CN108658086B - Method for preparing sodalite and high-silicon mordenite from residue of aluminum extraction by fly ash acid method and utilization method of fly ash - Google Patents
Method for preparing sodalite and high-silicon mordenite from residue of aluminum extraction by fly ash acid method and utilization method of fly ash Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 170
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 166
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000010881 fly ash Substances 0.000 title claims abstract description 153
- 229910052665 sodalite Inorganic materials 0.000 title claims abstract description 126
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 105
- 238000000605 extraction Methods 0.000 title claims abstract description 98
- 239000010703 silicon Substances 0.000 title claims abstract description 95
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 70
- QPILZZVXGUNELN-UHFFFAOYSA-N sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000000047 product Substances 0.000 claims abstract description 107
- 229910001868 water Inorganic materials 0.000 claims abstract description 99
- 239000000706 filtrate Substances 0.000 claims abstract description 98
- 239000002893 slag Substances 0.000 claims abstract description 92
- 239000012452 mother liquor Substances 0.000 claims abstract description 81
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 78
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 75
- 238000002386 leaching Methods 0.000 claims abstract description 65
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 62
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 59
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 31
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 230000029087 digestion Effects 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 66
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 61
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 60
- 239000007787 solid Substances 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 51
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 39
- 229910052593 corundum Inorganic materials 0.000 claims description 34
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 27
- 229910052681 coesite Inorganic materials 0.000 claims description 26
- 229910052906 cristobalite Inorganic materials 0.000 claims description 26
- 229910052682 stishovite Inorganic materials 0.000 claims description 26
- 229910052905 tridymite Inorganic materials 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 42
- 239000011734 sodium Substances 0.000 description 41
- 238000002441 X-ray diffraction Methods 0.000 description 36
- 239000002808 molecular sieve Substances 0.000 description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 34
- 229910001483 soda nepheline Inorganic materials 0.000 description 32
- 239000000243 solution Substances 0.000 description 23
- 229910020489 SiO3 Inorganic materials 0.000 description 22
- 239000007788 liquid Substances 0.000 description 20
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 17
- 230000002194 synthesizing effect Effects 0.000 description 13
- 238000007885 magnetic separation Methods 0.000 description 12
- 229910052911 sodium silicate Inorganic materials 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000012265 solid product Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002910 solid waste Substances 0.000 description 8
- 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 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 229910052863 mullite Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 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 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010117 shenhua Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052664 nepheline Inorganic materials 0.000 description 2
- 239000010434 nepheline Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OPIFSICVWOWJMJ-HAAGFXOZSA-N 5-bromo-4-chloro-3-indolyl alpha-D-mannoside Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC1=CNC2=CC=C(Br)C(Cl)=C12 OPIFSICVWOWJMJ-HAAGFXOZSA-N 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000668854 Howardia biclavis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- 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
- C01B39/26—Mordenite type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
- C01F7/22—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with halides or halogen acids
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of fly ash acid method aluminum extraction residues or fly ash utilization, and discloses a method for preparing sodalite and high-silicon mordenite by using fly ash acid method aluminum extraction residues and a utilization method of fly ash. The method comprises the following steps: (1) carrying out alkaline roasting on the residue of the acid-method aluminum extraction of the fly ash to obtain roasted slag; (2) carrying out high-temperature water leaching digestion reaction on the roasted slag charge to obtain a water leaching product; (3) preparing the water leaching product into sodalite synthesis mother liquor; carrying out sodalite hydrothermal crystallization on the sodalite synthesis mother liquor to obtain sodalite powder and first filtrate; (4) and carrying out hydrothermal crystallization on the first filtrate and sodium fluoride to obtain high-silicon mordenite and a second filtrate. The method realizes the digestion of the residue of aluminum extraction by the acid method of fly ash, improves the utilization rate of the residue of aluminum extraction by the acid method of fly ash, and utilizes fly ash.
Description
Technical Field
The invention relates to the field of utilization of fly ash acid method aluminum extraction residue and fly ash, in particular to a method for preparing sodalite and high-silicon mordenite by using fly ash acid method aluminum extraction residue and a utilization method of fly ash.
Background
The high-alumina fly ash is a novel aluminum resource peculiar to China, and the amount of prospect resources of the high-alumina fly ash is about 100 million tons of alumina. The bauxite resource reserves found in China are only 32 hundred million tons, the resource guarantee years are only about 20 years according to the estimation of the current mining scale, and the current external dependence of aluminum resources is as high as 55 percent. Therefore, the development and utilization of the high-alumina fly ash have practical significance for relieving the shortage of bauxite resources in China, ensuring the safety of the aluminum industry in China and enhancing the sustainable development capability of the aluminum industry.
The currently developed fly ash aluminum extraction process can be roughly divided into three major types, namely an acid method, an alkaline method and an acid-base combination method, and can produce qualified alumina products, but the process faces the problems of large emission amount of aluminum extraction residues and incapability of being effectively consumed to different degrees. Taking Shenhua group 'combined impurity removal one-step acid dissolution' process for extracting aluminum oxide as an example, each 100 tons of Al is produced2O3About 130 tons of aluminum extraction residue will be discharged. The residue discharge rate of the alkaline aluminum extraction process is higher. According to the relevant regulations of aluminum industry admission conditions issued by the Ministry of industry and belief in 2013, the comprehensive utilization rate of solid wastes of a newly-built system for producing alumina by using high-alumina fly ash is required to reach more than 96%. Therefore, the development of high-value and high-efficiency digestion technology for the residue of extracting aluminum from fly ash is urgently needed.
One of the obvious features of the residue after extracting aluminium from fly ash is rich in silicon (calcium) and poor in aluminium. At present, the utilization of the fly ash aluminum extraction residue mainly focuses on the preparation of silicon products (water glass, white carbon black, silicon micropowder and the like), the manufacture of basic building materials (cement, ceramic tiles, autoclaved bricks and the like), and the production of heat preservation, refractory materials and other fields. The application directions all have contradictions among the economic added value of products, the market capacity and the utilization rate of residues to different degrees, so that the overall utilization rate of the existing aluminum extraction residues from the fly ash is low, and the application and popularization of the high-alumina fly ash aluminum extraction technology are directly limited.
Molecular sieves are a class of materials having a uniform microporous structure. Due to the advantages of high adsorption capacity, strong thermal stability and the like which are not possessed by other adsorbents, the molecular sieve is important and widely applied to various application occasions such as catalysis, adsorption separation, ion exchange and the like.
Sodalite (Na)3[Al6Si6O24]) Is one of the earliest types of zeolites entering inorganic functional materials. The crystal is of an SOD type structure, has a six-membered ring channel window, can be used for preparing photochromic materials, and other researches show that the sodalite is a potential hydrogen absorption material.
Mordenite (Mordenite) is another commonly used aluminosilicate molecular sieve, which has a large number of five-membered ring structures and is connected in parallel in pairs, main channels are straight cylindrical twelve-membered rings, the cross section of each hole is oval, and the size of each hole is 0.65nm multiplied by 0.68 nm. The conventional mordenite has a silicon-aluminum ratio of 9-11 and has a chemical formula of Na [ Al [ [ Al ]8Si40O96]·24H2And O. The mordenite with higher silica-alumina ratio (such as more than 17) is called high-silica mordenite, and when the mordenite is used for alkylation, alkane isomerization, hydrocracking, modification, dewaxing and dimethylamine synthesis reaction, the catalytic activity, selectivity and thermal stability of the mordenite are obviously improved compared with those of the conventional MOR type molecular sieve, and the application prospect is wide.
