CN113353949A - Synthetic zeolite of fly ash and coal gangue aluminum extraction slag and comprehensive utilization method thereof - Google Patents
Synthetic zeolite of fly ash and coal gangue aluminum extraction slag and comprehensive utilization method thereof Download PDFInfo
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- CN113353949A CN113353949A CN202110739515.3A CN202110739515A CN113353949A CN 113353949 A CN113353949 A CN 113353949A CN 202110739515 A CN202110739515 A CN 202110739515A CN 113353949 A CN113353949 A CN 113353949A
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- fly ash
- zeolite
- coal gangue
- aluminum extraction
- extraction slag
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000010457 zeolite Substances 0.000 title claims abstract description 119
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 118
- 239000010881 fly ash Substances 0.000 title claims abstract description 116
- 239000003245 coal Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 72
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 62
- 238000000605 extraction Methods 0.000 title claims abstract description 58
- 239000002893 slag Substances 0.000 title claims abstract description 52
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 92
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000003513 alkali Substances 0.000 claims abstract description 57
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 45
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000032683 aging Effects 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 25
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 13
- 239000010883 coal ash Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 19
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 36
- 238000001179 sorption measurement Methods 0.000 description 32
- 239000002910 solid waste Substances 0.000 description 12
- -1 silicon-aluminum-oxygen Chemical compound 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001172 regenerating effect Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010900 secondary nucleation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/56—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
Abstract
The invention relates to a synthetic zeolite of fly ash and coal gangue aluminum extraction slag and a comprehensive utilization method thereof, comprising the following steps: and (3) pretreating the fly ash to obtain fly ash clinker. Mixing the fly ash clinker and the coal gangue aluminum extraction slag to obtain a raw material. Mixing the raw materials with water to obtain a mixed solution, and stirring and aging the mixed solution under the assistance of ultrasonic waves. And carrying out hydrothermal crystallization treatment on the mixed solution to obtain a crystal solution. The liquid in the crystal solution was filtered to obtain zeolite. The zeolite is used to absorb carbon dioxide or sulfur dioxide. Reacting carbon dioxide with a sodium aluminate solution to generate sodium carbonate; or the sulfur dioxide is generated into sulfuric acid. Sodium carbonate is used as the alkali needed by coal ash pretreatment and coal gangue extraction of alumina by an alkaline method; or the sulfuric acid is used as coal gangue and is used as acid needed by extracting the alumina by an acid method. The fly ash and the coal gangue aluminum extraction slag are utilized to synthesize zeolite with high added value, and the fly ash and the coal gangue aluminum extraction slag are utilized with high added value.
Description
Technical Field
The invention relates to the field of comprehensive utilization of solid wastes, in particular to a synthetic zeolite prepared from fly ash and coal gangue aluminum extraction slag and a comprehensive utilization method thereof.
Background
The fly ash and coal gangue are industrial wastes, the fly ash is ash formed by losing organic matters and water during combustion of coal, and is powdery aluminosilicate solid waste. The coal gangue is a main industrial solid waste separated from lump coal in the coal dressing process, and the silicon-aluminum content of the coal gangue is also high. The utilization of the fly ash is concentrated on the low-added-value utilization in the aspects of building industry and road engineering at present, and the application of the fly ash in the high-added-value field is less. The main treatment approach of the coal gangue is to go back to the pit for burying and extracting aluminum and silicon. For coal gangue, the process of extracting aluminum is relatively easy and is divided into an alkaline process and an acid process. A part of the supply of alumina in China is obtained from extracting aluminum from coal gangue. About 80% of aluminum is dissolved out by alkaline extraction, but a large amount of aluminum extraction waste residues are generated after aluminum extraction, and the aluminum extraction waste residues are not recycled in the prior art. The current application method by taking the fly ash and the coal gangue as raw materials comprises the steps of manufacturing a cast stone (CN201210304295.2) for pit backfill, cast stone manufacture or application in the fields of construction, road pavement and the like, and only utilizes the solid wastes such as the fly ash and the coal gangue with low added value to prepare the fly ash and the coal gangue into disposable products. Extracting aluminum and silicon or extracting some rare metals (CN202010610571.2), and applying to the fields of building and road paving (CN201911404523.1), firing ceramic tiles (CN201310476296.X) and the like. A large amount of residues are generated after the aluminum extraction process is carried out on the fly ash and the coal gangue, and secondary damage is caused to the environment.
Disclosure of Invention
Technical problem to be solved
The invention provides a synthetic zeolite of fly ash and coal gangue aluminum extraction slag and a comprehensive utilization method thereof, aiming at solving the problems of less application in the high-added-value field in the prior art and the reutilization of aluminum extraction waste slag generated after aluminum extraction of coal gangue.
