CN118239497A - Preparation method of Na-X, na-X/P molecular sieve - Google Patents
Preparation method of Na-X, na-X/P molecular sieve Download PDFInfo
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- CN118239497A CN118239497A CN202211667996.2A CN202211667996A CN118239497A CN 118239497 A CN118239497 A CN 118239497A CN 202211667996 A CN202211667996 A CN 202211667996A CN 118239497 A CN118239497 A CN 118239497A
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 71
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 60
- 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 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 38
- 229910014130 Na—P Inorganic materials 0.000 claims abstract description 35
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000499 gel Substances 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 22
- 235000019353 potassium silicate Nutrition 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- -1 alkali metal salt Chemical class 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 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 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 2
- 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 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 239000001164 aluminium sulphate Substances 0.000 claims 1
- 235000011128 aluminium sulphate Nutrition 0.000 claims 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 27
- 229910021536 Zeolite Inorganic materials 0.000 description 26
- 239000010457 zeolite Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 22
- 238000001179 sorption measurement Methods 0.000 description 15
- 230000005496 eutectics Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 2
- 229910052676 chabazite Inorganic materials 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a preparation method of a Na-X, na-X/P molecular sieve, which comprises the following steps: step 1, dissolving an aluminum source in water to obtain an aluminum source solution; step 2, dissolving an alkali source in water to obtain an alkali source solution, and then adding the alkali source solution into an aluminum source solution to obtain a mixed solution; step 3, adding a silicon source into the mixed solution under the stirring condition, adding water after the silicon source is added, and stirring to obtain gel; step 4, adding Na-P seed crystal into the gel, and then aging and dynamic crystallization; the addition amount of Na-P seed crystal is 1% -3% of the gel mass; the dynamic crystallization conditions are as follows: stirring at 100-220 rpm, crystallizing at 90-100deg.C, heating at 0.5-30deg.C/h, and crystallizing for 0.5-6h; and 5, washing and drying the crystallized product to obtain the Na-X, na-X/P molecular sieve.
Description
Technical Field
The invention belongs to the field of molecular sieve catalytic material synthesis, and particularly relates to a preparation method of a Na-X, na-X/P molecular sieve.
Background
The X-type zeolite molecular sieve belongs to an isometric crystal system, has a cubic faujasite structure (FAU), and has the same silica framework and alumina framework structure as natural faujasite. The FAU framework structure comprises two types of three-dimensional cavity structures, wherein the large cavity structure is a super cage, and the diameter of a pore canal is 12.7 angstroms; the small cavity structure is p cage with an aperture diameter of 7.4 angstroms. The X zeolite was successfully synthesized by R.M.Milton and his colleagues D.W.Breck in 1949-1954, and the molecular sieve has a good application prospect in adsorption separation. The Na-P zeolite is aluminosilicate zeolite formed by connecting silicon oxygen tetrahedron and aluminum oxygen tetrahedron through oxygen atoms, the structure is two-dimensional staggered pore canal which is composed of two eight-membered oxygen ring channels of 3.1 angstrom 4.4 angstrom and 2.6 angstrom 4.9 angstrom, and the topological structure is GIS. The Na-P zeolite has high cation exchange capacity, and can be used for gas separation, removal of heavy metals in water, use as a detergent auxiliary agent and the like. In different adsorption scenes, zeolite with different adsorption capacities is needed to be applied, in the prior art, the change of the adsorption capacity is achieved by adopting the grading of Na-A/X Na-Y/X molecular sieves, other miscellaneous crystals are easy to appear in the synthesis process, and the alkalinity of the solution in the synthesis process is too high, so that the reaction kettle is corroded.
The patent CN113548673A prepares NaX, naA, naP, naX/NaA eutectic, naX/NaP eutectic, naA/NaP eutectic or NaX/NaA/NaP eutectic molecular sieves, and utilizes lithium slag to prepare the molecular sieves, so that the synthesis cost is reduced, but the method needs to use an ultrasonic method for alkali dissolution, and the adsorption capacity cannot be accurately regulated and controlled.
Patent CN110194467A uses NaY mother liquor to prepare 13X molecular sieve, and uses NaY to provide silicon source to reduce waste water discharge, but the adsorption capacity of the molecular sieve synthesized by the method is single.
