CN114477213A - Submicron 4A type molecular sieve and preparation method thereof - Google Patents
Submicron 4A type molecular sieve and preparation method thereof Download PDFInfo
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- CN114477213A CN114477213A CN202210042985.9A CN202210042985A CN114477213A CN 114477213 A CN114477213 A CN 114477213A CN 202210042985 A CN202210042985 A CN 202210042985A CN 114477213 A CN114477213 A CN 114477213A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 99
- 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 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003245 coal Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003513 alkali Substances 0.000 claims abstract description 36
- 239000010453 quartz Substances 0.000 claims abstract description 27
- 239000002699 waste material Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 189
- 239000000203 mixture Substances 0.000 claims description 34
- 239000012535 impurity Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 31
- 238000001354 calcination Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 15
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910020489 SiO3 Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 238000002441 X-ray diffraction Methods 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 6
- 230000004927 fusion Effects 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910020453 SiO2+2NaOH Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910001483 soda nepheline Inorganic materials 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010879 coal refuse Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 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
- C01B39/14—Type A
- C01B39/18—Type A from a reaction mixture containing at least one aluminium silicate or aluminosilicate of a clay type, e.g. kaolin or metakaolin or its exotherm modification or allophane
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Dispersion 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 discloses a submicron 4A type molecular sieve and a preparation method thereof, which can be used for preparing cubic or spherical 4A type molecular sieve and comprises the following steps: s1: preparing coal gangue rich in quartz; s2: activating coal gangue; s3: alkali dissolves out insoluble substances; s4: preparing pure submicron 4A molecular sieve. The submicron 4A molecular sieve prepared by the invention has single crystal phase, is a regular blocky cube or sphere with obvious edge angles, has uniform crystal grain size, has the average grain diameter of about 0.5 mu m, and contains Ca2+Exchange amount of 323mg CaCO3On a dry basis per gram. The method utilizes the coal gangue rich in quartz to prepare the submicron 4A type molecular sieve, has low raw material cost, can consume a large amount of coal gangue, and does not generate waste residue, waste alkali and waste liquid; meanwhile, the preparation process is simple, the requirements on the process and equipment are not high, and the prepared submicron 4A type molecular sieve has high purity and strong calcium ion exchange capacity.
Description
Technical Field
The invention relates to the technical field of resource recycling of solid wastes and molecular sieve manufacturing, in particular to a submicron 4A molecular sieve and a preparation method thereof.
Background
Coal gangue is one of the largest industrial solid wastes generated in the coal mining process. The large amount of stacked coal gangue not only occupies cultivated land, but also causes various pollutions to the atmosphere, soil, water and the like, and brings great harm to the life of human beings. The comprehensive utilization of coal gangue has become a global concern at the end of the last century.
The pore diameter of the 4A molecular sieve in the prior art is
Adsorbing water, methanol, ethanol, hydrogen sulfide, sulfur dioxide, carbon dioxide, ethylene and propylene, and having a diameter larger than that of the adsorbed water
The selective adsorption performance of any molecule (including propane) on water is higher than that of any other molecule, the method is widely applied to the drying of gas and liquid, and can also be used for refining and purifying certain gas or liquid, such as the preparation of argon, and the method is one of the most industrially used molecular sieve varieties. The diameter specification of the existing spherical molecular sieve is generally as follows: 0.5-1.0mm, and 1.6-2.5mm strip. The 4A molecular sieve is called 4A molecular sieve because the effective pore diameter is 0.4nm, and the spatial network structure of the 4A molecular sieve is composed of silicon-oxygen tetrahedral units [ SiO ]4]And alundum tetrahedron [ AlO4]The units are arranged in a staggered mode.
