CN110395745B - P-A type molecular sieve prepared from spontaneous combustion coal gangue and preparation method thereof - Google Patents
P-A type molecular sieve prepared from spontaneous combustion coal gangue and preparation method thereof Download PDFInfo
- Publication number
- CN110395745B CN110395745B CN201910830954.8A CN201910830954A CN110395745B CN 110395745 B CN110395745 B CN 110395745B CN 201910830954 A CN201910830954 A CN 201910830954A CN 110395745 B CN110395745 B CN 110395745B
- Authority
- CN
- China
- Prior art keywords
- coal gangue
- spontaneous combustion
- molecular sieve
- type molecular
- combustion coal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003245 coal Substances 0.000 title claims abstract description 108
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 90
- 230000002269 spontaneous effect Effects 0.000 title claims abstract description 90
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- 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 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 108
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 241000202755 Areca Species 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 238000000498 ball milling Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052782 aluminium Chemical group 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910001387 inorganic aluminate Inorganic materials 0.000 claims description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- -1 hydroxide ions Chemical class 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 14
- 229920000573 polyethylene Polymers 0.000 description 14
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052665 sodalite Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 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 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 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 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052652 orthoclase Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/14—Type A
- C01B39/16—Type A from aqueous solutions of an alkali metal aluminate and an alkali metal silicate excluding any other source of alumina or silica but seeds
-
- 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
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
A P-A type molecular sieve prepared by using spontaneous combustion coal gangue and ｃA preparation method thereof belong to the field of porous material synthesis. The specific surface areｃA of the P-A type molecular sieve prepared by the spontaneous combustion coal gangue is 4.5-6.5m2·g‑1The grain diameter is 3.18-4.25 um. It is composed ofThe preparation method comprises the following steps: and respectively adding sodium aluminate and pulverized spontaneous combustion coal gangue into the sodium hydroxide aqueous solution, heating the obtained mixture, cooling, performing solid-liquid separation, and drying to obtain the P-A type molecular sieve. The raw materials are cheap and easy to obtain, the operation conditions are loose, and the purity of the prepared P-A type molecular sieve is higher and can reach 50-65%. Meanwhile, a new way is provided for recycling, refining and efficiently utilizing the coal gangue, the effect of changing waste into valuable is achieved, and the requirement of environmental protection and low carbon is met.
Description
Technical Field
The invention relates to the field of porous material synthesis, in particular to ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue and ｃA preparation method thereof.
Background
China is the country with the largest coal mining amount in the world, and the coal gangue is a co-associated mineral of coal, is generated in the coal mining and washing processing processes, and becomes an industrial solid waste due to difficult utilization.
The molecular sieve is a crystalline silicate or aluminosilicate, and is formed by connecting silicon-oxygen tetrahedron or aluminum-oxygen tetrahedron through oxygen bridges, and according to the connection structure, the molecular sieve can be divided into an A-type molecular sieve, an octahedral zeolite molecular sieve (X, Y-type molecular sieve), a mordenite molecular sieve (M-type molecular sieve), a high-silicon zeolite molecular sieve (ZSM-type molecular sieve) and other molecular sieves, wherein the A-type molecular sieve is the most common model. Although the method and process for synthesizing molecular sieve by using pure chemical reagents are mature, the method has the disadvantages of strict requirements on the performance of raw materials (the raw materials must be high-purity and high-activity), high price of the raw materials and high production cost. The method is mainly synthesized by a hydrothermal method of mixing water glass and aluminum hydroxide in industry, and has the advantages of complex production process, long reaction time, low yield, filling of a guiding agent or a template agent and higher process cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the P-A type molecular sieve prepared by the spontaneous combustion coal gangue and the preparation method thereof, the preparation method not only can prepare the P-A type molecular sieve with single crystal phase, but also has the advantages of low production cost, simple process, good repeatability, convenience for industrial production, cheap and easily obtained raw materials, loose operation conditions and higher purity of the prepared P-A type molecular sieve which can reach 50-65%. Meanwhile, a new way is provided for recycling, refining and efficiently utilizing the coal gangue, the effect of changing waste into valuable is achieved, and the requirement of environmental protection and low carbon is met.
