CN108658091B - Method for preparing NaY type molecular sieve and high-silicon mordenite by using fly ash acid method aluminum extraction residues and utilization method of fly ash - Google Patents
Method for preparing NaY type molecular sieve and high-silicon mordenite by using fly ash acid method aluminum extraction residues and utilization method of fly ash Download PDFInfo
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- CN108658091B CN108658091B CN201710196582.9A CN201710196582A CN108658091B CN 108658091 B CN108658091 B CN 108658091B CN 201710196582 A CN201710196582 A CN 201710196582A CN 108658091 B CN108658091 B CN 108658091B
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- 238000000034 method Methods 0.000 title claims abstract description 193
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 191
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000010881 fly ash Substances 0.000 title claims abstract description 168
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 166
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000000605 extraction Methods 0.000 title claims abstract description 125
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 111
- 239000010703 silicon Substances 0.000 title claims abstract description 100
- 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 70
- 239000000706 filtrate Substances 0.000 claims abstract description 151
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229910001868 water Inorganic materials 0.000 claims abstract description 115
- 239000002893 slag Substances 0.000 claims abstract description 93
- 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 61
- 238000001914 filtration Methods 0.000 claims abstract description 52
- 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 27
- 238000004321 preservation Methods 0.000 claims abstract description 11
- 238000007654 immersion Methods 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 107
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 101
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 89
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 64
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 59
- 239000007787 solid Substances 0.000 claims description 54
- 229910052593 corundum Inorganic materials 0.000 claims description 49
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 49
- 238000002386 leaching Methods 0.000 claims description 48
- 239000000377 silicon dioxide Substances 0.000 claims description 45
- 238000005406 washing Methods 0.000 claims description 42
- 229910052681 coesite Inorganic materials 0.000 claims description 40
- 229910052906 cristobalite Inorganic materials 0.000 claims description 40
- 229910052682 stishovite Inorganic materials 0.000 claims description 40
- 229910052905 tridymite Inorganic materials 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 39
- 239000012452 mother liquor Substances 0.000 claims description 35
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 32
- 238000004064 recycling Methods 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims 1
- 230000029087 digestion Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- 239000011734 sodium Substances 0.000 description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 39
- 238000002441 X-ray diffraction Methods 0.000 description 36
- 229910001483 soda nepheline Inorganic materials 0.000 description 35
- 229910020489 SiO3 Inorganic materials 0.000 description 25
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 230000002194 synthesizing effect Effects 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 13
- 229910052911 sodium silicate Inorganic materials 0.000 description 13
- 238000001816 cooling Methods 0.000 description 11
- 238000007885 magnetic separation Methods 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- 238000009775 high-speed stirring Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 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 6
- 239000012265 solid product Substances 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process 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
- 239000010453 quartz Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000004611 spectroscopical analysis 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
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 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
- 239000010117 shenhua Substances 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- 238000001228 spectrum Methods 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 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
- 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 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
- 239000006229 carbon black Substances 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 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
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000012535 impurity 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
- 239000007791 liquid phase 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
- 239000010413 mother solution Substances 0.000 description 1
- 238000003825 pressing 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 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
- 239000002910 solid waste Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- General Life Sciences & Earth Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to the field of utilization of fly ash acid method aluminum extraction residues and fly ash, and discloses a method for preparing NaY type molecular sieve 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; sequentially carrying out high-temperature water immersion and heat preservation filtration on the roasted slag charge to obtain a first filtrate; (2) carrying out NaY type molecular sieve hydrothermal crystallization on the first filtrate to obtain a NaY type molecular sieve and a molecular sieve filtrate; (3) and carrying out hydrothermal crystallization on the molecular sieve 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 aluminum residue extracted by a fly ash acid method and fly ash, in particular to a method for preparing a NaY-type molecular sieve and high-silicon mordenite by extracting aluminum residue by a fly ash acid method 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.
The NaY type molecular sieve is an artificially synthesized molecular sieve with an octahedral zeolite structure, the diameter of a pore channel is 0.74nm, the high-temperature stability and the good catalytic activity of the NaY type molecular sieve are widely applied in the fields of hydrocracking, desulfurization and the like, the application in the field of synthetic detergents is increasingly emphasized by people, and the demand is continuously increased.
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 pore channels are straight cylindrical twelve-membered rings, the cross section of an orifice is oval, the size of the orifice is 0.65nm × 0.68.68 nm, the silicon-aluminum ratio of the conventional Mordenite is 9-11, and the chemical formula is Na [ Al ] Al8Si40O96]·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.).
CN102658194B discloses a method for preparing NaY type molecular sieve by fly ash: the fly ash is roasted to remove carbon, added with NaOH to be melted at high temperature, aged and hydrothermally crystallized to prepare the NaY type molecular sieve containing P zeolite mixed crystals. The method can only utilize the fly ash to produce the NaY type molecular sieve, but can not completely utilize silicon and aluminum in the fly ash.
CN101928010A discloses a preparation method of a NaY type molecular sieve, which comprises the following steps: a. mixing desilication liquid generated in the pre-desilication process of the process for extracting aluminum oxide from high-alumina fly ash with an aluminum source to prepare mother liquid; b. mixing the mother solution with a guiding agent to form silicon-aluminum sol; c. aging the silica-alumina sol, and crystallizingFiltering, washing and drying to obtain NaY type molecular sieve, wherein Na in the mother liquor2O、Al2O3、SiO2And H2The molar ratio of O is 4-18: 1: 5-15: 100-420.