(II) technical scheme
In order to solve the problems, the invention provides a synthetic zeolite of fly ash and coal gangue aluminum extraction slag and a comprehensive utilization method thereof, wherein the method comprises the following steps:
s1: pretreating the fly ash to obtain fly ash clinker mixed with alkali;
s2: mixing the fly ash clinker and the coal gangue aluminum extraction slag to obtain a raw material;
s3: mixing the raw materials with water to obtain a mixed solution, and carrying out ultrasonic treatment and aging on the mixed solution under the stirring condition;
s4: carrying out hydrothermal crystallization treatment on the mixed solution to obtain a crystal solution;
s5: filtering liquid in the crystal solution to obtain zeolite, and putting the zeolite into an oven to be dried for 6 to 10 hours, wherein the temperature in the oven is 100 to 120 ℃;
s6: absorbing carbon dioxide or sulfur dioxide by using zeolite, and then carrying out gas desorption on the zeolite adsorbed with the carbon dioxide or the sulfur dioxide to realize enrichment of the carbon dioxide or the sulfur dioxide;
s7: the enriched carbon dioxide reacts with the sodium aluminate solution to generate sodium carbonate; or
Generating sulfuric acid from the enriched sulfur dioxide;
s8: the generated sodium carbonate is used as alkali required by coal ash pretreatment and used as alkali required by coal gangue for extracting aluminum oxide by an alkali method; or
The generated sulfuric acid is used as the acid needed by the coal gangue for producing alumina by an acid method.
Preferably, the pretreating fly ash comprises:
mechanically grinding the fly ash for 15 to 45 minutes to ensure that the fly ash can pass through a 325-mesh sieve, and roasting for 1 to 4 hours at the roasting temperature of 700 to 900 ℃;
grinding and mixing the fly ash and alkali, then carrying out ultrasonic treatment for 15 to 45 minutes under the working environment with the ultrasonic power of 500W, the amplitude of 100 percent and the frequency of 25kHz to obtain a first mixed material, and roasting the first mixed material for 4 to 6 hours to obtain a fly ash clinker, wherein the roasting temperature of the first mixed material is 500 to 800 ℃.
Preferably, in S2, the mass ratio of the fly ash clinker to the coal gangue aluminum extraction slag is 20: 1-1: 10.
Preferably, the mass ratio of the alkali to the fly ash in the first mixed material is 1.5: 1-2.5: 1;
the alkali comprises sodium carbonate and sodium hydroxide, wherein the mass content of the sodium hydroxide in the alkali is up to 25-40%.
Preferably, the mass ratio of the raw material to the water in the step S3 is 1: 5-1: 10.
Preferably, the coal gangue aluminum extraction slag is waste slag obtained by producing aluminum oxide from coal gangue through an acid method or an alkaline method.
Preferably, the sodium aluminate solution is a solution generated in the process of producing alumina by the coal gangue through an alkaline method.
Preferably, in S3, the aging time is 1 hour to 3 hours, the aging temperature is 60 ℃ to 80 ℃, and the stirring speed is 300rpm to 400 rpm.
Preferably, the rotation speed of the stirring is 350 rpm.
Preferably, in S4, the temperature of the hydrothermal crystallization is 100 to 120 ℃, and the time of the hydrothermal crystallization treatment is 12 to 48 hours.
(III) advantageous effects
The invention utilizes the fly ash and the coal gangue aluminum extraction slag to be utilized and organically combined to generate the zeolite with high added value, and can simultaneously utilize the fly ash and the coal gangue aluminum extraction slag. The synthesized zeolite can be comprehensively utilized, and the synthetic zeolite taking solid waste as a raw material as an adsorbent can save great production cost. Meanwhile, the investment cost generated by filling the fly ash and the coal gangue is saved. The zeolite molecular sieve synthesized by the two solid wastes has higher economic benefit than the zeolite molecular sieve directly used in low value-added fields such as road pavement and the like. The zeolite after gas adsorption and cyclic desorption regeneration can still be utilized with lower added value. Meanwhile, the method has good environmental benefits.
Drawings
FIG. 1 is a schematic view of a process for synthesizing zeolite from fly ash and coal gangue aluminum extraction slag and a comprehensive utilization method thereof when carbon dioxide is absorbed by zeolite;
FIG. 2 is a schematic view of a process for synthesizing zeolite from fly ash and coal gangue aluminum extraction slag and a comprehensive utilization method thereof when sulfur dioxide is absorbed by zeolite.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The invention takes fly ash and coal gangue aluminum extraction slag as raw materials, and utilizes silicon and aluminum elements in the fly ash and coal gangue aluminum extraction slag. The active ingredients in the zeolite are activated by pretreatment of mechanical grinding, ultrasound, alkali fusion and the like to be converted into sodium silicate and aluminate, and then hydrothermal crystallization synthesis is carried out, crystal nuclei are formed in the hydrothermal process, and the crystal nuclei grow gradually to form the zeolite with the silicon-aluminum-oxygen tetrahedral structure.
As shown in figure 1, the invention provides a synthetic zeolite of fly ash and coal gangue aluminum extraction slag and a comprehensive utilization method thereof, wherein the method comprises the following steps:
s1: and (3) pretreating the fly ash to obtain fly ash clinker mixed with the fly ash and alkali.