In order to achieve the aim, the invention provides ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue, and the specific surface areｃA of the P-A type molecular sieve is 4.5-6.5m2·g-1The particle size is 3.18-4.25um, and the structure of the P-A type molecular sieve prepared by the spontaneous combustion coal gangue is SiO4Tetrahedron and AlO4The tetrahedra are connected to each other by a common oxygen atom to form a spatial network structure in a staggered arrangement.
The P-A type molecular sieve crystal prepared from the spontaneous combustion coal gangue is composed of tetrahedron as ｃA basic structural unit; wherein, the central atom of the tetrahedron is Si atom or Al atom, the adjacent tetrahedrons are connected by the bridge oxygen bond to form a secondary structural unit, and the secondary structural unit is a multi-membered ring or a cage.
The framework structure of the P-A type molecular sieve prepared from the spontaneous combustion coal gangue is as follows: the beta cage is positioned at eight vertex positions of the cube, six four-membered rings of the beta cage are connected with each other through bridge oxygen bonds, a gamma cage is formed at the joint, the eight beta cages and the eight gamma cages enclose an alpha cage, and the alpha cages are communicated with each other through the eight-membered rings along the directions of three crystal axes to form a three-dimensional pore channel.
The invention relates to ｃA preparation method of ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue, which comprises the following steps:
(1) dissolving sodium hydroxide in deionized water to obtain a sodium hydroxide aqueous solution; wherein, according to the mass ratio, H2O：NaOH＝(40-70)：1；
(2) Adding sodium aluminate and pulverized spontaneous combustion coal gangue into a sodium hydroxide aqueous solution respectively, and stirring uniformly to obtain a mixture solution; wherein, sodium aluminate is used for adjusting the ratio of silicon to aluminum in the mixture solution, and according to the mass ratio, Si/Al is 1.3-1.9; adjusting the ratio of sodium to silicon in the mixture solution by using sodium hydroxide, wherein the ratio of Na/Si is 0.8-1.4 according to the mass ratio;
(3) heating the mixture to react at the temperature of 60-100 ℃ for 3-6h to obtain a mixed product;
(4) and cooling the mixed product, carrying out solid-liquid separation, and drying the solid to obtain the P-A type molecular sieve.
In the preparation method of the P-A type molecular sieve prepared from the spontaneous combustion coal gangue, in the step (2), citric acid can be added into the sodium hydroxide aqueous solution and stirred uniformly to obtain ｃA mixture; wherein the addition mass of the citric acid is 1/5-1/10 of the total mass of the solid matter.
In the step (2), the pulverized spontaneous combustion coal gangue powder with the particle size larger than 200 meshes accounts for more than or equal to 90% of the total spontaneous combustion coal gangue powder by mass.
In the step (2), a ball mill is adopted for grinding, the ball milling rotating speed is 40-55r/min, the ball milling time is 30-90min, and the material-ball ratio is 1: (15-5).
In the step (3), the reaction time is preferably 4-6 h.
In the step (4), before solid-liquid separation, the cooled mixed product can be washed by deionized water to ensure that the pH value is 9-10.
In the step (4), the solid-liquid separation is preferably one of suction filtration and filter pressing.
In the step (4), the solid is dried at the temperature of 90-110 ℃ for 1-3 h.
A P-A type molecular sieve prepared from spontaneous combustion coal gangue is prepared by the above preparation method.
The mass purity of the prepared P-A type molecular sieve prepared by the spontaneous combustion coal gangue is 50-65%.