In the patent CN101704533A, CN105600803A, CN101289197A, seed crystal X zeolite is added in the process of synthesizing the X zeolite, so that the synthesis time is shortened, the relative crystallinity of a synthesized product is improved, but the adsorption capacity of the synthesized molecular sieve is also relatively single.
Disclosure of Invention
The invention aims to provide a preparation method of a Na-X, na-X/P molecular sieve, which aims to solve the problems that the adsorption capacity of the existing Na-X zeolite is basically fixed, the concentration of inorganic alkali solution used in the synthesis process is higher, and the corrosion of a synthesis reaction kettle is easy to cause.
In order to achieve the above purpose, the invention provides a preparation method of a Na-X, na-X/P molecular sieve, which comprises the following steps:
step 1, dissolving an aluminum source in water to obtain an aluminum source solution;
Step 2, dissolving an alkali source in water to obtain an alkali source solution, and then adding the alkali source solution into an aluminum source solution to obtain a mixed solution;
Step 3, adding a silicon source into the mixed solution under the stirring condition, adding water after the silicon source is added, and stirring to obtain gel;
Step 4, adding Na-P seed crystal into the gel, and then aging and dynamic crystallization; the addition amount of Na-P seed crystal is 1% -3% of the gel mass; the dynamic crystallization conditions are as follows: stirring at 100-220 rpm, crystallizing at 90-100deg.C, heating at 0.5-30deg.C/h, and crystallizing for 0.5-6h;
and 5, washing and drying the crystallized product to obtain the Na-X, na-X/P molecular sieve.
According to the preparation method of the Na-X, na-X/P molecular sieve, the silicon source is calculated by the content of silicon dioxide, and the molar ratio of H 2 O to the silicon source in the gel is 52-75:1.
According to the preparation method of the Na-X, na-X/P molecular sieve, the molar ratio of a silicon source to an aluminum source is 1.2-3.7:1, preferably 1.5-3.5:1, and the molar ratio of an alkali source to the silicon source is 1.4-4.1:1, preferably 1.6-4.0:1.
The preparation method of the Na-X, na-X/P molecular sieve comprises the steps of preparing an alkali source comprising alkali metal oxide and/or alkali metal hydroxide and an alkali metal salt, wherein the molar ratio of the alkali metal salt to the alkali metal oxide and/or the alkali metal hydroxide is 0.1-0.4:1, a step of; the alkali metal salt is a carbonate and/or bicarbonate, preferably a carbonate.
The Na-X, na-X/P molecular sieve is prepared from Na, preferably sodium hydroxide and sodium carbonate.
The preparation method of the Na-X, na-X/P molecular sieve provided by the invention further comprises the step of selecting at least one metal oxide and/or hydroxide from K, li, mg, ca and selecting at least one metal oxide and/or hydroxide from K, li, mg, ca, wherein the molar ratio of the metal oxide and/or hydroxide to the silicon source is 0.01-0.5:1.
The preparation method of the Na-X, na-X/P molecular sieve provided by the invention comprises the steps of ageing for 1-8 hours at the temperature of 40-80 ℃; the drying condition is that the drying is carried out for 2-3 hours at 100-120 ℃.
According to the preparation method of the Na-X, na-X/P molecular sieve, the stirring paddle is one or more of a straight blade flat push paddle, a straight blade downward pressing paddle and an anchor type paddle in the crystallization process.
According to the preparation method of the Na-X, na-X/P molecular sieve, the diameter of the blade is D, the distance between the blade and the inner wall of the crystallization kettle is less than 0.5D, the distance between the lower edge of the blade and the bottom of the crystallization kettle is less than 0.2D, and the width of the blade of the straight blade flat pushing paddle and the straight blade downward pressing paddle is not less than one tenth of the height in the crystallization kettle.
The preparation method of the Na-X, na-X/P molecular sieve provided by the invention comprises the steps that the aluminum source is one or more of water-soluble aluminum salt, alkali metal aluminate, aluminum alkoxide and metal aluminum, and preferably one or more of aluminum sulfate, sodium metaaluminate, aluminum nitrate, aluminum hydroxide, hydrated aluminum oxide and aluminum isopropoxide; the silicon source is one or more of water glass, white carbon black, sodium silicate, tetraethoxysilane, silica gel and diatomite, and preferably water glass.
