CN115385356A - Method for preparing 13X molecular sieve by using fly ash solid phase - Google Patents
Method for preparing 13X molecular sieve by using fly ash solid phase Download PDFInfo
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- CN115385356A CN115385356A CN202210960461.8A CN202210960461A CN115385356A CN 115385356 A CN115385356 A CN 115385356A CN 202210960461 A CN202210960461 A CN 202210960461A CN 115385356 A CN115385356 A CN 115385356A
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- 239000010881 fly ash Substances 0.000 title claims abstract description 116
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 84
- 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 84
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007790 solid phase Substances 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 75
- 238000000227 grinding Methods 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000001816 cooling Methods 0.000 claims abstract description 40
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 238000000967 suction filtration Methods 0.000 claims abstract description 11
- 239000002910 solid waste Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 59
- 239000000843 powder Substances 0.000 claims description 37
- 238000005303 weighing Methods 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 31
- 230000004927 fusion Effects 0.000 claims description 29
- -1 polytetrafluoroethylene Polymers 0.000 claims description 23
- 235000011837 pasties Nutrition 0.000 claims description 22
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 19
- 229910001220 stainless steel Inorganic materials 0.000 claims description 19
- 239000010935 stainless steel Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003245 coal Substances 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
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 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
- 239000011734 sodium Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 67
- 229910052573 porcelain Inorganic materials 0.000 description 17
- 238000001914 filtration Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000004127 vitreous body Anatomy 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- C01B39/22—Type X
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
The invention relates to a comprehensive utilization technology of fly ash, and aims to provide a method for preparing a 13X molecular sieve by utilizing a solid phase of fly ash. The method comprises the following steps: uniformly mixing the fly ash and solid sodium hydroxide, grinding and calcining; cooling and grinding the mixture to obtain activated fly ash clinker; then evenly mixing the mixture with hydrochloric acid and seed crystals of a 13X molecular sieve and grinding the mixture into paste; performing crystallization reaction for 0.5 to 3 days at the temperature of between 80 and 100 ℃; and cooling to room temperature, carrying out suction filtration on the product, and drying to obtain the 13X molecular sieve. The invention takes the solid waste fly ash as the raw material, has wide source and reduces the pollution of the fly ash to the environment. According to the invention, a silicon source and an aluminum source are not required to be added, a solid-phase synthesis method is adopted, the generation of a large amount of wastewater in the synthesis process of the molecular sieve is reduced, the yield of the molecular sieve prepared from the fly ash is improved, the high-value comprehensive utilization cost of the fly ash is reduced, and the method has a good economic value.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of fly ash, in particular to a method for preparing a 13X molecular sieve by utilizing a fly ash solid phase.
Background
Coal, the second largest energy source worldwide, provides 30% of the world's non-renewable energy. The fly ash is a main byproduct of coal used for thermal power generation and is also one of bulk industrial solid wastes. About 50% of the fly ash is deposited in a landfill, and harmful elements in the fly ash can invade soil along with the washing of rainwater to cause large-area pollution. In general, siO in fly ash 2 And Al 2 O 3 About more than 60 percent, and simultaneously contains a small amount of transition metal and rare earth metal, and the waste of the fly ash causes serious resource waste. Therefore, it is very important to treat and utilize fly ash with high value.
Zeolite molecular sieves are a class of crystalline silicates having uniform channels and are composed of TO 4 A three-dimensional skeleton structure of tetrahedra (T is an atom of Si, al, P, etc.) formed by sharing an oxygen atom, wherein TO 4 Tetrahedra are the basic units of molecular sieves. Because the molecular sieve has a unique pore structure, larger specific surface area, good hydrothermal stability and ion exchange performance, and surface-adjustable Lewis and Bronsted acid centers, the molecular sieve can be used as a catalyst, a catalyst carrier, an ion exchanger, an adsorbent and the like and is widely applied to various fields of fine chemical industry, petrochemical industry, environmental protection and the like. The 13X molecular sieve is also called NaX type molecular sieve, belongs to a cubic crystal system, has a FAU type topological structure and has a pore diameter of about
Adsorbability less than
The molecule can realize the co-adsorption of water and carbon dioxide and the co-adsorption of water and hydrogen sulfide gas, is mainly applied to the drying of medicines and air compression systems, and can also be used as a catalyst carrier.
