CN110627087A - Method for synthesizing low-silicon faujasite raw powder by liquid phase seed crystal method - Google Patents
Method for synthesizing low-silicon faujasite raw powder by liquid phase seed crystal method Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 68
- 239000010703 silicon Substances 0.000 title claims abstract description 68
- 239000013078 crystal Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000000843 powder Substances 0.000 title claims abstract description 48
- 239000007791 liquid phase Substances 0.000 title claims abstract description 40
- 239000012013 faujasite Substances 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 60
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 35
- 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 abstract description 34
- 239000012670 alkaline solution Substances 0.000 claims abstract description 34
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 34
- 239000011734 sodium Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- 239000011591 potassium Substances 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 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 15
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 239000002801 charged material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 239000011863 silicon-based powder Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229910014306 BSiO2 Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000010413 mother solution Substances 0.000 claims 1
- 238000010899 nucleation Methods 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052665 sodalite Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A method for synthesizing low-silicon faujasite raw powder by a liquid phase crystal seed method belongs to the technical field of molecular sieves. The method for synthesizing the low-silicon faujasite raw powder by the liquid phase seed crystal method comprises the following steps: s1, preparing seed crystals; respectively preparing a first solution containing an aluminum element and a sodium element and a second solution containing a silicon element and a sodium element according to the material ratio of liquid-phase crystal seed synthesis, mixing and stirring the first solution and the second solution uniformly, and then reacting to obtain liquid-phase crystal seeds; s2, preparing raw powder; respectively preparing an aluminum-containing alkaline solution containing at least one element of potassium and sodium and a silicon-containing alkaline solution containing at least one element of potassium and sodium according to the material proportion of the raw powder, mixing and stirring the aluminum-containing alkaline solution and the silicon-containing alkaline solution uniformly, adding liquid phase crystal seeds in the mixing process, aging and crystallizing, and finally separating and drying to obtain the LSX raw powder. The invention can directly synthesize and prepare the high-quality LSX raw powder by the conventional raw materials for synthesizing the molecular sieve.
Description
Technical Field
The invention relates to a technology in the field of molecular sieves, in particular to a method for synthesizing low-silicon faujasite raw powder by a liquid phase crystal seed method.
Background
Generally, artificially synthesized Faujasite (FAU) is classified into X-type and Y-type molecular sieves according to the silica-alumina ratio, and the silica-alumina molar ratio (SiO)2/Al2O3) Faujasites in the range of 2.0-2.2 are known as low silicon faujasites, also known as low silicon type X molecular sieves (LSX). Related research has found that LSX is an excellent adsorbent, which makes it useful in oxygen enrichment, hydrogen storage, gas purification and drying, tail gas treatment, environmental protection, and hydrocarbon fluidsThe method has application in the fields of phase adsorption separation and the like. The wide application prospect of LSX promotes each mechanism to continuously optimize and improve the production process flow, improves the product quality and reduces the process cost, thereby meeting the market application requirements.
At present, LSX is directly synthesized, and relates to material mixing, so that gelation phenomenon is easily generated in the material mixing process, impurity phases are generated, and the crystallinity of a product is influenced. In order to solve the problems, the material mixing process needs to be finely controlled and matched with low-temperature long-time aging treatment. In addition, impurity phases are very likely to be generated in other steps of the LSX synthesis, and the degree of crystallization is not high due to improper temperature control. In order to improve the quality of the LSX product, a method for synthesizing the LSX product by taking LSX powder as seed crystal is developed at home at present. However, the quality of the LSX product prepared by the method is greatly affected by the quality of the LSX powder seed crystal, so that a batch of LSX raw powder with better quality is synthesized first to ensure the smooth implementation of the powder seed crystal method. The current high-quality LSX raw powder depends on the precise and strict control of the synthesis process, and has lower operational flexibility, higher requirements on the parameter control of the current high-quality LSX raw powder synthesis process and lower production operational flexibility.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for synthesizing low-silicon faujasite raw powder by a liquid phase crystal seed method, and high-quality LSX raw powder can be synthesized by controlling the requirements through lower process parameters.