In order to fully utilize coal gangue, the document of the Chinese patent application CN201811032949.4 discloses a method for preparing a 4A molecular sieve from coal gangue, which takes the coal gangue as a raw material, and the raw material is pretreated, activated, aged and crystallized to synthesize 4A zeolite. Mainly comprises the following steps: 1. pretreatment of raw materials: grinding the coal gangue by using a ball mill, sieving, and then carrying out ultrasonic crushing to obtain coal gangue powder with uniform particle size distribution for later use; 2. activating coal gangue: uniformly mixing the coal gangue and alkali according to a certain mass ratio, and then placing the mixture in a high-temperature furnace for activation treatment; 3. mixing activated coal gangue and water according to a certain proportion, and aging for a certain time at a certain temperature under the ultrasonic condition; 4. after the aging is finished, adjusting the temperature and continuously crystallizing for a certain time; 5. after crystallization is finished, high-quality 4A zeolite is obtained through post-treatment. The invention introduces ultrasonic treatment in the process, the average particle size of the synthesized 4A zeolite is 2-3 mu m, the particle size is mainly cubic, and the calcium exchange value of the product is 300-310 mg/g. Taking out a product obtained by crystallization, naturally cooling to room temperature, filtering, washing and drying to obtain the 4A molecular sieve. The record shows that the prepared 4A molecular sieve has larger grain diameter, is strip-shaped (blocky cube) and has high impurity content; the preparation process needs ultrasonic waves and has high preparation cost; the waste residue, waste alkali and waste liquid generated by filtration, washing and the like are easy to cause secondary pollution, in addition, the calcium exchange value of the waste alkali and waste liquid is required to be further improved, and the comprehensive cost is also required to be further reduced.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a method for preparing a submicron-sized 4A-type molecular sieve to solve the above-mentioned problems. The method has the advantages that the submicron 4A type molecular sieve is prepared by utilizing the coal gangue rich in quartz, the cost of raw materials is low, the coal gangue can be greatly consumed, and waste residues, waste alkali and waste liquid are not generated; meanwhile, the preparation process is simple, the requirements on the process and equipment are not high, and the prepared submicron 4A type molecular sieve has high purity and strong calcium ion exchange capacity.
The invention also aims to provide the submicron 4A molecular sieve prepared by the method, which has a single crystal phase, is regular cube or sphere in appearance, has uniform crystal grain size and high purity, has an average grain diameter of about 0.5 mu m, and contains Ca2+The exchange capacity can reach 314-323 mg CaCO3On a dry basis per gram.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a submicron 4A molecular sieve is characterized in that the method comprises the following steps:
s1: preparing coal gangue which is rich in quartz and has quartz phase as a main mineral phase;
s2: activating coal gangue: calcining the coal gangue to remove carbon elements, sieving, uniformly mixing the coal gangue with solid NaOH according to a set proportion, putting the mixture into a muffle furnace for calcining, taking out and grinding the mixture, and then calcining for the second time;
s3: alkali dissolution of insoluble substances: weighing a set amount of solid NaOH, adding deionized water, fully dissolving NaOH to obtain a NaOH solution, adding the product obtained in the step S2 into the NaOH solution, and aging at room temperature to obtain a mixture; carrying out suction filtration on the mixture to separate solid from liquid and filter impurities; then adding the filtered impurities into the coal gangue in the step S1 for reuse, and repeating the steps to finally avoid generating waste residues;
s4: preparation of pure cubic submicron 4A molecular sieve: according to the proportion composition of 4A type molecular sieve, n (SiO)2)/(Al2O3)＝2.0，n(Na2O)/n(SiO2)＝0.8～3.0，n(H2O)/n(Na2O) 30-50, adding a set amount of NaOH into the filtrate obtained by filtering the impurities in the step S3, and adding Na into the NaOH after the NaOH is dissolved2SiO3·9H2O, in the heated state, is treated with Na2SiO3·9H2Adding NaAlO after dissolving O2And aging at room temperature for 0-12 hours, pouring the aged product into a reaction kettle, crystallizing at 80-100 ℃ for 3-12 hours, performing suction filtration, washing until the pH value is 8-9, and drying to obtain the cubic submicron 4A type molecular sieve.