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 any one or mixture of more than two of kaolin, coal gangue, sodium metasilicate nonahydrate, activated silica powder and silica sol, and the mixture ratio of any two or more is arbitrary; 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 an NaY type molecular sieve and high-silicon mordenite by extracting the aluminum extraction residue of 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. the mole ratio of silicon to aluminum in the fly ash acid method aluminum extraction residue can not be completely matched with the high-silicon molecular sieve and the low-silicon molecular sieve, if the fly ash acid method aluminum extraction residue is directly used for synthesizing a low-silicon molecular sieve (such as a Y-type molecular sieve, the silicon-aluminum ratio is about 3-5), 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 residue of extracting aluminum by acidifying fly ash, the low-activity components such as mullite, quartz, anatase and the like are further enriched compared with the original fly ashAnd the utilization rate of the residue of the aluminum extraction by the acidification 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 residue of the acidified aluminum extraction of the fly ash, realize the high-efficiency consumption of the residue of the acidified aluminum extraction of the fly ash and realize the joint production of the NaY-type molecular sieve and the high-silicon mordenite.
In order to achieve the purpose, the invention provides a method for preparing NaY type molecular sieve and high-silicon mordenite by extracting aluminum residue 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; sequentially carrying out high-temperature water immersion and heat preservation filtration on the roasted slag charge to obtain a first filtrate;
(2) carrying out NaY type molecular sieve hydrothermal crystallization on the first filtrate to obtain a NaY type molecular sieve and a molecular sieve filtrate;
(3) and carrying out hydrothermal crystallization on the molecular sieve 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 NaY type molecular sieve 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, not only can obtain the NaY type molecular sieve, but also can adjust the silica-alumina ratio in the filtrate generated by synthesizing the NaY type molecular sieve, 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, NaY type molecular sieve 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 the NaY type molecular sieve prepared by the 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 NaY type molecular sieve and high-silicon mordenite by extracting aluminum residue from fly ash by an acid method, as shown in figure 1, comprising 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; then sequentially carrying out high-temperature water immersion and heat preservation filtration to obtain a first filtrate;
(2) carrying out NaY type molecular sieve hydrothermal crystallization on the first filtrate to obtain a NaY type molecular sieve and a molecular sieve filtrate;
(3) and carrying out hydrothermal crystallization on the molecular sieve 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 Toigel2Is about 78.7 wt%, 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 (3) 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. The fly ash acid method aluminum extraction residue can also be mixed with the first filter residue obtained from the heat preservation and filtration for recycling.
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 (1), the high-temperature water leaching process comprises: removing iron from the roasted slag, mixing the roasted slag with water, and performing water leaching to obtain a water leaching product; the water immersion temperature is 95-105 ℃, and the water immersion time is 15-20 min; the amount of water is 150-200 ml relative to 100g of the roasted slag charge. Wherein the removal of iron from the roasted slag may be carried out by using dryAnd realizing a method 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 invention, in the step (1), the water leaching product is subjected to solid-liquid separation through heat preservation and filtration, and the first filtrate is obtained. Preferably, in step (1), the filtration process comprises: diluting, filtering and washing the water leaching product by using part of the second filtrate to obtain slurry, and filtering the slurry to obtain first filter residue and the first filtrate; the filtering temperature is kept between 60 and 80 ℃.
According to the invention, the dosage of the second filtrate is 250-350 ml relative to 100g of the roasting slag charge.
In a preferred embodiment of the present invention, when the three processes of the alkaline roasting, the high-temperature water leaching and the heat-preservation dilution filtering involve condition parameters within the above-defined ranges, the first filter residue can be obtained with a minimum yield (i.e. the ratio of the dry basis weight of the first filter residue to the dry basis weight of the fly ash acid-extraction aluminum residue). Therefore, the fly ash acid method aluminum extraction residue has the highest one-time consumption efficiency mu when no external silica-aluminum source is introduced. The one-time consumption efficiency mu of the fly ash acid method aluminum extraction residue can be calculated by the following formula:
μ＝[(M-M1)/(M+Mout)]×100％；
mu is the one-time consumption efficiency of the residue of aluminum extraction by the acid method of the fly ash;
m is the dry basis weight of the fly ash acid method aluminum extraction residue for alkaline roasting in the step (1);
M1the dry basis weight of the first filter residue obtained in the step (1);
Moutis a complete reaction systemThe dry basis mass of the external silica-alumina source introduced.
In the invention, no external silicon-aluminum source is introduced, so Mout＝0。
The first time consumption efficiency mu and the first filter residue M1Mass and external silico-aluminium source MoutThe mass is in inverse proportional relation, and is in direct proportional relation with the final consumption efficiency of the fly ash acid method aluminum extraction residue.
In the invention, silicon and aluminum elements in the residue of aluminum extraction by the acid method of fly ash can be converted into active components by the alkali method roasting, high-temperature water leaching and heat-preservation filtering, and Na is used2SiO3And NaAlSiO4The form of (A) is extracted, and the ratio of silicon to aluminum is adjusted to adapt to the needs of subsequent molecular sieve synthesis. Preferably, SiO in the first filtrate2With Al2O3The molar ratio of (10-25): 1. preferably SiO in the first filtrate2With Al2O3The molar ratio of (12-20): 1; more preferably (13-16.5): 1.
in the present invention, the chemical composition (molar ratio) of the first filtrate may be controlled to SiO2:Al2O3:Na2O:CO3 2-:H2O＝(12～17):1:(11～20):(6～10):(390～430)。
When the low-silicon molecular sieve NaY is synthesized by the conventional technology, the silicon-aluminum ratio in the hydrothermal crystallization mother liquor is usually regulated and limited to (3-6): 1 or so; when synthesizing high-silicon molecular sieve high-silicon mordenite, the ratio of silicon to aluminum in the hydrothermal crystallization mother liquor is generally limited to 20:1 or more. The pure NaY type molecular sieve or high-silicon mordenite can be more easily synthesized under the condition of the silicon-aluminum 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 after the aluminum extraction by the acid method of the fly ash, if an NaY type molecular sieve or high-silicon mordenite is produced according to the conventional technology, an external aluminum source is required to be added respectively to adjust the silicon-aluminum ratio to (2-3): 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 (A) will directly result in an acid process of fly ashThe reduction of the once consumption efficiency mu of the aluminum extraction residue further influences the overall consumption efficiency of the fly ash acid method aluminum extraction residue, namely the quality of the fly ash acid method aluminum extraction residue consumed for preparing a unit mass product 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, filtering and washing the water leaching product, so that the concentration of a filtering system can be reduced, the hydrolysis of sodium metasilicate in the water leaching product can be inhibited, the filtering efficiency can be improved, the filtering loss can be reduced, the yield of first filter residue can be reduced, and the one-time consumption efficiency of the fly ash acid method aluminum extraction residue can be improved. Meanwhile, the recycling of the sodium carbonate in the system is realized. The filtration can adopt a suction filtration or a filter pressing mode.