The principle of the P-A type molecular sieve prepared from the spontaneous combustion coal gangue and the preparation method thereof is that the spontaneous combustion coal gangue is in ｃA metastable state through grinding, dislocation, point defect and structural defect are generated on the surfaces of coal gangue particles through grinding, the amorphous degree of silicon oxide and aluminum oxide is increased, the specific surface areｃA of the particles is increased, the free energy of the surfaces of the particles is increased, and therefore the activity is improved. Under the action of an aluminum source (sodium aluminate) and an alkali source (sodium hydroxide), depolymerization of covalent bonds occurs, an ionic solution is formed, ｃA three-dimensional network structure is gradually formed, and the P-A type molecular sieve is formed.
Compared with the prior art, the P-A type molecular sieve prepared by using the spontaneous combustion coal gangue and the preparation method thereof have the beneficial effects that:
1) the invention takes the spontaneous combustion coal gangue as the raw material, does not need to be calcined, saves energy, adopts ｃA mechanical grinding mode to grind the spontaneous combustion coal gangue to more than 200 meshes, improves the utilization rate of silicon and aluminum in the coal gangue, and can improve the production efficiency of the P-A type molecular sieve;
2) the P-A type molecular sieve synthesized by the method has single crystal phase and high quality purity which can reach 50-65%;
3) the preparation stage of the invention adopts sodium hydroxide which can be used as ｃA sodium source to adjust the sodium-silicon ratio and provide hydroxide ions to provide an alkaline environment, the silicon-aluminum ratio in ｃA synthetic framework is strictly controlled, the requirements of the P-A type molecular sieve are met, and meanwhile, the preparation process is simple, the process is easy to control, the production cost is low, and no pollution is caused to the environment.
4) The method for preparing the P-A type molecular sieve by using the coal gangue improves the comprehensive utilization rate and the added value of the coal gangue, expands the raw material source for preparing the molecular sieve, reduces the cost, changes waste into valuable and prolongs the industrial chain of coal processing. And environmental protection, energy conservation and emission reduction, circular economy and low-carbon economy can be realized.
Drawings
FIG. 1 is an XRD pattern of a pyrophoric coal gangue, the main feedstock employed in the examples of the present invention;
FIG. 2 is an XRD pattern of ｃA type P-A molecular sieve prepared in example 1 of the present invention;
FIG. 3 is an SEM photograph of ｃA P-A type molecular sieve prepared in example 1 of the present invention;
FIG. 4 is an XRD pattern of sodalite prepared in this comparative example;
fig. 5 is an SEM image of sodalite prepared by this comparative example.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
The spontaneous combustion gangue powder used in the examples comprises the following components in percentage by mass as shown in table 1:
TABLE 1 spontaneous combustion coal gangue powder components and mass percentage of each component
The raw materials of the embodiment and the spontaneous combustion coal gangue are tested and analyzed, the XRD pattern is shown in figure 1, and the main mineral compositions of the original spontaneous combustion coal gangue obtained through the figure 1 are quartz hematite, mullite, a small amount of kaolinite, orthoclase, hydromica and hematite.
Examples all starting materials were:
the method comprises the following steps of:
② excitant: sodium aluminate is chemically pure, and sodium hydroxide is chemically pure;
(iii) an auxiliary agent: citric acid is chemically pure, deionized water.
Example 1
A preparation method of ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue comprises the following steps:
(1) weighing raw materials according to the following proportion; wherein, the silicon-aluminum ratio is 1.3, the sodium-silicon ratio is 0.8, and the water-sodium ratio is 40;
(2) mixing 0.78g of sodium hydroxide with 31.2mL of deionized water, and uniformly stirring to obtain a NaOH aqueous solution;
(3) placing the spontaneous combustion coal gangue into a ball milling tank of a ball mill, wherein the mass ratio of the material to the ball is 1:10, the ball milling rotating speed is 40r/min, and the ball milling time is 30min to obtain spontaneous combustion coal gangue powder; wherein, in the spontaneous combustion coal gangue powder, the spontaneous combustion coal gangue powder with the grain diameter larger than 200 meshes accounts for 91 percent of the total spontaneous combustion coal gangue powder by mass.