Another method for preparing submicron-sized type 4A molecular sieve, which is characterized in that it is a type 4A molecular sieve for preparing spheres, comprising the following steps:
s1: preparing coal gangue which is rich in quartz and has quartz as a main mineral phase;
s2: activating coal gangue: calcining the coal gangue to remove carbon elements, sieving, uniformly mixing the coal gangue with solid NaOH according to a set proportion, putting the mixture into a muffle furnace for calcining, taking out and grinding the mixture, and then calcining for the second time;
s3: alkali dissolution of insoluble substances: weighing a set amount of solid NaOH, adding deionized water, fully dissolving NaOH to obtain a NaOH solution, adding the product obtained in the step S2 into the NaOH solution, and aging at room temperature to obtain a mixture; carrying out suction filtration on the mixture to separate solid from liquid and filter impurities; then adding the filtered impurities into the coal gangue in the step S1 for reuse, and repeating the steps to finally avoid generating waste residues;
s4: preparation of pure submicron 4A molecular sieves: according to the proportion composition of 4A type molecular sieve, n (SiO)2)/(Al2O3)＝2.0，n(Na2O)/n(SiO2)＝0.8～3.0，n(H2O)/n(Na2O) 30 to 50, and adding NaOH and Na in set amounts to 1/2 volumes of the filtrate obtained by filtering the impurities in step S32SiO3·9H2Dissolving O to obtain a first solution; to an additional 1/2 volumes of filtrate was added a set amount of NaAlO2Obtaining a second solution after the second solution is dissolved; then adding Na2SiO3Slowly dripping the mixed solution into the second solution to obtain a mixed solution after dripping is finished; and aging the mixed solution at room temperature for 0-12 hours, pouring the aged product into a reaction kettle, crystallizing at 80-100 ℃ for 3-12 hours, performing suction filtration, washing until the pH value is 8-9, and drying to obtain the spherical submicron 4A molecular sieve.
The submicron-grade 4A molecular sieve prepared by the method has a single crystal phase, is in the shape of a regular block cube or sphere with obvious edges and corners, has uniform crystal grain size and high purity, has an average grain diameter of about 0.5 mu m, and contains Ca2+The exchange amount is 314-323 mg CaCO3On a dry basis per gram.
Compared with the prior art, the preparation method and the material provided by the invention have the beneficial effects that:
1. according to the technical scheme provided by the invention, the pure submicron 4A type molecular sieve is prepared by adopting the solid waste rich in quartz coal gangue, so that a new idea is provided for recycling the coal gangue and preparing inorganic non-metallic materials. The method for preparing the submicron 4A-type molecular sieve by using the coal gangue rich in quartz as the main raw material has low raw material cost, can consume a large amount of coal gangue, and reduces environmental pollution; meanwhile, the preparation process provided by the invention is simple, the requirements on the process and equipment are not high, and the purity and the calcium ion exchange capacity of the prepared submicron-grade 4A type molecular sieve can reach the industrial standard.
2. The preparation method provided by the invention utilizes the coal gangue rich in quartz as a main raw material, NaOH as an activating agent and an alkali source, adopts a secondary calcination method, and utilizes simple equipment, process and operation flow to prepare the pure and high-performance submicron 4A type molecular sieve.
3. The preparation method provided by the invention not only makes full use of the silicon element and the aluminum element in the coal gangue, but also can reuse impurities and alkali liquor generated in the production process, and does not generate waste residues and waste liquid. Specifically, the alkali liquor in the impurities filtered in the step S3 is added with solid sodium hydroxide to reach the concentration of the synthesized molecular sieve because the concentration of the alkali liquor is lower than that of the synthesized molecular sieve, and then the alkali liquor is added into the coal gangue again, so that the steps are repeated without generating waste residues and waste alkali. On one hand, the material cost can be saved, and on the other hand, the environmental pollution can be reduced.
4. The technical scheme provided by the invention can change the morphology of the prepared submicron-scale 4A molecular sieve by adjusting partial procedures under the basically same technical concept, can be randomly selected from cubes and spheres, and improves the applicability of the invention.
5. The phase of the submicron 4A type molecular sieve prepared by the invention is a 4A type molecular sieve, the average particle size of the molecular sieve is about 0.5 mu m and is far smaller than that of the prior art (only 15-25% of the diameter of the prior art), and the smaller diameter size enables the submicron 4A type molecular sieve to have unique advantages, can be applied to screening of more products, and remarkably improves comprehensive properties such as screening efficiency and the like.
6. According to the technical scheme provided by the invention, coal gangue rich in quartz is selected as a main raw material, NaOH is used as an activating agent and an alkali source, a product after secondary activation is added into a NaOH solution with a certain concentration, and insoluble substances are dissolved out by alkali, so that the aim of removing impurities is fulfilled; and then according to the condition of synthesizing the 4A molecular sieve, adding alkali, a silicon source and an aluminum source into the filtrate after impurity removal to prepare the pure submicron 4A molecular sieve, wherein the whole preparation process is simple, the number of used equipment is small, the process condition is easy to control, and the industrial implementation is facilitated.