According to the present invention, preferably, the method further comprises: and (3) drying the first filter residue, and then recycling the first filter residue, adding the first filter residue into the fly ash acid method aluminum extraction residue in the step (1).
In the invention, the first filter residue can be washed by water at 80-90 ℃ before drying.
According to the invention, step (2) utilizes the first filtrate obtained in step (1) to synthesize the NaY type molecular sieve. 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 (2), the hydrothermal crystallization of the NaY molecular sieve comprises: a) adding a directing agent into the first filtrate to prepare NaY molecular sieve mother liquor, and adjusting the composition of the NaY molecular sieve mother liquor to meet Na2O:Al2O3:SiO2:H2O ═ 11.1 to 23.7: 1: (12.9-18.4): (380-550); b) carrying out hydrothermal crystallization on the product obtained in the step a) at 95-105 ℃ for 18-36 h to obtain a NaY type molecular sieve hydrothermal crystallization product; c) filtering the NaY type molecular sieve hydrothermal crystallization product to obtain second filter residue and the molecular sieve filtrate; and drying the second filter residue to obtain the NaY type molecular sieve. The XRD spectrum of the solid product finally obtained can be determined by XRD (X-ray diffraction) method, as shown in FIG. 2, and compared with the standard spectrumAnd determining to obtain the NaY type molecular sieve.
In the present invention, the directing agent is commercially available or can be prepared by the following method: sodium metaaluminate, sodium hydroxide, water glass and deionized water are mixed according to the proportion of Na2O:Al2O3:SiO2:H2Mixing materials according to the molar mass ratio of O to 10.66:1:9.8:215, and aging at 35 ℃ for 24 hours to obtain the NaY molecular sieve directing agent. The adjustment may be by CO2And adjusting the sodium-silicon ratio of the mother liquor in a gas carbon separation mode to finally enable the composition of the NaY type molecular sieve mother liquor to meet the limit.
According to the invention, by limiting the hydrothermal crystallization conditions of the NaY type molecular sieve in the step (2), pure NaY type molecular sieve and molecular sieve filtrate with chemical composition suitable for hydrothermal crystallization of the high-silicon mordenite in the step (3) can be obtained. The content of silicon and aluminum in the molecular sieve filtrate generated in the step (2) is obviously changed compared with that in the first filtrate, and preferably SiO in the molecular sieve filtrate2With Al2O3The molar ratio of (35-45): 1, more preferably (30-45): 1. the chemical composition (molar ratio) in the molecular sieve filtrate can be SiO2:Al2O3:Na2O:CO3 2-:H2O＝(30～45):1:(59～95):(27～47):(1610～2260)。
According to the present invention, preferably, in step (3), the hydrothermal crystallization of the high-silicon mordenite comprises: i) adding sodium fluoride solid into the molecular sieve filtrate to obtain synthetic liquid; ii) introducing CO into the synthetic fluid2Carrying out carbonation to ensure that the pH value of the synthetic liquid 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 third filter residue and the second filtrate; and washing, drying and roasting the third 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 inventionOptionally, the amount of the sodium fluoride solid added is SiO in the synthetic liquid210 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 heat preservation and filtration process in the step (1); and (3) evaporating and crystallizing the other part of the second filtrate to obtain sodium carbonate, and recycling the sodium carbonate to the alkali roasting process 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 NaY type molecular sieve 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 24 or more, preferably 24.4 to 33.5.
The present invention will be described in detail below by way of examples.
In the following examples, the sample was scanned (2. theta.) at 4 to 75 ℃ under 40Kv to 40mA by XRD (X-ray diffraction) using a D8ADVANCE X-ray diffractometer (Bruker, Germany) and the result of the scanning was compared with a standard card No. 43 to 0168 (PDF2004 edition) to determine that the sample was a NaY molecular sieve;
the material obtained is determined to be mordenite by an XRD (X-ray diffraction) method and a D8ADVANCE type X-ray diffractometer of Bruker company in Germany under the condition of 40Kv-40mA for scanning (2 theta) at 4-75 degrees, and the scanning result is compared with a standard card (PDF2004 edition) No. 29-1257.
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 one-time 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 1
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 residue from the acid extraction of aluminum from fly ash are shown in table 2.
Preparation example 2
This preparation illustrates the preparation of the NaY directing agent.
Sodium metaaluminate, sodium hydroxide, water glass and deionized water are mixed according to the proportion of Na2O:Al2O3:SiO2:H2Mixing according to the molar mass ratio of O to 10.7:1:9.8:215, and aging at 35 ℃ for 24 hours to obtain the NaY directing agent.
SiO in the guiding agent2The content was 152.6 g/L.
