 DEG C. Said three sections of crystallization temperatures are respectively20～90 DEG C, 90～150 DEG C and 150～250 DEG C, be preferably 20～60 DEG C, 110～130 DEG C and 180～210 DEG C. Further preferably total crystallization time is controlled at 30-90 hour. For example, a tool of the present inventionIn the embodiment of body, crystallization process is at 25-35 DEG C of crystallization 5-10 hour, 100-150 DEG C crystallization 10-20Hour, 150-200 DEG C crystallization 10-45 hour.
The process of said recovery product is by those skilled in the art are familiar with, for example comprise filtration, washing,Dry and roasting etc. Said dry can be to carry out at 100-110 DEG C, said roasting can beUnder 400-600 DEG C of constant temperature, carry out.
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; ESEM shape appearance figureThe Quanta200F type ESEM of being produced by FEI Co. is measured.
Comparative example 1
Process and the product of SAPO-34 molecular sieve prepared in the explanation of this comparative example according to CN101633508A.
85% orthophosphoric acid (analyzing pure) 11g is joined in 10g deionized water, and rapid stirring evenly obtains ASolution; Separately take 7g dry glue powder and be dissolved in 10g deionized water, stir and add again template 6g tetremBase ammonium hydroxide, stirs, more above-mentioned A solution is added, and stirs and within 2 hours, obtains uniform colloidal sol.The 1g acidic silicasol that is 30% by mass fraction joins respectively in above-mentioned colloidal sol, stirs to obtain moleRatio is 0.1SiO2:1Al2O3:1P205:0.2TEAOH:1.4TEA:60H2The initial crystallization colloidal sol of O, then willInitial crystallization colloidal sol is placed in 100 milliliters of stainless steel closed reactors, 120 DEG C of crystallization 5h; Still temperature drop is to chamberAfter temperature, add 7g triethylamine, then be warming up to 190 DEG C and continue crystallization 8 hours, take out during to room temperature until still temperature dropCrystallization product, filters or is centrifugally washed till neutrality by deionized water, is placed in the thermostatic drying chamber of 100-110 DEG CDry, finally put into Muffle furnace and be warming up to 550 DEG C of constant temperature calcinings and within 4 hours, obtain the former powder of product.
This comparative sample ESEM shape appearance figure (SEM) is shown in accompanying drawing 1, and crystal grain is cube, and it is 2 micro-that crystal grain is greater thanRice.
Comparative example 2
Process and the product of SAPO-34 molecular sieve prepared in the explanation of this comparative example according to CN101633508A.
Identical with the raw material proportioning of comparative example 1 and the process of recovery product, difference is said initial crystalline substanceChange the crystallization condition difference of colloidal sol in closed reactor: 180 DEG C of crystallization 50h, get to room temperature until still temperature dropGo out crystallization product.
The XRD spectra of this comparative sample is shown in Fig. 2, this figure locate out in 2 θ=26.6 ° peak show this sample have α-Low temperature tridymite stray crystal produces.
Comparative example 3
The explanation of this comparative example adopts process and the product of the conventional crystallization of phosphorus aluminium glue, non-segmentation crystallization.
The pure phosphatase 79 .2g of 85% analysis is joined to 30g deionized water for stirring even, be dissolved in 7gSB powderThe uniform mixture of 25g deionized water for stirring mixes, and the mixture that rapid stirring obtains for 2 hours is placed in 120The dry phosphorus aluminium glue that obtains solid content 85% in DEG C thermostatic drier, by 30g tetraethyl ammonium hydroxide and 3g matterThe acidic silicasol that amount mark is 30% adds in above-mentioned phosphorus aluminium glue, and the mixture obtaining that stirs is placed inIn 100 milliliters of closed reactors, 170 DEG C of crystallization 80h; To room temperature, take out crystallization product until still temperature drop, mistakeFilter or be centrifugally washed till neutrality by deionized water, it is dry that solid product is placed in the thermostatic drying chamber of 100-110 DEG C,Finally put into Muffle 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 is1Al2O3:0.8P205:0.30SiO2:TEAOH:50H2O。
The stereoscan photograph (SEM) of gained sample is shown in Fig. 3, although show that this sample crystallization is complete, crystal grainSize is greater than 1 micron.
Comparative example 4
With comparative example 1, difference is the mode of crystal pattern employing segmentation crystallization in this comparative example, crystallization conditionSegmentation according to aged at room temperature 10h, 150 DEG C of crystallization 10h and 200 DEG C of crystallization 40h is carried out.