The pretreatment of the fly ash comprises the following steps:
the fly ash is ground for 15 minutes to 45 minutes and then roasted for 0.5 hour to 4 hours, the roasting temperature of the fly ash is 700 ℃ to 900 ℃, and in a specific embodiment, the fly ash is mechanically ground to pass through a 325-mesh sieve. The calcination may be carried out in a muffle furnace, the calcination time is preferably 2 hours, and the calcination temperature of the fly ash is preferably 800 ℃.
Mixing fly ash and alkali, performing ultrasonic treatment for 15-45 minutes in an ultrasonic environment to obtain a first mixed material, wherein the ultrasonic power is 500W, the amplitude is 100%, and the frequency is 25kHz, and then roasting the first mixed material for 4-6 hours to obtain fly ash clinker, wherein the roasting of the first mixed material can be performed in a muffle furnace at 500-800 ℃, and the alkali and the fly ash are fused together by roasting the first mixed material to obtain the fly ash clinker, so that the subsequent extraction of zeolite is facilitated. The roasting time is not too short, otherwise the generation reaction of the soluble silicate and the aluminate can not be completed, and the activation is not sufficient. When the roasting temperature is low, the activation is insufficient, and enough energy cannot be provided for the activation; when the roasting temperature is high, the fly ash can generate crystal form transformation; the calcination temperature should be higher than the melting point (318.4 ℃) of sodium hydroxide and lower than the boiling point of sodium hydroxide, and higher temperature can promote the forward progress of the fusion reaction of the fly ash and the alkali. The roasting temperature of the invention is 500-800 ℃, which can fully activate the fly ash clinker.
In a preferred embodiment, the mass ratio of alkali to fly ash in the first mixed material is from 1:1 to 2.5: 1. Wherein the alkali comprises sodium carbonate and sodium hydroxide, and the mass content of the sodium hydroxide in the alkali is up to 40%. Under the condition that the mass ratio of alkali to fly ash in the first mixed material is too small, effective substances in the fly ash cannot be fully activated and decomposed, and when the mass ratio of alkali to fly ash in the first mixed material is too large, products after activation and calcination are easy to agglomerate, and under the condition that the liquid-solid ratio is certain, the alkalinity of a hydrothermal crystallization reaction system is also increased, so that mixed crystals are easy to generate, and the phase is impure; according to the invention, the mass ratio of the alkali to the fly ash in the first mixed material is set to 1: 1-2.5: 1, so that effective substances in the fly ash can be well activated and decomposed, and the fly ash is not easy to agglomerate and generate mixed crystals.
Table 1 is a table of the ingredients of fly ash clinker used in the subsequent examples;
table 1:
| SiO2 | Al2O3 | Fe2O3 | CaO | K2O | TiO2 | MgO | others |
| 57.89％ | 22.17％ | 8.03％ | 6.82％ | 2.17％ | 0.89％ | 0.95％ | 0.99％ |
S2: mixing the fly ash clinker and the coal gangue aluminum extraction slag to obtain a raw material, wherein the ratio of the fly ash clinker to the coal gangue aluminum extraction slag is 20: 1-1: 10.
S3: mixing the raw materials with water to obtain a mixed solution, and carrying out ultrasonic treatment and aging on the mixed solution under the stirring condition. Specifically, the mixed solution is placed on a magnetic stirrer and is stirred and aged under the assistance of ultrasonic waves, the aging time is 1 hour to 3 hours, the aging temperature is 60 ℃ to 80 ℃, the stirring rotating speed is 300rpm to 400rpm, and the stirring rotating speed is preferably 350 rpm. The ultrasonic power at this time was 500W, 100% amplitude, 25 KHz. In this step, the mixed solution can be placed on a magnetic stirrer for stirring and aging, and the aging of the mixed solution can be accelerated by using ultrasonic waves, so that the efficiency is improved. In addition, the gangue aluminum extraction slag is waste slag obtained by extracting alumina from gangue through an acid method or an alkaline method, and when the gangue aluminum extraction slag is waste slag obtained by extracting alumina from gangue through the acid method, the pH value of the gangue aluminum extraction slag needs to be adjusted to 9-10 in a filtering or alkali adding mode, so that the gangue aluminum extraction slag is weakly alkaline waste slag.
Table 2 is a composition table of coal gangue used in the subsequent examples;
table 2:
the mass ratio of the raw material to water is 1:5 to 1:10 in step S3, wherein the water is ultrapure water.
S4: and carrying out hydrothermal crystallization treatment on the mixed solution to obtain a crystal solution, wherein the temperature of the hydrothermal crystallization is 100-120 ℃, and the time of the hydrothermal crystallization treatment is 12-48 hours.
For the crystallization temperature in the present invention:
when the temperature is too low, crystallization is difficult, and the crystallization time is prolonged; the high temperature is easy to agglomerate, and the high crystallization temperature can reduce the purity of the synthesized molecular sieve;
crystallization time:
the crystallization time is short, the reaction is possibly not sufficiently carried out, and the zeolite crystals are not completely crystallized; the crystallization time is too long, secondary nucleation is easy to occur, the phenomenon of crystal transformation occurs to form mixed crystals, and the purity of the synthesized zeolite can be reduced;
by adopting the crystallization temperature and the crystallization time in the invention to carry out hydrothermal crystallization, high-purity crystals can be generated in the mixed solution to form high-purity zeolite.