The industrial synthesis of zeolite molecular sieves usually uses chemical raw materials such as water glass, sodium aluminate or aluminum hydroxide, and the cost is relatively high. Many researchers have conducted research on hydrothermal synthesis of molecular sieves from the same type of raw materials (including fly ash, coal gangue, kaolin, etc.).
CN103641133B discloses a method for synthesizing a sodalite molecular sieve by using fly ash: stirring and rinsing the fly ash, filtering and drying, adding 4-6 times of 4mol/L NaOH solution, stirring, and crystallizing for 100-400 min under the conditions of 147kPa and 121 ℃, wherein the obtained solid phase product contains spherical sodalite as a main crystal phase, quartz, mullite and other mixed crystals and a certain proportion of amorphous silicon aluminum. The method takes fly ash as a raw material, and the method also generates waste materials, so that silicon and aluminum in the fly ash cannot be fully utilized.
CN102173433B discloses a method for synthesizing single-phase sodalite by fly ash: firstly, pre-activating the fly ash by an alkali fusion method, then adding an aluminum hydroxide solution and a sodium hydroxide solution, uniformly mixing, and then placing in a constant-temperature drying oven for crystallization for 12-48 h at 100-140 ℃, thus obtaining a pure single-phase sodalite material. The method takes fly ash as a raw material, and the method also needs an additional aluminum source and generates waste materials, so that silicon and aluminum in the fly ash cannot be fully utilized.
Hydrothermally synthesizing sodalite and its characterization by fly ash (Yaoshitong, Chinese non-ferrous metals academic report, vol. 19, 2 nd, 2009, 2 months, p.366-37) by using fly ash obtained after magnetic separation and iron removal, alkali roasting, hydrochloric acid leaching and impurity removal, which is approximately equal to fly ash acid method aluminum extraction slag, as a raw material, adding sodium chloride, sodium carbonate and water to prepare silica-alumina gel, and performing hydrothermal crystallization at 120 ℃ for 24 hours to prepare the purer sodalite molecular sieve. The method takes fly ash as a raw material, and the method also generates waste materials, so that silicon and aluminum in the fly ash cannot be fully utilized.
CN1230518A discloses a method for synthesizing high-silicon mordenite, SiO thereof2/Al2O3The molecular ratio is 15-30, water glass, inorganic acid, inorganic alkali and aluminium salt or aluminate are used as raw materials, and the molecular ratio in the reaction mixture is Na2O/Al2O3＝1-10；SiO2/Al2O3＝10-30；H2O/Al2O3200-.
CN101804995A discloses a method for preparing high-silicon mordenite by using mineral raw materials, which is characterized by comprising the following steps: 1) according to SiO in the silicon source2Al in the aluminum source2O3Inorganic alkali, fluoride, template agent: h2The molar ratio of O is (20-50), 1, (2-5) to (5-10): (1.5-6) 300-600), selecting an aluminum source, a silicon source, inorganic alkali, fluoride, a template agent and water; the aluminum source is coal gangue or kaolin; the silicon source is kaolin and coal gangueAny one or mixture of more than two of stone, sodium metasilicate nonahydrate, activated silica powder and silica sol, wherein the mixture of any two or more is in any proportion; 2) mixing a silicon source, an aluminum source, inorganic alkali, fluoride, a template agent and water, pulping, stirring and mixing at room temperature to 80 ℃ to form gel, and obtaining an initial gel mixture; adjusting the pH value of the initial gel mixture to 11-13, and performing hydrothermal crystallization synthesis reaction in a reaction kettle, wherein the hydrothermal crystallization synthesis reaction is performed under the condition of crystallization at 160-180 ℃ for 48-70 hours to obtain a crystallization product; and filtering and washing the crystallized product until the pH value is 7-8, drying, roasting at 500 ℃ for 5-10h, and demolding to obtain the high-silicon mordenite (the silica-alumina ratio is 12-20).
In the prior art, one of aluminum and silicon in the fly ash acid method aluminum extraction residue is excessive and needs to be prepared by adding a silicon source or an aluminum source, but the method is not favorable for efficiently dissolving the fly ash acid method aluminum extraction residue.
Therefore, the existing technology for preparing the molecular sieve by using the fly ash acid method aluminum extraction residue to realize the consumption of the fly ash acid method aluminum extraction residue cannot meet the requirement of fully utilizing the silicon and aluminum in the fly ash acid method aluminum extraction residue, and a method for more effectively preparing the molecular sieve by using the fly ash acid method aluminum extraction residue and realizing the high-efficiency consumption of the fly ash acid method aluminum extraction residue is needed.
Disclosure of Invention
The invention aims to solve the problems of how to improve the consumption efficiency of the acidified aluminum extraction residue of the fly ash by preparing a molecular sieve, co-producing high-silicon type and low-silicon type molecular sieves and how to utilize the fly ash, and provides a method for preparing sodalite and high-silicon mordenite by extracting the aluminum residue from the fly ash by an acid method and a utilization method of the fly ash.
The inventor of the invention finds in research that the material composition of the residue of aluminum extraction by the acid method of fly ash has specificity compared with fly ash: the silicon content is more enriched than that of common fly ash, the aluminum content is obviously reduced, and acid soluble elements such as Fe, Mg and the like are greatly removed in the process of extracting aluminum by an acid method, wherein SiO2With Al2O3Molar ratio (which can be expressed as silicon to aluminum ratio, or SiO)2/Al2O3) About 10: 1.if the fly ash acid method aluminum extraction residue is directly used for synthesizing a low-silicon molecular sieve (such as sodalite, the silica-alumina ratio is about 2), the Si is obviously excessive, and an aluminum source needs to be added; when the Al-Si-Al-Si zeolite is used for synthesizing high-silicon molecular sieve (such as high-silicon mordenite with Si/Al ratio greater than 18), Al element is excessive, and a silicon source is required to be added. Obviously, an external aluminum source or silicon source is introduced, other resources are additionally consumed, and the utilization rate of the residue obtained by acidifying the fly ash and extracting aluminum cannot be effectively improved. On the other hand, in the acidified aluminum extraction residue of the fly ash, low-activity components such as mullite, quartz, anatase and the like are further enriched compared with the original fly ash, so that the utilization rate of the acidified aluminum extraction residue of the fly ash is restricted to be improved. Therefore, how to reasonably and better utilize silicon and aluminum resources in the fly ash acidification aluminum extraction residue needs not to add silicon or aluminum, and the factors need to be comprehensively considered. The inventor provides the invention to improve the consumption efficiency of the fly ash acidification aluminum extraction residue, realize the high-efficiency consumption of the fly ash acidification aluminum extraction residue and realize the co-production of sodalite and high-silicon mordenite.
In order to achieve the aim, the invention provides a method for preparing sodalite and high-silicon mordenite by extracting aluminum residues from fly ash by an acid method, which comprises the following steps:
(1) carrying out alkaline roasting on the residue of the acid-method aluminum extraction of the fly ash to obtain roasted slag;
(2) carrying out high-temperature water leaching digestion reaction on the roasted slag charge to obtain a water leaching product;
(3) preparing the water leaching product into sodalite synthesis mother liquor; carrying out sodalite hydrothermal crystallization on the sodalite synthesis mother liquor to obtain sodalite powder and first filtrate;
(4) and carrying out hydrothermal crystallization on the first filtrate and sodium fluoride to obtain high-silicon mordenite and a second filtrate.