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 taken and added with 140ml of deionized water (the amount of water is 200ml relative to 100g of the roasted slag), water leaching is carried out for 20min at 100 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved out2SiO3And 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) taking 100g (equivalent to 70g of roasting slag) of all water-leached products under the high-speed stirring state, adding 100ml of sodium carbonate solution (the concentration is 15 weight percent for the second filtrate recycled from the step (6)) to dilute, carrying out suction filtration at the temperature of 60 ℃, adding 100ml of the sodium carbonate solution to wash (corresponding to 286ml of the total dosage of the second filtrate relative to 100g of roasting slag); adding a certain amount of hot water (about 80 ℃) for washing to obtain a first filtrate with the volume of 400ml for synthesizing the NaY type molecular sieve; drying the obtained first filter residue to obtain 6.05g of filter residue, and recycling the filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝16.5:1:17.1:9.9:424。
(4) Get firstA filtrate 100ml was added 3g of directing agent (from preparation 2) and passed through CO2And regulating the sodium-silicon ratio in a gas carbon separation mode, and taking the sodium-silicon ratio as a NaY molecular sieve synthesis mother liquor. The chemical composition of the NaY molecular sieve mother liquor is Na2O:Al2O3:SiO2:H2O＝16.9：1：16.3：420；
Carrying out hydrothermal crystallization on the NaY molecular sieve mother liquor at 95 ℃ for 24 hours, and filtering an obtained hydrothermal crystallization product to obtain second filter residue and a molecular sieve filtrate; further washing and drying the second filter residue, and analyzing the obtained product by XRD to obtain a spectrogram shown in figure 2, comparing the spectrogram with a standard card, and determining the spectrogram as a NaY type molecular sieve;
the chemical composition (molar ratio) of the molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O＝30.2:1:65.2:37:1610；
(5) Adding 1.05g NaF solid (GR grade purity, not less than 99.0%, Shanghai Hu test) into 100ml of the obtained molecular sieve filtrate to obtain a synthetic solution (the addition of NaF is about SiO in the synthetic solution)215 mol%) of;
introducing CO into the synthetic liquid under the stirring state2Carrying out carbonation until the pH value is 11.03; then carrying out hydrothermal crystallization for 40h at the temperature of 180 ℃, and filtering the obtained hydrothermal crystallization product to obtain third filter residue and second filtrate; further washing, drying and roasting the third filter residue, and analyzing an obtained product by XRD to obtain a spectrogram shown in figure 3, comparing the spectrogram with a standard card, and determining the high-silicon mordenite; EDS analysis shows that the mordenite has a silicon-aluminum ratio of 24.4;
(6) mixing the second filtrate (Na as main component)2CO3Part containing a small amount of Si and Al) is recycled and added into the sodium carbonate solution in the step (3) for diluting, filtering and washing the water leaching product; 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 one-time consumption efficiency mu of the residue of the aluminum extraction by the fly ash acid method is 87.90 percent; the first filter residue can be regarded as residue for extracting aluminum by the acid method of fly ash after recyclingThe overall efficiency of the absorption is approximately 100%; 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 Na2CO3Mixing and grinding 65g of solid powder, roasting at 890 ℃ for 60min, 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), water leaching is carried out for 18min at 95 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved out2SiO3And 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 93g (equivalent to 70g of roasting slag), adding 100ml of sodium carbonate solution (recycled from the second filtrate in the step (6) with the concentration of 20 weight percent) into the water-soaked product, diluting, keeping the temperature, carrying out suction filtration at 80 ℃, adding 100ml of the sodium carbonate solution, washing (corresponding to 286ml of the total dosage of the second filtrate relative to 100g of roasting slag), adding a certain amount of hot water (about 90 ℃) into the mixture, washing to obtain a first filtrate with the volume of 400ml, and using the first filtrate to synthesize the NaY type molecular sieve; drying the obtained first filter residue to obtain 6.93g, and recycling the first filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝15.2:1:14.9:7.2:428。
(4) 100ml of the first filtrate were taken, 5g of directing agent (from preparation 2) were added and passed through CO2And regulating the sodium-silicon ratio in a gas carbon separation mode, and taking the sodium-silicon ratio as a NaY molecular sieve synthesis mother liquor. The chemical composition of the NaY molecular sieve mother liquor is Na2O:Al2O3:SiO2:H2O＝14.7：1：14.9：418；
Carrying out hydrothermal crystallization on the NaY molecular sieve mother liquor at 100 ℃ for 36 hours, and filtering the obtained hydrothermal crystallization product to obtain second filter residue and molecular sieve filtrate; further washing and drying the second filter residue, and analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, and determining the obtained spectrogram as the NaY type molecular sieve;
the chemical composition (molar ratio) of the molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O＝33.4:1:59.1:27.6:1680；
(5) 0.7g of NaF solid was added to 100ml of the obtained molecular sieve filtrate to obtain a synthetic solution (the amount of NaF added was about SiO in the synthetic solution)210 mol% of);
introducing CO into the synthetic liquid under the stirring state2Carbonizing to pH 12.0; then carrying out hydrothermal crystallization at the temperature of 150 ℃ for 36 hours, and filtering the obtained hydrothermal crystallization product to obtain third filter residue and second filtrate; further washing, drying and roasting the third 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 24.7;
(6) mixing the second filtrate (Na as main component)2CO3Part containing a small amount of Si and Al) is recycled and added into the sodium carbonate solution in the step (3) for diluting, filtering and washing the water leaching product; 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 one-time consumption efficiency mu of the residue of the aluminum extraction by the fly ash acid method is 86.14 percent; after the first filter residue is recycled, the overall consumption efficiency of the residue generated in the aluminum extraction by the fly ash acid method is considered to be approximately 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 Na2CO3Mixing and grinding 50g of solid powder, roasting at 830 ℃ for 120min, and quickly roasting after roastingAir cooling and crushing to below 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) under the high-speed stirring state, 100g of water leaching products (which are 70g of roasted slag), 100ml of sodium carbonate solution (the concentration is 25 weight percent and is recycled from the second filtrate in the step (6)) is added into the water leaching products for dilution, and the solution is subjected to suction filtration at the temperature of 70 ℃; adding 100ml of near-saturated sodium carbonate solution for washing (equivalent to that the total dosage of the second filtrate is 286ml relative to 100g of roasted slag), and adding a certain amount of hot water (about 70 ℃) for washing to obtain a first filtrate with the volume of 400ml for synthesizing the NaY type molecular sieve; drying the obtained first filter residue to obtain 6.60g of filter residue, and recycling the filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝13.2:1:11.2:6.5:399。