Since the first time in 1985, holler et al used the traditional hydrothermal method to synthesize zeolite from fly ash, synthesis techniques such as alkali fusion hydrothermal method, microwave-assisted method, and seed crystal-assisted synthesis were gradually emerging. However, the above synthesis methods all require a large amount of water as a solvent, and the product has low yield, impure crystal form and low crystallinity; after crystallization is completed, the separation of the molecular sieve from the mother liquor requires a large amount of clean water for cleaning, which can bring alkaline pollution to the environment.
Therefore, the development of a low-energy consumption and low-pollution synthesis process is the key point of the industrial production of zeolite by using fly ash.
Disclosure of Invention
The invention mainly aims to overcome the defects in the prior art and provides a method for preparing a 13X molecular sieve by utilizing a fly ash solid phase.
In order to solve the technical problem, the solution of the invention is as follows:
the method for preparing the 13X molecular sieve by using the fly ash solid phase comprises the following steps:
(1) High temperature alkali fusion
Weighing fly ash and solid sodium hydroxide according to the mass ratio of 1.0-1.5, uniformly mixing and grinding the fly ash and the solid sodium hydroxide, and calcining the mixture for 2-6 hours at the temperature of 650-900 ℃; cooling and grinding the mixture into powder to obtain activated fly ash clinker;
(2) Solid phase synthesis of 13X molecular sieve
Taking fly ash clinker, hydrochloric acid and seed crystal of 13X molecular sieve, uniformly mixing and grinding the mixture to be pasty; the addition amount of each reaction raw material is controlled so that the molar ratio of each component in the mixture is in the following range: na (Na) 2 O:SiO 2 :Al 2 O 3 :H 2 O seed =0.36 to 0.72;
then placing the mixture into a reaction kettle, and carrying out crystallization reaction for 0.5-3 days at the temperature of 80-100 ℃; and after the reaction is finished, cooling to room temperature, carrying out suction filtration and drying on a product to obtain the 13X molecular sieve.
As a preferable scheme of the invention, the fly ash used is the main solid waste fly ash discharged after the combustion of the fly ash from a coal-fired power plant, and the total content of silicon dioxide and aluminum oxide accounts for more than 80 percent of the mass of the fly ash.
As a preferable scheme of the invention, the mass fraction of the hydrochloric acid is 36.5%, and the mass ratio of the hydrochloric acid to the fly ash clinker is 2.0-2.6.
As a preferred embodiment of the present invention, the grinding is performed in an agate mortar.
As a preferable scheme of the invention, the reaction kettle is a polytetrafluoroethylene stainless steel reaction kettle.
Description of the inventive principles:
the fly ash is also called fly ash, is the main solid waste discharged by coal-fired power plant pulverized coal combustion, contains a small amount of carbon, crystals (quartz and mullite) and a large amount of aluminosilicate glass body, and mainly contains silicon dioxide and alumina (accounting for more than 60 percent).
In the process of synthesizing the molecular sieve by the fly ash in a solid phase, the fly ash subjected to high-temperature alkali fusion is fully and uniformly mixed with a small amount of water from hydrochloric acid to form a dispersion system which takes a silicon-aluminum compound as a dispersoid and an adsorbed water dispersant. Wherein, hydroxide radicals are automatically dispersed on the surface of the silicon-aluminum compound, so that the entropy value of a solid phase system is obviously increased, and the influence of entropy change on the system is obviously larger than the change of energy and enthalpy. Therefore, the total free energy of the system is reduced, so that the positive ions and the negative ions of sodium ions and hydroxyl ions in the system are automatically dispersed to form an electric field gradient, and the self-diffusion of the charged ions is promoted by the potential energy gradient and the concentration gradient of the charged ions. Meanwhile, the hydroxyl depolymerizes and rearranges the silicon-aluminum compound, and a small amount of water is used as a filler of the porous zeolite, so that the zeolite structure of the molecular sieve is formed. Because the alkalinity of the clinker after alkali fusion is higher, which is not beneficial to the crystallization of the 13X molecular sieve, hydrochloric acid is needed to be added to neutralize partial alkali in the clinker after alkali fusion, so that the alkalinity of the clinker is suitable for the crystallization of the 13X molecular sieve.