The invention also provides a utilization method of the fly ash, which comprises the following steps: carrying out acid method aluminum extraction on the fly ash to obtain fly ash acid method aluminum extraction residue and aluminum oxide; the sodalite and the high-silicon mordenite are prepared from the residue of the acid-method aluminum extraction of the fly ash by the method.
Through the technical scheme, the method can better utilize silicon and aluminum resources in the fly ash acid method aluminum extraction residue, realizes effective consumption of the fly ash acid method aluminum extraction residue, and generates considerable environmental benefits; meanwhile, high-value and efficient resource utilization of the residue generated in the aluminum extraction by the fly ash acid method is realized.
The utilization method of the fly ash acid method aluminum extraction residue provided by the invention can utilize silicon and aluminum in the fly ash acid method to produce molecular sieve products without separating and extracting part of silicon, and can omit the operation of extraction and separation. In addition, the method provided by the invention can fully and efficiently consume the residue of aluminum extraction by the acid method of fly ash without additionally introducing an external aluminum source.
In order to realize better utilization of the fly ash acid method aluminum extraction residue, the method of the invention particularly limits the synthesis of the molecular sieve with low silica-alumina ratio, so that the sodalite can be obtained, and the silica-alumina ratio in the filtrate generated by synthesizing the sodalite can be adjusted, thereby being suitable for synthesizing the high silica-alumina ratio high silica mordenite, and fully utilizing the silica and alumina resources in the fly ash acid method aluminum extraction residue. The invention skillfully utilizes the fly ash acid method aluminum extraction residue to synthesize the molecular sieve for multiple times, and limits that the low silicon-aluminum ratio molecular sieve is synthesized firstly and then the high silicon-aluminum ratio molecular sieve is synthesized, thereby realizing the purposes of efficiently dissolving the fly ash acid method aluminum extraction residue and producing high value-added products.
The method provided by the invention can also utilize the fly ash to produce alumina, sodalite and high-silicon mordenite, so that the fly ash is fully utilized and no waste residue is discharged.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of a method provided by the present invention;
FIG. 2 is an XRD spectrum of sodalite prepared according to the present invention;
FIG. 3 is an XRD spectrum of the high-silicon mordenite prepared by the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first purpose of the invention is to provide a method for preparing sodalite and high-silicon mordenite by extracting aluminum residues from fly ash by an acid method, which is shown in figure 1 and comprises the following steps:
(1) carrying out alkaline roasting on the residue of the acid-method aluminum extraction of the fly ash to obtain roasted slag;
(2) carrying out high-temperature water leaching digestion reaction on the roasted slag charge to obtain a water leaching product;
(3) preparing the water leaching product into sodalite synthesis mother liquor; carrying out sodalite hydrothermal crystallization on the sodalite synthesis mother liquor to obtain sodalite powder and first filtrate;
(4) and carrying out hydrothermal crystallization on the first filtrate and sodium fluoride to obtain high-silicon mordenite and a second filtrate.
In the invention, the residue of extracting aluminum from fly ash by acid method mainly comprises: SiO 22、Al2O3And TiO2，SiO2About 70 to 80 wt%, Al2O3In an amount of about 10 to 15 wt% and TiO2Is present in an amount of about 3 to 8 wt%. Such as the acid-stripping of aluminum residues from the fly ash of Toigel2In an amount of about 78.7Weight% of Al2O3In an amount of about 13.4% by weight and TiO2Is present in an amount of about 5.2 wt%. Further XRD analysis of the residue from acid extraction of aluminum from fly ash shows that Al is present2O3Substantially of mullite (3 Al)2O3·SiO2) In the form of TiO2The carrier is anatase and rutile; about 85% of the Si is present in amorphous form, the remainder being present in mullite and quartz. The low-activity components such as mullite, quartz, anatase and the like are further enriched compared with the original fly ash, and the activity of silicon and aluminum elements is poor, so that the utilization of the residue of extracting aluminum by acidifying the fly ash is not facilitated to produce the molecular sieve.
According to the invention, the step (1) is used for treating the fly ash acid method aluminum extraction residue, so that silicon and aluminum elements in the fly ash acid method aluminum extraction residue can be activated and can participate in the synthesis and utilization of the molecular sieve more effectively, and the content of the silicon and aluminum elements in the obtained first filtrate can be reasonably adjusted to meet the requirement of reaction raw materials for synthesizing the molecular sieve with low silicon-aluminum ratio. In the step (1), the alkaline roasting aims at fully decomposing mineral components with stable crystal structures, such as mullite, quartz and the like, at a lower roasting temperature so as to fully activate Si and Al elements in the mineral components. The activation of Si and Al elements can be realized by adding alkaline substances into the acidified aluminum extraction residues of the fly ash and roasting the residues together. Preferably, in step (1), the alkali roasting process comprises: mixing and grinding 100 parts by weight of the fly ash acid-process aluminum extraction residue and 100-130 parts by weight of a sodium carbonate-containing material, roasting the obtained ground product at 830-890 ℃ for 60-120 min, and then crushing to below 200 meshes to obtain the roasted slag material.
In the invention, in the step (1), after the roasting is completed, the roasted product can be rapidly cooled by air, and the roasted slag charge is obtained by cooling.
In the present invention, the sodium carbonate-containing material may be sodium carbonate solid powder directly used, or part of the second filtrate obtained in step (4) may be recycled as shown in fig. 1. The main component in the second filtrate is sodium carbonate, and sodium carbonate solid obtained by evaporating and crystallizing part of the second filtrate can be utilized.
According to the invention, in the step (1), the high-temperature water leaching can further leach silicon and aluminum elements in the roasted slag, and specifically can dissolve Na in the roasted slag out by water2SiO3And NaAlSiO4. Preferably, in step (2), the high-temperature water leaching digestion reaction process comprises: removing iron impurities from the roasted slag, and mixing the roasted slag with water to obtain a water leaching product; the reaction temperature is 90-120 ℃, and the reaction time is 10-60 min; the amount of water is 150-200 ml relative to 100g of the roasted slag charge. Wherein the iron removal of the roasted slag can be realized by adopting a dry magnetic separation mode. The high temperature water leaching process may be carried out at atmospheric or autogenous pressure. The water leaching product is a solid-liquid mixture, and the solid is Na dissolved out by leaching the roasted slag charge with water2SiO3And NaAlSiO4The remaining product, the mineral phase composition of which is amorphous aluminosilicate and a small amount of crystalline NaAlSiO4(ii) a The liquid is Na-containing2SiO3And NaAlSiO4The solution of (1).
According to the present invention, in the step (3), the sodalite is hydrothermally crystallized. The water leaching product is prepared into mother liquor suitable for synthesizing the sodalite molecular sieve. Preferably, in the step (3), the process of preparing is as follows: and mixing the water leaching product with the second filtrate, wherein the dosage of the second filtrate is 700-1200 ml relative to 100g of the roasted slag charge.