The invention comprises the following steps:
s1, preparing seed crystals; respectively preparing a first solution containing an aluminum element and a sodium element and a second solution containing a silicon element and a sodium element according to the material ratio of liquid-phase crystal seed synthesis, mixing and stirring the first solution and the second solution uniformly, and then reacting to obtain liquid-phase crystal seeds; preferably, the liquid phase seed crystal is prepared by reacting for 10-240min at 20-80 ℃;
s2, preparing raw powder; respectively preparing an aluminum-containing alkaline solution containing at least one element of potassium and sodium and a silicon-containing alkaline solution containing at least one element of potassium and sodium according to the material proportion of the raw powder, mixing and stirring the aluminum-containing alkaline solution and the silicon-containing alkaline solution uniformly, adding liquid phase crystal seeds in the mixing process, aging and crystallizing, and finally separating and drying to obtain the LSX raw powder.
In step S1, the molar ratio of the charged materials is ANa2O·BSiO2·Al2O3·CH2O, wherein A is 5-20, B is 2-20, and C is 100-1000.
In the materials charged in step S1:
the aluminum element is from an aluminum source, and the aluminum source is one or more of aluminum hydroxide, aluminum oxide, pseudo-boehmite, alumina sol, sodium metaaluminate and aluminum powder;
the silicon element is from a silicon source, and the silicon source is one or more of silicon oxide, sodium silicate, silica gel, silica sol and silicon powder;
the sodium element is all from sodium hydroxide except the silicon source and/or the aluminum source.
In step S2, the molar ratio of all the charged materials is aNa2O·bK2O·xSiO2·Al2O3·yH2O, wherein a/(a + b) is 0.7-0.8, (a + b)/x is 2.0-3.5, x is 1.8-2.5, y/a is 16-20; preferably, Al is used2O3The mole ratio of the liquid phase seed crystal in all the materials is 0.01-10%.
In the materials charged in step S2:
the aluminum element is from an aluminum source, and the aluminum source is one or more of aluminum hydroxide, aluminum oxide, pseudo-boehmite, alumina sol, sodium metaaluminate, potassium metaaluminate and aluminum powder;
the silicon element is from a silicon source, and the silicon source is one or more of silicon oxide, sodium silicate, potassium silicate, silica gel, silica sol and silicon powder;
the potassium element except the silicon source and/or the aluminum source is introduced and is completely derived from potassium hydroxide;
the sodium element is all from sodium hydroxide except the silicon source and/or the aluminum source.
In step S2, the aluminum-containing alkaline solution is added into the silicon-containing alkaline solution at a uniform speed at a stirring speed of 500-2000rpm, the adding time is 5-20min, the liquid phase seed crystal is added after the adding is finished for 5-10min, and the stirring is continued for 10-60min, so as to obtain a uniform fluid.
In step S2, aging at 20-80 deg.C for 1-24 hr, heating to crystallization temperature within 0.5-2 hr, crystallizing at 70-100 deg.C for 1-6 hr while stirring at 50-500rpm, and cooling to crystallization temperature of not higher than 40 deg.C within 0.5-2 hr.
After crystallization is finished, the crystallized product is filtered and washed by deionized water until the pH value of a washing liquid is less than 11, and then the crystallized product is dried overnight at the temperature of 100-125 ℃ to obtain LSX raw powder, wherein the washing liquid and the mother liquid can be calibrated for recycling.
Technical effects
Compared with the prior art, the method introduces the seed crystal for LSX synthesis, adopts the liquid-phase seed crystal as the guiding agent and the template agent, is easier to form high crystallinity in the synthesis process, avoids the generation of impurity phases, strengthens the operation flexibility of the synthesis process, reduces the requirement on parameter control of each section, and solves the problems that the traditional process needs to strictly control the feeding, mixing, stirring, heating and system uniformity and has high requirement on deviation control in the process amplification process.
Detailed Description
The present invention will be described in detail with reference to specific embodiments. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
The method for synthesizing the low-silicon faujasite raw powder by the liquid phase seed crystal method comprises the following steps:
s1, preparing seed crystals; respectively preparing a first solution containing an aluminum element and a sodium element and a second solution containing a silicon element and a sodium element according to the material ratio of liquid-phase crystal seed synthesis, mixing and stirring the first solution and the second solution uniformly, and then reacting to obtain liquid-phase crystal seeds; preferably, the liquid phase seed crystal is prepared by reacting for 10-240min at 20-80 ℃;
s2, preparing raw powder; respectively preparing an aluminum-containing alkaline solution containing at least one element of potassium and sodium and a silicon-containing alkaline solution containing at least one element of potassium and sodium according to the material proportion of the raw powder, mixing and stirring the aluminum-containing alkaline solution and the silicon-containing alkaline solution uniformly, adding liquid phase crystal seeds in the mixing process, aging and crystallizing, and finally separating and drying to obtain the LSX raw powder.