(4) Adding 3g of spontaneous combustion coal gangue powder into the prepared NaOH aqueous solution, and uniformly stirring; then adding 0.79g of sodium aluminate powder, and stirring uniformly again; finally, 0.6g of citric acid is added and fully and uniformly stirred to obtain a mixture solution;
(5) transferring the obtained mixture solution into a polyethylene bottle, placing the polyethylene bottle in an oven, heating at 100 deg.C for 3h, taking out, naturally cooling to room temperature, washing the product with deionized water until pH is 10, filtering, and drying to obtain the final product with specific surface area of 5.2m2·g-1The P-A type molecular sieve of (1).
The P- ｃA type molecular sieve prepared in this example is analyzed and tested, and its XRD pattern is shown in fig. 2, and it is found that characteristic peaks of the P- ｃA type molecular sieve appear at positions where 2 θ is 7.1 °, 11.2 °, 12.5 °, 16.2 °, 24.1 ° and the like in different degrees, and the characteristic peak has ｃA sharp peak shape and good crystallinity. The diffraction peak of the product is matched with the standard PDF card of the P-A type molecular sieve, and the P-A type molecular sieve is successfully synthesized by utilizing the coal gangue.
The SEM image of the P-A type molecular sieve is shown in figure 3, and the P-A type molecular sieve is shown in figure 3 to be in ｃA cubic structure, complete in crystal structure, uniform in size and 3.18-4.25um in particle size.
Example 2
A preparation method of ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue comprises the following steps:
(1) weighing raw materials according to the following proportion; wherein, the silicon-aluminum ratio is 1.3, the sodium-silicon ratio is 1, and the water-sodium ratio is 70;
(2) mixing 1.07g of sodium hydroxide with 74.9mL of deionized water, and uniformly stirring to obtain a NaOH aqueous solution;
(3) placing the spontaneous combustion coal gangue into a ball milling tank of a ball mill, wherein the mass ratio of the material to the ball is 1:15, the ball milling rotating speed is 45r/min, and the ball milling time is 45min to obtain spontaneous combustion coal gangue powder; wherein, in the spontaneous combustion coal gangue powder, the spontaneous combustion coal gangue powder with the grain diameter larger than 200 meshes accounts for 91 percent of the total spontaneous combustion coal gangue powder by mass.
(4) Adding 3g of coal gangue powder into the prepared NaOH aqueous solution, and uniformly stirring; then adding 0.6g of sodium aluminate powder, and stirring uniformly again; finally, 0.61g of citric acid is added and fully and uniformly stirred to obtain a mixture solution;
(5) transferring the obtained mixture solution into a polyethylene bottle, placing the polyethylene bottle in an oven, heating at 70 deg.C for 6h, taking out, naturally cooling to room temperature, washing the solid product with deionized water until pH is 10, filtering, and drying to obtain the final product with specific surface area of 6.4m2·g-1P-A type molecular sieve.
Example 3
A preparation method of ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue comprises the following steps:
(1) weighing raw materials according to the following proportion; wherein, the silicon-aluminum ratio is 1.5, the sodium-silicon ratio is 0.8, and the water-sodium ratio is 60;
(2) mixing 0.9g of sodium hydroxide with 54mL of deionized water, and uniformly stirring to obtain a NaOH aqueous solution;
(3) placing the spontaneous combustion coal gangue into a ball milling tank of a ball mill, wherein the mass ratio of the spontaneous combustion coal gangue to the material ball is 1:10, the ball milling rotating speed is 50r/min, and the ball milling time is 60min, so as to obtain spontaneous combustion coal gangue powder; wherein, in the spontaneous combustion coal gangue powder, the spontaneous combustion coal gangue powder with the grain diameter larger than 200 meshes accounts for 91 percent of the total spontaneous combustion coal gangue powder by mass.
(4) Adding 3g of coal gangue powder into the prepared NaOH aqueous solution, and uniformly stirring; then adding 0.52g of sodium aluminate powder, and stirring uniformly again; finally, 0.54g of citric acid is added and fully and uniformly stirred to obtain a mixture solution;
(5) transferring the obtained mixture solution into a polyethylene bottle, placing the polyethylene bottle in an oven, heating at 100 deg.C for 3h, taking out, naturally cooling to room temperature, performing solid-liquid separation, washing the solid product with deionized water until pH is 10, filtering, and drying to obtain the final product with specific surface area of 4.5m2·g-1P-A type molecular sieve.