Preferably, the pH of the sodalite synthesis mother liquor is 14 or more, and preferably, the pH is 14 to 15.
In the invention, through the steps, silicon and aluminum elements in the fly ash acid-process aluminum extraction residue can be converted into active components by using Na2SiO3And NaAlSiO4The form of the sodium-containing catalyst is extracted, and the ratio of silicon to aluminum is adjusted to meet the synthesis requirement of the sodalite molecular sieve. Preferably, SiO is contained in the sodalite synthesis mother liquor2With Al2O3The molar ratio of (10-25): 1. preferably (11-20): 1, more preferablySelecting (11-14): 1.
in the present invention, the chemical composition (molar ratio) of the sodalite synthesis mother liquor may be controlled to SiO2:Al2O3:Na2O:CO3 2-:H2O＝(10～25):1:(20～35):(3～5):(600～800)。
In a preferred embodiment of the present invention, when the conditions involved in the two processes of alkaline roasting and high-temperature water leaching are within the above-defined ranges, the insoluble matter content in the water leaching product is the lowest, so that the synthesis of pure sodalite products is facilitated, and the discharge problem of secondary solid waste is avoided. When no external silica-alumina source is introduced, the fly ash acid method aluminum extraction residue has the highest absorption efficiency mu. The consumption efficiency mu of the fly ash acid method aluminum extraction residue can be calculated by the following formula:
μ＝M/(M+Mout)×100％；
wherein mu is the consumption efficiency of the residue of aluminum extraction by the acid method of fly ash;
m is the dry basis weight of the fly ash acid method aluminum extraction residue for alkaline roasting in the step (1);
Moutis the dry basis mass of the external silica-alumina source introduced into the whole reaction system.
In the invention, no external silicon-aluminum source is introduced, so Mout＝0。
The absorption efficiency mu and the external silicon-aluminum source MoutThe masses are all in inverse proportion.
In the prior art, when synthesizing low-silicon molecular sieve sodalite, the silicon-aluminum ratio in hydrothermal crystallization mother liquor is usually regulated to be 2: about 1 (close to the theoretical silica-alumina ratio of sodalite); when synthesizing a high-silicon molecular sieve, the ratio of silicon to aluminum in the hydrothermal crystallization mother liquor is generally limited to 20:1 or more. The pure sodalite or high-silicon mordenite can be more easily synthesized under the condition of the silica-alumina ratio of the mother liquor.
But the method provided by the invention is used for improving the consumption efficiency of the residue of aluminum extraction by the acid method of the fly ash. Aiming at the material properties of the residue of the acid extraction of aluminum from fly ash, such as the production of sodalite or high silicon by the conventional technologyThe mordenite needs to be added with an external aluminum source respectively to adjust the silicon-aluminum ratio to 2:1, or adding an external silicon source to increase the silicon-aluminum ratio to be more than 20: 1. And an external silicon, aluminum source (i.e., M)out) The introduction of the method directly causes the reduction of the consumption efficiency mu of the aluminum extraction residues by the acid method of the fly ash, and further influences the overall consumption efficiency of the aluminum extraction residues by the acid method of the fly ash, namely the quality of the aluminum extraction residues by the acid method of the fly ash consumed for preparing products with unit mass is reduced.
In the second filtrate obtained in the present invention, the concentration of sodium carbonate may be 15 to 25% by weight. The second filtrate is used for diluting the water leaching product, so that the alkalinity required by the sodalite hydrothermal synthesis can be supplemented, and the cyclic utilization of sodium carbonate in a system is realized.
According to the present invention, sodalite is further hydrothermally crystallized by using the obtained sodalite synthesis mother liquor. And the synthesis conditions enable the composition of silicon and aluminum elements in the molecular sieve filtrate obtained after synthesis to be suitable for further synthesizing the high-silicon mordenite. Preferably, in the step (3), the temperature for the sodalite hydrothermal crystallization is 90 ℃ to 120 ℃, and the time for the sodalite hydrothermal crystallization is 10h to 48 h. Further, washing and filtering a product obtained by the sodalite hydrothermal crystallization reaction to obtain first filter residue and first filtrate; and washing, drying and roasting the first filter residue to obtain the sodalite powder. The washing, filtering and drying can be conventional technical means and are not described in detail. The XRD spectrum of the finally obtained solid product can be determined by XRD (X-ray diffraction) method, as shown in fig. 2, and compared with the standard spectrum, the sodalite molecular sieve is determined.
According to the invention, the first filtrate is also obtained through step (3). And (4) continuously utilizing the first filtrate to synthesize the high silica alumina ratio molecular sieve such as the high silica mordenite. The content of silicon and aluminum in the first filtrate generated in the step (3) is changed, and SiO in the first filtrate is preferred2With Al2O3The molar ratio of (35-45): 1, more preferably (38-42): 1. the chemical composition (molar ratio) in the molecular sieve filtrate can be SiO2:Al2O3:Na2O:CO3 2-:H2O＝(35～45):1:(70～100):(10～15):(2100～2500)。
According to the present invention, preferably, in the step (4), the hydrothermal crystallization of the high-silicon mordenite comprises: i) adding sodium fluoride solid into the molecular sieve filtrate to obtain a synthetic mother liquor; ii) introducing CO into the synthesis mother liquor2Carrying out carbonation to ensure that the pH of the synthetic mother liquor is 11-14; iii) carrying out hydrothermal crystallization on the product obtained in the step ii) at the temperature of 140-190 ℃ for 15-72 h to obtain a high-silicon mordenite hydrothermal crystallization product; iv) filtering the high-silicon mordenite hydrothermal crystallization product to obtain a second filter residue and a second filtrate; and washing, drying and roasting the second filter residue to obtain the high-silicon mordenite. The solid finally obtained can be confirmed to be high-silicon mordenite by an XRD (X-ray diffraction) method, as shown in fig. 3.
According to the invention, the sodium fluoride solid is preferably added in an amount of SiO in the synthetic fluid 210 to 20 mol% of the amount of the catalyst. The sodium fluoride solid is high-grade pure NaF with the purity of more than or equal to 99 weight percent, and can be purchased from Shanghai Hu test company as high-grade pure NaF (more than or equal to 99 percent).
According to the invention, the second filtrate can be further utilized, and preferably, a part of the second filtrate is recycled to the high-temperature water leaching and dissolving reaction in the step (2); and (3) evaporating and crystallizing the other part of the second filtrate to obtain a sodium carbonate solid, and recycling the sodium carbonate solid to the alkaline roasting in the step (1). Therefore, the residue of aluminum extraction by the acid method of fly ash can be completely utilized, and no waste is generated.
The second object of the invention is to provide a utilization method of fly ash, which comprises the following steps: carrying out acid method aluminum extraction on the fly ash to obtain fly ash acid method aluminum extraction residue and aluminum oxide; the sodalite and the high-silicon mordenite are prepared from the residue of the acid-method aluminum extraction of the fly ash by the method.
Wherein the fly ash can be fine ash collected from flue gas discharged from coal fired power plants after coal combustion. May be mainly composed of SiO2、Al2O3And TiO2。SiO2About 20 to 40 wt%, Al2O3In an amount of about 45 to 60 wt% and TiO2Is present in an amount of about 1.5 to about 4.5 wt%. For example fly ash from the power plant of Shenhua inner Mongolian China, where SiO is present2Is about 32.43 wt%, Al2O3In an amount of about 50.42 wt% and TiO2Is present in an amount of about 2.14 wt%.