The invention has the beneficial effects that:
The Na-P zeolite is used as seed crystal, the Na-X zeolite and Na-X/P zeolite are synthesized in the process of heteronuclear crystal transformation and competitive growth in the crystallization process by the preparation of the seed crystal and the raw materials, the temperature rising rate and the crystallization mode are regulated according to the different quantity of the added seed crystal, for example, the rotating speed of a stirring paddle and the form of the stirring paddle are regulated, the disturbance degree of the material is changed, and the growth proportion of Na-X and Na-P can be controlled, so that the adsorption capacity of the synthesized product is accurate, the content of Na-P in the obtained product is 0 to 95 percent, and the adsorption capacity of the material is flexibly adjustable from 10 to 35.2. And the addition of Na-P can effectively reduce the addition amount of inorganic alkali in the raw materials, so that the alkalinity of the mixed materials is reduced, and the long-term use of the reaction kettle is ensured.
Drawings
Fig. 1 shows XRD patterns of examples 1 to 5 of the present invention.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
Raw material or equipment source: comprises raw material names, specifications, manufacturers, etc
Evaluation analysis method:
XRD testing was performed on a Bruker diffractometer. A Cu target K α light source (λ= 0.15432 nm), a graphite monochromator, a tube voltage of 40kV and a tube current of 40mA were used. The scanning speed in the interval of 5-55 deg. is 10 deg./min. Qualitative analysis was performed using X-ray diffraction cards (JCPDS).
The dried molecular sieve is used for testing the adsorption capacity, the testing principle is that a balance is used for weighing and reading the weight, and a pressure sensor is used for reading the pressure, so that the weight value of a sample under a certain pressure is obtained, and the adsorption capacity of a product at 25 ℃ on carbon dioxide can be obtained.
Specific examples:
Example 1
(1) Firstly, 31.70g of sodium aluminate Y is dissolved in 42.56g of water and stirred to be a clear solution;
(2) Dissolving 42.55g of alkali source M1 sodium hydroxide and 12.40g of M2 sodium carbonate in 183.64g of water, stirring to obtain a clear solution, and then dropwise adding the clear solution in the step (1) to obtain a mixed solution;
(3) Slowly dropwise adding 151.34g of water glass X into the mixed solution in the step (2) under intense stirring after the aluminum source and the alkali source are completely mixed;
(4) Adding 361.69g of water, and uniformly mixing to obtain gel, wherein the molar ratio of H 2 O to water glass X (calculated by SiO 2) in the final gel is 53:1;
(5) Adding 3 percent of Na-P seed crystal, 25.23g of Na-P seed crystal into the mixed material;
(6) Aging the obtained mixture at 80 ℃ for 1h;
(7) Crystallizing the gel at 100deg.C under sealed condition for 6 hr; the temperature rising speed is 20 ℃/h, the crystallization reaction is carried out under the dynamic condition, the rotating speed of the stirring paddle is 200 rpm, and the paddle is in the shape of a straight blade downward pressing paddle.
(8) Washing the crystallized product with distilled water, drying at 100deg.C for 2 hr,
The proportion of the obtained gel is as follows: x: y=3.7:1, mx=1.4:1, m2:m1=0.1h 2 O: x=53. As shown in FIG. 1, the main characteristic peak positions of Na-X of the molecular sieve are 6.1 degrees, 23.61 degrees and 32.01 degrees, and are the same as the characteristic peak positions on PDF #38-0237 standard cards. The Na-P main characteristic peak positions of the molecular sieve are 12.46 degrees, 17.73 degrees, 21.65 degrees, 28.18 degrees and 33.44 degrees, the characteristic peak positions of the molecular sieve are the same as those of a PDF #44-0052 standard card, the product is a Na-X/P eutectic molecular sieve, the Na-P zeolite content of the synthesized product is 95 percent, and the Na-X zeolite content is 5 percent.