7. The submicron 4A molecular sieve provided by the invention has the advantages of high purity and submicron scale, and can be widely applied to drying of gas and liquid, refining and purification of certain gas or liquid, softening of water body as a detergent auxiliary agent, or forming agent of perfumed soap, abrasive agent of toothpaste, and the like.
Drawings
FIG. 1 is an X-ray diffraction analysis (XRD) pattern of coal refuse used in the example of the present invention;
FIG. 2 is an X-ray diffraction pattern (XRD pattern) of the molecular sieve prepared in example 1 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) picture of the molecular sieve prepared in example 1 of the present invention;
FIG. 4 is an X-ray diffraction analysis (XRD) pattern of the molecular sieve prepared in example 2 of the present invention;
fig. 5 is a Scanning Electron Microscope (SEM) image of the molecular sieve prepared in example 2 of the present invention.
Detailed Description
The technical solution of the present invention will now be described in detail with reference to the accompanying drawings and embodiments.
Example 1:
referring to fig. 1 to fig. 3, the first sub-micron size type 4A molecular sieve provided in this embodiment is a method for preparing cubic type 4A molecular sieve, which comprises the following steps:
s1: preparing coal gangue which is rich in quartz and has quartz phase as a main mineral phase;
s2: activating coal gangue: calcining the coal gangue to remove carbon elements, sieving, uniformly mixing the coal gangue with solid NaOH according to the ratio of 1: 1-1: 1.5, calcining in a muffle furnace, taking out, grinding, and then calcining for the second time;
the method comprises the following specific steps: calcining the coal gangue at 650 ℃ for 2 hours, removing carbon elements, sieving by a 200-mesh sieve, and taking 4g of treated coal gangue according to the weight ratio of the coal gangue: mixing NaOH at a ratio of 1:1.5 uniformly; calcining the mixture for 1 hour at 250 ℃ in a muffle furnace, then taking out the mixture for grinding, uniformly mixing the mixture, then putting the mixture into the muffle furnace again, calcining the mixture for 2 hours at 400 ℃ to fully perform alkali fusion on quartz and alkali in the coal gangue;
s3: alkali dissolution of insoluble substances: weighing a set amount of solid NaOH, adding deionized water, fully dissolving NaOH to obtain a NaOH solution, adding the product obtained in the step S2 into the NaOH solution, and aging at room temperature to obtain a mixture; carrying out suction filtration on the mixture to separate solid from liquid and filter impurities; then adding the filtered impurities into the coal gangue in the step S1 for reuse, and repeating the steps to finally avoid generating waste residues;
comprises the following steps: adding the solid mixture obtained after the alkali fusion in the S2 into NaOH solution of about 1mol/L, standing at room temperature for 12h, heating the mixture to 90 ℃ for reaction for 2h to dissolve aluminosilicate and silicate, and performing suction filtration on the product obtained after the alkali fusion so as to separate solid from liquid, wherein the generated solid can be added into the coal gangue again and reused after the alkali fusion;
the step of adding the filtered impurities into the coal gangue in the step S1 for reuse is specifically as follows: adding solid sodium hydroxide into the alkali liquor in the impurities filtered in the step S1 as the concentration of the alkali liquor is lower than that of the synthesized molecular sieve, and adding the alkali liquor into the coal gangue after the concentration of the synthesized molecular sieve is reached, and repeating the steps until no waste residue is generated;
s4: preparation of pure submicron 4A molecular sieves: according to the proportion composition of 4A type molecular sieve, n (SiO)2)/(Al2O3)＝2.0，n(Na2O)/n(SiO2)＝0.8～3.0，n(H2O)/n(Na2O) 30-50, adding a set amount of NaOH into the filtrate obtained by filtering the impurities in the step S3, and adding Na into the NaOH after the NaOH is dissolved2SiO3·9H2O, in the heated state, is treated with Na2SiO3·9H2Adding NaAlO after dissolving O2And aging at room temperature for 0-12 hours, pouring the aged product into a reaction kettle, crystallizing at 80-100 ℃ for 3-12 hours, performing suction filtration, washing until the pH value is 8-9, and drying to obtain the submicron 4A molecular sieve.