Gained sample XRD spectra is shown in Fig. 4, and this figure goes out peak and shows that this sample has AEI knot in 2 θ=16.02 °Structure stray crystal produces.
Embodiment 1
Take 7g dry glue powder and be dissolved in 10g deionized water, after stirring, with the pure phosphatase 11 1g of 85% analysisJoin the solution that 10g deionized water for stirring evenly obtains and mix, dryly at 80 DEG C obtain 85% and admittedly containThe phosphorus aluminium glue of amount.
Phosphorus aluminium glue is moved in 100 milliliters of crystallizing kettles, add 30g tetraethyl ammonium hydroxide, 5.2g triethylamine,The acidic silicasol of 3g mass fraction 30% and 17g water, stir, closed reactor, and crystallization condition is pressedAccording to the segment processing of aged at room temperature 10h, 150 DEG C of crystallization 10h and 200 DEG C of crystallization 40h, treat that still temperature drop is to chamberAfter temperature, take out crystallization product, filter or be centrifugally washed till neutrality by deionized water, be placed in the constant temperature of 100-110 DEG CDry in drying box, finally put into Muffle furnace and be warming up to 550 DEG C of constant temperature calcinings and within 4 hours, obtain sample.
XRD diffraction spectrogram and the stereoscan photograph of gained sample are shown in respectively Fig. 5 and Fig. 6, XRD diffraction spectraThe spectrum peak-to-peak type that figure shows is sharp-pointed, without stray crystal phase, shows that product is the SAPO-34 molecular sieve of pure phase; ScanningElectromicroscopic photograph SEM pattern shows that crystal grain is the cube of lamellar stack, and crystal grain is at 300nm-500nm.
Embodiment 2
Take 7gSB powder and be dissolved in 25g deionized water, rapid stirring 1 hour, with the pure phosphoric acid of 85% analysis9.2g joins the solution mixing that 30g deionized water for stirring evenly obtains, in 120 DEG C of thermostatic driersThe dry phosphorus aluminium glue that obtains solid content 85%.
Phosphorus aluminium glue is moved in 100 milliliters of crystallizing kettles, add 30g tetraethyl ammonium hydroxide and 3g mass fractionBe 30% acidic silicasol, stir, closed reactor, crystallization condition is according to aged at room temperature 10h, 140The segment processing of DEG C crystallization 10h and 170 DEG C of crystallization 70h. To room temperature, take out crystallization product until still temperature drop,Filter or be centrifugally washed till neutrality by deionized water, it is dry that product is placed in the thermostatic drying chamber of 100-110 DEG C,Finally putting into Muffle furnace is warming up to 550 DEG C of constant temperature calcinings and within 4 hours, obtains the former powder of product.
The XRD diffraction spectrogram of gained sample is shown in Fig. 7, and the spectrum peak-to-peak type that XRD diffraction spectrogram shows is sharp-pointed, showsProduct is the SAPO-34 molecular sieve of pure phase.
Embodiment 3
Take 27gSB powder and be dissolved in 70g deionized water, rapid stirring 1 hour, with the pure phosphorus of 85% analysisAcid 55g joins the solution mixing that 60g deionized water for stirring evenly obtains, in 80 DEG C of thermostatic driersThe dry solid content that obtains is 80% phosphorus aluminium glue.
Phosphorus aluminium glue is moved in 100 milliliters of crystallizing kettles, add 140g tetraethyl ammonium hydroxide and 3g quality to divideSeveral 30% acidic silicasol, stirs, airtight crystallizing kettle, and crystallization condition is aged at room temperature 10h, 150DEG C crystallization 10h and 180 DEG C of crystallization 50h segment processing are taken out crystallization product until still temperature drop, mistake to room temperatureFilter or be centrifugally washed till neutrality by deionized water, the thermostatic drying chamber that is placed in 100-110 DEG C is dry, finally putsEnter in Muffle furnace, to be warming up to 550 DEG C of constant temperature calcinings and within 4 hours, to obtain 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 that sheet is foldedThe cube adding, crystallite dimension is 300nm-500nm.
Comparative example 5-6
The SAPO-34 product of this comparative example explanation comparative example 1 and 2 is in the catalysis in methanol to olefins reactionResults of property. The sample compressing tablet of the comparative example after roasting 1 and 2 is sieved, chooses 20-40 object sample,Be labeled as C-1 and C-2. Evaluating apparatus is fixed bed reactors, and appreciation condition is: loaded catalyst is3g, reactant is methyl alcohol, mass space velocity 1h-1, carrier gas is nitrogen, nitrogen flow is 350ml/min, reaction450 DEG C of temperature, reaction pressure is 0.1Mpa, and product is taking ethene and propylene as target product, and reaction is producedThing is by gas-chromatography on-line analysis, and catalytic reaction the results are shown in Table 1.