(4) 100ml of the first filtrate were taken, 7g of directing agent (from preparation 2) were added and passed through CO2And regulating the sodium-silicon ratio in a gas carbon separation mode, and taking the sodium-silicon ratio as a NaY molecular sieve synthesis mother liquor. The chemical composition of the NaY molecular sieve mother liquor is Na2O:Al2O3:SiO2:H2O＝11.2：1：13.0：387；
Carrying out hydrothermal crystallization on the NaY molecular sieve mother liquor at 105 ℃ for 28.0h, and filtering the obtained hydrothermal crystallization product to obtain second filter residue and molecular sieve filtrate; further washing and drying the second filter residue, and analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, and determining the obtained spectrogram as the NaY type molecular sieve;
the chemical composition (molar ratio) of the molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O＝41:1:62.2:38.8:2155；
(5) To 100ml of the obtained molecular sieve filtrate, 1.4g of NaF solid was added to obtain a synthetic solution (the amount of NaF added was about SiO in the synthetic solution)220 mol% of);
introducing CO into the synthetic liquid under the stirring state2Carbonation to pH 13.838; then carrying out hydrothermal crystallization for 15h at the temperature of 190 ℃, and filtering the obtained hydrothermal crystallization product to obtain third filter residue and second filtrate; further washing, drying and roasting the third filter residue, 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 the mordenite with the silicon-aluminum ratio of 33.5;
(6) mixing the second filtrate (Na as main component)2CO3Part containing a small amount of Si and Al) is recycled and added into the sodium carbonate solution in the step (3) for dilution, filtration and washing of 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 one-time consumption efficiency mu of the residue of the aluminum extraction by the fly ash acid method is 86.80%; after the first filter residue is recycled, the overall consumption efficiency of the residue generated in the aluminum extraction by the fly ash acid method is considered to be approximately 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 Na2CO3Mixing and grinding 65g of solid powder, roasting at 890 ℃ for 60min, 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 and iron removal, 70g of the roasted slag is added with 105ml of deionized water 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) taking 100g (equivalent to 70g of roasting slag) of all water-leached products under the high-speed stirring state, adding 100ml of sodium carbonate solution (the concentration is 20 weight percent for the second filtrate recycled from the step (6)) to dilute, carrying out suction filtration at 80 ℃, and adding 100ml of the sodium carbonate solution to wash (corresponding to 286ml of the total dosage of the second filtrate relative to 100g of roasting slag); adding a certain amount of hot water (about 90 ℃) for washing to obtain a first filtrate with the volume of 400ml for synthesizing the NaY type molecular sieve; drying the obtained first filter residue to obtain 6.45g of filter residue, and recycling the filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝13.4:1:15.7:7.8:420。
(4) 100ml of the first filtrate were taken, 10g of directing agent (from preparation 2) were added and passed through CO2And regulating the sodium-silicon ratio in a gas carbon separation mode, and taking the sodium-silicon ratio as a NaY molecular sieve synthesis mother liquor. The chemical composition of the NaY molecular sieve mother liquor is Na2O:Al2O3:SiO2:H2O＝15.2：1：13.1：401；
Carrying out hydrothermal crystallization on the NaY molecular sieve mother liquor at 100 ℃ for 36 hours, and filtering the obtained hydrothermal crystallization product to obtain second filter residue and molecular sieve filtrate; further washing and drying the second filter residue, and analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, and determining the obtained spectrogram as the NaY type molecular sieve;
the chemical composition (molar ratio) of the molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O＝41:1:85.7:39.9:2260；
(5) To 100ml of the obtained molecular sieve filtrate, 1.4g of NaF solid was added to obtain a synthetic solution (the amount of NaF added was about SiO in the synthetic solution)220 mol% of);
introducing CO into the synthetic liquid 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 filtering the obtained hydrothermal crystallization product to obtain third filter residue and second filtrate; further washing, drying and roasting the third 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)2CO3Part containing a small amount of Si and Al) is recycled and added into the sodium carbonate solution in the step (3) for dilution, filtration and washing of 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 one-time consumption efficiency mu of the residue of the aluminum extraction by the fly ash acid method is 87.10 percent; after the first filter residue is recycled, the overall consumption efficiency of the residue generated in the aluminum extraction by the fly ash acid method is considered to be approximately 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 removing iron, 70g of the roasted slag is added into 140ml of deionized water 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) taking 100g (equivalent to 70g of roasting slag) of all water-leached products under the high-speed stirring state, adding 100ml of sodium carbonate solution (the concentration is 25 weight percent for the second filtrate recycled from the step (6)) to dilute, carrying out suction filtration at the temperature of 60 ℃, adding 100ml of the sodium carbonate solution to wash (corresponding to 286ml of the total dosage of the second filtrate relative to 100g of roasting slag); adding a certain amount of hot water (about 80 ℃) for washing to obtain a first filtrate with the volume of 400ml for synthesizing the NaY type molecular sieve; drying the obtained first filter residue to obtain 5.98g of filter residue, and recycling the filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝16.5:1:19.3:9.6:430。
(4) 100ml of the first filtrate were taken, 7g of directing agent (from preparation 2) were added and passed through CO2And regulating the sodium-silicon ratio in a gas carbon separation mode, and taking the sodium-silicon ratio as a NaY molecular sieve synthesis mother liquor. The chemical composition of the NaY molecular sieve mother liquor is Na2O:Al2O3:SiO2:H2O＝23.7：1：18.4：550；
Carrying out hydrothermal crystallization on the NaY molecular sieve mother liquor at 95 ℃ for 24 hours, and filtering an obtained hydrothermal crystallization product to obtain second filter residue and a molecular sieve filtrate; further washing and drying the second filter residue, and analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, and determining the obtained spectrogram as the NaY type molecular sieve;
the chemical composition (molar ratio) of the molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O＝32.2:1:95.1:46.6:2100。