The embodiment specifically includes: according to the proportion of each component for synthesizing the 4A molecular sieve, taking n (SiO)2)/(Al2O3)＝2.0，n(Na2O)/n(SiO2)＝2.2，n(H2O)/n(Na2O) — 37 for example, the concentration of sodium hydroxide in the filtrate was calculated as: 2.3mol/L according to the mixture ratio of the 4A molecular sieve, the mass of NaOH to be supplemented is 1.0g by calculation, and 4.0g of Na is added into the NaOH after the NaOH is dissolved2SiO3·9H2O，Treating with Na under heating2SiO3·9H2After dissolving O, 2.4g of NaAlO was added2And then aging at room temperature for 12h, crystallizing at 90 ℃ for 3h, and performing suction filtration, washing and drying to obtain a sample I.
In the coal gangue rich in quartz in the step S1, the main mineral phase is a quartz phase, as shown in the attached figure 1. The components and the weight percentage content are as follows:
as the coal gangue rich in quartz selected in each batch is naturally formed, the content of each component can be changed to a certain extent, and the technical effect recorded by the invention can be achieved as long as the content is in the content range. Therefore, the specific values of the components are not listed in this example.
The phase and morphology of the submicron 4A molecular sieve prepared in this example are shown in FIGS. 2-3. The XRD pattern shows that the synthesized molecular sieve is a typical 4A type molecular sieve, and the SEM pattern shows that the synthesized 4A molecular sieve has an average particle size of about 0.5 mu m, is in the shape of a blocky cube, has a single crystalline phase, is in the shape of a sphere without edges and corners, has uniform crystal grain size and high purity. The Ca of the synthesized 4A-type molecular sieve was determined according to the method of QB/T1768-20032+Exchange amount of 323mg CaCO3On a dry basis per gram.
Example 2:
the embodiment of the invention provides a method for preparing a second submicron-scale 4A type molecular sieve, which is a spherical 4A type molecular sieve, and comprises the following steps:
s1: preparing coal gangue which is rich in quartz and has quartz phase as a main mineral phase;
s2: activating coal gangue: calcining the coal gangue to remove carbon elements, sieving, uniformly mixing the calcined coal gangue with solid NaOH according to the ratio of 1: 1-1: 1.5, calcining in a muffle furnace, taking out, grinding, and then calcining for the second time;
s3: alkali dissolution of insoluble substances: weighing a set amount of solid NaOH, adding deionized water, fully dissolving NaOH to obtain a NaOH solution, adding the product obtained in the step S2 into the NaOH solution, and aging at room temperature to obtain a mixture; carrying out suction filtration on the mixture to separate solid from liquid and filter impurities; then adding the filtered impurities into the coal gangue in the step S1 for reuse, and repeating the steps to finally avoid generating waste residues;
s4: preparation of pure submicron 4A molecular sieves: according to the proportion composition of 4A type molecular sieve, n (SiO)2)/(Al2O3)＝2.0，n(Na2O)/n(SiO2)＝0.8～3.0，n(H2O)/n(Na2O) 30 to 50, and adding NaOH and Na in set amounts to 1/2 volumes of the filtrate obtained by filtering the impurities in step S32SiO3·9H2Dissolving O to obtain a first solution; to an additional 1/2 volumes of filtrate was added a set amount of NaAlO2Obtaining a second solution after the second solution is dissolved; then adding Na2SiO3Slowly dripping the mixed solution into the second solution to obtain a mixed solution after dripping is finished; and aging the mixed solution at room temperature for 0-12 hours, pouring the aged product into a reaction kettle, crystallizing at 80-100 ℃ for 3-12 hours, performing suction filtration, washing until the pH value is 8-9, and drying to obtain the spherical submicron 4A molecular sieve.
The embodiment specifically includes: to 1/2 volumes of the filtrate, 1.0g NaOH was added to dissolve the filtrate, and 4.0g Na was added2SiO3·9H2O, heating Na2SiO3·9H2And dissolving the O. In a separate vessel containing 1/2 volumes of filtrate was added 2.4g NaAlO2And then, dissolving the compound. Then adding Na2SiO3The mixed solution is slowly dripped into NaAlO2After the solution is added dropwise, the mixed solution is aged for 12 hours at room temperature and crystallized for 3 hours at 90 ℃. And carrying out suction filtration, washing and drying to obtain a second sample.
