CN116022810A - Modified A-type molecular sieve and preparation method thereof - Google Patents
Modified A-type molecular sieve and preparation method thereof Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 238000011068 loading method Methods 0.000 claims abstract description 13
- 229910052751 metal Chemical class 0.000 claims abstract description 9
- 239000002184 metal Chemical class 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 85
- 239000008367 deionised water Substances 0.000 claims description 72
- 229910021641 deionized water Inorganic materials 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000005406 washing Methods 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 33
- 238000005342 ion exchange Methods 0.000 claims description 32
- 230000032683 aging Effects 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 29
- 239000000499 gel Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000000967 suction filtration Methods 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- -1 activated aluminas Chemical class 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 24
- 239000005977 Ethylene Substances 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 20
- 230000007935 neutral effect Effects 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a modified A-type molecular sieve, which is characterized by comprising an A-type molecular sieve and a metal salt active component, wherein the metal salt active component comprises a component M1 and a component M2, and metal ions in the component M1 comprise Mg 2+ 、Ca 2+ And Sr 2+ Wherein the component M2 is Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ And Ni 2+ One of the following; the loading of the component M1 is 1.5-30.0wt% and the loading of the component M2 is 1.5-8.0wt% calculated by metal oxide; the modified type a molecular sieve has an average crystallite size of no greater than 1 μm.
Description
Technical Field
The invention relates to the field of molecular sieves, in particular to a modified A-type molecular sieve and a preparation method thereof.
Background
Type a molecular sieves were first successfully synthesized by united states carbonization (UCC) in 1954 and delivered to industry in 1957. The empirical formula of the chemical composition of the A-type molecular sieve is (M 2+ ,M + )O·Al 2 O 3 ·SiO 2 ·yH 2 O, which has an adjustable regular three-dimensional pore canal, is widely used in the fields of selective adsorption, ion exchange, catalysis and the like.
The synthesis method of the A-type molecular sieve comprises a solvent (water) thermal synthesis method, a xerogel conversion method, a microwave radiation method and the like.
The solvent (hydro) thermal synthesis method is the most developed and widely used synthesis method in molecular sieve synthesis. The solvent (hydro) thermal synthesis method uses alkali metal or organic amine as a structure directing agent, the crystallization temperature is generally higher than 100 ℃, and the synthesized molecular sieve has larger crystal grains and the size is generally 3-5 mu m. Because the small-size A-type molecular sieve with the grain size between 1 and 1000nm has larger specific surface area, shorter diffusion distance and more accessible active center, the selective adsorption performance of the molecular sieve can be obviously improved in the aspect of adsorption separation.
CN 103435062B discloses a simple and rapid synthesis method of nano a-type molecular sieve. According to the method, acid is used as a catalyst for hydrolysis of the ethyl orthosilicate, so that the hydrolysis rate of the ethyl orthosilicate is increased, and simultaneously, tetramethyl ammonium hydroxide is introduced in the preparation process, so that the synthesis period of the molecular sieve is shortened, and the nano A-type molecular sieve obtained by the method has the particle size smaller than 100nm and is uniformly distributed. CN 104276584a discloses a method for preparing submicron NaA molecular sieve by hydrothermal crystallization with sodium silicate, sodium aluminate and deionized water as raw materials and polyethylene glycol 1000 (PEG 1000) as a dispersing agent. According to the method disclosed in CN 106542541A, saccharide compound is added as inhibitor to inhibit the growth of crystal nucleus and shorten crystallization time, so that the A-type molecular sieve with the grain size of 0.5-1 μm is prepared. According to the method disclosed in CN 110498423A, a cellulose derivative is used as a gelling aid and added into a gel system to prepare the nano A-type molecular sieve.
The preparation method of the small-size A-type molecular sieve is the most commonly used method for preparing the nano-scale A-type molecular sieve in the laboratory range at present. Although the addition of the organic template agent, the dispersing agent, the inhibitor and the like can greatly promote the nucleation process of the molecular sieve, the organic template agent is generally expensive, the energy consumption for removing the organic template agent is high, and the yield of the molecular sieve is reduced after the dispersing agent and the inhibitor are added, so that the method is not beneficial to industrial production.