Comparative example 7-8
The SAPO-34 product of this comparative example explanation comparative example 3 and comparative example 4 is in methanol to olefins reactionCatalytic performance result. The sample compressing tablet of the comparative example after roasting 1 and 2 is sieved, choose 20-40 objectSample, is labeled as C-3 and C-4. Evaluating apparatus is fixed bed reactors, and appreciation condition is: catalyst dressThe amount of filling out is 3g, and reactant is methyl alcohol, mass space velocity 1h-1, carrier gas is nitrogen, nitrogen flow is 350ml/min,450 DEG C of reaction temperatures, reaction pressure is 0.1Mpa, product is taking ethene and propylene as target product, anti-Answer product by gas-chromatography on-line analysis, catalytic reaction the results are shown in Table 1 evaluation method and the same comparative example of condition5-6, catalytic reaction the results are shown in Table 1.
Embodiment 4-6
The catalysis of embodiment 1-3 explanation embodiment 1-3 gained SAPO-34 sample in methanol to olefins reactionThe impact of performance. 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 catalytic reaction the results are shown in Table 1.
Table 1
As can be seen from Table 1, compare with traditional hydrothermal synthesis method, adopt the dry glue of phosphorus aluminium as phosphorus aluminiumSource and segmentation crystallization, the SAPO-34 molecular sieve that preparation method provided by the invention obtains is two in MTO reactionAlkene selectively 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 He Lv source, phosphorus source according to (0.6～1.2) P2O5:Al2O3:(20～60)H2Mole proportioning of O is mixedEvenly, dryly obtain solid content and be not less than 60% the dry glue A of phosphorus aluminium;
(2) dry phosphorus aluminium glue A is contacted to mix with template, silicon source obtain mixture B, wherein, with phosphorus1 mole of Al in the dry glue A of aluminium2O3Meter, the addition of said template is 1～2.5 mole, instituteThe silicon source addition of saying is with SiO2Count 0.1～1 mole;
(3) mixture B be placed under closed reactor self-generated pressure to crystallization and reclaim product, wherein, saidCrystallization be that order points three sections is carried out in temperature range from low to high, the crystallization temperature of adjacent two sectionsSpend not identical and rear one section of crystallization temperature higher than the last period temperature crystallization be no less than 40 DEG C, saidThree 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 ammonium hydrogen phosphate, phosphoric acid and biphosphateOne or more in ammonium.
3. according to the process of claim 1 wherein, said aluminium source is dry glue powder, boehmite, alkoxylThe mixture of one or several in aluminium.
4. according to the process of claim 1 wherein, mole proportioning in He Lv source, said phosphorus source is(0.9-1.1)P2O5:Al2O3。
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 be selected from tetraethyl ammonium hydroxide, triethylamine,The mixture of one or several in diethylamine and morpholine.
7. according to the process of claim 1 wherein, said template is tetraethyl ammonium hydroxide and triethylamineMixture.
8. according to the method for claim 7, 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 acidic silicasol, white carbon, fine grain siliconAny one or several mixtures in glue and positive esters of silicon acis.
10. according to the process of claim 1 wherein, said silicon source addition is with SiO2Counting 0.2～0.8 rubsYou.
11. according to the method for claim 10, and wherein, said silicon source addition is with SiO2Count 0.3～0.45Mole.
12. according to the process of claim 1 wherein, said crystallization, and its total time is controlled 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 CWith 180～210 DEG C.
14. according to the method for claim 1, and said crystallization is at 25-35 DEG C of crystallization 5-10 hour, 100-150 DEG CCrystallization 10-20 hour, 150-200 DEG C crystallization 10-45 hour.
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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 |
| CN108928836B (en) * | 2018-08-22 | 2022-01-11 | 江西西林科新材料有限公司 | Synthesis method of nano SAPO-34 molecular sieve |
| 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 |
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| CN102464340A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing silicoaluminophosphate (SAPO)-34 molecular sieve |
| 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 |
| CN103172084A (en) * | 2013-04-11 | 2013-06-26 | 太原大成环能化工技术有限公司 | Solid phase preparation method of aluminosilicophosphate eutectic molecular sieve |
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| CN102464340A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing silicoaluminophosphate (SAPO)-34 molecular sieve |
| 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 |
| CN103172084A (en) * | 2013-04-11 | 2013-06-26 | 太原大成环能化工技术有限公司 | Solid phase preparation method of aluminosilicophosphate eutectic molecular sieve |
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