In the present invention, the proper amount of 13X molecular sieve seed crystal has no influence on the particle size of the product, but the crystallization time is shortened.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes the solid waste fly ash as the raw material, has wide source, reduces the pollution of the fly ash to the environment and provides a new idea for the high-value industrial utilization of the fly ash.
2. The invention selects high-temperature alkali fusion as the only pretreatment mode, thereby avoiding the waste of a large amount of water resources in the processes of acid leaching and the like in the traditional process; and moreover, the product obtained after high-temperature alkali fusion is used as the only source of silicon aluminum and alkali, the interference of other impurities is avoided in the synthesis process, and the purity of the product is improved.
3. The method directly takes the fly ash clinker subjected to high-temperature alkali fusion as a raw material, does not need to add a silicon source and an aluminum source, adopts a solid-phase synthesis method, reduces the generation of a large amount of wastewater in the synthesis process of the molecular sieve, improves the yield of the molecular sieve prepared from the fly ash, reduces the high-value comprehensive utilization cost of the fly ash, and has good economic value.
Drawings
FIG. 1 is an XRD spectrum of fly ash used in the present invention;
FIG. 2 is a scanning electron micrograph of fly ash used in the present invention;
FIG. 3 is an XRD spectrogram of a product of the fly ash of the present invention after high temperature alkali fusion;
FIG. 4 is a scanning electron microscope image of a product of the fly ash after high-temperature alkali fusion;
FIG. 5 is an XRD spectrum of a product synthesized according to the present invention;
FIG. 6 is a scanning electron micrograph of a product synthesized according to the present invention;
FIG. 7 shows the calcium ion exchange capacity and the magnesium ion exchange capacity of the synthesized product of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following detailed description and accompanying drawings:
the fly ash samples used in the examples of the present invention are fly ash, which is the main solid waste discharged after the combustion of pulverized coal in coal-fired power plants at certain places in China, and the chemical composition of the fly ash measured by XRF is shown in Table 1, wherein SiO is SiO 2 And Al 2 O 3 The total content of (A) is more than 80%. The X-ray diffraction pattern of the fly ash is shown in figure 1, and the fly ash contains quartz and mullite; the scanning electron micrograph is shown in figure 2, and it can be seen from the figure that the fly ash is composed of a large number of vitreous bodies.
TABLE 1 composition of oxides of the components in fly ash
| Composition (A) | SiO 2 | Al 2 O 3 | Fe 2 O 3 | CaO | K 2 O | TiO 2 | Others |
| Content wt/%) | 52 | 29.2 | 3.33 | 2 | 1.46 | 1.19 | 10.82 |
Example 1: solid-phase synthesis of 13X molecular sieve under the conditions of fly ash/sodium hydroxide = 1.0
(1) High-temperature alkali fusion: weighing 10g of fly ash and 10g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
The X-ray diffraction pattern (figure 3) of the fly ash subjected to high-temperature alkali fusion shows that quartz and mullite in the fly ash are changed into aluminosilicate after activation, and a scanning electron microscope (figure 4) shows that a large amount of vitreous bodies are damaged.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder in a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 O
the structure of the product is 13X molecular sieve (figure 5) by X-ray diffraction analysis, and the synthesized product presents a uniform shape through a scanning electron micrograph. FIG. 6 is a Scanning Electron Micrograph (SEM) of a 13X molecular sieve product prepared by solid phase synthesis using fly ash clinker powder.