Aguado s et al (j.am. Chem. Soc.,2012, 134:14635-14637.) utilize Ag + The exchange mode is used for modifying the A-type molecular sieve, and the content of Ag in the obtained product can reach 36.7 percent, the content of Ca is only 0.48 percent, the content of Na is only 0.92 percent, and the pore channel size of the molecular sieve is between the dynamic sizes of ethylene and ethane, so that the ethane molecules can be completely removed, and the selectivity of the molecular sieve to the ethylene is obviously improved. Van Zand voort I. Et al (micropor. Mesopor. Mat.,2018, 263:142-149) prepared Ag modified type A molecular sieves using the same procedure. Through N 2 、H 2 、CH 4 、C 2 H 4 、C 2 H 6 CO and CO 2 The adsorption separation result of the coexisting system shows that compared with the Ca modified A-type molecular sieve, the molecular sieve has high ethylene selectivity after being modified by Ag. However, due to Ag + In a reducing atmosphere such as H 2 And CO is easy to be reduced into simple substance Ag and then is agglomerated into Ag particles with larger size, so that the adsorption capacity of ethylene is reduced by 20%, and the Ag modification is more expensive due to higher use amount of Ag, so that the application of the Ag modified A-type molecular sieve in industry is hindered.
Disclosure of Invention
The invention aims at solving the problems existing in the prior art and provides a modified 5A molecular sieve which is different from the prior art and a preparation method of the modified 5A molecular sieve.
In order to achieve the object of the invention, a first aspect of the invention provides a modified type A molecular sieve, which is characterized in that the modified type A molecular sieve consists of a type A molecular sieve and a metal salt active component, wherein the metal salt active component comprises a component M1 and a component M2, and metal ions in the component M1 comprise Mg 2+ 、Ca 2+ And Sr 2+ Wherein the component M2 is Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ And Ni 2+ One of the following; the loading of the component M1 is 1.5-30.0wt% calculated by metal oxide, and the loading of the component M2 is 1.5-8.0wt%; the average grain size of the modified A-type molecular sieve is not more than 1 mu m.
In order to achieve the object of the present invention, a second aspect of the present invention provides a process for preparing the modified type a molecular sieve of the present invention described above, which comprises the preparation of the type a molecular sieve and ion exchange modification.
The modified A-type molecular sieve provided by the invention has small grain size, low modified metal content, higher ethylene adsorption capacity and adsorption selectivity, and can provide a high-quality adsorbent for application in the aspect of ethylene/ethane adsorption separation. The preparation method of the modified A-type molecular sieve provided by the invention is simple, low in cost, strong in operability and has a relatively strong industrial application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of a modified type A molecular sieve sample of example 1.
FIG. 2 is an adsorption curve of the modified type A molecular sieve of example 1 for pure gases of ethylene and ethane at 25℃and 0-100kPa.
Detailed Description
The invention provides a modified A-type molecular sieve, which consists of an A-type molecular sieve and a metal salt active component, wherein the metal salt active component comprisesComprises a component M1 and a component M2, wherein metal ions in the component M1 comprise Mg 2+ 、Ca 2+ And Sr 2+ Wherein the component M2 is Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ And Ni 2+ One of the following; the loading of the component M1 is 1.5-30.0wt%, preferably 5.0-26.0wt% and the loading of the component M2 is 1.5-8.0wt%, preferably 1.5-7.1wt% calculated by metal oxide; the modified type a molecular sieve has an average crystallite size of not more than 1 μm, preferably not more than 0.9 μm, more preferably an average size of 0.70 to 0.85 μm.
The combination of the component M1 and the component M2 can be Mg and Ni 2+ Ca and Fe 2+ Sr and Co 2+ Mg and Fe 3+ Ca and Fe 2+ Ca and Ni 2+ Sr and Fe 2+ Ca and Ni 2+ Sr and Ni 2+ Etc.