S5: and filtering liquid in the crystal solution to obtain the zeolite, and putting the zeolite into an oven for drying treatment.
Through the steps, the zeolite is synthesized by using the fly ash and the coal gangue aluminum extraction slag, so that high-value utilization of the fly ash is realized, the aluminum extraction waste slag generated after the aluminum extraction from the coal gangue is recycled, the recycling of wastes is realized, and the production value is improved.
S6: absorbing carbon dioxide or sulfur dioxide by using zeolite, and then carrying out gas desorption on the zeolite adsorbed with the carbon dioxide or the sulfur dioxide to realize enrichment of the carbon dioxide or the sulfur dioxide;
s7: the enriched carbon dioxide reacts with a sodium aluminate solution to generate sodium carbonate, wherein the sodium aluminate solution is a solution generated in the process of producing alumina by using a coal gangue through an alkaline method; or
Generating sulfuric acid from the enriched sulfur dioxide;
s8: the generated sodium carbonate is used as alkali required by the pretreatment of the fly ash and is used as alkali required by the production of alumina from coal gangue through an alkali method; or
The generated sulfuric acid is used as the acid needed by the coal gangue for producing alumina by an acid method.
In the steps, the zeolite is used for absorbing carbon dioxide, then the carbon dioxide is desorbed, the carbon dioxide is used for generating sodium carbonate, the sodium carbonate is used for alkali required by coal ash pretreatment and is used as alkali required by coal gangue for producing alumina through an alkali method, the purpose that the zeolite is used for absorbing the carbon dioxide, and the carbon dioxide is used for generating the sodium carbonate to further act in the step of synthesizing the zeolite (used as alkali required by coal ash pretreatment and coal gangue alkali method for extracting alumina) is achieved, the cost for producing the zeolite is saved, and the utilization of positive feedback is achieved.
In the same step, the zeolite can be used for absorbing sulfur dioxide, the sulfur dioxide is used for generating sulfuric acid, the sulfuric acid is used as acid required by the coal gangue for producing alumina through an acid method, the sulfur dioxide is absorbed by the zeolite to provide raw materials for the coal gangue for producing the alumina through the acid method, the cost for extracting the alumina from the coal gangue is reduced, the cost for generating the coal gangue aluminum extraction slag is also reduced, and the cost for producing the zeolite is further reduced.
Finally, after the zeolite is adsorbed and desorbed for a plurality of times, the adsorption performance of the zeolite is reduced, and the zeolite can be used in the aspects of formaldehyde purification bags for new house decoration, cement building materials and the like.
The method provided by the invention is illustrated below by means of specific examples:
example 1:
the first step is as follows: pretreating the fly ash to obtain fly ash clinker mixed with alkali;
the pretreatment of the fly ash comprises the following steps:
grinding the fly ash for 30min, and sieving with a 325-mesh sieve;
roasting the ground fly ash at the high temperature of 800 ℃ for 2h to remove carbon;
mixing and grinding fly ash, solid sodium carbonate and solid sodium hydroxide according to the mass ratio of 1:1.5:0.5, then carrying out ultrasonic treatment for 30min under the working environment with the ultrasonic power of 500W, the amplitude of 100 percent and the frequency of 25kHz, and then placing the mixture into a muffle furnace to roast for 4h at the temperature of 650 ℃ to obtain fly ash clinker;
the second step is that: mixing the fly ash clinker and the coal gangue aluminum extraction slag to obtain a raw material, wherein the mixing ratio is 20:1, the silicon-aluminum ratio (n (Si: Al)) is 2.32, and in the examples and the subsequent examples, the silicon-aluminum ratio is the molar ratio of a silicon element to an aluminum element and is suitable for synthesizing X-type zeolite;
the third step: mixing the raw materials and ultrapure water according to the mass ratio of 1:10 to obtain a mixed solution, placing the mixed solution on a magnetic stirrer, and stirring and aging the mixed solution under the assistance of ultrasonic waves, wherein the aging time is 1-3 hours, the aging temperature is 60-80 ℃, the rotating speed of the magnetic stirrer is 350rpm, the ultrasonic power is 500W, the amplitude is 100%, and the frequency is 25 kHz.
The fourth step: and (3) loading the aged mixed solution into polytetrafluoroethylene, and putting the polytetrafluoroethylene into a reaction kettle for hydrothermal crystallization for 14 hours at the temperature of 100 ℃ to obtain a crystal solution.
The fifth step: and carrying out suction filtration on the crystal solution to obtain zeolite, and drying the zeolite in an oven at 105 ℃.
And a sixth step: the synthesized zeolite was characterized by X-ray diffraction to give a crystallinity of 82.87%.
The seventh step: the adsorption of sulfur dioxide or carbon dioxide with the zeolite is carried out until the zeolite is saturated with the absorbed gas.