The phase and the appearance of the sample are shown in the attached figures 4-5. From the XRD pattern, the synthesized molecular sieve is a typical type 4A molecular sieve, and from the SEM pattern, the average particle size of the synthesized molecular sieve is about 0.5 μm, and the synthesized molecular sieve of this example has less distinct edges and corners of a cubic shape, and is approximately spherical, compared to the molecular sieve synthesized in example 1.
The Ca of the synthesized 4A-type molecular sieve was determined according to the method of QB/T1768-20032+The exchange amount was 314mg CaCO3On a dry basis per gram.
The reaction mechanism and the chemical reaction equation in the above embodiment of the present invention are as follows:
1) removing coal and organic matters in the roasting process;
2) part of the less active kaolin is converted to highly active metakaolin during calcination:
Al2O3·2SiO2·2H2O→Al2O3·2SiO2+2H2O (1)
3) and (2) adding sodium hydroxide, so that the two-step activation is more thorough, and quartz, alumina, partial kaolin and the sodium hydroxide react to generate aluminosilicate and silicate:
Al2O3·2SiO2·2H2O+NaOH→NaAlSiO4+Na2SiO3+H2O
SiO2+2NaOH→Na2SiO3+H2O
Al2O3+2NaOH→2NaAlO2+H2O
Al2O3+SiO2+2NaOH→2NaAlSiO4+H2O (2)
4) adding the solid mixture after alkali fusion into NaOH solution at a certain temperature, dissolving aluminosilicate and silicate in the NaOH solution, filtering out impurities, wherein the impurities comprise unreacted quartz, alumina and the like, and adding the impurities into the coal gangue for recycling.
NaAlSiO4+Na2SiO3+ NaOH (heating) → Nax(SiO2)y·(AlO2)z·2H2O
5) Aging and crystallizing to obtain the pure submicron 4A molecular sieve.
The invention is characterized in that the coal gangue rich in quartz is used as a raw material, sodium hydroxide is used as an activating agent and an alkali source, and secondary calcination is adoptedThe sintering method utilizes simple equipment and operation flow to prepare the pure submicron 4A type molecular sieve with high performance. The method not only makes full use of silicon element and aluminum element in the coal gangue, but also separates impurities generated in the production process and adds the impurities into the coal gangue, and the impurities are reused after alkali fusion without generating waste residues; in addition, the alkali liquor generated in the production process can be recycled, no waste liquor is generated, and the aim of circular economy is fulfilled. The particle size of the submicron 4A type molecular sieve prepared by the invention is about 0.5 μm, and the Ca of the submicron 4A type molecular sieve synthesized by the invention is determined according to the method of QB/T1768-2+The exchange capacity is: 314-323 mg CaCO3The dry basis is obviously superior to similar products prepared by the prior art, and the comprehensive cost can be reduced by 30-40%.
It should be noted that, in other embodiments of the present invention, different schemes obtained by specifically selecting steps, components, ratios, and process parameters described in the present invention can achieve the technical effects described in the present invention, and therefore, the present invention is not listed one by one.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. All equivalent changes in the components, proportions and processes according to the present invention are intended to be covered by the scope of the present invention.
Claims (8)
1. A method for preparing a submicron 4A molecular sieve is characterized in that the method comprises the following steps:
s1: preparing coal gangue which is rich in quartz and has quartz phase as a main mineral phase;
s2: activating coal gangue: calcining the coal gangue to remove carbon elements, sieving, uniformly mixing the coal gangue with solid NaOH according to a set proportion, putting the mixture into a muffle furnace for calcining, taking out and grinding the mixture, and then calcining for the second time;
s3: alkali dissolution of insoluble substances: weighing a set amount of solid NaOH, adding deionized water, fully dissolving NaOH to obtain a NaOH solution, adding the product obtained in the step S2 into the NaOH solution, and aging at room temperature to obtain a mixture; carrying out suction filtration on the mixture to separate solid from liquid and filter impurities; then adding the filtered impurities into the coal gangue in the step S1 for reuse, and repeating the steps to finally avoid generating waste residues;
s4: preparation of pure cubic submicron 4A molecular sieve: according to the proportion composition of 4A type molecular sieve, n (SiO)2)/(Al2O3)＝2.0，n(Na2O)/n(SiO2)＝0.8～3.0，n(H2O)/n(Na2O) 30-50, adding a set amount of NaOH into the filtrate obtained by filtering the impurities in the step S3, and adding Na into the NaOH after the NaOH is dissolved2SiO3·9H2O, in the heated state, is treated with Na2SiO3·9H2Adding NaAlO after dissolving O2And aging at room temperature for 0-12 hours, pouring the aged product into a reaction kettle, crystallizing at 80-100 ℃ for 3-12 hours, performing suction filtration, washing until the pH value is 8-9, and drying to obtain the cubic submicron 4A type molecular sieve.