In the modified A-type molecular sieve, the loading amounts of the component M1 and the component M2 are obtained through an X-ray fluorescence spectrum. For example, the elemental analysis can be performed by using the relationship that the intensity of the fluorescent radiation of each element is proportional to the concentration thereof, as measured by a ZSX100E X radiation fluorescence spectrometer of Rigaku corporation, japan, with a light pipe voltage of 40kV and a light pipe current of 250 mA. In a preferred embodiment, the modified type A molecular sieve has a loading of 18.6wt% of component M1 and a loading of 1.68wt% of component M2, calculated as metal oxide.
The average grain size of the modified A-type molecular sieve is obtained by observation and statistics of a scanning electron microscope. For example, it can be measured by S4800 scanning electron microscope (Hitachi, japan) with an acceleration voltage of 20kV, a working distance of 8mm, and a magnification of 5k-50k. And measuring the size of each grain according to a scale on the picture, measuring not less than 100 grains, and then counting. In a preferred embodiment, the modified type a molecular sieve has an average crystallite size of 793nm.
In the invention, the ethylene adsorption amount of the modified type A molecular sieve can be measured by an intelligent weight adsorption Instrument (IGA) of Hiden Isochema company, the test temperature is 30 ℃, and the test pressure is 0-100kPa. In the invention, the ethylene selectivity of the modified A-type molecular sieve in a mixed system with the ethylene/ethane volume ratio of 1:1 can be calculated by an IAST-DSLF model. In the modified A-type molecular sieve provided by the invention, the introduction of the component M1 mainly adjusts the pore canal size of the A-type molecular sieve to ensure that the pore canal size is between the dynamic sizes of ethylene and ethane, thereby enhancing the molecular sieving effect; the introduction of the component M2 mainly enhances pi-complexation of adsorption active sites of the molecular sieve on ethylene molecules, and obviously improves the selectivity of ethylene on the premise of slightly improving the adsorption capacity of ethylene. In a preferred embodiment, the modified type A molecular sieve has an ethylene adsorption of 3.61mmol/g. In a preferred embodiment, the modified type a molecular sieve has an ethylene selectivity of 11.8 in a mixed system having an ethylene/ethane volume ratio of 1:1.
The invention also provides a method for preparing the modified A-type molecular sieve, which comprises the following steps: a preparation step of a type A molecular sieve and an ion exchange modification step.
The preparation method of the A-type molecular sieve comprises the following steps:
(1) Raw materials of sodium hydroxide, an aluminum source, a silicon source and deionized water are mixed according to Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O molar ratio 2.5-4.0:0.8-1.0:1.9-3.8:100-150, uniformly mixing at room temperature to obtain initial reaction gel;
(2) Aging the initial reaction gel in the step (1) at 25-40 ℃ for 4-120 hours to obtain a mixed solution;
(3) Crystallizing the mixed solution obtained in the step (2) for 2-12h under the hydrothermal reaction condition of 50-90 ℃ and obtaining the A-type molecular sieve after suction filtration, washing and drying.
In the step (1), the raw materials of sodium hydroxide, an aluminum source, a silicon source and Na of deionized water 2 O：Al 2 O 3 ：SiO 2 ：H 2 The molar ratio of O is 2.5-4.0:0.8-1.0:1.9-3.8:100-150, preferably Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 The molar ratio of O is 2.5-3.5:0.9-1.0:1.9-2.5:110-130; the aluminum source is selected from aluminum salts, aluminates, activated alumina, aluminum alkoxides, pseudo-boehmiteAt least one of diaspore, preferably at least one of aluminate, pseudo-boehmite; the silicon source is at least one of white carbon black, silica sol, silica gel, water glass, active silicon dioxide and orthosilicate, and the silicon source is at least one of tetraethoxysilane, water glass and silica sol; the above mixture was stirred at room temperature to obtain an initial reaction gel.
In the step (2), the initial reaction gel is aged to obtain a mixed solution, wherein the aging temperature is 25-40 ℃, preferably 30-40 ℃, and the aging time is 4-120 hours, preferably 12-72 hours.
In the step (3), the mixed solution is crystallized in a hydrothermal reaction kettle at the crystallization temperature of 50-90 ℃, preferably 70-90 ℃ for 2-12 hours, preferably 4-12 hours, and the A-type molecular sieve is obtained after suction filtration and washing.