The step of absorbing sulfur dioxide or carbon dioxide by using zeolite specifically comprises the following steps:
10g of zeolite sample is mixed with quartz sand and then put into an adsorption column, and a gas cylinder is used as a gas supply system. CO 22Gas or SO2As a feed gas, N2As balance gas, CO2In the case of a mixed gas (the mixed gas is a mixed gas of a raw material gas and a balance gas, in this case, the mixed gas is CO2And N2Mixed gas of (2) or SO2In the case of a mixed gas (the mixed gas is a mixed gas of a raw material gas and a balance gas, in this case, the mixed gas is SO2And N2Mixed gas of (2) was 0.2% by volume. The flow rate of the mixed gas was 1.5L/min. The pressure was maintained at 3 MPa. First pass N2Post purge CO adjustment2Or SO2The desired gas mixture is formed until breakthrough. Gas outlet CO2Or SO2From the initial concentration (i.e. CO)2Volume percent concentration in the mixed gas or SO2Volume percent concentration in the mixed gas) was the same and maintained for more than 5min, breakthrough, i.e., zeolite adsorption saturation, was considered to have been reached.
In this example, zeolite to CO was measured2Has an adsorption amount of 2.96mmol/g, SO2The amount of adsorbed (D) was 2.52 mmol/g.
Eighth step: and desorbing and regenerating the zeolite saturated in adsorption by high-temperature heating or nitrogen reverse blowing to obtain enriched carbon dioxide or sulfur dioxide.
Reacting the enriched carbon dioxide gas with a sodium aluminate solution to generate sodium carbonate, and taking the generated sodium carbonate as alkali required by coal ash pretreatment and as alkali required by coal gangue for producing alumina by an alkali method; or the enriched sulfur dioxide is used for generating sulfuric acid, and the generated sulfuric acid is used as acid required by the coal gangue for producing alumina through an acid method.
Example 2:
the first step is as follows: pretreating the fly ash to obtain fly ash clinker mixed with alkali;
the fly ash pretreatment was the same as that of example 1.
The second step is that: mixing the fly ash clinker with the coal gangue aluminum extraction slag to obtain a raw material, wherein the mixing ratio is 10:1, and the silicon-aluminum ratio (n (Si: Al)) is 2.42 at the moment, so that the raw material is suitable for synthesizing X-type zeolite;
the third step: mixing the raw materials and ultrapure water according to the mass ratio of 1:10 to obtain a mixed solution, placing the mixed solution on a magnetic stirrer, and stirring and aging the mixed solution under the assistance of ultrasonic waves, wherein the aging time is 1-3 hours, the aging temperature is 60-80 ℃, the rotating speed of the magnetic stirrer is 350rpm, the ultrasonic power is 500W, the amplitude is 100%, and the frequency is 25 kHz.
The fourth step: and (3) loading the aged mixed solution into polytetrafluoroethylene, and putting the polytetrafluoroethylene into a reaction kettle for hydrothermal crystallization for 18 hours at the temperature of 100 ℃ to obtain a crystal solution.
The fifth step: and carrying out suction filtration on the crystal solution to obtain zeolite, and drying the zeolite in an oven at 105 ℃.
And a sixth step: the synthesized zeolite was characterized by X-ray diffraction to give a crystallinity of 80.28%.
The seventh step: zeolite is used to adsorb sulfur dioxide or carbon dioxide.
Wherein, the step of absorbing sulfur dioxide or carbon dioxide by zeolite is the same as the first embodiment. In this example, zeolite to CO was measured2The adsorption amount of (A) was 2.87mmol/g, and the adsorption amount of SO2 was 2.43 mmol/g.
Eighth step: and desorbing and regenerating the zeolite saturated in adsorption by high-temperature heating or nitrogen reverse blowing to obtain enriched carbon dioxide or sulfur dioxide.
Reacting the enriched carbon dioxide gas with a sodium aluminate solution to generate sodium carbonate, and taking the generated sodium carbonate as alkali required by coal ash pretreatment and as alkali required by coal gangue for producing alumina by an alkali method; or the enriched sulfur dioxide is used for generating sulfuric acid, and the generated sulfuric acid is used as acid required by the coal gangue for producing alumina through an acid method.
Example 3:
the first step is as follows: pretreating the fly ash to obtain fly ash clinker mixed with alkali;
the fly ash pretreatment was the same as that of example 1.
The second step is that: mixing the fly ash clinker with the coal gangue aluminum extraction slag to obtain a raw material, wherein the mixing ratio is 1:1, and the silicon-aluminum ratio (n (Si: Al)) is 3.8 at the moment, so that the raw material is suitable for synthesizing Y-type zeolite;
the third step: mixing the raw materials and ultrapure water according to the mass ratio of 1:10 to obtain a mixed solution, placing the mixed solution on a magnetic stirrer, and stirring and aging the mixed solution under the assistance of ultrasonic waves, wherein the aging time is 1-3 hours, the aging temperature is 60-80 ℃, the rotating speed of the magnetic stirrer is 350rpm, the ultrasonic power is 500W, the amplitude is 100%, and the frequency is 25 kHz.
The fourth step: and (3) loading the aged mixed solution into polytetrafluoroethylene, and putting the polytetrafluoroethylene into a reaction kettle for hydrothermal crystallization for 24 hours at the temperature of 110 ℃ to obtain a crystal solution.