Example 4
A preparation method of ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue comprises the following steps:
(1) weighing raw materials according to the following proportion; wherein, the silicon-aluminum ratio is 1.5, the sodium-silicon ratio is 1.4, and the water-sodium ratio is 40;
(2) mixing 1.78g of sodium hydroxide with 71.2mL of deionized water, and uniformly stirring to obtain a NaOH aqueous solution;
(3) placing the spontaneous combustion coal gangue into a ball milling tank of a ball mill, wherein the mass ratio of the spontaneous combustion coal gangue to the material ball is 1:10, the ball milling rotating speed is 50r/min, and the ball milling time is 60min, so as to obtain spontaneous combustion coal gangue powder; wherein, in the spontaneous combustion coal gangue powder, the spontaneous combustion coal gangue powder with the grain diameter larger than 200 meshes accounts for 90 percent of the total spontaneous combustion coal gangue powder by mass.
(4) Adding 3g of coal gangue powder into the prepared NaOH aqueous solution, and uniformly stirring; then adding 0.52g of sodium aluminate powder, and stirring uniformly again; finally, 0.68g of citric acid is added and fully and uniformly stirred to obtain a mixture solution;
(5) transferring the obtained mixture solution into a polyethylene bottle, placing the polyethylene bottle in an oven, heating at 70 deg.C for 6h, taking out, naturally cooling to room temperature, washing the solid product with deionized water to pH 10, filtering, and drying to obtain the final product with specific surface area of 5.3m2·g-1P-A type molecular sieve.
Example 5
A preparation method of ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue comprises the following steps:
(1) weighing raw materials according to the following proportion; wherein, the silicon-aluminum ratio is 1.7, the sodium-silicon ratio is 1.2, and the water-sodium ratio is 40.
(2) Mixing 1.55g of sodium hydroxide with 62mL of deionized water, and uniformly stirring to obtain a NaOH aqueous solution;
(3) placing the spontaneous combustion coal gangue into a ball milling tank of a ball mill, wherein the mass ratio of the spontaneous combustion coal gangue to the material ball is 1:5, the ball milling rotating speed is 50r/min, and the ball milling time is 60min, so as to obtain spontaneous combustion coal gangue powder; wherein, in the spontaneous combustion coal gangue powder, the spontaneous combustion coal gangue powder with the grain diameter larger than 200 meshes accounts for 92 percent of the total spontaneous combustion coal gangue powder by mass.
(4) Adding 3g of coal gangue powder into the prepared NaOH aqueous solution, and uniformly stirring; then adding 0.34g of sodium aluminate powder, and stirring uniformly again; finally, 0.60g of citric acid is added and fully and uniformly stirred to obtain a mixture solution;
(5) transferring the obtained mixture solution into a polyethylene bottle, placing the polyethylene bottle in an oven, heating at 100 deg.C for 3h, taking out, naturally cooling to room temperature, washing the solid product with deionized water to pH 10, filtering, and drying to obtain the final product with specific surface area of 6.1m2·g-1P-A type molecular sieve.
Example 6
A preparation method of ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue comprises the following steps:
(1) weighing raw materials according to the following proportion; wherein, the silicon-aluminum ratio is 1.9, the sodium-silicon ratio is 1, and the water-sodium ratio is 50.
(2) Mixing 1.38g of sodium hydroxide with 69mL of deionized water, and uniformly stirring to obtain a NaOH aqueous solution;
(3) placing the spontaneous combustion coal gangue into a ball milling tank of a ball mill, wherein the mass ratio of the material to the ball is 1:15, the ball milling rotating speed is 55r/min, and the ball milling time is 45min to obtain spontaneous combustion coal gangue powder; wherein, in the spontaneous combustion coal gangue powder, the spontaneous combustion coal gangue powder with the grain diameter larger than 200 meshes accounts for 92 percent of the total spontaneous combustion coal gangue powder by mass.