Wherein, the ion exchange modification step can be carried out according to the following operation sequence:
(1) Mixing the soluble salt containing the component M1 with an A-type molecular sieve and deionized water according to a mass ratio of 0.1-2.5:1:10, exchanging the mixed solution for 30-120min at 50-90 ℃, and then carrying out suction filtration, washing and drying;
(2) Mixing the soluble salt containing the component M2 with the product of the step (1) according to the mass ratio of the soluble salt containing the component M2, the A-type molecular sieve and the deionized water of 0.02-0.5:1:10, exchanging the mixed solution for 30-120min at the temperature of 50-90 ℃, and then carrying out suction filtration, washing and drying.
Alternatively, the ion exchange modification step is:
(1) Mixing the soluble salt containing the component M2 with an A-type molecular sieve and deionized water according to a mass ratio of 0.1-2.5:1:10, exchanging the mixed solution for 30-120min at 50-90 ℃, and then carrying out suction filtration, washing and drying;
(2) Mixing the soluble salt containing the component M1 with the product of the component (1) according to the mass ratio of the soluble salt containing the component M1, the A-type molecular sieve and the deionized water of 0.02-0.5:1:10, exchanging the mixed solution for 30-120min at the temperature of 50-90 ℃, and then carrying out suction filtration, washing and drying.
Alternatively, the ion exchange modification step is: the soluble salt containing the component M1, the soluble salt containing the component M2, the A-type molecular sieve and deionized water are mixed according to the mass ratio of 0.1-2.5:0.1-2.5: mixing at a ratio of 1:10, exchanging the mixed solution at 50-90deg.C for 30-120min, and vacuum filtering, washing, and drying.
In the ion exchange step, the soluble salt is selected from at least one of nitrate and chloride.
In the present invention, the definition in the broadest scope and each preferred definition can be combined with each other to form a new technical solution, and are also regarded as being disclosed in the present specification.
The present invention is illustrated below by way of examples, which should not be construed as limiting the scope of the invention.
Examples
I. Instrument for measuring and controlling the intensity of light
Hydrothermal reaction equipment (KLJX-811 type homogeneous reactor manufactured by Kagaku chemical equipment Co., ltd.).
Magnetic stirring equipment (DF-101S heat collection type magnetic heating stirrer manufactured by Jiangsu gold instrument technology Co., ltd.).
Vacuum filtration equipment with Buchner funnel and suction flask (SHZ-D (III) circulating water type vacuum pump manufactured by Wawa Instrument Co., ltd., consolidated city).
II. Raw materials
The type A molecular sieve synthesis reagents were all analytically pure and purchased from Beijing enoki technologies.
The reagents for ion exchange modification were all chemically pure and purchased from Alfa Aesar, usa.
Ethylene (purity > 99.99%) and ethane (99.95%) were purchased from helium northdistribution gas industry limited, beijing.
Detection method of III.A type molecular sieve
Chemical composition of modified type a molecular sieves: the elemental analysis was performed by using the relationship in which the intensity of the fluorescent radiation of each element was proportional to the concentration thereof, as measured by a ZSX100E X radiation fluorescence spectrometer of Rigaku corporation, japan, with a light tube voltage of 40kV and a light tube current of 250 mA.
Average crystallite size of modified type a molecular sieve: the acceleration voltage was 20kV, the working distance was 8mm, and the magnification was 5k-50k, as measured using S4800 scanning electron microscope from Hitachi, japan. And measuring the size of each grain according to a scale on the picture, measuring not less than 100 grains, and then counting.
Example 1
2.47g NaOH, 1.68g pseudo-boehmite, 8g water glass (SiO) were added to 33mL deionized water 2 251.5g/L, na 2 O is 176.65 g/L), stirring to obtain gel, transferring into a high-pressure hydrothermal kettle, aging at 30deg.C for 72h, heating to 90deg.C after aging, and crystallizing for 4h; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; the resulting 4A molecular sieve was weighed into 4g and 9.24g of Mg (NO 3 ) 2 ·6H 2 Mixing 10g of deionized water, performing ion exchange for 1h under the water bath condition of 80 ℃, filtering, washing to be neutral by using the deionized water, and drying at the constant temperature of 100 ℃; a further 4g of the dried sample were weighed and 1.097gNi (NO 3 ) 2 ·6H 2 Mixing O, performing ion exchange at 80 ℃ for 1h, filtering, washing with deionized water to be neutral, and drying at a constant temperature of 100 ℃ to obtain the modified A-type molecular sieve.