The fifth step: and carrying out suction filtration on the crystal solution to obtain zeolite, and drying the zeolite in an oven at 105 ℃.
And a sixth step: characterization of the synthesized zeolite by X-ray diffraction gave a crystallinity of 79.49%.
The seventh step: zeolite is used to adsorb sulfur dioxide or carbon dioxide.
Wherein, the step of absorbing sulfur dioxide or carbon dioxide by zeolite is the same as the first embodiment. In this example, zeolite to CO was measured2Has an adsorption amount of 2.82mmol/g, SO2The amount of adsorbed (D) was 2.37 mmol/g.
Eighth step: and desorbing and regenerating the zeolite saturated in adsorption by high-temperature heating or nitrogen reverse blowing to obtain enriched carbon dioxide or sulfur dioxide.
Reacting the enriched carbon dioxide gas with a sodium aluminate solution to generate sodium carbonate, and taking the generated sodium carbonate as alkali required by coal ash pretreatment and as alkali required by coal gangue for producing alumina by an alkali method; or the enriched sulfur dioxide is used for generating sulfuric acid, and the generated sulfuric acid is used as acid required by the coal gangue for producing alumina through an acid method.
Example 4:
the first step is as follows: pretreating the fly ash to obtain fly ash clinker mixed with alkali;
the pretreatment of fly ash was the same as that of example 1;
the second step is that: mixing the fly ash clinker with the coal gangue aluminum extraction slag to obtain a raw material, wherein the mixing ratio is 1:2, and the silicon-aluminum ratio (n (Si: Al)) is 4.7, so that the raw material is suitable for synthesizing Y-type zeolite;
the third step: mixing the raw materials and ultrapure water according to the mass ratio of 1:10 to obtain a mixed solution, placing the mixed solution on a magnetic stirrer, and stirring and aging the mixed solution under the assistance of ultrasonic waves, wherein the aging time is 1-3 hours, the aging temperature is 60-80 ℃, the rotating speed of the magnetic stirrer is 350rpm, the ultrasonic power is 500W, the amplitude is 100%, and the frequency is 25 kHz.
The fourth step: and (3) loading the aged mixed solution into polytetrafluoroethylene, and putting the polytetrafluoroethylene into a reaction kettle for hydrothermal crystallization for 34 hours at the temperature of 110 ℃ to obtain a crystal solution.
The fifth step: and carrying out suction filtration on the crystal solution to obtain zeolite, and drying the zeolite in an oven at 105 ℃.
And a sixth step: characterization of the synthesized zeolite by X-ray diffraction gave a crystallinity of 80.94%.
The seventh step: zeolite is used to adsorb sulfur dioxide or carbon dioxide.
Wherein, the step of absorbing sulfur dioxide or carbon dioxide by zeolite is the same as the first embodiment. In this example, zeolite to CO was measured2Has an adsorption amount of 3.35mmol/g, SO2The amount of adsorbed (D) was 1.92 mmol/g.
Eighth step: and desorbing and regenerating the zeolite saturated in adsorption by high-temperature heating or nitrogen reverse blowing to obtain enriched carbon dioxide or sulfur dioxide.
Reacting the enriched carbon dioxide gas with a sodium aluminate solution to generate sodium carbonate, and taking the generated sodium carbonate as alkali required by coal ash pretreatment and as alkali required by coal gangue for producing alumina by an alkali method; or the enriched sulfur dioxide is used for generating sulfuric acid, and the generated sulfuric acid is used as acid required by the coal gangue for producing alumina through an acid method.
Example 5:
the first step is as follows: pretreating the fly ash to obtain fly ash clinker mixed with alkali;
the pretreatment of the fly ash is the same as that of the fly ash in example 1;
the second step is that: mixing the fly ash clinker with the coal gangue aluminum extraction slag to obtain a raw material, wherein the mixing ratio is 1:10, and the ratio of silicon to aluminum (n (Si: Al)) is 7, so that the raw material is suitable for synthesizing Y-type zeolite;
the third step: mixing the raw materials and ultrapure water according to the mass ratio of 1:10 to obtain a mixed solution, placing the mixed solution on a magnetic stirrer, and stirring and aging the mixed solution under the assistance of ultrasonic waves, wherein the aging time is 1-3 hours, the aging temperature is 60-80 ℃, the rotating speed of the magnetic stirrer is 350rpm, the ultrasonic power is 500W, the amplitude is 100%, and the frequency is 25 kHz.
The fourth step: and (3) loading the aged mixed solution into polytetrafluoroethylene, and putting the polytetrafluoroethylene into a reaction kettle for hydrothermal crystallization for 34 hours at the temperature of 110 ℃ to obtain a crystal solution.
The fifth step: and carrying out suction filtration on the crystal solution to obtain zeolite, and drying the zeolite in an oven at 105 ℃.
And a sixth step: characterization of the synthesized zeolite by X-ray diffraction gave a crystallinity of 79.07%.
The seventh step: zeolite is used to adsorb sulfur dioxide or carbon dioxide.
Wherein, the step of absorbing sulfur dioxide or carbon dioxide by zeolite is the same as the first embodiment. In this example, zeolite to CO was measured2Has an adsorption amount of 3.27mmol/g, SO2The adsorption amount of (B) was 1.87 mmol/g.