Example 2: solid-phase synthesis of 13X molecular sieve under the conditions of coal ash/sodium hydroxide = 1.2
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, grinding and mixing the mixture uniformly to be pasty, then adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product by suction, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 O
example 3: solid-phase synthesis of 13X molecular sieve under the conditions of fly ash/sodium hydroxide = 1.5
(1) High-temperature alkali fusion: weighing 10g of fly ash and 15g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, grinding and mixing the mixture uniformly to be pasty, then adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product by suction, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to ensure that the molar ratio ranges are as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 O
example 4: solid-phase synthesis of 13X molecular sieve at 650 deg.C
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 650 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, grinding and mixing the mixture uniformly to be pasty, then adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product by suction, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 O
example 5: solid-phase synthesis of 13X molecular sieve at 700 deg.C
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 700 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, grinding and mixing the mixture uniformly to be pasty, then adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product by suction, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to ensure that the molar ratio ranges are as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 O
example 6: solid-phase synthesis of 13X molecular sieve at 900 deg.C
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2 hours at 900 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, grinding and mixing the mixture uniformly to be pasty, then adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product by suction, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 O
example 7: solid-phase synthesis of 13X molecular sieve under the condition of calcination time of 4h
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 4h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder in a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 O
example 8: solid-phase synthesis of 13X molecular sieve under the condition of calcination time of 6h
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 6 hours at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder in a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 O
example 9: siO 2 2 Solid phase synthesis of 13X molecular sieve under the condition of seed crystal =0.1
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.1g of 13X molecular sieve seed crystal into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 0.75 day at 80 ℃, cooling the mixture to room temperature, carrying out suction filtration on the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 0.1 seed crystal of O
Example 10: siO 2 2 Solid phase synthesis of 13X molecular sieve under the condition of seed crystal =0.2
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.2g of 13X molecular sieve seed crystal into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 0.5 day at 80 ℃, cooling the mixture to room temperature, carrying out suction filtration on the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 0.2 seed crystal of O
Example 11: solid phase synthesis of 13X molecular sieve under low alkalinity condition
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.0g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.1g of 13X molecular sieve seed crystal into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃ to obtain complete crystallization, cooling the mixture to room temperature, carrying out suction filtration on the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.36Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.0H 2 0.1 seed crystal of O
Example 12: at H 2 O/SiO 2 Solid-phase synthesis of 13X molecular sieve under condition of =5.0
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder in a mortar, dropwise adding 2.4g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.1g of seed crystal of a 13X molecular sieve, grinding and mixing uniformly to be pasty, adding the pasty mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 1 day at the temperature of 80 ℃ to obtain complete crystallization, cooling to room temperature, carrying out suction filtration on a product, and drying to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.60Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :5.0H 2 0.1 seed crystal of O
Example 13: solid phase synthesis of 13X molecular sieve under higher alkalinity condition
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.6g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.1g of 13X molecular sieve seed crystal into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at the temperature of 80 ℃ to obtain complete crystallization, cooling the mixture to room temperature, carrying out suction filtration on the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to ensure that the molar ratio ranges are as follows:
0.72Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :5.5H 2 0.1 seed crystal of O
Example 14: solid-phase synthesis of 13X molecular sieve under the condition of crystallization time of 2 days
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder in a mortar, dropwise adding 2.4g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.1g of seed crystal of a 13X molecular sieve, grinding and mixing uniformly to be pasty, adding the pasty mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2 days at 80 ℃, completely crystallizing, cooling to room temperature, carrying out suction filtration on a product, and drying to obtain the product.
The addition amount of each reaction raw material is controlled to ensure that the molar ratio ranges are as follows:
0.60Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 0.1 seed crystal of O
Example 15: solid-phase synthesis of 13X molecular sieve under the condition of crystallization time of 3 days
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.4g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.1g of 13X molecular sieve seed crystal into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture at 80 ℃ for 3 days to obtain complete crystallization, cooling the mixture to room temperature, carrying out suction filtration on the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.60Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 0.1 seed crystal of O
Example 16: solid phase synthesis of 13X molecular sieve at crystallization temperature of 90 DEG C
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder into a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.1g of 13X molecular sieve seed crystal into the mortar, grinding and mixing the mixture uniformly to be pasty, adding the mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing the mixture for 1 day at 90 ℃, completely crystallizing the mixture, cooling the mixture to room temperature, filtering the product, and drying the product to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 0.1 seed crystal of O
Example 17: solid phase synthesis of 13X molecular sieve at crystallization temperature of 100 DEG C
(1) High-temperature alkali fusion: weighing 10g of fly ash and 12g of sodium hydroxide, mixing in a mortar, grinding and mixing uniformly, transferring to a porcelain boat, fully calcining for 2h at 800 ℃, cooling to obtain calcined clinker, and grinding into powder to obtain activated fly ash clinker.