(5) To 100ml of the obtained molecular sieve filtrate, 1.05g of NaF solid was added to obtain a synthetic solution (the amount of NaF added was about SiO in the synthetic solution)215 mol%) of;
introducing CO into the synthetic liquid 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 third filter residue and second filtrate; further washing, drying and roasting the third filter residue, analyzing the obtained product by XRD to obtain a spectrogram, comparing the spectrogram with a standard card, determining the high-silicon mordenite, and analyzing by EDS to obtain the high-silicon mordeniteThe mordenite silicon-aluminum ratio is 27.8;
(6) mixing the second filtrate (Na as main component)2CO3Part containing a small amount of Si and Al) is recycled and added into the sodium carbonate solution in the step (3) for dilution, filtration and washing of 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 one-time consumption efficiency mu of the residue of the aluminum extraction by the fly ash acid method is 88.40%; after the first filter residue is recycled, the overall consumption efficiency of the residue generated in the aluminum extraction by the fly ash acid method is considered to be approximately 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 Na2CO3Mixing and grinding 65g of solid powder, roasting at 890 ℃ for 60min, quickly cooling with air after roasting is finished, and crushing to be less than about 180 meshes to obtain roasted slag;
(2) after the roasted slag is subjected to dry magnetic separation and iron removal, 70g of the roasted slag is added into 105ml of deionized water to be soaked for 15min at 100 ℃ and normal pressure, and Na in the roasted slag is 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 93g (equivalent to 70g of roasting slag), adding 100ml of sodium carbonate solution (the concentration is 20 weight percent and is recycled from the second filtrate in the step (6)) to dilute, carrying out suction filtration at 80 ℃, adding 100ml of the sodium carbonate solution to wash (corresponding to 286ml of the total dosage of the second filtrate relative to 100g of roasting slag); adding a certain amount of hot water (about 90 ℃) for washing to obtain a first filtrate with the volume of 400ml for synthesizing the NaY type molecular sieve; drying the obtained first filter residue to obtain 6.21g of filter residue, and recycling the filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝13.4:1:15.6:7.8:411。
(4) 100ml of the first filtrate were taken, 7g of directing agent (from preparation 2) were added and passed through CO2And regulating the sodium-silicon ratio in a gas carbon separation mode, and taking the sodium-silicon ratio as a NaY molecular sieve synthesis mother liquor. The chemical composition of the NaY molecular sieve mother liquor is Na2O:Al2O3:SiO2:H2O＝15.5：1：13.3：406；
Carrying out hydrothermal crystallization on the NaY molecular sieve mother liquor at 100 ℃ for 36 hours, and filtering the obtained hydrothermal crystallization product to obtain second filter residue and molecular sieve filtrate; further washing and drying the second filter residue, and analyzing an obtained product by XRD (X-ray diffraction), comparing an obtained spectrogram with a standard card, and determining the obtained spectrogram as the NaY type molecular sieve;
the chemical composition (molar ratio) of the molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O＝44.1:1:82.7:40.7:2170；
(5) 0.7g of NaF solid was added to 100ml of the obtained molecular sieve filtrate to obtain a synthetic solution (the amount of NaF added was about SiO in the synthetic solution)210 mol% of);
introducing CO into the synthetic liquid under the stirring state2Carbonation to pH 13.838; then carrying out hydrothermal crystallization for 15h at the temperature of 190 ℃, and filtering the obtained hydrothermal crystallization product to obtain third filter residue and second filtrate; further washing, drying and roasting the third 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 31.6;
(6) mixing the second filtrate (Na as main component)2CO3Part containing a small amount of Si and Al) is recycled and added into the sodium carbonate solution in the step (3) for dilution, filtration and washing of water leaching products; the remaining part of the second filtrate is evaporated and crystallized to obtain Na2CO3Recycling the solid to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1)。
The one-time consumption efficiency mu of the residue of the aluminum extraction by the fly ash acid method is 87.12 percent; after the first filter residue is recycled, the overall consumption efficiency of the residue generated in the aluminum extraction by the fly ash acid method is considered to be approximately 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 taken and added with 700ml of deionized water (the amount of water is 1000ml relative to 100g of the roasted slag), water leaching is carried out for 40min at 100 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved out2SiO3And 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 650g (equivalent to 70g of roasting slag) of all water-leached products, carrying out suction filtration at the temperature of 60 ℃, and then adding 100ml of 15 weight percent sodium carbonate solution for washing (equivalent to 286ml of the total dosage of the sodium carbonate solution relative to 100g of roasting slag); and adding a certain amount of hot water (about 80 ℃) for washing, drying the obtained first filter residue to obtain 20.08g of filter residue, wherein the one-time consumption efficiency mu of the fly ash acid method aluminum extraction residue is only 59.84% by calculation.
In the high-temperature water leaching process of the comparative example 1, the dosage of the added water is too much and exceeds the liquid-solid ratio range of 150-200 ml of water relative to 100g of the roasting slag defined by the invention, so that the alkalinity of a water leaching product is reduced, the dissolution rates of silicon and aluminum are seriously low, the yield of first filter residue is high, and the aim of efficiently dissolving the aluminum extraction residue by the fly ash acid method cannot be fulfilled.
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 iron removal, 70g of the roasted slag is taken and added with 140ml of deionized water (the amount of water is 200ml relative to 100g of the roasted slag), water leaching is carried out for 20min at 100 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved out2SiO3And 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) taking 100g of all water-immersed products (which is 70g of roasted slag) under the high-speed stirring state, adding 100ml of boiling water into the water-immersed products for dilution, carrying out suction filtration at the temperature of 60 ℃, and adding 100ml of boiling water for flushing (equivalent to 286ml of the total adding amount of the boiling water relative to 100g of the roasted slag); adding a certain amount of hot water (about 80 ℃) for washing to obtain a first filtrate with the volume of 400ml for synthesizing the NaY type molecular sieve; drying the obtained first filter residue to obtain 18.13g, and recycling the first filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝8.9:1:12.2:7.7:426。
(4) And (3) taking 100ml of the first filtrate, adding 3g of directing agent (from preparation example 2), directly performing hydrothermal crystallization at 95 ℃ for 24h to synthesize the NaY type molecular sieve, and filtering the obtained hydrothermal crystallization product to obtain a solid product.