Eighth step: and desorbing and regenerating the zeolite saturated in adsorption by high-temperature heating or nitrogen reverse blowing to obtain enriched carbon dioxide or sulfur dioxide.
Reacting the enriched carbon dioxide gas with a sodium aluminate solution to generate sodium carbonate, and taking the generated sodium carbonate as alkali required by coal ash pretreatment and as alkali required by coal gangue for producing alumina by an alkali method; or the enriched sulfur dioxide is used for generating sulfuric acid, and the generated sulfuric acid is used as acid required by the coal gangue for producing alumina through an acid method.
Comparative example 1:
at present, the combined application of the coal gangue and the fly ash which are two solid wastes is mainly focused on the application of the coal gangue and the fly ash which are used as building materials or road paving materials, such as coal mine filling, pit backfilling and the like. For example, in chinese patents CN202010531259.4 and CN201911404523.1, the present invention only utilizes two types of solid wastes with low added value, and the present invention synthesizes zeolite from fly ash and gangue slag obtained through dealumination step as raw materials and utilizes them comprehensively, which belongs to high added value utilization of solid wastes.
Comparative example 2:
chinese patent CN201410279241.4 discloses a CO which takes organic amine loaded on MOFs as a novel MOFs group2The adsorbent utilizes a large amount of organic matters, improves the material synthesis cost, and is not beneficial to safety and environment, and the raw materials adopted in the invention are industrial wastes and reagents with wide sources and low price. CO of the material synthesized in this patent2The adsorption capacity is 2.5mmol/g, and the CO of the zeolite material synthesized by the invention2The adsorption capacity is higher than that of the MOFs-based CO2An adsorbent. Comparative example 3:
chinese patent CN201910110758.3 discloses a SO2An adsorbent for synthesizing SO from three metal salts and Mg-Al hydrotalcite and its preparing process2And (4) carrying out adsorption. Compared with the present invention, the raw materials used are numerous and the process is complicated, and in addition, SO is used in the patent2The maximum sulfur capacity of the adsorption is 0.12g/g, and the adsorption capacity is smaller than that of the zeolite synthesized in the invention.
Comparative example 4:
SO disclosed by Chinese patent CN201510894499.X2The adsorption capacity of the adsorbent is 40-60 mg SO2The adsorption capacity of the X zeolite and the adsorption capacity of the Y zeolite synthesized by the invention are both stronger than that of the adsorbent.
In the embodiment, the two solid wastes of the fly ash and the coal gangue aluminum extraction slag are utilized and organically combined to generate the zeolite with high added value, so that the fly ash and the coal gangue aluminum extraction slag can be simultaneously utilized. The synthesized zeolite can be comprehensively utilized, and the synthesized X zeolite and the synthesized Y zeolite both have good selective adsorption and high adsorption capacity, and have good adsorption effect on carbon dioxide and sulfur dioxide gas. The zeolite can be regenerated after being saturated by adsorption, and the gas which is enriched by adsorption and desorption can be used for industrial production and can be recycled or byproduct products can be generated. The zeolite after repeated adsorption and desorption regeneration can be used as a formaldehyde purification bag of a new house and can be applied to the aspect of lower added value of cement and the like.
From the economic benefit, the zeolite molecular sieve synthesized by taking solid waste as raw material as adsorbent can save great production cost. Meanwhile, the investment cost generated by filling the fly ash and the coal gangue is saved. The zeolite with high added value synthesized by the two solid wastes can create higher economic benefit than the zeolite directly used in low added value fields such as road pavement and the like. The zeolite after gas adsorption and cyclic desorption regeneration can still be utilized with lower added value. Meanwhile, the method has good environmental benefits.
It should be understood that the above description of specific embodiments of the present invention is only for the purpose of illustrating the technical lines and features of the present invention, and is intended to enable those skilled in the art to understand the contents of the present invention and to implement the present invention, but the present invention is not limited to the above specific embodiments. It is intended that all such changes and modifications as fall within the scope of the appended claims be embraced therein.
Claims (10)
1. A synthetic zeolite of fly ash and coal gangue aluminum extraction slag and a comprehensive utilization method thereof are characterized in that the method comprises the following steps:
s1: pretreating the fly ash to obtain fly ash clinker mixed with alkali;
s2: mixing the fly ash clinker and the coal gangue aluminum extraction slag to obtain a raw material;
s3: mixing the raw materials with water to obtain a mixed solution, and carrying out ultrasonic treatment and aging on the mixed solution under the stirring condition;
s4: carrying out hydrothermal crystallization treatment on the mixed solution to obtain a crystal solution;
s5: filtering liquid in the crystal solution to obtain zeolite, and putting the zeolite into an oven to be dried for 6 to 10 hours, wherein the temperature in the oven is 100 to 120 ℃;
s6: absorbing carbon dioxide or sulfur dioxide by using zeolite, and then carrying out gas desorption on the zeolite adsorbed with the carbon dioxide or the sulfur dioxide to realize enrichment of the carbon dioxide or the sulfur dioxide;
s7: the enriched carbon dioxide reacts with the sodium aluminate solution to generate sodium carbonate; or
Generating sulfuric acid from the enriched sulfur dioxide;
s8: the generated sodium carbonate is used as alkali required by coal ash pretreatment and used as alkali required by coal gangue for extracting aluminum oxide by an alkali method; or
The generated sulfuric acid is used as the acid needed by the coal gangue for producing alumina by an acid method.