In step S1, the molar ratio of the charged materials is ANa2O·BSiO2·Al2O3·CH2O, wherein A is 5-20, B is 2-20, and C is 100-1000.
In the materials charged in step S1:
the aluminum element is from an aluminum source, and the aluminum source is one or more of aluminum hydroxide, aluminum oxide, pseudo-boehmite, alumina sol, sodium metaaluminate and aluminum powder;
the silicon element is from a silicon source, and the silicon source is one or more of silicon oxide, sodium silicate, silica gel, silica sol and silicon powder;
the sodium element is all from sodium hydroxide except the silicon source and/or the aluminum source.
In step S2, the molar ratio of all the charged materials is aNa2O·bK2O·xSiO2·Al2O3·yH2O, wherein a/(a + b) is 0.7-0.8, (a + b)/x is 2.0-3.5, x is 1.8-2.5, y/a is 16-20; preferably, Al is used2O3The mole ratio of the liquid phase seed crystal in all the materials is 0.01-10%.
In the materials charged in step S2:
the aluminum element is from an aluminum source, and the aluminum source is one or more of aluminum hydroxide, aluminum oxide, pseudo-boehmite, alumina sol, sodium metaaluminate, potassium metaaluminate and aluminum powder;
the silicon element is from a silicon source, and the silicon source is one or more of silicon oxide, sodium silicate, potassium silicate, silica gel, silica sol and silicon powder;
the potassium element except the silicon source and/or the aluminum source is introduced and is completely derived from potassium hydroxide;
the sodium element is all from sodium hydroxide except the silicon source and/or the aluminum source.
In step S2, the aluminum-containing alkaline solution is added into the silicon-containing alkaline solution at a uniform speed at a stirring speed of 500-2000rpm, the adding time is 5-20min, the liquid phase seed crystal is added after the adding is finished for 5-10min, and the stirring is continued for 10-60min, so as to obtain a uniform fluid.
In step S2, aging at 20-80 deg.C for 1-24 hr, heating to crystallization temperature within 0.5-2 hr, crystallizing at 70-100 deg.C for 1-6 hr while stirring at 50-500rpm, and cooling to crystallization temperature of not higher than 40 deg.C within 0.5-2 hr.
After crystallization is finished, the crystallized product is filtered and washed by deionized water until the pH value of a washing liquid is less than 11, and then the crystallized product is dried overnight at the temperature of 100-125 ℃ to obtain LSX raw powder, wherein the washing liquid and the mother liquid can be calibrated for recycling.
Example 1
S1, preparing seed crystals; this example is in accordance with 15Na2O·10SiO2·Al2O3·180H2Preparing a first solution and a second solution, mixing and stirring the first solution and the second solution uniformly, and reacting at 40 ℃ for 60min to obtain liquid-phase seed crystals;
s2, preparing raw powder; according to the total material 4.745Na2O·1.755K2O·2SiO2·Al2O3·110.5H2Respectively preparing an aluminum-containing alkaline solution and a silicon-containing alkaline solution by using O (the liquid phase seed crystal accounts for 5% of the total material in terms of molar ratio of aluminum oxide) containing the liquid phase seed crystal; uniformly mixing aluminum-containing alkaline solution and silicon-containing alkaline solution within 10min at a stirring speed of 600rpm, adding liquid phase seed crystal after 5min of material addition, continuously stirring for 15min, then loading into a reaction vessel, aging for 2h at 80 ℃, heating to 70 ℃ within 0.5h, completing crystallization in 70 ℃ water bath for 5h at a stirring speed of 100rpm, cooling the crystallized product to 30 ℃ within 0.5h after crystallization, filtering, and washing until the pH value of the washing solution is reduced<And 11, drying the product at the temperature of 100 ℃ overnight to obtain LSX raw powder.
In step S1, the first solution is prepared by dissolving sodium metaaluminate in water and then adding sodium hydroxide, and the second solution is water glass (liquid-2, GB/T4209-.
In step S2, the aluminum-containing alkaline solution is prepared by dissolving sodium metaaluminate in water and then adding sodium hydroxide and potassium hydroxide, and the silicon-containing alkaline solution is water glass (liquid-2, GB/T4209-2008 industrial sodium silicate).