Example 2
(1) First, 32.59g of sodium aluminate Y is dissolved in 43.75g of water and stirred to be a clear solution;
(2) Dissolving 24.47g of alkali source M1 sodium hydroxide and 28.53g of M2 sodium carbonate in 253.35g of water, stirring to obtain a clear solution, and then dropwise adding the clear solution in the step (1) to obtain a mixed solution;
(3) Slowly dropwise adding 151.34g of water glass X into the mixed solution in the step (2) under intense stirring after the aluminum source and the alkali source are completely mixed;
(4) Adding 252.12g of water, and uniformly mixing to obtain gel, wherein the molar ratio of H 2 O to water glass X (calculated by SiO 2) in the final gel is 50:1;
(5) Adding 16.18g of Na-P seed crystal accounting for 2 percent of the total weight of the mixture into the mixture;
(6) Aging the obtained mixture at 40 ℃ for 6 hours;
(7) Crystallizing the gel at 95deg.C under sealed condition for 0.5 hr; the temperature rising rate is 18 ℃/h, the rotation speed of a downward pressing type paddle is selected to carry out crystallization reaction, and the paddle is in the shape of a straight blade downward pressing paddle.
(8) Washing the crystallized product with distilled water, and drying at 90 ℃ for 3 hours, wherein the proportion of the obtained gel is as follows: x: y=3.6:1, mx=1.6:1, m2:m1=0.2, h 2 O: x=50.
As shown in fig. 1, the main characteristic peak positions of na—x of the molecular sieve are 6.1 °, 9.86 °, 11.73 °, 15.45 °, 18.43 °, 20.07 °, 23.61 °, 27.39 °, 30.33 °, 32.01 °, 33.63 °. The same as the characteristic peak position on the PDF #38-0237 standard card. The Na-P main characteristic peak positions of the molecular sieve are 12.46 degrees, 17.73 degrees, 21.65 degrees, 28.18 degrees and 33.44 degrees, the characteristic peak positions of the molecular sieve are the same as those of a PDF #44-0052 standard card, the product is a Na-X/P eutectic molecular sieve, the Na-P zeolite content of the synthesized product is 36 percent, and the Na-X zeolite content is 64 percent.
Example 3
(1) Firstly, 39.10g of sodium aluminate Y is dissolved in 52.48g of water and stirred to be a clear solution;
(2) Dissolving 79.37g of alkali source M1 sodium hydroxide and 23.14g of M2 sodium carbonate in 342.58g of water, stirring to obtain a clear solution, and then dropwise adding the clear solution in the step (1) to obtain a mixed solution;
(3) Slowly dropwise adding 151.34g of water glass X into the mixed solution in the step (2) under intense stirring after the aluminum source and the alkali source are completely mixed;
(4) Adding 283.15g of water, and uniformly mixing to obtain gel, wherein the molar ratio of H 2 O to water glass X (calculated by SiO 2) in the final gel is 60:1;
(5) Adding 9.7g of Na-P seed crystal accounting for 1 percent of the total weight of the mixture into the mixture;
(6) Aging the obtained mixture at 60 ℃ for 3 hours;
(7) Crystallizing the gel for 4 hours under the airtight condition of 80 ℃; the temperature rising speed is 30 ℃/h, the rotation speed of 220rpm of the anchor type paddle is selected for crystallization reaction, and the paddle is the anchor type paddle.
(8) The crystallized product was washed with distilled water and dried at 100℃for 2 hours. The proportion of the obtained gel is as follows: x: y=3.0:1, mx=2.1:1, m2:m1=0.1, h 2 O: x=60.
As shown in fig. 1, the main characteristic peak positions of na—x of the molecular sieve are 6.1 °, 9.86 °, 11.73 °, 15.45 °, 18.43 °, 20.07 °, 23.61 °, 27.39 °, 30.33 °, 32.01 °, 33.63 °. The same as the characteristic peak position on the PDF #38-0237 standard card. The Na-P main characteristic peak positions of the molecular sieve are 12.46 degrees, 17.73 degrees, 21.65 degrees, 28.18 degrees and 33.44 degrees, the characteristic peak positions of the molecular sieve are the same as those of a PDF #44-0052 standard card, the product is a Na-X/P eutectic molecular sieve, the Na-P zeolite content of the synthesized product is 10 percent, and the Na-X zeolite content is 90 percent.