Fig. 1 is a scanning electron microscope image of a modified type a molecular sieve, and it can be seen from the image that the prepared modified type a molecular sieve presents regular cubes and has uniform particles.
Example 2
Adding 3.5g of NaOH, 1.35g of sodium metaaluminate and 1.88g of solid silica gel into 38.5mL of deionized water, stirring to prepare gel, transferring into a high-pressure hydrothermal kettle, aging at 30 ℃ for 72h, heating to 80 ℃ after aging is finished, and crystallizing for 6h; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; weighing 4g and 3g of anhydrous calcium chloride and 10g of deionized water, mixing, performing ion exchange for 1h under the water bath condition of 80 ℃, performing suction filtration, washing with deionized water to be neutral, and drying at the constant temperature of 100 ℃; a further 4g of dried sample was weighed and 0.25g FeCl 2 ·4H 2 O mixing, and performing ion at 80 DEG CExchanging for 1h, filtering, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Example 3
2.47g NaOH, 3.36g aluminum isopropoxide and 8g water glass (SiO) were added to 33mL deionized water 2 251.5g/L, na 2 O is 176.65 g/L), stirring to obtain gel, transferring into a high-pressure hydrothermal kettle, aging at 25deg.C for 4 hr, heating to 80deg.C after aging, and crystallizing for 12 hr; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; the obtained 4A molecular sieve was weighed into 4g and 9.69g SrCl 2 ·6H 2 Mixing 10g of deionized water, performing ion exchange for 1h under the water bath condition of 80 ℃, filtering, washing to be neutral by using the deionized water, and drying at the constant temperature of 100 ℃; a further 4g of the dried sample was weighed out, and 1.197g of CoCl 2 ·6H 2 Mixing O, performing ion exchange at 80 ℃ for 1h, filtering, washing with deionized water to be neutral, and drying at a constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Example 4
Adding 5.27g of NaOH, 3.36g of aluminum isopropoxide and 13.02g of tetraethyl orthosilicate into 44.5mL of deionized water, stirring to prepare gel, transferring into a high-pressure hydrothermal kettle, aging at 40 ℃ for 24 hours, heating to 90 ℃ after aging is finished, and crystallizing for 12 hours; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; the resulting 4A molecular sieve was weighed into 4g and 1.36g FeCl 3 ·6H 2 Mixing 10g of deionized water, performing ion exchange for 1h under the water bath condition of 80 ℃, filtering, washing to be neutral by using the deionized water, and drying at the constant temperature of 100 ℃; a further 4g of the dried sample was weighed out and 1.16g of Mg (NO 3 ) 2 ·6H 2 Mixing O, performing ion exchange at 80 ℃ for 1h, filtering, washing with deionized water to be neutral, and drying at a constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Example 5
To 41.5mL of deionized water was added 3.29g of NaOH,1.34g of pseudo-boehmite and 1.88g of solid silica gel, stirring to prepare gel, transferring the gel into a high-pressure hydrothermal kettle, aging for 96 hours at 30 ℃, heating to 70 ℃ after aging is finished, and crystallizing for 2 hours; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; weighing 4g and 3g of anhydrous calcium chloride and 10g of deionized water, mixing, performing ion exchange for 1h under the water bath condition of 80 ℃, performing suction filtration, washing with deionized water to be neutral, and drying at the constant temperature of 100 ℃; a further 4g of dried sample was weighed out and 0.125g FeCl 2 ·4H 2 Mixing O, performing ion exchange at 80 ℃ for 1h, filtering, washing with deionized water to be neutral, and drying at a constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Example 6