And (3) carrying out XRD test on the dried LSX raw powder at a sweep speed of 5 ℃/min, wherein the result shows that the LSX phase main peak (111) peak value 2936, the heterocrystal sodalite phase main peak (110) peak value 66 and the ratio of the LSX phase main peak value to the heterocrystal sodalite phase main peak (110) peak value is 44.48.
Example 2
S1, preparing seed crystals; according to 15Na2O·10SiO2·Al2O3·180H2Preparing silicon-containing liquid and aluminum-containing liquid, preparing first solution and second solution, mixing and stirring the first solution and the second solution uniformly, and then reacting at 40 ℃ for 60min to obtain liquid-phase seed crystal.
S2, preparing raw powder; according to the total material 3.75Na2O·1.25K2O·2SiO2·Al2O3·75H2Preparing an aluminum-containing alkaline solution and a silicon-containing alkaline solution respectively by using the liquid-phase seed crystal containing O and 5% of the total material in terms of molar ratio of aluminum oxide; uniformly mixing aluminum-containing alkaline solution and silicon-containing alkaline solution within 10min at a stirring speed of 600rpm, adding liquid phase seed crystal after 5min of material addition, continuously stirring for 15min, then loading into a reaction vessel, aging for 2h at 80 ℃, heating to 70 ℃ within 0.5h, completing crystallization in 70 ℃ water bath for 5h at a stirring speed of 100rpm, cooling the crystallized product to 30 ℃ within 0.5h after crystallization, filtering, and washing until the pH value of the washing solution is reduced<And 11, drying the product at the temperature of 100 ℃ overnight to obtain LSX raw powder.
In step S1, the first solution is prepared by dissolving sodium metaaluminate in water and then adding sodium hydroxide, and the second solution is water glass (liquid-2, GB/T4209-.
In step S2, the aluminum-containing alkaline solution is prepared by dissolving sodium metaaluminate in water and then adding sodium hydroxide and potassium hydroxide, and the silicon-containing alkaline solution is water glass (liquid-2, GB/T4209-.
XRD test is carried out on the dried LSX raw powder at the sweep speed of 5 ℃/min, and the result shows that the LSX phase main peak (111) peak value 2632, the heterocrystal sodalite phase main peak (110) peak value 112 and the ratio of 23.5 are obtained.
Comparative example 1
This example was carried out according to the total amount of 4.745Na2O·1.755K2O·2SiO2·Al2O3·110.5H2O respectively preparing a silicon-containing liquid and an aluminum-containing liquid, dissolving sodium metaaluminate serving as the aluminum-containing liquid in water, adding sodium hydroxide and potassium hydroxide to form a clear solution, uniformly adding water glass (liquid-2, GB/T4209-supplement 2008 industrial sodium silicate) into the aluminum-containing liquid within 10min, stirring for 30min, putting into a reaction container, carrying out water bath at 70 ℃ for 3h, reacting at 100 ℃ for 2h, filtering and washing the reaction product until the pH value is adjusted to be the same as the pH value<11, the product was dried at 100 ℃ overnight to give a LSX powder.
XRD test is carried out on the dried powder at the sweep speed of 5 ℃/min, and the result shows that the LSX phase main peak (111) peak value 2136, the heterocrystal sodalite phase main peak (110) peak value 60 and the ratio is 35.6.
Comparative example 2
This example followed a total of 3.75Na2O·1.25K2O·2SiO2·Al2O3·75H2Preparing silicon-containing liquid and aluminum-containing liquid respectively by O, dissolving sodium metaaluminate in water, adding sodium hydroxide and potassium hydroxide to form clear solution, adding water glass (liquid-2, GB/T4209-2008 industrial sodium silicate) into the aluminum-containing liquid uniformly in 10min, stirring for 30min, placing into a reaction container, carrying out water bath at 70 ℃ for 3h, reacting at 100 ℃ for 2h, filtering and washing the reaction product until the pH value is adjusted to be equal to<11, the product was dried at 100 ℃ overnight to give a LSX powder.
XRD test of the dried powder at sweep speed of 5 deg.C/min showed 1958 as the major peak of LSX phase (111), 272 as the major peak of heterocrystal sodalite phase (110), and a ratio of 7.20.
From comparative examples 1 and 2, it can be seen that as the concentration of Si/Al in the reaction mass increases, the crystallinity of the product decreases significantly and the impurity phase of the product increases significantly under the same conditions.