2. The method for synthesizing zeolite from fly ash and coal gangue aluminum extraction slag and comprehensively utilizing the zeolite as claimed in claim 1, wherein the pretreatment of fly ash comprises:
mechanically grinding the fly ash for 15 to 45 minutes to ensure that the fly ash can pass through a 325-mesh sieve, and roasting for 1 to 4 hours at the roasting temperature of 700 to 900 ℃;
grinding and mixing the fly ash and alkali, then carrying out ultrasonic treatment for 15 to 45 minutes under the working environment with the ultrasonic power of 500W, the amplitude of 100 percent and the frequency of 25kHz to obtain a first mixed material, and roasting the first mixed material for 4 to 6 hours to obtain a fly ash clinker, wherein the roasting temperature of the first mixed material is 500 to 800 ℃.
3. The synthetic zeolite of fly ash and coal gangue aluminum extraction slag and the comprehensive utilization method thereof as claimed in claim 2, wherein,
in S2, the mass ratio of the fly ash clinker to the coal gangue aluminum extraction slag is 20: 1-1: 10.
4. The method for synthesizing zeolite from fly ash and coal gangue aluminum extraction slag and comprehensively utilizing the zeolite as claimed in claim 2, wherein the mass ratio of alkali to fly ash in the first mixed material is 1.5: 1-2.5: 1;
the alkali comprises sodium carbonate and sodium hydroxide, wherein the mass content of the sodium hydroxide in the alkali is up to 25-40%.
5. The synthetic zeolite prepared from fly ash and coal gangue aluminum extraction slag and the comprehensive utilization method thereof as claimed in any one of claims 1-4, wherein the mass ratio of the raw material to water in step S3 is 1: 5-1: 10.
6. The zeolite synthesized from fly ash and coal gangue aluminum extraction slag and the comprehensive utilization method thereof as claimed in any one of claim 4, wherein the coal gangue aluminum extraction slag is waste residue of coal gangue after alumina is produced by acid method or alkaline method.
7. The method for synthesizing zeolite from fly ash and coal gangue aluminum extraction residue and the comprehensive utilization method thereof as claimed in any one of claims 1-4, wherein the sodium aluminate solution is a solution generated in the process of producing alumina from coal gangue by an alkaline method.
8. The method for synthesizing zeolite from fly ash and coal gangue aluminum extraction slag and the comprehensive utilization method thereof as claimed in any one of claims 1-4, wherein in S3, the aging time is 1-3 hours, the aging temperature is 60-80 ℃, and the stirring speed is 300-400 rpm.
9. The synthetic zeolite of fly ash and coal gangue aluminum extraction slag and the comprehensive utilization method thereof as claimed in claim 8, wherein the stirring rotation speed is 350 rpm.
10. The method for synthesizing zeolite from fly ash and coal gangue aluminum extraction residue and the comprehensive utilization method thereof as claimed in any one of claims 1-4, wherein in S4, the temperature of hydrothermal crystallization is 100-120 ℃, and the time of hydrothermal crystallization treatment is 12-48 hours.
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| CN113893815A (en) * | 2021-11-17 | 2022-01-07 | 太原科技大学 | Ceramsite-zeolite composite high-performance adsorbing material and preparation method thereof |
| CN113996142A (en) * | 2021-09-08 | 2022-02-01 | 中国大唐集团科学技术研究总院有限公司华东电力试验研究院 | System and method for manufacturing zeolite and capturing carbon dioxide in flue gas by using fly ash |
| CN115779850A (en) * | 2022-11-01 | 2023-03-14 | 深圳市中金岭南有色金属股份有限公司凡口铅锌矿 | Silica-based stone powder material, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800643A (en) * | 2016-03-07 | 2016-07-27 | 中国科学院过程工程研究所 | Method for preparing 13X molecular sieve by cooperation of coal gangue and coal ash desilication liquid |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800643A (en) * | 2016-03-07 | 2016-07-27 | 中国科学院过程工程研究所 | Method for preparing 13X molecular sieve by cooperation of coal gangue and coal ash desilication liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113996142A (en) * | 2021-09-08 | 2022-02-01 | 中国大唐集团科学技术研究总院有限公司华东电力试验研究院 | System and method for manufacturing zeolite and capturing carbon dioxide in flue gas by using fly ash |
| CN113893815A (en) * | 2021-11-17 | 2022-01-07 | 太原科技大学 | Ceramsite-zeolite composite high-performance adsorbing material and preparation method thereof |
| CN115779850A (en) * | 2022-11-01 | 2023-03-14 | 深圳市中金岭南有色金属股份有限公司凡口铅锌矿 | Silica-based stone powder material, preparation method and application |
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