Adding 3.95g of NaOH, 1.52g of pseudo-boehmite and 7.54g of tetraethyl orthosilicate into 38.5mL of deionized water, stirring to prepare gel, transferring into a high-pressure hydrothermal kettle, aging at 40 ℃ for 24 hours, heating to 60 ℃ after aging is finished, and crystallizing for 10 hours; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; weighing 4g of the obtained 4A molecular sieve, 2g of anhydrous calcium chloride and 10g of deionized water, mixing, performing ion exchange for 1h under the water bath condition of 80 ℃, performing suction filtration, washing with deionized water to be neutral, and drying at the constant temperature of 100 ℃; a further 4g of the dried sample was weighed out and 0.366g of Ni (NO 3 ) 2 ·6H 2 Mixing O, performing ion exchange at 80 ℃ for 1h, filtering, washing with deionized water to be neutral, and drying at a constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Example 7
1.07g NaOH, 1.08g sodium metaaluminate and 8g water glass (SiO) were added to 35.9mL deionized water 2 251.5g/L, na 2 O is 176.65 g/L), stirring to obtain gel, transferring into a high-pressure hydrothermal kettle, aging at 30deg.C for 96 hr, heating to 70deg.C after aging, and crystallizing for 8 hr; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; the obtained 4A molecular sieve was weighed into 4g and 4.620g of anhydrousCalcium chloride, 0.731g Ni (NO) 3 ) 2 ·6H 2 Mixing 10g of deionized water, carrying out ion exchange for 1h under the water bath condition of 80 ℃, carrying out suction filtration, washing to be neutral by using the deionized water, and drying at the constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Example 8
Adding 4.74g of NaOH, 1.08g of sodium metaaluminate and 1.88g of solid silica gel into 44.5mL of deionized water, stirring to prepare gel, transferring into a high-pressure hydrothermal kettle, aging at 30 ℃ for 120 hours, heating to 50 ℃ after aging is finished, and crystallizing for 12 hours; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; the obtained 4A molecular sieve was weighed into 4g and 9.69g SrCl 2 ·6H 2 Mixing 10g of deionized water, performing ion exchange for 1h under the water bath condition of 80 ℃, filtering, washing to be neutral by using the deionized water, and drying at the constant temperature of 100 ℃; a further 4g of dried sample was weighed out and 0.75g FeCl 2 ·4H 2 Mixing O, performing ion exchange at 80 ℃ for 1h, filtering, washing with deionized water to be neutral, and drying at a constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Example 9
1.81g NaOH, 1.35g sodium metaaluminate and 8g water glass (SiO) were added to 33mL deionized water 2 251.5g/L, na 2 O is 176.65 g/L), stirring to obtain gel, transferring into a high-pressure hydrothermal kettle, aging at 30deg.C for 36h, heating to 70deg.C after aging, and crystallizing for 10h; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; weighing 4g and 3g of anhydrous calcium chloride and 10g of deionized water, mixing, performing ion exchange for 1h under the water bath condition of 80 ℃, performing suction filtration, washing with deionized water to be neutral, and drying at the constant temperature of 100 ℃; a further 4g of the dried sample was weighed out and 0.366g of Ni (NO 3 ) 2 ·6H 2 Mixing O, performing ion exchange at 80 ℃ for 1h, filtering, washing with deionized water to be neutral, and drying at a constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Example 10
Adding 4.61g of NaOH, 1.35g of sodium metaaluminate and 11.98g of tetraethyl orthosilicate into 29.6mL of deionized water, stirring to prepare gel, transferring into a high-pressure hydrothermal kettle, aging at 40 ℃ for 12 hours, heating to 60 ℃ after aging is finished, and crystallizing for 12 hours; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; the resulting 4A molecular sieve was weighed into 4g and 4.84g SrCl 2 ·6H 2 Mixing 10g of deionized water, performing ion exchange for 1h under the water bath condition of 80 ℃, filtering, washing to be neutral by using the deionized water, and drying at the constant temperature of 100 ℃; a further 4g of the dried sample was weighed out and 1.463g of Ni (NO 3 ) 2 ·6H 2 Mixing O, performing ion exchange at 80 ℃ for 1h, filtering, washing with deionized water to be neutral, and drying at a constant temperature of 100 ℃ to obtain the modified A-type molecular sieve. The scanning electron microscope diagram of the modified A-type molecular sieve is the same as the characteristic of figure 1.