From the comparison between example 1 and comparative example 1, and between example 2 and comparative example 2, it can be seen that the crystallinity of the product is remarkably improved and the impurity phase of the product is remarkably reduced under the same conditions when the liquid phase seed crystal is added in example 1 and example 2.
It is to be emphasized that: the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. A method for synthesizing low-silicon faujasite raw powder by a liquid phase seed crystal method is characterized by comprising the following steps:
s1, preparing seed crystals; respectively preparing a first solution containing an aluminum element and a sodium element and a second solution containing a silicon element and a sodium element according to the material ratio of liquid-phase crystal seed synthesis, mixing and stirring the first solution and the second solution uniformly, and then reacting to obtain liquid-phase crystal seeds;
s2, preparing raw powder; respectively preparing an aluminum-containing alkaline solution containing at least one element of potassium and sodium and a silicon-containing alkaline solution containing at least one element of potassium and sodium according to the material proportion of the raw powder, mixing and stirring the aluminum-containing alkaline solution and the silicon-containing alkaline solution uniformly, adding liquid phase crystal seeds in the mixing process, aging and crystallizing, and finally separating and drying to obtain the LSX raw powder.
2. The method for synthesizing low-silicon faujasite raw powder according to claim 1, wherein the feed material is fed in the step S1 according to the molar ratio ANa2O·BSiO2·Al2O3·CH2O, wherein A is 5-20, B is 2-20, and C is 100-1000.
3. The method for synthesizing low-silicon faujasite raw powder according to claim 1 or 2, characterized in that in the material charged in step S1:
the aluminum element is from an aluminum source, and the aluminum source is one or more of aluminum hydroxide, aluminum oxide, pseudo-boehmite, alumina sol, sodium metaaluminate and aluminum powder;
the silicon element is from a silicon source, and the silicon source is one or more of silicon oxide, sodium silicate, silica gel, silica sol and silicon powder;
the sodium element is all from sodium hydroxide except the silicon source and/or the aluminum source.
4. The method for synthesizing low-silicon faujasite raw powder by liquid phase seed crystal method as claimed in claim 1, wherein the liquid phase seed crystal is prepared by reacting at 20-80 deg.C for 10-240 min.
5. The method for synthesizing low-silicon faujasite raw powder according to claim 1, wherein the total amount of the charged materials is aNa molar ratio in step S22O·bK2O·xSiO2·Al2O3·yH2O, wherein a/(a + b) is 0.7-0.8, and (a + b)/x is 2.0-3.5, x is 1.8-2.5, and y/a is 16-20.
6. The method for synthesizing low-silicon faujasite powder by liquid phase seeding method according to claim 1, wherein Al is used2O3The mole ratio of the liquid phase seed crystal in all the materials is 0.01-10%.
7. The method for synthesizing low-silicon faujasite raw powder according to claim 1 or 6, wherein in the charged material of step S2:
the aluminum element is from an aluminum source, and the aluminum source is one or more of aluminum hydroxide, aluminum oxide, pseudo-boehmite, alumina sol, sodium metaaluminate, potassium metaaluminate and aluminum powder;
the silicon element is from a silicon source, and the silicon source is one or more of silicon oxide, sodium silicate, potassium silicate, silica gel, silica sol and silicon powder;
the potassium element except the silicon source and/or the aluminum source is introduced and is completely derived from potassium hydroxide;
the sodium element is all from sodium hydroxide except the silicon source and/or the aluminum source.
8. The method as claimed in claim 3, wherein in step S2, the aluminum-containing alkaline solution is uniformly added into the silicon-containing alkaline solution at a stirring speed of 500-2000rpm for 5-20min, and after the addition is completed for 5-10min, the liquid-phase seed crystal is added and the stirring is continued for 10-60min to obtain a uniform fluid.
9. The method of synthesizing low-silicon faujasite raw powder according to claim 3, wherein in step S2, aging is carried out at 20-80 ℃ for 1-24 hours, then heating is carried out within 0.5-2 hours to crystallization temperature, crystallization is carried out at 70-100 ℃ for 1-6 hours, stirring is carried out at 50-500rpm during aging and crystallization, and crystallization product is cooled to not higher than 40 ℃ within 0.5-2 hours after crystallization is finished.
10. The method as claimed in claim 1, wherein the method comprises filtering the crystallized product, washing with deionized water until the pH of the washing solution is less than 11, and drying at 125 deg.C for one night to obtain LSX raw powder, wherein the washing solution and the mother solution can be calibrated for recycling.
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