The obtained solid product is detected by XRD to be a mixture of amorphous aluminosilicate and various molecular sieves, namely, the pure NaY type molecular sieve cannot be obtained.
In comparative example 2, the water leaching product is diluted and filtered and washed by using boiling water, and a sodium carbonate solution is not adopted, so that Si in a liquid phase of the water leaching product is highly hydrolyzed in the dilution and filtering processes to generate solid-phase hydrated silicon dioxide, so that serious filtering loss is generated, the yield of first filter residue is greatly increased, and the once-dissolving efficiency mu of the fly ash acid method aluminum extraction residue is reduced to 63.74%. Meanwhile, the first filtrate is directly subjected to hydrothermal synthesis according to conventional hydrothermal synthesis conditions, and a pure NaY type molecular sieve cannot be obtained.
In addition, the synthesis mother liquor suitable for synthesizing the high-silicon mordenite cannot be obtained in the steps (1) to (3), and pure high-silicon mordenite cannot be obtained. The tail liquid after synthesizing the NaY molecular sieve or the main component of the molecular sieve filtrate is sodium carbonate which only contains trace Si and Al, and the tail liquid or the molecular sieve filtrate can not be used as a silica-alumina source to further synthesize any other type of molecular sieve.
Comparative example 3
(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 taken and added with 140ml of deionized water (the amount of water is 200ml relative to 100g of the roasted slag), water leaching is carried out for 20min at 100 ℃ and normal pressure, and Na in the roasted slag is leached and dissolved out2SiO3And 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) taking 100g (equivalent to 70g of roasting slag) of all water-leached products under the high-speed stirring state, adding 100ml of sodium carbonate solution (the concentration is 15 weight percent for the second filtrate recycled from the step (5)) to dilute, carrying out suction filtration at the temperature of 60 ℃, adding 100ml of the sodium carbonate solution to wash (corresponding to 286ml of the total dosage of the second filtrate relative to 100g of roasting slag); adding a certain amount of hot water (about 80 ℃) for washing to obtain a first filtrate with the volume of 400ml for synthesizing the NaY type molecular sieve; drying the obtained first filter residue to obtain 6.13g of filter residue, and recycling the filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝13.0:1:12.5:9.5:424。
(4) Adding sodium metaaluminate (NaAlO) into 400ml of the first filtrate2)26.25g of solid and 325ml of deionized water are used for preparing NaY molecular sieve synthesis mother liquor, and the chemical composition (molar ratio) of the NaY molecular sieve synthesis mother liquor is SiO2:Al2O3:Na2O:CO3 2-:H2O＝4:1:5.8:3.0:240。
And then adding 12g of directing agent (from preparation example 2) into the NaY synthesis mother liquor to synthesize the NaY type molecular sieve, performing hydrothermal crystallization for 24 hours at 95 ℃, and filtering the obtained hydrothermal crystallization product to obtain a solid product. The obtained solid product is detected by XRD, and the phase composition of the solid product is determined to be pure NaY type molecular sieve.
(5) Second filtrate (main component is Na)2CO3Only containing a small amount of Si and Al) is recycled and added into the sodium carbonate solution in the step (3) for diluting, filtering and washing the water leaching product; 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).
In comparative example 3, NaY type molecular sieve synthesis mother liquor is prepared conventionally, but aluminum source sodium metaaluminate (M) needs to be addedout26.25g), the absorption efficiency mu of the fly ash acid method aluminum extraction residue is only 57.16 percent; and the obtained second filtrate mainly contains sodium carbonate, only contains trace silicon and aluminum, and cannot be used as a silicon and aluminum source to further prepare ZSM-5 or any other type of molecular sieve, namely, the obtained product only contains one NaY type molecular sieve.
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 60min at 890 ℃, quickly cooling the mixture by 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 into 140ml of deionized water (corresponding to 100g of the roasted slag)Burning slag charge, the amount of water is 200ml), soaking in water at 100 deg.C and normal pressure for 20min, leaching to dissolve Na in the baked slag charge2SiO3And 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) taking 100g (equivalent to 70g of roasting slag) of all water-leached products under the high-speed stirring state, adding 100ml of sodium carbonate solution (the concentration is 15 weight percent for the second filtrate recycled from the step (6)) to dilute, carrying out suction filtration at the temperature of 60 ℃, adding 100ml of the sodium carbonate solution to wash (corresponding to 286ml of the total dosage of the second filtrate relative to 100g of roasting slag); adding a certain amount of hot water (about 80 ℃) for washing to obtain a first filtrate with the volume of 400ml for synthesizing the NaY type molecular sieve; drying the obtained first filter residue to obtain 6.25g of filter residue, and recycling the filter residue to the alkaline roasting of the fly ash acid-process aluminum extraction residue in the step (1);
the first filtrate had a chemical composition (molar ratio) of SiO2:Al2O3:Na2O:CO3 2-:H2O＝12.6:1:19:9:440。
(4) Taking 400ml of the whole first filtrate (70.0 g of the first filtrate in terms of roasting slag), adding 866ml of deionized water for hydrolysis (the total volume of hydrolysate is 1237ml relative to 100g of roasting slag); sodium metasilicate (Na) is also added2SiO3) 122.07g of solid, which is used as the hydrothermal crystallization mother liquor of the high-silicon mordenite after being completely dissolved, and the chemical composition (molar ratio) of the solid is SiO2:Al2O3:Na2O:CO3 2-:H2O＝32.6:1:39:9:1402。
(5) 1.4g of NaF solid was added to 100ml of the obtained hydrothermal crystallization mother liquor to obtain a synthetic liquor (the amount of NaF added was about SiO in the synthetic liquor)220 mol% of);
introducing CO into the synthetic liquid under the stirring state2Carbonizing to pH 12.0; then carrying out hydrothermal crystallization for 36h at the temperature of 180 ℃, and carrying out hydrothermal crystallization on the obtained productFiltering to obtain third filter residue and second filtrate; further washing, drying and roasting the third filter residue, carrying out XRD analysis on the obtained product to obtain a spectrogram similar to that shown in figure 3, determining the obtained product as high-silicon mordenite, and carrying out EDS analysis on the obtained mordenite to obtain the silicon-aluminum ratio of 27.6;
(6) mixing the second filtrate (Na as main component)2CO3Part containing a small amount of Si and Al) is recycled and added into the sodium carbonate solution in the step (3) for diluting, filtering and washing the water leaching product; 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).