2. The method of claim 1, wherein the submicron 4A molecular sieve is a cubic submicron 4A molecular sieve prepared in step S4, and the cubic submicron 4A molecular sieve has a single crystal phase, a regular cubic shape with distinct edges, uniform crystal size, high purity, an average particle size of about 0.5 μm, and Ca2+Exchange amount of 323mg CaCO3On a dry basis per gram.
3. Another method for preparing submicron-sized type 4A molecular sieve, which is characterized in that it is a type 4A molecular sieve for preparing spheres, comprising the following steps:
s1: preparing coal gangue which is rich in quartz and has quartz phase as a main mineral phase;
s2: activating coal gangue: calcining the coal gangue to remove carbon elements, sieving, uniformly mixing the calcined coal gangue with solid NaOH according to a set proportion, calcining the mixture in a muffle furnace, taking out the calcined coal gangue, grinding the calcined coal gangue, and then calcining the mixture for the second time;
s3: alkali dissolution of insoluble substances: weighing a set amount of solid NaOH, adding deionized water, fully dissolving NaOH to obtain a NaOH solution, adding the product obtained in the step S2 into the NaOH solution, and aging at room temperature to obtain a mixture; carrying out suction filtration on the mixture to separate solid from liquid and filter impurities; then adding the filtered impurities into the coal gangue in the step S1 for reuse, and repeating the steps to finally avoid generating waste residues;
s4: preparation of pure cubic submicron 4A molecular sieve: according to the proportion composition of 4A type molecular sieve, n (SiO)2)/(Al2O3)＝2.0，n(Na2O)/n(SiO2)＝0.8～3.0，n(H2O)/n(Na2O) 30 to 50, and adding NaOH and Na in set amounts to 1/2 volumes of the filtrate obtained by filtering the impurities in step S32SiO3·9H2Dissolving O to obtain a first solution; to an additional 1/2 volumes of filtrate was added a set amount of NaAlO2Obtaining a second solution after the second solution is dissolved; then adding Na2SiO3The mixed solution is slowly dripped into NaAlO2In the solution second solution, after the dropwise addition is finished, obtaining a mixed solution; and aging the mixed solution at room temperature for 0-12 hours, pouring the aged product into a reaction kettle, crystallizing at 80-100 ℃ for 3-12 hours, performing suction filtration, washing until the pH value is 8-9, and drying to obtain the spherical submicron 4A molecular sieve.
4. The method of claim 2, wherein the spherical submicron 4A molecular sieve prepared in step S4 has a single crystal phase, a spherical shape without edges, a uniform crystal size, a high purity, an average particle size of about 0.5 μm, and Ca2+The exchange amount was 314mg CaCO3On a dry basis per gram.
5. The method of producing a submicron-sized type 4A molecular sieve according to claim 1 or 2,
in the step S3, the step of adding the filtered impurities into the coal gangue in the step S1 for reuse specifically includes: and (4) adding solid sodium hydroxide into the alkali liquor in the impurities filtered in the step (S1) because the concentration of the alkali liquor is lower than that of the synthesized molecular sieve, and adding the alkali liquor into the coal gangue after the concentration of the synthesized molecular sieve is reached, wherein the steps are repeated, and finally, no waste residue is generated.
6. The method of producing a submicron-sized type 4A molecular sieve according to claim 1 or 2,
the coal gangue rich in quartz in the step S1 comprises the following components in percentage by weight:
7. the method for preparing a pure submicron 4A molecular sieve according to claim 1 or 2, characterized in that in step S2, coal gangue is calcined to remove carbon element, sieved and uniformly mixed with solid NaOH at a ratio of 1: 1-1: 1.5.
8. A submicron sized 4A molecular sieve prepared according to the method of any one of claims 1 to 7.
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