(4) Adding 3g of coal gangue powder into the prepared NaOH aqueous solution, and uniformly stirring; then adding 0.15g of sodium aluminate powder, and stirring uniformly again; finally, 0.55g of citric acid is added and fully and uniformly stirred to obtain a mixture solution;
(5) transferring the obtained mixture solution into a polyethylene bottle, placing the polyethylene bottle in an oven, heating at 70 deg.C for 6h, taking out, naturally cooling to room temperature, washing the solid product with deionized water to pH 10, filtering, and drying to obtain the final product with specific surface area of 5.7m2·g-1P-A type molecular sieve.
Comparative example 1
A method for preparing sodalite by using spontaneous combustion coal gangue comprises the following steps:
(1) weighing raw materials according to the following proportion; wherein, the silicon-aluminum ratio is 2, the sodium-silicon ratio is 1.5, and the water-sodium ratio is 75.
(2) Mixing 2.12g of sodium hydroxide with 159mL of deionized water, and uniformly stirring to obtain a hydroxide aqueous solution;
(3) placing the spontaneous combustion coal gangue into a ball milling tank of a ball mill, wherein the mass ratio of the spontaneous combustion coal gangue to the material ball is 1:10, the ball milling rotating speed is 50r/min, and the ball milling time is 45min, so as to obtain spontaneous combustion coal gangue powder; wherein, in the spontaneous combustion coal gangue powder, the spontaneous combustion coal gangue powder with the grain diameter larger than 200 meshes accounts for 92 percent of the total spontaneous combustion coal gangue powder by mass.
(4) Adding 3g of coal gangue powder into the prepared NaOH aqueous solution, and uniformly stirring; then, 0.1g of sodium aluminate powder is added and stirred uniformly again; finally, 0.4g of citric acid is added and fully and uniformly stirred to obtain a mixture solution; transferring the obtained mixed solution into a polyethylene bottle, placing the polyethylene bottle in an oven, heating at 80 deg.C for 6h, taking out, naturally cooling to room temperature, washing the solid product with deionized water to pH 10, filtering, and drying to obtain product with specific surface area of 3.7m2·g-1。
The XRD and SEM images of the prepared product are shown in figure 4 and figure 5 respectively, and the XRD and SEM images can judge that spherical hydroxyl sodalite crystals are generated, which shows that the crystallization product is converted into sodalite from the P-A type molecular sieve along with the increase of the silicｃA-aluminｃA ratio, the sodium-silicｃA ratio and the citric acid content, the increase of the crystallization temperature and the extension of the crystallization time.
Having described various embodiments of the present invention, the foregoing description is intended to be illustrative, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the spirit of the invention.
Claims (7)
1. A preparation method of ｃA P-A type molecular sieve prepared from spontaneous combustion coal gangue is characterized by comprising the following steps:
(1) dissolving sodium hydroxide in deionized water to obtain a sodium hydroxide aqueous solution; wherein, according to the mass ratio, H2O：NaOH=(40-70)：1；
(2) Adding sodium aluminate and pulverized spontaneous combustion coal gangue into a sodium hydroxide aqueous solution respectively, and stirring uniformly to obtain a mixture solution; wherein, sodium aluminate is used for adjusting the silicon-aluminum ratio in the mixture solution, and according to the mass ratio, Si/Al = 1.3-1.9; adjusting the ratio of sodium to silicon in the mixture solution by using sodium hydroxide, wherein Na/Si =0.8-1.4 in mass ratio;
the pulverized spontaneous combustion coal gangue powder with the grain size larger than 200 meshes accounts for more than or equal to 90 percent of the total spontaneous combustion coal gangue powder by mass;
the grinding adopts a ball mill, the ball milling rotating speed is 40-55r/min, the ball milling time is 30-90min, and the material-ball ratio is 1: (15-5);
(3) heating the mixture to react at the temperature of 60-100 ℃ for 3-6h to obtain a mixed product;
(4) and cooling the mixed product, carrying out solid-liquid separation, and drying the solid to obtain the P-A type molecular sieve.