The acid method for extracting aluminum in the invention can adopt a method known in the art, and is not described in detail herein.
In the present invention, the silica-alumina ratio of the high-silica mordenite obtained is 30 or more, preferably 30.7 to 36.9.
The present invention will be described in detail below by way of examples.
In the following examples, (2. theta.) was scanned by XRD (X-ray diffraction) using an X-ray diffractometer of D8ADVANCE model of Bruker, Germany, under a condition of 40Kv-40mA for 4. about.75 °. Comparing the scanning result with a standard card No. 37-0476 (PDF2004 edition), and determining that the obtained substance is sodalite;
the X-ray diffractometer model D8ADVANCE of Bruker company in Germany is adopted to scan (2 theta) for 4-75 degrees under the condition of 40Kv-40mA by an XRD (X-ray diffraction) method. The scanning result is compared with a standard card 29-1257 (PDF2004 edition), and the obtained substance is determined to be high-silicon mordenite.
Through an SEM-EDS (scanning electron microscope with an energy spectrometer), X-man 50 type EDS of Oxford company in UK is adopted and matched with Navo NanoSEM 450 type SEM of FEI company in America, chemical component signals of a mordenite sample are collected under the voltage of 15Kv, and the silicon-aluminum ratio of the high-silicon mordenite is calculated.
The calculation method of the consumption efficiency mu of the fly ash acid method aluminum extraction residue is as described above.
The fly ash comes from Shenhua inner Mongolian China power plant, the specific composition content is shown in Table 1,
TABLE 1
| Composition of | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | Fe2O3 | MgO | Na2O |
| Content by weight% | 50.42 | 32.43 | 0.19 | 4.0 | 0.37 | 3.03 | 2.14 | 1.71 | 0.18 | 0.03 |
The fly ash acid method aluminum extraction residue comes from an alumina plant of the Niger energy Limited liability company, and the specific composition content is shown in Table 2.
TABLE 2
| Composition of | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | Fe2O3 | ZrO2 | Na2O |
| Content by weight% | 13.4 | 78.7 | 0.14 | 0.35 | 0.16 | 0.37 | 5.2 | 0.45 | 0.29 | - |
Preparation example
This preparation illustrates the preparation of fly ash to obtain fly ash acid process aluminum extraction residue.
Adding 5mol/L hydrochloric acid solution into 100g of fly ash, stirring and reacting for 30min at 150 ℃, filtering and washing to obtain an aluminum-rich solution and fly ash aluminum extraction residues by an acid method. The chemical components of the fly ash acid method aluminum extraction residue are shown in table 2.
Example 1
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO360g of solid powder, mixing and grinding the solid powder, roasting the mixture for 90min at 860 ℃, quickly cooling the mixture in air after roasting is finished, and crushing the mixture to be below 200 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for iron removal, 70g of the roasted slag is added with 140ml of deionized water (the amount of water is 200ml relative to 100g of the roasted slag) to be subjected to water leaching for 20min at 100 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) adding 500ml of sodium carbonate solution (recycled from the second filtrate in the step (6) with the concentration of 15 weight percent) into 100g of water leaching product (equivalent to 70g of roasting slag), and preparing sodalite synthesis mother liquor (equivalent to 714ml of the total dosage of the second filtrate relative to 100g of roasting slag); controlling the pH value of the obtained sodalite synthesis mother liquor to be 14.3;
the chemical composition (molar ratio) of the sodalite synthesis mother liquor is SiO2:Al2O3:Na2O:CO3 2-:H2O＝12:1:25:3.5:600；
(4) Putting the sodalite synthesis mother liquor into a reaction kettle, and carrying out hydrothermal crystallization for 21h at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; further washing and drying the first filter residue, and analyzing the obtained solid product by XRD to obtain a spectrogram shown in figure 2, and comparing the spectrogram with a standard card to determine that the solid product is sodalite;
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝42:1:90:13:2240；
(5) 0.7g of NaF solid (GR, super grade purity ≥ 99.0%, Shanghai Hu test) was added to 65ml of the obtained first filtrate to obtain a synthesis mother liquor (the amount of NaF added was about SiO in the synthesis mother liquor)210 mol% of);
introducing CO into the synthetic mother liquor under the stirring state2Carbonation to pH 13.838; then carrying out hydrothermal crystallization for 72h at the temperature of 140 ℃, and filtering the obtained hydrothermal crystallization product to obtain second filter residue and second filtrate; further washing, drying and roasting the second filter residue, carrying out XRD analysis on the obtained product to obtain a spectrogram shown in figure 3, comparing the spectrogram with a standard card to determine high-silicon mordenite, and carrying out EDS analysis on the high-silicon mordenite to obtain a mordenite silicon-aluminum ratio of 36.9;
(6) mixing the second filtrate (Na as main component)2CO3A small amount of Si and Al) is recycled and added into the step (3) to be used for preparing sodalite synthesis mother liquor by water leaching products; the remaining part of the second filtrate is evaporated and crystallized to obtain Na2CO3And (4) recycling the solid to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1).
The whole process basically has no solid waste residue discharge, and the overall consumption efficiency of the residue for extracting aluminum by the fly ash acid method is approximately equal to 100 percent; na (Na)2CO3、CO2And the recycling of NaF is realized.
Example 2
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO365g of solid powder, mixed and ground, and then roasted at 890 ℃ to 100 DEG Cmin, after roasting, quickly cooling by air, and crushing to be less than about 180 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for iron removal, 70g of the roasted slag is added with 105ml of deionized water (the amount of water is 150ml relative to 100g of the roasted slag) to be subjected to water leaching for 18min at 95 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) 600ml of a sodium carbonate solution (the concentration of the second filtrate recycled from the step (6) is 20 weight percent) is added into 93g of the water leaching product (which is equivalent to 70g of the roasting slag), so as to prepare sodalite synthesis mother liquor (the total dosage of the second filtrate is 857ml relative to 100g of the roasting slag); controlling the pH value of the obtained sodalite synthesis mother liquor to be 14.3;
the chemical composition (molar ratio) of the sodalite synthesis mother liquor is SiO2:Al2O3:Na2O:CO3 2-:H2O＝11.3:1:27:3.8:720；
(4) Putting the sodalite synthesis mother solution into a reaction kettle, and carrying out hydrothermal crystallization for 21 hours at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; further washing and drying the first filter residue, and analyzing an obtained solid product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, and determining the solid product as sodalite;
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝42:1:90:13:2240；
(5) To 100ml of the obtained first filtrate, 1.05g of NaF solid was added to obtain a synthesis mother liquor (the amount of NaF added was about SiO in the synthesis mother liquor)215 mol%) of; (ii) a
Introducing CO into the synthetic mother liquor under the stirring state2Carbonizing to pH 12.0; then carrying out hydrothermal crystallization for 48 hours at the temperature of 150 ℃, and carrying out the obtained hydrothermal crystallizationFiltering the product to obtain second filter residue and second filtrate; further washing, drying and roasting the second filter residue, analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, determining the obtained product as the high-silicon mordenite, and analyzing by EDS (electronic discharge spectroscopy) to obtain the mordenite with the silicon-aluminum ratio of 32.9;
(6) mixing the second filtrate (Na as main component)2CO3A small amount of Si and Al) is recycled and added into the step (3) to be used for preparing sodalite synthesis mother liquor by water leaching products; the remaining part of the second filtrate is evaporated and crystallized to obtain Na2CO3And (4) recycling the solid to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1).