Comparative example 1
2.47g NaOH, 1.68g pseudo-boehmite, 8g water glass (SiO) were added to 33mL deionized water 2 251.5g/L, na 2 O is 176.65 g/L), stirring to obtain gel, transferring into a high-pressure hydrothermal kettle, aging at 30deg.C for 72h, heating to 90deg.C after aging, and crystallizing for 4h; and (3) carrying out suction filtration on the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at a constant temperature of 100 ℃ to obtain the 4A molecular sieve.
Comparative example 2
2.47g NaOH, 1.68g pseudo-boehmite, 8g water glass (SiO) were added to 33mL deionized water 2 251.5g/L, na 2 O is 176.65 g/L), stirring to obtain gel, transferring into a high-pressure hydrothermal kettle, aging at 30deg.C for 72h, heating to 90deg.C after aging, and crystallizing for 4h; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; the resulting 4A molecular sieve was weighed into 4g and 9.24g of Mg (NO 3 ) 2 ·6H 2 Mixing 10g of deionized water, carrying out ion exchange for 1h under the water bath condition of 80 ℃, carrying out suction filtration, washing to be neutral by using the deionized water, and drying at the constant temperature of 100 ℃.
Comparative example 3
At 3Into 3mL of deionized water was added 2.47g of NaOH, 1.68g of pseudo-boehmite, 8g of water glass (SiO) 2 251.5g/L, na 2 O is 176.65 g/L), stirring to obtain gel, transferring into a high-pressure hydrothermal kettle, aging at 30deg.C for 72h, heating to 90deg.C after aging, and crystallizing for 4h; filtering the obtained hydrothermal reaction product, washing with deionized water to neutrality, and drying at constant temperature of 100 ℃ to obtain a 4A molecular sieve; the resulting 4A molecular sieve was weighed 4g and 1.097gNi (NO 3 ) 2 ·6H 2 Mixing with O, performing ion exchange at 80deg.C for 1 hr, filtering, washing with deionized water to neutrality, and drying at 100deg.C.
The data of the type and content of the component M1, the type and content of the component M2, and the grain size of the modified type A molecular sieves prepared in examples 1 to 10 are shown in Table 1.
The molecular sieve conditions and data prepared in comparative examples 1-3 are set forth in Table 1.
Test case
The molecular sieves prepared in examples and comparative examples were subjected to respective measurements of adsorption curves and ethylene adsorption amounts of ethylene and ethane on the molecular sieves at 25℃and 0 to 100kPa in a 1:1 ethylene/ethane volume ratio mixed system using an intelligent gravimetric adsorption apparatus (IGA) from Hiden Isochema company, and then calculated by IAST-DSLF model to obtain ethylene adsorption selectivity.
The adsorption curve of ethylene and ethane pure gas of the modified 5A molecular sieve of example 8 is shown in FIG. 2.
Ethylene adsorption amounts and selectivities of the modified type a molecular sieves prepared in examples 1 to 10 and the type a molecular sieves prepared in comparative examples described above are shown in table 1.
TABLE 1
Claims (11)
1. A-type modified molecular sieve is characterized by comprising a A-type molecular sieve and a metal salt active component, wherein the metal salt active component comprises a component M1 and a component M2, and metal ions in the component M1 comprise Mg 2+ 、Ca 2+ And Sr 2+ Wherein the component M2 is Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ And Ni 2+ One of the following; the loading of the component M1 is 1.5-30.0wt% and the loading of the component M2 is 1.5-8.0wt% calculated by metal oxide; the modified type a molecular sieve has an average crystallite size of no greater than 1 μm.
2. The modified type a molecular sieve of claim 1, wherein the loading of component M1 is from 5.0 to 26.0wt% and the loading of component M2 is from 1.5 to 7.5wt%.
3. The modified type a molecular sieve of claim 1, wherein the modified type a molecular sieve has an average crystallite size of no more than 0.9 μm, preferably a crystallite size of 0.70 to 0.85 μm.
4. A process for preparing a modified type a molecular sieve as claimed in any one of claims 1 to 3, comprising a step of preparing a type a molecular sieve and a step of ion exchange modification.