Example 4
(1) Firstly, 19.55g of sodium aluminate Y is dissolved in 26.24g of water and stirred to be a clear solution;
(2) Dissolving 105.75g of alkali source M1 sodium hydroxide and 117.14g of M2 sodium carbonate in 444.88g of water, stirring until the solution is clear, and then dropwise adding the clear solution in the step (1) to obtain a mixed solution;
(3) After completely mixing an aluminum source and an alkali source, slowly dropwise adding 90.80g of water glass X into the mixed solution in the step (2) under intense stirring;
(4) Adding 36.31g of water, and uniformly mixing to obtain gel, wherein the molar ratio of H2O to water glass X (calculated by SiO 2) in the final gel is 73:1;
(5) Adding 8.4g of Na-P seed crystal accounting for 1 percent of the total weight of the mixture into the mixture;
(6) Aging the obtained mixture at 40 ℃ for 8 hours;
(7) Crystallizing the gel at 80deg.C under sealed condition for 1 hr; the temperature rising speed is 13 ℃/h, the rotation speed of the anchor type paddle 220rpm is selected to carry out crystallization reaction in a ventilated state, and the paddle is in the shape of the anchor type paddle.
(8) The crystallized product was washed with distilled water and dried at 100℃for 2 hours.
The proportion of the obtained gel is as follows: x: y=3.6:1, mx=4:1, m2:m1=0.38, h 2 O: x=73.
As shown in fig. 1, the main characteristic peak positions of the molecular sieve are 6.1 °, 9.86 °, 11.73 °, 15.45 °, 18.43 °, 20.07 °, 23.61 °, 27.39 °, 30.33 °, 32.01 °, 33.63 °. The characteristic peak positions are the same as those on PDF #38-0237 standard card, which shows that the Na-X molecular sieve is prepared and obtained without other miscellaneous crystals.
Example 5
(1) Firstly, 28.53g of sodium aluminate Y is dissolved in 38.29g of water and stirred to be a clear solution;
(2) Dissolving 43.49g of alkali source M1 sodium hydroxide and 38.04g of M2 sodium carbonate in 119.57g of water, stirring until the solution is clear, and then dropwise adding the clear solution in the step (1) to obtain a mixed solution;
(3) Slowly dropwise adding 139.21g of water glass X into the mixed solution in the step (2) under intense stirring after the aluminum source and the alkali source are completely mixed;
(4) Adding 475.66g of water, and uniformly mixing to obtain gel, wherein the molar ratio of H 2 O to water glass X (calculated by SiO 2) in the final gel is 62:1;
(5) 17.6g Na-P seed crystal accounting for 2 percent of the total weight of the mixture is added into the mixture;
(6) Aging the obtained mixture at 80 ℃ for 2 hours;
(7) Crystallizing the gel at 100deg.C under sealed condition for 2 hr; the temperature rising rate is 0.5 ℃/h, the crystallization reaction is carried out at the rotating speed of 100 minutes of the straight blade paddle, and the paddle is in the shape of a straight blade downward pressing paddle.
(8) Washing the crystallized product with distilled water, drying at 100deg.C for 2 hr,
The proportion of the obtained gel is as follows: x: y=3.7:1, mx=1.7:1, m2:m1=0.3, h 2 O: x=62.
As shown in FIG. 1, the main characteristic peak positions of Na-X of the molecular sieve are 6.1 DEG, 9.86 DEG, 11.73 DEG, 15.45 DEG, 23.61 DEG, 27.39 DEG and 32.01 deg. The same as the characteristic peak position on the PDF #38-0237 standard card. The Na-P main characteristic peak positions of the molecular sieve are 12.46 degrees, 17.73 degrees, 21.65 degrees, 28.18 degrees and 33.44 degrees, the characteristic peak positions of the molecular sieve are the same as those of a PDF #44-0052 standard card, the product is a Na-X/P eutectic molecular sieve, the Na-P zeolite content of the synthesized product is 82 percent, and the Na-X zeolite content of the synthesized product is 18 percent.