The whole process basically has no solid waste residue discharge, and the overall consumption efficiency of the residue for extracting aluminum by the fly ash acid method is approximately equal to 100 percent; na (Na)2CO3、CO2And the recycling of NaF is realized.
Example 3
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO350g of solid powder, mixing and grinding the solid powder, roasting the mixture for 120min at 830 ℃, quickly cooling the mixture by air after roasting is finished, and crushing the mixture to be less than about 150 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for removing iron, 70g of the roasted slag is added with 130ml of deionized water (the amount of water is 186ml relative to 100g of the roasted slag) to be subjected to water leaching for 15min at 105 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) adding 600ml of sodium carbonate solution (the concentration is 25 weight percent for the second filtrate obtained in the step (6)) into 100g of the water leaching product (which is equivalent to 70g of roasting slag), and preparing sodalite synthesis mother liquor (the total dosage of the second filtrate is 714ml relative to 100g of roasting slag); controlling the pH value of the obtained sodalite synthesis mother liquor to be 14.7;
the chemical composition (molar ratio) of the sodalite synthesis mother liquor is SiO2:Al2O3:Na2O:CO3 2-:H2O＝11.8:1:22:3.0:700；
(4) Putting the sodalite synthesis mother liquor into a reaction kettle, and carrying out hydrothermal crystallization for 21h at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; further washing and drying the first filter residue, and analyzing an obtained solid product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, and determining the solid product as sodalite;
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝38:1:70:11.5:2260；
(5) To 100ml of the obtained first filtrate, 1.4g of NaF solid was added to obtain a synthesis mother liquor (the amount of NaF added was about SiO in the synthesis mother liquor)220 mol% of); (ii) a
Introducing CO into the synthetic mother liquor under the stirring state2Carrying out carbonation until the pH value is 11.03; then carrying out hydrothermal crystallization for 15h at the temperature of 190 ℃, and filtering the obtained hydrothermal crystallization product to obtain second filter residue and second filtrate; further washing, drying and roasting the second filter residue, analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, determining the obtained product as the high-silicon mordenite, and analyzing by EDS (electronic discharge spectroscopy) to obtain the mordenite with the silicon-aluminum ratio of 30.7;
(6) mixing the second filtrate (Na as main component)2CO3A small amount of Si and Al) is recycled and added into the step (3) to be used for preparing sodalite synthesis mother liquor by water leaching products; the remaining part of the second filtrate is evaporated and crystallized to obtain Na2CO3And (4) recycling the solid to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1).
The whole process basically has no solid waste residue discharge, and the overall consumption efficiency of the residue for extracting aluminum by the fly ash acid method is approximately equal to 100 percent; na (Na)2CO3、CO2And the recycling of NaF is realized.
Example 4
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO365g of solid powder, mixed and ground at 890 DEG CRoasting for 100min, quickly cooling by air after roasting is finished, and crushing to be below 180 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for iron removal, 70g of the roasted slag is added with 105ml of deionized water (the amount of water is 150ml relative to 100g of the roasted slag) to be subjected to water leaching for 18min at 95 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) 600ml of sodium carbonate solution (the concentration of the second filtrate recycled from the step (6) is 20 weight percent) is added into 100g of the water leaching product (which is equivalent to 70g of roasting slag), and sodalite synthesis mother liquor (the total dosage of the second filtrate is 714ml relative to 100g of roasting slag) is prepared; controlling the pH value of the obtained sodalite synthesis mother liquor to be 14.3;
the chemical composition (molar ratio) of the sodalite synthesis mother liquor is SiO2:Al2O3:Na2O:CO3 2-:H2O＝11.3:1:27:3.8:720；
(4) Putting the sodalite synthesis mother solution into a reaction kettle, and carrying out hydrothermal crystallization for 21 hours at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; further washing and drying the first filter residue, and analyzing an obtained product by XRD to obtain a spectrogram, comparing the spectrogram with a standard card and determining the spectrogram as sodalite;
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝42:1:90:13:2240；
(5) 0.7g of NaF solid was added to 100ml of the obtained first filtrate to obtain a synthesis mother liquor (the amount of NaF added was about SiO in the synthesis mother liquor)210 mol% of);
introducing CO into the synthetic mother liquor under the stirring state2Carbonation to pH 13.838; then carrying out hydrothermal crystallization for 50h at the temperature of 150 ℃, and obtaining the hydrothermal crystallization productFiltering the mixture to obtain second filter residue and second filtrate; further washing, drying and roasting the second filter residue, analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, determining the obtained spectrogram as high-silicon mordenite, determining the obtained spectrogram as mordenite, and analyzing the obtained mordenite by EDS (electron-ray diffraction) to obtain a mordenite silicon-aluminum ratio of 35.1;
(6) mixing the second filtrate (Na as main component)2CO3A small amount of Si and Al) is recycled and added into the step (3) to be used for preparing sodalite synthesis mother liquor by water leaching products; the remaining part of the second filtrate is evaporated and crystallized to obtain Na2CO3And (4) recycling the solid to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1).
The whole process basically has no solid waste residue discharge, and the overall consumption efficiency of the residue for extracting aluminum by the fly ash acid method is approximately equal to 100 percent; na (Na)2CO3、CO2And the recycling of NaF is realized.
Example 5
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO360g of solid powder, mixing and grinding the solid powder, roasting the mixture for 90min at 860 ℃, quickly cooling the mixture in air after roasting is finished, and crushing the mixture to be below 200 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for iron removal, 70g of the roasted slag is added with 105ml of deionized water (the amount of water is 150ml relative to 100g of the roasted slag) to be subjected to water leaching for 18min at 95 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) adding 600ml of sodium carbonate solution (the concentration is 25 weight percent for the second filtrate obtained in the step (6)) into 100g of the water leaching product (which is equivalent to 70g of roasting slag), and preparing sodalite synthesis mother liquor (the total dosage of the second filtrate is 714ml relative to 100g of roasting slag); controlling the pH value of the obtained sodalite synthesis mother liquor to be 14.3;
chemical composition of sodalite synthesis mother liquorMole ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝12:1:25:3.5:600；
(4) Putting the sodalite synthesis mother solution into a reaction kettle, and carrying out hydrothermal crystallization for 21 hours at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; further washing and drying the first filter residue, and analyzing an obtained product by XRD to obtain a spectrogram, comparing the spectrogram with a standard card and determining the spectrogram as sodalite;
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝42:1:90:13:2240；
(5) To 100ml of the obtained first filtrate, 1.05g of NaF solid was added to obtain a synthesis mother liquor (the amount of NaF added was about SiO in the synthesis mother liquor)215 mol%) of;
introducing CO into the synthetic mother liquor under the stirring state2Carbonizing to pH 12.0; then carrying out hydrothermal crystallization for 44 hours at the temperature of 180 ℃, and filtering the obtained hydrothermal crystallization product to obtain second filter residue and second filtrate; further washing, drying and roasting the second filter residue, analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, determining the obtained product as the high-silicon mordenite, and analyzing by EDS (electronic discharge spectroscopy) to obtain the mordenite with the silicon-aluminum ratio of 32.6;
(6) mixing the second filtrate (Na as main component)2CO3A small amount of Si and Al) is recycled and added into the step (3) to be used for preparing sodalite synthesis mother liquor by water leaching products; the remaining part of the second filtrate is evaporated and crystallized to obtain Na2CO3And (4) recycling the solid to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1).