5. The method of claim 4, wherein the step of preparing the type a molecular sieve comprises:
(1) Raw materials of sodium hydroxide, an aluminum source, a silicon source and deionized water are mixed according to Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O molar ratio 2.5-4.0:0.8-1.0:1.9-3.8:100-150, uniformly mixing at room temperature to obtain initial reaction gel;
(2) Aging the initial reaction gel in the step (1) at 25-40 ℃ for 4-120 hours to obtain a mixed solution;
(3) Crystallizing the mixed solution obtained in the step (2) for 2-12h under the hydrothermal reaction condition of 50-90 ℃ and obtaining the A-type molecular sieve after suction filtration, washing and drying.
6. The method according to claim 5, wherein the aluminum source is at least one selected from the group consisting of aluminum salts, aluminates, activated aluminas, aluminum alkoxides, pseudo-boehmite; preferably, the aluminum source is at least one of aluminate and pseudo-boehmite.
7. The method according to claim 5, wherein the silicon source is at least one selected from the group consisting of white carbon black, silica sol, silica gel, water glass, activated silica, and orthosilicate; preferably, the silicon source is at least one selected from tetraethoxysilane, water glass and silica sol.
8. The method according to claim 4, wherein the ion exchange modification step is:
(1) Mixing the soluble salt containing the component M1 with an A-type molecular sieve and deionized water according to a mass ratio of 0.1-2.5:1:10, exchanging the mixed solution for 30-120min at 50-90 ℃, and then carrying out suction filtration, washing and drying;
(2) Mixing the soluble salt containing the component M2 with the product of the step (1) according to the mass ratio of the soluble salt containing the component M2, the A-type molecular sieve and the deionized water of 0.02-0.5:1:10, exchanging the mixed solution for 30-120min at the temperature of 50-90 ℃, and then carrying out suction filtration, washing and drying.
9. The method according to claim 4, wherein the ion exchange modification step is:
(1) Mixing the soluble salt containing the component M2 with an A-type molecular sieve and deionized water according to a mass ratio of 0.1-2.5:1:10, exchanging the mixed solution for 30-120min at 50-90 ℃, and then carrying out suction filtration, washing and drying;
(2) Mixing the soluble salt containing the component M1 with the product of the component (1) according to the mass ratio of the soluble salt containing the component M1, the A-type molecular sieve and the deionized water of 0.02-0.5:1:10, exchanging the mixed solution for 30-120min at the temperature of 50-90 ℃, and then carrying out suction filtration, washing and drying.
10. The method according to claim 4, wherein the ion exchange modification step is: the soluble salt containing the component M1, the soluble salt containing the component M2, the A-type molecular sieve and deionized water are mixed according to the mass ratio of 0.1-2.5:0.1-2.5: mixing at a ratio of 1:10, exchanging the mixed solution at 50-90deg.C for 30-120min, and vacuum filtering, washing, and drying.
11. The method according to any one of claims 8 to 10, wherein the soluble salt is at least one selected from the group consisting of nitrate and chloride.
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| CN104692410A (en) * | 2013-12-06 | 2015-06-10 | 天津工业大学 | Method for synthesizing A molecular sieve by crystallizing wet gel |
| CN104828837A (en) * | 2015-05-22 | 2015-08-12 | 山东理工大学 | Method for synthesizing submicron order NaA molecular sieve |
| CN109970075A (en) * | 2019-03-26 | 2019-07-05 | 上海工程技术大学 | A kind of method of low temperature synthesis A type molecular sieve film |
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| CN1544327A (en) * | 2003-11-20 | 2004-11-10 | 江西师范大学 | Nanometer A type molecular sieve preparation method |
| CN101205166A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院兰州化学物理研究所 | Adsorbent for low-concentration ethane separation and preparation thereof |
| CN104692410A (en) * | 2013-12-06 | 2015-06-10 | 天津工业大学 | Method for synthesizing A molecular sieve by crystallizing wet gel |
| CN104828837A (en) * | 2015-05-22 | 2015-08-12 | 山东理工大学 | Method for synthesizing submicron order NaA molecular sieve |
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