2. The method for preparing the P-A type molecular sieve from the spontaneous combustion coal gangue as claimed in claim 1, wherein in the method for preparing the P-A type molecular sieve from the spontaneous combustion coal gangue, citric acid is added into the sodium hydroxide aqueous solution in the step (2), and the mixture is obtained by uniformly stirring; wherein the addition mass of the citric acid is 1/5-1/10 of the total mass of the solid matter.
3. The method for preparing the P-A type molecular sieve by using the spontaneous combustion coal gangue as claimed in claim 1, wherein in the step (4), before solid-liquid separation, deionized water is adopted to wash the cooled mixed product to ensure that the pH value is 9-10;
the solid-liquid separation is one of suction filtration and filter pressing;
and drying the solid for 1-3h at the drying temperature of 90-110 ℃.
4. A P-A type molecular sieve prepared from spontaneous combustion coal gangue, which is characterized by being prepared according to any one of claims 1 to 3The preparation method is adopted to prepare; the specific surface areｃA of the P-A type molecular sieve prepared by the spontaneous combustion coal gangue is 4.5-6.5m2·g-1The particle size is 3.18-4.25um, and the structure of the P-A type molecular sieve prepared by the spontaneous combustion coal gangue is SiO4Tetrahedron and AlO4The tetrahedra are connected to each other by a common oxygen atom to form a spatial network structure in a staggered arrangement.
5. The P-A type molecular sieve prepared from the spontaneous combustion coal gangue as claimed in claim 4, wherein the mass purity of the prepared P-A type molecular sieve prepared from the spontaneous combustion coal gangue is 50-65%.
6. The P-A type molecular sieve prepared from the spontaneous combustion coal gangue as claimed in claim 4, wherein the P-A type molecular sieve crystal prepared from the spontaneous combustion coal gangue is composed of tetrahedrons as basic structural units; wherein, the central atom of the tetrahedron is Si atom or Al atom, the adjacent tetrahedrons are connected by the bridge oxygen bond to form a secondary structural unit, and the secondary structural unit is a multi-membered ring or a cage.
7. The P-A type molecular sieve prepared from the spontaneous combustion coal gangue as claimed in claim 4, wherein the framework structure of the P-A type molecular sieve prepared from the spontaneous combustion coal gangue is as follows: the beta cage is positioned at eight vertex positions of the cube, six four-membered rings of the beta cage are connected with each other through bridge oxygen bonds, a gamma cage is formed at the joint, the eight beta cages and the eight gamma cages enclose an alpha cage, and the alpha cages are communicated with each other through the eight-membered rings along the directions of three crystal axes to form a three-dimensional pore channel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910830954.8A CN110395745B (en) | 2019-09-04 | 2019-09-04 | P-A type molecular sieve prepared from spontaneous combustion coal gangue and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910830954.8A CN110395745B (en) | 2019-09-04 | 2019-09-04 | P-A type molecular sieve prepared from spontaneous combustion coal gangue and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110395745A CN110395745A (en) | 2019-11-01 |
| CN110395745B true CN110395745B (en) | 2021-02-26 |
Family
ID=68329685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910830954.8A Active CN110395745B (en) | 2019-09-04 | 2019-09-04 | P-A type molecular sieve prepared from spontaneous combustion coal gangue and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110395745B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939492B (en) * | 2021-04-14 | 2022-09-23 | 沈阳建筑大学 | Preparation method of coal gangue geopolymer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298628C (en) * | 2004-12-07 | 2007-02-07 | 中国日用化学工业研究院 | Method for preparing A type zeolite by gangue |