Example 6
(1) Firstly, 51.26g of aluminum sulfate Y is dissolved in 68.79g of water and stirred to be a clear solution;
(2) Dissolving 24.47g of alkali source M1 sodium hydroxide, 28.53g of M2 sodium carbonate and 27.29g of M3 potassium hydroxide in 117.75g of water, stirring to obtain a clear solution, and then dropwise adding the clear solution in the step (1) to obtain a mixed solution;
(3) Slowly dropwise adding 95.58g of water glass X into the mixed solution in the step (2) under vigorous stirring after the aluminum source and the alkali source are completely mixed;
(4) Adding 569.53g of water, and uniformly mixing to obtain gel, wherein the molar ratio of H 2 O to water glass X (calculated by SiO 2) in the final gel is 60:1;
(5) Adding 9.4g of Na-P seed crystal accounting for 1 percent of the total weight of the mixture into the mixture;
(6) Aging the obtained mixture at 40 ℃ for 6 hours;
(7) Crystallizing the gel for 4 hours under the airtight condition of 90 ℃; the temperature rising speed is 16 ℃/h, the crystallization reaction is carried out under the rotation speed of 220 rpm of the anchor type paddle, and the paddle is the anchor type paddle.
(8) Washing the crystallized product with distilled water, drying at 100deg.C for 2 hr,
The proportion of the obtained gel is as follows: x: y=1.4:1, mx=2.1:1, m2:m1=0.4, m3:m1=0.3, h 2 O: x=60.
The content of the synthesized Na-P zeolite is 5% and the content of Na-X zeolite is 95%.
The main characteristic peak positions of Na-X of the molecular sieve are 6.1 degrees, 9.86 degrees, 11.73 degrees, 15.45 degrees, 18.43 degrees, 20.07 degrees, 23.61 degrees, 27.39 degrees, 30.33 degrees, 32.01 degrees and 33.63 degrees. The same as the characteristic peak position on the PDF #38-0237 standard card. The Na-P main characteristic peak positions of the molecular sieve are 12.46 degrees, 21.65 degrees, 28.18 degrees and 33.44 degrees, the characteristic peak positions of the molecular sieve are the same as those of a PDF #44-0052 standard card, the product is a Na-X/P eutectic molecular sieve, the Na-P zeolite content of the synthesized product is 82 percent, and the Na-X zeolite content is 18 percent.
Comparative example 1
(1) Firstly, 31.70g of sodium aluminate Y is dissolved in 42.56g of water and stirred to be a clear solution;
(2) Dissolving 42.55g of alkali source M1 sodium hydroxide and 12.40g of M2 sodium carbonate in 183.64g of water, stirring to obtain a clear solution, and then dropwise adding the clear solution in the step (1) to obtain a mixed solution;
(3) Slowly dropwise adding 151.34g of water glass X into the mixed solution in the step (2) under intense stirring after the aluminum source and the alkali source are completely mixed;
(4) Adding 361.69g of water, and uniformly mixing to obtain gel, wherein the molar ratio of H 2 O to water glass X (calculated by SiO 2) in the final gel is 53:1;
(5) Adding 3 percent of Na-P seed crystal, 25.23g of Na-P seed crystal into the mixed material;
(6) Aging the obtained mixture at 80 ℃ for 1h;
(7) Crystallizing the gel at 100deg.C under sealed condition for 6 hr;
(8) Washing the crystallized product with distilled water, drying at 100deg.C for 2 hr,
The proportion of the obtained gel is as follows: x: y=3.7:1, mx=1.4:1, m2:m1=0.1h 2 O: x=53. The product obtained is a mixture of chabazite and Na-X.
Comparative example 2
(1) Firstly, 51.26g of sodium aluminate Y is dissolved in 68.79g of water and stirred to be a clear solution;
(2) Dissolving 24.47g of alkali source M1 sodium hydroxide, 28.53g of M2 sodium carbonate and 27.29g of M3 potassium hydroxide in 117.75g of water, stirring to obtain a clear solution, and then dropwise adding the clear solution in the step (1) to obtain a mixed solution;
(3) Slowly dropwise adding 95.58g of water glass X into the mixed solution in the step (2) under vigorous stirring after the aluminum source and the alkali source are completely mixed;
(4) Adding 569.53g of water, and uniformly mixing to obtain gel, wherein the molar ratio of H2O to water glass X (calculated by SiO 2) in the final gel is 60:1;
(5) Adding 9.4g of Na-P seed crystal accounting for 1 percent of the total weight of the mixture into the mixture;
(6) Aging the obtained mixture at 40 ℃ for 6 hours;
(7) The gel obtained was crystallized for 4 hours at 90℃under closed conditions.
(8) Washing the crystallized product with distilled water, drying at 100deg.C for 2 hr,
The proportion of the obtained gel is as follows: x: y=1.4:1, mx=2.1:1, m2:m1=0.4, m3:m1=0.3, h 2 O: x=60,
A mixture of synthesized Na-X and chabazite.