The whole process basically has no solid waste residue discharge, and the overall consumption efficiency of the residue for extracting aluminum by the fly ash acid method is approximately equal to 100 percent; na (Na)2CO3、CO2And the recycling of NaF is realized.
Example 6
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO360g of solid powder, mixed and ground at 86%Roasting at 0 ℃ for 90min, quickly cooling with air after roasting is finished, and crushing to be below 200 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for iron removal, 70g of the roasted slag is added with 105ml of deionized water (the amount of water is 150ml relative to 100g of the roasted slag) to be subjected to water leaching for 18min at 95 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) adding 800ml of sodium carbonate solution (the concentration of the second filtrate recycled from the step (6) is 20 weight percent) into 100g of water leaching product (equivalent to 70g of roasting slag), and preparing sodalite synthesis mother liquor (the total dosage of the second filtrate is 1142ml relative to 100g of roasting slag); controlling the pH value of the obtained sodalite synthesis mother liquor to be 14.2;
the chemical composition (molar ratio) of the sodalite synthesis mother liquor is SiO2:Al2O3:Na2O:CO3 2-:H2O＝12:1:25:3.5:800；
(4) Putting the sodalite synthesis mother solution into a reaction kettle, and carrying out hydrothermal crystallization for 21 hours at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; further washing and drying the first filter residue, and analyzing an obtained product by XRD to obtain a spectrogram, comparing the spectrogram with a standard card and determining the spectrogram as sodalite;
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝42:1:90:13:2450；
(5) To 65ml of the obtained first filtrate, 1.4g of NaF solid was added to obtain a synthesis mother liquor (the amount of NaF added was about SiO in the synthesis mother liquor)220 mol% of);
introducing CO into the synthetic mother liquor under the stirring state2Carrying out carbonation until the pH value is 11.03; then carrying out hydrothermal crystallization for 72h at the temperature of 140 ℃, and obtaining the hydrothermal crystallization productFiltering the mixture to obtain second filter residue and second filtrate; further washing, drying and roasting the second filter residue, analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, determining the obtained product as the high-silicon mordenite, and analyzing by EDS (electronic discharge spectroscopy) to obtain the mordenite with the silicon-aluminum ratio of 31.1;
(6) mixing the second filtrate (Na as main component)2CO3A small amount of Si and Al) is recycled and added into the step (3) to be used for preparing sodalite synthesis mother liquor by water leaching products; the remaining part of the second filtrate is evaporated and crystallized to obtain Na2CO3And (4) recycling the solid to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1).
The whole process basically has no solid waste residue discharge, and the overall consumption efficiency of the residue for extracting aluminum by the fly ash acid method is approximately equal to 100 percent; na (Na)2CO3、CO2And the recycling of NaF is realized.
Comparative example 1
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO360g of solid powder, mixing and grinding the solid powder, roasting the mixture for 90min at 860 ℃, quickly cooling the mixture in air after roasting is finished, and crushing the mixture to be below 200 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for removing iron, 70g of the roasted slag is added with 350ml of deionized water (the amount of water is 500ml relative to 100g of the roasted slag) to be soaked in water for 20min at 100 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) under the high-speed stirring state, taking 410g (70 g in terms of containing roasting slag) of all water leaching products as sodalite synthesis mother liquor, wherein the chemical composition (molar ratio) of the mother liquor is SiO2:Al2O3:Na2O:CO3 2-:H2O-12: 1:25:3.5: 1500; the pH value of the sodalite synthesis mother liquor is 14.0.
(4) Putting the sodalite synthesis mother liquor into a reaction kettle, and carrying out hydrothermal crystallization for 21h at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; and further washing and drying the first filter residue, and analyzing by XRD to obtain a solid product which is a mixed phase of amorphous substances, nepheline and sodalite.
In the high-temperature water leaching process of the comparative example 1, the dosage of water is too much and exceeds the liquid-solid ratio range of 150-200 ml relative to 100g of the roasting slag material, so that the alkalinity of a water leaching system is reduced, silicon and aluminum are not fully dissolved out, impurities exist in a sodalite product, and the qualified sodalite product cannot be obtained.
Comparative example 2
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO360g of solid powder, mixing and grinding the solid powder, roasting the mixture for 90min at 860 ℃, quickly cooling the mixture in air after roasting is finished, and crushing the mixture to be below 200 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for removing iron, 70g of the roasted slag is taken and added with 800ml of deionized water (the amount of water is 1143ml relative to 100g of the roasted slag) to be used as sodalite synthesis mother liquor to directly synthesize the sodalite.
(3) Transferring the sodalite mother liquor into a summer-heat reaction kettle, and carrying out hydrothermal reaction for 21h at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; and further washing and drying the first filter residue, and analyzing by XRD to obtain a solid product which is a mixed phase of amorphous substances, nepheline and sodalite.
Comparative example 2 omits the high-temperature water leaching process of the roasted slag charge and directly carries out sodalite hydrothermal synthesis, which may cause the crystallization of sodalite around the roasted slag charge, and prevents the further dissolution of silicon and aluminum in the slag charge, so that the impurity content in the sodalite product is too high, namely a pure sodalite product cannot be obtained, and the high-efficiency absorption of the residue of extracting aluminum by the fly ash acid method cannot be realized.
Comparative example 3
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO360g of solid powder, mixing and grinding, roasting at 860 ℃ for 90min, quickly cooling by air after roasting is finished, and crushing to about 200 meshesThen, obtaining a roasting slag charge;
(2) after the roasted slag is subjected to dry magnetic separation for iron removal, 70g of the roasted slag is added with 140ml of deionized water (the amount of water is 200ml relative to 100g of the roasted slag) to be subjected to water leaching for 20min at 100 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) adding 500ml of sodium carbonate solution (recycled from the first filtrate in the step (5) with the concentration of 15 wt%) into 100g of the water leaching product (equivalent to 70g of the roasting slag), and adding sodium metaaluminate (NaAlO)2) 47.15g of solid is prepared into sodalite synthesis mother liquor, and the chemical composition (molar ratio) of the sodalite synthesis mother liquor is SiO2:Al2O3:Na2O:CO3 2-:H2O＝12:6:27.3:3.1:711。
(4) Putting the sodalite synthesis mother liquor into a reaction kettle, and carrying out hydrothermal crystallization for 21h at 120 ℃; filtering the obtained hydrothermal crystallization product to obtain first filter residue and first filtrate; and further washing and drying the first filter residue, and analyzing the obtained solid product by XRD to obtain a spectrogram, comparing the spectrogram with a standard card, and determining the spectrogram as sodalite.
(5) First filtrate (main component is Na)2CO3A small amount of Si and Al) is recycled as the sodium carbonate solution in the step (3); the rest part of the first filtrate is evaporated and crystallized to obtain Na2CO3And (4) recycling the solid to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1).