| CN100582004C (en) * | 2008-01-08 | 2010-01-20 | 中国日用化学工业研究院 | Method for preparing high whiteness A-type zeolite from coal gangue |
| CN108190908A (en) * | 2018-03-27 | 2018-06-22 | 天津工业大学 | A kind of method of Synthesizing 4 A Zeolite from Gangue |
| CN108483460A (en) * | 2018-06-04 | 2018-09-04 | 陕西师范大学 | A method of using gangue be raw material two-step method Synthesis of 4 A-type Zeolite by Hydrothermal |
-
2019
- 2019-09-04 CN CN201910830954.8A patent/CN110395745B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110395745A (en) | 2019-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020100373A4 (en) | Method for preparing ssz-13 molecular sieve by using fly ash | |
| CN107640775B (en) | Method for preparing ZSM-5 molecular sieve by using solid waste | |
| AU2020101871A4 (en) | A Method for Preparing ZSM-5 Zeolite by Using Solid wastes | |
| CN103449467B (en) | Method for preparing 13X molecular sieve through using high-alumina fly ash, and 13X molecular sieve | |
| CN106517237B (en) | Flyash acid system residue of aluminum-extracted prepares the method for NaY type molecular sieve and type ZSM 5 molecular sieve and the utilization method of flyash | |
| CN101734683A (en) | 13X-type molecular sieve and preparation method thereof | |
| CN104326480B (en) | The method that a kind of use waterglass and lime slurry prepare microporous calcium silicate | |
| CN107381524B (en) | The method and NaP molecular sieve of NaP molecular sieve are prepared using white clay as raw material | |
| CN108928834B (en) | MCM-41 mesoporous molecular sieve, and preparation method and application thereof | |
| CN108483460A (en) | A method of using gangue be raw material two-step method Synthesis of 4 A-type Zeolite by Hydrothermal | |
| CN112408401A (en) | Method for preparing silicon dioxide aerogel by utilizing industrial solid waste fly ash and silicon dioxide aerogel prepared by method | |
| CN110395745B (en) | P-A type molecular sieve prepared from spontaneous combustion coal gangue and preparation method thereof | |
| CN108658092B (en) | Method for preparing P-type molecular sieve and high-silicon mordenite from aluminum residue extracted by fly ash acid method and utilization method of fly ash | |
| CN108928829B (en) | SBA-15 mesoporous molecular sieve, preparation method and application thereof | |
| CN101928010B (en) | Preparation method of NaY type molecular sieve | |
| CN109292793A (en) | A kind of preparation method of P type zeolite molecular sieve | |
| CN113845128A (en) | MOR zeolite molecular sieve and preparation method thereof | |
| CN108946754B (en) | SBA-15 mesoporous molecular sieve, preparation method and application thereof, and method for producing alumina and SBA-15 mesoporous molecular sieve from fly ash | |
| CN115385356A (en) | Method for preparing 13X molecular sieve by using fly ash solid phase | |
| CN112573536A (en) | Nano P-type zeolite, preparation method and application thereof | |
| CN110451518B (en) | Method for synthesizing SAPO-34 molecular sieve by using hectorite | |
| CN108658090B (en) | Method for preparing 13X type molecular sieve and high-silicon mordenite by extracting aluminum residue from fly ash through acid method and utilization method of fly ash | |
| CN108658086B (en) | Method for preparing sodalite and high-silicon mordenite from residue of aluminum extraction by fly ash acid method and utilization method of fly ash | |
| CN110510627A (en) | The preparation method of P type zeolite molecular sieve and resulting P type zeolite molecular sieve | |
| CN103073023A (en) | Method for preparing 13X zeolite molecular sieve by kaolin containing illite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240126 Address after: 101200 room 205-211526, No. 40, Fuqian West Street, Pinggu town, Pinggu District, Beijing (cluster registration) Patentee after: BEIJING YONGBO TECHNOLOGY CO.,LTD. Country or region after: China Address before: 110168 No. 9 Hunnan East Road, Hunnan District, Shenyang City, Liaoning Province Patentee before: SHENYANG JIANZHU University Country or region before: China |
|
| TR01 | Transfer of patent right |