Example 7:
The adsorption capacities of the zeolite thus synthesized were measured using the zeolite prepared in example 1, example 2, example 3, example 4, and the specific results and data are shown in Table 1, and it can be seen from Table 1 that the contents of Na-P and Na-X were different and the adsorption capacities for carbon dioxide were also different.
TABLE 1 adsorption Capacity of products for carbon dioxide for Na-P and Na-X content
Table 2 proportion of the components in examples and comparative examples
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the Na-X, na-X/P molecular sieve is characterized by comprising the following steps:
step 1, dissolving an aluminum source in water to obtain an aluminum source solution;
Step 2, dissolving an alkali source in water to obtain an alkali source solution, and then adding the alkali source solution into an aluminum source solution to obtain a mixed solution;
Step 3, adding a silicon source into the mixed solution under the stirring condition, adding water after the silicon source is added, and stirring to obtain gel;
Step 4, adding Na-P seed crystal into the gel, and then aging and dynamic crystallization; the addition amount of Na-P seed crystal is 1% -3% of the gel mass; the dynamic crystallization conditions are as follows: stirring at 100-220 rpm, crystallizing at 90-100deg.C, heating at 0.5-30deg.C/h, and crystallizing for 0.5-6h;
and 5, washing and drying the crystallized product to obtain the Na-X, na-X/P molecular sieve.
2. The method for preparing a Na-X, na-X/P molecular sieve according to claim 1, wherein the molar ratio of H 2 O to silicon source in the gel is 52-75:1, based on the silicon dioxide content.
3. The method for preparing a Na-X, na-X/P molecular sieve according to claim 1, wherein the molar ratio of the silicon source to the aluminum source is 1.2-3.7:1, preferably 1.5-3.5:1, and the molar ratio of the alkali source to the silicon source is 1.4-4.1:1, preferably 1.6-4.0:1.
4. The method for preparing a Na-X, na-X/P molecular sieve according to claim 1, wherein the alkali source comprises an alkali metal oxide and/or an alkali metal hydroxide, and an alkali metal salt, and the molar ratio of the alkali metal salt to the alkali metal oxide and/or the alkali metal hydroxide is 0.1 to 0.4:1, a step of; the alkali metal salt is a carbonate and/or bicarbonate, preferably a carbonate.
5. The method for preparing a Na-X, na-X/P molecular sieve according to claim 4, wherein the alkali metal is Na, preferably the alkali source is sodium hydroxide and sodium carbonate.
6. The method for preparing a Na-X, na-X/P molecular sieve according to claim 5, wherein the alkali source further comprises an oxide and/or hydroxide of at least one metal selected from K, li, mg, ca and the molar ratio of the oxide and/or hydroxide of at least one metal selected from K, li, mg, ca to the silicon source is 0.01-0.5:1.
7. The method for preparing a Na-X, na-X/P molecular sieve according to claim 1, wherein the aging condition is aging for 1-8 hours at 40-80 ℃; the drying condition is that the drying is carried out for 2-3 hours at 100-120 ℃.
8. The method for preparing Na-X, na-X/P molecular sieves according to claim 1, wherein the stirring paddle is one or more of a straight blade flat push paddle, a straight blade down press paddle, and an anchor paddle.
9. The method for preparing the Na-X, na-X/P molecular sieve according to claim 8, wherein the diameter of the blade is D, the distance between the blade and the inner wall of the crystallization kettle is less than 0.5D, the distance between the lower edge of the blade and the bottom of the crystallization kettle is less than 0.2D, and the width of the blade of the straight blade flat pushing paddle and the straight blade downward pressing paddle is not less than one tenth of the height in the crystallization kettle.
10. The method for preparing a Na-X, na-X/P molecular sieve according to claim 1, wherein the aluminium source is one or more of water-soluble aluminium salts, alkali metal aluminates, aluminium alkoxides and metallic aluminium, preferably one or more of aluminium sulphate, sodium metaaluminate, aluminium nitrate, aluminium hydroxide, hydrated alumina, aluminium isopropoxide; the silicon source is one or more of water glass, white carbon black, sodium silicate, tetraethoxysilane, silica gel and diatomite, and preferably water glass.
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