Adjusting the composition of the first filtrate for the synthesis of high-silicon mordenite in comparative example 4, additional silicon source of sodium metasilicate (M)out122.07g) results in the production of only high-silicon mordenite and results in a single-pass efficiency μ of only 25.43% in the fly ash acid-stripping residue. The main component of the obtained second filtrate is sodium carbonate, only contains trace silicon and aluminum, and cannot be used as a silicon and aluminum source to further prepare NaY or any other types of molecular sieves; namely, the obtained product only contains one 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 method can produce and obtain the NaY type molecular sieve and the high-silicon mordenite with high added values simultaneously when 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 alumina, NaY-type molecular sieve and high-silicon mordenite is realized without additionally adding a silicon source or an aluminum source.
Claims (12)
1. A method for preparing NaY type molecular sieve and high-silicon mordenite by using fly ash acid method 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; sequentially carrying out high-temperature water immersion and heat preservation filtration on the roasted slag charge to obtain a first filtrate;
(2) carrying out NaY type molecular sieve hydrothermal crystallization on the first filtrate to obtain a NaY type molecular sieve and a molecular sieve filtrate;
the molar ratio of chemical compositions in the molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O＝(30～45):1:(59～95):(27～47):(1610～2260)；
(3) Carrying out hydrothermal crystallization on the molecular sieve 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 molecular sieve filtrate to obtain synthetic liquid;
ii) introducing CO into the synthetic fluid2Carrying out carbonation to ensure that the pH value of the synthetic liquid 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 third filter residue and the second filtrate; and washing, drying and roasting the third 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 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.
3. The method as claimed in claim 1, wherein, in the step (1), the high temperature water immersion process comprises: removing iron from the roasted slag, and mixing the roasted slag with water to obtain a water leaching product; the water immersion temperature is 95-105 ℃, and the water immersion time is 15-20 min.
4. The method according to claim 3, wherein the amount of water used is 150 to 200ml per 100g of the roasted slag.
5. The method of claim 3, wherein in step (1), the incubation filtering comprises: diluting, filtering and washing the water leaching product with part of the second filtrate to obtain first filter residue and the first filtrate; the filtering temperature is kept between 60 and 80 ℃.
6. A method according to claim 5, wherein the second filtrate is used in an amount of 250 to 350ml per 100g of the roasted slag.
7. The method of claim 5, wherein the first filtrate is SiO2With Al2O3The molar ratio of (10-25): 1.
8. the method of claim 5, wherein the method further comprises: and (3) drying the first filter residue, and then recycling the first filter residue, adding the first filter residue into the fly ash acid method aluminum extraction residue in the step (1).
9. The method as claimed in claim 1, wherein, in the step (2), the NaY type molecular sieve is hydrothermally crystallized by:
a) adding a directing agent into the first filtrate to prepare NaY molecular sieve mother liquor, and adjusting the composition of the NaY molecular sieve mother liquor to meet Na2O:Al2O3:SiO2:H2O＝(11.1～23.7)：1：(12.8～18.4)：(386～550)；
b) Carrying out hydrothermal crystallization on the product obtained in the step a) at 95-105 ℃ for 18-36 h to obtain a NaY type molecular sieve hydrothermal crystallization product;
c) filtering the NaY type molecular sieve hydrothermal crystallization product to obtain second filter residue and the molecular sieve filtrate; and drying the second filter residue to obtain the NaY type molecular sieve.
10. 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.
11. The method of claim 1, wherein the method further comprises:
recycling a part of the second filtrate to the heat-preservation filtering process in the step (1); and (3) evaporating and crystallizing the other part of the second filtrate to obtain sodium carbonate, and recycling the sodium carbonate to the alkali roasting process in the step (1).
12. 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 NaY type molecular sieve and the high-silicon mordenite are prepared by the method of any one of claims 1 to 11 from the fly ash acid method aluminum extraction residue.
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| CN102173433A (en) * | 2011-03-09 | 2011-09-07 | 南京理工大学 | Process for synthesizing single-phase sodalite from fly ash |
| CN105967201A (en) * | 2016-06-23 | 2016-09-28 | 中国神华能源股份有限公司 | Method for producing P-type zeolite from fly ash acid sludge |
| CN106517237A (en) * | 2016-12-01 | 2017-03-22 | 神华集团有限责任公司 | Method for preparing NaY-type molecular sieve and ZSM-5 type molecular sieve by use of fly ash acid-process aluminum extraction residues and utilization method of fly ash |
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| CN102173433A (en) * | 2011-03-09 | 2011-09-07 | 南京理工大学 | Process for synthesizing single-phase sodalite from fly ash |
| CN105967201A (en) * | 2016-06-23 | 2016-09-28 | 中国神华能源股份有限公司 | Method for producing P-type zeolite from fly ash acid sludge |
| CN106517237A (en) * | 2016-12-01 | 2017-03-22 | 神华集团有限责任公司 | Method for preparing NaY-type molecular sieve and ZSM-5 type molecular sieve by use of fly ash acid-process aluminum extraction residues and utilization method of fly ash |
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