(2) Solid-phase synthesis of 13X molecular sieve: weighing 2.2g of the fly ash clinker powder in a mortar, dropwise adding 2.2g of hydrochloric acid with the mass fraction of 36.5% into the mortar, adding 0.1g of seed crystal of a 13X molecular sieve, grinding and mixing uniformly to be pasty, adding the pasty mixture into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 1 day at 100 ℃, completely crystallizing, cooling to room temperature, carrying out suction filtration on a product, and drying to obtain the product.
The addition amount of each reaction raw material is controlled to make the molar ratio range as follows:
0.48Na 2 O:1.0SiO 2 :0.33Al 2 O 3 :4.5H 2 0.1 seed crystal of O
Example 18: determination of calcium ion and magnesium ion exchange capacity of 13X molecular sieve
The products of examples 1-17 were tested for calcium exchange capacity on 13X molecular sieves with reference to the test protocol published in QB/T1768-2003 national industry Standard, with the results using mg CaCO 3 Expressed in terms of/g dry basis. Meanwhile, a test scheme is expanded, the magnesium exchange capacity of the 13X molecular sieve is measured, and mg MgCO is used as a test result 3 Expressed in terms of/g dry basis.
Further, 13X molecular sieves were synthesized according to the conventional methods described in the publications (Wang Yuyao, zhang Jiang, yu Jigong, proceedings of advanced chemical sciences, 2020, 41) and the ion exchange capacity was measured according to the same test methods as described above, and the results are shown in fig. 7.
As can be seen from FIG. 7, in example 9 of the present invention, the 13X molecular sieve had a good calcium and magnesium ion exchange capacity, each 219mg CaCO 3 Per g dry basis and 203mg MgCO 3 On a dry basis, the result is obviously superior to the similar products prepared by the prior art. In addition, the ion exchange performance of the products prepared by other embodiments of the invention is basically equivalent to that of the similar products prepared by the prior art, which has potential significance for industrial hard water softening.
In conclusion, the method belongs to a solid-phase preparation method of the zeolite molecular sieve, has the advantages of simple process, low cost, environmental protection and higher raw material utilization rate and yield in the crystallization process of the molecular sieve. Therefore, the product of the invention can meet the application requirements of molecular sieve products.
Although the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention will still fall within the technical scope of the present invention without departing from the contents of the technical solution of the present invention.
Claims (5)
1. A method for preparing a 13X molecular sieve by utilizing a fly ash solid phase is characterized by comprising the following steps:
(1) High temperature alkali fusion
Weighing fly ash and solid sodium hydroxide according to the mass ratio of 1.0-1.5, uniformly mixing and grinding the fly ash and the solid sodium hydroxide, and calcining the mixture for 2-6 hours at the temperature of 650-900 ℃; cooling and grinding the mixture into powder to obtain activated fly ash clinker;
(2) Solid phase synthesis of 13X molecular sieve
Taking fly ash clinker, hydrochloric acid and seed crystal of 13X molecular sieve, uniformly mixing and grinding the mixture to be pasty; the addition amount of each reaction raw material is controlled to enable the molar ratio of each component in the mixture to be in the following range: na (Na) 2 O:SiO 2 :Al 2 O 3 :H 2 O seed =0.36 to 0.72;
then placing the mixture into a reaction kettle, and carrying out crystallization reaction for 0.5-3 days at the temperature of 80-100 ℃; and cooling to room temperature after the reaction is finished, and performing suction filtration and drying on a product to obtain the 13X molecular sieve.
2. A method according to claim 1, characterized in that the fly ash used is fly ash, the main solid waste discharged after combustion of pulverized coal from coal fired power plants, and it contains more than 80% by mass of silica and alumina.
3. The method according to claim 1, wherein the mass fraction of the hydrochloric acid is 36.5%, and the mass ratio of the hydrochloric acid to the fly ash clinker is 2.0-2.6.
4. The method of claim 1, wherein the grinding is performed in an agate mortar.
5. The method of claim 1, wherein the reaction vessel is a polytetrafluoroethylene stainless steel reaction vessel.
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