In the comparative example 3, the sodalite synthesis mother liquor with the regular ratio of 2:1 is prepared according to the conventional method, so that a pure sodalite product can be synthesized; but requires the addition of aluminum source sodium metaaluminate (M)out47.15g), the absorption efficiency mu of the fly ash acid method aluminum extraction residue is only 51.46 percent; and the obtained first filtrate mainly contains sodium carbonate, only contains a small amount of silicon and aluminum, and cannot be used as a silicon source or an aluminum source to further prepare ZSM-5 or any other type of molecular sieve, namely the obtained first filtrateThe product is only one of sodalite.
Comparative example 4
(1) Adding 50g of residue of aluminum extraction by fly ash acid method into Na2CO360g of solid powder, mixing and grinding the solid powder, roasting the mixture for 90min at 860 ℃, quickly cooling the mixture in air after roasting is finished, and crushing the mixture to be below 200 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation for iron removal, 70g of the roasted slag is added with 140ml of deionized water (the amount of water is 200ml relative to 100g of the roasted slag) to be subjected to water leaching for 20min at 100 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved2SiO3And NaAlSiO4To obtain a solid-liquid mixed water leaching product; wherein the solid is dissolved Na2SiO3And NaAlSiO4The remaining product after that; the liquid is Na-containing2SiO3And NaAlSiO4The solution of (1);
(3) to about 100g (70 g in terms of roasted slag) of the total water-leached product was added sodium metasilicate (Na)2SiO3) 100.65g of solid, and 1300ml of deionized water are added to prepare a high-silicon mordenite hydrothermal crystallization mother liquor, wherein the chemical composition (molar ratio) is SiO2:Al2O3:Na2O:CO3 2-:H2O＝40:1:41.5:3.5:2450；
(4) Taking 65ml of the high-silicon mordenite hydrothermal crystallization mother liquor prepared in the step (3), and adding 1.4g of NaF solid to obtain a synthetic mother liquor (the adding amount of NaF is about SiO in the synthetic mother liquor)220 mol% of);
introducing CO into the synthetic mother liquor under the stirring state2Carbonizing to pH 12.0; then carrying out hydrothermal crystallization for 72h at the temperature of 180 ℃, and filtering the obtained hydrothermal crystallization product to obtain filter residue and filtrate; further washing, drying and roasting filter residues, analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, determining the high-silicon mordenite, and analyzing by EDS (electronic discharge spectroscopy) to obtain a mordenite silicon-aluminum ratio of 36.2;
the main component of the filtrate is Na by detection2CO3And only a small amount of Si and Al. Cannot be used as a silica-alumina source for further synthesis of sodalite or any other type of componentAnd (5) screening by using a secondary screen.
Adjusting the composition of the aqueous leaching product in comparative example 4 for the synthesis of high silicon mordenite requires the addition of a silicon source of sodium metasilicate (M)out100.65g) resulting in a single digestion efficiency μ of only 33.19% of the fly ash acid aluminum extraction residue and the resulting product was only one of the high silicon mordenite.
From the above examples, it can be seen that the method provided by the present invention can fully utilize the residue of the acid extraction of aluminum from fly ash without the need of adding additional silicon source or aluminum source. The sodalite molecular sieve and the high-silicon mordenite with high added values can be simultaneously produced and obtained while efficiently dissolving the residue of the aluminum extraction by the fly ash acid method.
In addition, the method provided by the invention can also realize the full utilization of the fly ash, and the conversion of the fly ash to produce the alumina, the sodalite molecular sieve and the high-silicon mordenite is realized without additionally adding a silicon source or an aluminum source.
Claims (10)
1. A method for preparing sodalite and high-silicon mordenite from fly ash acid-process aluminum extraction residues comprises the following steps:
(1) carrying out alkaline roasting on the residue of the acid-method aluminum extraction of the fly ash to obtain roasted slag;
(2) carrying out high-temperature water leaching digestion reaction on the roasted slag charge to obtain a water leaching product;
(3) preparing the water leaching product into sodalite synthesis mother liquor; carrying out sodalite hydrothermal crystallization on the sodalite synthesis mother liquor to obtain sodalite powder and first filtrate;
the molar mass ratio of chemical compositions in the first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O＝(35～45):1:(70～100):(10～15):(2100～2500)；
(4) Carrying out hydrothermal crystallization on the first filtrate and sodium fluoride to obtain high-silicon mordenite and a second filtrate;
wherein, the process of the hydrothermal crystallization of the high-silicon mordenite comprises the following steps:
i) adding sodium fluoride solid into the first filtrate to obtain a synthetic mother liquor;
ii) introducing CO into the synthesis mother liquor2Carrying out carbonation to ensure that the pH of the synthetic mother liquor is 11-14;
iii) carrying out hydrothermal crystallization on the product obtained in the step ii) at the temperature of 140-190 ℃ for 15-72 h to obtain a high-silicon mordenite hydrothermal crystallization product;
iv) filtering the high-silicon mordenite hydrothermal crystallization product to obtain a second filter residue and a second filtrate; and washing, drying and roasting the second filter residue to obtain the high-silicon mordenite.
2. The method of claim 1, wherein in step (1), the alkaline roasting comprises: mixing and grinding 100 parts by weight of the fly ash acid-process aluminum extraction residue and 100-130 parts by weight of sodium carbonate, roasting the obtained ground product at 830-890 ℃ for 60-120 min, and then crushing to below 200 meshes to obtain the roasted slag charge.
3. The method according to claim 1, wherein in step (2), the process of high-temperature water leaching digestion reaction comprises: removing iron impurities from the roasted slag, mixing the roasted slag with water, and performing water leaching to obtain a water leaching product; the reaction temperature is 90-120 ℃, and the reaction time is 10-60 min; the amount of water is 150-200 ml relative to 100g of the roasted slag charge.
4. The method of claim 1, wherein in the step (3), the formulating is achieved by: and mixing the water leaching product with the second filtrate, wherein the dosage of the second filtrate is 700-1200 ml relative to 100g of the roasted slag charge.
5. The method according to claim 1, wherein in the step (3), the pH of the sodalite synthesis mother liquor is 14 or more.
6. The method as claimed in claim 1, wherein, in the step (3), the temperature for the hydrothermal crystallization of the sodalite is 90 ℃ to 120 ℃ and the time for the hydrothermal crystallization of the sodalite is 10h to 48 h.
7. The method according to claim 6, wherein a product obtained by the sodalite hydrothermal crystallization reaction is washed and filtered to obtain a first filter residue and the first filtrate; and washing, drying and roasting the first filter residue to obtain the sodalite powder.
8. The method of claim 1, wherein the sodium fluoride solids are added in an amount of SiO in the synthesis solution210 to 20 mol% of the amount of the catalyst.
9. The method of any of claims 1-8, wherein the method further comprises:
recycling a part of the second filtrate to the high-temperature water leaching and dissolving reaction in the step (2); and (3) evaporating and crystallizing the other part of the second filtrate to obtain a sodium carbonate solid, and recycling the sodium carbonate solid to the alkaline roasting in the step (1).
10. A method for utilizing fly ash, the method comprising: carrying out acid method aluminum extraction on the fly ash to obtain fly ash acid method aluminum extraction residue and aluminum oxide; the sodalite and high-silicon mordenite are prepared from the fly ash acid-method aluminum extraction residue by the method of any one of claims 1 to 9.
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